JP2002060568A - Conductive olefin resin composition - Google Patents

Abstract

(57) [Abstract] [Purpose] Irrespective of the shape and thickness of a molded article, uniform cross-links can be formed, and thus uniform conductivity can be obtained. At high temperatures, the cross-links dissociate and have thermoplasticity. Provided is a so-called thermoreversible crosslinkable conductive olefin resin composition. [Structure] The following component (A), (B ₁ ) and / or (B)
₂ ) component (C), and the ratio of the number of hydroxyl groups of (B ₁ ) and / or (B ₂ ) to the number of carboxylic anhydride groups of component (A) is 0.1 to 5; And a conductive olefin-based resin composition having a volume resistivity of 10 ^-1 to 10 ⁹ Ω · cm. (A) a modified olefin resin modified with an ethylenically unsaturated carboxylic anhydride, wherein the average number of carboxylic acid anhydride groups per molecule is 1 or more (B ₁ ) Hydroxyl group-containing compound having two or more hydroxyl groups (B ₂ ) Hydroxyl group-containing polymer having an average number of hydroxyl groups of 1 or more per molecule (C) Conductive filler

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive olefin-based resin composition, and more particularly, it can form a uniform cross-link regardless of the shape and thickness of a molded product, thereby providing a uniform conductivity. The present invention relates to a so-called thermoreversible crosslinkable conductive olefin-based resin composition which has a thermoplastic property by dissociating crosslinks at a high temperature.

[0002]

2. Description of the Related Art Olefinic resins such as polyethylene and polypropylene are excellent in moldability, mechanical strength, transparency, chemical resistance, etc., and are variously molded such as extrusion molding, injection molding, hollow molding, compression molding, and rotational molding. It is widely used in various fields by shaping it into a desired shape in the molten state by the method, and by adding a conductive filler such as carbon black, it imparts conductivity not originally possessed by the conductive olefin resin. The composition has been applied in various fields.

[0003] Among them, a conductive olefin resin composition includes:
In addition to being a packaging material that dislikes the accumulation of static electricity, when energized, current passes through the chain of conductive fillers and heat is generated by Joule heat, while the chain of conductive fillers expands due to volume expansion of the resin due to temperature rise. As a result of the dissociation of the parts and the increase in the electric resistance, the passing current is controlled, so-called PTC (“Positive Temperature Coefficient”;
It is useful as a self-temperature control heating element exhibiting (positive temperature coefficient) characteristics and as a semiconductive layer in power cables.

However, since the olefin resin is a crystalline resin, there is a problem that various physical properties extremely fluctuate at a temperature higher than the melting point. The conductivity decreases as the temperature rises, and the self-temperature control function can be effectively exhibited.However, the phenomenon that the conductivity increases when the melting point is exceeded is observed.In the semiconductive layer of the power cable, particularly, The inner semiconductive layer is located closest to the conductor, and the temperature rise due to heat generation of the conductor during power supply is large, and if it exceeds the melting point, the mechanical strength etc. will be extremely reduced, etc. Usually, a crosslinking treatment is performed by blending an organic peroxide, irradiating radiation, or utilizing a silanol condensation reaction.

However, in these conventional crosslinking treatments, the crosslinking reaction on the inner side hardly proceeds with respect to the surface side of the molded body, and the problem becomes remarkable especially in a thick molded body. Crosslinking is likely to be insufficient or non-uniform depending on the part of the resin, while on the other hand, from the standpoint of environmental protection and resource saving, under the situation where reuse of used resin is increasingly required, these The crosslinked resin no longer had thermoplasticity and could not be reused by melt molding.

On the other hand, under low temperature, a crosslink is formed,
In contrast to some conventional techniques as a method of dissociating the cross-links at high temperature to impart thermoplasticity, the present invention is applied to a thermo-reversible cross-linkable olefin resin composition having excellent cross-linking reaction rate and cross-linking dissociation reaction rate. The applicant has previously filed a patent application for an olefin resin composition comprising a specific ethylenically unsaturated carboxylic anhydride-modified olefin resin and a specific hydroxyl group-containing compound or a specific hydroxyl group-containing polymer. See Japanese Unexamined Patent Publication No. Hei 11-106578 and JP-A-2000-34376.)

[0007]

SUMMARY OF THE INVENTION The present invention has been made with respect to the above-mentioned prior art, and therefore, the present invention can form a uniform cross-link regardless of the shape and thickness of a molded article, Accordingly, it is an object of the present invention to provide a so-called thermoreversible crosslinkable conductive olefin-based resin composition which can provide uniform conductivity and has a thermoplastic property by dissociation of crosslinks at high temperatures.

[0008]

The present inventor has conducted various studies on a conductive olefin resin composition suitable for use in the above-described self-temperature control heating element and a semiconductive layer in a power cable. The inventors have found that a system in which a conductive filler is blended with the olefin resin composition described in the above-mentioned patent application is optimal, and have completed the present invention. That is, the present invention provides the following component (A) , (B
₁ ) or / and the component (B ₂ ), and the component (C), and the ratio of the number of hydroxyl groups of the component (B ₁ ) and / or (B ₂ ) to the number of carboxylic anhydride groups of the component (A) Is 0.
And a volume resistivity of 10 ^-1 to 10 ⁹ Ω · cm.
And a conductive olefin resin composition.

