JP2021195476A - Modified siloxane diacid anhydride and positive type photosensitive polyimide resin composition - Google Patents

Abstract

To provide an organically modified siloxane diacid anhydride, and a positive type photosensitive polyimide resin composition obtained using the same which is excellent in adhesion.SOLUTION: A modified siloxane diacid anhydride is obtained by reacting (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 a carbon-carbon double bond and an acid anhydride group one by one in one molecule, has an acid anhydride group at a terminal, and is represented by the following formula. In the formula, G has a protected acidic group and has a main chain having 1 to 50 carbon atoms; X represents an organic group having an acid anhydride group in the structure; R represents an organic group having 1 to 20 carbon atoms; and n and m are integers of 1 to 50.SELECTED DRAWING: None

Description

The present invention relates to a modified siloxane diic anhydride and a positive photosensitive polyimide resin composition.

Photosensitive resins, which can easily form patterns by photolithography, are materials widely used in the electronics field such as semiconductors and displays. Among these photosensitive resins, a polyimide-based photosensitive resin is mentioned as a material having high heat resistance, and a composition using a polyimide resin having an acidic group in a polymer has been proposed.

As described in Patent Document 1, many methods for obtaining a polyimide resin having a siloxane structure in its molecule have been proposed for the purpose of imparting flexibility to the polyimide resin because of its high rigidity. However, the siloxane diamine compound used during synthesis has low purity and has problems such as poor bonding in electrical wiring due to volatilization of small molecule siloxane at high temperature and lack of adhesion to various substrates. There is.

On the other hand, Patent Document 2 also proposes a technique for obtaining a polyimide resin using a diacid anhydride having a siloxane structure. However, as described above, there is a problem that the polyimide resin lacks adhesion.

Japanese Unexamined Patent Publication No. 2005-056921 Patent No. 5873529

It is an object of the present invention to provide an organically modified siloxane diic anhydride and a positive photosensitive polyimide resin composition obtained by using the same and having excellent adhesion.

As a result of repeated studies to achieve the above, the positive photosensitive polyimide resin composition based on the organically modified siloxane diacid anhydride and the polyimide resin obtained by using the organically modified siloxane diacid anhydride has flexibility and , We have found that it has excellent adhesion. The present invention comprises the following.

[1]. Component (A) is an organic compound having two carbon-carbon double bonds and an acid-degradable group in one molecule, component (B) is a silicon compound having two SiH groups in one molecule, and component (C) is one molecule. A modified siloxane diacid anhydride having the following structure, which is obtained by reacting a compound having a carbon-carbon double bond and one acid anhydride group in the compound, and having an acid anhydride group at the terminal.

(In the above chemical formula, G has a protected acidic group, has 1 to 50 carbon atoms in the main chain, and is a kind of H atom, O atom, N atom, halogen atom, or S atom. Alternatively, it is represented by an organic group containing two or more kinds, X is an organic group having an acid anhydride group in the structure, R is an organic group represented by 1 to 20 carbon atoms, and n and m are 1 to 50. (It is an integer)

[2]. The modified siloxane diic acid anhydride according to [1], wherein the component (C) is selected from the compounds described below.

[3]. The modified siloxane diacid anhydride according to [1] or [2], wherein the component (A) is a compound having at least an N atom or an S atom.

[4]. A polyimide resin obtained by reacting the modified siloxane diic anhydride according to any one of [1] to [3] with a diamine compound or a diisocyanate compound.

[5]. The polyimide resin according to [4], wherein the component (A) is represented by the following general formula (a). (Z in the following general formula is tert-butoxycarbonyl group, benzyloxycarbonyl group, trimethylsilyl group, tert-butyldimethylsilyl group, methoxymethyl group, ethoxymethyl group, tetrahydropyranyl group, acetyl group, benzyl group, p- Represents a protecting group selected from methoxybenzyl groups)

[6]. The polyimide resin according to [4] or [5], wherein the component (A) is represented by the following general formula (b). (Z in the following general formula is tert-butoxycarbonyl group, benzyloxycarbonyl group, trimethylsilyl group, tert-butyldimethylsilyl group, methoxymethyl group, ethoxymethyl group, tetrahydropyranyl group, acetyl group, benzyl group, p- Represents a protecting group selected from methoxybenzyl groups)

[7]. [4] A positive photosensitive composition containing the polyimide resin according to [6] and a photoacid generator as essential components.

