JPH04159360A - resin composition - Google Patents

Abstract

PURPOSE:To prepare a resin compsn. giving a molded article having a good surface appearance, a high heat distortion temp., and a low bending modulus by compounding a polycarbonate resin, a thermoplastic polyurethane, and a specific copolymer. CONSTITUTION:100 pts.wt. resin compsn. comprising 30-80wt.% polycarbonate resin and 70-20wt.% thermoplastic polyurethane is compounded with 0.5-20 pts.wt. copolymer of an a-olefin with glycidyl (meth)acrylate to give a resin compsn., which can be molded by injection molding, extrusion molding, compression molding, etc., giving a molded article having a good surface appearance, a high heat distortion temp., and a low bending modulus.

Description

Detailed Description of the Invention <Industrial Application Field> The present invention relates to a resin composition that provides a molded article with a good surface appearance, a low flexural modulus, and a high heat distortion temperature. .

<Conventional technology> Polycarbonate resin has excellent transparency, high impact strength,
It is widely used because it has excellent properties such as high flexural modulus. However, it has drawbacks such as thickness dependence of impact strength and susceptibility to deterioration by hydrocarbon solvents, and depending on the application, it is required to have a low flexural modulus.

By blending thermoplastic polyurethane with polycarbonate resin, it is possible to eliminate thickness dependence, improve resistance to hydrocarbon solvents, and lower flexural modulus.

However, molded products obtained by blending thermoplastic polyurethane with polycarbonate resin have flow patterns on their surfaces and are of no commercial value.

Furthermore, JP-A No. 2-43254 proposes a composition in which polycarbonate resin is blended with thermoplastic polyurethane and a specific graft polymer;
No. 62 proposes a composition in which a specific polyurethane is blended with a polycarbonate resin. However, flow patterns also occur on the surface of molded products obtained by injection molding these compositions, and the results are still insufficient for practical use.

<Object of the invention> The object of the present invention is to provide a resin composition that provides a molded article with a good surface appearance, a high heat distortion temperature, and a low flexural modulus. .

In order to achieve the above object, the inventor has made extensive studies and found that
The inventors have found that the above problems can be solved by blending a copolymer of α-olefin and glycidyl (meth)acrylate with thermoplastic polyurethane into polycarbonate resin, and have completed the present invention.

<Structure of the invention> The present invention comprises (A) polycarbonate resin 30 to 80% heavy talk (B
J Thermoplastic polyurethane 0.5 to 20 weight 1 part of a copolymer of (C) ■ α-olefin and ■ glycidyl methacrylate and/or glycidyl acrylate is blended into the vootim part of a resin composition consisting of 70 to 20 weight % of thermoplastic polyurethane. This relates to the 'm[f composition.

The polycarbonate resin M resin, which is component (A) in the present invention, is produced from a divalent phenol and a carbonate precursor by a solution method or a melt Wi method. As the divalent phenol, 2,2-bis(4-droxyphenyl)
The main target is propane (commonly known as Suffl, Nord A), but part or all of it may be replaced with other dihydric phenols.

Other dihydric phenols include, for example, his<4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-dihydroxyphenyl (4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-
Examples include human Oxy-3,5-dibromophenyl)propane, bis(4-hydroxyphenyl)ether, bis(4-droxyphenyl) sulfide, bis(4-hydroxyphenyl)sulfone, etc.Carbonate precursor For example, carbonyl halide, carbonyl ester, herobomate, etc. can be mentioned.

The degree of polymerization of the polycarbonate resin is usually 13.000 to 50.000, preferably 1, expressed as a viscosity average molecular weight.
5,000 to 35,000. In producing such a polycarbonate resin, an appropriate molecular weight regulator, catalyst for accelerating the reaction, etc. can be used as necessary.

Component (B), the thermoplastic polyurethane, contains (1) an organic polyisocyanate, (2) a compound reactive with isocyanates, and (2) has 2 to 3 functional groups and has a molecular weight of approximately 50 to 40.
obtained by reaction of 0 chain extenders.

(2) Organic polyisocyanates include, for example, methylene bis(phenylisocyanate) [e.g., 4,4°-isomer, 2.4°-isomer, mixtures thereof, etc.], p- or p-phenylene diisocyanate, chlorophenylene diisocyanate, xylylene diisocyanate, 2
, 4- or 2゜6-toluene diisocyanate, toridine diisocyanate, hexamethylene diisocyanate, methylene bis(cyclohexyl isocyanate)
[For example, 4,4°-isomer, 2.4°-isomer, mixtures thereof, etc.].

