JP3532280B2 - Thermoplastic resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ABS resin composition which is excellent in impact resistance and workability and which hardly causes delamination during injection molding.

[0002]

2. Description of the Related Art ABS resins are widely used in the fields of automobile parts, electric / electronic products, etc. because they are excellent in rigidity and heat distortion resistance. ABS resins are typically obtained by grafting a styrenic monomer and another monomer such as acrylonitrile onto a rubbery polymer, and various resins are known depending on the type and usage ratio of the rubbery polymer or monomer. ing. Further, many of them are required to have further improved impact resistance and workability. In order to achieve such an object, it is already known that it is effective to blend an ethylene / carbon monoxide / (meth) acrylic acid ester copolymer with an ABS resin (for example, JP-A-3-287653). No. 5,125,253, and No. 6-116469.

[0003]

However, in such a blend, the compatibility of the two is not necessarily sufficiently large, and therefore when a large amount of the copolymer is blended or a large product is manufactured by injection molding. In some cases, delamination was sometimes observed in the molded product.

Therefore, the present inventors have conducted studies to prevent the delamination phenomenon without substantially impairing the properties such as rigidity, heat distortion resistance, impact resistance and workability of the blend system. . As a result, they have found that the method of adding a small amount of polyester elastomer is very effective, and arrived at the present invention. Therefore, an object of the present invention is to provide an ABS resin composition which is excellent in rigidity, thermal deformation resistance, impact resistance, and workability and which hardly causes delamination.

[0005]

Means for Solving the Problems The present invention comprises: ABS resin (A) 85 to 99 parts by weight; ethylene; carbon monoxide;
Weight ratio of (meth) acrylic acid ester copolymer (B-1) to polyester elastomer (B-2) 40/60 ~
It relates to a thermoplastic resin composition comprising 1 to 15 parts by weight of component (B) consisting of 90/10. A used in the present invention
The BS resin (A) is produced from a rubbery polymer, a styrene monomer and another vinyl monomer, and can be obtained by a known method such as a graft method or a graft blend method. Examples of the rubbery polymer include butadiene rubber, styrene / butadiene copolymer rubber,
Acrylonitrile / butadiene copolymer rubber, ethylene /
Representative examples include propylene copolymer rubber, ethylene / propylene / non-conjugated diene copolymer rubber, and acrylic rubber.

Styrene-based monomers include styrene,
One or more of vinyltoluene, α-methylstyrene, monochlorostyrene, dibromostyrene and the like can be used. Further, as the other vinyl monomer,
Acrylonitrile, acrylonitrile such as methacrylonitrile, unsaturated carboxylic acid ester such as methyl acrylate, ethyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, diethyl maleate, acrylic acid, methacrylic acid, maleic anhydride Representative examples include unsaturated carboxylic acids such as and maleimides such as N-methylmaleimide, N-ethylmaleimide, and N-phenylmaleimide.

As these ABS resins, those having a rubber polymer content of 5 to 35% by weight, particularly 10 to 30% by weight are preferable from the viewpoint of rigidity and heat distortion resistance. Further, the ratio of the styrene monomer as the hard resin component to the other monomer is 40 to 90% by weight, particularly 40 to 80% by weight, whereas the latter is 10 to 60% by weight, particularly 20 to 60% by weight.
It is desirable that they are copolymerized in a ratio such that

Specific examples of the combination of the monomer components constituting the ABS resin include, for example, acrylonitrile / butadiene / styrene, acrylonitrile / butadiene / styrene / α-methylstyrene, acrylonitrile / butadiene / styrene / N-phenylmaleimide, acrylonitrile / For example, butadiene / styrene / methyl methacrylate, which are obtained by grafting a styrene-based monomer and other vinyl monomer in the presence of polybutadiene rubber or styrene / butadiene copolymer rubber, or such a grafting method. The product is further copolymerized by a graft blending method or the like obtained by blending a copolymer of a styrene-based monomer and another vinyl monomer.

The ethylene / carbon monoxide / (meth) acrylic acid ester copolymer (B-1) used in the present invention is usually 30 to 94% by weight of ethylene, preferably 5% by weight.
0-85% by weight, carbon monoxide 3-30% by weight, preferably 5-20% by weight, (meth) acrylic acid ester 3
It is desirable that the copolymer is copolymerized in a proportion of ˜50 wt%, preferably 5-40 wt%. Such a copolymer is
Similar to the production of polyethylene by the high pressure method, it can be obtained by randomly copolymerizing each component using a radical initiator under high temperature and high pressure. Such copolymers and their production methods are already well known.

