JP2001064403A - Master batch and resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a master batch enabling the containing of an additive for a high-viscosity polymer. SOLUTION: A master batch consisting of (A) an additive for a polymer having a kinetic viscosity of >=5000 centi-strokes determined at 25 deg.C according to JIS-K2410 standard and (B) a powdery body having an average particle diameter of 0.001-100 μm which does not melt at 250 deg.C. Especially, the component A is a polyorganosiloxane, and the component B is silica.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a masterbatch and a resin composition obtained by adding the same. More specifically, the present invention relates to a resin composition that exhibits excellent mechanical strength by using such a masterbatch.

[0002]

2. Description of the Related Art Polymers such as thermoplastic resins and elastomers have excellent impact resistance and moldability compared to metals, glass, etc., and are used in automobile parts, electric / electronic materials, and building materials. Used in a variety of fields. In recent years, various polymer additives have been used in such a field for higher functionality. For example, liquid paraffin (mineral oil) is added to improve processability, and a flame retardant is added to impart flame retardancy.
Usually, a melt extrusion method is employed as the production method. However, in melt extrusion, not only a special feed facility is required to add a liquid, particularly high-viscosity polymer additive, but also handling is complicated. Moreover,
When a high-viscosity liquid polymer additive and a polymer are melt-mixed, poor dispersion of the high-viscosity additive not only reduces productivity, but also impairs appearance and decreases mechanical properties. There was a problem of doing.

To solve this problem, for example, there is a conventional technique in which a resin and a liquid polymer additive are absorbed at a relatively low temperature without melting and mixing the resin and the liquid polymer additive.
A resin composition comprising an oil absorbing resin and a liquid additive or a method for improving properties is disclosed. For example, a resin composition composed of an oil-impregnated resin obtained by adsorbing a liquid oil to a porous styrene divinylbenzene copolymer and a thermosetting resin (Japanese Patent Publication No. 7-122024), and an additive added to an oil-absorbing crosslinked polymer For preventing bleeding of an additive using a resin modifying additive and a resin composition comprising a resin (JP-A-5-214)
No. 114), a method of obtaining a matte appearance by kneading a specific cross-linked polymer into a resin (Japanese Patent Laid-Open No. 6-5)
No. 7007), a method of improving impact resistance by kneading a specific crosslinked polymer into a resin (Japanese Patent Laid-Open No. 6-7)
No. 3190), a powdery flame retardant obtained by impregnating amorphous silica with a phosphorus-based flame retardant (Japanese Patent Application Laid-Open No. Hei 7-331244), and a phosphorus-based flame retardant supported on inorganic powder (Japanese Patent No. 2588331). ), A method for producing a resin composition in which a liquid additive solidified by a gelling agent is mixed with a synthetic resin (Japanese Patent Publication No. 56-42619), and a solution in which a phosphate compound is dissolved in a solvent is melt-kneaded into polypropylene. A method of dispersing (JP-A-4-1233) and a masterbatch comprising an additive for resin and an oil-absorbing polymer (JP-A-9-52956) are known. The liquid additive used in the above publication has a low viscosity, and is not necessarily effective for forming a masterbatch of a high-viscosity additive. In particular, a high-concentration masterbatch is required for a high-viscosity additive.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a masterbatch which does not have the above-mentioned problems, that is, contains a high-viscosity additive in view of the above situation. .

[0005]

Means for Solving the Problems As a result of intensive studies on a master batch containing an additive for polymers, the present inventors have found that
By using a specific powder, it was surprisingly found that a polymer additive could be contained at a high concentration, and the present invention was completed. That is, the present invention relates to (A) JIS-K241
A polymer additive having a kinematic viscosity at 0.degree. C. at 25.degree. C. of 5000 centistokes or more;
A masterbatch comprising 001 to 100 μm and a powder that does not melt at 250 ° C., in particular, a masterbatch wherein (A) is a polyorganosiloxane and (B) is silica. The component (A) is a component for imparting functionality such as abrasion resistance, flame retardancy and fluidity to the polymer, and the component (B) is a component for retaining the component (A). Here, (B) is an average particle diameter of 0.001 to 1000.
It is important that the powder has a particle size of μm and does not melt at 250 ° C., and it has been found that by satisfying this requirement, a high-viscosity additive can be maintained at a high concentration, thereby completing the present invention. Hereinafter, the present invention will be described in detail.

