JPS6332811B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to resin compositions that are cured by irradiation with active energy rays such as ultraviolet rays and electron beams, and particularly to adhesiveness and chemical resistance to supports such as glass, ceramics, and plastic films, and mechanical resistance. The present invention relates to an active energy ray-curable resin composition that has excellent physical strength, high sensitivity and high resolution as a pattern forming material, and is suitable for forming a pattern consisting of a highly accurate cured film. This active energy ray-curable resin composition is a resin composition that can be shaped into a solid photoreceptor sheet (dry film). [Prior art] In recent years, active energy ray-curable resins have been used in paints,
It is widely used as ink, sealing material, resist material, and pattern forming material. In addition, active energy ray-curable resins as pattern-forming materials were initially used to create printing plates, but more recently they have been used in electronic industry fields such as printed wiring and integrated circuits, as well as in the As disclosed in Japanese Patent No. 57-43876, it is also being used as a structural material for precision equipment such as inkjet recording heads. However, the active energy ray-curable resins used for pattern formation, especially the dry film type, have excellent adhesion to supports such as glass, ceramics, or plastic films. I stopped talking. On the other hand, although the known photocurable paints and adhesives used for glass, metals, ceramics, etc. have excellent adhesion of the cured product, they require exposure to strong active energy rays or long-term irradiation. Moreover, they generally do not have properties suitable for pattern formation. That is, even if an attempt was made to obtain a pattern by irradiating active energy rays in a pattern using these materials and removing unexposed areas by development, it was not possible to obtain a precise, high-resolution pattern. In this way, with conventional technology, precise patterns with excellent adhesion can be formed on various supports,
Moreover, there was no material whose pattern had high durability as a structural material. [Problems to be Solved by the Invention] The purpose of the present invention is to solve problems that could not be achieved with such conventional active energy ray-curable resins, not only when used in liquid form and applied to a support. , an active film that has excellent adhesion to the support when used in the form of a dry film, has high sensitivity to active energy rays, and can form precise, high-resolution patterns. An object of the present invention is to provide an energy ray-curable resin composition. Another object of the present invention is that it can be shaped into a dry film that is convenient for pattern formation, and that the pattern that is hardened and formed by irradiation with active energy rays and heat treatment as required has chemical resistance. Another object of the present invention is to provide an active energy ray-curable resin composition that has excellent mechanical strength and high durability as a structural material. [Means for Solving the Problems] The active energy ray-curable resin composition of the present invention mainly contains structural units derived from (i) one or more monomers selected from the group consisting of alkyl methacrylate, acrylonitrile, and styrene. In the backbone chain, (A) hydroxyl group-containing acrylic monomer, (B)
Amino or alkylamino group-containing acrylic monomer, (C) carboxyl group-containing acrylic or vinyl monomer, (D) N-vinylpyrrolidone or its derivative, (E) vinylpyridine or its derivative, and (F) acrylamide represented by the following general formula A graft copolymer polymer having branch chains mainly derived from one or more monomers selected from the group consisting of derivatives; (However, R ¹ is hydrogen or has 1 carbon atom
-3 alkyl or hydroxyalkyl group, ^R2 represents hydrogen or an alkyl or acyl group optionally having a hydroxyl group having 1 to 4 carbon atoms). (ii) a monomer having an ethylenically unsaturated bond; (iii) an epoxy resin comprising at least one compound having one or more epoxy groups in the molecule; Therefore, it contains as an essential component a polymerization initiator that generates a Lewis acid. [Preferred embodiments for carrying out the invention] The graft copolymer polymer (i), which is an essential component of the active energy ray-curable resin composition of the present invention, has relatively rigid properties that are suitable as a structural material. It is made by adding branch chains, which are mainly composed of the above-mentioned hydrophilic monomers (A) to (F), to the main chain and exhibits excellent adhesion to the support. When constructing the graft copolymer polymer, the monomers (A) to (F) above used to structure the branch chains are specifically shown as (A), the 2-hydroxy Ethyl (meth)acrylate (hereinafter, when referred to as (meth)acrylate, it is meant to include both acrylate and methacrylate), 2-
Hydroxypropyl (meth)acrylate, 3-
Chloro-2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, or 1 , 4-cyclohexanedimethanol and monoesters of acrylic acid or methacrylic acid.
M5700 (manufactured by Toagosei Kagaku Co., Ltd.), TONEM100 (caprolactone acrylate, Union Carbide Co., Ltd.)
