Modified siloxane diisocyanate compound, polyimide resin, and positive-type photosensitive polyimide resin composition

Abstract

To provide a positive photosensitive resin composition having excellent flexibility and adhesion, a polyimide resin contained in the composition, and a modified siloxane diisocyanate compound to be materials for the polyimide resin.SOLUTION: A reaction of (A) an organic compound having two carbon-carbon double bonds and an acid decomposable group in one molecule, (B) a silicon compound having two SiH groups in one molecule, and (C) a compound having one carbon-carbon double bond and one isocyanate group in one molecule yields a modified siloxane diisocyanate compound represented by the following structure having an isocyanate group at a terminal. The modified siloxane diisocyanate compound is used to give a positive photosensitive polyimide resin composition.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a modified siloxane diisocyanate compound and a positive-type photosensitive polyimide resin composition. [Background technology]

[0002] Photosensitive resins, which can be easily patterned by photolithography, are widely used in the electronics field such as semiconductors and displays. Among these photosensitive resins, polyimide-based photosensitive resins are known to have high heat resistance, and compositions using polyimide resins having acidic groups in the polymer have been proposed.

[0003] Polyimide resins have high rigidity, and in order to impart flexibility, many methods have been proposed for obtaining polyimide resins having a siloxane structure in the molecule, as described in Patent Document 1. However, the siloxane diamine compounds used in the synthesis have low purity, and there are problems such as poor bonding in electrical wiring due to the volatilization of low molecular weight siloxanes at high temperatures, and poor adhesion to various substrates. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2005-056921 A Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention provides a positive-type photosensitive resin composition which has flexibility and excellent adhesion. [Means for solving the problem]

[0006] As a result of extensive investigations aimed at achieving the above, it has been discovered that a positive-type photosensitive polyimide resin composition based on an organically modified siloxane diisocyanate compound and a polyimide resin obtained using the same has flexibility and excellent adhesion.

[0007] [1]. A modified siloxane diisocyanate compound having an isocyanate group at the end and represented by the following structure, obtained by reacting (A) an organic compound having two carbon-carbon double bonds and an acid-decomposable group per molecule, (B) a silicon compound having two SiH groups per molecule, and (C) a compound having one carbon-carbon double bond and one isocyanate group per molecule.

[0008] [ka]

[0009] (In the above chemical formula, G is represented by an organic group having a protected acidic group, a main chain carbon number of 1 to 50, and containing one or more atoms selected from H atoms, O atoms, N atoms, halogen atoms, and S atoms; X is an organic group having an isocyanate group in the structure; R is an organic group having 1 to 20 carbon atoms; and n and m are integers of 1 to 50.)

[0010] [2] The modified siloxane diisocyanate compound according to [1], characterized in that component (C) is allyl isocyanate.

[0011] [3] The modified siloxane diisocyanate compound according to [1] or [2], characterized in that component (A) is represented by the following general formula (a): (Z in the following general formula represents a protecting group selected from a tert-butoxycarbonyl group, a benzyloxycarbonyl group, a trimethylsilyl group, a tert-butyldimethylsilyl group, a methoxymethyl group, an ethoxymethyl group, a tetrahydropyranyl group, an acetyl group, a benzyl group, and a p-methoxybenzyl group).

[0012] [ka]

[0013] [4] The modified siloxane diisocyanate compound according to [1] or [2], characterized in that component (A) is represented by the following general formula (b): (Z in the following general formula represents a protecting group selected from a tert-butoxycarbonyl group, a benzyloxycarbonyl group, a trimethylsilyl group, a tert-butyldimethylsilyl group, a methoxymethyl group, an ethoxymethyl group, a tetrahydropyranyl group, an acetyl group, a benzyl group, and a p-methoxybenzyl group).

[0014] [ka]

[0015] [5] A polyimide resin obtained by reacting the modified siloxane diisocyanate according to any one of [1] to [4] with a diacid anhydride.

