JPH0627239B2 - Low gloss thermoplastic resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a low-gloss thermoplastic resin composition.

[Prior Art] Demand for thermoplastic resins is rapidly increasing because they have characteristics such as lightness, molding processability, and electrical insulation properties, and their use in the field of metal substitution is greatly expanding.

In addition, research and development of polymer alloys aiming at obtaining highly functional polymers that cannot be obtained by a single polymer by actively mixing two or more polymers having different properties have been actively conducted in recent years. It is being appreciated. For example, regarding a polyamide resin, a method of improving impact resistance, which is a defect, while keeping its advantages (wear resistance, chemical resistance, etc.) (JP-A-57-149353), and heat treatment under high load There is a method for improving the deformation temperature and the molding shrinkage ratio (Japanese Patent Laid-Open No. 59-25836), and many alloying techniques have been developed and put into practical use.

On the other hand, in the field of automobile interior parts, household electrical equipment parts, etc., there is a demand for products with reduced gloss on the surface of molded products for the purpose of giving a feeling of calmness, etc. Is increasing.

As a general matting method, the surface of the mold is textured, the surface of the molded article is coated with a liquid matting agent, and the inorganic filler is mixed with the resin (Japanese Patent Publication No. 49-4458).
No. 2), a method of adding a rubbery polymer after polymerization (Japanese Patent Publication No. 44-25897, Japanese Patent Publication No. 48-24034).
JP-A-59-89346, JP-A-60-
No. 18536 and Japanese Patent Publication No. 62-59725), and a method of adding a rubber-modified thermoplastic resin (Japanese Patent Laid-Open No. Sho 5).
JP-A-4-142259, JP-A-56-133353, JP-A-59-161459 and JP-A-60-20.
2143 and JP-A-62-101616).

[Problems to be Solved by the Invention] In the method by improving the die surface, there are problems of expensive die manufacturing cost and security control, and sufficient matting effect cannot be achieved. Further, in the method of coating, the coating process is costly and there is a risk of deterioration of the resin surface due to the solvent. The mixing of the inorganic filler has a drawback that the mechanical properties of the resin, particularly the impact strength, are significantly lowered, 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 further causes the gloss not to disappear uniformly (glossiness).

The method of adding the rubber-modified thermoplastic resin has a problem that the matting degree varies depending on molding conditions.

An object of the present invention is to provide a low-gloss thermoplastic resin composition having a matte appearance, excellent thermal and mechanical physical properties, and further having a surface property with a dazzling sensation without glare.

[Means for Solving the Problems] The present inventors have arrived at the present invention as a result of intensive studies to solve the above problems.

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

The ABS resin (A) used in the present invention means a diene rubber (a), a vinyl cyanide monomer (b), an aromatic vinyl monomer (c) and, if necessary, another copolymerizable monomer. A graft copolymer which is composed of a monomer (d) and in which the whole amount of the monomer is graft-copolymerized on the diene rubber (a), or a part of the monomer is graft-copolymerized on the diene rubber (a). It is a resin composition of the above graft copolymer and a copolymer obtained by copolymerizing the remaining monomers.

Examples of the (A) diene rubber (a) that constitutes the ABS resin include polybutadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, and polyisoprene rubber. Alternatively, two or more kinds can be used in combination.

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

Examples of vinyl cyanide (II) include acrylonitrile and methacrylonitrile, with acrylonitrile being preferred.

Examples of the aromatic vinyl (c) include styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene and the like. Above all, styrene and /
Alternatively, α-methylstyrene is preferably used.

As other copolymerizable monomer (d), α, β-unsaturated carboxylic acid esters such as methyl methacrylate, ethyl methacrylate, -t-butyl methacrylate, cyclohexyl methacrylate, maleic anhydride, and anhydrous Α, β-unsaturated dicarboxylic acid anhydrides such as itaconic acid, imide compounds of α, β-unsaturated dicarboxylic acids such as N-phenylmaleimide, N-methylmaleimide, Nt-butylmaleimide, etc. You can

The composition ratio of the ABS resin (A) is not particularly limited, but with respect to 100 parts by weight of the ABS resin, the diene rubber (a) is preferable in terms of molding processability and impact resistance of the obtained thermoplastic resin composition. The amount is preferably 5 to 80 parts by weight, more preferably 15 to 75 parts by weight. Similarly, vinyl cyanide (II) is preferably 3 to 50 parts by weight, particularly 5 to 45 parts by weight, and further 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 further 20
It can be preferably used in the range of ˜80 parts by weight.

