JPH1171439A - Resin composition for forming - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for forming which gives formed products excellent in slidableness and abrasion resistance and shows good formability such as flowability, mold releasing property, resistance to fouling of mold and the like. SOLUTION: The resin composition contains (A) 100 parts by weight of polyacetal resin or ABS resin and (B) 0.1-15 parts by weight of a liquid graft modified ethylene-α-olefin random copolymer which is obtained by grafting a carboxylic acid-based monomer (b-1) selected from among an unsaturated carboxylic acid, an acid anhydride, and an ester having 3-10 carbon atoms, or an ethylene-like unsaturated monomer having a hydroxyl group (b-2) onto an ethylene-α-olefin random copolymer as a trunk polymer containing 20-80 mol.% of ethylene, said graft modified ethylene-α-olefin random copolymer containing 0.1-20 weight % of grafted monomer and having number average molecular weight of 500-10,000 and molecular weight distribution (Mw/Mn) of 1.2-3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a molding resin composition, and more particularly to a molding resin composition for obtaining a molded article having slidability and abrasion resistance.

[0002]

2. Description of the Related Art Engineering plastics such as polyacetal resin, ABS resin, polyamide resin, polyphenylene oxide resin, polyimide resin, thermoplastic polyester resin, polycarbonate resin, epoxy resin, thermosetting unsaturated polyester resin and phenol resin have melting points or Since it has a high softening point and excellent mechanical properties, it is widely used in various industrial fields such as the automobile industry, the electric and electronic industries. However,
The resin used for parts having sliding parts, such as gears of precision equipment, is required to have a low coefficient of friction, that is, to be excellent in slidability, and also to be excellent in wear resistance. These resins by themselves are insufficient in slidability and abrasion resistance.

[0003] Therefore, conventionally, there is a type in which grease or the like is impregnated as a slidability improving agent. However, grease oozing out on the surface of a molded product stains surrounding parts and maintains its effect as a slidability improving agent. Sex is not enough. As another method, there is a method of containing a fluorine-based resin or an olefin-based polymer. Although this method improves the slidability of the resin, the fluorine-based resin is generally expensive, and these polymer additives are used. Is poor in compatibility with the above-mentioned resin, so that phase separation occurs on the surface of the molded article and the polymer additive is peeled off, and as a result, there are difficulties in processing and molding such as poor releasability from a mold. Was.

[0004]

An object of the present invention is to provide a molded product having a low coefficient of friction, excellent slidability, excellent wear resistance, good fluidity and good mold release properties, and An object of the present invention is to provide a molding resin composition which is excellent in moldability such as no resin stain.

[0005]

The present invention relates to the following molding resin composition. (1) (A) selected from the group consisting of polyacetal resin, ABS resin, polyamide resin, polyphenylene oxide resin, polyimide resin, thermoplastic polyester resin, polycarbonate resin, epoxy resin, thermosetting unsaturated polyester resin and phenol resin 100 parts by weight of at least one resin, and (B) (i) ethylene units account for 20 to 80 mol% of all structural units,
An ethylene / α-olefin random copolymer in which α-olefin units occupy 20 to 80 mol% is used as a trunk polymer and is selected from the group consisting of unsaturated carboxylic acids having 3 to 10 carbon atoms, acid anhydrides and esters thereof. A graft-modified copolymer obtained by graft-polymerizing at least one carboxylic acid-based monomer (b-1) and / or an ethylenically unsaturated monomer (b-2) having a hydroxyl group onto the backbone polymer. (Ii) the ratio of the graft monomer in the graft-modified copolymer is 0.1 to 20% by weight, (iii) the number average molecular weight Mn is 500 to 10,000, and (iv) the molecular weight distribution ( (Mw / Mn) is from 1.2 to 3;
A molding resin composition comprising 0.1 to 15 parts by weight of an α-olefin random copolymer. (2) The molding resin composition according to the above (1), wherein the unmodified ethylene / α-olefin random copolymer is an ethylene / propylene random copolymer. (3) The molding resin composition according to the above (1) or (2), wherein the graft monomer is maleic anhydride. (4) The molding resin composition according to the above (1) or (2), wherein the graft monomer is a (meth) acrylate. (5) The molding resin composition according to the above (1) or (2), wherein the graft monomer is a (meth) acrylate having a hydroxyl group in an ester portion. (6) The molding resin composition according to the above (1) or (2), wherein the graft monomer is an unsaturated alcohol. (7) The resin composition for molding according to any one of the above (1) to (6), wherein the resin (A) is a polyacetal resin. (8) The resin composition for molding according to any one of the above (1) to (6), wherein the resin (A) is an ABS resin.

In the present specification, “(meth) acryl” means “acryl” and / or “methacryl”.

As described above, the molding resin composition of the present invention comprises a resin containing a specific resin (A) and a small amount of a specific liquid modified ethylene / α-olefin random copolymer (B). A composition.

First, the resin (A) used in the present invention will be described. The resin (A) used in the present invention is a thermoplastic resin such as a polyacetal resin, an ABS resin, a polyamide resin, a polyphenylene oxide resin, a polyimide resin, a thermoplastic polyester resin, a polycarbonate resin, an epoxy resin, and a thermosetting unsaturated polyester resin. And a thermosetting resin such as a phenol resin. These resins (A) can be used alone or in combination of two or more.

