ETHYLENE VINYL ACETATE COPOLYMER RESIN COMPOSITION, GRAFT COPOLYMER, THERMOPLASTIC RESIN COMPOSITION, AND MOLDED RESIN ARTICLE

Abstract

An ethylene-vinyl acetate copolymer resin composition includes: an (A) ethylene-vinyl acetate copolymer; a (B) vinyl copolymer; and a (C) organic peroxide. The (B) vinyl copolymer and the (C) organic peroxide are impregnated in the (A) ethylene-vinyl acetate copolymer. The (A) ethylene-vinyl acetate copolymer includes 1 to 20 wt % of a vinyl acetate. The (B) vinyl copolymer is formed of a (b-1) styrene, (b-2) at least one of acrylonitrile and glycidyl methacrylate, a (b-3) t-butylperoxymethacryloyloxyethyl carbonate, and a (b-4) polymerization initiator. A content of the (C) organic peroxide is 0.1 to 3 parts by weight relative to 100 parts by weight of the (A) ethylene-vinyl acetate copolymer.

Claims

1. An ethylene-vinyl acetate copolymer resin composition, comprising: an (A) ethylene-vinyl acetate copolymer; a (B) vinyl copolymer; and a (C) organic peroxide, wherein the (B) vinyl copolymer and the (C) organic peroxide are impregnated in the (A) ethylene-vinyl acetate copolymer, the (A) ethylene-vinyl acetate copolymer includes 1 to 20 wt % of a vinyl acetate, the (B) vinyl copolymer is formed of a (b-1) styrene, (b-2) at least one of acrylonitrile and glycidyl methacrylate, a (b-3) t-butylperoxymethacryloyloxyethyl carbonate, and a (b-4) polymerization initiator, and a content of the (C) organic peroxide is 0.1 to 3 parts by weight relative to 100 parts by weight of the (A) ethylene-vinyl acetate copolymer.

2. The ethylene-vinyl acetate copolymer resin composition according to claim 1, wherein a content of the (A) ethylene-vinyl acetate copolymer is 50 to 90 parts by weight relative to 100 parts by weight of the (A) ethylene-vinyl acetate copolymer, the (b-1) styrene, and the (b-2) at least one of acrylonitrile and glycidyl methacrylate.

3. The ethylene-vinyl acetate copolymer resin composition according to claim 1, wherein a 10 hour half-life period temperature of the (b-4) polymerization initiator is 50 to 75° C., and a 10 hour half-life period temperature of the (C) organic peroxide is 95 to 130° C.

4. A graft copolymer obtained by melt-kneading the ethylene-vinyl acetate copolymer resin composition according to claim 1, comprising: a main chain formed of the (A) ethylene-vinyl acetate copolymer; and a side chain formed of a vinyl copolymer including the (b-1) styrene and the (b-2) at least one of acrylonitrile and glycidyl methacrylate.

5. A thermoplastic resin composition, comprising: a (X) thermoplastic resin; and the (Y) graft copolymer according to claim 4, wherein a content of the (Y) graft copolymer according to claim 4 is 1 to 25 parts by weight relative to 100 parts by weight of the (X) thermoplastic resin.

6. The thermoplastic resin composition according to claim 5, wherein the (X) thermoplastic resin is a thermoplastic resin mixed with one or two or more kinds of resin selected from a polyacetal resin, a polyamide resin, a polycarbonate resin, and an ABS resin.

7. The thermoplastic resin composition according to claim 5 , further comprising one or more kinds of lubricant selected from a fatty acid ester, a fatty acid amide, a polyethylene wax, and a paraffin wax as a (Z-1) lubricant, wherein a content of the (Z-1) lubricant is 1 to 5 parts by weight relative to 100 parts by weight of the (X) thermoplastic resin.

8. The thermoplastic resin composition according to claim 5, further comprising one or more kinds of filler selected from calcium carbonate and potassium titanate as a (Z-2) inorganic filler, wherein a content of the (Z-2) inorganic filler is 3 to 8 parts by weight relative to 100 parts by weight of the (X) thermoplastic resin.

9. A molded resin article obtained by molding the thermoplastic resin composition according to claim 5.

Description

EXAMPLE

[0119] Hereinafter, the present invention will be further specifically described with reference to examples and comparative examples.

1. (Y) Graft copolymer [0120] [Manufacturing of ethylene-vinyl acetate copolymer resin composition]

[0121] In examples 1-1 to 1-13 and comparative examples 1-1 to 1-4, ethylene-vinyl acetate copolymer resin compositions having compositions shown in Table 1 were manufactured. As an example, a manufacturing process for the ethylene-vinyl acetate copolymer resin composition according to the example 1-1 will be described in the following. Note that also the ethylene-vinyl acetate copolymer resin compositions according to other examples and comparative examples were manufactured in a process similar to that in the example 1-1. [0122] [Manufacturing of ethylene-vinyl acetate copolymer resin composition according to example 1-1]

[0123] Two thousand five hundred g of pure water was put in a stainless autoclave with an internal volume of 5 L, and then, 2.5 g of polyvinyl alcohol was dissolved herein as a suspension agent. Seven hundred g of an ethylene vinyl acetate copolymer (“Ultracene 510” (trade name) manufactured by TOSOH corporation, the VAc content of 6%, MFR=2.5 g/10 min) was put therein, and stirred and dispersed.

[0124] Separately, a solution obtained by dissolving 4.0 g of a radical polymerization initiator, 9.0 g of a radical (co)polymer organic peroxide, and 3.5 g of a crosslinking agent in 210 g of styrene (St) and 90 g of glycidyl methacrylate (GMA) was generated, and this solution was put in an autoclave and stirred.

[0125] Di (3,5,5-trimethylhexanoyl) peroxide (“Peroyl 355” (trade name), 10 hour half-life period temperature=59° C., manufactured by NOF CORPORATION) was used as the radical polymerization initiator, t-butylperoxymethacryloyloxyethyl carbonate (MEC) was used as the radical (co)polymer organic peroxide, and 2,5-dimethyl-2,5-di(t-butylperoxy) hexane (“Perhexa 25B” (trade name), 10 hour half-life period temperature=118° C., manufactured by NOF CORPORATION) was used as the crosslinking agent.

[0126] Then, the temperature of the autoclave was increased to 60 to 65° C., and the solution was stirred for 3 hours. Accordingly, a monomer composition including the radical polymerization initiator and the radical (co)polymer organic peroxide was impregnated in the ethylene vinyl acetate copolymer.

[0127] After that, the temperature of the autoclave was increased to 80 to85° C., and it was held at the time for 7 hours for polymerization. Then, by washing and drying it, an ethylene-vinyl acetate copolymer resin composition in which a poly(St/GMA/MEC) copolymer that is the (B) vinyl copolymer and 2,5-dimethyl-2,5-di(t-butylperoxy) hexane that is the (C) organic peroxide were impregnated in the (A) ethylene-vinyl acetate copolymer was obtained.

[0128] The poly(St/GMA/MEC) copolymer was extracted by ethyl acetate from the obtained ethylene-vinyl acetate copolymer resin composition. As a result of measurement by gel permeation chromatography (GPC), it has been found that the weight average molecular weight of the poly(St/GMA/MEC) copolymer was 400,000. [0129] [Description of comparative examples 1-1 to 1-4]

[0130] The ethylene-vinyl acetate copolymer resin composition according to the comparative example 1-1 does not include the (C) organic peroxide unlike the above-mentioned embodiments.

[0131] In the ethylene-vinyl acetate copolymer resin composition according to the comparative example 1-2, the content of a vinyl acetate in the (A) ethylene-vinyl acetate copolymer is larger than that in the above-mentioned embodiments.

[0132] In the ethylene-vinyl acetate copolymer resin composition according to the comparative example 1-3, the content of the (C) organic peroxide is larger than that in the above-mentioned embodiments.

[0133] In the ethylene-vinyl acetate copolymer resin composition according to the comparative example 1-4, low-density polyethylene is used instead of the (A) ethylene-vinyl acetate copolymer.

TABLE-US-00001 TABLE 1 (B) Vinyl copolymer (A) (b-4) EVA copolymer Polymerization (C) MFR.sup. Parts (b-1) (b-2) (b-3) initiator Organic peroxide VAc (g/ by St AN GMA MEC T10 T10 Parts by Kind (%) 10 min) weight Parts by weight Kind (° C.) Kind (° C.) weight Example 1-1 EVA 6 2.5 70 21 9 0.9 R355 59 25B 118 0.35 Example 1-2 EVA 6 2.5 70 21 9 0.9 R355 59 25B 118 0.70 Example 1-3 EVA 6 2.5 70 21 9 0.9 R355 59 BuE 99 0.35 Example 1-4 EVA 6 2.5 70 21 9 0.9 BW 74 25B 118 0.35 Example 1-5 EVA 6 2.5 70 21 9 0.9 BW 74 BuE 99 0.35 Example 1-6 EVA 6 2.5 70 21 9 0.9 R355 59 25B 118 0.35 Example 1-7 EVA 6 2.5 70 21 6 3 0.9 R355 59 25B 118 0.35 Example 1-8 EVA 6 2.5 50 35 15 1.5 R355 59 25B 118 0.35 Example 1-9 EVA 6 2.5 50 35 15 1.5 R355 59 25B 118 0.35 Example 1-10 EVA 6 2.5 50 35 10 5 1.5 R355 59 25B 118 0.35 Example 1-11 EVA 15 3.0 70 21 9 0.9 R355 59 25B 118 0.35 Example 1-12 EVA 15 3.0 70 21 9 0.9 R355 59 25B 118 0.35 Example 1-13 EVA 15 3.0 70 21 6 3 0.9 R355 59 25B 118 0.35 Comparative EVA 6 2.5 70 21 9 0.9 R355 59 — — — example 1-1 Comparative EVA 32 30 70 21 9 0.9 R355 59 25B 118 0.35 example 1-2 Comparative EVA 6 2.5 70 21 9 0.9 R355 59 25B 118 3.50 example 1-3 Comparative LDPE — 4 70 21 9 0.9 R355 59 25B 118 0.35 example 1-4 .sup.190° C./2.16 kgf

[0134] Meanings of abbreviations in Table 1 are as follows.