Hereinafter, each component of the present invention will be described in detail. In the present invention, the polymer additive used as (A) is a component for imparting a special function to the polymer, and the kinematic viscosity at 25 ° C. specified in JIS-K2410 is 5000 centistokes or more. There is no particular limitation. Here, (A) is a wear resistance improver, a plasticizer, a heat stabilizer, a light stabilizer, a flame retardant, a colorant, a foaming agent, a lubricant, a fragrance, a smoke suppressant, a tackifier, a preservative, and a heat insulator. ,
Selected from impact resistance improvers, repellents, wetting agents, surfactants, emulsifiers, destabilizers, coagulants, defoamers, antifreezes, creaming agents, thickeners, heat-sensitive agents, and foaming agents It is at least one polymer additive, and most preferably a silicon-containing wear resistance improver.

The amount of (A) used in the masterbatch is preferably 0.0001 to 99% by weight, more preferably 1 to 90% by weight, further preferably 10 to 80% by weight, and most preferably 30 to 80% by weight. 70% by weight. The above-mentioned abrasion resistance improver (A) is a component for improving the scratch resistance and abrasion resistance of the polymer, and is particularly preferably a silicon-containing abrasion resistance improver, and specifically, a high molecular weight polyorganosiloxane. It can be suitably used. Such a high molecular weight polyorganosiloxane has a viscous syrup-like to gum-like form, and is preferably a linear polymer or a linear polymer containing a small amount of branches. JIS-K24
It is an essential condition that the kinematic viscosity at 10 (25 ° C.) is not less than 5000 centistokes (hereinafter, referred to as CS). When the kinematic viscosity of the component (C) exceeds 5000 CS, an excellent effect of improving abrasion resistance and touch feeling is exhibited.

[0008] Regarding the upper limit of the kinematic viscosity, the range in which the viscosity can be actually measured is up to about several million CS. It is possible to obtain a good masterbatch. In addition, even if a gum-like high molecular weight polyorganosiloxane in a region where the viscosity cannot be measured is used, a favorable composition can be obtained, and thus the upper limit is not limited. The kinematic viscosity (25 ° C.) of the high molecular weight polyorganosiloxane used in the present invention is 5,000 CS or more, more preferably 10,000 CS or more, and most preferably 50,000 CS.
That is all. The high molecular weight polyorganosiloxanes useful in the present invention are generally random polymers containing alkyl, vinyl and / or aryl substituted siloxane units, the structure of which is shown in Chemical Formula 1. Among them, R1
Most preferred are polydimethylsiloxanes in which R4 is all methyl groups.

[0009]

Embedded image (R1 to R4 are hydrocarbons having 1 to 20 carbon atoms and may be the same or different. N is an integer of 1 or more;
The kinematic viscosity at 5 ° C. varies in the range of 5000 CS or more. The flame retardant (A) is a halogen-based or phosphorus-based flame retardant. In particular, among phosphorus-based flame retardants, organic phosphorus compounds are preferred.

Examples of the above-mentioned organic phosphorus compounds include phosphine, phosphine oxide, biphosphine, phosphonium salt, phosphinate, phosphate, phosphite and the like. More specifically, triphenyl phosphate, methyl neopentyl phosphite, pentaerythritol diethyl diphosphite, methyl neopentyl phosphonate, phenyl neopentyl phosphate, pentaerythritol diphenyl diphosphate, dicyclopentyl hypophosphate , Dineopentyl hypophosphite, phenylpyrocatechol phosphite, ethyl pyrocatechol phosphate and dipyrocatechol hypopositive phosphate. Here, as the organic phosphorus compound, an aromatic phosphate ester monomer (formula 2) and an aromatic phosphate ester condensate (formula 3) are particularly preferred.

