JPS5998159A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition giving a molded article having excellent heat deformation temperature and mechanical properties such as impact resistance, etc., by compounding an aromatic polyester with a specific vinyl copolymer and a polyhydric epoxy compound. CONSTITUTION:The objective composition is prepared by compounding (A) 100pts.wt. of an aromatic polyester such as polyethylene terephthalate with (B) 5-200pts.wt., preferably 10-80pts.wt. of a vinyl copolymer composed of an aromatic vinyl compound (preferably styrene or alpha-methylstyrene) and an alpha, beta- unsaturated cyclic imide compound (preferably maleimide or N-methylmaleimide), (C) 0.5-100pts.wt., preferably 2-50pts.wt. of a polyhydric epoxy compound (preferably a copolymer of ethylene and glycidyl methacrylate) and preferably (D) triphenylamine, etc. to promote the reaction of the epoxy compound with the carboxylic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an aromatic polyester resin composition that can provide molded articles with excellent mechanical properties, including heat distortion temperature and impact resistance.

Aromatic polyesters represented by polyethylene, terephthalate, and polybutylene ethylene terephthalate are used in a wide range of fields such as electrical and electronic equipment parts and automobile parts due to their excellent properties, but they are also used as reinforcing agents such as glass fibers. Heat Distortion Temperature (ASTM D-648
-72) is low.

Attempts have been made to improve the heat deformation temperature of aromatic polyester using modifiers other than reinforcing agents. Among them, styrene and α, β- The method of blending an unsaturated cyclic imide copolymer as a modifier certainly increases the heat distortion temperature of polyethylene terephthalate. However, the compositions obtained by these methods have very low mechanical properties such as impact resistance, making it difficult to put them into practical use.j)
There was a problem that

The inventors of the present invention have conducted intensive studies to solve the above problems, and have found that by incorporating a polyvalent ehoquino compound into the aromatic polyester together with a specific vinyl copolymer, the heat distortion temperature can be increased. It was discovered that a composition with excellent mechanical properties, typified by impact resistance, could be obtained, and the present invention was achieved.

That is, the present invention provides a resin composition comprising a vinyl copolymer comprising an aromatic vinyl monomer and an α,β-unsaturated cyclic imide compound and a polyvalent epoxy compound (Bl) in an aromatic polyester. It is about things.

The aromatic polyester used in the present invention is a polyester having an aromatic ring in the chain unit of the polymer, and is mainly composed of an aromatic dicarbono acid (or its ester-forming derivative) and a diol (or its ester-forming derivative). It is a polymer or copolymer obtained by a condensation reaction as a component.

The aromatic dicarboxylic acids mentioned here include terephthalic acid,
Isophthalic acid, FukuIL acid, 2.6-Natsutalenodicarboxylic acid, 2.7-Natsutalenodicarboxylic acid, 1.5-sulphthalenodicarboxylic acid, bis(P-carboxyphenyl)methane, anthracenedicarboxylic acid, 3,3'-diphenyldicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenyl etherdicarboxylic acid, 1,2-bis(4-carboxyphenoxy)ethane,
4,4'-diphenylsulfonedicarboxylic acid, 4.4
Examples include '-terphenylenedicarboxylic acid or its ester-forming derivatives, and two or more thereof may be used in combination.

In addition, if the acid component is 40 mol% or less, aliphatic dicarphonic acids such as adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, etc. Dicarboxylic acids other than aromatic dicarboxylic acids such as ring dicarboxylic acids and their ester-forming derivatives may be substituted.

In addition, as the diol component, aliphatic diols having 2 to 2 degrees of carbon atoms, ie, ethylene glycol, 1,2-furopanediol, propylene glycol, 1',4-butanediol, neopentyl glycol, 1,5-pentanereol, Examples include 1,6-hexanediol, decamethylene glycol, cyclohexanediol, and 1,4-cyclohexane dimetatool, and two or more of them may be used in combination.

In addition, some of the diol components have a molecular weight of 400 to 6,000 liters.
may be substituted with long chain glycols such as polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, and mixtures thereof.

Examples of preferred aromatic polyesters used in the present invention include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexylene dimethylene terephthalate, polyethylene-2,6-nuclate, polyethylene-1,2 -diphenoxyethane-4
, 4'-dicarboxylate, etc. Among them, polyethylene terephthalate and polybutylene terephthalate, which have appropriate mechanical strength, are most preferred.

Further, it is preferable that these aromatic polyesters have a relative viscosity in the range of 1.2 to 1.8 when a 0.5% orthochlorophenol solution is measured at 25°C.

Next, the tetraaromatic vinyl monomer used in the present invention and α
, and a β-unsaturated cyclic imide compound, the aromatic vinyl monomer in the vinyl polymer is a compound represented by the following general formula (1), and among them, a styrene derivative in which Ar is a benzene ring is preferable.

