JP7426776B2 - How to form a bank pattern - Google Patents

Description

The present invention relates to a method for forming a bank pattern of a cured film obtained from a photosensitive resin composition. The method for forming a bank pattern of a cured film using this photosensitive resin composition is particularly suitable as a method for forming an interlayer insulating film in a liquid crystal display or an EL display, or a light shielding wall or partition wall compatible with an inkjet method.

2. Description of the Related Art In recent years, full-color display substrate manufacturing technology using inkjet has been actively studied in the manufacturing process of display elements such as thin film transistor (TFT) type liquid crystal display elements and organic EL (electroluminescent) elements. For example, in the production of color filters for liquid crystal display elements, in contrast to conventional printing, electrodeposition, dyeing, or pigment dispersion methods, sections defining pre-patterned pixels (hereinafter referred to as banks) are blocked from light. A color filter and a method for manufacturing the same (Patent Document 1) have been proposed, in which the color filter is formed of a photosensitive resin layer and ink droplets are dropped in an area surrounded by the banks. Furthermore, a method has been proposed (Patent Document 2) in which a bank is prepared in advance for an organic EL display element, and ink that becomes a light emitting layer is similarly dropped onto the bank to produce an organic EL display element.
However, when using the inkjet method to drop ink droplets into an area surrounded by banks, in order to prevent the ink droplets from overflowing beyond the bank and into neighboring pixels, the substrate is made to have ink-philic properties (hydrophilicity). The surface must be water repellent.

In order to achieve the above objectives, it is proposed that continuous plasma (ozone) treatments such as oxygen gas plasma treatment and fluorine gas plasma treatment can be used to make the substrate hydrophilic and the banks water repellent. (Patent Document 3), but the process is complicated. In addition, a proposal has been made to incorporate a fluorine-based surfactant or a fluorine-based polymer into a photosensitive organic thin film (Patent Document 4), but consideration must be given to not only photosensitivity but also coating properties, such as compatibility and amount Not only is there a lot to be done, but the UV ozone treatment during hydrophilic treatment of the substrate reduces the water repellency of the surface, making it impractical.

In addition, in order to achieve the above purpose, a layer containing a hydrophilic compound is provided in the lower layer of the bank material having liquid repellency, and by developing and removing it together with the upper layer bank material, the bank material has lyophilic properties due to the components of the bank material. Methods for preventing the bank opening from being contaminated have been proposed (Patent Documents 5 to 7). However, this method has the problem that moisture absorption is likely to occur due to the high hydrophilicity of the lower layer, and the pattern is likely to peel off during the development process.

In addition, in order to achieve the above purpose, an organic layer is provided as a lower layer of a bank material having liquid repellency, and after forming a pattern with the upper layer bank material, the lower layer is removed by a dry etching process, thereby improving the structure of the bank opening. A method of improving liquid properties has been proposed (Patent Document 8). However, this method has the problem of complicating the process.

Furthermore, Patent Document 9 and Patent Document 10 propose a method for forming a pattern by performing one exposure step and one development step on two stacked organic layers. However, none of these methods was aimed at forming a bank pattern having liquid repellency. Furthermore, in the method of Patent Document 9, since the lower organic layer does not have photosensitivity, precise process control is required in order to control the dimensions of the pattern. In the method of Patent Document 10, it was necessary to perform heat treatment after the exposure step, and the process was complicated.

Japanese Patent Application Publication No. 2000-187111 Japanese Patent Application Publication No. 11-54270 Japanese Patent Application Publication No. 2000-353594 Japanese Unexamined Patent Publication No. 10-197715 Japanese Patent Application Publication No. 2010-33925 Japanese Patent Application Publication No. 2010-73340 Japanese Patent Application Publication No. 2010-129344 Japanese Patent Application Publication No. 2011-216250 Patent No. 4182358 Patent No. 5083566

The present invention provides a method for forming a bank pattern in which residues such as components of the liquid-repellent resist material are unlikely to remain in areas other than the banks even when using liquid-repellent banks that are simple in process and advantageous in terms of production cost. I will provide a.

The present inventors coated a first photosensitive resin composition containing an alkali-soluble resin having an amide group on a substrate directly or through another layer to provide a lower layer film, and on this lower layer film. A second photosensitive resin composition containing a polymer as a liquid repellent component is applied to form a resist film, and the resist film is exposed and developed to form a bank. In this development process, the lower layer film in the non-bank area is removed together with the resist film in the non-bank area, thereby reducing the resist film residue containing lyophobic components on the substrate and maintaining the lyophilic property of the opening. The present invention was completed by discovering that water repellency and liquid repellency can be efficiently imparted to the membrane surface.
Here, an area on the substrate where a bank is located is defined as a bank part, and an area other than the bank is defined as a non-bank part.

That is, the present invention relates to the following.
1. A method of forming a bank and a region demarcated by the bank on a substrate, the method of forming a bank pattern for forming an organic thin film in the region demarcated by the bank,
Forming a lower layer film by applying a first photosensitive resin composition containing the following components (A), (C) and (D) onto a substrate directly or via another layer to form a lower layer film. process and
A resist film forming step of forming a resist film by applying a second photosensitive resin composition containing the following components (a), (b), (c) and (d) on the lower layer film. and,
A method for forming a bank pattern, comprising the steps of forming a bank by exposing and developing the resist film, and in the developing process, a lower layer film in a non-bank part is removed together with the resist film in a non-bank part.
(A) Component: alkali-soluble resin having an amide group,
(C) Component: solvent,
(D) Component: photosensitizer,
(a) Component: alkali-soluble resin,
Component (b): a polymer having a liquid repellent group (b1),
(c) Component: solvent,
(d) Component: Photosensitizer.
2. The method for forming a bank pattern according to 1 above, wherein the first photosensitive resin composition satisfies at least one of the following (Z1) to (Z4).
(Z1): further contains a crosslinking agent as component (E);
(Z2): Component (A), the alkali-soluble resin having an amide group, further has a self-crosslinking group, or at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group. further having a reactive group;
(Z3): A photoradical generator whose (D) component is (D-2), further containing a compound having two or more ethylenic double bonds as the (F) component;
(Z4): A photoacid generator in which the (D) component is (D-3), and the (G) component further contains two functional groups that form a covalent bond with the acid generated from (D-3). Contains a compound having the above.
3. The method for forming a bank pattern according to 1 or 2 above, wherein the second photosensitive resin composition satisfies at least one of the following (z1) to (z4).
(z1): further contains a crosslinking agent as component (e);
(z2): The alkali-soluble resin of component (a) further has a self-crosslinking group, or a group that reacts with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group. further has;
(z3): A photoradical generator whose (d) component is (d-2), further containing a compound having two or more ethylenic double bonds as the (f) component;
(z4): A photoacid generator in which the (d) component is (d-3), and the (g) component further includes two functional groups that form a covalent bond with the acid generated from (d-3). Contains a compound having the above.
4. 3. The method for forming a bank pattern according to any one of 1 to 3 above, wherein component (D) and/or (d) is a quinonediazide compound.
5. 2. The method for forming a bank pattern according to 2 above, wherein component (D) is a quinonediazide compound and further satisfies either (Z1) or (Z2).
6. 3. The method for forming a bank pattern according to 3 above, wherein component (d) is a quinonediazide compound and further satisfies either (z1) or (z2).
7. 5. The method for forming a bank pattern as described in 5 above, wherein the component (D) is diazonaphthoquinone. 8. 7. The method for forming a bank pattern as described in 6 above, wherein the component (d) is diazonaphthoquinone. 9. 1 above, wherein the liquid repellent group (b1) is at least one group selected from a fluoroalkyl group having 3 to 10 carbon atoms, a polyfluoroether group, a silyl ether group, and a polysiloxane group represented by the following formula 4. 9. The method of forming a bank pattern according to any one of 8 above.
-(SiR ¹ R ² -O) _n -SiR ¹ R ² R ^3Formula 4
(However, R ¹ and R ² independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, R ³ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and n represents 1 to 200 carbon atoms.) (Represents an integer.)
10. Any one of the above 1 to 9, wherein the alkali-soluble resin having an amide group as the component (A) and/or the alkali-soluble resin as the component (a) has a number average molecular weight of 2,000 to 50,000 in terms of polystyrene. The method for forming a bank pattern described in .
11. The method for forming a bank pattern according to any one of items 2 to 10 above, wherein the component (E) is 1 part by mass to 50 parts by mass relative to 100 parts by mass of the component (A).
12. The method for forming a bank pattern according to any one of items 1 to 11 above, characterized in that the component (b) is contained in an amount of 0.1 part by mass to 20 parts by mass based on 100 parts by mass of the component (a). .
13. 13. The method for forming a bank pattern according to any one of 1 to 12 above, wherein the polymer of component (b) is an acrylic polymer.
14. 14. The method for forming a bank pattern as described in 13 above, wherein the acrylic polymer as the component (b) has a number average molecular weight of 2,000 to 100,000 in terms of polystyrene.
15. Component (e) is contained in an amount of 1 part by mass to 50 parts by mass with respect to a total of 100 parts by mass of components (a) and (b), as described in any one of 3 to 14 above. How to form a bank pattern.
16. 16. The method for forming a bank pattern as described in any one of 1 to 15 above, wherein the component (b) is a polymer further having the following (b2).
(b2): at least one group selected from an N-alkoxymethylamide group, a blocked isocyanate group, and a trialkoxysilyl group.
17. 17. The method for forming a bank pattern as described in any one of 1 to 16 above, wherein the component (b) is a polymer further having the following (b3).
(b3): at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group.
18. 12. The method for forming a bank pattern according to any one of 1 to 11 above, wherein the component (a) is a resin having a liquid-repellent group (b1) and does not contain the component (b).
19. The method for forming a bank pattern as described in 18 above, wherein the polymerized unit having the liquid-repellent group (b1) occupies 5 to 30 parts by mass in the 100 parts by mass of component (a).
20. 20. The method for forming a bank pattern as described in 18 or 19 above, wherein the component (e) is 1 part by mass to 50 parts by mass relative to 100 parts by mass of the component (a).
21. 21. The method for forming a bank pattern as described in any one of 1 to 20 above, wherein the other layer is an organic electroluminescent hole injection layer.
22. A cured film formed by the method for forming a bank pattern according to any one of 1 to 21 above.
23. 23. A display element having the cured film described in 22 above.
24. 23. A display element comprising the cured film described in 22 above as an image-forming partition wall.
25. A photosensitive resin composition for forming a lower layer film of a resist film, containing the following components (A), (C) and (D).
(A) Component: alkali-soluble resin having an amide group,
(C) Component: solvent,
(D) Component: Photosensitizer.

According to the method for forming a bank pattern of the present invention, even if a liquid-repellent bank, which is simple in process and advantageous in terms of production cost, is used, the liquid-repellent resist material is not applied to the substrate surface in the non-bank area. By suppressing residues such as components, it is possible to form a bank pattern that improves the lyophilicity of the substrate surface. In other words, it is possible to achieve both the liquid repellency of the bank and the lyophilic property of the non-bank portion, and it is possible to form a uniform organic thin film within the region partitioned by the bank.

FIG. 1 is a schematic cross-sectional view showing a manufacturing method for forming a bank and a region defined by the bank on a substrate.

The details of the bank pattern forming method of the present invention will be explained below.
A method for forming a bank pattern of the present invention is a method for forming a bank and a region demarcated by the bank on a substrate, the method comprising forming a bank pattern for forming an organic thin film in the region demarcated by the bank. In the method,
Forming a lower layer film by applying a first photosensitive resin composition containing the following components (A), (C), and (D) onto the substrate directly or via another layer to form a lower layer film. process and
A resist film forming step of forming a resist film by applying a second photosensitive resin composition containing the following components (a), (b), (c) and (d) on the lower layer film. and,
A bank pattern forming method comprising: forming a bank by exposing and developing the resist film; and a bank forming step in which a lower layer film in a non-bank part is removed together with the resist film in a non-bank part in the developing process. be.
(A) component: alkali-soluble resin having an amide group (C) component: solvent (D) component: photosensitizer (a) component: alkali-soluble resin (b) component: polymer having a liquid-repellent group (b1) ( c) Component: Solvent (d) Component: Photosensitizer

In the second photosensitive resin composition of the present invention, the component (b) is preferably a polymer further having the following (b2).
(b2): at least one group selected from an N-alkoxymethylamide group, a blocked isocyanate group, and a trialkoxysilyl group.
In the second photosensitive resin composition of the present invention, the component (b) is preferably a polymer further having the following (b3).
(b3): at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group.

It is preferable that the first photosensitive resin composition of the present invention further satisfies at least one of the following (Z1) to (Z4).
(Z1): further contains a crosslinking agent as component (E);
(Z2): Component (A), the alkali-soluble resin having an amide group, further has a self-crosslinking group, or at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group. further having a reactive group;
(Z3): A photoradical generator whose (D) component is (D-2), further containing a compound having two or more ethylenic polymerizable groups as the (F) component;
(Z4): A photoacid generator in which the (D) component is (D-3), and the (G) component is a functional group that forms a covalent bond with the acid generated from the (D-3) component. Contains compounds that have more than one.

It is preferable that the second photosensitive resin composition of the present invention further satisfies at least one of the following (z1) to (z4).
(z1): further contains a crosslinking agent as component (e);
(z2): The alkali-soluble resin of component (a) further has a self-crosslinking group, or a group that reacts with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group. further has;
(z3): A photoradical generator whose (d) component is (d-2), further containing a compound having two or more ethylenic polymerizable groups as the (f) component;
(z4): A photoacid generator in which the component (d) is (d-3), and the component (g) is a functional group that forms a covalent bond with the acid generated from the component (d-3). Contains compounds that have more than one.

The photosensitive resin composition of the present invention is preferably a positive photosensitive resin composition in which component (D) and/or (d) is a quinonediazide compound.

Hereinafter, a method for forming a bank pattern according to the present invention will be described with reference to FIG.

<Lower film formation process>
In the manufacturing method of the present invention, first, a first photosensitive resin composition consisting of a monomer having an amide group and a monomer having an alkali-soluble group, which will be described later, is coated on the substrate 11 directly or via another layer, and then prebaked. Then, a lower layer film 12 having no liquid repellency is provided.

The details of each component of the lower layer film will be explained below.

<(A) component>
Component (A) of the present invention is an alkali-soluble resin having an amide group. Having an amide group forms hydrogen bonds within or between molecules, and exhibits solvent resistance when coating the upper resist film, which will be described later. Do not come into contact with. The resin of component (A) contains an alkali-soluble group to impart alkali solubility, and examples of the alkali-soluble group include a phenolic hydroxy group, a carboxyl group, an acid anhydride group, an imide group, a sulfonyl group, Included are phosphate groups, boronic acid groups, and active methylene and methine groups. The phenolic hydroxy group and carboxyl group are not only alkali-soluble groups, but also heat-reactive sites (sites that can form a crosslinking structure with the crosslinking agent of component (E)), as will be described later.
In addition, component (A) is not particularly limited in terms of other structure or functional groups as long as it is an alkali-soluble resin having the above-mentioned amide group. For example, when containing a compound having two or more functional groups that form a covalent bond with the (G) acid described below, the (A) component may not have a reactive site with the (G) component; ), the reactive site may be a group that can form a covalent bond with component (G) by the action of an acid, or a group that can form a covalent bond with component (G) by heating. There are no particular limitations.

The active methylene group herein refers to a methylene group (-CH ₂ -) having a carbonyl group at an adjacent position and having reactivity with a nucleophilic reagent. Furthermore, in the present invention, the active methine group refers to the active methylene group having a structure in which one hydrogen atom of the methylene group is substituted with an alkyl group, and has reactivity with nucleophilic reagents.

（式（Ａ１）中、Ｒはアルキル基、アルコキシ基又はフェニル基を表し、破線は結合手を表す。） Among active methylene groups and active methine groups, active methylene groups are preferred, and active methylene groups represented by the following formula (A1) are more preferred.

(In formula (A1), R represents an alkyl group, an alkoxy group, or a phenyl group, and the broken line represents a bond.)

In the above formula (A1), the alkyl group represented by R includes, for example, an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 5 carbon atoms is preferable.
Examples of such alkyl groups include methyl, ethyl, n-propyl, and i-propyl groups.
Among these, methyl, ethyl, n-propyl and the like are preferred.

In the above formula (A1), examples of the alkoxy group represented by R include an alkoxy group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms is preferable.
Examples of such alkoxy groups include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, and t-butoxy groups.
Among these, methoxy, ethoxy, i-propoxy, n-propoxy and the like are preferred.

Examples of the group represented by the above formula (A1) include the following structures. In addition, in the structural formula, a broken line represents a bond.

Among the alkali-soluble resins of component (A) above, those having an amide group, at least one group selected from the group consisting of a phenolic hydroxy group and a carboxyl group as an alkali-soluble group, and having a number average molecular weight It is preferable to use an alkali-soluble resin having an alkali-soluble resin of 2,000 to 50,000.

The alkali-soluble resin of the above-mentioned component (A) may be any alkali-soluble resin having such a structure, and there are no particular limitations on the main chain skeleton and the type of side chains of the polymer constituting the resin.

However, the alkali-soluble resin as component (A) has a number average molecular weight within the range of 2,000 to 50,000. If the number average molecular weight is too high (more than 50,000), development residues are likely to be generated and the sensitivity will be greatly reduced, while if the number average molecular weight is too small (less than 2,000), development will be difficult. In this case, a considerable amount of film loss may occur in the exposed areas, resulting in insufficient curing.

Examples of the alkali-soluble resin as component (A) include acrylic resins, polyhydroxystyrene resins, polyimide precursors, and polyimides. Among them, acrylic resins (acrylic polymers) can be mentioned as preferred resins.

Further, in the present invention, an alkali-soluble resin made of a copolymer (hereinafter referred to as a specific copolymer) obtained by polymerizing a plurality of types of monomers can also be used as the component (A). In this case, the alkali-soluble resin of component (A) may be a blend of multiple types of specific copolymers.

That is, the above-mentioned specific copolymer contains a monomer having an amide group as well as a monomer exhibiting alkali solubility, that is, at least one group selected from the group consisting of a carboxyl group and a phenolic hydroxy group as a suitable alkali soluble group. and optionally at least one monomer selected from the group of monomers copolymerizable with these monomers, as essential structural units, the number average molecular weight of which is 2,000. 50,000. If the number average molecular weight is more than 50,000, residue may be produced.
Note that the monomer having an amide group may also have an alkali-soluble group.

The above monomers having an amide group include, for example, acrylamide, methacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-phenylmethacrylamide, N-phenylacrylamide, 4-hydroxyphenyl Examples include methacrylamide and 4-hydroxyphenylacrylamide, which can be used alone or in combination of two or more. Among them, methacrylamide is preferred.

The above-mentioned "monomer having at least one selected from the group consisting of a carboxyl group and a phenolic hydroxy group" includes a monomer having a carboxyl group and a monomer having a phenolic hydroxy group. These monomers are not limited to those having one carboxyl group or phenolic hydroxy group, but may have a plurality of them.

Specific examples of the above monomers will be listed below, but the invention is not limited to these.
Examples of monomers having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl) phthalate, mono-(2-(methacryloyloxy)ethyl) phthalate, N-(carboxyphenyl) ) maleimide, N-(carboxyphenyl)methacrylamide, N-(carboxyphenyl)acrylamide, and the like.

Examples of the monomer having a phenolic hydroxy group include hydroxystyrene, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, N-(hydroxyphenyl)maleimide, and 4-hydroxyphenylmethacrylate.

In the production of the alkali-soluble resin (specific copolymer) of component (A), the ratio of monomers that exhibit alkali solubility, for example, the ratio of monomers having at least one group selected from the group consisting of carboxyl groups and phenolic hydroxy groups. The ratio is preferably 5% by mass or more, more preferably 10% by mass or more of all the monomers used for producing the alkali-soluble resin (specific copolymer) of component (A). When the monomer that exhibits alkali solubility (monomer having at least one group selected from the group consisting of carboxyl group and phenolic hydroxy group) is less than 5% by mass, the alkali-soluble resin (acrylic polymer) is dissolved in alkali. There is a lack of sex.

