JP7628435B2 - Photosensitive resin composition - Google Patents

Description

The present invention relates to a photosensitive resin composition that has a low dielectric constant and dielectric loss and can be patterned by photolithography.

Photosensitive resins, which can be easily patterned by photolithography, are materials that are widely used in the electronics field, such as semiconductors and displays. As described in Patent Documents 1 and 2, various photosensitive resin compositions have been proposed as interlayer insulating films for electronic devices. Due to the dramatic improvement of communication technology in recent years, electronic devices are required to process large volumes of information and signals at high speed. On the other hand, there are cases where miniaturization, weight reduction, and improved productivity are required, and good patterning properties are also required.

JP 2004-117709 A Patent No. 3873261 Japanese Patent Application Publication No. 11-84659

In recent years, dielectric delay and transmission loss caused by insulating films between wiring have become an issue, and it has been discovered that in order to improve the performance of electronic devices, photosensitive resins used as interlayer insulating films between metal wiring need materials with even lower dielectric constants and dielectric loss.
An object of the present invention is to provide a photosensitive resin composition which has a low dielectric constant and dielectric loss and which can be well patterned by photolithography.

As a result of repeated investigations to solve the above problems, it was found that a photosensitive resin composition having (A) a saturated hydrocarbon polymer structure having a molecular weight of 1,000 to 100,000, (B) at least one organic structure having a molecular weight of 500 or less and selected from the group consisting of a trisubstituted isocyanurate structure, a trisubstituted triazine structure, a condensed ring structure having 7 to 16 carbon atoms, an alicyclic hydrocarbon structure having 6 to 12 carbon atoms, and a linear or branched alkyl ether structure having 6 to 24 carbon atoms, (C) at least one photocationically polymerizable functional group selected from the group consisting of an alicyclic epoxy group, a glycidyl group, and an oxetanyl group, and (D) a siloxane bond, in which (A) is bonded to at least two Si atoms and (B) is bonded to at least one Si atom, can be well patterned by photolithography and has excellent electrical properties such as a low dielectric constant and low dielectric loss. The present invention comprises the following.

[1]. A photosensitive resin composition comprising (A) a saturated hydrocarbon polymer structure having a molecular weight of 1,000 to 100,000; (B) at least one organic structure having a molecular weight of 500 or less and selected from the group consisting of a trisubstituted isocyanurate structure, a trisubstituted triazine structure, a condensed ring structure having 7 to 16 carbon atoms, an alicyclic hydrocarbon structure having 6 to 12 carbon atoms, and a linear or branched alkyl ether structure having 6 to 24 carbon atoms; (C) at least one photocationically polymerizable functional group selected from the group consisting of an alicyclic epoxy group, a glycidyl group, and an oxetanyl group; and (D) a siloxane bond, in which (A) is bonded to at least two Si atoms and (B) is bonded to at least one Si atom.

[2]. The photosensitive resin composition according to [1], in which (A) is 15 to 85% by weight relative to 100% by weight of the compound.

[3]. The photosensitive resin composition according to [1] or [2], wherein (A) is at least one selected from the group consisting of isobutylene polymers, hydrogenated isoprene polymers, and hydrogenated butadiene polymers.

[4]. Furthermore, the following formulas (X1) and (X2)

The photosensitive resin composition according to any one of [1] to [3], which contains a structure (E) which is at least one acidic group selected from the group consisting of structures represented by the following formulas, a phenolic hydroxyl group, and a carboxyl group.

[5]. The (D) is represented by the following general formula (I):

(wherein R ¹ and R ² may be the same or different and represent an organic group having 1 to 10 carbon atoms, n represents a number from 1 to 10, and m represents a number from 0 to 10).
The photosensitive resin composition according to any one of [1] to [4], wherein the cyclic polyorganosiloxane bond is represented by the following formula:

[6]. The photosensitive resin composition according to any one of [1] to [5], further comprising a cationic polymerization initiator.

[7]. A compound (δ) having a siloxane bond and at least two hydrosilyl groups;
The method includes a step (I) of hydrosilylating a compound (β) having a molecular weight of 500 or less and having at least one alkenyl group and at least one organic structure selected from the group consisting of a tri-substituted isocyanurate structure, a tri-substituted triazine structure, a fused ring structure having 7 to 16 carbon atoms, an alicyclic hydrocarbon structure having 6 to 12 carbon atoms, and a linear or branched alkyl ether structure having 6 to 24 carbon atoms;
The reaction product obtained in step (I),
The method includes a step (II) of hydrosilylating a compound (γ) having at least one photocationically polymerizable functional group selected from the group consisting of an alicyclic epoxy group, a glycidyl group, and an oxetanyl group, and at least one alkenyl group,
The method for producing a photosensitive resin composition includes a step (III) of hydrosilylating the reaction product obtained in the step (II) and a saturated hydrocarbon polymer (α) having at least two alkenyl groups and a molecular weight of 1,000 to 100,000.

[8]. The method for producing a photosensitive resin composition according to [7], wherein (α) includes at least one selected from the group consisting of isobutylene polymers, hydrogenated isoprene polymers, and hydrogenated butadiene polymers.

[9] In the step (I),
At least one alkenyl group and a group represented by the following formula (X1) or (X2):

The method for producing a photosensitive resin composition according to [7] or [8], further comprising a compound (ε) having at least one acidic group selected from the group consisting of each structure represented by the formula:

[10]. The method for producing a photosensitive resin composition according to [9], wherein (ε) includes at least one selected from the group consisting of diallyl isocyanuric acid, monoallyl isocyanuric acid, diallyl bisphenol A, diallyl bisphenol S, vinylphenol, allylphenol, butenoic acid, pentenoic acid, hexenoic acid, heptenoic acid, and undecylenic acid.

[11]. The (β) is vinyl norbornene, triallyl isocyanurate, triallyl cyanurate, diallyl monomethyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl monobenzyl isocyanurate, 1,3-bis(allyloxy)adamantane, 1,3-bis(vinyloxy)adamantane, 1,4-cyclohexane dimethanol divinyl ether, dicyclopentadiene, vinylcyclohexene, diallyl ether, 1,2,4-trivinylcyclohexane, trimethylolpropane triallyl ether, 1,3,5-tris(allyloxy)adamantane The method for producing a photosensitive resin composition according to any one of [7] to [10], which contains at least one member selected from the group consisting of: pentane, 1,3,5-tris(vinyloxy)adamantane, pentaerythritol tetraallyl ether, 2,5-diallylphenol allyl ether, vinyl adamantane, monoallyl dimethyl isocyanurate, monoallyl diglycidyl isocyanurate, monoallyl dibenzyl isocyanurate, monoallyl dipropyl isocyanurate, camphene, β-pinene, and 2,2-bis(4-hydroxycyclohexyl)propane diallyl ether.

[12]. The method for producing a photosensitive resin composition according to any one of [7] to [11], wherein (γ) includes at least one selected from the group consisting of vinylcyclohexene oxide, allyl glycidyl ether, diallyl monoglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, and allyl oxetanyl ether.

The present invention provides a photosensitive resin composition that has a low dielectric constant and dielectric loss and allows for good patterning by photolithography.

(Photosensitive Resin Composition)
The photosensitive resin composition includes (A) a saturated hydrocarbon polymer structure having a molecular weight of 1,000 to 100,000; (B) at least one organic structure having a molecular weight of 500 or less and selected from the group consisting of a 3-substituted isocyanurate structure, a 3-substituted triazine structure, a condensed ring structure having 7 to 16 carbon atoms, an alicyclic hydrocarbon structure having 6 to 12 carbon atoms, and a linear or branched alkyl ether structure having 6 to 24 carbon atoms; (C) at least one photocationically polymerizable functional group selected from the group consisting of an alicyclic epoxy group, a glycidyl group, and an oxetanyl group; and (D) a compound having a siloxane bond, in which (A) is bonded to at least two Si atoms and (B) is bonded to at least one Si atom.

The method for producing the compounds having the essential structures (A) to (D) of the present invention is not particularly limited, but the method using the hydrosilylation reaction is preferred because it is the simplest and can be obtained in the highest yield.

