Photosensitive resin composition

Abstract

To provide a photosensitive resin composition which has low dielectric constant and dielectric loss and enables patterning by photolithography.SOLUTION: A photosensitive resin composition has: (A) a saturated hydrocarbon-based polymer structure having a molecular weight of 1000-100000; (B) at least one organic structure which has a molecular weight of 500 or less, and is selected from a 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 photo-cationic polymerizable functional group selected from a group consisting of an alicyclic epoxy group, a glycidyl group and an oxetanyl group; and (D) a siloxane bond, wherein the (A) is bonded to at least two Si atoms, and the (B) is bonded to at least one Si atom.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a photosensitive resin composition which has a low dielectric constant and dielectric loss and can be patterned by photolithography. [Background technology]

[0002] Photosensitive resins, which can be easily patterned by photolithography, are widely used materials in the electronics field, such as semiconductors and displays, and various photosensitive resin compositions have been proposed as interlayer insulating films for electronic devices, as described in Patent Documents 1 and 2. Due to the dramatic improvement of communication technology in recent years, electronic devices are required to process large amounts of information and signals at high speed. On the other hand, there are cases where miniaturization, weight reduction, and improved productivity are required, and it is also becoming necessary for them to have good patterning properties. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2004-117709 A [Patent Document 2] Patent No. 3873261 Japanese Patent Application Publication No. 11-84659 Summary of the Invention [Problem to be solved by the invention]

[0004] In recent years, dielectric delay and transmission loss caused by insulating films between wiring have become an issue, and it has been found 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. [Means for solving the problem]

[0005] As a result of repeated investigations to solve the above problems, it has been found that a photosensitive resin composition having (A) a saturated hydrocarbon polymer structure having a molecular weight of 1000 to 100000, (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 straight-chain 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 low dielectric constant and low dielectric loss. The present invention comprises the following.

[0006] [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 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 straight-chain 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, wherein (A) is bonded to at least two Si atoms and (B) is bonded to at least one Si atom.

[0007] [2] The photosensitive resin composition according to [1], wherein the amount of (A) is 15 to 85% by weight based on 100% by weight of the compound.

[0008] [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.

[0009] [4].Furthermore, the following formulas (X1) and (X2)

[0010] [ka]

[0011] The photosensitive resin composition according to any one of [1] to [3], comprising a structure (E) which is at least one acidic group selected from the group consisting of structures represented by the following formula (1):

[0012] [5] The (D) is represented by the following general formula (I):

[0013] [ka]

[0014] (R in the formula 1 , R 2 represents an organic group having 1 to 10 carbon atoms and may be the same or different, 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:

[0015] [6] The photosensitive resin composition according to any one of [1] to [5], further comprising a cationic polymerization initiator.

[0016] [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 3-substituted isocyanurate structure, a 3-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 the 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, A method for producing a photosensitive resin composition, comprising: 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.

[0017] [8] The method for producing a photosensitive resin composition according to [7], wherein the (α) comprises at least one member selected from the group consisting of an isobutylene polymer, a hydrogenated isoprene polymer, and a hydrogenated butadiene polymer.

[0018] [9] In the step (I), At least one alkenyl group and a group represented by the following formula (X1) or (X2):

[0019] [ka]

[0020] 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 a structure represented by the following formula (1):

[0021]

[10] . The method for producing a photosensitive resin composition according to [9], wherein the (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.

[0022]

[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) 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 adamantane, 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.

[0023]

[12] . The method for producing a photosensitive resin composition according to any one of [7] to

[11] , wherein (γ) includes at least one member selected from the group consisting of vinylcyclohexene oxide, allyl glycidyl ether, diallyl monoglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, and allyl oxetanyl ether. Effect of the Invention

[0024] According to the present invention, it is possible to provide a photosensitive resin composition which has a low dielectric constant and dielectric loss and which allows good patterning by photolithography. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0025] (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 straight-chain 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.

[0026] Hereinafter, the method for preparing the compounds having the essential structures (A) to (D) of the present invention is not particularly limited, but the method using a hydrosilylation reaction is preferred because it is the simplest and can be obtained in high yield.

