JPH0222356A - Thermoplastic resin composition having low gloss - Google Patents

Abstract

PURPOSE:To obtain a commposition having good matte appearance and excellent thermal and mechancal properties by compounding an ABS resin, a polyamide resin and a polyglutarimide resin. CONSTITUTION:The objective resin composition can be prduced by compounding (A) 1-90 pts.wt. of an ABS resin having a graft ratio of 20-80% and produced by the graft-polymerization of an aromatic vinyl monomer, a vinyl cyanide monomer and, asnecessary, other copolymerizable monomer to a diene rubber having an average particle diameter of 0.1-3mum, (B) 1-80 pts.wt. of a polyamide resin and (C) 1-60 pts.wt. of a polyglutarimide resin having an imide content of 30-80mol% and a melt-viscosity of 6,000-12,000 poise at 270 deg.C (at a shearing rate of 500cm<-1>). The sum of the components A, B and C is 100 pts.wt.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to low gloss thermoplastic resin compositions.

[Prior Art] Demand for thermoplastic resins is rapidly increasing because they have characteristics such as lightness, moldability, and electrical insulation properties, and their applications in the field of metal replacement are also expanding significantly.

In addition, in recent years, research and development of polymer alloys has been actively conducted with the aim of obtaining highly functional polymers that cannot be obtained with a single polymer by mixing two or more polymers with different properties. It is being said. For example, regarding polyamide resin, there is a method to improve its shortcomings, impact resistance, while taking advantage of its advantages (abrasion resistance, chemical resistance, etc.) (Japanese Patent Application Laid-open No. 57-149353). There are methods for improving the deformation temperature and molding shrinkage rate (Japanese Patent Laid-Open No. 59-25836), and many alloying techniques have been developed and put into practical use.

On the other hand, in fields such as automobile interior parts and household electrical appliance parts, there is a demand for molded products with less glossy surfaces due to safety issues such as blinding and to create a sense of calm. is increasing.

Common matting methods include applying texture to the surface of the mold, applying a liquid matting agent to the surface of the molded product, and mixing an inorganic filler with the resin (Japanese Patent Publication No. 49-4458
2), a method of adding a rubbery polymer after polymerization (Japanese Patent Publication No. 44-25897, Japanese Patent Publication No. 48-24034)
No. 1, JP-A-59-89346, JP-A-60-
18536 and Japanese Patent Publication No. 62-59725), a method of adding a rubber-modified thermoplastic resin (Japanese Patent Application Laid-open No. 54-1988)
-142259, JP 56-133353, JP 59-161459, JP 60-202
143, and Japanese Patent Laid-Open No. 101616/1983).

[Problems to be Solved by the Invention] The method of improving the mold surface has problems with expensive mold production costs and security management, and a sufficient matting effect cannot be achieved. Furthermore, in the method of painting, the painting process is costly and there is a risk that the resin surface may deteriorate due to the solvent. Mixing an inorganic filler has the disadvantage that the mechanical properties of the resin, particularly the impact strength, are greatly reduced, and the appearance of the molded product is poor.

In addition, the method of adding a rubbery polymer causes a decrease in heat resistance and rigidity, and also causes the gloss not to disappear uniformly (uneven gloss).

The method of adding a rubber-modified thermoplastic resin has problems such as the degree of matting varying depending on molding conditions.

An object of the present invention is to provide a low-gloss thermoplastic resin composition that has a matte appearance, excellent thermal and mechanical properties, and has a surface that is free from glare and has a textured appearance.

[Means for Solving the Problems] The present inventors have made extensive studies to solve the above problems, and as a result, have arrived at the present invention.

That is, in the present invention, the average particle diameter of the graft rubber containing (A) is 0.1 to 3 μm.
ABS resin 1 whose graft ratio is 20 to 80%
~90 parts by weight (B) 1 to 80 parts by weight of polyamide resin, and (C) imide content of 30 to 80 mol%, melt viscosity at 270°C of 6000 to 12000 poise (shear strength 500c)
The present invention provides a low-gloss thermoplastic resin composition comprising 1 to 60 parts by weight of a polyglutarimide resin (m-"), and the total amount of (A) to (C) is 100 parts by weight.