[0016] [6] A positive-type photosensitive resin composition comprising, as essential components, the polyimide resin according to [5] and a photoacid generator. Effect of the Invention

[0017] According to the present invention, by using an organically modified siloxane diisocyanate compound, a polyimide resin having excellent adhesion can be obtained, and further, a positive-type photosensitive polyimide resin composition can be obtained based on the polyimide resin. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] (Modified siloxane diisocyanate compound) It has been discovered that the above-mentioned modified siloxane diisocyanate compound can be obtained by reacting (A) an organic compound having two carbon-carbon double bonds and an acid-decomposable group per molecule, (B) a silicon compound having two SiH groups per molecule, and (C) a compound having one carbon-carbon double bond and one isocyanate group per molecule, to obtain a modified siloxane diisocyanate compound having an isocyanate group at its terminal, as represented by the following structure:

[0019] [ka]

[0020] (In the above chemical formula, G is represented by an organic group having a protected acidic group, a main chain carbon number of 1 to 50, and containing one or more atoms selected from H atoms, O atoms, N atoms, halogen atoms, and S atoms; X is an organic group having an isocyanate group in the structure; R is an organic group having 1 to 20 carbon atoms; and n and m are integers of 1 to 50.)

[0021] The structure G here is not particularly limited as long as it is an organic group having 1 to 50 carbon atoms and any one of H, O, N, F, and S atoms and has an acid-decomposable group in the molecule.

[0022] An acid decomposable group refers to a functional group that is decomposed by an acid substance and changes to an acidic group. An example of an acid decomposable group is a protected acidic group, which is a functional group that is often used by being introduced into a photosensitive resin. In the case of a photosensitive resin, this acid decomposable group is decomposed by an acid substance generated by exposure from a compounded photoacid generator, and changes to an acidic group, thereby changing the solubility in an alkaline developer, and functioning as a patternable photosensitive resin.

[0023] Furthermore, in the polyimide resin obtained by the present invention, compared with a resin having a siloxane molecule not having Structure G, it is effective in improving adhesion to a substrate and resin strength, and from the viewpoint of introducing Structure G without impairing the heat resistance, which is a characteristic feature of polyimide resins, a method of introducing Structure G using the hydrosilylation reaction described below is preferred.

[0024] Each essential component for obtaining a modified siloxane diisocyanate compound by hydrosilylation will be described below.

[0025] (Component (A): an organic compound having two carbon-carbon double bonds and an acid-decomposable group in one molecule) The modified siloxane diisocyanate compound can be obtained by reacting an organic compound having two carbon-carbon double bonds and an acid-decomposable group in one molecule of component (A) with components (B) and (C) described below. There are no particular limitations on the organic compound having two carbon-carbon double bonds and an acid-decomposable group in one molecule of component (A) in the present invention. From the standpoint of availability, a compound represented by the following general formula (a):

[0026] [ka]

[0027] (Z in the general formula represents a protecting group selected from a tert-butoxycarbonyl group, a benzyloxycarbonyl group, a trimethylsilyl group, a tert-butyldimethylsilyl group, a methoxymethyl group, an ethoxymethyl group, a tetrahydropyranyl group, an acetyl group, a benzyl group, and a p-methoxybenzyl group.) Alternatively, a compound represented by the following general formula (b) can be suitably used.

[0028] [ka]

[0029] (Z in the general formula represents a protecting group selected from a tert-butoxycarbonyl group, a benzyloxycarbonyl group, a trimethylsilyl group, a tert-butyldimethylsilyl group, a methoxymethyl group, an ethoxymethyl group, a tetrahydropyranyl group, an acetyl group, a benzyl group, and a p-methoxybenzyl group.) From the viewpoint of heat resistance, it is preferable to use a compound represented by the following general formula (a).

