JP2017066216A - Abs resin composition, and resin molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ABS resin composition that can have excellent slidability.SOLUTION: The ABS resin composition contains (X) ABS resin and (Y) graft copolymer. The main chain of the (Y) graft copolymer is composed of (A) ethylene-vinyl acetate copolymer. The side chain of the (Y) graft copolymer is composed of (B) vinyl copolymer containing (b-1) styrene and (b-2) at least one of acrylonitrile and glycidyl methacrylate. The main chains of the (Y) graft copolymer are crosslinked. With this configuration, the ABS resin composition that can have excellent slidability can be provided.SELECTED DRAWING: None

Description

  The present invention relates to an ABS resin composition that can be used as a sliding member, and a resin molded product.

  Acrylonitrile-butadiene-styrene copolymer (ABS) resin is excellent in impact resistance, heat resistance, workability and the like.

  For this reason, ABS resin is used in a wide range of fields such as automobile parts and OA equipment. On the other hand, ABS resin is expected to be applied to sliding members such as bearings because of its excellent properties as described above. However, it has higher wear resistance and dynamic friction coefficient compared to crystalline resins such as polyacetal and polyethylene. There is room for improvement in slidability. In addition, a squeaking noise may occur when the parts rub against each other.

General techniques for improving the slidability of a thermoplastic resin are disclosed in Patent Document 1 and Patent Document 2.
Patent Document 1 discloses a technique for forming a hard coat layer by applying and curing an ultraviolet curable acrylic hard coat agent on the surface of a finally formed thermoplastic resin.
Patent Document 2 discloses a technique for applying a fluorine-based or silicone-based coating composition on the surface of an ABS resin as a surface treatment agent in order to suppress or reduce the generation of itching sound.

Japanese Unexamined Patent Publication No. Hei 6-1000079 JP-A-3-217425

  However, in the techniques described in Patent Document 1 and Patent Document 2, since it is necessary to perform a coating process, work time and cost burden increase. In this respect, if the slidability of the ABS resin composition itself can be improved, excellent slidability can be obtained without performing a coating process.

  In view of the circumstances as described above, an object of the present invention is to provide an ABS resin composition and a resin molded product that can provide excellent slidability.

In order to achieve the above object, an ABS resin composition according to an embodiment of the present invention contains (X) an ABS resin and (Y) a graft copolymer.
The main chain of the (Y) graft copolymer comprises (A) an ethylene-vinyl acetate copolymer.
The side chain of the (Y) graft copolymer comprises (B) a vinyl copolymer containing (b-1) styrene and (b-2) at least one of acrylonitrile and glycidyl methacrylate.
The main chains of the (Y) graft copolymer are cross-linked.
With this configuration, it is possible to provide an ABS resin composition that provides excellent slidability.

The main chains of the (Y) graft copolymer may be crosslinked with (C) an organic peroxide.
With this configuration, the main chains of the (A) ethylene-vinyl acetate copolymer are selectively cross-linked, and the dispersibility of the (Y) graft copolymer with respect to the (X) ABS resin is improved.

When the content of the (X) ABS resin is 100 parts by weight, the content of the (Y) graft copolymer may be 1 to 25 parts by weight.
With this configuration, the slidability and appearance quality of the ABS resin composition are further improved, and the generation of squeaking noise during sliding can be further suppressed.

When the total content of (A) the ethylene-vinyl acetate copolymer, (b-1) styrene, and (b-2) acrylonitrile and at least one of glycidyl methacrylate is 100 parts by weight, The content of the (A) ethylene-vinyl acetate copolymer may be 50 to 90 parts by weight.
With this configuration, an ABS resin composition having particularly good slidability can be obtained.

  The resin molded product according to one embodiment of the present invention is obtained by molding the ABS resin composition.

  It is possible to provide an ABS resin composition and a resin molded product that can provide excellent slidability.

  Hereinafter, an embodiment of the present invention will be described.

<ABS resin composition>
The ABS resin composition according to this embodiment contains (X) ABS resin and (Y) graft copolymer.

  The (Y) graft copolymer used in this ABS resin composition comprises a specific main chain and side chains, and is obtained by selectively crosslinking the main chains with an organic peroxide. By using such a (Y) graft copolymer, the (Y) graft copolymer is well dispersed in the (X) ABS resin. Thereby, (X) ABS resin composition having excellent slidability is obtained while maintaining the original excellent mechanical properties of ABS resin.

<(X) ABS resin>
The (X) ABS resin according to the present embodiment is mainly composed of a copolymer mainly composed of three components of acrylonitrile, butadiene, and styrene, and is not limited to a specific type, and is manufactured by a known method. Can be used. Examples thereof include those obtained by radical copolymerization of acrylonitrile and styrene in the presence of butadiene. (X) The contents of acrylonitrile, butadiene, and styrene in the ABS resin are not particularly limited.

