JP3099396B2 - Sliding property improving agent and sliding property improving method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a slidability improver for thermoplastic polyester resins, which maintains excellent physical and mechanical properties of thermoplastic polyester resins and polyamide resins, and particularly remarkably improves sliding properties. Also, the present invention relates to a slidability improver for polyamide resin and a method for improving slidability of a thermoplastic polyester resin or polyamide resin using the same, and is used in a wide range of fields such as electric and electronic mechanical parts, precision mechanical parts, and automobile parts. Can be done.

[0002]

2. Description of the Related Art Conventionally, thermoplastic polyester resins represented by polybutylene terephthalate resin and polyethylene terephthalate resin have excellent physical properties such as mechanical properties, heat resistance, electrical properties, dimensional stability, and chemical resistance. It is widely used for industrial parts such as connectors and plugs, and various housings such as cases and covers.

[0003] However, thermoplastic polyester resins have a self-lubricating property but a low solubility limit PV value.
In many cases, it cannot be used in the field where sliding characteristics are required, and there is a great limitation on the application. Therefore, if it becomes possible to improve the sliding characteristics of the thermoplastic polyester resin, it is possible to obtain a sliding component having excellent characteristics such as the physical characteristics and the processing characteristics of the thermoplastic polyester resin, and various types. Application to the field becomes possible.

On the other hand, polyamide resins are excellent in physical properties such as mechanical properties, heat resistance, chemical resistance and the like, and are also excellent in self-lubricating properties. Therefore, industrial parts such as tanks, various housings such as cases and covers, etc. , Gears, bearing sliding members, etc.

However, the performance required of sliding members has recently become increasingly severe, and polyamide resins have been required to have even higher sliding characteristics.

In order to improve the sliding characteristics of a thermoplastic polyester resin, Japanese Patent Laid-Open Publication No.
No. 0138, a method of blending a solid lubricant, a lubricant and a polyoxyalkylene compound with a thermoplastic polyester resin, and Japanese Unexamined Patent Publication No. Sho 59-140253, in which potassium titanate fiber and a fluororesin are blended with a polybutylene terephthalate resin. Method, JP-A-63-213
No. 551 discloses a method of blending a polybutylene terephthalate resin with a tetrafluoroethylene resin.
No. 297455 discloses a polyester resin with carbon fibers,
A method of blending ultrahigh molecular weight polyethylene and the like are disclosed, and it is shown that a thermoplastic polyester resin having excellent sliding properties can be obtained.

In order to improve the sliding properties of polyamide resin, Japanese Patent Application Laid-Open No. 60-96649 discloses a method of blending powdery high-density polyethylene and potassium titanate whisker with polyamide resin.
JP-A-144351 discloses a method of blending an ultra-high molecular weight polyethylene powder having a specific particle size with a polyamide resin, and JP-A-62-218453 discloses a method of blending a carbon fiber and a polyethylene having a specific molecular weight with a polyamide resin. It is disclosed that a polyamide resin having excellent sliding properties can be obtained.

[0008]

However, in the case of thermoplastic polyester resins, Japanese Unexamined Patent Publication No.
In the method of blending a lubricating oil as disclosed in Japanese Patent Application Laid-Open No. 8-140, there is a problem that the lubricating oil bleeds out and becomes sticky on the surface of the molded article.
In the method of blending a fluororesin or ultra-high molecular weight polyethylene as disclosed in JP-A-3-213551 and JP-A-63-297455, the sliding properties of a thermoplastic polyester resin are improved to some extent, but the fluororesin or ultra-high Since there is no compatibility between the high molecular weight polyethylene and the thermoplastic polyester resin, not only the excellent physical properties of the thermoplastic polyester resin, especially the mechanical properties are impaired, but also the obtained molded product causes a delamination phenomenon. And cause a phenomenon of adhesion to a mold.

Further, polyamide resins are disclosed in
In the method of blending high-density polyethylene, ultra-high-molecular-weight polyethylene, polyethylene, etc., as disclosed in Japanese Patent Application Laid-Open Nos. 0-96649, 60-144351 and 62-218453, the sliding properties of polyamide resin are as follows. Although improved to some extent, even if the shape is powdered, the particle size is specified, or even if the molecular weight is specified, there is no compatibility between polyethylene and polyamide resin, so the excellent physical properties of polyamide resin, especially In addition to the mechanical properties being impaired, there is a problem that the obtained molded article causes a layered peeling phenomenon or a phenomenon of adhesion to a mold.

As described above, the conventional methods for improving the slidability of a thermoplastic polyester resin or a polyamide resin have advantages and disadvantages, and the development of a slidability improving agent for a thermoplastic polyester resin or a polyamide resin free of these problems. Was desired.

The present invention relates to a thermoplastic polyester resin which maintains excellent physical and mechanical properties of a thermoplastic polyester resin and a polyamide resin, and particularly remarkably improves sliding properties, a slidability improving agent for a polyamide resin and An object of the present invention is to provide a method for improving the slidability of a thermoplastic polyester resin or a polyamide resin using the same.

[0012]

Means for Solving the Problems Accordingly, the present inventors have:
As a result of diligent research to solve these conventional problems, as a slidability improver for thermoplastic polyester resin or polyamide resin, when a compound mainly composed of a specific multi-phase structure thermoplastic resin is blended, thermoplastic polyester resin or The sliding properties of the polyamide resin are significantly improved, and the physical properties of the thermoplastic polyester resin composition and the polyamide resin composition, especially the mechanical properties, are excellent. The inventors have found that the resin has excellent dispersibility in thermoplastic polyester resin and polyamide resin, and have completed the present invention.

That is, the first invention has a density of 0.90.
0 to 5 to 95% by weight of polyethylene of 0 g / cm ³ or more and 95 to 5% by weight of a vinyl (co) polymer composed of at least one vinyl monomer, and the particle size of the dispersed resin is 0.001 to It is a slidability improver for a thermoplastic polyester resin or a polyamide resin mainly composed of a multiphase thermoplastic resin having a thickness of 10 μm.