The present invention is to provide a positive photosensitive polyimide resin composition based on an organically modified siloxane diic anhydride and a polyimide resin having excellent adhesion obtained by using the same.

(Modified siloxane diic acid anhydride)
The above-mentioned modified siloxane diichydride is (A) an organic compound having two carbon-carbon double bonds and an acid-degradable group in one molecule, and (B) silicon having two SiH groups in one molecule. By reacting a compound, (C) a compound having a carbon-carbon double bond and one acid anhydride group in one molecule, a siloxane diacid anhydride represented by the following structure having an acid anhydride group at the terminal is reacted. I found that I could get something.

(In the above chemical formula, G has an acid-degradable group, has 1 to 50 carbon atoms in the main chain, and is one of H atom, O atom, N atom, halogen atom, and S atom, or It is represented by an organic group containing two or more kinds, X is an organic group having an acid anhydride group in the structure, R is an organic group represented by 1 to 20 carbon atoms, and n and m are integers of 1 to 50. Is)

The structure G referred to here is an organic having 1 to 50 carbon atoms in the main chain and containing one or more of H atom, O atom, N atom, halogen atom and S atom. It is not particularly limited as long as it is a group and has an acid-degradable group in the molecule.

An acid-degradable group is a functional group that is decomposed by an acid substance and changed to an acidic group. Examples of acid-degradable groups include protected acidic groups, which are functional groups often used when introduced into photosensitive resins. In the case of a photosensitive resin, this acid-degradable group is decomposed by an acid substance generated by exposure from the compounded photoacid generator and changed to an acidic group, so that the solubility in an alkaline developer changes. , Functions as a patternable photosensitive resin.

Further, the polyimide resin obtained by the present invention is effective for improving the adhesion to the substrate and the resin strength as compared with the resin having a siloxane molecule having no structure G, and is a feature of the polyimide resin. From the viewpoint of introduction without impairing a certain heat resistance, the method of introduction using the hydrosilylation reaction described below is preferable.

Hereinafter, each essential component for obtaining a modified siloxane diic acid anhydride by hydrosilylation will be described.

(Component (A): Organic compound having two carbon-carbon double bonds and an acid-degradable group in one molecule)
The above-mentioned modified siloxane diacid anhydride includes an organic compound having two carbon-carbon double bonds and an acid-degradable group in one molecule of the component (A), and the components (B) and (C) described later. It can be obtained by reacting. The present invention is not particularly limited as long as it is an organic compound having two carbon-carbon double bonds and an acid-degradable group in one molecule which is the component (A) in the present invention. From the viewpoint of availability, the compound represented by the following general formula (a),

(Z in the general formula is tert-butoxycarbonyl group, benzyloxycarbonyl group, trimethylsilyl group, tert-butyldimethylsilyl group, methoxymethyl group, ethoxymethyl group, tetrahydropyranyl group, acetyl group, benzyl group, p-methoxy. Represents a protecting group selected from benzyl groups)

Alternatively, the compound represented by the following general formula (b) can be preferably used.

(Z in the general formula is tert-butoxycarbonyl group, benzyloxycarbonyl group, trimethylsilyl group, tert-butyldimethylsilyl group, methoxymethyl group, ethoxymethyl group, tetrahydropyranyl group, acetyl group, benzyl group, p-methoxy. Represents a protecting group selected from benzyl groups)

From the viewpoint of heat resistance, the compound represented by the following general formula (a) can be preferably used.

(Z in the general formula is tert-butoxycarbonyl group, benzyloxycarbonyl group, trimethylsilyl group, tert-butyldimethylsilyl group, methoxymethyl group, ethoxymethyl group, tetrahydropyranyl group, acetyl group, benzyl group, p-methoxy. Represents a protecting group selected from benzyl groups)

In addition, an organic compound (A') having a carbon-carbon double bond having no acid-degradable group can also be used in the reaction in combination with the component (A).