<(Y) Graft copolymer>
The main chain of the (Y) graft copolymer according to this embodiment is composed of (A) an ethylene-vinyl acetate copolymer. The side chain of the (Y) graft copolymer consists of a vinyl copolymer of (b-1) styrene and (b-2) at least one of acrylonitrile and glycidyl methacrylate.

  The (Y) graft copolymer which concerns on this embodiment is bridge | crosslinked by the carbon-carbon bond of main chains. The carbon-carbon bond between the main chains is obtained, for example, by the action of an organic peroxide (C) described later.

More specifically, when (Y) the graft copolymer is produced, (C) radicals generated by decomposition of the organic peroxide extract (A) hydrogen from the ethylene-vinyl acetate copolymer. Thereby, the carbon radical contained in (A) ethylene-vinyl acetate copolymer is produced | generated. (A) The hydrogen abstraction reaction from an ethylene-vinyl acetate copolymer generally reacts in the order of -OCOCH ₃ > (-CH ₂ -or-CH-). The carbon radicals are recombined to form a carbon-carbon bond between the main chains of the (Y) graft copolymer.

  The content of the (Y) graft copolymer is preferably 1 to 25 parts by weight, and more preferably 1 to 15 parts by weight, when the content of the (X) ABS resin is 100 parts by weight.

  By making the content of the (Y) graft copolymer 1 part by weight or more, the slidability of the ABS resin composition is improved, and by making the content of the (Y) graft copolymer 3 parts by weight or more. The slidability of the ABS resin composition is further improved.

  On the other hand, the mechanical properties and appearance quality of the ABS resin composition are improved by keeping the content of the (Y) graft copolymer to 25 parts by weight or less, and the content of the (Y) graft copolymer is 15 weights. The mechanical properties and appearance quality of the ABS resin composition are further improved by keeping the content below the part.

  The (Y) graft copolymer which concerns on this embodiment is obtained by melt-kneading the ethylene-vinyl acetate copolymer resin composition demonstrated below.

<Ethylene-vinyl acetate copolymer resin composition>
The ethylene-vinyl acetate copolymer resin composition according to this embodiment includes (A) an ethylene-vinyl acetate copolymer (EVA), (B) a vinyl copolymer, (C) an organic peroxide, Containing. (B) The vinyl copolymer and (C) the organic peroxide are impregnated in the (A) ethylene-vinyl acetate copolymer.

[(A) Ethylene-vinyl acetate copolymer (EVA)]
In the ethylene-vinyl acetate copolymer (A) according to this embodiment, the content of vinyl acetate in the structural unit is preferably 1 to 20% by weight, and more preferably 3 to 10% by weight. .

  (A) In the ethylene-vinyl acetate copolymer, the slidability of the ABS resin composition is improved by keeping the vinyl acetate content to 20% by weight or less, and the vinyl acetate content to 10% by weight or less. By fastening, the slidability of the ABS resin composition is further improved. Furthermore, in these cases, the heat resistance of the (Y) graft polymer is improved.

  On the other hand, in the ethylene-vinyl acetate copolymer (A), by setting the vinyl acetate content to 1% by weight or more, (C) the crosslinking reaction by the organic peroxide is likely to proceed, and (A) By setting the content of vinyl acetate in the ethylene-vinyl acetate copolymer to 3% by weight or more, the crosslinking reaction by (C) organic peroxide further proceeds.

  Further, (A) the ethylene-vinyl acetate copolymer can be arbitrarily selected using its fluidity as an index. For example, the melt flow rate (MFR) of the ethylene-vinyl acetate copolymer (A) is preferably 0.1 to 25 (g / 10 min) at 190 ° C. by a measurement method based on JIS K 7210. 1.0 to 10 (g / 10 min) is more preferable.

  (A) In the ethylene-vinyl acetate copolymer, the slidability of the ABS resin composition is improved by keeping MFR at 25 (g / 10 min) or less and further MFR at 10 (g / 10 min) or less. On the other hand, in the (A) ethylene-vinyl acetate copolymer, by setting the MFR to 0.1 (g / 10 min) or more and further setting the MFR to 1.0 (g / 10 min) or more, the (Y) graft Workability in the polymer production process is improved.

[(B) Vinyl copolymer]
The vinyl copolymer (B) according to this embodiment includes (b-1) styrene, (b-2) at least one of acrylonitrile and glycidyl methacrylate, and (b-3) t-butylperoxymethacryloyloxyethyl. It is comprised by the vinyl monomer composition which consists of a carbonate and (b-4) polymerization initiator.

