JPH0749463B2 - Epoxy resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to an epoxy resin composition.

[Prior Art] Conventionally, there is an epoxy resin composition comprising an epoxy resin composed of a polyether polyol-based NCO urethane prepolymer and an epoxy compound having a hydroxyl group and an epoxy group in the molecule, and a curing agent (for example, JP-B-43-26517). Issue).

[Problems to be Solved by the Invention] However, the cured product of this product has low electric insulation.

[Means for Solving Problems] The present inventors have arrived at the present invention as a result of earnestly examining an epoxy resin composition having excellent electric insulation. That is, the present invention relates to an epoxy resin (A) obtained by modifying an epoxy resin (a) having an epoxy group at the terminal from an NCO urethane prepolymer and an epoxy-containing monool compound with an amino group-containing organopolysiloxane (b), and a curing agent. (B)
It is an epoxy resin composition consisting of.

Examples of NCO urethane prepolymers include NCO urethane prepolymers made from polyols and organic polyisocyanates.

A high molecular weight polyol and / or a low molecular weight polyol can be used as the polyol.

Examples of the polymer polyol include polyether polyol, polybutadiene polyol, castor oil, polyester polyol and polycarbonate polyol.

As the polyether polyol, an alkylene oxide adduct of a low molecular weight polyol can be used.

Low molecular weight polyols include diols such as ethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol; triols such as glycerin, trimethylolpropane, and mixtures of two or more thereof.

The molecular weight per hydroxyl group of low molecular weight polyol is usually 30-30
It is 0, preferably 30 to 200.

As the alkylene oxide, ethylene oxide,
Examples thereof include propylene oxide, 1,2-, 1,3- or 2,3-butylene oxide, tetrahydrofuran, styrene oxide, epichlorohydrin and a mixture of two or more of these.

Further, polytetramethylene glycol (PTMG) which can be obtained by ring-opening polymerization of tetrahydrofuran is also included.
Regarding polytetramethylene glycol, JP-A-58-11
518 publication.

Examples of the polybutadiene polyol include hydroxyl group-terminated polybutadiene oligomers (hydroxy group-terminated liquid polymers of polybutadiene). Specific examples of the polybutadiene polyol include Poly Bd manufactured by ARCO, Inc. in the United States and NISSO-PBG series manufactured by Nippon Soda Co., Ltd. Poly Bd includes butadiene homopolymer type and copolymer type (styrene butadiene copolymer, acrylonitrile butane diene copolymer, etc.). Its chemical structure is as follows.

Homopolymer type n: 55 (for R-45M) 50 (for R-45HT) Copolymer type X: C ₆ H ₅ (CS-15) a = 0.75, b = 0.25, n = 54 X: CN (CN-15) a = 0.85, b = 0.15, n = 78 to 87 Also, for NISSO-PBG series The chemical structure is as follows.

Polybutanediene polyols are also described in JP-A-55-98220, Japan Rubber Association magazine No. 45 (1972), pages 449 to 450, and Sirantz (Damsys, Rainhold, 1967). Also, those described in JP-A-56-84715 can be used.

Examples of the polyester polyol include a polyester polyol obtained by polycondensing a dicarboxylic acid, its ester or halide, and a low molecular weight polyol. Examples of the dicarboxylic acid include fatty acid dicarboxylic acids (adipic acid, sebacic acid, maleic acid, dimer acid, etc.), aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, etc.) and their anhydrides. Among the dicarboxylic acids, preferred are the aliphatic dicarboxylic acids, and particularly preferred is adipic acid. Examples of the low molecular weight polyol include those described above, and preferred are ethylene glycol and 1,4-butanediol. In addition, lactones (eg, ε-caprolactone)
A polylactone polyol obtained by ring-opening polymerization in the presence of a low molecular weight polyol (eg, ethylene glycol) such as polycaprolactone diol (PCL) can also be used.

Examples of the polycarbonate polyol include those obtained by reacting the low molecular weight polyol (dihydric alcohol) with a carbonic acid diester (dimethyl carbonate, diethyl carbonate, etc.).

Preferred of these are polyether polyols,
Polybutadiene polyol and castor oil.

The molecular weight of the polymer polyol is usually 500 to 5000, preferably 60 to 400.

The number of functional groups is usually 2-3.

Examples of the low molecular weight polyol include the low molecular weight polyol described in the section of the polyether polyol and its alkylene oxide low molar adduct.

