JPH03166253A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition excellent in molding processability and heat resistance by blending a resin composition composed of a methacrylimide-containing polymer and thermoplastic polyester with a specific polyfunctional compound. CONSTITUTION:A composition obtained by blending 100 pts.wt. resin composition composed of (A) 1-99 pts.wt. polymer containing >=10wt.% methacrylimide units expressed by the formula (R is H or 1-20C aliphatic, aromatic or alicyclic hydrocarbon group), e.g. a polymer prepared by thermally reacting polymethyl methacrylate with ammonia or a primary amine in an autoclave using a solvent and forming imide rings and (B) 99-1 pt.wt. thermoplastic polyester with (C) 0.05-10 pts.wt. one or more compounds, having <=5000 molecular weight and selected from polyfunctional epoxy compounds, polyfunctional oxazoline compounds and polyfunctional isocyanate compounds.

Description

Detailed Description of the Invention (Industrial Technical Field) The present invention involves blending a compound having a specific functional group into a thermoplastic resin composition consisting of a methacrypimide-containing polymer and thermoplastic polyester μ. The present invention relates to a thermoplastic wood QFf composition having excellent shape processability and heat resistance.

(Prior Art and Problems to be Solved by the Invention) A mixture of a megcuriimide-containing polymer and a thermoplastic polyester P has high heat resistance, and can form a composition with excellent mechanical strength and melt flowability. It is disclosed in Japanese Patent Application Laid-Open No. 59-41355. However, in the case of assemblies made by simply mixing a methacrinoleimide-containing polymer and a thermoplastic polyester, sink marks and cracks tend to appear during melt-forming, and there is a problem with the shape-processing process.

(Means for Solving the Problems) As a result of intensive study on the above-mentioned drawbacks of a combination made of a methacrylic imide-containing polymer and a thermoplastic polyester μ, the present inventors found that this combination has a specific property. The inventors have discovered that the formability can be significantly improved by incorporating a specific amount of a compound having a functional group, and have arrived at the present invention.

That is, the gist of the present invention is that tA. ) At least 10 methacrylimide units represented by the following general formula (wherein R represents 1 hydrogen atom or an aliphatic, aromatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms) Containing methacrinoreimide-containing polymer 1-qqTtlj
(A) and 03) (width) Atsumachi pear polyester μ99~1 ton Amabe, the total amount of (A) and 03) is 100 weight I
(C) At least one compound ψ selected from polyfunctional epoxidized products, polyfunctional oxazoline compounds, and polyfunctional isocyanate compounds [105 to 10 parts by weight is added to the thermoplastic resin composite in Part A]. It is made of thermoplastic resin composition.

The methacryimide-containing polymer (Al,
It is a polymer i or copolymer containing a cyclic imide unit represented by the above general formula (1).

If it contains 10 or more of the above cyclic imide units,
Any methacrinoleimide-containing polymer having any chemical structure can be used.

Generally, R is hydrogen or a methyμ, ethyl brobiμ, petit, or fe diμ group.

The method for producing the methacriimide-containing polymer is not particularly limited. For example, polymethacrylinoleic acid methi and ammonia! or a primary amine such as methamine or ethylamine in a suitable solvent (e.g. benzene, toene, kylene,
Aromatic hydrocarbons such as ethymubenzene or methanol,
Using Apco μ alone or a mixed solution of two or more of them such as ethanol or propano P, react by heating at 170 to 350°C in an autoclave to form an imide ring. method is useful. The residue
The reaction may be carried out in an extruder as described in JP-A-52-65989.

The cyclic imide unit represented by the above general formula (1) must be contained at least 10 times by weight in the polymer, and if it is less than 10 times by weight, the inherent heat resistance of the methacrylic imide polymer cannot perform.