[0135] EVA: ethylene vinyl acetate copolymer (any of the following three kinds is appropriately used in each example and comparative example) [0136] (I) “Ultracene 510” manufactured by TOSOH corporation, VAc content of 6%, MFR=2.5(g/10 min) [0137] (II) “Ultracene 537” manufactured by TOSOH corporation, VAc content of 15%, MFR=3.0(g/10 min) [0138] (III) “Ultracene 750” manufactured by TOSOH corporation. VAc content of 32%, MFR=30(g/10 min)

[0139] LDPE: low-density polyethylene (“SUMIKATHENE G401” manufactured by Sumitomo Chemical Co., Ltd., density=0.926 g/cm.sup.3)

[0140] St: styrene

[0141] GMA: glycidyl methacrylate

[0142] AN: acrylonitrile

[0143] MEC: t-butylperoxymethacryloyloxyethyl carbonate

[0144] R355: di (3,5,5-trimethylhexanoyl) peroxide

[0145] BW: benzoyl peroxide (“NYPER BW”, 10 hour half-life period temperature=74° C., manufactured by NOF CORPORATION)

[0146] 25B: 2,5-dimethyl-2,5-di (t-butylperoxy) hexane

[0147] BuE: t-butylperoxy-2-ethylhexyl monocarbonate (“PERBUTYL E”, 10 hour half-life period temperature=99° C., manufactured by NOF CORPORATION) [0148] [Manufacturing of (Y) graft copolymer]

[0149] In examples 2-1 to 2-13 and comparative examples 2-1 to 2-4, as shown in Table 2, the ethylene-vinyl acetate copolymer resin compositions according to the examples 1-1 to 1-13 and the comparative examples 1-1 to 1-4 were respectively used to manufacture graft copolymers. As an example, a manufacturing process for the graft copolymer according to the example 2-1 will be described in the following. Note that also the graft copolymer according to other examples and comparative examples were manufactured in a process similar to that in the example 2-1.

[Manufacturing of graft copolymer according to example 2-1]

[0150] First, the ethylene-vinyl acetate copolymer resin composition obtained in the example 1-1 was melt-kneaded at 200° C. by a Labo Plastomill single screw extruder (manufactured by Toyo Seiki Seisaku-sho Ltd.) to cause a grafting reaction. Accordingly, a graft copolymer including a main chain formed of an ethylene vinyl acetate copolymer and a side chain formed of poly(St/GMA) was obtained.

[0151] When the MFR (220° C/10 kgf) of the obtained graft copolymer was measured, it was 0.6 (g/10 min), and it was confirmed that the grafting reaction and the crosslinking reaction of the ethylene vinyl acetate copolymer progressed. Further, when the obtained graft copolymer was observed with a scanning electron microscope (“JEOL JSM T300” manufactured by JEOL Ltd.), spherical resins with a particle size of 0.1 to 0.2 μm were uniformly dispersed.

TABLE-US-00002 TABLE 2 Ethylene- vinyl acetate copolymer MFR .sup. resin composition (g/10 min) Example 2-1 Example 1-1 0.6 Example 2-2 Example 1-2 0.1 Example 2-3 Example 1-3 1.1 Example 2-4 Example 1-4 0.7 Example 2-5 Example 1-5 0.1 Example 2-6 Example 1-6 0.1 Example 2-7 Example 1-7 0.1 Example 2-8 Example 1-8 0.2 Example 2-9 Example 1-9 0.1 Example 2-10 Example 1-10 0.2 Example 2-11 Example 1-11 1.0 Example 2-12 Example 1-12 0.1 Example 2-13 Example 1-13 0.2 Comparative example 2-1 Comparative example 1-1 4.5 Comparative example 2-2 Comparative example 1-2 12.8 Comparative example 2-3 Comparative example 1-3 <0.01 Comparative example 2-4 Comparative example 1-4 2.6 .sup. 220° C./10 kgf
2. Thermoplastic resin composition

[0152] In examples 3 to 12, as the thermoplastic resin composition, a polyacetal resin composition, a polyamide resin composition, a polycarbonate resin composition, an ABS resin composition, a PC/ABS resin composition were manufactured. [0153] <Polyacetal resin composition>

[0154] In the examples 3 and 4, a polyacetal resin was used as the (X) thermoplastic resin according to the present invention to manufacture a polyacetal resin composition. [0155] [Manufacturing of polyacetal resin composition]

[0156] In examples 3-1 to 3-15 and comparative examples 3-1 to 3-5, a predetermined amount of the above-mentioned graft copolymer was appropriately dry-blended in a polyacetal resin (“DURACON M90-44 (trade name) manufactured by Polyplastics Co., Ltd.) with the mixing ratio shown in Table 3, they were melt-kneaded by a twin-screw extruder set to be 190° C., and thus, a polyacetal resin composition was obtained. In Table 3, the polyacetal resin was abbreviated as “POM”.

[0157] In the example 4, the polyacetal resin composition was manufactured by a method similar to that in the example 3-1 except that the (Z-1) lubricant or the (Z-2) inorganic filler was added with the mixing ratio shown in Table 4.

[0158] Note that the polyacetal resin composition according to the comparative example 3-1 was manufactured only with a polyacetal resin, and the graft copolymer was not used. The graft copolymers obtained in the examples 2-1 to 2-13 were used in the examples 3-1 to 3-15, and the graft copolymers according to the comparative examples 2-1 to 2-4 were respectively used in the comparative examples 3-2 to 3-5. [0159] [Manufacturing of evaluation material]

[0160] The polyacetal resin compositions according to the examples 3-1 to 3-15, examples 4-1 to 4-8, and the comparative examples 3-1 to 3-5 were molded by an injection molding machine, and thus, the evaluation materials according to the examples 3-1 to 3-15 and the comparative examples 3-1 to 3-5 were manufactured. As conditions of the injection molding, the barrel temperature was 200° C. and the mold temperature was 90° C.

[Evaluation method] [0161] Tensile strength

[0162] Conforming to JIS K-7113, the test was performed at the speed of 50 mm/min. The target value of a tensile strength was determined depending on the kind of the (X) thermoplastic resin, and was not less than 50 MPa in the case where a polyacetal resin was used. [0163] Flexural modulus

[0164] Conforming to JIS K-7203, the test was performed at the speed of 2 mm/min. The target value of a flexural modulus was determined depending on the kind of the (X) thermoplastic resin, and was not less than 1.5 GPa in the case where a polyacetal resin was used.

[0165] Sliding property evaluation 1 (thrust friction wear test)

[0166] Test machine: friction wear tester EFM-III-F manufactured by Orientec Co., Ltd.

[0167] Evaluation material: cylindrical material with an inner diameter of 20 mm and an outer diameter of 25.6

[0168] Quality of evaluation material: polyacetal resin composition having the composition shown in Table 3

[0169] Mate material: cylindrical material with an inner diameter of 20 mm and an outer diameter of 25.6 mm

[0170] Quality of mate material: (1) carbon steel (S45C), (2) the same material as the evaluation material

[0171] Test conditions (when the quality of the mate material is (1)): load 50 N, linear speed 50 cm/sec

[0172] Test conditions (when the quality of the mate material is (2)): load 20 N, linear speed 50 cm/sec

[0173] Test time: 100 minutes

[0174] In this test, the wear amount (mg) and dynamic friction coefficient of each evaluation material were obtained for each quality of the mating materials (1) and (2). The target values of the wear amount and dynamic friction coefficient are determined depending on the kind of the (X) thermoplastic resin. In the case where a polyacetal resin was used, the target value of the wear amount was set to not more than 2.0 mg and the target value of the dynamic friction coefficient was set to not more than 0.25 in the case where the mating member was the (1) carbon steel (S45C). Further, in the case where the mating material was the same material as the (2) evaluation material, the target value of the wear amount was set to not more than 2.0 mg and the target value of the dynamic friction coefficient was set to not more than 0.25.

[0175] Sliding property evaluation 2 (reciprocating sliding test)

[0176] Testing machine: Rubbing tester manufactured by Imoto Machinery Co., Ltd. 1566-A

[0177] Evaluation material: flat plate with a length of 80 mm, a width of 10 mm, and a height of 4 mm

[0178] Quality of evaluation material: polyacetal resin composition having the composition shown in Tables 3 and 4

[0179] Mating material: cylindrical material with a diameter of 10 mm

[0180] Quality of mating material: Duracon M90-44 (manufactured by Polyplastics Co., Ltd.)

