JP2001215702A - Imide type photosensitive resin composition, insulating film and method for forming same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an imide type photosensitive resin composition which can be post-baked at a relatively low temperature and gives an insulating film having heat resistance and acid, alkali and heat resistances and to provide an insulating film and a method for forming the film. SOLUTION: The imide type photosensitive resin composition comprises (1) an imidosiloxane oligomer which is half-esterified after pre-baking at the latest, (2) a photosensitive monomer, (3) a photopolymerization initiator, (4) an auxiliary crosslinking agent, (5) a fine inorganic filler and (6) a solvent, and the proportions of the components 2-5 are 0.1-100 pts.wt. photosensitive monomer, 0.01-30 pts.wt. photopolymerization initiator, 1-75 pts.wt. auxiliary crosslinking agent and 1-50 pts.wt. fine inorganic filler, on the basis of 100 pts.wt. half-esterified imidosiloxane oligomer 1. The insulating film is formed using the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an imide-based photosensitive resin composition, an insulating film and a method for forming the same. More specifically, the present invention relates to (1) an imide siloxane oligomer which is terminally esterified after prebaking. , (2) a photosensitive monomer, (3) a photopolymerization initiator, (4) a crosslinking aid, (5) a fine inorganic filler and (6) a composition for an imide-based insulating film comprising a solvent,
The present invention relates to an insulating film and a method for forming the same.

[0002]

2. Description of the Related Art Overcoat materials for wiring boards and insulating materials such as semiconductor integrated circuits and semiconductor package multilayer substrates are required to have high heat resistance and insulating properties. Various polyimides having both high heat resistance and heat resistance have been proposed.

Conventionally, as a method of selectively forming a polyimide resin film on a fine portion, a polyimide resin is applied to the entire surface of an element substrate, and the surface is partially protected by a photoresist, and is then covered with hydrazine or the like. A method of etching a polyimide resin film, that is, an alkali etching method is known. However, in this method, the process is complicated and toxic hydrazine must be used as an etching solution.

Further, a photosensitive polyimide resin having photosensitivity, for example, a resin in which a photopolymerizable acryloyl group is introduced into a polyamic acid which is a precursor of the polyimide resin through an ester bond (Japanese Patent Publication No. 55-30207, Japanese Patent Publication No. 55-3
No. 41422) and those in which an acryloyl group is introduced into an amic acid in a salt structure (Japanese Patent Publication No. 59-52222).
In addition, an etching method using an organic solvent as a developer has been proposed. Also, an alkali-developable photosensitive polyimide has been developed. For example, a photosensitive polyimide made of a positive polymer in which naphthoquinonediazide is introduced into a carboxyl group of a polyamic acid (JP-A-6-258835)
And a polyamic acid having a photopolymerizable acryloyl group introduced through an ester bond and having a carboxyl group in the side chain to form a polyamic acid soluble in a basic aqueous solution. Polyimide (JP-A-10
-95848). A polyimide film obtained by these methods is used as an insulating film. However, these photosensitive polyimide resins have a problem in that postbaking requires high-temperature heating of 200 ° C. or more, and the resulting insulating film has low heat resistance, acid resistance, alkali resistance, and solvent resistance.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to enable postbaking at a relatively low temperature and to obtain an insulating film having heat resistance, acid resistance, alkali resistance and solvent resistance. An object of the present invention is to provide an imide-based photosensitive resin composition, an insulating film, and a method for forming an insulating film.

[0006]

That is, the present invention provides:
(1) Imidosiloxane oligomer which is half-esterified at the latest after prebaking, (2) photosensitive monomer, (3) photopolymerization initiator, (4) crosslinking assistant: [epoxy resin +
Epoxy curing agent] or [equivalent diamine + glycidyl (meth) acrylate], (5) fine inorganic filler and
(6) Consisting of a solvent, the proportion of each component, (1) half esterified imide siloxane oligomer-100 parts by weight,
(2) photosensitive monomer-0.1 to 100 parts by weight, (3) photopolymerization initiator 0.01 to 30 parts by weight, (4) crosslinking aid 1 to 75 parts by weight and (5) fine inorganic filler-1 To 50 parts by weight of an imide-based photosensitive resin composition.

Further, the present invention provides a polyimide-based insulating resin obtained by applying the above-mentioned imide-based photosensitive resin composition to a substrate, prebaking to form a thin film, exposing, alkali developing, and postbaking. About the membrane. Further, the present invention relates to a method for forming a polyimide-based insulating film, which is formed by applying the above-mentioned imide-based photosensitive resin composition to a substrate, pre-baking to form a thin film, exposing to light, developing with alkali, and post-baking. .

[0008]

Embodiments of the present invention will be described below. 1) The above imide-based photosensitive resin composition wherein the imide siloxane oligomer is a half-esterified imide siloxane oligomer which has already been half-esterified. 2) The imide-based photosensitive resin composition as described above, wherein the imide siloxane oligomer is a mixture obtained by mixing the imide siloxane oligomer and an esterifying agent and half-esterifying during prebaking. 3) The crosslinking assistant comprises a combination of an epoxy resin and an epoxy curing agent, or comprises an imide siloxane oligomer.
The imide-based photosensitive resin composition described above, comprising a diamine compound in an amount equivalent to the terminal acid component and a glycidyl group-containing reactive monomer such as glycidyl (meth) acrylate.

4) (1) When the terminal half-esterified imide siloxane oligomer has the formula H ₂ N—Bz (R ₁ ) _m -A- in an amount of 0 to 90 mol% in tetracarboxylic dianhydride or aromatic diamine. (R ₂ ) _m Bz-NH ₂ (where Bz is a benzene ring and R ₁ or R
₂ is a substituent such as hydrogen, lower alkyl, lower alkoxy, etc., and A is O, S, CO, SO ₂ , SO, CH ₂ , C
(CH ₃ ) ₂ , OBzO, Bz, OBzC (CH ₃ ) ₂ OB
a divalent group such as z, and m is an integer of 1 to 4. )
An aromatic diamine compound having a plurality of benzene rings, represented by the formula:

H ₂ N-Bz (R ₃ ) _n (X) _y —NH ₂ or the formula H ₂ N-Bz (R ₃ ) _n (X) _y -A- (X) _y (R ₄ ) _n B
z-NH ₂ (wherein, Bz is a benzene ring, R ₃ and R ₄ are hydrogen atoms, A is a direct bond, O, S, CO, SO ₂ , S
O, CH ₂ , C (CH ₃ ) ₂ , OBzO, Bz, OBzC
X is a divalent group such as (CH ₃ ) ₂ BzO, X is a carboxyl group or a hydroxyl group, n is 2 or 3, y is 1 or 2, and n + y = 4. An aromatic diamine compound having a polar group represented by the formula:

H ₂ N—R ₅ — [— Si (R ₆ ) ₂ —O—] _{l
-Si (R 5) 2 -R 5} -NH 2 ( where in the formula, R ₅ represents a divalent hydrocarbon residue, R ₆
Independently represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, and 1 represents 3 to 50. Is reacted with the diaminopolysiloxane represented by the formula (1) in such a ratio that the tetracarboxylic dianhydride becomes excessive with respect to the total amount of the diamine components. The above-mentioned imide-based photosensitive resin composition obtained by reacting.

