JPS59196306A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:A thermosetting resin composition excellent in heat resistance, etc., easily curable, and suitable for use in paints, etc., obtained by mixing a curable resin obtained from a polycyanate ester having a plurality of cyanato groups in the molecule with a heat-curing monomer. CONSTITUTION:A polycyanate ester (A) having at least two cyanato groups in the molecule (e.g., 1,4-dicyanatobenzene) or its prepolymer is reacted with a compound (B) having both a 1,2-epoxy group and a radical-polymerizable double bond in the molecule (e.g., glycidyl acrylate) in such a ratio that 0.25-2 1,2- epoxy groups of component B are present per cyanato group of component A at a temperature of 90-140 deg.C in the presence of a radial polymerization inhibitor. The produced curable resin is mixed with a heat-curing monomer (prepolymer), e.g., phenolic resin, to obtain the purpose thermosetting resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention uses a novel curable resin as a composition component! ! ) Regarding a curable resin composition.

Conventionally, cyanate esters or their prepolymers,
It has been known to mix a photopolymerizable or photocrosslinkable monomer or a prepolymer thereof and a thermosetting monomer such as an epoxy resin or a prepolymer thereof and to cure the mixture using light and heat in combination or by heat curing. .

However, under practical conditions, the radical polymerizability and photopolymerizability of cyanate esters or their prepolymers themselves are small, and cyanate esters or their prepolymers themselves have low radical polymerizability and photopolymerizability, and in order to cure in a short time, it is necessary to cure at 170°C.
It is necessary to cure the above mixture at a temperature of 170°C or higher, and radical copolymerization and photococuring become extremely insufficient. It had the disadvantage of being non-uniform.

The present invention has been made through intensive studies to obtain a curable resin that can be cured by radical polymerization or photocuring while retaining the excellent heat resistance and electrical properties of cyanate esters or their prepolymer cured products. By using the new curable resin completed as a result, conventionally known cyanate esters or their prepolymers, radically polymerizable II
! A thermosetting resin composition that is easier to cure and provides a cured product with significantly superior uniformity, etc., than a cured product of a mixture of p-isomer or its prepolymer and a thermosetting monomer or its prepolymer. This is what I found.

That is, the present invention provides a polyfunctional cyanate ester containing two or more cyanato groups in the a1 molecule, the cyanate ester prepolymer, and an L2-epoxy group and a radically polymerizable unsaturated divalent bond in the a6 molecule. A compound having 1 cyanato group in a and 0.25 to 2 1,2-epoxy groups in b at a temperature of 90 to 140'C in the coexistence of a radical polymerization inhibitor 1. This is a thermosetting resin composition obtained by mixing a C, i', jt curable monomer or a prepolymer thereof with a curable resin obtained by reaction.

The manufacturing reaction of the novel curable resin, which is one component used in the thermosetting resin composition of the present invention, involves selectively reacting the cyanato group of component a and the 1,2-epoxy group of component b as described below. It is obtained by suppressing the reaction of the unsaturated double bond of component b as much as possible.

First, the ratio of the cyanato group of component a to the 1,2-epoxy group of component b is as described above <1:0.25 to 1:2, preferably in the range of i:o, s to 1:1.5. The reaction temperature, time, etc. for selective reaction are
This will vary depending on the type and amount of impurities contained, the use/non-use, type and amount of catalyst, etc., but it is usually at a temperature of 90 to 140°C, preferably 95 to 130°C, most preferably 100°C. ~125°C, time 3-4
0 hours, preferably 4 to 30 hours. temperature is 90°
If the temperature is less than 140°C, the reaction between the cyanato group and the epoxy group will be insufficient, and even if both components form a gelatinous mass, the two components will separate and a homogeneous product will not be obtained. It usually gels before a homogeneous product is obtained.

The reaction is carried out in the presence of radical polymerization inhibitors (reagents and others), without a catalyst, or in the presence of a catalyst that has a small effect of accelerating the multimerization reaction of cyanato groups at this temperature and a large effect of accelerating the epoxy group Φ reaction, without a solvent or without a catalyst. In the presence of a solvent,
Perform by batch method or continuous method.

