JP5417623B2 - Polyimide-based photocurable resin composition, pattern forming method, and film for protecting substrate - Google Patents

Description

  The present invention relates to a photocurable resin composition containing polyimide silicone, a pattern forming method thereof, and a protective film such as a wiring using the composition. In particular, it relates to a protective insulating film for semiconductor elements, an insulating film for multilayer printed circuit boards, a solder protective film, a coverlay film, a MEMS application, and the like because of its excellent heat resistance, chemical resistance, insulation and flexibility.

  Conventionally, as a photosensitive polyimide-based material, a material using a polyamic acid which is a polyimide precursor, for example, a material in which a photosensitive group is introduced into a carboxyl group of a polyamic acid by an ester bond (Patent Documents 1 and 2) A material composed of a polyamic acid and an amine compound having a photosensitive group (Patent Document 3) has been proposed. However, in these proposals, after forming a patterned film, an imidization treatment at a high temperature exceeding 300 ° C. is essential in order to obtain a target polyimide film. There are problems that the material is restricted and the copper of the wiring is oxidized.

  As this improvement, photosensitive polyimide using a solvent-soluble resin that has already been imidized for the purpose of lowering the post-curing temperature has been proposed (Patent Document 4, Patent Document 5, and Patent Document 6).

  On the other hand, there has also been proposed a positive type in which a polyimide skeleton having a phenolic hydroxyl group (Patent Document 7) or a polyamide skeleton (Patent Documents 8 and 9) and diazonaphthoquinone are combined.

  In addition, using polyimide as the base resin and developing with emphasis on fine pattern formation, the side chain alcohol group of the ring-solvated solvent-soluble polyimide and the alkoxy group-containing melamine compound are produced by a photoacid generator. A composition (Patent Document 10) that undergoes photocrosslinking is known.

JP-A-49-115541 JP-A-55-45746 JP 54-145794 A Japanese Patent Laid-Open No. 10-274850 JP-A-10-265571 JP-A-13-335619 Japanese Patent Laid-Open No. 3-209478 Japanese Examined Patent Publication No. 1-46862 Japanese Patent Laid-Open No. 11-65107 JP 2006-133757 A

  However, all of the compositions described in Patent Documents 4 to 6 use (meth) acryl groups to impart photosensitivity to the resin, and are susceptible to oxygen damage due to the photocuring mechanism. For example, it is difficult to improve the resolving power because the film tends to be reduced, and the material cannot satisfy all the required characteristics.

  In the compositions described in Patent Documents 7 to 9, it is difficult to form a thick film exceeding 20 μm from the viewpoint of light transmittance of the composition, and the resin molecular weight is sufficient to ensure developability. There are problems such as low molecular weight and the addition amount of diazonaphthoquinone, which is a photosensitizer, to a large amount with respect to the resin, making it difficult to obtain the inherent curing characteristics of the resin.

  The composition described in Patent Document 10 has a problem that it cannot be developed with an alkaline aqueous solution having a small environmental load.

  The present invention has been made in view of the above circumstances, and it is possible to easily form a fine pattern with a thick film exceeding 20 μm by development with an alkaline aqueous solution having a low environmental load. Provided is a photocurable resin composition containing polyimide silicone and a pattern forming method capable of providing a film with excellent film characteristics and reliability as a protective film by heat treatment at a relatively low temperature of 220 ° C. or lower after formation. There is to do.

As a result of intensive studies to achieve the above object, the present inventor has found that a photocurable resin composition having a composition described later, which contains a polyimide silicone having a primary alcohol in the resin molecule, is not affected by oxygen damage. A thin film can be easily formed and can be exposed with light of a wide wavelength, and a fine pattern can be formed by a pattern forming method described later. Further, after the photocurable resin composition and the pattern are formed The cured film obtained by heating has been found to be excellent in heat resistance and electrical insulation, and has led to the present invention.
That is, the present invention relates to the following.
<1> As a component (A ), a polyimide silicone represented by the following general formula (1) having a primary alcoholic hydroxyl group,
As the component (B), one or more selected from the group consisting of formalin or an amino condensate modified with formalin and alcohol and a phenol compound having an average of two or more methylol groups or alkoxymethylol groups in one molecule Compound,
(C) The photocurable resin composition characterized by containing a photo-acid generator as a component.