[0011]

Embedded image

[0012]

Embedded image (However, Ar1, Ar2, Ar3, Ar4, Ar5
, Ar6 represents a phenyl group, a xylyl group, an ethylphenyl group, an isopropylphenyl group, a butylphenyl group,
An aromatic group selected from 4'-dioxydiarylalkane groups. N represents an integer of 0 to 3;
Represents the above integer. (B) in the present invention is not particularly limited as long as the requirements of the present invention are satisfied. For example, silicon-containing compounds, thermosetting resins, metals, metal-containing compounds, halogen-containing compounds,
It is a powder of a nitrogen-containing compound, a reinforcing agent, a ceramic, a light stabilizer, a colorant, and the like, and among them, a silicon-containing compound such as silica is preferable. The average particle size is 0.001 μm
10 μm, preferably 0.01 μm to 10 μm
m, more preferably 0.1 μm to 5 μm, most preferably 0.1 μm to 2 μm.

[0013] As (B) of the present invention, a surface-treated powder is particularly preferable and has excellent mechanical strength. As the surface treatment agent, for example, an organic acid or a silane coupling agent is known. Among the above organic acids, higher fatty acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid and montanic acid are preferred. The silicon-containing compound is amorphous silicon dioxide such as silica or silicone resin, silicate, etc., and silica is particularly preferable. The thermosetting resin is a phenol resin, a melamine resin, an epoxy resin, an unsaturated polyester resin, a furan resin, a urea resin, a xylene resin,
Silicone resin, diallyl phthalate, aramid and the like. The metal is aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium,
It is a simple substance of nickel, copper, tungsten, tin, antimony or the like, or a composite thereof.

The metal-containing compounds include aluminum oxide, iron oxide, titanium oxide, manganese oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide,
Cobalt oxide, bismuth oxide, chromium oxide, tin oxide,
Simple substance such as antimony oxide, nickel oxide, copper oxide, tungsten oxide, or a composite (alloy) thereof, aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, zeolite, calcium hydroxide, barium hydroxide, basic Hydrates of inorganic metal compounds such as magnesium carbonate, zirconium hydroxide, and tin oxide hydrate;
Zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesium carbonate, mu calcium, calcium carbonate, barium carbonate, kaolin, montmorillonite,
Bentonite, clay, mica, talc and the like.

The halogen-containing compound includes an aromatic halogen compound, a halogenated cyanurate resin, a halogenated polyphenylene ether, and the like, and is preferably decabromodiphenyl oxide, brominated polystyrene, brominated cross-linked polystyrene, brominated polyphenylene oxide, or polydiene. Halogen-based flame retardants such as bromophenylene oxide, decabromodiphenyl oxide bisphenol condensate, and halogen-containing phosphoric acid ester.

The nitrogen-containing compounds include melamine, melam, melem, melon (product of deammonification of three to three molecules of melem at 600 ° C. or higher), melamine cyanurate, melamine phosphate, succinoguanamine, And triazine skeleton-containing compounds such as poguanamine and methylglutalogamine. The amount of (B) is 0.1 to 200 parts by weight in the masterbatch, preferably 1 to 200 parts by weight.
150 parts by weight, more preferably 1 to 100 parts by weight, still more preferably 5 to 50 parts by weight, most preferably 10 to 50 parts by weight
Parts by weight.

The amount of (A) used in the masterbatch is preferably 1 to 99.9999% by weight, more preferably 10 to 99% by weight, still more preferably 20 to 90% by weight, and most preferably 30 to 90% by weight. 70% by weight. In the masterbatch of the present invention, if necessary, a compatibilizer is blended for improving the retention of (A), and an antiadhesive is blended for improving the handleability of the masterbatch.
Further, a polymer can be blended for improving the flexibility and strength of the masterbatch.

