JP2011123277A - Photo-curable resin composition, film-shaped adhesive, and adhesive sheet using the composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photo-curable resin composition capable of forming a pattern and also having a function as an adhesive that performs thermo compression bonding of substrates to each other and an adhesive using the same. <P>SOLUTION: The photo-curable resin composition contains a polyimide silicone having a primary alcoholic hydroxyl group, as a component (A); at least one compound selected from the group consisting of an amino condensation product modified with formalin or a formalin-alcohol and a phenol compound having two or more in average of methylol group or alkoxymethylol group in one molecule thereof, as a component (B); a photo-acid generator as a component (C); and a multifunctional epoxy compound as a component (D). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a photocurable resin composition that can form a pattern and also has a function as an adhesive capable of thermocompression bonding substrates, and a film-like adhesive and an adhesive sheet using the same.

  In recent years, in semiconductor package technology at the wafer level, there is a demand for a material that can form a fine pattern and also has a function as an adhesive that bonds wafer substrates together. As such a curable resin composition capable of forming a pattern, the following resins and compositions thereof have been reported so far.

  For example, a composition comprising a carboxyl group-containing polymer, a bismaleimide, an allyl group-containing polymer, an ethylenically unsaturated compound, an organic peroxide, a photopolymerization initiator and the like has been reported (Patent Document 1). In addition, a composition comprising a methacryl-modified bisphenol containing a hydroxyl group or a carboxyl group, an epoxy resin, a polyfunctional acrylate and the like has been reported (Patent Document 2).

  Polyimide is prominent as a resin having high adhesion and heat resistance to a silicon substrate and a metal surface, and compositions using this as a base resin have been reported (Patent Document 3 and Patent Document 4). Moreover, the composition which combined the carboxyl group containing polyimide, the epoxy resin, and the photobase generator has been reported (patent document 5). Furthermore, as a product developed using polyimide as a base resin with an emphasis on fine pattern formation, the side chain alcohol group of a ring-closed solvent-soluble polyimide and the alkoxy group-containing melamine compound are based on a photoacid generator. A composition that undergoes photocrosslinking is known (Patent Document 6).

JP 2006-323089 JP 2009-9110 International Publication No. 2007/004569 JP 2008-274269 A JP 2009-167381 A JP 2006-133757 A

  The compositions described in Patent Document 1 and Patent Document 2 are compositions that can be patterned by alkali development, but cannot be said to satisfy sufficient performance with respect to curability, substrate adhesion at high temperatures, and reliability. .

  The compositions described in Patent Document 3 and Patent Document 4 are compositions comprising a polyimide having a carboxyl group in the side chain, a polyfunctional acrylic, a photopolymerization initiator, etc., but the curing system is used for crosslinking by radical polymerization. There is a possibility that reaction inhibition by oxygen may occur, and there is a problem that patterning property with high sensitivity and a remaining film at the time of development are insufficient.

  The composition described in Patent Document 5 is cured by epoxy crosslinking with a base generated by light and is excellent in sticking property at a low temperature, but it is insufficient in terms of fine patterning property. Moreover, although the composition of patent document 6 is excellent as a protective film of wiring, the bonding adhesiveness of a board | substrate is not enough.

  In the present invention, a fine pattern can be formed, and thereafter a substrate such as silicon or glass can be bonded with high precision and strength by thermocompression bonding through this pattern layer and post-curing, and various types It is an object to provide a composition capable of having reliability and a dry film thereof.

The present invention relates to the following.
<1> Polyimide silicone having a primary alcoholic hydroxyl group as component (A),
As the component (B), one or more kinds selected from the group consisting of an amino condensate modified with formalin or formalin-alcohol and a phenol compound having two or more methylol groups or alkoxymethylol groups on average in one molecule Compound,
(C) As a component, a photoacid generator,
(D) The photocurable resin composition characterized by containing a polyfunctional epoxy compound as a component.
<2> The photocurable resin composition according to <1>, wherein the component (A) is a polyimide silicone represented by the following general formula (1).

[In Formula (1),
k and m are positive integers and are numbers satisfying 0.01 ≦ k / (k + m) <1.
X is a tetravalent organic group represented by the following general formula (2).

(In the formula (2), R ¹ is independently a monovalent hydrocarbon group having 1 to 8 carbon atoms, R ² is independently a trivalent organic group, and n is an average of It is a number from 1 to 120.)
Y is a divalent organic group, at least a part of which is represented by the general formula (3).

(In Formula (3), A is

May be the same or different from each other, and B and C are each an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and may be the same or different from each other. A is 0 or 1, b is 0 or 1, and c is an integer of 0 to 10. In formula (3), R ³ is a monovalent group selected from a phenolic hydroxyl group or an alcoholic hydroxyl group-containing organic group, and at least one of R ³ is a primary alcoholic hydroxyl group-containing organic group. )
W is a tetravalent organic group other than X. ]

<3> The photocurable resin composition according to <2>, wherein in General Formula (1), W is a tetravalent organic group containing at least one kind represented by the following formula.

<4> 100 parts by mass of component (A), 0.5-50 parts by mass of component (B), 0.05-20 parts by mass of component (C), 0.05-100 parts by mass of component (D) The photocurable resin composition according to any one of <1> to <3>, which is contained.
<5> The component (D) is at least one polyfunctional epoxy compound selected from the group consisting of a polyfunctional epoxy compound having a bisphenol skeleton, a phenol novolac polyfunctional epoxy compound, and a polyfunctional epoxy silicone. The photocurable resin composition according to any one of <1> to <4>.
<6> A film adhesive formed by forming the photocurable resin composition according to any one of <1> to <5> into a film.
<7> (I) a base film layer;
(II) a photocurable resin layer formed by forming the photocurable resin composition according to any one of <1> to <5> into a film having a thickness of 1 to 200 μm;
(III) An adhesive sheet comprising a cover film layer.

  According to the present invention, it is possible to form a fine pattern, and thereafter, a substrate such as silicon, glass, etc. can be bonded with high precision and firmly by thermocompression bonding through this pattern layer and post-curing, And the composition which can combine various reliability, and its dry film are provided. Furthermore, development at the time of pattern formation can be performed with an alkaline aqueous solution having a small environmental load, and the heat curing temperature can be set to 220 ° C. or lower.

2 is a 1H-NMR chart of polyimide silicone of Synthesis Example 1. FIG. 2 is a 1H-NMR chart of polyimide silicone of Synthesis Example 2. FIG. 6 is a 1H-NMR chart of polyimide silicone of Synthesis Example 3. FIG. 6 is a 1H-NMR chart of polyimide silicone of Synthesis Example 4. FIG.

  Hereinafter, the present invention will be described in more detail.

(A) Component The polyimide silicone containing a primary alcoholic hydroxyl group, which is the (A) component in the photocurable resin composition of the present invention, is preferably represented by the following general formula (1).

  Further, X in the formula (1) has a structure represented by the formula (2). By including the unit, flexibility is imparted to the polymer main chain skeleton, and flexibility is imparted to the resin itself.

In formula (2), R ¹ is independently a monovalent hydrocarbon group having 1 to 8 carbon atoms, such as an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, or a hexyl group. A cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; an aryl group such as a phenyl group; an aralkyl group such as a benzyl group or a phenethyl group; an alkenyl group such as a vinyl group, an allyl group, a propenyl group, an isopropenyl group, or a butenyl group. Can be mentioned. From the viewpoint of easy availability of raw materials, a methyl group, an ethyl group, a phenyl group, and a vinyl group are preferable.

In the formula (2), R ² is a trivalent organic group independently of each other. For example, an alkyl succinic anhydride such as propyl succinic anhydride, norbornyl anhydride, propyl nadic acid anhydride, phthalic acid Examples thereof include a carboxyl group or a residue obtained by removing a carboxyl group anhydride from an anhydride or the like. Preferred are norbornyl anhydride and propyl succinic anhydride. N is an integer of 1 to 120, preferably 3 to 80, more preferably 5 to 50.

  Examples of X include the following structures.

In the above structure, n ₁ and n ₂ are 0 or an integer of 1 or more and satisfy n ₁ + n ₂ = n.
N ₃ and n ₄ are 0 or an integer of 1 or more and satisfy n ₃ + n ₄ = n.
N ₅ and n ₆ are 0 or an integer of 1 or more and satisfy n ₅ + n ₆ = n.

  More specific examples of X include the following structures.

  X is obtained by reacting an organohydrogenpolysiloxane with an acid anhydride having an unsaturated group, for example, succinic acid anhydride, norbornyl acid anhydride, propyl nadic acid anhydride, or phthalic acid anhydride. It can be derived from the resulting modified silicone. Depending on the distribution of the number of siloxane units in the organohydrogenpolysiloxane, the number of siloxane units of the resulting acid anhydride-modified polysiloxane is also distributed. Therefore, n in the formula (2) represents the average value.

  At least a part of Y in the general formula (1) is a divalent organic group having a primary alcoholic hydroxyl group represented by the following general formula (3).

  In formula (3), A is independently selected from any of the following divalent organic groups.

In formula (3), a is 0 or 1, b is 0 or 1, c is an integer of 0 to 10, and c is an integer of 1 to 10.
In formula (3), B and C are each an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and may be the same or different from each other, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. Of these, a methyl group and a hydrogen atom are preferable from the viewpoint of easy availability of raw materials.
In the above formula (3), R ³ is a monovalent group selected from a phenolic hydroxyl group or an alcoholic hydroxyl group-containing organic group, and at least one of R ³ is a primary alcoholic hydroxyl group-containing organic group. Specific examples include —OH, —OCH ₂ CH (OH) CH ₂ OH, and —OCH (CH ₂ OH) CH ₂ OH.
Examples of the group represented by the formula (3) include the following groups.

  The other part of Y may be a divalent organic group other than that represented by the general formula (3). That is, the polyimide silicone represented by the formula (1) is preferably a polyimide silicone represented by the general formula (1-1).

In formula (1-1), X and W are as described above.
Y ₁ is a divalent organic group represented by the general formula (3), and Y ₂ is a divalent organic group other than that represented by the general formula (3).
p and r are positive integers, q and s are 0 or positive integers, and satisfy p + q = k and r + s = m (k and m are as described above).

Y ₂ is a divalent organic group other than that represented by the general formula (3), that is, a divalent organic group having no primary alcoholic hydroxyl group. Specifically, it is preferably at least one selected from the group consisting of a divalent organic group represented by the following formula (4) and a divalent organic group represented by the formula (5).

In the above formula, D is independently a divalent organic group similar to A above. e and f are independently 0 or 1, and g is 0 or 1.
Examples of the formula (4) include the following groups.

In the formula (5), R ⁴ independently of each other is a monovalent hydrocarbon group having 1 to 8 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, phenyl group , Etc. Among these, a methyl group and a phenyl group are particularly preferable from the viewpoint of obtaining raw materials.
In formula (5), h is an integer of 1 to 80, preferably 1 to 20.

  In the formula (1), W may be various known groups as long as it is a tetravalent organic group other than X, and the following groups are exemplified.

  The molecular weight of the component (A) polyimide silicone resin having each of the above structures is preferably 5,000 to 200,000, particularly preferably 8,000 to 100,000, in terms of number average molecular weight. If the molecular weight is too small, the strength of the resulting coating film may be lowered when the polyimide silicone resin is used. On the other hand, if the molecular weight is too large, the polyimide silicone resin is poorly compatible with the solvent and the handling may be lowered.

  Furthermore, the number k of repeating units including X is a positive integer, preferably 1 to 500, more preferably 3 to 300. The number m of repeating units including W is a positive integer, preferably 1 to 500, more preferably 3 to 300.

  Further, the ratio k / (k + m) of k satisfies 0.01 ≦ k / (k + m) <1. Preferably they are 0.1 or more and less than 1, More preferably, they are 0.2 or more and 0.95 or less, Especially preferably, they are 0.5 or more and 0.9 or less. If the ratio is less than 0.01, it is difficult to achieve sufficient flexibility.

  The polyimide silicone as component (A) preferably has an OH number of 20 to 200 KOHmg / g, particularly 30 to 150 KOHmg / g based on JIS0070.

  In order to produce the polyimide silicone of component (A), first, a diamine having a phenolic hydroxyl group, an acid anhydride-modified silicone, an acid dianhydride, and optionally a phenolic hydroxyl group and a diamine having no carboxyl group are reacted. To obtain a polyamic acid.

  Examples of the diamine having a phenolic hydroxyl group include 3,3′-diamino-4,4′-dihydroxybiphenyl, 2,2′-diamino-4,4′-dihydroxybiphenyl, and 2,2-bis (4-amino). -3-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 9,9-bis (3-amino-4-hydroxyphenyl) fluorene, 2,2'-methylenebis [6 -(4-amino-3,5-dimethylbenzyl) -4-methyl] phenol, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 2,2-bis (3-amino-4-hydroxyphenyl) Examples thereof include diamines having a phenol group such as hexafluoropropane.

  Examples of the acid anhydride-modified silicone include the following compounds.

n is an integer of 1 to 120, preferably 3 to 80, more preferably 5 to 50.
n ₅ and n ₆ are 0 or an integer of 1 or more, and satisfy n ₅ + n ₆ = n.

  Examples of acid dianhydrides used for polymerization of polyamic acid include 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic acid diacid, and the like. Anhydride, 2,3 ′, 3,4′-biphenyltetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid Acid anhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, 1,2,3,4-butanetetra Carboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 4,4′-hexafluoropropylidenebisphthalic dianhydride, 2,2-bis (p-trimellitox Phenyl) propane, 1,3-tetramethyldisiloxane bis phthalic dianhydride, 4,4'-oxydiphthalic anhydride.

  Examples of the diamine having no phenolic hydroxyl group and carboxyl group include 4,4′-diaminobenzanilide, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone, 3 , 3′-dimethyl-4,4′-diaminobiphenyl, 4,4 ′-(p-phenylenediisopropylidene) dianiline, 4,4 ′-(m-phenylenediisopropylidene) dianiline, 1,3-bis ( 4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis 4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4′-bis (4-aminophenoxy) biphenyl, 9,9-bis (4-aminophenyl) ) Fluorene and the like.