(A) A modified olefin resin modified with an ethylenically unsaturated carboxylic anhydride,
Modified olefin resin having an average number of carboxylic anhydride groups of 1 or more per molecule (B ₁ ) Hydroxy group-containing compound having 2 or more hydroxyl groups (B ₂ ) Average number of hydroxyl groups of 1 molecule per molecule Or more hydroxyl-containing polymer (C) conductive filler

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION As the modified olefin resin modified with an ethylenically unsaturated carboxylic anhydride as the component (A) constituting the conductive olefin resin composition of the present invention, basically, Examples include a copolymer of an α-olefin and an ethylenically unsaturated carboxylic anhydride, and a graft of an α-olefin-based resin with an ethylenically unsaturated carboxylic anhydride.

The α-olefin in the former copolymer is, for example, ethylene, propylene, 1-
Butene, 3-methyl-1-butene, 1-pentene, 3-
Methyl-1-pentene, 4-methyl-1-pentene, 1
-Hexene, 1-octene, 1-decene and the like.

The ethylenically unsaturated carboxylic anhydride in the former copolymer includes, for example, 2-succinic acid
Octen-1-yl anhydride, 2-dodecene succinate-1
-Yl anhydride, 2-octadecene-1-yl succinate, maleic anhydride, 2,3-dimethylmaleic anhydride, bromomaleic anhydride, dichloromaleic anhydride, citraconic anhydride, itacone Acid anhydride, 1-
Butene-3,4-dicarboxylic anhydride, 1-cyclopentene-1,2-dicarboxylic anhydride, 1,2,3,6-
Tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, exo-3,6-epoxy-1,
2,3,6-tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, endo-bicyclo [2.2.2] Oct-5-ene-2,3-dicarboxylic anhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic anhydride and the like. Maleic anhydride is preferred.

The former copolymer includes, in addition to the binary copolymer of the α-olefin and the ethylenically unsaturated carboxylic acid anhydride, (meth) acrylic acid [here, “(Meth) acryl” means acryl and methacryl. ], Ethylenically unsaturated carboxylic acids such as maleic acid, vinyl esters such as vinyl acetate and vinyl propionate, ethylenically unsaturated carboxylic esters such as (meth) acrylate, (meth) acrylamide, N-methyl (meth) ) A ternary or higher copolymer obtained by copolymerizing other monomers such as ethylenically unsaturated amides such as acrylamide, styrene, and other ethylenically unsaturated compounds such as (meth) acrylonitrile may be used. These copolymers can be produced by a conventionally known polymerization method such as bulk, solution, suspension and the like.

The α-olefin resin in the latter graft is, for example, a homopolymer of ethylene such as low density / medium density / high density polyethylene (branched or linear), ethylene and propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene,
-Octene, copolymers with other α-olefins such as 1-decene, ethylene, ethylenically unsaturated carboxylic acids such as (meth) acrylic acid and maleic acid, vinyl esters such as vinyl acetate and vinyl propionate, Ethylenically unsaturated carboxylic esters such as (meth) acrylic esters,
Ethylenes such as copolymers with other monomers such as ethylenically unsaturated amides such as (meth) acrylamide and N-methyl (meth) acrylamide, and other ethylenically unsaturated compounds such as styrene and (meth) acrylonitrile Resin, propylene homopolymer, propylene, ethylene, 1-
Butene, 3-methyl-1-butene, 1-pentene, 3-
Methyl-1-pentene, 4-methyl-1-pentene, 1
-Hexene, 1-octene, copolymers with other α-olefins such as 1-decene, propylene and isoprene,
1,3-butadiene, 1,3-pentadiene, 1,4-
Propylene resins such as copolymers with other monomers such as dienes such as hexadiene, 1,5-hexadiene and 1,9-decadiene, and other 1-butene, 4-methyl-1-pentene, 1-hexene, etc. And α-olefin homopolymers and copolymers.

As the ethylenically unsaturated carboxylic anhydride in the latter graft, the same ones as those described in the copolymer can be used. These grafts are prepared by melt kneading, solution, It can be produced by a grafting method such as suspension.

The modified olefin resin of the component (A) in the present invention is a resin modified by the above-mentioned ethylenically unsaturated carboxylic acid anhydride. It is preferably modified by an acid ester.

Here, the modified olefin resin modified with the ethylenically unsaturated carboxylic anhydride and the ethylenically unsaturated carboxylic acid ester may be the same as that of the above-mentioned ethylenically unsaturated carboxylic anhydride-modified olefin resin. As in the above, basically, a copolymer and a graft are mentioned. Specifically, examples of the copolymer include the α-olefin, the ethylenically unsaturated carboxylic anhydride, and the ethylenically unsaturated carboxylic acid anhydride. Examples of the copolymer and the graft with the carboxylic acid ester include the above-mentioned ethylenically unsaturated carboxylic anhydride of the α-olefin-based resin and the co-graft with the ethylenically unsaturated carboxylic acid ester, and the ethylenically unsaturated carboxylic acid. Graft of the α-olefin resin obtained by copolymerizing an anhydride with an ethylenically unsaturated carboxylic acid ester, ethylene Graft body due the ethylenically unsaturated carboxylic acid anhydrides of the α- olefin resin obtained by copolymerizing an unsaturated carboxylic acid ester.

