JPS5934731B2 - resin composition - Google Patents

Description

Detailed Description of the Invention The present invention provides a single tapered block of vinyl cyanide and/or methacrylic acid ester-conjugated diene-aromatic vinyl copolymer resin (hereinafter referred to as a multicomponent copolymer), aromatic vinyl, and conjugated diene. The present invention relates to a thermoplastic resin composition comprising a copolymer (hereinafter referred to as a block copolymer), particularly a resin composition with low surface gloss.

Multi-component copolymers are used in a variety of applications because of their excellent moldability, impact resistance, chemical resistance, and good surface gloss.

However, depending on the intended use, not all of these properties are necessarily required, and it may be desirable to have a matte surface on the surface of the molded product without degrading other physical properties. be.

Fields where such matting is required include camera and suitcase housings and automobile interior parts. Methods for making a multi-component copolymer matte include applying texture or a leather pattern to the surface of the mold or roll, or sandblasting the molded product or painting it matte, but the former method is not suitable. In the case of the latter, a sufficient matting effect cannot be obtained, and in the case of the latter, there is a problem of secondary processing cost, and in the case of painting, there is a problem of chemical deterioration due to thinner.

Furthermore, a method of adding an inorganic filler such as talc, heavy calcium carbonate, silica, etc. to the multi-component copolymer to roughen the surface of the molded product and make it matte, or a method using Japanese Patent Publication No. 48-383 or Japanese Patent Publication No. 48
There is a method of adding an organic filler as shown in No. 10628. However, in either method, the matting effect is poor and the impact strength and moldability of the multi-component copolymer are reduced. As a result of intensive research into a method for matting a multi-component copolymer without causing a decrease in the physical properties of the multi-component copolymer, the present inventors have found that when an appropriate amount of a single tapered block copolymer is blended into a multi-component copolymer, It was discovered that a good matting effect can be obtained without deteriorating the physical properties, and the present invention was completed.

That is, the present invention provides a semi-tapered block copolymer of an aromatic beer-conjugated diene containing 50 to 90% by weight of a conjugated diene to 100 parts by weight of a vinyl cyanide and/or methacrylate ester-conjugated diene-aromatic vinyl copolymer resin. The present invention relates to a thermoplastic resin composition containing 3 to 20 parts by weight of a polymer.

The multi-component copolymer used in the present invention may be produced by any known method and is not particularly limited.

Furthermore, vinyl cyanide monomers used include acrylonitrile, methacrylonitrile, etc., and methacrylic acid esters include methyl methacrylate, ethyl methacrylate, etc., and they can be used in combination.
Conjugated diene compounds include 1,3-butadiene, 1,3
-pentadiene, isoprene, 1,3-hexadiene, etc., among which 1,3-butadiene and isoprene are generally used. As the aromatic vinyl compound, styrene, α-methylstyrene, 0-methylstyrene, P-ethylstyrene, 1,3-dimethylstyrene, vinylnaphthalene, etc. are used singly or in combination.

On the other hand, the semi-tapered block copolymer used in the present invention is an aromatic diene-conjugated diene block copolymer containing 50 to 90% by weight of a conjugated diene which has been anionically polymerized using an organolithium compound as a catalyst. If the content of conjugated diene in the single-tapered block copolymer is less than 50% by weight, the compatibility with the multicomponent copolymer increases, so no matting effect can be expected; As the compatibility with the copolymer decreases, the impact strength decreases significantly and layer separation phenomenon occurs.

The structure of the single tapered block copolymer is represented by S-B-S.

Here, S represents a block made of aromatic vinyl, and B represents a block made of a conjugated diene. It is a polymer. For example, a single tapered block copolymer is produced by first forming a block consisting of an aromatic vinyl monomer using an organic alkali metal compound as a catalyst, and then adding a mixture of aromatic vinyl and a conjugated diene to form a block consisting of a conjugated diene monomer. After forming a block consisting of the same and further forming a tapered portion, a block consisting of an aromatic vinyl monomer can be manufactured.

The aromatic vinyl and conjugated diene of the semi-tapered block copolymer in the present invention can be the same as the aromatic vinyl and conjugated diene used in the multi-component copolymer; Preferably the same one.

The ratio of the single tapered block copolymer blended into the multi-component copolymer in the present invention is in the range of 3 to 20 parts by weight per 100 parts by weight of the multi-component copolymer, and less than 3 parts by weight may cause a matting effect. If the amount exceeds 20 parts by weight, the rigidity decreases and the appearance becomes noticeably rough, resulting in an undesirable molded product.

As explained above, the resin composition according to the present invention is a resin composition that can change the gloss of the resin over a wide range without changing its physical properties such as impact strength and moldability, and has a good matting effect. It is used for automobile interior parts, miscellaneous goods, camera and suitcase housings. The present invention will be further explained in detail below with reference to Examples, but the scope of the present invention is not limited thereby.