Examples of the compatibilizer (A) for improving the retention and the like include aliphatic hydrocarbons, higher fatty acids, higher fatty acid amides and higher aliphatic alcohols. Preferably 0.01 to 20% by weight, more preferably 0.1 to 10% by weight, most preferably 1 to 5% by weight. Aliphatic hydrocarbons as the compatibilizer include liquid paraffin, natural paraffin, microwax, polyolefin wax, synthetic paraffin, and partial oxides thereof, or fluorides and chlorides.

The higher fatty acids include saturated fatty acids and unsaturated fatty acids such as ricinoleic acid, lysinberidic acid and 9-oxy-12-octadecenoic acid. The higher fatty acid amide is a monoamide of a saturated fatty acid such as phenylstearic acid amide, methylol stearic acid amide, methylol-rubehenic acid amide, coconut fatty acid diethanolamide,
N, N'-2-substituted monoamides such as lauric acid diethanolamide, coconut oil fatty acid diethanolamide, oleic acid diethanolamide, and the like. Further, methylenebis (12-hydroxyphenyl) stearic acid amide, ethylenebisstearic acid Saturated fatty acid bisamides such as amide, ethylenebis (12-hydroxyphenyl) stearic acid amide, hexamethylenebis (12-hydroxyphenyl) stearic acid amide, and aromatic compounds such as m-xylylenebis (12-hydroxyphenyl) stearic acid amide Bisamide.

Higher aliphatic alcohol as the compatibilizer
Is 1 such as stearyl alcohol and cetyl alcohol.
Alcohols, polyhydric alcohols such as sorbitol and mannitol, and polyoxyethylene dodecylamine;
Allylated ethers having a polyalkylene ether unit such as polyoxyethylene allylated ether; polyoxyethylene lauryl ether; Dodecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether,
Polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, and polyoxyethylene alkyl phenyl ether such as polyoxyethylene nonyl phenyl ether;
Ter, polyepichlorohydrin ether, polyoxyethylene bisphenol A ether, polyoxyethylene ethylene glycol, polyoxypropylene bisphenol A ether, polyoxyethylene polyoxypropylene glycol ether It is a divalent alcohol having a polyalkylene ether unit such as ter.

The anti-adhesion agent blended to improve the handleability of the masterbatch of the present invention is melted at 250 ° C., for example, organic acid metal salts such as metal soaps, metal oxides, inorganic salts and waxes. , Minerals, fibers and the like, and one or more of these can be used. Among them, a powder compound having an average particle diameter of 0.01 to 300 μm is preferable. If the average particle size is less than 0.01 μm, the powders will aggregate, and if it exceeds 300 μm, the retention of (A) tends to decrease.

The metal salts of organic acids as one of the above antiadhesives include, for example, butyric acid, caproic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachiic acid and the like. Linear unsaturated fatty acids such as oleic acid, linoleic acid and linoleic acid; branched fatty acids such as isostearic acid; hydroxyl group-containing fatty acids such as ricinoleic acid and 12-hydroxystearic acid; benzoic acid; naphthenic acid; abietic acid Lithium, copper, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, aluminum, cerium, and titanium salts of organic carboxylic acids represented by rosin acids such as dextropimaric acid , Zirconium salt, lead salt, chromium salt, manganese salt, cobalt , And nickel salts.

In the masterbatch of the present invention, if necessary, the polymer compounded for improving the flexibility and strength of the masterbatch may be an organic, inorganic, or an organic / inorganic hybrid. It is a united resin, a thermoplastic resin, a thermosetting resin or the like, and among them, the thermoplastic resin is particularly preferable. The above rubber-like polymer preferably has a glass transition temperature (Tg) of -30 ° C or lower, and if it exceeds -30 ° C, the impact resistance tends to decrease. Examples of such rubbery polymers include diene rubbers such as polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene), and saturated rubbers obtained by hydrogenating the diene rubbers, isoprene rubber, chloroprene rubber, and polyacrylic rubber. Acrylic rubber such as butyl acrylate, ethylene-propylene copolymer rubber, ethylene-propylene-diene monomer terpolymer rubber (EPD)
M), a crosslinked rubber or a non-crosslinked rubber such as an ethylene-octene copolymer rubber, and a thermoplastic elastomer containing the above rubber component.