((A) Structure: Saturated hydrocarbon polymer structure having a molecular weight of 1,000 to 100,000)
The monomer used to obtain the saturated hydrocarbon polymer with respect to the above structure (A) is not particularly limited, but can be obtained by a method of polymerizing an olefin compound having 2 to 6 carbon atoms such as ethylene, propylene, 1-butene, isobutylene, etc. as the main monomer, a method of homopolymerizing a diene compound such as butadiene, isoprene, etc., a method of copolymerizing the above olefin compound with a diene compound, and then hydrogenating the copolymer, etc. From the viewpoints of ease of introducing a functional group to the terminal, ease of molecular weight control, and ability to increase the number of terminal functional groups, an isobutylene polymer, a hydrogenated isoprene polymer, or a hydrogenated butadiene polymer is preferred.

The isobutylene polymer may be formed of all isobutylene units, or may contain monomer units copolymerizable with isobutylene in an amount of preferably 50% by weight or less, more preferably 30% by weight or less, and particularly preferably 10% by weight or less in the isobutylene polymer. Specific examples of copolymer components include 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, 4-methyl-1-pentene, hexene, vinylcyclohexane, β-pinene, camphene, etc.

As in the case of the isobutylene polymer, the hydrogenated butadiene polymer and other saturated hydrocarbon polymers may contain other monomer units in addition to the main monomer unit. Furthermore, the saturated hydrocarbon polymer used as the (A) structure of the present invention may contain a small amount, preferably 10% or less, of monomer units that leave double bonds after polymerization, such as polyene compounds such as butadiene, isoprene, 1,13-tetradecadiene, 1,9-decadiene, and 1,5-hexadiene, as long as the object of the present invention is achieved.

The saturated hydrocarbon polymer constituting the (A) structure, preferably an isobutylene polymer, a hydrogenated isoprene polymer, or a hydrogenated butadiene polymer, preferably has a number average molecular weight of 1,000 to 100,000, and more preferably has a liquid or fluidity of about 2,000 to 50,000 from the standpoint of ease of handling, etc.

In addition, the ratio of the (A) structure in the compound having the essential structures (A) to (D) in the present invention is preferably 15 to 85% by weight, more preferably 20 to 80% by weight, and particularly preferably 30 to 70% by weight, relative to 100% by weight of the compound. If the ratio of the (A) structure is too low, the performance of low dielectric constant and low dielectric loss will not be achieved, while if the ratio is too high, patterning by photolithography will become impossible, and it is not preferable from the viewpoint of the occurrence of tack on the surface of the coating film or cured product obtained by curing the resin composition and the decrease in resin strength.

The (A) structure is also bonded to at least two Si atoms. The cured product obtained by having such a structure exhibits excellent electrical properties, particularly low dielectric loss. There are no particular limitations on the method for introducing the (A) structure bonded to at least two Si atoms, but from the viewpoint of easy and convenient introduction of the structure, a method using a hydrosilylation reaction is preferred. In this case, it is preferable to use a saturated hydrocarbon-based polymer (component (α) described later) having a molecular weight of 1,000 to 100,000 and at least two alkenyl groups in the molecule that can react with a compound having a SiH group.

(Component (α): A saturated hydrocarbon polymer having at least two alkenyl groups and a molecular weight of 1,000 to 100,000)
Among the (α) components, from the viewpoint of being less likely to gel and easier to control the reaction, a polymer having two alkenyl groups at both ends of the polymer is more preferred when a reaction product is obtained by a hydrosilylation reaction. As the (α) component, various methods for introducing an alkenyl group into a saturated hydrocarbon polymer have been proposed, and these methods can be roughly divided into a method for introducing an alkenyl group after polymerization and a method for introducing an alkenyl group during polymerization. As a method for introducing an alkenyl group after polymerization, for example, a saturated hydrocarbon polymer having a terminal alkenyl group is produced by converting a hydroxyl group at the end, main chain, or side chain into an -ONa group or -OK group, and then reacting with an organic halogen compound represented by the general formula (II).

[In the formula, Y is a halogen atom such as a chlorine atom or an iodine atom, and R ³ is a divalent organic group represented by -R ⁴ -, -R ⁴ -OC(=O)-, or -R ⁴ -C(=O)- (R ⁴ is a divalent hydrocarbon group having 1 to 20 carbon atoms, and preferred examples include an alkylene group, a cycloalkylene group, an arylene group, and an aralkylene group).]

The method of converting the terminal hydroxyl group of the terminal hydroxy saturated hydrocarbon polymer into an oxymetal group includes a method of reacting with an alkali metal such as Na or K; a metal hydride such as NaH; a metal alkoxide such as _NaOCH3 ; or a caustic alkali such as caustic soda or caustic potassium. In the above-mentioned method, a terminal alkenyl-containing saturated hydrocarbon polymer having almost the same molecular weight as the terminal hydroxy saturated hydrocarbon polymer used as the starting material is obtained, but if a polymer with a higher molecular weight is desired, the molecular weight can be increased by reacting the polymer with a polyvalent organic halogen compound containing two or more halogen atoms in one molecule, such as methylene chloride, bis(chloromethyl)benzene, bis(chloromethyl)ether, etc., before reacting with the organic halogen compound of general formula (II), and then reacting the polymer with the organic halogen compound of general formula (II), a saturated hydrocarbon polymer with a higher molecular weight and an alkenyl group at the end can be obtained.

Specific examples of the organic halogen compound represented by the general formula (II) include, but are not limited to, allyl chloride, allyl bromide, vinyl(chloromethyl)benzene, allyl(chloromethyl)benzene, allyl(bromomethyl)benzene, allyl(chloromethyl)ether, allyl(chloromethoxy)benzene, 1-hexenyl(chloromethoxy)benzene, and allyloxy(chloromethyl)benzene. Of these, allyl chloride is preferred because it is inexpensive and reacts easily.

There are no particular limitations on the method for introducing alkenyl groups into saturated hydrocarbon polymers having covalently bonded Cl groups, but examples include a method of carrying out a Friedel-Crafts reaction between various alkenyl phenyl ethers and Cl groups, a method of carrying out a substitution reaction between allyltrimethylsilane or the like and Cl groups in the presence of a Lewis acid, and a method of introducing hydroxyl groups by the Friedel-Crafts reaction between various phenols and Cl groups, and then further using the above-mentioned method for introducing alkenyl groups in combination.

Methods for introducing alkenyl groups during polymerization include, for example, a method for producing an isobutylene-based polymer having an allyl end by adding allyltrimethylsilane to a polymerization system in cationic polymerization of a cationic polymerizable monomer containing isobutylene using a compound having a halogen atom, the carbon atom to which the halogen atom is bonded being bonded to an aromatic ring carbon and/or a compound having a halogen atom, the carbon atom to which the halogen atom is bonded being a tertiary carbon atom, as an initiator and chain transfer agent, and a Lewis acid as a catalyst; and a method for producing a saturated hydrocarbon-based polymer having an alkenyl group at the main chain or side chain end by adding a non-conjugated diene such as 1,9-decadiene or an alkenyloxystyrene such as p-hexenyloxystyrene to a polymerization system.

The Lewis acid, which is a component used as a cationic polymerization catalyst, is represented by MX'n (M is a metal atom, X' is a halogen atom), for example, BCl ₃ , Et ₂ AlCl, EtAlCl ₂ , AlCl ₃ , SnCl ₄ , TiCl ₄ , VCl ₅ , FeCl ₃ , BF _{3 ,} etc., but is not limited thereto. Among these Lewis acids, BCl ₃ , SnCl ₄ , BF ₃ , TiCl _{4 ,} etc. are preferred, and TiCl ₄ is particularly preferred. The amount of the Lewis acid used is preferably 0.1 to 10 times, more preferably 2 to 5 times, the number of moles of the initiator/chain transfer agent.