Further, the second invention has a density of 0.900.
g / cm ³ or more of 5 to 95% by weight of a polyethylene, and 95 to 5% by weight of a vinyl (co) polymer composed of at least one vinyl monomer.
It is a slidability improver for a thermoplastic polyester resin or a polyamide resin whose main components are a multiphase thermoplastic resin having a thickness of 001 to 10 μm and a lubricant.

[0015] A third invention relates to a thermoplastic polyester resin or a polyamide resin as a slidability improving agent.
Polyethylene 5-9 having a density of 0.900 g / cm ³ or more
5% by weight and 95 to 5% by weight of a vinyl (co) polymer comprising at least one vinyl monomer, wherein the dispersed resin has a particle size of 0.001 to 10 μm in a multiphase thermoplastic resin. And a method for improving the slidability of a thermoplastic polyester resin or a polyamide resin.

Further, a fourth invention relates to a method for improving the slidability of a thermoplastic polyester resin or a polyamide resin by using polyethylene 5 having a density of 0.900 g / cm ³ or more.
-95% by weight, and 95-5% by weight of a vinyl (co) polymer comprising at least one vinyl monomer, wherein the particle size of the dispersed resin is 0.001-10 μm. A method for improving the slidability of a thermoplastic polyester resin or a polyamide resin, which comprises mixing a resin and a lubricant.

The thermoplastic polyester resin to be used in the present invention is mainly composed of a polycondensation reaction containing a dicarboxylic acid compound and a diol compound as main components, a polycondensation reaction containing an oxycarboxylic acid compound as a main component, or a mixture of these three components. It is a polymer or copolymer obtained by a polycondensation reaction or the like as a component.

The dicarboxylic acid compound referred to herein includes:
Terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracenedicarboxylic acid, 4,4′-diphenyletherdicarboxylic acid, 1,2-bis (phenoxy) ethane-4,
At least one or more such as 4'-dicarboxylic acid or an ester-forming derivative thereof are exemplified.

The diol compound may have 2 to 2 carbon atoms.
10 aliphatic diols, ie, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6
-Hexanediol, decamethylenediglycol, cyclohexanediol or the like, or a molecular weight of 400 to 600
0 long-chain glycols, that is, at least one or more of polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol and the like.

Further, as the oxycarboxylic acid compound,
Examples include at least one or more of oxycarboxylic acids such as oxybenzoic acid, oxynaphthoic acid, and diphenyleneoxycarboxylic acid, and ester-forming derivatives thereof. Among these, polyethylene terephthalate,
Polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polyethylene-2,6-naphthalate, polyethylene-1,2-
The slidability improver of the present invention is preferably used for bis (phenoxy) ethane-4,4'-dicarboxylate and the like.

The polyamide resins to be used in the present invention include nylon 6, nylon 66, nylon 610, nylon 11, nylon 12, nylon 612, and nylon 4.
And aromatic polyamide resins such as polyhexadiamine terephthalamide, polyhexamethylene diamine isophthalamide, and xylene group-containing polyamide, and two or more types of raw material monomers used for these are copolymerized. Or a mixture of two or more of these polyamide resins.

As the polyethylene in the thermoplastic resin having a multi-phase structure used as the slidability improving agent of the present invention, a polyethylene having a density of 0.900 g / cm ³ or more is used from the viewpoint of slidability.

[0023]

[0024]

[0025]

[0026]

The vinyl (co) polymer in the thermoplastic resin having a multi-phase structure used as the sliding property improving agent of the present invention includes, specifically, styrene, nucleus-substituted styrene (eg, methylstyrene, dimethylstyrene) , Ethyl styrene, isopropyl styrene, chlorostyrene, etc.), α-substituted styrene (eg, α-methyl styrene, α-ethyl styrene, etc.)
(Meth) acrylic acid such as alkyl ester of acrylic acid or methacrylic acid having 1 to 7 carbon atoms (eg, methyl, ethyl, propyl, isopropyl, butyl, etc. of (meth) acrylic acid); Acid ester monomers; unsaturated acid glycidyl ester monomers such as glycidyl esters of α, β-unsaturated acids (eg, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate); 2-hydroxyethyl methacrylate (Meth) acrylic acid hydroxyalkyl ester monomers such as hydroxypropyl methacrylate, polyethylene glycol monomethacrylate, and polypropylene glycol monomethacrylate; vinyl cyanide monomers such as acrylonitrile or methacrylonitrile Vinyl ester monomers such as vinyl acetate and vinyl propionate; (meth) acrylamide monomers such as acrylamide and methacrylamide; mono-, di-esters, fumaric acid and itaconic acid of (meth) acrylic acid and (anhydrous) maleic acid Vinyl monomers such as unsaturated carboxylic acids such as acid, citraconic acid and crotonic acid and derivatives thereof such as amides, imides, esters and anhydrides;
It is a (co) polymer obtained by polymerizing one or more species.

Among these, particularly, vinyl aromatic monomers, (meth) acrylate monomers, vinyl cyanide monomers, vinyl ester monomers and unsaturated acid glycidyl ester monomers, unsaturated acids Carboxylic acids and their derivatives are preferably used. In particular, 0 to 50% by weight of a vinyl cyanide monomer and 50 to 10% of a vinyl aromatic monomer.
0% by weight of a vinyl copolymer, or a vinyl (co) polymer containing 50% by weight or more of a (meth) acrylate monomer or an unsaturated acid glycidyl ester alone in a vinyl (co) polymer. The vinyl (co) polymer containing the monomer or unsaturated carboxylic acid and its derivative in an amount of 0.01% by weight or more is the most preferable embodiment because of its good dispersibility in a thermoplastic polyester resin or a polyamide resin.

The multi-phase thermoplastic resin used as the slidability improver of the present invention refers to a polyethylene (vinyl) (co) polymer matrix or a vinyl (co) polymer which is a different component in a polyethylene or vinyl (co) polymer matrix. It refers to polyethylene in which spherical particles are uniformly dispersed.

The dispersed polymer has a particle size of 0.001.
10 to 10 μm, preferably 0.01 to 5 μm. When the dispersed resin particle diameter is less than 0.001 μm or 5 μm
If it exceeds, the dispersibility when blended with the thermoplastic polyester resin or polyamide resin is low, and for example, the appearance is deteriorated or the mechanical properties are lowered, which is not preferable.