5) The above-mentioned composition for a polyimide-based insulating film, further comprising (7) a required amount of a silane coupling agent. 6) Post-baking temperature is 200 ° C. or less, especially 160 ° C.
The above-mentioned method for forming a polyimide-based insulating film at a temperature of 180 ° C.

In the present invention, (1) it is necessary to use an imide siloxane oligomer which is half-esterified at the latest after prebaking, and the imide siloxane oligomer is already mixed with other components when it is mixed. A terminally esterified imide siloxane oligomer which has been esterified, or a mixture of an imide siloxane oligomer and an esterifying agent,
May be half-esterified at the time of curing.

The above-mentioned terminally esterified imide siloxane oligomer is obtained by reacting, for example, tetracarboxylic dianhydride with a smaller amount of diaminopolysiloxane as diamine and aromatic diamine to form an amic acid oligomer. Imidization, imide oligomer
Can be obtained by half-esterifying the acid anhydride terminal of the above with an esterifying agent. Alternatively, the step of forming an amic acid may be omitted, and the imide oligomer may be formed in one step at a relatively high temperature, followed by half esterification. At the time of the above-mentioned imidation, an imidization catalyst such as imidazoles may be added.

The reaction between the tetracarboxylic dianhydride and the diamine may be carried out by any of random, block or a mixture-recombination reaction of two reaction solutions. Further, the above-mentioned imide oligomer and half esterification reaction product can be used as they are without isolation from a solution.

The tetracarboxylic dianhydride includes:
3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic acid Dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, pyromellitic dianhydride, 2,3 6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5 8-naphthalenetetracarboxylic dianhydride, 2,2-bis (2,5-dicarboxyphenyl) propane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1-bis (3,4-dicarboxyphenyi ) Aromatic tetracarboxylic dianhydrides such as sulfone dianhydride.

As the alicyclic tetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride,
Examples include cyclohexanetetracarboxylic dianhydride and methylcyclohexenetetracarboxylic dianhydride. The above tetracarboxylic dianhydrides may be used alone or in combination of two or more. In particular, as a tetracarboxylic dianhydride having a high solubility in a solvent to obtain a high-concentration amic acid ester and a high heat resistance of the obtained imide insulating film, 2,3,
3 ′, 4′-biphenyltetracarboxylic dianhydride,
3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) e-
Terdianhydride and the like are preferred.

The aromatic diamine compound having a plurality of benzene rings, which is one component of the above-mentioned diamine, includes a compound represented by the formula H ₂ N-Bz (R ₁ ) _m -A- (R ₂ ) _m Bz-NH ₂ (where, Wherein Bz is a benzene ring and R ₁ or R
₂ is a substituent such as hydrogen, lower alkyl, lower alkoxy, etc., and A is O, S, CO, SO ₂ , SO, CH ₂ , C (C
_{H 3) 2, OBzO, Bz} , a divalent radical such as _{OBzC (CH 3) 2 OBz,} m is an integer of 1 to 4. ), Preferably benzene such as 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, and 1,4-bis (4-aminophenyl) benzene An aromatic diamine having three rings,
Alternatively, aromatic diamines having four benzene rings such as bis [4- (4-aminophenoxy) phenyl] sulfone and 2,2-bis [4- (4-aminophenoxy) phenyl] propane may be used.

The aromatic diamine compound having a polar group, which is a component of the diamine, has the formula H ₂ N—Bz (R ₃ ) _n (X) _y —NH ₂ or the formula H ₂ N—Bz (R ₃ ) _{n (X) y -A- (X} ) y (R 4) n B
z-NH ₂ (wherein, Bz is a benzene ring, R ₃ and R ₄ are hydrogen atoms, A is a direct bond, O, S, CO, SO ₂ , S
O, CH ₂ , C (CH ₃ ) ₂ , OBzO, Bz, OBzC
X is a divalent group such as (CH ₃ ) ₂ BzO, X is a carboxyl group or a hydroxyl group, n is 2 or 3, y is 1 or 2, and n + y = 4. ).

Examples of the aromatic diamine compound having a polar group include diaminophenol compounds such as 2,4-diaminophenol, and 3,3′-diamino, 4,4 ′.
-Dihydroxybiphenyl, 4,4'-diamino,
3,3'-dihydroxybiphenyl, 4,4'-diamino, 2,2'-dihydroxybiphenyl, 4,4 '
Hydroxybiphenyl compounds such as -diamino, 2,2 ', 5,5'-tetrahydroxybiphenyl,
3'-diamino, 4,4'-dihydroxydiphenylmethane, 4,4'-diamino, 3,3'-dihydroxydiphenylmethane, 4,4'-diamino, 2,2'-
Dihydroxydiphenylmethane, 2,2-bis [3-
Amino, 4-hydroxyphenyl] propane, 2,2
-Bis [4-amino, 3-hydroxyphenyl] propane, 2,2-bis [3-amino, 4-hydroxyphenyl] hexafluoropropane, 4,4'-diamino, 2,2 ', 5,5'- Hydroxydiphenylalkane compounds such as tetrahydroxydiphenylmethane, 3,3′-diamino, 4,4′-dihydroxydiphenylether, 4,4′-diamino, 3,3′-dihydroxydiphenylether, , 4'-diamino, 2,2'-dihydroxydiphenyl ether,
Hydroxydiphenyl ether compounds such as 4,4'-diamino, 2,2 ', 5,5'-tetrahydroxydiphenyl ether; 3,3'-diamino, 4,4'-
Dihydroxydiphenylsulfone, 4,4′-diamino, 3,3′-dihydroxydiphenylsulfone,
4,4′-diamino, 2,2′-dihydroxydiphenylsulfone, 4,4′-diamino, 2,2 ′, 5
Hydroxydiphenylsulfone compounds such as 5'-tetrahydroxydiphenylsulfone; bis (hydroxyphenoxyphenyl) alkane compounds such as 2,2-bis [4- (4-amino, 3-hydroxyphenoxy) phenyl] propane; Bis (hydroxyphenoxy) biphenyl compounds such as 4,4'-bis (4-amino, 3-hydroxyphenoxy) biphenyl;
Examples thereof include diamine compounds having an OH group such as bis (hydroxyphenoxyphenyl) sulfone compounds such as 2,2-bis [4- (4-amino, 3-hydroxyphenoxy) phenyl] sulfone.