The thermoplastic polyester/L' (B) used in the present invention consists essentially of at least one acid selected from terephthalic acid, 6-naphthalene dicarboxylic acid, isophthalic acid, etc., ethylene glycol, It is obtained by polycondensation with at least one diol Iv fraction selected from polyalkylene glycols such as propylene glycol, ethylene glycol μ, hexylene glycol p, polyethylene glycol, and polytetramethylene glycol p, Specifically, polyethylene terephthalate (
pFXT), polypropylene terephthalate (PP〒
), polybutylene terephthalate (PBT), polyhexylene terephthalate (PHT), polyethylene naphthalate (PFXN), polybutylene naphthalate (PB
In addition to N), copolymerized polyesters such as polyethylene isophthalate terephthalate (PI!iT/Ko) and polybutylene terephthalate isophthalate (PBT/I) can be mentioned. Among these polyesters, other tertiary components such as adipic acid, sepanoic acid, dodecanedicarboxylic acid, hexadecanedicarboxylic acid, octadecanedicarboxylic acid, dimer acid, and phthalocyanate are added to these polyesters within 50 m/I/4. μ acid, 4,4'-diphenyldicarboxylic acid, sulfisophthalic acid, ethylene oxide adduct of bisphenol/L/A, etc. can be copolymerized. A blend formed by mixing two or more of these thermoplastic polyesters μ can also be applied to the present invention.

The degree of polymerization of the thermoplastic polyester μ used in the present invention is not particularly limited, but [η]=Q. 4-1. 5
(phenol/L//tetrachloroethane mixed solvent weight ratio 121, measured at 25°C).

Furthermore, the polyfunctional epoxy compound used as part (C) in the present invention is a compound having two or more epoxy groups, and bisphenol-based epoxy compounds such as bisphenol/vA diglycidyl ether, halogenated bisphenol/vA diglycidyl ether, etc. Compound, a~kipphenol/I/
Phenol p-based epoxy compounds such as Shigri V dimu-ether, phenomu-phthalein epoxide, glycol-μ epoxy compounds such as polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, glycerin triglycidyl ether μ, etc. Compound, Lid/I/Ester-based epoxy compound such as acid diglycidi~ester, N
, N-diglycidylaniline, etc., and triglycidyl p-isocyanurate. Two or more of these can also be used in combination.

Further, the polyfunctional oxazoline compound used in the present invention is a compound having two or more oxazoline groups, and has 2.2'-
(1,5-phenylene)bis(2-oxazoline) 2
．． Examples include 2'-(1.4-phenylene)bis(2-oxazoline), and two or more of these can also be used in combination.

The polyfunctional isocyanate compound used in the present invention is a compound having two or more inocyanate groups, and examples thereof include tri-μ-ylene diisocyanate, diphenylmethane diisocyanate, diphenyl diisocyanate, and triphenylene diisocyanate. Examples include tantriisocyanate, hexamethylene diisocyanate, naphthalene diisocyanate, etc., and two or more of these can also be used in combination.

These polyfunctional compounds (C) are added to the methacrylic imide-containing polymer) from 1 to 99 parts by weight, preferably from 5 to 95 parts by weight, and from 99 to 1 parts by weight of thermoplastic polyester μ(B). Used in the range of 0.05 to 10 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the total amount of the tree IIH#Jl, preferably 95 to 5 parts by weight. be done. If the amount of the polyfunctional compound (C) is less than 0.05 parts by weight, the effect of improving formability will not be sufficient, and if it exceeds 10 parts by weight, fluidity will deteriorate, which is not desirable.

The polyfunctional compound preferably has a molecular size of i1 s, o o o or less in order to be uniformly dispersed and reacted in the compound.

A thermal decomposition inhibitor and an ultraviolet absorber may be added to the resin composition of the present invention in order to improve heat resistance, light resistance, and +mt oxidative deterioration resistance. ``Furthermore, plasticizers, pigments, lubricants, etc. can also be used.Furthermore, fibrous materials such as gawase fibers and carbon fibers can be added for reinforcement.