The number average degree of polymerization of the vinyl (co) polymer in the thermoplastic resin having a multiphase structure used as the slidability improving agent of the present invention is 5 to 10,000, preferably 10 to 5,000. When the number average polymerization degree is less than 5, it is possible to improve the sliding properties of the thermoplastic polyester resin or the polyamide resin, but the dispersibility when blended with the thermoplastic polyester resin or the polyamide resin is low and the mechanical property is low. It is not preferable because physical properties are deteriorated. On the other hand, if the number average degree of polymerization exceeds 10,000, the melt viscosity is high, and the moldability is lowered and the surface gloss is lowered.

The thermoplastic resin having a multi-phase structure used as the slidability improving agent of the present invention contains 5 to 95% by weight of polyethylene,
Preferably, it comprises 20 to 90% by weight. Therefore, the amount of the vinyl (co) polymer is 95 to 5% by weight, preferably 80 to 10% by weight. If the polyethylene content is less than 5% by weight, the effect of improving the sliding properties is insufficient, which is not preferred. On the other hand, if the content of polyethylene exceeds 95% by weight, the effect of improving the sliding properties can be sufficiently obtained, but the mechanical properties and heat resistance are undesirably reduced.

In producing the thermoplastic resin having a multi-phase structure used as the slidability improving agent of the present invention, the thermoplastic resin is also produced by a grafting method such as a chain transfer method and an ionizing radiation irradiation method which are well known. Is possible, but most preferred is
This is based on one of the following methods.

Hereinafter, a method for producing a thermoplastic resin having a multi-phase structure used as the slidability improver of the present invention will be described in detail.

That is, the first method is to use polyethylene 10
0 parts by weight are suspended in water, and 5 to 400 parts by weight of at least one vinyl monomer is separately added to a radical (co) polymerizable organic peroxide represented by the following general formula (a) or (b). Radical polymerization wherein at least one or a mixture of two or more of the above is 0.1 to 10 parts by weight with respect to 100 parts by weight of the vinyl monomer, and the decomposition temperature for obtaining a half-life of 10 hours is 40 to 90 ° C. The initiator is used in an amount of 0.0 with respect to 100 parts by weight of the total of the vinyl monomer and the radical (co) polymerizable organic peroxide.
A solution prepared by dissolving 1 to 5 parts by weight is added, and the mixture is heated under the condition that decomposition of the radical polymerization initiator does not substantially occur, and the vinyl monomer, the radical (co) polymerizable organic peroxide and the radical polymerization start are started. The agent is impregnated into polyethylene, and when the impregnation rate reaches the initial 10% by weight or more, the temperature of the aqueous suspension is increased, and the vinyl monomer and the radical (co) polymerizable organic peroxide are separated. It is copolymerized in polyethylene to obtain a grafted precursor (A).

This grafting precursor is also a multiphase thermoplastic resin. Therefore, this grafting precursor (A)
Can also be used as a slidability improver for thermoplastic polyester resins or polyamide resins.

The grafting precursor (A) is used in an amount of 100 to 3
By kneading under melting at 00 ° C., it is also possible to obtain a thermoplastic resin having a multi-phase structure which can be used as a sliding property improving agent for a thermoplastic polyester resin or a polyamide resin of the present invention. At this time, the polyethylene (B) and / or vinyl (co) polymer (C) may be separately mixed with the grafting precursor (A) and kneaded while being melted. Alternatively, a thermoplastic resin having a multi-phase structure which can be used as a slidability improving agent for a polyamide resin can be obtained.

Among them, the most preferred as the slidability improver for thermoplastic polyester resin or polyamide resin is a multiphase thermoplastic resin obtained by kneading the grafting precursor (A).

The radical (co) polymerizable organic peroxide represented by the general formula (a) is represented by the formula

Embedded image (Wherein, R ₁ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R ₂ is a hydrogen atom or a methyl group, R 3 and R ₄ are each an alkyl group having 1 to 4 carbon atoms, and R ₅ is a 1 to 2 carbon atom. 12
An alkyl group, a phenyl group, an alkyl-substituted phenyl group, or a cycloalkyl group having 3 to 12 carbon atoms. m is 1 or 2. ).

The radical (co) polymerizable organic peroxide represented by the general formula (b) is represented by the formula

Embedded image (Wherein, R ₆ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₇ is a hydrogen atom or a methyl group, R ₈ and R ₉ are each an alkyl group having 1 to 4 carbon atoms, and R ₁₀ is a carbon atom having 1 carbon atom. ~ 12
An alkyl group, a phenyl group, an alkyl-substituted phenyl group, or a cycloalkyl group having 3 to 12 carbon atoms. n is 0,
1 or 2. ).