The ABS resin (A) used in the present invention refers to diene rubber (
b), vinyl cyanide monomer (b), aromatic vinyl monomer (c), and if necessary other copolymerizable monomers (
A graft copolymer consisting of (d), in which the monomer is graft copolymerized with the diene rubber (a), or a graft copolymer in which a part of the monomer is graft copolymerized with the diene rubber (a). It is a resin composition of a copolymer and a copolymer obtained by copolymerizing the remaining monomers.

(A) Examples of the diene rubber (a) constituting the ABS resin include polybutadiene rubber, acrinitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, polyisoprene rubber, etc. can be used alone or in combination of two or more.

In the present invention, polybutadiene and/or styrene-butadiene copolymer rubber is preferably used.

Examples of the vinyl cyanide (b) include acrylonitrile and methacrinitrile, with acrylonitrile being particularly preferred.

Examples of the aromatic vinyl (c) include styrene, α-methylstyrene, p-methylstyrene, and pt-butylstyrene. Among them, styrene and/or α-methylstyrene are preferably used.

Other copolymerizable monomers (d) include α, β-unsaturated carboxylic acid esters such as methyl methacrylate, ethyl methacrylate, t-butyl methacrylate, and cyclohexyl methacrylate, maleic anhydride, and anhydride. Examples include α,β-unsaturated dicarboxylic acid anhydrides such as itaconic acid, and imide compounds of α,β-unsaturated dicarboxylic acids such as phenylmaleimide, N-methylmaleimide, and Nt-butylmaleimide. can.

There is no particular restriction on the composition ratio of ABS resin (A), but from the viewpoint of moldability and impact resistance of the resulting thermoplastic resin composition, diene rubber (A) is used for 100 parts by weight of ABS resin. It is preferably 5 to 80 parts by weight, more preferably 15 to 75 parts by weight. Similarly, vinyl cyanide (b) is preferably 3 to 50 parts by weight, particularly preferably 5 to 45 parts by weight, and more preferably 7 to 40 parts by weight.

The aromatic vinyl (c) is preferably 10 to 90 parts by weight, particularly preferably 15 to 85 parts by weight, and more preferably 20 to 90 parts by weight.
It can be preferably used in a range of 80 parts by weight.

The average particle diameter of the diene rubber constituting the ABS resin (A) is preferably 0.1 to 3 μm, particularly 0°12 to 2.5 μm.
μm is preferred. Further, the grafting rate is preferably 20 to 80%, particularly preferably 25 to 75%.

If it is outside the above range, it will not be possible to simultaneously satisfy both the impact resistance and low gloss achievement of the resulting resin composition.

The graft ratio here represents the percentage of the weight of the grafted component/the weight of the diene rubber.

In addition, the content of diene rubber (a) in the entire thermoplastic resin composition should be 1 to
It is preferably in the range of 60% by weight, especially from 3 to 55% by weight.
% by weight, preferably in the range of 5 to 50% by weight.

There are no particular restrictions on the method for producing the ABS resin (A), and commonly known methods such as bulk polymerization, solution polymerization, bulk suspension polymerization, suspension polymerization, and emulsion polymerization can be used. Also, separately (
It is also possible to obtain the above composition by blending copolymerized resins (graft).

