WO1998010009A1

WO1998010009A1 - Process for preparing polyimide-containing polyhydric phenol resin, epoxy resin composition comprising the same, and cured product thereof

Info

Publication number: WO1998010009A1
Application number: PCT/JP1997/003138
Authority: WO
Inventors: Masashi Kaji; Yukihiro Wada; Kazuhiko Inoue; Kiyokazu Yonekura
Original assignee: Nippon Steel Chemical Co., Ltd.
Priority date: 1996-09-05
Filing date: 1997-09-05
Publication date: 1998-03-12
Also published as: JPH1081748A

Abstract

A process for preparing a polyimide-containing polyhydric phenol resin comprising reacting an acid anhydride with a diamine compound in the presence of a polyhydric phenol resin containing two or more phenolic hydroxyl groups per molecule to conduct an imidation reaction while conducting a dehydration reaction; a polyimide-containing polyhydric phenol resin prepared by this process; an epoxy resin composition comprising the polyimide-containing polyhydric phenol resin as a part or the whole of a curing agent component for an epoxy resin; and a cured product thereof. A curing agent for an epoxy resin having excellent heat resistance, high toughness, high adhesion and other excellent properties can be provided without lowering the glass transition temperature and the mechanical strength of the cured product.

Description

Specification

Process for producing polyimide-containing polyphenolic resin

In addition, the epoxy resin composition and its cured product

Technical field

The present invention relates to a polyimide-containing polyvalent phenolic resin having excellent heat resistance, high toughness, and high adhesiveness, and useful as a curing agent for epoxy resins. The present invention also relates to a method for producing the same, and an epoxy resin composition and a cured product thereof.

Background technology

Conventionally, curing agents for epoxy resin compositions used in the fields of powder coatings, semiconductor encapsulating materials and the like include phenol novolacs, phenols and phenols. Lanolekyl resin is widely used. However, the resulting cured product is generally brittle, and has problems in adhesion to various substrates, adhesiveness, and the like. As a method of overcoming the above problems, a method of adding one component of rubber or elastomer is being studied (

Journal of Material Science, 21, 2462 (1986)). However, these methods have problems such as a reduction in the glass transition point and a decrease in mechanical strength.

As a method for solving the above problem, it is conceivable to combine with a polyimide having excellent thermal and mechanical properties. In general, since polyimide is an organic polymer compound having high heat resistance and good electric and mechanical properties, it is a protective material and an insulating material in the field of electronic devices. They are widely used as adhesives, films, and structural materials. Polyimide generally has a high melting point or high glass transition point In many cases, the temperature exceeds or is close to the thermal decomposition temperature, making it difficult to perform melt molding.In addition, the method of melting and mixing is used for the same reason. It has also been difficult to form a composite with other materials such as epoxy resin.

For this reason, proposals for fusible polyimide polymers are often made. For example, Japanese Patent Application Laid-Open

No. 3,132,2 proposes a crystalline silicone imid copolymer. Further, Japanese Patent Application Laid-Open No. Sho 61-250301 discloses a special pillomerite imid. Copolymer as a fusible polyimid copolymer. Proposed . In the above-mentioned Japanese Patent Application Laid-Open No. Sho 61-21032, the melting point of the copolymer is in the range of 140 to 210 ° C. as far as the embodiment is concerned. Also, in Japanese Patent Application Laid-Open No. 61-250301, in order to form a phenol, the copolymer is melt-pressed at 400 ° C. I have to heat it to C. Therefore, even with these materials, it has still been difficult to form a composite with other materials such as epoxy resin by a method such as melt mixing. .

Accordingly, an object of the present invention is to exhibit excellent properties such as heat resistance, high toughness, and high adhesion without reducing the glass transition point and mechanical strength of the cured product. An object of the present invention is to provide a method for producing a polyimide-containing polyvalent phenolic resin which is particularly useful as a curing agent for epoxy resins.

Disclosure of the invention

In general, polyimide has a high melting point and is difficult to compound with other materials such as epoxy resin. Polyimides are polymerized in polyhydric phenolic resins, which are common curing agents for xylene resins, resulting in a polymer formed by polymerization. The present inventors have found that the imide is uniformly melted or dispersed in the polyhydric fluorinated resin, and have led to the present invention.

That is, the present invention provides a method for reacting an acid anhydride with a diamine compound in the presence of a polyvalent phenolic resin containing two or more phenolic hydroxyl groups in one molecule. In addition, the present invention provides a method for producing a polyimide-containing polyvalent phenolic resin, which comprises performing an imidization reaction while performing a dehydration reaction.

Further, the present invention uses the above-mentioned polyimide-containing polyvalent phenolic resin as a part or the whole of a curing agent component for an epoxy resin. Characteristic epoxy resin composition o

Further, the present invention is a cured epoxy resin obtained by curing the epoxy resin composition.