), Light Ester HO-mpp (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.), Light Ester M-600A (trade name of 2-hydroxy-3-phenoxypropyl acrylate, manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.) Known and dihydric alcohols, e.g. 1,10
-Decanediol, neopentyl glycol, bis(2-hydroxyethyl) terephthalate, a monoester of an addition reaction product of bisphenol A and ethylene oxide or propylene oxide, and (meth)acrylic acid, etc. can be used. The amino or alkylamino group-containing acrylic monomer (B) includes (meth)acrylamide,
N,N-dimethylaminoethyl (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, N,N-di-t-butylaminoethyl (meth)acrylamide, etc. Can be mentioned. The carboxyl group-containing acrylic or vinyl monomer (C) may be (meth)acrylic acid, fumaric acid, itaconic acid, or Aronix M-5400, Aronix M manufactured by Toagosei Kagaku Co., Ltd.
-Some examples include those known as 5500. (E) vinylpyridine or its derivatives include 2-vinylpyridine, 4-vinylpyridine,
2-vinyl-6-methylpyridine, 4-vinyl-
Examples include 1-methylpyridine, 2-vinyl-5-ethylpyridine, (4-pipenylinoethyl)pyridine, and the like. All of the monomers (A) to (E) above have hydrophilicity, and the composition of the present invention can be used for glass,
It provides strong adhesion when bonded to supports such as ceramics and plastics. Examples of acrylamide derivatives represented by the general formula (F) include N-methylol (meth)acrylamide, N-propoxymethyl (meth)acrylamide, Nn-butoxymethyl (meth)acrylamide, and β-hydroxyethoxymethyl (meth)acrylamide.
Acrylamide, N-ethoxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, α-hydroxymethyl-N-methylolacrylamide, α-hydroxyethyl-N
-Butoxymethylacrylamide, α-hydroxypropyl-N-propoxymethylacrylamide, α-ethyl-N-methylolacrylamide, α-propyl-N-methylolacrylamide, and other hydrophilic and thermally crosslinkable monomers are mentioned. These monomers F have not only hydrophilic properties but also condensation crosslinking properties when heated, and generally water molecules or alcohol are released at temperatures of 100°C or higher to form crosslinked bonds, and the graft copolymer polymer itself is also cured. Afterwards, a network structure is formed and the resulting pattern is further improved in chemical resistance, mechanical strength, etc., thereby making the present invention more effective. In addition, by adding a portion of monomers that ring-open and crosslink by heat, such as glycidyl (meth)acrylate, to the monomers (A) to (F) above to form a branch chain, the monomers (F The same effect as in ) can be obtained. In addition to the above thermal crosslinking, for the same purpose, photopolymerizable side chains may be introduced into some of the branch chains of the graft copolymer of the present invention, and the graft copolymer polymer may be crosslinked with active energy rays. It is valid. Such methods for imparting photopolymerizability to branch chains include, for example, copolymerizing monomers containing carboxyl groups such as (meth)acrylic acid, or monomers containing amino groups or tertiary amine groups. A partial urethane compound of polyisocyanate having one isocyanate group and one or more acrylic ester groups in one molecule, and a branched hydroxyl group,
A method of reacting with an amino group or a carboxyl group, a method of reacting a branched hydroxyl group with acrylic acid chloride, a method of reacting a branched hydroxyl group with an acid anhydride, and then reacting with glycidyl (meth)acrylate, Methods such as a method of condensing the hydroxyl group of and the condensation crosslinking monomer exemplified in (F) to leave an acrylamide group on the side chain, a method of reacting the hydroxyl group of the branch chain with glycidyl (meth)acrylate, etc. can be used. . When the branch chains of the graft copolymer polymer in the present invention are thermally crosslinkable, it is preferable to perform heating after forming a pattern by irradiation with active energy rays. On the other hand, even when the branch chain is photopolymerizable, there is no problem in heating within an allowable range in terms of the heat resistance of the support, and in fact, more favorable results can be obtained. In addition to those derived only from hydrophilic monomers as exemplified in (A) to (F) above, the branch chains may be derived from various hydrophobic monomers that exhibit various other functions.
The branched chain may be used as a component of the copolymerization in the range of up to about 25% by weight. The monomers constituting the backbone chain of the graft copolymer polymer in the present invention are methyl methacrylate,
These include alkyl methacrylates in which the alkyl group has 1 to 4 carbon atoms, such as ethyl methacrylate, isobutyl methacrylate, and t-butyl methacrylate, acrylonitrile, and styrene. In addition to those derived only from the above monomers,
For example, methyl acrylate, ethyl acrylate, n-butyl acrylate, lauryl acrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, vinyl acetate, etc.