[0027] ((A) Structure: Saturated hydrocarbon polymer structure with a molecular weight of 1,000 to 100,000) The monomer used to obtain the saturated hydrocarbon polymer with respect to the above (A) structure 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 and a diene compound, and then hydrogenating the copolymer, etc. From the viewpoints of easiness in introducing a functional group to the terminal, ease of molecular weight control, and ability to increase the number of terminal functional groups, it is preferable to use an isobutylene polymer, a hydrogenated isoprene polymer, or a hydrogenated butadiene polymer.

[0028] The isobutylene polymer may be formed of all monomer units from 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 the copolymer component include 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, 4-methyl-1-pentene, hexene, vinylcyclohexane, β-pinene, camphene, etc.

[0029] The hydrogenated butadiene polymer and other saturated hydrocarbon polymers may contain other monomer units in addition to the main monomer units, as in the case of the isobutylene polymer. 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, within the range in which the object of the present invention is achieved.

[0030] The saturated hydrocarbon polymer constituting the (A) structure, preferably an isobutylene polymer, a hydrogenated isoprene polymer, or a hydrogenated butadiene polymer, has a number average molecular weight of 1,000 to 100,000, and is preferably a liquid having flowability of about 2,000 to 50,000 from the viewpoint of ease of handling.

[0031] 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, based on 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 is not exhibited, while if the ratio is too high, patterning by photolithography becomes impossible, and it is not preferable from the viewpoint of tack generation on the surface of the coating film / cured product obtained by curing the resin composition and reduction in resin strength.

[0032] The (A) structure is bonded to at least two Si atoms. The cured product having such a structure exhibits excellent electrical properties, particularly low dielectric loss. The method for introducing the (A) structure bonded to at least two Si atoms is not particularly limited, 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 preferred to use a saturated hydrocarbon polymer (component (α) described later) having a molecular weight of 1000 to 100000 and having at least two alkenyl groups in the molecule, which can react with a compound having a SiH group.

[0033] (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, a polymer having two alkenyl groups at both ends of the polymer is more preferred from the viewpoint of being less likely to gel and easier to control the reaction when a reaction product is obtained by hydrosilylation reaction. As the (α) component, various methods for introducing alkenyl groups into a saturated hydrocarbon polymer have been proposed, but they can be roughly divided into a method for introducing alkenyl groups after polymerization and a method for introducing alkenyl groups during polymerization. As a method for introducing alkenyl groups after polymerization, for example, a saturated hydrocarbon polymer having terminal alkenyl groups is produced by converting hydroxyl groups at the terminal, main chain, or side chain into -ONa groups or -OK groups, and then reacting with an organic halogen compound represented by general formula (II).

[0034] [ka]

[0035] [wherein Y is a halogen atom such as a chlorine atom or an iodine atom; R 3 -R 4 -, -R 4 -OC(=O)- or -R 4 -C(=O)-(R 4is a divalent hydrocarbon group having 1 to 20 carbon atoms, and preferred specific examples include an alkylene group, a cycloalkylene group, an arylene group, and an aralkylene group.

[0036] 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 method, a terminal alkenyl group-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, or bis(chloromethyl)ether, 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) to obtain a saturated hydrocarbon polymer with a higher molecular weight and an alkenyl group at the end.

[0037] 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, allyloxy(chloromethyl)benzene, etc. Among these, allyl chloride is preferred because it is inexpensive and easily reacts.

[0038] The method for introducing an alkenyl group into a saturated hydrocarbon polymer having a covalently bonded Cl group is not particularly limited, and examples thereof include a method of carrying out a Friedel-Crafts reaction of various alkenyl phenyl ethers with a Cl group, a method of carrying out a substitution reaction of allyltrimethylsilane or the like with a Cl group in the presence of a Lewis acid, and a method of introducing a hydroxyl group by the Friedel-Crafts reaction of various phenols with a Cl group, and then further using the above-mentioned method for introducing an alkenyl group in combination.