The curable resin obtained by the above reaction is used for a and b.
Although it depends on the type and amount of both components and the use or non-use of a solvent, for example, when using 2,2-bis(4-cyanatophenyl)propane as the a component and glycidyl methacrylate as the b component without a solvent, it is usual. , a viscous, transparent liquid that is unreacted; an abb component self-condensation product; a monomer, trimer, trimer, etc. of component A that is composed of one or more components B bonded to it, etc. It is estimated that

In addition, the reaction rate of the co-reactant of both components a and b or the reaction rate of component b varies depending on the use or non-use of a catalyst, the purity of the a and b components used, etc. In this case, the reaction amount of component b with respect to 1 mole of component a is 0.1
Even if the amount is about 5 to 0.3 mol, it is usually obtained as a viscous and transparent liquid in the absence of a solvent. It is possible to obtain a cured product with significantly higher heat resistance.

The curable resin produced by the above method exhibits the excellent properties as described above even when used as is as a component of the present invention, and can be used as is or concentrated under reduced pressure at a temperature of about 20 to 105°C to form a solvent. It is also preferable to remove all or a portion of low molecular weight compounds and low boiling point compounds such as unreacted substances of component b and use the mixture as a viscous liquid, paste or solid at room temperature.

In addition, the polyfunctional cyanate ester which is component a used in the production of the above-mentioned curable resin is preferably expressed by the following general formula (1) % formula % (1) (m in the formula is 2 or more, usually 5 is the following integer, R is an aromatic organic group, and the cyanato group is bonded to the aromatic ring of the organic group. A specific example is 1.3-
or 1,4-dicyanatobenzene, L3,5-tricyanatobenzene, 1.3-, L4-, L6-, L8-. 2
．． 6- or 2,7-dicyanatonafucrene, L3,6-
Tricyanatonaphthalene, 4.4'-dicyanatobiphenyl, bis(4-dicyanatophenyl)methane, 2.2
-bis(4-cyanatophenyl)propane, 2,2-his(3,5-dichloro-4-cyanatophenyl)propane, 2,2-bis(3,5-dibromo-4-cyanatophenyl)propane , bis(4-cyanatophenyl)ether, bis(4-cyanatophenyl)dioether, bis(4-cyanatophenyl)sulfone, tris(4-cyanatophenyl)phosphite, tris(4-cyanatophenyl) phosphates, cyanate esters from aromatic polycarbonate oligomers and cyanogen halides, and cyanate esters from novolacs and cyanogen halides. In addition to these, the special public interest
8, 43-18468, 44-4791, 4
5-11712, 46-41112, 47-268
53 and JP-A No. 51-63149, No. 51-1499
Cyanic acid esters described in No. 5, No. 51-114494, etc. may also be used. These cyanate esters may be commercially available products and may be used as they are or after being purified.

Alternatively, the above-mentioned polyfunctional cyanate ester can be used as a prepolymer obtained by polymerizing it in the presence of a mineral acid, a Lewis acid, a salt such as sodium carbonate or lithium chloride, or a phosphate ester such as tributylbosphine. I can do it.

These prepolymers generally have a sym=triazine ring in the molecule, which is formed by trimerization of the cyanide group in the cyanate ester. In the present invention, it is preferable to use the prepolymer having a number average molecular weight of 300 to 6,000.

Furthermore, the polyfunctional cyanate esters described above can also be used in the form of prepolymers with amines.

As the compound having a 1,2-epoxy group and a radically polymerizable unsaturated double bond in the molecule, which is component b, a preferable substance has one L2-epoxy group in the molecule and a radically polymerizable unsaturated double bond. It has one or more saturated double bonds, particularly preferably a glycidyl group as the 1,2-epoxy group and acryloyl or methacryloyl as the unsaturated double bond. Specifically, glycidyl acrylate, glycidyl methacrylate, glycidyl cinnamate (glycidyl cinnamate), epoxy obtained by reacting an epoxy compound containing two or more epoxy groups in the molecule with the carboxyl group of an unsaturated carboxylic acid. Compounds with a glycidyl group and acryloyl or methacryloyl, such as compounds with a group and an unsaturated double bond, allyl glycidyl ether (1-allyloxy-2,3-epoxypropane), 1-(3-methyl- 2-butenyloxy)-2,3-epoxypropane, 1-(3-butenyloxy)-213-epoxypropane, 1-(2-methyl-2-propenyl)-2,
Examples include 3-epoxypropane, -allyloxy-3,4-epoxybutane, and 1-allyloxy-4,5-epoxypenkune.

A radical polymerization inhibitor is generally used as a radical polymerization inhibitor, and is a reagent or the like that quickly reacts with radicals and converts them into stable radicals or neutral substances.