A radical represented by the general formula (a) (co)
As the polymerizable organic peroxide, specifically, t-butyl peroxyacryloyloxyethyl carbonate; t-amyl peroxyacryloyloxyethyl carbonate;
t-hexylperoxyacryloyloxyethyl carbonate; 1,1,3,3-tetramethylbutylperoxyacryloyloxyethyl carbonate; cumylperoxyacryloyloxyethyl carbonate; p-isopropylcumylperoxyacryloyloxyethyl carbonate; t -Butyl peroxymethacryloyloxyethyl carbonate; t-amylperoxymethacryloyloxyethyl carbonate; t-hexylperoxymethacryloyloxyethyl carbonate; 1,1,3,3-
Tetramethylbutyl peroxymethacryloyloxyethyl carbonate; cumyl peroxymethacryloyloxyethyl carbonate; p-isopropylcumylperoxymethacryloyloxyethyl carbonate; t-butylperoxymethacryloyloxyethyl carbonate; t
T-hexyl peroxyacryloyloxyethoxyethyl carbonate; 1,1,3,3-tetramethylbutylperoxyacryloyloxyethoxyethyl carbonate; cumyl peroxyacryloyloxyethoxyethyl carbonate; 1,1-p-isopropylcumylperoxyacryloyloxyethoxyethyl carbonate; t-butylperoxymethacryloyloxyethoxyethyl carbonate; t-amylperoxymethacryloyloxyethoxyethyl carbonate; t-hexylperoxymethacryloyloxyethoxyethyl carbonate; 3,3-tetramethylbutyl peroxymethacryloyloxyethoxyethyl carbonate; cumyl peroxymethacrylic Acetoxyphenyl ethoxyethyl carbonate; p-isopropyl cumyl peroxy methacryloyloxy-ethoxyethyl carbonate; t-butyl peroxy-acryloyloxy isopropyl carbonate; t-
Amyl peroxyacryloyloxyisopropyl carbonate; t-hexylperoxyacryloyloxyisopropyl carbonate; 1,1,3,3-tetramethylbutylperoxyacryloyloxyisopropyl carbonate; cumyl peroxyacryloyloxyisopropyl carbonate; p-isopropylcumyl Peroxyacryloyloxyisopropyl carbonate; t-butyl peroxymethacryloyloxyisopropyl carbonate; t-amylperoxymethacryloyloxyisopropyl carbonate; t-hexylperoxymethacryloyloxyisopropyl carbonate; 1,1,3,3-
Tetramethylbutyl peroxymethacryloyloxyisopropyl carbonate; cumyl peroxymethacryloyloxyisopropyl carbonate, p-isopropylcumylperoxymethacryloyloxyisopropyl carbonate and the like can be exemplified.

Further, compounds represented by the general formula (b) include t-butylperoxyallyl carbonate,
t-amyl peroxy allyl carbonate, t-hexyl peroxy allyl carbonate, 1,1,3,3-tetramethylbutyl peroxy allyl carbonate, p-
Menthane peroxy allyl carbonate, cumyl peroxy allyl carbonate, t-butyl peroxy methallyl carbonate, t-amyl peroxy methallyl carbonate, t-hexyl peroxy methallyl carbonate, 1,1,3,3-tetramethyl butyl peroxy methallyl carbonate , P-menthane peroxy methallyl carbonate, cumyl peroxy methallyl carbonate, t-butyl peroxy allyloxyethyl carbonate, t-amyl peroxy allyloxy ethyl carbonate, t-hexyl peroxy allyloxy ethyl carbonate, t-butyl peroxy metalaryloxy ethyl Carbonate, t-amyl peroxy metalaryloxyethyl carbonate, t-hexyl peroxy metalaryloxyethyl carbonate, t-butyl Le peroxy allyloxy isopropyl carbonate, t-amyl peroxy allyloxy isopropyl carbonate, t-hexyl peroxy allyloxy isopropyl carbonate, t- butyl peroxy meth Lilo carboxylate isopropyl carbonate, t-amyl peroxy meth Lilo carboxylate isopropyl carbonate,
Examples thereof include t-hexyl peroxy metalaryloxy isopropyl carbonate.

Among them, preferably, t-butyl peroxyacryloyloxyethyl carbonate, t-butylperoxymethacryloyloxyethyl carbonate, t-butyl
Butyl peroxyallyl carbonate and t-butyl peroxymethallyl carbonate.

In the second method, the thermoplastic resin having a multi-phase structure obtained by the above-described first method, polyethylene (B)
And / or blending a vinyl (co) polymer (C) with a lubricant, or adding a multi-phase thermoplastic resin, polyethylene (B) and / or vinyl (co) polymer (C) to 100 to 100% in advance. This is a method for producing a slidability improving agent for a thermoplastic polyester resin or a polyamide resin, in which a melt-mixed material at a temperature of 300 ° C. is mixed with a lubricant.

The third method is to use polyethylene 100
Parts by weight in water, and separately adding 5 to 400 parts by weight of at least one vinyl monomer with a radical polymerization initiator having a decomposition temperature of 40 to 130 ° C. to obtain a half-life of 10 hours. A solution prepared by dissolving 0.01 to 5 parts by weight with respect to 100 parts by weight of the monomer is added, and the mixture is heated under the condition that decomposition of the radical polymerization initiator does not substantially occur, and the vinyl monomer and the radical polymerization start are started. When the impregnation rate of the aqueous suspension reaches 10% by weight or more, the temperature of the aqueous suspension is increased, and the vinyl monomer is (co) polymerized in the polyethylene to form a polyphase. Obtain a structural thermoplastic resin.

The multiphase thermoplastic resin may be used as it is as a slidability improver for thermoplastic polyester resin or polyamide resin, or the multiphase thermoplastic resin may be kneaded under melting at 100 to 300 ° C. It may be used as a slidability improver for thermoplastic polyester resin or polyamide resin.

At this time, the polyethylene (B) and / or the vinyl (co) polymer (C) are separately mixed with the multi-phase thermoplastic resin, and the mixture is kneaded while being melted. A thermoplastic resin having a multiphase structure which can be used as a slidability improver can be obtained.

Further, the fourth method is to combine the multi-phase thermoplastic resin, the polyethylene (B) and / or the vinyl (co) polymer (C) obtained by the above-mentioned third method with a lubricant. A thermoplastic resin to be blended or to be blended with a lubricant in which a multi-phase thermoplastic resin, polyethylene (B) and / or vinyl (co) polymer (C) is dissolved and mixed in the range of 100 to 300 ° C. in advance. This is a method for producing a sliding property improving agent for a polyester resin or a polyamide resin.

Either of these production methods can be used to obtain a multi-phase thermoplastic resin for use in the thermoplastic polyester resin or polyamide resin slidability improver of the present invention. Among them, the methods according to the first method and the second method are particularly preferable. What is necessary is that the grafting efficiency of the thermoplastic resin having a multiphase structure used as the slidability improving agent of the present invention is high and secondary aggregation does not occur due to heat. This is because a thermoplastic polyester resin or a polyamide resin having excellent mobility is excellent in physical properties, mechanical properties, moldability, and the like.

In the case of using only the multi-phase structure thermoplastic resin, the multi-phase structure thermoplastic resin used as the slidability improving agent of the present invention is 1 to 100 parts by weight based on 100 parts by weight of the thermoplastic polyester resin or polyamide resin. Parts, preferably 4 to 70 parts by weight.

