JPH11335555A - Siloxane modified polyimide resin composition and its cured item - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin compsn. which is excellent in storage stability, is curable at a low temp., and gives a cured item excellent in heat resistance, stress relaxation characteristics, electrocorrosion resistances, and chemical resistance, esp. resistance to a tin plating liquid. SOLUTION: This compsn. is obtd. by dissolving 100 pts.wt. siloxane-modified polyimide resin obtd. by the polycondensation of an arom. tetracarboxylic dianhydride, a siloxanediamine, and another arom. diamine component, 1-50 pts.wt. epoxy resin, and 0.1-10 pts.wt. triazinethiol compd. of the formula (wherein R1 is -SH, -N(D4 H9 )2 , or -HNC6 H5 ; and M is H or an alkali metal) in an org. solvent. The siloxane-modified polyimide resin may be a siloxane- modified polyimideamic acid resin which has imide parts formed by the polycondensation of an arom. tetracarboxylic dianhydride and a siloxanediamine and amic acid parts formed by the polycondensation of an arom. tetracarboxylic dianhydride and another arom. diamine component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a siloxane-modified polyimide resin composition and a cured product thereof, and more particularly, to an interlayer insulating film or a surface protective film of a wiring component such as a printed board, a die bonding agent for a semiconductor package, The present invention relates to a siloxane-modified polyimide resin composition that can be used as a liquid sealant, other heat-resistant adhesives for electronic materials, and the like, and a cured product thereof.

[0002]

2. Description of the Related Art Use of an aromatic polyimide varnish or an aromatic polyimide precursor (aromatic polyamic acid) varnish as an electrically insulating protective film such as an interlayer insulating film is disclosed in, for example, Japanese Patent Application Laid-Open No. 62-242393. Various proposals have already been made. Such a varnish is applied on a flexible wiring board by screen printing or the like, and is cured to form a protective film. At this time, the terminal leads of the conductor pattern not covered with the protective film are subjected to plating for bonding (bonding) with the semiconductor bumps. On the other hand, TAB (Tape Automated B
and applied to liquid crystal driver ICs such as notebook personal computers. In the bonding method, gang bonding in which a combination of a gold bump / tin plating lead is collectively processed as a eutectic alloy of gold and tin is mainly used. Therefore, in this application, a flexible wiring board covered with a protective film is treated with an electroless tin plating bath before bonding to an IC chip. In general, the electroless tin plating bath is often strongly acidic, and the treatment is performed at a high temperature of 70 ° C. or more and under severe conditions. Therefore, there is a problem that the protective film on the flexible wiring board is eroded.

However, the materials which have been used as protective films and the like have low tin plating resistance to the tin plating solution, and cannot be said to have sufficient properties when used in these applications.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a composition having excellent storage stability, capable of being cured at a low temperature of 180 ° C. or lower, and having heat resistance, stress relaxation properties, electrolytic corrosion resistance, chemical resistance, and the like after curing. In particular, it is an object of the present invention to provide a resin composition which gives an excellent cured product having resistance to a tin plating solution.

[0005]

Means for Solving the Problems As a result of intensive studies on such problems, the present inventors have found that an aromatic tetracarboxylic dianhydride and siloxane diamine are polycondensed with another aromatic diamine component. A siloxane-modified polyimide resin, or a polyimide amic acid copolymer resin having an imide moiety composed of an aromatic tetracarboxylic dianhydride and a siloxane diamine and an amic acid moiety composed of an aromatic tetracarboxylic dianhydride and an aromatic diamine The present inventors have found that a siloxane-modified polyimide-based resin composition which is uniformly dissolved in an organic solvent together with an epoxy resin and a triazinethiol compound can achieve the above object, and have completed the present invention.

That is, the present invention provides 100 parts by weight of a siloxane-modified polyimide resin obtained by polycondensing an aromatic tetracarboxylic dianhydride, siloxane diamine and another aromatic diamine component, and 1 to 50 parts by weight of an epoxy resin. And a siloxane-modified polyimide resin composition obtained by dissolving 0.1 to 10 parts by weight of a triazine thiol compound represented by the following general formula (1) in an organic solvent.