[0039] Examples of methods for introducing an alkenyl group during polymerization include a method for producing an isobutylene-based polymer having an allyl terminal by using, as an initiator and chain transfer agent, a compound having a halogen atom and in which the carbon atom to which the halogen atom is bonded is bonded to an aromatic ring carbon and / or a compound having a halogen atom and in which the carbon atom to which the halogen atom is bonded is a tertiary carbon atom, and using a Lewis acid as a catalyst, when cationic polymerizing an isobutylene-containing cationically polymerizable monomer, by adding allyltrimethylsilane to the polymerization system; and a method for producing a saturated hydrocarbon-based polymer having an alkenyl group at the main chain or side chain terminal by adding a non-conjugated diene such as 1,9-decadiene or an alkenyloxystyrene such as p-hexenyloxystyrene to the polymerization system.

[0040] 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, BCl3, Et2AlCl, EtAlCl2, AlCl3, SnCl4, TiCl4, VCl5, FeCl3, BF3, etc., but is not limited thereto. Among these Lewis acids, BCl3, SnCl4, BF3, TiCl4, etc. are preferred, and TiCl4 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.

[0041] 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 not previously subjected to a hydrosilylation reaction with a compound having a SiH group, but is instead added to the photosensitive resin composition as a curing agent. However, this is not preferred because it gives rise to problems such as the saturated hydrocarbon polymer and the usual photosensitive resin component being easily separated, making it difficult to obtain a uniform film / cured product.

[0042] ((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 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) 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.

[0043] 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.

[0044] 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 substituted with halogen atoms. The alkyl group having 1 to 12 carbon atoms or the alkyl ether group having 1 to 12 carbon atoms is preferable.

[0045] The fused ring structure having 7 to 16 carbon atoms includes a norbornane structure, an adamantane structure, 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.

[0046] Examples of the alicyclic hydrocarbon structure having 6 to 12 carbon atoms include a cyclohexane structure, a cyclooctane structure, and a cyclododecane structure, and a compound having a cyclohexane structure, which is particularly highly available, is preferred.

[0047] Examples of the linear or branched alkyl ether structure having 6 to 24 carbon atoms include a pentaerythritol structure and a trimethylolpropane structure.

[0048] Among these structures, from the viewpoint of excellent compatibility with the saturated hydrocarbon polymer structure of the (α) structure, a tri-substituted isocyanurate structure, a fused ring structure having 7 to 16 carbon atoms, and an alicyclic hydrocarbon structure having 6 to 12 carbon atoms are preferred, and among these, a tri-substituted isocyanurate structure is particularly preferred from the viewpoint of easily improving the adhesion of the cured product.

[0049] 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, based on 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.

[0050] The (B) structure is bonded to at least one Si atom. Having such a structure is essential from the viewpoint of improving adhesion to a substrate and improving the strength of the obtained 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 (A) structure, a method of obtaining the structure by hydrosilylation reaction of a SiH group-containing compound with a compound (below-described (β) component) 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 condensed ring structure having 7 to 16 carbon atoms, a condensed ring structure having 6 to 12 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.

[0051] (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 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) 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 alkyl ethers 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.

[0052] From the viewpoint of obtaining a coating film and a cured product with little coloration and with 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 is preferred.

[0053] 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 preferable. These compounds for introducing the (B) structure may be used in combination of two or more kinds according to the properties required for the application.

[0054] ((C) Structure: 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 polymerizes and crosslinks with the cationic species generated from the photopolymerization initiator when light energy is applied from the outside, and there are no particular limitations on the reaction and crosslinking form.

[0055] 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.

[0056] On the other hand, crosslinkable silyl groups such as alkoxysilyl groups are also known as functional groups that undergo crosslinking by cationic species generated by a photopolymerization initiator. However, since silanol groups remain in the coating film and cured product after photocrosslinking, such groups are not preferred from the viewpoint of deterioration of electrical properties such as dielectric constant and dielectric loss tangent.