Furthermore, unlike the technology of the present invention, a method for introducing the (A) structure after curing can be considered in which the (α) component is added to the photosensitive resin composition as a curing agent rather than being subjected to a hydrosilylation reaction between the (α) component and a compound having a SiH group in advance. However, this is not preferred because it causes problems such as the saturated hydrocarbon polymer and the normal photosensitive resin component easily separating, making it difficult to obtain a uniform film or cured product.

((B) Structure: Molecular weight of 500 or less, and at least one organic structure selected from the group consisting of a 3-substituted isocyanurate structure, a 3-substituted triazine structure, a condensed ring structure having 7 to 16 carbon atoms, an alicyclic hydrocarbon structure having 6 to 12 carbon atoms, and a linear or branched alkyl ether structure having 6 to 24 carbon atoms)
In the present invention, the (B) structure is an essential structure, and by introducing the (B) structure, the adhesion and strength of the coating film obtained from the final photosensitive resin composition can be improved. If the molecular weight of the compound used exceeds 500, problems such as low strength and adhesion of the final cured product will occur, which is not preferable.

The molecular weight of the (B) structure of the present invention is 500 or less, and preferably 350 or less. The lower limit of the molecular weight is preferably 100 or more, and more preferably 150 or more.

The above-mentioned tri-substituted isocyanurate structure represents a structure having substituents other than hydrogen atoms on the three nitrogen atoms of isocyanuric acid, and the above-mentioned tri-substituted triazine structure represents a structure having substituents other than hydrogen atoms on the three nitrogen atoms of a triazine ring. Examples of the substituent include an alkyl group having 1 to 12 carbon atoms, an alkyl ether group having 1 to 12 carbon atoms, and an aryl group having 6 to 18 carbon atoms, and some or all of the hydrogen atoms of these groups may be replaced with halogen atoms. An alkyl group having 1 to 12 carbon atoms or an alkyl ether group having 1 to 12 carbon atoms is preferable.

Examples of the fused ring structure having 7 to 16 carbon atoms include a norbornane structure, an adamantane structure, and a tricyclo[5.2.1.0 ^2,6 ]decane structure, and the hydrogen atoms on these structures may be substituted with an alkyl group having 1 to 12 carbon atoms, an alkyl ether group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. From the viewpoint of availability, compounds having a norbornane structure are preferred.

Examples of the alicyclic hydrocarbon structure having 6 to 12 carbon atoms include a cyclohexane structure, a cyclooctane structure, and a cyclododecane structure, and compounds having a cyclohexane structure, which are particularly readily available, are preferred.

Examples of the linear or branched alkyl ether structure having 6 to 24 carbon atoms include a pentaerythritol structure and a trimethylolpropane structure.

Of these structures, tri-substituted isocyanurate structures, condensed ring structures having 7 to 16 carbon atoms, and alicyclic hydrocarbon structures having 6 to 12 carbon atoms are preferred from the viewpoint of excellent compatibility with the saturated hydrocarbon polymer structure of the (α) structure, and tri-substituted isocyanurate structures are particularly preferred from the viewpoint of the tendency of the cured product to have high adhesion.

In addition, the ratio of the (B) structure in the compound having the essential structures (A) to (D) in the present invention is preferably 10 to 45% by weight, more preferably 10 to 40% by weight, and particularly preferably 15 to 35% by weight, relative to 100% by weight of the compound. If the ratio of the (B) structure is too low, it is not preferable because the cured product becomes too flexible and tackiness is easily generated on the surface.

The above (B) structure is also bonded to at least one Si atom. Having such a structure is essential from the viewpoint of improving adhesion to the substrate and improving the strength of the resulting cured product. There is no particular limitation on the method of introducing the (B) structure bonded to at least one Si atom, but similar to the above (A) structure, a method of obtaining the structure by hydrosilylation reaction of a SiH group-containing compound with a compound ((β) component described later) having a molecular weight of 500 or less and having at least one alkenyl group and at least one organic structure selected from the group consisting of a trisubstituted isocyanurate structure, a trisubstituted triazine structure, a condensed ring structure having 7 to 16 carbon atoms, an alicyclic hydrocarbon structure having 6 to 12 carbon atoms, and a linear or branched alkyl ether structure having 6 to 24 carbon atoms is preferred from the viewpoint of easily obtaining a uniform composition.

(Component (β): a compound having a molecular weight of 500 or less and having at least one alkenyl group and at least one organic structure selected from the group consisting of a tri-substituted isocyanurate structure, a tri-substituted triazine structure, a fused ring structure having 7 to 16 carbon atoms, an alicyclic hydrocarbon structure having 6 to 12 carbon atoms, and a linear or branched alkyl ether structure having 6 to 24 carbon atoms)
Specific examples of the (β) component include diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, diarylidene pentaerythritol, diallyl monomethyl isocyanurate, diallyl monopropyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl monobenzyl isocyanurate, 1,4-butanediol divinyl ether, nonanediol divinyl ether, 1,4-cyclohexane dimethanol divinyl ether, triethylene glycol divinyl ether, bisphenol S diallyl ether, 1, Examples of such an alkyl ether include 3-bis(allyloxy)adamantane, 1,3-bis(vinyloxy)adamantane, dicyclopentadiene, vinylcyclohexene, diallyl ether, bisphenol A diallyl ether, 2,5-diallylphenol allyl ether, vinyl adamantane, monoallyl dimethyl isocyanurate, monoallyl diglycidyl isocyanurate, monoallyl dibenzyl isocyanurate, monoallyl dipropyl isocyanurate, camphene, β-pinene, and 2,2-bis(4-hydroxycyclohexyl)propane diallyl ether.

From the viewpoint of low coloration of the resulting coating film and cured product and high heat resistance, diallyl monomethyl isocyanurate, diallyl monopropyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl monobenzyl isocyanurate, vinylcyclohexene, dicyclopentadiene, vinyladamantane, monoallyl dimethyl isocyanurate, monoallyl diglycidyl isocyanurate, monoallyl dibenzyl isocyanurate, monoallyl dipropyl isocyanurate, or 2,2-bis(4-hydroxycyclohexyl)propane diallyl ether are preferred.

In particular, from the viewpoint of high heat resistance and light resistance, diallyl monomethyl isocyanurate, diallyl monopropyl isocyanurate, monoallyl dimethyl isocyanurate, monoallyl diglycidyl isocyanurate, monoallyl dibenzyl isocyanurate, or monoallyl dipropyl isocyanurate are more preferred. These compounds for introducing the (B) structure may be used in combination of two or more types according to the characteristics required for the application.

(Structure (C): at least one photocationically polymerizable functional group selected from the group consisting of an alicyclic epoxy group, a glycidyl group, and an oxetanyl group)
The (C) structure is necessary for exhibiting photosensitivity, and indicates a functional group that undergoes polymerization and crosslinking due to a cationic species generated from a photopolymerization initiator when light energy is applied from the outside, and there are no particular limitations on the reaction and crosslinking form.

Many functional groups that polymerize with cationic species are known, and among them, epoxy groups, vinyloxy groups, oxetanyl groups, etc. are preferred from the viewpoint of high reactivity and excellent stability. Furthermore, epoxy groups and oxetanyl groups are preferred from the viewpoint of excellent electrical properties of coating films and cured products. Furthermore, alicyclic epoxy groups are preferred from the viewpoint of low hygroscopicity and easy production of coating films and cured products with excellent electrical properties. Each functional group may have two or more different functional groups.

On the other hand, crosslinkable silyl groups such as alkoxysilyl groups are also known as functional groups that crosslink with cationic species generated by photopolymerization initiators, but since silanol groups remain in the coating film and cured product after photocrosslinking, they are not preferred from the viewpoint of deteriorating electrical properties such as dielectric constant and dielectric loss tangent.

In addition, the ratio of the (C) structure in the compound having the essential structures (A) to (D) in the present invention is preferably 1 to 25% by weight, more preferably 2 to 20% by weight, and particularly preferably 3 to 15% by weight, relative to 100% by weight of the compound. If the ratio of the (C) structure is too low, crosslinking by the photopolymerization reaction is insufficient, and the pattern shape after exposure collapses, which is not preferable.