The backbone may be used as a copolymerization component in an amount up to 50% by weight. In the composition of the present invention, the backbone chain imparts high cohesive strength to the composition. The composition of the present invention can be provided in various forms depending on the purpose of use, such as a solution or a solid film, but if it is to be put to practical use as a dry film, the composition may be maintained in a film form. In order to achieve this, it is preferable to use a relatively rigid backbone having a glass transition temperature of about 50° C. or higher. In this case, the backbone chain used may be composed of two or more types having different glass transition temperatures. Furthermore, if the composition of the present invention is used in the form of a solution, it is also possible to use a backbone chain with a low glass transition temperature that imparts flexibility to the composition. However, even in this case, in order to obtain a pattern with excellent chemical resistance and high mechanical strength, it is preferable that the backbone chain has a high glass transition temperature. The graft copolymer polymer used in the present invention is
They are roughly classified into non-curable, photo-crosslinkable, and thermally crosslinkable, but in any case, the curing process of the composition of the present invention (i.e., active energy ray irradiation and, if necessary, In addition to imparting shape retention to the composition and enabling precise patterning, the resulting curing pattern also has excellent adhesion, chemical resistance, and high mechanical strength. It is something to give. The above-mentioned graft copolymer polymer used in the composition of the present invention can be produced by a known method, and specifically, for example, "Basics and Applications of Polymer Alloys", pp. 10-35 (edited by the Society of Polymer Engineers). , published by Tokyo Kagaku Dojin Co., Ltd., 1981). Examples of these methods include a chain transfer method, a method using radiation, an oxidative polymerization method, an ion graft copolymerization method, and a macromonomer method. The graft copolymer used in the present invention has a more pronounced surfactant effect when the branch chain lengths are uniform.
It is preferable to use the following methods, and among them, the macromonomer method is particularly preferable because it is advantageous in terms of material design. The weight average molecular weight of the graft copolymer is preferably in the range of about 5,000 to 300,000, and when used as a dry film, the weight average molecular weight is preferably in the range of about 30,000 to 300,000. The monomer (ii) having an ethylenically unsaturated bond used in the composition of the present invention, together with the epoxy resin (iii) described later, enables the composition of the present invention to exhibit curability with active energy rays, and particularly A component for imparting excellent sensitivity to active energy rays to the composition of the present invention, preferably under atmospheric pressure.
It has a boiling point of 100°C or higher, and preferably has two or more ethylenically unsaturated bonds,
Various known monomers that are cured by irradiation with active energy rays can be used. Specific examples of such monomers having two or more ethylenically unsaturated bonds include acrylic esters or methacrylic esters of polyfunctional epoxy resins having two or more epoxy groups in one molecule. , acrylic esters or methacrylic esters of alkylene oxide adducts of polyhydric alcohols, polyester acrylates with acrylic ester groups at the molecular chain ends of polyesters with a molecular weight of 500 to 3,000, consisting of dibasic acids and dihydric alcohols, polyhydric alcohols A reaction product of an isocyanate and an acrylic acid monomer having a hydroxyl group can be mentioned. The above monomers ~ may be urethane modified products having a urethane bond in the molecule. Examples of monomers belonging to this category include acrylic acid or methacrylic acid esters of polyfunctional epoxy resins, which are exemplified as those used in epoxy resin (iii) described below. Examples of monomers belonging to this group include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6 hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, Examples include pentaerythritol tri(meth)acrylate, product names KAYARAD HX-220, HX-620,
D-310, D-320, D-330, DPHA, R-604,
DPCA-20, DPCA-30, DPCA-60, DPCA-
120 (manufactured by Nippon Kayaku Co., Ltd.), trade name NK ester
BPE-200, BPE-500, BPE-1300, A-BPE
-4 (manufactured by Shin-Nakamura Chemical Co., Ltd.), etc. can be used. Monomers belonging to the product name Aronix M-6100, M-6200, M-6250, M-6300,
-6400, M-7100, M-8030, M-8060, M-
8100 (manufactured by Toagosei Kagaku Co., Ltd.), etc. The product name Aronix M- belongs to polyester and contains urethane bonds.
1100, Aronix M-1200 (manufactured by Toagosei Kagaku Co., Ltd.), and the like. Monomers belonging to this group include polyisocyanates and hydroxyl group-containing monomers such as tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, and diphenylmethane diisocyanate. Reactants with acrylic monomers are listed, and the product name is Sumidyur N.