[0057] 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, based on 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 is destroyed, which is not preferable.

[0058] The method for introducing the (C) structure is not particularly limited, but similarly 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 (component (γ) described below) is preferred from the viewpoint of easily obtaining a uniform composition.

[0059] (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.

[0060] ((D) Structure: Siloxane bond) The method of introduction of the (D) structure is not particularly limited, but it can be easily introduced by hydrosilylation of a siloxane compound having a SiH group. In addition, the sol-gel reaction of an alkoxysilyl group is also a simple method of introducing a siloxane structure, and is commonly used, but when obtaining a resin composition with a low dielectric constant and low dielectric loss as in this case, silanol groups remain in the composition molecule after the reaction, and the silanol groups significantly increase the dielectric constant and dielectric loss, so this is not preferable as the method of the present invention.

[0061] 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, based on 100% by weight of the compound. If the proportion of the (D) structure is too low, the crosslink density becomes too low, and it is not preferable in terms of the occurrence of tack on the surface of the coating film / cured product obtained by curing the resin composition and the decrease in resin strength.

[0062] 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.

[0063] (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.

[0064] Among these, from the viewpoint of imparting flexibility to the cured product,

[0065] [ka]

[0066] (In the formula, R 6 , R 7 represents an organic group having 1 to 6 carbon atoms and may be the same or different, n represents a number from 1 to 50, and m represents a number from 0 to 10.) Preferably, the organopolysiloxane has at least two SiH groups in one molecule, and is represented by the formula: 6 , R 7 From the viewpoints of availability and heat resistance, it is particularly preferred that the group is a methyl group, and from the viewpoint of increasing the strength of the cured product, it is particularly preferred that the group is a phenyl group.

[0067] Of these, from the viewpoint of high heat resistance of the cured product,

[0068] [ka]

[0069] (In the formula, R 8 represents an organic group having 1 to 6 carbon atoms, and n represents a number from 0 to 50. and R is an organopolysiloxane having at least two SiH groups in one molecule and a T or Q structure in the molecule. 8 From the viewpoints of availability and heat resistance, it is particularly preferable that the group is a methyl group.

[0070] From the viewpoints of availability and good hydrosilylation reactivity, a compound represented by the following general formula (I):

[0071] [ka]

[0072] (R in the formula 1 , R 2 represents an organic group having 1 to 10 carbon atoms and may be the same or different, n represents a number from 1 to 10, and m represents a number from 0 to 10), and has at least three SiH groups in one molecule.

[0073] Substituent R in the compound represented by formula (I) 1 , R 2 is 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.

[0074] ((E) Structure: 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.

[0075] The following formulas (X1) and (X2)

[0076] [ka]

[0077] 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 applied 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 with an alkaline developer.

[0078] In the compound having the essential structures (A) to (D) of the present invention, the (E) structure is not essential, but since the range of application is broadened 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, based on 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.

[0079] As with the above structure, this (E) structure can be easily and preferably prepared by subjecting a compound having at least one alkenyl group, and at least one acidic group selected from the group consisting of each of the structures represented by the above formulae (X1) and (X2), a phenolic hydroxyl group, and a carboxyl group (the (ε) component described below) to a hydrosilylation reaction.

[0080] (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, and among these, diallyl isocyanuric acid, monoallyl isocyanuric acid, diallyl bisphenol A, diallyl bisphenol S, vinylphenol, and allylphenol are particularly preferred from the viewpoint of 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 above-listed organic compounds having no acidic group, may be reacted simultaneously to express the properties required for the application.

[0081] (Hydrosilylation reaction) A catalyst may be used in the hydrosilylation reaction of components (α) to (ε) in order to facilitate the smooth progress of the reaction.

