JP2851890B2 - Sliding material comprising cyclic olefin resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a sliding material comprising a cyclic olefin resin composition containing a cyclic olefin resin, an ethylene polymer and a slidable filler, and more particularly to a sliding material. The present invention relates to a sliding material comprising a cyclic olefin resin composition suitable for obtaining an injection-moldable sliding material having good dynamic characteristics and excellent heat resistance and dimensional stability.

Technical Background of the Invention As a sliding material, conventionally, a fluororesin such as polytetrafluoroethylene, a polyacetal resin, a polyimide resin, and the like have been used. However, there is a restriction on the molding method for fluororesin, and polyacetal resin can be injection-molded, but the width of molding conditions is narrow, and fluorocarbon and polyacetal resins have poor dimensional accuracy.
Further, there has been a problem that fluororesins and polyimide resins are expensive and inferior in economy.

Ultra-high molecular weight polyolefins, for example, ultra-high molecular weight polyethylene, are superior to general-purpose polyolefins, for example, general-purpose polyethylene, in impact resistance, abrasion resistance, slidability, chemical resistance, tensile strength, and the like. It can be used as a moving material. However, ultra-high molecular weight polyethylene has a very high melt viscosity and poor fluidity compared to general-purpose polyethylene, so it is very difficult to mold it by ordinary extrusion or injection molding, and most of it is formed by compression molding. At present, only a small part is extruded in a rod shape at an extremely low speed.

If such ultra-high-molecular-weight polyethylene having inferior melt fluidity is molded by a usual injection molding method, a shear fracture flow occurs in the process of filling the resin into the mold cavity,
The resulting molded article delaminates in a mica-like manner, and not only does not give a molded article having the excellent properties of ultra-high molecular weight polyethylene, but also results in an inferior general-purpose polyethylene molded article. Was. Further, heat resistance, dimensional accuracy, etc. may be insufficient depending on the application.

On the other hand, cyclic olefins have an ethylenic double bond in the ring. Conventionally, such a cyclic olefin is reacted with an α-olefin such as ethylene to form a cyclic olefin / ethylene random copolymer. It was often used as such. This random copolymer has excellent properties such as transparency, heat resistance, chemical resistance, electrical properties, mechanical strength, moldability, etc., and molded articles made from this copolymer have excellent dimensional stability. It also has

The cyclic olefin as described above has α as described above.
-It is already known that a polymer excellent in transparency, water resistance and thermal properties can be obtained by opening a cyclic olefin itself in addition to being used as a copolymer with an olefin (Japanese Patent Application See the specification of Sho 60-26024).

Such a cyclic olefin resin has excellent transparency,
Although it has water resistance and thermal properties, as a result of further studies by the present inventors, by blending such a cyclic olefin resin with a slidable filler, good sliding properties are obtained. It has also been found that a cyclic olefin-based resin composition suitable for obtaining an injection-moldable sliding material excellent in heat resistance and dimensional accuracy can be obtained.

An object of the present invention is to provide a sliding material comprising a cyclic olefin resin composition suitable for obtaining an injection-moldable sliding material having good sliding characteristics and excellent heat resistance and dimensional accuracy. It is an object.

SUMMARY OF THE INVENTION The cyclic olefin resin composition forming the sliding material according to the present invention comprises: [A] a cyclic olefin resin: 100 parts by weight, and [B] a glass transition temperature (Tg) within a range of 0 ° C or less. It is characterized by containing a certain ethylene copolymer: 5 to 150 parts by weight and [C] a slidable filler: 1 to 70 parts by weight.

Since the cyclic olefin-based resin composition forming the sliding material according to the present invention contains a specific amount of the cyclic olefin-based resin, the ethylene-based polymer and the slidable filler, the sliding properties are good and the heat resistance is high. It is suitable for obtaining an injection-moldable sliding material having excellent properties and dimensional accuracy.

Next, the cyclic olefin resin composition according to the present invention will be described in detail.

[A] Cyclic olefin-based resin The cyclic olefin-based resin [A] blended in the cyclic olefin-based resin composition according to the present invention is obtained by (a) ring-opening polymerization of a cyclic olefin represented by the following formula [I]. And / or (b) a cyclic olefin-based random copolymer which is a copolymer of ethylene and a cyclic olefin represented by the following formula [I]: It is a cyclic olefin-based resin that is appropriately blended with a copolymer.

(In the formula, n is 0 or 1, m is 0 or a positive integer, and R ^{1 to} R ¹⁸ are each independently an atom selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group. R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond; R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group.) However, in the above formula [I], n is 0 or 1, and m is 0 or positive It is an integer, preferably 0 to 3.

R ^{1 to} R ¹⁸ each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group. Here, as the halogen atom,
For example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom can be mentioned. Examples of the hydrocarbon group include, independently of each other, usually an alkyl group having 1 to 10 carbon atoms, and a cycloalkyl group having 5 to 15 carbon atoms. Specific examples of the alkyl group include: Methyl group, ethyl group, isopropyl group, isobutyl group, n-amyl group, neopentyl group, n-hexyl group, n-octyl group, n-decyl group, 2-ethylhexyl group and the like. As a specific example,
Examples include a cyclohexyl group, a methylcyclohexyl group, and an ethylcyclohexyl group.