(Biuret derivative of hexamethylene diisocyanate), Sumidyur L (trimethylolpropane modified product of tolylene diisocyanate) (the above,
A reaction product obtained by adding a hydroxyl group-containing (meth)acrylic acid ester to a polyisocyanate compound known as Sumitomo Bayer Urethane Co., Ltd.) can be used. The hydroxyl group-containing acrylic monomer mentioned here is typically a (meth)acrylic acid ester, with hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate being preferred. Further, other hydroxyl group-containing acrylic monomers mentioned above for producing monomers represented by the linear polymer formula can also be used. In addition to the monomers having two or more ethylenically unsaturated bonds as described above, monomers having only one ethylenically unsaturated bond, such as those listed below, can also be used. Examples of such monomers having one ethylenically unsaturated bond include carboxyl group-containing unsaturated monomers such as acrylic acid and methacrylic acid; glycidyl group-containing unsaturated monomers such as glycidyl acrylate and glycidyl methacrylate. Monomer; _C2 - _C8 hydroxyalkyl ester of acrylic acid or methacrylic acid such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate; polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate Monoesters of acrylic acid or methacrylic acid and polyethylene glycol or polypropylene glycol such as acrylate, polypropylene glycol monomethacrylate; methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, acrylic Acrylic acids such as octyl acrylate, lauryl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, etc. or _C1 - _C12 alkyl or cycloalkyl esters of methacrylic acid; other monomers such as styrene, vinyltoluene, methylstyrene, vinyl acetate, vinyl chloride, vinyl isobutyl ether,
Acrylonitrile, acrylamide, methacrylamide, acrylic or methacrylic acid adducts of alkyl glycidyl ethers, vinylpyrrolidone, dicyclopentenyloxyethyl (meth)acrylate, ε-caprolactone-modified hydroxyalkyl (meth)acrylate, tetrahydrofurfuryl acrylate, phenolic acid Examples include ethyl acrylate and the like. By using the above-mentioned monomer (ii) having an ethylenically unsaturated bond, a sufficient hardening type with high sensitivity to active energy rays is added to the composition of the present invention. The epoxy resin (iii) consisting of one or more compounds containing one or more epoxy groups in one molecule used in the resin composition of the present invention refers to the above-mentioned monomer (ii) having an ethylenically unsaturated bond. Through the action of the polymerization initiator (iv) described below, the composition of the present invention exhibits sufficient curability with high sensitivity to active energy rays. The present invention can be applied in liquid form onto various supports made of ceramics, etc., and then cured to form a cured film, or when used in the form of a dry film adhered to various supports. It is a component for imparting better adhesion to the support, water resistance, chemical resistance, dimensional stability, etc. to the cured film made of the resin composition. In the resin composition of the present invention, any epoxy resin can be used without particular limitation as long as it is made of one or more compounds containing one or more epoxy groups in one molecule. However, for example, consideration must be given to the chemical resistance and mechanical strength of the cured film obtained by curing the resin composition of the present invention, high durability as a structural material, or various patterns made of the cured film of the composition. Considering the workability when forming on a support, the resolution of the formed pattern, etc., it is preferable to use an epoxy resin made of one or more compounds containing two or more epoxy groups in one molecule. The above-mentioned epoxy resins containing two or more epoxy groups in one molecule include epoxy resins represented by bisphenol A type, novolac type, and alicyclic type, or bisphenol S, bisphenol F, and tetrahydroxyphenylmethane. Tetraglycidyl ether, resorcinol diglycidyl ether, glycerin triglycidyl ether, pentaerythritol triglycidyl ether, isocyanuric acid triglycidyl ether and the following general formula (However, R is an alkyl group or an oxyalkyl group, and Ro is

【formula】

〔Effect of the invention〕

The active energy ray-curable resin composition of the present invention mainly consists of a monomer (ii) having an ethylenically unsaturated bond as essential components, an epoxy resin (iii), and a polymerization initiator (iv) that generates a Lewis acid. ) has very excellent sensitivity and resolution to active energy rays as a pattern forming material,
Using this, a pattern with high precision and high resolution can be formed. Moreover, the properties of the graft copolymer polymer (i) and the epoxy resin (ii) as essential components are effectively utilized in the active energy ray-curable resin composition of the present invention. In addition to the excellent adhesion to the support and mechanical strength provided mainly by the graft copolymer polymer (i), the excellent adhesion and mechanical strength provided mainly by the epoxy resin (iii) It has excellent chemical resistance and dimensional stability, and the pattern formed by the composition has these excellent properties when viewed as a coating material, making it suitable for protective coatings or coatings that require long-term durability. Suitable as a structural member. Furthermore, when a graft copolymer polymer having curability is used, it is possible to obtain an active energy ray-curable resin composition that has even better adhesion, mechanical strength, or chemical resistance. The active energy ray-curable resin composition of the present invention can be used as a protective coating for glass, an adhesive, an insulating layer of a liquid crystal display element, or a transparent or opaque coloring on a glass plate, imparting waterproof properties, imparting water repellency, and stain resistance. It can be used for surface modification such as imparting properties. Also,
