JPH02219850A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin composition excellent in applicability, colorability, etc., and not undergoing delamination, etc., by mixing a graft copolymer prepared by mixing a graft copolymer prepared by introducing a specified vinyl monomer into a graft component with an aromatic polycarbonate. CONSTITUTION:A graft copolymer comprising 5-60wt.% rubbery polymer and 95-40wt.% copolymer of a monomer of formula I (wherein R1 is H or CH3; and R2 is a 5-12C cycloalkyl, a 6-12C alkyl, an aryl or the like) with a copolymerizable vinyl monomer and having a weight ratio of the monomer of formula I to the graft copolymer-rubbery polymer of 0.01-0.5, a vinyl copolymer (B) obtained by copolymerizing 1-50wt.% compound of formula I (e.g. cyclohexyl acrylate) with another copolymerizable vinyl monomer (e.g. methyl methacrylate), and an aromatic polycarbonate are mixed together in a weight ratio satisfying formulas II and III (wherein the total of components A and B is 100 pts.wt.) to produce a resin composition.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention provides a resin composition comprising an aromatic polycarbonate and a graft copolymer containing a rubbery polymer, which has improved paintability, colorability, and layer release properties. Regarding.

Therefore, even if it is an improvement, it cannot be a fundamental solution.

(Prior Art) A resin composition formed by mixing a graft copolymer containing a rubbery polymer and a polycarbonate resin is used for the purpose of improving the impact resistance or heat resistance of the graft copolymer, or for the purpose of improving the impact resistance or heat resistance of the graft copolymer. This is a polymer blend that is commonly used for the purpose of improving moldability or thickness dependence of impact strength. However, these compositions have drawbacks such as solvent resistance such as paintability, coloring property, and delamination. This is thought to be due to the fact that

In order to solve such problems, JP-A-62-295950 discloses a method of blending a (meth)acrylate-butadiene graft copolymer having a specific composition into a polycarbonate resin at a predetermined ratio. , which are originally incompatible blend systems (problem to be solved by the invention) The purpose of the present invention is to improve the compatibility of blends of polycarbonate resin and graft copolymer, which have been conventionally incompatible. By creating a blend, various properties can be improved through this compatibilization. - For example, the purpose is to prevent cranking during painting, eliminate color unevenness during coloring, and improve delamination of molded pieces.

(Means for Solving the Problems) As a result of intensive studies on blends of polycarbonate resins and graft copolymers that have such excellent compatibility, the present inventors have identified a graft component of the graft copolymer. The present invention was completed based on the discovery that the above object could be achieved by introducing a vinyl monomer.

That is, the present invention provides: (A) The proportion of the rubbery polymer in the graft copolymer is 5 to 60 wtχ, and the proportion of the copolymer of the formula (I) and a vinyl monomer that can be copolymerized therewith is 95%. A graft copolymer having a weight ratio of formula (I)/(graft copolymer-rubber polymer) of 0.01 to 0.5.

(C) an aromatic polycarbonate, the total of (A) and (B) being 100 parts by weight. When 50≦(A)≦100 parts by weight, and the weight ratio is is a cycloalkyl group with ~12 C atoms, or with one or several alkyl substituents, or from 6 to 1
an aryl group optionally having an alkyl or oxyalkyl substituent having 2 C atoms; A is an optionally branched alkylene group having 1 to 6 C atoms; or 2 (B) A resin composition containing 1.0 to 50-tx of the compound of formula (I).

The present invention will be specifically explained below.

As the rubbery polymer of the graft copolymer (A) used in the present invention, any polymer having a glass transition temperature of 0° C. or lower can be used. Specifically, diene rubbers such as polybutadiene, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, acrylic rubbers such as polyisoprene, polychloroprene, butyl polyacrylate, ethylene-propylene rubber, ethylene-propylene - Block copolymers such as diene ternary copolymer rubber and styrene-butadiene block copolymer rubber, hydrogenated products thereof, and the like can be used.

Preferred examples include polybutadiene, styrene-butadiene copolymer rubber, and ethylene-propylene-diene ternary copolymer rubber.