Further, in the above formula [I], R ^{15 to} R ¹⁸ may be bonded to each other (together) to form a monocyclic or polycyclic ring, and this ring may have a crosslinked structure. Further, this monocyclic or polycyclic ring may have a double bond. Moreover, the structure which combined these rings may be sufficient.

That is, the above R ^{15 to} R ¹⁸ may be bonded to each other (jointly) to form, for example, a monocyclic or polycyclic ring as shown below.

In the above formula, the carbon atoms with 1 and 2 represent the carbon atoms of the alicyclic structure to which the groups represented by R ^{15 to} R ¹⁸ are bonded in the formula [I].

In such a structure, that is, in the formula [I], R ¹⁵
Structure to R ¹⁸ are bonded to form a monocyclic or polycyclic one another, the More specifically represented, can be represented by the structural formula shown for example the following formula [I ']. Although the following formula [I '] shows only the case where m = 0 and n = 0 in the above formula [I], in the present invention, m = 0 and n
It is not limited only to the case of = 0. Needless to say, the compound represented by the following formula [I '] is included in the category of the compound represented by the above formula [I].

(In the formula [I '], p is 0 or an integer of 1 or more;
And r are 0, 1 or 2, and R ^{1 to} R ¹⁵ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group,
Represents an atom or group from the group consisting of an aromatic hydrocarbon group and an alkoxy group, wherein R ⁵ (or R ⁶ ) and R ⁹ (or
R ⁷ ) may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be directly bonded without any group. In addition, in the above formula [I], R ¹⁵ and R ¹⁶ or
R ¹⁷ and R ¹⁸ may form an alkylidene group. Such an alkylidene group can be usually an alkylidene group having 3 to 10 carbon atoms, and specific examples thereof include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, and an isobutylidene group. be able to.

The cyclic olefin represented by the formula [I] can be easily produced by condensing a cyclopentadiene and a corresponding olefin or a cyclic olefin by a Diels-Alder reaction.

Specific examples of the cyclic olefin represented by the formula [I] include, for example, Bicyclo [2,2,1] hept-2-ene derivatives such as; Tetracyclo such [4,4,0,1 ^2.5, 1 ^7.10] -3-dodecene derivatives; Hexacyclo such as [6,6,1,1 ^3.6, 1 ^10.13, 0 ^2.7 0 ^9.14]
-4-heptadecene derivatives; Octacyclo [8,8,0,1 ^2.9 , 1 ^4.7 , 1 ^11.18 , 1 ^13.16 ,
0 ^3.8 , 0 ^12.17 ] -5-docosene derivative; Pentacyclo such as [6,6,1,1 ^3.6, 0 ^2.7 0 ^9.14] -4
Hexadecene derivatives; A heptacyclo-5-icosene derivative or a heptacyclo-5-heneicosene derivative; Tricyclo [4,3,0,1 ^2.5] -3-decene derivatives such as; Tricyclo [4,4,0,1 ^2.5] -3-undecene derivatives such as; Pentacyclo such as [6,5,1,1 ^3.6, 0 ^2.7 0 ^9.13] -4
Pentadecene derivatives; Diene compounds such as; Pentacyclo such [4,7,0,1 ^2.5, 0 ^8.13, 1 ^9.12] -3
Pentadecene derivatives; Heptacyclo such as [7,8,0,1 ^3.6, 0 ^2.7, 1 ^10.17, 0 ^11.16,
1 ^12.15 ] -4-Eicosene derivative; Nonacyclo [9,10,1,1 ^4.7 , 0 ^3.8 , 0 ^2.10 , 0 ^12.21 , 1
^13.20, 0 ^14.19, may be mentioned 1 ^15.18] -5-pentacosene derivatives.

And furthermore, Can be mentioned.

Examples of the polycyclic olefin represented by the above formula [I] include, in addition to the above compounds, 1,4,5,8-dimethano-
1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a- Octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-
1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-propyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a- Octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3
-Dimethyl 1,4,5,8-dimetano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-methyl-3-ethyl-1,4,
5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-chloro-1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2-bromo-1,4,5,
8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2,3-dichloro-1,
4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-cyclohexyl-1,4,5,8-dimethano-
1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-n
-Butyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-isobutyl-1,4,5,8-dimethano-1,2 And octahydronaphthalenes such as 3,4,4a, 5,8,8a-octahydronaphthalene.

Next, [A] constituting the cyclic olefin resin blended in the cyclic olefin resin composition according to the present invention, (a) a cyclic olefin ring-opening polymer, a ring-opening copolymer and a hydrogenated product thereof, and (B) The cyclic olefin-based random copolymer will be described in detail below.