(2) As the isocyanate-reactive compound, any compound already known for the production of polyurethane can be used. For example, polyneedle polyol, polyester polyol, amine-terminated polycarbonate, hydroxy- or amine-terminated polybutadiene.
Examples include acrylonitrile cobolymer.

Polyether polyols include, for example, polyoxyethylene glycol, polyoxypropylene glycol optionally end-capped with ethylene oxide residues, random or block copolymers of ethylene oxide and propylene oxide,
Propoxylated trihydric or tetrahydric alcohols such as glycerin, trimethylolbucoban, pentaerythritol, etc., with terminals capped with ethylene oxide, polytetramethylene glycol, random combinations of tetrahydrofuran and ethylene oxide or propylene oxide or block copolymers, and compounds obtained by reacting any of the above with two or more polyfunctional carboxylic acids or esters derived from these acids. Examples of polyester polyols include those obtained by polymerizing α-caprolactone using an initiator such as ethylene glycol and ethanolamine, and phthalic acid, terephthalic acid, succinic acid, glutaric acid, adipic acid, and azelain It.
Examples include those produced by esterifying polyfunctional carboxylic acids such as ethylene glycol, butanediol, glycerol, trimethylolpropane, and other polyhydric alcohols.

(2) Preferred chain extenders are aliphatic straight-chain or branched chain diols, including cycloaliphatic, having about 2 to 8 carbon atoms in the chain; such diols include:
For example ethylene glycol, 1,2- or 1,3-
Propanediol, 1.3-11,4- or 2.3
-butanediol, 1.3- or 1.5-bentanediol, 1.2- or 1.6-hexanediol, 3-methylpentane-1°5-diol, 1,4-cyclohexane dimetatool, etc. and these Examples include mixtures of two or more diols.

Thermoplastic polyurethane is produced by any commonly known method using the above-mentioned components (1) and (0).

For example, a method in which ■Mi■ and ◎ components are heated to 60°C to 135°C, respectively, and then the ■, ■, and ◎ components are mixed substantially simultaneously; A preferred method is to mix the mixture with component (2).

The resulting thermoplastic polyurethane is optionally cut or milled to the desired particle size.

The copolymer of component (C) is a copolymer of (1) α-olefin and (2) glycidyl methacrylate and/or glycidyl acrylate. ■ Examples of α-olefins include ethylene, propylene, butene-1, isobutylene, pentene-1, hexene-1, heptene-1, octene-1, dodecene-1,4-methylpentene-1, etc., especially Ethylene and propylene are preferred. (C)
Glycidyl methacrylate and/or in the copolymer of components
Alternatively, the amount of glycidyl acrylate is preferably in the range of 1 to 2011%. If less than 1% by weight is used, it is difficult to sufficiently improve the appearance of the molded product obtained from the composition, and if it exceeds 20% by weight, gel will occur and the appearance of the molded product obtained will deteriorate. Impact strength also tends to decrease.

In addition, the copolymer of component (C) may be a random copolymer, a block copolymer, or a graft copolymer, and may further contain a vinyl compound other than α-olefin, glycidyl methacrylate, or glycidyl acrylate. It may also be included as a copolymerization component. Examples of copolymerizable vinyl compounds include styrene, vinyl acetate, methyl methacrylate, methyl acrylate, ethyl acrylate,
Vinyl chloride, α-methylstyrene, divinylbenzene,
Examples include acrylic acid, tetrafluoroethylene, difluoroethylene, vinylidene chloride, acrylonitrile, and acrylamide. The amount of vinyl compound in the copolymer of component (C) is usually 401! Up to %.

The blending ratio of (A) polycarbonate resin and (8) thermoplastic polyurethane in the composition of the present invention is (A
) component is 30 to 80% by weight, and component (B) is 70 to 20% by weight. If the amount of component (A) is less than 30% by weight, only a product with a low heat distortion temperature will be obtained, and if it exceeds 80% by weight, moldability will deteriorate.

The blending ratio of the copolymer (C) is 0.5 to 20 parts by weight per 100 parts by weight of the composition consisting of components (A) and (8). If the blending amount of component (C) is less than 0.5 part by weight, the flow pattern on the surface of the molded product will not be eliminated;
Even if the amount exceeds 0 parts by weight, the effect of component (C) will not be improved any further, and on the contrary, the appearance may deteriorate, and the thermal deformation density also tends to decrease. Particularly preferred blending amount is 1 to
It is 10 parts by weight.

