JPH0463086B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] Regarding the copolymer composition used as a molding material, adhesive, paint, etc. of the present invention, specifically, a copolymer composition suitable for producing a cured product having excellent mechanical strength. relating to things. [Prior Art] Epoxy resins are widely used in various molding materials, adhesives, paints, etc. due to their excellent properties. However, the disadvantage of epoxy resin is that it is not flexible and has poor impact resistance. Various improvements have been attempted in the past to overcome these drawbacks, including adding both a polyisocyanate compound and a curing agent for epoxy resin to a mixture of an uncured epoxy resin and a polyol compound such as polyoxypropylene glycol. An attempt has been made to produce a cured product by adding . However, even in the cured product obtained by this method, the above-mentioned drawbacks are not sufficiently improved, and there is also the problem that the ingredients leached (bleed) onto the surface of the cured product. [Problems to be Solved by the Invention] The present invention provides a copolymer composition that overcomes the above-mentioned problems and provides a cured product that has excellent impact resistance and flexibility and does not bleed. The purpose is to provide. [Means for Solving the Problems] The copolymer composition of the present invention is produced by copolymerizing a diene monomer and an epoxy group-containing monomer in the presence of a polymerization initiator and/or chain transfer agent capable of introducing a hydroxyl group. The present invention is characterized in that a polyisocyanate compound and a curing agent for epoxy resin are blended into a copolymer having a hydroxyl group and an epoxy group in the molecular chain obtained by the above method. The diene monomer is not particularly limited, but usually a diolefin-based unsaturated unsubstituted, 2-substituted, or 2,3-substituted 1,3-diene having 4 to 12 carbon atoms is used. Examples of the substituent here include an alkyl group, an aryl group, a halogen, a cyano group, and a nitro group. Specific monomers include 1,3-butadiene, isoprene, 1,
3-pentadiene, chloroprene, 2,3-dichlorobutadiene, 2-cyano-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, etc. are used. The epoxy group-containing monomer is not particularly limited, but unsaturated glycidyl esters such as glycidyl acrylate, glycidyl methacrylate, and allylglucidyl ether can be used. The polymerization initiator and/or chain transfer agent capable of introducing hydroxyl groups into the copolymer is not particularly limited, but usually δ,δ'-azobis(δ'-cyano)-
An azo compound having a hydroxyl group such as n-pentanol, a mixture of an azo compound such as 2,2'-azobisisobutyronitrile and a mercaptoalkanol such as mercaptoethanol, hydrogen peroxide, etc. are used. Among these, hydrogen peroxide is preferred. The blending ratio of the diene monomer and the epoxy group-containing monomer is not particularly limited, but usually the epoxy group-containing monomer is used in an amount of 50 to 2% by weight to 50 to 98% by weight of the diene monomer. The copolymer used in the present invention is basically obtained by copolymerizing a diene monomer and an epoxy group-containing monomer, but if necessary, a part of the diene monomer can be replaced with an ethylenically unsaturated monomer. An α-olefin addition polymerizable monomer having 2 to 22 carbon atoms is used instead. Specifically, styrene, α-methylstyrene, vinyltoluene, methyl methacrylate, acrylic acid, vinyl chloride, vinylidene chloride, acrylonitrile, acrylamide, 2-ethylhexyl acrylate, n-octadecyl acrylate,
These include maleic anhydride, butene, and 2-hydroxyethyl methacrylate. Although the polymerization reaction does not particularly require a solvent, it is usually preferably carried out in a solvent such as alcohol, a mixture of alcohol and water, ether, ketone, aliphatic hydrocarbon, aromatic hydrocarbon, or halogenated hydrocarbon. Such solvents include methanol,
Examples include ethanol, n-propanol, isopropanol, butanol, propyl ether, tetrahydrofuran, ethyl acetate, cellosolve, cellosolve acetate, ethyl cellosolve, acetone, and mixtures thereof. The amount of solvent used is not particularly limited, but usually the total amount (monomer, solvent,
5 to 500% by weight of hydrogen peroxide, etc.), preferably 30% by weight
~300% by weight. When hydrogen peroxide is used as an initiator, there are no particular restrictions, but hydrogen peroxide usually
0.1 to 50 parts by weight per 100 parts by weight, preferably
0.3 to 30 parts by weight are used. Hydrogen peroxide is usually
It is used as a 30-80% aqueous solution, preferably about 50% aqueous solution. Polymerization reaction conditions vary depending on the type of diene monomer used, the amount used, etc., and cannot be unambiguously specified, but are usually under stirring, at a reaction temperature of 50 to 200°C,
Preferably 80~150℃, reaction pressure 0~200Kg/ ^cm2
G, preferably 1 to 100 Kg/cm ² G for 0.1 to 24 hours,
Preferably by reacting for 0.2 to 20 hours,
A desired liquid copolymer having a hydroxyl group and an epoxy group in its molecular chain can be produced. This copolymer preferably has an average number of functional hydroxyl groups of 1.0 or more. It is thought that the hydroxyl group present in the molecule acts as a curing accelerator during the subsequent curing treatment. The copolymer used in the present invention has, for example, the following structure. (Here, R represents a methyl group or hydrogen, a, b
represents the proportion of structural units in the copolymer, and is a positive decimal number that adds up to 1. n is a positive number representing the degree of polymerization of the copolymer, and n = 5 to 500, preferably