(A) Cyclic olein ring-opening polymer, ring-opening copolymer and hydrogenated product thereof The cyclic olefin ring-opening polymer and ring-opening copolymer used in the present invention are represented by the above-mentioned formula [I]. An olefin is subjected to ring-opening polymerization in the presence of a catalyst comprising a metal halide such as ruthenium, rhodium, palladium, osmium, indium or platinum, a nitrate or an acetylacetone compound, and a reducing agent such as an alcohol. can get. These may be homopolymers or copolymers of cyclic olefins. For example, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a
Those obtained by polymerizing octahydronaphthalenes with each other, and those obtained by copolymerizing the above naphthalenes with norbornene (for example, bicyclo [2,2,1] hept-2-ene).

Such a cyclic olefin ring-opening polymer and a ring-opening copolymer can easily hydrogenate the remaining double bond by a known method in the presence of a hydrogenation catalyst. Provide molding materials with excellent heat stability and weather resistance.

As the hydrogenation catalyst used in this case, a heterogeneous catalyst or a homogeneous catalyst generally used for hydrogenating olefins can be used.

Examples of such a heterogeneous catalyst include nickel, palladium, platinum or a catalyst in which these metals are supported on a carrier such as carbon, silica diatomaceous earth, alumina, and titanium oxide. Specific examples include , Nickel / silica, nickel / diatomaceous earth, palladium / carbon, palladium / silica, palladium / diatomaceous earth, and palladium / alumina.

Examples of the homogeneous catalyst include a catalyst based on a metal belonging to Group VIII of the periodic system. Specific examples include nickel / triethylamine naphthenate, n-butyllithium naphthenate, and nickel acetylacetonate. / A catalyst comprising a Ni or Co compound such as triethylaluminum and an organometallic compound of a Group I-III metal, and a Rh compound.

The hydrogenation reaction can be performed in a homogeneous or heterogeneous system depending on the type of catalyst.

The pressure of the hydrogen gas at the time of such hydrogenation is usually set at 1 to 150 atm, and the reaction temperature is usually set at 0 to 100 ° C, preferably at 20 to 100 ° C.

The hydrogenation rate can be arbitrarily adjusted by changing the hydrogen pressure, the reaction temperature, the reaction time, the catalyst concentration, and the like. However, as the hydrogenated product used in the present invention, from the viewpoint of heat aging resistance and light resistance. More preferably, at least 50% of the double bonds present in the polymer or copolymer are hydrogenated, particularly preferably at least 80%, more preferably at least 90%.

Further, in the present invention, when producing the above-mentioned ring-opening polymer, ring-opening polymer or hydrogenated product, the above-mentioned formula [I] may be used as long as the properties of the obtained polymer and the like are not impaired. Cyclic olefins other than the cyclic olefins represented can also be polymerized. Examples of such a cyclic olefin include cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclohexene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, 2,3,3a, 7a-tetrahydro- 4,7-methano-1H-indene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene and the like can be mentioned. Such other cyclic olefins can be used alone or in combination, and are usually used in an amount of 0 to 20 mol%.

By performing ring-opening polymerization or ring-opening copolymerization as described above, for example, the cyclic olefin represented by the above formula [I] is ring-opened and at least a part thereof is represented by the following formula [II]. It is considered that the structure has the following structure.

However, in the above formula [II], m, n and R ^{1 to} R
¹⁸ has the same meaning as in the above formula [I].

A hydrogenated product produced by hydrogenating a double bond is considered to have a structure represented by, for example, the following formula [m].

However, in the above formula [III], m, n and R ^{1 to} R
¹⁸ has the same meaning as in the above formula [I].

In the present invention, the ring-opening polymer and the ring-opening copolymer and the hydrogenated product can be used individually or in combination.

(B) Cyclic olefin random copolymer The cyclic olefin random copolymer (b) used in the present invention comprises a structural unit derived from ethylene and a structural unit derived from the cyclic olefin as essential structural units. However, in addition to these two essential constitutional units, other copolymerizable unsaturated monomer components may be contained as necessary within a range not to impair the object of the present invention.
Specific examples of the unsaturated monomer units which may be added as necessary and which may be copolymerized include propylene, 1-butene,
4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,
-Hexadecene, 1-octadecene, 1-eicosene and the like. Among them, α having 3 to 20 carbon atoms
-Olefins are preferred. Further, cyclic olefins such as norbornene, ethylidene norbornene, and dicyclopentadiene, and cyclic dienes can also be used. These unsaturated monomer components may be contained in an amount less than equimolar to a structural unit derived from ethylene in the produced random copolymer.

In the cyclic olefin-based random copolymer (b) used in the present invention, the constitutional unit derived from ethylene is contained in the range of 40 to 85 mol%, preferably 50 to 75 mol%. . The structural unit derived from the cyclic olefin is 15 to 60 mol%, preferably 25 to 50 mol%.
Desirably, it is contained in the range of mol%. In the present invention, the structural units derived from ethylene and the structural units derived from the cyclic olefin are randomly arranged, and a substantially linear cyclic olefin-based random copolymer is formed. The fact that the cyclic olefin-based random copolymer is substantially linear and does not have a gel-like crosslinked structure can be confirmed by completely dissolving the copolymer in decalin at 135 ° C.