Specifically, diphenylpicrylhydrazyl, tree p
-nitrophenylmethyl, phenothiazine, benzoquinone, p-tert-butylcatechol, hydroquinone,
Hydroquinone monoalkyl ether, nitrohenzene,
Examples include organic compounds such as dialkyldidiolbamic acid gold salts; and oxygen and oxygen-containing gases. The amount of the radical polymerization inhibitor used as a reagent is preferably 0.01 to 0.1% based on the total amount of the raw material compounds used, and it is further preferable to introduce oxygen or an oxygen-containing gas into the reaction system and use it together.

The catalyst used to selectively promote the reaction between the cyanato group of component a and the 1,2-epoxy group of component b is known as a curing catalyst used for epoxy resins as described above. N, which has a small promoting effect on the trimerization reaction under the above reaction conditions, is suitable.
N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, N,N-dimethyl-
p~Luanisidine p-halogeno-N, N-dimethylaniline, 2-N-ethylanilinoethanol, tri-n-
Butylamine, pyridine, quinoline, N~methylmorpholine, triethanolamine, triethylenediamine,
N, N, Nlh'-tetramethylbutanediamine, N-
A quaternary ammonium salt of a tertiary 'ymine such as methylpiperidine and a monohalogenated alkyl represented by I'1-X (X is CI, Br, 1, etc.)
R4N"-X-), 2-methylimidazole,
2-undecylimidazole, 2-heptadecyl imidazole, 2-phenylimidazole, 2-ethyl-4-
Methylimidazole, ■-benzyl-2-methylimidazole, 1-propyl-2-methylimidazole, 1-
Cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethylimidazole, 1-cyanoethyl-2
-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-
4-methylimidazole, 1-guanamine ethyl-2-
Imidazoles exemplified by methylimidazole and the following organic acids and acid anhydrides added to these imidazoles; trichloroacetic acid, oxalic acid,
Maleic acid, maleic anhydride, para-toluenesulfonic acid, toluenesulfonic acid, phthalic anhydride, p-dichlorophthalic anhydride, succinic acid, larallic anhydride, pyromellitic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, hexahydro Acids and acid anhydrides such as trimellitic anhydride, hexahydropyromellitic anhydride, and isocycinanuric acid IF3 ・0(C2H5)2, B F 3 ・
Examples include 0(CH3)2, BF3/piperidine adduct, triphenylphosphine, triphenylphosphite, triphenylphosphate, triphenylantimony, and iodine.

There are no particular restrictions on the thermosetting monomer or prepolymer thereof as component C of the present invention to be mixed with the above curable resin, but it may be selected as appropriate from the viewpoint of properties such as heat resistance of the cured product. . Suitable examples include cyanate ester resins (so-called triazine resins: Japanese Patent Publication No. 41-1928, etc.), Schiff hepta-acid ester-7reimide resins (so-called bismaleimide 1-lyazine resins: special Publication No. 54-30440 etc.), Schiff heptaic acid 1 stell-maleimide-epoxy resin (Special Publication No. 1972)
-31279etc); Maleimide resins such as polyfunctional maleimides and pre-reacted products of the maleimides and polyfunctional amines (trade name: Kerimid 601.R);
honeP.

ulenc, etc.), thermosetting polyimide resins such as thermosetting polyimide resins with acetylene groups at the ends (product name: Thermid 600.Gulf oil c)
epoxy resins having two or more glycidoxy groups in the molecule; unsaturated polyester resins; unsaturated alkyd resins; C2-orL4-polybutadiene; modified polybutadiene resins such as epoxidized 1.2-orL4-polybutadiene; Thermosetting polyurethane resins include: phenolic resins; acrylic resins having OH groups or COOH groups; silicone resins, and modified resins such as mixtures and pre-reacted products thereof.

The blending ratio of the novel curable resin produced from components a and b of the present invention described in detail above and the thermoplastic resin of component C is not particularly limited, but usually component C is added to all of the composition. 1 to 99 wt%, preferably 5 to 80 wt%, most preferably 10 to Hwt%, based on the resin component.

Further, the method for preparing the thermosetting resin composition of the present invention may be a conventionally known method, for example, stirring the novel curable resin of the present invention and the thermosetting monomer of component C or its prepolymer. A method in which one component is simply mixed in a solvent, a method in which one component is dissolved in a solvent and the mixture is simply mixed, a method in which the solvent is removed after mixing, a method in which the component is mixed without a solvent at room temperature or heated using a Nigu, Roll, Banbury mixer, Henschel mixer, extruder, etc. Examples include a method of mixing.