When the multi-phase thermoplastic resin and the lubricant are used, 1 to 100 parts by weight of the multi-phase thermoplastic resin is used.
It is preferably 4 to 70 parts by weight, 0.1 to 50 parts by weight of a lubricant, and preferably 0.5 to 20 parts by weight. If the amount of the multi-phase thermoplastic resin is less than 1 part by weight, the effect of improving the sliding properties, which is the object of the present invention, is not preferred, which is not preferable. On the other hand, when the amount of the multi-phase structure thermoplastic resin exceeds 100 parts by weight, the mechanical strength and the heat resistance are lowered, which is not preferable.

The thermoplastic resin having a multi-phase structure used as the slidability improver of the present invention exhibits an excellent slidability improvement effect by itself. However, 100 parts by weight of a thermoplastic polyester resin or a polyamide resin, Structural thermoplastic resin 1-1
When 0.1 to 50 parts by weight of the lubricant is blended with respect to 00 parts by weight, a more excellent sliding property improving effect is exhibited. If the amount of the lubricant is less than 0.1 part by weight, the effect of improving the slidability is not obtained. If the amount exceeds 50 parts by weight, the mechanical properties and the surface state of the resin composition are undesirably reduced.

The lubricant used in the present invention is usually added to improve the slidability of the resin. Examples of the lubricant include spindle oil, refrigerating machine oil, turbine oil, machine oil, cylinder oil, Mineral oils such as gear oils; hydrocarbons such as liquid paraffin, paraffin wax and polyethylene wax; fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, montanic acid; hexyl alcohol, octyl alcohol Alcohols such as acetyl, cetyl alcohol, stearyl alcohol, behenyl alcohol, glycols, glycerin, polyglycerol, pentaerythritol; stearyl stearate, behenyl behenate, pentaerythritol tristearate Rate, pentaerythritol tetrastearate Fatty acid esters such as glycerin monostearate and glycerin monobehenate; fatty acid amides such as stearylamide, palmitylamide, oleylamide, methylenebisstearamide and ethylenebisstearamide; metal soaps such as calcium stearate and magnesium stearate Natural wax such as montan wax; one or more kinds such as silicone can be used. Among them, fatty acids, alcohols,
Fatty acid esters, silicones, mineral oils and the like can be preferably used.

In the present invention, the method of improving the slidability when a multiphase thermoplastic resin is used as the slidability improving agent is as follows:
This is achieved by melt-mixing a thermoplastic polyester resin or a polyamide resin with a multiphase thermoplastic resin or a multiphase thermoplastic resin and a lubricant as a slidability improving agent.

Regarding the temperature conditions at the time of melt mixing,
150 to 350 for thermoplastic polyester resin
C., preferably at 200 to 280 ° C. under melting. If the temperature is lower than 150 ° C., the melting is insufficient or the melt viscosity is high, and the mixing becomes insufficient.
It is not preferable because phase separation and delamination appear in the molded product.
On the other hand, when the temperature exceeds 350 ° C., the resin to be mixed is decomposed, and the molded product is colored, or the mechanical properties are deteriorated.

In the case of polyamide resins,
It is preferable to mix under melting at 400 ° C., preferably 200 to 330 ° C. If the temperature is lower than 150 ° C., the melting is insufficient, the melt viscosity is high, the mixing is insufficient, and phase separation or delamination appears in the molded product, which is not preferable. On the other hand, when the temperature exceeds 400 ° C., the resin to be mixed is decomposed, and the molded product is colored and the mechanical properties are deteriorated.

The method of melt mixing can be carried out by a kneader usually used for kneading thermoplastic resins such as a Banbury mixer, a pressure kneader, a single-screw extruder, a twin-screw extruder, and a mixing roll. Productivity,
A twin-screw extruder is particularly preferred in view of the mechanical properties of the obtained resin.

In the present invention, inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide, organic flame retardants such as halogen-based, phosphorus-based, etc., calcium sulfate, calcium carbonate, silicate and the like may be used without departing from the scope of the present invention. Powdered and granular fillers such as calcium, clay, diatomaceous earth, talc, alumina, silica sand, glass powder, iron oxide, metal powder, graphite, silicon carbide, silicon nitride, silica, boron nitride, aluminum nitride, carbon black, molybdenum disulfide; Metal powder such as mica, glass plate, sericite, pyrophyllite, aluminum flake, etc., flat or flaky filler such as graphite; hollow filler such as shirasu balloon, metal balloon, glass balloon, pumice, glass fiber, Mineral fiber such as carbon fiber, silicon carbide fiber, asbestos, wollastonite Which fibrous filler, potassium titanate whisker, calcium sulfate whisker, monocrystalline fibrous filler such as an inorganic filler such as carbon whisker,
Organic fillers such as wood flour, antioxidants, UV inhibitors, lubricants, dispersants, coupling agents, foaming agents, crosslinking agents, additives such as colorants, and other polyolefin-based resins, polyamide resins, polyester resins, Polycarbonate resin, A
Engineering plastics such as BS resin, polyphenylene ether, polyoxymethylene, polyphenylene sulfide, and fluorine resin may be added.

[0059]

The present invention will be described in more detail with reference to the following examples. In addition, about the dynamic friction coefficient measured in this Example and the comparative example, it measures on the following measurement conditions and shows the obtained value. [Measurement of dynamic friction coefficient] Testing machine: friction and wear testing machine model EFM-III-F (high-speed type) manufactured by Orientec Co., Ltd. Counterpart material: cylindrical material having an inner diameter of 20 mm and outer diameter of 25.6 mm Material S45C test piece: 30 mm Square, 3 mm thick flat plate Test conditions: load 5 kg / cm ² , linear velocity 30 cm / sec
c Also, the tensile strength, flexural modulus and heat denaturation temperature measured in the present example and comparative example are respectively shown in J below.
It was measured according to IS. [Tensile strength] JIS K-7113 Test speed 10 mm / mm [Bending elastic modulus] JIS K-7203 Test speed 2 mm / mm [Heat deformation temperature] JIS K-7207 Load 18.5 kg / cm ² The presence or absence of the delamination was visually determined.