Utilizing its excellent chemical resistance, it is useful as a masking material for glass etching or metallizing such as electroless copper plating, and as a solder mask for printed wiring boards. It is also useful for forming fine liquid flow paths, cooling paths, or nozzles using water resistance, especially nozzles in inkjet recording heads. Furthermore, it is possible to obtain a photosensitive liquid or dry film for screen printing plates that has unprecedented durability and is used for both water-based and oil-based inks. [Example] Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 A living polymer (2-hydroxyethyl methacrylate/butyl acrylate (=80/20 weight ratio)) obtained by an anionic polymerization method is reacted with P-vinylbenzyl chloride to form a vinyl group at one end of the molecular chain. A macromonomer (p-vinylbenzyl poly-2-hydroxyethyl methacrylate/butyl acrylate) having a weight average molecular weight of about 1800 was obtained. 30 parts by weight of this macromonomer and 70 parts by weight of methyl methacrylate were solution polymerized in methyl cellosolve, ^and a thermoplastic graft copolymer polymer (GP-
1) was obtained. Note that the glass transition temperature of the polymethyl methacrylate chain constituting the main chain of GP-1 is 100°C. Using this GP-1, an active energy ray-curable resin composition having the following composition was prepared. GP-1 100 parts by weight Epicote 1001〓1 25〃 Celloxide 2021〓2 25〃 Trimethylolpropane triacrylate
50 〃 Triphenylsulfonium tetrafluoroborate 10 〃 Irgakiure 651 15 〃 Crystal Violet 1 〃 Hydroquinone 0.2 〃 Methyl cellosolve acetate 300 〃 〓 1: Bisphenol A type epoxy resin manufactured by Yuka Ciel Epoxy Co., Ltd. Epoxy equivalent, 450 ~500 〓2: Alicyclic type epoxy resin manufactured by Daicel Chemical Co., Ltd.Epoxy equivalent, 128-145 This composition was applied to a 16 μm polyethylene terephthalate film (Lumirror T type) so that the thickness after drying was 20 μm. It was applied with a bar coater.
The coating film was protected by pressure laminating a 25 μm polyethylene film thereon. on the surface
A thermal oxide layer of 5000 Å was formed. A 4-inch silicon wafer was ultrasonically cleaned in 1,1,1-trichloroethane, dried, and preheated to 80°C.The above film was then placed in a hot roll laminator (HRL-24, (manufactured by Dupont), roll temperature
80℃, roll pressure 1Kg/cm ² , lamination speed
Laminated at 1m/mim. Next, a resolution test mask is placed in close contact with the mask, and the illuminance on the irradiated surface is
Exposure was performed for 40 seconds using a semiconductor exposure light source (PLA-501, manufactured by Canon Inc.) using a deep UV lamp of 8 mW/cm ² . After exposure, the polyethylene terephthalate film was peeled off and developed by spraying at 35° C. for 60 seconds using a mixed solution of 1,1,1-trichloroethane/ethanol (=70/30 weight ratio). The resin composition of the developer accurately reproduced a pattern of lines/intervals with a width of 100 μm. Next, this substrate was dried by heating at 80° C., post-exposure was performed at 10 J/cm ² , and further heated at 150° C. for 60 minutes to fully cure the resin composition. Next, using a dicing saw for semiconductor manufacturing (DAD-2H/6 manufactured by Disco Corporation), the resin layer was completely cut with a diamond blade (thickness: 0.040 mm) at a feed speed of 3 mm/sec to a depth that reached the substrate. The cured film without a pattern was cut in a grid pattern at a pitch of 0.5 mm, and the patterned portion was cut at a pitch of 0.5 mm so as to divide the pattern. When an industrial cellophane tape was used for this substrate and a tape peeling test was conducted on the effect film without a pattern, the result was 100/100, indicating good adhesion. Furthermore, when the cross section of the pattern was observed under a microscope, it was found that the side surface of the pattern was almost perpendicular to the substrate and could be used as a structural material. Next, this substrate was immersed in a NaOH aqueous solution with a pH of 10 and a solution of diethylene glycol/water (=50/50 weight ratio) and subjected to a pressure vacuum test at 121°C and 2 atm for 20 hours. When the board was cleaned and air-dried and a tape peel test was performed, it showed 100/100 adhesion in all test solutions, and no changes in quality such as whitening or blistering of the cured film were observed, indicating that it has excellent chemical and alkali resistance. It turned out to be excellent. Example 2 Living polymer obtained by anionic polymerization method (N-methylol methacrylamide/2-hydroxyethyl methacrylate (=30/70 weight ratio))
and p-vinylbenzyl chloride are reacted,
A macromonomer (p-vinylbenzyl poly-N-methylolmethacrylamide/2-hydroxyethyl methacrylate) having a weight average molecular weight of about 1500 and having a vinyl group at one end of the molecular chain was obtained. 30 parts by weight of this macromonomer and 70 parts by weight of methyl methacrylate were solution-polymerized in methyl cellosolve, resulting in a graft copolymer polymer having a weight average molecular weight of 7.7×10 ⁴ and having thermal crosslinking properties (this is referred to as GP-2).