Embedded image (Wherein R ₁ is —SH, —N (C ₄ H ₉ ) ₂ , —HNC ₆
Indicates H _5, M represents a hydrogen atom or an alkali metal atom)

Further, the present invention provides an imide moiety formed by polycondensation of an aromatic tetracarboxylic dianhydride and a siloxane diamine, and a polyaddition of an aromatic tetracarboxylic dianhydride and another aromatic diamine component. Modified Polyimide Amic Acid Resin 10 Having Amic Acid Site
0 parts by weight, 1 to 50 parts by weight of an epoxy resin, and 0.1 to 0.1 parts by weight of the triazine thiol compound represented by the general formula (1).
It is a siloxane-modified polyimide resin composition obtained by dissolving 10 parts by weight in an organic solvent.

Further, the present invention is a cured product obtained by heat-curing the above siloxane-modified polyimide resin composition.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The siloxane-modified polyimide resin used in the present invention is a siloxane-modified polyimide resin obtained by polycondensing an aromatic tetracarboxylic dianhydride, a siloxane diamine and another aromatic diamine component, or an aromatic tetracarboxylic acid. A siloxane modified polyimide amic acid resin having an imide moiety formed by polycondensation of dianhydride and siloxane diamine and an amic acid moiety formed by polyaddition of an aromatic tetracarboxylic dianhydride and another aromatic diamine component. Say.

As a siloxane-modified polyimide resin,
A siloxane modification having an imide moiety formed by polycondensation of an aromatic tetracarboxylic dianhydride and a siloxane diamine and an amic acid moiety formed by polyaddition of an aromatic tetracarboxylic dianhydride and another aromatic diamine component When a polyimide amic acid copolymer resin is used, it is necessary that all of the imides be stable imide except for the site formed by adding the aromatic tetracarboxylic dianhydride and the aromatic diamine.

The aromatic tetracarboxylic dianhydride constituting the siloxane-modified polyimide resin includes, for example, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride , Naphthalene-1,2,5,6-tetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride Product, naphthalene-1,2,6,7-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetra Carboxylic anhydride, 4,8-dimethyl
-1,2,3,5,6,7-hexahydronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,
5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5 , 8-tetracarboxylic dianhydride, 1,4,5,8-tetrachloronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenyltetracarboxylic Acid dianhydride, 2,2 ', 3,3'-diphenyltetracarboxylic dianhydride, 2,3,3', 4'-diphenyltetracarboxylic dianhydride, 3,3 '', 4,4 `` -p-terphenyltetracarboxylic dianhydride, 2,2 '', 3,3 ''-p-terphenyltetracarboxylic dianhydride, 2,3,3 '', 4 ''-p -Terphenyltetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -propane dianhydride, Bis (2,3-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride Bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3.4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, bis (3,4-di (Carboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, perylene-2, 3,8,9-tetracarboxylic dianhydride, perylene-3,4,9,10-tetracarboxylic dianhydride, perylene-4,5,10,11-tetracarboxylic dianhydride, perylene-5 , 6,11,12-tetracarboxylic dianhydride, phenanthrene-1,2,7,8-tetracarboxylic dianhydride, phenanthrene-1,2,6,7-tetracarboxylic dianhydride, phenanthrene- 1,2,9,10-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride Anhydride,
Pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride and the like, It is not limited to these. These aromatic tetracarboxylic dianhydrides may be used alone or in combination of two or more. Among these, bis (3,4-dicarboxyphenyl) sulfone dianhydride is particularly preferable because the polyimide resin having the siloxane unit has excellent solubility in an organic solvent, excellent adhesion to a copper surface, and the like. is there.