The intrinsic viscosity [η] of the cyclic olefin random copolymer (b) used in the present invention measured in decalin at 135 ° C. is in the range of 0.01 to 10 dl / g, preferably 0.05 to 5 dl / g.

The cyclic olefin random copolymer (b) used in the present invention has a softening temperature (TMA) of at least 70 ° C., preferably 90 to 250 ° C., more preferably 100 to 100 ° C., as measured by a thermomechanical analyzer. It is desirable to be in the range of 200 ° C.

The glass transition temperature (Tg) of the cyclic olefin random copolymer (b) used in the present invention is usually 50 to 50%.
It is desirable to be in the range of 230 ° C, preferably 70 to 210 ° C.

The crystallinity of the cyclic olefin random copolymer (b) used in the present invention determined by X-ray diffraction analysis is 0 to 10%, preferably 0 to 7%, and particularly preferably 0 to 5%. Is desirable.

As the cyclic olefin-based random copolymer (b) constituting the resin composition according to the present invention, only a copolymer having the physical properties in the above range may be used, but some of the copolymers outside the above range may be used. It may be contained, and in this case, the physical property value of the entirety of the cyclic olefin-based random copolymer (b) may be within the above range.

Such a cyclic olefin random copolymer (b)
Is ethylene, a cyclic olefin, and optionally another α
-With an olefin in a hydrocarbon solvent in the presence of a catalyst formed from a hydrocarbon-soluble vanadium compound and a halogen-containing organoaluminum compound.

As the hydrocarbon solvent used here, for example, an aliphatic hydrocarbon, an alicyclic hydrocarbon, an aromatic hydrocarbon, or the like can be used. Further, among the monomers used in the preparation of the cyclic olefin-based resin, a compound which is liquid at the reaction temperature can be used as a reaction solvent. These solvents can be used alone or in combination.

As the vanadium compound used as a catalyst in this reaction, a compound represented by the formula VO (OR) _a V _b or the formula V (OR) _c X _d can be mentioned.

In the above formula, R is a hydrocarbon group, and 0 ≦ a ≦
3, 0 ≦ b ≦ 3, 2 ≦ a + b ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d
≦ 4, 3 ≦ c + d ≦ 4.

As these vanadium compounds, specifically, VOCl ₃ , VO (OC ₂ H ₅ ) Cl ₂ , VO (OC ₂ H ₅ ) ₂ Cl, VO (O-iso-C ₃ H ₇ ) Cl ₂ , VO (On-C ₄ H ₉ ) Cl ₂ , VO (OC ₂ H ₅ ) ₃ , VOBr ₂ , VCl ₄ , VOCl ₂ , VO (On-C ₄ H ₉ ) ₃ , VCl ₃ .2OC ₈ H ₁₇ OH is used. These vanadium compounds can be used alone or in combination.

Such a vanadium compound may be an adduct of the vanadium compound represented by the above formula and an electron donor.

Examples of electron donors that form adducts with the above-mentioned vanadium compounds include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, and alkoxy. Examples include oxygen-containing electron donors such as silane, and nitrogen-containing electron donors such as ammonia, amine, nitrile, and isocyanate.

As the organoaluminum compound used as a catalyst together with the above-mentioned vanadium compound, a compound having at least one A1-carbon bond in a molecule can be used.

Examples of organoaluminum compounds that can be used in the present invention, wherein _{^{R 19 e Al (OR 20)}} f H g X h ( wherein R ¹⁹ and R ^20, 1-15, preferably 1-4 X is a halogen, e is 0 ≦ e ≦ 3, f is 0 ≦
f <3, g is 0 ≦ g <3, h is 0 ≦ h <3, and e + f + g + h = 3. An organoaluminum compound represented by the formula: M ¹ AlR ²¹ ₄ (wherein M ¹ is Li, Na, K, and R ²¹ is a hydrocarbon group containing 1 to 15, preferably 1 to 4 carbon atoms) May be the same or different from each other.), And a complex alkylated product of a Group I metal and aluminum.

The concentration of the above-mentioned vanadium compound in the reaction system is usually 0.
It is used in an amount of from 01 to 5 gram atoms / liter, preferably from 0.05 to 3 gram atoms / liter. The organoaluminum compound is used in such an amount that the ratio of aluminum atoms to vanadium atoms (Al / V) in the polymerization reaction system is 2 or more, preferably 2 to 50, and particularly preferably 3 to 20.

The cyclic olefin random copolymer (b) constituting the resin composition according to the present invention is described in, for example, JP-A-60-1687.
No. 08, JP-A-61-120816, JP-A-61-115912
JP-A-61-115916, JP-A-61-271308, JP-A-61-272216, JP-A-62-252406, and JP-A-62-252407. By appropriately selecting conditions according to the method proposed by the applicant,
Can be manufactured.

Such a cyclic olefin random copolymer (b)
In the formula, the structural unit derived from the cyclic olefin represented by the formula [I] is considered to form a repeating unit having a structure represented by the following formula [IV].