  (B) Content of each monomer (b-1), (b-2), (b-3), (b-4) in a vinyl copolymer can be determined suitably. However, when the total content of (b-1) styrene and (b-2) at least one of acrylonitrile and glycidyl methacrylate is 100 parts by weight, (b-1) the content of styrene is 50 to 99. It is preferable that it is a weight part. Thereby, an ABS resin composition that is particularly excellent in slidability and mechanical properties can be obtained.

  Further, when the total content of (A) ethylene-vinyl acetate copolymer, (b-1) styrene, and (b-2) acrylonitrile and at least one of glycidyl methacrylate is 100 parts by weight, A) The content of the ethylene-vinyl acetate copolymer is preferably 50 to 90 parts by weight. In this case, particularly good slidability in the ABS resin composition can be obtained.

…（１） (B-3) t-Butylperoxymethacryloyloxyethyl carbonate in the vinyl copolymer (B-3) is a compound represented by the following chemical formula (1). When the ethylene-vinyl acetate copolymer resin composition according to this embodiment is melt-kneaded, the peroxide bond of (b-3) t-butylperoxymethacryloyloxyethyl carbonate is thermally decomposed to generate radicals. (Y) A graft copolymer is obtained.

... (1)

  (B) The polymerization initiator (b-4) in the vinyl copolymer is not limited to a specific type, and known ones such as organic peroxides and azo initiators can be used. However, the 10-hour half-life temperature of the polymerization initiator (b-4) is preferably 50 to 75 ° C.

  Here, the 10-hour half-life temperature (hereinafter also referred to as "T10") is (b-4) a polymerization bond concentration or azo bond contained in a polymerization initiator or (C) an organic peroxide. When a solution dissolved in benzene so as to have a concentration of 0.1 mol / liter is thermally decomposed, the (b-4) polymerization initiator or (C) organic peroxide has a half-life in 10 hours. It is the temperature that reaches.

  (B-4) By setting the 10-hour half-life temperature of the polymerization initiator to 50 ° C. or more, rapid decomposition of the (b-4) polymerization initiator is suppressed, and the polymerization temperature is easily controlled. On the other hand, by setting the 10-hour half-life temperature of (b-4) the polymerization initiator to 75 ° C. or less, (b-4) good decomposition of the polymerization initiator can be obtained, and (Y) the graft copolymer (B-4) The polymerization initiator itself and other monomers are less likely to remain.

  In order to make it difficult for (A) ethylene-vinyl acetate copolymer to remain (b-4) the polymerization initiator itself and other monomers, (B) the polymerization temperature for obtaining the vinyl copolymer is set to It is possible to raise it.

  However, when the polymerization temperature is increased, the difference between the polymerization temperature and the 10-hour half-life temperature of the (C) organic peroxide is reduced. Therefore, during the polymerization reaction for obtaining the (B) vinyl copolymer, the (C) organic Peroxide is easily decomposed. Therefore, (C) the organic peroxide may be insufficient during melt-kneading, and (A) the ethylene-vinyl acetate copolymer may not be able to perform a sufficient crosslinking reaction. For this reason, it is not preferable to raise the polymerization temperature for obtaining the (B) vinyl copolymer.

(B-4) Examples of the organic peroxide that can be used as the polymerization initiator include the following. For each substance, the 10 hour half-life temperature is shown in parentheses.
t-Butylperoxyneoheptanoate (T10 = 51 ° C.)
t-Hexylperoxypivalate (T10 = 53 ° C.)
t-Butyl peroxypivalate (T10 = 55 ° C.)
Di (3,5,5-trimethylhexanoyl) peroxide (T10 = 59 ° C.)
Dilauroyl peroxide (T10 = 62 ° C)
1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (T10 = 65 ° C.)
2,5-Dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane (T10 = 66 ° C.)
t-Hexylperoxy-2-ethylhexyl hexanoate (T10 = 70 ° C.)
Di (4-methylbenzoyl) peroxide (T10 = 71 ° C.)
t-Butylperoxy-2-ethylhexanoate (T10 = 72 ° C.)
Dibenzoyl peroxide (T10 = 74 ° C)

(B-4) Examples of the azo compound that can be used as a polymerization initiator include the following. For each substance, the 10 hour half-life temperature is shown in parentheses.
2,2-azobis (2,4-dimethylvaleronitrile) (T10 = 51 ° C.)
2,2-azobis (isobutyronitrile) (T10 = 65 ° C.)
2,2-azobis (2-methylbutyronitrile) (T10 = 67 ° C.)

[(C) Organic peroxide]
The (C) organic peroxide according to the present embodiment can crosslink the (A) ethylene-vinyl acetate copolymer by thermally decomposing during melt kneading to generate radicals.
(C) An organic peroxide is not limited to a specific kind, A well-known thing can be utilized. However, the 10-hour half-life temperature of (C) the organic peroxide is preferably 95 to 130 ° C.