The thermosetting resin composition of the present invention has the property of undergoing a crosslinking reaction when heated to become a cured (Δ) resin even as it is, but a curing agent or a curing catalyst is usually added and mixed in order to promote heat curing. These thermosetting catalysts or curing agents include 2-methylimidazole, 2-undecylimidazole, 2-hepcudecylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole,
■-Hensyl-2-methylimidazole, ■-Propyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, l-cyanoethyl-2-ethylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2- phenylimidazole,
Imidazoles exemplified by 1-cyanoethyl-2-ethyl-4-methylimidazole and ■-guanaminoethyl-2-methylimidazole, as well as adducts of carboxylic acids or their anhydrides to these imidazoles, etc. , N, N-dimethylbenzi) L<amine, N, N-
dimethylaniline, N, N-dimethyltoluidine, N,
N-dimethyl-anisidine, p-halogeno-N, N-
Dimethylaniline, 2-N-ethylanilinoethanol, trilobylamine, pyridine, quinoline, N-
Tertiary amines such as methylmorboline, triethanolamine, triethylenediamine, N,N,N:N'-tetramethylbutanediamine, N-methylpiperidine;
Phenol, xylenol, cresol, resorcinol,
Phenols such as catechol and phloroglycin; organic metal salts such as lead naphthene, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, iron acetylacetonate; 5nC14 , ZnCl2, Al
Inorganic metal salts such as Cl3; peroxides such as benzoyl peroxide, lauroyl peroxide, caprylic peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl di-perphthalate; maleic anhydride, phthalic anhydride , acid anhydrides such as lauric anhydride, pyromellitic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, hexahydrotrimellitic anhydride, and hexahydropyromellitic anhydride; furthermore, ab compounds such as azobisisobutylnitrile, Examples include curing catalysts for epoxy resins. The amount of these catalysts to be added is sufficient within the range of catalyst amounts in a general sense, and may be used, for example, in an amount of 10 tvt% or less based on the total composition.

The thermosetting temperature of the thermosetting resin composition of the present invention described in detail above varies depending on the presence or absence of a curing agent and catalyst, the types of composition components, etc., but is usually selected within the range of 100 to 300°C. good.

This curable resin composition is used for various purposes such as paints, inks, cast products, molded products, laminates, tapes, sheets, films, and adhesives. The thermosetting resin composition of the present invention may contain various additives as desired, as long as the original properties of the composition are not impaired. Natural or synthetic resins include natural products such as rosin, shellac, copal, and oil-modified rosin; dicyclopentadiene and its prepolymers; polyvinyl acecool resins such as polyvinyl formal, polyvinyl acecool, and polyvinyl butyral; phenoxy resins. ; Petroleum resin; low molecular weight liquid to high molecular weight ela such as butadiene-acrylonitrile copolymer, polychloroprene, butadiene-styrene copolymer, polyisoprene, butyl rubber, natural rubber, etc.
Stic rubbers: polyethylene, polypropylene, polybutene, poly-4-methylpentene-1, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyltoluene, polyvinylphenol, AS resin, ABS resin, MBS resin, poly-4-phen fluorinated ethylene, fluorinated ethylene-propylene copolymer, 4-fluorinated ethylene-6
- Vinyl compound polymers such as fluorinated ethylene copolymer and vinylidene fluoride; polycarbonate, polyester carbonate, polyphenylene ether, polysulfone, polyester, polyether sulfone, polyamide,
Examples include polyimide, polyaimide, polyesterimide, polyphenylene sulfide, and the like. As reinforcing materials and fillers, various glass cloths such as cloth, roving cloth, chopped mat, and surfacing mat, quartz glass cloth, carbon fiber cloth, and other asbestos,
Inorganic fibers such as rock wool and slag wool, fully aromatic nylon cloth, blended fabrics of glass fiber and fully aromatic nylon fibers, synthetic fiber cloths such as acrylic, vinylon, polyester, nylon, and polyimide, cotton cloth, linen cloth, and felt. , kraft paper, cotton paper, paper-glass mixed paper, semi-carbon fiber cloth, etc., as well as chopped fibers that make up these cloths and papers; glass powder, glass bulbs, silica, alumina, silica alumina, aluminum hydroxide, asbestos. , calcium carbonate, calcium silicate, wollastonite, carbon black, kaolin clay, calcined kaolin, mica, talc, iron oxide, synthetic mica, natural mica, semiconductors, boron nitride, other ceramics, aluminum, copper, iron, etc. Various known ones can be mentioned. In addition to these additives, various known additives such as dyes, pigments, thickeners, lubricants, coupling agents, and flame retardants are included, and may be used in appropriate combinations as desired.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

Example-1 2,2-his(4-cyanatophenyl)propane (cyanato group equivalent: 139) 50 g, glycidyl methacrylate (epoxy equivalent: M142, hereinafter referred to as GMA)
50 g and 0.06 g of phenothiazine were placed in a glass container, heated to a temperature of 120 to 125° C. while blowing air, and reacted with stirring for 10 hours.