The diamine components constituting the siloxane-modified polyimide resin are an aromatic diamine and a siloxane diamine. Such aromatic diamines include:
For example, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,6-
Dimethyl-m-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 2,4-diaminomesitylene, 4,4'-methylenedi-o-toluidine, 4,4'-methylenedi-2,6-xylidine, 4 , 4'-Methylene-2,6-diethylaniline, 2,4-
Toluenediamine, m-phenylene-diamine, p-phenylene-diamine, 4,4'-diamino-diphenylpropane, 3,3'-diamino-diphenylpropane, 4,4'-diamino-diphenylethane, 3,3'- Diamino-diphenylethane, 4,4'-diamino-diphenylmethane, 3,3'-diamino-diphenylmethane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 4,4'-diamino-diphenyl sulfide , 3,3'-diamino-diphenyl sulfide, 4,4'-diamino-diphenyl sulfone, 3,3'-diamino-diphenyl sulfone, 4,4'-diamino-diphenyl ether, 3,3'-diamino-diphenyl ether, benzidine , 3,3'-diamino-biphenyl, 3,3'-dimethyl-4,4'-diamino-biphenyl, 3,3'-dimethoxy-benzidine, 4,4'-diamino-p-terphenyl, 3,3 '-Diamino-p-terphenyl, (P-amino-cyclohexyl) methane, bis (p-β-amino-t-butylphenyl) ether, bis (p-β-methyl-δ-aminopentyl) benzene, p-bis (2-methyl-4- Amino-pentyl) benzene, p-bis (1,1-dimethyl-5-amino-pentyl) benzene, 1,5-diamino-naphthalene, 2,6-diamino-naphthalene, 2,4-bis (β-amino- t-butyl)
Toluene, 2,4-diamino-toluene, m-xylene-2,5-
Diamine, p-xylene-2,5-diamine, m-xylylene-
Diamine, p-xylylene-diamine, 2,6-diamino-pyridine, 2,5-diamino-pyridine, 2,5-diamino-1,3,4
-Oxadiazole, piperazine, 1,3-bis (3-aminophenoxy) benzene and the like, but are not limited thereto.

The aromatic diamine having a functional group reactive with the epoxy resin includes, for example, 2,5-aminophenol, 3,5-diaminophenol, 4,4 ′-(3,3′-dihydroxy) diaminobiphenyl , 4,4 '-(2,2'-dihydroxy)
Diaminobiphenyl, 2,2'-bis (3-amino-4-dihydroxyphenyl) hexafluoropropane, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,4 '-(3,3'- Dicarboxy) diaminobiphenyl, 3,3'-dicarboxy-
4,4'-diaminodiphenyl ether and the like.
These may be used alone or in combination of two or more.

The siloxane diamine used in the siloxane-modified polyimide resin is preferably represented by the following general formula (2).

Embedded image

Here, R_Two, R_ThreeRepresents a divalent hydrocarbon group
Shown, preferably a divalent hydrocarbon group having 2 to 6 carbon atoms,
More preferably, it is a methylene group or a phenyl group. Ma
R _Four~ R₇Represents a hydrocarbon group having 1 to 6 carbon atoms, respectively.
Shown, preferably methyl group, ethyl group, propyl group or
Is preferably a phenyl group. Average repeating unit n is 1 to 30,
Preferably it is 1-20, More preferably, it is 1-12.
When the average repeating unit n exceeds 12, chemical resistance and circuit
Adhesion with the pattern decreases.

As such siloxane diamine,
For example, ω, ω′-bis (2-aminoethyl) polydimethylsiloxane, ω, ω′-bis (3-aminopropyl) polydimethylsiloxane, ω, ω′-bis (4-aminophenyl) polydimethylsiloxane, ω , Ω'-bis (3-aminopropyl) polydiphenylsiloxane, ω, ω'-bis (3-aminopropyl) polymethylphenylsiloxane, and the like. These may be used alone or in combination of two or more.

The molar ratio of the siloxane diamine to the aromatic diamine is preferably from 30/70 to 99/1, and more preferably from 50/50 to 99/1. If the molar ratio of the siloxane diamine is lower than 30, the shrinkage of the cured product increases, and the flexible wiring board using the same is warped,
If it exceeds 99, a problem occurs in heat resistance.

The molecular weight of the siloxane-modified polyimide resin can be controlled by adjusting the molar ratio of the monomer components, similarly to a general polycondensation polymer. That is, the diamine mixture is 0.8 to 1.2 mol, preferably 0.95 to 1.05 mol, more preferably 0.98 to 1 mol per 1 mol of the aromatic tetracarboxylic dianhydride mixture.
1.02 mol. If this molar ratio is lower than 0.8 or higher than 1.2, only low molecular weight ones can be obtained, and sufficient heat resistance cannot be obtained.

The siloxane-modified polyimide resin composition of the present invention is obtained by the following method. A predetermined amount of silicone diamine is gradually added to a solution in which an aromatic tetracarboxylic dianhydride is dissolved or suspended in an organic solvent. The mixture is 1
Polymerization and imidization are carried out for 10 to 24 hours while removing condensed water at a temperature of 50 ° C. or higher to obtain a siloxane polyimide oligomer having an acid anhydride at a terminal. The imidation ratio (%) of the siloxane polyimide oligomer is substantially 100% as measured by an infrared absorption spectrum analysis method, and preferably has no amic acid site. Subsequently, after cooling the reaction mixture to around room temperature, an aromatic diamine having a reactive functional group was added so that the acid anhydride and all the diamine components became substantially equimolar, and further imidized at a temperature of 150 ° C. or more. Perform the reaction. The desired siloxane-modified polyimide resin composition can be obtained by uniformly dissolving the epoxy resin and the triazine thiol compound in the polyimide resin having the siloxane unit.