Reference Example 1 (Production of Multiphase Thermoplastic Resin A) Pure water 25 was placed in a stainless steel autoclave having an internal volume of 5 l.
Then, 2.5 g of polyvinyl alcohol was dissolved as a suspending agent. Non-polar α-olefin polymer (trade name “Lexlon F41”, manufactured by Nippon Petrochemical Co., Ltd., low-density polyethylene, density: 0.924 g /
cm ³ ), and dispersed by stirring. Separately, 1.5 g of benzoyl peroxide (trade name "Niper B", manufactured by NOF Corporation) as a radical polymerization initiator and 6 g of t-butylperoxymethacryloyloxyethyl carbonate as a radical (co) polymerizable organic peroxide are vinyl. It was dissolved in 210 g of a styrene monomer as a monomer and 90 g of an acrylonitrile monomer, and this solution was charged into the autoclave and stirred. Next, the autoclave was heated to 60 to 65 ° C. and stirred for 2 hours to convert a vinyl monomer containing a radical polymerization initiator and a radical (co) polymerizable organic peroxide into a nonpolar α-olefin polymer. Was impregnated. Next, after confirming that the total amount of the impregnated vinyl monomer, radical (co) polymerizable organic peroxide and radical polymerization initiator is 10% by weight or more, the temperature is raised to 80 to 85%. C. and maintained at that temperature for 7 hours to complete the polymerization, washed with water and dried to obtain a grafted precursor. The styrene-acrylonitrile copolymer in the graft precursor was extracted with ethyl acetate, and the number average degree of polymerization was measured by GPC.
00. Then, the grafted precursor is subjected to a Labo Plastomill-screw extruder (manufactured by Toyo Seiki Seisaku-sho, Ltd.).
At 200 ° C. and a grafting reaction was performed to obtain a thermoplastic resin A having a multiphase structure. This multi-phase structure thermoplastic resin is scanned with a scanning electron microscope (“JEOL JSM T
300 "(manufactured by JEOL Ltd.).
It was a thermoplastic resin having a multiphase structure in which true spherical resins of 3 to 0.4 μm were uniformly dispersed. At this time, the graft efficiency of the styrene-acrylonitrile copolymer was 62.3% by weight.
Met.

Reference Example 2 (Production of thermoplastic resin B having a multi-phase structure) In Reference Example 1, instead of 210 g of a styrene monomer and 90 g of an acrylonitrile monomer as a vinyl monomer, 300 g of a methyl methacrylate monomer was used. A multiphase thermoplastic resin B was obtained in the same manner as in Reference Example 1, except that 0.6 g of n-dodecyl mercaptan was added as a molecular weight modifier. At this time, the number average polymerization degree of the methyl methacrylate polymer was 700, and the average particle diameter of the resin dispersed in the resin composition was 0.1 to 0.2 μm.

Reference Example 3 (Production of Multi-Phase Thermoplastic Resin C) In Reference Example 1, a low-density polyethylene as a nonpolar α-olefin polymer was replaced with a high-density polyethylene (trade name “STAFFLEN E780”, Nippon Petrochemical Co., Ltd.) A multi-phase thermoplastic resin C was obtained in the same manner as in Reference Example 1 except that the density was changed to 0.963 g / cm ³ ). At this time, the number average polymerization degree of the styrene-acrylonitrile copolymer was 85.
0, and the average particle size of the resin dispersed in the resin composition was 0.3 to 0.4 μm.

Reference Example 4 (Production of Multi-Phase Thermoplastic Resin D) In Reference Example 1, low-density polyethylene as a nonpolar α-olefin polymer was converted to ultra-high-molecular-weight polyethylene (trade name “Lubmer L4000”, Mitsui Petrochemical Co., Ltd.). A multiphase thermoplastic resin D was obtained according to Reference Example 1, except that the density was changed to 0.966 g / cm ³ (manufactured by Kogyo Co., Ltd.).
At this time, the number average degree of polymerization of the styrene-acrylonitrile copolymer was 870, and the average particle diameter of the resin dispersed in the resin composition was 0.3 to 0.4 μm.

Reference Example 5 (Production of Multi-Phase Thermoplastic Resin E) In Reference Example 1, a low-density polyethylene as a nonpolar α-olefin polymer was replaced with a linear low-density polyethylene (trade name: Linirex AJ5310, Nippon Oil) A multi-phase thermoplastic resin E was obtained in the same manner as in Reference Example 1 except that the density was changed to 0.923 g / cm ³ (manufactured by Chemical Co., Ltd.).
At this time, the number average polymerization degree of the styrene-acrylonitrile copolymer was 920, and the average particle diameter of the resin dispersed in the resin composition was 0.2 to 0.3 μm.

Reference Example 6 (Production of Multiphase Thermoplastic Resin F) The 67% by weight of the grafted precursor obtained in Reference Example 1 was
Low-density polyethylene (trade name “Lexlon F41”, Nippon Petrochemical Co., Ltd.) as a nonpolar α-olefin (co) polymer
(Manufactured by Toyo Seiki Seisakusho Co., Ltd.) at 200 ° C. to obtain a multi-phase thermoplastic resin F. At this time, the average particle diameter of the resin dispersed in the resin composition was 0.3 to 0.4 μm.

Reference Example 7 (Production of Multi-Phase Thermoplastic Resin G) Pure water 25 was placed in a stainless steel autoclave having an internal volume of 5 l.
Then, 2.5 g of polyvinyl alcohol was dissolved as a suspending agent. Among them, 5 g of benzoyl peroxide (trade name "Niper B", manufactured by NOF Corporation) as a radical polymerization initiator, 700 g of a styrene monomer as a vinyl monomer and acrylonitrile monomer 3
The solution was poured into the autoclave and stirred. Next, the autoclave was heated to 80 to 85 ° C.
And maintained at that temperature for 7 hours to complete the polymerization,
After washing with water and drying, a styrene-acrylonitrile copolymer as a vinyl polymer was obtained. The number average polymerization degree of this styrene-acrylonitrile copolymer was 850. 71% by weight of the grafted precursor obtained in Reference Example 1
Then, 29% by weight of a styrene-acrylonitrile copolymer obtained by the above method as a vinyl copolymer was mixed with a Labo Plastomill-screw extruder (manufactured by Toyo Seiki Seisaku-Sho, Ltd.) for 2 hours.
It was extruded at 00 ° C. to obtain a multi-phase thermoplastic resin G. At this time, the average particle size of the resin dispersed in the resin composition was 0.4 to 0.5 μm.