[0181] Test conditions: load 3 kgf, linear speed 100 mm/sec, 5000 reciprocations

[0182] In this test, the wear amount (mg) of each evaluation material was obtained. The target value of the wear amount was set to not more than 10.0 mg.

Evaluation of Squeaking Sound

[0183] The obtained evaluation material and a polyacetal resin (“Duracon M90-44” (trade name) manufactured by Polyplastics Co., Ltd.) were respectively cut as a plate for squeaking sound evaluation test (60 mm×100 mm×2 mm) and a plate for a mate material to be rubbed (50 mm×25 mm×2 mm), and after deburring, the condition was adjusted at the temperature of 25° C. and the humidity of 50% for 12 hours.

[0184] The plate for squeaking sound evaluation test and each plate as a mate material were fixed to a stick-slip measuring device SSP-02 manufactured by manufactured by Ziegler instruments GmbH, and the squeaking sound risk value at the time when they were rubbed with each other under the conditions of a load=40 N and a speed=1 mm/sec was measured. Note that as the squeaking sound risk value is reduced, the risk of generation of squeaking sound is lower. The criteria for judging the squeaking sound risk value are as follows. [0185] Squeaking sound risk value 1 to 3: risk of generation of squeaking sound is low [0186] Squeaking sound risk value 4 to 5: risk of generation of squeaking sound is slightly high [0187] Squeaking sound risk value 6 to 10: risk of generation of squeaking sound is high

[0188] In these examples and comparative examples, the target value of the squeaking sound risk value was not more than 3.

[Evaluation results]

[0189] The evaluation results of the evaluation materials according to the examples 3-1 to 3-15 and the comparative examples 3-1 to 3-5 are shown in Table 3.

[0190] The evaluation results of the evaluation materials according to the examples 4-1 to 4-8 are shown in Table 4.

TABLE-US-00003 TABLE 3 (X) Evaluation of sliding properties Thermo- (Y) Mechanical (1) (2) Against plastic resin Graft copolymer properties Against S45C same material Reciprocating Parts Parts Tensile Flexural Wear Dynamic Wear Dynamic sliding test Squeaking by by strength modulus amount friction amount friction Wear sound Kind weight Kind weight (mpa) (GPa) (mg) coefficient (mg) coefficient amount (mg) risk value Example 3-1 POM 100 Example 2-1  11 50 1.9 0.8 0.18 1.8 0.16 5.4 1 Example 3-2 POM 100 Example 2-1  1 60 2.3 1.9 0.23 2.0 0.22 9.8 3 Example 3-3 POM 100 Example 2-1  5 54 1.9 1.6 0.20 1.9 0.19 4.8 2 Example 3-4 POM 100 Example 2-2  11 51 2.0 0.1 0.18 0.4 0.15 3.4 1 Example 3-5 POM 100 Example 2-3  11 50 1.8 1.1 0.17 1.3 0.14 6.9 1 Example 3-6 POM 100 Example 2-4  11 51 2.0 1.2 0.19 1.8 0.17 7.8 2 Example 3-7 POM 100 Example 2-5  11 51 1.9 1.4 0.18 1.8 0.18 6.7 2 Example 3-8 POM 100 Example 2-6  11 50 2.3 0.6 0.18 1.9 0.20 3.5 2 Example 3-9 POM 100 Example 2-7  11 50 2.2 0.5 0.18 1.1 0.16 4.3 1 Example 3-10 POM 100 Example 2-8  11 51 1.8 1.8 0.19 1.9 0.17 9.0 2 Example 3-11 POM 100 Example 2-9  11 50 2.2 0.8 0.19 2.0 0.20 9.8 2 Example 3-12 POM 100 Example 2-10 11 52 1.8 1.7 0.21 2.0 0.20 9.1 3 Example 3-13 POM 100 Example 2-11 11 50 2.0 1.6 0.20 1.8 0.18 6.7 2 Example 3-14 POM 100 Example 2-12 11 50 2.1 2.0 0.20 1.9 0.17 4.2 2 Example 3-15 POM 100 Example 2-13 11 51 1.9 2.0 0.19 1.9 0.21 8.9 2 Comparative POM 100 — — 61 2.4 83.4 0.34 66.4 0.30 20.3 10 example 3-1 Comparative POM 100 Comparative 11 48 1.6 12.1 0.23 2.7 0.19 14.5 7 example 3-2 example 2-1 Comparative POM 100 Comparative 11 53 2.0 3.6 0.16 3.9 0.18 14.7 8 example 3-3 example 2-2 Comparative POM 100 Comparative 11 52 1.7 2.2 0.15 5.9 0.19 17.7 6 example 3-4 example 2-3 Comparative POM 100 Comparative 11 52 1.8 4.5 0.24 3.5 0.23 16.8 3 example 3-5 example 2-4 Target value 50 1.5 2.0 0.25 2.0 0.25 10.0 3 or more or more or less or less or less or less or less or less

TABLE-US-00004 TABLE 4 (X) Thermo- (Z-2) plastic (Y) Inorganic Mechanical resin Graft copolymer (Z-1) Lubricant filler properties Parts Parts Parts Parts Tensile Flexural by by by by strength modulus Kind weight Kind weight Kind weight Kind weight (MPa) (GPa) Example 4-1 POM 100 Example 2-1 5 SS 1 — — 54 1.9 Example 4-2 POM 100 Example 2-1 5 SS 3 — — 52 1.8 Example 4-3 POM 100 Example 2-1 5 GMS 1 — — 53 1.9 Example 4-4 POM 100 Example 2-1 5 SA 1 — — 54 2.0 Example 4-5 POM 100 Example 2-1 5 PEWAX 1 — — 53 2.0 Example 4-6 POM 100 Example 2-1 5 PLWAX 1 — — 53 1.9 Example 4-7 POM 100 Example 2-1 5 — — CaCO.sub.3 5 56 2.8 Example 4-8 POM 100 Example 2-1 5 — — TiK 5 57 2.8 Target value 50 1.5 or more or more Evaluation of sliding properties (1) (2) Against Against S45C same material Reciprocating Wear Dynamic Wear Dynamic sliding test Squeaking amount friction amount friction Wear amount sound (mg) coefficient (mg) coefficient (mg) risk value Example 4-1 1.6 0.16 1.0 0.18 4.6 1 Example 4-2 1.0 0.16 1.5 0.17 3.0 1 Example 4-3 1.2 0.18 1.3 0.19 5.1 1 Example 4-4 0.8 0.16 1.0 0.16 3.3 1 Example 4-5 0.9 0.15 1.2 0.16 4.4 1 Example 4-6 1.0 0.16 1.4 0.16 4.2 1 Example 4-7 1.7 0.20 1.8 0.20 2.0 2 Example 4-8 1.3 0.19 1.6 0.19 1.5 3 Target value 2.0 0.25 2.0 0.25 10.0 3 or less or less or less or less or less or less

[0191] Meanings of abbreviations in Table 4 are as follows. [0192] SS: stearyl stearate [0193] GMS: glycerin monostearate [0194] SA: stearic acid amide [0195] PEWAX: polyethylene wax [0196] PLWAX: paraffin wax [0197] CaCO.sub.3: calcium carbonate (cubic, fatty acid treated) [0198] TiK: potassium titanate

Mechanical Properties

[0199] In any of the evaluation materials according to the examples 3-1 to 3-15 and the examples 4-1 to 4-8, a large value not less than 50 MPa of a tensile strength and a large value not less than 1.5G Pa of a flexural modulus were obtained. Meanwhile, in the evaluation material according to the comparative example 3-2 that includes no (C) organic peroxide, the tensile strength has a small value less than 50 MPa.

Sliding Property Evaluation

[0200] In any of the evaluation materials according to the examples 3-1 to 3-15 and the examples 4-1 to 4-8, a small value of not more than 2.0 mg of the wear amount and a small value of not more than 0.25 of the dynamic friction coefficient were obtained in a thrust friction wear test in which the mate material was the (1) carbon steel (S45C).

[0201] Further, in any of the evaluation materials according to the examples 3-1 to 3-15 and the examples 4-1 to 4-8, a small value of not more than 2.0 mg of the wear amount and a small value of not more than 0.25 of the dynamic friction coefficient were obtained even in a thrust friction wear test in which the mate material was the (2) evaluation material, i.e., in a thrust friction wear test using the evaluation materials with each other.

[0202] Furthermore, in any of the evaluation materials according to the examples 3-1 to 3-15 and the examples 4-1 to 4-8, a small value of not more than 10.0 mg of the wear amount was obtained in a reciprocating sliding test.

[0203] Meanwhile, in any of the evaluation materials according to the comparative examples 3-1 to 3-5, the wear amount had a value larger than 2.0 mg in a thrust friction wear test in which the mate material was the (1) carbon steel (S45C). In addition, in the evaluation material according to the comparative example 3-1 that includes no (Y) graft copolymer, the dynamic friction coefficient had a value larger than 0.25.

[0204] Further, in any of the evaluation materials according to the comparative examples 3-1 to 3-5, the wear amount had a value larger than 2.0 mg even in a thrust friction wear test in which the mate material was the (2) evaluation material, i.e., in a thrust friction wear test using the evaluation materials with each other. In addition, in the evaluation material according to the comparative example 3-1 that includes no (Y) graft copolymer, also the dynamic friction coefficient had a value larger than 0.25.

[0205] Furthermore, in any of the evaluation materials according to the comparative examples 3-1 to 3-5, the wear amount had a value larger than 10.0 mg in a reciprocating sliding test.