I got it. The glass transition temperature of the polymethyl methacrylate chain that makes up the main chain of GP-2 is
It is 100℃. Using this GP-2, an active energy ray-curable resin composition having the following composition was prepared. GP-2 100 parts by weight Epicote 828〓3 30〃 Epicote 152〓4 30〃 Neopentyl glycol diacrylate
40 〃 Triphenylsulfonium tetrafluoroborate 10 〃 Benzophenone 10 〃 Michler's ketone 5 〃 Crystal violet 1 〃 Hydroquinone 0.1 〃 Paratoluenesulfonic acid 5 〃 Methyl cellosolve acetate 300 〃 〃 3: Manufactured by Yuka Ciel Epoxy Co., Ltd. screw Phenol A type epoxy resin Epoxy equivalent, 183-193 〓4: Cresol novolac type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd. Epoxy equivalent, 172-179 This composition was applied to a 16 μm polyethylene terephthalate film (Lumirrer T type). ) was coated with a bar coater so that the thickness after drying was 20 μm.
The coating film was protected by pressure laminating a 25 μm polyethylene film thereon. A polyimide film (1 μm thick Fotonis UR-3100, manufactured by Toray Industries, Inc.) formed on a silicon wafer was ultrasonically cleaned in 1,1,1-trichloroethane, dried, and preheated to 80°C. Place the above film on the hot roll laminator (HRL-24,
(manufactured by Dupont) at a roll temperature of 80°C and a roll pressure of 1 kg/cm and a lamination speed of 1 m/mim. Next, a resolution test mask was placed in close contact with the mask, and the illuminance on the irradiated surface was 8 mW/ ^cm2.
Semiconductor exposure light source using UV lamp (PLA-
501 (manufactured by Canon Inc.) for 40 seconds.
After exposure, the polyethylene terephthalate film was peeled off and developed by spraying at 35° C. for 60 seconds using a mixed solution of 1,1,1-trichloroethane/ethanol (=70/30 weight ratio). After development, the resin composition accurately reproduced a pattern of lines/intervals with a width of 100 μm. Next, this substrate was dried by heating at 80°C, post-exposure was performed at 10J/ ^cm2 , and then at 150°C for 60°C.
The resin composition was heated for a minute to fully cure the resin composition. Next is the dicing saw for semiconductor manufacturing (DAD).
The resin layer was completely cut using a diamond blade (thickness: 0.040 mm) at a feeding speed of 3 mm/sec to a depth that reached the substrate. The cured film without a pattern was cut in a grid pattern at a pitch of 0.5 mm, and the patterned portion was cut at a pitch of 0.5 mm so as to divide the pattern. When a tape peeling test was carried out using industrial cellophane tape on this substrate, the result was 100/100 on the patterned area and on the cured film without a pattern, indicating good adhesion. Furthermore, when the cross section of the pattern was observed under a microscope, it was found that the side surface of the pattern was approximately perpendicular to the substrate, and that it could be used as a structural material. Next, this substrate was immersed in a NaOH aqueous solution with a pH of 10 and a solution of diethylene glycol/water (=50/50 weight ratio) and subjected to a pressure vacuum test at 121°C and 2 atm for 20 hours. When the board was cleaned and air-dried and a tape peel test was performed, it showed 100/100 adhesion in all test solutions, and no changes in quality such as whitening or blistering of the cured film were observed, indicating that it has excellent chemical and alkali resistance. It turned out to be excellent. Example 3 A living polymer (3-chloro-2-hydroxypropyl methacrylate/N-vinylpyrrolidone (=90/10 molar ratio)) obtained by an anionic polymerization method is reacted with acrylic acid chloride to form one end of the molecular chain. Weight average molecular weight with vinyl groups in approx.
2500 macromonomers (acrylic acid poly-3-chloro-2-hydroxypropyl methacrylate/
N-vinylpyrrolidone) was obtained. 25 parts by weight of this macromonomer, 65 parts by weight of methyl methacrylate, and 10 parts by weight of dimethylaminoethyl methacrylate were copolymerized in methyl isobutyl ketone (weight average molecular weight: 6.5×10 ⁴ ). Then this copolymer
In a polymer solution in which 100 parts by weight of hexamethylene diisocyanate and 2-hydroxyethyl acrylate are dissolved, NCO group equivalent: OH group equivalent =
11 parts by weight of the partial urethane compound obtained by the reaction at a ratio of 2.0:1.1 was added and reacted, converting 30% of the 3-chloro-2-hydroxypropyl methacrylate component into acrylic urethane, and photopolymerizable branch chains. A graft copolymer polymer having acrylic ester groups (this will be referred to as GP-3) was obtained. The glass transition temperature of the copolymer chain of methyl methacrylate and dimethylaminoethyl methacrylate that constitutes the main chain of GP-3 is 90°C. This GP-
No. 3 was used to prepare an active energy ray-curable resin composition having the following composition. GP-3 100 parts by weight Epiclon 840〓5 20 〃 Epiclon 830〓6 20 〃 Epiclon N-730〓7 20 〃 Acrylic acid ester of triglycidyl ether of trimethylolpropane 40 〃 Diphenyliodonium tetrafluoroborate 10 〃 Irgaquia 651 15 〃 Crystal Violet 1 〃 Hydroquinone 0.2 〃 Methyl cellosolve acetate 300 〃 〓 5: Bisphenol A type epoxy resin manufactured by Dainippon Ink & Chemicals Co., Ltd. Epoxy equivalent weight, 180-190 〓 6: Dainippon Ink & Chemicals Co., Ltd. ) Bisphenol F type epoxy resin epoxy equivalent, 170-190 〓7: Phenol novolak type epoxy resin manufactured by Dainippon Ink & Chemicals Co., Ltd. Epoxy equivalent, 170-190 This composition was added to the cleaning liquid Daiflon ( 10 cm
It was coated onto 10 cm of Virex glass using a bar coater so that the thickness after drying was approximately 50 μm.