R1-C: C-R3m Ar-(X)n [However, R1 and R3 in the formula are each a hydrogen atom, and have a carbon number of 1
~10 hydrocarbon groups, halogens, Ar is an aromatic group having 6 to 24 carbon atoms, X is a hydrogen atom,
Hydrocarbon group having 1 to 2 carbon atoms, alkoxy group having 1 to 2 carbon atoms, halogen, -CN, -N02, -NR2,
S 03M (M halukali or alkaline earth metal), n is an integer of 1 to 5] Specific examples of aromatic hinyl monomers include styrene, α-methylstyrene, β-methylstyrene, α, β- Dimethylstyrene, P-methylstyrene, m-methylstyrene,
0-methylstyrene, 2,5-dimethylstyrene, 3.
5-dimethylstyrene, 2,4.6-1-rimethylene-restyrene, P-ethylstyrene, P-isopropyrestyrene, p-tert-butylstyrene, P-chlorostyrene, 2,5-dichlorostyrene, P- Examples include bromomethylstyrene, P-fluorostyrene, P-methoxystyrene, P-acetoxystyrene, P-cyanostyrene, and sodium P-vinylbenzenesulfonate, with styrene and α-methylstyrene being particularly preferred.

Further, the α,β-unsaturated cyclic imide compound is a compound represented by the following general formula (n) or (I).

(However, R4, R5, and R7 in the formula are each selected from a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a levoxyalkyl group, a carboxyalkenyl group, and /SS rosin, and R8 is It is selected from a hydrocarbon group having 1 to 10 carbon atoms and a carboxy-substituted hydrocarbon group, and R6
and R9 is selected from hydrogen, a substituted or unsubstituted anolykyl group having 1 to 20 carbon atoms, an alkyl group, an aryl group, and the like.

Specific examples of α,β-unsaturated cyclic imide compounds include maleimide, methylmaleimide, dimethylmaleimide, itacoimide, N-methifremaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, and N-butylmaleimide.
Do, N-t-butylmaleimide, N-lauriJ remaleimide, N-phenylmaleimide, N(p-chlorophenyl)maleimide, N-(P-chlorophenyl)maleimide, N-(P-triJ) ) maleimide, N-(P
-anilyl)maleimide, N-(P-ethylphenyl)
Maleimide, N-(4'-diphenyl)maleimide, N
-(1-1-butyl)maleimide and the like can be mentioned, and maley EF, N-methylmaleimide, and N-phenylmaleimide are particularly preferably used.

A vinyl copolymer comprising an aromatic vinyl monomer and an α,β-unsaturated cyclic imide compound can be produced in the presence of rubber. Examples of the rubber in this case include polybutadiene, styrene/butadiene copolymer, butadiene/acrylonitrile copolymer, isobutylene/isoprene copolymer, polyisoprene, polychloroprene, and ethylene/propylene/genterpolymer.

In addition, the vinyl copolymer is composed of aromatic vinyl monomer and α,
It can also be obtained by reacting a vinyl copolymer comprising a β-unsaturated acid anhydride with a primary amine in an organic solvent.

The copolymerization composition of the vinyl copolymer is α, β-unsaturated cyclic imide compound 5 to 40% by weight, especially 5 to 25% by weight, aromatic vinyl monomer 95 to 60% by weight, especially 95 to 75% by weight.
% by weight and a range of 0 to 30% by weight rubber is suitable.

Examples of preferred vinyl copolymers (2) include styrene/maleimide copolymers, styrene 7N-phenylmaleimide copolymers, and polybutadieno-containing products thereof.

The vinyl copolymer used in the present invention is preferably contained in an amount of 5 to 200 parts by weight, more preferably 10 to 80 parts by weight, per 100 parts by weight of the aromatic polyester. If the amount added is less than 5 parts by weight, the heat distortion temperature will not be improved sufficiently, and if it is more than 200 parts by weight, it will tend to impair the mechanical properties of the aromatic polyester, making it difficult to achieve the object of the present invention.

Further, the (Bl polyepoxy compound) used in the present invention is a compound having at least two epoxy groups in the molecule, for example, a bisphenol type epoxy compound obtained by reacting bisphenol A and epichlorohydrin in various ratios, Novolac-type epoxy compounds obtained from novolac resin and epichlorohydrin, polygrindyl esters obtained from polycarboxylic acids and epichlorohydrin, etc., alicyclic compound-type epoxies obtained from alicyclic compounds (e.g. dicyclopentadiene) Glycidyl ethers obtained from aliphatic compounds (e.g., butanediol, glycerin, etc.) and eruclofrehydrin, epoxidized polybutadiene, and unsaturated monomers having epoxy groups bodies (e.g., unsaturated glycidifurester, unsaturated glycine ether, etc.)
and other unsaturated monomers (for example, α-olefin, vinyl ester, etc.). Suitable examples of these epoxy compounds include polyglycidyl esters represented by the following general formula (■l), bisphenol type epoxy compounds represented by the following general formula ff+, and α-olefin/α,β-unsaturated acids I
Examples include J si'; rLr x 7° chill copolymer.