The (meth) acrylic acid ester in the copolymer means an ester of acrylic acid or methacrylic acid. Specific examples thereof include methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, isobutyl methacrylate and the like.

As such a copolymer, 190 ° C.,
Melt flow rate at 2160g load is 0.1
It is preferable to use one having a viscosity of 200 g / 10 minutes, particularly about 1 to 50 g / 10 minutes.

The polyester elastomer (B-2) used in the present invention has polyester having aromatic dicarboxylic acid and glycol as main components as a hard segment and polyoxyalkylene glycol as a soft segment (polyester / polyether elastomer). Or a block copolymer having an aliphatic polyester as a soft segment (polyester / polyester elastomer).

The aromatic dicarboxylic acid constituting the hard segment is preferably terephthalic acid or terephthalic acid and isophthalic acid, some of which are phthalic acid,
It may be substituted with 2,6-naphthalenedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid or the like. Moreover, if it is a small amount, it may be substituted with an aliphatic dicarboxylic acid.

As the glycol constituting the hard segment, ethylene glycol, 1,3-propanediol, 1,4-tetramethylene glycol, 1,6-hexamethylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, 1, Glycols having a molecular weight of about 200 or less, such as 3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol, and particularly those having ethylene glycol and / or tetramethylene glycol as a main component are preferable.

Examples of the polyoxyalkylene glycol which can be used as the soft segment of the polyester / polyether elastomer include polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxyethylene / polyoxypropylene glycol and the like. be able to.
These have a molecular weight of about 400 to 6000, especially 600.
It is preferably about 5,000. Such a polyester elastomer contains a polyoxyalkylene glycol unit in an amount of 5 to 80% by weight, particularly 15 to 70% by weight, and has a melting point of 100 to 220 ° C., especially 1
20 ~ 200 ℃, 230 ℃, 2160g
Melt flow rate under load 0.1-1000g
It is preferable to use / 10 minutes, especially 1 to 100 g / 10 minutes. As such a polyester elastomer, those commercially available under the trade name of Hytrel, Perprene, etc. can be used.

The polyester / polyester elastomer has an aliphatic polyester unit such as polyε-caprolactone or polybutylene adipate in place of the polyoxyalkylene glycol unit of the soft segment in the above polyester / polyether elastomer. Those having similar properties are preferably used. More specifically, for example, a commercially available product under the trade name of Grelax can be exemplified.

In the present invention, the ABS resin (A), the copolymer (B-1) and the polyester elastomer (B-2) are used in a proportion of ABS based on the total amount of 100 parts by weight. The resin (A) is 85 to 99.
The amount is preferably 85 to 98 parts by weight, and the total amount of (B-1) and (B-2) is 1 to 15 parts by weight, preferably 2 to 15 parts by weight. Use ratio of ABS resin is 8
When the amount is less than 5 parts by weight, excellent properties of the resin, such as rigidity and heat distortion resistance, are impaired. The ratio of the component (B-1) to the component (B-2) is slightly different depending on the use ratio of the component (B-1) and the component (A), but is 40/60 to 90/10 by weight, preferably 40
It is about / 60 to 80/20. If the amount of the component (B-2) used is too small, the delamination tendency is not significantly improved. However, since it is not economical to use the component too much, it is preferable to use the above proportion. .

Various additives may be added to the composition of the present invention as required. As such additives, for example, antioxidants, weathering stabilizers, ultraviolet absorbers,
Examples thereof include pigments, dyes, lubricants, antistatic agents, flame retardants and inorganic fillers. Also, if necessary, other polymers can be blended.

[0019]

EFFECTS OF THE INVENTION According to the present invention, it is possible to provide an ABS resin composition which is excellent in rigidity, heat distortion resistance, impact resistance and workability and has a reduced tendency of delamination even in injection molding. Therefore, the allowable range of quality design is widened, and a large-sized molded product having good physical properties can be easily manufactured. Taking advantage of these features, not only injection molding but also extrusion molding and various other molding methods can be used to process automobile parts, electronic / electrical products, daily necessities and the like.

[0020]

The present invention will be described in detail below with reference to examples. The raw material resins used in Examples and Comparative Examples are shown in Table 1.
It is as follows.