These resins (A) can be used as such as described in publications such as “Engineering Plastics” (edited by Makihiro and Rikio Kobayashi, published by Sangyo Tosho Co., Ltd.) and “FPR Design Handbook”. It is a well-known resin, and its definition is clear. Hereinafter, preferred embodiments of each resin will be described.

(1) Polyacetal resin Typically, a resin obtained by ring-opening polymerization of formalin or trioxane together with ethylene oxide, if desired, in the presence of a cationic catalyst, wherein a polyoxymethylene chain has a main skeleton In the present invention, a copolymer type resin is preferable. Such a polyacetal resin is commercially available, for example, Iupital (Mitsubishi Engineering Plastics Co., Ltd.)
And the like, and can be preferably used in the present invention.

(2) ABS resin Typically, ABS resin is an impact-resistant resin obtained by graft-polymerizing acrylonitrile and styrene to polybutadiene. In the present invention, the polybutadiene component is 5 to 5%.
40% by weight, and the weight ratio of styrene component to acrylonitrile component (styrene / acrylonitrile) is 70 /
Those having a ratio of 30 to 80/20 are preferred. Such an A
The BS resin is commercially available, and includes, for example, Stylac (trade name) (Asahi Kasei Kogyo Co., Ltd.) and Psycholac (Ube Saikon Co., Ltd.), which can be preferably used in the present invention.

(3) Polyamide resin Typically, a resin obtained by polycondensation of a diamine and a dicarboxylic acid, or ring-opening polymerization of caprolactam. In the present invention, an aliphatic diamine and an aliphatic or aromatic resin are used. A polycondensation reaction product of an aromatic dicarboxylic acid is preferred. Such polyamide resins are commercially available, for example, trade names such as Leona (Asahi Kasei Kogyo Co., Ltd.) and Zytel (Dupont).
Japan Limited) and the like, which can be preferably used in the present invention.

(4) Polyphenylene oxide resin Typically, a resin obtained by oxidative coupling of 2,6-dimethylphenol in the presence of a copper catalyst, but other resins may be blended with this resin. The modified polyphenylene oxide resin modified by the method described in the above can also be used in the present invention. In the present invention,
A blend modification of a styrenic polymer is preferred. Such polyphenylene oxide resins are commercially available,
For example, trade names such as Zylon (Asahi Kasei Kogyo Co., Ltd.) and Iupiace (Mitsubishi Engineering Plastics Co., Ltd.) can be mentioned, and they can be preferably used in the present invention.

(5) Polyimide resin Typically, a resin obtained by polycondensation of tetracarboxylic acid and diamine to form an imide bond in the main skeleton. Those formed from diaminodiphenyl ether are preferred.
Such a polyimide resin is commercially available, for example, trade name Vespel (DuPont Japan Limited) and the like, and can be preferably used in the present invention.

(6) Thermoplastic polyester resin A resin typically obtained by polycondensation of a dicarboxylic acid and a diol. In the present invention, polyethylene terephthalate, polybutylene terephthalate, polyethylene 2,6-naphthalene Dicarboxylate, polycyclohexane terephthalate and the like are preferably used. Such thermoplastic polyester resins are commercially available, for example, the trade name Rynite (Dupont Japan)
Limited) and the like, which can be preferably used in the present invention.

(7) Polycarbonate resin Typically, a resin obtained by reacting an aromatic diol (for example, bisphenol A) with phosgene. In the present invention, diethylene glycol diallyl carbonate is preferred. Such polycarbonate resins are commercially available, for example, brand name NOVARE
X (Mitsubishi Chemical Co., Ltd.), Panline (Teijin Kasei Co., Ltd.), Lexan (Nihon GE Plastics Co., Ltd.) and the like can be preferably used in the present invention.

The above resins (1) to (7) are thermoplastic resins. The resins (8) to (10) described below are thermosetting resins, and a description will be given of a resin before thermosetting.

(8) Epoxy resin Typically, an epoxy resin is a resin obtained by reacting an aromatic diol (for example, bisphenol A) with epichlorohydrin in the presence of an alkali. 5000 bisphenol A type epoxy resin, bisphenol F type epoxy resin,
Bisphenol S type epoxy resins are preferred. Such epoxy resins are commercially available and include, for example, trade names such as EPOMIC (Mitsui Petrochemical Co., Ltd.), EPICLON (Dainippon Ink and Chemicals Co., Ltd.), and Sumiepoxy (Sumitomo Chemical Co., Ltd.). And can be preferably used in the present invention.

(9) Thermosetting unsaturated polyester resin A resin typically obtained by an esterification reaction between an aliphatic unsaturated dicarboxylic acid and an aliphatic diol. In the present invention, maleic acid is used. Resins obtained by subjecting an unsaturated dicarboxylic acid such as fumaric acid or the like to an esterification reaction with a diol such as ethylene glycol or diethylene glycol are preferred. Such thermosetting unsaturated polyester resins are commercially available, and include, for example, Rigolac (trade name) and Sumicon (Sumitomo Bakelite Co., Ltd.), which are preferably used in the present invention. Can be.

(10) Phenol Resin The present invention includes both the so-called novolak type and the resol type, but a novolak type cured with hexamethylenetetramine or a solid resol mainly containing a dimethylene ether bond is preferred. Such phenolic resins are commercially available, and include, for example, SUMICON PM (Sumitomo Bakelite Co., Ltd.) and Nikka Line (Nippon Synthetic Chemical Industry Co., Ltd.), which can be preferably used in the present invention. .

In the present invention, among the above resins (1) to (10), (1) polyacetal resin and (2) AB
S resin is preferably used as resin (A).

Next, the liquid modified ethylene / α-olefin random copolymer (B) (hereinafter, also simply referred to as modified copolymer (B)) used in the molding resin composition of the present invention will be described. The modified copolymer (B) used in the molding resin composition of the present invention contains 20 to 80 mol%, preferably 30 to 70 mol% of ethylene units in all structural units,
More preferably, the liquid ethylene / α-olefin random copolymer occupies 40 to 60 mol%, and the α-olefin unit accounts for 20 to 80 mol%, preferably 30 to 70 mol%, and more preferably 40 to 60 mol%. A copolymer (hereinafter also simply referred to as an unmodified copolymer (B ′)) is used as a backbone polymer, and an unsaturated carboxylic acid having 3 to 10 carbon atoms is added to the backbone polymer.
It is a modified product obtained by graft polymerization of at least one carboxylic acid monomer (b-1) selected from the group consisting of acid anhydrides and esters and / or an ethylenically unsaturated monomer (b-2) having a hydroxyl group.

The α-olefin of the unmodified copolymer (B ′) includes propylene, butene-1, pentene-
1,4-methylpentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene-1, undecene-1, dodecene-1, tridecene-1, tetradecene-1, hexadecene-1, heptacene Α-olefins having 3 to 20 carbon atoms such as -1, octadecene-1, nonadecene-1 and eicosene-1 can be exemplified. Among them, propylene is most preferable in terms of the productivity of the unmodified copolymer (B ′) and the like.

The unmodified copolymer (B ') has a non-conjugated diene unit such as dicyclopentadiene, ethylidene norbornene or 1,6-hexadiene as a structural unit in addition to an ethylene unit and an α-olefin unit. It can be contained in a small amount within a range not to impair the achievement of the object of the present invention, but the total amount of the ethylene unit and the α-olefin unit is 90 to 100% by mole, particularly 95 to 100% by mole. Is preferred.

The proportion of the graft monomer in the modified copolymer (B), that is, the proportion of the skeleton component of the graft monomer in the modified copolymer (B) (hereinafter sometimes referred to as the graft ratio) is 0.1. -20% by weight, preferably 1-1
It is 5% by weight, more preferably 2 to 12% by weight. When the graft ratio is within the above range, the affinity between the resin (A) and the modified copolymer (B) is improved, resulting in improved processability.

The number average molecular weight Mn of the unmodified copolymer (B ′) as the backbone polymer is preferably from 500 to 9
900, more preferably 600 to 8000, particularly preferably 700 to 5,000. The ratio (Mw / Mn) of the weight average molecular weight Mw to the number average molecular weight Mn, which is a rough standard of the molecular weight distribution of the unmodified copolymer (B ′), is preferably from 1.1 to 2.8. Preferably 1.1 to 2.
6, particularly preferably 1.1 to 2.2.

The number average molecular weight Mn of the modified copolymer (B) used in the present invention is 500 to 10,000, preferably 6
It is in the range of 00-8000, more preferably 700-5000. Further, Mw / Mn is in the range of 1.2 to 3, preferably 1.2 to 2.8. When the number average molecular weight Mn is in the above range, when the resin (A) and the modified copolymer (B) are mixed, evaporation of the modified copolymer (B) due to heating can be avoided. And the mixing operation is well maintained. Then, the condition that the molecular weight distribution of the modified copolymer (B) is narrow, that is, the Mw / Mn of the modified copolymer (B) is 1.2 to 3, and the condition of the number average molecular weight Mn are combined, The result is that the resin composition of the present invention is excellent in various properties such as slidability, abrasion resistance, and moldability.

The above number average molecular weights Mn and Mw / M of the modified copolymer (B) and the unmodified copolymer (B ')
n is gel permeation chromatography (GP
The measurement was carried out by method C) using monodisperse polystyrene as a standard substance and tetrahydrofuran (THF) as a solvent. Therefore, Mn and Mw / Mn are values in terms of polystyrene.

The modified copolymer (B) is prepared by using the unmodified copolymer (B ') as a backbone polymer and having 3 to 10 carbon atoms.
At least one carboxylic acid monomer (b-1) selected from the group consisting of unsaturated carboxylic acids, acid anhydrides and esters thereof, and / or an ethylenically unsaturated monomer (b-2) having a hydroxyl group, 0.1 to 20% by weight, preferably 1 to 20% by weight based on the unmodified copolymer (B ')
It can be obtained by graft polymerization at a ratio of 15% by weight, more preferably 2 to 12% by weight.

