JPS5966455A - Curable resin composition - Google Patents

Abstract

PURPOSE:To provide a resin composition having excellent heat resistance, moisture resistance, chemical resistance, abrasion resistance, adhesivity, sticking property, etc., by compounding a cyanic acid ester-maleimide resin with a thermoplastic polyurethane resin. CONSTITUTION:To objective composition is prepared by mixing (A) a curable resin composition containing at least (i) a polyfunctional cyanic acid ester having two or more cyanato group in the molecule (e.g. 1,3-dicyanatobenzene), its prepolymer (preferably having a number-average molecular weight of 300-6,000) or its prepolymer with an amine and (ii) a polyfunctional maleimide having two or more maleimide groups in the molecule, its prepolymer, or its prepolymer with an amine, and (B) a thermoplastic polyurethane resin. There is no particular restriction in the ratio of the components; however, it is preferable to use 50- 99wt%, especially 60-95wt% of the component (A) for the use requiring heat resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a curable resin composition having excellent heat resistance, moisture resistance, chemical resistance, abrasion resistance, adhesion, and adhesion. A polyfunctional cyanate ester containing two or more groups, a prepolymer of the cyanate ester, or a prepolymer of the cyanate ester and an amine, and a polyfunctional cyanate ester containing two or more N-maleimide groups in the b9 molecule. A curable resin composition obtained by mixing a curable resin composition (A) containing maleimide, a prepolymer of the maleimide, or a prepolymer of the maleimide and an amine as an essential component, and a thermoplastic polyurethane resin (B). .

Conventionally, thermoplastic polyurethane resins have poor heat resistance, chemical resistance, etc., and are not suitable for applications where they are used at high temperatures or where they come into contact with chemicals, solvents, and the like. On the other hand, the cyanate ester-maleimide resin consisting of component a, 1) of the present invention was excellent in heat resistance, chemical resistance, etc., but had poor adhesion.

There were cases where adhesion was insufficient.

The inventors of the present invention have conducted extensive research in order to eliminate the above-mentioned drawbacks, and have found that by combining cyanate ester-maleimide resin and thermoplastic polyurethane resin, they have improved heat resistance, moisture resistance, chemical resistance, and resistance. Abrasion Resistance 7 We succeeded in obtaining a curable resin composition with excellent adhesion and adhesion, leading to the present invention.

One aspect of the present invention will be explained below.

The curable resin composition (A) of the present invention is prepared as described above.
component as an essential component. First, preferred polyfunctional cyanate esters as component a are:
The following general formula (1)% formula% () (in the formula, m is an integer of 2 or less and 9 is usually 5 or less, R is an aromatic organic group, and the cyanato group is attached to the aromatic ring of the organic group. It is a compound represented by A specific example is 1.3-
or 1,4-dicyanatobenzene, 1,3.5-1-
Licyanatobenzene, 1.3-, L4-. 1.6-.
1.8-. 2,6- or 2,7-dicyanatonaphthalene, 1,3,6-) dicyanatonaphthalene, 4,4-dicyanatobiphenyl, bis(4-diaminophenyl)methane, 2,2-bis(4-dicyanatonaphthalene) anatophenyl)propane, 2,2-bis(3,5-dichloro-4-cyanatophenyl)propane, 2,2-bis(3,5-dibromo-4-cyanaI.phenyl)propane, bis(4- cyanatophenyl) ether, bis(4-cyanatophenyl) thioether, bis(4-cyanatophenyl) sulfone, tris(4-cyanatophenyl) bosphite,
These include tris(4-cyanatophenyl)bosphate and cyanic acid esters obtained by reacting novolacs with cyanogen halides. In addition to these, Tokuko Sho 4
1-1.928. 43-18468, 44-479
1. 45-11712. 46-old month 2. Same 47-2
Cyanic acid esters described in JP-A-6853 and JP-A-51-63149 can also be used.

In addition, the above-mentioned polyfunctional cyanate ester can be mixed with a mineral acid, a salt such as a Lewis acid, sodium carbonate or lithium chloride,
It can be used as a prepolymer obtained by polymerization in the presence of phosphoric acid esters such as tributylphosphine. These prepolymers generally have a sy++r-4 riazine ring in the molecule, which is formed by trimerization of the cyanide group in the cyanate ester. In the present invention, the number average molecular weight is 300 to 6,00.
Preferably, 0 of the prepolymers are used.

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

Examples of amines that can be suitably used include meta or paraphenylenediamine, meta or paraxylylenediamine, 1,4- or 1,3-cyclohexanediamine, hexahydroxylylenediamine, 4,4'-diaminobiphenyl, Bis(4-aminophenyl)methane 1bis(
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, 212-bis(4-amino-3-chlorophenyl)propane, bis(4-amino-3-chlorophenyl)
Methane, 2,2-bis(4-amino-3,5-dibromophenyl)propane, bis(4-aminophenyl)phenylmethane, 3,4-diaminophenyl-4'-aminophenylmethane, 1,1-bis (4-aminophenyl)
-1-phenylethane and the like.