(Actual 74 examples) Hereinafter, the present invention will be explained in more detail with reference to Examples.

(1) Heat distortion temperature is A day TM D 64B-56
(loading claw 1B.56k97cm"), Izod impact 9 strength pa ASTM D 256-56 Method A
Measured according to

(2> A river constant elemental analysis fl of imidized fat (regret) of methacriimide-containing polymer (A) (measurement p4aHw coder (MT-3)
(manufactured by Yanagimoto Seisakusho) to determine nitrogen content.

Also, proton NMR, rNM-yx-1oo (Jg
oL) y. Measurement was performed using a pectrometer at 100 MHz. The amount of imidization mentioned here refers to the following general 11
4 model? The methacrylimide shown f. 41 We assumed a repeating structure of Wn unit and metac ■ri lvq methi μ unit, and set the value of X as imidization'FIc. In order to make a decisive run at this Dereag-131shoff
) Using a viscometer, measure the flow time (ts) of a chloroform solution with a sample polymer concentration of α5 and the flow time (to) of chloroform at 25 degrees Celsius and n111.
and the relative viscosity ηre of the polymer from the ts/to value.
This is the value obtained by finding l and then calculating from the following formula.

(In the formula, C is the polymer concentration (r/1ood).) Synthesis Example Methyl methacrylate μ Polymer (PMMA, intrinsic viscosity αs1) *
OQ heavy pickle part, Topen 80 heavy part, methanol/L/20
The temperature was raised to 250°C, stirred and dissolved, and 21.7 parts by weight of methylamine (7μ ratio to methacrylic acid methyl p unit in PMMA = 0.7) was added, and the internal pressure was 60.
kg/cm"a for 3 hours. After the reaction, a methacryimide-containing polymer (A-1) was obtained.

After drying, it was powdered and used as a sample. The imidization amount (4) of this polymer (A-1) was 70.

Examples 1 to 6, Comparative Examples 1 to 3 Methacrypimide-containing polymer (A-
1), polyethylene terephthalate ([η] = 0.
7 2) Also polybutylene terephthalate ([η)
= o. a s )> and the polyfunctional compounds shown in Table 1 were blended and pelletized at 290°C using a 40-φ extruder. Using this pellet, a 6Illlφ in-line screw injection molding machine was used to form
A test specimen with mold dimensions of 12.8 fins in width and 128 cm in length was molded. The cylinder/lIA degree is 280℃, the mold temperature is 70℃, and the short shot pressure is determined for the shape.When obtaining the shape, the short shot pressure is +150k+?
/cm”, holding pressure short shot pressure +1 2 0
k97cm'' for 7 seconds, and the hollow-shaped product was taken out after cooling for 30 seconds.

The thickness of each test piece was measured at five points, and the smallest value was taken as the sink mark index.

The results are shown in Table 1, and it can be seen that sink marks are improved by blending a specific polyfunctional compound.

(Effect of the invention) Formability can be significantly improved by blending a specific polyfunctional compound into a thermoplastic resin composition consisting of a methacryimide-containing polymer and thermoplastic polyester μ. . Therefore, the thermoplastic resin composition of the present invention can be used in a wide range of applications.

Claims (1)

[Claims] 1. (A) The following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (1) (In the formula, R is a hydrogen atom or an aliphatic or aromatic group having 1 to 20 carbon atoms. 1 to 99 parts by weight of a methacrylimide-containing polymer containing at least 10% by weight of methacrylimide units represented by (or representing an alicyclic hydrocarbon group); and (B) 99 to 1 part by weight of a thermoplastic polyester; (C) At least one compound selected from a polyfunctional epoxy compound, a polyfunctional oxazoline compound, and a polyfunctional isocyanate compound for a thermoplastic resin composition in which the total amount of components (A) and (B) is 100 parts by weight. A thermoplastic resin composition containing 0.05 to 10 parts by weight.