The method for introducing the (C) structure is not particularly limited, but similar to the (A) structure, a method of subjecting a SiH group-containing compound to a hydrosilylation reaction with a compound having at least one photocationically polymerizable functional group selected from the group consisting of an alicyclic epoxy group, a glycidyl group, and an oxetanyl group, and at least one alkenyl group (the (γ) component described below) is preferred from the viewpoint of easily obtaining a uniform composition.

(Component (γ): a compound having at least one photocationically polymerizable functional group selected from the group consisting of an alicyclic epoxy group, a glycidyl group, and an oxetanyl group, and having at least one alkenyl group)
Specific examples of the (γ) component include vinylcyclohexene oxide, allyl glycidyl ether, diallyl monoglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, allyl oxetanyl ether, and the like. From the viewpoint of excellent reactivity, vinylcyclohexene oxide, which is a compound having an alicyclic epoxy group, is preferred.

((D) Structure: Siloxane bond)
The method of introducing (D) structure is not particularly limited, but it can be introduced simply by hydrosilylation of the siloxane compound having SiH group.In addition, the sol-gel reaction of alkoxysilyl group is also a simple method of introducing siloxane structure, and is commonly used, but when obtaining a resin composition with low dielectric constant and low dielectric loss as in this case, after reaction, silanol group remains in the composition molecule, and silanol group significantly increases dielectric constant and dielectric loss, so it is not preferable for the method of the present invention.

In addition, the proportion of the (D) structure in the compound having the essential structures (A) to (D) in the present invention is preferably 4 to 30% by weight, more preferably 7 to 25% by weight, and particularly preferably 10 to 25% by weight, relative to 100% by weight of the compound. If the proportion of the (D) structure is too low, the crosslink density will be too low, and it is not preferable from the viewpoint of the occurrence of tack on the surface of the coating film or cured product obtained by curing the resin composition and the decrease in resin strength.

When using a hydrosilylation reaction as described above, the method of introducing a compound having a siloxane bond and at least two hydrosilyl groups in one molecule (component (δ) described below) by hydrosilylation reaction is simple and preferable.

(Component (δ): a compound having a siloxane bond and at least two hydrosilyl groups)
Examples of the compound of the component (δ) include the compounds described in International Publication WO96/15194.

Among these, from the viewpoint of imparting flexibility to the cured product,

(In the formula, R ⁶ and R ⁷ may be the same or different and represent an organic group having 1 to 6 carbon atoms, n represents a number from 1 to 50, and m represents a number from 0 to 10.)
In terms of availability and heat resistance, R ⁶ and R ⁷ are preferably methyl groups, and in terms of increasing the strength of the cured product, R 6 and R 7 are preferably phenyl groups.

Of these, from the viewpoint of high heat resistance of the cured product,

(In the formula, R ⁸ represents an organic group having 1 to 6 carbon atoms, and n represents a number from 0 to 50.)
In view of availability and heat resistance, it is particularly preferred that R ⁸ is a methyl group.

In addition, from the viewpoint of availability and good hydrosilylation reactivity, the following general formula (I):

(wherein R ¹ and R ² are the same or different and represent an organic group having 1 to 10 carbon atoms, n is a number from 1 to 10, and m is a number from 0 to 10) and has at least three SiH groups in one molecule.

The substituents R ¹ and R ² in the compound represented by general formula (I) are preferably selected from the group consisting of C, H, and O, more preferably a hydrocarbon group, and even more preferably a methyl group. From the viewpoints of availability and reactivity, the compound represented by general formula (I) is preferably 1,3,5,7-tetramethylcyclotetrasiloxane. The above-mentioned various compounds can be used alone or in combination of two or more kinds.

(Structure (E): Structure having at least one acidic group)
Furthermore, the above structure (E) has an acidic group in its molecule, which makes it possible to impart alkaline developability to the photosensitive resin composition, and is therefore preferable from the viewpoint of broadening the range of application uses.

The following formulas (X1) and (X2)

Any structure having at least one acidic group selected from the group consisting of the structures represented by the formula (I), a phenolic hydroxyl group, and a carboxyl group can be used without limitation. By having an acidic group, the photosensitive resin composition becomes soluble in an alkaline aqueous solution, and can function as a photosensitive resin composition that can be patterned using an alkaline developer.

In the compounds having the essential structures (A) to (D) of the present invention, the (E) structure is not essential, but since it broadens the range of applications as described above, it is preferable to have the (E) structure, and the proportion of the (E) structure is preferably 3 to 35% by weight, more preferably 4 to 30% by weight, and particularly preferably 5 to 20% by weight, relative to 100% by weight of the compound. If the proportion of the (D) structure is too low, it is not preferable because it will result in poor patterning due to insufficient solubility in an alkaline developer.

As with the above structure, this (E) structure is preferably prepared by subjecting a compound having at least one alkenyl group and at least one acidic group selected from the group consisting of the structures represented by the above formulas (X1) and (X2), a phenolic hydroxyl group, and a carboxyl group (the (ε) component described below) to a hydrosilylation reaction.

(Component (ε): a compound having at least one alkenyl group and at least one acidic group)
Specific examples of the (ε) component include diallyl isocyanuric acid, monoallyl isocyanuric acid, diallyl bisphenol A, diallyl bisphenol S, vinylphenol, allylphenol, butenoic acid, pentenoic acid, hexenoic acid, heptenoic acid, and undecylenic acid. Among these, diallyl isocyanuric acid, monoallyl isocyanuric acid, diallyl bisphenol A, diallyl bisphenol S, vinylphenol, and allylphenol are preferred from the viewpoint of particularly high heat resistance, and diallyl isocyanuric acid and monoallyl isocyanuric acid are particularly preferred from the viewpoint of excellent electrical properties of the coating film and cured product. Two or more of the above-listed compounds, including the organic compounds not having an acidic group described above, may be reacted simultaneously to express the properties required for the application.

(Hydrosilylation reaction)
A catalyst may be used in the hydrosilylation reaction of components (α) to (ε) in order to facilitate the reaction.

As the catalyst for the hydrosilylation reaction, for example, the following can be used: Platinum alone, solid platinum supported on alumina, silica, carbon black or other carriers, chloroplatinic acid, complexes of chloroplatinic acid with alcohols, aldehydes, ketones or the like, platinum-olefin complexes (e.g., Pt(CH ₂ ═CH ₂ ) ₂ (PPh ₃ ) ₂ , Pt(CH ₂ ═CH ₂ ) ₂ Cl ₂ ), platinum-vinylsiloxane complexes (e.g., Pt(ViMe ₂ SiOSiMe ₂ Vi) _n , Pt[(MeViSiO) ₄ ] _m ), platinum-phosphine complexes (e.g., Pt(PPh ₃ ) ₄ , Pt(PBu ₃ ) ₄ ), platinum-phosphite complexes (e.g., Pt[P(OPh) ₃ ] ₄ , Pt[P(OBu) ₃ ] ₄ ) (wherein Me represents a methyl group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, and n and m represent integers), dicarbonyldichloroplatinum, Karstedt's catalyst, and also the platinum-hydrocarbon complexes described in U.S. Pat. Nos. 3,159,601 and 3,159,662 to Ashby, and the platinum alcoholate catalysts described in U.S. Pat. No. 3,220,972 to Lamoreaux. Additionally, platinum chloride-olefin complexes described in U.S. Pat. No. 3,516,946 to Modic are also useful in the present invention.

Examples of catalysts other than platinum compounds include RhCl(PPh) ₃ , _RhCl3 , _RhAl2O3 , _RuCl3 , _IrCl3 , _FeCl3 , _AlCl3 , _PdCl2.2H2O , _NiCl2 , _TiCl4 , etc. Among these, chloroplatinic acid, platinum- _olefin complex, platinum-vinylsiloxane complex, etc. are preferred from the viewpoint of catalytic activity. These catalysts may be used _alone or in combination of two or more kinds.

When (α) to (ε) are subjected to a hydrosilylation reaction, the order of reaction is as follows: first, the (β), (γ), (ε) and (δ) components, which are susceptible to steric hindrance, are reacted under conditions in which a large amount of SiH groups remain in the reaction product; and after all the alkenyl groups have disappeared, the (α) component, which is relatively less susceptible to steric hindrance, is reacted successively, thereby efficiently introducing the desired structure.