  (C) By making the 10-hour half-life temperature of an organic peroxide 95 degreeC or more, (C) An organic peroxide becomes difficult to decompose | disassemble at the time of the polymerization reaction for obtaining a vinyl copolymer. Therefore, since (B) the organic peroxide is difficult to decrease during the polymerization reaction for obtaining the vinyl copolymer (B), the crosslinking reaction of the (A) ethylene-vinyl acetate copolymer is insufficient during the melt kneading. Can be prevented.

  On the other hand, by setting the 10-hour half-life temperature of the (C) organic peroxide to 130 ° C. or less, the (C) organic peroxide is favorably decomposed during melt-kneading. Thereby, the crosslinking reaction of (A) ethylene-vinyl acetate copolymer proceeds well.

Examples of the (C) organic peroxide that can be used in the present embodiment include the following. For each substance, the 10 hour half-life temperature is shown in parentheses.
t-Hexylperoxyisopropyl monocarbonate (T10 = 95 ° C.)
t-Butylperoxy-3,5,5-trimethylhexanoate (T10 = 97 ° C.)
t-Butyl peroxylaurate (T10 = 98 ° C.)
t-Butylperoxyisopropyl monocarbonate (T10 = 99 ° C.)
t-Butylperoxy-2-ethylhexyl monocarbonate (T10 = 99 ° C.)
t-Hexylperoxybenzoate (T10 = 99 ° C.)
2,5-Dimethyl-2,5-di (benzoylperoxy) hexane (T10 = 100 ° C.)
t-Butyl peroxyacetate (T10 = 102 ° C.)
2,2-di (t-butylperoxy) butane (T10 = 103 ° C.)
t-Butyl peroxybenzoate (T10 = 104 ° C.)
n-Butyl-4,4-di (t-butylperoxy) valerate (T10 = 105 ° C.)
Di (2-t-butylperoxyisopropyl) benzene (T10 = 119 ° C.)
Dicumyl peroxide (T10 = 116 ° C)
Di-t-hexyl peroxide (T10 = 116 ° C.)
2,5-Dimethyl-2,5-di (t-butylperoxy) hexane (T10 = 118 ° C.)
t-Butyl cumyl peroxide (T10 = 120 ° C.)
Di-t-butyl peroxide (T10 = 124 ° C.)

  The content of (C) the organic peroxide according to this embodiment is preferably 0.1 to 3 parts by weight when the content of (A) the ethylene-vinyl acetate copolymer is 100 parts by weight. (C) By making content of an organic peroxide into 0.1 weight part or more, it can prevent that the crosslinking reaction of (A) ethylene-vinyl acetate copolymer runs short. On the other hand, by keeping the content of (C) the organic peroxide at 3 parts by weight or less, good fluidity can be obtained in the (Y) graft copolymer obtained by melt kneading.

[Other additives]
The ABS resin composition according to the present embodiment may contain additives other than the above as necessary. Examples of such additives include mineral oils, hydrocarbons, fatty acids, alcohols, fatty acid esters, fatty acid amides, lubricants such as metal soaps, natural waxes, silicones, inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide, Organic flame retardants such as halogen and phosphorus, metal powder, talc, calcium carbonate, potassium titanate, glass fiber, carbon fiber, wood powder and other organic or inorganic fillers, antioxidants, UV inhibitors, lubricants, Examples include additives such as dispersants, coupling agents, foaming agents, colorants, and engineering plastics such as other polyolefin resins, polyesters, polyacetals, polyamides, polycarbonates, polyphenylene ethers, and the like.

<Resin molded product>
Since the ABS resin composition according to this embodiment is a thermoplastic resin, it can be easily molded into various shapes by injection molding, extrusion molding, or the like. The resin molded product obtained by molding the ABS resin composition according to this embodiment is excellent in mechanical properties and slidability, so that it can be used in a wide range of fields such as electrical parts, electronic parts, mechanical parts, precision equipment parts, and automobile parts. Can be used.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples.

<Ethylene-vinyl acetate copolymer resin composition>
[Production of ethylene-vinyl acetate copolymer resin composition]
For Production Examples 1-1 to 1-13 and Comparative Production Examples 1-1 to 1-3, ethylene-vinyl acetate copolymer resin compositions were produced with the compositions shown in Table 1. As an example of this, the production process of the ethylene-vinyl acetate copolymer resin composition according to Production Example 1-1 is shown below. In addition, the ethylene-vinyl acetate copolymer resin composition which concerns on another manufacture example and a comparative manufacture example was also manufactured by the process similar to manufacture example 1-1.