Specific examples of the component (A') include diallyl phthalate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, diallylidene pentaerythritol, and diallyl monomethylisocyanurate. Dialyl monopropyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl monobenzyl isocyanurate, diallyl dimethyl glycol uryl, 1,4-butanediol divinyl ether, nonanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, tri Ethylene glycol divinyl ether, bisphenol S diallyl ether, divinylbenzene, divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, 1,3-bis (allyloxy) adamantan, 1,3-bis (Vinyloxy) adamantan, dicyclopentadiene, vinylcyclohexene, 1,5-hexadiene, 1,9-decadien, diallyl ether, bisphenol A diallyl ether, 2,5-diallylphenol allyl ether, represented by the following general formula (c). Compound to be

And so on.

As the component (A'), diallyl monomethylisocyanurate is used from the viewpoint that the obtained cured product is less colored and has high heat resistance. Dialyl monopropyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl monobenzyl isocyanurate, vinylcyclohexene, dicyclopentadiene, and diallyl ether of 2,2-bis (4-hydroxycyclohexyl) propane are preferred.

In particular, diallyl monomethylisocyanurate represented by the following general formula (d) from the viewpoint of high heat resistance and light resistance. Dialyl monopropyl isocyanurate and its derivatives are particularly preferred.

(R in the formula indicates a hydrogen atom or a monovalent organic group having 1 to 50 carbon atoms)
The compound represented by is preferable.

(Component (B): Silicon compound having two SiH groups in one molecule)
The component (B) can be used without particular limitation as long as it is a silicon compound having two SiH groups, that is, a compound having two SiH groups in the molecule. The most commonly available ones are SiH group-terminated linear polysiloxanes, which are monopolymers of dimethylsiloxane units, diphenylsiloxane units, methylphenylsiloxane units, and copolymers of each siloxane unit. The above is not particularly limited as long as it is a polyorganosiloxane polymer whose end is closed with a dimethylhydrogensilyl group. Specifically, for example, 1,1,3,3-tetramethyldisiloxane, 1,1,3,3,5,5,-hexamethyltrisiloxane, 1,1,5,5-tetramethyl-3. , 3-Diphenyltrisiloxane and the like are exemplified as preferable examples. Further, silicon-based compounds other than the polysiloxane compound at the end of the SiH group can also be used, and for example, 1,4-bis (dimethylsilyl) benzene, 1,4-bis (diphenylsilyl) benzene, and 1,4-bis ( Methylphenylsilyl) benzene, etc. are specifically mentioned.

(Component (C): A compound having one carbon-carbon double bond and one acid anhydride group in one molecule)
As the component (C), any compound having one carbon-carbon double bond and one acid anhydride group in one molecule can be used without particular limitation. Specific examples include maleic anhydride, citraconic anhydride, itaconic acid anhydride, allylsuccinic anhydride, nadic acid anhydride, methylnagic acid anhydride, tetrahydrophthalic anhydride, tetrahydromethylphthalic anhydride, and tetramethyl. Phthalic anhydride is mentioned. From the viewpoint of reactivity, nadic acid anhydride, methyl nagic acid anhydride, and allyl succinic acid anhydride are preferable.

(Reaction of components (A), (B), (C))
A hydrosilylation reaction is used as a method for obtaining a modified siloxane diic acid anhydride by reacting the components (A), (B) and (C). In this case, a catalyst may be used for the purpose of allowing the reaction to proceed smoothly.

As the catalyst for the hydrosilylation reaction, for example, the following can be used. Platinum alone, a carrier such as alumina, silica, carbon black, etc. on which solid platinum is supported, platinum chloride acid, a complex of platinum chloride acid with alcohol, aldehyde, ketone, etc., a platinum-olefin complex (for example, Pt (CH) ₂ = CH ₂ ) ₂ (PPh ₃ ) ₂ , Pt (CH ₂ = CH ₂ ) ₂ Cl ₂ ), Platinum-vinylsiloxane complex (for example, Pt (ViMe ₂ SiOSiMe ₂ Vi) _n , Pt [(MeViSiO) ₄ ] _m ), platinum-phosphine complex (eg Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ), platinum-phosphite complex (eg Pt [P (OPh) ₃ ] ₄ , Pt [P (OBu) _{3). 4} ) (In the formula, 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 catalyst. Also, the platinum-hydrogen complex described in Ashby's US Pat. Nos. 3,159,601 and 3159662, and the platinum alcoholate described in Lamoreoux's US Pat. No. 3220972. Examples include catalysts. Further, the platinum chloride-olefin complex described in Modic's US Pat. No. 3,516,946 is also useful in the present invention.