The above graft monomer having 3 to 1 carbon atoms
0 unsaturated carboxylic acid and its acid anhydride (b-1), specifically, acrylic acid, methacrylic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, bicyclo [2.2.1] hept- 2-ene-5,6
-Dicarboxylic acid and the like (above, unsaturated carboxylic acid); maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic acid Such as anhydrides
Unsaturated carboxylic acid anhydride).
Of these, the use of maleic anhydride is preferred.

Examples of the unsaturated carboxylic acid ester (b-1) include methyl acrylate, methyl methacrylate, methyl maleate, monomethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citrate, and tetrahydroanhydride. Examples thereof include dimethyl phthalate, dimethyl bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylate, and 2-hydroxyethyl (meth) acrylate. Among them, 2-
The use of hydroxyethyl (meth) acrylate is preferred. In addition, 2-hydroxyethyl (meth) acrylate can also be regarded as a graft monomer belonging to (meth) acrylic acid ester (b-2) having a hydroxyl group in an ester portion described later. Carboxylic acid monomer (b-1)
Can be used alone or in combination of two or more.

Examples of the hydroxyl group-containing ethylenically unsaturated monomer (b-2) include (meth) acrylic acid esters having a hydroxyl group in the ester portion, unsaturated alcohols, hydroxyl group-containing styrene derivatives, and hydroxyvinyl ethers. Of these, (meth) acrylates having a hydroxyl group in the ester portion and unsaturated alcohols are preferred.

(Meth) having a hydroxyl group in the ester moiety
Examples of the acrylate (b-2) include mono (meth) acrylate compounds of polyhydric alcohols, and specific examples thereof include 2-hydroxyethyl (meth) acrylate,
-Hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol mono (meth) acrylate, polyethylene glycol mono (meth) ) Acrylates and the like can be mentioned. Among these, 2-hydroxyethyl (meth) acrylate is preferred.

Specific examples of the unsaturated alcohol (b-2) include allyl alcohol, 2-methyl-3-buten-1-ol, 2-methyl-3-buten-2-ol, and 3-methyl-3. -Buten-1-ol, 10-undecene-1-ol, 1-octen-3-ol, 2-
Methanol norbornene, 2-butene-1,4-diol and the like can be mentioned. Among these, allyl alcohol, 2-methyl-3-buten-1-ol, 2-methyl-3-butene-2-ol can be easily obtained because it has an appropriate reactivity and thus a uniform graft copolymer can be obtained. Oars are preferred.

The hydroxyl group-containing styrene derivative (b-2)
Specific examples include hydroxystyrene. Specific examples of the hydroxy vinyl ether (b-2) include hydroxymethyl vinyl ether, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxymethylpropenyl ether, hydroxyethylpropenyl ether, hydroxypropylpropenyl ether, hydroxybutylpropenyl ether, Examples include hydroxymethylbutenyl ether, hydroxyethylbutenylether, hydroxypropylbutenylether, and hydroxybutylbutenylether.

Other examples of the ethylenically unsaturated monomer (b-2) having a hydroxyl group include N-methylol acrylamide, 2- (meth) acryloyloxyethyl acetyl phosphate, glycerin monoallyl ether, allyloxyethanol and the like. Can also be used.
Hydroxyl-containing ethylenically unsaturated monomer (b-2)
Can be used alone or in combination of two or more.

When the carboxylic acid monomer (b-1) is used as the graft monomer, the liquid modified ethylene / α-olefin random copolymer (B) used in the present invention is
For example, the unmodified copolymer (B ′) produced by appropriately selecting the polymerization conditions from the polymerization method described in Japanese Patent Publication No. 2-1163 by the applicant of the present application is also It can be produced by selecting graft conditions from the graft polymerization method described in 1-34525 and performing graft polymerization.

When an ethylenically unsaturated monomer (b-2) having a hydroxyl group is used as the graft monomer, the liquid-modified ethylene / α-olefin random copolymer (B) used in the present invention is, for example, a compound as disclosed by the present applicant. 2-
Unmodified copolymer produced by appropriately selecting polymerization conditions from the polymerization method described in No. 1163
(B ′) can be produced by selecting a graft condition from the graft polymerization method described in JP-A-5-271355 and performing graft polymerization.

The liquid modified ethylene / α-olefin random copolymer (B) is used in an amount of 0.1 to 15 parts by weight, preferably 0.2 to 10 parts by weight, per 100 parts by weight of the resin (A).
Parts by weight, more preferably 0.5 to 6 parts by weight. The resin composition for molding of the present invention, in which the modified copolymer (B) is blended in the above ratio with respect to the resin (A), is excellent in slidability, wear resistance, and moldability.

In the present invention, the mixing method of the resin (A) and the liquid-modified ethylene / α-olefin random copolymer (B) is not particularly limited, and any conventionally known mixing method may be employed. Can be. For example, the above resin (A)
Is a thermoplastic resin, the two can be uniformly dispersed and mixed by kneading while melting the resin (A).
As a kneading means, a single-screw extruder, a twin-screw extruder, a kneader, a plastomill or the like can be used. Kneading temperature,
The kneading time and other conditions are appropriately selected depending on the types of the resin (A) and the modified copolymer (B) to be used, the mixing ratio, and the like.