On the other hand, the siloxane-modified polyimide amic acid resin composition is obtained by the following method. A predetermined amount of silicone diamine is gradually added to a solution in which an aromatic tetracarboxylic dianhydride is dissolved or suspended in an organic solvent. The mixture is removed at a temperature of 150 ° C. or higher while removing condensed water.
Polymerization and imidization are performed for up to 24 hours to obtain a siloxane polyimide oligomer having an acid anhydride at a terminal. The imidation ratio (%) of the siloxane polyimide oligomer is substantially 100% as measured by an infrared absorption spectrum analysis method, and preferably has no amic acid site. continue,
After cooling the reaction mixture to around room temperature, an aromatic diamine is added so that the acid anhydride and all the diamine components become substantially equimolar, and reacted at a temperature of 10 to 60 ° C. to obtain a siloxane polyimide polyamic acid resin. When an aromatic diamine having a reactive functional group with respect to the epoxy resin is used, imidization may be further performed. By uniformly dissolving the epoxy resin and the triazine thiol compound in the polyimide amic acid resin having the siloxane unit, a target siloxane-modified polyimide amic acid resin composition can be obtained.

The epoxy resin used in the present invention is not particularly limited as long as it can be mixed with a siloxane-modified polyimide resin or a siloxane-modified polyimide amic acid resin. As such an epoxy resin, a liquid or powdery epoxy resin having an epoxy equivalent of about 100 to 1,000 is preferable, and examples thereof include bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4′-biphenol, and 2,2. '-Phenols such as biphenol, hydroquinone, resorcin, and tris- (4-hydroxyphenyl) methane, 1,1,2,2-
Trivalent or higher phenols such as tetrakis (4-hydroxyphenyl) ethane, phenol novolak and o-cresol novolak, and glycidyl ether compounds derived from halogenated bisphenols such as tetrabromobisphenol A and bromophenol novolak. Can be These may be used alone or in combination of two or more. If the epoxy equivalent is lower than 100, the shrinkage of the cured product increases, and the flexible wiring board using the same warps. If it exceeds 1,000, the reactivity with the siloxane-modified polyimide resin or siloxane-modified polyimide amic acid resin decreases. .

The compounding amount of the epoxy resin in the polyimide resin composition of the present invention may be a siloxane-modified polyimide resin or a siloxane-modified polyimide amic acid resin.
It is 1 to 50 parts by weight, preferably 2 to 30 parts by weight based on 0 parts by weight. If the amount of the epoxy resin is too large, the composition gels or the elasticity of the cured film increases, and if the amount is too small, the chemical resistance decreases.

The polyimide resin composition of the present invention may contain, if necessary, an epoxy resin curing agent for the purpose of accelerating curing, in addition to the polyimide resin having a siloxane unit and the epoxy resin.

The triazine thiol compound represented by the general formula (1) is blended as an essential component in the polyimide resin composition of the present invention. In the general formula (1), M represents a hydrogen atom or an alkali metal, and sodium is preferable as the alkali metal. Such triazine thiol compounds include, for example, 1,3,5-triazine-2,4,6-
Trithiol, 1,3,5-triazine-2,4,6-trithiol sodium, 2-dibutylamino-1,3,5-triazine-4,6
-Dithiol compounds and the like. These triazine thiol compounds may be used alone or in combination of two or more.

The amount of the triazine thiol compound is 0.1 to 10 parts by weight, preferably 0.3 to 5 parts by weight, based on 100 parts by weight of the siloxane-modified polyimide copolymer resin. If the amount of the triazine thiol compound is too large, the chemical resistance deteriorates. If the amount is too small, the resistance to the tin plating solution is not sufficient.