In the alkali-soluble resin of component (A), the amount of amide groups introduced is preferably 5 to 60% by mass, more preferably 5 to 40% by mass, based on the total repeating units. For example, in the production of a specific copolymer, the ratio of the monomer having an amide group to all the monomers used in the production of the specific copolymer can be, for example, 5 to 40% by mass.

The alkali-soluble resin that is component (A) of the present invention is a resin copolymerized with a monomer having a hydroxyalkyl group and a polymerizable unsaturated group in order to further stabilize the pattern shape after curing. It is preferable.

Examples of monomers having a hydroxyalkyl group and a polymerizable unsaturated group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl acrylate, 2-hydroxyethyl methacrylate, Examples include 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, glycerin monomethacrylate, and 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone.

In the production of the alkali-soluble resin (specific copolymer) of component (A), when using a monomer having a hydroxyalkyl group and a polymerizable unsaturated group, the ratio of monomers used in the production of the specific copolymer shall be The amount is preferably 5% to 60% by weight, more preferably 10% to 50% by weight, most preferably 20% to 40% by weight, based on the monomer. If the monomer having a hydroxyalkyl group and a polymerizable unsaturated group is less than 5% by mass, the effect of stabilizing the pattern shape of the copolymer may not be obtained. If the amount is 60% by mass or more, the proportion of alkali-soluble groups in component (A) may be insufficient, resulting in deterioration of properties such as developability.

The alkali-soluble resin that is component (A) of the present invention can be further copolymerized with an N-substituted maleimide compound in order to increase the Tg of the copolymer.

Examples of the N-substituted maleimide compound include N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. From the viewpoint of transparency, compounds having no aromatic ring are preferred, and from the viewpoint of developability, transparency, and heat resistance, compounds having an alicyclic skeleton are more preferred, and among them, cyclohexylmaleimide is most preferred.

In the production of the alkali-soluble resin (specific copolymer) as component (A), the ratio when using N-substituted maleimide is preferably 5 to 60% by weight with respect to all the monomers used in the production of the specific copolymer. %, more preferably 10% to 50% by weight. If the amount of N-substituted maleimide is less than 5% by mass, the effect of improving the Tg of the copolymer may not be obtained. If it is 60% by mass or more, the solubility in the solvent may decrease.

When the first photosensitive resin composition of the present invention satisfies requirement (Z2), the alkali-soluble resin (A) used in the present invention further has a self-crosslinking group, or a hydroxy group, a carboxyl group, It is preferable that the copolymer further has a group (hereinafter also referred to as a crosslinkable group) that reacts with at least one group selected from the group consisting of an amide group and an amino group. For example, requirement (Z2) can be satisfied by introducing into the alkali-soluble resin (A) a repeating unit having at least one group selected from the group consisting of the self-crosslinkable group and the crosslinkable group. .

Examples of the self-crosslinking group include N-alkoxymethyl group, N-hydroxymethyl group, alkoxysilyl group, epoxy group, oxetanyl group, vinyl group, and blocked isocyanate group.

Examples of the crosslinkable group include N-alkoxymethyl group, N-hydroxymethyl group, alkoxysilyl group, epoxy group, vinyl group, blocked isocyanate group, and the like.

When such self-crosslinkable groups or crosslinkable groups are contained in the alkali-soluble resin of component (A), the content of such self-crosslinkable groups or crosslinkable groups is based on the total of all repeating units in the resin of component (A). The content of units having a functional group is preferably 10% by mass to 70% by mass, particularly preferably 20% by mass to 60% by mass.

The alkali-soluble resin of component (A) further contains self-crosslinkable groups such as N-alkoxymethyl group, N-hydroxymethyl group, alkoxysilyl group, epoxy group, oxetanyl group, vinyl group and blocked isocyanate group, and N-alkoxy When the repeating unit has at least one type of crosslinkable group such as a methyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group, and a blocked isocyanate group, for example, it has radical polymerizability, An unsaturated compound having at least one type selected from crosslinkable groups such as epoxy groups, oxetanyl groups, vinyl groups, and blocked isocyanate groups, and self-crosslinkable groups such as N-alkoxymethyl groups, N-hydroxymethyl groups, and alkoxysilyl groups. (monomer) may be copolymerized.

Examples of monomers having radical polymerizability and an N-alkoxymethyl group include N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, and N-methylolacrylamide. Can be mentioned.

Examples of monomers having radical polymerizability and further having an N-hydroxymethyl group include N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, and the like.

Examples of monomers having radical polymerizability and an alkoxysilyl group include 3-acryloyloxytrimethoxysilane, 3-acryloyloxytriethoxysilane, 3-methacryloyloxytrimethoxysilane, and 3-methacryloyloxytriethoxysilane. Can be mentioned.

Examples of monomers having radical polymerizability and further having an epoxy group include glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-propylacrylate glycidyl, α-n-butyl glycidyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, Examples include 6,7-epoxyheptyl α-ethyl acrylate, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, and p-vinylbenzylglycidyl ether. Among these, glycidyl methacrylate, 6,7-epoxyheptyl methacrylate, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether, 3,4-epoxycyclohexyl methacrylate, etc. Preferably used. These may be used alone or in combination.

Examples of monomers having radical polymerizability and further having an oxetanyl group include (meth)acrylic esters having an oxetanyl group. In this specification, the term "(meth)acrylic acid" refers to both acrylic acid and methacrylic acid.
Among such monomers are 3-(methacryloyloxymethyl)oxetane, 3-(acryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyl-oxetane, 3-(acryloyloxymethyl)-3- Ethyl-oxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyl-oxetane, 3- (acryloyloxymethyl)-2-phenyl-oxetane, 2-(methacryloyloxymethyl)oxetane, 2-(acryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, 2-(acryloyloxy methyl)-4-trifluoromethyloxetane is preferred, and 3-(methacryloyloxymethyl)-3-ethyl-oxetane, 3-(acryloyloxymethyl)-3-ethyl-oxetane, and the like are preferably used.

Examples of monomers having radical polymerizability and further having a vinyl group include 2-(2-vinyloxyethoxy)ethyl acrylate and 2-(2-vinyloxyethoxy)ethyl methacrylate.

Examples of monomers that have radical polymerizability and further have a blocked isocyanate group include 2-(0-(1'-methylpropylideneamino)carboxyamino)ethyl methacrylate and 2-(3,5-dimethylpyrazolyl) methacrylate. carbonylamino)ethyl and the like.

When the first photosensitive resin composition of the present invention satisfies (Z2), it has radical polymerizability and contains N-alkoxymethyl group, N-hydroxymethyl group, alkoxysilyl group, epoxy group, oxetanyl group, vinyl At least one group selected from self-crosslinkable groups such as groups and blocked isocyanate groups, and crosslinkable groups such as N-alkoxymethyl groups, N-hydroxymethyl groups, alkoxysilyl groups, epoxy groups, vinyl groups, and blocked isocyanate groups. Based on the total of all repeating units that the alkali-soluble resin (A) has, preferably 10% by mass to 70% by mass, particularly preferably 20% by mass. Contains from 60% by mass. If the amount of this structural unit is less than 10% by mass, the heat resistance and surface hardness of the resulting cured film tends to decrease, while if the amount of this structural unit exceeds 70% by mass, the storage of the photosensitive resin composition Stability tends to decrease.

In addition, in the present invention, the alkali-soluble resin (specific copolymer, e.g., acrylic polymer) of component (A) may also be formed using monomers other than the above-mentioned monomers (hereinafter referred to as other monomers) as a constituent unit. It may also be a copolymer. Specifically, the other monomer may be any monomer as long as it is copolymerizable with at least one selected from the group consisting of the above-mentioned monomers having a carboxyl group and monomers having a phenolic hydroxy group, and has the characteristics of component (A). There is no particular limitation as long as it does not cause any damage. Specific examples of such monomers include acrylic ester compounds, methacrylic ester compounds, N-substituted acrylamide compounds, maleimide, acrylonitrile, styrene compounds, and vinyl compounds.
Specific examples of the other monomers will be listed below, but the invention is not limited to these.

Examples of the acrylic ester compounds include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, glycidyl acrylate, phenoxyethyl acrylate, 2,2,2- Trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminoethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxy Butyl acrylate, 2-methyl-2-adamantyl acrylate, γ-butyrolactone acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, diethylene glycol mono Examples thereof include acrylate, caprolactone 2-(acryloyloxy)ethyl ester, and poly(ethylene glycol)ethyl ether acrylate.

Examples of the methacrylic acid ester compounds include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, phenoxyethyl methacrylate, 2,2,2- Trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxy Butyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate, diethylene glycol mono Examples include methacrylate, caprolactone 2-(methacryloyloxy)ethyl ester, and poly(ethylene glycol)ethyl ether methacrylate.

Examples of the N-substituted acrylamide compound include N-methylacrylamide, N-methylmethacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, Examples include N-butoxymethylacrylamide and N-butoxymethylmethacrylamide.

Examples of the styrene compound include styrene having no hydroxyl group, such as styrene, α-methylstyrene, chlorostyrene, and bromostyrene.

Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, cyclohexyl vinyl ether, vinylnaphthalene, vinylanthracene, vinylcarbazole, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo[4.1.0]heptane, 1,2 -epoxy-5-hexene, 1,7-octadiene monoepoxide, and the like.

In the production of the alkali-soluble resin (specific copolymer) that is component (A), the ratio of the above other monomers is preferably 80% by mass or less based on all the monomers used in the production of the specific copolymer. , more preferably 50% by mass or less, still more preferably 20% by mass or less. If it exceeds 80% by mass, the essential components (essential monomers constituting component (A)) will be relatively reduced, making it difficult to obtain the full effect of the present invention.

The method for obtaining the alkali-soluble resin (specific copolymer) that is component (A) used in the present invention is not particularly limited, but for example, it has a group selected from an amide group and a carboxyl group, and a carboxyl group that is an alkali-soluble group. , a monomer having at least one group selected from phenolic hydroxy groups, etc., and optionally a monomer having a hydroxyalkyl group, an N-substituted maleimide compound, and optionally an N-alkoxymethyl group, an N-hydroxymethyl group, Self-crosslinking groups such as alkoxysilyl groups, epoxy groups, oxetanyl groups, vinyl groups and blocked isocyanate groups, and N-alkoxymethyl groups, N-hydroxymethyl groups, alkoxysilyl groups, epoxy groups, vinyl groups, blocked isocyanate groups, etc. A polymerization reaction is carried out at a temperature of 50 to 110°C in a solvent containing a monomer having at least one group selected from crosslinking groups, optionally other copolymerizable monomers, and optionally a polymerization initiator. It can be obtained by At that time, the solvent used is not particularly limited as long as it dissolves the monomer and alkali-soluble resin (specific copolymer) constituting the alkali-soluble resin (specific copolymer). Specific examples include the solvents listed below for component (C).

The alkali-soluble resin (specific copolymer) of component (A) thus obtained is usually in the form of a solution dissolved in a solvent. In the present invention, the obtained solution of the alkali-soluble resin (specific copolymer) as component (A) may be used as it is in the preparation of the photosensitive resin composition described below.

In addition, the solution of the alkali-soluble resin (specific copolymer) of component (A) obtained as described above is reprecipitated by adding it to diethyl ether, water, etc. under stirring, and the generated precipitate is filtered. - After washing, the powder of the specific copolymer can be obtained by drying at room temperature or by heating under normal pressure or reduced pressure. By such an operation, the polymerization initiator and unreacted monomer coexisting with the specific copolymer can be removed, and as a result, purified powder of the specific copolymer can be obtained. If sufficient purification is not possible in one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
In the present invention, the powder of the above-mentioned specific copolymer may be used as it is as the alkali-soluble resin of component (A), or the powder may be redissolved in, for example, component (C) described later to form a solution. It may also be used as

In addition, as the alkali-soluble resin of component (A), polyimide precursors such as polyamic acid, polyamic acid ester, partially imidized polyamic acid, etc., and polyimides such as carboxylic acid group-containing polyimide can also be used. As long as it is soluble, it can be used without particular limitation on its type.

The polyamic acid, which is a polyimide precursor, can generally be obtained by polycondensing (i) a tetracarboxylic dianhydride compound and (j) a diamine compound.

The above (a) tetracarboxylic dianhydride compound is not particularly limited, and specific examples include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3' , 4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride Aromatic tetracarboxylic acids such as 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2, 3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-cyclohexane tetra Carboxylic dianhydride, alicyclic tetracarboxylic dianhydride such as 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride; 1,2,3,4 - Aliphatic tetracarboxylic dianhydrides such as butane tetracarboxylic dianhydride can be mentioned.
These may be used alone or in combination of two or more.

The diamine compound (j) is also not particularly limited, and includes, for example, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,6-diamino-1 , 3-benzenedicarboxylic acid, 2,5-diamino-1,4-benzenedicarboxylic acid, bis(4-amino-3-carboxyphenyl) ether, bis(4-amino-3,5-dicarboxyphenyl) ether, Bis(4-amino-3-carboxyphenyl)sulfone, bis(4-amino-3,5-dicarboxyphenyl)sulfone, 4,4'-diamino-3,3'-dicarboxybiphenyl, 4,4'- Diamino-3,3'-dicarboxy-5,5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dicarboxy-5,5'-dimethoxybiphenyl, 1,4-bis(4-amino -3-carboxyphenoxy)benzene, 1,3-bis(4-amino-3-carboxyphenoxy)benzene, bis[4-(4-amino-3-carboxyphenoxy)phenyl]sulfone, bis[4-(4- Diamine compounds having a carboxyl group such as amino-3-carboxyphenoxy)phenyl]propane, 2,2-bis[4-(4-amino-3-carboxyphenoxy)phenyl]hexafluoropropane; 2,4-diaminophenol; 3,5-diaminophenol, 2,5-diaminophenol, 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, bis(3-amino-4-hydroxyphenyl)ether, bis(4-amino-3-hydroxy) phenyl) ether, bis(4-amino-3,5-dihydroxyphenyl) ether, bis(3-amino-4-hydroxyphenyl)methane, bis(4-amino-3-hydroxyphenyl)methane, bis(4-amino -3,5-dihydroxyphenyl)
Methane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, bis(4-amino-3,5-dihydroxyphenyl)sulfone, 2,2-bis(3 -Amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-amino-3,5-dihydroxyphenyl)hexafluoro Propane, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethoxybiphenyl, 1,4-bis(3-amino-4-hydroxyphenoxy)benzene, 1,3-bis(3-amino-4-hydroxyphenoxy)benzene, 1,4-bis (4-amino-3-hydroxyphenoxy)benzene, 1,3-bis(4-amino-3-hydroxyphenoxy)benzene, bis[4-(3-amino-4-hydroxyphenoxy)phenyl]sulfone, bis[4 - Diamine compounds having a phenolic hydroxy group such as (3-amino-4-hydroxyphenoxy)phenyl]propane, 2,2-bis[4-(3-amino-4-hydroxyphenoxy)phenyl]hexafluoropropane; 1 , 3-diamino-4-mercaptobenzene, 1,3-diamino-5-mercaptobenzene, 1,4-diamino-2-mercaptobenzene, bis(4-amino-3-mercaptophenyl)ether, 2,2-bis Diamine compound having a thiophenol group such as (3-amino-4-mercaptophenyl)hexafluoropropane; 1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-5-sulfonic acid, 1,4 -Diaminobenzene-2-sulfonic acid, bis(4-aminobenzene-3-sulfonic acid) ether, 4,4'-diaminobiphenyl-3,3'-disulfonic acid, 4,4'-diamino-3,3' Examples include diamine compounds having a sulfonic acid group such as -dimethylbiphenyl-6,6'-disulfonic acid. Also, p-phenylenediamine, m-phenylenediamine, 4,4'-methylene-bis(2,6-ethylaniline), 4,4'-methylene-bis(2-isopropyl-6-methylaniline), 4, 4'-methylene-bis(2,6-diisopropylaniline), 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, o- Tolidine, m-tolidine, 3,3',5,5'-tetramethylbenzidine, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(3-aminophenoxy)phenyl] Propane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 4,4'-diaminodiphenyl ether, 3,4- Diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 2,2-bis(4-anilino)hexafluoropropane, 2,2-bis(3-anilino)hexafluoropropane, 2,2-bis(3-amino-4 -tolyl)hexafluoropropane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, 2,2 -Diamines such as bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(trifluoromethyl)benzidine, etc. Compounds can be mentioned.
These may be used alone or in combination of two or more.

When the polyamic acid used in the present invention is produced from (i) a tetracarboxylic dianhydride compound and (j) a diamine compound, the blending ratio of both compounds, that is, the total number of moles of (j) diamine compound/(i) The total number of moles of the tetracarboxylic dianhydride compound is preferably 0.7 to 1.2. As in normal polycondensation reactions, the closer this molar ratio is to 1, the higher the degree of polymerization of the produced polyamic acid and the higher the molecular weight.

Furthermore, when polymerization is performed using an excessive amount of a diamine compound, the terminal amino groups of the remaining polyamic acid can be protected by reacting the terminal amino groups with a carboxylic acid anhydride.
Examples of such carboxylic anhydrides include phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrogenated phthalic anhydride, and methyl-5-norbornene-2,3-dicarboxylic acid. Examples include anhydride, itaconic anhydride, and tetrahydrophthalic anhydride.

In the production of polyamic acid, the reaction temperature for the reaction between the diamine compound and the tetracarboxylic dianhydride compound can be selected from any temperature from -20 to 150°C, preferably from -5 to 100°C. In order to obtain a high molecular weight polyamic acid, the reaction temperature is appropriately selected within the range of 5°C to 40°C and the reaction time is within the range of 1 to 48 hours. In order to obtain a partially imidized polyamic acid having a low molecular weight and high storage stability, it is more preferable to select a reaction temperature from 40°C to 90°C and a reaction time of 10 hours or more.
Further, the reaction temperature when protecting the terminal amino group with an acid anhydride can be selected from any temperature from -20 to 150°C, preferably from -5 to 100°C.

The reaction between the diamine compound and the tetracarboxylic dianhydride compound can be carried out in a solvent. Solvents that can be used in this case include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, and tetramethylurea. , pyridine, dimethylsulfone, hexamethylsulfoxide, m-cresol, γ-butyrolactone, ethyl acetate, butyl acetate, ethyl lactate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, 2- Ethyl methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-ethoxypropionate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene Glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, carbitol acetate, ethyl cellosolve Acetate, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone and the like can be mentioned. These may be used alone or in combination. Furthermore, even a solvent that does not dissolve polyamic acid may be mixed with the above solvent and used as long as the polyamic acid produced by the polymerization reaction does not precipitate.

The solution containing polyamic acid thus obtained can be used as it is for preparing a photosensitive resin composition. Alternatively, the polyamic acid can be isolated by precipitation in a poor solvent such as water, methanol, or ethanol, and then recovered and used.

Further, as the component (A), any polyimide can be used. The polyimide used in the present invention is one obtained by chemically or thermally imidizing a polyimide precursor such as the above-mentioned polyamic acid by 50% or more.

The polyimide used in the first photosensitive resin composition of the present invention preferably has an amide group and also a group selected from a carboxyl group and a phenolic hydroxy group to provide alkali solubility.
As a method for introducing an amide group into polyimide, a method using a monomer having an amide group, a method of capping an amine terminal with an acid anhydride having an amide group, and the like are used.
The method for introducing a carboxyl group or a phenolic hydroxy group into polyimide includes a method using a monomer having a carboxyl group or a phenolic hydroxy group, a method of capping the amine end with an acid anhydride having a carboxyl group or a phenolic hydroxy group, Alternatively, a method may be used in which the imidization rate is set to 99% or less when imidizing a polyimide precursor such as polyamic acid.