  In the synthesis of the polyamic acid, the ratio of the diamine component to the acid dianhydride component is appropriately determined according to the adjustment of the molecular weight of the polyimide and the like, and is usually 0.95 to 1.05, preferably 0.98 to 1. 02 range. In order to introduce a reactive functional group into the polyimide silicone terminal, a functional acid anhydride such as amino alcohol, amino thiol, trimellitic anhydride and an amine compound can be added. In this case, the addition amount is preferably 20 mol% or less with respect to the acid dianhydride component or the diamine component.

  The reaction of diamine and acid dianhydride is usually carried out in a solvent. Such a solvent may be any solvent that dissolves polyimide. Specific examples of the solvent include ethers such as tetrahydrofuran and anisole; ketones such as cyclohexanone, 2-butanone, methyl isobutyl ketone, 2-heptanone, 2-octanone and acetophenone; butyl acetate, methyl benzoate, γ- Esters such as butyrolactone; cellosolves such as butyl cellosolve acetate and propylene glycol monomethyl ether acetate; amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone, and toluene, xylene and the like Aromatic hydrocarbons are mentioned, preferably ketones, esters and cellosolves, particularly preferably γ-butyrolactone, propylene glycol monomethyl ether acetate, N, N-dimethylacetamide, n- Methyl-2-pyrrolidone. These solvents may be used alone or in combination of two or more. Usually, in consideration of the yield per batch, the dissolution viscosity, etc., the polyimide concentration is adjusted within a range of 10 to 40% by mass.

  Next, a polyimide having a phenolic hydroxyl group represented by the general formula (6) is obtained by a dehydration ring-closing reaction of the polyamic acid obtained above, and then glycidol is reacted, and further an acid anhydride is reacted as necessary. Thus, a polyimide silicone represented by the general formula (1) is obtained.

In formula (6), X, W, k, and m are as described above.
Y ′ is at least partly a divalent organic group represented by the following general formula (7).

In formula (7), A, B, C, a, b, and c are as described above, and R ³ is an —OH group.

  That is, for the synthesis of polyimide, the polyamic acid solution obtained above is usually heated to a temperature range of 80 to 200 ° C., preferably 140 to 180 ° C., or an acetic anhydride / pyridine mixed solution is added to the polyamic acid solution. The resulting solution is heated to about 50 ° C., whereby a polyimide can be obtained by advancing a dehydration ring-closing reaction to the acid amide portion of the polyamic acid.

  By adding a necessary equivalent amount of glycidol to a polyimide organic solvent solution having a phenolic hydroxyl group in the molecule represented by the general formula (6) thus obtained and heating, the target general formula ( A polyimide having an alcoholic hydroxyl group represented by 1) can be obtained. The amount of glycidol charged needs to be appropriately changed according to the amount of alcoholic hydroxyl group introduced, but it is usually preferably 0.3 to 3 times mol with respect to the phenolic hydroxyl group. The reaction temperature is 40 ° C to 180 ° C, preferably 60 ° C to 130 ° C. The reaction time is from a few minutes to 12 hours. A catalyst such as triethylamine may be added for the purpose of accelerating the reaction.

  Examples of the acid anhydride that is reacted as needed after the glycidol reaction include phthalic anhydride, norbornene anhydride, cyclohexyl anhydride, methylcyclohexyl anhydride, succinic anhydride, and the like.

In the reaction of the acid anhydride, a required equivalent amount is added and heated to obtain a polyimide silicone having a target carboxyl group and also having an alcoholic hydroxyl group.
The reaction temperature at this time is 10 to 120 ° C., preferably 20 to 90 ° C., and the reaction time is 1 h to 12 h. A catalyst may be added for the purpose of accelerating the reaction.

Component (B) The component (B) used in the present invention is a component that causes a curing reaction with the component (A) described above and can easily form a pattern, and further increases the strength of the cured product. Is.
Such component (B) is selected from the group consisting of an amino condensate modified with formalin or formalin-alcohol and a phenol compound having an average of two or more methylol groups or alkoxymethylol groups in one molecule. More than one kind of compound.

  The compound of the component (B) preferably has a weight average molecular weight of 150 to 10,000, particularly 200 to 3,000. If the weight average molecular weight is less than 150, photocurability may not be obtained in a sufficient photocurable resin composition, and if it exceeds 10,000, the heat resistance after curing of the composition may be deteriorated.

  Examples of the amino condensate modified with formalin or formalin-alcohol as the component (B) include melamine condensate modified with formalin or formalin-alcohol, or urea condensate modified with formalin or formalin-alcohol. It is done.

  The melamine condensate modified with formalin or formalin-alcohol is modified, for example, by first methylating a melamine monomer with formalin according to a known method, or by further alkoxylation with alcohol to modify the following formula (8): It can prepare by setting it as the modified | denatured melamine shown by these. In addition, as said alcohol, a lower alcohol, for example, C1-C4 alcohol, is preferable.

In the formula, R ³ may be the same or different and is a methylol group, an alkoxymethyl group containing a C 1-4 alkoxy group or a hydrogen atom, at least one of which is a methylol group or the above alkoxymethyl group.
Specific examples of the modified melamine of the general formula (8) include trimethoxymethyl monomethylol melamine, dimethoxymethyl monomethylol melamine, trimethylol melamine, hexamethylol melamine, hexamethoxymethylol melamine and the like.
Subsequently, the modified melamine of the general formula (8) or this multimer (for example, an oligomer such as a dimer or trimer) is subjected to addition condensation polymerization with formaldehyde to a desired molecular weight according to a conventional method, and formalin or formalin- A melamine condensate modified with alcohol is obtained. In addition, the monomer of General formula (8) and 1 or more types of modified | denatured melamine condensates of its condensate can be used as (B) component.

  Further, a urea condensate modified with formalin or formalin-alcohol is modified by, for example, modifying a urea condensate having a desired molecular weight with formalin by methylolation according to a known method, or by further modifying this with alkoxylation with alcohol. Can be prepared.

  Specific examples of the modified urea condensate include, for example, methoxymethylated urea condensate, ethoxymethylated urea condensate, propoxymethylated urea condensate and the like. One or more modified urea condensates can be used as the component (B).

  Among the components (B), as a phenol compound having two or more methylol groups or alkoxymethylol groups on average in one molecule, for example, (2-hydroxy-5-methyl) -1,3-benzenedimethanol, 2,2 ′, 6,6′-tetramethoxymethylbisphenol A and the like can be mentioned.

  These amino condensates or phenol compounds of component (B) can be used alone or in combination of two or more.

  The content of the amino condensate or phenol compound as the component (B) of the present invention is preferably 0.5 to 50 parts by mass, particularly 1 to 30 parts by mass with respect to 100 parts by mass of the polyimide silicone of the component (A). Is preferred. If it is less than 0.5 parts by mass, sufficient curability may not be obtained at the time of light irradiation. Conversely, if it exceeds 50 parts by mass, the ratio of polyimide bonds in the photocurable resin composition is reduced, resulting in a cured product. There is a possibility that sufficient effects cannot be exhibited.

Component (C) The photoacid generator of component (C) in the photocurable resin composition of the present invention preferably generates an acid upon irradiation with light having a wavelength of 240 nm to 500 nm and becomes a curing catalyst. Since the composition of the present invention has excellent compatibility with the photoacid generator, a wide range of acid generators can be used. Examples of such photoacid generators include onium salts, diazomethane derivatives, glyoxime derivatives, β-ketosulfone derivatives, disulfone derivatives, nitrobenzyl sulfonate derivatives, sulfonate ester derivatives, imido-yl-sulfonate derivatives, oxime sulfonate derivatives, iminos. Examples thereof include sulfonate derivatives and triazine derivatives.