(Photopolymerization initiator)
The photosensitive resin composition of the present invention functions as a photosensitive resin composition by incorporating a photocationic polymerization initiator.

The photocationic polymerization initiator that can be used is not particularly limited, and examples thereof include metal fluoroboron complex salts and boron trifluoride complex compounds as described in U.S. Pat. No. 3,379,653, bis(perfluoroalkylsulfonyl)methane metal salts as described in U.S. Pat. No. 3,586,616, aryldiazonium compounds as described in U.S. Pat. No. 3,708,296, aromatic onium salts of Group VIa elements as described in U.S. Pat. No. 4,058,400, aromatic onium salts of Group Va elements as described in U.S. Pat. No. 4,069,055, dicarbonyl chelates of Group IIIa to Va elements as described in U.S. Pat. No. 4,068,091, thiopyrylium salts as described in U.S. Pat. No. 4,139,655, and MF ₆ as described in U.S. Pat. No. 4,161,478. ^- anion (wherein M is selected from phosphorus, antimony and arsenic), arylsulfonium complex salts as described in U.S. Pat. No. 4,231,951, aromatic iodonium complex salts and aromatic sulfonium complex salts as described in U.S. Pat. No. 4,256,828, bis[4-(diphenylsulfonio)phenyl]sulfide-bishexafluorometal salts (e.g., phosphates, arsenates, antimonates, etc.) as described by W. R. Watt et al. in Journal of Polymer Science, Polymer Chemistry Edition, Vol. 22, p. 1789 (1984), aromatic iodonium complex salts and aromatic sulfonium complex salts in which the anion is B(C ₆ F ₅ ) ₄ ^- , and the like.

Preferred photocationic polymerization initiators include arylsulfonium complex salts, aromatic sulfonium salts and iodonium salts of halogen-containing complex ions, and aromatic onium salts of Group II, V and VI elements, sulfonate esters, and carboxylate esters. Some of these salts are commercially available as FX-512 (3M), UVR-6990 and UVR-6974 (Union Carbide), UVE-1014 and UVE-1016 (General Electric), KI-85 (Degussa), and SP-152 and SP-172 (Asahi Denka).

An example of a sulfonium salt is CPI-210S (manufactured by San-Apro Co., Ltd.). It can be used alone or in combination of two or more types.

The content of the photocationic polymerization initiator in the photosensitive resin composition is not particularly limited, but from the viewpoint of curability, it is preferably 0.01 to 10 parts by weight per 100 parts by weight of the photosensitive resin composition. If the amount of photoacid generator is small, it may take a long time to cure or a sufficiently cured product may not be obtained. Furthermore, if the amount of photoacid generator is large, it may be undesirable because color may remain in the cured product, coloring may occur due to rapid curing, or heat resistance or light resistance may be impaired.

(Basic Compound)
The photosensitive resin composition may contain a basic compound to improve the film remaining rate and resolution. The basic compound acts as a quencher. That is, by blending an appropriate amount of the basic compound in the photosensitive resin composition, it is possible to prevent crosslinking by the photoacid generator from reaching the unexposed portion. This improves the film remaining rate, and the contrast between the exposed and unexposed portions becomes clear, improving the resolution.

The amount of the basic compound is preferably 0.001 to 0.2 parts by weight, and more preferably 0.01 to 0.15 parts by weight, per 1 part by weight of the photoacid generator. If the weight ratio is 0.001 or more, the basic compound can fully exert its effect as a quencher. If the weight ratio is 0.2 or less, crosslinking can be performed sufficiently.

The basic compound is not particularly limited, but examples include primary, secondary and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, amide derivatives and imide derivatives. Among these, aromatic amines and heterocyclic amines are preferably used as the basic compound.

Examples of the aromatic amines and heterocyclic amines include aniline, pyrrole, oxazole, thiazole, imidazole, pyrazole, furazan, pyrroline, pyrrolidine, imidazoline, imidazolidine, pyridine, pyridazine, pyrimidine, pyrazine, pyrazoline, pyrazolidine, piperidine, piperazine, morpholine, indole, isoindole, 1H-indazole, indoline, quinoline, cinnoline, quinazoline, quinoxaline, phthalazine, purine, pteridine, carbazole, phenanthridine, acridine, phenazine, 1,10-phenanthroline, adenine, adenosine, guanine, guanosine, uracil, and uridine, as well as derivatives thereof. Examples of the heterocyclic amines include 2,6-lutidine.

Among these, morpholine derivatives are preferably used as the basic compound. Specific examples of morpholine derivatives include bis(2-morpholinoethyl)ether, 4,4'-carbonyldimorpholine, 4-[2-(ethoxycarbonyl)ethyl]morpholine, and 4-(p-tolyl)morpholine.

These basic compounds may be used alone or in combination of two or more.

(Addition of photopolymerizable compound)
A photopolymerizable compound may be added to the photosensitive resin composition of the present invention for the purpose of improving the photosensitivity and the patterning resolution.

Specific examples of the above epoxy compounds and oxetane compounds include novolak phenol type epoxy resins, biphenyl type epoxy resins, dicyclopentadiene type epoxy resins, cyclohexyl epoxy group-containing polyorganosiloxanes (cyclic or linear), glycidyl group-containing polyorganosiloxanes (cyclic or linear), bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, 2,2'-bis(4-glycidyloxycyclohexyl)propane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, ε-caprolactone-modified 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, ester, vinylcyclohexene dioxide, 2-(3,4-epoxycyclohexyl)-5,5-spiro-(3,4-epoxycyclohexane)-1,3-dioxane, bis(3,4-epoxycyclohexyl)adipate, 1,2-cyclopropanedicarboxylic acid bisglycidyl ester, triglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, diallyl monoglycidyl isocyanurate, 1,4-bis{(3-ethyl-3-oxetanyl)methoxy}methyl}benzene, bis{1-ethyl(3-oxetanyl)}methyl ether, 3-ethyl-3-(phenoxymethyl)oxetane, and 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane.

(Photosensitizer)
The photosensitive resin composition of the present invention may contain a photosensitizer. By adding a photosensitizer, the photosensitive resin composition can improve its sensitivity to visible light and the like, and can also be made sensitive to high wavelength light such as g-line (436 nm), h-line (405 nm) and i-line (365 nm). By using these sensitizers in combination with the above-mentioned cationic polymerization initiator, radical polymerization initiator and photoacid generator, the curing property of the photosensitive resin composition can be adjusted. Examples of the sensitizer include anthracene-based compounds and thioxanthone-based compounds.

Specific examples of the anthracene-based compounds include anthracene, 9,10-dimethoxyethylanthracene, 9,10-dimethylanthracene, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diethoxyanthracene, 1,4-dimethoxyanthracene, 9-methylanthracene, 2-ethylanthracene, 2-tert-butylanthracene, 2,6-di-tert-butylanthracene, 9,10-diphenyl-2,6-di-tert-butylanthracene, etc. In particular, from the viewpoint of easy availability, anthracene, 9,10-dimethylanthracene, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diethoxyanthracene, etc. are preferred as the anthracene-based compounds.

As the anthracene-based compound, anthracene is preferred from the viewpoint of excellent transparency of the cured product, and 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diethoxyanthracene, etc. are preferred from the viewpoint of excellent compatibility with the curable composition.

(solvent)
Furthermore, when used as a photosensitive resin composition, it is often used by coating a substrate, and therefore it is diluted in a solvent to form a photosensitive resin composition. Usable solvents are not particularly limited, and specific examples thereof include hydrocarbon solvents such as xylene, toluene, hexane, and heptane; ether solvents such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, and diethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as butyl acetate, ethyl lactate, and isobutyl isobutyrate; glycol solvents such as propylene glycol 1 monomethyl ether 2 acetate (PGMEA) and ethylene glycol diethyl ether; and halogen-based solvents such as chloroform, methylene chloride, and 1,2-dichloroethane.