Such a polyimide can be obtained by synthesizing a polyimide precursor such as the above-mentioned polyamic acid, followed by chemical imidization or thermal imidization.
As a method for chemical imidization, a method is generally used in which excess acetic anhydride and pyridine are added to a polyimide precursor solution and the mixture is reacted at room temperature to 100°C. Further, as a method for thermal imidization, a method is generally used in which a polyimide precursor solution is heated at a temperature of 180° C. to 250° C. while being dehydrated.

Further, as the alkali-soluble resin of component (A), a phenol novolac resin can be further used.

Moreover, polyester polycarboxylic acid can also be used as the alkali-soluble resin of component (A). Polyester polycarboxylic acid can be obtained from acid dianhydride and diol by the method described in WO 2009/051186.
Examples of the acid dianhydride include the above-mentioned (i) tetracarboxylic dianhydride.
Examples of diols include aromatic diols such as bisphenol A, bisphenol F, 4,4'-dihydroxybiphenyl, benzene-1,3-dimethanol, and benzene-1,4-dimethanol; hydrogenated bisphenol A, hydrogenated bisphenol F , 1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol and other alicyclic diols; and ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol Examples include aliphatic diols such as.

Furthermore, in the present invention, the alkali-soluble resin of component (A) may be a mixture of multiple types of alkali-soluble resins.

<(C) component>
Component (C) used in the present invention is used as a solvent to dissolve component (A) and, if necessary, component (D), component (E), component (F), and component (G), which will be described later. The type and structure of the solvent are not particularly limited as long as it dissolves the other additives mentioned below that are added by.

Examples of such component (C) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, and propylene glycol. Monomethyl ether acetate, propylene glycol propyl ether, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone , ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate , ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide, and Examples include N-methylpyrrolidone.

These solvents can be used alone or in combination of two or more.
Among these components (C), propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate, butyl lactate, etc. have good coating properties and are safe. Propylene glycol monomethyl ether, propylene glycol propyl ether, ethyl lactate, butyl lactate and the like are particularly preferred from the viewpoint of solubility of component (A). These solvents are commonly used as solvents for photoresist materials.

<(D) component>
Examples of the photosensitizer as component (D) include (D-1) a 1,2-quinonediazide compound, (D-2) a photoradical generator, and (D-3) a photoacid generator.

(D-1) The 1,2-quinonediazide compound is a compound having either a hydroxy group or an amino group, or both a hydroxy group and an amino group, and these hydroxy groups or amino groups (hydroxy group and If the amino group has both amino groups, preferably 10 mol% to 100 mol%, particularly preferably 20 mol% to 95 mol% of the total amount thereof is esterified with 1,2-quinonediazide sulfonic acid, or Amidated compounds can be used.
Examples of the 1,2-quinonediazide sulfonic acid include 1,2-naphthoquinone-2-diazide-5-sulfonic acid, 1,2-naphthoquinone-2-diazide-4-sulfonic acid, and 1,2-benzoquinone-2- Examples include diazide-4-sulfonic acid, and the chloride of 1,2-quinonediazide sulfonic acid can be used in the reaction with the above-mentioned compound having either a hydroxy group or an amino group, or both.
As the 1,2-quinonediazide compound (D-1), diazonaphthoquinone can be used.

Examples of the compound having a hydroxy group include phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcinol, catechol, methyl gallic acid, ethyl gallic acid, 1,3,3-tris(4-hydroxyphenyl ) Butane, 4,4-isopropridendiphenol, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 4,4'-dihydroxyphenylsulfone, 4,4 -hexafluoroisopropylidene diphenol, 4,4',4''-trishydroxyphenylethane, 1,1,1-trishydroxyphenylethane, 4,4'-[1-[4-[1-(4- hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3, Phenolic compounds such as 4,4'-tetrahydroxybenzophenone, 2,2',3,4,4'-pentahydroxybenzophenone, 2,5-bis(2-hydroxy-5-methylbenzyl)methyl, ethanol, 2- Aliphatic compounds such as propanol, 4-butanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 2-methoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-butoxypropanol, ethyl lactate, butyl lactate Examples include alcohols.

In addition, the compounds containing the amino group include aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminodiphenyl, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine. , 4,4'-diaminophenylmethane, 4,4'-diaminodiphenyl ether, and other anilines, and aminocyclohexane.

Furthermore, examples of compounds containing both a hydroxy group and an amino group include o-aminophenol, m-aminophenol, p-aminophenol, 4-aminoresorcinol, 2,3-diaminophenol, and 2,4-diaminophenol. , 4,4'-diamino-4''-hydroxytriphenylmethane, 4-amino-4',4''-dihydroxytriphenylmethane, bis(4-amino-3-carboxy-5-hydroxyphenyl) ether, Bis(4-amino-3-carboxy-5-hydroxyphenyl)methane, 2,2-bis(4-amino-3-carboxy-5-hydroxyphenyl)propane, 2,2-bis(4-amino-3- Examples include aminophenols such as carboxy-5-hydroxyphenyl)hexafluoropropane, and alkanolamines such as 2-aminoethanol, 3-aminopropanol, and 4-aminocyclohexanol.

These 1,2-quinonediazide compounds can be used alone or in combination of two or more.

When the first photosensitive resin composition of the present invention is a positive photosensitive resin composition, the content of the compound having a quinonediazide group as component (D-1) is as follows: 100 mass of component (A) The amount is preferably 5 parts by mass to 100 parts by mass, more preferably 8 parts by mass to 50 parts by mass, and even more preferably 10 parts by mass to 40 parts by mass. When the amount is less than 5 parts by mass, the difference in dissolution rate in the developer between the exposed area and the unexposed area of the positive photosensitive resin composition becomes small, and patterning by development may be difficult. In addition, if it exceeds 100 parts by mass, the 1,2-quinonediazide compound may not be sufficiently decomposed by short exposure, resulting in a decrease in sensitivity, or the component (D-1) may absorb light, causing the cured film to deteriorate. Transparency may be reduced.

(D-2) The photoradical generator is not particularly limited as long as it generates radicals upon exposure to light. Specific examples include aromatic ketones such as benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-ethylanthraquinone, and phenanthrene, benzoin methyl ether, and benzoin ethyl. Ether, benzoin ethers such as benzoin phenyl ether, benzoin such as methylbenzoin and ethylbenzoin, 2-(o-chlorophenyl)-4,5-phenylimidazole dimer, 2-(o-chlorophenyl)-4,5- Di(m-methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methylphenyl)imidazole dimer, 2-benzyl-2-dimethylamino-1-(4 -morpholinophenyl)-butanone, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole , 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole and other halomethyloxadiazole compounds, 2,4-bis(trichloromethyl)-6-p-methoxystyryl- S-triazine, 2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl-1,3-butadienyl)-S-triazine, 2-trichloromethyl-4-amino-6-p-methoxy Styryl-S-triazine, 2-(naphth-1-yl)-4,6-bis-trichloromethyl-S-triazine, 2-(4-ethoxy-naphth-1-yl)-4,6-bis-trichloro Halomethyl-S-triazine compounds such as methyl-S-triazine, 2-(4-butoxy-naphth-1-yl)-4,6-bis-trichloromethyl-S-triazine, 2,2-dimethoxy-1, 2-diphenylethan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone, 1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) -Butanone-1,1-hydroxy-cyclohexyl-phenylketone, benzyl, benzoylbenzoic acid, methyl benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl sulfide, benzyl methyl ketal, dimethylaminobenzoate, p-dimethylaminobenzoic acid Isoamyl, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 1-(4-phenylthiophenyl)-1,2 -Octanedione-2-(O-benzoyloxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), 4 -benzoyl-methyldiphenyl sulfide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-(dimethylamino) -2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis(2,4,6-trimethylbenzoyl) ) phosphine oxide, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone, etc. .
The above photoradical generators are easily available as commercial products, and specific examples include IRGACURE 173, IRGACURE 500, IRGACURE 2959, IRGACURE 754, IRGACURE 907, IRGACURE 369, IRGACURE 1300, IRGAC URE 819, IRGACURE 819DW, IRGACURE 1880, IRGACURE 1870, DAROCURE TPO, DAROCURE 4265, IRGACURE 784, IRGACURE OXE01, IRGACURE OXE02, IRGACURE 250 (all BASF ), KAYACURE DETX-S, KAYACURE CTX, KAYACURE BMS, KAYACURE 2-EAQ (and above) , manufactured by Nippon Kayaku Co., Ltd.), TAZ-101, TAZ-102, TAZ-103, TAZ-104, TAZ-106, TAZ-107, TAZ-108, TAZ-110, TAZ-113, TAZ-114, Examples include TAZ-118, TAZ-122, TAZ-123, TAZ-140, and TAZ-204 (manufactured by Midori Kagaku Co., Ltd.).
These photoradical generators can be used alone or in combination of two or more.

When the first photosensitive resin composition of the present invention contains component (D-2), the content thereof is 0.1 parts by mass to 30 parts by mass based on 100 parts by mass of component (A). is preferred, more preferably 0.5 parts by mass to 20 parts by mass, particularly preferably 1 part by mass to 15 parts by mass. If this ratio is too small, the exposed portions may be insufficiently cured, resulting in failure to form a pattern, or even if pattern formation is possible, the film may have low reliability. Furthermore, if this ratio is excessive, the transmittance of the coating film may decrease or poor development may occur in unexposed areas.

The photoacid generator (D-3) is not particularly limited as long as it is a compound that photodecomposes and generates an acid when irradiated with ultraviolet rays. Examples of acids generated when photoacid generators are photodecomposed include hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p- Toluenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzene Sulfonic acid, 1H,1H,2H,2H-perfluorooctanesulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzenesulfonic acid, etc. Examples include acids or hydrates and salts thereof.

Examples of photoacid generators include diazomethane compounds, onium salt compounds, sulfonimide compounds, disulfone compounds, sulfonic acid derivative compounds, nitrobenzyl compounds, benzointosylate compounds, iron arene complexes, halogen-containing triazine compounds, and acetophenone derivative compounds. and cyano group-containing oxime sulfonate compounds. Any conventionally known or conventionally used photoacid generator can be applied in the present invention without particular limitation. In the present invention, the photoacid generator (D) component may be used alone or in combination of two or more. Specific examples include compounds represented by the following formulas [PAG-1] to [PAG-41].

When the first photosensitive resin composition of the present embodiment contains component (D-3), the content is preferably 0.01 parts by mass to 20 parts by mass with respect to 100 parts by mass of component (A). parts, more preferably 0.1 parts by weight to 10 parts by weight, still more preferably 0.5 parts by weight to 8 parts by weight. By setting the content of component (D-3) to 0.01 parts by mass or more, sufficient thermosetting properties and solvent resistance can be imparted. However, if the amount is more than 20 parts by mass, unexposed areas may develop poorly or the storage stability of the composition may deteriorate.

<(E) component>
Component (E) is a crosslinking agent, and is introduced into the first photosensitive resin composition of the present invention when it satisfies requirement (Z1). More specifically, it is a compound having a structure capable of forming a bridged structure through a thermal reaction with a heat-reactive site (for example, a carboxyl group and/or a phenolic hydroxy group) of component (A). Specific examples will be given below, but the invention is not limited to these. The thermal crosslinking agent is selected from, for example, (E1) a crosslinkable compound having two or more substituents selected from an alkoxymethyl group and a hydroxymethyl group, and (E2) a crosslinkable compound represented by the following formula (1). is preferred. These crosslinking agents can be used alone or in combination of two or more.

When the crosslinkable compound having two or more substituents selected from the alkoxymethyl group and hydroxymethyl group of component (E1) is exposed to high temperatures during thermosetting, the crosslinking reaction proceeds through a dehydration condensation reaction. . Examples of such compounds include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine, and phenoplast compounds.

Specific examples of alkoxymethylated glycoluril include 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4 , 6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1,3,3-tetrakis(methoxymethyl) Examples include urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, and 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolinone. Commercially available products include compounds such as glycoluril compounds (product names: Cymel (registered trademark) 1170, Powder Link (registered trademark) 1174) manufactured by Mitsui Cytec Co., Ltd., and methylated urea resins (product name: UFR (registered trademark) 65). ), butylated urea resin (product name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea/formaldehyde resin manufactured by DIC Corporation (high condensation type, product name: Beckamine ( Examples include registered trademarks) J-300S, P-955, N), etc.

Specific examples of alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine. Commercially available products include Mitsui Cytec Co., Ltd. (product name: Cymel (registered trademark) 1123), Sanwa Chemical Co., Ltd. (product names: Nikalac (registered trademark) BX-4000, BX-37, and BL-). 60, BX-55H), etc.

Specific examples of alkoxymethylated melamine include hexamethoxymethylmelamine and the like. Commercially available products include methoxymethyl type melamine compounds (trade name: Cymel (registered trademark) 300, Cymel 301, Cymel 303, Cymel 350), butoxymethyl type melamine compounds (trade name: Mycoat (registered trademark)) manufactured by Mitsui Cytec Co., Ltd. ) 506, 508), methoxymethyl type melamine compounds manufactured by Sanwa Chemical (trade name: Nikalak (registered trademark) MW-30, Nikalak MW-22, Nikalak MW-11, Nikalak MW-100LM, MS-001, Nikalak (registered trademark) MX-002, MX-730, MX-750, MX-035), butoxymethyl type melamine compounds (trade name: Nikalac (registered trademark) MX-45, MX-410, MX-302), etc. Can be mentioned.

It may also be a compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound, and a benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group. Examples include high molecular weight compounds made from melamine and benzoguanamine compounds as described in US Pat. No. 6,323,310. Examples of commercial products of the melamine compound include the trade name Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), and commercial products of the benzoguanamine compound include the trade name Cymel (registered trademark) 1123 (trade name). (manufactured by Mitsui Cytec Co., Ltd.), etc.

Specific examples of phenoplast compounds include 2,6-bis(hydroxymethyl)phenol, 2,6-bis(hydroxymethyl)cresol, 2,6-bis(hydroxymethyl)-4-methoxyphenol, 3 , 3',5,5'-tetrakis(hydroxymethyl)biphenyl-4,4'-diol, 3,3'-methylenebis(2-hydroxy-5-methylbenzenemethanol), 4,4'-(1-methyl ethylidene)bis[2-methyl-6-hydroxymethylphenol], 4,4'-methylenebis[2-methyl-6-hydroxymethylphenol], 4,4'-(1-methylethylidene)bis[2,6- bis(hydroxymethyl)phenol], 4,4'-methylenebis[2,6-bis(hydroxymethyl)phenol], 2,6-bis(methoxymethyl)phenol, 2,6-bis(methoxymethyl)cresol, 2 , 6-bis(methoxymethyl)-4-methoxyphenol, 3,3',5,5'-tetrakis(methoxymethyl)biphenyl-4,4'-diol, 3,3'-methylenebis(2-methoxy-5 -methylbenzene methanol), 4,4'-(1-methylethylidene)bis[2-methyl-6-methoxymethylphenol], 4,4'-methylenebis[2-methyl-6-methoxymethylphenol], 4, Examples include 4'-(1-methylethylidene)bis[2,6-bis(methoxymethyl)phenol], 4,4'-methylenebis[2,6-bis(methoxymethyl)phenol], and the like. It is also available as a commercial product, and specific examples include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF, BI25X-TPA ( As mentioned above, examples include those manufactured by Asahi Yokuzai Kogyo Co., Ltd.).

Furthermore, as the component (E1), an acrylamide compound substituted with a hydroxymethyl group or an alkoxymethyl group, such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-butoxymethylmethacrylamide, or Polymers made using methacrylamide compounds can also be used.

Such polymers include, for example, poly(N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methyl methacrylate, and N-ethoxymethyl. Examples include a copolymer of methacrylamide and benzyl methacrylate, and a copolymer of N-butoxymethylacrylamide, benzyl methacrylate, and 2-hydroxypropyl methacrylate. The weight average molecular weight of such a polymer is from 1,000 to 50,000, preferably from 1,500 to 20,000, more preferably from 2,000 to 10,000.

（式中、ｋは２乃至１０の整数、ｍは０乃至４の整数を示し、Ｒ¹¹はｋ価の有機基を表す） Moreover, the first photosensitive resin composition of the present invention can contain a crosslinkable compound represented by the following formula (1) as the component (E2).

(In the formula, k represents an integer of 2 to 10, m represents an integer of 0 to 4, and R ¹¹ represents a k-valent organic group)

Component (E2) is not particularly limited as long as it is a compound having a cycloalkene oxide structure represented by formula (1). Specific examples thereof include the following formulas E2-1 and E2-2, and the commercial products shown below.

Commercially available products include Epolead GT-401, Epolead GT-403, Epolead GT-301, Epolead GT-302, Celloxide 2021, Celloxide 3000 (product name manufactured by Daicel Corporation), and Denacol EX-, an alicyclic epoxy resin. 252 (product name manufactured by Nagase ChemteX Corporation), CY175, CY177, CY179 (product names manufactured by Huntsman Corporation), Araldite CY-182, CY-192, CY-184 (product names manufactured by Huntsman Corporation ), Epicron 200, Epicron 400 (product names manufactured by DIC Corporation), Epicort 871, Epicoat 872 (product names manufactured by Mitsubishi Chemical Corporation), ED-5661, ED-5662 (product names manufactured by Mitsubishi Chemical Corporation) Co., Ltd. product name), etc. Moreover, these crosslinkable compounds can be used alone or in combination of two or more types.

Among these, compounds represented by Formula E2-1 and Formula E2-2, Epolead, which have a cyclohexene oxide structure from the viewpoint of heat resistance, solvent resistance, process resistance such as long-term baking resistance, and transparency. GT-401, GT-403, GT-301, GT-302, Celoxide 2021, and Celoxide 3000 are preferred.

In addition, as component E, a cross-linked structure is formed by a thermal reaction with a thermally reactive site (for example, a carboxyl group and/or a phenolic hydroxy group) of component (A) other than those shown as component (E1) and component (E2). Compounds that can form can also be used. Specifically, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexane Diol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N', -tetraglycidyl-m-xylene diamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, and N,N,N',N',-tetraglycidyl-4,4'-diaminodiphenylmethane, etc. Epoxy compounds, VESTANAT B1358/100, VESTAGON BF 1540 (all are isocyanurate-type modified polyisocyanates, manufactured by Degussa Japan Co., Ltd.), Takenate (registered trademark) B-882N, Takenate B-7075 (all are isocyanurate-type modified polyisocyanates) Examples include isocyanate compounds such as polyisocyanate (manufactured by Mitsui Chemicals, Inc.).

In addition, as component E, a polymer having two or more structures that can form a cross-linked structure by thermal reaction with the heat-reactive moiety (for example, carboxyl group and/or phenolic hydroxy group) of component (A) may be used. I can do it. Specifically, for example, polymers produced using compounds having an epoxy group such as glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3-methacryloxypropyltrimethoxy Polymers produced using compounds having alkoxysilyl groups such as silane, 2-isocyanatoethyl methacrylate (Karens MOI [registered trademark], manufactured by Showa Denko K.K.), 2-isocyanatoethyl acrylate (Karens AOI [registered trademark], manufactured by Showa Denko KK), 2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate (Karens MOI-BM [registered trademark], (manufactured by Showa Denko K.K.), 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (Karens MOI-BP [registered trademark], manufactured by Showa Denko K.K.), etc. Examples include polymers produced using These compounds may be used alone or in combination to produce a polymer, or may be used in combination with other compounds to produce a polymer.

When component (A) has a group that reacts with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group, a hydroxy group, a carboxyl group, an amide group, A compound having two or more groups represented by amino groups can be used as the component (E).

These crosslinking compounds can be used alone or in combination of two or more.