The polyamide resin (B) constituting the composition of the present invention is:
Polyamides obtained by ring-opening polymerization of lactams such as ε-caprolactam and ω-dodecalactam; polyamides derived from amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid;
Ethylenediamine, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2.2.4-/2,2.4-trimethylhexamethylenediamine, 1,3- and 1.4-bis(amino methyl)cyclohexane, bis(4,4'-
adipic acid, speric acid, sebacic acid, dodecanedioic acid, with aliphatic, cycloaliphatic, aromatic diamines such as aminocyclohexyl)methane, meta- and para-xylylene diamine;
1,3- and 1,4-cyclohexanedicarboxylic acid,
These include polyamide resins derived from aliphatic, alicyclic, and aromatic dicarboxylic acids such as isophthalic acid, terephthalic acid, and dimer acid, and copolymerized polyamide resins and mixed polyamide resins of these. Among these, polycaproamide (nylon 6), polyundecaneamide (nylon 11), polydodecanamide (nylon 12), polyhexamethylene adipamide (nylon 66), and copolymers containing these as components are usually used. Polyamide resins are useful.

Polyamide resin polymerization methods are usually known melt polymerization,
Solid phase polymerization and methods combining these can be employed. In addition, the degree of polymerization of polyamide resin is not particularly limited;
Any polyamide resin having a relative viscosity (measured by dissolving 1 g of polymer in 100 ml of 98% concentrated sulfuric acid and measuring at 25°C) within the range of 2.0 to 5.0 can be selected depending on the purpose.

The polyglutarimide (C) constituting the composition of the present invention is a polymer or copolymer containing a cyclic imide unit represented by the following formula (I).

(However, R, R2 and R3 in the formula each represent hydrogen or a substituted or unsubstituted alkyl group or aryl group having 1 to 20 carbon atoms.) Any chemical structure containing the above cyclic imide unit Although polyglutarimide can also be applied to the present invention, usually R1 and R2 in the cyclic imide unit are hydrogen or a methyl group, and R3 is hydrogen, a methyl group, an ethyl group, a propyl group, or a butyl group. or phenyl group is used in boat fishing. There are no particular restrictions on the method for producing polyglutarimide, but for example,
A method of forming a glutarimide ring by reacting polymethyl methacrylate with ammonia or a primary amine such as methylamine or ethylamine in an extruder, which is described in Japanese Patent No. 2-63989, is useful.

Cyclic imide unit (I) in polyglutarimide resin (C)
') content is preferably 30 to 80 mol%, and 34 to 7
6 mol% is more preferable, and 38 to 72 mol% is particularly preferable.

The melt viscosity (270°C; shear rate 500cm') is 6
000 to 12,000 poise is preferable, and 6,500 to 11
500 poise is more preferable, and 7000 to 11000 poise is particularly preferable.

When the content of cyclic imide units exceeds 80 mol%, or when the melt viscosity of the polyglutarimide resin exceeds 12,000 poise, the resulting resin has poor moldability. Furthermore, when the imide unit content is less than 30% or when the melt viscosity of the polyglutarimide resin is less than 6000 poise, the surface gloss is not sufficiently reduced and the impact resistance is also poor.

The resin composition of the present invention contains 1 to 90 parts of ABS resin (A) per 100 parts by weight of (A), (B) and (C).
Parts by weight, preferably 3 to 85 parts by weight, particularly preferably 5 parts by weight
~80 parts by weight and 1 to 80 parts by weight of polyamide resin (B), preferably 3 to 75 parts by weight, particularly preferably 5 to 70 parts by weight.
Parts by weight, and polyglutarimide resin (C) 1-60
Parts by weight, preferably 3 to 55 parts by weight, particularly preferably 5 parts by weight
Consists of ~50 multiplex parts.

If the proportion of (A) is less than 1 part by weight, the impact resistance of the molded article will be low, while if it exceeds 90 parts by weight, a satisfactory low-gloss resin will not be obtained. If the proportion of (B) is less than 1 part by weight, a satisfactory low-gloss resin cannot be obtained, while if it exceeds 80 parts by weight, the impact resistance of the resin will be poor.

Further, if the proportion of (C) is less than 14 parts by weight, uniform low gloss of the molded product cannot be achieved, and if it exceeds 60 parts by weight, molding processability is significantly deteriorated, which is not preferable.