[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 the formula (3), R ³ is a monovalent group selected from a phenolic hydroxyl group or an alcoholic hydroxyl group-containing organic group and may be the same or different from each other , and at least one of R ³ is a primary group. It is an alcoholic hydroxyl group-containing organic group. )
W is a tetravalent organic group other than X. ]
<2> The light according to <1>, comprising 100 parts by mass of the component (A), 0.5 to 50 parts by mass of the component (B), and 0.05 to 20 parts by mass of the component (C). Curable resin composition.
<3><1> or <2> characterized by containing 50 to 2000 parts by mass of an organic solvent as component (D) with respect to 100 parts by mass of the total amount of components (A) to (C). The photocurable resin composition as described.
< 4 > The light according to any one of <1> to <3>, wherein the polyimide silicone represented by the general formula (1) is a polyimide silicone represented by the following general formula (1-1). Curable resin composition.

[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). ]
< 5 > Monovalent in which c + 1 R ³ in the general formula (3) of the polyimide silicone is selected from —OH, —OCH ₂ CH (OH) CH ₂ OH, —OCH (CH ₂ OH) CH ₂ OH. <1>-<4> The photocurable resin composition according to any one of <1> to <4> .
< 6 > Any one of <1> to <5> , wherein W in the general formula (1) of the polyimide silicone is a tetravalent organic group containing at least one kind represented by the following formula: The photocurable resin composition described in 1.

< 7 > The photocurable resin composition according to any one of <1> to <6> , wherein the polyimide silicone has an OH value of 20 to 200 KOHmg / g.
< 8 > Y ₂ in the general formula (1-1) of the polyimide silicone is a divalent organic group represented by the following general formula (4) and a divalent organic group represented by the following general formula (5). The photocurable resin composition according to any one of <1> to <7> , wherein the photocurable resin composition is at least one selected from the group consisting of:

(In the formula (4), D is each independently one of the following divalent organic groups:

e and f are independently 0 or 1, and g is 0 or 1. )

(In Formula (5), R ⁴ is independently a monovalent hydrocarbon group having 1 to 8 carbon atoms, and h is an integer of 1 to 80.)
< 9 > The photocurable resin composition according to any one of <1> to <8>, wherein the polyimide silicone has a phenol group, a thiol group, or a carboxyl group at a terminal of the polyimide silicone polymer. object.
< 10 > (i) A step of forming a film of the photocurable resin composition according to any one of <1> to < 9 > on a substrate, (ii) having a wavelength of 240 to 500 nm through a photomask A pattern forming method comprising: exposing the film with light having a wavelength; and (iii) developing with a developer.
< 11 > The pattern forming method according to < 10 >, comprising a step of performing a heat treatment after the (ii) exposure step and before the (iii) development step.
< 12 > A protective film obtained by post-curing a film of a photocurable resin composition patterned by the method according to <10> or <11> at a temperature in the range of 120 ° C to 300 ° C.

  By using the photocurable resin composition containing the polyimide silicone having the primary alcohol group of the present invention, it is possible to expose with light of a wide wavelength and easily form a thin film without being affected by oxygen, or 20 μm. It is possible to provide a photocurable resin composition capable of forming a thick film exceeding the thickness. In addition, it is possible to form a pattern with excellent resolving power, and the cured film obtained from this composition is excellent in adhesion to a substrate, heat resistance, and electrical insulation, and is used in electrical, electronic parts, semiconductor elements, etc. It is suitably used as a protective film.

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 which is the component (A) of the present invention contains a primary alcoholic hydroxyl group.
As said polyimide silicone, what is shown by following General formula (1) is preferable.

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 the formula (2), R ¹ is independently a monovalent hydrocarbon group having 1 to 8 carbon atoms, and examples thereof include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and 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, 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 general formula (3).

  In formula (3), A is independently of each other 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 5,000 to 200,000, preferably 8,000 to 100,000, in terms of number average molecular weight. A polyimide resin having a molecular weight of less than the lower limit has a low strength of the resulting film. On the other hand, a polyimide resin having a molecular weight exceeding the upper limit has poor compatibility with a solvent and is difficult to handle.

  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 formalin or an amino condensate modified with formalin and 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.

  (B) As a compound of a component, the thing of a weight average molecular weight 150-10000, especially 200-3000 is preferable. If the weight average molecular weight is less than 150, sufficient photocurability may not be obtained, and if it exceeds 10,000, the heat resistance after curing of the composition may be deteriorated.

The amino condensate modified with formalin or formalin and alcohol as the component (B) includes, for example, formalin or melamine condensate modified with formalin and alcohol, or urea condensate modified with formalin or formalin and alcohol. It is done.