When the resin (A) is a thermosetting resin, since the uncured resin is usually in a liquid state, it can be uniformly mixed using a device such as a homomixer or a Henschel mixer.

From the resin composition of the present invention obtained as described above, molded articles can be obtained by various molding methods. The obtained molded article is excellent in slidability, wear resistance and the like.
Further, the resin composition is also excellent in moldability. Therefore, the resin composition of the present invention is used in fields where slidability and wear resistance are required, for example, gears, rotating shafts, bearings, etc., but can also be used in applications where the above properties are not required. It is.

As the molding method, there are extrusion molding method, injection molding method, vacuum molding method, blow molding method, compression molding method, transfer molding method, RIM molding method, casting, depending on the difference between thermoplastic resin and thermosetting resin. A molding method widely used for thermoplastic resins and thermosetting resins, such as a molding method, can be employed. When the resin (A) is a thermosetting resin, the resin composition of the present invention comprises:
A curing agent may be contained, or a curing agent may be added and mixed at the time of molding without containing the curing agent.

The molding resin composition of the present invention comprises a heat stabilizer, a weather stabilizer, a flame retardant, an antistatic agent, a nucleating agent, a coloring agent,
Additives such as a foaming agent, a filler and a reinforcing agent can be blended within a range that does not impair the purpose of the present invention.

[0045]

Since the molding resin composition of the present invention contains a specific resin (A) and a specific liquid modified copolymer (B), a molded article having excellent sliding properties and abrasion resistance is produced. The moldability is good, and the moldability is good, and there is no resin stain on the mold.

[0046]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described with reference to embodiments. However, the present invention is not limited to these examples.

Synthesis Example 1 of Modified Copolymer (B) A 2 liter glass reactor equipped with a stirrer equipped with a nitrogen blowing tube, a water-cooled condenser, a thermometer and two dropping funnels was used.
Ethylene unit content 48 mol% (propylene unit content 52
Mol%), number average molecular weight Mn3300, Mw / Mn1.
1.0 kg of ethylene-propylene random copolymer
And replaced with nitrogen for 2 hours to drive off dissolved oxygen.
Thereafter, the temperature in the reactor was raised to 160 ° C., and 150 g of maleic anhydride previously charged in each of the two dropping funnels was used.
(Liquified by heating to 60 ° C.) and 30 g of di-tert-butyl peroxide were added dropwise over 10 hours. After completion of the dropwise addition, the reaction is further carried out for 2 hours, then the temperature in the reactor is raised to 180 ° C., and unreacted maleic anhydride and decomposed products of di-tert-butyl peroxide are removed under reduced pressure (20 Torr). As a result, a brown highly viscous liquid was obtained.

The obtained liquid acid-modified ethylene / propylene random copolymer has a number average molecular weight Mn of 3750 and Mw
/ Mn was 2.2. The graft ratio was 9.8% by weight. The graft ratio was determined by quantifying the oxygen content by elemental analysis, and calculating the succinic anhydride skeleton component from the value.

Synthesis Example 2 of Modified Copolymer (B) As raw materials, ethylene unit content was 52 mol% (propylene unit content was 48 mol%), number average molecular weight (Mn) was 5220,
1.0 kg of ethylene / propylene random copolymer having a molecular weight distribution (Mw / Mn) of 1.7 and 25 g of maleic anhydride
And 5 g of di-tert-butyl peroxide, and the reaction was carried out in the same manner as in Synthesis Example 1 except that the dripping time was changed to 2 hours. The number average molecular weight Mn was 5440, and Mw / M was used.
A liquid acid-modified ethylene / propylene random copolymer having n of 1.9 and a graft ratio of 2.2% by weight was obtained.

Synthesis Example 3 of Modified Copolymer (B) As raw materials, ethylene unit content 52 mol% (propylene unit content 48 mol%), number average molecular weight Mn 5220, Mw
/ Mn 1.7 ethylene / propylene random copolymer 1.0 kg, maleic anhydride 69 g and di-tert
The reaction was carried out in the same manner as in Synthesis Example 1 except that 14 g of -butyl peroxide was used and the dripping time was changed to 5 hours. The number average molecular weight Mn was 5620, Mw / Mn was 2.2, and the graft ratio was 5.2 weight. % Of a liquid acid-modified ethylene / propylene random copolymer.

Synthesis Example 4 of Modified Copolymer (B) Ethylene unit content 56 mol% (propylene unit content 44 mol%), number average molecular weight Mn 7700, Mw
/ Mn 1.8 ethylene / propylene random copolymer 1.0 kg, maleic anhydride 36 g and di-tert
Using 7.2 g of butyl peroxide and a dropping time of 5 g.
A reaction was carried out in the same manner as in Synthesis Example 1 except that the time was changed to a liquid acid-modified ethylene / propylene random having a number average molecular weight Mn of 7910, Mw / Mn of 2.0, and a graft ratio of 3.1% by weight. A copolymer was obtained.