Examples of the aromatic diamine compound having a polar group include 3,5-diaminobenzoic acid, 2,4
Benzenecarboxylic acids such as diaminobenzoic acid, 3,
3'-diamino, 4,4'-dicarboxybiphenyl,
4,4'-diamino, 3,3'-dicarboxybiphenyl, 4,4'-diamino, 2,2'-dicarboxybiphenyl, 4,4'-diamino, 2,2 ', 5,5'-tetra Carboxybiphenyl compounds such as carboxybiphenyl, 3,3′-diamino, 4,4′-dicarboxydiphenylmethane, 4,4′-diamino, 3,3′-
Dicarboxydiphenylmethane, 4,4'-diamino,
2,2'-dicarboxydiphenylmethane, 2,2-bis [3-amino, 4, -carboxyphenyl] propane, 2,2-bis [4-amino, 3-carboxyphenyl] propane, 2,2-bis [ Carboxydiphenylalkane compounds such as [3-amino, 4-carboxyphenyl] hexafluoropropane, 4,4′-diamino, 2,2 ′, 5,5′-tetracarboxybiphenyl;
3,3'-diamino, 4,4'-dicarboxydiphenyl ether, 4,4'-diamino, 3,3'-dicarboxydiphenyl ether, 4,4'-diamino, 2,3
Carboxydiphenyl ether compounds such as 2′-dicarboxydiphenyl ether, 4,4′-diamino, 2,2 ′, 5,5′-tetracarboxydiphenyl ether; 3,3′-diamino; 4,4′-dicarboxydiphenyl sulfone, 4,4′-diamino, 3,3′-dicarboxydiphenyl sulfone, 4,4′-diamino,
Carboxydiphenylsulfone compounds such as 2,2 ′, 5,5′-tetracarboxydiphenylsulfone,
Bis (carboxyphenoxyphenyl) alkane compounds such as 2,2-bis [4- (4-amino, 3-carboxyphenoxy) phenyl] propane, and 4,4′-bis (4-amino, 3-carboxyphenoxy) biphenyl COO such as bis (carboxyphenoxyphenyl) sulfone compounds such as bis (carboxyphenoxy) biphenyl compounds such as 2,2-bis [4- (4-amino, 3-carboxyphenoxy) phenyl] sulfone
Diamine compounds having an H group can be exemplified.

The diaminopolysiloxane, which is another component of the diamine, has the formula: H ₂ N—R ₅ — [— Si (R ₆ ) ₂ —O—] ₁ —Si (R ₅ )
₂ -R ₅ -NH ₂ (where in the formula, R ₅ represents a divalent hydrocarbon residue, R ₆
Independently represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, and 1 represents 3 to 50. The compound represented by the formula (1) is preferably a compound in which R ₅ and R ₆ are a plurality of methylene groups or phenylene groups having 2 to ₆ carbon atoms, particularly 3 to 5 carbon atoms. In the above formula, l is 4 to 30,
Particularly, it is preferably from 4 to 20. In addition, if l in the above formula is 3 to 50, the compound may be a uniform compound or a mixture of compounds having different l. In the case of a mixture, l of the average value calculated from amino equivalents
Is preferably in the range of 3 to 50, particularly 4 to 30, and especially 4 to 20.

Examples of specific compounds of the above diaminopolysiloxane include α, ω-bis (2-aminoethyl) polydimethylsiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, α, ω- Bis (4-aminophenyl) polydimethylsiloxane, α, ω-bis (4-amino-3-methylphenyl) polydimethylsiloxane, α, ω-bis (3-aminopropyl) polydiphenylsiloxane, α, ω-bis (4-aminobutyl)
And polydimethylsiloxane.

In the present invention, it is necessary that the imide siloxane oligomer is half-esterified in the step before the alkali development, whereby the alkali development can be easily performed. Half-esterified imidosiloxane oligomer used in the present invention
Can be obtained by half-esterifying the imide siloxane oligomer obtained as described above with an esterifying agent at the acid anhydride terminal of the imide siloxane oligomer.

As an esterifying agent for half-esterifying the acid anhydride terminal of the imide siloxane oligomer, a compound having one alcoholic OH group, for example,
Methanol, ethanol, isopropanol, butanol
Aliphatic alcohols such as ethyl, ethyl cellosolve, butyl cellosolve, propylene glycol ethyl ether and ethyl carbitol; cyclic alcohols such as benzyl alcohol and cyclohexanol; and 2-hydroxyethyl methacrylate. And hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl acrylate.

When an imide siloxane oligomer and an esterifying agent are mixed and used as a half ester during prebaking, the boiling point is higher than the heating temperature of the prebaker, preferably. It is preferable to use a compound having one alcoholic OH group having a boiling point of 80 ° C. or higher. Such compounds include ethyl cellosolve,
Hydroxyalkyl (meth) such as 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate
Acrylate.

In producing the above-mentioned terminally esterified imide siloxane oligomer, the reaction ratio of each component is as follows:
An amount in which the tetracarboxylic dianhydride is in excess with respect to the total amount of the diamine, preferably 1.05 to 2 mol, more preferably 1.05 to 2 mol of the tetracarboxylic dianhydride with respect to 1 mol of the diamine.
An equivalent ratio of about 1.5 mol is preferred. The amount of the compound having one alcoholic OH group, which is an esterifying agent for ring-opening half-esterification of an excess unreacted anhydride ring, is 1.1% of the excess diacid anhydride group. It is preferably 20 to 20 equivalents, particularly preferably 1.5 to 5 equivalents. The reaction product may be used as it is, or may be used by removing excess esterifying alcohols by heating or distillation under reduced pressure.