[0030] [ka]

[0031] (Z in the general formula represents a protecting group selected from a tert-butoxycarbonyl group, a benzyloxycarbonyl group, a trimethylsilyl group, a tert-butyldimethylsilyl group, a methoxymethyl group, an ethoxymethyl group, a tetrahydropyranyl group, an acetyl group, a benzyl group, and a p-methoxybenzyl group.) In addition, an organic compound (A') having a carbon-carbon double bond but no acid-decomposable group can also be used in the reaction in combination with the component (A).

[0032] Specific examples of the component (A') include diallyl phthalate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, diarylidene pentaerythritol, and diallyl monomethyl isocyanurate. Diallyl monopropyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl monobenzyl isocyanurate, diallyl dimethyl glycoluril, 1,4-butanediol divinyl ether, nonanediol divinyl ether, 1,4-cyclohexane dimethanol divinyl ether, triethylene glycol divinyl ether, diallyl ether of bisphenol S, divinylbenzene, divinyl biphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, 1,3-bis(allyloxy)adamantane, 1,3-bis(vinyloxy)adamantane, dicyclopentadiene, vinylcyclohexene, 1,5-hexadiene, 1,9-decadiene, diallyl ether, bisphenol A diallyl ether, 2,5-diallylphenol allyl ether, and a compound represented by the following general formula (c):

[0033] [ka]

[0034] etc.

[0035] As component (A'), from the viewpoints of low coloration of the resulting cured product and high heat resistance, diallyl monomethyl isocyanurate, diallyl monopropyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl monobenzyl isocyanurate, vinylcyclohexene, dicyclopentadiene, and diallyl ether of 2,2-bis(4-hydroxycyclohexyl)propane are preferred.

[0036] In particular, from the viewpoint of high heat resistance and light resistance, diallyl monomethyl isocyanurate, diallyl monopropyl isocyanurate, and derivatives thereof represented by the following general formula (d) are preferred.

[0037] [ka]

[0038] (wherein R represents a hydrogen atom or a monovalent organic group having 1 to 50 carbon atoms). Preferred is a compound represented by the following formula:

[0039] (Component (B): Silicon compound having two SiH groups in one molecule) As component (B), any silicon compound having two SiH groups, that is, any compound having two SiH groups with a Si atom in the molecule, can be used without any particular limitation. The most commonly available one is a linear polysiloxane having a SiH group terminal, but there is no particular limitation as long as it is a homopolymer of dimethylsiloxane unit, diphenylsiloxane unit, or methylphenylsiloxane unit, or a polyorganosiloxane polymer in which the terminals of each copolymer of siloxane unit are blocked with dimethylhydrogensilyl groups. Specifically, for example, 1,1,3,3-tetramethyldisiloxane, 1,1,3,3,5,5,-hexamethyltrisiloxane, 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane, etc. are exemplified as preferred examples. Furthermore, silicon-based compounds other than polysiloxane compounds having SiH groups at their ends can also be used. Specific examples of such compounds include 1,4-bis(dimethylsilyl)benzene, 1,4-bis(diphenylsilyl)benzene, and 1,4-bis(methylphenylsilyl)benzene.

[0040] (Component (C): A compound having one carbon-carbon double bond and one isocyanate group per molecule) As component (C), any compound having one carbon-carbon double bond and one isocyanate group per molecule can be used without any particular limitation. Specific examples include allyl isocyanate, vinyl isocyanate, 4-vinylphenyl isocyanate, and 3-isopropenyl-α,α-dimethylbenzyl isocyanate. From the viewpoint of availability, allyl isocyanate is preferred.

[0041] (Reaction of components (A), (B), and (C)) The method for obtaining the modified siloxane diisocyanate compound by reacting components (A), (B), and (C) is a hydrosilylation reaction, in which a catalyst may be used to facilitate the reaction.

[0042] 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.

[0043] Examples of catalysts other than platinum compounds include RhCl(PPh)3, RhCl3, RhAl2O3, RuCl3, IrCl3, FeCl3, AlCl3, PdCl2·2H2O, NiCl2, TiCl4, etc.