(others)
The photosensitive resin composition may contain antioxidants, ultraviolet absorbers, silane coupling agents, fillers, colorants, release agents, flame retardants, flame retardant assistants, surfactants, defoamers, emulsifiers, leveling agents, anti-repellents, ion trapping agents (antimony-bismuth, etc.), thixotropy imparting agents, tackifiers, storage stability improvers, ozone degradation inhibitors, light stabilizers, thickeners, plasticizers, reactive diluents, antioxidants, heat stabilizers, electrical conductivity imparting agents, antistatic agents, radiation shielding agents, nucleating agents, phosphorus-based peroxide decomposers, lubricants, pigments, rust inhibitors, metal deactivators, thermal conductivity imparting agents, and physical property adjusters, as long as the objects and effects of the present invention are not impaired.

(Pattern formation method)
The photosensitive resin composition is applied onto a substrate in a layer form having a thickness of 1 to 10 μm, and dried to obtain a laminate (substrate/photosensitive resin composition). The laminate is exposed to light and then developed with a developer to form a pattern.

As a light source for photocuring (exposing) the photosensitive resin composition, a light source that emits light with the absorption wavelength of the polymerization initiator and sensitizer used may be used, and a light source having a wavelength in the range of 200 to 450 nm (e.g., a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a high-power metal halide lamp, a xenon lamp, a carbon arc lamp, or a light-emitting diode, etc.) can usually be used.

The exposure dose for photocuring the photosensitive resin composition is not particularly limited, but is preferably 1 to 10,000 mJ/ ^cm2 , more preferably 1 to 3,000 mJ/ ^cm2 . If the exposure dose is too low, the photosensitive resin composition may not cure. If the exposure dose is too high, discoloration may occur due to rapid curing. The curing time is preferably in the range of 1 to 600 seconds, more preferably 1 to 150 seconds. If the curing time is too long, the rapid curing characteristic of photocuring is not utilized.

In order to remove the solvent and improve the physical properties of the cured product, heat may be applied before or after photocuring to perform pre-baking and after-baking. The curing temperature can be set appropriately, but is preferably 40 to 400°C, and more preferably 60 to 350°C.

There are no limitations on the type of developer that can be used, as long as it can remove the unexposed areas. Generally, organic solvents and alkaline aqueous solutions are often used as developers, and in the case of solvent development, cyclopentanone, cyclohexanone, and PGMEA (propylene glycol monomethyl ether acetate) are often used industrially.

The developer used in the development with an alkaline aqueous solution can be any commonly used developer without any particular limitations. Specific examples of the developer include organic alkaline aqueous solutions such as tetramethylammonium hydroxide (TMAH) aqueous solution and choline aqueous solution, and inorganic alkaline aqueous solutions such as potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, potassium carbonate aqueous solution, sodium carbonate aqueous solution and lithium carbonate aqueous solution. The aqueous solution may contain alcohol and a surfactant to adjust the dissolution rate. The concentration of the aqueous solution is preferably 25% by weight or less, more preferably 10% by weight or less, and even more preferably 5% by weight or less, from the viewpoint of easily achieving a contrast between the exposed and unexposed areas.

There are no particular limitations on the method of development using a developer, and the unexposed areas can be dissolved and removed by commonly used development methods such as immersion or spraying to form the desired pattern.

(Electrical characteristics)
The photosensitive resin composition of the present invention is characterized by excellent electrical properties such as dielectric constant and dielectric dissipation factor, and can suppress signal delay when performing high-speed signal processing in devices having fine wiring or small devices.

Photosensitive resins that are generally used as interlayer insulating films between metal wiring contain many polar groups in the composition to exhibit photosensitivity, and are prone to moisture absorption, so most have high dielectric constants and dielectric loss. When compared at a frequency of 10 GHz, the value of excellent electrical properties that do not cause signal delays is preferably a dielectric constant of 2.8 or less, and more preferably 2.5 or less. The value of dielectric loss (tan δ) is also a very important parameter, and the value of tan δ is preferably 0.01 or less, and more preferably 0.007 or less.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

(Patterning Evaluation)
A patterning evaluation sample was prepared using the resin composition obtained in the examples and comparative examples. First, the resin composition obtained in the examples and comparative examples was spin-coated on a glass substrate so that the film thickness was 5 μm, and heated on a hot plate heated to 110 ° C. for 2 minutes. Next, using an exposure device (high pressure mercury lamp, manual exposure machine, manufactured by Dai Nippon Kaken Co., Ltd.), exposure was performed with an optimal integrated light amount for each resin composition through a mask engraved with a line and space pattern of 5 μm or 20 μm (soft contact exposure), and the sample was left for 1 minute after exposure. Thereafter, the sample was immersed in a developer (organic solvent developer: cyclopentanone, alkaline developer: TMAH 2.38% aqueous solution) for 180 seconds, and then washed with water for 30 seconds to form a pattern. Then, the sample was heated on a hot plate at 200 ° C. for 60 minutes to obtain a sample for patterning evaluation.

The pattern shape of the obtained patterning evaluation sample was observed using a 3D measuring laser microscope (LEXT OLS4000, manufactured by Olympus) and a stylus-type surface shape measuring instrument (Dektak150, manufactured by Veeco), and the state of the 5 μm or 20 μm line and space was evaluated according to the following criteria.

<Evaluation criteria>
◎: Practical level as a high-resolution material (no residual film on 5 μm line and space)
○: Practical level (no residual film in 20 μm line and space)
×: Not suitable for practical use (film remains in 20 μm line and space)

(Electrical property evaluation)
The 65% solution of the photosensitive resin composition obtained in each of the Examples and Comparative Examples was coated on a PET film with a thickness of 50 μm using a bar coater, and then heated on a hot plate at 110° C. for 2 minutes. Next, the film was exposed to 1000 mJ/cm ² using the same exposure device as above, and then heated on a hot plate at 150° C. for 10 minutes to obtain a 5 cm×5 cm film with a thickness of 50 μm. The film was then sandwiched between glass substrates and heated at 200° C. for 60 minutes to obtain a film for measuring the dielectric constant and dielectric loss tangent.

The dielectric constant and dielectric loss tangent of the obtained film sample were measured and evaluated by the cavity resonator perturbation method using a vector network analyzer (Agilent Technologies, E8361A) at room temperature of 24°C and humidity of 45%.

(Production Example 1) Production of Saturated Hydrocarbon Polymer A1 650 mL of methylene chloride and 100 mL of n-hexane were charged into a 3 L autoclave under nitrogen flow, then 50 mL of a methylene chloride solution in which 15 mmol of 1,4-bis(1-chloro-1-methylethyl)benzene was dissolved, and 6.0 mmol of α-picoline were added, and the vessel body was immersed in a dry ice-acetone bath at -70°C and cooled for 1 hour while stirring. Next, 224 g of dehydrated isobutylene was introduced, and the mixture was cooled to -70°C under nitrogen flow. Then, 14.2 g (75 mmol) of polymerization initiator TiCl ₄ was added to start polymerization, and 1 hour later, 10.3 g (90 mmol) of allyltrimethylsilane was added. After another 1 hour of reaction, the reaction mixture was poured into methanol to stop the reaction. After the polymer was precipitated and separated, the polymer was dissolved in n-hexane, washed three times with pure water, and the solvent was distilled off to obtain an allyl-terminated saturated hydrocarbon polymer A1. The molecular weight of the saturated hydrocarbon polymer A1 was measured by GPC and was found to be 11,000 in terms of polystyrene.

(Production Example 2) Production of Saturated Hydrocarbon Polymer A2 50 mL of toluene was added to 300 g of hydrogenated polyisoprene (Idemitsu Petrochemical Co., Ltd., trade name Epol) having hydroxyl groups at both ends, and dehydrated by azeotropic degassing. 48 g of t-BuOK dissolved in 200 mL of tetrahydrofuran was added. After reacting at 50°C for 1 hour, 47 mL of allyl chloride was added dropwise over about 30 minutes. After the dropwise addition, the reaction was continued at 50°C for 1 hour, and after the reaction was completed, 30 g of aluminum silicate was added to the reaction solution to adsorb the generated salt, and the mixture was stirred at room temperature for 30 minutes. After separating the aluminum silicate by filtration and purification, it was confirmed by ¹ H-NMR analysis that an allyl group had been introduced to the end, and a saturated hydrocarbon polymer A2 having an allyl end was obtained. The molecular weight of the saturated hydrocarbon polymer A2 was 6400 in terms of polystyrene as a result of GPC measurement.