The above-mentioned terminally esterified imide siloxane oligomer is prepared by, for example, dissolving tetracarboxylic dianhydride in a solvent, adding diaminopolysiloxane and an aromatic diamine to the resulting solution, and reacting the solution by a conventional method. The obtained imide siloxane oligomer solution is cooled, the above-mentioned esterifying agent is added thereto, and half-esterified by reacting at a temperature of 80 ° C. or less, preferably 30 to 80 ° C. for about 0.1 to several hours. It can be obtained by:

The (2) photosensitive monomer in the present invention is a compound having a photopolymerizable unsaturated double bond in the molecule, preferably a compound further having a siloxane bond, and particularly a compound having two or more unsaturated double bonds. Compounds having a double bond are suitable. Examples of such compounds include diaminosiloxane and polyvalent (meth) acrylic acid derivative compounds [eg, tris (2-acryloyloxyethyl) isocyanurate]
And an esterified product of polysiloxanediol and (meth) acrylic acid (for example, X-22-164B, manufactured by Shin-Etsu Chemical Co., Ltd.). By using the photosensitive monomer having a siloxane bond, the compatibility with the terminal half-esterified imide oligomer is improved, and an insulating film having a good surface condition can be obtained.

As the above-mentioned diaminosiloxane or polysiloxane diol, those containing about 2 to 30 siloxane units of —Si (—R) ₂ O—, especially about 2 to 15 are suitable. Examples of the polyvalent (meth) acrylic acid derivative compound include trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate. To, Tris (2
Acrylates of (-hydroxyethyl) isocyanuric acid and their methacrylates, and also diacrylate compounds such as dipropylene glycol diacrylate.

The above-mentioned addition reaction between the polyvalent (meth) acrylic acid derivative compound and the diaminosiloxane is carried out by mixing an excess polyvalent (meth) acrylic acid derivative compound with diaminosiloxane, at a temperature of 0 to 80 ° C. and a molar ratio of 2 : 1 to 40: 1,
It is particularly preferable to carry out the reaction at a ratio of about 4: 1 to 20: 1. When the amount of the polyvalent (meth) acrylic acid derivative is small and approaches the equimolar, the gelation of the reactant proceeds and the operability is reduced. On the other hand, if the content is too large, the siloxane content is decreased, the compatibility with the terminal half-esterified imide siloxane oligomer is reduced, and the smoothness of the coating film is also undesirably reduced. The above addition reaction may be performed in a solvent. Examples of the solvent include ether solvents such as triglyme and diglyme, and ethylene glycol.
Alcohols such as rumonobutyl ether; ketones such as methyl n-amyl ketone; ethyl pyruvate;
Esters such as -methoxypropionate can be used.

(2) As the photosensitive monomer, other acrylic acid compounds containing no siloxane, including the polyvalent acrylic acid derivative compound used in the reaction, can be used in combination. The content of siloxane in the compound is preferably at least 5% by weight, particularly preferably at least 8% by weight. When the content of siloxane is small, the compatibility with the terminal half-esterified siloxane imide oligomer deteriorates, and the photosensitivity also decreases. In particular, the photocurability of the resist surface decreases.

The amount of the photosensitive monomer (2) used is (1)
There is no particular limitation as long as it is compatible with the terminal half-esterified siloxane imide oligomer.
It is preferable to use 1 to 100 parts by weight, particularly 1 to 50 parts by weight. (2) If the amount of the photosensitive monomer is too large, the adhesion to the substrate and the heat resistance of the insulating film obtained after the heat treatment are poor, which is not preferable. If the amount is too small, sufficient photosensitivity cannot be obtained.

The photopolymerization initiator (3) in the present invention includes, for example, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, acetophenone, benzoin, 2-methylbenzoin, benzoinmethylether, benzoinethyl Ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-t-
Butylanthraquinone, 1,2-benzo-9,10-anthraquinone, methylanthraquinone, thioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio ) Phenyl] -2-morpholino-propane-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, diacetylbenzyl, benzyldimethylketal, benzyldiethylketal, 2
(2′-furylethylidene) -4,6-bis (trichloromethyl) -S-triazine, 2 [2 ′ (5 ″ -methylfuryl) ethylidene] -4,6-bis (trichloromethyl) -S-triazine, 2 (p-methoxyphenyl)-
4,6-bis (trichloromethyl) -S-triazine,
2,6-di (p-azidobenzal) -4-methylcyclohexanone, 4,4'-diazidochalcone, di (tetraalkylammonium) -4,4'-diazidostilbene-2,2'-disulfonate, etc. Is mentioned.

The above (3) photopolymerization initiator is used in an amount of (1) half-esterified siloxane imide oligomer-100.
0.01 to 30 parts by weight, especially 0.5 to
30 parts by weight, and particularly preferably 1 to 20 parts by weight. As an aid of the above (3) photopolymerization initiator, ethyl 4-dimethylaminobenzoate, methyl 4-diethylaminobenzoate, methyl dimethylaminoanthranilate and the like can be used in combination.

The above-mentioned siloxane imide oligomer, ha
Examples of the reaction solvent for obtaining the ester and the photosensitive monomer include nitrogen-containing solvents such as N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N, N-diethylformamide, N −
Solvents containing sulfur atoms such as methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam and the like, including dimethylsulfoxide, diethylsulfoxide, dimethylsulfone, diethylsulfone, hexamethylsulfformamide and the like. Oxygen solvent, for example γ-
Butyrolactone, a phenolic solvent such as Crezo-
Diglyme solvents such as toluene, phenol, xylenol, etc., such as diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), tetraglyme, acetone, ethylene glycol, dioxane, tetrahydrofuran, etc. be able to. If necessary, an aromatic hydrocarbon solvent such as benzene, toluene and xylene, or another organic solvent such as solvent naphtha and benzonitrile may be used in combination.

In the present invention, (4) a crosslinking aid, preferably a combination of an epoxy resin and an epoxy curing agent, or a diamine in an amount equivalent to the terminal carboxyl group component of the half-esterified imide siloxane oligomer; Glycidyl (meth) acrylate is used. Said,
The amount of the (4) crosslinking aid used is 1 to 75 parts by weight of the (4) crosslinking aid based on 100 parts by weight of the (1) half-esterified imidosiloxane oligomer.

The epoxy resin may be any resin having an epoxy group at both ends, and is particularly preferably a liquid having an epoxy equivalent of about 100 to 1,000 and a molecular weight of about 300 to 5000. Alternatively, a solid epoxy resin is preferable. For example, bisphenol A type or bisphenol F type epoxy resin (manufactured by Yuka Shell Co., Ltd .: Epicoat 806, Epicoat 825, etc.), 3
Functional or higher epoxy resin (manufactured by Yuka Shell Co., Ltd .: Epicoat 152, Epicoat 154, Epicoat 180 series)
And Epicoat 157 series, Epicoat 1032 series, and MT0163 manufactured by Ciba Geigy Co., Ltd.).

The amount of the epoxy resin used is preferably 2 to 30 parts by weight based on 100 parts by weight of the half-esterified imidosiloxane oligomer. If too much or too little is used, the adhesion will decrease,
Since the heat resistance and chemical resistance deteriorate after curing, the above range is appropriate.