Of the above thermoplastic elastomers, a styrene-based thermoplastic elastomer is particularly preferable, and a block copolymer comprising an aromatic vinyl unit and a conjugated diene unit,
Or the conjugated diene unit portion is a partially hydrogenated block copolymer, particularly from the viewpoint of thermal stability,
Hydrogenated styrenic thermoplastic elastomers are more preferred. The aromatic vinyl monomer constituting the block copolymer is, for example, styrene, α-methylstyrene, paramethylstyrene, p-chlorostyrene, p-bromostyrene, 2,4,5-tribromostyrene and the like. Yes, styrene is most preferred, but other aromatic vinyl monomers described above may be copolymerized mainly with styrene.

The conjugated diene monomer constituting the block copolymer includes 1,3-butadiene, isoprene and the like. In the block structure of the block copolymer, a polymer block composed of an aromatic vinyl unit is represented by S, and a polymer block composed of a conjugated diene and / or a partially hydrogenated unit thereof is represented by B. In this case, SB, S (BS) n (where n is 1 to 3)
), A linear block copolymer of S (BSB) n (where n is an integer of 1 to 2) or (SB) n X
(However, n is an integer of 3 to 6. X is a residue of a coupling agent such as silicon tetrachloride, tin tetrachloride, or a polyepoxy compound.)
Star shape with the B part as the bonding center
It is preferably a block copolymer. Above all, SB
Type 2, SBS type 3, and SBSB type 4 linear-block copolymers are preferred.

The proportion of the aromatic vinyl monomer in the above block copolymer is from 1 to 99% by weight, preferably from 10 to 99% by weight.
It is from 90 to 90% by weight, more preferably from 20 to 80%, and most preferably from 30 to 70%. Within the above range, excellent impact strength is exhibited. One hydrogenated styrene-based thermoplastic elastomer of the rubbery polymer that can be compounded in the masterbatch of the present invention is obtained by hydrogenating the above-described block copolymer composed of an aromatic vinyl unit and a conjugated diene unit by a known method. Is obtained by For example, FLRamp, etal, J.Ame
R. Chem. Soc., 83, 4672 (1961) .Method of hydrogenation using triisobutylborane catalyst, Hung Yu Chen, J. Pol
ym.Sci.Polym.Letter Ed., 15,271 (1977), a method of hydrogenation using toluenesulfonyl hydrazide, or an organic cobalt-organoaluminum catalyst or an organic nickel-organoaluminum system described in JP-B-42-8704. Hydrogenation using a catalyst,
JP-A-52-41890 using a catalyst capable of selectively hydrogenating a 1,2-vinyl bond prior to a 1,4-bond
JP-A-59-13 using a catalyst capable of hydrogenation under mild conditions of low temperature and low pressure.
No. 3203 and JP-A-60-220147.

The most preferred thermoplastic resin among the polymers that can be blended in the masterbatch of the present invention is:
There is no particular limitation as long as it is compatible or uniformly dispersed with (A) and (B). For example, polystyrene-based, polyphenylene ether-based, polyolefin-based, polyvinyl chloride-based, polyamide-based, polyester-based, polyphenylene sulfide-based, polycarbonate-based, polymethacrylate-based, or a mixture of two or more of them can be used. . In particular, as the thermoplastic polymer, a polyphenylene ether-based, polystyrene-based, or polycarbonate-based thermoplastic resin is preferable.