When component (E) is selected as the crosslinking agent in the first photosensitive resin composition of the present invention, the content is 1 part by mass to 50 parts by mass, preferably 1 part by mass, per 100 parts by mass of component (A). The amount is from 1 part to 40 parts by weight, more preferably from 1 part to 30 parts by weight. If the content of the crosslinkable compound is small, the density of the crosslinks formed by the crosslinkable compound is not sufficient, so it has the effect of improving heat resistance, solvent resistance, resistance to long firing, etc. after pattern formation. may not be obtained. On the other hand, if it exceeds 50 parts by mass, uncrosslinked crosslinkable compounds will be present, and the heat resistance after pattern formation, solvent resistance, resistance to long-term baking, etc. will decrease, and the photosensitive resin composition Storage stability may deteriorate.

<(F) component>
Component (F) is a compound having two or more ethylenic polymerizable groups. The compound having two or more ethylenic polymerizable groups as used herein means a compound that has two or more polymerizable groups in one molecule, and those polymerizable groups are located at the end of the molecule. , those polymerizable groups mean at least one type of polymerizable group selected from the group consisting of acrylate groups, methacrylate groups, vinyl groups, and allyl groups.
This (F) component, a compound having two or more ethylenic polymerizable groups, has compatibility with each component in the solution of the negative photosensitive resin composition in the first photosensitive resin composition of the present invention. From the viewpoint of being good and not affecting the developability, a compound having a molecular weight (weight average molecular weight when the compound is a polymer) of 1,000 or less is preferable.

Specific examples of such compounds include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, and pentaerythritol triacrylate. Erythritol trimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,3,5-triacryloylhexahydro-S-triazine, 1,3,5-trimethacryloylhexahydro-S-triazine, tris(hydroxyethyl acryloyl) isocyanurate, tris(hydroxyethyl methacryloyl) isocyanurate, triacryloyl Formal, trimethacryloyl formal, 1,6-hexanediol acrylate, 1,6-hexanediol methacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethanediol diacrylate, ethanediol dimethacrylate, 2-hydroxypropanediol diacrylate Acrylate, 2-hydroxypropanediol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, isopropylene glycol diacrylate, isopropylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, N,N'-bis(acryloyl ) Cysteine, N,N'-bis(methacryloyl)cysteine, thiodiglycol diacrylate, thiodiglycol dimethacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, bisphenol F diacrylate, bisphenol F dimethacrylate, bisphenol S diacrylate , bisphenol S dimethacrylate, bisphenoxyethanol fluorene acrylate, bisphenoxyethanol fluorene methacrylate, diallyl ether bisphenol A, o-diallyl bisphenol A, diallyl maleate, triallyl trimellitate, and the like.

The above polyfunctional acrylate compounds are easily available as commercial products, and specific examples thereof include KYARAD T-1420, KYARAD DPHA, KYARAD DPHA-2C, KYARAD D-310, KYARAD D-330, and KYARAD DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, R-526, NPGDA, PEG400DA, MANDA, R-167, HX -220, HX620, R-551, R-712, R-604, R-684, GPO-303, TMPTA, THE-330, TPA-320, TPA-330, PET-30, RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210, M-240, M-6200, M-309, M-400, M-402, M-405, M-450, M-7100, M-8030, M-8060, M-1310, M-1600, M-1960, M-8100, M-8530, M-8560, M-9050 (manufactured by Toagosei Co., Ltd.), Viscoat 295, 300, 360, GPT, 3PA, 400, 260, 312, 335HP (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), A-9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, AD -TMP, ATM-35E, A-TMMT, A-9550, A-DPH, TMPT, 9PG, 701, 1206PE, NPG, NOD-N, HD-N, DOD-N, DCP, BPE-1300N, BPE-900 , BPE-200, BPE-100, BPE-80N, 23G, 14G, 9G, 4G, 3G, 2G, 1G (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).
These compounds having two or more ethylenic polymerizable groups can be used alone or in combination of two or more.

When component (F) is contained in the first photosensitive resin composition of the present invention, the content is preferably from 5 parts by mass to 200 parts by mass, more preferably from 5 parts by mass to 100 parts by mass of component (A). is from 10 parts by weight to 150 parts by weight, particularly preferably from 50 parts by weight to 150 parts by weight. If this ratio is too small, the exposed portions will be insufficiently cured, and pattern formation may not be possible, or even if pattern formation is possible, the film may have low reliability. Moreover, if this ratio is excessive, tack may occur in the coating film after prebaking, or unexposed areas may become poorly dissolved during development.

<(G) component>
Component (G) used in the first photosensitive resin composition of the present invention is a compound having two or more functional groups that form a covalent bond with an acid. Examples of functional groups that form covalent bonds with acids include epoxy groups, alkoxymethyl groups, and hydroxymethyl groups.

Examples of compounds having two or more epoxy groups include tris(2,3-epoxypropyl)isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxyethyl)cyclohexane, and glycerol. Triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidyl phenylglycidyl ether, 1,1,3-tris[p-(2,3-epoxypropoxy)phenyl]propane, diglycidyl 1,2-cyclohexanedicarboxylate ester, 4,4'-methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether and bisphenol-A-diglycidyl ether, and pentaerythritol polyglycidyl ether.

Furthermore, as the compound having two or more epoxy groups, commercially available compounds may be used because they are easily available. Specific examples (product names) are listed below, but are not limited to: Epoxy resins with amino groups such as YH-434 and YH434L (manufactured by Shinnikka Epoxy Manufacturing Co., Ltd.); Epolead GT- Epoxy resins having a cyclohexene oxide structure such as 401, GT-403, GT-301, GT-302, Celoxide 2021, Celoxide 3000 (manufactured by Daicel Corporation); Epicoat 1001, 1002, 1003, 1004 Bisphenol A epoxy resins such as , 1007, 1009, 1010, 828 (manufactured by Yuka Shell Epoxy Co., Ltd. (currently Mitsubishi Chemical Corporation)); Epicote 807 (manufactured by Yuka Shell Epoxy Co., Ltd.) Bisphenol F-type epoxy resins such as (manufactured by Mitsubishi Chemical Corporation); EPPN201, EPPN202 (manufactured by Yuka Shell Epoxy Co., Ltd. (currently Mitsubishi Chemical Corporation)); , manufactured by Nippon Kayaku Co., Ltd.; EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (all manufactured by Nippon Kayaku Co., Ltd.); ), Cresol novolac type epoxy resin such as Epicoat 180S75 (manufactured by Yuka Shell Epoxy Co., Ltd. (currently Mitsubishi Chemical Corporation)); Denacol EX-252 (manufactured by Nagase ChemteX Co., Ltd.), CY175, CY177, CY179, Araldite CY-182, CY-192, CY-184 (the above, Huntsman
Corporation), Epicron 200, 400 (manufactured by Dainippon Ink and Chemicals Co., Ltd. (currently DIC Corporation)), Epicort 871, 872 (manufactured by Yuka Shell Epoxy Co., Ltd. (currently Mitsubishi Chemical Corporation) Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX- Aliphatic polystyrene such as 622, EX-411, EX-512, EX-522, EX-421, EX-313, EX-314, EX-321 (manufactured by Nagase ChemteX Co., Ltd.) glycidyl ether etc.

Further, as the compound having two or more epoxy groups, a polymer having epoxy groups can also be used.
The above polymer having an epoxy group can be produced, for example, by addition polymerization using an addition polymerizable monomer having an epoxy group. Examples include addition polymers such as polyglycidyl acrylate, copolymers of glycidyl methacrylate and ethyl methacrylate, copolymers of glycidyl methacrylate, styrene and 2-hydroxyethyl methacrylate, and condensation polymers such as epoxy novolak. .

Alternatively, the above-mentioned polymer having an epoxy group can also be produced by reacting a polymer compound having a hydroxy group with a compound having an epoxy group such as epichlorohydrin or glycidyl tosylate.

The weight average molecular weight of such a polymer is, for example, 300 to 20,000.

These compounds having two or more epoxy groups can be used alone or in combination of two or more.

Examples of compounds having two or more substituents selected from alkoxymethyl groups and hydroxymethyl groups include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine, and phenoplast compounds. .

Specific examples of the alkoxymethylated glycoluril are as described in paragraph [0108] above.

Specific examples of alkoxymethylated benzoguanamine are as described in paragraph [0109] above.

Specific examples of alkoxymethylated melamine are as described in paragraph [0110] above.

It may also be a compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound, and a benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group. Examples include high molecular weight compounds made from melamine and benzoguanamine compounds as described in US Pat. No. 6,323,310. Examples of commercial products of the melamine compound include the trade name Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), and commercial products of the benzoguanamine compound include the trade name Cymel (registered trademark) 1123 (trade name). (manufactured by Mitsui Cytec Co., Ltd.), etc.

Specific examples of the phenoplast compound are as described in paragraph [0112] above.

Furthermore, as component (G), an acrylamide compound substituted with a hydroxymethyl group or an alkoxymethyl group, such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-butoxymethylmethacrylamide, or Polymers made using methacrylamide compounds can also be used.

Such polymers include, for example, poly(N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methyl methacrylate, and N-ethoxymethyl. Examples include a copolymer of methacrylamide and benzyl methacrylate, and a copolymer of N-butoxymethylacrylamide, benzyl methacrylate, and 2-hydroxypropyl methacrylate. The weight average molecular weight of such a polymer is from 1,000 to 50,000, preferably from 1,500 to 20,000, more preferably from 2,000 to 10,000.

When the first photosensitive resin composition of the present invention contains a compound having two or more functional groups that form a covalent bond with the acid of component (G), the content is based on 100 parts by mass of component (A). The amount is preferably 5 parts by mass to 200 parts by mass, and more preferably 50 parts by mass to 150 parts by mass. If this ratio is too small, the photocurability of the negative photosensitive resin composition may decrease; on the other hand, if it is too large, the developability of unexposed areas will decrease, resulting in residual film and residue. It may be the cause.

<Other additives>
Furthermore, the first photosensitive resin composition used in the present invention may optionally contain a leveling agent, a rheology modifier, a pigment, a dye, a storage stabilizer, an antifoaming agent, as long as the effects of the present invention are not impaired. It may contain an adhesion promoter or a solubility promoter such as polyhydric phenol or polyhydric carboxylic acid.

<Resist film formation process>
After forming the lower layer film 12 as described above, a second photosensitive resin composition containing a liquid-repellent component is applied onto the lower layer film 12 and prebaked to form a resist film 13 for the liquid-repellent bank. (Figure 1). Usually, this second photosensitive resin composition is applied to the entire surface of the lower layer film 12 to form the resist film 13 for the liquid-repellent bank.
The details of each component of the resist film for the liquid-repellent bank will be described below.

<(a) Component>
Component (a) of the present invention is a resin having an alkali-soluble group. Examples of the alkali-soluble group include a phenolic hydroxy group, a carboxyl group, an acid anhydride group, an imide group, a sulfonyl group, a phosphoric acid, a boronic acid, and an active methylene group and an active methine group.

The active methylene group refers to a methylene group (-CH ₂ -) that has a carbonyl group at an adjacent position and is reactive with nucleophilic reagents. Furthermore, in the present invention, the active methine group refers to the active methylene group having a structure in which one hydrogen atom of the methylene group is substituted with an alkyl group, and has reactivity with nucleophilic reagents.

（式（ａ１）中、Ｒはアルキル基、アルコキシ基又はフェニル基を表し、破線は結合手を表す。） Among active methylene groups and active methine groups, active methylene groups are preferred, and active methylene groups represented by the following formula (a1) are more preferred.

(In formula (a1), R represents an alkyl group, an alkoxy group, or a phenyl group, and the broken line represents a bond.)

In the above formula (a1), the alkyl group represented by R includes, for example, an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 5 carbon atoms is preferable.
Examples of such alkyl groups include methyl, ethyl, n-propyl, and i-propyl groups.
Among these, methyl group, ethyl group, n-propyl group, etc. are preferred.

In the above formula (a1), examples of the alkoxy group represented by R include an alkoxy group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms is preferable.
Examples of such alkoxy groups include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, and t-butoxy groups.
Among them, methoxy group, ethoxy group, n-propoxy group, etc. are preferred.

Examples of the group represented by the above formula (a1) include the following structures. In addition, in the structural formula, a broken line represents a bond.

Among the above alkali-soluble groups, an alkali-soluble resin having at least one organic group selected from the group consisting of a phenolic hydroxy group and a carboxyl group and having a number average molecular weight of 2,000 to 50,000. It is preferable that there be.

The alkali-soluble resin of the above-mentioned component (a) may be any alkali-soluble resin having such a structure, and there are no particular limitations on the main chain skeleton and the type of side chains of the polymer constituting the resin.

However, the alkali-soluble resin of component (a) has a number average molecular weight within the range of 2,000 to 50,000. If the number average molecular weight is too high (more than 50,000), development residues are likely to be generated and the sensitivity will be greatly reduced, while if the number average molecular weight is too small (less than 2,000), development will be difficult. In this case, a considerable amount of film loss may occur in the exposed areas, resulting in insufficient curing.

Examples of the alkali-soluble resin as component (a) include acrylic resins, polyhydroxystyrene resins, polyimide precursors, and polyimides.

Further, in the present invention, an alkali-soluble resin made of a copolymer (hereinafter referred to as a specific copolymer) obtained by polymerizing a plurality of types of monomers can also be used as the component (a). In this case, the alkali-soluble resin as component (a) may be a blend of multiple types of specific copolymers.

That is, the above-mentioned specific copolymer comprises a monomer exhibiting alkali solubility, that is, a monomer having at least one selected from the group consisting of a phenolic hydroxy group and a carboxyl group, and a monomer copolymerizable with these monomers. It is a copolymer formed of at least one selected monomer as an essential structural unit, and has a number average molecular weight of 2,000 to 50,000. If the number average molecular weight is more than 50,000, residue may be produced.

The above-mentioned "monomer having at least one selected from the group consisting of a phenolic hydroxy group and a carboxyl group" includes a monomer having a phenolic hydroxy group and a monomer having a carboxyl group. These monomers are not limited to those having one phenolic hydroxy group or carboxyl group, but may have multiple phenolic hydroxy groups or carboxyl groups.

Specific examples of the above monomers will be listed below, but the invention is not limited to these.
Examples of monomers having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl) phthalate, mono-(2-(methacryloyloxy)ethyl) phthalate, N-(carboxyphenyl) ) maleimide, N-(carboxyphenyl)methacrylamide, N-(carboxyphenyl)acrylamide, and the like.

Examples of the monomer having a phenolic hydroxy group include hydroxystyrene, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, N-(hydroxyphenyl)maleimide, and 4-hydroxyphenylmethacrylate.

The ratio of the unsaturated carboxylic acid derivative and/or phenolic hydroxy group to the monomer having a polymerizable unsaturated group in the production of the alkali-soluble resin of component (a) is Of the monomers, preferably 5 mol% to 90 mol%, more preferably 10 mol% to 60 mol%, most preferably 10 mol% to 30 mol%. When the unsaturated carboxylic acid derivative is less than 5% by weight, the alkali solubility of the polymer is insufficient.

The alkali-soluble resin which is component (a) of the present invention is a resin copolymerized with a monomer having a hydroxyalkyl group and a polymerizable unsaturated group in order to further stabilize the pattern shape after curing. It is preferable.

Examples of monomers having a hydroxyalkyl group and a polymerizable unsaturated group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl acrylate, 2-hydroxyethyl methacrylate, Examples include 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, glycerin monomethacrylate, and 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone.

The ratio of the monomer having a hydroxyalkyl group and a polymerizable unsaturated group in the production of the alkali-soluble resin of component (a) is preferably 5% by mass to 60% by mass, more preferably 10% by mass to 50% by mass, most preferably A preferable range is 20% by mass to 40% by mass. If the monomer having a hydroxyalkyl group and a polymerizable unsaturated group is less than 5% by mass, the effect of stabilizing the pattern shape of the copolymer may not be obtained. If the amount is 60% by mass or more, the alkali-soluble groups of component (a) may be insufficient, and properties such as developability may deteriorate.

The alkali-soluble resin which is component (a) of the present invention is preferably one further copolymerized with an N-substituted maleimide compound from the viewpoint of increasing the Tg of the copolymer.

N-Substituted Maleimide Compounds Examples of maleimide compounds include N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. From the viewpoint of transparency, those having no aromatic ring are preferred, and from the viewpoint of developability, transparency, and heat resistance, those having an alicyclic skeleton are more preferred, and among them, cyclohexylmaleimide is the most preferred.

The proportion of N-substituted maleimide in the production of the alkali-soluble resin of component (a) is preferably 5% by mass to 60% by mass, more preferably 10% by mass to 50% by mass, and most preferably 20% by mass to 40% by mass. %. If the N-substituted maleimide content is less than 5% by mass, the copolymer may have a low Tg and poor heat resistance. If the content is 60% by mass or more, transparency may decrease.

When the second photosensitive resin composition of the present invention satisfies the requirement (z2), the alkali-soluble resin of component (a) used in the present invention further has a self-crosslinking group, or has a hydroxy group, a carboxyl group, etc. The copolymer is preferably a copolymer further having a group (hereinafter also referred to as a crosslinkable group) that reacts with at least one group selected from the group consisting of a group consisting of an amide group, an amide group, and an amino group.

Examples of the self-crosslinking group include N-alkoxymethyl group, N-hydroxymethyl group, alkoxysilyl group, epoxy group, oxetane group, vinyl group and blocked isocyanate group.

Examples of the crosslinkable group include N-alkoxymethyl group, N-hydroxymethyl group, alkoxysilyl group, epoxy group, vinyl group, blocked isocyanate group, and the like.

When such a self-crosslinkable group or crosslinkable group is contained in the alkali-soluble resin of component (a), the content is 0.1 to 0.9 per repeating unit in the resin of component (a). The number is preferably from 0.1 to 0.8 from the viewpoint of developability and solvent resistance.

The alkali-soluble resin of component (a) further contains self-crosslinking groups such as N-alkoxymethyl group, N-hydroxymethyl group, alkoxysilyl group, epoxy group, oxetane group, vinyl group, and blocked isocyanate group, and N-alkoxymethyl In the case of having a repeating unit having at least one type of crosslinking group selected from group, N-hydroxymethyl group, alkoxysilyl group, epoxy group, vinyl group, blocked isocyanate group, etc., for example, it has radical polymerizability and epoxy an unsaturated compound having at least one type selected from crosslinkable groups such as a group, an oxetane group, a vinyl group, a blocked isocyanate group, and a self-crosslinkable group such as an N-alkoxymethyl group, an N-hydroxymethyl group, and an alkoxysilyl group. What is necessary is to copolymerize.

Examples of unsaturated compounds having radical polymerizability and having an N-alkoxymethyl group include N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, and N-methylolacrylamide. etc.

Examples of monomers having radical polymerizability and further having an N-hydroxymethyl group include N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, and the like.

Examples of monomers having radical polymerizability and an alkoxysilyl group include 3-acryloyloxytrimethoxysilane, 3-acryloyloxytriethoxysilane, 3-methacryloyloxytrimethoxysilane, and 3-methacryloyloxytriethoxysilane. Can be mentioned.

Examples of unsaturated compounds having radical polymerizability and further having an epoxy group include glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-propylacrylate glycidyl, α-n-butyl acrylate. Glycidyl, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl acrylate-6, Examples include 7-epoxyheptyl, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether, and 3,4-epoxycyclohexyl methacrylate. Among these, glycidyl methacrylate, 6,7-epoxyheptyl methacrylate, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether, 3,4-epoxycyclohexyl methacrylate, etc. Preferably used. These may be used alone or in combination.

Examples of the unsaturated compound having radical polymerizability and further having an oxetane group include (meth)acrylic acid ester having an oxetane group. Among such monomers, 3-(methacryloyloxymethyl)oxetane, 3-(acryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyl-oxetane, 3-(acryloyloxymethyl)- 3-ethyl-oxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(acryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyl-oxetane, 3-(acryloyloxymethyl)-2-phenyl-oxetane, 2-(methacryloyloxymethyl)oxetane, 2-(acryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, 2-( Acryloyloxymethyl)-4-trifluoromethyloxetane is preferred, and 3-(methacryloyloxymethyl)-3-ethyl-oxetane, 3-(acryloyloxymethyl)-3-ethyl-oxetane, and the like are preferably used.