A curing agent for epoxy resins such as hydrazides and imidazoles is used together with the epoxy compound. This curing agent also functions as an imidization catalyst when the half-esterified imide siloxane oligomer and the diamine compound are heated and imidized. The appropriate amount of the epoxy resin curing agent used is about 0.1 to 10 parts by weight based on 100 parts by weight of the half-esterified imidosiloxane oligomer. Alternatively, a phenol novolak type curing agent having a hydroxyl group may be used in an amount of about 0 to 10 parts by weight based on 100 parts by weight of the half-esterified imide siloxane oligomer.

Alternatively, (4) when a reactive monomer containing a diamine and a glycidyl group in an amount equivalent to the terminal carboxyl group component of the half-esterified imide siloxane oligomer is used as a crosslinking aid, Glycidyl acrylate, glycidyl methacrylate, etc., as a reactive monomer containing a glycidyl group, using any of the above-mentioned diamine compounds having a plurality of benzene rings, or an alicyclic diamine compound or an aliphatic diamine compound. Glycidyl (meth) acrylate can be used.

The glycidyl group-containing reactive monomer is prepared by previously reacting a polar group such as COOH in a diamine residue of an imide siloxane oligomer with a glycidyl group of a glycidyl group-containing reactive monomer. It may be present in the composition.

In the present invention, it is preferable to use (5) a fine inorganic filler such as Aerosil, talc, mica, barium sulfate and the like. This fine inorganic filler
May be of any size and form,
The average particle diameter is 0.001 to 15 μm, especially 0.005 to
Those having a thickness of 10 μm are preferred. Cracks occur when the resulting coating film is bent when using a material outside this range,
It is not preferable because the bent portion is whitened. In the present invention, it is particularly preferable to use a combination of Aerosil (silica on fine powder) and at least one of talc, mica and barium sulfate.

In the present invention, (5) a fine inorganic filler
Is used in an amount of 1 to 50 parts by weight based on 100 parts by weight of the (1) half-esterified imidosiloxane oligomer. If the amount is too large, cracks occur due to bending of the coating film, and if the amount is too small, the solder heat resistance and the discoloration of the copper foil deteriorate, so the above range is necessary. Also,
When Aerosil is used in combination with at least one of talc, mica and barium sulfate, Aerosil is converted to a half-esterified imide siloxane oligomer-10.
It is preferable to use at least one of talc, mica, and barium sulfate in an amount of 1 to 10 parts by weight, particularly 2 to 10 parts by weight based on 0 parts by weight.

As the solvent (6), for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide,
Polar solvents such as N, N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, ethers such as diethylene glycol dimethyl ether (DG), triethylene glycol dimethyl ether (TG), propylene glycol diethyl ether; System solvents.
In addition to these solvents, alcohols such as ethyl cellosolve, butyl cellosolve, propylene glycol monobutyl ether, methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, ketones such as cyclohexanone, methyl acetate, ethyl acetate, butyl acetate ,
Ethyl lactate, diethyl oxalate, diethyl malonate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propylene glycol monomethyl ether
Esters such as teracetate and hydrocarbons such as toluene and xylene can also be used. These solvents can be used alone or in combination of two or more.

In particular, there can be mentioned organic polar solvents which can be used for obtaining the (1) half-esterified imide siloxane oligomer, but it is preferable to use one having a boiling point of 140 ° C. or more and 210 ° C. or less. In particular, when diethylene glycol dimethyl ether (DG), triethylene glycol dimethyl ether (TG), γ-butyrolactone, or the like is used, the dissipation due to evaporation of the solvent is reduced, and the application of the solution composition is suitable without any trouble. It is best because it can be done. In the present invention, it is preferable to use a total of 50 to 300 parts by weight of the solvent (6) based on 100 parts by weight of the imidosiloxane oligomer.

The imide-based photosensitive resin composition of the present invention comprises:
(1) Imidosiloxane oligomer which is half-esterified after prebaking, (2) photosensitive monomer, (3) photopolymerization initiator, (4) crosslinking aid, (5) fine inorganic filler and
It can be easily obtained by adding a predetermined amount of the solvent (6) and, if necessary, a suitable amount of the silane coupling agent (7), and uniformly stirring and mixing. When mixed, they are mixed in a solvent to form a half-esterified imidosiloxane oligomer.
To a solution composition of When mixed with a solvent to form a solution composition, the reaction solution of the half-esterified imide siloxane oligomer may be used as it is, or the reaction solution may be diluted with an appropriate organic solvent. Examples of the silane coupling agent include γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrisilane. Methoxysilane and the like can be mentioned. The amount used is preferably from 0 to 10 parts by weight based on 100 parts by weight of the half-esterified imidosiloxane oligomer. The solution composition for an imide-based insulating film preferably has a solution viscosity of 100 to 600 poise at room temperature from the viewpoint of workability, physical properties of the solution, and properties of the protective film.

After applying the imide-based photosensitive resin composition of the present invention to a substrate, pre-baking to form a thin film, exposure, alkali development, and post-baking to obtain a polyimide-based insulating film. Can be. In the above process, first,
The imide-based photosensitive resin composition is applied to a suitable support, for example, a printed board, ceramic, an aluminum substrate, a silicon wafer, or the like. As the application method,
There are methods such as spin coating, printing, and roll coating using a spinner. Next, at a temperature of 100 ° C. or less,
In the case of a high enemy, it is dried by heating at a temperature of 50 to 80 ° C. for about 10 to 60 minutes and prebaking to dry the coating film to form a thin film. In the present invention, when a mixed system of an imide siloxane oligomer and an esterifying agent is used as the half-esterified imide siloxane oligomer, the half-esterified imide siloxane oligomer is formed in this prebaking.

After the above steps, the desired pattern is irradiated with actinic radiation to expose. The actinic radiation preferably has a wavelength in the range of 300 to 500 nm, such as ultraviolet light and visible light. Next, the unirradiated portion is developed to obtain a pattern.
In the method for forming a pattern of the imide-based photosensitive resin composition of the present invention, an alkaline aqueous solution is used as a developer. This developer contains a small amount of methanol, ethanol,
n-propanol, isopropanol, N-methyl-2
-A water-soluble organic solvent such as pyrrolidone may be contained.