Synthesis Example 5 of Modified Copolymer (B) As raw materials, ethylene unit content: 52 mol% (propylene unit content: 48 mol%), number average molecular weight: Mn 5220, Mw
/ Mn 1.7 ethylene / propylene random copolymer 908 g, 2-hydroxyethyl methacrylate 69 g
The reaction was carried out in the same manner as in Synthesis Example 1 except that 14 g of di-tert-butyl peroxide was used and the dripping time was changed to 5 hours. In order to remove the polymer of 2-hydroxyethyl methacrylate mixed in the reaction product, clay treatment was finally performed to obtain a milky white highly viscous liquid. The number average molecular weight Mn of the obtained liquid acid derivative-modified ethylene / propylene random copolymer is 5630, and Mw / Mn is 2.
1. The graft ratio was 5.6% by weight.

Synthesis Example 6 of Modified Copolymer (B) In a 500 ml glass-made reactor equipped with a stirrer equipped with a nitrogen blowing tube, a water-cooled condenser, a thermometer and two dropping funnels, an ethylene unit content of 48 mol% (propylene unit) Content 52 mol%), number average molecular weight Mn 3300, Mw / Mn
1.7 ethylene / propylene random copolymer 200
g was replaced with nitrogen for 2 hours to drive out dissolved oxygen. Thereafter, the temperature in the reactor was raised to 160 ° C., and allyl alcohol 2 previously charged in each of the two dropping funnels was used.
0 g and 4 g of di-tert-butyl peroxide in 3
It was dropped over time. After the completion of the dropwise addition, the reaction was further performed for 1 hour. Then, the temperature in the reactor was increased to 180 ° C., and unreacted allyl alcohol and decomposition products of di-tert-butyl peroxide were removed under reduced pressure (10 Torr). To obtain a white translucent viscous liquid.

The number average molecular weight Mn of the obtained liquid modified ethylene / propylene random copolymer was 3450, Mw /
Mn was 2.1. The graft ratio was 6.7% by weight. The graft ratio was determined by quantifying the hydroxyl group content in the sample by measuring the hydroxyl value by the acetylation method, and calculating the content of the hydroxyl group-containing graft monomer component from the value. The hydroxyl value is measured by heating a sample with an excess acetic anhydride / pyridine solution to acetylate, then adding distilled water to decompose acetic anhydride into acetic acid, and using phenolphthalein as an indicator in a 1N sodium hydroxide solution. It was determined from the difference from the value obtained when the same operation was performed in a system in which no sample was placed.

Synthesis Example 7 of Modified Copolymer (B) Ethylene unit content 48 mol% (propylene unit content 52 mol%), number average molecular weight Mn 3300, Mw
360 g of ethylene / propylene random copolymer having a / Mn of 1.7 and 40 g of 2-hydroxyethyl methacrylate
The reaction was carried out in the same manner as in Synthesis Example 6 except that 8 g of di-tert-butyl peroxide was used, and the number average molecular weight Mn was 3310, Mw / Mn was 2.4, and the graft ratio was 9.1% by weight. A liquid modified ethylene / propylene random copolymer was obtained.

Synthesis Example 8 of Modified Copolymer (B) Ethylene unit content 48 mol% (propylene unit content 52 mol%), number average molecular weight Mn 3300, Mw
/ Mn 1.7 ethylene / propylene random copolymer 250 g, 2-methyl-3-buten-2-ol 18 g
The reaction was carried out in the same manner as in Synthesis Example 6 except that 4 g of di-tert-butyl peroxide and di-tert-butyl peroxide were used, and the number average molecular weight Mn was 3380, Mw / Mn was 2.0, and the graft ratio was 5.1% by weight. To obtain a liquid modified ethylene / propylene random copolymer.

Synthesis Example 9 of Modified Copolymer (B) Ethylene unit content 52 mol% (propylene unit content 48 mol%), number average molecular weight Mn 5220, Mw
The reaction was carried out in the same manner as in Synthesis Example 8 except that 250 g of an ethylene / propylene random copolymer having a Mw / Mn of 1.7 and a Mw / Mn of 1.
9. A colorless and transparent liquid-modified ethylene / propylene random copolymer having a graft ratio of 4.8% by weight was obtained.

Synthesis Example 10 of Modified Copolymer (B) Ethylene unit content 56 mol% (propylene unit content 44 mol%), number average molecular weight Mn 7700, Mw
The reaction was carried out in the same manner as in Synthesis Example 8 except that 250 g of an ethylene / propylene random copolymer having a Mw / Mn of 1.8 and a Mw / Mn of 2.86 were used.
2. Liquid modified ethylene with a graft ratio of 4.5% by weight
A propylene random copolymer was obtained.

Example 1 100 parts by weight of a polyacetal resin [trade name: Duracon-M90, manufactured by Polyplastics Co., Ltd.] and 2 parts by weight of the liquid acid-modified ethylene / propylene random copolymer obtained in Synthesis Example 1 were 30 mm biaxial. The resin mixture was melt-mixed using an extruder [manufactured by Nippon Steel Works], and the obtained resin mixture was molded using a sheet forming machine [manufactured by Kawasaki Yuko Co., Ltd.] at a molding temperature of 250 ° C and 200 mm x
It was compression molded into a sheet of 00 mm x 3 mm. Of the resulting molded product
(1) friction characteristics, (2) workability, compatibility, (3) mold release,
(4) Mold contamination and (5) Mold shrinkage were evaluated by the following methods. Table 1 shows the evaluation results of the above (1) to (5).