Among the photoacid generators, examples of the onium salt include compounds represented by the following general formula (9).
(R ⁴ ) _h M ⁺ L ⁻ (9)
In the formula, R ⁴ represents an optionally substituted linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. M ⁺ represents iodonium or sulfonium, L ⁻ represents a non-nucleophilic counter ion, and h represents 2 or 3.
In the above R ⁴ , examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, a 2-oxocyclohexyl group, a norbornyl group, an adamantyl group, and the like. As the aryl group, for example, alkoxyphenyl groups such as o-, m- or p-methoxyphenyl, ethoxyphenyl, m- or p-tert-butoxyphenyl: 2-, 3- or 4-methylphenyl, ethyl Examples thereof include alkylphenyl groups such as phenyl, 4-tert-butylphenyl, 4-butylphenyl and dimethylphenyl. Examples of the aralkyl group include groups such as benzyl and phenethyl.

Examples of non-nucleophilic counter ions of L ⁻ include halide ions such as chloride ions and bromide ions; fluoroalkyl sulfonates such as triflate, 1,1,1-trifluoroethanesulfonate, and nonafluorobutanesulfonate; tosylate and benzene Aryl sulfonates such as sulfonate, 4-fluorobenzene sulfonate, 1,2,3,4,5-pentafluorobenzene sulfonate; alkyl sulfonates such as mesylate and butane sulfonate; hexafluorophosphate ion, fluorinated alkyl fluorophosphate ion, etc. Is mentioned.

  Among the photoacid generators, examples of the diazomethane derivative include compounds represented by the following general formula (10).

In the formula, R ⁵ may be the same or different and is a linear, branched or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, an aryl group or halogenated aryl group having 6 to 12 carbon atoms, Alternatively, it represents an aralkyl group having 7 to 12 carbon atoms.

Examples of the alkyl group in R ⁵ include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group. Examples of the halogenated alkyl group include trifluoromethyl, 1,1,1-trifluoroethyl, 1,1,1-trichloroethyl, nonafluorobutyl, and the like.
As an aryl group, for example, phenyl; alkoxyphenyl group such as o-, m- or p-methoxyphenyl, ethoxyphenyl, m- or p-tert-butoxyphenyl; 2-, 3- or 4-methylphenyl, ethyl Examples thereof include alkylphenyl groups such as phenyl, 4-tert-butylphenyl, 4-butylphenyl and dimethylphenyl. Examples of the halogenated aryl group include fluorobenzene, chlorobenzene, 1,2,3,4,5-pentafluorobenzene and the like. Examples of the aralkyl group include a benzyl group and a phenethyl group.

  Among the photoacid generators, examples of the glyoxime derivative include compounds represented by the following general formula (11).

In the formula, R ⁶ and R ⁷ may be the same or different, and are a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group, an aryl group having 6 to 12 carbon atoms or a halogenated group. An aryl group or an aralkyl group having 7 to 12 carbon atoms is represented. Further, R ⁷ may be bonded to each other to form a cyclic structure, and when forming a cyclic structure, R ⁷ represents a linear or branched alkylene group having 1 to 6 carbon atoms.

Examples of the alkyl group, halogenated alkyl group, aryl group, halogenated aryl group and aralkyl group of R ⁶ and R ⁷ include those exemplified for R ⁵ above. Examples of the alkylene group for R ⁷ include a methylene group, an ethylene group, a propylene group, a butylene group, and a hexylene group.

  Specific examples of the photoacid generator of component (C) include, for example, diphenyliodonium trifluoromethanesulfonate, trifluoromethanesulfonate (p-tert-butoxyphenyl) phenyliodonium, diphenyliodonium p-toluenesulfonate, and p-toluenesulfone. Acid (p-tert-butoxyphenyl) phenyliodonium, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate , Tris (p-tert-butoxyphenyl) sulfonium trifluoromethanesulfonate, p-toluenesulfonic acid triphenylsulfonium, p Toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid bis (p-tert-butoxyphenyl) phenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, nonafluorobutane Triphenylsulfonium sulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl trifluoromethanesulfonate (2-oxocyclohexyl) sulfonium, cyclohexylmethyl p-toluenesulfonate ( 2-oxocyclohexyl) sulfonium, dimethylphenylsulfonium trifluoromethanesulfonate, p- Dienephenylsulfonium trifluorosulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, bis (4-tert-butylphenyl) iodonium hexafluorophosphate, diphenyl (4-thiophenoxyphenyl) sulfonium hexafluoroantimony Onium salts such as nates;

  Bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (xylenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (cyclopentylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis ( Isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-amylsulfonyl) diazomethane, bis ( Isoamylsulfonyl) diazomethane, bis (sec-amylsulfonyl) diazomethane, bis (tert-amylsulfonyl) diazomethane, 1-silane Diazomethane derivatives such as rohexylsulfonyl-1- (tert-butylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-amylsulfonyl) diazomethane, 1-tert-amylsulfonyl-1- (tert-butylsulfonyl) diazomethane ;

  Bis-o- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-o- (p-toluenesulfonyl) -α-diphenylglyoxime, bis-o- (p-toluenesulfonyl) -α-dicyclohexyl Glyoxime, bis-o- (p-toluenesulfonyl) -2,3-pentanedione glyoxime, bis- (p-toluenesulfonyl) -2-methyl-3,4-pentanedione glyoxime, bis-o- ( n-butanesulfonyl) -α-dimethylglyoxime, bis-o- (n-butanesulfonyl) -α-diphenylglyoxime, bis-o- (n-butanesulfonyl) -α-dicyclohexylglyoxime, bis- o- (n-butanesulfonyl) -2,3-pentanedione glyoxime, bis-o- (n-butanesulfonyl) -2-methyl -3,4-pentanedione glyoxime, bis-o- (methanesulfonyl) -α-dimethylglyoxime, bis-o- (trifluoromethanesulfonyl) -α-dimethylglyoxime, bis-o- (1,1,1) 1-trifluoroethanesulfonyl) -α-dimethylglyoxime, bis-o- (tert-butanesulfonyl) -α-dimethylglyoxime, bis-o- (perfluorooctanesulfonyl) -α-dimethylglyoxime, bis- o- (cyclohexanesulfonyl) -α-dimethylglyoxime, bis-o- (benzenesulfonyl) -α-dimethylglyoxime, bis-o- (p-fluorobenzenesulfonyl) -α-dimethylglyoxime, bis-o- (P-tert-butylbenzenesulfonyl) -α-dimethylglyoxime, bis o- (xylene sulfonyl)-.alpha.-dimethylglyoxime, glyoxime derivatives such as bis-o-(camphorsulfonyl)-.alpha.-dimethylglyoxime;

Β-ketosulfone derivatives such as 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane and 2-isopropylcarbonyl-2- (p-toluenesulfonyl) propane;
Disulfone derivatives such as diphenyldisulfone and dicyclohexyldisulfone; nitrobenzyl sulfonate derivatives such as 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate;

Sulfonic acid ester derivatives such as 1,2,3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris (p-toluenesulfonyloxy) benzene ;
Phthalimido-yl-triflate, phthalimido-yl-tosylate, 5-norbornene 2,3-dicarboximido-yl-triflate, 5-norbornene 2,3-dicarboximido-yl-tosylate, 5-norbornene 2,3 -Imido-yl-sulfonate derivatives such as dicarboximido-yl-n-butylsulfonate, n-trifluoromethylsulfonyloxynaphthylimide;
oxime sulfonate derivatives such as α- (benzenesulfonium oxyimino) -4-methylphenylacetonitrile;
(5- (4-Methylphenyl) sulfonyloxyimino 5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5- (4- (4-methylphenylsulfonyloxy) phenylsulfonyloxyimino) -5H -Iminosulfonate derivatives such as -thiophen-2-ylidene)-(2-methylphenyl) -acetonitrile;
2- (methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4, And triazine derivatives such as 6-bis (trichloromethyl) -s-triazine;

  Among these, imido-yl sulfonates, imino sulfonates, oxime sulfonates and the like are preferably used.