The polyimide-containing polyfunctional phenolic resin of the present invention is obtained by reacting an acid anhydride with a diammine compound in the presence of a polyhydric phenolic resin, and dehydrating the polyanhydride. It can be obtained by performing an imidization reaction while performing the reaction. At this time, the polyvalent phenolic resin to be used only needs to contain two or more phenolic hydroxyl groups in one molecule. Bisphenol A, Bisphenol F, Bisphenol S, Fluorine Bisphenol, 4,4'-Biphenol , 2,2'-Hyphen phenols, hydranoquinones, azonoresins, naphthalene phenols, etc. Compounds and tris ( 4-Hydroxy shift methane, 1,1,2,2-Tetrax (4-Hydroxy shift) ethane, fenor Trivalent or higher valents represented by non-novolak, 0-reno-norenovolak, naphtho-noreno-borac, polyvinyl alcohol, etc. Knolls, and also phenols, naphthols, or bisphenol A, bisphenol F, bisphenol S, Full-lens bisphenol, 4,4'-biphenyl, 2,2'-biphenol, nitroquinone, resole Divalent phenols such as benzophenone, naphthalene monophosphate, etc. can be converted to honolemonoaldehyde, acetonolehydride, benzene phenol, p- Hi With condensing agents such as hydroxybenzanolide, p-xylylene glycol, methyl ether and p-xylylene glycol And polyhydric fluorinated compounds synthesized by the above reaction. Preference is given to phenolic phenols and phenolic phenols obtained by condensing phenolic compounds with phenolic phenols. Of novolac resin or phenols or naphthones such as p-xylylene glycol core resin And aralkyl resins obtained by reaction with an agent.

When the polyimide-containing polyvalent phenolic resin of the present invention is used as an epoxy resin curing agent, the use of a novolak resin as a synthetic raw material can A cured product having excellent moldability and heat resistance can be obtained, and when an alkyl resin is used, a cured product having particularly excellent moisture resistance can be obtained. The softening point of these polyhydric phenolic resins is not particularly limited, but is usually in the range of 40 ° C. to 150 ° C. Here, the alkyl resin is represented by the following general formula (1), and is an alkyl-substituted or unsubstituted benzene ring or naphtha. It can be obtained by reacting a phenolic hydroxyl group-containing compound having a ren ring with an aromatic crosslinking agent ^) o

(

(In the formula, A represents an alkyl-substituted or unsubstituted benzene ring or naphthalene ring, and when two or more are contained in one molecule, they may be the same or different. R 1 IV 2 represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and p represents 1 or

An integer of 2 and m represents a number from 0 to 15)

Examples of the phenolic hydroxyl group-containing compound include phenol, 0-cresol, m-cresol, p-cresol, and ethylphenol. Noles, 2,4-xylene, 2,5—xylene, 2,6-xyleno-norre, isopropynolefenols, Benzene ring-containing compounds such as monobutyl phenol, phenyl phenol, phenol, resorcinol, and hydroquinone; Examples thereof include naphtholene ring-containing compounds such as 1-naphthol, 2-naphthol, and naphthalene diols.

The aromatic cross-linking agent is 0-body, m-body, p It can be any of the bodies, but is preferably an m-body or a p-body. Specifically, P-xylylene glycol, α, a'-methodoxy-P-xylene, a, '-geethoxyx p-xylene Len, a, a '-iso-isopropinole p-xylene, α, a' — dibutoxy 1-p-xylene, m-xylene KO-NO, a, a-dimention 1 m-Xylene, hi, a'-dietinoic 1 m-Xylene, α, a'-diisopropo Xy — m-quinylene, a, a '— jibutoki m-xylen, 1,4-di (2-hydroxy 2-ethyl) benzene Benzene, 1,4-di (2-methoxy-1-ethyl) benzene, benzene, 1,4-di (2-hydroxy- 2-ethyl) benzene 1,4-di (2-ethoxy 1-2-ethyl) benzene, 1,4-di (2-isopropoxy-1- Chinole) Benzene, 1,4-di (2-hydroquinone 2-propynole) Benzene, 1,4-di (2-methoxy 2-phenyl) Lopinore) Benzen, 1, 4-di

(2-Hydroquinone-2-propynole) Benzene, 1,4-di (2-ethoxy-1-2-propynole) Benzene, 1,4- Di- (2-isopropoxy-1-2-propynole) benzene, 1,3-di- (2-hydroquinone-2-ethyl) benzene, 1 , 3, -Di (2-methoxy-2-ethyl) benzene, 1,3, -Di (2-hydroxy1-2-propynole) benzene, 1 , 3-di (2-methoxy-1--2-propyl) benzen, 1,2-divinylbenzen, 1,3-divinylnorbenzen, 1,4- Divinylbenzene, 1,2-diene (2-propenyl) benzene, 1,3-diene

Examples include (2-pronil) benzene and 1,4-di (2-pronil) benzene.