Examples of monomers having radical polymerizability and further having a vinyl group include 2-(2-vinyloxyethoxy)ethyl acrylate and 2-(2-vinyloxyethoxy)ethyl methacrylate.

Examples of monomers that have radical polymerizability and further have a blocked isocyanate group include 2-(0-(1'-methylpropylideneamino)carboxyamino)ethyl methacrylate and 2-(3,5-dimethylpyrazolyl) methacrylate. carbonylamino)ethyl and the like.

When the second photosensitive resin composition of the present invention satisfies (z1), it has radical polymerizability and contains N-alkoxymethyl group, N-hydroxymethyl group, alkoxysilyl group, epoxy group, oxetane group, vinyl At least one group selected from self-crosslinkable groups such as groups and blocked isocyanate groups, and crosslinkable groups such as N-alkoxymethyl groups, N-hydroxymethyl groups, alkoxysilyl groups, epoxy groups, vinyl groups, and blocked isocyanate groups. Preferably 10% by mass to 70% by mass, particularly preferably 20% by mass of structural units derived from an unsaturated compound having Contains 60% by mass. If the amount of this structural unit is less than 10% by mass, the heat resistance and surface hardness of the resulting cured film tends to decrease, while if the amount of this structural unit exceeds 70% by mass, the storage of the radiation-sensitive resin composition Stability tends to decrease.

Further, in the present invention, the acrylic polymer as component (a) may be a copolymer formed using monomers other than the above-mentioned monomers (hereinafter referred to as other monomers) as constituent units. Specifically, the other monomers may be monomers that can be copolymerized with at least one selected from the group consisting of the above-mentioned monomers having a carboxyl group and monomers having a phenolic hydroxy group, and which have the characteristics of component (a). There is no particular limitation as long as it does not cause any damage. Specific examples of such monomers include acrylic ester compounds, methacrylic ester compounds, maleimide, acrylamide compounds, acrylonitrile, styrene compounds, and vinyl compounds.
Specific examples of the other monomers will be listed below, but the invention is not limited to these.

Examples of the acrylic ester compounds include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, glycidyl acrylate, phenoxyethyl acrylate, 2,2,2- Trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminoethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxy Butyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate, diethylene glycol monoacrylate, caprolactone Examples include 2-(acryloyloxy)ethyl ester, poly(ethylene glycol)ethyl ether acrylate, and the like.

Examples of the methacrylic acid ester compounds include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, phenoxyethyl methacrylate, 2,2,2- Trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxy Butyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate, Examples include diethylene glycol monomethacrylate, caprolactone 2-(methacryloyloxy)ethyl ester, poly(ethylene glycol)ethyl ether methacrylate, and the like.

Examples of the acrylamide compound include N-methylacrylamide, N-methylmethacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, and N-butoxy. Examples include methylacrylamide, N-butoxymethylmethacrylamide, and the like.

Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, cyclohexyl vinyl ether, vinylnaphthalene, vinylanthracene, vinylcarbazole, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo[4.1.0]heptane, 1,2 -epoxy-5-hexene, 1,7-octadiene monoepoxide, and the like.

Examples of the styrene compound include styrene having no hydroxyl group, such as styrene, α-methylstyrene, chlorostyrene, and bromostyrene.

In the production of the alkali-soluble resin as component (a), the ratio of the other monomers is preferably 80% by mass or less, more preferably 50% by mass or less, and even more preferably 20% by mass or less. If it exceeds 80% by mass, the essential components will be relatively reduced, making it difficult to fully obtain the effects of the present invention.

The method for obtaining the alkali-soluble resin which is component (a) used in the present invention is not particularly limited, but for example, a carboxyl group, a phenolic hydroxy group, and a carboxylic acid or phenolic hydroxy group are generated by the action of heat or acid. A monomer having at least one selected from the group consisting of groups, a monomer having a hydroxyalkyl group, optionally an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetane group, a vinyl group, and a blocked isocyanate. A monomer having at least one group selected from a self-crosslinkable group such as a group and a crosslinkable group such as an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group, and a blocked isocyanate group, It is obtained by carrying out a polymerization reaction at a temperature of 50° C. to 110° C. in a solvent in which other copolymerizable monomers and, if desired, a polymerization initiator are present. At this time, the solvent used is not particularly limited as long as it dissolves the monomers constituting the alkali-soluble resin and the acrylic polymer having a specific functional group. Specific examples include the solvents listed below for component (c).

The acrylic polymer having a specific functional group obtained in this manner is usually in the form of a solution dissolved in a solvent.

In addition, the solution of the specific copolymer obtained as described above is reprecipitated by adding it to diethyl ether, water, etc. under stirring, and after filtering and washing the generated precipitate, under normal pressure or reduced pressure. By drying at room temperature or by heating, powder of the specific copolymer can be obtained. By such an operation, the polymerization initiator and unreacted monomer coexisting with the specific copolymer can be removed, and as a result, purified powder of the specific copolymer can be obtained. If sufficient purification is not possible in one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
In the present invention, the powder of the above-mentioned specific copolymer may be used as it is, or the powder may be redissolved in, for example, component (c) described later and used in the form of a solution.

In addition, as the alkali-soluble resin of component (a), polyimide precursors such as polyamic acid, polyamic acid ester, partially imidized polyamic acid, etc., and polyimides such as polyimide containing carboxylic acid groups can also be used. As long as it is soluble, it can be used without particular limitation on its type.

The polyamic acid, which is a polyimide precursor, can generally be obtained by polycondensing (i) a tetracarboxylic dianhydride compound and (j) a diamine compound.

The above (i) tetracarboxylic dianhydride compound is not particularly limited, and specific examples include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3' , 4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride Aromatic tetracarboxylic acids such as 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2, 3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-cyclohexane tetra Carboxylic dianhydrides, cycloaliphatic tetracarboxylic dianhydrides such as 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, 1,2,3, Mention may be made of aliphatic tetracarboxylic dianhydrides such as 4-butanetetracarboxylic dianhydride.
These may be used alone or in combination of two or more.

The diamine compound (j) is also not particularly limited, and includes, for example, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,6-diamino-1 , 3-benzenedicarboxylic acid, 2,5-diamino-1,4-benzenedicarboxylic acid, bis(4-amino-3-carboxyphenyl) ether, bis(4-amino-3,5-dicarboxyphenyl) ether, Bis(4-amino-3-carboxyphenyl)sulfone, bis(4-amino-3,5-dicarboxyphenyl)sulfone, 4,4'-diamino-3,3'-dicarboxybiphenyl, 4,4'- Diamino-3,3'-dicarboxy-5,5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dicarboxy-5,5'-dimethoxybiphenyl, 1,4-bis(4-amino -3-carboxyphenoxy)benzene, 1,3-bis(4-amino-3-carboxyphenoxy)benzene, bis[4-(4-amino-3-carboxyphenoxy)phenyl]sulfone, bis[4-(4- Amino-3-carboxyphenoxy)phenyl]propane, 2,2-bis[4-(4-amino-3-carboxyphenoxy)phenyl]hexafluoropropane, 2,4-diaminophenol, 3,5-diaminophenol, 2 , 5-diaminophenol, 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, bis(3-amino-4-hydroxyphenyl) ether, bis(4-amino-3-hydroxyphenyl) ether, bis(4- Amino-3,5-dihydroxyphenyl) ether, bis(3-amino-4-hydroxyphenyl)methane, bis(4-amino-3-hydroxyphenyl)methane, bis(4-amino-3,5-dihydroxyphenyl) Methane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, bis(4-amino-3,5-dihydroxyphenyl)sulfone, 2,2-bis(3 -Amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-amino-3,5-dihydroxyphenyl)hexafluoro Propane, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethoxybiphenyl, 1,4-bis(3-amino-4-hydroxyphenoxy)benzene, 1,3-bis(3-amino-4-hydroxyphenoxy)benzene, 1,4-bis (4-amino-3-hydroxyphenoxy)benzene, 1,3-bis(4-amino-3-hydroxyphenoxy)benzene, bis[4-(3-amino-4-hydroxyphenoxy)phenyl]sulfone, bis[4 -(3-amino-4-hydroxyphenoxy)phenyl]propane, 2,2-bis[4-(3-amino-4-hydroxyphenoxy)phenyl]hexafluoropropane and other diamine compounds having a phenolic hydroxy group, 1, 3-diamino-4-mercaptobenzene, 1,3-diamino-5-mercaptobenzene, 1,4-diamino-2-mercaptobenzene, bis(4-amino-3-mercaptophenyl)ether, 2,2-bis( Diamine compounds having a thiophenol group such as 3-amino-4-mercaptophenyl)hexafluoropropane, 1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-5-sulfonic acid, 1,4-diamino Benzene-2-sulfonic acid, bis(4-aminobenzene-3-sulfonic acid) ether, 4,4'-diaminobiphenyl-3,3'-disulfonic acid, 4,4'-diamino-3,3'-dimethyl Examples include diamine compounds having a sulfonic acid group such as biphenyl-6,6'-disulfonic acid. Also, p-phenylenediamine, m-phenylenediamine, 4,4'-methylene-bis(2,6-ethylaniline)
, 4,4'-methylene-bis(2-isopropyl-6-methylaniline), 4,4'-methylene-bis(2,6-diisopropylaniline), 2,4,6-trimethyl-1,3-phenylene diamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, o-tolidine, m-tolidine, 3,3',5,5'-tetramethylbenzidine, bis[4-(3-amino phenoxy)phenyl]sulfone, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 4,4'-diamino -3,3'-dimethyldicyclohexylmethane, 4,4'-diaminodiphenyl ether, 3,4-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 2,2-bis(4-anilino)hexafluoropropane, 2,2 -bis(3-anilino)hexafluoropropane, 2,2-bis(3-amino-4-tolyl)hexafluoropropane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4- aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy) ) phenyl]hexafluoropropane, 2,2'-bis(trifluoromethyl)benzidine, and other diamine compounds.
These may be used alone or in combination of two or more.

When the polyamic acid used in the present invention is produced from (i) a tetracarboxylic dianhydride compound and (j) a diamine compound, the blending ratio of both compounds, that is, the total number of moles of (j) diamine compound/(i) The total number of moles of the tetracarboxylic dianhydride compound is preferably 0.7 to 1.2. As in normal polycondensation reactions, the closer this molar ratio is to 1, the higher the degree of polymerization of the produced polyamic acid and the higher the molecular weight.

Furthermore, when polymerization is performed using an excess of a diamine compound, the terminal amino groups of the remaining polyamic acid can be protected by reacting the terminal amino groups with a carboxylic acid anhydride.
Examples of such carboxylic anhydrides include phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrogenated phthalic anhydride, and methyl-5-norbornene-2,3-dicarboxylic acid. Examples include anhydride, itaconic anhydride, and tetrahydrophthalic anhydride.

In the production of polyamic acid, the reaction temperature for the reaction between the diamine compound and the tetracarboxylic dianhydride compound can be selected from any temperature from -20°C to 150°C, preferably from -5°C to 100°C. In order to obtain a high molecular weight polyamic acid, the reaction temperature is suitably selected within the range of 5°C to 40°C and the reaction time is within the range of 1 hour to 48 hours. In order to obtain a partially imidized polyamic acid having a low molecular weight and high storage stability, it is more preferable to select a reaction temperature from 40°C to 90°C and a reaction time of 10 hours or more.
Further, the reaction temperature when protecting the terminal amino group with an acid anhydride can be selected from any temperature from -20°C to 150°C, preferably from -5°C to 100°C.

The reaction between the diamine compound and the tetracarboxylic dianhydride compound can be carried out in a solvent. Solvents that can be used in this case include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, Hexamethyl sulfoxide, m-cresol, γ-butyrolactone, ethyl acetate, butyl acetate, ethyl lactate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, 3 - Ethyl ethoxypropionate, ethyl 2-ethoxypropionate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol Monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, carbitol acetate, ethyl cellosolve acetate, cyclohexanone, methyl ethyl ketone, Examples include methyl isobutyl ketone and 2-heptanone. These may be used alone or in combination. Furthermore, even a solvent that does not dissolve polyamic acid may be mixed with the above solvent and used as long as the polyamic acid produced by the polymerization reaction does not precipitate.

The solution containing polyamic acid thus obtained can be used as it is for preparing a photosensitive resin composition. Alternatively, the polyamic acid can be isolated by precipitation in a poor solvent such as water, methanol, or ethanol, and then recovered and used.

Further, as the component (a), any polyimide can be used. The polyimide used in the present invention is one obtained by chemically or thermally imidizing a polyimide precursor such as the above-mentioned polyamic acid by 50% or more.

The polyimide used in the second photosensitive resin composition of the present invention preferably has a group selected from a carboxyl group and a phenolic hydroxy group in order to impart alkali solubility.
The method for introducing a carboxyl group or a phenolic hydroxy group into polyimide includes a method using a monomer having a carboxyl group or a phenolic hydroxy group, a method of capping the amine end with an acid anhydride having a carboxyl group or a phenolic hydroxy group, Alternatively, a method may be used in which the imidization rate is set to 99% or less when imidizing a polyimide precursor such as polyamic acid.

Such a polyimide can be obtained by synthesizing a polyimide precursor such as the above-mentioned polyamic acid and then performing chemical imidization or thermal imidization.
As a method for chemical imidization, a method is generally used in which excess acetic anhydride and pyridine are added to a polyimide precursor solution and the mixture is reacted at room temperature to 100°C. Further, as a method for thermal imidization, a method is generally used in which a polyimide precursor solution is heated at a temperature of 180° C. to 250° C. while being dehydrated.

Further, as the alkali-soluble resin of component (a), a phenol novolac resin can be further used.

Moreover, polyester polycarboxylic acid can also be used as the alkali-soluble resin of component (a). Polyester polycarboxylic acid can be obtained from acid dianhydride and diol by the method described in WO2009/051186.
Examples of the acid dianhydride include the above-mentioned (i) tetracarboxylic dianhydride.
Examples of diols include aromatic diols such as bisphenol A, bisphenol F, 4,4'-dihydroxybiphenyl, benzene-1,3-dimethanol, and benzene-1,4-dimethanol, hydrogenated bisphenol A, and hydrogenated bisphenol F. , 1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol and other alicyclic diols, and ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol Examples include aliphatic diols such as.

Moreover, in the present invention, the alkali-soluble resin of component (a) may be a mixture of multiple types of alkali-soluble resins.

<(b) component>
Component (b) is a polymer having a liquid repellent group (b1).

In the present invention, examples of the polymer include polyimide, polyamic acid, polyamide, polyurea, polyurethane, phenol resin, epoxy resin, polysiloxane, polyester, and acrylic polymer, and preferred polymers include acrylic polymer. can be mentioned.

Here, the acrylic polymer is obtained using a monomer having a polymerizable unsaturated group such as acrylic ester, methacrylic ester, styrene, maleimide, etc., that is, a polymerizable group containing a C=C double bond in its structure. refers to polymers that are

Examples of polyamic acids, polyimides, polyamides, and polyureas include polyamic acids obtained by reacting diamines with acid dianhydrides, polyimides obtained by imidizing the polyamic acids, and polyamides or diamines obtained by reacting diamines with dicarboxylic anhydrides. is a polyurea obtained by reacting with a diisocyanate, and is a polymer obtained from a monomer mixture containing at least one monomer having a fluoroalkyl group or a fluoroalkoxy group and at least one monomer having a hydroxy group.

Examples of the polyurethane include polyurethanes obtained by reacting a diol having a fluoroalkyl group or a fluoroalkoxy group and a diol having an amino group with a diisocyanate.

Examples of the phenol resin include novolac resins obtained by polymerizing formaldehyde and a phenol having a fluoroalkyl group or a fluoroalkoxy group.

Examples of the epoxy resin include epoxy resins obtained by reacting bisphenol A and/or bisphenol F having a fluoroalkyl group or fluoroalkoxy group with glycidyl ether.

The polysiloxane is obtained by polymerizing a silane monomer mixture containing a trialkoxysilane having a fluoroalkyl group or a dialkoxysilane silane having a fluoroalkyl group, and a trialkoxysilane having an amino group or a dialkoxysilane having an amino group. Examples include the resulting polymers.

Examples of the polyester include polyesters obtained by reacting dicarboxylic acid or tetracarboxylic dianhydride with a diol having a fluoroalkyl group or a fluoroalkoxy group.

<(b1) Introduction of liquid repellent group>
Examples of the liquid-repellent group include at least one group selected from a fluoroalkyl group having 3 to 10 carbon atoms, a polyfluoroether group, a silyl ether group, and a polysiloxane group.

The fluoroalkyl group has 3 to 10 carbon atoms, preferably 4 to 10 carbon atoms.
Such fluoroalkyl groups include 2,2,2-trifluoroethyl group, 2,2
, 3,3,3-pentafluoropropyl group, 2-(perfluorobutyl)ethyl group, 3-perfluorobutyl-2-hydroxypropyl group, 2-(perfluorohexyl)ethyl group, 3-perfluorohexyl- 2-hydroxypropyl group, 2-(perfluorooctyl)ethyl group, 3-perfluorooctyl-2-hydroxypropyl group, 2-(perfluorodecyl)ethyl group, 2-(perfluoro-3-methylbutyl)ethyl group , 3-(perfluoro-3-methylbutyl)-2-hydroxypropyl group, 2-(perfluoro-5-methylhexyl)ethyl group, 2-(perfluoro-5-methylhexyl)-2-hydroxypropyl group, Examples include 2-(perfluoro-7-methyloctyl)ethyl group and 2-(perfluoro-7-methyloctyl)-2-hydroxypropyl group.

In order to introduce a fluoroalkyl group having 3 to 10 carbon atoms into the polymer that is the component (b) of the present invention, a monomer having a fluoroalkyl group having 3 to 10 carbon atoms may be copolymerized.

Specific examples of the monomer having a fluoroalkyl group having 3 to 10 carbon atoms when component (b) is an acrylic polymer include 2,2,2-trifluoroethyl acrylate, 2,2,2-trifluoroethyl acrylate, and 2,2,2-trifluoroethyl acrylate. Fluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2-(perfluorobutyl)ethyl acrylate, 2-(perfluorobutyl) ) Ethyl methacrylate, 3-perfluorobutyl-2-hydroxypropyl acrylate, 3-perfluorobutyl-2-hydroxypropyl methacrylate, 2-(perfluorohexyl)ethyl acrylate, 2-(perfluorohexyl)ethyl methacrylate, 3- Perfluorohexyl-2-hydroxypropyl acrylate, 3-perfluorohexyl-2-hydroxypropyl methacrylate, 2-(perfluorooctyl)ethyl acrylate, 2-(perfluorooctyl)ethyl methacrylate, 3-perfluorooctyl-2- Hydroxypropyl acrylate, 3-perfluorooctyl-2-hydroxypropyl methacrylate, 2-(perfluorodecyl)ethyl acrylate, 2-(perfluorodecyl)ethyl methacrylate, 2-(perfluoro-3-methylbutyl)ethyl acrylate, 2 -(perfluoro-3-methylbutyl)-ethyl methacrylate, 3-(perfluoro-3-methylbutyl)-2-hydroxypropyl acrylate, 3-(perfluoro-3-methylbutyl)-2-hydroxypropyl methacrylate, 2-(perfluoro-3-methylbutyl)-2-hydroxypropyl methacrylate Fluoro-5-methylhexyl)ethyl acrylate, 2-(perfluoro-5-methylhexyl)ethyl methacrylate, 2-(perfluoro-5-methylhexyl)-2-hydroxypropyl acrylate, 2-(perfluoro-5- Methylhexyl)-2-hydroxypropyl methacrylate, 2-(perfluoro-7-methyloctyl)ethyl acrylate, 2-(perfluoro-7-methyloctyl)ethyl methacrylate, 2-(perfluoro-7-methyloctyl)- Examples include 2-hydroxypropyl acrylate and 2-(perfluoro-7-methyloctyl)-2-hydroxypropyl methacrylate.