Further, examples of catalysts other than platinum _{compounds, RhCl (PPh) 3, RhCl} 3, RhAl 2 O 3, RuCl 3, IrCl 3, FeCl 3, AlCl 3, PdCl 2 · 2H 2 O, NiCl 2, TiCl 4 , Etc. can be mentioned.

Among these, platinum chloride acid, platinum-olefin complex, platinum-vinylsiloxane complex and the like are preferable from the viewpoint of catalytic activity. Further, these catalysts may be used alone or in combination of two or more.

Regarding the reaction order of the components (A), (B), and (C), first, the components (A) and (B) are reacted by hydrosilylation under the condition that the amount of SiH group is increased, and then the component (C) is reacted. A modified siloxane diichydride can be obtained by sequentially reacting with and introducing an acid anhydride group at the terminal.

(About polyimide resin)
The polyimide resin obtained by using the modified siloxane diacid anhydride of the present invention is generally obtained by reaction with a diamine compound or a diisocyanate compound, and is not particularly limited.

Examples of the diamine used for the polyimide synthesis of the present invention include [bis (4-amino-3-carboxy) phenyl] methane, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4, 4'-Diaminophenyl ethane, 4,4'-diaminophenyl ether, 4,4'-didiaminophenyl sulfide, 4,4'-didiaminophenyl sulfone, 1,5-diaminonaphthalene, 3,3-dimethyl-4 , 4'-Diaminobiphenyl, 5-amino-1- (4'-aminophenyl) -1,3,3-trimethylindan, 6-amino-1- (4'-aminophenyl) -1,3,3- Trimethylindan, 4,4'-diaminobenzanilide, 3,5-diamino-3'-trifluoromethylbenzanilide, 3,5-diamino-4'-trifluoromethylbenzanilide, 3,4'-diaminodiphenyl ether, 2,7-Diaminofluorene, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4'-methylene-bis (2-chloroaniline), 2,2', 5,5'-tetrachloro- 4,4'-Diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'- Diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane , 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] ) Phenyl] Hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) -biphenyl, 1, 3'-bis (4-aminophenoxy) benzene, 1,3'-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 4,4'-(p-phenylene isopropylidene) ) Bisaniline, 4,4'-(m-phenylene isopropylidene) bisaniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-bis [4-( 4-Amino-2-trifluoromethyl) phenoxy] -aromatic diamines such as octafluorobiphenyl; two amino groups bonded to an aromatic ring such as diaminotetraphenylthiophene and heteroatoms other than the nitrogen atom of the amino groups. Aromatic diamines with; 1,1-methoxylylene diamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1,4 -Diaminocyclohexane, Isophorondiamine, Tetrahydrodicyclopentadiene diamine, Hexahydro-4,7-Metanoindanylenedimethylenediamine, Tricyclo [6,2,1,02.7] -Undecylendimethyldiamine, 4,4 Examples thereof include aliphatic diamines such as ′ -methylenebis (cyclohexylamine), alicyclic diamines and the like, and derivatives thereof, and a mixture thereof can be preferably used alone or in an arbitrary ratio.

Further, for the purpose of improving the solubility of the resin in the solvent and ensuring the coatability, it is preferable that the above-mentioned polyimide resin has an alicyclic structure or a sulfone group in the polymer molecule. The method for introducing the alicyclic structure into the polymer molecule is not limited, but it can be easily introduced by using a diamine as a raw material or a tetracarboxylic dian compound having these structures. Although the diamine compound has been described, a diisocyanate compound in which the amino group of the diamine compound is replaced with an isocyanate group can also be used in the same manner as the diamine compound.

(Positive photosensitive polyimide resin composition)
A positive photosensitive resin composition can be obtained by adding a photoacid generator to the polyimide resin obtained by the above method. The type of photoacid generator used in the present invention is not particularly limited, and a plurality of photoacid generators may be used in combination.