Reference Example 8 (Production of Multi-Phase Thermoplastic Resins H and I) In Reference Example 1, except that t-butylperoxymethacryloyloxyethyl carbonate as a radical (co) polymerizable organic peroxide was not used. According to Reference Example 1, a multi-phase thermoplastic resin H was obtained. At this time, the number average polymerization degree of the styrene-acrylonitrile copolymer was 860, and the average particle diameter of the resin dispersed in the resin composition was 0.1.
It was 3 to 0.4 μm. This multi-phase thermoplastic resin H
Was extruded at 200 ° C. with a Labo Plastomill-screw extruder (manufactured by Toyo Seiki Seisaku-sho, Ltd.) to obtain a multi-phase thermoplastic resin I.

REFERENCE EXAMPLE 9 (Production of Multiphase Thermoplastic Resin J) 67% by weight of the multiphase thermoplastic resin H obtained in Reference Example 8 and low density polyethylene (commercially available) as a non-polar α-olefin (co) polymer 33% by weight (Rexlon F41, manufactured by Nippon Petrochemical Co., Ltd.) was extruded at 200 ° C. with a Labo Plastomill-screw extruder (manufactured by Toyo Seiki Seisaku-sho, Ltd.) to obtain a multi-phase thermoplastic resin J. . At this time, the average particle diameter of the resin dispersed in the resin composition is 0.5 to 0.6 μm.
m.

Reference Example 10 (Production of Multiphase Thermoplastic Resin K) The polyphase thermoplastic resin H obtained in Reference Example 8 (71% by weight) was obtained in Reference Example 7 as a vinyl (co) polymer. 29% by weight of a styrene-acrylonitrile copolymer was extruded at 200 ° C. with a Labo Plastomill-screw extruder (manufactured by Toyo Seiki Seisaku-sho, Ltd.) to obtain a multi-phase thermoplastic resin K.
At this time, the average particle diameter of the resin dispersed in the resin composition was 0.5 to 0.6 μm.

Reference Examples 11 to 17 (Production of Multiphase Thermoplastic Resins L to R) The multiphase thermoplastic resins A and H obtained in Reference Examples 1 and 8
71% by weight, stearyl stearate as a lubricant,
(Nippon Oil & Fats Co., Ltd. Unistar M9676, mineral oil (Idemitsu Kosan Co., Ltd. Daphne Mechanic Oil # 100), dimethylpolysiloxane (SH20 manufactured by Toray Silicone Co., Ltd.)
0) were blended in the compositions shown in Table 1 to obtain multi-phase thermoplastic resins L to R.

[Table 1]

Examples 1 to 21 Reference examples 1 to 10 were applied to polybutylene terephthalate resin (trade name "Duranex 2002", manufactured by Polyplastics Co., Ltd.) as a thermoplastic polyester resin as a slidability improver. -Phase thermoplastic resin AK obtained by
Was dry-blended at the ratios shown in Tables 2 to 4 at 230 ° C.
Twin screw extruder (Kurimoto Iron Works Co., Ltd.)
Manufactured by KRC Kneader Model S-1). Then 2
Each test piece was prepared using an in-line screw type injection molding machine (manufactured by Tabata Machine Industry Co., Ltd., TS-35-FV25 type) set at 30 ° C, and the tensile strength, flexural modulus,
The heat deformation temperature and the coefficient of kinetic friction (on steel) were measured. The results are shown in Tables 2 to 4.

[Table 2]

[Table 3]

[Table 4]

Examples 22 to 27 In Example 1, a polyethylene terephthalate resin (intrinsic viscosity 0.74) was used instead of the polybutylene terephthalate resin used as the thermoplastic polyester resin, and glass fibers (average fiber length) were used as the inorganic filler. 3.0
mm and a diameter of 13 μm) were blended in the proportions shown in Table 5, and a test piece was prepared and examined in accordance with Example 1 except that the extrusion molding temperature and the injection molding temperature were each performed at 280 ° C. Table 5 shows the results.

[Table 5]

Examples 28 to 40 Polybutylene terephthalate resin (trade name "Duranex 2002", manufactured by Polyplastics Co., Ltd.) as a thermoplastic polyester resin, polyethylene terephthalate resin (intrinsic viscosity 0.74), inorganic filler Glass fiber (average fiber length: 3.0 mm, diameter: 13 μm), and the multiphase thermoplastic resins L to R obtained in Reference Examples 11 to 17 were blended in the proportions shown in Tables 6 to 7 as slidability improvers. Each test piece was prepared according to Examples 1 and 22 except that
The tensile strength, flexural modulus, heat deformation temperature, and dynamic friction coefficient (on steel) were measured. The results are shown in Tables 6 and 7.

[Table 6]

[Table 7]

Comparative Examples 1 to 9 In Example 1, a polyethylene resin and a stearyl stearate (Nippon Oil & Fat Co., Ltd., Unistar M9676) were used in place of the multi-phase thermoplastic resin as the slidability improving agent. Except for use, each test piece was prepared according to Example 1, and the tensile strength, flexural modulus, heat deformation temperature, and dynamic friction coefficient (to steel) were measured according to Example 1. Table 8 shows the results.