Examples of the alkaline compound for providing the above alkaline aqueous solution include hydroxides, carbonates, hydrogencarbonates, and amine compounds of alkali metals, alkaline earth metals or ammonium ions. Sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, Tetraisopropylammonium hydroxide, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylethanolamine, triethanolamine, triisopropanol Emissions, etc. can be mentioned tri-isopropylamine, an aqueous solution with compounds of other long as it exhibits basicity can also be naturally used. The concentration of the alkaline compound is usually 0.1 to 20% by weight.
It is preferable that

As the alkali developing method, various methods such as spraying, paddle, dipping, and ultrasonic waves can be adopted. The pattern formed by development is rinsed.
Examples of the rinsing liquid include water and an acidic aqueous solution.

Next, heat treatment is carried out to
Post-esterified imide siloxane oligomer-crosslinking aid, preferably a combined system of an epoxy resin and an epoxy curing agent, or a combined system of an amino compound mainly composed of an aromatic diamine compound and a reactive monomer having a glycidyl group. To form a heat-resistant final pattern. The post bake is at 200 ° C
Hereinafter, it is particularly preferable to carry out at 160 to 180 ° C. for about 10 to 60 minutes.

The insulating film obtained from the imide-based photosensitive resin composition of the present invention is made of a flexible copper-clad cover cover.
And a solder-resist film. The insulating film preferably has a radius of curvature of 100 m.
m or more, especially 300 mm or more flexibility, 260 ° C × 10
It has solder heat resistance of more than 2 seconds, solvent resistance to solvents such as acetone and methanol, alkali resistance, acid resistance, and electric characteristics.

[0054]

Embodiments of the present invention will be described below. The compounds used in each of the following examples are shown below with their abbreviations. a-BPDA: 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride DAPSi: α, ω-bis (3-aminopropyl) polydimethylsiloxane DABA: 3,5-diaminobenzoic acid MBAA: bis ( 3-carboxy, 4-aminophenyl) methane BAPP: 2,2-bis [4- (4-aminophenoxy) phenyl] propane TG: triglyme DG: diglyme

In each of the following examples, physical properties were evaluated as follows: Viscosity: E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.), 25 ° C., ST
Measured by using a tar. Viscosity stability: Shown as the ratio of the viscosity after storage for 90 days to the viscosity after one day of storage. Radius of curvature: Measured as follows. Based on JIS C-6481, UPILEX-75
S (manufactured by Ube Industries) formed a 35 μm thick insulating film and measured. Electrical properties: evaluated from surface resistance and volume resistance. Surface resistance: Measured according to JIS C-2103. Volume resistance: Measured according to JIS C-2103. Solvent resistance: After immersion in acetone (25 ° C) for 30 minutes,
The case where the acetone-soluble content was less than 2% was indicated by ○, and the case where it was 2% or more was indicated by ×. Solder heat resistance: evaluated at 260 ° C. for 10 seconds. The case where no abnormality occurred was indicated by ○, and the case where abnormality such as blistering occurred was indicated by ×.

[Production of half-esterified imidosiloxane oligomer] Reference Example 1 a-BPDA was placed in a glass flask having a capacity of 2000 ml.
176.09 g (598.5 mmol) and 254.26 g of methyltriglyme (TG) were charged and heated and stirred at 180 ° C. in a nitrogen atmosphere. 270.14 g of α, ω-bis (3-aminopropyl) polydimethylsiloxane (DAPSi, amino equivalent 448, n = 10) (301.
5 mmol) and 100 g of TG, and the mixture was heated and stirred at 180 ° C. for 60 minutes. Further, MBAA42.5 was added to the reaction solution.
1 g (148.5 mmol) and 100 g of TG were added,
After heating and stirring at 180 ° C. for 6 hours, filtration was performed. The resulting imide siloxane oligomer-reaction solution has a solid content of 5%.
0% by weight, solution viscosity 400 centipoise (measurement conditions: 3
0 ° C). [Ratio of each component] Acid component: 100 mol of a-BPDA
%, Diamine component: DAPSi 67 mol%, MBAA
33 mol%, acid component / diamine component = 1.33.

[Production of photosensitive imide siloxane oligomer having a terminal half ester] Reference Example 2 100 g of the imide siloxane oligomer reaction solution obtained in Reference Example 1 was added to glycidyl methacrylate (GM).
A) 1.13 g was added, and the mixture was stirred at 60 ° C. for one and a half hours.
Reaction with carboxylic acid of AA. Subsequently, 2.86 g of isopropyl alcohol (IPA) was added, and the mixture was heated and stirred at 60 ° C. for 2 hours to half-esterify the anhydrous rings at both ends, followed by filtration to half-esterify both ends. Thus, a reaction solution of an imidosiloxane oligomer having a crosslinkable group in the molecule was obtained.

[Production of Photosensitive Monomer] Reference Example 3 126.9 g of tris (2-acryloyloxyethyl) isocyanurate [M-315, manufactured by Toagosei Co., Ltd.] (300 mmol) and 120 g of methyl diglyme (DG) were stirred and dissolved at room temperature in a nitrogen atmosphere. Next, α, ω-bis (3-aminopropyl) polydimethylsiloxane (D
APSi, amino equivalent 460, n = 10) 46.0 g
(100 mmol) and 52.9 g of DG, and then 2
After stirring for a period of time, a photosensitive monomer, which is a reaction product obtained by adding one tris (2-acryloyloxyethyl) isocyanurate to both ends of diaminopolysiloxane,
Was obtained.

Example 1 50 g of the imidosiloxane oligomer solution (solid content: 49.9%) obtained in Reference Example 1 was placed in a glass container protected from light.
g to 2-hydroxyethyl methacrylate (HEMA)
1.25 g of the photosensitive monomer obtained in Reference Example 3 (solid content 5
(0%) of 15.39 g, and 2.57 g of Irgacure 907 (manufactured by Ciba Geigy) and 2,4 as photopolymerization initiators.
-Diethylthioxanthone (DETX, manufactured by Nippon Kayaku)
0.51 g, p-dimethylaminobenzoic acid ethyl ester (EDDMAB, manufactured by Nippon Kayaku) as a photopolymerization accelerator
1.02 g, silicon-based defoamer (manufactured by Dow Corning Co., Ltd.
DB-100) 0.13 g, Aerosil (average particle size:
2.56 g, talc (average particle size: 1.8)
μm), stirred at room temperature (25 ° C.) for 2 hours, allowed to stand overnight, and then uniformly mixed with a triple roll to obtain a photosensitive imide siloxane oligomer composition. The solution viscosity was 150 poise.