Squeaking Sound Risk Evaluation

[0206] In any of the evaluation materials according to the examples 3-1 to 3-15 and the examples 4-1 to 4-8, the squeaking sound risk value was a small value not more than 3. Meanwhile, in the evaluation materials according to the comparative examples 3-1 to 3-5, the squeaking sound risk had a value larger than 3.

<Polyamide resin composition>

[0207] In the examples 5 to 8, a polyamide resin was used as the (X) thermoplastic resin according to the present invention to manufacture a polyamide resin composition.

[0208] Specifically, in the examples 5 to 8, respectively, the following four kinds of (X) polyamide resins were mixed with the (Y) graft copolymer, a polyamide resin composition was obtained. [0209] Nylon 66: “Zytel 103 HSL” (trade name) manufactured by DuPont Co. (hereinafter abbreviated as “PA66”). [0210] Nylon 66 including glass fiber: “Zytel 103 HSL 33HS1L” (trade name) manufactured by DuPont Co. (hereinafter abbreviated as “PA66GGF”) [0211] Nylon 6: “Amilan CM 1017 A” (trade name) manufactured by Toray Industries, Inc. (abbreviated as “PA6”). [0212] Nylon MXD6: “MX Nylon 56001” (trade name) manufactured by Mitsubishi Gas Chemical Company, Inc. (abbreviated as “PAMXD”)

[0213] [Manufacturing of polyamide resin composition (PA66)]

[0214] In the example 5, the PA66 was used as the (X).

[0215] In examples 5-1 to 5-15 and comparative examples 5-1 to 5-5, the (Y) graft copolymer was added to the (X) polyamide resin (PA66) with the mixing ratio shown in Table 5, they were melt-kneaded by a twin-screw extruder set to be 270° C., and thus, a polyamide resin composition was obtained.

[0216] Note that the polyamide resin composition according to the comparative example 5-1 was manufactured only with the (X) polyamide resin, and the (Y) graft copolymer was not used. The (Y) graft copolymers obtained in the examples 2-1 to 2-13 were used in the examples 5-1 to 5-15, and the (Y) graft copolymers obtained in the comparative examples 2-1 to 2-4 were respectively used in the comparative examples 5-2 to 5-5.

[Manufacturing of evaluation material (PA66)]

[0217] In the examples 5-1 to 5-15 and the comparative examples 5-1 to 5-5, the method of manufacturing the evaluation material is similar to that in the examples 3-1 to 3-15 and the comparative examples 3-1 to 3-5 except that the barrel temperature was 275° C. and the mold temperature was 80° C.

[Evaluation method (PA66)]

[0218] In the examples 5-1 to 5-15 and the comparative examples 5-1 to 5-5, the sliding property evaluation 2 was not performed and only the sliding property evaluation 1 was performed in the evaluation method. The sliding property evaluation 1 was performed in the same method as that in the example 3.

[Evaluation results (PA66)]

[0219] The evaluation results of the evaluation materials according to the examples 5-1 to 5-15 and the comparative examples 5-1 to 5-5 are shown in Table 5. The target values of each evaluation were appropriately changed depending on the kind of the (X) thermoplastic resin, and were as shown in Table 5.

TABLE-US-00005 (X) Evaluation of sliding properties Squeaking Thermo- (Y) Mechanical (1) (2) Against sound risk value plastic resin Graft copolymer properties Against S45C same material (2) Parts Parts Tensile Flexural Wear Dynamic Wear Dynamic (1) Against by by strength modulus amount friction amount friction Against same Kind weight Kind weight (MPa) (GPa) (mg) coefficient (mg) coefficient S45C material Example 5-1 PA66 100 Example 2-1  11 80 2.5 0.3 0.25 1.1 0.30 1 2 Example 5-2 PA66 100 Example 2-1  1 90 2.8 1.9 0.34 3.4 0.33 3 3 Example 5-3 PA66 100 Example 2-1  5 85 2.7 1.5 0.30 3.1 0.31 1 2 Example 5-4 PA66 100 Example 2-2  11 81 2.5 0.2 0.22 0.9 0.28 2 2 Example 5-5 PA66 100 Example 2-3  11 80 2.4 0.5 0.26 1.2 0.30 1 2 Example 5-6 PA66 100 Example 2-4  11 81 2.5 0.4 0.25 1.3 0.31 1 2 Example 5-7 PA66 100 Example 2-5  11 81 2.4 0.3 0.26 1.2 0.32 2 2 Example 5-8 PA66 100 Example 2-6  11 81 2.3 0.6 0.27 1.4 0.30 2 2 Example 5-9 PA66 100 Example 2-7  11 80 2.4 0.9 0.24 1.2 0.31 1 2 Example 5-10 PA66 100 Example 2-8  11 81 2.5 1.8 0.27 2.2 0.30 2 2 Example 5-11 PA66 100 Example 2-9  11 82 2.3 1.9 0.28 2.6 0.32 2 2 Example 5-12 PA66 100 Example 2-10 11 82 2.4 1.2 0.27 2.3 0.30 2 2 Example 5-13 PA66 100 Example 2-11 11 81 2.5 1.7 0.28 2.1 0.31 2 2 Example 5-14 PA66 100 Example 2-12 11 81 2.4 1.9 0.28 2.4 0.31 2 2 Example 5-15 PA66 100 Example 2-13 11 80 2.4 2.0 0.29 2.3 0.32 2 2 Comparative PA66 100 — — 93 2.9 2.3 0.61 31.2 0.34 9 10 example 5-1 Comparative PA66 100 Comparative 11 78 2.1 2.1 0.24 5.6 0.32 4 5 example 5-2 example 2-1 Comparative PA66 100 Comparative 11 82 2.3 1.9 0.28 6.9 0.31 5 5 example 5-3 example 2-2 Comparative PA66 100 Comparative 11 79 2.3 1.7 0.25 4.2 0.29 3 3 example 5-4 example 2-3 Comparative PA66 100 Comparative 11 81 2.4 2.2 0.17 5.3 0.30 3 3 example 5-5 example 2-4 Target value 80 2.3 2.0 0.35 5.0 0.35 3 3 or more or more or less or less or less or less or less or less

[0220] As is evident from Table 5, the target values for each of mechanical properties, sliding property evaluation, and the squeaking sound risk value were achieved in the examples 5-1 to 5-15.

[0221] In contrast, in the comparative example 5-1, the wear amount and the dynamic friction coefficient in the case where the mate material was the (1) carbon steel (S45C) exceeded the respective target values, and the wear amount in the case where the mate material was the same material as the (2) evaluation material significantly exceeded the target value. Further, in the comparative example 5-1, the squeaking sound risk value in any of the case where the mate material was the (1) carbon steel (S45C) and the case where the mate material was the same material as the (2) evaluation material significantly exceeded the target value.

[0222] In the comparative example 5-2, the tensile strength and the flexural modulus didn't satisfy the respective target values. Further, in the comparative example 5-2, the wear amount in the case where the mate material was the (1) carbon steel (S45C) and in the case where the mate material was the same material as the (2) evaluation material exceeded the target value. Furthermore, in the comparative example 5-2, the squeaking sound risk value in any of the case where the mate material was the (1) carbon steel (S45C) and the case where the mate material was the same material as the (2) evaluation material exceeded the target value.

[0223] In the comparative example 5-3, the wear amount in the case where the mate material was the same material as the (2) evaluation material exceeded the target value. Further, in the comparative example 5-3, the squeaking sound risk value in any of the case where the mate material was the (1) carbon steel (S45C) and the case where the mate material was the same material as the (2) evaluation material exceeded the target value.

[0224] In the comparative example 5-4, the tensile strength didn't satisfy the target value.

[0225] In the comparative example 5-5, the wear amount in any of the case where the mate material was the (1) carbon steel (S45C) and the case where the mate material was the same material as the (2) evaluation material exceeded the target value.

[Manufacturing of polyamide resin composition (PA66GF)]

[0226] In the example 6, the PA66GF was used as the (X).

[0227] In examples 6-1 to 6-6 and a comparative example 6-1, a predetermined amount of the (Y) graft copolymer was appropriately was dry-blended in the (X) polyamide resin (PA66GF) with the mixing ration shown in Table 6, they were melt-kneaded by a twin-screw extruder set to be 270° C., and thus, a polyamide resin composition was obtained.

[0228] Note that the polyamide resin composition according to the comparative example 6-1 was manufactured only with the (X) polyamide resin, and the (Y) graft copolymer was not used. In the examples 6-1 to 6-6, the (Y) graft copolymers obtained in the examples 2-1, 2-6, 2-7, and 2-11 were used.

[Manufacturing of evaluation material (PA66GF)]

[0229] In the examples 6-1 to 6-6 and the comparative example 6-1, the method of manufacturing the evaluation material is similar to that in the examples 3-1 to 3-15 and the comparative examples 3-1 to 3-5 except that the barrel temperature was 275° C. and the mold temperature was 80° C.

[Evaluation method (PA66GF)]

[0230] In the examples 6-1 to 6-6 and the comparative example 6-1, the sliding property evaluation 2 was not performed and only the sliding property evaluation 1 was performed in the evaluation method. The sliding property evaluation 1 was performed in the same method as that in the example 3.