The organic solvent used in the polyimide resin composition of the present invention is not particularly limited, but may be used alone as long as it can uniformly dissolve the present resin composition.
A mixed solvent using two or more kinds may be used. Examples of such organic solvents include phenol solvents, pyrrolidone solvents, amide solvents such as acetamide solvents, oxane solvents such as dioxane and trioxane, ketone solvents such as cyclohexanone, and methyl diglyme. A glyme-based solvent such as methyltriglyme is exemplified. If necessary, an aromatic hydrocarbon-based solvent such as benzene or toluene or an aliphatic hydrocarbon-based solvent such as hexane or decane can be mixed and used in such a solvent as far as it can be uniformly dissolved.

In the present invention, the organic solvent used in the reaction is not limited, but may be the above-mentioned organic polar solvent, and may have a boiling point of 150 ° C. or higher due to the problem of shortening the reaction time and dissipating the solvent. And preferably 2
Organic polar solvents having a temperature of 00 ° C. or higher, such as methyltriglyme, are preferred.

The polyimide resin composition of the present invention may contain, if necessary, a curing accelerator, a coupling agent, a filler, a pigment, a thixotropy-imparting agent, a defoaming agent, in addition to the components described above. May be appropriately blended.

[0029]

The present invention will be described in more detail with reference to the following examples. The abbreviations used in the examples and the like are the following compounds. DSDA: bis (3,4-dicarboxyphenyl) sulfone dianhydride ODPA: bis (3,4-dicarboxyphenyl) ether dianhydride PSX: ω, ω′-bis (3-aminopropyl) polydimethylsiloxane ( Average molecular weight 850) BAPP: 2,2-bis [4- (4-aminophenoxy) phenyl] propane DABA: 3,5-diaminobenzoic acid HAB: 4,4 ′-(3,3′-dihydroxy) diaminobiphenyl YD : Bisphenol A type epoxy resin YD-011 manufactured by Toto Kasei Co., Ltd. YDCN: o-cresol novolac type epoxy resin YDCN-701P manufactured by Toto Kasei Co., Ltd. EPPN: Tris (4-hydroxyphenyl) methane manufactured by Nippon Kayaku Co., Ltd. -Type polyfunctional epoxy resin EPPN-502H TT: Disnet F (1,3,5-triazine-2,4,6-trithiol) manufactured by Sankyo Chemical Co., Ltd. BTT: Sankyo Chemical Co., Ltd. Sunnet DB (2-dibutylamino-1,3,5-triazine-4,6-dithiol)

The characteristics of the resin composition were evaluated by the following items and evaluation methods. [Logarithmic viscosity] Logarithmic viscosity as a measure of the molecular weight of the polyimide resin having a siloxane unit obtained in the production example,
Dissolve the polyimide resin uniformly in methyldiglyme,
A solution having a concentration of 0.5 g / 100 ml was prepared, measured at a temperature of 30 ° C. using an Ubbelohde viscometer, and calculated by the following equation. η (logarithmic viscosity) = ln (t / t ₀ ) /0.5 t: transit time between marked lines of the measurement solution (sec) t ₀ : transit time between marked lines of pure solvent of methyldiglyme (se
c)

[Elastic Modulus] A copper foil (1 ounce rolled foil, manufactured by Mitsui Kinzoku Co., Ltd.) having a thickness of 35 μm has a thickness of 15 to 20 after heat treatment.
A solution composition of a polyimide resin having a siloxane unit prepared to each composition so as to be μm was cast at 80 ° C.
And then heat-treated at 160 ° C. for 60 minutes to form a coating film. After completely removing the copper from the copper foil formed with the specific film with an etching solution, a 12.5 × 20 cm specific film test piece was prepared and attached to a tensile tester (manufactured by Toyo Seiki Co., Ltd., STROGRAPH-R1), and the load was 100 kg. The elastic modulus was measured at a tensile speed of 5 mm / min.

[Solder heat resistance] Each composition was coated on a roughened copper surface of a copper foil having a copper thickness of 18 μm (manufactured by Mitsui Kinzoku Co., Ltd., 0.5 oz rolled foil) so that the film thickness after heat treatment was 15 to 20 μm. The solution composition of the prepared polyimide resin having a siloxane unit is cast, pre-dried at 80 ° C. for 15 minutes, and heat-treated at 160 ° C. for 60 minutes to form a coating film. Create a 1 x 2 cm coated foil, 26
The film is immersed in a molten solder bath set at 0 ° C. for 60 seconds, and the presence or absence of peeling of the specific film from the copper surface or a change in the specific film appearance is determined.な し indicates no abnormality and × indicates abnormality.