10 to 200) The thus obtained copolymer is cured using a normal polyisocyanate compound and a curing agent for epoxy resins, if necessary in the presence of a curing accelerator.
A hardened product is obtained through hardening treatment. A polyisocyanate compound has 2 molecules in one molecule.
A compound having one or more isocyanate groups, which has an isocyanate group reactive with the hydroxyl group of the copolymer. Examples of polyisocyanate compounds include the usual aromatic, aliphatic and cycloaliphatic ones, such as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate (MDI), liquid modified diphenylmethane diisocyanate. , xylylene diisocyanate, cyclohexyl diisocyanate, cyclohexanephenylene diisocyanate, naphthalene-1,5-diisocyanate, isopropylbenzene-2,4-diisocyanate, addition reaction products of polypropylene glycol and tolylene diisocyanate, among others, MDI, liquid modified diphenyl Preferred are methane diisocyanate, tolylene diisocyanate, and the like. The curing agent for epoxy resins is not particularly limited, but polyamines, polyamides, dibasic acids, or anhydrides thereof, etc. are usually used. Specifically, the polyamines include diethylenetriamine, triethylenetetramine, imidazole, metaphenylenediamine, diaminodiphenylmethane, etc., and the polyamides include polyamide oligomers produced by the condensation reaction of dimer acid and polyamines.
Examples of dibasic acids or anhydrides include phthalic acid or anhydride, hexahydrophthalic acid or hexahydrophthalic anhydride, methyl-3,6-endo-methylene-δ ⁴ -tetrahydrophthalic acid or methyl-3 anhydride, 6-endo-methylene-δ ⁴ −
Etrahydrophthalic acid, pyromellitic acid, pyromellitic anhydride, etc. are mentioned. The amount of the polyisocyanate compound is not particularly limited, but it is usually 0.1 parts by weight per 100 parts by weight of the copolymer.
~500 parts by weight, preferably 5 to 200 parts by weight. The amount of curing agent for epoxy resin is not particularly limited, but it is usually 0.1 to 100 parts by weight of the copolymer.
It is blended in an amount of 500 parts by weight, preferably 5 to 200 parts by weight. The curing accelerator is not particularly limited, but includes, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylethanolamine, dimethylaminoethanol, and tri(dimethylaminomethyl)phenol, 2-methylimidazole, Imidazoles such as 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecyl imidazole, tributylphosphine, methyldiphenylphosphine, diphenylphosphine, triphenylphosphine, phenylphosphine, etc. organic phosphines, tetraphenol phosphionium tetraphenylborate, 2-ethyl-4
Examples include tetraphenyl boron salts such as methylimidazole tetraphenyl borate. The amount of the curing accelerator is not particularly limited, but it is usually used in an amount of 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the total amount of the copolymer and the curing agent for epoxy resin. Curing reaction is 10-300℃, preferably 20-200℃
It is carried out for 0.5 to 200 hours, preferably 1 to 100 hours. The copolymer composition of the present invention may also contain inorganic fillers, mold release agents, colorants, coupling agents, and the like, if necessary. [Examples] The present invention will be explained below with reference to Examples, but the scope of the present invention is not limited to these Examples. Table 1 shows the manufacturing conditions for the copolymers used in the examples of the present invention and the results of measurements on various properties of the copolymers. Table 2 shows the formulations, curing conditions, and physical properties of the cured products of the copolymer compositions of Examples and Comparative Examples of the present invention. In addition, the numerical values in the table mean parts by weight unless otherwise stated. [Production example of copolymer] Production examples 1 to 5 The ingredients shown in the proportions shown in Table 1 were charged into a stainless steel pressure-resistant container equipped with a stirrer, and after raising the temperature for 60 minutes, polymerization was carried out under the conditions shown. I went there. After that, air is blown onto the outer surface of the container to lower the temperature.
The indicated post-treatments were carried out to obtain a copolymer. Production Examples 6 to 8 The temperature was raised for 30 minutes, 0.05 parts by weight of 4-t-
A copolymer was obtained by carrying out the reaction in the same manner as in Production Examples 1 to 5, except that 1 part by weight of toluene containing butylcatechol was added to stop the polymerization. [Preparation of copolymer composition and production of cured product] A copolymer composition was prepared by stirring and mixing predetermined amounts of each of the components shown in Table 2 in a beaker at 25° C. for 3 minutes. This composition was placed in a suction bell of a beaker and degassed by suction using a vacuum pump. This composition was then poured into a silicone mold and cured in an oven under the indicated conditions. After this cured product was left at 25° C. for 24 hours, its physical properties were measured.

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〔Effect of the invention〕

The cured product obtained by the present invention has excellent impact resistance and flexibility, and there is no bleeding of ingredients onto the surface of the cured product, so the industrial value of the present invention is extremely large.

Claims (1)

[Claims] 1 obtained by copolymerizing a diene monomer and an epoxy group-containing monomer in the presence of a polymerization initiator and/or chain transfer agent capable of introducing a hydroxyl group,
A copolymer composition characterized in that a polyisocyanate compound and a curing agent for epoxy resin are blended into a copolymer having a hydroxyl group and an epoxy group in its molecular chain.