[0021]

[Table 1] Raw materials used

The molding and measurement of the test pieces for evaluation of physical properties were performed under the following conditions and methods. (1) Molding of test pieces for physical property evaluation Composition pellets obtained by melt-kneading were injection-molded by an injection molding machine at a cylinder temperature of 240 ° C. and a mold temperature of 60 ° C. to measure a 2 mm thick square plate and Izod impact strength. A test piece was prepared.

(2) Izod impact strength Using injection molded test pieces having a thickness of 3.2 mm and a thickness of 6.4 mm, V notches were formed, and 2 according to ASTM D256.
It was measured at 3 ° C.

(3) MFR (melt flow rate) According to JIS K7210, the measurement temperature was 240 ° C. and 270 ° C., and the load was 5 kg.

(4) Compatibility (Evaluation of Delamination Property of Molded Article) A 2 mm thick square plate molded by injection molding was bent several times,
The condition of the bent portion was evaluated according to the following three grades. ◯: Does not cut even after bending several times (low peeling of bamboo skin) Δ: Does not cut after bending (bamboo peel peeling is observed) ×: Cuts after bending once (bamboo peel peeling) Many)

Example 1 Preparation of Component B 80 parts by weight of ethylene / carbon monoxide / n-butyl acrylate copolymer shown in Table 1 and polyester elastomer 2
0 parts by weight and 30 mmφ twin-screw extruder (rotating in the same direction) (L
/ D = 25) and melt-kneaded at 220 ° C. to obtain a component B composition.

Preparation and Evaluation of ABS Composition 90 parts by weight of ABS resin shown in Table 1 and 10 parts by weight of the component B were melt-kneaded at 220 ° C. using a 40 mmφ single screw extruder (L / D = 28). Various physical properties were measured using the obtained ABS resin composition pellets or test pieces obtained by injection molding from the pellets. Table 2 shows the composition of the composition, and Table 3 shows the results of measurement of physical properties.

[Example 2] An ABS resin composition was prepared in the same manner as in Example 1 except that the composition of component B was changed to B-1 / B-2 = 60/40 in Example 1, and the physical properties thereof were prepared. Was measured. The results are shown in Table 3.

[Examples 3 to 4] ABS having the composition shown in Table 2 was prepared in the same manner as in Examples 1 to 2 except that the polyester elastomer shown in Table 1 was used as the polyester elastomer.
A resin composition was prepared and its physical properties were measured. The results are shown in Table 3.
Shown in.

[Comparative Example 1] The physical properties of the ABS resin containing no component B were measured in the same manner as in Example 1. The results are shown in Table 3.

[Comparative Example 2] Without blending the polyester elastomer, only the ethylene / carbon monoxide / n-butyl acrylate copolymer was blended into the ABS resin as the B component,
Physical properties were measured in the same manner as in Example 1. The results are shown in Table 3.

[Examples 5 to 8] A having the composition shown in Table 2 was prepared in the same manner as in Examples 1 to 4 except that the ABS resin was used as the component A.
A BS resin composition was prepared and its physical properties were measured. The results are shown in Table 3.

[Comparative Example 3] The physical properties of the ABS resin containing no component B were measured in the same manner as in Example 1. The results are shown in Table 3.

[Comparative Example 4] Without blending the polyester elastomer, only the ethylene / carbon monoxide / n-butyl acrylate copolymer was blended into the ABS resin as the B component,
Physical properties were measured in the same manner as in Example 1. The results are shown in Table 3.

As is clear from Table 3, according to the present invention, a composition having improved impact resistance and fluidity of ABS resin can be obtained. Further, as is clear from comparison with Comparative Examples 2 and 4, the composition obtained by the present invention is a composition in which an ethylene / carbon monoxide / (meth) acrylic acid ester copolymer alone is blended with an ABS resin. Compared with the above, the compatibility between the ABS resin and the modifier is excellent, and it is effective in preventing the delamination phenomenon of the molded product.

[0036]

[Table 2] Composition of formulation E / CO / nBA: Ethylene / carbon monoxide / n-butyl acrylate copolymer

[0037]

[Table 3] Physical properties of the compound

Continuation of front page (51) Int.Cl. ⁷ Identification code FI B29K 55:02

Claims (2)

(57) [Claims] 1. An ABS resin (A) in an amount of 85 to 99 parts by weight, an ethylene / carbon monoxide / (meth) acrylic acid ester copolymer (B-1) and a polyester elastomer (B).
-2 ) a thermoplastic resin composition comprising 1 to 15 parts by weight of component (B) having a weight ratio of 40/60 to 90/10 . 2. An injection molded product comprising the thermoplastic resin composition according to claim 1.