[Composition of the composition] Imidosiloxane oligomer (Reference Example 1): 100 parts by weight HEMA: 2.5 parts by weight Photosensitive monomer (Reference Example 3): 30 parts by weight Photopolymerization initiator (Irgacure 907) : 5 parts by weight Photopolymerization initiator (DETX): 1 part by weight Photopolymerization accelerator (EDMAB): 2 parts by weight Antifoaming agent (DB-100): 0.25 parts by weight Fine inorganic filler (Aerosil): 5 parts by weight Part Fine inorganic filler (talc): 10 parts by weight Solvent (TG): 100.4 parts by weight Solvent (DG): 30 parts by weight

[Addition of Epoxy Resin, Formulation Example 1] 50 g of the photosensitive imide siloxane oligomer composition prepared in the above composition and an epoxy resin (Epicoat 152, manufactured by Yuka Shell Co., Ltd.) in a light-shielded glass container. 2 g, epoxy curing agent (2-ethyl-4-methylimidazole 0.032)
g) was added and stirred at room temperature for 1 hour to obtain a composition.

[Half esterification, formation of insulating film] The solution composition for a photosensitive insulating film was coated on a copper foil (thickness: 35 μm, shiny surface) using a glass rod,
The resultant was dried by heating for 0 minutes to form a half-esterified film having a thickness of 20 to 30 μm. Attach a negative film to the dried film and use a UV exposure machine for 250m
J, 400 mJ irradiation, 1% Na at room temperature (25 ° C.)
_It was immersed in an aqueous solution of ₂ CO _3, and the unexposed portions were removed by water spray to obtain a resolution of 150 μm. Then 1
Heating and curing was performed in a dryer at 60 ° C. for 1 hour to obtain an insulating film.

[Evaluation Results of Composition and Cured Film] Viscosity of composition Before adding epoxy: 150 poise After adding epoxy: 150 poise Viscosity stability Before adding epoxy: 1.1 After adding epoxy: 2 Radius of curvature:> 300 mm Solder Heat resistance: 260 ° C. × 10 seconds, no abnormal appearance (no change) Solvent resistance: acetone, 25 ° C., 5 minutes… No abnormal appearance: Methanol, 25 ° C., immersed for 1 hour… No abnormal appearance: N-methyl Pyrrolidone, 25 ° C, 5 minutes swelling Acid resistance: 10% sulfuric acid, immersion at 25 ° C for 1 hour… No abnormal appearance Alkaline resistance: 10 caustic soda, 25 ° C, immersing for 1 hour…
No appearance abnormality Electrical properties Volume resistance:> 1 × 10 ¹⁶ Ω · cm Surface resistance:> 1 × 10 ¹⁶ Ω

Example 2 TG was added to the light-shielded glass container, and the terminal huff ester photosensitive imide siloxane oligomer solution obtained in Reference Example 2 was added to TG.
Was added to 50 g of a solution in which the concentration of the oligomer was adjusted to 50% by weight, and 3.22 g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) was obtained. 15 g of monomer liquid, 2.5 g of Irgacure 907 (manufactured by Ciba Geigy) and 0.5 g of 2,4-diethylthioxanthone (DETX, manufactured by Nippon Kayaku) as a photopolymerization initiator, p-dimethylamino as a photopolymerization accelerator 1.0 g of benzoic acid ethyl ester (EDMAB, manufactured by Nippon Kayaku Co., Ltd.), 0.125 g of a silicon-based antifoaming agent (manufactured by Dow Corning, DB-100), 2.5 g of Aerosil (average particle size: 0.01 μm) , Talc (average particle size: 1.
After stirring for 2 hours at room temperature (25 ° C.), the mixture was allowed to stand overnight, and then uniformly mixed with a triple roll to obtain a photosensitive imide siloxane oligomer composition. The solution viscosity was 150 poise.

[Composition of the composition] Terminal half ester imide siloxane oligomer (Reference Example 2): 100 parts by weight Diamine (BAPP): 6.44 parts by weight Photosensitive monomer (Reference Example 3): 30 parts by weight Photopolymerization initiator (Irgacure 907): 5 parts by weight Photopolymerization initiator (DETX): 1 part by weight Photopolymerization accelerator (EDMAB): 2 parts by weight Defoamer (DB-100): 0.25 parts by weight Fine inorganic Filler (Aerosil): 5 parts by weight Fine inorganic filler (talc): 10 parts by weight Solvent (TG): 100 parts by weight Solvent (DG): 30 parts by weight

[Formation of Insulating Film] The solution composition for a photosensitive insulating film was coated on a copper foil (thickness: 35 μm, shiny surface) using a glass rod, and dried by heating at 80 ° C. for 20 minutes.
A dried film having a thickness of 20 to 30 μm was formed. A negative film was attached to the dried film, and 250 mJ, 4
After irradiation with 00 mJ, 1% Na ₂ CO ₃ at room temperature (25 ° C.)
It was immersed in an aqueous solution, and the unexposed portions were removed by water spray. Then 180 ° C
Was heated and cured in a dryer for 1 hour to obtain an insulating film.

[Evaluation Results of Composition and Cured Film] Viscosity of composition: 150 poise Viscosity stability: 1.1 Radius of curvature:> 300 mm Soldering heat resistance: no abnormalities in appearance at 260 ° C. × 10 seconds (no change) Solvent property: acetone, 25 ° C, 1 hour: No abnormal appearance Acetone, 25 ° C, overnight: No abnormal appearance: Methanol, 25 ° C, 1 hour immersion: No abnormal appearance: N-methylpyrrolidone, 25 ° C, 20 Minutes: No appearance abnormality Acid resistance: 10% sulfuric acid, immersed in 25 ° C for 1 hour ... No abnormality in appearance Alkaline resistance: 10 caustic soda, 25 ° C, immersed for 1 hour ...
No appearance abnormality Electrical properties Volume resistance:> 1 × 10 ¹⁶ Ω · cm Surface resistance:> 1 × 10 ¹⁶ Ω

Example 3 A dry film was formed from this solution for a photosensitive insulating film in the same manner as in Example 2, and a negative film was attached to the dry film.
After irradiation with 250 mJ and 400 mJ using a V exposure machine,
It was immersed in a 1% aqueous solution of Na ₂ CO ₃ at room temperature (25 ° C.), and the unexposed portion was removed by water spray.
Got the resolution. Subsequently, the film was cured by heating in a dryer at 160 ° C. for 1 hour to obtain an insulating film.