Examples of the polyfluoroether group include an Rf group having a polyfluoroether structure represented by the following formula 2.
-(X-O) _n -Y...Formula 2
In the formula 2, X is a divalent saturated hydrocarbon group having 1 to 10 carbon atoms or a fluorinated divalent saturated hydrocarbon group having 1 to 10 carbon atoms, and They represent the same group or different groups, and Y is a hydrogen atom (limited to cases where a fluorine atom is not bonded to a carbon atom adjacent to an oxygen atom adjacent to Y), a monovalent saturated carbon having 1 to 20 carbon atoms. It represents a hydrogen group or a fluorinated monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 2 to 50. However, the total number of fluorine atoms in Formula 2 is 2 or more.

As an embodiment of X and Y in Formula 2, preferably, A group, in which each unit enclosed by n represents the same group or a different group, and Y is an alkyl group having 1 to 20 carbon atoms that has been fluorinated by removing one hydrogen atom, or an alkyl group having 1 to 20 carbon atoms. Examples include those having 20 to 20 perfluorinated alkyl groups.

More preferably, as an embodiment of X and Y in Formula 2, and Y represents a perfluorinated alkyl group having 1 to 20 carbon atoms.

In Formula 2, n represents an integer from 2 to 50. n is preferably 2 to 30, more preferably 2 to 15. When n is 2 or more, liquid repellency is good. When n is 50 or less, the polymer as component (b) is combined with a monomer having an Rf group, a hydroxy group, a carboxyl group, an amide group, an amino group, an N-alkoxymethylamide group, a blocked isocyanate group, or a trialkoxy group. When synthesized by copolymerization with a monomer having a silyl group or other monomers, the compatibility of the monomers becomes good.

Further, the total number of carbon atoms in the Rf group consisting of the polyfluoroether structure represented by Formula 2 is preferably 2 to 50, more preferably 2 to 30. Within this range, the polymer as component (b) exhibits good liquid repellency. In addition, the polymer as component (b) may be a monomer having an Rf group and a monomer having a hydroxy group, a carboxyl group, an amide group, an amino group, an N-alkoxymethylamide group, a blocked isocyanate group, or a trialkoxysilyl group. When synthesized by copolymerization with other monomers, the compatibility of the monomers becomes good.

_{Specific examples of _ _ _ _ _ _ _ _ _} Examples include CF ₂ CF ₂ CF (CF ₃ )- and CF ₂ CF (CF ₃ )CF ₂ -.

Specific examples of Y include -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CHF ₂ , -(CF ₂ ) ₂ CF ₃ , -(CF ₂ ) ₃ CF ₃ , -(CF ₂ ) ₄ CF ₃ , -(CF ₂ ) ₅ CF ₃ , -(CF ₂ ) ₆ CF ₃ , -(CF ₂ ) ₇ CF ₃ , -(CF ₂ ) ₈ CF ₃ , -(CF ₂ ) ₉ CF ₃ , and (CF ₂ ) ₁₁ CF ₃ and -(CF ₂ ) ₁₅ CF ₃ are mentioned.

A preferred embodiment of the Rf group having a polyfluoroether structure represented by Formula 2 includes the Rf group represented by Formula 3.
-C _p-1 F _2(p-1) -O- (C _p F _2p -O) _n-1 -C _q F _2q+1 ...Formula 3
In formula 3, p represents an integer of 2 or 3, each unit enclosed by n is the same group, q represents an integer of 1 to 20, and n represents an integer of 2 to 50.

Specifically, as the Rf group represented by formula 3,
-CF ₂ O (CF ₂ CF ₂ O) _n-1 CF ₃ (n is 2 to 9),
-CF( _CF3 )O( _CF2CF ( _CF3 )O) _{n -1 C6F13} (n is 2 to 6),
-CF(CF ₃ )O(CF ₂ CF(CF ₃ )O) _n-1 C ₃ F ₇ (n is 2 to 6)
are preferred from the viewpoint of ease of synthesis.

All of the Rf groups in the polymer that is component (b) may be the same or different.

The above-mentioned silyl ether group means a group in which the hydroxy group of an alcohol is protected with a trialkylsilyl group, and is preferably a group represented by the following formula.
-X ⁴ -Si(O-SiX ¹ X ² X ³ ) ₃
(In the formula, X ¹ , X ² , and X ³ each independently represent an alkyl group having 1 to 3 carbon atoms, and X ⁴ represents an alkylene group having 1 to 6 carbon atoms.)

In order to introduce a silyl ether group into the polymer which is the component (b) of the present invention, a monomer having a silyl ether group may be copolymerized.

When component (b) is an acrylic polymer, examples of the monomer having a silyl ether group include methacryloxypropyltris(trimethylsiloxy)silane and acryloxypropyltris(trimethylsiloxy)silane.

Examples of the polysiloxane group include a group having a polysiloxane structure represented by Formula 4. Hereinafter, the group having a polysiloxane structure represented by Formula 4 will be referred to as pSi group.
-(SiR ¹ R ² -O) _n -SiR ¹ R ² R ³ ...Formula 4
(However, R ¹ and R ² independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, R ³ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and n represents 1 to 200 carbon atoms.) represents an integer).

R ¹ and R ² independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and each siloxy unit may be the same or different. Since the polymer that is component (b) exhibits good liquid repellency, R ¹ and R ² are preferably hydrogen atoms, methyl groups, or phenyl groups, and furthermore, R ¹ and R 2 of all siloxy units It is preferred that ² is a methyl group. Further, R ³ may contain a nitrogen atom, an oxygen atom, or the like.

Methods for introducing pSi groups into the polymer that is component (b) include methods of copolymerizing monomers having pSi groups, various modification methods in which a polymer having a reactive site is reacted with a compound having pSi groups, and pSi groups. Examples include a method using a polymerization initiator having the following.

Examples of the monomer having a pSi group include CH ₂ =CHCOO (pSi), CH ₂ =C(CH ₃ )COO (pSi), and the like. However, pSi represents a pSi group. Monomers having pSi groups may be used alone or in combination of two or more.

Examples of various modification methods for reacting a polymer having a reactive site with a compound having a pSi group include the following methods.

A method in which a monomer having an epoxy group is copolymerized in advance, and then a compound having a carboxyl group at one end and a pSi group at one end is reacted. A method in which a monomer having an epoxy group is copolymerized in advance, and then a compound having an amino group at one end and a pSi group at one end is reacted. A method in which a monomer having an epoxy group is copolymerized in advance, and then a compound having a mercapto group at one end and a pSi group at one end is reacted. A method in which a monomer having an amino group is copolymerized in advance, and then a compound having a carboxyl group at one end and a pSi group at one end is reacted.

A method in which a monomer having an amino group is copolymerized in advance, and then a compound having an epoxy group at one end and a pSi group at one end is reacted. A method in which a monomer having a carboxyl group is copolymerized in advance, and then a compound having an epoxy group at one end and a pSi group at one end is reacted. A method in which a monomer having a carboxyl group is copolymerized in advance, and then a compound having an amino group at one end and a pSi group at one end is reacted. A method in which a monomer having a carboxyl group is copolymerized in advance, and then a compound having a silyl chloride group at one end and a pSi group at one end is reacted. A method in which a monomer having a hydroxy group is copolymerized in advance, and then a compound having a silyl chloride group at one end and a pSi group at one end is reacted.

The polymerization initiator having a pSi group may include a group having a divalent polysiloxane structure in the main chain of the initiator molecule, or a monovalent polysiloxane in the terminal portion or side chain of the initiator molecule. A group having a structure may also be included. Examples of the initiator containing a group having a divalent polysiloxane structure in the main chain of the initiator molecule include compounds having alternating groups having a divalent polysiloxane structure and an azo group. Commercially available products include VPS-1001 and VPS-0501 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).

Component (b) is preferably a polymer further having (b2) a group selected from an N-alkoxymethylamide group, a blocked isocyanate group, and a trialkoxysilyl group.

<(b2): Introduction of group selected from N-alkoxymethylamide group, blocked isocyanate group, and trialkoxysilyl group>
In order to introduce a group selected from an N-alkoxymethylamide group, a blocked isocyanate group, and a trialkoxysilyl group, the polymer as component (b) should be selected from an N-alkoxymethylamide group, a blocked isocyanate group, and a trialkoxysilyl group. It is sufficient to copolymerize monomers having selected groups.

When component (b) is an acrylic polymer, examples of the monomer having an N-alkoxymethylamide group include N-hydroxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, and N-ethoxymethyl (meth)acrylamide. ) acrylamide, and (meth)acrylamide compounds substituted with a hydroxymethyl group or an alkoxymethyl group such as N-butoxymethyl (meth)acrylamide.

When component (b) is an acrylic polymer, examples of the monomer having a blocked isocyanate group include 2-(0-(1'-methylpropylideneamino)carboxyamino)ethyl methacrylate, 2-(3 , 5-dimethylpyrazolyl)carbonylamino)ethyl, and the like.

When component (b) is an acrylic polymer, examples of the monomer having a trialkoxysilyl group include 3-trimethoxysilylpropyl acrylate, 3-triethoxysilylpropyl acrylate, 3-trimethoxysilylpropyl methacrylate, 3-trimethoxysilylpropyl acrylate, and 3-trimethoxysilylpropyl acrylate. Examples include triethoxysilylpropyl methacrylate.

Component (b) is preferably a polymer further having (b3) at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group.

<(b3) Introduction of at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group>
In order to introduce at least one group selected from the group consisting of (b3) hydroxy group, carboxyl group, amide group, and amino group into the polymer that is component (b) of the present invention, (b3) hydroxy group, carboxyl group , an amide group, and an amino group may be copolymerized.

When component (b) is an acrylic polymer, examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl) phthalate, mono-(2-( Examples include methacryloyloxy)ethyl) phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, and N-(carboxyphenyl)acrylamide.

When component (b) is an acrylic polymer, examples of the monomer having a hydroxy group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and 4-hydroxybutyl Acrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, glycerin monomethacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2-(acryloyloxy)ethyl ester, caprolactone 2-( methacryloyloxy) ethyl ester, poly(ethylene glycol) acrylate, poly(propylene glycol) acrylate, poly(ethylene glycol) ethyl ether acrylate, poly(ethylene glycol) ethyl ether methacrylate, 5-acryloyloxy-6-hydroxynorbornene-2- Carboxylic-6-lactone, and 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, p-hydroxystyrene, α-methyl-p-hydroxystyrene, N-hydroxyphenylmaleimide, N-hydroxy Examples include phenylacrylamide, N-hydroxyphenylmethacrylamide, p-hydroxyphenylacrylate, p-hydroxyphenylmethacrylate and the like. Among these, monomers selected from 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are preferred.

When component (b) is an acrylic polymer, examples of the monomer having an amide group include acrylamide, methacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, and the like. Among them, methacrylamide is preferred.

When component (b) is an acrylic polymer, examples of the monomer having an amino group include aminoethyl acrylate, aminoethyl methacrylate, aminopropyl acrylate, and aminopropyl methacrylate.

In the case where component (b) is an acrylic polymer, the method for producing the polymer of component (b) includes a monomer having a liquid repellent group, for example, a monomer having a fluoroalkyl group having 3 to 10 carbon atoms; A monomer having a polyfluoroether group, a monomer having at least one group selected from the group consisting of an N-alkoxymethylamide group, a blocked isocyanate group and a trialkoxysilyl group, optionally a hydroxy group, a carboxyl group, an amide group and A monomer having at least one group selected from the group consisting of amino groups, and optionally a further monomer other than the above (hereinafter also referred to as "other monomer A"), in a solvent in the presence of a polymerization initiator at 50°C to 110°C. It is obtained by carrying out a polymerization reaction at a temperature of . At that time, the solvent used is not particularly limited as long as it dissolves the monomers constituting the alkali-soluble polymer and the polymer having a specific functional group. Specific examples include the solvents listed below for component (c).

Specific examples of other monomers b include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, and methoxytriethylene. Glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate , 8-ethyl-8-tricyclodecyl methacrylate, methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, glycidyl acrylate, cyclohexyl acrylate, isobornyl acrylate, Methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminomethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, γ-butyrolactone acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tri Examples include cyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, styrene, vinylnaphthalene, vinylanthracene, and vinylbiphenyl. .

The polymer having a specific functional group obtained in this way is usually in the form of a solution dissolved in a solvent.

In addition, the solution of the specific copolymer obtained as described above is reprecipitated by adding it to diethyl ether, water, etc. under stirring, and after filtering and washing the generated precipitate, under normal pressure or reduced pressure. By drying at room temperature or by heating, powder of the specific copolymer can be obtained. By such an operation, the polymerization initiator and unreacted monomer coexisting with the specific copolymer can be removed, and as a result, purified powder of the specific copolymer can be obtained. If sufficient purification is not possible in one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
In the present invention, the powder of the above-mentioned specific copolymer may be used as it is, or the powder may be redissolved in, for example, component (c) described later and used in the form of a solution.

In the polymer of component (b) above, the amount of the liquid-repellent group (b1) introduced is preferably 5 mol% to 60 mol%, and 5 mol% to 40 mol%, based on the total repeating units. It is more preferable. If the amount is less than 5 mol%, the liquid repellency may not be effective. If the amount is more than 60 mol%, problems such as aggregation may occur.

In the polymer of component (b) above, the amount of the group (b2) selected from N-alkoxymethylamide group, blocked isocyanate group, and trialkoxysilyl group introduced is 5 mol% to 70 mol% based on the total repeating units. The content is preferably 5 mol% to 50 mol%. If the amount is less than 5 mol%, problems may arise in the heat resistance and solvent resistance of the resulting film. If the amount is more than 60 mol%, developability may be affected.

When introducing at least one group (b3) selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group in the polymer of component (b) above, the amount of introduction should be determined based on the total repeating units. It is preferably 5 mol% to 60 mol%, more preferably 5 mol% to 40 mol%. If the amount is less than 5 mol %, the effect of improving the heat resistance and solvent resistance of the obtained film may not be obtained. If the amount is more than 60 mol%, the number of liquid-repellent repeating units will be too small.

Further, the number average molecular weight of the polymer of component (b) is preferably 2,000 to 100,000. More preferably 3,000 to 50,000, still more preferably 4,000 to 10,000. If the number average molecular weight is greater than 100,000, residue may be produced.

Moreover, in the present invention, the polymer of component (b) may be a mixture of multiple types of specific copolymers.

The ratio of component (b) to component (a) is 0.1 parts by mass to 20 parts by mass of component (b) per 100 parts by mass of component (a).

When component (a) has the (b1) liquid repellent group in component (b), component (a) can also serve as component (b), and in this case, it is not necessary to use component (b). do not have.
In this case, it is preferable that the polymerized unit (monomer) having the liquid-repellent group (b1) accounts for 5 to 30 parts by weight in 100 parts by weight of component (a).

<(c) component>
Component (c) used in the present invention includes component (a), component (b), and, if necessary, component (d), component (e), component (f), and component (g), which will be described later. The solvent dissolves and dissolves other additives mentioned below that are added as desired, and there are no particular limitations on the type and structure of the solvent as long as it has such a dissolving ability.

Examples of such component (c) include the same component as the component (C) used in the composition for forming the upper layer film described above.

These solvents can be used alone or in combination of two or more.
Among these components (c), solvents that do not have a hydroxy group in view of not dissolving the lower layer film, such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, Cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Ethyl ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like are preferred. These solvents are commonly used as solvents for photoresist materials.
When using a solvent having a hydroxyl group, it is preferable to use it in combination with a solvent not having a hydroxyl group from the viewpoint of not dissolving the underlying film as described above. The solvent to be used in combination is not particularly limited, and may be one or more solvents as long as they have good coating properties and do not dissolve the underlying film. In this case, from the viewpoint of not dissolving the lower layer film, the amount of the solvent having a hydroxyl group is preferably 70% by weight or less, more preferably 60% by weight or less, even more preferably 50% by weight or less, based on the entire component (c), and Most preferably, it is less than or equal to % by weight.

<(d) component>
Examples of the photosensitizer as the component (d) include (d-1) a 1,2-quinonediazide compound, (d-2) a photoradical generator, and (d-3) a photoacid generator.

(d-1) As the 1,2-quinonediazide compound, the same compounds as (D-1) mentioned in the component (D) used in the composition for forming the upper layer film mentioned above can be mentioned.

When the second photosensitive resin composition of the present invention is a positive photosensitive resin composition, the content when containing the compound having a quinonediazide group as component (d-1) is as follows: component (a) and ( The amount is preferably 5 parts by weight to 100 parts by weight, more preferably 8 parts to 50 parts by weight, and even more preferably 10 parts by weight to 40 parts by weight, based on a total of 100 parts by weight of component b). Or, if component (a) has the liquid repellent group (b1) in component (b) and does not contain component (b), the content of component (d-1) is 100% of component (a). The amount is preferably 5 parts by mass to 100 parts by mass, more preferably 8 parts by mass to 50 parts by mass, and even more preferably 10 parts by mass to 40 parts by mass. When the amount is less than 5 parts by mass, the difference in dissolution rate in the developer between the exposed area and the unexposed area of the positive photosensitive resin composition becomes small, and patterning by development may be difficult. In addition, if it exceeds 100 parts by mass, the 1,2-quinonediazide compound may not be sufficiently decomposed by short exposure, resulting in a decrease in sensitivity, or the (d-1) component may absorb light, causing the cured film to deteriorate. Transparency may be reduced.

(d-2) The photoradical generator is not particularly limited as long as it generates radicals upon exposure to light. Specific examples include the same ones as (D-2) listed in component (D) used in the composition for forming the upper layer film described above.

When the second photosensitive resin composition of the present invention contains component (d-2), the content is from 0.1 part by mass to 100 parts by mass of the total of components (a) and (b). The amount is preferably 30 parts by weight, more preferably 0.5 parts by weight to 20 parts by weight, and particularly preferably 1 part by weight to 15 parts by weight. Or, if component (a) has the liquid repellent group (b1) in component (b) and does not contain component (b), the content of component (d-2) is 100% of component (a). It is preferably 0.1 parts by mass to 30 parts by mass, more preferably 0.5 parts by mass to 20 parts by mass, and particularly preferably 1 part by mass to 15 parts by mass. If this ratio is too small, the exposed portions may be insufficiently cured, resulting in failure to form a pattern, or even if pattern formation is possible, the film may have low reliability. Furthermore, if this ratio is excessive, the transmittance of the coating film may decrease or poor development may occur in unexposed areas.

The photoacid generator (d-3) is not particularly limited as long as it is a compound that photodecomposes and generates an acid when irradiated with ultraviolet rays. The acid generated when the photoacid generator is photodecomposed is the acid generated when the photoacid generator listed in (D-3) of the component (D) used in the composition for forming the upper layer film mentioned above is photodecomposed. The same acids that occur in

Examples of the photoacid generator include the same photoacid generators listed in (D-3) of component (D) used in the composition for forming the upper layer film described above.

When the second photosensitive resin composition of the present embodiment contains component (d-3), the content is preferably 0 with respect to a total of 100 parts by mass of components (a) and (b). The amount is from .01 parts by weight to 20 parts by weight, more preferably from 0.1 parts by weight to 10 parts by weight, even more preferably from 0.5 parts by weight to 8 parts by weight. Or, if component (a) has the liquid repellent group (b1) in component (b) and does not contain component (b), the content of component (d-3) is 100% of component (a). It is preferably 0.01 parts by mass to 20 parts by mass, more preferably 0.1 parts by mass to 10 parts by mass, and still more preferably 0.5 parts by mass to 8 parts by mass. By setting the content of component (d-3) to 0.01 parts by mass or more, sufficient thermosetting properties and solvent resistance can be imparted. However, if the amount is more than 20 parts by mass, unexposed areas may develop poorly or the storage stability of the composition may deteriorate.