Formalin or a melamine condensate modified with formalin and alcohol is modified by, for example, first converting a melamine monomer to methylol with formalin according to a known method, or further modifying this by alkoxylation with alcohol, to obtain 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 ⁴ 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, but at least one 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.
Next, the modified melamine of the general formula (8) or this multimer (for example, an oligomer such as a dimer or a trimer) is subjected to addition condensation polymerization with formaldehyde according to a conventional method until the desired molecular weight is obtained, and the component (B) A formalin or a melamine condensate modified with formalin and 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.

In addition, preparation of a urea condensate modified with formalin or formalin and alcohol can be performed by, for example, modifying a urea condensate having a desired molecular weight with methylol in a known manner, or modifying the urea condensate with alcohol to further modify the urea condensate. 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).

  Furthermore, as a phenol compound having two or more methylol groups or alkoxymethylol groups on average in one molecule of component (B), 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, relative to 100 parts by mass of the polyimide silicone resin of the component (A). Part 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 of the present invention cannot be expressed.

Component (C) The photoacid generator of component (C) preferably generates an acid upon irradiation with light having a wavelength of 240 nm to 500 nm and becomes a curing catalyst. Since the resin composition of the present invention is excellent in 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 In the photocurable resin composition of this invention, you may mix | blend the organic solvent as needed as (D) component. Examples of the organic solvent include components such as the above-described polyimide resin of component (A), component (B) of formalin or an amino condensate modified with formalin and alcohol, a phenol compound, and component (C) of a photoacid generator. Soluble solvents are preferred.

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 blending amount of the organic solvent is preferably 50 to 2,000 parts by mass, particularly preferably 100 to 1,000 parts by mass with respect to 100 parts by mass of the total amount (total solids) of the components (A) to (C). . If the amount is less than 50 parts by mass, the compatibility of each of the components (A) to (C) 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.

Other additive components In addition to the above components, an additive component may be further blended in the photosensitive curable resin composition of the present invention.

As such an additional component, for example, an epoxy group is used for the purpose of improving the reliability of the film and the adhesion to the substrate by causing a crosslinking reaction with the base polymer (that is, the component (A)) by heat curing after patterning. A polyfunctional epoxy compound containing 2 or more per molecule may be added.
As the structure of the epoxy group, an alicyclic epoxy compound having a phenol glycidyl ether type or a cyclohexene oxide group, an epoxy compound having a double bond in an organosiloxane containing a hydrosilyl group, introduced by a hydrosilylation reaction, Etc. are preferable.

As the former phenol structure, a novolac type, a bisphenol type, a biphenyl type, a phenol aralkyl type, a dicyclopentadiene type, a naphthalene type, and an 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 ⁹ represents an organic group containing an epoxy group, R ¹⁰ represents a monovalent hydrocarbon group, and R ¹¹ 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 ⁹ is preferably a glycidoxypropyl group or a cyclohexylepoxyethyl group, most preferably a glycidoxypropyl group.

  In addition, epoxy group-containing cyclic siloxane (13);

In the formula, R ⁹ and R ¹⁰ are in the range of 0.2 ≦ t / (t + u) ≦ 1.

  Bissilyl group-substituted compound (14);

In the formula, R ¹² is a divalent organic group, specifically, a linear alkylene group such as ethylene, propylene, and hexylene group, a disubstituted cyclic saturated hydrocarbon group such as disubstituted cyclopentylene group and cyclohexylene group, It includes a divalent aromatic group such as a phenylene group and a biphenylene group, and a structure in which a plurality of these groups are connected. 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 said polyfunctional epoxy compound can be used individually by 1 type or in mixture of 2 or more types. The compounding amount of the polyfunctional epoxy compound is preferably 0.05 to 100 parts by mass, more preferably 0.1 to 50 parts by mass, and further preferably 1 to 30 parts by mass with respect to 100 parts by mass of the polyimide (A). Part. 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.

  As another additive component, for example, a surfactant conventionally used for improving the coating property 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" (all 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 base resins, 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.

As a pattern formation method which forms a pattern using the said photocurable resin composition, the following process is included.
(I) forming a film of the photocurable resin composition described above on a substrate;
(Ii) a step of exposing the film with light having a wavelength of 240 nm to 500 nm through a photomask;
If necessary, a step of heating after exposure (so-called PEB step),
(Iii) A step of developing with a developer.
A fine pattern can be obtained by the above three steps.

  In the pattern forming method of the present invention, a film of the photocurable composition is first formed on a substrate. Examples of the substrate include silicon, glass, and quartz wafers, as well as plastic and ceramic circuit boards.

  The film can be formed by employing a known lithography technique. For example, it can apply | coat by methods, such as a dip method, a spin coat method, and a roll coat method. The coating amount can be appropriately selected according to the purpose, but is preferably 0.1 to 100 μm. As a method for forming the film, a method can be used in which the photocurable composition is separately formed into a film and bonded to a substrate.