[0082] Examples of catalysts that can be used for the hydrosilylation reaction include the following: platinum alone, solid platinum supported on a support such as alumina, silica, or carbon black, chloroplatinic acid, complexes of chloroplatinic acid with alcohols, aldehydes, ketones, etc., platinum-olefin complexes (e.g., Pt(CH2=CH2)2(PPh3)2, Pt(CH2=CH2)2Cl2), platinum-vinylsiloxane complexes (e.g., Pt(ViMe2SiOSiMe2Vi). n , Pt[(MeViSiO)4] m), platinum-phosphine complexes (e.g., Pt(PPh3)4, Pt(PBu3)4), platinum-phosphite complexes (e.g., Pt[P(OPh)3]4, Pt[P(OBu)3]4) (wherein Me is a methyl group, Bu is a butyl group, Vi is a vinyl group, Ph is a phenyl group, and n and m are integers), dicarbonyldichloroplatinum, Karstedt's catalyst, and also platinum-hydrocarbon complexes described in U.S. Pat. Nos. 3,159,601 and 3,159,662 to Ashby, and platinum alcoholate catalysts described in U.S. Pat. No. 3,220,972 to Lamoreaux. In addition, platinum chloride-olefin complexes described in U.S. Pat. No. 3,516,946 to Modic are also useful in the present invention.

[0083] 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 complexes, platinum-vinylsiloxane complexes, etc. are preferred from the viewpoint of catalytic activity. These catalysts may be used alone or in combination of two or more kinds.

[0084] In addition, in the hydrosilylation reaction of (α) to (ε), the order of reaction can be such that the (β), (γ), (ε) and (δ) components, which are susceptible to steric hindrance, are reacted first under conditions in which a large amount of SiH groups remain in the reaction product, and then, 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.

[0085] (Photopolymerization initiator) The photosensitive resin composition of the present invention functions as a photosensitive resin composition by incorporating a photocationic polymerization initiator.

[0086] 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 MF6 as described in U.S. Pat. No. 4,161,478. - Group VIa elements in the form of anions (where M is selected from phosphorus, antimony and arsenic), arylsulfonium complexes as described in U.S. Pat. No. 4,231,951, aromatic iodonium complexes and aromatic sulfonium complexes 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), and salts of the anion B(C6F5)4. - and aromatic iodonium complex salts and aromatic sulfonium complex salts represented by the formula:

[0087] 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, carboxylate esters, etc. 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).

[0088] An example of the sulfonium salt is CPI-210S (manufactured by San-Apro Co., Ltd.) These may be used alone or in combination of two or more.

[0089] The content of the photocationic polymerization initiator in the photosensitive resin composition is not particularly limited, but is preferably 0.01 to 10 parts by weight relative to 100 parts by weight of the photosensitive resin composition from the viewpoint of curability. If the amount of the photoacid generator is small, it may take a long time to cure or a sufficiently cured cured product may not be obtained. In addition, if the amount of the photoacid generator is large, it may be undesirable because the color remains in the cured product, the product may be colored due to rapid curing, the heat resistance may be impaired, or the light resistance may be impaired.

[0090] (Basic compounds) 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.

[0091] The amount of the basic compound is preferably 0.001 to 0.2 parts by weight, more preferably 0.01 to 0.15 parts by weight, per 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 fully performed.

[0092] The basic compound is not particularly limited, and examples thereof include primary, secondary and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, amide derivatives and imide derivatives, etc. Among these, aromatic amines and heterocyclic amines are preferably used as the basic compound.

[0093] Examples of the aromatic amines and the 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, and derivatives thereof.In addition, examples of the heterocyclic amines include 2,6-lutidine.

[0094] Among them, morpholine derivatives can be preferably used as the basic compound. Specific examples of the morpholine derivatives include bis(2-morpholinoethyl)ether, 4,4'-carbonyldimorpholine, 4-[2-(ethoxycarbonyl)ethyl]morpholine, and 4-(p-tolyl)morpholine.

[0095] These basic compounds may be used alone or in combination of two or more kinds.

[0096] (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.

[0097] Specific examples of the 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 ... 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.

[0098] (Photosensitizer) The photosensitive resin composition of the present invention may contain a photosensitizer. By adding a photosensitizer, the photosensitive resin composition can be improved in sensitivity to visible light, and can 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 curability of the photosensitive resin composition can be adjusted. Examples of the sensitizer include anthracene-based compounds and thioxanthone-based compounds.