Example 1 A single tapered block copolymer was prepared in a nitrogen atmosphere using cyclohexane as a polymerization solvent and Sec. It was produced by an anionic polymerization method using butyllithium.

12k of cyclohexane in an autoclave with an internal volume of 201
Next, 0.45 kg of styrene was added at once with stirring and dissolved in cyclohexane.

Maintaining the autoclave internal temperature at 25°C, Sec.
．． 80 mmol of a cyclohexane solution of butyllithium was added, and the internal temperature was raised to 60°C. After about 60 minutes, the polymerization of styrene was completed, and a mixture of 0.45 kg of styrene and 2.1 kg of butadiene was charged into the autoclave at once.
After a further 60 minutes, the polymers were precipitated from the polymer solution containing these polymers by a steam stripping method to obtain a powdery polymer. Analysis of the single-tapered block copolymer thus obtained revealed that it contained 70% by weight of polyptadiene, and viscoelasticity measurements confirmed that it was a single-tapered block copolymer.

Next, commercially available acrylonitrile-butadiene-styrene copolymer resin (trade name, Denka ABSGR-1000) 10
The amount of the single tapered styrene-butadiene block copolymer obtained by the above method was added to 0 parts by weight as shown in Table 1, and mixed in a pen shell mixer.

By melt-kneading this mixture in a 40m/mφ extruder manufactured by Nakatani Kikai, a pellet-shaped matte ABS is produced.
produced resin.

This pellet-shaped erased ABS resin is made by Meiki SJ.
Predetermined test pieces were molded using a -35A injection molding machine, and their Izot impact strength, melt flow, surface gloss, and tensile strength were measured. Table 1 shows the results of each physical property. Comparative Example 1 Acrylonitrile-butadiene-styrene copolymer resin (
In the same manner as in Example 1, 30 parts by weight of the single tapered styrene-butadiene block copolymer produced in Example 1 was added to 100 parts by weight (trade name: Denka ABSGR-1000). Evaluation of physical properties and table
Shown in 1.

Example 2 The single tapered styrene-butadiene block copolymer used in Example 1 was added to a commercially available acrylonitrile-butadiene-styrene-d/methylstyrene copolymer resin (trade name, Denka ABSHH) as shown in Table 2. The physical properties were evaluated after extrusion and molding in the same manner as in Example 1 by adding a small amount of

Table 2 shows the results of each physical property. Comparative Example 2 Acrylonitrile-butadiene-styrene-alpha/methylstyrene copolymer resin (trade name, Denka ABSHH) 10
The single tapered type styrene-butadiene block copolymer produced in Example 1 was not included and 30 parts by weight was added to 0 parts by weight, and the physical properties were evaluated in the same manner as in Example 1. Table 12 shows the results. show.

Example 3 The polymerization method was the same as in Example 1, but the composition ratio of styrene and butadiene in the mixture of styrene-butadiene, which was added after the polymerization of the styrene initially charged was completed, was varied, and the composition ratio of styrene and butadiene was changed.
A semi-tapered styrene-butadiene copolymer as shown in No. 3 was produced.

A commercially available acrylonitrile-butadiene-styrene copolymer resin (trade name: Denka ABSGR-2000) was prepared in the same manner as in Example 1.
) 10 parts by weight per 100 parts by weight, and after extrusion and molding, the physical properties were evaluated as shown in Table 3. Comparative Example 3 The same polymerization method as in Example 1 was used, but the composition ratio of styrene and butadiene in the mixture of styrene-butadiene, which was added after the polymerization of the styrene initially charged was completed, was varied, and the composition ratio of styrene and butadiene was changed.
A single tapered styrene-butadiene copolymer as shown in No. 3 was produced.

The thus obtained PROC copolymer was added in the same manner as in Example 1 to 100 parts by weight of commercially available Denka ABSGR-2000, and its physical properties were evaluated after extrusion and molding, which are also shown in Table 3. Comparative Example 4 Clear cut type block copolymer without tapered part (
Denka AB sells the product (product name: Califrex 1102).
The physical properties were evaluated after extrusion and molding in the same manner as in Example 1 by adding 10 parts by weight to 100 parts by weight of SGR-2000. Table 4
Shown below.

Example 4 The block copolymer used in Example 1 was added to a commercially available methyl methacrylate-butadiene-styrene copolymer resin (trade name: Dencastyrol TP-R) in amounts as shown in Table 5. Example 1 Physical properties were evaluated after extrusion and molding in the same manner as above.

Claims (1)

[Claims] 1 Vinyl cyanide and/or methacrylate ester-
To 100 parts by weight of conjugated diene-aromatic vinyl copolymer resin,
Aromatic vinyl-conjugated diene semi-tapered block copolymer containing 50 to 90% by weight of conjugated diene
A low gloss resin composition comprising parts by weight.