Specific examples of the formula (I) compounds used in the present invention, that is, acrylic esters and methacrylic esters having a cyclic hydrocarbon in the ester group, include cyclohexyl acrylate, cyclohexyl methacrylate,
3.3.5-trimethylcyclohexyl methacrylate, cyclopentyl methacrylate, 3-cyclohexylpropyl methacrylate, phenyl methacrylate, 4
-t-butylphenyl methacrylate, 4-methoxyphenyl methacrylate, benzyl methacrylate, 1-
Phenylethyl methacrylate, 2-phenylethyl acrylate, 2-phenylethyl methacrylate, 3-
Examples include phenylpropyl acrylate, 3-phenylpropyl methacrylate, 2-phenoxyethyl methacrylate, and 2-naphthyl methacrylate.

Copolymerizable vinyl monomers include alkyl (meth)acrylates such as methyl methacrylate, methyl acrylate, and ethyl acrylate; (meth)acrylic acids such as acrylic acid and methacrylic acid; aromatics such as styrene and α-methylstyrene; Vinyl cyanide monomers such as acrylonitrile and methacrylate trile; α, β-unsaturated carboxylic acids such as maleic anhydride; maleimide monomers such as N-phenylmaleimide; glycidyl such as glycidyl methacrylate Group-containing monomers are used.

Preferred are alkyl (meth)acrylates, aromatic vinyl monomers, vinyl cyanide monomers, etc., and more preferred are methyl methacrylate, ethyl acrylate, styrene, and acrylonitrile.

The proportion of rubbery polymer in the graft copolymer is 5 to 60-
Although it is used within the range of tχ, it is preferably within the range of 10 to 50 wtX in terms of impact resistance and workability. 5T, 4tχ
If it is less than 6, the impact resistance and reinforcement effect will not be sufficient.
If it exceeds 0 wtX, the fluidity of the resin will decrease and the processability will deteriorate.

The weight ratio of the compound of formula (I)/(graft copolymer-rubber polymer) is 0. It is necessary that the range is O1 to 0.5, preferably in the range of 0.1 to 0.4. When it is less than 0.01, the compatibilizing effect is not sufficient, and when it exceeds 0.5, an incompatible system is formed, which is not preferable.

The graft copolymer can be produced using known methods such as emulsion polymerization, bulk polymerization, and suspension polymerization.

Grafting ratio of the graft copolymer produced at this time 11)
can be set arbitrarily, but a preferable range is 5 to 200%. If the grafting rate is less than 5%, the rubbers will coagulate and the appearance of the molded piece will deteriorate. If it exceeds 200%, impact resistance and reinforcing effects decrease, which is not preferable.

As the other vinyl monomer that can be copolymerized in the vinyl copolymer (B) in the present invention, one of the above-mentioned vinyl monomers that can be used in producing the graft copolymer (A) is used. You can freely choose a species or two or more species. Preferred are alkyl (meth)acrylates, aromatic vinyl monomers, and vinyl cyanide monomers, and more preferred are methyl methacrylate, ethyl acrylate, styrene, and acrylonitrile.

The molecular weight of the vinyl copolymer (B) ranges from s.ooo to 200,000 from the viewpoint of mechanical strength and moldability, but preferably from 10,000 to 8.
It is in the range of 0.000.

As the aromatic polycarbonate (C) used in the present invention, a reaction product of dihydric phenol and hydrogen can generally be used. As the dihydric phenol, 2°2-his-(4-hydroxyphenyl)-propane, known as bisphenol A, is preferred. Alternatively, part or all of bisphenol A may be substituted with other dihydric phenol.

Examples include Eva, bis-(4-hydroxyphenyl)-alkane, hydroquinone, 4,4'-dihydroxydiphenyl, and bis-(4-hydroxyphenyl)-cycloalkane.

The molecular weight of the aromatic polycarbonate can be used in the range of 10.000 to 200.000 from the viewpoint of mechanical strength and moldability, and the preferable range is 20,000 to 80.0.
It is 00.

Blends of graft copolymers, vinyl copolymers, and aromatic polycarbonates can be produced by melt blending using a conventional extruder or by a solution blending method in which they are dissolved in a solvent and then blended.