[Production of ethylene-vinyl acetate copolymer resin composition according to Production Example 1-1]
In a 5 L stainless steel autoclave, 2500 g of pure water was added, and 2.5 g of polyvinyl alcohol was dissolved as a suspending agent. In this, ethylene-vinyl acetate copolymer (trade name “Ultrasen 510”, manufactured by Tosoh Corporation, VAc content 6%, MFR = 2.5 (g / 10 min) 700 g was added and dispersed by stirring. It was.

  Separately, 4.0 g of radical polymerization initiator, 9.0 g of radical (co) polymerizable organic peroxide, and 3.5 g of crosslinking agent were added to 210 g of styrene (St) and 90 g of glycidyl methacrylate. A solution dissolved in (GMA) was produced, and this solution was put into an autoclave and stirred.

  Di (3,5,5-trimethylhexanoyl) peroxide (trade name “Perroyl 355”, 10 hour half-life temperature = 59 ° C., manufactured by NOF Corporation) was used as the radical polymerization initiator. T-Butylperoxymethacryloyloxyethyl carbonate (MEC) is used as the polymerizable organic peroxide, and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (trade name “ "Perhexa 25B", 10 hour half-life temperature = 118 ° C, manufactured by NOF Corporation) was used.

  Then, the autoclave is heated to 60 to 65 ° C. and stirred for 3 hours, whereby a monomer composition containing a radical polymerization initiator and a radical (co) polymerizable organic peroxide is converted into an ethylene-vinyl acetate copolymer. Impregnated inside.

  Thereafter, the autoclave was heated to 80 to 85 ° C., held at that temperature for 7 hours for polymerization, washed with water and dried to obtain (B) a poly (St / GMA / MEC) copolymer which is a vinyl copolymer. (C) ethylene-impregnated ethylene-vinyl acetate copolymer with (C) 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, which is an organic peroxide. A vinyl acetate copolymer resin composition was obtained.

  A poly (St / GMA / MEC) copolymer was extracted with ethyl acetate from the obtained ethylene-vinyl acetate copolymer resin composition. As a result of measurement by gel permeation chromatography (GPC), it was found that the weight average molecular weight of the poly (St / GMA / MEC) copolymer was 400,000.

[Description of Comparative Production Examples 1-1 to 1-3]
In the ethylene-vinyl acetate copolymer resin composition according to Comparative Production Example 1-1, unlike the above embodiment, (C) no organic peroxide is added, and the crosslinking reaction between main chains is not performed. .

  In the ethylene-vinyl acetate copolymer resin composition according to Comparative Production Example 1-2, the vinyl acetate content in the (A) ethylene-vinyl acetate copolymer is 32% by weight, and the MFR is 30 (g / 10 min). ) And higher than Production Examples 1-1 to 1-13.

  In the ethylene-vinyl acetate copolymer resin composition according to Comparative Production Example 1-3, low density polyethylene is used instead of (A) the ethylene-vinyl acetate copolymer.

The meaning of each abbreviation in Table 1 is as follows.
EVA: ethylene-vinyl acetate copolymer (In each example and each comparative example, any one of the following three types is used as appropriate)
(I) “Ultrasen 510”, manufactured by Tosoh Corporation, VAc content 6%, MFR = 2.5 (g / 10 min)
(II) “Ultrasen 537”, manufactured by Tosoh Corporation, VAc content 15%, MFR = 3.0 (g / 10 min)
(III) “Ultrasen 750”, manufactured by Tosoh Corporation, VAc content 32%, MFR = 30 (g / 10 min)
LDPE: Low-density polyethylene ("Sumikasen G401" manufactured by Sumitomo Chemical Co., Ltd., density = 0.926 g / cm ³ )
St: Styrene GMA: Glycidyl methacrylate AN: Acrylonitrile MEC: t-Butylperoxymethacryloyloxyethyl carbonate R355: Di (3,5,5-trimethylhexanoyl) peroxide BW: Benzoyl peroxide (“Nyper BW”, 10 Time half-life temperature = 74 ° C, manufactured by NOF Corporation)
25B: 2,5-dimethyl-2,5-di (t-butylperoxy) hexane BuE: t-butylperoxy-2-ethylhexyl monocarbonate (“perbutyl E”, 10 hour half-life temperature = 99 ° C., day (Oil Co., Ltd.)

<(Y) Graft copolymer>
[Production of (Y) Graft Copolymer]
About Production Examples 2-1 to 2-13 and Comparative Production Examples 2-1 to 2-3, as shown in Table 2, Production Examples 1-1 to 1-13 and Comparative Production Examples 1-1 to 1-3, respectively, A (Y) graft copolymer was produced using the ethylene-vinyl acetate copolymer resin composition according to the present invention. As an example of this, the production process of the (Y) graft copolymer according to Production Example 2-1 is shown below. In addition, the (Y) graft copolymer which concerns on another manufacture example and a comparative manufacture example was also manufactured by the process similar to manufacture example 2-1.