[0099] Specific examples of the anthracene-based compound 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 compound.

[0100] 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, and the like are preferred from the viewpoint of excellent compatibility with the curable composition.

[0101] (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.

[0102] (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.

[0103] (Pattern formation method) The photosensitive resin composition is applied onto a substrate in a layer 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.

[0104] As a light source for photocuring (exposing) the photosensitive resin composition, a light source that emits light having an 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) can usually be used.

[0105] The exposure dose for photocuring the photosensitive resin composition is not particularly limited, but is preferably 1 to 10,000 mJ / cm. 2 , more preferably 1 to 3000 mJ / cm 2 If the exposure dose is too low, the photosensitive resin composition may not be cured. If the exposure dose is too high, the composition may be discolored 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 cannot be utilized.

[0106] 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 appropriately set, but is preferably 40 to 400°C, and more preferably 60 to 350°C.

[0107] There are no limitations on the developer, so long as it can remove unexposed areas. Generally, organic solvents and alkaline aqueous solutions are often used as developers, and in the case of solvent development, cyclopentanone, cyclohexanone, PGMEA (propylene glycol monomethyl ether acetate), etc. are often used industrially.

[0108] In addition, the developer used in the development with an alkaline aqueous solution can be used without any particular limitation as long as it is a commonly used one. 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, a surfactant, etc. to adjust the dissolution rate, etc. 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.

[0109] There is no particular limitation on the method of development using a developer, and the desired pattern can be formed by dissolving and removing the unexposed areas using commonly used development methods such as immersion or spraying.

[0110] (Electrical characteristics) The photosensitive resin composition of the present invention has excellent electrical properties such as dielectric constant and dielectric dissipation factor, and can suppress signal delay when performing high-speed signal processing in devices with fine wiring or small devices.

[0111] Photosensitive resins 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 of them have high dielectric constants and dielectric loss. For excellent electrical properties that do not cause signal delay, a dielectric constant of 2.8 or less is preferable, and 2.5 or less is more preferable, when compared at a frequency of 10 GHz. The value of dielectric loss (tan δ) is also a very important parameter, and a tan δ value of 0.01 or less is preferable, and a value of 0.007 or less is more preferable. EXAMPLES

[0112] The present invention will be described in more detail below based on examples, but the present invention is not limited to the following examples.

[0113] (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. After that, 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.

[0114] 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.

[0115] <Evaluation criteria> ◎: Practical level as a high-resolution material (no residual film on 5μm line and space) ○: Practical level (no residual film on 20μm line and space) ×: Not suitable for practical use (film remains in 20 μm line and space)

[0116] (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 to a thickness of 50 μm using a bar coater, and then heated on a hot plate at 110° C. for 2 minutes. Then, the film was exposed to light at 1000 mJ / cm 2 using the same exposure device as above. 2 After exposure, the film was heated on a hot plate at 150°C for 10 minutes and cut into a 5 cm x 5 cm film with a thickness of 50 μm. This 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.

[0117] The dielectric constant and dielectric loss tangent of the obtained film sample were measured and evaluated by a cavity resonator perturbation method using a vector network analyzer (E8361A, manufactured by Agilent Technologies) at room temperature of 24° C. and humidity of 45%.

[0118] (Production Example 1) Production of Saturated Hydrocarbon Polymer A1 In a 3L autoclave, 650mL of methylene chloride and 100mL of n-hexane were charged under nitrogen flow, then 50mL of methylene chloride solution in which 15mmol of 1,4-bis(1-chloro-1-methylethyl)benzene was dissolved, and 6.0mmol of α-picoline was added, and the container body was immersed in a dry ice-acetone bath at -70°C and cooled for 1 hour while stirring. Next, 224g of dehydrated isobutylene was introduced and cooled to -70°C under nitrogen flow. Then, 14.2g (75mmol) of polymerization initiator TiCl4 was added to start polymerization, and after 1 hour, 10.3g (90mmol) 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. As a result of GPC measurement, the molecular weight of the saturated hydrocarbon polymer A1 was 11,000 in terms of polystyrene.