[Evaluation results (PA66GF)]

[0231] The evaluation results of the evaluation materials according to the examples 6-1 to 6-6 and the comparative example 6-1 are shown in Table 6. The target values of each evaluation were appropriately changed depending on the kind of the (X) thermoplastic resin, and were as shown in Table 6.

TABLE-US-00006 TABLE 6 (X) Evaluation of sliding properties Squeaking Thermo- (Y) Mechanical (1) (2) Against sound risk value plastic resin Graft copolymer properties Against S45C same material (2) Parts Parts Tensile Flexural Wear Dynamic Wear Dynamic (1) Against by by strength modulus amount friction amount friction Against same Kind weight Kind weight (MPa) (GPa) (mg) coefficient (mg) coefficient S45C material Example 6-1 PA66GF 100 Example 2-1  11 106 4.6 1.9 0.32 1.9 0.19 1 2 Example 6-2 PA66GF 100 Example 2-1  1 119 5.4 2.0 0.35 4.5 0.29 3 3 Example 6-3 PA66GF 100 Example 2-1  5 112 4.9 2.0 0.35 3.8 0.22 2 3 Example 6-4 PA66GF 100 Example 2-6  11 105 4.7 1.9 0.32 1.8 0.19 1 2 Example 6-5 PA66GF 100 Example 2-7  11 106 4.6 2.0 0.33 2.0 0.21 1 2 Example 6-6 PA66GF 100 Example 2-11 11 105 4.5 2.0 0.32 2.0 0.22 2 2 Comparative PA66GF 100 — — 125 5.8 2.3 0.38 5.8 0.31 9 9 example 6-1 Target value 100 4.5 2.0 0.35 5.0 0.35 3 3 or more or more or less or less or less or less or less or less

[0232] As is evident from Table 6, the target values for each of mechanical properties, sliding property evaluation, and the squeaking sound risk value were achieved in the examples 6-1 to 6-6.

[0233] In contrast, in the comparative example 6-1, the wear amount and the dynamic friction coefficient in the case where the mate material was the (1) carbon steel (S45C) exceeded the respective target values. Further, the wear amount in the case where the mate material was the same material as the (2) evaluation material exceeded the target value. Furthermore, in the comparative example 6-1, the squeaking sound risk value in any of the case where the mate material was the (1) carbon steel (S45C) and the case where the mate material was the same material as the (2) evaluation material significantly exceeded the target value.

[Manufacturing of polyamide resin composition (PA6)]

[0234] In the example 7, the PA6 was used as the (X).

[0235] In examples 7-1 to 7-6 and a comparative example 7-1, a predetermined amount of the (Y) graft copolymer was appropriately was dry-blended in the (X) polyamide resin (PA6) with the mixing ration shown in Table 7, they were melt-kneaded by a twin-screw extruder set to be 240° C., and thus, a polyamide resin composition was obtained.

[0236] Note that the polyamide resin composition according to the comparative example 7-1 was manufactured only with the (X) polyamide resin, and the (Y) graft copolymer was not used. In the examples 7-1 to 7-6, the (Y) graft copolymers obtained in the examples 2-1, 2-6, 2-7, and 2-11 were used.

[Manufacturing of evaluation material (PA6)]

[0237] In the examples 7-1 to 7-6 and the comparative example 7-1, the method of manufacturing the evaluation material is similar to that in the examples 3-1 to 3-15 and the comparative examples 3-1 to 3-5 except that the barrel temperature was 245° C. and the mold temperature was 80° C.

[Evaluation method (PA6)]

[0238] In the examples 7-1 to 7-6 and the comparative example 7-1, the sliding property evaluation 2 was not performed and only the sliding property evaluation 1 was performed in the evaluation method. The sliding property evaluation 1 was performed in the same method as that in the example 3.

[Evaluation results (PA6)]

[0239] The evaluation results of the evaluation materials according to the examples 7-1 to 7-6 and the comparative example 7-1 are shown in Table 7. The target values of each evaluation were appropriately changed depending on the kind of the (X) thermoplastic resin, and were as shown in Table 7.

TABLE-US-00007 TABLE 7 (X) Evaluation of sliding properties Squeaking Thermo- (Y) Mechanical (1) (2) Against sound risk value plastic resin Graft copolymer properties Against S45C same material (2) Parts Parts Tensile Flexural Wear Dynamic Wear Dynamic (1) Against by by strength modulus amount friction amount friction Against same Kind weight Kind weight (MPa) (GPa) (mg) coefficient (mg) coefficient S45C material Example 7-1 PA6 100 Example 2-1  11 60 2.2 0.8 0.20 4.7 0.24 2 2 Example 7-2 PA6 100 Example 2-1  1 74 2.4 1.7 0.33 5.0 0.34 3 3 Example 7-3 PA6 100 Example 2-1  5 65 2.4 1.5 0.28 5.0 0.28 2 2 Example 7-4 PA6 100 Example 2-6  11 61 2.1 0.9 0.21 4.6 0.23 2 2 Example 7-5 PA6 100 Example 2-7  11 62 2.2 1.2 0.22 4.5 0.23 2 2 Example 7-6 PA6 100 Example 2-11 11 62 2.2 1.0 0.24 4.7 0.24 2 2 Comparative PA6 100 — — 81 2.7 2.0 0.70 Melted 9 9 example 7-1 Target value 60 2.0 2.0 0.35 5.0 0.35 3 3 or more or more or less or less or less or less or less or less

[0240] As is evident from Table 7, the target values for each of mechanical properties, sliding property evaluation, and the squeaking sound risk value were achieved in the examples 7-1 to 7-6.

[0241] In contrast, in the comparative example 7-1, the dynamic friction coefficient in the case where the mate material was the (1) carbon steel (S45C) significantly exceeded the target value. Further, the evaluation material was melt in a thrust friction wear test in which the mate material was the same material as the (2) evaluation material. Furthermore, in the comparative example 7-1, the squeaking sound risk value in any of the case where the mate material was the (1) carbon steel (S45C) and the case where the mate material was the same material as the (2) evaluation material significantly exceeded the target value.

[Manufacturing of polyamide resin composition (PAMXD)]

[0242] In the example 8, the PAMXD was used as the (X).

[0243] In examples 8-1 to 8-6 and a comparative example 8-1, a predetermined amount of the (Y) graft copolymer was appropriately was dry-blended in the (X) polyamide resin (PAMXD) with the mixing ration shown in Table 8, they were melt-kneaded by a twin-screw extruder set to be 250° C., and thus, a polyamide resin composition was obtained.

[0244] Note that the polyamide resin composition according to the comparative example 8-1 was manufactured only with the (X) polyamide resin, and the (Y) graft copolymer was not used. In the examples 8-1 to 8-6, the (Y) graft copolymers obtained in the examples 2-1, 2-6, 2-7, and 2-11 were used.

[Manufacturing of evaluation material (PAMXD)]

[0245] In the examples 8-1 to 8-6 and the comparative example 8-1, the method of manufacturing the evaluation material is similar to that in the examples 3-1 to 3-15 and the comparative examples 3-1 to 3-5 except that the barrel temperature was 255° C. and the mold temperature was 80° C.

[Evaluation method (PAMXD)]

[0246] In the examples 8-1 to 8-6 and the comparative example 8-1, the sliding property evaluation 2 was not performed and only the sliding property evaluation 1 was performed in the evaluation method. The sliding property evaluation 1 was performed in the same method as that in the example 3.

[Evaluation results (PAMXD)]

[0247] The evaluation results of the evaluation materials according to the examples 8-1 to 8-6 and the comparative example 8-1 are shown in Table 8. The target values of each evaluation were appropriately changed depending on the kind of the (X) thermoplastic resin, and were as shown in Table 8.

TABLE-US-00008 TABLE 8 (X) Evaluation of sliding properties Squeaking Thermoplastic (Y) Mechanical (1) (2) Against sound risk value resin Graft copolymer properties Against S45C same material (2) Parts Parts Tensile Flexural Wear Dynamic Wear Dynamic (1) Against by by strength modulus amount friction amount friction Against same Kind weight Kind weight (MPa) (GPa) (mg) coefficient (mg) coefficient S45C material Example 8-1 PAMXD 100 Example 2-1  11 82 3.5 1.2 0.18 3.8 0.23 2 2 Example 8-2 PAMXD 100 Example 2-1  1 90 4.0 2.0 0.26 5.0 0.33 3 3 Example 8-3 PAMXD 100 Example 2-1  5 86 3.8 1.9 0.20 4.9 0.28 2 3 Example 8-4 PAMXD 100 Example 2-6  11 81 3.5 1.1 0.19 3.7 0.24 1 2 Example 8-5 PAMXD 100 Example 2-7  11 81 3.6 1.2 0.19 3.4 0.22 2 2 Example 8-6 PAMXD 100 Example 2-11 11 82 3.5 1.3 0.18 3.6 0.23 2 3 Comparative PAMXD 100 — — 95 4.2 5.0 0.66 35.0 0.37 9 10 example 8-1 Target value 80 3.5 2.0 0.35 5.0 0.35 3 3 or more or more or less or less or less or less or less or less

[0248] As is evident from Table 8, the target values for each of mechanical properties, sliding property evaluation, and the squeaking sound risk value were achieved in the examples 8-1 to 8-6.