[Production of (Y) Graft Copolymer According to Production Example 2-1]
First, the ethylene-vinyl acetate copolymer resin composition obtained in Production Example 1-1 is melt-kneaded at 200 ° C. with a lab plast mill single-screw extruder (manufactured by Toyo Seiki Seisakusho Co., Ltd.) to cause a grafting reaction. As a result, an (Y) graft copolymer having a main chain composed of an ethylene-vinyl acetate copolymer and a side chain composed of poly (St / GMA) was obtained.

  When the MFR (220 ° C./10 kgf) of the obtained (Y) graft copolymer was measured, it was 0.6 (g / 10 min), and the grafting reaction and the crosslinking reaction of the ethylene-vinyl acetate copolymer proceeded. I confirmed that Further, when the obtained (Y) graft copolymer was observed with a scanning electron microscope (“JEOL JSM T300”, manufactured by JEOL Ltd.), a true spherical resin having a particle size of 0.1 to 0.2 μm was uniform. It was confirmed that they were dispersed.

  As is apparent from Table 2, in Production Examples 2-1 to 2-13, the grafting reaction and the crosslinking reaction of (A) the ethylene-vinyl acetate copolymer proceed, so that (Y) the graft copolymer The MFR was 0.1 or more and 1.1 or less, and appropriate fluidity was obtained.

  On the other hand, in Comparative Production Example 2-1, the cross-linking reaction between main chains of (A) ethylene-vinyl acetate copolymer did not proceed, and the MFR of (Y) graft copolymer was 4.5 (g / g). 10 min) and a high value compared with Production Example 2-1.

  In Comparative Production Example 2-2, the MFR of (Y) graft copolymer obtained because (A) the ethylene-vinyl acetate copolymer had a high MFR was 12.8 (g / 10 min), and Production Example 2-1 The value was higher than that.

  In Comparative Production Example 2-3, since (A) low-density polyethylene is used instead of the ethylene-vinyl acetate copolymer, the cross-linking reaction between the main chains hardly proceeds, and (Y) the graft copolymer. MFR of 2.6 (g / 10 min) was higher than that of Production Example 2-1.

<ABS resin composition>
[Production of ABS resin composition]
With respect to Examples 1-1 to 1-15 and Comparative Examples 1-1 to 1-5, (X) ABS resin (trade name “Toyolac 700-314”, standard grade, Toray Industries, Inc., with the mixing ratio shown in Table 3. (Shown as “ABS1” in Table 3), the above (Y) graft copolymer was appropriately dry blended in a predetermined amount, and melt-kneaded in a twin-screw extruder set at 240 ° C., An ABS resin composition was obtained.

  In Examples 1-1 and 1-4 to 1-15, the content of the (Y) graft copolymer obtained in Production Examples 2-1 to 2-13 was 10 parts by weight (100 parts by weight of (X)). ABS resin composition was produced.

  In Examples 1-2 and 1-3, the content of the (Y) graft copolymer obtained in Production Example 2-1 was 1 part by weight, and 15 parts by weight ((X) was 100 parts by weight). An ABS resin composition was produced.

  The ABS resin composition according to Comparative Example 1-1 was produced using only the (X) ABS resin without using the (Y) graft copolymer. In Comparative Example 1-2, an ABS resin composition in which the content of the (Y) graft copolymer obtained in Production Example 2-1 is 30 parts by weight (when (X) is 100 parts by weight) is produced. did. In Comparative Examples 1-3 to 1-5, the content of the (Y) graft copolymer obtained in Comparative Production Examples 2-1 to 2-3 is 10 parts by weight (when (X) is 100 parts by weight) The ABS resin composition was manufactured.

  About Example 2-1 and Comparative Example 2-1, (X) ABS resin (trade name “Absolac 300”, standard grade, manufactured by Styroluth, shown as “ABS2” in Table 3) at the blending ratio shown in Table 3) On the other hand, a predetermined amount of the above (Y) graft copolymer was appropriately dry blended and melt-kneaded with a twin screw extruder set at 240 ° C. to obtain an ABS resin composition.

In Example 2-1, an ABS resin composition in which the content of the (Y) graft copolymer obtained in Production Example 2-1 is 10 parts by weight (when (X) is 100 parts by weight) is produced. did.
The ABS resin composition according to Comparative Example 2-1 was produced using only the (X) ABS resin without using the (Y) graft copolymer.

  About Example 2-1 and Comparative Example 2-1, the preparation of the evaluation material and the evaluation method are the same as those in Examples 1-1 to 1-15 and Comparative Examples 1-1 to 1-5.