[0044] Among these, from the viewpoint of catalytic activity, preferred are chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes, etc. These catalysts may be used alone or in combination of two or more kinds.

[0045] The order of reaction of components (A), (B), and (C) is as follows: first, components (A) and (B) are reacted by hydrosilylation under conditions that increase the amount of SiH groups, and then component (C) is reacted successively to introduce isocyanate groups to the terminals. This produces a modified siloxane diisocyanate.

[0046] (About polyimide resin) The polyimide resin obtained by using the modified siloxane diisocyanate compound of the present invention is generally obtained by reaction with a diacid anhydride, but is not particularly limited thereto.

[0047] Examples of the diacid anhydride used for synthesizing the polyimide of the present invention include 2,2'-hexafluoropropylidenediphthalic dianhydride, 2,2-bis(4-hydroxyphenyl)propane dibenzoate-3,3',4,4'-tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic dianhydride, Aliphatic or alicyclic tetracarboxylic dianhydrides such as 3,5,6-tricarboxynorbonane-2-acetic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, and bicyclo[2,2,2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, and 3,3',4,4'-biphenylsulfone tetracarboxylic acid. Dianhydrides, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenylethertetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride Phenylsulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,Examples of the aromatic tetracarboxylic acid dianhydride include 4'-diphenylmethane dianhydride and other aromatic tetracarboxylic acid dianhydrides, and derivatives thereof. These may be used alone or in any combination.

[0048] (Positive-type photosensitive polyimide resin composition) The polyimide resin obtained by the above method can be made into a positive-type photosensitive resin composition by adding a photoacid generator. The photoacid generator used in the present invention is not particularly limited in type, and multiple types can be used in combination.

[0049] Preferred photoacid generators include aromatic sulfonium salts and iodonium salts, oxime sulfonates, imide sulfonates, and carboxylates. Among these, oxime sulfonates and imide sulfonates are preferred because they have high photosensitivity. The acid compound generated by light is not particularly limited, but is preferably one with an acid strength that can efficiently decompose the acid decomposable group, such as CF3SO3 - H + , C4F9SO3 - H + , B(C6F5)4 - H + , PF6 - H + , SbF6 - H + etc.

[0050] The content of the photoacid generator in the positive 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 component (A). 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.

[0051] (Photosensitizer) The positive photosensitive resin composition may contain a photosensitizer. By adding a photosensitizer, the positive 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 curing property of the positive photosensitive resin composition can be adjusted. Examples of the sensitizer include anthracene-based compounds and thioxanthone-based compounds.

[0052] Specific examples of the anthracene-based compound include anthracene, 2-ethyl-9,10-dimethoxyanthracene, 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.

[0053] 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.

[0054] (solvent) When used as a photosensitive resin composition, it is usually used by coating a substrate, so it is diluted with a solvent to form a photosensitive resin composition. The solvent that can be used is not particularly limited, and specifically includes hydrocarbon solvents such as benzene, 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, glycol solvents such as propylene glycol-1-monomethyl ether-2-acetate (PGMEA) and ethylene glycol diethyl ether, and halogen solvents such as chloroform, methylene chloride, and 1,2-dichloroethane.

[0055] (Pattern formation method) The positive photosensitive resin composition is applied onto a substrate in a layer having a thickness of 1 to 5 μm, and dried to obtain a laminate (substrate / photosensitive resin composition). The laminate is exposed to light and then developed with an alkaline developer to form a pattern.

[0056] As a light source for exposing the positive photosensitive resin composition, a light source that emits light having an absorption wavelength of the photoacid generator 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.

[0057] The exposure dose for reacting the positive 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 positive photosensitive resin composition may not react, whereas if the exposure dose is too high, the reaction may proceed excessively, failing to obtain a pattern of the desired shape.