Of course, the --linked polyfunctional cyanate esters, their prepolymers, and prepolymers with amines can be used in the form of mixtures.

Suitable polyfunctional maleimides as component b of the present invention are represented by the following general formula (2) (wherein R is an aromatic or alicyclic organic group having a valence of 1 to 1, usually 5 or less, x', x2 is hydrogen, halogen, or an alkyl group, and 5m is usually an integer of 2 to 5.

) is a compound represented by Maleimides represented by the above formula can be prepared by a method known per se, in which maleic anhydride and polyamines containing 2-5 amino groups are reacted, maleamic acid is prepared, and then maleamic acid is dehydrated and cyclized. can be manufactured. It is preferable that the polyamines used are aromatic polyamines in terms of the heat resistance of the final resin, but if the recirculation properties and flexibility of the resin are desired, alicyclic amines may be used alone or in combination. good. Also,
It is desirable that the polyamines be primary amines in terms of reactivity, but secondary amines can also be used. Suitable amines include amines 2 which are used in the form of a prepolymer with the above-mentioned component a, and s-)melamines having a lyazine ring, and melamines having a lyazine ring, which are produced by reacting aniline with polymerine and linking Hensen rings with methylene bonds. These include polyamines, etc.

In the present invention, the polyfunctional maleimide described above is used in the form of a prepolymer, instead of being used in the form of a so-called monomer.
It can also be used in the form of prepolymers with the amines mentioned above.

What is the thermoplastic polyurethane resin that is component B of the present invention?1
A thermoplastic polymer obtained by reacting dihydroxy compounds (including polyethers and polyesters) having two or more hydroxyl groups in the molecule with diisocyanates having two sardine-1-groups. It may be a crosslinking agent that is a trifunctional or more-functional or -1- functional group within a range that maintains thermoplasticity, or it may have a functional group such as - or NGO.

Specific examples of dihydroxy compounds include:

Ethylene glycol, 1,2- and 1,3-propanediol, ], 3-. L4- and 2,3-butanediol.

Diols such as 1,6-hexanediol, 1,8-octanediol; diethylene glycol.

1~lyethylene glycol, polyethylene glycol,
dipropylene glycol, polypropylene glycol,
Polyether-type diols such as dibutylene glycol and polybutylene gellicol; aromatic rings such as 2,2-bis(4-bitroxyphenyl)propane and 1,4-phenylene-bis(β-hydroxyethyl ether) and these diols and dicarboxylic acids such as succinic acid, adipic acid, superric acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid,
Molecules with fucuric anhydride, etc.! Examples include polyesters having a weight of 10,00 (l or less, preferably 800 to 5,000).

In addition, as diisocyanates, 2,2-bis(4-
isocyanatophenyl)propane, bis(4-isocyanatophenyl)methane, bis(4-isocyanatophenyl)sulfone, bis(4-isocyanatophenyl)ether, ■, 1-bis(4-isocyanatophenyl)cyclohexane, Methyl-bis(3-isocyanatophenyl)phosphine oxide, 1,5-diisocyanatonaphthalene, m-xylylene diisocyanate, p-xylylene diisocyanate, bis(4-isocyanatohexyl)methane, hexamethylene diisocyanate, etc. Illustrated.

The method for preparing the curable resin composition of the present invention includes a method of dissolving or uniformly dispersing component A and component B in a solvent and mixing them, and a method of preparing the component without a solvent.

Component B is mixed at room temperature or under heating using a Banbury mixer, a Henschel mixer, or a roll.

Depends on the method of uniformly mixing using an extruder etc.

Although there are no particular limitations on the ratio of the amounts used of both components A and B in the present invention, in heat-resistant applications, it is preferable to use component A in an amount of 50 to 99 wt%, preferably 60 to 95 wt%.

Although the present invention requires the above-mentioned components, other resin components can be used in combination. These include esters of (meth)acrylic acid such as insect-functional or polyfunctional hydroxy compounds, epoxy esters of (meth)acrylic acid, alkenyl esters of (methanoacrylic acid), and their preforms. Polymer; diallylphthale-1.

Polyallyl compounds such as divinylbenzene, diallylbenzene, l-realkenyl isocyanurate and their prepolymers; dicyclpentadiene and their prepolymers; epoxy resins; phenolic resins; polyvinyl formal, polyvinyl acetal,
Polyvinyl acetal resin such as polyvinyl butyral; phenoxy resin; acrylic resin with 011 group or C0OH group; silicone resin; alkyd resin; polybutadiene, butadiene-acrylonitrile copolymer,
Liquids such as polychloroprene, butadiene-styrene copolymer, polyisoprene, butyl rubber, natural rubber, etc.
Aastic rubbers may also be used as appropriate.

The curable resin composition of the present invention itself has the property of being bonded and reticulated by heating to become a heat-resistant resin, and this is intended to promote crosslinking and reticulation.