Furthermore, the cyclic imide unit in the resin composition is preferably 3 to 40% by weight, more preferably 5 to 37% by weight, and 7 to 3% by weight.
Particularly preferred is 5% by weight.

If the cyclic imide unit exceeds 40% by weight, the molding processability of the resulting resin will be extremely poor, and if it is less than 3% by weight, sufficient low gloss will not be achieved, and the compatibility of the constituent components will be poor, resulting in poor resin moldability. It is not preferred because it has poor impact resistance.

Regarding the method for producing the thermoplastic resin composition of the present invention (7), there are no particular limitations, and generally known methods can be adopted. Namely, ABS resin (A), polyamide resin (B)
, and polyglutarimide resin (C) in the form of pellets, powder, small pieces, etc., are uniformly mixed using a high-speed stirrer, etc., and then melt-kneaded using a single-screw or multi-screw extruder with sufficient kneading capacity. Various methods can also be employed, such as melt-kneading using a Banbury mixer or a rubber roll machine. In addition, ABS resin (A) and polyamide resin (B), polyamide resin (B), polyamide resin (B) and polyglutarimide resin (C), ABS resin (A) and polyglutarimide resin (C), etc. It is also possible to pre-knead and then adjust the blending ratio to a predetermined ratio and knead.

The thermoplastic resin composition of the present invention comprises ABS resin (A), polyamide resin (B), and polyglutarimide resin (
In addition to C), polystyrene (ps), styrene/acrylonitrile copolymer (SAN), polymethyl methacrylate (PMMA), styrene/methyl methacrylate/acrylonitrile copolymer, α-methylstyrene/ Acrylonitrile copolymer, α-methylstyrene/styrene/acrylonitrile copolymer, α-methylstyrene/methyl methacrylate/acrylonitrile copolymer, p-methylstyrene/acrylonitrile copolymer, styrene/N-phenylmaleimide copolymer Vinyl polymers such as methacrylic acid resin-butadiene-styrene terpolymer (MBS) resin, ABS resin, AAS
Resin, polycarbonate, polybutylene terephthalate, polyethylene terephthalate and other thermoplastic resins may be appropriately mixed, polyethylene, polypropylene, ethylene/propylene copolymer, ethylene/butene-1 copolymer, ethylene/propylene/dicyclopentadiene copolymer. Polyolefin rubbers such as ethylene/propylene 15-ethylidene 2-norbornene copolymer, ethylene/propylene/1,4-hexadiene copolymer, ethylene/vinyl acetate copolymer and ethylene/butyl acrylate copolymer It is also possible to adjust the physical properties and characteristics to more desirable properties by appropriately mixing them.

Depending on the purpose, pigments, dyes, glass fibers, metal fibers,
Reinforcing agents and fillers such as metal flakes and carbon fibers, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, lubricants, plasticizers, antistatic agents, and flame retardants can be added.

[Examples] In order to explain the present invention more specifically, Examples and Comparative Examples will be described below, but these Examples do not limit the present invention. Here, unless otherwise specified, "parts" represent parts by weight, and "%" represent weight %. The imide content of the polyglutarimide resin was calculated from the integral ratio by measuring the 'H-NMR spectrum at 120°C in a DMSO solvent. In addition, after the finally obtained resin composition was molded by injection molding, various physical properties were measured by the following test methods.

Izotsu impact strength: ASTM D-25 6 inch notched 23℃ (kgcm/cm) Heat distortion temperature: A
STM D-648 % inch with notch 18.8kg/cJ load (°C) Surface gloss: Suga Test Instruments Digital angle gloss meter 0GV-5
Using D, the surface reflected light of the textured surface of the molded product was measured at an incident angle of 60°C.

Surface appearance: The molded product was visually evaluated.