  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 10 to 5000 mJ / cm ² , for example. 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 a 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 120 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.

  Thus, the cured film obtained from the photocurable resin composition is excellent in adhesion to a substrate, heat resistance, and electrical insulation, and is suitably used as a protective film for electricity, electronic parts, semiconductor elements, and the like. In addition, fine pattern formation is possible, and the formed film is excellent in adhesion to substrates, electrical characteristics, mechanical characteristics, etc., semiconductor element protective film, wiring protective film, cover lay film, solder resist, etc. Is preferably used.

  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 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 1H-NMR analysis of this polymer, 10 ppm peaks derived from phenolic hydroxyl groups were 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. 1). As a result of gel permeation chromatography (GPC) analysis, the number average molecular weight of this polymer was 39000, and the OH value based on JIS K0070 was 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. Next, while adjusting 91.5 g (0.25 mol) of 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane so that the temperature of the reaction system does not exceed 50 ° C., the flask Added in. 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 (Comparative Example)]
In Synthesis Example 1, the same operation as in Synthesis Example 1 was performed except that the glycidol was not reacted with the polyimide silicone solution before the glycidol was reacted. That is, the polyimide silicone obtained by precipitation collection was designated as A′-1. did. A′-1 is a polyimide silicone having no primary alcoholic hydroxyl group.

[Synthesis Example 6 (Comparative Example)]
In a flask equipped with a stirrer, a thermometer, and a nitrogen displacement device, 77.5 g (0.25 mol) of 4,4′-oxydiphthalic dianhydride and 500 g of N, N-dimethylacetamide were charged. Next, 51.6 g (0.2 mol) of 2,2-bis (4-amino-3-hydroxyphenyl) propane and diaminosiloxane (the residue of which is represented by the general formula (5) A solution of 42.0 g (0.05 mol) in 200 g of N, N-dimethylacetamide was added dropwise into the flask while adjusting the temperature of the reaction system so that it did not exceed 50 ° C. . After completion of dropping, the mixture was further stirred at room temperature for 10 hours. Next, after attaching a reflux condenser with a moisture receiver to the flask, 150 g of toluene was added, the temperature was raised to 150 ° C. and the temperature was maintained for 6 hours, and a brown solution was obtained.
After the brown solution thus obtained was cooled to room temperature (25 ° C.), a polyimide solution having a phenolic hydroxyl group (resin solid content 20.5%) was obtained. Next, 300 g of this polyimide solution and 13.3 g of glycidol were charged into a flask and heated at 120 ° C. for 5 hours. After completion of the reaction, the reaction solution was cooled to room temperature, the reaction solution was poured into methanol, and the deposited precipitate was filtered and dried to obtain polyimide A′-2. As a result of gel permeation chromatography (GPC) analysis, the number average molecular weight of this polymer was 63200.

[Examples 1-6, Comparative Examples 1-2]
Using polyimide silicones A-1 to A-4 synthesized in Synthesis Examples 1 to 4 as the component (A), a crosslinking agent, a photoacid generator, other additives, a solvent, etc. are blended in the composition described in Table 1, Then, after stirring, mixing, and dissolving, microfiltration was performed with a 0.2 micron filter made of Teflon (registered trademark) to obtain the photocurable resin compositions of the present invention up to Examples 1-6. For comparison, a similar experiment was performed using A′-1 and 2 synthesized in Synthesis Examples 5 and 6.
Using a spin coater, two 6-inch silicon wafers primed with hexamethyldisilazane and one copper substrate with a 2 micron film thickness plated on the entire 6-inch silicon wafer are listed in the table. The composition of each example was coated at a film thickness of. Of the three wafers prepared, one silicon substrate was heat-dried with a hot plate at 90 ° C. for 2 minutes to remove the solvent, and then a line width of 1 μm to 50 μm with equally spaced lines and spaces. Irradiation was performed with the light having the wavelengths described in Table 1 and the exposure dose through the quartz mask. Here, NSR-1755i7A represents a Nikon stepper type exposure apparatus. After irradiation, it was heated at 90 ° C. for 2 minutes and then cooled.
Thereafter, the coated substrate was immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide for 8 minutes for development. The line width resolved at this time is shown in Table 1. The film thickness after development is also shown.
Under the same conditions, the remaining silicon wafer and copper substrate were coated with the composition of each example described in Table 1, and pre-baked for solvent removal. Furthermore, using a mask aligner MA8 manufactured by Sousse Co., Ltd. on the entire surface of the substrate without using a quartz mask, the light source wavelength was irradiated with light in a broadband, followed by heating after exposure, to a 2.38% aqueous solution of tetramethylammonium hydroxide. Immersion was also continued. The film remaining after this operation was further heated in an oven at 220 ° C. for 1 hour to obtain a cured film. Using this cured film, the insulation and adhesiveness of each film were measured as shown in Table 2. For evaluation of adhesion, the substrate was left in a pressure cooker at a saturated atmospheric pressure for 24 hours, and then the number of peels was measured by a cross-cut peel test. The dielectric breakdown strength was measured based on JISC2103.