To 60 wt parts of this reactant, an epoxy equivalent of 450 to 50
40 wt parts of 0 bisphenol A type epoxy resin were added and dissolved and mixed in methyl ethyl ketone. The gelation time of this mixture at 160°C was 15 minutes. Further, as a catalyst, 410.2 wt parts of dicumyl baroxa and 0.02 wt part of zinc octylate were mixed. The gelation time of this mixed solution at 160°C was 240 seconds.

A glass cloth with a thickness of 0.2 mm was impregnated with the mixed solution, and
℃, 5 minutes drying, kelization time 60 seconds (at 170℃)
, a prepreg with a resin amount of 43wt% was created, and this was
A laminate was produced by stacking the sheets and molding them at 40 kg/cII+ for 6 hours at 150°C.

The glass transition temperature of this laminate was 196°C.

Comparative Example-1 2,2-bis(4-cyanatophenyl)propane at 14
The reaction was carried out at 0°C for 16 hours to produce a cyanate ester resin prepolymer. 50 wt parts of this resin and GMA 5
0 wt part, epoxy resin 67 I similar to Example-1
VT part was added, dissolved and mixed in methyl ethyl ketone, and 0.33 wt part of dicumyl peroxide and 0.033 ut part of zinc octylate were mixed as catalysts.

A glass cloth with a thickness of 0.2 mm was impregnated with this mixed solution and dried at 120°C for 15 minutes, but GMA evaporated during drying and only 75 wt% of the amount deposited remained as a resin component (84 wt% of the amount of added GMA remained). % evaporated during drying).

Example-2 42 g of L4-dicyanatobenzene and 50 g of glycidyl methacrylate were mixed with 0.5 g of benzyldimethylamine.
The mixture was reacted with 0.04 g of phenothiazine at 125 to 130° C. for 6 hours while blowing air (hereinafter referred to as resin A).

In addition, 2,2-bis(4-cyanatophenyl)propane was heated at 140° C. for 6 hours to prepare a cyanate ester resin prepolymer (hereinafter referred to as resin B).

After mixing 50 wt parts each of resins A and B at 80°C, L
0.3 parts of -butyl peroxybenzoate was mixed and cast into a plate with a thickness of 3 mm, and cured by heating at 160°C for 5 hours. The glass transition temperature of this cured product is 225°C
Met.

Comparative Example-2 (1), 4-dicyanatobenzene was heated at 135° C. for 5 hours (hereinafter referred to as resin C).

Further, 2,2-bis(4-cyanatophenyl)propane was heated at 140°C for 6 hours to produce a cyanate ester resin prepolymer (hereinafter referred to as resin).

After mixing 50 wt parts each of resins C and D at 80°C, 0.3 wt part of t-butyl baroxyhenzoate was mixed, a plate with a thickness of 3 mm was cast, and the mixture was heated and cured at 160°C for 5 hours. .

The glass transition temperature of this cured product was 183°C.

Example-3 2,2-bis(4-cyanatophenyl)propane 70g
30 g of GMA and 0.04 g of phenothiazine were placed in a glass container, and the temperature was raised to 120~120°C while blowing air.
The mixture was heated to 125°C and reacted for 9 hours with stirring.

Using 80 parts of this reactant, 20 w of an unsaturated alkyd resin produced from maleic anhydride and ethylene glycol.
t parts were mixed, and 0.5 wt part of benzoyl peroxide was mixed therein.

Apply this on a metal plate to a thickness of 30μ, and rotate it at 160°.
C for 20 minutes to obtain a coating film with a surface hardness of 6H.

Patent applicant: Mitsubishi Gas Chemical Co., Ltd. Representative Kazuyoshi Nagano

Claims (1)

[Scope of Claims] A polyfunctional cyanate ester containing two or more cyanato groups in the a9 molecule, the cyanate ester prepolymer, and a 1,2-epoxy group and a radically polymerizable unsaturated diamide in the soo molecule. A compound having a double bond is mixed in a ratio of 0.25 to 2 1,2-epoxy groups in b to 1 cyanato group in a, in the coexistence of a radical polymerization inhibitor, at a temperature of 90 to 140°C. A thermosetting resin composition obtained by mixing a C0 thermosetting monomer or its prepolymer with the curable resin obtained by reacting with