The masterbatch of the present invention may contain other additives such as an organic / inorganic pigment, a heat stabilizer, an antioxidant, an ultraviolet absorber, a light stabilizer, etc.
Flame retardants, silicone oil, anti-blocking agents, foaming agents, antistatic agents, antibacterial agents and the like can be added. For the production of the masterbatch of the present invention, a usual resin composition,
General methods such as a Banbury mixer, a kneader, a single-screw extruder, and a twin-screw extruder used for the production of the elastomer composition can be employed.

By blending the masterbatch of the present invention with a polymer, it is possible to impart a special function to the polymer. The polymer in which the masterbatch can be blended may be an organic, inorganic or organic / inorganic hybrid, such as a rubber-like polymer, a thermoplastic resin, or a thermosetting resin. A thermoplastic resin is preferred, and a resin composition comprising (C) a rubber-like polymer and (D) a thermoplastic resin is particularly preferred, and very preferably a resin composition comprising (C) a cross-linkable rubber-like polymer and (D) a thermoplastic resin. Is a resin composition.

In the present invention, the crosslinkable rubber-like polymer (C) preferably has a glass transition temperature (Tg) of -30 ° C. or lower. Examples of such a rubber-like polymer include polybutadiene and poly (styrene). -Butadiene), diene rubbers such as poly (acrylonitrile-butadiene), and acrylic rubbers such as saturated rubber obtained by hydrogenating the diene rubber, isoprene rubber, chloroprene rubber, polybutyl acrylate, and ethylene-propylene copolymer rubber, ethylene -Crosslinked rubber or non-crosslinked rubber such as propylene-diene monomer terpolymer rubber (EPDM) and ethylene-octene copolymer rubber, and thermoplastic elastomer containing the above rubber component.

In the present invention, among the crosslinkable rubbery polymers (C), ethylene / α-olefin copolymers are particularly preferable, and ethylene and α-olefins having 3 to 20 carbon atoms are more preferable. Examples of the α-olefin having 3 to 20 carbon atoms include propylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1, heptene-1, octene-1, nonene-1, decene-1,
Undecene-1, dodecene-1 and the like. Among them, hexene-1, 4-methylpentene-1, octene-1
Is particularly preferable, and an α-olefin having 6 to 12 carbon atoms is particularly preferable, and octene-1 is most preferable.
Octene-1 is excellent in softening effect even in a small amount, and the obtained copolymer is excellent in mechanical strength.

The ethylene / α-olefin copolymer (C) preferably used in the present invention is preferably produced using a known metallocene catalyst. Generally, a metallocene-based catalyst is composed of a cyclopentadienyl derivative of a group IV metal such as titanium or zirconium and a co-catalyst, and is not only highly active as a polymerization catalyst, but also has a higher polymer yield than a Ziegler-based catalyst. Has a narrow molecular weight distribution, and the distribution of the comonomer α-olefin having 3 to 20 carbon atoms in the copolymer is uniform.

The ethylene / α-olefin copolymer (C) used in the present invention preferably has an α-olefin copolymerization ratio of 1 to 60% by weight, more preferably 10 to 50% by weight, and most preferably. Is from 20 to 45% by weight. α-olefin copolymerization ratio is 60% by weight
If it exceeds 1, the hardness, tensile strength and the like of the composition are greatly reduced, while if it is less than 1% by weight, the flexibility and the mechanical strength are reduced. (C) The density of the ethylene / α-olefin copolymer is preferably in the range of 0.8 to 0.9 g / cm ³ . By using an olefin-based elastomer having a density in this range, an elastomer composition having excellent flexibility and low hardness can be obtained.

(C) Ethylene α used in the present invention
The olefin copolymer preferably has a long-chain branch. The presence of the long-chain branch enables the density to be lower than the ratio (% by weight) of the copolymerized α-olefin without lowering the mechanical strength. Hardness and high strength elastomer can be obtained. The olefin elastomer having a long chain branch is described in US Pat. No. 5,278,272.