A 16 μm thick polyethylene terephthalate film (Lumirror T type) was laminated on the surface of this composition. Next, a mask for resolution testing was placed in close contact with the irradiated surface, and a high-pressure mercury lamp was used so that the illuminance near 254 nm was 34 mW/cm ² on the irradiated surface.
Exposure for seconds. After exposure, the polyethylene terephthalate film was peeled off and development was carried out using 1,1,1-trichloroethane at 35° C. for 60 seconds by spraying. The resolution of the resin composition after development accurately reproduced a pattern of lines/intervals with a width of 150 μm. Next, this substrate was heated and dried at 80℃ for 10 minutes.
Post-exposure of 10 J/cm ² was performed, and the resin composition was further heated at 150° C. for 30 minutes to fully cure the resin composition. When a cross-cut tape peeling test using industrial cellophane tape was conducted on this substrate, it showed 100/100 adhesion, with complete adhesion except for clear scratches on the cross-cuts. In addition, this substrate was placed in a NaOH aqueous solution with a pH of 12 at 80°C.
After being immersed at ℃ for 24 hours, the tape was washed with water, dried, and subjected to a cross-cut tape peel test again, but no deterioration in adhesion such as peeling or lifting was observed. Example 4 Living polymer obtained by anionic polymerization method (butoxymethylacrylamide/2-hydroxyethyl methacrylate (=70/30 weight ratio))
was reacted with acrylic acid chloride to obtain a macromonomer (acrylic acid polybutoxymethylacrylamide/2-hydroxyethyl methacrylate) having a weight average molecular weight of about 3000 and having a vinyl group at one end of the molecular chain. 25 parts by weight of this macromonomer, 70 parts by weight of methyl methacrylate, and 5 parts by weight of acrylonitrile were polymerized in methyl cellosolve, and a graft copolymer polymer having a weight average molecular weight of 6.8×10 ⁴ and having thermal crosslinkability (GP-4 ) was obtained. Furthermore, this
The glass transition temperature of the copolymer chain of polymethyl methacrylate chain and polyacrylonitrile chain that constitutes the main chain of GP-4 is 105°C. Using this GP-4, an active energy ray-curable resin composition having the following composition was prepared. GP-4 100 parts by weight Epicron N-665 8 30 〃 Celloxide 2021 30 〃 Neopentyl glycol diacrylate
40 〃 Diphenyliodonium tetrafluoroborate 10 〃 Benzophenone 10 〃 Michler's ketone 5 〃 Crystal violet 1 〃 Hydroquinone 0.1 〃 Paratoluenesulfonic acid 5 〃 Methyl cellosolve acetate 300 〃 〃 8: Manufactured by Dainippon Ink and Chemicals Co., Ltd. Cresol novolac type epoxy resin Epoxy equivalent: 200-230 This composition was coated on a 16 μm thick polyethylene terephthalate film (Lumirror T type) using a bar coater so that the dry thickness would be 50 μm. A 35 μm thick epoxy copper clad laminate that has been degreased and washed with hydrochloric acid is preheated to 80°C, and the above film is placed in a hot roll laminator (HRL-24,
(manufactured by Dupont) at a roll temperature of 80° C., a roll pressure of 1 Kg/cm ² , and a lamination speed of 1 m/min. This was exposed for 15 seconds using the same exposure machine as in Example 3 using a circuit pattern negative mask. After exposure, using a mixture of 1,1,1-trichloroethane/butyl cellosolve (=70/30),
Development was carried out using a spray method at ℃ for 60 seconds. After development, the resin composition accurately reproduced a pattern of lines/intervals with a width of 100 μm. Next, this substrate was heated and dried at 80℃ for 10 minutes.