(In the formula, R8 represents a 72rekilene group having 4 to 40 carbon atoms, a phenylene group, a partially hydrogenated phenylene group, or a cyclohexylene group) (However, in the formula, m is a number of O to 20. Specific examples of polyvalent epoxy compounds (B) include hexahydrophthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, phthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, and ethylene. /methacrylic acid glycidyl ester copolymer, ethylene/vinyl acetate/glycidyl methacrylate copolymer, ethylene/vinyl acetate/glycidyl methacrylate copolymer, and ethylene/glycidyl acrylate copolymer. /glycidyl methacrylate copolymer is most preferred.

The amount of the polyepoxy compound (B) used in the present invention is 0.5 parts by weight per 100 parts by weight of the aromatic polyester.
It is preferably 100 parts by weight, more preferably 2 to 50 parts by weight. If the amount added is less than 0.5 parts by weight, the impact resistance will not be improved sufficiently, and io.

If the amount exceeds 1 part by weight, the mechanical properties of the aromatic polyester tend to be impaired, making it difficult to achieve the object of the present invention.

Incidentally, when a compound that promotes the reaction between the epoxy compound and the carboxylic acid is further added to the composition of the present invention, it is possible to obtain the effect that the impact resistance can be further improved. These compounds include triphenylamine, 2,4.
Tertiary amines such as 6-tris(dimethylaminomethyl)phenol, phosphite esters such as triphenyl phosphite and triisodecyl phosphite, phosphonium compounds such as triphenylallylphosphonium bromide, and tertiary phosphines such as triphenylphosphine. , carboxylic acid metal salts such as lithium stearate and calcium stearate, sulfonic acid metal salts such as sodium dodecylbenzenesulfonate and sodium 3,5-dicarbomethoxybenzenesulfonate, and sulfuric acid ester salts such as sodium lauryl sulfate. It is preferable to add 0.001 to 5 parts by weight per 100 parts by weight of the aromatic polyester.

The composition of the present invention may contain conventional additives such as antioxidants, ultraviolet absorbers, heat stabilizers, lubricants, mold release agents, colorants including dyes and pigments, fibers, etc., to the extent that the object of the present invention is not impaired. solid and granular fillers and reinforcements (e.g. glass fibers, glass peas, carbon fibers, calcium carbonate, magnesium carbonate, barium sulfate, Wl powder silicic acid, wollastenite, talc, clay, mica, sericite, zeolite, pennite) , dolomite, kaolin, etc.), nucleating agents,
It may be modified with a flame retardant, other thermoplastic resin, etc. These additives may be added singly or in combination of two or more.

Among these various additives, addition of crystal nucleating agents typified by inorganic oxides such as talc and various metal soaps such as sodium stearate and barium stearate is particularly important in the case of polyethylene terephthalate. In addition, the use of plasticizers such as dibenzoic acid esters of various salts such as 1-lyethylene glycol and neopentyl glycol improves the crystallinity of polyethylene terephthalate I, improves its fluidity, and improves the surface gloss of molded products. effective for its purpose.

The method for producing the composition of the present invention is not particularly limited, but preferably a method of melt-kneading an aromatic polyester, a vinyl copolymer (the king of polyester and polyvalent epoxy compound fBl) using an extruder is preferable. Can be mentioned.

The resin composition of the present invention can be easily molded by conventional methods such as injection molding and extrusion molding, and the resulting molded product exhibits excellent properties.

The effects of the present invention will be explained in further detail with reference to Examples below.

Examples 1-4, Comparative Examples 1-5 Polyethylene terephthalate 1-10 with relative viscosity 1.41
A vinyl copolymer and a polyvalent epoxy compound of the types and proportions shown in Table 1 were triblended with respect to 0 parts by weight, and the mixture was melt-mixed and pelletized using a screw extruder set at 280°C. The resulting pellets were then molded using a 5-ounce screw in-line injection molding machine set at 280°C, and were molded using ASTM bending test pieces, heat distortion temperature measurement test pieces, and Izotsu impact test pieces (each with a /4
inch width) was created. Table 1 shows the results of measuring the characteristics of these test pieces.

In addition, measurements were conducted in the same manner on samples to which no vinyl copolymer and/or polyvalent epoxy compound was added. These results are also shown in Table 1.

As is clear from the results in Table 1, the composition in which only a vinyl copolymer is blended with an aromatic polyester (ratio example 2.3) improves the heat distortion temperature, but has poor impact resistance. The composition containing only the polyvalent polyvalent compound (Comparative Example 4.5) does not satisfy either the heat distortion temperature or the impact resistance. On the other hand, the compositions of the present invention (Examples 1 to 4) in which both a vinyl copolymer and a polyvalent engineered polyester compound were blended into an aromatic polyester had high thermal deformation due to the interaction of both modifiers. It is clear that the temperature is maintained and that there is a synergistic effect of improving impact resistance.

Patent applicant Higashi Shikikai Co., Ltd.

Claims (1)

[Claims] A resin composition comprising (2) a vinyl copolymer consisting of an aromatic vinyl monomer and an α,β-unsaturated cyclic imide compound and a (Bl polyepoxy compound) in an aromatic polyester.