  The said photo-acid generator (C) can be used individually by 1 type or in mixture of 2 or more types. 0.05-20 mass parts is preferable with respect to 100 mass parts of polyimide silicone of (A) component, and, as for the compounding quantity of a photo-acid generator (C), 0.2-5 mass parts is especially preferable. If the blending amount is less than 0.05 parts by mass, sufficient photocurability may not be obtained, and if it exceeds 20 parts by mass, the curability in the thick film may deteriorate due to light absorption of the acid generator itself. is there.

(D) component (D) component in the photocurable resin composition of this invention is a polyfunctional epoxy compound which contains 2 or more of epoxy groups in 1 molecule. The polyfunctional epoxy compound undergoes a crosslinking reaction with the base polymer, that is, the component (A) by heat curing after patterning, and is a component for developing high substrate adhesion at the time of substrate bonding.

  As polyfunctional epoxy compounds, glycidyl ethers of phenol, cycloaliphatic epoxy compounds having cyclohexene oxide groups, and epoxy compounds having unsaturated bonds introduced into organosiloxanes containing hydrosilyl groups by hydrosilylation reaction Are preferred.

As the phenol structure of the glycidyl ether of phenol, novolak type, bisphenol type, biphenyl type, phenol aralkyl type, dicyclopentadiene type, naphthalene type, and amino group-containing type can be applied.
Examples of glycidyl ethers of phenol include glycidyl ethers of bisphenol A type, AD type, S type and F type, glycidyl ether of hydrogenated bisphenol A, glycidyl ether of ethylene oxide adduct bisphenol A, glycidyl of propylene oxide adduct bisphenol A Ether, glycidyl ether of phenol novolac resin, glycidyl ether of cresol novolac resin, glycidyl ether of naphthalene resin, glycidyl ether of dicyclopentadiene phenol resin, trifunctional epoxy compound of aminophenol, and the like can be used.

  As the alicyclic epoxy compound having a cyclohexene oxide group, Celoxide 3000 and 2021P manufactured by Daicel Chemical Industries, Ltd. can be used.

  As an epoxy compound having an unsaturated bond introduced into an organosiloxane containing a hydrosilyl group by a hydrosilylation reaction, an epoxy compound having an unsaturated bond to an organosiloxane containing a hydrosilyl group, such as allyl glycidyl ether, Various polyfunctional epoxy compounds obtained by a method of reacting vinyl cyclohexyl epoxide or the like can be used.

As specific structures, compounds represented by the following formulas (12) to (14) are applicable.
That is, epoxy group-containing organopolysiloxane (12);

In the formula, R ⁸ represents an organic group containing an epoxy group, R ⁹ represents a monovalent hydrocarbon group, and R ¹⁰ represents a hydrogen atom or an alkyl group. Further, (m + p) ≧ 1, n ≧ 0, q ≧ 0, (r + s) ≧ 0, 0.1 ≦ (m + p) / (m + n + p + q) ≦ 1.0, 0 ≦ (r + s) / (m + n + p + q + r + s) ≦ 0. The range is 05. Specifically, R ⁸ is preferably a glycidoxypropyl group or a cyclohexylepoxyethyl group, most preferably a glycidoxypropyl group.

  Epoxy group-containing cyclic siloxane (13);

In the formula, R ⁸ and R ⁹ are in the range of 0.2 ≦ t / (t + u) ≦ 1 as above.

  Bissilyl group-substituted compound (14);

In the formula, R ¹¹ is a divalent organic group, specifically, a linear alkylene group such as ethylene, propylene or hexylene group, a disubstituted cyclic saturated hydrocarbon group such as disubstituted cyclopentylene group or cyclohexylene group, It includes a divalent aromatic group such as a phenylene group or a biphenylene group, and a structure in which a plurality of these groups are linked. v and w are integers of 1 to 3.

  As the compounds represented by the formulas (12) to (14), specifically, compounds having the following structures are particularly suitable. Here, x is an integer of 1 to 10, y is an integer of 1 to 5, and z is an integer of 1 to 10.

  The polyfunctional epoxy compound of the said (D) component can be used individually by 1 type or in mixture of 2 or more types. The amount of component (D) is preferably 0.05 to 100 parts by weight, more preferably 0.1 to 50 parts by weight, and still more preferably 1 to 30 parts per 100 parts by weight of polyimide silicone of component (A). Part by mass. If the amount is less than 0.05 parts by mass, the adhesion to the substrate may be insufficient, and if it exceeds 100 parts by mass, the toughness of the cured film is lost and the brittleness tends to become brittle.

  You may mix | blend the organic solvent with the photocurable resin composition of this invention as needed. As an organic solvent, the solvent which can melt | dissolve each component, such as an amino condensate modified with the polyimide resin mentioned above, formalin, or formalin-alcohol, a phenol compound, and a photo-acid generator, is preferable.

  Examples of such an organic solvent include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-amyl ketone; 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1 Alcohols such as ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether; propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, 3-methoxypropionic acid , Esters of ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono-tert-butyl ether acetate, γ-butyrolactone, N-methyl-2-pyrrolidone, N, N- Examples thereof include amides such as dimethylacetamide, and these can be used alone or in combination of two or more.

  Among these, ethyl lactate, cyclohexanone, cyclopentanone, γ-butyrolactone, N, N-dimethylacetamide, and mixed solvents thereof, which have the most excellent solubility of the photoacid generator, are preferable.

  The amount of the organic solvent used is preferably 50 to 2,000 parts by mass, and particularly preferably 100 to 1,000 parts by mass with respect to 100 parts by mass of the total solid content of the components (A) to (D). If the amount is less than 50 parts by mass, the compatibility of each of the components (A) to (D) may be insufficient. Conversely, if the amount exceeds 2,000 parts by weight, the compatibility is not significantly changed. There is a possibility that the viscosity becomes too low to be suitable for resin coating.

  In addition to the above components, an additive component may be further added to the photocurable resin composition of the present invention. As such an additive component, for example, a surfactant conventionally used for improving coating properties can be added. The surfactant is preferably a nonionic one, for example, a fluorine-based surfactant, specifically perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkylamine oxide, fluorine-containing organosiloxane compound. Etc.