Preferred photoacid generators include aromatic sulfonium salts and iodonium salts, oxime sulfonates, imide sulfonates and carboxylic acid esters. Among these, oxime sulfonates and imide sulfonates are preferable because the light sensitivity is high. Although not particularly limited acid compound produced by light, preferably it has an acid strength to decompose an acid-decomposable group efficiently, for _{^{example, CF 3 SO 3 - H +}} , C 4 F 9 SO 3 - H + _{, B (C 6 F 5)} 4 - H +, PF 6 - H +, SbF 6 - H + , and the like.

The content of the photoacid generator in the positive photosensitive resin composition is not particularly limited, but from the viewpoint of curability, it is 0.01 to 10 parts by weight with respect to 100 parts by weight of the component (A). It is preferable to have. 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. Further, if the amount of the photoacid generator is large, the color may remain on the cured product, the color may be colored due to rapid curing, the heat resistance may be impaired, or the light resistance may be impaired, which may not be preferable.

(Photosensitizer)
The positive photosensitive resin composition may contain a photosensitizer. By adding a photosensitizer, the sensitivity of the positive photosensitive resin composition to visible light and the like can be improved, and further, g-line (436 nm), h-line (405 nm), i-line (365 nm) and the like can be improved. Sensitivity can be given to high-wavelength light. By using these sensitizers in combination with the above-mentioned cationic polymerization initiator, radical polymerization initiator, photoacid generator and the like, the curability of the above-mentioned positive photosensitive resin composition can be adjusted. can. Examples of the sensitizer include anthracene-based compounds and thioxanthone-based compounds.

Specific examples of the anthracene-based compound include anthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dimethylanthracene, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-. Diethoxyanthracene, 1,4-dimethoxyanthracene, 9-methylanthracene, 2-ethylanthracene, 2-tert-butyl anthracene, 2,6-di-tert-butyl anthracene, 9,10-diphenyl-2,6-di -Tart-butyl anthracene and the like can be mentioned. From the viewpoint of being particularly easily available, as the anthracene-based compound, anthracene, 9,10-dimethylanthracene, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diethoxyanthracene and the like are preferable.

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

(solvent)
Further, when used as a photosensitive resin composition, since it is often used by coating it on a substrate, it is diluted with a solvent to obtain a photosensitive resin composition, but the solvent that can be used is not particularly limited and is not particularly limited. Specifically, hydrocarbon solvents such as benzene, toluene, hexane and heptane, ether solvents such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane and diethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone and the like. Examples thereof include a ketone solvent such as propylene glycol-1-monomethyl ether-2-acetate (PGMEA) and a glycol solvent such as ethylene glycol diethyl ether, and a halogen solvent such as chloroform, methylene chloride and 1,2-dichloroethane.

(About pattern formation method)
The laminate (base material / photosensitive resin composition) obtained by coating the positive photosensitive resin composition on a substrate in a layered manner with a thickness of 1 to 5 μm and drying it is exposed to an alkaline developer. A pattern can be formed by developing with.

As the light source for exposing the positive photosensitive resin composition, a light source that emits the absorption wavelengths of the photoacid generator and the sensitizer to be used may be used, and usually includes a wavelength in the range of 200 to 450 nm. A light source (eg, high pressure mercury lamp, ultrahigh pressure mercury lamp, metal halide lamp, high power metal halide lamp, xenon lamp, carbon arc lamp, light emitting diode, etc.) can be used.

The exposure amount for reacting the positive photosensitive resin composition is not particularly limited, but is preferably 1 to 10000 mJ / cm ² , more preferably 1 to 3000 mJ / cm ² . If the exposure amount is small, the positive photosensitive resin composition may not react. If the amount of exposure is large, the reaction may proceed excessively and the pattern of the desired shape may not be obtained.

Further, for the purpose of removing the solvent and improving the physical properties of the cured product, heat may be applied before and after exposure to prebake and afterbake. The curing temperature can be appropriately set, but is preferably 40 to 400 ° C, more preferably 60 to 350 ° C.

There is no particular limitation on the patterning formation with the alkaline developer, and a desired pattern can be formed by dissolving and removing the exposed portion by a developing method such as a commonly used dipping method or spraying method.