[0249] In contrast, in the comparative example 8-1, the wear amount and the dynamic friction coefficient in the case where the mate material was the (1) carbon steel (S45C) significantly exceeded the target value. Further, the wear amount in the case where the mate material was the same material as the (2) evaluation material significantly exceeded the target value, and also the dynamic friction coefficient exceeded the target value. Furthermore, in the comparative example 8-1, the squeaking sound risk value in any of the case where the mate material was the (1) carbon steel (S45C) and the case where the mate material was the same material as the (2) evaluation material significantly exceeded the target value.

<Polycarbonate resin composition>

[0250] In the example 9, a polycarbonate resin was used as the (X) thermoplastic resin according to the present invention to manufacture a polycarbonate resin composition.

[Manufacturing of polycarbonate resin composition]

[0251] In examples 9-1 to 9-15 and comparative examples 9-1 to 9-6, a predetermined amount of the (Y) graft copolymer was appropriately dry-blended in the (X) polycarbonate resin (“Tarflon A2200” (trade name), standard grade, manufactured by Idemitsu Kosan Co., Ltd., shown as “PC1” in Table 9 and Table 10) with the mixing ratio shown in Table 9 and Table 10, they were melt-kneaded by a twin-screw extruder set to be 260° C., and thus, a polycarbonate resin composition was obtained.

[0252] Note that the polycarbonate resin composition according to the comparative example 9-1 was manufactured only with the (X) polycarbonate resin, and the (Y) graft copolymer was not used. The (Y) graft copolymers obtained in the examples 2-1 to 2-13 were used in the examples 9-1 to 9-15, and the (Y) graft copolymers according to the comparative examples 2-1 to 2-4 were used in the comparative examples 9-2 to 9-6.

[Manufacturing of evaluation material]

[0253] In the examples 9-1 to 9-15 and the comparative examples 9-1 to 9-6, the method of manufacturing the evaluation material is similar to that in the examples 3-1 to 3-15 and the comparative examples 3-1 to 3-5 except that the barrel temperature was 265° C. and the mold temperature was 80° C.

[Evaluation method]

[0254] In the examples 9-1 to 9-15 and the comparative examples 9-1 to 9-6, the sliding property evaluation 2 was not performed and only the sliding property evaluation 1 was performed in the evaluation method.

[0255] The mate material in the sliding property evaluation 1 was the (1) carbon steel (S45C), a (2) neat PC1 resin, a (3) polyethylene terephthalate resin, and a (4) polyethylene naphthalate resin. Note that the neat PC1 resin described herein is the (X) polycarbonate resin to which the (Y) graft copolymer is not added.

[0256] The test conditions in the case where the mate material was the (1) were a load: 50 N and a linear speed of 10 cm/sec, and the test conditions in the case where the mate material was the (2) to (4) were a load: 20 N and a linear speed: 10 cm/sec.

[0257] Further, the other conditions other than the above-mentioned mate material and test conditions (a load and linear speed) were similar to those in the example 3.

[Evaluation results]

[0258] The evaluation results of the evaluation materials according to the examples 9-1 to 9-15 and the comparative examples 9-1 to 9-6 are shown in Table 9 and Table 10. The target values of each evaluation were appropriately changed depending on the kind of the (X) thermoplastic resin, and were as shown in Table 9 and Table 10.

TABLE-US-00009 TABLE 9 (X) Evaluation of sliding properties Squeaking Thermo- (Y) Mechanical (1) (2) Against sound risk value plastic resin Graft copolymer properties Against S45C neat PC1 (2) Parts Parts Tensile Flexural Wear Dynamic Wear Dynamic (1) Against by by strength modulus amount friction amount friction Against neat Kind weight Kind weight (MPa) (GPa) (mg) coefficient (mg) coefficient S45C PC1 Example 9-1 PC1 100 Example 2-1  11 52 1.7 1.5 0.20 3.1 0.21 1 2 Example 9-2 PC1 100 Example 2-1  1 60 2.1 2.2 0.24 5.0 0.25 3 3 Example 9-3 PC1 100 Example 2-1  3 58 2.0 2.0 0.22 4.8 0.25 3 3 Example 9-4 PC1 100 Example 2-2  11 51 1.8 1.2 0.19 3.0 0.22 1 2 Example 9-5 PC1 100 Example 2-3  11 51 1.8 1.3 0.19 2.9 0.22 1 2 Example 9-6 PC1 100 Example 2-4  11 51 1.9 1.4 0.19 2.9 0.22 1 1 Example 9-7 PC1 100 Example 2-5  11 52 1.8 1.4 0.22 3.0 0.21 2 2 Example 9-8 PC1 100 Example 2-6  11 52 1.8 1.5 0.19 4.0 0.21 1 2 Example 9-9 PC1 100 Example 2-7  11 51 1.8 1.4 0.20 2.6 0.21 1 2 Example 9-10 PC1 100 Example 2-8  11 49 1.7 2.1 0.24 3.8 0.24 2 2 Example 9-11 PC1 100 Example 2-9  11 49 1.6 2.2 0.24 3.6 0.23 2 3 Example 9-12 PC1 100 Example 2-10 11 50 1.7 2.1 0.25 3.6 0.22 2 3 Example 9-13 PC1 100 Example 2-11 11 52 1.6 2.0 0.24 3.9 0.23 2 3 Example 9-14 PC1 100 Example 2-12 11 50 1.8 2.0 0.24 3.7 0.22 2 2 Example 9-15 PC1 100 Example 2-13 11 51 1.7 2.4 0.25 3.7 0.25 2 3 Comparative PC1 100 — — 63 2.2 6.5 0.35 39.1 0.38 8 10 example 9-1 Comparative PC1 100 Example 2-1  30 41 1.4 2.0 0.23 7.2 0.25 2 3 example 9-2 Comparative PC1 100 Comparative 11 51 1.7 3.2 0.23 8.3 0.23 2 2 example 9-3 example 2-1 Comparative PC1 100 Comparative 11 52 1.6 3.5 0.24 9.4 0.29 3 4 example 9-4 example 2-2 Comparative PC1 100 Comparative 11 52 1.5 2.4 0.22 4.2 0.24 3 5 example 9-5 example 2-3 Comparative PC1 100 Comparative 11 52 1.8 2.0 0.20 7.2 0.22 1 2 example 9-6 example 2-4 Target value 40 1.5 2.5 0.25 5.0 0.25 3 3 or more or more or less or less or less or less or less or less

TABLE-US-00010 TABLE 10 (X) Thermo- (Y) Evaluation of sliding properties plastic resin Graft copolymer (3) Against PET (4) Against PEN Parts Parts Wear Dynamic Wear Dynamic by by amount friction amount friction Kind weight Kind weight (mg) coefficient (mg) coefficient Example 9-1 PC1 100 Example 2-1  11 3.3 0.22 3.5 0.20 Example 9-2 PC1 100 Example 2-1  1 4.9 0.25 5.0 0.25 Example 9-3 PC1 100 Example 2-1  3 4.5 0.25 4.9 0.25 Example 9-8 PC1 100 Example 2-6  11 3.1 0.21 3.4 0.21 Example 9-9 PC1 100 Example 2-7  11 3.2 0.22 3.5 0.21 Example 9-13 PC1 100 Example 2-11 11 4.1 0.24 4.3 0.24 Comparative PC1 100 — — Melted Melted example 9-1 Target value 5.0 0.25 5.0 0.25 or less or less or less or less

[0259] As is evident from Table 9 and Table 10, the target values for each of mechanical properties, sliding property evaluation, and the squeaking sound risk value were achieved in the examples 9-1 to 9-15.

[0260] In contrast, in the comparative example 9-1, the wear amount and the dynamic friction coefficient in any of the case where the mate material was the (1) carbon steel (S45C) and the case where the mate material was the (2) neat PC1 resin significantly exceeded the respective target values. Further, the evaluation material was melt in a thrust friction wear test in which the mate material was any of the (3) polyethylene terephthalate resin and the (4) polyethylene naphthalate resin. Furthermore, the squeaking sound risk value in any of the case where the mate material was the (1) carbon steel (S45C) and the case where the mate material was the (2) neat PC1 resin exceeded the target value.

[0261] In the comparative example 9-2, the flexural modulus didn't satisfy the target value. Further, in the comparative example 9-2, the wear amount in the case where the mate material was the (2) neat PC1 resin exceeded the target value.

[0262] In the comparative example 9-3, the wear amount in any of the case where the mate material was the (1) carbon steel (S45C) and the case where the mate material was the (2) neat PC1 resin exceeded the target value.

[0263] In the comparative example 9-4, the wear amount in the case where the mate material was the (1) carbon steel (S45C) exceeded the target value. Further, the wear amount and the dynamic friction coefficient in the case where the mate material was the (2) neat PC1 resin exceeded the respective target values. Further, the squeaking sound risk value in the case where the mate material was the (2) neat PC1 resin exceeded the target value.

[0264] In the comparative example 9-5, the squeaking sound risk value in the case where the mate material was the (2) neat PC1 resin exceeded the target value.

[0265] In the comparative example 9-6, the wear amount in the case where the mate material was the (2) neat PC1 resin exceeded the target value.

<ABS resin composition>

[0266] In an example 10, an ABS resin was used as the (X) thermoplastic resin according to the present invention to manufacture an ABS resin composition.

[Manufacturing of ABS resin composition]

[0267] In examples 10-1 to 10-15 and comparative examples 10-1 to 10-6, a predetermined amount of the (Y) graft copolymer was appropriately dry-blended in the (X) ABS resin (“Toyolac 700-314” (trade name), standard grade, manufactured by manufactured by Toray Industries, Inc. shown as “ABS1” in Table 11) with the mixing ratio shown in Table 11, they were melt-kneaded by a twin-screw extruder set to be 240° C., and thus, an ABS resin composition was obtained.