[0058] In order to remove the solvent and improve the physical properties of the cured product, heat may be applied before or after exposure 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.

[0059] There is no particular limitation on the method for forming a pattern using an alkaline developer, and the desired pattern can be formed by dissolving and removing the exposed area using a commonly used developing method such as an immersion method or a spray method.

[0060] In addition, the developer used in the alkaline development can be any commonly used developer without any particular limitation. 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 surfactants 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. EXAMPLES

[0061] The present invention will be described in more detail below based on examples, but the present invention is not limited to the following examples.

[0062] (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 2 μm, and heated on a hot plate heated to 100 ° 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 50 μm line and space pattern (soft contact exposure), and the sample was left for 1 minute after exposure. After that, the sample was immersed in an alkaline developer (2.38% aqueous TMAH 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 230 ° C for 30 minutes to obtain a sample for patterning evaluation.

[0063] 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 50 μm line and space was evaluated according to the following criteria.

[0064] <Evaluation criteria> ○: Practical level (no residual film on 50μm line and space) ×: Not suitable for practical use (film remains in 50 μm line and space)

[0065] (Adhesion evaluation) The polyimide resin solutions obtained in the examples and comparative examples were spin-coated on a Cu film-coated wafer substrate to a thickness of 5 μm, and then heated on a hot plate at 250° C. for 1 hour to form a polyimide resin film. A scut test was performed to evaluate the adhesion to the Cu thin film.

[0066] Evaluation index 0: No peeling 1: 1-10% peeling 2: 20-30% peeling 3: 50% peeling 4: 70-80% peeling 5: 90% or more peeling

[0067] (Heat resistance evaluation) Using a thermogravimetric analyzer (TGA, manufactured by Shimadzu Corporation), the temperature was raised from room temperature to 500°C at a rate of 10°C / min, and evaluation was performed using the 1% weight loss temperature as an index.

[0068] (Synthesis Example 1) A 500 mL four-neck flask was charged with 100 g of toluene and 15 g of 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane, 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 11 g of diallylisocyanuric acid protected with a tert-butoxycarbonyl group, 10 g of 1'4'-dioxane, and 0.0163 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% platinum) was added dropwise over 30 minutes. Three hours after the completion of the dropwise addition, 1 The reaction rate of the allyl group was confirmed to be 100% by H-NMR, and the mixture was cooled to 60°C. Then, a mixed solution of 0.85 g of allyl isocyanate and 3 g of toluene was added dropwise. Five hours after the end of the addition, 1 The reaction rate of the double bond of allyl isocyanate was confirmed to be 100% by H-NMR, and the reaction was terminated by cooling. Toluene was distilled off under reduced pressure to obtain a modified siloxane compound A having an isocyanate group at the end.

[0069] Next, 20g of N,N-dimethylformamide as a solvent, 2.5g of the modified siloxane compound A obtained above, and 1.5g of 2,2-bis(4-aminophenyl)hexafluoropropane were added to a 200mL flask, and the mixture was stirred at room temperature for 30 minutes under a nitrogen atmosphere. 5g of N,N-dimethylformamide, 0.8g of pyridine, and 1.5g of acetic anhydride were added to the flask in order, and the mixture was stirred for 3 hours while heating to 90°C. After the mixture returned to room temperature, 500mL of isopropyl alcohol was added to the flask, and the precipitate was collected. The mixture was washed three times with 500mL of isopropyl alcohol, and the precipitate was dried under reduced pressure at 80°C for 6 hours to obtain polyimide resin A.