When reacting the phenolic hydroxyl group-containing compound with the aromatic cross-linking agent, the molar ratio of the two is determined by the phenolic hydroxyl group-containing compound. The aromatic cross-linking agent is not more than 1 mol per 1 mol of the compound, preferably in the range of 0.1 to 0.9 mol. If the amount of the aromatic cross-linking agent is less than 0.1 mol, the amount of the unreacted phenolic hydroxyl group-containing compound becomes large, which is not industrially desirable and exceeds 0.9 mol. If this occurs, the softening point of the resin will increase, which will hinder molding workability.

The preferred softening point of the aralkyl-type polyvalent phenolic compound used in the present invention is from 40 to 150 ° C, more preferably from 50 to 1 ° C. 20 ° C. If it is lower than this, there is a problem of blocking during storage, and if it is higher than this, there is a problem in kneadability and moldability in preparing the epoxy resin composition. Also, the preferred melt viscosity at 150 ° C is less than or equal to 20 centimeters voice, and more preferably less than or equal to 5 centimeters voice. . If it is higher than this, there are problems in kneadability and moldability during the preparation of the epoxy resin composition.

Preferable examples of the aranoleky type polyvalent phenolic compound used in the present invention include phenol or naphthol, and p-xylile. Polyvinyl alcohol or α, a'-dimethyxoxy P-quinlene-derived phenolic resin and naphtha larkyl Available from Mitsui Toatsu Chemicals, Inc., Millex XL-225-3L, XL-225-LL, XL—225-M Meiwa Kasei Co., Ltd. MEH-7800, New Japan Examples include SN-180 manufactured by Tekko Chemical Co., Ltd.

As the acid anhydride used for obtaining the polyimide-containing polyhydric resin containing polyimide of the present invention, it is used for synthesizing ordinary polyimide. Use most tetracarboxylic oleic anhydride be able to . For example, pyromellitic dianhydride, 3,3,, 4,4'-benzophenenotetracarboxylic dianhydride, 2,3,3 ', 4 '-Benzopentanonetracarboxylic dianhydride, 2,2', 3,3'-Benzopentanonetracarboxylic dianhydride, 3,3 ', 4,4'-Biphenyltetracarboxylic dianhydride, 2,2,3,3'-Biphenyltetracarboxylic dianhydride Anhydride, 2,3,3,, 4'-biphenyltetracarboxylic dianhydride, bis (2,3-dicarboxif) Tan dianhydride, bis (3,4-dicanoleboxyl) 1 methane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) 1 Propane dianhydride, bis (3,4-dicanole box) 2-ether dianhydride, bis 3,4-dicanoleboxylphenyl) sulfon dianhydride, 3,3 ', 4,4'-tetracarboxylic dibenzoyloxybenzene Anhydride, 1,2,5,6-naphthalene dihydrotetracarboxylic dianhydride, 2.3,6,7-naphthalene tetracarboxylic dianhydride Anhydrides, thiophenes — 2,3,4,5-tetracarboxylic dianhydride, virazine-2,3,5,6-ditetracarboxylic dianhydride Anhydrides, pyridines-2,3,5,6-tetracarboxylic dianhydride. These carboxylic dianhydrides may be used alone or in combination of two or more.

Among the above-mentioned acid anhydrides, especially from the viewpoint of improving the heat resistance of the obtained polyimide, pyromellitic dianhydride, 3, 3 ′, 4, 4′-benzyl Zofenontetracarboxylic dianhydride, 3,3 ', 4,4'-Biphenylenolate tetracarboxylic dianhydride, bis (3,4- Dicarboxyvinyl) sulfon dianhydride is suitably selected. Among them, thermoplastic polyimides and epoxy resins In order to improve the compatibility with the resin, bis (3,4-dicarboxylvinyl) sulfoni anhydride is preferred.

The acid anhydride is used to block the terminal group of the polyimide, and is used for phthalic anhydride, 4-chlorophthalic anhydride, and anhydrous tetraethyl anhydride. It is also possible to use dicarboxylic anhydrides such as phthalanol anhydride, 4-hydroxyphthalic anhydride, naphthalic anhydride, and maleic anhydride. .

As the diamine component, aromatic diamines, polycyclic diamines, aliphatic diamines, diaminopolysiloxanes Etc. are selected.