[0119] (Production Example 2) Production of Saturated Hydrocarbon Polymer A2 50 mL of toluene was added to 300 g of hydrogenated polyisoprene having hydroxyl groups at both ends (Idemitsu Petrochemical Co., Ltd., product name Epole), and the mixture was 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 approximately 30 minutes. After the dropwise addition, the mixture was reacted at 50°C for 1 hour. 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 purification, 1 The introduction of an allyl group to the terminal was confirmed by H-NMR analysis, and an allyl-terminated saturated hydrocarbon polymer A2 was obtained. The molecular weight of the saturated hydrocarbon polymer A2 was 6,400 in terms of polystyrene as a result of GPC measurement.

[0120] (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., product name NISSO PB GI-3000), and the mixture was 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 mixture was reacted at 50°C for 1 hour. 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 purification, 1 The introduction of an allyl group to the terminal was confirmed by H-NMR analysis, and an allyl-terminated saturated hydrocarbon polymer A3 was obtained. The molecular weight of the saturated hydrocarbon polymer A3 was 3200 in terms of polystyrene as a result of GPC measurement.

[0121] (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 8g of monomethyl diallyl isocyanurate, 15g of toluene, 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 25g of the saturated hydrocarbon polymer A1 obtained in the above Production Example 1 and 25g of toluene was added dropwise. The mixture was further reacted for 3 hours. 1 After confirming that the reaction rate of all alkenyl groups was 100% by H-NMR, the reaction was terminated by cooling to room temperature. The solvents toluene and dioxane were removed from the reaction solution by vacuum distillation, and the solution was diluted with isobutyl isobutyrate to a 65% solution to obtain hydrosilylation reaction product solution B1.

[0122] (Synthesis Example 2) A 300 mL four-neck flask was charged with 30 g of toluene and 10 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and the gas phase was replaced with nitrogen, and then the flask 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. The mixture was further reacted for 3 hours. 1 After confirming that the reaction rate of all alkenyl groups was 100% by H-NMR, the reaction was terminated by cooling to room temperature. The solvents toluene and dioxane were removed from the reaction solution by vacuum distillation, and the solution was diluted with isobutyl isobutyrate to a 65% solution to obtain hydrosilylation reaction product solution B2.

[0123] (Synthesis Example 3) 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 25g of the saturated hydrocarbon polymer A1 obtained in the above Production Example 1, 4g of vinylnorbornene, and 25g of toluene was added dropwise. The mixture was further reacted for 3 hours. 1 After confirming that the reaction rate of all alkenyl groups was 100% by H-NMR, the reaction was terminated by cooling to room temperature. The solvents toluene and dioxane were removed from the reaction solution by vacuum distillation, and the solution was diluted with isobutyl isobutyrate to a 65% solution to obtain hydrosilylation reaction product solution B3.

[0124] (Synthesis Example 4) 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 8g of diallyl monomethyl isocyanurate, 6g of monoallyl isocyanuric acid, 40g of 1'4-dioxane, and 18mg of a xylene solution of platinum vinylsiloxane complex (containing 3wt% platinum) was added dropwise over 30 minutes. The mixture was allowed to react for 2 hours, followed by the addition of 3.7g of vinylcyclohexene oxide and 3.7g 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 25g of the saturated hydrocarbon polymer A1 obtained in the above Production Example 1 and 25g of toluene was then added dropwise. The mixture was allowed to react for another 3 hours. 1 After confirming that the reaction rate of all alkenyl groups was 100% by H-NMR, the reaction was terminated by cooling to room temperature. The solvents toluene and dioxane were removed from the reaction solution by vacuum distillation, and the solution was diluted with isobutyl isobutyrate to a 65% solution to obtain hydrosilylation reaction product solution B4.