A post-exposure of 10 J/cm ² was carried out, and the resin component was further cured by heating at about 150° C. for 60 minutes. Next, using 45° Baume ferric chloride at 30°C, spray pressure 1 kg/
The copper was removed by etching at cm ² for 90 seconds to obtain a copper circuit. The resist could be used as it is as a protective film for circuits. Comparative Example 1 An active energy ray-curable resin composition having the following composition was prepared. Epicote 1001 50 parts by weight Epicote 152 20 〃 Celloxide 2021 30 〃 Diphenyliodonium tetrafluoroborate 10 〃 Crystal Violet 0.3 〃 Toluene 50 〃 Methyl ethyl ketone 100 〃 This composition was coated as a bar on the same wafer used in Example 1. Thickness after coating with coater is approximately 20μm
It was applied so that The film surface was sticky after drying. Next, a 16 .mu.m polyethylene terephthalate film was laminated thereon, a resolution test mask was closely attached, and the same exposure machine as in Example 1 was used to expose the film for 150 seconds. After exposure, peel off the polyethylene terephthalate film 1,1,1-
Development was carried out for 60 seconds in an ultrasonic cleaner using a mixed solution of trichloroethane/ethanol (=70/30 weight ratio). After development, the resin surface remains as an irregular pattern of fine unevenness due to the contact of the mask.
Even 150 μm line/spacing patterns could not be resolved satisfactorily. Comparative example 2 Methyl methacrylate, hydroxyethyl methacrylate and butyl acrylate (=60/30/
10 molar ratio) in methyl isobutyl ketone to obtain a thermoplastic linear polymer (referred to as LP-1) with a weight average molecular weight of 8.8×10 ⁴ . Using LP-1, an epoxy resin shown below and an active energy ray-curable resin composition containing no polymerization initiator for the epoxy resin were obtained. LP-1 100 parts by weight triethylene glycol dimethacrylate
50 〃 Acrylic acid ester of triglycidyl ether of trimethylolpropane 50 〃 Benzophenone 10 〃 Michler's ketone 5 〃 Crystal violet 0.3 〃 Hydroquinone 0.1 〃 Methyl cellosolve 350 〃 Using this composition, 1,1,1-trichlor was used for development. Pattern formation was performed in exactly the same manner as in Example 1 except that ethane was used. The obtained pattern had almost the same resolution as Example 1. However, when the substrate was cut using a dicing saw and subjected to a pressure vacuum test in the same manner as in Example 1, no cured film remained on the substrate at the time the substrate was removed from the test liquid. As is clear from the above Examples and Comparative Examples, the active energy ray-curable resin composition of the present invention is capable of forming a high-resolution pattern, and at the same time has high adhesion to the support. and
It is also found that it has excellent mechanical strength and chemical resistance.

Claims (1)

[Scope of Claims] 1 (i) A backbone chain mainly composed of structural units derived from one or more monomers selected from the group consisting of alkyl methacrylate, acrylonitrile, and styrene, (A) a hydroxyl group-containing acrylic monomer, ( B) an acrylic monomer containing an amino or alkylamino group, (C) an acrylic or vinyl monomer containing a carboxyl group, (D) N-vinylpyrrolidone or its derivative, (E) vinylpyridine or its derivative, and (F) a compound represented by the following general formula. a graft copolymer polymer having a branch chain mainly derived from one or more monomers selected from the group consisting of acrylamide derivatives; (However, R ¹ is hydrogen or has 1 carbon atom
-3 alkyl or hydroxyalkyl group, ^R2 represents hydrogen or an alkyl or acyl group optionally having a hydroxyl group having 1 to 4 carbon atoms). (ii) a monomer having an ethylenically unsaturated bond; (iii) an epoxy resin comprising at least one compound having one or more epoxy groups in the molecule; An active energy ray-curable resin composition comprising: a polymerization initiator that generates a Lewis acid. 2 The content of the graft copolymer polymer in (i) above is G
G/
(G+M+E) ranges from 0.2 to 0.8 and E/(E
+M) is in the range of 0.3 to 0.7, and the polymerization initiator (iv) is in the range of 100 parts by weight of (G+M+E).
The active energy ray-curable resin composition according to claim 1, wherein the active energy ray-curable resin composition is contained in a range of 0.2 to 15 parts by weight. 3. A patent claim characterized in that the polymerization initiator (iv) consists of an aromatic halonium salt compound, or a photosensitive aromatic onium salt compound containing an element belonging to group a or group a of the periodic table. The active energy ray-curable resin composition according to any one of items 1 to 2. 4 Based on 100 parts by weight of the total amount of the graft copolymer polymer of (i), the monomer of (ii), and the resin of (iii),
The active energy ray-curable resin according to any one of claims 1 to 3, which contains 0.1 to 20 parts by weight of a radical polymerization initiator that can be activated by the action of active energy rays. Composition.