(In the formula, n, m and R ^{1 to} R ¹⁸ are the same as defined in the above formula [I].) In the present invention, the above-mentioned cyclic olefin ring-opening polymer, ring-opening copolymer or A part of the hydrogenated product (a) or the cyclic olefin random copolymer (b) (the above (a) and (b) are abbreviated as a cyclic olefin resin [A]) is partially maleic anhydride May be modified with an unsaturated carboxylic acid or the like. Such a modified product is obtained by using the cyclic olefin resin [A] as described above.
And an unsaturated carboxylic acid, an anhydride thereof, and a derivative such as an alkyl ester of an unsaturated carboxylic acid. In this case, the content of the component unit derived from the modifier in the modified cyclic olefin resin [A] is usually 0.001 to 0.001.
5% by weight. Such a modified cyclic olefin-based resin can be produced by blending a modifier with the cyclic olefin-based resin [A] so as to obtain a desired modification rate and graft-polymerizing the same, or a modified product having a high modification rate in advance. And then mixing the modified product with an unmodified cyclic olefin-based resin [A].

[B] Ethylene Polymer Next, the ethylene polymer [B] used in the cyclic olefin resin composition according to the present invention will be described.

In the present invention, as the ethylene copolymer, a resin having a glass transition temperature (Tg) of 0 ° C. or less as measured by a thermomechanical analyzer is used.

Further, 135 of the ethylene polymer used in the present invention.
The intrinsic viscosity [η] measured in decalin at 0 ° C. is usually
It is in the range of 01 to 10 dl / g, preferably 0.08 to 7 dl / g.

As such an ethylene-based polymer, the following polymers (c) to (g) are preferably used.

The polyethylene (c) used in the present invention may be a low-density or high-density polyethylene in which a homopolymer of ethylene or an α-olefin is copolymerized in a small amount, or a part or all of these polymers may be graft-modified with a radical polymerizable monomer. Can be exemplified.
The intrinsic viscosity of such a polyethylene (c) measured in decalin at 135 ° C. is usually 0.01 to 10 dl / min, preferably 0.08 dl / min.
Dl7 dl / g and the glass transition temperature is in the range of 0 ° C. or less. Here, examples of the radical polymerizable monomer include carboxylic acids such as maleic anhydride, acrylic acid, ethyl acrylate, hydroxyethyl acrylate, glycidyl acrylate, ethyl methacrylate, and glycidyl methacrylate, and derivatives thereof, vinyl acetate, and benzoic acid. Examples thereof include vinyl esters such as vinyl, styrene, and vinylsilanes.

In the present invention, the cyclic olefin random copolymer (d) that can be used as an ethylene-based polymer includes a structural unit derived from ethylene, a structural unit derived from an α-olefin other than ethylene, and the above-mentioned formula [I] A cyclic olefin random copolymer comprising a structural unit derived from a cyclic olefin represented by the formula, and the intrinsic viscosity measured in decalin at 135 ° C is usually 0.01 to 10 dl / g, preferably 0.08 to 7 dl / g. And the glass transition temperature is usually 0
It is a cyclic olefin random copolymer at a temperature of not more than ℃.
Here, α-olefins other than ethylene include α-olefins having 3 to 20 carbon atoms, and specific examples of such α-olefins include propylene, 1-butene and 4-olefin. Methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1
-Tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene.

In such a cyclic olefin random copolymer (d), the amount of the structural unit derived from ethylene is usually
40 to less than 100 mol%, preferably 50 to 98 mol%,
The amount of structural units derived from α-olefins other than ethylene is usually from 0 to 50 mol%, preferably from 1 to 40 mol%, and the amount of structural units derived from cyclic olefins is usually from 0 to 20 mol%. %, Preferably in the range of 1 to 15 mol%.

The cyclic olefin used in the present invention may be used alone or in combination. For example,
1,4,5,8-Dimethano-1,2,3,4,4a, 5,8,8a-Polymerized octahydronaphthalenes, and the above-mentioned naphthalenes and norbornene (for example, bicyclo [2, 2,1] hept-2-ene).

Such a cyclic olefin random copolymer (d)
Are disclosed in, for example, JP-A-60-168708, JP-A-61-120816,
-115912, 61-225916, 61-271308, 61-
It can be produced using the methods described in publications such as 272216 and 62-252406.

In the present invention, the ethylene / α-olefin copolymer (e) used as the ethylene-based polymer [B] is a copolymer formed from ethylene and at least one type of α-olefin. The glass transition temperature of the copolymer is in the range of 0 ° C. or less.

As the α-olefin constituting the ethylene / α-olefin copolymer, an α-olefin having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms is usually used. Such α
-Specific examples of the olefin include propylene, 1-
Butene, 1-hexene, 4-methyl-1-pentene, 1
-Octene and 1-decene, which can be used alone or in combination. The content of ethylene in such an ethylene / α-olefin copolymer varies depending on the type of α-olefin, but is generally in the range of 50 to less than 100 mol%.

In the present invention, the ethylene / α-olefin / diene copolymer (f) used as the ethylene-based polymer [B] includes ethylene, at least one α-olefin, and at least one non-conjugated diene. The glass transition temperature formed from
It is an olefin / diene copolymer.

Here, the α-olefin constituting the ethylene / α-olefin / diene copolymer usually has 3 carbon atoms.
-20, preferably 3-10 alpha-olefins are used. Specific examples of such α-olefins include:
Propylene, 1-butene, 1-hexene, 4-methyl-
Examples thereof include 1-pentene, 1-octene and 1-decene, which can be used alone or in combination. In such an ethylene / α-olefin / diene copolymer, the ethylene content is α
-Although it depends on the type of olefin, generally 50 to
It is in the range of less than 100 mol%.

Specific examples of the diene component in the copolymer as described above include 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, and 6-methyl-1,5-heptadiene. , Chain-conjugated dienes such as 7-methyl-1,6-octadiene; cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-
Cyclic non-conjugated dienes such as ethylidene-2-norbornene, 5-methylene-2-norbononene, 5-isopropylidene-2-norbornene; 2,3-diisopropylidene-5-norbornene, 2-
Propenyl-2,5-norbornadiene and the like can be mentioned. Such diene components can be used alone or in combination.

The content of the repeating unit derived from the diene component in the copolymer is usually 1 to 20 mol%,
Preferably it is 2 to 15 mol%.

In the present invention, (g) the copolymer of ethylene and the polar monomer used as the ethylene copolymer [B] is 0%.
It has a glass transition temperature of below ℃. Specific examples of the polar monomer of the copolymer as described above include vinyl acetate, methyl acrylate, ethyl acrylate, butyl acrylate, acrylates such as glycidyl acrylate,
Examples thereof include methacrylates such as methyl methacrylate, ethyl methacrylate, and glycidyl methacrylate. Such polar monomers can be used alone or in combination.

The ethylene polymers as described above can be used alone or in combination.

In the cyclic olefin resin composition of the present invention, the ethylene polymer [B] as described above is used in an amount of 5 to 150 parts by weight based on 100 parts by weight of the cyclic olefin resin [A]. Used in quantity. By using the ethylene-based polymer [B] within the above range, impact strength,
The sliding characteristics are improved. By adjusting the amount of the ethylene-based polymer [B] to the cyclic olefin-based resin [A] in the range of preferably 5 to 100 parts by weight, more preferably 10 to 80 parts by weight, impact strength, rigidity, A resin composition having particularly excellent properties such as heat deformation temperature and hardness can be obtained.

[C] Sliding filler [C] Sliding filler used in the cyclic olefin resin composition according to the present invention will be described below.

As the slidable filler [C], those conventionally known as slidable fillers are used without particular limitation.
Specifically, the following compounds are used.

Graphite powder, polytetrafluoroethylene resin (PTFE), ethylene tetrafluoride-hexafluoropropylene copolymer resin (FEP), ethylene tetrafluoride-perfluoroalkoxyethylene copolymer resin (PFA), trifluorochloride Fluororesin powders such as ethylene resin (PCTFE), ethylene tetrafluoride-ethylene copolymer resin (ETFE), and vinylidene fluoride resin, molybdenum fluoride powder, molybdenum sulfide powder, titanium oxide powder, and boron nitride powder.

These slidable fillers [C] are preferably used in the form of a powder, and the average particle size thereof is desirably 0.1 to 50 μm, preferably 0.2 to 20 μm.

In the cyclic olefin resin composition according to the present invention, the above-mentioned sliding filler [C] is used in an amount of 1 to 70 parts by weight, preferably 3 parts by weight, per 100 parts by weight of the cyclic olefin resin [A].
To 50 parts by weight, more preferably 5 to 30 parts by weight.

Other additives The cyclic olefin-based resin composition of the present invention contains the cyclic olefin-based resin [A], the ethylene-based polymer [B], and the slidable filler [C] as described above.
Add rubber component to improve impact strength, heat stabilizer, weather stabilizer, antistatic agent, slip agent, antiblocking agent, antifogging agent, lubricant, dye, pigment, natural oil, synthetic oil, wax And the like can be blended, and the blending ratio is an appropriate amount. For example, as a stabilizer to be blended as an optional component, specifically, tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, β- (3,5-di- t-butyl-4-hydroxyphenyl) propionic acid alkyl ester, 2,2'-oxamidobis [ethyl-3 (3,5-
Phenolic antioxidants such as di-t-butyl-4-hydroxyphenyl)] propionate; fatty acid metal salts such as zinc stearate, calcium stearate and calcium 12-hydroxystearate; glycerin monostearate; glycerin monolaurate; glycerin Examples include fatty acid esters of polyhydric alcohols such as distearate, pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate. These may be blended alone or in combination. For example, tetrakis [methylene-3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane and zinc stearate may be used. Examples thereof include a combination with glycerin monostearate.

In the present invention, it is particularly preferable to use a combination of a phenolic antioxidant and a fatty acid ester of a polyhydric alcohol.
It is preferable that the polyhydric alcohol is a polyhydric alcohol fatty acid ester in which a part of the alcoholic hydroxyl group of the polyhydric alcohol having a valency or higher is esterified.

As the fatty acid ester of such a polyhydric alcohol, specifically, glycerin monostearate, glycerin monolaurate, glycerin monomyristate, glycerin monopalmitate, glycerin distearate, glycerin fatty acid esters such as glycerin dilaurate, Pentaerythritol monostearate, pentaerythritol monolaurate, pentaerythritol dilaurate, pentaerythritol distearate,
Fatty acid esters of pentaerythritol such as pentaerythritol tristearate are used.

Such a phenolic antioxidant is used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 3 parts by weight, more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the cyclic olefin resin composition. The fatty acid ester of the polyhydric alcohol is used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the composition.

In the cyclic olefin resin composition of the present invention, silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, as long as the object of the present invention is not impaired. Basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flake, glass beads, calcium silicate, montmorillonite, bentonite, aluminum powder, molybdenum sulfide And fillers such as boron fiber, silicon carbide fiber, polyethylene fiber, polypropylene fiber, polyester fiber, and polyamide fiber.

As the method for producing the cyclic olefin resin composition according to the present invention, known methods can be applied. The cyclic olefin resin component [A], the ethylene polymer [B], and the slidable filler [C], A method of mechanically blending other components to be added with an extruder or a kneader or a suitable good solvent for each component, for example, a hydrocarbon solvent such as hexane, heptane, decane, cyclohexane, benzene, toluene, and xylene. Examples of the method for dissolving the solvent at the same time or separately dissolving and then mixing and then removing the solvent further include a method of combining these two methods.

The cyclic olefin-based resin composition of the present invention thus obtained has excellent sliding properties in addition to excellent properties such as heat resistance, rigidity, and dimensional accuracy inherent to the cyclic olefin-based resin. It is suitably used for producing materials.

Examples of applications of the cyclic olefin resin composition of the present invention include home appliances, gears for OA equipment, bearings, rollers, tape reels, keyboard substrates, automobile door mirror gears, inner handles, ventilators, wiper gears, door locks, Examples include a window regulator, a switch, and a relay component.

The cyclic olefin-based resin composition of the present invention can be molded using a known method.

For example, extrusion molding using a single-screw extruder, vented extruder, twin-screw extruder, co-kneader, plasticizer, mixtruder, gear-type extruder, screwless extruder, planetary screw extruder, or injection molding , Blow molding, rotational molding, foam molding and the like.

Effect of the Invention Since the cyclic olefin resin composition of the present invention is composed of a cyclic olefin resin formed from a specific cyclic olefin, an ethylene polymer and a slidable filler, heat resistance, rigidity, It has the excellent properties of cyclic olefin resin such as dimensional accuracy, also has excellent impact resistance and slidability, and it can injection-mold molded products without occurrence of delamination. Particularly preferably used.

[Examples] Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited to these Examples.

The methods for measuring and evaluating various physical properties in the present invention are described below.

(1) Melt flow index (MFR _T ) Measured at a predetermined temperature T ° C. and a load of 2.16 kg according to ASTM D1238.

(2) Preparation of Test Specimen Using an injection molding machine IS-55EPN manufactured by Toshiba Machine _{Co., Ltd.} and a predetermined test specimen mold, molding was performed under the following molding conditions. The test pieces were left for 48 hours at room temperature after molding and then measured.

Molding conditions: cylinder temperature 280 ° C, mold temperature 80 ° C, injection pressure primary / secondary = 1000/800 kg / cm ² injection speed (primary) 50% (3) Bending test The bending test was performed according to ASTM D790.

Specimen shape: 5 x 1/2 x 1/8 ^t inch, distance between spans 51 mm Test speed: 20 mm / min Test temperature: 23 ° C (4) Heat deformation temperature (HDT) This was performed according to ASTM D628.

Specimen shape: 5 × 1/4 × 1/2 ^t inch Load: 264 psi (5) Softening temperature (TMA) Measured by thermal deformation behavior of a 1 mm thick sheet using a Thermo Mechanical Analyzer manufactured by DuPont. That is, put a quartz needle on the sheet, apply a load of 49 g, and apply 5 ° C /
The temperature rises at the speed of min, and the temperature at which the needle enters
TMA.

(6) Glass transition temperature (Tg) Temperature rise rate 10 ° C. using DSC-20 manufactured by SEIKO Electronic Industries, _Ltd.
/ min.

(7) Izod impact strength (kg · cm / cm) A notched test piece was used according to ASTM D256.

(8) Dynamic friction coefficient Using a Matsubara friction and wear tester (manufactured by Toyo Baldwin), under the conditions of a compressive load of 7.5 kg / cm ² and a sliding speed of 12 m / min3
It was performed for 0 minutes, and the friction coefficient was determined. The mating material was SUS 304, and the sliding surface roughness was processed to 6 s.

Test piece: Injection molded square plate (130 mm × 120 mm × 3 mm) was used.

(9) Limit PV value (kg / cm ² · m / min) Using a Matsubara type friction and wear tester (manufactured by Toyo Baldwin), slip speed 12 m / min, compressive load from 2.5 kg / cm ² to 2.5
kg / cm ² step by step to 25 kg / cm ²
The PV value (load x speed) at which the resin melted by frictional heat for 30 minutes was determined. The mating material was SUS 304, and the sliding surface roughness was processed to 6 s.