[Production of evaluation materials]
Examples 1-1 to 1-15 and Comparative Example 1 were formed by molding the ABS resin compositions obtained in Examples 1-1 to 1-15 and Comparative Examples 1-1 to 1-5 using an injection molding machine. Evaluation materials obtained in -1 to 1-5 were produced. The injection molding conditions were a barrel temperature of 245 ° C. and a mold temperature of 80 ° C.

[Evaluation method]
-Tensile strength Based on JIS K-7113, it carried out as test speed 50mm / min. The target value of tensile strength was determined according to the type of (X) ABS resin, and was 40 MPa or more.

-Flexural modulus Based on JIS K-7203, it carried out as test speed 2mm / min. The target value of the flexural modulus was determined according to the type of (X) ABS resin and was set to 2.0 GPa or more.

・ Slidability evaluation (thrust friction and wear test)
Testing machine: Friction and abrasion testing machine EFM-III-F manufactured by Orientec Co., Ltd.
Evaluation material: Cylindrical material having an inner diameter of 20 mm and an outer diameter of 25.6 mm Evaluation material material: ABS resin composition having the composition shown in Table 3 Partner material: Cylindrical material having an inner diameter of 20 mm and an outer diameter of 25.6 mm Counterpart material material: (1) Carbon Steel (S45C), (2) Neat ABS resin Test conditions (when the mating material is (1)): Load 50 N, linear velocity 10 cm / sec
Test conditions (when the mating material is (2)): Load 20N, linear velocity 10cm / sec
Test time: 100 minutes In this test, the wear amount (mg) and the dynamic friction coefficient of each evaluation material were determined for each counterpart material (1) and (2).
The target values of the wear amount and the dynamic friction coefficient are determined according to the type of (X) ABS resin. In this example and the comparative example, when the counterpart material was (1) carbon steel (S45C), the target value of the wear amount was set to 5.0 mg or less, and the target value of the dynamic friction coefficient was set to 0.25 or less. Further, when the counterpart material is (2) neat ABS, the target value of the wear amount was set to 5.0 mg or less, and the target value of the dynamic friction coefficient was set to 0.25 or less. The neat ABS resin referred to here is an ABS resin to which no graft copolymer is added.

・ Evaluation of stagnation sound The obtained evaluation material was cut into a plate for stagnation sound evaluation test (60 mm × 100 mm × 2 mm) and a neat ABS resin plate (50 mm × 25 mm × 2 mm) as a mating material for rubbing. After deburring, conditions were adjusted for 12 hours at a temperature of 25 ° C. and a humidity of 50%. Further, a stainless plate was also prepared as a plate for the mating material (50 mm × 25 mm × 2 mm).

  Itching sound when the plate for the stagnation sound evaluation test and each plate as the counterpart material are fixed to a Ziegler stick-slip measuring device SSP-02 and rubbed together under the conditions of load = 40 N and speed = 1 mm / s. The risk value was measured. The stagnation sound risk value indicates that the smaller the value, the lower the risk of stagnation sound generation. The criteria for determining the risk of stagnation sound are as follows.

Itchy sound risk values 1-3: Low risk of squeaking noises Smoke sound risk value 4-5: Slightly high risk of squeaking sounds Smoke noise risk values 6-10: High risk of sneezing sound generation

  The target value of the stagnation sound risk value is determined according to the type of (X) ABS resin. In this example and comparative example, the target value of the stagnation sound risk value when the counterpart material is (1) carbon steel (S45C) is 3 or less, and the squeeze risk when the counterpart material is (2) neat ABS resin. The target value was set to 3 or less.

  Table 3 shows the evaluation materials according to Examples 1-1 to 1-15, Example 2-1 and Comparative Examples 1-1 to 1-5, and Comparative Example 2-1. (S45C) and (2) The results of the slidability evaluation and the squeaking noise evaluation of the thrust type friction wear test when neat ABS resin is used are shown.

The meaning of each abbreviation in Table 3 is as follows.
ABS1: “Toyolac 700-314”, standard grade, manufactured by Toray Industries, Inc. ABS2: “Absolac300”, manufactured by Styrolution

[Evaluation results]
(Examples)
-Mechanical properties In all the evaluation materials according to Examples 1-1 to 1-15 and Example 2-1, the tensile strength is a large value of 40 MPa or more, and the flexural modulus is a high value of 2.0 GPa or more. there were.

Slidability evaluation In the evaluation materials according to Examples 1-1 to 1-15 and Example 2-1, in the thrust type frictional wear test in which the counterpart material is (1) carbon steel (S45C), the amount of wear As a result, a low value of 5.0 mg or less and a dynamic friction coefficient of 0.25 or less were obtained.