[Tin plating solution resistance] Non-adhesive type copper-clad laminate having a circuit formed by copper (S Nippon Steel Chemical Co., Ltd.
C18-40-00WE: 18 μm electrolytic copper foil laminated on 40 μm thick polyimide resin) and a film thickness after heat treatment of 15 to
A solution composition of a polyimide resin having a siloxane unit prepared in each composition so as to have a thickness of 20 μm was cast, and the solution was adjusted to 80 μm.
After pre-drying at 15 ° C for 15 minutes, heat treatment is performed at 160 ° C for 60 minutes to form a coating film. A 3.5 x 6 cm specific film test piece was prepared, and a copper surface treatment solution (Chip Polish 1 Co., Ltd.)
51L-2) for 15 seconds, washed with pure water, and then immersed in a tin plating solution (Tineposit LT-34, Shipley Far East Co., Ltd.) for 4 minutes at 70 ° C. After washing with pure water and drying, the width of the polyimide resin cured film having a siloxane unit on the copper circuit, which was discolored from the end face, was defined as the tin plating solution erosion amount.

[Acetone-soluble component] A copper foil (1 ounce rolled foil manufactured by Mitsui Kinzoku Co., Ltd.) having a thickness of 35 μm has siloxane units prepared in various compositions such that the film thickness after heat treatment is 15 to 20 μm. The solution composition of the polyimide resin is cast, pre-dried at 80 ° C. for 15 minutes, and heat-treated at 160 ° C. for 60 minutes to form a coating film. After completely removing the copper with an etching solution, the copper foil on which the specific film was formed was used to form a specific film of 10 × 10 cm, and the temperature was 25 ° C.
The sample is immersed in the acetone solution set in the above, taken out after 30 minutes, and the amount of weight loss of the specific film after drying is measured as the acetone-soluble matter.

Production Example 1 80.8 g (0.226 mol) of DSDA and 118 g of triglyme were charged into a Dean-Shyurark-type reactor equipped with a stirrer and a nitrogen inlet tube, and 140.0 g (0.165 mol) of PSX under a nitrogen atmosphere. Was added dropwise using a dropping funnel and stirred at room temperature for about 2 hours. Subsequently, the reaction solution was heated to 195 ° C. under a nitrogen atmosphere,
The mixture was heated and stirred for 15 hours while removing water. Then, the reaction solution was cooled to room temperature, and 24.8 g of BAPP (0.061
l) and 118 g of diglyme and add about 5 at room temperature under a nitrogen atmosphere.
The mixture was stirred for an hour to obtain a siloxane-modified polyimide resin solution having a solid content of 51 parts by weight. Viscosity of resin composition solution (temperature
(25 ° C.) was 240 poise and the logarithmic viscosity was 0.32.

Production Example 2 78.8 g (0.219 mol) of DSDA was placed in the same reactor as in Production Example 1.
And Triglyme 110g, PSX 1 under nitrogen atmosphere
32.0 g (0.156 mol) was added dropwise using a dropping funnel, and the mixture was stirred at room temperature for about 2 hours. Subsequently, the reaction solution was heated to 195 ° C. under a nitrogen atmosphere, and heated and stirred for 15 hours while removing water. Then, the reaction solution was cooled to room temperature, and DA
9.7 g (0.063 mol) of BA and 110 g of triglyme were added, and the mixture was stirred under a nitrogen atmosphere at room temperature for about 1 hour.
The mixture was heated and stirred for 2 hours while heating at 195 ° C. to remove water. The reaction solution is cooled to room temperature, and triglyme is added.
60 g was added to obtain a siloxane-modified polyimide resin solution having a solid concentration of 44 parts by weight. Viscosity of resin composition solution (temperature 25
C) was 150 poise and the logarithmic viscosity was 0.27.

Production Examples 3 and 4 A siloxane-modified polyimide resin solution was obtained in the same manner as in Production Examples 1 and 2, except that the aromatic tetracarboxylic dianhydride and aromatic diamine components shown in Table 1 were used.

The composition (mol) of Production Examples 1 to 4 and the solid content, viscosity and logarithmic viscosity of the obtained siloxane-modified polyimide resin solution are shown in Table 1.