Here, as the ethylenically unsaturated carboxylic acid ester, an ester of an alkyl group having 1 to 20 carbon atoms is preferable, for example, methyl (meth) acrylate,
Ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate , Stearyl (meth) acrylate, dimethyl maleate, etc., of which alkyl (meth) acrylate is preferred.

In the present invention, among these modified olefin resins as the component (A), the copolymer
Binary or more copolymers containing ethylene as the α-olefin and maleic anhydride as the ethylenically unsaturated carboxylic anhydride are preferable, and ethylene and maleic anhydride, and the ethylenically unsaturated A ternary or higher copolymer containing (meth) acrylic acid alkyl ester as a carboxylic acid ester is particularly preferable. Further, as the graft, a graft of ethylene homopolymer as the α-olefin resin, maleic anhydride as the ethylenically unsaturated carboxylic anhydride, or the ethylenically unsaturated carboxylic anhydride A co-graft of maleic anhydride as the product and the alkyl (meth) acrylate as the ethylenically unsaturated carboxylic acid ester, and ethylene and the ethylenically unsaturated carboxylic acid ester as the α-olefin resin ( Of a copolymer with an alkyl (meth) acrylate,
A graft with maleic anhydride as the ethylenically unsaturated carboxylic anhydride is particularly preferred.

In the present invention, the modified olefin resin of the component (A) has a content of the ethylenically unsaturated carboxylic anhydride unit of 0.1% by weight or more, especially 0.5% by weight.
It is preferable that the average number of carboxylic acid anhydride groups per molecule of the modified olefin-based resin is 1 based on the number-average molecular weight of the modified olefin-based resin and a multiplier of the content. It is essential that the number be at least 1.5, and preferably at least 1.5. When the average number of carboxylic acid anhydride groups is less than 1, the crosslinkability of the composition itself is poor.

In the present invention, the component (A) is preferably a modified olefin resin modified by the ethylenically unsaturated carboxylic anhydride and the ethylenically unsaturated carboxylic acid ester, The ratio of the number of carboxylic acid ester groups derived from the ethylenically unsaturated carboxylic acid ester to the number of carboxylic acid anhydride groups derived from the ethylenically unsaturated carboxylic acid anhydride is 0.5 to 2
It is preferably 0, and more preferably 0.5 to 15. If the ratio of the number of carboxylic acid ester groups to the number of carboxylic anhydride groups is less than the above range, the crosslink dissociation itself as a composition tends to be inferior, whereas if the ratio exceeds the above range, the crosslinkability itself as a composition tends to be inferior. Become.

Incidentally, the component (A) in the present invention includes:
As long as the average number of carboxylic acid anhydride groups per molecule, or the ratio of the number of carboxylic acid ester groups to the number of carboxylic acid anhydride groups, satisfies the above range, the modified olefin resin or unmodified unsatisfied with the above range It may be diluted with an olefin resin or the like.

The hydroxyl group-containing compound of the component (B ₁ ) and / or the hydroxyl group-containing polymer of the component (B ₂ ) constituting the conductive olefin resin composition of the present invention is the modified olefin of the component (A). It has a function of forming a crosslink by bonding to a carboxylic acid anhydride group of the system resin.

As the hydroxyl group-containing compound of the component (B ₁ ), it is essential that the compound has two or more hydroxyl groups. If the number of hydroxyl groups is less than 2, the crosslinkability of the composition itself is inferior. Become. Further, among the hydroxyl group-containing compounds having two or more hydroxyl groups, those having no hydroxyl group bonded to a primary carbon atom and having two or more hydroxyl groups bonded to a secondary carbon atom are preferable. If the number of the hydroxyl groups bonded to the secondary carbon atoms is less than 2, the crosslinking property itself as the composition tends to be insufficient, and even if the number of the hydroxyl groups bonded to the secondary carbon atoms is two or more, When it has a hydroxyl group bonded to a primary carbon atom, the crosslinking dissociation itself of the composition tends to be insufficient.

Specific examples of the hydroxyl-containing compound having no hydroxyl group bonded to a primary carbon atom and having two or more hydroxyl groups bonded to a secondary carbon atom as the component (B ₁ ) in the present invention include: Include compounds represented by the following general formula (I).

[0026]

Embedded image

[In the formula (I), R ¹ and R ² each independently represent a linear or cyclic alkylene group having 1 to 20 carbon atoms, a and b are integers of 0 or more, and c is 1 or more. Indicates an integer. ]

Specific examples of the compound represented by the general formula (I) include, for example, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,2-cyclopentanediol, 1,3-cyclopentanediol,
1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,
4-cyclooctanediol, 1,5-cyclooctanediol, 1,3,5-cyclohexanetriol, inositol and the like, among which 1,2-cyclopentanediol, 1,3-cyclopentanediol, 2
-Cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclooctanediol, 1,5-cyclooctanediol, and 1,3,5-cyclohexanetriol are preferred.