Further, the developer used in alkaline development can be used without particular limitation as long as it is generally used. Specific examples of the developer include organic alkaline aqueous solutions such as tetramethylammonium hydroxide (TMAH) aqueous solution and choline aqueous solution, potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, potassium carbonate aqueous solution, sodium carbonate aqueous solution and lithium carbonate aqueous solution. Examples thereof include an inorganic alkaline aqueous solution. The aqueous solution may contain alcohol, a surfactant and the like for adjusting the dissolution rate and the like. The concentration of the aqueous solution is preferably 25% by weight or less, more preferably 10% by weight or less, still more preferably 5% by weight or less, from the viewpoint that the contrast between the exposed portion and the unexposed portion is easily obtained. ..

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the following examples.

(Evaluation of patterning property)
A patterning property evaluation sample was prepared using the resin compositions obtained in Examples and Comparative Examples. First, the resin compositions obtained in Examples and Comparative Examples were spin-coated on a glass substrate so as to have a film thickness of 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 Dainippon Kaken Co., Ltd.), exposure was performed with the optimum integrated light intensity for each resin composition through a mask engraved with a 50 μm line and space pattern (soft). Contact exposure), left for 1 minute after exposure. Then, it was immersed in an alkaline developer (TMAH 2.38% aqueous solution) for 180 seconds and then washed with water for 30 seconds to form a pattern. Then, it was heated on a hot plate at 230 ° C. for 30 minutes to obtain a sample for evaluation of patterning property.

The pattern shape of the obtained patterning property evaluation sample was observed using a 3D measurement laser microscope (LEXT OLS4000, manufactured by Olympus) and a stylus type surface shape measuring instrument (Dektak150, manufactured by Veeco), and a 50 μm line and space was observed. The condition was evaluated according to the following criteria.

<Evaluation criteria>
◯: Practical level (no residual film in 50 μm line and space)
×: Level not suitable for practical use (remaining film on 50 μm line and space)

(Adhesion evaluation)
The polyimide resin solutions obtained in Examples and Comparative Examples were spin-coated on a Cu film-forming wafer substrate with a film thickness of 5 μm and then heated on a hot plate at 250 ° C. for 1 hour to form a polyimide resin film. Next, a cross-cut test was performed according to JIS K5600-V-VI (ISO2409) to evaluate the adhesion to the Cu thin film.

● 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

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

(Synthesis Example 1)
Toluene (100 g) and 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane (15 g) were placed in a 500 mL four-necked flask, the gas phase portion was replaced with nitrogen, and the mixture was heated and stirred at an internal temperature of 105 ° C. A mixed solution of 11 g of diallyl isocyanuric acid protected with a tert-butoxycarbonyl group, 10 g of 1'4'-dioxane, and 0.0163 g of a xylene solution of a platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise over 30 minutes. Three hours after the completion of the dropping ^{, it was confirmed by 1} H-NMR that the reaction rate of the allyl group was 100%, and the mixture was cooled at 60 ° C. Then, a mixed solution of 1.5 g of allyl succinic anhydride and 3 g of toluene was added dropwise. Five hours after the completion of the dropping, ¹ H-NMR confirmed that the reaction rate of the double bond of the allyl succinic anhydride was 100%, and the cooling reaction was completed. Toluene was distilled off under reduced pressure to obtain a modified siloxane compound A having an acid anhydride group at the end.

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

(Synthesis Example 2)
Toluene (100 g) and 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane (15 g) were placed in a 500 mL four-necked flask, the gas phase portion was replaced with nitrogen, and the mixture was heated and stirred at an internal temperature of 105 ° C. A mixed solution of 15 g of diallyl bisphenol S protected with a tert-butoxycarbonyl group, 10 g of 1'4'-dioxane, and 0.0163 g of a xylene solution of a platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise over 30 minutes. Three hours after the completion of the dropping ^{, it was confirmed by 1} H-NMR that the reaction rate of the allyl group was 100%, and the mixture was cooled at 60 ° C. Then, a mixed solution of 1.5 g of allyl succinic anhydride and 3 g of toluene was added dropwise. Five hours after the completion of the dropping, ¹ H-NMR confirmed that the reaction rate of the double bond of the allyl succinic anhydride was 100%, and the cooling reaction was completed. Toluene was distilled off under reduced pressure to obtain a modified siloxane compound B having an acid anhydride group at the end.