The diene rubber constituting the ABS resin (A) has an average particle size of preferably 0.1 to 3 μm, and particularly 0.12 to 2.5.
μm is preferred. The graft ratio is preferably 20 to 80%, particularly preferably 25 to 75%.

When the amount is out of the above range, both impact resistance and low gloss achievement of the obtained resin composition cannot be satisfied at the same time.

Here, the graft ratio represents the percentage of the weight of the grafted component / the weight of the diene rubber.

Further, the content of the diene rubber (a) in the total thermoplastic resin composition is 1 to 1 from the balance of impact resistance and rigidity of the molded product.
It is preferably in the range of 60% by weight, particularly 3 to 55.
It is preferably in the range of 5% by weight, more preferably 5 to 50% by weight.

The method for producing the ABS resin (A) is not particularly limited, and commonly known methods such as bulk polymerization, solution polymerization, bulk suspension polymerization, suspension polymerization, and emulsion polymerization can be used. It is also possible to obtain the above composition by blending separately (grafted) copolymerized resins.

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 (aminomethyl) ) Cyclohexane, bis (4,4'-
Aminocyclohexyl) methane, aliphatic, alicyclic, aromatic diamines such as meta and para-xylylenediamine and adipic acid, suberic acid, sebacic acid, dodecanedioic acid,
1,3- and 1,4-cyclohexanedicarboxylic acid,
A polyamide resin derived from an aliphatic, alicyclic, or aromatic dicarboxylic acid such as isophthalic acid, terephthalic acid, or dimer acid, and a copolyamide resin or a mixed polyamide resin thereof. Of these, polycaproamide (nylon 6), polyundecane amide (nylon 11), polydodecane amide (nylon 12), polyhexamethylene adipamide (nylon 66), and copolymers containing these as the main components are usually used. Polyamide resins are useful.

The polymerization method of the polyamide resin is usually a known melt polymerization,
Solid state polymerization and methods combining these can be employed. The degree of polymerization of the polyamide resin is not particularly limited,
A polyamide resin having a relative viscosity (measured at 25 ° C. in which 1 g of polymer is dissolved in 100 ml of 98% concentrated sulfuric acid at 25 ° C.) in the range of 2.0 to 5.0 can be arbitrarily selected according to the purpose.

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

(However, each of R ₁ , R ₂ and R ₃ in the formula represents hydrogen or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or an aryl group.) Any chemical compound as long as it contains the above cyclic imide unit. Although a polyglutarimide having a structure can be applied to the present invention, usually, R ₁ and R ₂ in the above cyclic imide unit are hydrogen or a methyl group, and R ₃ is hydrogen, a methyl group, an ethyl group. Those which are propyl, butyl, or phenyl are commonly used. The method for producing polyglutarimide is not particularly limited, but for example, JP-A-52
A method of forming a glutarimide ring by reacting polymethylmethacrylate described in JP-A-63989 with ammonia or a primary amine such as methylamine or ethylamine by an extruder is useful.

The content of the cyclic imide unit (I) in the polyglutarimide resin (C) is preferably 30 to 80 mol%, and 34 to
76 mol% is more preferable, and 38 to 72 mol% is particularly preferable.

The melt viscosity (270 ° C .; shear rate 500 cm ⁻¹ ) is 60.
00 to 12000 poise is preferable, 6500 to 115
00 poise is more preferable, and 7000 to 11000 poise is particularly preferable.

When the content of the cyclic imide unit exceeds 80 mol%, or when the melt viscosity of the polyglutarimide resin exceeds 12,000 poise, the moldability of the obtained resin is poor. Further, 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 insufficiently lowered and the impact resistance is also poor.