Test piece: Injection molded square plate (130 mm × 120 mm × 3 mm) was used.

(10) Mold Shrinkage (%) Using an injection-molded square plate (130 mm × 120 mm × 3 mm), the vertical and horizontal dimensions were measured, and the mold shrinkage based on the mold dimensions was measured.

Example 1 As the [A] component, the ethylene content measured by ¹³ C-NMR was 62 mol%, the MFR _{260 ° C.} was 35 g / 10 min, the intrinsic viscosity [η] measured in decalin at 135 ° C. was 0.47 dl / g, and the softening temperature. (TMA)
Is 148 ° C, Tg is 137 ° C, ethylene and tetracyclo [4.4.
0.1 ^2,5 .1 ^7,10 ] -3-dodecene 4 kg of pellets of a random copolymer (ethylene / TCD-3 random copolymer) with
Propylene random copolymer (ethylene content: 80mol
%, Tg: −54 ° C., MFR _{230 ° C .} : 0.7 g / 10 min, intrinsic viscosity [η]: 2.2 dl / g, 1 kg of pellets, and fluorine resin TLP- manufactured by DuPont-Mitsui Fluorochemicals _{Co., Ltd.} 1
After sufficiently mixing 10.25kg of 0F, twin-screw extruder (Ikegai
_It was melt-blended at a cylinder temperature of 220 ° C. using PCM45 manufactured by K.K. and pelletized with a pelletizer.

A test piece was prepared from the obtained pellets by the method described above, and the physical properties were evaluated.

 Table 1 shows the results.

Examples 2 to 5 The same operation as in Example 1 was performed except that the component [B] was changed.

 Table 1 shows the results.

Examples 6 to 8 The same operation as in Example 1 was performed except that the component [C] was changed.

 Table 2 shows the results.

Comparative Example 1 Physical properties were measured in the same manner as in Example 1 using only the component [A] used in Example 1.

As a result, bending strength 32800 kg / cm ² , bending strength 800 kg / c
m ² , Izod impact strength 1 kg · cm / cm, HDT 125 ° C, dynamic friction coefficient 0.6, limit PV value 100 kg / cm ² · m / min, molding shrinkage (vertical / horizontal) 0.6 / 0.6%.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 45/00 C08L 45/00 65/00 65/00 // (C08L 23/04 27:12) (C08L 65/00 23:04 27: 12)

Claims (4)

(57) [Claims] (A) a cyclic olefin resin: 100 parts by weight; [B] an ethylene polymer having a glass transition temperature (Tg) in the range of 0 ° C. or less: 5 to 150 parts by weight; A sliding material comprising a cyclic olefin-based resin composition, comprising: a sliding filler: 1 to 70 parts by weight. 2. The cyclic olefin resin [A] is: (a) a cyclic olefin ring-opening polymer, a ring-opening copolymer or a ring-opening copolymer obtained by ring-opening polymerization of a cyclic olefin represented by the following formula [I]: A hydrogenated product, and / or (b) a copolymer of ethylene and a cyclic olefin represented by the following formula [I] having an intrinsic viscosity [η] of 0.01 to 10 dl / g, glass transition temperature (Tg)
A sliding material comprising the olefin-based resin composition according to claim 1, characterized in that it is a cyclic olefin-based resin obtained by mixing a cyclic olefin random copolymer having a temperature of 70 ° C or higher. (In the formula, n is 0 or 1, m is 0 or a positive integer, and R ^{1 to} R ¹⁸ are each independently an atom selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group. R ^{15 to} R ¹⁸ may be engaged with each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond; , R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group.) 3. The method according to claim 1, wherein the ethylene polymer [B] is at least one polymer selected from the group consisting of the following (c) to (g). A sliding material comprising the cyclic olefin resin composition of the above. (C) polyethylene having a glass transition temperature (Tg) of 0 ° C. or less; (d) a structural unit derived from ethylene, a structural unit derived from α-olefin other than ethylene, and a cyclic olefin represented by the above formula [I] The intrinsic viscosity [η] measured in decalin at 135 ° C. or 0.01 to 10 dl / g, and the glass transition temperature (Tg) is 0 ° C.
(E) an amorphous or low-crystalline ethylene / α having a glass transition temperature (Tg) of 0 ° C. or less, which is formed from ethylene and at least one kind of α-olefin; (F) an ethylene-α-olefin having a glass transition temperature (Tg) of 0 ° C. or less formed from ethylene, at least one α-olefin, and at least one non-conjugated diene; A diene copolymer; and (g) a copolymer having a glass transition temperature (Tg) of 0 ° C. or lower formed from ethylene and a polar monomer having at least one type of polymerizable unsaturated bond. 4. The method according to claim 1, wherein the slidable filler [C] is at least one selected from the group consisting of graphite, fluororesin powder, molybdenum fluoride and boron nitride. A sliding material comprising the cyclic olefin resin composition of the above.