(Production Example 3) Production of Saturated Hydrocarbon Polymer A3 50 mL of toluene was added to 300 g of hydrogenated polybutadiene having hydroxyl groups at both ends (manufactured by Nippon Soda Co., Ltd., trade name NISSO PB GI-3000), and dehydrated by azeotropic degassing. 48 g of t-BuOK dissolved in 200 mL of tetrahydrofuran was added. After reacting at 50°C for 1 hour, 47 mL of allyl chloride was added dropwise over about 30 minutes. After the dropwise addition, the reaction was continued at 50°C for 1 hour, and after the reaction was completed, 30 g of aluminum silicate was added to the reaction solution to adsorb the generated salt, and the mixture was stirred at room temperature for 30 minutes. After separating the aluminum silicate by filtration and purification, it was confirmed by ¹ H-NMR analysis that an allyl group had been introduced to the end, and a saturated hydrocarbon polymer A3 having an allyl end was obtained. The molecular weight of the saturated hydrocarbon polymer A3 was 3200 in terms of polystyrene as a result of GPC measurement.

(Synthesis Example 1)
30 g of toluene and 10 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed in a 300 mL four-neck flask, and the gas phase was replaced with nitrogen, and then the mixture was heated and stirred at an internal temperature of 105° C. A mixture of 8 g of monomethyl diallyl isocyanurate, 15 g of toluene, and 18 mg of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% platinum) was added dropwise over 30 minutes. Next, 3.7 g of vinylcyclohexene oxide and 3.7 g of toluene were added and reacted for 1 hour. After confirming that the reaction rate of all alkenyl groups was 100%, a mixture of 25 g of the saturated hydrocarbon polymer A1 obtained in the above Production Example 1 and 25 g of toluene was added dropwise. After further reacting for 3 hours and confirming that the reaction rate of all alkenyl groups was 100% by ¹ H-NMR, the mixture was cooled to room temperature and the reaction was terminated. The solvents, toluene and dioxane, were removed from the reaction solution under reduced pressure, and the resulting solution was diluted with isobutyl isobutyrate to a 65% solution, yielding hydrosilylation reaction product solution B1.

(Synthesis Example 2)
30 g of toluene and 10 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed in a 300 mL four-neck flask, and the gas phase was replaced with nitrogen, and then the mixture was heated and stirred at an internal temperature of 105° C. A mixture of 4 g of vinylnorbornene, 10 g of toluene, and 6 mg of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% platinum) was added dropwise over 60 minutes. Next, 3.7 g of vinylcyclohexene oxide and 3.7 g of toluene were added and reacted for 1 hour. After confirming that the reaction rate of all alkenyl groups was 100%, a mixture of 25 g of the saturated hydrocarbon polymer A2 obtained in Production Example 2 and 25 g of toluene was added dropwise. After further reacting for 3 hours and confirming that the reaction rate of all alkenyl groups was 100% by ¹ H-NMR, the mixture was cooled to room temperature and the reaction was terminated. The solvents toluene and dioxane were removed from the reaction solution under reduced pressure, and the resulting solution was diluted with isobutyl isobutyrate to a 65% solution, yielding hydrosilylation reaction product solution B2.

(Synthesis Example 3)
30 g of toluene and 10 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed in a 300 mL four-neck flask, and the gas phase was replaced with nitrogen, and then the mixture was heated and stirred at an internal temperature of 105° C. A mixture of 6 g of monoallyl isocyanuric acid, 30 g of 1'4-dioxane, and 18 mg of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% platinum) was added dropwise over 30 minutes. Next, 3.7 g of vinylcyclohexene oxide and 3.7 g of toluene were added and reacted for 1 hour. After confirming that the reaction rate of all alkenyl groups was 100%, a mixture of 25 g of the saturated hydrocarbon polymer A1 obtained in the above Production Example 1, 4 g of vinylnorbornene, and 25 g of toluene was added dropwise. After further reacting for 3 hours and confirming that the reaction rate of all alkenyl groups was 100% by ¹ H-NMR, the mixture was cooled to room temperature and the reaction was terminated. The solvents toluene and dioxane were removed from the reaction solution under reduced pressure, and the resulting solution was diluted with isobutyl isobutyrate to a 65% solution, yielding hydrosilylation reaction product solution B3.

(Synthesis Example 4)
30 g of toluene and 10 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed in a 300 mL four-neck flask, and the gas phase was replaced with nitrogen, and then the mixture was heated and stirred at an internal temperature of 105° C. A mixture of 8 g of diallyl monomethyl isocyanurate, 6 g of monoallyl isocyanuric acid, 40 g of 1'4-dioxane, and 18 mg of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% platinum) was added dropwise over 30 minutes. The mixture was allowed to react for 2 hours, followed by the addition of 3.7 g of vinylcyclohexene oxide and 3.7 g of toluene, and then allowed to react for 1 hour. After confirming that the reaction rate of all alkenyl groups was 100%, a mixture of 25 g of the saturated hydrocarbon polymer A1 obtained in the above Production Example 1 and 25 g of toluene was then added dropwise. The mixture was allowed to react for another 3 hours, and after confirming that the reaction rate of all alkenyl groups was 100% by ¹ H-NMR, the mixture was cooled to room temperature and the reaction was terminated. The solvents toluene and dioxane were removed from the reaction solution under reduced pressure, and the resulting solution was diluted with isobutyl isobutyrate to a 65% solution, yielding hydrosilylation reaction product solution B4.

(Synthesis Example 5)
30 g of toluene and 10 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed in a 300 mL four-neck flask, and the gas phase was replaced with nitrogen, and then the mixture was heated and stirred at an internal temperature of 105°C. A mixture of 8 g of diallyl monomethyl isocyanurate, 6 g of monoallyl isocyanuric acid, 40 g of 1'4-dioxane, and 18 mg of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% platinum) was added dropwise over 30 minutes. The mixture was allowed to react for 2 hours, followed by the addition of 3.7 g of vinylcyclohexene oxide and 3.7 g of toluene, and then allowed to react for 1 hour. After confirming that the reaction rate of all alkenyl groups was 100%, a mixture of 25 g of the saturated hydrocarbon polymer A3 obtained in the above Production Example 3 and 25 g of toluene was then added dropwise. The mixture was allowed to react for another 3 hours, and after confirming that the reaction rate of all alkenyl groups was 100% by ¹ H-NMR, the mixture was cooled to room temperature and the reaction was terminated. The solvents, toluene and dioxane, were removed from the reaction solution under reduced pressure, and the resulting solution was diluted with isobutyl isobutyrate to a 65% solution, yielding hydrosilylation reaction product solution B5.

Comparative Synthesis Example 1
30g of toluene and 10g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed in a 300mL four-neck flask, and the gas phase was replaced with nitrogen, and then the mixture was heated and stirred at an internal temperature of 105°C. A mixture of 6g of monoallyl isocyanuric acid, 30g of 1'4-dioxane, and 18mg of a xylene solution of platinum vinylsiloxane complex (containing 3wt% platinum) was added dropwise over 30 minutes. Next, 3.7g of vinylcyclohexene oxide and 3.7g of toluene were added and reacted for 1 hour. After confirming that the reaction rate of all alkenyl groups was 100%, a mixture of 4g of vinylnorbornene and 10g of toluene was added dropwise. After further reacting for 1 hour and confirming that the reaction rate of all alkenyl groups was 100% by ^1H -NMR, the mixture was cooled to room temperature and the reaction was terminated. The solvents toluene and dioxane were removed from the reaction solution under reduced pressure, and the resulting solution was diluted with isobutyl isobutyrate to a 65% solution, yielding hydrosilylation reaction product solution B6.