The molecular weight of the low molecular weight polyol is usually 50 to 500, preferably 6
0 to 400.

The number of functional groups is usually 2-3.

As the organic polyisocyanate in the present invention, an aliphatic polyisocyanate having 2 to 12 carbon atoms (excluding carbons in the NCO group), an alicyclic polyisocyanate having 4 to 15 carbon atoms, and an aromatic aliphatic polyisocyanate having 8 to 12 carbon atoms Isocyanate, carbon number 6
.About.20 aromatic polyisocyanates and modified products of these polyisocyanates (carbodiimide group, uretdione group, uretoimine group, urea group, buret group and / or isocyanurate group-containing modified product, etc.) can be used. Such polyisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexane diisocyanate, lysine diisocyanate, 2, 6-diisocyanate methyl caproate, bis (2-isodianate ethyl) fumarate, bis (2-isocyanate ethyl)
Carbonate, 2-isocyanate ethyl-2,6-diisocyanate hexanoate; isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclomexylene diisocyanate,
Methylcyclohexylene diisocyanate (hydrogenated TD
I), bis (2-isocyanateethyl) 4-cyclohexene-1,2-dicarboxylate; xylylene diisocyanate, diethylbenzene diisocyanate; water-modified HDI, trimerized IPDI, etc .; tolylene diisocyanate (TDI), crude TDI, diphenylmethane diisocyanate (MDI), polyphenylmethane polyisocyanate (crude MDI), modified MDI (carbodiimide modified MDI, etc.), naphthylene diisocyanate; and these 2
Mixtures of more than one species are mentioned. Of these, preferred are IPDI and TDI.

The NCO / OH equivalent ratio of the organic polyisocyanate and the polyol is usually 1.2 or more, preferably 1.6 to 3.

In the NCO urethane prepolymerization reaction, the reaction temperature may be the same as the temperature usually used in carrying out the urethane prepolymerization reaction in the industry, and is usually 20 to 150.
C, preferably 50 to 100C. This reaction may be carried out in the presence of a catalyst and a solvent, if necessary.

The production of the urethane prepolymer can be performed by a production apparatus usually used in the industry.

Examples of the epoxy-containing monool compound used in the present invention include glycidol, ethylene glycol monoglycidyl ether, glycerin diglycidyl ether, and a commercially available epoxy resin having one hydroxyl group (Epicote 1001 and the like). Of these, glycidol is preferred.

The HCO / OH equivalent ratio of the NCO urethane prepolymer and the epoxy-containing monool compound is generally 0.5 to 1, preferably 0.7 to 0.9.
Is.

The reaction between the NCO urethane prepolymer and the epoxy compound having a hydroxyl group and an epoxy group in the molecule is the same as the NCO described above.
It is the same as the case described in the section of the urethane prepolymerization reaction.

As the amino group-containing organopolysiloxane, a general formula, (In the formula, R is CH ₃ or OCH ₃ , n is an integer of 10 to 400, and m is 1.
Is an integer from ~ 100. ).

When the epoxy resin (a) having an epoxy group at the terminal from the NCO urethane prepolymer and the epoxy-containing monool compound is modified with the amino group-containing organopolysiloxane (b), the epoxy equivalent of (a) and that of (b) The active hydrogen equivalent ratio (a) / (b) is usually 1.1 to 1000, preferably 2 to 500.

The reaction temperature is generally 10 to 150 ° C, preferably 50 to 100 ° C.

The epoxy equivalent of the epoxy resin (A) modified by the addition reaction with the amino group-containing organopolysiloxane (b) is usually 200 to 3000, preferably 500 to 2000.

In addition, other epoxy resins may be used in the present invention, if necessary.

The base epoxy resin (A) used in the present invention may be an ordinary one, for example, (1) a phenol ether type epoxy resin [a condensate of bisphenols and epichlorohydrin, a condensate of a novolac phenol resin and epichlorohydrin], (2) Ether-based epoxy resin [condensation product of polyol and epichlorohydrin, Japanese Patent Application No.
Condensation product of polyether polyol such as polyalkylene ether epoxide described in 62-100293 and epichlorohydrin], (3) Ester-based epoxy resin [glycidyl methacrylate and ethylenic double bond monomer (gacrytonitrile) Etc.)],
(4) Glycidyl amine epoxy resins such as glycidyl amine epoxy resins [condensates of amines and epichlorohydrin] and cycloaliphatic epoxy resins, epoxidized polybutadiene, non-glycidyl epoxy resins such as epoxidized soybean oil, and these Examples include a mixture of two or more kinds.