It is usually used containing a catalyst. Such catalysts include 2-methylimidazole and 2-undecylimidazole. 2-heptadecylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole,
1-Benzyl-2-methylimidazole. 1-propyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole.

1-dianoethyl-2-ethylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethylimidazole
-Ethyl-4-methylimidasol.

Imidazoles exemplified by 1-guanamine ethyl-2-methylimidazole, and adducts of carboxylic acids or their anhydrides to these imidazoles, N,N-dimethylhensylamine, N,N-dimethyl Aniline, N,N-dimethyltoluidine, N,N
-dimethyl-p-anisidine, p-halogeno-N, N
-dimethylaniline, 2-N-ethylanilinoethanol, 1-di-n-butylamine.

Pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine.

N, N, N', N'-teI-ramethylbutanediamine,
Tertiary amines such as N-methylpiperidine; phenol, xylenol, cresol, resorcinol.

Catechol 2 Phenols such as phloroglycin; lead naphthenate, lead stearate, naphthenic acid + 11! Organometallic salts such as zinc octylate, tin oleate, dibnyltin malate, manganese naphthenate, cobalt naphthenate, iron acetylacetonate;
5nC14, ZnCl2. Inorganic metal salts such as AlCl3; peroxides such as benzoyl peroxide, lauroyl peroxide 1 capsule caprylic per 1-oxide 1 acetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl dibar phthalate; maleic anhydride; Phthalic anhydride, lauric anhydride, pyromellitic anhydride, trimellitic anhydride, hexahydrophthalic anhydride.

Acid anhydrides such as hexahydrotrimellitic anhydride and hexahydropyromellitic anhydride; furthermore, azo compounds such as azobisnitrile are included. The amount of these catalysts to be added is sufficient within the range of catalytic amounts in a general sense, and may be used, for example, in an amount of 10 wt % or less based on the total composition.

The temperature for curing the curable resin composition of the present invention is:
Although it varies depending on the presence or absence of a curing agent and catalyst, 1 the type of bottom composition, 3, etc.9, it is generally sufficient to select a temperature within the range of 100 to 300°C. This composition is used for various purposes, but when used for manufacturing molded products, laminate products, adhesive structures, etc., it is preferable to apply pressure during heat curing, and generally speaking, the pressure is 0.1 to 0. 500kg/cn
! , preferably selected appropriately within the range of 5 to 150 kg/cII+.

Various additives can be added to the curable resin composition of the present invention as desired, as long as the original properties of the composition are not impaired. These additives include various known additives such as natural or synthetic resins; fibrous reinforcing materials; fillers; dyes and pigments; thickeners; lubricants; coupling agents; and flame retardants. They are used in appropriate combinations.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. In addition, parts in Examples and Comparative Examples are parts by weight unless otherwise specified.

Example-1 4 2.2-bis(4-cyanatophenyl)propane 500
and 500 parts of bis(4-maleimidophenyl)methane were preliminarily reacted at 150°C for 60 minutes.

Completely thermoplastic polyurethane resin (product name: Elastolan P, -580PNAT, B-hon Elastolan 91)
)) 600 parts were added to a mixed solvent of N,N-dimethylformamide and methylethylcarbonate at 50°C.

It was melted while stirring.

To this solution, 0.1 part of iron acetylacetate was added as a catalyst and mixed uniformly, and then impregnated in a glass woven cloth and dried to obtain a B-stage prepreg.

8 sheets of this prepreg are stacked and 35μ electrolytic copper foil is placed on both the top and bottom surfaces at a temperature of 175°C and a pressure of 40kg/cJ.
Lamination molding was carried out for 120 minutes.

The test results of the copper-clad laminates obtained are shown in Table 1.

Example-2 2,2-bis(4-cyanatophenyl)propane 9oo
qt+100 parts of tobis(4-maleimidophenyl)ether 5 were preliminarily reacted at 150°C for 150 minutes.

To this, incomplete thermoplastic polyurethane resin (product name: T
Add 500 copies of ex1n, Mobay■), N, N-
It was dissolved in a mixed solvent of dimethylformamide and methyl ethyl quinone at 50° C. with stirring.

0.1 part of zinc octylate was added as a catalyst to this solution, mixed uniformly, impregnated into a glass woven cloth and dried.
A (He prepreg was used. The procedure was the same as in Example-1 except that this prepreg was used. Table 1 shows the test results of the obtained copper-clad laminate.

Comparative Example 1 Table 1 shows the results of Example 1, except that the fully thermoplastic polyurethane resin was not used.

6 Table 1 7

Claims (1)

[Scope of Claims] A polyfunctional cyanate ester containing two or more cyanato groups in the a8 molecule, a prepolymer of the cyanate ester, or a prepolymer of the cyanate ester and an amine, and a polyfunctional cyanate ester containing two or more cyanato groups in the a8 molecule; - A curable resin composition (A) containing a polyfunctional maleimide containing two or more maleimide groups, a prepolymer of the maleimide, or a prepolymer of the maleimide and an amine, and a thermoplastic polyurethane resin (B). ) A curable resin composition formed by mixing