<(e) Component>
Component (e) is a crosslinking agent, and is introduced into the second photosensitive resin composition of the present invention when it satisfies requirement (z1). More specifically, it is a compound having a structure capable of forming a bridged structure through a thermal reaction with a thermally reactive site (for example, a carboxyl group and/or a phenolic hydroxy group) of component (a). Specific examples will be given below, but the invention is not limited to these. The thermal crosslinking agent is, for example, one selected from (e1) a crosslinkable compound having two or more substituents selected from an alkoxymethyl group and a hydroxymethyl group, and (e2) a crosslinkable compound represented by the following formula (5). is preferred. These crosslinking agents can be used alone or in combination of two or more.

When the crosslinkable compound having two or more substituents selected from the alkoxymethyl group and hydroxymethyl group of component (e1) is exposed to high temperatures during thermosetting, the crosslinking reaction proceeds through a dehydration condensation reaction. . Examples of such compounds include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine, and phenoplast compounds.

As specific examples of the alkoxymethylated glycoluril, the same ones listed in the component (E) used in the composition for forming the upper layer film described above can be used.

As specific examples of the alkoxymethylated benzoguanamine, those listed in the component (E) used in the composition for forming the upper layer film described above can be used.

As specific examples of the phenoplast compound, the same compounds as those listed in component (E) used in the composition for forming the upper layer film described above can be used.

Furthermore, as the component (e1), an acrylamide compound substituted with a hydroxymethyl group or an alkoxymethyl group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-butoxymethylmethacrylamide, or Polymers made using methacrylamide compounds can also be used.

As such a polymer, the same polymer as (E1) listed in the component (E) used in the composition for forming the upper layer film described above can be used.

Further, in the second photosensitive resin composition of the present invention, as the component (e2), the same components as (E2) listed in the component (E) used in the composition for forming the upper layer film described above can be used. .

In addition, as component e, a cross-linked structure is formed by a thermal reaction with a thermally reactive site (for example, a carboxyl group and/or a phenolic hydroxy group) of component (a) other than those shown as component (e1) and component (e2). Compounds that can form can also be used. Specifically, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexane Diol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N', -tetraglycidyl-m-xylene diamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, and N,N,N',N',-tetraglycidyl-4,4'-diaminodiphenylmethane, etc. Epoxy compounds, VESTANAT B1358/100, VESTAGON BF 1540 (all are isocyanurate-type modified polyisocyanates, manufactured by Degussa Japan Co., Ltd.), Takenate (registered trademark) B-882N, Takenate B-7075 (all are isocyanurate-type modified polyisocyanates) Examples include isocyanate compounds such as polyisocyanate (manufactured by Mitsui Chemicals, Inc.).

In addition, as component e, a polymer having two or more structures that can form a cross-linked structure by thermal reaction with the heat-reactive moiety (for example, carboxyl group and/or phenolic hydroxy group) of component (a) may be used. I can do it. Specifically, for example, polymers produced using compounds having an epoxy group such as glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3-methacryloxypropyltrimethoxy Polymers produced using compounds having alkoxysilyl groups such as silane, 2-isocyanatoethyl methacrylate (Karens MOI [registered trademark], manufactured by Showa Denko KK), 2-isocyanatoethyl acrylate (Karens AOI [registered trademark], manufactured by Showa Denko KK), 2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate (Karens MOI-BM [registered trademark], Compounds having blocked isocyanate groups such as 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (Karens MOI-BP [registered trademark], manufactured by Showa Denko Co., Ltd.) Examples include polymers produced using These compounds may be used alone or in combination to produce a polymer, or may be used in combination with other compounds to produce a polymer.

When component (a) has a group that reacts with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group, a hydroxy group, a carboxyl group, an amide group, A compound having two or more groups represented by amino groups can be used as the component (e).

These crosslinking compounds can be used alone or in combination of two or more.

When component (e) is selected as the crosslinking agent in the second photosensitive resin composition of the present invention, the content is 1 part by mass to 50 parts by mass based on the total of 100 parts by mass of components (a) and (b). Part by weight, preferably 1 part by weight to 40 parts by weight, more preferably 1 part to 30 parts by weight. Or, when component (a) has the liquid repellent group (b1) in component (b) and does not contain component (b), the content of component (e) is 100 parts by mass of component (a). 1 part by weight to 50 parts by weight, preferably 1 part to 40 parts by weight, more preferably 1 part to 30 parts by weight. If the content of the crosslinkable compound is small, the density of the crosslinks formed by the crosslinkable compound is not sufficient, so it has the effect of improving heat resistance, solvent resistance, resistance to long firing, etc. after pattern formation. may not be obtained. On the other hand, if it exceeds 50 parts by mass, uncrosslinked crosslinkable compounds will be present, and the heat resistance after pattern formation, solvent resistance, resistance to long-term baking, etc. will decrease, and the photosensitive resin composition Storage stability may deteriorate.

<(f) component>
Component (f) is a compound having two or more ethylenic polymerizable groups. The compound having two or more ethylenic polymerizable groups as used herein means a compound that has two or more polymerizable groups in one molecule, and those polymerizable groups are located at the end of the molecule. , those polymerizable groups mean at least one type of polymerizable group selected from the group consisting of acrylate groups, methacrylate groups, vinyl groups, and allyl groups.
This component (f), a compound having two or more ethylenic polymerizable groups, has compatibility with each component in the solution of the negative photosensitive resin composition in the second photosensitive resin composition of the present invention. From the viewpoint of being good and not affecting the developability, a compound having a molecular weight (weight average molecular weight when the compound is a polymer) of 1,000 or less is preferable.

Specific examples of such compounds include those listed in component (F) used in the composition for forming the upper layer film described above.

When the second photosensitive resin composition of the present invention contains component (f), the content is 5 parts by mass to 200 parts by mass based on 100 parts by mass of the total of components (a) and (b). The amount is preferably from 10 parts by weight to 150 parts by weight, and particularly preferably from 50 parts by weight to 150 parts by weight. Or, if component (a) has the liquid repellent group (b1) in component (b) and does not contain component (b), the content of component (f) is 100% by mass of component (a). The amount is preferably from 5 parts by weight to 200 parts by weight, more preferably from 10 parts by weight to 150 parts by weight, particularly preferably from 50 parts by weight to 150 parts by weight. If this ratio is too small, the exposed portions will be insufficiently cured, and pattern formation may not be possible, or even if pattern formation is possible, the film may have low reliability. Furthermore, if this ratio is excessive, tackiness may occur in the coating film after prebaking, or unexposed areas may become poorly dissolved during development.

<(g) Component>
Component (g) used in the second photosensitive resin composition used in the present invention is a compound having two or more functional groups that form a covalent bond with an acid. As such a functional group that forms a covalent bond with an acid, the same functional groups as those listed in component (G) used in the composition for forming the upper layer film described above can be used.

When the second photosensitive resin composition used in the present invention contains a compound having two or more functional groups that form a covalent bond with the acid of component (g), the content is as follows: component (a) and (b). The amount is preferably from 5 parts by weight to 200 parts by weight, more preferably from 50 parts by weight to 150 parts by weight, based on a total of 100 parts by weight of the components. Or, if component (a) has the liquid repellent group (b1) in component (b) and does not contain component (b), the content of component (g) is 100 parts by mass of component (a). The amount is preferably 5 parts by mass to 200 parts by mass, more preferably 50 parts by mass to 150 parts by mass. If this ratio is too small, the photocurability of the negative photosensitive resin composition may decrease; on the other hand, if it is too large, the developability of unexposed areas will decrease, resulting in residual film and residue. It may be the cause.

<Other additives>
Furthermore, the second photosensitive resin composition used in the present invention may optionally contain a leveling agent, a rheology modifier, a pigment, a dye, organic/inorganic fine particles, storage stability, etc., as long as the effects of the present invention are not impaired. It may contain a solubility promoter such as an antifoaming agent, an antifoaming agent, an adhesion promoter, or a solubility promoter such as a polyhydric phenol or a polyhydric carboxylic acid.

<Bank formation process>
After forming the resist film 13, the lower film 12 and the resist film 13 are patterned at once by exposing and developing the resist film 13 to form a bank. A region (non-bank portion) partitioned by the bank is formed in the opening 14 (FIG. 1).

As shown in FIG. 1, when the first and second photosensitive resin compositions are positive-type photosensitive resin compositions, the exposed area is a non-bank area, and during the development process, the lower layer of the non-bank area The resist film is removed together with the resist film in the non-bank portion, and an opening 14 is formed. Alternatively, when the first and second photosensitive resin compositions of the present invention are negative photosensitive resin compositions, the exposed portion becomes a bank portion, and in the development process, the lower layer film of the non-bank portion and the non-bank portion are bonded to each other. It is removed together with the resist film on the other side.

In the conventional second photosensitive resin composition containing a liquid-repellent component, a residue is left behind during the development process, and it is difficult to remove it completely. If the residue is left behind, defects such as unevenness will occur in the organic thin film during the process of further forming the organic thin film in the area partitioned by the bank. If a bank is formed using the bank pattern forming method of the present invention, the bank has a good liquid-repellent effect and does not easily leave residue on the substrate or on other layers interposed on the substrate, so that a clean organic thin film can be produced.

Here, other layers that can be formed on the substrate 11 include, for example, in the case of an organic electroluminescent device, an anode, a cathode, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, and a block layer. , a light emitting layer and the like. When the bank pattern forming method of the present invention is used for an organic electroluminescent device, an organic electroluminescent hole injection layer is particularly suitable as the other layer. The other layer consists of at least one layer.

<Photosensitive resin composition>
The first photosensitive resin composition used in the present invention is a photosensitive resin composition containing the following components (A), (C) and (D), and optionally contains component (E). A crosslinking agent, a compound having two or more ethylenic polymerizable groups (component (F)), a compound having two or more functional groups that form a covalent bond with an acid (component (G)), and one or more other additives. It is a composition that can further contain.
(A) Component: alkali-soluble resin having an amide group,
(C) Component: solvent,
(D) Component: Photosensitizer.

Among them, preferred examples of the first photosensitive resin composition used in the present invention are as follows.
[1]: A photosensitive resin composition containing 5 to 100 parts by mass of component (D) per 100 parts by mass of component (A), and these components dissolved in component (C), further comprising: A first photosensitive resin composition, wherein the component (D) is component (D-1).
[2]: A photosensitive resin composition containing 5 to 100 parts by mass of component (D) per 100 parts by mass of component (A), and these components are dissolved in component (C), Furthermore, a photosensitive resin composition containing a crosslinking agent as a component (E) from 1 part by mass to 50 parts by mass per 100 parts by mass of component (A), further comprising a crosslinking agent as a component (D-1). ) component of the first photosensitive resin composition.
[3]: 5 parts by mass to 200 parts by mass of component (F) per 100 parts by mass of component (A), 0.1 part by mass per 100 parts by mass of the total of components (A) and (F). A first photosensitive resin composition containing from 30 parts by mass of component (D), which is dissolved in component (C), and further wherein component (D) is component (D-2). Photosensitive resin composition.

The proportion of solids in the first photosensitive resin composition used in the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is, for example, 1% by mass to 80% by mass. and, for example, from 5% by weight to 60% by weight, or from 10% by weight to 50% by weight. Here, the solid content refers to the total components of the photosensitive resin composition excluding component (C).

The method for preparing the first photosensitive resin composition used in the present invention is not particularly limited, but for example, component (A) (specific polymer) is dissolved in component (C), and this solution is A covalent bond is formed with the photosensitive agent (D), the crosslinking agent (E) if necessary, the compound having two or more ethylenic polymerizable groups (F), and the acid (G). There is a method of mixing compounds having two or more functional groups in a predetermined ratio to form a homogeneous solution, or a method of further adding and mixing other additives as necessary at an appropriate stage of this preparation method. Can be mentioned.

In preparing the first photosensitive resin composition used in the present invention, a solution of a copolymer obtained by a polymerization reaction in component (C) can be used as it is; in this case, component (A), ( When adding component D), if necessary, component (E), component (F), component (G), etc. to make a homogeneous solution, it is also possible to add component (C) for the purpose of concentration adjustment. good. At this time, the component (C) used in the process of forming the specific copolymer and the component (C) used for concentration adjustment during the preparation of the first photosensitive resin composition may be the same. , may be different.

The prepared solution of the first photosensitive resin composition is preferably used after being filtered using a filter having a pore size of about 0.2 μm.

The second photosensitive resin composition used in the present invention is a photosensitive resin composition containing the following components (a), (b), (c), and (d), and, if desired, (e) A crosslinking agent, (f) a compound having two or more ethylenic polymerizable groups, (g) a compound having two or more functional groups that form a covalent bond with an acid, and other additives. The composition may further contain one or more of these.
(a) Component: alkali-soluble resin,
Component (b): a polymer having a liquid repellent group (b1),
(c) Component: solvent,
(d) Component: Photosensitizer.

Preferred examples of the second photosensitive resin composition used in the present invention are as follows.
[1]: A second photosensitive resin composition containing 0.1 parts by mass to 20 parts by mass of component (b) per 100 parts by mass of component (a), and these components are dissolved in component (c). thing.
[2]: Contains 0.1 parts by mass to 20 parts by mass of component (b) and 5 parts by mass to 100 parts by mass of component (d) per 100 parts by mass of component (a), and these components contain (c A second photosensitive resin composition comprising a photosensitive resin composition dissolved in component (d), wherein the component (d) is component (d-1).
[3]: Contains 0.1 parts by mass to 20 parts by mass of component (b) and 5 parts by mass to 100 parts by mass of component (d) per 100 parts by mass of component (a), and these components contain (c Component (e) is a photosensitive resin composition dissolved in component (e), in which the crosslinking agent (e) is added in an amount of 1 part by mass to 50 parts by mass per 100 parts by mass of the total of components (a) and (b). % of the photosensitive resin composition, wherein the component (d) is the component (d-1).
[4]: 0.1 to 20 parts by mass of component (b) per 100 parts by mass of component (a), 5 to 200 parts by mass per 100 parts by mass of the total of components (a) and (b). Contains 0.1 to 30 parts by mass of component (d) per 100 parts by mass of component (f), component (a), component (b), and component (f), and these are ( A second photosensitive resin composition which is a photosensitive resin composition dissolved in component (c), wherein the component (d) is component (d-2).
[5]: Component (a) contains a liquid repellent group (b1), and 100 parts by mass of component (a) containing a liquid repellent group (b1) contains 5 mass of polymerized units containing a liquid repellent group (b1) in component (a). A second photosensitive resin composition comprising component (a) in an amount of 30 to 30 parts by mass.

The proportion of solid content in the second photosensitive resin composition used in the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is, for example, 1% by mass to 80% by mass. and, for example, from 5% by weight to 60% by weight, or from 10% by weight to 50% by weight. Here, the solid content refers to the total components of the second photosensitive resin composition excluding component (c).

The method for preparing the second photosensitive resin composition used in the present invention is not particularly limited, but for example, component (b) is dissolved in component (c), and component (a) is added to this solution. Alkali-soluble resin, (d) component photosensitizer, optionally (e) component crosslinking agent, (f) component compound having two or more ethylenic polymerizable groups, (g) component acid. A method in which compounds having two or more bond-forming functional groups are mixed in a predetermined ratio to form a homogeneous solution, or other additives are further added as necessary at an appropriate stage of this preparation method. An example is a method of mixing.

In preparing the second photosensitive resin composition used in the present invention, the solution of the copolymer obtained by the polymerization reaction in the component (c) can be used as it is; in this case, the solution of the copolymer obtained by the polymerization reaction in the component (b) As in the preparation of the first photosensitive resin composition, components (a), (d), and if necessary, components (e), (f), and (g) are added to the solution to form a uniform solution. At this time, component (c) may be added for the purpose of concentration adjustment. At this time, the component (c) used in the process of forming the specific copolymer and the component (c) used for concentration adjustment during the preparation of the second photosensitive resin composition may be the same. , may be different.

The prepared solution of the second photosensitive resin composition is preferably used after being filtered using a filter having a pore size of about 0.2 μm.

<Coating film and cured film as lower layer film>
The first photosensitive resin composition used in the present invention is applied to semiconductor substrates (e.g., silicon/silicon dioxide-coated substrates, silicon nitride substrates, substrates coated with metals (e.g., aluminum, molybdenum, chromium), glass substrates, quartz substrates, etc.). (substrate, ITO substrate, etc.) by spin coating, flow coating, roll coating, slit coating, spin coating following slit coating, inkjet coating, etc., and then pre-drying on a hot plate or oven, etc. A coating film can be formed. Thereafter, this coating film is heat-treated to form a photosensitive resin film as a lower layer film.

As conditions for this heat treatment, for example, a heating temperature and heating time appropriately selected from a temperature range of 70° C. to 160° C. and a time range of 0.3 to 60 minutes are adopted. The heating temperature and heating time are preferably 80°C to 140°C and 0.5 to 10 minutes.

Further, the film thickness of the photosensitive resin film formed from the first photosensitive resin composition is, for example, 0.1 μm to 30 μm, further, for example, 0.2 μm to 10 μm, and further, for example, 0.3 μm to 8 μm. be.

<Coating film and cured film as resist film>
Applying the second photosensitive resin composition used in the present invention onto the lower layer film obtained above by spin coating, flow coating, roll coating, slit coating, spin coating following slit, inkjet coating, etc. Thereafter, a coating film can be formed by preliminary drying on a hot plate or oven. Thereafter, this coating film is heat-treated to form a photosensitive resin film as a resist film.

As conditions for this heat treatment, for example, a heating temperature and heating time appropriately selected from a temperature range of 70° C. to 160° C. and a time range of 0.3 to 60 minutes are adopted. The heating temperature and heating time are preferably 80°C to 140°C and 0.5 to 10 minutes.

Further, the thickness of the photosensitive resin film formed from the second photosensitive resin composition is, for example, 0.1 μm to 30 μm, further, for example, 0.2 μm to 10 μm, and further, for example, 0.3 μm to 8 μm. be.

A mask with a predetermined pattern is attached to the lower layer film obtained above and the resist film on the lower layer film is irradiated with light such as ultraviolet rays, and developed with an alkaline developer. Either the exposed area or the unexposed area is washed out, and the remaining patterned film is heated at 80°C to 140°C for 0.5 to 10 minutes to form a sharp relief pattern on the edge. can get.

Examples of alkaline developers that can be used include aqueous solutions of alkali metal hydroxides such as potassium carbonate, sodium carbonate, potassium hydroxide, and sodium hydroxide; hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline Examples include alkaline aqueous solutions such as quaternary ammonium aqueous solutions and amine aqueous solutions such as ethanolamine, propylamine, and ethylenediamine. Furthermore, surfactants and the like can also be added to these developers.

Among the above, a 0.1 to 2.58% by mass aqueous solution of tetraethylammonium hydroxide is generally used as a photoresist developer, and this is also used in the first and second photosensitive resin compositions of the present invention. Good development can be achieved using an alkaline developer without causing problems such as swelling of the film.

Moreover, as a developing method, any of the liquid piling method, dipping method, rocking immersion method, etc. can be used. The developing time at that time is usually 15 to 180 seconds.

After development, the photosensitive resin film is washed with running water for, for example, 20 to 120 seconds, and then air-dried using compressed air or compressed nitrogen or by spinning to remove moisture on the substrate, and then pattern formation. A film is obtained.

Subsequently, the pattern-formed film is post-baked for thermosetting, specifically by heating using a hot plate, an oven, etc., to improve heat resistance, transparency, flattening properties, etc. A film with low water absorption, excellent chemical resistance, and a good relief pattern can be obtained.