The resin composition of the present invention contains 1 to 90 ABS resins (A) based on 100 parts by weight of (A), (B) and (C).
Parts by weight, preferably 3 to 85 parts by weight, particularly preferably 5
-80 parts by weight and polyamide resin (B) 1-80 parts by weight, preferably 3-75 parts by weight, particularly preferably 5-7.
0 parts by weight, and polyglutarimide resin (C) 1 to 6
0 parts by weight, preferably 3 to 55 parts by weight, particularly preferably 5 to 50 parts by weight.

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

Further, if the proportion of (C) is less than 1 part by weight, uniform low gloss of the molded product cannot be achieved, and if it exceeds 60 parts by weight, the moldability is remarkably deteriorated, which is not preferable.

Further, 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.
5% by weight is particularly preferred.

If the cyclic imide unit exceeds 40% by weight, the molding processability of the obtained resin is remarkably poor, and if it is less than 3% by weight, sufficient gloss reduction is not achieved, and the compatibility of the constituent components is poor, and the resin resistance is low. It is not preferable because it is inferior in impact.

The method for producing the thermoplastic resin composition of the present invention is not particularly limited, and a generally known method can be adopted.
That is, ABS resin (A), polyamide resin (B),
And a method and a Banbury method in which the polyglutarimide resin (C) is uniformly mixed in a pellet, powder, or strip state using a high-speed stirrer, and then melt-kneaded with a single-screw or multi-screw extruder having sufficient kneading ability. Various methods such as a method of melt-kneading using a mixer or a rubber roll machine can be adopted. 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 carry out preliminary kneading and then adjust the mixture ratio to a predetermined value and then knead.

The thermoplastic resin composition of the present invention contains, in addition to the ABS resin (A), the polyamide resin (B), and the polyglutarimide resin (C), polystyrene (PS),
Styrene / acrylonitrile copolymer (SAN), polymethylmethacrylate (PMMA), styrene / methyl methacrylate / acrylonitrile copolymer, α-methylstyrene / acrylonitrile copolymer, α-methylstyrene / styrene / acrylonitrile copolymer , Vinyl polymers such as α-methylstyrene / methyl methacrylate / acrylonitrile copolymer, p-methylstyrene / acrylonitrile copolymer, styrene / N-phenylmaleimide copolymer, methacrylic acid resin-butadiene-styrene ternary Copolymer (MBS) resin, AES resin, AAS
Resin, polycarbonate, polybutylene terephthalate, polyethylene terephthalate, and other thermoplastic resins are appropriately mixed, polyethylene, polyethylene propylene, ethylene / propylene copolymer, ethylene / butene-1 copolymer, ethylene / propylene / dicyclopentadiene copolymer Polyolefin rubber such as polymer, ethylene / propylene / 5-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 to more desirable physical properties and characteristics by appropriately mixing

Depending on the purpose, pigments and 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 describe the present invention more specifically, examples and comparative examples will be described below, but these examples do not limit the present invention. Here, "parts" means "parts by weight" and "%" means "% by weight" unless otherwise specified. The imide content of the polyglutarimide resin was calculated by measuring the ¹ H-NMR spectrum at 120 ° C. in a DMSO solvent and calculating the integral ratio. The finally obtained resin composition was molded by an injection molding method, and then the physical properties were measured by the following test methods.

Izod impact strength: ASTM D-256 1/2 inch with notch 23 ° C (kgcm / cm) Heat distortion temperature: ASTM D-648 1/2 inch 18.6kg / cm ² load (° C) Surface gloss: Suga Test Instruments Co., Ltd. ) Digital Deflection Angle Gloss Meter OGV-5D was used to measure the surface reflection of the grain surface of the molded product at an incident angle of 60 ° C.

Surface appearance: The molded product was visually evaluated.