  Commercially available products can be used. For example, Florard “FC-4430” (all manufactured by Sumitomo 3M), Surflon “S-141” and “S-145” (all Asahi Glass Co., Ltd.) ), Unidyne "DS-401", "DS-4031" and "DS-451" (all manufactured by Daikin Industries, Ltd.), MegaFuck "F-8151" (manufactured by Dainippon Ink Industries, Ltd.) "X-70-093" (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. Among these, Fluorard “FC-4430” (manufactured by Sumitomo 3M Limited) and “X-70-093” (manufactured by Shin-Etsu Chemical Co., Ltd.) are preferable.

  Further, as another additive component, a light absorbing agent such as a photoacid generator can be added in order to improve the light absorption efficiency. Examples of such a light absorber include diaryl sulfoxide, diaryl sulfone, 9,10-dimethylanthracene, 9-fluorenone and the like. In addition, for adjusting sensitivity, a basic compound, specifically, a tertiary amine compound such as triethanolamine, or a nitrogen-containing atom compound such as benzotriazole or pyridine may be added.

  Further, as adhesion improvers, silane coupling agents such as epoxy silane coupling agents KBM-403, KBM-402, KBE-403, KBE-402, amine silane coupling agents KBM-903, KBM- It is also possible to add 603, KBM-573 (manufactured by Shin-Etsu Chemical Co., Ltd.) or the like alone. Moreover, what hydrolyzed and condensed these hydrolyzable silanes with an appropriate amount of water may be added. As addition amount of these silane coupling agents, 0.1-10 mass parts with respect to 100 mass parts of (A) component, More preferably, 0.2-5 mass parts is preferable.

  When using the photocurable resin composition of this invention for a resist material etc., the other arbitrary addition components normally used for a resist material etc. can be added. In addition, the addition amount of the said addition component can be made into a normal amount in the range which does not prevent the effect of this invention.

  The photocurable resin composition of the present invention is prepared by a usual method. The above components and the above organic solvent, additives and the like are stirred and mixed as necessary, and then the solid content is filtered through a filter or the like as necessary. By doing so, the photocurable resin composition of the present invention can be prepared.

  The photocurable resin composition of the present invention thus prepared is suitable as a material such as a protective film for semiconductor elements, a protective film for wiring, a coverlay film, a solder resist, and a fine processing photoresist. Used. Furthermore, it is suitable as an adhesive used when laminating semiconductor elements or substrates, which will be described in detail later.

  The photocurable resin composition of the present invention can form a fine pattern and can be used as an adhesive for bonding substrates together.

The pattern formation method which forms a pattern using the photocurable resin composition of this invention is demonstrated. The pattern forming method includes the following steps.
(I) forming a film of the photocurable resin composition of the present invention on a substrate;
(Ii) a step of exposing with light having a wavelength of 240 nm to 500 nm through a photomask, and a step of heating after exposure if necessary (so-called PEB step)
(Iii) A step of developing with an alkali developer.
A fine pattern can be obtained by the above three steps.

  In the pattern forming method, first, the photocurable resin composition is formed on a substrate. Examples of the substrate include silicon, glass, and quartz wafers, plastic and ceramic circuit substrates, and substrates having a resin film on the substrate surface.

  Examples of the film forming method include a coating method, which can be performed by employing a known lithography technique. For example, it can apply | coat by methods, such as a dip method, a spin coat method, a roll coat method, using the solution which mix | blended the organic solvent with the photocurable resin composition. The coating amount can be appropriately selected according to the purpose, but is preferably 0.1 to 200 μm.

  Moreover, as a film forming method, a method of laminating a film adhesive obtained by separately forming a photocurable resin composition on a substrate can also be employed. The film adhesive will be described later.

  Here, in order to efficiently perform the photocuring reaction, a solvent or the like may be volatilized in advance by preheating as necessary. Preheating can be performed, for example, at 40 to 140 ° C. for about 1 minute to 1 hour.

Next, the film is exposed to light having a wavelength of 240 to 500 nm through a photomask and cured. For example, the photomask may be formed by cutting a desired pattern. In addition, the material of the photomask is preferably one that shields the light having the wavelength of 240 to 500 nm. For example, chromium is preferably used, but is not limited thereto. Examples of the light having a wavelength of 240 to 500 nm include light of various wavelengths generated by a radiation generator, for example, ultraviolet light such as g-line and i-line, and far-ultraviolet light (248 nm). The exposure amount is preferably, for example, 10 to 5000 mJ / cm ² . Here, heat treatment may be performed after exposure in order to further increase the development sensitivity as necessary. The post-exposure heat treatment can be performed at 40 to 140 ° C. for 0.5 to 10 minutes, for example.

  After the exposure or after the exposure, the film is developed with an alkali developer. The developer is preferably an organic solvent system used as a solvent, such as dimethylacetamide or cyclohexanone, or an aqueous alkali solution such as tetramethylammonium hydroxide or sodium carbonate. The development can be performed by a normal method, for example, by immersing a pattern formed product. Thereafter, washing, rinsing, drying, and the like are performed as necessary to obtain a composition film having a desired pattern.

The pattern formation method is as described above. However, when it is not necessary to form a pattern, for example, when a simple uniform film is to be formed, the same as described in the pattern formation method except that the photomask is not used. You can do this.
Further, the obtained pattern is further heated at 70 to 300 ° C. for about 10 minutes to 10 hours using an oven or a hot plate, whereby the crosslinking density can be increased and the remaining volatile components can be removed. As a result, it is possible to form a film that has excellent adhesion to the substrate, heat resistance, strength, and electrical properties.

Next, the process in the case of using the photocurable resin composition of this invention as an adhesive agent is shown below.
(I) forming a film of the photocurable resin composition of the present invention on a substrate;
(Ii) a step of exposing with light having a wavelength of 240 nm to 500 nm through a photomask, and a step of heating after exposure if necessary (so-called PEB step)
(Iii) A step of developing with an alkali developer (iv) A step of thermocompression bonding with another substrate in a reduced pressure atmosphere (v) A heating step for post-curing.

  Steps (i) to (iii) are the same as the pattern formation described above. In the case where a pattern is not formed, exposure may be performed without using a photomask in step (ii).

  In the step (iv), the thermocompression bonding temperature is preferably 40 to 300 ° C., more preferably 50 to 250 ° C., and the pressure for pressure bonding is preferably 0.01 to 100 MPa, more preferably 0.05 to 30 MPa.

  Thereafter, the substrates can be firmly bonded to each other through a heating step for post-curing. The post-curing temperature is preferably 80 to 300 ° C, more preferably 120 to 280 ° C.

The film adhesive and adhesive sheet of the present invention will be described below.
The film adhesive is formed by forming the photocurable resin composition of the present invention into a film. The film adhesive can be produced, for example, by applying a photocurable resin composition on the surface of a base film and drying it as necessary. The film thickness is preferably 0.1 to 200 μm, more preferably 1 to 200 μm, and particularly preferably 1 to 100 μm.

The adhesive sheet preferably has the following three-layer structure, for example.
(I) a base film layer,
(II) a photocurable resin layer formed by forming the photocurable resin composition into a film having a film thickness of 0.1 to 200 μm,
(III) Cover film layer.
Such a three-layer structure is easy to handle, and the adhesive layer can be easily formed by transferring the photocurable resin layer onto the substrate to be bonded. For example, as the film forming step of the step (i) in the pattern formation process or the bonding process between the substrates as described above, the cover film of the adhesive sheet is peeled off and bonded so that the photocurable resin layer and the substrate are in contact with each other. A step of forming the photocurable resin layer on the substrate by transferring the photocurable resin layer to the substrate by removing the film can be applied.