As the above-mentioned hydroxyl-containing compound having no hydroxyl group bonded to a primary carbon atom and having two or more hydroxyl groups bonded to a secondary carbon atom as the component (B ₁ ), A compound represented by the formula (II) is also included.

[0030]

Embedded image

[In the formula (II), R ³ and R ⁶ each independently represent a linear or cyclic alkyl group, alkoxy group or aromatic group having 1 to 20 carbon atoms, and R ⁴ and R ⁵ represent Each independently represents a linear or cyclic alkylene group having 1 to 20 carbon atoms, a carbonyl group, an aromatic group, or an oxy group; d and e
Represents an integer of 0 or more, and f represents an integer of 1 or more. ]

As the compound represented by the general formula (II), specifically, for example, 2,3-butanediol,
2,4-pentanediol, 2,5-hexanediol, 1,1,1,5,5,5-hexafluoro-2,
2,4,4-pentane tetrol and the like, among which
2,3-butanediol, 2,4-pentanediol,
2,5-hexanediol is preferred.

Further, as the above-mentioned hydroxyl-containing compound having no hydroxyl group bonded to a primary carbon atom and having two or more hydroxyl groups bonded to a secondary carbon atom as the component (B ₁ ), A compound represented by the formula (III) is also included.

[0034]

Embedded image

[In the formula (III), R ⁷ and R ⁹ each independently represent a cyclic alkylene group having 5 to 20 carbon atoms;
⁸ represents a chain or cyclic alkylene group having 1 to 20 carbon atoms, a carbonyl group, an aromatic group, or an oxy group, g and h
Represents an integer of 1 or more. ]

Specific examples of the compound represented by the general formula (III) include, for example, 4,4'-isopropylidene-dicyclohexanol, α, α'-bis (4-hydroxycyclohexyl) -1 , 4-Diisopropylbenzene, α, α'-bis (4-hydroxycyclohexyl)
-1,4-diisopropylcyclohexane, 4,4′-
Methylenebis (cyclohexanol), 2,2′-methylenebis (4-methylcyclohexanol) and the like, among which 4,4′-isopropylidene-dicyclohexanol, α, α′-bis (4-hydroxycyclohexyl) ) -1,4-Diisopropylbenzene, α, α′-
Bis (4-hydroxycyclohexyl) -1,4-diisopropylcyclohexane is preferred.

The hydroxyl-containing compound having no hydroxyl group bonded to a primary carbon atom and having two or more hydroxyl groups bonded to a secondary carbon atom as the component (B ₁ ) in the present invention is (A) If the modified olefin-based resin as component (A) is not modified with an ethylenically unsaturated carboxylic acid ester, or even if the modified olefin-based resin as component (A) is modified with an ethylenically unsaturated carboxylic acid ester, It is preferably used when the ratio of the number of carboxylic ester groups to the number of carboxylic anhydride groups is less than 0.5.

The hydroxyl-containing compound (B ₁ ) does not have the above-mentioned hydroxyl group bonded to the primary carbon atom,
Examples of the hydroxyl group-containing compound other than the compound having two or more hydroxyl groups bonded to the secondary carbon atom include, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 2,2-dimethyl- 1,3-propanediol,
1,4-butanediol, 1,5-pentanediol,
Aliphatic diols such as 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, neopentyl glycol, and alicyclic rings such as 1,2-cyclohexane dimethylol and 1,4-cyclohexane dimethylol Formula diols, trimethylolethane, trimethylolpropane, trimethylolhexane, trimethyloldodecane, glycerol, diglycerol, tetraglycerol, hexaglycerol, octaglycerol,
Aliphatic polyhydric alcohols such as decaglycerol, pentaerythritol and dipentaerythritol, glycerol, diglycerol, tetraglycerol, hexaglycerol, octaglycerol, decaglycerol, ethylene of aliphatic polyhydric alcohols such as pentaerythritol and dipentaerythritol Carboxylic acids such as propionate, pivalate, caproate, caprylate, caprate, laurate, palmitate, stearate, and oleate such as oxide or / and propylene oxide adducts, glycerol, (poly) glycerol such as mono, di, tri, and tetra. Ester, sorbitol mono, di, tri, tetra, etc., propionate, pivalate, caproate, caprylate, caprate, laurate, palmitate Carboxylic acid esters such as stearate, oleate, erythrose, tetroses such as erythrulose, arabinose, pentoses such as xylose, glucose, fructose, mannose, sorbose, sugars such as hexoses such as galactose, and erythritol derived therefrom, Tetritols such as threitol, arabitol, sugar alcohols such as pentitol such as xylitol, sorbitol, mannitol, iditol, and hexitol such as dulcitol, among which 1,2-cyclohexane dimethylol,
4-cyclohexane dimethylol and pentaerythritol are preferred.

As the hydroxyl group-containing polymer of the component (B ₂ ), the number of hydroxyl groups per molecule of the hydroxyl group-containing polymer, which is determined based on the multiplier of the number average molecular weight of the hydroxyl group-containing polymer and the content of the hydroxyl group, is as follows. It is essential that the average number of bonds is 1 or more, and preferably 1.5 or more.
If the average number of hydroxyl groups bonded per molecule is less than 1, the crosslinkability itself of the composition will be poor. As the component (B ₂ ) in the present invention, as long as the average number of hydroxyl groups per molecule satisfies the above range, it is diluted with a polymer containing or not containing a hydroxyl group having an average number of hydroxyl groups of less than 1 or the like. May be done.

Examples of the hydroxyl group-containing polymer of the component (B ₂ ) in the present invention include ethylene- (meth) acrylate 2-hydroxyethyl copolymer, (meth) acrylate 2-hydroxyethyl graft polyethylene, ethylene -Saponified vinyl acetate copolymer, polyvinyl alcohol, low molecular weight polyolefin polyols, polyalkylene ether glycols, polyoxyalkylene polyols, hydroxyl-terminated diene polymers and their hydrogenated products or adipates, hydroxyl-terminated polycaprolactone, etc. These have a number average molecular weight of 500
It is preferably from 10,000 to 10,000. Among them, low molecular weight polyolefin polyols, polyalkylene ether glycols, polyoxyalkylene polyols, hydroxyl-terminated diene polymers and hydrogenated products thereof are preferred.

In the conductive olefin resin composition of the present invention, the modified olefin resin of the component (A) and the hydroxyl group-containing compound of the component (B ₁ ), and / or
The composition ratio of the component (B ₂ ) with the hydroxyl group-containing polymer is as follows:
It is essential that the ratio of the number of hydroxyl groups of the component (B ₁ ) and / or the number of hydroxyl groups of the component (B ₂ ) to the number of carboxylic acid anhydride groups of the component (A) is 0.1 to 5, and 0.1 to 3. Is preferred.
If the ratio of the number of hydroxyl groups to the number of carboxylic anhydride groups is less than the above range, the crosslinkability of the composition itself will be poor, while if the ratio is more than the range, the crosslink dissociation itself of the composition will be inferior. In this case, the object of the present invention cannot be achieved.

The conductive filler of the component (C) constituting the conductive olefin resin composition of the present invention is not particularly limited, but includes furnace black, acetylene black, Ketjen black, channel black, and thermal black. Carbon black such as black, and graphite conductive material such as carbon fiber, activated carbon, charcoal, aluminum, silver, copper, iron,
Nickel, zinc, stainless steel powder, flake,
Metallic conductive filler such as fibrous, zinc oxide, tin oxide,
Metal oxide conductive fillers such as iron oxide, copper oxide, titanium oxide, aluminum oxide, indium oxide, zirconium oxide, aluminum-doped zinc oxide, antimony-doped tin oxide, tin-doped indium oxide, and tin oxide-coated titanium oxide. Of these, carbon black is preferred.

The particle size of the powdery conductive filler is preferably 1 mm or less.
More preferably, it is 0 μm or less. In addition, the composition ratio as the component (C) in the conductive olefin-based resin composition of the present invention is such that the volume fraction with respect to the entire composition is 50% by volume.
It is preferably less than 10 parts by weight, for example, in the case of carbon black, it is particularly preferably 10 to 110 parts by weight with respect to 100 parts by weight in total of the component (A) and the component (B ₁ ) and / or the component (B ₂ ). preferable. When the composition ratio of the conductive filler of the component (C) is less than the above range, the conductivity of the composition tends to be insufficient. On the other hand, when the composition ratio is more than the above range, the moldability and mechanical properties of the composition are poor. It tends to be impaired.

The conductive olefin resin composition of the present invention comprises the modified olefin resin (A),
₁ ) The hydroxyl group-containing compound of the component and / or the hydroxyl group-containing polymer of the component (B ₂ ) and the conductive filler of the component (C) are essential components, and in addition to these components, 6-di-t-butyl-p-cresol, stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2′-methylenebis (4-methyl-6-t-butylphenol) ), 4,
4'-butylidenebis (4-methyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t
-Butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3 ′, 5 ′ -Di-t-butyl-4'-hydroxybenzyl) benzene, tetrakis [methylene-3- (3 ',
5'-di-t-butyl-4'-hydroxyphenyl) propionate] phenols such as methane, dilauryl-
3,3′-thiodipropionate, dimyristyl-3,
3'-thiodipropionate, distearyl-3,3 '
Sulfur-based compounds such as thiodipropionate and pentaerythritol tetra (β-lauryl-thiopropionate), tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-); Butylphenyl)-
An antioxidant such as a phosphorus-based antioxidant such as 4,4′-biphenylenediphosphonite is used in combination with the component (A) and (B ₁ ) or / and (B).
₂ ) It is preferable to add about 0.01 to ₂ parts by weight based on 100 parts by weight in total with the components.

The conductive olefin resin composition of the present invention may further contain, in addition to the above-mentioned antioxidant, various commonly used additives such as an ultraviolet absorber, a light stabilizer, a nucleating agent, and a neutralizer. Agents, lubricants, antiblocking agents, dispersants, flow improvers, mold release agents, flame retardants, coloring agents, fillers, and the like may be added.

The conductive olefin resin composition of the present invention comprises the component (A), the component (B ₁ ) and / or the component (B ₂ ).
The components, and the component (C), and other optional components used as required, are uniformly mixed by a Henschel mixer, a ribbon blender, a V-type blender, or the like, or a method of melt molding, or uniformly mixed. After, single or multi-screw extruder, roll, Banbury mixer, kneader,
A method of melt-kneading with a Brabender or the like to form pellets and then melt-molding, or mixing the component (A) with components other than the component (B ₁ ) and / or the component (B ₂ ) by the method described above. The components are melt-kneaded, and separately the components (B ₁ ) and / or (B ₂ ) and components other than the component (A) are mixed and melt-kneaded by the above-mentioned method, and then both are mixed and melt-molded. It can be prepared by a method or the like.

The conductive olefin resin composition of the present invention as described above can be molded by various molding methods commonly used for thermoplastic resins, such as injection molding, extrusion molding, hollow molding, compression molding, and rotational molding. Can be formed into a desired shape in a molten state to obtain a cross-linked molded body. Also, even when a used molded body is reused, the same shape is again formed into a desired shape in a molten state by a similar molding method. To form a crosslinked molded article.

The conductive olefin-based resin composition of the present invention constituting the obtained cross-linked molded article has a volume resistivity of 10 ⁻¹ to 10 ⁹ Ω · cm, and has excellent conductivity. Furthermore, regardless of the shape and thickness of the molded article, uniform crosslinks can be formed, and thus uniform conductivity can be obtained. At high temperatures, the crosslinks dissociate and have thermoplasticity. However, even after being formed into a crosslinked molded article, it can be reused by melt molding.

[0049]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist of the invention. The modified olefin resin of the component (A) used in Examples and Comparative Examples, (B ₁ )
The hydroxyl group-containing compound of the component, the hydroxyl group-containing polymer of the component (B ₂ ), and the conductive filler of the component (C) are as follows.

(A) Modified olefin resin A-1; ethylene-1-hexene copolymer resin (density 0.900 g / cm ³ , melt flow rate 16.5 g)
/ 10 minutes, "KS560" manufactured by Nippon Polychem Co., Ltd.) 100 parts by weight, maleic anhydride 1.0 part by weight, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane 0.05 part by weight Was uniformly mixed with a Henschel mixer, and then a twin-screw extruder (cylinder diameter 30 mm, L / D32,
A graft reaction was carried out by supplying the mixture to a melt-kneaded mixture (“PCM-30” manufactured by Ikegai Co., Ltd.) to obtain a modified olefin resin of maleic anhydride of an ethylene-1-hexene copolymer resin. The resulting modified olefin-based resin was subjected to reprecipitation purification treatment to remove ungrafted products, and then the maleic anhydride unit content was measured by infrared absorption spectrum to be 0.1.
7% by weight, number average molecular weight 23000 measured by gel permeation chromatography, average of carboxylic acid anhydride groups per molecule of modified olefin resin determined based on the number average molecular weight and the multiplier of maleic anhydride unit content 1.6 bonds, melt flow rate 6.5 g /
The melting point was 86 ° C. as measured by a differential scanning calorimeter for 10 minutes.

A-2: Ethylene-maleic anhydride-ethyl acrylate terpolymer resin (maleic anhydride unit content 2.5% by weight, ethyl acrylate unit content measured by infrared absorption spectrum) 12.5% by weight, a ratio of the number of carboxylic acid ester groups to the number of carboxylic acid anhydride groups of 4.9, a number average molecular weight of 19,800 measured by gel permeation chromatography, and a multiplier based on the number average molecular weight and the maleic anhydride unit content. Average number of carboxylic anhydride groups per molecule of modified olefin-based resin determined by the method described above, melting point: 95 ° C. measured by a differential scanning calorimeter, “Bondane TX803” manufactured by Sumitomo Chemical Co., Ltd.
0 ").

A-3: Ethylene-ethyl acrylate copolymer resin (Ethyl acrylate unit content: 19.0% by weight, melt flow rate: 5.0 g / 10 min, “A-702” manufactured by Mitsui Dupont Chemical Co., Ltd.) 100 parts by weight, 1.5 parts by weight of maleic anhydride, 2,5-dimethyl-2,5-
Using 0.08 parts by weight of bis (t-butylperoxy) hexane, a graft reaction was carried out in the same manner as in the case of the above-mentioned A-1, and an ethylene-ethyl acrylate copolymer resin modified with maleic anhydride was used. A resin was obtained. The resulting modified olefin-based resin was prepared by removing the ungrafted product by reprecipitation purification treatment, and then measuring the amount of maleic anhydride units by 1.0% by weight and measuring the number of carboxylic acid esters based on the number of carboxylic acid anhydride groups. Radix ratio 1
8.6, number average molecular weight 31,000 measured by gel permeation chromatography, average of carboxylic acid anhydride groups per molecule of modified olefinic resin determined based on the number average molecular weight and a multiplier of maleic anhydride unit content 3.1 bonds, melt flow rate 2.0g / 1
At 0 minute, the melting point was 82 ° C. as measured by a differential scanning calorimeter.

A-4: Ethylene-1-hexene copolymer resin (density 0.900 g / cm ³ , melt flow rate 16.5 g / 10 min, “KS56” manufactured by Nippon Polychem Co., Ltd.)
0 ") 100 parts by weight, maleic anhydride 1.0 part by weight,
2.3 parts by weight of 2-ethylhexyl acrylate, 2,5-
Using 0.12 parts by weight of dimethyl-2,5-bis (t-butylperoxy) hexane, a graft reaction was carried out in the same manner as in the case of A-1, and the maleic acid of the ethylene-1-hexene copolymer resin was obtained. An olefin resin modified with an anhydride and 2-ethylhexyl acrylate was obtained. The resulting modified olefin-based resin had a maleic anhydride unit content of 0.8% by weight as determined by infrared absorption spectrum after removing ungrafted products by reprecipitation purification treatment, and acrylic acid 2-
Ethylhexyl unit content 1.3% by weight, ratio of the number of carboxylic acid ester groups to the number of carboxylic acid anhydride groups 0.9,
Number average molecular weight 22000 measured by gel permeation chromatography, average number of carboxylic acid anhydride groups per molecule of modified olefin resin determined based on the number average molecular weight and a multiplier of maleic anhydride unit content 1. Eight specimens had a melt flow rate of 7.0 g / 10 min and a melting point of 86 ° C. as measured by a differential scanning calorimeter.

[0054] (B ₁₎ hydroxyl group-containing compound B ₁ -1; 2,5-hexanediol. B ₁ -2; 1,4-cyclohexane dimethylol. (B ₂₎ a hydroxyl group-containing polymer B ₂ -1; low molecular weight polyolefin polyol (hydroxyl group content 1.3 wt%, number average molecular weight of 1,500, a number average molecular weight and on the basis of the multiplier hydroxyl content obtained hydroxyl group-containing polymer Average number of hydroxyl group bonds per molecule: 1.1, "Polytail H" manufactured by Mitsubishi Chemical Corporation).

(C) Conductive filler C-1; carbon black (“DENKA BLACK” manufactured by Denki Kagaku Kogyo KK). C-2: carbon black ("Black Pearl 3600" manufactured by Cabot Corporation).

Examples 1 to 6 The components (A), (B ₁ ) and / or (B ₂ ) and (C) shown in Table 1 were used, and tetrakis [methylene-3- () was used as an antioxidant. 3 ', 5'-Di-t-butyl-4'-hydroxyphenyl) propionate] methane ("IRGANOX1010" manufactured by Ciba-Geigy Japan)
And tris (2,4-di-t-butylphenyl) phosphite (IRGAFOS16 manufactured by Ciba-Geigy Japan)
8 ") was added in an amount of 0.1 part by weight based on 100 parts by weight of the total of the component (A) and the component (B ₁ ) and / or the component (B ₂ ), and then dry-blended with a Henschel mixer. , Twin screw extruder (cylinder diameter 30 mm, L / D3
2. It is supplied to Ikegai Co., Ltd. “PCM-30”), melt-kneaded into pellets, and then extruded (cylinder diameter 20 m).
m, L / D20) to form a sheet having a thickness of 1 mm by melt extrusion.

With respect to each of the obtained sheets, the volume resistivity was measured by the following method, and the results are shown in Table 1. Using a sample punched out into a sheet with a volume resistivity of 20 mm x 80 mm,
The resistance was measured at 23 ° C. using a digital multimeter in accordance with SRIS 2301, and the resistivity per unit volume was calculated from the value.

Separately, each of the pellets obtained above is
Roll, temperature 140 ℃, rotation speed 20rpm / 16rpm
After kneading for 2 minutes under the conditions of m and clearance 1 mm, immediately press for 2 minutes at a temperature of 140 ° C. and under a pressure of 1.02 MPa, and cool under a pressure of 12.2 MPa to obtain a 200 mm × 200 mm size. A plate-shaped molded body having a thickness of 10 mm is press-formed, and the obtained plate-shaped molded body is
Heat treatment was performed for 5 hours in an oven set at 0 ° C.

With respect to each of the obtained plate-like molded bodies, the volume resistivity and the deformation ratio under heat and pressure were measured by the methods described below, and the results are shown in Table 1. Volume specific resistance thickness direction of the plate-shaped molded body 0 ~ 2mm, and cut out a portion of 4 ~ 6mm, using a sample punched out of them in the size of 20mm × 80mm, using a digital multimeter according to SRIS 2301, The resistance was measured at the melting point of the component (A) and at a temperature 30 ° C. higher than the melting point, and the resistivity per unit volume was calculated from those values. Heat and pressure deformation rate Using a sample cut out from 0 to 2 mm in the thickness direction and 4 to 6 mm in thickness direction, and cut out from them to a size of 30 mm × 30 mm, set between pressing plates, and weighed 3 kg at 120 ° C. atmosphere. The thickness after pressurizing for 1 hour under a load was measured with a dial gauge, and the percentage of the decrease in thickness with respect to the thickness before pressurization was calculated.

Comparative Examples 1 to 3 The following silane compound-modified olefin resins (A ') shown in Table 1 were used in place of the component (A) and the components (B ₁ ) and / or (B ₂ ) in Examples 1 to 6. ) And the silanol condensation catalyst (B '), and that the heat treatment of the plate-like molded body by press molding was performed by immersing it in warm water at 80 ° C for 5 hours. In the same manner as in 1 to 6, the sheet was extruded, and the volume resistivity was measured.
Separately, a plate-like molded body was press-molded, and the volume resistivity and the deformation ratio under heating and pressure were measured. The results are shown in Table 1.

(A ′) Silane Compound Modified Olefin Tree
Fat A'-1; ethylene-1-hexene copolymer resin (density 0.900 g / cm ³ , melt flow rate 16.5 g)
/ 10 minutes, "KS560" manufactured by Nippon Polychem Co., Ltd.) 100 parts by weight, 2.0 parts by weight of vinyltrimethoxysilane, 0.3 parts by weight of t-butylperoxy-2-ethylhexanoate, A graft reaction was carried out in the same manner as in the case of the above to obtain an olefin resin modified with vinyltrimethoxysilane of an ethylene-1-hexene copolymer resin. The resulting modified olefin-based resin had a vinyltrimethoxysilane unit content of 1.1% by weight, a melt flow rate of 7.0 g / 10 minutes, and a melting point of 86 ° C. measured by a differential scanning calorimeter.

A′-2: Ethylene-ethyl acrylate copolymer resin (ethyl acrylate unit content: 19.0% by weight, melt flow rate: 5.0 g / 10 min, “A-702” manufactured by Mitsui Dupont Chemical Company) Using 100 parts by weight, 2.0 parts by weight of vinyltrimethoxysilane, and 0.3 parts by weight of t-butylperoxy-2-ethylhexanoate, a graft reaction was carried out in the same manner as in the case of A-1. An olefin resin modified from ethylene-ethyl acrylate copolymer resin with vinyltrimethoxysilane was obtained. The resulting modified olefin resin had a vinyltrimethoxysilane unit content of 1.2% by weight and a melt flow rate of 2.0 g.
/ 10 min. And melting point of 82 ° C. measured by a differential scanning calorimeter.

(B ') Silanol condensation catalyst B'-1; ethylene homopolymer (density 0.919 g / c
100 parts by weight of m ³ , melt flow rate 2.0 g / 10 minutes) and 1.0 part by weight of dibutyltin dilaurate were uniformly mixed with a Henschel mixer, and then a twin-screw extruder (cylinder diameter 30 mm, L / D32, Ikegaisha) "PCM-3"
0 ") and melt-kneaded to produce a silanol condensation catalyst masterbatch.

[0064]

[Table 1]

[0065]

According to the present invention, it is possible to form a uniform cross-link regardless of the shape and thickness of a molded article, and thus to provide a uniform conductivity, and at high temperature, the cross-link is dissociated and has thermoplasticity. The conductive olefin-based resin composition of the present invention can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01B 1/22 H01B 1/22 Z 1/24 1/24 Z F term (Reference) 4J002 BB071 BB072 BB081 BB202 BB211 BE022 BE032 BL012 CH022 DA017 DA027 DA037 DA077 DA087 DA097 DA107 DE097 DE107 DE117 DE137 DE147 EC046 EC056 EC066 EH056 EL086 FA047 FD117 GQ02 GQ05 5G301 DA18 DA43 DD04 DD08

Claims (7)

[Claims] (1) The following component (A), (B)₁) Or / and
(B_Two) Component, and (C) component,
(B) relative to the number of carboxylic anhydride groups of component (A) ₁)or
Is / and (B_Two) The ratio of the number of hydroxyl groups of the component is 0.1 to 5
And the volume resistivity is 10^-1-10⁹Ω · cm
A conductive olefin-based resin composition, comprising: (A) Modified by ethylenically unsaturated carboxylic anhydride
Modified olefin resin, per molecule
Modifications in which the average number of carboxylic acid anhydride groups is 1 or more
Olefin resin (B₁) A hydroxyl-containing compound having two or more hydroxyl groups (B_Two) The average number of hydroxyl groups bonded per molecule is 1 or more
(C) Conductive filler 2. The hydroxyl group-containing compound as the component (B ₁ ) does not have a hydroxyl group bonded to a primary carbon atom but has two or more hydroxyl groups bonded to a secondary carbon atom. 4. The conductive olefin resin composition according to item 1. 3. The conductive olefin resin composition according to claim 1, wherein the ethylenically unsaturated carboxylic anhydride in the component (A) is maleic anhydride. 4. The modified olefin resin of component (A)
It is modified with an ethylenically unsaturated carboxylic acid anhydride and an ethylenically unsaturated carboxylic acid ester, and the ratio of the number of carboxylic acid ester groups to the number of carboxylic acid anhydride groups in the modified olefin resin is 0.5 to 0.5. The conductive olefin resin composition according to any one of claims 1 to 3, wherein the composition is 20. 5. The conductive olefin resin composition according to claim 4, wherein the ethylenically unsaturated carboxylic acid ester in the modified olefin resin (A) is an alkyl (meth) acrylate. 6. The conductive olefin resin composition according to claim 1, wherein the conductive filler as the component (C) is carbon black. 7. The content of the conductive filler of the component (C) is 10 to 110 parts by weight based on 100 parts by weight of the total of the component (A) and the component (B ₁ ) and / or the component (B ₂ ). The conductive olefin resin composition according to any one of claims 1 to 6.