The aromatic diamines include, for example, diamines such as 0-, m- and p-phenylamine, 2,4-diaminotorenene and the like. Toluenes, 1,4-diaminino-2-methoxybenzen, 2,5-diaminoxylens, 1,3-diaminino-4 _______________________________________ either, chloronobenzen, 1,4-diamino-1,2,5-diamine, 1,3-diamino 4-disopropynolebenzen, Ν, Ν '-diphenyl 1, 4-diphenylamine, 4, 4 '— Diamino diphenyl 1, 2,2 -pun, 4,4'-diamino diphenyl methane, 2,2 '-diaminotinole , 4,4'-Jaminostinolene, 4,4'-Jamino diphenyl ether, 3,4'-Ja Noji phenyl ether, 4,4, -Jaminoji jinore norezu, 4,4'-Jiamino jiji no jinore honhon, 3,3'-Diaminotinololephon, 4,4'-Di (metaminolinenolose) dipheninolenorrenone, 4,4 4,4, -Diaminophenyl benzoyl benzoyl benzoyl benzoyl benzoyl benzoyl benzoate , 2,2'-Dimethylbenzendin, 2,2, -Diaminobenzofon, 4,4, -Diaminobenzof'eno , 4,4'-diamino benzene, 4— (4'-aminofu ninore kanorebamoinore) 1 aniline, vis (4 -amino) (Finyl) 1 phosphine, vis (4-（ノーー)-チホフフ(Minno Fen) (Minore Nos) No Fino Fushidoshi, Bis (4-Amino Fino) No. Fino Fino Foshiki, B N-N-N-N-N-N-N-N-N-N-N-N-N-N-N-N-N-N-N-N-N-N Methylamine, 4, 4'-diamino Diphenyl urea, 1,5-Diamino nonaphthalene, 1,8-Diamino nonaphthalene, 1,5-Diamino nonaquinone , Dinamino lantern, vis (4-aminophenol) 1 gennosilane, vis (4-aminofenol) 2,4-bis [4- (4-aminophenol) vinyl] prono. , Business [4-(

4-Aminophenoquinone) Fe2nole] Snorehon, 4, 4'_ bis (4-Aminofenoxy) phenyl, 1, 4-bi (4-Aminofenoxy) Benzene, 1,3 -vis (4 -Aminofenoxy) Benzene, 1,3 -vis (3- Aminophoxy) Benzene, 2,2-vis [4- (4-Aminophenyl) phenyl] And so on.

In addition, examples of the heterocyclic diamines include 2,6-diaminopyridin, 2,4-diaminopyridin, and 2,4-diamine. Minnow

5-triazine, 2,7-diaminodibenzofuran, 3,7-diaminofenothiazine, 2,4-diamino-6 -Feninole S-triazine and the like. Furthermore, examples of the aliphatic diamine include dimethylmethylamine, trimethylenediamine, tetramethylenediamine, and hexadiamine. Same methylamine, heptamerene amine, octamethylamine, nonamethylamine, decamethylamine 2,2-dimethylpropylamine, 2,5-dimethylhexamethylenediamine, 2,5-dimethylbenzene To the methylbenzene, 4,4'-dimethylamine, to the methylbenzene, 3 -methylphenylamine, 3-Methyl pentamethylamine, 5-methylnon-methylamine, 2,11-Diamine decane, 1,12 -Jiaminota Decacan, 1,2-bi (N-N-, N-, N-, N-, N- and N-) Aminopropane, N, N'-dimethyl-1,6-diaminohexane, and the like.

Further, examples of diaminopolysiloxanes include, for example, the following. In the following chemical formula, 1 represents the number of repeated siloxane bonds.

CHa CHa

H ₂ N- (CH ₂ ) s- (Si-O), 1-Si- (CH _a ) 8-NH ₈

CH. CHz

H, C ヽ CH _a CH.. CCH ₃

H

₂ NQ> — (Si-0), — Si-(• NH,

CH CH

H ₂ N- (CH ₂ ) CH2) a -NH _;

C 2 H 5 C 2 H S

H ₂ N- (CH-(i-0), one Si- (CH ₂ ) ₃ -NH ₂

C 2 HBC 2 H 5 H ₂ N- (CH ₂ ) 3 (CH ₂ ) 3-NH

H eN

The diamines such as the aromatic diamines, heterocyclic diamines, aliphatic diamines, and diaminopolysiloxanes are one kind. Among the above diamine compounds, which may be used in combination of two or more, aromatic diamines are particularly preferred from the viewpoint of improving the heat resistance of the obtained polyimide. Is preferred. To further improve the compatibility with the epoxy resin as a thermoplastic polyimide, 2,2-bis [4- (4-aminophenol) is used. E 2 Nore] Prono. And bis (3-aminopropyl) polymethylsiloxane are preferred. The molar ratio between tetracarboxylic anhydride and the diammine compound should be adjusted appropriately according to the purpose of use of the polyimide-containing polyvalent phenolic resin. I can do it. Tetracarboxylic anhydride Z diamin The molar ratio of the compound is 0.8 to 1.2 when the heat resistance and the mechanical strength are emphasized, and 0 when the blend property with the epoxy resin and the melt mixing property are emphasized. When the moldability (particularly fluidity) of the epoxy resin composition is taken into account, the value is set to 1.2 to 5.0, and the low-molecular-weight polymer is used. It can also be used as an imido compound.