Comparative Synthesis Example 2
30g of toluene and 10g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed in a 300mL four-neck flask, and the gas phase was replaced with nitrogen, and then the mixture was heated and stirred at an internal temperature of 105°C. A mixture of 6g of monoallyl isocyanuric acid, 30g of 1'4-dioxane, and 18mg of a xylene solution of platinum vinyl siloxane complex (containing 3wt% platinum) was added dropwise over 30 minutes. Next, 5.2g of trimethoxyvinylsilane and 3.7g of toluene were added and reacted for 1 hour. After confirming that the reaction rate of all alkenyl groups was 100%, a mixture of 4g of vinylnorbornene and 10g of toluene was added dropwise. After further reacting for 1 hour and confirming that the reaction rate of all alkenyl groups was 100% by ^1H -NMR, the mixture was cooled to room temperature and the reaction was terminated. The solvents toluene and dioxane were removed from the reaction solution under reduced pressure, and the resulting solution was diluted with isobutyl isobutyrate to a 65% solution, yielding hydrosilylation reaction product solution B7.

Example 1
Photosensitive resin composition 1 was prepared by dissolving 1 g of the hydrosilylation reaction product solution B1 described in Synthesis Example 1, 0.02 g of a photopolymerization initiator CPI-210S (manufactured by San-Apro Co., Ltd.), and 0.02 g of 9,10-dibutoxyanthracene.

Example 2
Photosensitive resin composition 2 was prepared in the same manner as in Example 1, except that 0.1 g of 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Celloxide 2021P, manufactured by Daicel Organic Synthesis Company) was further added as a photopolymerizable compound.

Example 3
Photosensitive resin composition 3 was prepared in the same manner as in Example 1, except that 1 g of the hydrosilylation reaction product solution B2 described in Synthesis Example 2 was used in place of B1.

Example 4
Photosensitive resin composition 4 was prepared in the same manner as in Example 1, except that 1 g of the hydrosilylation reaction product solution B3 described in Synthesis Example 3 was used instead of B1. 0.02 g of photopolymerization initiator CPI-210S (manufactured by San-Apro Ltd.) and 0.02 g of 9,10-dibutoxyanthracene were dissolved in the solution.

Example 5
Photosensitive resin composition 5 was prepared in the same manner as in Example 4, except that 0.1 g of 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Celloxide 2021P, manufactured by Daicel Organic Synthesis Company) was further added as a photopolymerizable compound.

Example 6
Photosensitive resin composition 6 was prepared in the same manner as in Example 1, except that 1 g of the hydrosilylation reaction product solution B4 described in Synthesis Example 4 was used in place of B1.

(Example 7)
Photosensitive resin composition 7 was prepared in the same manner as in Example 1, except that 1 g of the hydrosilylation reaction product solution B5 described in Synthesis Example 5 was used in place of B1.

(Comparative Example 1)
Photosensitive resin composition 8 was prepared in the same manner as in Example 1, except that 1 g of the hydrosilylation reaction product solution B6 described in Comparative Synthesis Example 1 was used in place of B1.

(Comparative Example 2)
Photosensitive resin composition 9 was prepared in the same manner as in Example 1, except that 1 g of the hydrosilylation reaction product solution B7 described in Comparative Synthesis Example 2 was used in place of B1.

(result)
The above-mentioned evaluations were carried out on the photosensitive resin compositions 1 to 9 obtained in Examples 1 to 7 and Comparative Examples 1 and 2. The results are shown in Table 1.

From the above evaluation results, as shown in Examples 1 to 7, it can be seen that a resin composition containing (A) a saturated hydrocarbon polymer structure having a molecular weight of 1,000 to 100,000, and (B) a compound having a molecular weight of 500 or less and at least one organic structure selected from the group consisting of a tri-substituted isocyanurate structure, a tri-substituted triazine structure, a condensed ring structure having 7 to 16 carbon atoms, an alicyclic hydrocarbon structure having 6 to 12 carbon atoms, and a linear or branched alkyl ether structure having 6 to 24 carbon atoms, and at least one photocationically polymerizable functional group selected from the group consisting of an alicyclic epoxy group, a glycidyl group, and an oxetanyl group, functions as a photosensitive resin composition that exhibits excellent patterning properties, a low dielectric constant, and a low dielectric loss tangent.

The present invention can be used for insulating interlayer films for electronic devices such as semiconductors and displays.

Claims (12)

(A) a saturated hydrocarbon polymer structure having a molecular weight of 1,000 to 100,000;
(B) a fused ring structure having 7 to 16 carbon atoms, which has a molecular weight of 100 or more and 500 or less, and which is a norbornane structure or a tricyclo[5.2.1.0 ^2,6 ]decane structure;
(C) at least one photocationically polymerizable functional group selected from the group consisting of an alicyclic epoxy group, a glycidyl group, and an oxetanyl group;
(D) a photosensitive resin composition containing a compound having a siloxane bond,
The (A) is bonded to at least two Si atoms,
The photosensitive resin composition, wherein the (B) is bonded to at least one Si atom. The photosensitive resin composition according to claim 1, wherein (A) is 15 to 85% by weight relative to 100% by weight of the compound. The photosensitive resin composition according to claim 1 or 2, wherein (A) is at least one selected from the group consisting of isobutylene polymers, hydrogenated isoprene polymers, and hydrogenated butadiene polymers. Furthermore, the following formulas (X1) and (X2)
The photosensitive resin composition according to any one of claims 1 to 3, further comprising a structure (E) which is at least one acidic group selected from the group consisting of structures represented by the following formula (1): The (D) is represented by the following general formula (I):
(In the formula, R ¹ and R ² may be the same or different and represent an organic group having 1 to 10 carbon atoms, n represents a number from 1 to 10, and m represents a number from 0 to 10.)
The photosensitive resin composition according to any one of claims 1 to 4, wherein the cyclic polyorganosiloxane bond is represented by the following formula: The photosensitive resin composition according to any one of claims 1 to 5, further comprising a cationic polymerization initiator. A compound (δ) having a siloxane bond and at least two hydrosilyl groups;
The method includes a step (I) of hydrosilylating a compound (β) having a molecular weight of 100 or more and 500 or less, and having at least one alkenyl group and a fused ring structure having 7 to 16 carbon atoms, which is a norbornane structure or a tricyclo[5.2.1.0 ^2,6 ]decane structure,
The reaction product obtained in step (I),
The method includes a step (II) of hydrosilylating a compound (γ) having at least one photocationically polymerizable functional group selected from the group consisting of an alicyclic epoxy group, a glycidyl group, and an oxetanyl group, and at least one alkenyl group,
The method for producing a photosensitive resin composition includes a step (III) of hydrosilylating the reaction product obtained in the step (II) and a saturated hydrocarbon polymer (α) having at least two alkenyl groups and a molecular weight of 1,000 to 100,000. The method for producing a photosensitive resin composition according to claim 7, wherein (α) includes at least one selected from the group consisting of isobutylene polymers, hydrogenated isoprene polymers, and hydrogenated butadiene polymers. In the step (I), at least one alkenyl group and a compound represented by the following formula (X1) or (X2)
The method for producing a photosensitive resin composition according to claim 7 or 8, further comprising a compound (ε) having at least one acidic group selected from the group consisting of each structure represented by the following formula (I): The method for producing a photosensitive resin composition according to claim 9, wherein (ε) includes at least one selected from the group consisting of diallyl isocyanuric acid, monoallyl isocyanuric acid, diallyl bisphenol A, diallyl bisphenol S, vinylphenol, allylphenol, butenoic acid, pentenoic acid, hexenoic acid, heptenoic acid, and undecylenic acid. The method for producing a photosensitive resin composition according to any one of claims 7 to 10, wherein the (β) is vinylnorbornene. The method for producing a photosensitive resin composition according to any one of claims 7 to 11, wherein (γ) contains at least one selected from the group consisting of vinylcyclohexene oxide, allyl glycidyl ether, diallyl monoglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, and allyl oxetanyl ether.