[Evaluation Results of Cured Film] Curvature radius:> 300 mm Soldering heat resistance: no abnormalities in appearance at 260 ° C. × 10 seconds (no change) Solvent resistance: acetone, 25 ° C., 10 minutes ... no abnormalities in appearance Acetone, 25 ℃, 10 minutes… No appearance abnormality: Methanol, 25 ° C, immersed for 1 hour… No appearance abnormality: N-methylpyrrolidone, 25 ° C, 5 minutes… Swelling No appearance abnormality Alkali resistance: 10 caustic soda, 25 ° C, soak for 1 hour ...
No appearance abnormality Electrical properties Volume resistance:> 1 × 10 ¹⁶ Ω · cm Surface resistance:> 1 × 10 ¹⁶ Ω

[0070]

Since the imide-based photosensitive resin composition and the insulating film of the present invention have the above-described structures, they have the following effects.

The imide-based photosensitive resin composition of the present invention comprises
It has good storage stability, is capable of alkali development, and is capable of postbaking at a relatively low temperature.

The insulating film of the present invention has good electrical properties, heat resistance, acid resistance and alkali resistance. Further, according to the present invention, an insulating film exhibiting good characteristics can be formed by a simple operation.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/1515 C08K 5/1515 5/17 5/17 C08L 83/10 C08L 83/10 // H05K 3 / 28 H05K 3/28 D (C08L 83/10 (C08L 83/10 63:00) 63:00) A (72) Inventor Mitsushi Taguchi 8-1, Goi South Coast, Ichihara City, Chiba Prefecture Ube Industries, Ltd. F term in molecular research institute (reference) 2H025 AA06 AA07 AA08 AA10 AB15 AB16 AB17 AC01 AD01 BC14 BC34 BC43 BC77 CB25 CB32 CC03 CC08 CC20 FA29 4J002 CD052 CP163 CP171 DG049 DJ019 DJ049 DJ059 EE037 EE047 EU037 EQ099 EV247 EV307 EX069 FD019 FD143 FD146 FD147 FD150 FD152 FD158 FD159 FD209 GH00 GQ01 HA05 4J011 PA09 PA13 PA35 PA36 PA47 PA86 PA99 PB22 PB30 PC02 PC08 QA12 QA22 QA23 QA24 QA3 3 QA39 QB25 RA10 SA02 SA03 SA12 SA14 SA15 SA16 SA18 SA20 SA25 SA28 SA32 SA34 SA38 SA46 SA48 SA54 SA58 SA61 SA63 SA64 SA78 SA80 SA83 TA06 TA08 TA09 TA10 UA01 UA06 VA01 WA01 4J035 BA02 CA01N GA06 GB02 LA03 LB16 5A314 AA27

Claims (10)

[Claims] (1) An imidosiloxane oligomer which is half-esterified at the latest after prebaking, (2) a photosensitive monomer, (3) a photopolymerization initiator, (4) a crosslinking aid, 5) a fine inorganic filler and (6) a solvent, wherein the proportion of each component is (1) half-esterified imide siloxane oligomer
(2) Photosensitive monomer-0.1 to 1
00 parts by weight, (3) 0.01 to 30 parts by weight of a photopolymerization initiator,
(4) 1 to 75 parts by weight of a crosslinking aid and (5) a fine inorganic filler
An imide-based photosensitive resin composition in an amount of 1 to 50 parts by weight. 2. The method according to claim 1, wherein the imidosiloxane oligomer is already
The imide-based photosensitive resin composition according to claim 1, which is a terminally esterified imide siloxane oligomer which has been esterified. 3. The imide-based photosensitive resin according to claim 1, wherein the imide siloxane oligomer is a mixture obtained by mixing an imide siloxane oligomer and an esterifying agent and half-esterifying the mixture during prebaking. Composition. 4. The esterifying agent according to claim 3, wherein the esterifying agent is a compound having a boiling point of 80 ° C. or more and having one alcoholic OH group.
3. The imide-based photosensitive resin composition according to item 1. 5. A reaction of a diamine compound and glycidyl (meth) acrylate in which the cross-linking assistant is a combination of an epoxy resin and an epoxy curing agent or an amount equivalent to the terminal acid component of an imidosiloxane oligomer. 2. The imide-based photosensitive resin composition according to claim 1, which is a combination system of a functional monomer. 6. The method according to claim 1, wherein (1) the terminal half-esterified imide siloxane oligomer has 0 to 90 mol% of the formula H ₂ N—Bz (R ₁ ) _m -A- in tetracarboxylic dianhydride or aromatic diamine. (R ₂ ) _m Bz-NH ₂ (where Bz is a benzene ring and R ₁ or R
₂ is a substituent such as hydrogen, lower alkyl, lower alkoxy, etc., and A is O, S, CO, SO ₂ , SO, CH ₂ , C
(CH ₃ ) ₂ , OBzO, Bz, OBzC (CH ₃ ) ₂ OB
a divalent group such as z, and m is an integer of 1 to 4. )
In aromatic diamine compound having a plurality of benzene rings represented, and the aromatic diamine of 10 to 100 mol% formula _{H 2 N-Bz (R 3} ) n (X) y -NH 2 or the formula H ₂ N-Bz (R ₃ ) _n (X) _y -A- (X) _y (R ₄ ) _n B
z-NH ₂ (wherein, Bz is a benzene ring, R ₃ and R ₄ are hydrogen atoms, A is a direct bond, O, S, CO, SO ₂ , S
O, CH ₂ , C (CH ₃ ) ₂ , OBzO, Bz, OBzC
X is a divalent group such as (CH ₃ ) ₂ BzO, X is a carboxyl group or a hydroxyl group, n is 2 or 3, y is 1 or 2, and n + y = 4. Aromatic diamine compounds having a polar group represented by), and the formula _{H 2 N-R 5 - [} - Si (R 6) 2 -O-] l -Si (R 5)
₂ -R ₅ -NH ₂ (where in the formula, R ₅ represents a divalent hydrocarbon residue, R ₆
Independently represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, and 1 represents 3 to 50. Is reacted with the diaminopolysiloxane represented by the formula (1) in such a ratio that the tetracarboxylic dianhydride becomes excessive with respect to the total amount of the diamine components. The imide-based photosensitive resin composition according to claim 2, which is obtained by reacting. 7. The composition for a polyimide-based insulating film according to claim 1, further comprising (7) a required amount of a silane coupling agent. 8. The imide-based photosensitive resin composition according to claim 1, applied to a substrate, prebaked to form a thin film, exposed to light, alkali-developed, and postbaked. The resulting polyimide insulating film. 9. An imide-based photosensitive resin composition according to claim 1, applied to a substrate, prebaked to form a thin film, exposed to light, alkali-developed, and postbaked. A method for forming a polyimide-based insulating film. 10. The method for forming a polyimide-based insulating film according to claim 9, wherein the post-baking is performed at a temperature of 200 ° C. or less, particularly 160 to 180 ° C.