[0268] Note that the ABS resin composition according to the comparative example 10-1 was manufactured only with the (X) ABS resin, and the (Y) graft copolymer was not used. The (Y) graft copolymers obtained in the examples 2-1 to 2-13 were used in the examples 10-1 to 10-15, and the (Y) graft copolymers according to the example 2-1 and the comparative examples 2-1 to 2-4 were respectively used in the comparative examples 10-2 to 10-6.

[Manufacturing of evaluation material]

[0269] In the examples 10-1 to 10-15 and the comparative examples 10-1 to 10-6, the method of manufacturing the evaluation material is similar to that in the examples 3-1 to 3-15 and the comparative examples 3-1 to 3-5 except that the barrel temperature was 245° C. and the mold temperature was 80° C.

[Evaluation method]

[0270] In the examples 10-1 to 10-15 and the comparative examples 10-1 to 10-6, the sliding property evaluation 2 was not performed and only the sliding property evaluation 1 was performed in the evaluation method.

[0271] The mate material in the sliding property evaluation 1 was the (1) carbon steel (S45C) and a neat ABS1 resin.

[0272] The test conditions in the case where the mate material was the (1) were a load: 50 N and a linear speed of 10 cm/sec, and the test conditions in the case where the mate material was the (2) neat ABS1 were a load: 20 N and a linear speed: 10 cm/sec. Note that the neat ABS1 resin described herein is the (X) ABS resin to which the (Y) graft copolymer is not added.

[0273] Further, the other conditions other than the above-mentioned mate material and test conditions (a load and linear speed) were similar to those in the example 3.

[Evaluation results]

[0274] The evaluation results of the evaluation materials according to the examples 10-1 to 10-15 and the comparative examples 10-1 to 10-6 are shown in Table 11. The target values of each evaluation were appropriately changed depending on the kind of the (X) thermoplastic resin, and were as shown in Table 11.

TABLE-US-00011 TABLE 11 (X) Evaluation of sliding properties Squeaking Thermo- (Y) Mechanical (1) (2) Against sound risk value plastic resin Graft copolymer properties Against S45C neat ABS1 (2) Parts Parts Tensile Flexural Wear Dynamic Wear Dynamic (1) Against by by strength modulus amount friction amount friction Against neat Kind weight Kind weight (MPa) (GPa) (mg) coefficient (mg) coefficient S45C ABS1 Example 10-1 ABS1 100 Example 2-1  10 45 2.3 2.8 0.18 3.6 0.17 1 2 Example 10-2 ABS1 100 Example 2-1  1 48 2.5 4.8 0.24 4.4 0.22 3 3 Example 10-3 ABS1 100 Example 2-1  15 43 2.1 1.6 0.15 2.5 0.14 1 1 Example 10-4 ABS1 100 Example 2-2  10 45 2.3 2.4 0.17 3.3 0.17 1 2 Example 10-5 ABS1 100 Example 2-3  10 46 2.3 2.6 0.18 33 0.18 2 2 Example 10-6 ABS1 100 Example 2-4  10 45 2.2 2.8 0.18 3.4 0.18 1 2 Example 10-7 ABS1 100 Example 2-5  10 45 2.2 2.7 0.18 3.1 0.17 2 2 Example 10-8 ABS1 100 Example 2-6  10 45 2.3 3.1 0.17 3.7 0.18 2 2 Example 10-9 ABS1 100 Example 2-7  10 46 2.3 3.0 0.18 3.2 0.17 1 2 Example 10-10 ABS1 100 Example 2-8  10 46 2.3 3.4 0.19 3.9 0.19 2 3 Example 10-11 ABS1 100 Example 2-9  10 46 2.3 3.3 0.19 3.8 0.19 2 3 Example 10-12 ABS1 100 Example 2-10 10 44 2.2 3.4 0.19 4.1 0.20 2 3 Example 10-13 ABS1 100 Example 2-11 10 44 2.2 3.7 0.22 3.9 0.19 2 2 Example 10-14 ABS1 100 Example 2-12 10 44 2.2 3.8 0.23 4.2 0.20 2 3 Example 10-15 ABS1 100 Example 2-13 10 45 2.3 3.1 0.20 4.1 0.20 3 3 Comparative ABS1 100 — — 49 2.5 18.2 0.33 22.4 0.39 9 10 Example 10-1 Comparative ABS1 100 Example 2-1  30 35 1.6 2.7 0.17 4.7 0.27 4 6 Example 10-2 Comparative ABS1 100 Comparative 10 43 2.2 7.6 0.20 6.8 0.19 2 2 Example 10-3 example 2-1 Comparative ABS1 100 Comparative 10 38 1.9 9.5 0.29 7.3 0.26 3 3 Example 10-4 example 2-2 Comparative ABS1 100 Comparative 10 37 1.8 3.5 0.28 5.5 0.24 2 3 Example 10-5 example 2-3 Comparative ABS1 100 Comparative 10 45 2.3 3.9 0.20 4.8 0.22 2 6 Example 10-6 example 2-4 Target value 40 2.0 5.0 0.25 5.0 0.25 3 3 or more or more or less or less or less or less or less or less

[0275] As is evident from Table 11, the target values for each of mechanical properties, sliding property evaluation, and the squeaking sound risk value were achieved in the examples 10-1 to 10-15.

[0276] In contrast, in the comparative example 10-1, the wear amount and the dynamic friction coefficient in any of the case where the mate material was the (1) carbon steel (S45C) and the case where the mate material was the (2) neat ABS1 resin significantly exceeded the respective target values. Further, the squeaking sound risk value in any of the case where the mate material was the (1) carbon steel (S45C) and the case where the mate material was the (2) neat ABS1 resin exceeded the target value.

[0277] In the comparative example 10-2, the tensile strength and the flexural modulus didn't satisfy the respective target values. Further, the dynamic friction coefficient in the case where the mate material was the (2) neat ABS1 resin exceeded the target value. Furthermore, in the comparative example 10-2, the squeaking sound in any of the case where the mate material was the (1) carbon steel (S45C) and the case where the mate material was the (2) neat ABS1 resin exceeded the target value.

[0278] In the comparative example 10-3, the wear amount in any of the case where the mate material was the (1) carbon steel (S45C) and the case where the mate material was the (2) neat ABS1 resin exceeded the target value.

[0279] In the comparative example 10-4, the tensile strength and the flexural modulus didn't satisfy the respective target values. Further, the wear amount and the dynamic friction coefficient in the case where the mate material was the (1) carbon steel (S45C) exceeded the respective target values. Furthermore, the wear amount and the dynamic friction coefficient in the case where the mate material was the (2) neat ABS1 resin exceeded the respective target values.

[0280] In the comparative example 10-5, the tensile strength and the flexural modulus didn't satisfy the respective target values. Further, the dynamic friction coefficient in the case where the mate material was the (1) carbon steel (S45C) exceeded the target value. Furthermore, the wear amount in the case where the mate material was the (2) neat ABS1 resin exceeded the target value.

[0281] In the comparative example 10-6, the squeaking sound risk value in the case where the mate material was the (2) neat ABS1 resin exceeded the target value.

<PC/ABS resin composition>

[0282] In the example 11, a PC/ABS resin was used as the (X) thermoplastic resin according to the present invention to manufacture a PC/ABS resin composition.

[Manufacturing of PC/ABS resin composition]

[0283] In examples 11-1 to 11-17 and comparative examples 11-1 to 11-6, a predetermined amount of the (Y) graft copolymer was appropriately dry-blended in the (x-1) PC resin (“Tarflon A2200” (trade name), standard grade, manufactured by Idemitsu Kosan Co., Ltd., shown as “PC2” in Table 12) and the (x-2) ABS resin (“Stylac 321” (trade name), standard grade, manufactured by Asahi Kasei Chemicals Corporation, shown as “ABS2” in Table 12) with the mixing ratio shown in Table 12, they were melt-kneaded by a twin-screw extruder set to be 240° C., and thus, a PC/ABS resin composition was obtained.

[0284] Note that in the examples 11-1 to 11-15, the mixing ratio between the PC resin and the ABS resin in the (X) PC/ABS resin was 70 parts by weight to 30 parts by weight. In the examples 11-1 to 11-15, the (Y) graft copolymers obtained in the examples 2-1 to 2-13 were used. In the examples 11 to 16, the mixing ratio between the PC resin and the ABS resin in the (X) PC/ABS resin was 90 parts by weight to 10 parts by weight. In the example 11-17, the mixing ratio between the PC resin and the ABS resin in the (X) PC/ABS resin was 60 parts by weight to 40 parts by weight. In the examples 11-16 and 11-17, the (Y) graft copolymer obtained in the example 2-1 was used.

[0285] The PC/ABS resin composition according to the comparative example 11-1 was manufactured only with the (X) PC/ABS resin, and the (Y) graft copolymer was not used. In the comparative example 11-2, the content of the (Y) graft copolymer obtained in the example 2-1 was 30 parts by weight (relative to 100 parts by weight of (X)). In the comparative example 11-3 to 11-6, the (Y) graft copolymers obtained in the comparative examples 2-1 to 2-4 were used.