[0070] (Synthesis Example 2) A 500 mL four-neck flask was charged with 100 g of toluene and 15 g of 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane, 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 15 g of diallylbisphenol S protected with a tert-butoxycarbonyl group, 10 g of 1'4'-dioxane, and 0.0163 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% platinum) was added dropwise over 30 minutes. Three hours after the completion of the dropwise addition, 1 The reaction rate of the allyl group was confirmed to be 100% by H-NMR, and the mixture was cooled to 60°C. Then, a mixed solution of 0.85 g of allyl isocyanate and 3 g of toluene was added dropwise. Five hours after the end of the addition, 1 The reaction rate of the double bond of allyl isocyanate was confirmed to be 100% by H-NMR, and the reaction was terminated by cooling. Toluene was distilled off under reduced pressure to obtain modified siloxane compound B having an isocyanate group at the end.

[0071] Next, 20g of N,N-dimethylformamide as a solvent, 2.5g of the modified siloxane compound A obtained above, and 1.5g of 2,2-bis(4-aminophenyl)hexafluoropropane were added to a 200mL flask, and the mixture was stirred at room temperature for 30 minutes under a nitrogen atmosphere. 5g of N,N-dimethylformamide, 0.8g of pyridine, and 1.5g of acetic anhydride were added to the flask in order, and the mixture was stirred for 3 hours while heating to 90°C. After the mixture returned to room temperature, 500mL of isopropyl alcohol was added to the flask, and the precipitate was collected. The mixture was washed three times with 500mL of isopropyl alcohol, and the precipitate was dried under reduced pressure at 80°C for 6 hours to obtain polyimide resin B.

[0072] (Synthesis Example 3) A 500 mL four-neck flask was charged with 100 g of toluene and 15 g of 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane, 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 8 g of diallyl isocyanuric acid protected with a tert-butoxycarbonyl group, 2 g of diallyl monomethyl isocyanurate, 10 g of 1'4'-dioxane, and 0.0163 g of a xylene solution of platinum vinyl siloxane complex (containing 3 wt% platinum) was added dropwise over 30 minutes. Three hours after the completion of the dropwise addition, 1 The reaction rate of the allyl group was confirmed to be 100% by H-NMR, and the mixture was cooled to 60°C. Then, a mixed solution of 0.85 g of allyl isocyanate and 3 g of toluene was added dropwise. Five hours after the end of the addition, 1 The reaction rate of the double bond of allyl isocyanate was confirmed to be 100% by H-NMR, and the reaction was terminated by cooling. Toluene was distilled off under reduced pressure to obtain modified siloxane compound C having an isocyanate group at the end.

[0073] Next, 20g of N,N-dimethylformamide as a solvent, 2.5g of the modified siloxane compound A obtained above, and 1.5g of 2,2-bis(4-aminophenyl)hexafluoropropane were added to a 200mL flask, and the mixture was stirred at room temperature for 30 minutes under a nitrogen atmosphere. 5g of N,N-dimethylformamide, 0.8g of pyridine, and 1.5g of acetic anhydride were added to the flask in sequence, and the mixture was stirred for 3 hours while heating to 90°C. After the mixture returned to room temperature, 500mL of isopropyl alcohol was added to the flask, and the precipitate was collected. The mixture was washed three times with 500mL of isopropyl alcohol, and the precipitate was dried under reduced pressure at 80°C for 6 hours to obtain polyimide resin C.

[0074] (Comparative Synthesis Example 1) In a 200mL flask, 20g of N,N-dimethylformamide, 1.0g of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1.0g of siloxane diamine (trade name: KF-8010, manufactured by Shin-Etsu Chemical Co., Ltd.), and 2.5g of 2,2'-hexafluoropropylidenediphthalic dianhydride were added as solvents, and the mixture was stirred at room temperature for 30 minutes under a nitrogen atmosphere. Furthermore, 5g of N,N-dimethylformamide, 0.8g of pyridine, and 1.5g of acetic anhydride were added in sequence to the flask, and the mixture was stirred for 3 hours while heating to 90°C. After the mixture returned to room temperature, 500mL of isopropyl alcohol was added to the flask, and the precipitate was collected. The mixture was washed three times with 500mL of isopropyl alcohol, and the obtained precipitate was dried under reduced pressure at 80°C for 6 hours to obtain polyimide resin E'.