◎ Very good ○ Good △ Somewhat bad × bad Reference Example 1 (Production of ABS resin (A)) A-1: Polybutadiene latex (rubber particle diameter 0.2)
40 parts of a monomer mixture consisting of 70% styrene and 30% acrylonitrile was emulsion-polymerized in the presence of 60 parts (solid content) of 5 μ, gel content 80%. The obtained graft copolymer is coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered and dried to give a powdery graft copolymer (A-1).
Was prepared. (Graft ratio 45%) A-2: Polybutadiene latex 60 used in A-1
40 parts of a monomer mixture consisting of 65% styrene, 30% acrynitrile and 5% methyl methacrylate in the presence of 10 parts (as solid content) is emulsion-polymerized and treated in the same manner as in A-1, to obtain a powder-like graft. A copolymer (A-2) was prepared. (Graft ratio 50%) A-3: Polybutadiene latex (rubber particle diameter 0.0
5 μ, gel content 80%) 35 parts of a monomer mixture consisting of 70% styrene and 30% acrylonitrile in the presence of 65 parts (as solid content) was emulsion polymerized, and the same treatment as in A-1 was performed to obtain a powder. The graft copolymer (A-3) was prepared. (Graft ratio 36%) Reference Example 2 (Production of polyglutarimide resin (C)) C-1: Polymethylmethacrylate pellets were charged into an extruder together with ammonia, and a generated gas was discharged from an exhaust port attached to the extruder. While degassing, extrusion was carried out at a resin temperature of 270 ° C. to produce polyglutarimide (C-1: imide content 38 mol%, melt viscosity 11,000 poise).

C-2: Polyglutarimide (C-2: imide content 49 mol%, melt viscosity 1 by the same method as C-1 except that methylamine was used instead of ammonia as the imidizing agent.
000 poise).

Examples 1 to 8 and Comparative Examples 1 to 5 CM-1010 (Toray Industries, Inc. nylon as ABS resin (A) and polyglutarimide resin (C) and polyamide resin (B) produced in Reference Examples 1 and 2 above 6: B-
1) or CM-3001 (nylon 6 manufactured by Toray Industries, Inc.)
6: B-2), and mixed in a Henschel mixer at the mixing ratios shown in Table 1, respectively, and then extruded by a 40 mmφ extruder at an extrusion temperature of 270 ° C., and each pelletized. Each test piece was prepared by subjecting it to injection molding under conditions of a temperature of 80 ° C. and a mold temperature of 80 ° C., and its physical properties were evaluated. These results are shown in Table-1.
Shown in.

The following is clear from the examples and comparative examples. That is, each of the resin compositions obtained by the present invention has a uniformly reduced gloss on the surface of the molded article and has a good balance between impact resistance and heat resistance. On the other hand, in the case where the polyamide resin (B) is not blended (Comparative Example 2), the reduction in surface gloss is insufficient. In addition, one containing no polyglutarimide resin (C) (Comparative Example 1), one having a small rubber particle size of ABS resin (A) (Comparative Example 3), one containing no ABS resin (A) (Comparative Example 4) In (), the surface gloss is not sufficiently reduced and the impact resistance is also poor. Further, in the case where the compounding composition is out of the range of the present invention (Comparative Example 5), the molding processability is remarkably inferior and the reduction of the surface gloss is insufficient.

[Effects of the Invention] The thermoplastic resin composition obtained by the present invention shows a marked improvement in surface low gloss without impairing the mechanical properties of the molded article, and is an exterior of automobile interior parts and household electric appliances. It is suitable as a molding material for parts and the like.

This effect is achieved with A with the specified rubber particle size and graft ratio.
It is first exhibited by mixing the BS resin (A), the polyamide resin (B), and the polyglutarimide resin (C) having the specified imide content and melt viscosity.

Claims (1)

[Claims] 1. (A) Grafting a diene rubber having an average particle diameter of 0.1 to 3 μm with an aromatic vinyl monomer, a vinyl cyanide monomer and, if necessary, another copolymerizable monomer. ABS resin 1 having a graft ratio of 20 to 80% obtained by polymerization
Polyglutar having 90 parts by weight, (B) 1 to 80 parts by weight of polyamide resin, and (C) an imide content of 30 to 80 mol% and a melt viscosity at 270 ° C. of 6000 to 12000 poise (shear rate of 500 cm ⁻¹ ). Imide resin 1-60
The total amount of (A), (B) and (C) is 10 parts by weight.
A low-gloss thermoplastic resin composition having 0 parts by weight.