[Evaluation Method] (1) Friction Characteristics (Slip Property, Wear Test) The friction and wear characteristics between the same materials (resin / resin) were evaluated by the following methods. According to the ASTM D-1894 method, the static friction coefficient and the kinetic friction coefficient were determined using a universal material testing machine (manufactured by Intesco Corporation) equipped with a jig for measuring slip properties. The abrasion test was performed under the following conditions, and the abrasion rate after the test was evaluated. Contact area: 2 cm ² Load: 0.2 kgf Sliding speed: 33 times / min Stroke length: 85 mm Sliding time: 6 hours

(2) Processability and compatibility At the stage of kneading with an extruder, the additives are well incorporated into the resin and the extrudability is good. When the pellets had some difficulty in stickiness and stickiness was present on the surface of the pellets, the evaluation was evaluated as “Poor”. When the additive was hardly taken into the resin, the extrudability was poor, and when the pellet surface was markedly sticky, the evaluation was ×. (3) Mold release properties The sheet molded by the sheet molding machine is not deformed and the mold can be released properly. ○, if partially deformed, △. When it was intense, it was evaluated as x.

(4) Mold Stainability After molding with the molding machine as described above, ○ indicates that the molding could be performed without contamination due to residual resin or the like on the surface of the mold, and △ indicates that the molding was partially contaminated. When the entire surface was extremely dirty, it was evaluated as x. (5) Mold Shrinkage The mold shrinkage was measured according to the method of JIS K6911.

Example 2 In the same manner as in Example 1, except that the liquid acid-modified ethylene / propylene random copolymer obtained in Synthesis Example 2 was used as the liquid acid-modified ethylene / propylene random copolymer. Then, the friction characteristics, workability, compatibility, mold releasability, mold contamination, and molding shrinkage of the obtained molded product were evaluated. Table 1 shows the evaluation results.

Example 3 In the same manner as in Example 1, except that the liquid acid-modified ethylene / propylene random copolymer obtained in Synthesis Example 3 was used as the liquid acid-modified ethylene / propylene random copolymer. Then, the friction characteristics, workability, compatibility, mold releasability, mold contamination, and molding shrinkage of the obtained molded product were evaluated. Table 1 shows the evaluation results.

Example 4 The procedure of Example 1 was repeated, except that the liquid acid-modified ethylene / propylene random copolymer obtained in Synthesis Example 4 was used as the liquid acid-modified ethylene / propylene random copolymer. Then, the friction characteristics, workability, compatibility, mold releasability, mold contamination, and molding shrinkage of the obtained molded product were evaluated. Table 1 shows the evaluation results.

Example 5 Example 1 was repeated except that the liquid acid-modified ethylene / propylene random copolymer obtained in Synthesis Example 5 was used instead of the liquid acid-modified ethylene / propylene random copolymer. In the same manner as described above, the friction characteristics, workability, compatibility, mold release properties, mold contamination, and mold shrinkage of the obtained molded product were evaluated. Table 1 shows the evaluation results.

Comparative Example 1 In the same manner as in Example 1 except that the liquid acid-modified ethylene / propylene random copolymer was not used, the friction characteristics, processability, compatibility, The mold releasability, mold contamination, and molding shrinkage were evaluated. Table 1 shows the evaluation results.

Comparative Example 2 In Example 1, an unmodified liquid ethylene / propylene random copolymer (ethylene unit content: 52 mol%, propylene unit content: 48 mol%, number average molecular weight: Mn 522)
0, Mw / Mn 1.7), in the same manner as in Example 1 except for the processability, compatibility, mold release, mold contamination, mold shrinkage, and friction characteristics of the obtained molded product. Was evaluated. Table 1 shows the evaluation results.

Examples 6 to 10 In Examples 1 to 5, instead of the polyacetal resin, an ABS resin [trade name: HM-1100, manufactured by Ube Sicon Co., Ltd.]
Except for using 1], in the same manner as in Examples 1 to 5, the friction characteristics, workability, compatibility, mold release properties,
The mold contamination and the molding shrinkage were evaluated. Table 1 shows the evaluation results.

Comparative Example 3 In the same manner as in Example 6 except that the liquid acid-modified ethylene / propylene random copolymer was not used, the friction characteristics, processability, compatibility, The mold releasability, mold contamination, and molding shrinkage were evaluated. Table 1 shows the evaluation results.

Comparative Example 4 In Example 6, an unmodified liquid ethylene / propylene random copolymer (ethylene unit content 52 mol%, propylene unit content 48 mol%, number average molecular weight Mn 522)
0, Mw / Mn 1.7), in the same manner as in Example 6, except for the friction characteristics, workability, compatibility,
The mold releasability, mold contamination, and molding shrinkage were evaluated. Table 1 shows the evaluation results.