The polyimide-containing polyhydric resin of the present invention reacts an acid anhydride with a diammine compound in the presence of a polyhydric phenolic resin. Although it is obtained as a result, the respective charging ratios in the reaction are not particularly limited, but are usually 100 parts by weight of the polyhydric phenolic resin. The total amount of the acid anhydride compound and the diamine compound is 5 to 200 parts by weight based on the total weight. If the amount is less than the above, the effect of improving the physical properties by the polyimide when the epoxy resin cured product is small is small. Large increase in viscosity makes handling difficult at the time of synthesis.

Regarding the order of adding tetracarboxylic anhydride and the diamine compound to the reaction system, the reaction is carried out by simultaneously adding tetracarboxylic anhydride and the diamine compound. Alternatively, a specific diamine compound may be added to the total amount of tetracarboxylic anhydride to react first, and then the remaining diamine compound may be added. May be further added and reacted. Conversely, a part of tetracarboxylic acid anhydride is added to the whole amount of the diamin compound and reacted first, and then the remaining tetracarboxylic acid anhydride is reacted. The reaction may be performed by adding a substance.

The imidization reaction is carried out while being dehydrated by heating under stirring. It is done. The reaction temperature is usually from 100 to 300 ° C. If it is lower than this, the reaction time is prolonged, and if it is higher than this, a decomposition reaction of the polyvalent phenolic resin as a reaction medium occurs. The reaction time is generally in the range of 1 to 40 hours. .

In addition, a solvent may be used for the imidization reaction. Examples of the solvent include N-methyl-2-pyrrolidone, N, N-dimethylaminoacetate, N, N-dimethylaminoacetone , Dimethyl alcohol, tetramethyl urea, pyridin, dimethyl alcohol, hexamethyl alcohol, amide, methyl Norehonorumamido, N-acetinore 2-pyrrolidone, ethylene glycolモモモレモモモモモモモモレレモモモモモモモモモレレレモレDiethylene glycol, methyl ether, cyclone, non-exhaustノ, ,, Ν-Ν レセアア、 Ν ,, Ν, Ν-, ジジジジテテテテテ2 1-pyrrolidone, Ν-method 1 £ — caprolactam, tetrahydrodibenzodioxodo (snoreholane) ) And so on. The imidization reaction can also be performed in a mixed solvent of the above solvents.

In addition, an aromatic solvent such as benzene, toluene, or quinrene may be used as an azeotropic solvent for prompt dehydration. Further, the reaction may be carried out under reduced pressure for quick dehydration.

Polyimide-containing polyvalent phenol obtained by the above reaction The epoxy resin is suitable as a curing agent for the epoxy resin, and by combining this with the epoxy resin, the epoxy resin composition can be obtained. it can . The epoxy resin used in this case is not particularly limited.

It is selected from those having two or more epoxy groups in one molecule. For example, bisphenol A, dihydroxy diphenyl methacrylates, dihydroxy diphenyl phenols, dihydroxy phenols, dihydroxy phenols Phenolene compounds, phenolic compounds, phenolic compounds, phenolic compounds, phenolic compounds, phenolic compounds Divalent phenols such as thiophene, etc., or tris (4-hydroxyphenyl) methane, 1,1,2,2-tetrax ( 4-Hydroxy phenols) or phenolic compounds such as phenols, phenols, cresols, naphthols, etc. Novolaks obtained by condensation with aldehydes such as honolemaldehyde, acetonolelide, benzolide, etc. Polyglycidyl ethers of polyvalent phenolic compounds such as aralkyl resins such as phenols, phenols, cresols, naphthones, etc. Glysyl ether compounds derived from halogenated bisphenols such as tetrabromobisphenol A and the like. can give . These epoxy resins may be used alone or in combination of two or more.o

Further, the epoxy resin composition of the present invention may contain an inorganic filler. In this case, from the viewpoint of increasing the filling of the inorganic filler, the epoxy resin to be used is selected from epoxy resins having excellent low viscosity. 3 ' , 5,5'-Tetramethylen -4,4'-Dihydrogen diphenylene, 3,3 ', 5,5'-Tetramethylen- 4,4'-dihydroxybiphenyl, 2,5-dihydroquinone dihydroquinone, 1,4-vis (3-methyl 1-Hydroxyminole) Benzene, 3,3 ', 5,5, -Tetramethylen-4,4, -Dihydroxy diphenyl Noresure feed, 3, 3'-di-no-shear-buti-noise-5, 5'-dimetho-noise-4, 4'-dihydroxy Feed, 4,4, -dihydroxy phenyl ether, 1,6-naphthene, etc. And so on.

Examples of the inorganic filler include molten silica, crystalline silica, aluminum, magnesium, titanium oxide, calcium carbonate, and glass. Fiber, talc, etc. Among them, molten silica is preferably used from the viewpoint of low thermal expansion and the like. The shape of the molten silica may be crushed or spherical, but from the viewpoint of improving the solder heat resistance, the crushed silica having an average particle size of 15 μm or less and an average particle size of 40 A spherical silica having an average particle diameter of 2 // m or less and a spherical silica having an average particle diameter of 2 // m or less are appropriately combined and used. The content of the inorganic filler is usually 30 to 95% by weight, but when used for a semiconductor sealing material, it is preferable from the viewpoint of improving solder heat resistance. Ranges from 65 to 95% by weight.

In the epoxy resin composition of the present invention, in addition to the polyimide-containing polyvalent fluorinated resin of the present invention, a known curing agent may be mixed and used. As the curing agent to be mixed and used, any of those generally known as curing agents for epoxy resins can be used. For example, acid anhydrides, amines and the like can be used. Phenol-based curing agents having a hydroxyl group, and preferably phenol-based hardeners. Packing, Cressorenovolak, Phenolnoreolanorekyl resin, Polyvinylinolefunorenore, Nafutonorenovolak, Naphto -Normal resin, naphthalene resin, naphthalene resin, naphthalene resin, naphthalene resin, and naphthalene resin.

When mixed with other curing agents, from the viewpoint of improving the high heat resistance, toughness and mechanical strength caused by the polyimide, the amount of the polyimide It is preferable to use 10% by weight or more of the multifunctional phenolic resin in the total hardener.

In addition, the epoxy resin composition of the present invention usually contains a curing accelerator. As the curing accelerator, any conventionally known curing accelerators can be used. For example

Amins such as, 1,8-diaza-bicyclo (5,4,0) ゥ decen-7, 2-pentene Nole 4-iminoazoles such as methyl imidazole, organic phosphines such as triphenyl phosphine, and zoleic acid And so on. These curing accelerators are used as a mixture of two or more as necessary. Usually, the amount of the curing accelerator used is 0.1 to 10 parts by weight based on 100 parts by weight of the epoxy resin.

If necessary, the epoxy resin composition of the present invention may further contain a coupling agent, a wax, a flame retardant, a low-stressing agent, a cosmetic, a release agent, and a lubricant. You may mix such as.

Furthermore, in the epoxy resin composition of the present invention, a polyester, a polyamide, a polyimid, a polyether, a polyether, or the like may be used. Oligomers or high molecular compounds such as urethane, petroleum resin, indicone malon resin, and phenolic resin may be appropriately compounded.

In the present invention, since the imidization reaction is carried out in the presence of a polyvalent phenol, the phenol resin and the polyimide resin are uniformly mixed.ヱ Knoll resin is obtained. In addition, during the imidization reaction, it is not known whether the hydroxyl group of the phenol resin reacts with the acid anhydride to form an ester bond, but such a case is assumed. Even if the reaction occurs, there is no decrease in the physical properties, and it is considered that effects such as improvement in solubility are produced.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a drawing showing an infrared absorption spectrum of the polyimide-containing polyvalent phenolic resin A of Example 1.

FIG. 2 is a drawing showing an infrared absorption spectrum of the polyimide-containing polyvalent phenolic resin D of Example 4.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described more specifically based on examples and comparative examples.

Example 1 [Production of Polyimide-Containing Polyhydric Resin A]

2 A glass of glass with a soft lip and a soft drip point of 75 ° C and a hydroxyl equivalent of 104 was added to a glass of glass. g, bis (3,4-dicanolefonoxynole) snorrenone dianhydride 85.69 g, 2,2-vis [4-(4-aminoff Enoquine) phenyl] pronocan 63.57 g, molecular weight 75 0 vis (3-aminopropinole) Polymethyl siloxane 6

2.11 g and mixed xylene 315 g were charged and heated to 150 ° C. with gentle stirring. Thereafter, the stirring rotation speed was set to 30 rpm, and the mixture was heated to 165 ° C and reacted for 18 hours. During this time, generated water was removed from the system by azeotropy with xylene. After the reaction, the remaining xylene was distilled off under reduced pressure to obtain a polyimid-containing polyhydric phenolic resin A621.6 g. The obtained polyimide-containing polyvalent phenolic resin A has a softening point of 103 ° C, and was measured with an ICI composite viscometer at 150 ° C. The melt viscosity in C was 7.4 vise. Figure 1 shows the infrared absorption spectrum.

Example 2 [Production of Polyimide-Containing Polyhydric Resin B]

2 A phenol-free phenolic glass with a softening point of 75 ° C and a hydroxyl equivalent of 104 was added to a glass of senora bunore made of glass with a liter capacity. , Bis (3,4-dicanole box) 2 6 23 g, 2, 2-bis [4-(4-aminophenol) No.) feninole] propane 86.38 g, molecular weight 7550 bis (3-amino propylinole) polymethylenesiloxane 9

3.89 g, phthalic anhydride 40.Og and mixed xylene 470 g were charged and reacted in the same manner as in Example 1 to obtain a polyimid-containing polyvalent phenol. As a result, 99.5 g of a reactive resin B was obtained. The obtained polyimide-containing polyvalent phenolic resin B has a softening point of 77.5 ° C, and was measured with an ICI composite viscometer. The melt viscosity at 0 ° C was 8.9 vise. Example 3 [Production of Polyimide-Containing Polyhydric Resin C]

2 Separable glass made of glass with a liter paste, a vinyl acryl resin with a softening point of 85 ° C and a hydroxyl equivalent of 170, 70.1. g, bis (3,4-dicanoleboxyl) sulphonic anhydride 11.8.30 g, 2,2-bis [4- (4-amino) 10 4 .36 g with a high molecular weight and a high molecular weight power of 1234 (3-amino propylinole) 93.84 g of oxane and 470 g of mixed xylene were charged and reacted in the same manner as in Example 1 to obtain a polyimid-containing polyvalent phenolic resin C 10 0.24 g were obtained. The softening point of the obtained polyimide-containing polyhydric phenolic resin C was 123 ° C.

Example 4 [Production of Polyimide-Containing Polyvalent Functional Resin D]

2 Phenol rubber with a softening point of 75 ° C and a hydroxyl equivalent of 104 is added to a glass slab made of glass with a stiffness of 4 liters. g, pyromellitic acid 47.6 g, high molecular weight 7500 bis (3-amino propylinole) polymethinolexyloxane 163.8 g and mixed xylen (470 g) were charged and reacted in the same manner as in Example 1 to obtain a polyimid-containing polyvalent phenolic resin D61.8.8 g. . The obtained polyimide-containing polyvalent phenolic resin D had a soft point of 87.5 ° C, and was measured with an ICI component viscometer. The melt viscosity at 150 ° C was 0.9 voice. Figure 2 shows the infrared absorption spectrum. Example 5 [Production of Polyimide-Containing Polyhydric Resin E]

2 Separable glass made of glass with ritorn

75 ° C, phenolic phenol with a hydroxyl equivalent of 104 43.8 g, 3,3 ', 4,4'-benzophenone tetracarboxylic 63.2 g of boric acid dianhydride, a bis (3-amino propyl) polymethyl siloxane having a molecular weight of 750.0 g, 147.2 g of mixed key 470 g of styrene was charged and reacted in the same manner as in Example 1 to obtain a polyimide-containing polyhydric phenolic resin E621.8 g. The obtained polyimide-containing polyvalent phenolic resin E had a softening point of 87.5 ° C, and was measured by an ICI component viscometer. The melt viscosity at 150 ° C was 0.9 vise.

Example 6 [Production of polyimide-containing polyvalent phenolic resin F]

A softening point is applied to a 2-liter glass separate flask.

8 4. C-hydroxyl equivalent of 204 2-naphthanol phenolic resin 70.1 g, bis (3,4-dicanole box) 2. 11.5 g of anhydride, 90.5 g of 2,2-bis [4- (4-aminophenol) vinyl] propane, phthalic anhydride 20.6 g and 470 g of mixed xylene were charged and reacted in the same manner as in Example 1 to obtain a polyimide-containing polyvalent phenolic resin F 79.5 g I got The obtained polyimide-containing polyhydric phenolic resin F had a softening point of 102.5 ° C, and was measured with an ICI composite viscometer. The melt viscosity at 0 ° C was 8.2 vise. Example ? ~ 1 2 and Comparative Examples 1 ~ 2

As epoxy resin components, bisphenol A-type epoxy resin (epicot 828 oiled shell: epoxy resin X) and softening point 7 1. C, 0-cresole novolac type epoxy resin (epoxy resin Y) having an epoxy equivalent of 197 was used, and Examples 1 to 6 were used as curing agents. Using the polyimide-containing polyhydric X-nolating resins A to F obtained in the above and a phenol-norenohol (hardening agent M) having a softening point of 68 ° C. Using triphenylphosphine as a ¾-ί-promoting accelerator, these were kneaded in the composition shown in Table 1 to prepare an epoxy resin composition. Was. These epoxy resin compositions were molded at 150 ° C., and the resulting mixture was heated at 175 ° C. A cured product specimen was prepared by post-curing for 12 hours at C, and then subjected to various physical property measurements. For adhesive strength, after forming a sample on a 35 / m copper foil, measure the peel strength in the 90-degree direction, and use the mechanical thermal analyzer for the o-glass transition point and coefficient of linear expansion. The temperature was determined at a heating rate of 10 ° C. In addition, the water absorption rate is 133 according to a presser-cooker-tester. C, It was obtained from the weight change rate after 96 hours under the condition of 3 atm. Table 2 shows the results.

【table 1 】

Example Example Comparative Example

7 8 9 10 1 1 12 1 2 Epoxy X 56.5 57 44 56 56 64.5 Resin

Y 43.5 55.5 Resin A 43.5

〃 B 43

Hard "C 56

Conversion

"D 44

Agent

"E 44

"F 56.5

Curing agent M 35.5 34.5 Curing accelerator 1 1 1 1 1 1 1 1 Carnauba, box 2 2 2 2 2 2 2 2

[Table 2]

Example Example Comparative Example

7 8 9 10 11 12 1 2 Glass transition point

(° C) 155 150 145 142 144 152 135 145 Coefficient of thermal expansion

«Tg.xlO ⁵ ) 7.4 7.0 7.1 7.3 8.1 7.5 6.9 6.5 Thermal expansion coefficient

OTg.xlO- ⁵ ) 18.8 18.4 18.3 19.2 19.4 18.9 18.3 17.8 Flexural strength

(kgf / mm ² ) 10 11 11 10 11.5 12 8.5 10 Flexural modulus

(kgf / mm ² ) 215 230 220 185 205 350 330 320 Adhesive strength

(kg / cm) 2.4 2.2 2.6 2.4 2.8 2.6 1.7 1.5 Water absorption

(wt¾) 2.2 2.1 1.6 2.1 2.2 1.5 2.1 2.0 Industrial applicability

When the polyimide-containing polyvalent phenolic resin of the present invention is used as an epoxy resin curing agent, the glass transition point and mechanical strength of the cured product are reduced. High performance such as heat resistance, high toughness, and high adhesiveness, molding materials and laminated materials It is suitably used as a base resin for various uses such as coating materials.

Claims

The scope of the claims

(1) Dehydration by reacting an acid anhydride with a diamine compound in the presence of a polyhydric phenolic resin containing two or more phenolic hydroxyl groups in one molecule A process for producing a polyimid-containing polyvalent phenolic resin, wherein the imidization reaction is carried out while performing the reaction.

(2) The polyvalent phenolic resin is a novolak resin obtained by condensing phenols and formaldehyde. 1. The method for producing the polyimide-containing polyvalent phenolic resin according to 1 above.

(3) The polyimide-containing polyvalent phenol according to claim 1, wherein the polyvalent phenolic resin is an aralkyl resin represented by the following general formula (1). Production method of conductive resin

(

(In the formula, A represents an alkyl-substituted or unsubstituted benzene ring or naphthalene ring, and when two or more are contained in one molecule, they may be the same or different. R i and R 2 each represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, p is an integer of 1 or 2 and m is a number of 0 to 15; Show)

(4) The acid anhydride is pyromellitic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3 ', 4, 4 '-Biphenyltetracarboxylic dianhydride, a small amount selected from bis (3,4-dicanolboxyl) sulfone dianhydride 2. The method for producing a polyimide-containing polyhydric phenolic resin according to claim 1, which is at least one kind of acid anhydride.

F) The diamine compound is a 2,2-vis [4- (4-aminophenol) phenyl] prono, bis (3-amino) 2. The process for producing a polyimide-containing polyhydric phenolic resin according to claim 1, which comprises poly (vinyl siloxane).

(6) In the presence of a polyhydric phenolic resin containing two or more phenolic hydroxyl groups in one molecule, an acid anhydride and a diammine compound are reacted to dehydrate. Polyimid-containing polyvalent phenolic resin obtained by performing an imidization reaction while performing a reaction.

(7) An epoxy resin characterized by using the polyimide-containing polyvalent phenolic resin described in claim 6 as part or all of the curing agent component. An epoxy resin composition consisting of an epoxy resin and a curing agent.

(8) A cured product obtained by curing the epoxy resin composition according to claim 7.