  In the evaluation materials according to Examples 1-1 to 1-15 and Example 2-1, in the thrust type frictional wear test in which the counterpart material is (2) neat ABS resin, the wear amount is 5.0 mg or less, The dynamic friction coefficient was a low value of 0.25 or less.

-Itching sound evaluation In any of the evaluation materials according to Examples 1-1 to 1-15 and Example 2-1, sliding when the counterpart material is (1) carbon steel (S45C) and (2) neat ABS resin. The squeaking noise risk value during movement was a small value of 3 or less.

(Comparative example)
(X) In Comparative Example 1-1 in which only the ABS resin is used, in a thrust type frictional wear test in which the counterpart material is (1) carbon steel (S45C), the wear amount is 5.0 (mg) and the dynamic friction coefficient is 0.1. It was over 25. Further, in Comparative Example 1-1, in the thrust type frictional wear test in which the counterpart material was (2) neat ABS resin, the wear amount was 5.0 (mg) and the dynamic friction coefficient exceeded 0.25. Furthermore, in Comparative Example 1-1, the risk of squeaking noise during sliding when the counterpart material was (1) carbon steel (S45C) and (2) neat ABS resin exceeded 3.

  In Comparative Example 1-2 in which the content of the (Y) graft copolymer according to Production Example 2-1 is 30 parts by weight (when (X) is 100 parts by weight), the tensile strength is 40 MPa or less and bending The elastic modulus was a low value of 2.0 GPa or less.

  (A) In Comparative Example 1-3 in which the main chains of the ethylene-vinyl acetate copolymer are not cross-linked, the wear amount is 5 in the thrust type frictional wear test in which the counterpart material is (1) carbon steel (S45C). 0.0 (mg). Moreover, in Comparative Example 1-3, the wear amount exceeded 5.0 (mg) in the thrust type frictional wear test in which the counterpart material was (2) neat ABS resin.

  (A) In Comparative Example 1-4 where the content of vinyl acetate in the ethylene-vinyl acetate copolymer was high and the MFR of the (Y) graft copolymer showed a high value, the counterpart material was (1) carbon steel ( In the thrust type frictional wear test of S45C), the wear amount was 5.0 (mg), and the dynamic friction coefficient exceeded 0.25. In Comparative Example 1-4, the amount of wear was 5.0 (mg) and the coefficient of dynamic friction exceeded 0.25 in the thrust friction wear test in which the counterpart material was (2) neat ABS resin.

  (A) In Comparative Example 1-5 in which low-density polyethylene was used instead of the ethylene-vinyl acetate copolymer, the risk of squeaking noise exceeded 3 when the counterpart material was (2) neat ABS resin.

  (X) In Comparative Example 2-1 using only ABS resin, in a thrust type frictional wear test in which the counterpart material is (1) carbon steel (S45C), the wear amount is 5.0 (mg) and the dynamic friction coefficient is 0. It was over 25. In Comparative Example 2-1, the amount of wear was 5.0 (mg) and the coefficient of dynamic friction exceeded 0.25 in the thrust type friction wear test in which the counterpart material was (2) neat ABS resin. Further, in Comparative Example 2-1, the risk of stagnation sound when the counterpart material was (1) carbon steel (S45C) and (2) neat ABS resin exceeded 3.

The embodiment of the present invention has been described above, but the present invention is not limited to the above-described embodiment, and it is needless to say that various modifications can be made without departing from the gist of the present invention.

Claims (5)

(X) an ABS resin, and (Y) a graft copolymer,
The main chain of the (Y) graft copolymer comprises (A) an ethylene-vinyl acetate copolymer,
The side chain of the (Y) graft copolymer comprises (B) a vinyl copolymer containing (b-1) styrene and (b-2) at least one of acrylonitrile and glycidyl methacrylate,
An ABS resin composition in which the main chains of the (Y) graft copolymer are cross-linked. The ABS resin composition according to claim 1,
An ABS resin composition in which the main chains of the (Y) graft copolymer are crosslinked with (C) an organic peroxide. The ABS resin composition according to claim 1 or 2,
When the content of the (X) ABS resin is 100 parts by weight, the content of the (Y) graft copolymer is 1 to 25 parts by weight. ABS resin composition. The ABS resin composition according to any one of claims 1 to 3,
When the total content of the (A) ethylene-vinyl acetate copolymer, the (b-1) styrene, and the (b-2) acrylonitrile and at least one of glycidyl methacrylate is 100 parts by weight, The ABS resin composition according to any one of claims 1 to 3, wherein the content of the (A) ethylene-vinyl acetate copolymer is 50 to 90 parts by weight. A resin molded product obtained by molding the ABS resin composition according to any one of claims 1 to 4.