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[Table 1]

Example 11 30 mm biaxial extrusion of 100 parts by weight of a polyacetal resin [trade name: DURACON-M90, manufactured by Polyplastics Co., Ltd.] and 2 parts by weight of the liquid-modified ethylene / propylene random copolymer obtained in Synthesis Example 6 above. The mixture was melt-mixed using a machine [manufactured by Nippon Steel Works] and the obtained resin mixture was molded using a sheet forming machine [manufactured by Kawasaki Yuko Co., Ltd.] at a molding temperature of 250 ° C. and 200 mm × 2
It was compression molded into a sheet of 00 mm x 3 mm. Of the resulting molded product
(1) friction characteristics, (2) workability, compatibility, (3) mold release,
(4) Mold contamination and (5) Mold shrinkage were evaluated by the above-mentioned method. Table 2 shows the evaluation results.

Example 12 The procedure of Example 11 was repeated, except that the liquid modified ethylene / propylene random copolymer obtained in Synthesis Example 7 was used as the liquid modified ethylene / propylene random copolymer. The friction characteristics, workability, compatibility, mold releasability, mold contamination, and mold shrinkage of the obtained molded product were evaluated. Table 2 shows the evaluation results.

Example 13 The procedure of Example 11 was repeated, except that the liquid modified ethylene / propylene random copolymer obtained in Synthesis Example 8 was used as the liquid modified ethylene / propylene random copolymer. The friction characteristics, workability, compatibility, mold releasability, mold contamination, and mold shrinkage of the obtained molded product were evaluated. Table 2 shows the evaluation results.

Example 14 The procedure of Example 11 was repeated, except that the liquid modified ethylene / propylene random copolymer obtained in Synthesis Example 9 was used as the liquid modified ethylene / propylene random copolymer. The friction characteristics, workability, compatibility, mold releasability, mold contamination, and mold shrinkage of the obtained molded product were evaluated. Table 2 shows the evaluation results.

Example 15 The procedure of Example 11 was repeated, except that the liquid modified ethylene / propylene random copolymer obtained in Synthesis Example 10 was used instead of the liquid modified ethylene / propylene random copolymer. Then, the friction characteristics, workability, compatibility, mold releasability, mold contamination, and molding shrinkage of the obtained molded product were evaluated. Table 2 shows the evaluation results.

Examples 16 to 20 In Examples 11 to 15, an ABS resin [manufactured by Toray Industries, trade name: Toyolac 500] was used instead of the polyacetal resin.
Except for using, the same procedures as in Examples 11 to 15 were carried out, and the obtained molded product had friction characteristics, workability, compatibility, mold release properties,
The mold contamination and the molding shrinkage were evaluated. Table 2 shows the evaluation results.

Comparative Example 5 In the same manner as in Example 16 except that the liquid-modified ethylene / propylene random copolymer was not used, the friction characteristics, processability, compatibility,
The mold releasability, mold contamination, and molding shrinkage were evaluated. Table 2 shows the evaluation results.

Comparative Example 6 In Example 16, an unmodified liquid ethylene / propylene random copolymer (ethylene unit content: 52 mol%, propylene unit content: 48 mol%, number average molecular weight: Mn 522)
0, Mw / Mn 1.7), in the same manner as in Example 16 except for using frictional properties, workability, compatibility, mold release properties, mold contamination, and mold shrinkage of the obtained molded article. Was evaluated.
Table 2 shows the evaluation results.

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[Table 2]

Claims (8)

[Claims] 1. A resin selected from the group consisting of (A) polyacetal resin, ABS resin, polyamide resin, polyphenylene oxide resin, polyimide resin, thermoplastic polyester resin, polycarbonate resin, epoxy resin, thermosetting unsaturated polyester resin, and phenol resin. 100 parts by weight of at least one resin to be used, and (B) (i) 20 to 8 ethylene units of all structural units
An ethylene / α-olefin random copolymer occupying 0 mol% and α-olefin units occupying 20 to 80 mol% is used as a trunk polymer, and is composed of an unsaturated carboxylic acid having 3 to 10 carbon atoms, an acid anhydride and an ester thereof. And at least one carboxylic acid monomer (b-1) and / or a hydroxyl group-containing ethylenically unsaturated monomer (b-2) selected from the group consisting of: A polymerized graft-modified copolymer, (ii) the proportion of the graft monomer in the graft-modified copolymer is 0.1 to 20% by weight, (iii) the number average molecular weight Mn is 500 to 10,000, (iv) 0.1 of liquid modified ethylene / α-olefin random copolymer having a molecular weight distribution (Mw / Mn) of 1.2 to 3
A resin composition for molding, characterized in that the composition contains from 15 to 15 parts by weight. 2. The molding resin composition according to claim 1, wherein the unmodified ethylene / α-olefin random copolymer is an ethylene / propylene random copolymer. 3. The molding resin composition according to claim 1, wherein the graft monomer is maleic anhydride. 4. The molding resin composition according to claim 1, wherein the graft monomer is a (meth) acrylate. 5. The molding resin composition according to claim 1, wherein the graft monomer is a (meth) acrylic ester having a hydroxyl group in the ester portion. 6. The molding resin composition according to claim 1, wherein the graft monomer is an unsaturated alcohol. 7. The molding resin composition according to claim 1, wherein the resin (A) is a polyacetal resin. 8. The resin according to claim 1, wherein the resin (A) is an ABS resin.
7. The molding resin composition according to any one of items 6 to 6.