  The adhesive sheet is, for example, a step of applying the photocurable resin composition of the present invention on the surface of a base film and drying as necessary to form a photocurable resin layer, and then covering the layer It can be manufactured by a process of covering with a film. The photocurable resin layer is preferably laminated to a thickness of 0.1 to 200 μm, more preferably 1 to 200 μm, and particularly preferably 1 to 100 μm.

  Polyethylene, polypropylene, PET, and polycarbonate can be used as the material for the base film and the cover film, but are not limited thereto.

  For example, an applicator, a bar coater, a roll coater, or a curtain flow coater is used for forming the coating film.

  The drying temperature is suitably in the range of 40 to 180 ° C, more preferably 60 to 130 ° C. Although a cover film can be affixed on a photocurable resin layer at room temperature, it can also be affixed, heating at about 40-60 degreeC.

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated in detail, this invention is not restrict | limited to the following example.

[Synthesis Example 1]
In a flask equipped with a stirrer, a thermometer, and a nitrogen displacement device, 31.0 g (0.15 mol) of 4,4′-oxydiphthalic dianhydride and an acid anhydride whose average structure is represented by the following formula (15) 155.1 g (0.15 mol) of modified siloxane and 600 g of N-methyl-2-pyrrolidone were charged. Then, 91.5 g (0.25 mol) of 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane was adjusted in the flask while adjusting the temperature of the reaction system so that it did not exceed 50 ° C. added. Thereafter, the mixture was further stirred at room temperature for 10 hours. Next, after attaching a reflux condenser with a moisture receiver to the flask, 100 g of xylene was added, the temperature was raised to 170 ° C. and the temperature was maintained for 6 hours, and a brown solution was obtained.

After cooling the brown solution thus obtained to room temperature (25 ° C.), a polyimide silicone solution having a phenolic hydroxyl group was obtained. Next, 23 g of glycidol was charged into this polyimide silicone solution in a flask and heated at 120 ° C. for 3 hours. After completion of the reaction, the reaction solution was cooled to room temperature, the reaction solution was poured into methanol, the deposited precipitate was filtered, dried, and the target polyimide silicone A-1 having a primary alcoholic hydroxyl group was obtained. As a result of ¹ H-NMR analysis of this polymer, 10 ppm peaks derived from phenolic hydroxyl groups decreased, and peaks derived from primary and secondary alcoholic hydroxyl groups were observed at 4.6 ppm and 4.8 ppm. The polymer was found to have a repeating unit structure represented by the following formula (FIG. 1). As a result of gel permeation chromatography (GPC) analysis, the polymer had a number average molecular weight of 39,000 and an OH number based on JIS K0070 of 100 KOH mg / g.

[Synthesis Example 2]
In a flask equipped with a stirrer, a thermometer, and a nitrogen displacement device, 45.5 ′ (hexafluoropropylidenebisphthalic dianhydride) 55.5 g (0.125 mol), and the average structure is represented by the following formula (16): 137.0 g (0.125 mol) of the acid anhydride-modified siloxane shown and 800 g of γ-butyrolactone were charged. Then, 91.5 g (0.25 mol) of 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane was adjusted in the flask while adjusting the temperature of the reaction system so that it did not exceed 50 ° C. added. Thereafter, the mixture was further stirred at room temperature for 10 hours. Next, after attaching a reflux condenser with a moisture receiver to the flask, 200 g of xylene was added, the temperature was raised to 170 ° C. and the temperature was maintained for 6 hours, and a brown solution was obtained.

After cooling the brown solution thus obtained to room temperature (25 ° C.), a polyimide silicone solution having a phenolic hydroxyl group was obtained. Next, 18.3 g of glycidol was charged into this polyimide silicone solution in a flask and heated at 120 ° C. for 3 hours. After completion of the reaction, the reaction solution was cooled to room temperature, the reaction solution was poured into methanol, the deposited precipitate was filtered, and dried, to obtain polyimide silicone A-2 having the desired primary alcoholic hydroxyl group. As a result of ¹ H-NMR analysis of this polymer, 10 ppm peaks derived from phenolic hydroxyl groups decreased, and peaks derived from primary and secondary alcoholic hydroxyl groups were observed at 4.6 ppm and 4.8 ppm. The polymer was found to have a repeating unit structure represented by the following formula (FIG. 2). As a result of gel permeation chromatography (GPC) analysis, the number average molecular weight of this polymer was 32,000, and the OH value based on JIS K0070 was 100 KOH mg / g.

[Synthesis Example 3]
In a flask equipped with a stirrer, a thermometer, and a nitrogen displacement device, 31.0 g (0.1 mol) of 4,4′-oxydiphthalic dianhydride, an acid anhydride having an average structure represented by the following formula (17) 184.2 g (0.1 mol) of modified siloxane and 800 g of γ-butyrolactone were charged. Next, 36.6 g (0.1 mol) of 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane and 23.4 g (0.08 mol) of 1,4-diaminophenoxybenzene were added to the reaction system. It was added into the flask while adjusting the temperature not to exceed 50 ° C. Thereafter, 4.4 g (0.02 mol) of p-aminophenol was added, and the mixture was further stirred at room temperature for 10 hours. Next, after attaching a reflux condenser with a moisture receiver to the flask, 200 g of xylene was added, the temperature was raised to 170 ° C. and the temperature was maintained for 6 hours, and a brown solution was obtained.

  After cooling the brown solution thus obtained to room temperature (25 ° C.), a polyimide silicone solution having a phenolic hydroxyl group was obtained. Next, 16.5 g of glycidol was charged into this polyimide silicone solution in a flask and heated at 120 ° C. for 3 hours. After completion of the reaction, the reaction solution was cooled to room temperature, the reaction solution was poured into methanol, the deposited precipitate was filtered, and dried, to obtain polyimide silicone A-3 having the desired primary alcoholic hydroxyl group. As a result of 1H-NMR analysis of this polymer, 10 ppm peak derived from phenolic hydroxyl group decreased, and peaks derived from primary and secondary alcoholic hydroxyl groups were observed at 4.6 ppm and 4.8 ppm. The polymer was found to have a repeating unit structure represented by the formula (FIG. 3). As a result of gel permeation chromatography (GPC) analysis, the polymer had a number average molecular weight of 19,000 and an OH value based on JIS K0070 of 39 KOH mg / g.