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: Cyclopentanone

E-1: Epicoat 828 (manufactured by Japan Epoxy Resin) Bifunctional epoxy resin E-2: EXA-850CRP (manufactured by Dainippon Ink Co., Ltd.) Bifunctional epoxy resin E-3: Celoxide 2021P (manufactured by Daicel Chemical Industries) Bifunctional epoxy resin

  As a result of the above, the compositions of Examples 1 to 6 showed a good resolution as a photosensitive material without reducing the film thickness over a wide film thickness exceeding 20 μm, The cured film has electrical properties such as good adhesion to various base materials and dielectric breakdown strength, and the results show that it is useful as a protective film for circuits and electronic parts.

Claims (12)

As the component (A) , a polyimide silicone represented by the following general formula (1) having a primary alcoholic hydroxyl group,
As the component (B), one or more selected from the group consisting of formalin or an amino condensate modified with formalin and alcohol and a phenol compound having an average of two or more methylol groups or alkoxymethylol groups in one molecule Compound,
(C) The photocurable resin composition characterized by containing a photo-acid generator as a component.

[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 the formula (3), R ³ is a monovalent group selected from a phenolic hydroxyl group or an alcoholic hydroxyl group-containing organic group and may be the same or different from each other, and at least one of R ³ is a primary group. It is an alcoholic hydroxyl group-containing organic group. )
W is a tetravalent organic group other than X. ]   The photocurable resin according to claim 1, comprising 100 parts by mass of component (A), 0.5 to 50 parts by mass of component (B), and 0.05 to 20 parts by mass of component (C). Composition.   (D) As a component, the organic solvent of 50-2000 mass parts is contained with respect to 100 mass parts of total amounts of (A)-(C) component, The photocurable property of Claim 1 or 2 characterized by the above-mentioned. Resin composition. The photocurable resin composition according to any one of claims 1 to 3, wherein the polyimide silicone represented by the general formula (1) is a polyimide silicone represented by the following 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). ] C + 1 R ³ in the general formula (3) of the polyimide silicone is selected from —OH, —OCH ₂ CH (OH) CH ₂ OH, —OCH (CH ₂ OH) CH ₂ OH , and at least R ³ one is _{-OCH 2 CH (OH) CH 2} OH, -OCH (CH 2 OH) CH 2 OH, it is selected Ru monovalent group in any one of claims 1 to 4, characterized in the The photocurable resin composition as described. The photocuring according to any one of claims 1 to 5 , wherein W in the general formula (1) of the polyimide silicone is a tetravalent organic group containing at least one kind represented by the following formula. Resin composition.

7. The photocurable resin composition according to claim 1 , wherein the polyimide silicone has an OH value of 20 to 200 KOH mg / g. Y ₂ in the general formula (1-1) of the polyimide silicone is composed of a divalent organic group represented by the following general formula (4) and a divalent organic group represented by the following general formula (5). The photocurable resin composition according to claim 1 , wherein the photocurable resin composition is at least one selected from the group consisting of:

(In the formula (4), D is each independently one of the following divalent organic groups:

e and f are independently 0 or 1, and g is 0 or 1. )

(In Formula (5), R ⁴ is independently a monovalent hydrocarbon group having 1 to 8 carbon atoms, and h is an integer of 1 to 80.) The said polyimide silicone has a phenol group, a thiol group, or a carboxyl group at the terminal of a polyimide silicone polymer, The photocurable resin composition of any one of Claims 1-8 characterized by the above-mentioned. (I) a step of forming a film of the photocurable resin composition according to any one of claims 1 to 9 on a substrate; (ii) the light having a wavelength of 240 to 500 nm through a photomask; A pattern forming method comprising: a step of exposing a film; and (iii) a step of developing with a developer. The pattern forming method according to claim 10 , comprising a step of performing a heat treatment after the (ii) exposure step and before the (iii) development step. A protective film obtained by post-curing a film of a photocurable resin composition patterned by the method according to claim 10 or 11 at a temperature in the range of 120 ° C to 300 ° C.

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