JPH0471095B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermosetting resin composition containing a novel curable resin as an essential component.

Conventionally, thermoplastic resins were prepared by mixing cyanate esters or their prepolymers with photopolymerizable or photocrosslinkable monomers or their prepolymers, and thermoplastic resins such as vinyl acetate or their prepolymers. Curable resin compositions have been known. In practical terms, the main purpose of mixtures of these thermoplastic resins and cyanates is to react with each other and create a polymer alloy that combines the excellent properties of both components, rather than simply blending them. Thermoplastic resins that react with cyanates have been limited.

The present invention is the result of intensive studies aimed at obtaining 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. This work was completed after discovering that by mixing the completed new curable resin with a thermoplastic resin or its low molecular weight prepolymer, a polymer alloy with higher heat resistance could be obtained compared to the previously known methods described above. be.

That is, the present invention provides: (a) a polyfunctional cyanate ester containing two or more cyanato groups in the molecule, the cyanate ester prepolymer, and (b) a 1,2-epoxy group and a radically polymerizable unsaturated double bond in the molecule. For one cyanato group of a, 1,2- of b
A thermoplastic resin or its low molecular weight compound is added to a curable resin obtained by reacting epoxy groups at a ratio of 0.25 to 2 in the presence of a radical polymerization inhibitor at a temperature of 90 to 140°C while blowing air. It is a thermosetting resin composition formed by mixing.

The reaction for producing the novel curable resin, which is an essential component of the present invention, involves selectively reacting the cyanato group of component a and the 1,2-epoxy group of component b, which will be explained below. The purpose is to suppress reactions of unsaturated bonds as much as possible.

First, the cyanato group of component a and the 1,2-
The ratio with the epoxy group is 1:0.25~ as shown above.
The ratio is 1:2, preferably 1:0.5 to 1:1.5, and the reaction temperature, time, etc. for selective reaction are
Although it varies depending on the type and amount of impurities contained in both components, use/non-use, type and amount of catalyst, etc., the temperature is usually 90 to 140°C, preferably 95 to 130°C. , most preferably at 100 to 125°C, and for a period of 3 to 40 hours, preferably 4 to 30 hours. If the temperature is below 90°C, the reaction between the cyanato group and the epoxy group will be insufficient, and even if both components become gelled, they will separate and a homogeneous product will not be obtained.
When the temperature exceeds 140°C, both the a and b components tend to gel, which usually occurs before a homogeneous product is obtained. The reaction is carried out in the presence of a radical polymerization inhibitor (reagent, etc.), 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 reaction of epoxy groups, without a solvent or at this temperature. It is carried out in the presence of a solvent by a batch method or a continuous method.

The curable resin obtained by the above reaction depends on the types and amounts of both components a and b used, and whether or not a solvent is used, but in the case of no solvent, it is usually a viscous and transparent liquid. It is presumed to consist of unreacted substances; self-condensation products of both components a and b; one or more components b bonded to monomers, trimers, pentamers, etc. of component a.

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 component a and b used, etc., but for example, as component a, 2,2-bis( 4-cyanatophenyl)
When propane is used as glycidyl methacrylate as component b, even if the reaction amount of component b per 1 mole of component a is about 0.15 to 0.3 mole, it is usually obtained as a viscous transparent liquid when it is solvent-free. This method is completely different from the method of the comparative example in which no reaction of the present invention is performed, and it is possible to obtain a cured product that is uniform, transparent, and has significantly higher heat resistance.

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

The components used in the thermosetting resin composition of the present invention will be explained below.

First, the polyfunctional cyanate ester which is component a used in the production of the novel curable resin of the present invention is preferably represented by the following general formula (1) R(-O-C≡N)m...(1 ) (in the formula, m is an integer of 2 or more and usually 5 or less, R is an aromatic organic group, and the cyanato group is bonded to the aromatic ring of the organic group) It is a compound. Specific examples include 1,3- or 1,4-dicyanatobenzene, 1,
3,5-tricyanatobenzene, 1,3-. 1,
4-. 1,6-. 1,8-. 2,6- or 2,7
-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4,4'-dicyanatobiphenyl, bis(4-dicyanatophenyl)methane,
2,2-bis(4-cyanatophenyl)propane, 2,2-bis(3,5-dichloro-4-cyanatophenyl)propane, 2,2-bis(3,5
-dibromo-4-cyanatophenyl)propane,
Bis(4-cyanatophenyl) ether, bis(4-cyanatophenyl) thioether, bis(4-cyanatophenyl) sulfone, tris(4
-cyanatophenyl) phosphite, tris(4
-cyanatophenyl) phosphate, cyanate esters from aromatic polycarbonate oligomers and cyanogen halides, and cyanate esters from novolak and cyanogen halides. In addition, special public works 41-1928, 43-18468, 44
-4791, 45-11712, 46-41112, 47-
26853 and JP-A No. 51-63149, No. 51-14995, No.
51-114494, etc., and these are used as commercially available products or after purification.

Alternatively, the polyfunctional cyanate ester described above is polymerized in the presence of a mineral acid, a Lewis acid, a salt such as sodium carbonate or lithium chloride, a phosphate ester such as tributylphosphine, etc. A sym-triazine ring formed by trimerization of a cyan group can generally be used as a prepolymer in the molecule. These prepolymers have a number average molecular weight
It is preferable to use 300 to 6000. Furthermore,
The polyfunctional cyanate esters mentioned 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 1,2-epoxy group in the molecule and is free from radical polymerization. It has one or more unsaturated 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 glucidyl group and acroyl 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)-2,3-epoxypropane, 1-(2-methyl-2-propenyl)-2,3-epoxypropane, 1-allyloxy- Examples include 3,4-epoxybutane and 1-allyloxy-4,5-epoxypentane.

The radical polymerization inhibitor used in the production reaction of the novel curable resin of the present invention is a reagent that is generally used as a radical polymerization inhibitor and quickly reacts with radicals to convert into stable radicals or neutral substances. Others. Specifically, diphenylpicrylhydrazyl, tri-p-nitrophenylmethyl, phenothiazine, benzoquinone, p-tert-
Examples include organic compounds such as butylcatechol, hydroquinone, hydroquinone monoalkyl ether, nitrobenzene, dialkyldithiocarbamic acid metal 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 compound used,
Furthermore, it is preferable to introduce oxygen or an oxygen-containing gas into the reaction system and use it in combination.

Furthermore, the cyanato group of component a and the 1,2-
It is a preferable embodiment to use a catalyst to selectively promote the reaction with epoxy groups, and examples of such catalysts include those known as curing catalysts used for epoxy resins as described above, and those with cyanato groups. Those that have a small promoting effect on the trimerization reaction under the above reaction conditions are suitable, and specifically, N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, N,N -dimethyl-p-anisidine, p-halogeno-N,N-
Dimethylaniline, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, N,N,N',
Tertiary amines such as N'-tetramethylbutanediamine, N-methylpiperidine, etc. and R
Quaternary ammonium salt (R ₄ N ⁺・X ^- ) with a monohalogenated alkyl represented by Heptadecylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 1-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-guanaminoethyl-
Imidazoles exemplified by 2-methylimidazole and those to which the following organic acids and acid anhydrides are added; trichloroacetic acid, oxalic acid, maleic acid, maleic anhydride, para-toluenesulfonic acid, Acids such as toluenesulfonic acid, phthalic anhydride, p-dichlorophthalic anhydride, succinic acid, lauric anhydride, pyromellitic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, hexahydro trimellitic anhydride, hexahydropyromellitic anhydride, isocycinuric acid, etc. and acid anhydride; _BF3.O ( _{C2H5 ) 2} ,
Examples include BF ₃ .O(CH ₃ ) ₂ , BF ₃ .piperidine adduct, triphenylphosphine, triphenylphosphite, triphenyl phosphate, triphenylantimony, and iodine.

The c-component thermoplastic resin or its prepolymer to be mixed with the novel curable resin described above may be any known one and is not particularly limited. Examples of these include polyvinyl acetal resins such as polyvinyl formal, polyvinyl acetal, and polyvinyl butyral; thermoplastic resin polyurethane resins; polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, butadiene-styrene copolymer, polyisoprene, butyl rubber, Non-crosslinked (non-vulcanized) rubbers such as natural rubber; polyethylene, polypropylene, polybutene, poly-4-methylpentene
1. Polyvinyl chloride, vinylidene chloride resin, polystyrene, polyvinyltriene, polyvinylphenol, AS resin, ABS resin, MBS resin, poly-4-fluorinated ethylene, fluorinated ethylene-propylene copolymer, 4-fluorinated ethylene- Vinyl compound polymers such as 6-fluorinated ethylene copolymer and vinylidene fluoride; polycarbonate, polyester carbonate, polyphenylene ether, polysulfone, polyester, polyether sulfone, polyamide, polyadimide, polyester imide, polyphenylene sulfate Examples include resins such as AID, and low molecular weight polymers (prepolymers) of these thermoplastic resins having a molecular weight of 10,000 or less, usually 1,000 to several thousand.

The blending ratio of the curable resin obtained by reacting the a and b components of the present invention described above and the thermoplastic resin of the c component is not particularly limited, but is based on 100 wt parts of the resin component in the composition. , c component from 0.1 to
It is preferable to use 99 parts by weight, preferably in the range of 0.5 to 95 parts by weight. In particular, when the characteristics of component a are to be utilized, it is preferable to use component c in an amount of 1 to 50 parts by weight.

In addition, the method of mixing the new curable resin and the thermoplastic resin as the c component may be a known method, for example, a method of simply stirring and mixing both components with or without heating, a common method of both components, or a method of mixing the two components with a common or respective solvent. A method of dissolving and mixing to form a solution or suspension solution, a method of removing the solvent from this solution to obtain a solvent-free composition,
Examples include a method in which the thermoplastic resin of component c is mixed as a powder without a solvent at room temperature or under heating in a kneader, roll, Banbury mixer, Henschel mixer, extruder, or the like.

The thermoplastic resin composition of the present invention undergoes a crosslinking reaction and cures by heating even without a catalyst, but for the purpose of promoting heat curing, 2
-Methylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-propyl-2-methylimidazole, 1
-cyanoethyl-2-methylimidazole, 1-
Cyanoethyl-2-ethylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-
Cyanoethyl-2-phenylimidazole, 1-
Imidazoles exemplified by cyanoethyl-2-ethyl-4-methylimidazole and 1-guanaminoethyl-2-methylimidazole;
Adducts of organic acids or their anhydrides to these imidazoles; N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-
Dimethyltoluidine, N,N-dimethyl-p-anisidine, p-halogeno-N,N-dimethylaniline, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N-
Methylmorpholine, triethanolamine, triethylenediamine, triethylenediamine, N,
N,N',N'-tetramethylbutanediamine, N
- Tertiary amines such as methylpiperidine; phenols such as phenol, xylenol, cresol, resorcin, catechol, phloroglycin; lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin Organic metal salts such as malate, manganese naphthenate, cobalt naphthenate, iron acetylacetone; inorganic metal salts such as SnCl ₄ , ZnCl ₂ , AlCl ₃ ; benzoyl peroxide, lauroyl peroxide, caprylic peroxide, acetyl peroxide, para Chlorobenzoyl peroxide, di-
Peroxides such as tert-butyl-di-perphthalate; maleic anhydride, phthalic anhydride, lauric anhydride, pyromellitic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, hexahydro trimellitic anhydride, hexahydropyromellitic anhydride, etc. Acid anhydrides; further examples include azo compounds such as azobisisobutylnitrile and curing catalysts for epoxy resins. The amount of these catalysts to be added is sufficient within a general catalytic amount range, and for example, it may be used in an amount of 10 wt % 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 100%
It is sufficient if the temperature is selected within the range of ~300℃. This curable resin is used in paints, cast products, molded products, laminates, tapes,
Used for various purposes such as sheets and films.

The curable resin composition of the present invention may contain various additives as desired, as long as the original properties of the composition are not impaired. These additives include natural products such as rosin, silica, copal, oil-modified rosin, esters of (meth)acrylic acid of monofunctional or polyfunctional hydroxy compounds,
Epoxy ester of (meth)acrylic acid, (meth)
(meth) such as alkenyl esters of acrylic acid
Esters of acrylic acid and prepolymers thereof; polyalkenyl compounds such as diallylfucrate, divinylbenzene, diallylbenzene, trialkenyl isocyanurate, etc. and prepolymers thereof; dicyclopentadiene and prepolymers thereof; cyanate ester trees; cyanate esters -maleimide resin; maleimide resin; epoxy resin;
Phenol resin; Phenoxy resin; Acrylic resin with OH or COOH group; Silicone resin; Unsaturated polyester resin; Alkyd resin;
Petroleum resin; etc. are exemplified and used as appropriate. As reinforcement and filler, cloth, roving cloth,
Various types of glass cloth such as chopped pine and surfing pine, quartz glass cloth, carbon fiber cloth, other inorganic fibers such as asbestos, rock wool, and slag wool, fully aromatic nylon cloth,
Blended fabric of glass fiber and fully aromatic nylon fiber,
Acrylic, vinylon, polyester, nylon,
Synthetic fiber cloth such as polyimide, cotton cloth, linen cloth, felt, kraft paper, cotton paper, paper-glass blend paper, semi-carbon fiber cloth, etc.
Fiber chips that make up paper; 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, semiconductor,
Examples include boron nitride, other ceramics, aluminum, copper, iron, and various other materials. In addition to these, various additives known as additives for the resin, such as dyes, pigments, thickeners, lubricants, coupling agents, and flame retardants, may be used in appropriate combinations as desired.

The present invention will be explained in more detail below using Examples and Comparative Examples.

Example 1 50 g of 2,2-bis(4-cyanatophenyl)propane (cyanato group equivalent: 139), 50 g of glycidyl methacrylate (epoxy equivalent: 142 or less, referred to as GMA), and 0.06 g of phenothiazine were placed in a glass container, and the temperature was adjusted while blowing air. 120~125℃
and reacted for 10 hours with stirring to produce a triazine-acrylate resin.

75 wt parts of this triazine-acrylate resin and 25 wt parts of a high polymerization degree polyvinyl acetate resin having an average degree of polymerization of 1300 to 1500 are mixed and dissolved in toluene, and further,
0.10wt part of dicumyl peroxide was mixed, and the mixture was coated on a polyimide film to a thickness of 30μ and dried. Layer a 35μ thick copper foil on top of this film and apply a pressure of 20
Kg/cm ² and pressed at a temperature of 160° C. for 2 hours.

The peel strength of the copper foil of this flexible copper-clad laminate was 1.8 kg/cm, and no blistering occurred even when it was floated in a 280° C. solder bath for 1 minute.

Comparative Example 1 A cyanate ester resin prepolymer was prepared by heating 2,2-bis(4-cyanatophenyl)propane at 140°C for 6 hours.

Example 1 was repeated except that 75 wt parts of this prepolymer was used in place of 75 wt parts of the triazine-acrylate resin in Example 1.

The peel strength of the copper foil of this flexible copper-clad laminate was 0.7 kg/cm, and blistering occurred when it was floated in a 280° C. solder bath for 1 minute.

Example 2 70 g of 2,2-bis(4-cyanatophenyl)propane, 50 g of GMA and 0.04 g of phenothiazine
Place it in a glass container and bring it to the temperature while blowing air into it.
The mixture was heated to 120 to 125°C and reacted for 9 hours with stirring to produce a triazine-acrylate resin.

70wt part of this triazine-acrylate resin and polyphenylene ether resin with a molecular weight of about 3000
30 wt parts were dissolved in 200 wt parts of toluene to form a solution.

This mixture was heated to 80°C, 0.1wt part of dicumyl peroxide and 0.01wt part of zinc octylate were added and mixed, coated on an aluminum plate, cured at 175°C for 2 hours according to JISK6850 method, and then pulled. A test piece for tensile strength measurement was made.

The tensile shear strengths of this test piece at 25°C and 200°C were 280 Kg/cm ² and 156 Kg/cm ² , respectively.

Example 3 1,4-dicyanatobenzene, 42 g, glycidyl acrylate 50 g, benzyldimethylamine
0.5 g and 0.04 g of phenothiazine were placed in a glass container and reacted at 125 to 130° C. for 6 hours while blowing air to produce a triazine-acrylate resin.

60 wt parts of this triazine-acrylate resin, 40 wt parts of thermoplastic polyurethane with a molecular weight of approximately 100,000 manufactured from caprolactone polyester and hexamethylene diisocyanate, and 0.2 wt part of t-butyl peroxybenzoate are mixed on a roll at 80°C to form a homogeneous mixture. I got it.

This mixture was molded into a 3 mm thick test piece and heated to 165°C.
It was heated and cured for 2 hours. 25℃ and 125℃ of cured product
The Shore D hardness was 90 and 88, respectively.

Claims (1)

[Scope of Claims] 1. A polyfunctional cyanate ester containing two or more cyanato groups in the molecule, the cyanate ester prepolymer, and b. A compound having a double bond is added to one cyanato group of a to 1,2- of b.
Epoxy groups are mixed at a ratio of 0.25 to 2 in the presence of a radical polymerization inhibitor, and the temperature is increased while blowing air.
A thermosetting resin composition prepared by mixing a curable resin reacted at 90 to 140°C with a thermoplastic resin or a low molecular weight compound thereof.