[0286] In examples 12-1 to 12-6 and comparative example 12-1, a predetermined amount of the (Y) graft copolymer was appropriately dry-blended in the commercially available (X) PC/ABS resin (“Bayblend T65XF” (trade name) manufactured by Bayer, shown as “PC/ABS” in Table 13) with the mixing ratio shown in Table 13, they were melt-kneaded by a twin-screw extruder set to be 240° C., and thus, a PC/ABS resin composition was obtained.

[Manufacturing of evaluation material]

[0287] In the examples 11-1 to 11-17 and 12-1 to 12-6 and the comparative examples 11-1 to 11-6 and 12-1, the method of manufacturing the evaluation material is similar to that in the examples 3-1 to 3-15 and the comparative examples 3-1 to 3-5 except that the barrel temperature was 245° C. and the mold temperature was 80° C.

[Evaluation method]

[0288] In the examples 11-1 to 11-17 and 12-1 to 12-6 and the comparative examples 11-1 to 11-6 and 12-1, the sliding property evaluation 2 was not performed and only the sliding property evaluation 1 was performed in the evaluation method.

[0289] The test conditions of the sliding property evaluation 1 in the case where the mate material was the (1) carbon steel (S45C) were a load: 50 N and a linear speed of 10 cm/sec. The test conditions of the sliding property evaluation 1 in the case where the mate material was the same material as the (2) evaluation material were a load: 20 N and a linear speed: 10 cm/sec.

[0290] Further, the other conditions other than the test conditions (a load and linear speed) were similar to those in the example 3.

[Evaluation results]

[0291] The evaluation results of the evaluation materials according to the examples 11-1 to 11-17 and 12-1 to 12-6 and the comparative examples 11-1 to 11-6 and 12-1 are shown in Table 11 and Table 12. The target values of each evaluation were appropriately changed depending on the kind of the (X) thermoplastic resin, and were as shown in Table 11 and Table 12.

TABLE-US-00012 TABLE 12 Evaluation of sliding properties (1) (2) Against Squeaking (X) Thermoplastic resin (Y) Graft Mechanical Against S45C same material sound risk value (x-1) PC (x-2) ABS copolymer properties Dynamic Dynamic (2) Parts Parts Parts Tensile Flexural Wear friction Wear friction (1) Against by by by strength modulus amount co- amount co- Against same Kind weight Kind weight Kind weight (MPa) (GPa) (mg) efficient (mg) efficient S45C material Example PC2 70 ABS2 30 Example 10 44 1.8 1.0 0.19 2.0 0.17 1 1 11-1 2-1  Example PC2 70 ABS2 30 Example 1 51 2.1 2.0 0.23 4.8 0.22 3 3 11-2 2-1  Example PC2 70 ABS2 30 Example 3 50 2.0 1.6 0.21 4.0 0.20 2 2 11-3 2-1  Example PC2 70 ABS2 30 Example 10 44 1.8 0.8 0.18 2.1 0.18 1 1 11-4 2-2  Example PC2 70 ABS2 30 Example 10 43 1.9 0.9 0.19 2.1 0.18 1 1 11-5 2-3  Example PC2 70 ABS2 30 Example 10 44 1.8 1.0 0.18 2.0 0.18 2 2 11-6 2-4  Example PC2 70 ABS2 30 Example 10 43 1.8 0.9 0.18 1.9 0.17 1 2 11-7 2-5  Example PC2 70 ABS2 30 Example 10 45 1.9 1.1 0.21 2.2 0.18 2 2 11-8 2-6  Example PC2 70 ABS2 30 Example 10 44 1.8 0.9 0.18 1.8 0.16 1 2 11-9 2-7  Example PC2 70 ABS2 30 Example 10 42 1.7 1.4 0.22 3.0 0.19 2 2 11-10 2-8  Example PC2 70 ABS2 30 Example 10 42 1.7 1.6 0.22 2.9 0.20 2 3 11-11 2-9  Example PC2 70 ABS2 30 Example 10 42 1.7 1.5 0.23 2.9 0.19 2 3 11-12 2-10 Example PC2 70 ABS2 30 Example 10 44 1.7 1.3 0.23 3.1 0.19 2 3 11-13 2-11 Example PC2 70 ABS2 30 Example 10 43 1.8 1.4 0.22 3.2 0.19 2 3 11-14 2-12 Example PC2 70 ABS2 30 Example 10 44 1.8 1.4 0.22 2.9 0.20 1 2 11-15 2-13 Example PC2 90 ABS2 10 Example 10 52 2.0 1.4 0.20 2.6 0.16 2 3 11-16 2-1  Example PC2 60 ABS2 40 Example 10 40 1.7 1.9 0.23 3.8 0.19 3 3 11-17 2-1  Compar- PC2 70 ABS2 30 — — 52 2.2 4.9 0.28 48.1 0.32 8 10 ative example 11-1 Compar- PC2 70 ABS2 30 Example 30 35 1.3 1.3 0.22 4.9 0.24 2 2 ative 2-1  example 11-2 Compar- PC2 70 ABS2 30 Compar- 10 43 1.6 2.4 0.20 6.0 0.20 2 2 ative ative example example 11-3 2-1  Compar- PC2 70 ABS2 30 Compar- 10 42 1.6 2.6 0.24 8.1 0.26 3 1 ative ative example example 11-4 2-2  Compar- PC2 70 ABS2 30 Compar- 10 42 1.3 1.7 0.22 2.3 0.21 3 5 ative ative example example 11-5 2-3  Compar- PC2 70 ABS2 30 Compar- 10 44 1.7 1.5 0.20 5.8 0.19 2 3 ative ative example example 11-6 2-4  Target value 40 1.5 2.0 0.25 5.0 0.25 3 3 or more or more or less or less or less or less or less or less

TABLE-US-00013 TABLE 13 (X) Evaluation of sliding properties Squeaking Thermo- (Y) Mechanical (1) (2) Against sound risk value plastic resin Graft copolymer properties Against S45C same material (2) Parts Parts Tensile Flexural Wear Dynamic Wear Dynamic (1) Against by by strength modulus amount friction amount friction Against same Kind weight Kind weight (IMPa) (GPa) (mg) coefficient (mg) coefficient S45C material Example 12-1 PC/ABS 100 Example 2-1  10 45 1.9 1.2 0.19 14 0.16 1 2 Example 12-2 PC/ABS 100 Example 2-1  1 48 2.1 1.9 0.25 4.6 0.21 3 3 Example 12-3 PC/ABS 100 Example 2-1  3 47 2.0 1.8 0.21 3.5 0.17 2 3 Example 12-4 PC/ABS 100 Example 2-6  10 44 1.9 1.1 0.18 1.3 0.17 1 2 Example 12-5 PC/ABS 100 Example 2-7  10 44 1.8 1.2 0.18 1.4 0.16 1 2 Example 12-6 PC/ABS 100 Example 2-11 10 45 1.8 1.4 0.20 2.6 0.20 2 2 Comparative PC/ABS 100 — — 50 2.2 5.8 0.28 40.5 0.33 9 10 example 12-1 Target value 40 1.5 2.0 0.25 5.0 0.25 3 3 or more or more or less or less or less or less or less or less

[0292] As is evident from Table 12 and Table 13, the target values for each of mechanical properties, sliding property evaluation, and the squeaking sound risk value were achieved in the examples 11-1 to 11-17 and the examples 12-1 to 12-6.

[0293] In contrast, in the comparative example 11-1, the wear amount and the dynamic friction coefficient in any of the case where the mate material was the (1) carbon steel (S45C) and the case where the mate material was the same material as the (2) evaluation material significantly exceeded the respective target values. Further, the squeaking sound risk value in any of the case where the mate material was the (1) carbon steel (S45C) and the case where the mate material was the same material as the (2) evaluation material exceeded the target value.

[0294] In the comparative example 11-2, the tensile strength and the flexural modulus didn't satisfy the respective target values.

[0295] In the comparative example 11-3, the wear amount in any of the case where the mate material was the (1) carbon steel (S45C) and the case where the mate material was the (2) evaluation material exceeded the target value.

[0296] In the comparative example 11-4, the wear amount in the case where the mate material was the (1) carbon steel (S45C) exceeded the target value. Further, the wear amount and the dynamic friction coefficient in the case where the mate material was the same material as the (2) evaluation material exceeded the respective target values. Furthermore, the squeaking sound risk value in the case where the mate material was the same material as the (2) evaluation material exceeded the target value.

[0297] In the comparative example 11-5, the flexural modulus didn't satisfy the target value. Further, the squeaking sound risk value in the case where the mate material was the same material as the (2) evaluation material exceeded the target value.

[0298] In the comparative example 11-6, the wear amount in the case where the mate material was the same material as the (2) evaluation material exceeded the target value.

[0299] In the comparative example 12-1, the wear amount and the dynamic friction coefficient in the case where the mate material was the (1) carbon steel (S45C) significantly exceeded the respective target values. Further, also the wear amount and the dynamic friction coefficient in the case where the mate material was the same material as the (2) evaluation material significantly exceeded the respective target values. Further, the squeaking sound risk value in any of the case where the mate material was the (1) carbon steel (S45C) and the case where the mate material was the same material as the (2) evaluation material exceeded the target value.

[0300] Although embodiments of the present invention have been described, the embodiments of the present invention are not limited to the above-mentioned embodiments and it goes without saying that various modifications can be made without departing from the essence of the present invention.