In addition to (a), the epoxy resin may be modified with an amino group-containing organopolysiloxane.

The amount of the other epoxy resin used in the present invention is generally 0 to 90% by weight, preferably 0 to 70% by weight, based on (A).

Examples of the curing agent (B) used in the present invention include "New Epoxy Resin" (Shokodo), pages 164 to 263, "Kunststoffe Handbuff" Band XI, "Polyacetale, Epoxy Hartsue, Fluoroharu". "Tige Polymelisate, Silicone, Und Zo Biter" (Carl Hanser Verlag Munich 1971) 10
Pp. 6-120, "Epoxy Resin and Products.
The one described on pages 301 to 347 of "Recent Advance" (Noyes Data Corporation, USA, published in 1977) can be used.

Polyamine can be used as an epoxy resin curing agent,
Specific examples thereof include C _{2 to} C ₆ alkylenediamines such as ethylenediamine, tetramethylenediamine, hexamethylenediamine, polyalkylene (C _{2 to} C ₆ ) polyamines such as diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, Triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, alkyl (C ₁ -C ₄ ) or hydroxyalkyl (C ₂ -C ₄ ) substitution products thereof such as dialkyl (C ₁ -C ₃ ) aminopropylamine, aminoethyl Ethanolamine, methyliminobispropylamine, alicyclic or heterocyclic containing aliphatic polyamines such as 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro "5,5] undecane aliphatic polyamines (C ₂ -C
_18); menthane diamine, N- aminoethylpiperazine, 1,3-diaminocyclohexane, isocyanate isophorone diamine, cycloaliphatic or heterocyclic polyamines such as hydrogenated methylenedianiline (C ₄ -C _15); xylylenediamine , Tetorakutoru -p- aromatic ring-containing aliphatic amines such as xylylenediamine (C ₈ ~C _15); phenylenediamine, toluenediamine, methylenedianiline, diaminodiphenyl sulfone, benzidine, 4,4'-bis (o- Toluidine), thiodianiline, dianisidine,
Methylenebis (o-chloroaniline), bis (3,4-diaminophenyl) sulfone, diamineminoditolyl sulfone, 2,6-diaminopyridine, 4-chloro-o-phenylenediamine, 4-methoxy-6-methyl-m. -Phenylenediamine, m-aminobenzylamine, 4,4'-
Aromatic polyamines such as diamino-3,3'-dimethyl-diphenylmethane (C ₆ -C _20); polyamide polyamine (a condensation product of the polyamine and a dimer acid), polyether polyamines.

Succinic acid, maleic acid, itaconic acid, azelaic acid, sebacic acid, phthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, nadic acid, methylnadic acid, dodecenylsuccinic acid, pyromellitic acid, trimellitic acid, Polycarboxylic acids such as chlorendic acid, metofaninic acid, benzophenonetetracarboxylic acid, cyclopentadienetetracarboxylic acid, phenylenebis (3-butane-1,2-dicarboxylic acid (C ₄ ~
_C30 ) and their anhydrides can also be used as hardeners.

Examples of other suitable hardeners include latent hardeners such as boron trifluoride amine complex, dicyandiamide.

Furthermore, polyisocyanates are also suitable curing agents, and polysulfide resins, imidazole compounds and other known curing agents can also be used.

Among these, preferred are polyamide polyamines, aromatic polyamines and acid anhydrides.

The epoxy curing agent is usually used in an amount in the vicinity of the epoxy group of the epoxy resin (polymer epoxide + other epoxy resin) in an equivalent amount (about the same equivalent number), but one of them is excessive (for example, about 10% or more). ) May exist.

If necessary, a curing accelerator and an additive can be used.

Specific examples of the curing accelerator include pyridine, quinoline, imidazole, N, N-dimethylcyclohexylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, triethylenediamine, N, N-dimethylamiline, N, N.
-Amines such as dimethylbenzylamine and tris (N, N-dimethylaminomethyl) phenol; basic alkali metal compounds such as sodium methoxide, caustic potash, potassium 2-ethylhexanoate; SnCl ₄ , FeCl ₃ , AlCl ₃ , SbCl ₅ , Z
Metal halides such as nCl ₂ , ZnBr ₂ , KI, LiCl; triethylaluminum, aluminum isopropoxide, tetraisopropyl titanate, diethyl zinc, n-butoxy lithium, zinc acetate, lead 2-ethylhexanoate, acetylacetonate compounds ( Fe, Co) and other organometallic compounds ;:
Quaternary ammonium compounds such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride and tetramethylammonium hydroxide; phosphorus-based compounds such as triarylkisphosphine, trialkylphosphine oxide and phosphonium salts; and Trialkyl-, triaryl- or tricycloalkylborate and the like can be mentioned.