[Synthesis Example 4]
Used in Synthesis Example 2 in which 31.0 g (0.1 mol) of 4,4′-oxydiphthalic dianhydride and the average structure is represented by formula (16) in a flask equipped with a stirrer, a thermometer and a nitrogen displacement device The acid anhydride-modified siloxane 164.4 g (0.15 mol) and γ-butyrolactone 800 g were charged. Next, 45.2 g (0.175 mol) of 2,2-bis (4-amino-3-hydroxyphenyl) propane and 14.6 g (0.05 mol) of 1,4-diaminophenoxybenzene were added at a temperature of the reaction system. It was added to the flask while adjusting so as not to exceed 50 ° C. Thereafter, 5.5 g (0.025 mol) of p-aminophenol was added, and the mixture was further stirred at room temperature for 10 hours. Next, after attaching a reflux condenser with a moisture receiver to the flask, 200 g of xylene was added, the temperature was raised to 170 ° C. and the temperature was maintained for 6 hours, and a brown solution was obtained.
After cooling the brown solution thus obtained to room temperature (25 ° C.), a polyimide silicone solution having a phenolic hydroxyl group was obtained. Next, 10.9 g of glycidol was charged into the polyimide silicone solution in a flask and heated at 120 ° C. for 3 hours. After completion of the reaction, the reaction solution was cooled to room temperature, the reaction solution was poured into methanol, the deposited precipitate was filtered and dried to obtain the target polyimide silicone A-4 having a primary alcoholic hydroxyl group. As a result of 1H-NMR analysis of this polymer, 10 ppm peak derived from phenolic hydroxyl group decreased, and peaks derived from primary and secondary alcoholic hydroxyl groups were observed at 4.6 ppm and 4.8 ppm. The polymer was found to have a repeating unit structure represented by the formula (FIG. 4). As a result of gel permeation chromatography (GPC) analysis, the polymer had a number average molecular weight of 22,000 and an OH value based on JIS K0070 of 51 KOH mg / g.

[Synthesis Example 5]
In Synthesis Example 1, except that glycidol was not reacted with the polyimide silicone solution before reacting glycidol, the same operation as in Synthesis Example 1 was performed, that is, the polyimide silicone obtained by precipitation collection was designated as A-5. . A-5 is a polyimide silicone having no primary alcoholic hydroxyl group.

[Examples 1-5, Comparative Examples 1-3]
As the component (A), polyimide silicones A-1 to A-5 synthesized in Synthesis Examples 1 to 4 were used, and other components were prepared by blending the components described in Tables 1 and 2. These compositions were applied on a PET film so as to have a thickness of 20 μm, and then dried with a dryer at 100 ° C., and then a polyethylene cover film was laminated to prepare a film adhesive. Evaluation was performed by the following method.

[Pattern evaluation]
The cover film of the film adhesive produced in the Example was peeled off, the 6-inch silicon wafer and the photoadhesive layer were bonded, and the film was pressed with a roll. Thereafter, the substrate PET film was peeled off to produce a substrate having the photoadhering layer transferred onto the silicon wafer. This adhesive layer was exposed at 600 mJ (illuminance measured at 365 nm) through a negative photomask on which a 10 mm square pattern was designed, and then a 2.38% aqueous solution of tetramethylammonium hydroxide. The unexposed part was dissolved and removed by immersing in 5 minutes. Thereby, a rectangular pattern is formed, and the film thickness change of the pattern is within ± 10% of the film thickness before exposure, ○, more than ± 10% and ± 20% or less Δ Those exceeding ± 20% were evaluated as x. For exposure, a mask aligner MA8 manufactured by Sooze was used, and the light source wavelength was broadband.

[Adhesion evaluation]
The substrate with the pattern after development was heated to 150 ° C. on a hot plate, and a 6-inch glass substrate was singly mounted thereon, and was bonded together under a load from above. The load pressure was 0.2 MPa and the load time was 3 minutes. Then, after heating and curing in an oven at 200 ° C. for 1 hour, the adhesion state between the pattern surface and the glass substrate was observed with an optical microscope. The case where bonding abnormalities such as voids are observed on the entire interface is x, which is uniformly bonded, but the case where some voids are included is Δ, the case where there are no voids and is uniformly bonded without gaps is .

[Reliability evaluation]
The silicon-glass substrate bonded in the above procedure was exposed to conditions of a temperature of 85 ° C. and a humidity of 85% for 200 hours, and then heated in an oven at 260 ° C. for 20 seconds. After cooling to room temperature, the adhesion state of the interface was confirmed with an optical microscope as described above. The case where bonding abnormality at the interface, such as a void, was observed was evaluated as x, and the case where the bonding was uniformly performed without a gap was evaluated as ◯.

B-1: Hexamethoxymethylolmelamine

B-2: Tetrakis (methoxymethyl) glycoluril (Nicalak MX-270, manufactured by Sanwa Chemical Co., Ltd.)

C-1: (p-Tolylsulfonium oxyimino) -p-methoxyphenylacetonitrile

C-2: 4- (thiophenoxy) phenyl-diphenylsulfonium hexafluorophosphate

D-1: Bifunctional epoxy resin Epicoat 828 (made by Japan Epoxy Resin Co., Ltd.)
D-2: Tetrafunctional epoxy silicone 1,2,3,4-tetrakis (glycidoxypropyl) -1,2,3,4-tetramethylcyclotetrasiloxane
D-3: Bifunctional epoxy resin Celoxide 2021P (manufactured by Daicel Chemical Industries)

Claims (7)

(A) polyimide silicone having a primary alcoholic hydroxyl group as a component;
As the component (B), at least one selected from the group consisting of an amino condensate modified with formalin or formalin-alcohol and a phenol compound having an average of two or more methylol groups or alkoxymethylol groups in one molecule. Compound,
(C) As a component, a photoacid generator,
(D) The photocurable resin composition characterized by containing a polyfunctional epoxy compound as a component. (A) Component is polyimide silicone represented by following General formula (1), The photocurable resin composition of Claim 1 characterized by the above-mentioned.

[In Formula (1),
k and m are positive integers and are numbers satisfying 0.01 ≦ k / (k + m) <1.
X is a tetravalent organic group represented by the following general formula (2).

(In the formula (2), R ¹ is independently a monovalent hydrocarbon group having 1 to 8 carbon atoms, R ² is independently a trivalent organic group, and n is an average of It is a number from 1 to 120.)
Y is a divalent organic group, at least a part of which is represented by the general formula (3).

(In Formula (3), A is

May be the same or different from each other, and B and C are each an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and may be the same or different from each other. A is 0 or 1, b is 0 or 1, and c is an integer of 0 to 10. In formula (3), R ³ is a monovalent group selected from a phenolic hydroxyl group or an alcoholic hydroxyl group-containing organic group, and at least one of R ³ is a primary alcoholic hydroxyl group-containing organic group. )
W is a tetravalent organic group other than X. ] In the said General formula (1), W is a tetravalent organic group containing at least 1 sort (s) represented by a following formula, The photocurable resin composition of Claim 2.

  100 parts by weight of component (A), 0.5-50 parts by weight of component (B), 0.05-20 parts by weight of component (C), 0.05-100 parts by weight of component (D) The photocurable resin composition according to any one of claims 1 to 3, wherein:   The component (D) is at least one polyfunctional epoxy compound selected from the group consisting of a polyfunctional epoxy compound having a bisphenol skeleton, a phenol novolac polyfunctional epoxy compound, and a polyfunctional epoxy silicone, The photocurable resin composition of any one of Claims 1-4.   The film adhesive formed by forming the photocurable resin composition of any one of Claims 1-5 in a film form. (I) a base film layer;
(II) a photocurable resin layer formed by forming the photocurable resin composition according to any one of claims 1 to 5 into a film having a film thickness of 0.1 to 200 μm;
(III) An adhesive sheet comprising a cover film layer.

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