[0075] Next, 3 g of polyimide resin E' was dissolved in 50 mL of THF, and 0.1 g of pyridine and 3 g of di-tert-butyl dicarbonate were added, and the mixture was stirred at 70° C. for 1 hour. 1 Completion of the protection reaction was confirmed by disappearance of the NH peak of isocyanuric acid by -NMR, yielding polyimide resin E in which the phenolic acid groups were protected.

[0076] Example 1 Photosensitive composition 1 was prepared by dissolving 0.50 g of polyimide resin A described in Synthesis Example 1 as a polyimide resin and 0.10 g of 1,8-naphthalenedicarboxylic acid imide trifluoromethylsulfonate as a photoacid generator in 3.5 g of PGMEA (propylene glycol monomethyl ether acetate) as a solvent.

[0077] Example 2 Photosensitive composition 2 was prepared by dissolving 0.50 g of polyimide resin B described in Synthesis Example 2 as a polyimide resin and 0.10 g of 1,8-naphthalenedicarboxylic acid imide trifluoromethylsulfonate as a photoacid generator in 3.5 g of PGMEA (propylene glycol monomethyl ether acetate) as a solvent.

[0078] Example 3 Photosensitive composition 3 was prepared by dissolving 0.50 g of polyimide resin C described in Synthesis Example 3 as a polyimide resin and 0.10 g of 1,8-naphthalenedicarboxylic acid imide trifluoromethylsulfonate as a photoacid generator in 3.5 g of PGMEA (propylene glycol monomethyl ether acetate) as a solvent.

[0079] Comparative Example 1 Photosensitive composition 4 was prepared by dissolving 0.50 g of polyimide resin E described in Comparative Synthesis Example 1 as a polyimide resin and 0.10 g of 1,8-naphthalenedicarboxylic acid imide trifluoromethylsulfonate as a photoacid generator in 3.5 g of PGMEA (propylene glycol monomethyl ether acetate) as a solvent.

[0080] (result) The above-mentioned evaluations were carried out on the polyimide resin solutions obtained in Examples 1 to 3 and Comparative Example 1. The results are shown in Table 1.

[0081] [Table 1] [Industrial Applicability]

[0082] The present invention can be utilized in various fields, such as insulating interlayer films for electronic devices such as semiconductors and displays, adhesives, coating agents, and sealants.

Claims

1. (A) an organic compound having two carbon-carbon double bonds and an acid-decomposable group in one molecule; (B) a silicon compound having two SiH groups in one molecule; (C) a modified siloxane diisocyanate compound having an isocyanate group at a terminal thereof, which is obtained by subjecting a compound having one carbon-carbon double bond and one isocyanate group per molecule to a hydrosilylation reaction; The organic compound (A) having two carbon-carbon double bonds and an acid-decomposable group per molecule is a compound represented by the following general formula (a) and / or the following general formula (b), in which Z represents an acid-decomposable group selected from a tert-butoxycarbonyl group, a benzyloxycarbonyl group, a trimethylsilyl group, a tert-butyldimethylsilyl group, a methoxymethyl group, an ethoxymethyl group, a tetrahydropyranyl group, an acetyl group, a benzyl group, and a p-methoxybenzyl group: 【Chemistry 1】 【Chemistry 2】 the silicon compound (B) having two SiH groups per molecule is a SiH group-terminated linear polysiloxane selected from 1,1,3,3-tetramethyldisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, and 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane; The modified siloxane diisocyanate compound (C) is characterized in that the compound having one carbon-carbon double bond and one isocyanate group per molecule is a compound selected from allyl isocyanate, vinyl isocyanate, 4-vinylphenyl isocyanate, and 3-isopropenyl-α,α-dimethylbenzyl isocyanate.

2. 2. The modified siloxane diisocyanate compound according to claim 1, wherein component (C) is allyl isocyanate.

Images