The amount of the curing accelerator used is usually 0.01-based on the weight of the epoxy resin (polymer epoxide + other epoxy resin).
20 (preferably 0.1-10)% by weight.

Additives include flame retardants (phosphorus compounds, halogen compounds, antimony compounds, etc.), polymerization initiators, reaction retarders, colorants, (pigments, dyes), internal mold release agents, antioxidants, antioxidants, plasticizers. Agents, fungicides and carbon black, zinc oxide, calcium oxide, lead dioxide, titanium oxide, diatomaceous earth, glass mats, glass fibers and their crushed materials (cut glass, milled crows, glass flakes, etc.), glass balloons, organic balloons, talc Known additives such as mica and other fillers can be used.

The composition of the present invention can be used for metals, ceramics, plastics (including film), fibers and the like.

The curing conditions for curing the composition of the present invention with a curing agent differ depending on the type of curing agent used. For example, when fatty acid amine or polyamidoamine is used, it is preferably cured at room temperature to 100 ° C. for 0.5 to 24 hours. When an aromatic amine or acid anhydride is used, it is cured at 60 to 200 ° C for 0.5 to 10 hours. The cured product can be post-cured if necessary. Post-curing is usually 60-250 ℃, 0.5-48 hours,
Preferably, it is carried out at 80 to 220 ° C. for 1 to 12 hours.

[Examples] Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited thereto.

In the following, "part" means "part by weight".

Example 1 Polypropylene glycol (molecular weight = 2,000) and TDI (NC
100 parts of epoxy resin (epoxy equivalent = 1,030) from NCO urethane polymer with O / OH equivalent ratio 2.0) and glycidol (NCO urethane prepolymer NCO / OH equivalent ratio 0.8) and amino group-containing organopolysiloxane (active hydrogen equivalent) = 1,90
0) 1.8 parts, epoxy equivalent / active hydrogen equivalent = 100) 60
Reaction at ℃ for 5 hours, epoxy resin (epoxy equivalent = 1,
060) was obtained. An epoxy resin composition containing 100 parts of this epoxy resin and 15 parts of polyamide polyamine (active hydrogen equivalent = 163) as a curing agent was cured at 100 ° C. for 2 hours to prepare a sheet molded article.

Example 2 A sheet molded article was prepared in the same manner as in Example 1 except that polybutadiene glycol (molecular weight = 2,000) was used instead of polypropylene glycol.

Comparative Example 1 Epoxy compounded with 100 parts of an epoxy resin (epoxy equivalent = 1,030) from the polypropyrin glycol of Example 1, NCO urethane polymer of TDI and glycidol and 16 parts of polyamide polyamine (active hydrogen equivalent = 163) as a curing agent. A sheet molded article was prepared in the same manner as in Example 1 except that the resin composition was used.

Test Example 1 The sheet molded articles obtained in Examples 1 and 2 and Comparative Example 1 were treated at 50 ° C
The volume resistivity was measured after standing at 95% relative humidity for 96 hours. The test results are shown in Table 1.

[Effects of the Invention] The composition of the present invention has the following effects.

(1) It has excellent electrical characteristics (electrical insulation, etc.).

(2) It has excellent water resistance.

Therefore, the composition of the present invention is a sealant for electronic and electrical fields,
It is useful as a potting material, an adhesive, a coating material, an adhesive in the fields of automobiles, vehicles, civil engineering, and construction, a coating material, and a molding material for industrial rolls.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-59-193918 (JP, A) JP-A-60-170621 (JP, A) JP-A-60-11526 (JP, A) JP-A-61- 228015 (JP, A) JP 63-17927 (JP, A) JP 63-77921 (JP, A) JP 62-260817 (JP, A)

Claims (1)

[Claims] 1. An epoxy resin (A) obtained by modifying an epoxy resin (a) having an epoxy group at the terminal from an NCO urethane prepolymer and an epoxy-containing monool compound with an amino group-containing organopolysiloxane (b), and a curing agent. (B)
An epoxy resin composition comprising: