JPS6333504B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel cyanate ester-based curable resin composition that has excellent adhesiveness, flexibility, heat resistance, low-temperature curability, etc., and specifically relates to a polyfunctional cyanate ester and the cyanate ester prepolymer. Alternatively, a prepolymer of the cyanate ester and an amine, a polyfunctional maleimide of a and b, a maleimide prepolymer, a prepolymer of the maleimide and an amine, or c an epoxy resin are mixed or curable by pre-reaction. In the resin composition (), the butadiene resin () and the acrylic acid epoxy ester represented by the following general formula (3) or the acrylic acid epoxy ester prepolymer () are combined in an amount of 30 to 95% by weight of the component () and the component (). ) 2.5 to 50% by weight and component ( ) in an amount of 2.5 to 50% by weight. General formula (3): (R in the formula represents a hydrogen atom or a methyl group). The curable resin composition () of the present invention is
-1928 Publication (component a), Publication No. 46-41112 (composition of a+c), Publication No. 54-30440 (composition of a+b), Publication No. 52-
31279 (composition of a+b+c) and others, and is excellent in various physical properties such as heat resistance, chemical resistance, adhesiveness, and electrical properties.
Although it has been put into practical use, it has the disadvantage of being inferior in terms of flexibility. Furthermore, cured products of acrylic acid epoxy esters, methacrylic acid epoxy esters, or prepolymers () of the epoxy esters were brittle, had poor flexibility, and had insufficient heat resistance. As a result of intensive research into improvements that take advantage of the characteristics of cyanate ester resin compositions, the present inventors have discovered a new curable resin composition that has good adhesion, flexibility, heat resistance, and can be cured at lower temperatures. This discovery led to the completion of the present invention. The constituent components of the present invention will be explained below. First, as mentioned above, the cyanate ester resin composition () of the present invention has component a as an essential component and b.
Alternatively, the c-component may be appropriately used. The polyfunctional cyanate ester which is essential component a is an organic compound having two or more cyanate ester groups, and a suitable cyanate ester has the following general formula 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 cyanate ester group is bonded to the aromatic ring of the organic group R] The compound represented by 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-cyanatophenyl)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)
These include phosphates, and cyanate esters obtained by the reaction of novolacs with cyanogen halides. In addition to these, Tokuko Sho 41-1928, Tokko Sho
43-18468, Special Publication 44-4791, Special Publication 45-11712,
Special Publication No. 46-41112, Special Publication No. 47-26853, and Special Publication No. 1983
Cyanic acid esters described in 51-63149 and the like can also be used. Further, a prepolymer obtained by polymerizing the above-mentioned polyfunctional cyanate ester in the presence of a catalyst such as a mineral acid, a Lewis acid, a salt such as sodium carbonate or lithium chloride, or a phosphate ester such as tributylphosphine. It can be used as 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 an average molecular weight of 400 to 6,000. Furthermore, the above-mentioned polyfunctional cyanate esters can also be used in the form of a premolymer with an amine. Examples of amines that can be suitably used include meta or paraphenylene diamine, meta or para xylylene diamine, 1,4- or 1,3-cyclohexane diamine, hexahydroxylylene diamine,
4,4'-diaminobiphenyl, bis(4-aminophenyl)methane, bis(4-aminophenyl)
Ether, bis(4-aminophenyl)sulfone, bis(4-amino-3-methylphenyl)methane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-aminophenyl)cyclohexane, 2,2- Bis(4-aminophenyl)propane, 2,2-bis(4-amino-3-
methylphenyl)propane, 2,2-bis(3,
5-dibromo-4-aminophenyl)propane,
bis(3-chloro-4aminophenyl)methane,
bis(4-aminophenyl)phenylmethane,
3,4-diaminophenyl-4'-aminophenylmethane, 1,1-bis(4-aminophenyl)-
1-phenylethane and the like. Of course, the polyfunctional cyanate esters mentioned above, their prepolymers, and prepolymers with amines can be used in the form of mixtures. Next, what is the polyfunctional maleimide that is component b?
When used in combination with the above-mentioned component a, a curable resin composition with even better heat resistance and moisture resistance can be obtained, and it is a compound having two or more maleimide groups. The polyfunctional maleimide suitably used in the present invention has the following general formula: [In the formula, R is 2 or more and usually 5 or less aromatic or alicyclic organic groups, X ¹ and X ² are hydrogen, halogen, or an alkyl group, and n is 2 or more and usually 5 It is as follows. ] It is a compound represented by Maleimides represented by the above formula can be produced by a method known per se, in which maleic anhydride and polyamines having two or more amino groups are reacted to prepare maleamic acid, and then maleamic acid is cyclodehydrated. Can be done. The polyvalent amines used are preferably aromatic amines in terms of the heat resistance of the final resin, but if flexibility and flexibility of the resin are desired, alicyclic amines may be used alone or in combination. It's okay. Furthermore, it is particularly desirable that the polyvalent amines be primary amines in terms of reactivity, but secondary amines can also be used. Suitable amines include those exemplified in the production of the prepolymer of polyfunctional cyanate ester and amine, melamine having an s-triazine ring, and melamine having an s-triazine ring, and converting benzene rings into methylene by reacting aniline with formalin. Polyamines connected by bonds are shown. In the present invention, the above-mentioned polyfunctional maleimide can be used in the form of a prepolymer instead of in the form of a so-called monomer, and furthermore, it can be used in the form of a prepolymer with the amine used in the synthesis of the polyfunctional maleimide. It can also be suitably used in the form of The epoxy resin as component c is used for improving adhesive strength, adjusting viscosity, etc., and is a compound having two or more epoxy groups in the molecule and a prepolymer thereof. Examples include polyol, polyhydroxybenzene, bisphenol, low molecular weight novolak type phenolic resin,
Hydroxyl group-containing silicone resins, polyglycidyl compounds obtained by reacting aniline, 3,5-diaminophenol, etc. with epihalohydrin, polyamides with epoxidized double bonds such as butadiene, pentadiene, vinylcyclohexene, dicyclopentyl ether, etc. These include epoxy compounds. The butadiene resin () of the present invention is a rubber obtained by polymerizing butadiene as an essential component, such as polybutadiene resin (polybutadiene rubber, syndiotactic 1,2-polybutadiene), styrene-butadiene copolymer resin ( Styrene-butadiene rubber, thermoplastic styrene-butadiene-styrene block copolymer rubber), acrylonitrile-butadiene copolymer resin, and polybutadiene resin which is liquid at room temperature and has a hydroxyl group or carboxyl group in the molecule and usually has an average molecular weight of 500 to 10,000. Examples include butadiene-acrylonitrile copolymer resins, and those obtained by preliminarily reacting these with epoxy resins. In the present invention, rubber that is liquid at room temperature is preferable, although it depends on the operating method etc.
In particular, it has a hydroxyl group or a carboxyl group in its molecule and usually has an average molecular weight of 500 to 10,000, preferably 700 to 10,000.
5000 polybutadiene resin and butadiene-acrylonitrile copolymer resin are preferred. The acrylic acid epoxy ester of the component () of the present invention is represented by the above general formula (3),
Glycidyl acrylate or glycidyl methacrylate may be mentioned. Moreover, those obtained by prepolymerizing these (meth)acrylic acid epoxy esters using organic peroxides, ionic polymerization catalysts, heat, or ultraviolet rays are also suitable since they are particularly resistant to air. The usage ratios of the above components (), (), and () are appropriately selected depending on the intended use, but preferably component () is 30 to 95 wt%, and components () and () are each used at 30 to 95 wt%. It is best to use it in the range of 2.5 to 50 wt%. For example, if heat resistance is particularly required, component () may be used at 50 wt% or more, furthermore, at least 60 wt%. Also, if it is to be liquid at room temperature, component ( ) may be used in the form of a monomer. Furthermore, the method for preparing the curable resin composition of the present invention from components (), (), and () is not particularly limited. For example, as component()()
A method of pre-reacting components a. and b of , and then simply mixing () and () with the pre-reaction, or a method of pre-reacting component c of component () with component (), and then pre-reacting component c of component () with component a or a of component (). It can be prepared by mixing b and component (), or by various other methods. Although the curing reaction of the curable resin composition of the present invention comprising the above components has not been clearly proven, it is estimated as follows. (2) Reaction of polyfunctional maleimide, Regarding the epoxy group of the epoxy resin, which is another component of the present invention, the reaction mechanism with hydroxyl group, carboxyl group, amino group, acid anhydride group, etc. is known. From the above, in the composition of the present invention, in addition to the reactions that are presumed to occur in a composition comprising a known polyfunctional cyanate ester, a polyfunctional maleimide, and an epoxy resin, Reaction with the epoxy group or unsaturated double bond of the acrylic acid epoxy ester newly added as a component, reaction between these and the above components if the butadiene resin has a hydroxyl group or carboxyl group as a terminal group, and further It is presumed that reactions with unsaturated double bonds may also occur. However, in order to assume that each component reacts proportionally to the amount of functional groups as estimated above and exhibits the performance as in the present example, it is necessary to assume that each functional group responds to its own unique temperature and other conditions. rate of reaction,
This is questionable because some of them have selectivity and others, and the main curing reaction is the mutual reaction of the same functional groups (self-polymerization reaction), and the mutual reactions of different functional groups are auxiliary. Some people believe that this is due to the promotion of finer mutual dispersion of each component and improvement of compatibility between each component. The curable resin composition of the present invention, which is composed of the above three components, has the property of becoming a heat-resistant resin by bonding and forming a network when heated. Contain and use. Such catalysts include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-ethyl 4-methylimidazole, 1-benzyl-2methylimidazole, 1-bropyl-
2-methylimidazole, 1-cyanoethyl-2
- Imidazoles exemplified by methylimidazole, 1-cyanoethyl-2ethyl-4methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-guanaminoethyl-2-methylimidazole; are trimellitic acid adducts of 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,
Tertiary amines such as triethylenediamine, N,N,N',N'-tetramethylbutanediamine, N-methylpiperidine; Phenols such as phenol, cresol, catechol, xylenol, resorcin, phloroglucin; Lead naphthenate,
Organometallic compounds such as lead stearate, zinc naphthenate, zinc octylate, tin dibutyltin maleate oleate, manganese naphthenate, cobalt naphthenate, iron acetylacetonate; SnCl ₄ ,
Examples include inorganic metal compounds such as ZnCl ₂ and AlCl ₃ ; peroxides such as benzoyl peroxide, lauroyl peroxide, caprylyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, and di-tertiary butyl diperphthalate. In addition, those generally known as curing agents or catalysts for epoxy resins, such as acid anhydrides such as pyromellitic anhydride and phthalic anhydride, can also be used in combination. The amount of the catalyst to be added is sufficient within the general range of the catalyst amount, for example, it may be used in an amount of 5% by weight or less based on the total composition. The 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 or synthetic resins and fibrous reinforcements for imparting new properties to the composition of the present invention; fillers;
Various known additives such as dyes and pigments; thickeners; lubricants; and flame retardants are included, and may be used in appropriate combinations as desired. The temperature for curing the curable resin composition of the present invention varies depending on the presence or absence of a curing agent and catalyst, the types of composition components, etc., but may be generally selected within the range of 100 to 250°C. When used in the production of molded products, laminated products, adhesive structures, etc., it is preferable to apply pressure during heat curing, and generally speaking,
Appropriately within the range of ~500Kg/ ^cm2 . The present invention will be explained below with reference to Examples and Comparative Examples. Example 1 400g of 1,3-dicyanabenzene was heated to 150℃ at 150℃.
A pre-reaction was carried out for a minute to obtain a cyanate ester prepolymer. 60g of polybutadiene resin with an average molecular weight of 1700 and an average of 2.2 carboxyl groups in the molecule.
and 240 g of bisphenol A type epoxy resin (number average molecular weight of 2 epoxy groups in the molecule: 2000) were mixed and reacted at 80°C for 180 minutes to obtain an epoxy-modified polybutadiene resin, and then the cyanate ester prepolymer was mixed at 80°C. Mixed evenly. Add 200g of glycidyl methacrylate to this mixed resin liquid.
After mixing at 80° C. and cooling to room temperature, 0.1 g of zinc octylate, 0.2 g of triethylenediamine, and 0.2 g of benzoyl peroxide as catalysts were further uniformly dissolved and mixed to obtain a liquid resin solution. The above resin liquid was applied to an epoxy resin test piece with a length of 125 mm, a width of 25 mm, and a thickness of 0.4 mm, and heated to obtain B-
After setting the stage, the longitudinal end of the specimen is 10mm
After overlapping the B-staged surfaces, heat at 120℃.
and cured for 24 hours. Table 1 shows the test results for this bonded part. Example 2 900 g of 2,2-bis(4-cyanatophenyl) ether and 100 g of bis(4-maleimidophenyl) ether were pre-reacted at 150°C for 120 minutes, and this was mixed with an epoxy-modified product obtained in the same manner as in Example 1. After uniformly mixing 300 g of polybutadiene resin and 300 g of glycidyl acrylate at 80°C and cooling to room temperature, 0.2 g of t-butyl peroxide, 0.4 g of zinc octylate, and 0.2 g of 2-ethylimidazole were added as catalysts. The mixture was mixed uniformly to obtain a liquid resin solution. Adhesion and bonded portion tests were conducted in the same manner as in Example 1 using this resin liquid. The results are shown in Table 1.

[Table] Example 3 50 g of butadiene-acrylonitrile copolymer (acrylic component 8.5%, viscosity 117 poise, average carboxyl group 1.16, hydroxyl group 1.41 in the molecule) and bisphenol A type epoxy resin (number average molecular weight 1500,
Average epoxy group in the molecule 2) 200g at 80℃
A preliminary reaction was carried out for 200 minutes to obtain an epoxy-modified butadiene-acrylonitrile copolymer. 800 g of 2,2-bis(4-cyanatophenyl)propane and 200 g of bis(4-maleimidophenyl)methane were pre-reacted at 150°C for 150 minutes, and this was dissolved in a mixed solvent of methyl ethyl ketone and dimethylformamide to form cyanate ester. A system resin solution was prepared. Furthermore, 400 g of glycidyl acrylate was dissolved in acetone along with 0.2 g of benzoyl peroxide,
A prepolymer solution was prepared by pre-reacting for 90 minutes under reflux. After adding 200 g of epoxy resin (ECN-1273, manufactured by Ciba Geigy) to the epoxy-modified butadiene-acrylonitrile copolymer, cyanate ester resin solution, and glycycyl acrylate prepolymer solution obtained above, they were uniformly dissolved and mixed. Then, 0.4 g of zinc octylate and 0.3 g of triethylenediamine were added as catalysts and uniformly dissolved and mixed to form a varnish. Impregnate a glass cloth with this varnish, dry it, and
-stage prepreg was made, and the temperature was 165℃ and the pressure was 40℃ using the prepreg and 35μ thick electrolytic copper foil.
Lamination molding was carried out for 120 minutes at Kg/cm ² to obtain a double-sided copper-clad laminate. The performance of this laminate is shown in Table 2. Comparative Example 1 A double-sided copper-clad laminate was produced in the same manner as in Example 3, except that the cyanate ester resin solution was not used. The performance of this laminate is shown in Table 2.

[Table] Example 4 900g of 1,3-dicyanatobenzene at 150℃
To the pre-reacted material pre-reacted for 300 minutes, 100 g of epoxy resin (ECN-1273, manufactured by Ciba Geigy),
Add 400 g of glycidyl methacrylate and 600 g of butadiene-acrylonitrile copolymer (7.2% acrylic component, average molecular weight 1800) and mix uniformly, then add 0.2 g of zinc octylate, 0.1 g of triethylenediamine, and 0.2 g of benzoyl peroxide as catalysts.
g was added and dissolved uniformly. This resin liquid was put into a mold and cast molded at 120°C for 150 minutes and at 160°C for 240 minutes to obtain a good cast product. This cast product was elastic and had excellent flexibility.

Claims (1)

[Scope of Claims] 1 a. A polyfunctional cyanate ester, a prepolymer of the cyanate ester, or a prepolymer of the cyanate ester and an amine, or a and b. a polyfunctional maleimide, a prepolymer of the maleimide, or Prepolymer of maleimide and amine or c.
In a curable resin composition () obtained by mixing or pre-reacting with an epoxy resin, a butadiene resin () and an acrylic acid epoxy ester represented by the following general formula (3) or the acrylic acid epoxy ester prepolymer () are used. , component()30
95% by weight, component () 2.5-50% by weight, and component () 2.5-50% by weight. General formula (3): (R in the formula represents a hydrogen atom or a methyl group).