Post-baking is generally carried out at a heating temperature selected from the range of 140°C to 270°C for 5 to 30 minutes when on a hot plate, and for 30 to 90 minutes when in an oven. This method is adopted.

Thus, by such post-baking, it is possible to obtain a cured film having a desirable pattern shape.

As described above, by using the patterning method of the cured film, it is possible to form a liquid-repellent bank pattern in which residues such as components of the liquid-repellent resist material do not easily remain in areas other than the banks. A uniform organic thin film can be formed.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. The molecular weight of the polymer was measured as follows.
[Measurement of molecular weight of polymer]
The molecular weight of the polymer was measured using a GPC system manufactured by JASCO Corporation as an apparatus and Shodex (registered trademark) KF-804L and 803L as columns under the following conditions.
Column oven: 40℃
Flow rate: 1ml/min Eluent: Tetrahydrofuran

The meanings of the abbreviations used in the following examples are as follows.
QDC: 1,2-naphthoquinone-2-diazido-5-sulfonyl chloride MMA: Methyl methacrylate HEMA: 2-hydroxyethyl methacrylate HPMA: 4-hydroxyphenyl methacrylate CHMI: N-cyclohexylmaleimide PFHMA: 2-(perfluorohexyl)ethyl Methacrylate TMSSMA: methacryloxypropyltris(trimethylsiloxy)silane KBM-503: 3-methacryloxypropyltriethoxysilane MAA: methacrylic acid MAAm: methacrylamide HPMA-QD: 1 mol of 4-hydroxyphenyl methacrylate and 1,2-naphthoquinone-2 - Compound synthesized by condensation reaction with 1.1 mol of diazido-5-sulfonyl chloride AIBN: α, α'-azobisisobutyronitrile QD1: α, α, α'-tris(4-hydroxyphenyl)-1 - Compound synthesized by condensation reaction of 1 mol of ethyl-4-isopropylbenzene and 2 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride QD2: 4,4',4"-(3-methyl-1- A compound synthesized by the condensation reaction of 1 mol of propanyl-3-ylidene)trisphenol and 2 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride.CST: A polymer of 85% hydroxystyrene and 15% styrene, and hydroxy Styrene polymer made by mixing 70% styrene and 30% styrene at a ratio of 3:7 (manufactured by Maruzen Petrochemical Co., Ltd.)
8KQ: 8KQ-2001 (Alkali-soluble UV-curable acrylic resin manufactured by Taisei Fine Chemical Co., Ltd.)
Poly-AA: Polyacrylic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
I907: 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (IRGACURE 907, manufactured by BASF)
DEAB: 4,4'-bis(diethylamino)benzophenone DPHA: Dipentaerythritol hexaacrylate OXE-02: IRGACURE OXE-02 (manufactured by BASF)
GT-401: Butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl) modified ε-caprolactone YH-434L: YH-434L manufactured by Shin Nikka Epoxy Manufacturing Co., Ltd. (currently Nippon Steel & Sumikin Chemical Co., Ltd.)
CEL-2021P: 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate PGME: Propylene glycol monomethyl ether PGMEA: Propylene glycol monomethyl ether acetate EL: Ethyl lactate CH: Cyclohexanone PMA-ST: Propylene glycol monomethyl ether Acetate dispersed silica sol (manufactured by Nissan Chemical Co., Ltd.)

<Synthesis example 1>
3.00 g of MAAm, 2.00 g of HPMA, 5.00 g of MMA, and 0.8 g of AIBN were dissolved in 43.2 g of PGME and reacted at 80°C for 20 hours to obtain an acrylic polymer solution (solid content concentration 30% by mass). obtained (P1). The obtained acrylic polymer had Mn of 2300 and Mw of 5500.

<Synthesis example 2>
3.00 g of MAAm, 3.00 g of HPMA, 4.00 g of CHMI, and 0.8 g of AIBN were dissolved in 43.2 g of PGME and reacted at 80°C for 20 hours to obtain an acrylic polymer solution (solid content concentration 30% by mass). was obtained (P2). The obtained acrylic polymer had Mn of 3000 and Mw of 6200.

<Synthesis example 3>
3.00 g of MAAm, 3.00 g of HPMA, 4.00 g of CHMI, and 0.8 g of AIBN were dissolved in 43.2 g of PGME and reacted at 80°C for 20 hours to obtain an acrylic polymer solution (solid content concentration 30% by mass). was obtained (P3). The obtained acrylic polymer had Mn of 3000 and Mw of 6400.

<Synthesis example 4>
3.00 g of MAAm, 3.00 g of HPMA, 4.00 g of CHMI, and 0.8 g of AIBN were dissolved in 43.2 g of PGME and reacted at 80°C for 20 hours to obtain an acrylic polymer solution (solid content concentration 30% by mass). was obtained (P4). The obtained acrylic polymer had Mn of 3,500 and Mw of 7,500.

<Synthesis example 5>
10.9 g of MAA, 25.5 g of HEMA, 28.7 g of MMA, 35.3 g of CHMI, and 6.0 g of AIBN were dissolved in 159.6 g of PGME and reacted at 80°C for 20 hours to form an acrylic polymer solution (solid content). A concentration of 40% by mass) was obtained (P5). The obtained acrylic polymer had Mn of 3,800 and Mw of 6,700.

<Synthesis example 6>
MAA 90.00g, HEMA 225.00g, HPMA 45.00g, MMA
An acrylic polymer solution (solid content concentration 40% by mass) was obtained by dissolving 180.00g, CHMI 360.00g, and AIBN 57.60g in PGME 1436.40g and reacting at 80°C for 20 hours (P6) . The obtained acrylic polymer had Mn of 3,100 and Mw of 6,100.

<Synthesis example 7>
HPMA-QD 2.50g, TMSSMA 2.58g, PFHMA 5.26g, MAA 0.70g, CHMI 1.46g, AIBN 0.33g to CH 51.3
An acrylic polymer solution (solid content concentration 20% by mass) was obtained by dissolving the mixture in 100 g and stirring at 110° C. for 20 hours (P7). The obtained acrylic polymer had Mn of 7,200 and Mw of 11,000.

<Synthesis example 8>
5.00 g of PFHMA, 3.83 g of KBM-503, 1.51 g of HEMA, and 0.52 g of AIBN were dissolved in 25.32 g of PGME and reacted at 80°C for 20 hours to form an acrylic polymer solution (solid content concentration 30 mass). %) was obtained (P8). The obtained acrylic polymer had Mn of 4,800 and Mw of 6,700.

<Synthesis example 9>
2.0 g of PFHMA, 5.0 g of HPMA, 3.0 g of CHMI, and 0.5 g of AIBN were dissolved in 24.5 g of PGME and reacted at 80°C for 20 hours to obtain an acrylic polymer solution (solid content concentration 30% by mass). was obtained (P9). The obtained acrylic polymer had Mn of 3000 and Mw of 6500.

Each of the components (A), (D), and (E) and the solvent (C) were mixed in the composition shown in Table 1 to prepare the first photosensitive resin compositions of the lower layer film materials 1 to 8.

Similarly, second photosensitive resin compositions of upper resist film materials 1 to 5 were prepared with the compositions shown in Table 2. Note that the composition ratios in Tables 1 and 2 represent solid content ratios.

[Evaluation 1 Evaluation of pattern shape]
The first photosensitive resin composition of Lower Layer Materials 1 to 8 was applied onto an ITO-glass substrate using a spin coater, and then prebaked on a hot plate at a temperature of 100°C for 120 seconds to form a film with a thickness of 0.2 μm. A coating of the underlying material was formed. Next, the second photosensitive resin compositions of upper layer materials 1 to 5 are applied onto the lower layer material coating using a spin coater, and then prebaked on a hot plate at a temperature of 100°C for 120 seconds to form a film with a film thickness of 1. A coating film of .1 μm of upper layer material was formed. This coating film was irradiated with ultraviolet rays with a light intensity of 2.6 mW/cm 2 at 365 nm for a certain period of time using an ultraviolet irradiation device PLA-600FA manufactured by Canon Inc. through a photomask on which a 50 μm line and space pattern was drawn. Thereafter, the coating film was immersed in a 2.38% by mass or 0.4% by mass aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH) for a predetermined period of time, and then washed with running ultrapure water for 30 seconds. Next, this coating film was post-baked by heating it at a temperature of 230° C. for 30 minutes to produce substrates of Examples 1 to 5 and Comparative Examples 6 to 9. In Comparative Examples 1 to 5, substrates were produced in the same manner as above without performing the coating and prebaking steps for lower layer materials 1 to 5. The state of the created line and space pattern was observed using an optical microscope. A sample in which the pattern was peeled off from the substrate was graded as "×", and a sample in which the pattern was formed without peeling was graded as "○". The results obtained are shown in Table 3.

[Evaluation 2 Bank contact angle evaluation]
After applying the first photosensitive resin composition of lower layer material 5 onto an ITO-glass substrate using a spin coater, prebaking was performed on a hot plate at a temperature of 100° C. for 120 seconds, and the lower layer material was coated with a film thickness of 0.2 μm. A coating film was formed. Next, the second photosensitive resin composition of the upper layer material 5 was applied onto the lower layer material coating film using a spin coater, and then prebaked on a hot plate at a temperature of 100°C for 120 seconds to obtain a film thickness of 1.1 μm. A coating film of the upper layer material was formed. This coating film was irradiated with ultraviolet rays having a light intensity of 2.6 mW/cm 2 at 365 nm for a certain period of time using an ultraviolet irradiation device PLA-600FA manufactured by Canon Inc. Thereafter, the coating film was immersed in a 2.38% by mass or 0.4% by mass TMAH aqueous solution for a predetermined period of time, and then washed with running ultrapure water for 30 seconds. Next, this coating film was post-baked by heating it at a temperature of 230° C. for 30 minutes to create the cured film on the ITO-glass substrate of Example 5. In Examples 1 to 4, a cured film on an ITO-glass substrate consisting of an upper layer material and a lower layer material was formed in the same manner as above without exposing to ultraviolet light. In Comparative Example 5, a cured film made of only the upper layer material on the ITO-glass substrate was formed in the same manner as above without performing the coating and pre-baking process of the lower layer material 5. In Comparative Examples 1 to 4, a cured film was formed on an ITO-glass substrate consisting only of the upper layer material in the same manner as above without performing the coating/prebaking process of the lower layer materials 1 to 4 and the exposure to ultraviolet light. The contact angle of anisole on this cured film was measured using Drop Master manufactured by Kyowa Interface Science Co., Ltd. The results obtained are shown in Table 3. Note that Evaluation 2 was not conducted for Comparative Examples 6 to 9 in which pattern peeling occurred in Evaluation 1.

[Evaluation 3: Evaluation of contact angle of exposed area on ITO substrate]
The first photosensitive resin composition of Lower Layer Materials 1 to 4 was applied onto an ITO-glass substrate using a spin coater, and then prebaked on a hot plate at a temperature of 100°C for 120 seconds to form a film with a thickness of 0.2 μm. A coating of the underlying material was formed. Next, the second photosensitive resin composition of upper layer materials 1 to 4 was applied onto the lower layer material coating film using a spin coater, and then prebaked on a hot plate at a temperature of 100°C for 120 seconds to form a film with a film thickness of 1. A coating film of .1 μm of upper layer material was formed. This coating film was irradiated with ultraviolet rays having a light intensity of 2.6 mW/cm 2 at 365 nm for a certain period of time using an ultraviolet irradiation device PLA-600FA manufactured by Canon Inc. Thereafter, the coating film was immersed in a 2.38% by mass or 0.4% by mass TMAH aqueous solution for a predetermined period of time, and then washed with running ultrapure water for 30 seconds. Next, this coating film was post-baked by heating it at a temperature of 230° C. for 30 minutes to prepare ITO-glass substrates on which the coating films of Examples 1 to 4 were developed and removed. In Example 5, the IT film was developed and removed in the same manner as above without being exposed to ultraviolet light.
An O-glass substrate was prepared. In Comparative Examples 1 to 4, ITO-glass substrates from which the coating films were developed and removed were prepared in the same manner as above without performing the coating and prebaking steps for lower layer materials 1 to 4. In Comparative Example 5, a cured film made of only the upper layer material was formed on an ITO-glass substrate in the same manner as above without performing the coating/prebaking process of the lower layer material 5 and the exposure to ultraviolet light. The contact angle of anisole on this cured film was measured using Drop Master manufactured by Kyowa Interface Science Co., Ltd. The results obtained are shown in Table 3. Note that Evaluation 3 was not conducted for Comparative Examples 6 to 9 in which pattern peeling occurred in Evaluation 1.

As shown in Table 3, all of Examples 1 to 5 using the lower layer material had smaller contact angles at the openings and better lyophilicity than Comparative Examples 1 to 5 that did not use the lower layer material. there were. Furthermore, in Evaluation 1, in Example 3 using the lower layer material, a good pattern was obtained with no residue observed in the space parts of the line & space pattern, whereas in Comparative Example 3, in which the lower layer material was not used, the space parts Particulate residue was observed. Furthermore, in Comparative Examples 6 to 9 in which a hydrophilic resin not containing an amide group was used as the lower layer material, the pattern peeled off during development and did not remain on the substrate in evaluation 1.

Claims (25)

A method of forming a bank and a region demarcated by the bank on a substrate, the method of forming a bank pattern for forming an organic thin film in the region demarcated by the bank,
A first photosensitive resin composition containing the following components (A), (C), (D) and (E) is applied directly onto the substrate or via another layer to form a lower layer film. a lower layer film forming step,
A resist film forming step of forming a resist film by applying a second photosensitive resin composition containing the following components (a), (b), (c) and (d) on the lower layer film. and,
A method for forming a bank pattern, comprising the steps of forming a bank by exposing and developing the resist film, and in the developing process, a lower layer film in a non-bank part is removed together with the resist film in a non-bank part.
Component (A): an alkali-soluble resin having an amide group (the amide group is derived from at least one monomer selected from acrylamide and methacrylamide),
(C) Component: solvent,
(D) Component: photosensitizer,
(E) Component: crosslinking agent,
(a) Component: Alkali-soluble resin (However, if component (a) contains a liquid repellent group (b1), component (b) may not be included),
Component (b): a polymer having a liquid repellent group (b1),
(c) Component: solvent,
(d) Component: Photosensitizer The method for forming a bank pattern according to claim 1, wherein the first photosensitive resin composition satisfies at least one of the following (Z2) to (Z4).
(Z2): Component (A), the alkali-soluble resin having an amide group, further has a self-crosslinking group, or at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group. further having a reactive group;
(Z3): A photoradical generator whose (D) component is (D-2), further containing a compound having two or more ethylenic double bonds as the (F) component;
(Z4): A photoacid generator in which the (D) component is (D-3), and the (G) component further contains two functional groups that form a covalent bond with the acid generated from (D-3). Contains a compound with or more than The method for forming a bank pattern according to claim 1 or 2, wherein the second photosensitive resin composition satisfies at least one of the following (z1) to (z4).
(z1): further contains a crosslinking agent as component (e);
(z2): The alkali-soluble resin of component (a) further has a self-crosslinking group, or a group that reacts with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group. further has;
(z3): A photoradical generator whose (d) component is (d-2), further containing a compound having two or more ethylenic double bonds as the (f) component;
(z4): A photoacid generator in which the (d) component is (d-3), and the (g) component further includes two functional groups that form a covalent bond with the acid generated from (d-3). Contains a compound with or more than 4. The method for forming a bank pattern according to claim 1, wherein the component (D) and/or (d) is a quinonediazide compound. 3. The method for forming a bank pattern according to claim 2, wherein component (D) is a quinone diazide compound, and further satisfies either (Z1) or (Z2). 4. The method for forming a bank pattern according to claim 3, wherein component (d) is a quinonediazide compound and further satisfies either (z1) or (z2). 6. The method for forming a bank pattern according to claim 5, wherein the component (D) is diazonaphthoquinone. 7. The method for forming a bank pattern according to claim 6, wherein the component (d) is diazonaphthoquinone. A claim in which the liquid repellent group (b1) is at least one group selected from a fluoroalkyl group having 3 to 10 carbon atoms, a polyfluoroether group, a silyl ether group, and a polysiloxane group represented by the following formula 4. The method for forming a bank pattern according to any one of claims 1 to 8.
-(SiR ¹ R ² -O) _n -SiR ¹ R ² R ^3Formula 4
(However, R ¹ and R ² independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, R ³ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and n represents 1 to 200 carbon atoms.) (Represents an integer.) Any one of claims 1 to 9, wherein the number average molecular weight of the alkali-soluble resin having an amide group as the component (A) and/or the alkali-soluble resin as the component (a) is 2,000 to 50,000 in terms of polystyrene. 1. The method for forming a bank pattern according to item 1. Formation of a bank pattern according to any one of claims 1 to 10, wherein the component (E) is 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the component (A). Method. The bank pattern according to any one of claims 1 to 11, characterized in that the component (b) is contained in an amount of 0.1 part by mass to 20 parts by mass per 100 parts by mass of the component (a). Formation method. 13. The method for forming a bank pattern according to claim 1, wherein the polymer of component (b) is an acrylic polymer. 14. The method for forming a bank pattern according to claim 13, wherein the acrylic polymer as the component (b) has a number average molecular weight of 2,000 to 100,000 in terms of polystyrene. According to any one of claims 3 to 14, the component (e) is present in an amount of 1 part by mass to 50 parts by mass with respect to a total of 100 parts by mass of components (a) and (b). The method for forming the bank pattern described above. 16. The method for forming a bank pattern according to claim 1, wherein component (b) further comprises a polymer having the following (b2).
(b2): at least one group selected from N-alkoxymethylamide group, blocked isocyanate group, and trialkoxysilyl group 17. The method for forming a bank pattern according to claim 1, wherein component (b) further comprises a polymer having the following (b3).
(b3): at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group 12. The method for forming a bank pattern according to claim 1, wherein the component (a) is a resin having a liquid-repellent group (b1) and does not contain the component (b). 19. The method for forming a bank pattern according to claim 18, wherein the polymerized unit having the liquid-repellent group (b1) occupies 5 parts by mass to 30 parts by mass in 100 parts by mass of component (a). 20. The method for forming a bank pattern according to claim 18, wherein the component (e) is contained in an amount of 1 part by mass to 50 parts by mass relative to 100 parts by mass of the component (a). 21. The method for forming a bank pattern according to claim 1, wherein the other layer is an organic electroluminescent hole injection layer. A bank pattern having a bank and a region partitioned by the bank on a substrate,
The bank includes, from the substrate side, at least a substrate, a lower layer film made of a first photosensitive resin composition containing the following components (A), (C), (D) and (E), and the following. a resist film made of a second photosensitive resin composition containing component (a), component (b), component (c), and component (d), and the area defined by the bank is the lower layer. A bank pattern without a film and the resist film.
Component (A): an alkali-soluble resin having an amide group (the amide group is derived from at least one monomer selected from acrylamide and methacrylamide),
(C) Component: solvent,
(D) Component: photosensitizer,
(E) Component: crosslinking agent,
(a) Component: Alkali-soluble resin (However, if component (a) contains a liquid repellent group (b1), component (b) may not be included),
Component (b): a polymer having a liquid repellent group (b1),
(c) Component: solvent,
(d) Component: Photosensitizer A display element having a bank pattern according to claim 22. A display element comprising the bank pattern according to claim 22 as an image forming partition. A photosensitive resin composition for forming a lower layer film for forming a lower layer film under a resist film containing a liquid repellent component for the bank in a bank pattern having a bank and a region defined by the bank on a substrate. hand,
A photosensitive resin composition for forming a lower layer film of a resist film, containing the following components (A), (C), (D) and (E).
Component (A): an alkali-soluble resin having an amide group (the amide group is derived from at least one monomer selected from acrylamide and methacrylamide),
(C) Component: solvent,
(D) Component: Photosensitizer (E) Component: Crosslinking agent

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