The ratio of aromatic polycarbonate contained in the resin composition can be designed at any ratio within the range of (U), and can be freely designed based on the balance between heat resistance and moldability, but the preferred range is This is the case when the aromatic polycarbonate is contained in the composition in a range of 20 to 8 Fwtχ. If it is less than 0605, the amount of the graft copolymer is small, and the effect of improving the moldability of the polycarbonate resin and the thickness dependence of impact strength is small. Moreover, when it is less than 20, the content of polycarbonate resin is small and no substantial effect of improving heat resistance is observed.

At this time, if necessary, use glass fiber, glass flakes,
Various additives such as antioxidants, ultraviolet absorbers, pigments, dyes, lubricants, plasticizers, flame retardants, and antistatic agents can be added.

(Examples) In order to explain the present invention more specifically, Examples and Comparative Examples will be described below, but these are not intended to limit the present invention.

Reference Example (I) Preparation of Graft Copolymer Polybutadiene latex (weight average particle diameter 3000, gel content 85%) 30wL'! A graft copolymer was obtained by emulsion polymerization of 70 wt % of the monomer mixture having the composition shown in Table 1 (based on solid content).

The number average molecular weight of the polymerized graft copolymer is 50゜OO
It was in the range of O to ao, ooo.

(2) Preparation of vinyl copolymer A monomer mixture having the composition shown in Table 1 was emulsion polymerized to obtain a vinyl copolymer.

The number average molecular weight of the obtained copolymer is 50,000 to 80
It was in the range of 0.000°.

(3) Aromatic polycarbonate-1 is a reaction product of bisphenol A and phosgene'#yJ (molecule 130.0
00) was used.

Examples 1 to 23 and Comparative Examples 1 to 3 Graft copolymer, vinyl copolymer, and aromatic polycarbonate were blended with the evaluation composition shown in Table 1, and pellets were melt-blended at 250''C using a small extruder.
Paintability, colorability, and delamination were measured using samples molded using a small injection molding machine. The results are shown in Table 1.

The measurement methods for evaluation in Examples and Comparative Examples are as follows; Measurement method ■ Paintability: After immersing a dumbbell test piece in a paint consisting of 50% thinner/50% paint for 20 seconds, Dry for 30 minutes in a hot air dryer at 80°C. The surface of the molded piece after drying was observed using a stereomicroscope to check for cracks.

O: No cracks Δ: No cracks, but paint suction is observed.

×...Cracks■ Coloration property: 0.1% of red coloring agent (venylon dye) was added during extrusion blending.
After coloring, a color plate was molded and the colorability was observed.

O: The color tone is uniform.

×...The color tone is uneven, and the image is white and blurred.

(2) In a tensile test (ASTMD-638) of layered peeled dumbbell molded pieces, the state of peeling at the time of breakage of the molded piece was visually observed.

O: No peeling is observed.

×: Peeling is observed.

(Effect of the invention) As can be seen from the above results, in the present invention, by introducing a specific (meth)acrylic ester monomer as a graft component of the graft copolymer, the phase with the aromatic polycarbonate can be improved. Solubility is increased, and practical properties such as paintability, colorability, and layer release are improved.

(1 idiot)

Claims (1)

[Scope of Claims] (A) The proportion of the rubbery polymer in the graft copolymer is 5 to 60 wt%, and the proportion of the copolymer of the formula (I) and a vinyl monomer that can be copolymerized with it is 5 to 60 wt%. 95-40wt%
A graft copolymer having a formula (I)/(graft copolymer-rubber polymer) weight ratio of 0.01 to 0.5. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 is H or CH_3, R_2 is X
or A-X, in which X is a cycloalkyl group with 5 to 12 C atoms, or a cycloalkyl group with one or several alkyl substituents, or a cycloalkyl group with 6 to 12 C atoms An aryl group which may have an alkyl or oxyalkyl substituent, and A
is an alkylene group having 1 to 6 C atoms, which may be branched, or an oxyalkylene group having 2 to 4 C atoms) (B) A compound of formula (I) is added to 1. Contains 0 to 50 wt%,
A vinyl copolymer obtained by copolymerizing this with other vinyl monomers that can be copolymerized, (C) aromatic polycarbonate, the total of (A) and (B) being 100 parts by weight. A resin composition in which: 50≦(A)≦100 parts by weight, and a weight ratio of 0.05≦(A)+(B)/(C)≦20.