Example 1 24 parts by weight of YD and 2 parts by weight of TT were mixed with 100 parts by weight of the solid content of the siloxane-modified polyimide resin obtained in Production Example 1, and the mixture was stirred at room temperature for about 2 hours to be uniformly dissolved. Thus, a siloxane-modified polyimide-based resin solution was obtained. This resin solution was cast on a predetermined base material, and preliminarily dried at 80 ° C. for 15 minutes.
Heat treatment was performed at 0 ° C. for 60 minutes to prepare a coating film. The elastic modulus, solder heat resistance, tin plating solution resistance, and acetone-soluble matter of this coating film were measured. Table 2 shows the results. In addition,
The amounts of the epoxy resin and the triazine thiol compound in Table 2 are shown in parts by weight.

Examples 2 to 7 and Comparative Examples 1 to 3 The epoxy resin and triazine thiol compound shown in Table 2 were used for 100 parts by weight of the solid content of the siloxane-modified polyimide resin as the base obtained in Production Examples 1 to 4. A siloxane-modified polyimide-based resin solution was obtained in the same manner as in Example 1 except that the solution was used. This resin solution is cast on a predetermined base material,
After preliminary drying at 80 ° C. for 15 minutes, heat treatment was performed at 160 ° C. for 60 minutes to form a coating film. The elastic modulus, solder heat resistance, tin plating solution resistance, and acetone-soluble matter of this coating film were measured.
Table 2 shows the results.

[0041]

[Table 1]

[0042]

[Table 2]

[0043]

Industrial Applicability The siloxane-modified polyimide resin composition of the present invention can be used for an interlayer insulating film or a surface protective film of a wiring component such as a printed board, and the cured product has excellent heat resistance, electrolytic corrosion resistance, and corrosion resistance. It has chemical properties, especially corrosion resistance to tin plating solutions.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 63:00) (72) Inventor Akira Tokumitsu 1 Tsukiji, Kisarazu-shi, Chiba Nippon Steel Chemical Co., Ltd. Electronic Materials Development Center

Claims (6)

[Claims] 1. 100 parts by weight of a siloxane-modified polyimide resin obtained by polycondensation of an aromatic tetracarboxylic dianhydride, a siloxane diamine and another aromatic diamine component, 1 to 50 parts by weight of an epoxy resin, and Triazine thiol compound represented by formula (1) 0.1 to 1
A siloxane-modified polyimide resin composition obtained by dissolving 0 parts by weight in an organic solvent. Embedded image (Wherein R ₁ is —SH, —N (C ₄ H ₉ ) ₂ , —HNC ₆
Indicates H _5, M represents a hydrogen atom or an alkali metal) 2. An imide moiety formed by polycondensing an aromatic tetracarboxylic dianhydride with siloxane diamine and an amic acid obtained by polyadding an aromatic tetracarboxylic dianhydride with another aromatic diamine component. 100 parts by weight of a siloxane-modified polyimide amic acid resin having a moiety, 1 to 50 parts by weight of an epoxy resin, and 0.1 to 10 parts by weight of a triazine thiol compound represented by the following general formula (1) are dissolved in an organic solvent. A siloxane-modified polyimide resin composition. Embedded image (Wherein R ₁ is —SH, —N (C ₄ H ₉ ) ₂ , —HNC ₆
Indicates H _5, M represents a hydrogen atom or an alkali metal) 3. A siloxane diamine represented by the following general formula (2):
The siloxane-modified polyimide resin composition according to claim 1 or 2, wherein the molar ratio of the siloxane diamine to the aromatic diamine is from 30/70 to 99/1. Embedded image (In the formula, R ₂ and R ₃ are the same or different divalent hydrocarbon groups, R _{4 to} R ₇ are the same or different C 1 to C 6 hydrocarbon groups, and n is an average. Repeating units 1-3
0 is shown) 4. An average repeating unit n of the siloxane diamine represented by the general formula (2) is 1 to 12, and a molar ratio of the siloxane diamine to the aromatic diamine is 50/5.
The siloxane-modified polyimide-based resin composition according to claim 3, which is 0 to 99/1. 5. An epoxy resin is used in an amount of 2 to 30 parts by weight based on 100 parts by weight of the siloxane-modified polyimide resin or the siloxane-modified polyimide amic acid resin.
The siloxane-modified polyimide resin composition according to any one of claims 1 to 4, wherein the epoxy resin has an epoxy equivalent of 100 to 1,000. 6. A cured product obtained by heating and curing the siloxane-modified polyimide resin composition according to claim 1.