[0125] (Synthesis Example 5) 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 8g of diallyl monomethyl isocyanurate, 6g of monoallyl isocyanuric acid, 40g of 1'4-dioxane, and 18mg of a xylene solution of platinum vinylsiloxane complex (containing 3wt% platinum) was added dropwise over 30 minutes. The mixture was allowed to react for 2 hours, followed by the addition of 3.7g of vinylcyclohexene oxide and 3.7g 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 25g of the saturated hydrocarbon polymer A3 obtained in the above Production Example 3 and 25g of toluene was then added dropwise. The mixture was allowed to react for another 3 hours. 1 After confirming that the reaction rate of all alkenyl groups was 100% by H-NMR, the reaction was terminated by cooling to room temperature. The solvents toluene and dioxane were removed from the reaction solution by vacuum distillation, and the solution was diluted with isobutyl isobutyrate to a 65% solution to obtain hydrosilylation reaction product solution B5.

[0126] (Comparative Synthesis Example 1) A 300mL four-neck flask was charged with 30g of toluene and 10g of 1,3,5,7-tetramethylcyclotetrasiloxane, and the gas phase was replaced with nitrogen, after which the flask was heated to an internal temperature of 105°C and stirred. 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. The mixture was allowed to react for another 1 hour. 1 After confirming that the reaction rate of all alkenyl groups was 100% by H-NMR, the reaction was terminated by cooling to room temperature. The solvents toluene and dioxane were removed from the reaction solution by vacuum distillation, and the solution was diluted with isobutyl isobutyrate to a 65% solution to obtain hydrosilylation reaction product solution B6.

[0127] (Comparative Synthesis Example 2) A 300mL four-neck flask was charged with 30g of toluene and 10g of 1,3,5,7-tetramethylcyclotetrasiloxane, and the gas phase was replaced with nitrogen, after which the flask was heated to an internal temperature of 105°C and stirred. A mixture of 6g of monoallylisocyanuric 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, 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. The mixture was allowed to react for another 1 hour. 1 After confirming that the reaction rate of all alkenyl groups was 100% by H-NMR, the reaction was terminated by cooling to room temperature. The solvents toluene and dioxane were removed from the reaction solution by vacuum distillation, and the solution was diluted with isobutyl isobutyrate to a 65% solution to obtain hydrosilylation reaction product solution B7.

[0128] 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.

[0129] 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.

[0130] 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 instead of B1.

[0131] 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 Co., Ltd.) and 0.02 g of 9,10-dibutoxyanthracene were dissolved in the solution.

[0132] 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.

[0133] 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 instead of B1.

[0134] 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 instead of B1.

[0135] 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.

[0136] 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.

[0137] (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.

[0138] [Table 1]

[0139] 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 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, 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 exhibiting excellent patterning properties, a low dielectric constant, and a low dielectric tangent. [Industrial Applicability]

[0140] The present invention can be used in insulating interlayer films for electronic devices such as semiconductors and displays.

Claims

1. (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 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) Siloxane bond A photosensitive resin composition comprising a compound having the formula: 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.

2. 2. The photosensitive resin composition according to claim 1, wherein the amount of (A) is 15 to 85% by weight based on 100% by weight of the compound.

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

4. Furthermore, the following formulas (X1) and (X2) 【Chemistry 1】 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):

5. The (D) is represented by the following general formula (I): 【Chemistry 2】 (In the formula R １ , R ２ represents an organic group having 1 to 10 carbon atoms and may be the same or different, 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:

6. The photosensitive resin composition according to any one of claims 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 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.

8. 8. The method for producing a photosensitive resin composition according to claim 7, wherein the (α) comprises at least one member selected from the group consisting of an isobutylene polymer, a hydrogenated isoprene polymer, and a hydrogenated butadiene polymer.

9. In the step (I), at least one alkenyl group and a compound represented by the following formula (X1) or (X2) 【Chemistry 3】 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):

10. 10. The method for producing a photosensitive resin composition according to claim 9, wherein the (ε) comprises 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 method for producing a photosensitive resin composition according to any one of claims 7 to 10, wherein the (β) is vinylnorbornene.

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

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