The impact resistance of the composition of the present invention can be further improved by adding an impact modifier. As the impact modifier, for example, two or more monomers selected from the group consisting of vinyl cyanide compounds, methacrylic esters, acrylic esters, and aromatic vinyl compounds in the presence of a rubber containing repeating units derived from butadiene. Examples include elastic polymers obtained by copolymerizing.

Rubbers containing repeating units derived from butadiene include:
Examples include polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, butadiene-acrylic acid ester copolymer, and the like. Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile. Examples of methacrylic esters and acrylic esters include methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, and octyl acrylate. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, alkoxystyrene, and halogenated styrene.

The above-mentioned elastic copolymer may be produced by any polymerization method such as bulk polymerization, solution polymerization, or emulsion polymerization, and the copolymerization method may be single-stage grafting or multi-stage grafting. Furthermore, it may be a mixture with a copolymer containing only the graft component produced as a by-product during production, or a mixture of two or more types of elastic copolymers.

The blending amount of the above elastic copolymer is as follows: (A) Polycarbonate resin (BJ)
It is preferable that the amount is 15 parts by weight or less per 100 parts by weight.

Furthermore, the composition of the present invention may contain, for example, an antioxidant, a flame retardant, an antistatic agent, an ultraviolet absorber, etc. in addition to the above-mentioned components within a range that does not impair its properties.

The composition of the present invention can be produced by mixing the constituent components in a mixer such as a tumbler, blender, Nauta mixer, Banbury mixer 1 mixed roll, or extruder.

<Effects of the Invention> The composition of the present invention can be formed by any molding method, such as injection molding,
It can be applied to extrusion molding, compression molding, etc., and the resulting molded products are
It has a good appearance, a high zero heat distortion temperature, and a low flexural modulus, making it extremely useful.

<Examples> The present invention will be described below with reference to Examples. In addition, evaluation in Examples is based on the following method.

(1) Appearance of molded product: A sample board of 90 aw x 50 rin x 2 shoes was molded, and the flow pattern appearing on the sample board was visually judged.

〇-Not visible.

△- Slightly noticeable.

X; clearly visible Oi) Flexural modulus: ASTI4 D-790 (to) Heat distortion temperature: ASTHD-648 (18,6 kOf/m
>0 Impact strength: ASTHD-256 (with isotto notch, 178#, 23°C) Examples 1 to 6 and Comparative Examples 1 to 3 After drying the polycarbonate resin at 120°C for 5 hours and the thermoplastic polyurethane at 80°C for 3 hours. , using a 30-diameter vent type extruder (VSK-30 manufactured by Nakatani) with the composition ratios (parts by weight) shown in Table 1, and a cylinder temperature of 250°C.
It was made into a beret.

After drying the obtained pellet at 105°C for 4 hours, a sample plate and a test piece were molded using an injection molding machine (Japan Steel Works ■ J-120S^) at a cylinder temperature of 230°C and a mold temperature of 40°C. . Using the obtained sample plates and test pieces, the appearance and mechanical properties were evaluated, and the results are shown in Table 1. In addition,
The symbols indicating the compounds in the composition ratio column in the table are as follows.

PC: Polycarbonate resin (Panlite L-1250 manufactured by Teidai Kasei ■, viscosity average molecule! 25.000TPP
υ-1: Polyether type thermoplastic polyurethane whose main components are 4,4'-diphenylmethane diisocyanate and polyoxytetramethylene glycol (Kurimilon UTPP II-2, manufactured by Kuraray Co., Ltd.): 4,4°-diphenylmethane diisocyanate and polybutylene adipate Polyester-type thermoplastic polyurethane (Lamiron U-1198 manufactured by Kuraray) E-GH^: Ethylene-glycidyl methacrylate copolymer (Sumitomo Chemical Co., Ltd.)
Bond First [) A-4101: Ethylene-glycidyl methacrylate-styrene copolymer (Modiva ^-410 manufactured by NOF ■
1) HBS: Graft copolymer made of polybutadiene rubber grafted with methyl methacrylate and styrene (CA-102 manufactured by Kureha Chemical Industry ■) (blank below)

Claims (1)

Scope of Claims: (A) 30-80% by weight of polycarbonate resin (B) 100 parts by weight of a resin composition consisting of 70-20% by weight of thermoplastic polyurethane, (C) 1α-olefin and 2-glycidyl methacrylate and/or or copolymer with glycidyl acrylate 0.
A resin composition containing 5 to 20 parts by weight.