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

(Synthesis Example 3)
Toluene (100 g) and 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane (15 g) were placed in a 500 mL four-necked flask, the gas phase portion was replaced with nitrogen, and the mixture was heated and stirred at an internal temperature of 105 ° C. 30 a mixture of 8 g of diallyl isocyanuric acid protected by a tert-butoxycarbonyl group, 2 g of diallyl monomethylisocyanurate, 10 g of 1'4'-dioxane, and 0.0163 g of a xylene solution of a platinum vinylsiloxane complex (containing 3 wt% as platinum). Dropped over minutes. Three hours after the completion of the dropping ^{, it was confirmed by 1} H-NMR that the reaction rate of the allyl group was 100%, and the mixture was cooled at 60 ° C. Then, a mixed solution of 1.5 g of allyl succinic anhydride and 3 g of toluene was added dropwise. Five hours after the completion of the dropping, ¹ H-NMR confirmed that the reaction rate of the double bond of the allyl succinic anhydride was 100%, and the cooling reaction was completed. Toluene was distilled off under reduced pressure to obtain a modified siloxane compound C having an acid anhydride group at the end.

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

(Synthesis Example 4)
Toluene (100 g) and 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane (15 g) were placed in a 500 mL four-necked flask, the gas phase portion was replaced with nitrogen, and the mixture was heated and stirred at an internal temperature of 105 ° C. A mixed solution of 11 g of diallyl isocyanuric acid protected with a tert-butoxycarbonyl group, 10 g of 1'4'-dioxane, and 0.0163 g of a xylene solution of a platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise over 30 minutes. Three hours after the completion of the dropping ^{, it was confirmed by 1} H-NMR that the reaction rate of the allyl group was 100%, and the mixture was cooled at 60 ° C. Then, a mixed solution of 1.2 g of itaconic acid anhydride and 3 g of toluene was added dropwise. Five hours after the completion of the dropping ^{, it was confirmed by 1} H-NMR that the reaction rate of the double bond of the itaconic acid anhydride was 100%, and the cooling reaction was completed. Toluene was distilled off under reduced pressure to obtain a modified siloxane compound D having an acid anhydride group at the end.

Next, in a 200 mL flask, 20 g of N, N-dimethylformamide, 2.5 g of the modified siloxane compound D obtained above, and 1.5 g of 2,2-bis (4-aminophenyl) hexafluoropropane were placed as a solvent. The mixture was charged and stirred at room temperature and a nitrogen atmosphere for 30 minutes. Further, 5 g of N, N-dimethylformamide, 0.8 g of pyridine and 1.5 g of acetic anhydride were sequentially put into a flask, and the mixture was stirred for 3 hours while heating at 90 ° C. After returning to room temperature, 500 mL of isopropyl alcohol was put into the flask, and the precipitate was collected. Further, washing with 500 mL liter of isopropyl alcohol was carried out three times, and the obtained precipitate was dried under reduced pressure at 80 ° C. for 6 hours to obtain a polyimide resin D.

(Composite Comparative Example 1)
In a 200 mL flask, 20 g of N, N-dimethylformamide, 1.0 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, and siloxane diamine (trade name: KF-8010, Shin-Etsu Chemical Co., Ltd.) were used as solvents. 1.0 g of (manufactured by Kogyo Co., Ltd.) and 2.5 g of 2,2'-hexafluoropropyridene diphthalic acid dianhydride were added, and the mixture was stirred at room temperature and in a nitrogen atmosphere for 30 minutes. Further, 5 g of N, N-dimethylformamide, 0.8 g of pyridine and 1.5 g of acetic anhydride were sequentially put into a flask, and the mixture was stirred for 3 hours while heating at 90 ° C. After returning to room temperature, 500 mL of isopropyl alcohol was put into the flask, and the precipitate was collected. Further, washing with 500 mL liter of isopropyl alcohol was carried out three times, and the obtained precipitate was dried under reduced pressure at 80 ° C. for 6 hours to obtain a polyimide resin E'.

Next, 3 g of polyimide resin E'was added to 50 mL of THF with 0.1 g of pyridine and 3 g of di-tert-butyl dicarbonate, and the mixture was stirred at 70 ° C. for 1 hour. The completion of the protection reaction was confirmed by the disappearance of the NH peak of isocyanuric acid by H ^{1-NMR, and the polyimide resin E in which the phenolic acid group was protected was obtained.}

(Example 1)
As the polyimide resin, 0.50 g of the polyimide resin A described in Synthesis Example 1 and 0.10 g of 1,8-naphthalenedicarboxylic acid imide trifluoromethyl sulfonate as a photoacid generator are used as a solvent PGMEA (propylene glycol monomethyl ether acetate) 3.5 g. The photosensitive composition 1 was prepared by dissolving in.