[Table 8]

Examples 41 to 61 Nylon 6 resin as polyamide resin (trade name "UB")
E-Nylon 1013B "manufactured by Ube Industries, Ltd.)
The multiphase thermoplastic resins A to K obtained in Reference Examples 1 to 10 were blended in the proportions shown in Tables 9 to 11 as slidability improvers, and the grafted precursor obtained in Reference Example 1 was prepared. Quantitative dry blending was performed and mixed by a coaxial twin screw extruder (manufactured by Kurimoto Iron Works Co., Ltd., KRC Kneader S-1) set at 240 ° C. Next, an in-line screw injection molding machine set to 240 ° C (TS-35, manufactured by Tabata Machine Industry Co., Ltd.)
(FV25 type), each test piece was prepared, and the tensile strength, flexural modulus, heat deformation temperature, and dynamic friction coefficient (on steel) were measured. The results are shown in Tables 9 to 11.

[Table 9]

[Table 10]

[Table 11]

Examples 62 to 67 In Example 41, nylon 66 resin (trade name "UBE Nylon 2020B" manufactured by Ube Industries, Ltd.) was used instead of nylon 6 resin as a polyamide resin, and glass fiber was used as an inorganic filler. (Average fiber length: 3.0 mm, diameter: 13 μm) were blended at the ratios shown in Table 12, and a test piece was prepared according to Example 41 except that the extrusion molding temperature and the injection molding temperature were each set at 275 ° C. , Tensile strength,
The flexural modulus, heat deformation temperature, and dynamic friction coefficient (on steel) were measured. Table 12 shows the results.

[Table 12]

Examples 68 to 73 In Example 41, nylon MXD6 resin (trade name “RE”) was used instead of nylon 6 resin as polyamide resin.
NY6002 (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and a test piece was prepared according to Example 41 except that the extrusion molding temperature and the injection molding temperature were each set to 260 ° C., and the tensile strength, flexural modulus and heat were measured. The deformation temperature and the coefficient of kinetic friction (on steel) were measured. Table 13 shows the results.

Examples 74 to 88 Nylon 6 resin as polyamide resin (trade name "UB")
E nylon 1013B "manufactured by Ube Industries, Ltd.), nylon 66 resin (trade name" UBE nylon 2020B "manufactured by Ube Industries, Ltd.), nylon MXD6 resin (trade name" REN ")
Y6002 "manufactured by Mitsubishi Gas Chemical Co., Ltd.), glass fiber (average fiber length 3.0 mm, diameter 13 μm) as an inorganic filler.
m), test pieces according to Examples 41 and 68, except that the multiphase thermoplastic resins N to R obtained in Reference Examples 11 to 17 were blended in the proportions shown in Tables 14 and 15 as slidability improvers. Was prepared, and the tensile strength, flexural modulus, heat deformation temperature, and dynamic friction coefficient (on steel) were measured. The results are shown in Tables 14 and 15.

[Table 14]

[Table 15]

Comparative Examples 10 to 18 In Example 1, a polyethylene resin and a stearyl stearate (Nippon Oil & Fat Co., Ltd., Unistar M9676) were used in place of the multiphase thermoplastic resin as the sliding property improving agent. Except for using, a test piece was prepared according to Example 1, and the tensile strength,
The flexural modulus, heat deformation temperature, and dynamic friction coefficient (on steel) were measured. Table 16 shows the results.

[Table 16]

When the thermoplastic resin having a multi-phase structure of the present invention is blended with a thermoplastic polyester resin or a polyamide resin as a slidability improving agent, the mechanical and physical properties of the thermoplastic polyester resin or the polyamide resin are not significantly impaired.
It became clear that the slidability can be greatly improved. Also,
It has been clarified that when the multi-phase structure thermoplastic resin of the present invention is used in combination with a lubricant as a slidability improving agent, a more excellent slidability improving effect is exhibited. Furthermore, it was revealed that the multi-phase thermoplastic resin of the present invention has an extremely good dispersibility in a thermoplastic polyester or polyamide resin, and that the appearance of a molded product does not show a delamination phenomenon.

[0081]

According to the present invention, the thermoplastic resin having a multiphase structure as a slidability improver can be used without significantly impairing the mechanical and physical properties of the thermoplastic polyester resin or polyamide resin.
The slidability can be greatly improved, and the slidability can be improved only by mixing under melting. Furthermore, since the degree of the sliding characteristics is determined by the mixing ratio of the multi-phase structure thermoplastic resin to be compounded, it is possible to easily produce many kinds and small quantities. In view of the above, the slidability improving agent and the slidability improving method of the present invention can be used in a wide range of applications such as automobile parts, home electric parts, precision machine parts, and the like.

[Table 13]

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-1-92270 (JP, A) JP-A-1-113456 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 67/00-67/04 C08L 77/00-77/12

Claims (4)

(57) [Claims] 1. A dispersion comprising: 5 to 95% by weight of polyethylene having a density of 0.900 g / cm ³ or more, and 95 to 5% by weight of a vinyl (co) polymer comprising at least one vinyl monomer. A slidability improving agent for a thermoplastic polyester resin or a polyamide resin containing a multiphase thermoplastic resin having a resin particle size of 0.001 to 10 μm as a main component. 2. A dispersion comprising 5 to 95% by weight of polyethylene having a density of 0.900 g / cm ³ or more and 95 to 5% by weight of a vinyl (co) polymer comprising at least one vinyl monomer. A slidability improving agent for a thermoplastic polyester resin or a polyamide resin containing a multiphase thermoplastic resin having a resin particle size of 0.001 to 10 μm and a lubricant as main components. 3. A thermoplastic polyester resin or polyamide resin having a density of 0.900 g /
vinyl-based (co) polymer 9 comprising 5 to 95% by weight of polyethylene of at least ³ cm ³ and at least one vinyl monomer
5 to 5% by weight, and the particle size of the dispersed resin is 0.00
A method for improving the slidability of a thermoplastic polyester resin or a polyamide resin, comprising blending a multiphase thermoplastic resin having a thickness of 1 to 10 μm. 4. A thermoplastic polyester resin or polyamide resin having a density of 0.900 g /
vinyl-based (co) polymer 9 comprising 5 to 95% by weight of polyethylene of at least ³ cm ³ and at least one vinyl monomer
5 to 5% by weight, and the particle size of the dispersed resin is 0.00
A method for improving slidability of a thermoplastic polyester resin or a polyamide resin, which comprises mixing a thermoplastic resin having a multiphase structure of 1 to 10 μm and a lubricant.