◎Very good O Good Δ Slightly poor
40 parts of a monomer mixture consisting of 70% styrene and 30% acrylonitrile was emulsion polymerized in the presence of 60 parts (in terms of solid content) (5μ, gel content 80%). The obtained graft copolymer was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered, and dried to prepare a powdery graft copolymer (A-1). (Graft rate 45%) A-2: Polybutadiene latex 60 used in A-1
40 parts of a monomer mixture consisting of 65% styrene, 30% acrinitrile, and 5% methyl methacrylate was emulsion polymerized in the presence of 5% (solid content) and treated in the same manner as A-1 to obtain a powdery graft. A copolymer (A-2) was prepared. (Graft rate 50%) A-3 = Polybutadiene latex (rubber particle size 0.0
Emulsion polymerization of 35 parts of a monomer mixture consisting of 70% styrene and 30% acrylonitrile was carried out in the presence of 65 parts (solid content equivalent) of gel content 80%), and the same treatment as A-1 was carried out to form a powder. A graft copolymer (A-3) was prepared. (Graft rate 36%) Reference example 2 (Production of polyglutarimide resin (C)) C-
1: Pellets of polymethyl methacrylate are charged into an extruder together with ammonia, and extrusion is performed at a resin temperature of 270°C while degassing the generated gas from an exhaust port attached to the extruder, and polyglutarimide (C-1: An imide content of 38 mol % and a melt viscosity of 11,000 poise was produced.

C-2: Polyglutarimide (C-2: imide content 49 mol%, melt viscosity 1
0000 poise) was produced.

Examples 1 to 8, Comparative Examples 1 to 5 The ABS resin (A) and polyglutarimide resin (C) manufactured in Reference Example 1.2 and the polyamide resin (B) were CM-1010 (Nylon 6 manufactured by Toshishi ■). : B-1
) or CM-3001 (east side type nylon 66:
B-2) were mixed in a Henschel mixer at the compounding ratio shown in Table 1, and then extruded using a 40 mmφ extruder at an extrusion temperature of 270°C to pelletize each pellet. Each test piece was prepared by injection molding at a mold temperature of 80°C2.
We evaluated its physical properties. Table these results.
Shown in 1.

The following is clear from the following margin examples and comparative examples. That is, all of the resin compositions obtained according to the present invention have uniformly reduced gloss on the surface of the molded product, and have a good balance between impact resistance and heat resistance.

In contrast, those that do not contain polyamide resin (B) (
In Comparative Example 2), the reduction in surface gloss was insufficient. Also,
In the case where polyglutarimide resin (C) is not blended (Comparative Example 1), the ABS resin (A) has a small rubber particle size (Comparative Example 3), and the ABS resin (A) is not blended (Comparative Example 4). In addition to insufficient reduction in surface gloss, impact resistance is also poor. Furthermore, when the composition is out of the scope of the present invention (Comparative Example 5), the molding processability is markedly inferior and the reduction in surface gloss is insufficient.

[Effects of the Invention] The thermoplastic resin composition obtained by the present invention shows a remarkable improvement in surface gloss reduction without impairing the mechanical properties of molded products, and is suitable for use in automobile interior parts and exteriors of household electrical appliances. It is suitable as a molding material for parts, etc.

This effect is achieved by A
This effect can only be achieved by mixing BS resin (A), polyamide resin (B), and polyglutarimide resin (C) having a specified imide content and melt viscosity.

Claims (1)

[Scope of Claims] (A) A diene rubber having an average particle size of 0.1 to 3 μm, containing an aromatic vinyl monomer, a vinyl cyanide monomer, and, if necessary, other copolymerizable monomers. 1 to 90 parts by weight of ABS resin with a graft ratio of 20 to 80% obtained by graft polymerization, (B) 1 to 80 parts by weight of a polyamide resin, and (C) an imide content of 30 to 80 mol% and melted at 270 ° C. It consists of 1 to 60 parts by weight of a polyglutarimide resin having a viscosity of 6,000 to 12,000 poise (shear rate of 500 cm^-^1), and the total amount of (A), (B) and (C) is 10 parts by weight.
0 parts by weight of a low gloss thermoplastic resin composition.