(Example 2)
As the polyimide resin, 0.50 g of the polyimide resin B described in Synthesis Example 2 and 0.10 g of 1,8-naphthalenedicarboxylic acid imide trifluoromethyl sulfonate as a photoacid generator are used as a solvent PGMEA (propylene glycol monomethyl ether acetate) 3.5 g. The photosensitive composition 2 was prepared.

(Example 3)
As the polyimide resin, 0.50 g of the polyimide resin C described in Synthesis Example 3 and 0.10 g of 1,8-naphthalenedicarboxylic acid imide trifluoromethyl sulfonate as a photoacid generator are used as a solvent PGMEA (propylene glycol monomethyl ether acetate) 3.5 g. The photosensitive composition 3 was prepared.

(Example 4)
As the polyimide resin, 0.50 g of the polyimide resin D described in Synthesis Example 4 and 0.10 g of 1,8-naphthalenedicarboxylic acid imide trifluoromethyl sulfonate as a photoacid generator are used as a solvent PGMEA (propylene glycol monomethyl ether acetate) 3.5 g. The photosensitive composition 4 was prepared.

(Comparative Example 1)
3. As the polyimide resin, 0.50 g of the polyimide resin E described in Synthetic Comparative Example 1 and 0.10 g of 1,8-naphthalenedicarboxylic acid imide trifluoromethyl sulfonate as a photoacid generator are used as a solvent PGMEA (propylene glycol monomethyl ether acetate). The photosensitive composition 5 was prepared by dissolving it in 5 g.

(result)
The polyimide resin solutions obtained in Examples 1 to 4 and Comparative Example 1 were evaluated as described above. The results are shown in Table 1.

The present invention can be used in various fields such as insulating interlayer films for electronic devices such as semiconductors and displays, adhesives, coating agents and encapsulants.

Claims (7)

(A) an organic compound having two carbon-carbon double bonds and an acid anhydride group in one molecule, (B) a silicon compound having two SiH groups in one molecule, and (C) carbon in one molecule. -A modified siloxane diic acid anhydride having the following structure, which is obtained by reacting a compound having a carbon double bond and one acid anhydride group at a time, and having an acid anhydride group at the terminal.

(In the above chemical formula, G has a protected acidic group, has 1 to 50 carbon atoms in the main chain, and is a kind of H atom, O atom, N atom, halogen atom, or S atom. Alternatively, it is represented by an organic group containing two or more kinds, X is an organic group having an acid anhydride group in the structure, R is an organic group represented by 1 to 20 carbon atoms, and n and m are 1 to 50. (It is an integer) The modified siloxane diic acid anhydride according to claim 1, wherein the component (C) is selected from the compounds described below.

The modified siloxane diic acid anhydride according to claim 1 or 2, wherein the component (A) is a compound having at least an N atom or an S atom.
A polyimide resin obtained by reacting the modified siloxane diic anhydride according to any one of claims 1 to 3 with a diamine compound or a diisocyanate compound. The polyimide resin according to claim 4, wherein the component (A) is represented by the following general formula (a). (Z in the following general formula is tert-butoxycarbonyl group, benzyloxycarbonyl group, trimethylsilyl group, tert-butyldimethylsilyl group, methoxymethyl group, ethoxymethyl group, tetrahydropyranyl group, acetyl group, benzyl group, p- Represents a protecting group selected from methoxybenzyl groups)

The polyimide resin according to claim 4 or 5, wherein the component (A) is represented by the following general formula (b). (Z in the following general formula is tert-butoxycarbonyl group, benzyloxycarbonyl group, trimethylsilyl group, tert-butyldimethylsilyl group, methoxymethyl group, ethoxymethyl group, tetrahydropyranyl group, acetyl group, benzyl group, p- Represents a protecting group selected from methoxybenzyl groups)

A positive photosensitive composition containing the polyimide resin according to any one of claims 4 to 6 and a photoacid generator as essential components.