The ethylene / α-olefin copolymer (C) preferably has a DSC melting point peak at room temperature or higher. When it has a melting point peak, the form is stable in the temperature range below the melting point, the handleability is excellent, and the stickiness is small. The melt index of (C) used in the present invention is 0.01 to 100 g / 10 min (19
(0 ° C., 2.16 kg load) is preferably used, and more preferably 0.2 to 10 g / 10 min.
If the amount exceeds 100 g / 10 minutes, the crosslinking property of the composition is insufficient.

(C) used in the present invention may be a mixture of a plurality of types. In such a case, it is possible to further improve the workability. In the present invention, one of the preferred crosslinkable rubbery polymers among (C) is a thermoplastic elastomer, and among them, a polystyrene-based thermoplastic elastomer is particularly preferred, and a block comprising an aromatic vinyl unit and a conjugated diene unit is preferred. Copolymers and block copolymers in which the conjugated diene unit is partially hydrogenated or epoxy-modified are mentioned.

The aromatic vinyl monomer constituting the block copolymer is, for example, styrene, α-methylstyrene, paramethylstyrene, p-chlorostyrene, p-bromostyrene, 2,4,5-tribromobenzene. Styrene is the most preferable, and styrene is most preferable. However, other aromatic vinyl monomers described above may be copolymerized mainly with styrene. Further, the conjugated diene monomer constituting the block copolymer,
Examples thereof include 1,3-butadiene and isoprene.

In the block structure of the block copolymer, a polymer block composed of an aromatic vinyl unit is represented by S, and a polymer block composed of a conjugated diene and / or a partially hydrogenated unit thereof is represented by B. When displaying with,
SB, S (BS) n (where n is an integer of 1 to 3), S
(BSB) n, where n is an integer of 1 to 2
A block copolymer or (SB) nX (where n is 3 to 6)
Integer. X is a residue of a coupling agent such as silicon tetrachloride, tin tetrachloride, and a polyepoxy compound. ), And is preferably a star-shaped (star) block copolymer having a portion B as a bonding center. Above all, type 2 of SB, type 3 of SBS,
SBSB Type 4 linear-block copolymers are preferred.

In the present invention, (D) the thermoplastic resin comprises:
There is no particular limitation as long as it is compatible or uniformly dispersed with (C). For example, polystyrene-based, polyphenylene ether-based, polyolefin-based, polyvinyl chloride-based, polyamide-based, polyester-based, polyphenylene sulfide-based, polycarbonate-based, polymethacrylate-based, or a mixture of two or more of them can be used. . In particular, an olefin resin such as a propylene resin is preferable as the thermoplastic resin.

Specific examples of the propylene resin most preferably used in the present invention include homo isotactic polypropylene, propylene and other α-olefins such as ethylene, butene-1, pentene-1 and hexene-1. Examples include an isotactic copolymer resin with olefin (including block and random). At least one or more thermoplastic resins (D) selected from these resins are (C) and (D)
Is used at a composition ratio of 1 to 99 parts by weight based on a total of 100 parts by weight. Preferably 5 to 90 parts by weight, more preferably 2
0 to 80 parts by weight, most preferably 20 to 70 parts by weight. If the amount is less than 1 part by weight, the fluidity and processability of the composition are reduced, and if it exceeds 99 parts by weight, the flexibility of the composition is insufficient, which is not desirable.

The propylene resin used in the present invention has a melt index of 0.1 to 100 g / 10.
Min (230 ° C., 2.16 kg load) is preferably used. If it exceeds 100 g / 10 minutes, the heat resistance and mechanical strength of the thermoplastic elastomer composition will be insufficient, and if it is less than 0.1 g / 10 minutes, the fluidity will be poor and the moldability will be reduced, which is not desirable. . In the present invention, among (D), a combination of an olefin-based random copolymer resin such as a random copolymer of ethylene and propylene or a polyethylene-based resin with an olefin-based block copolymer resin or a polypropylene-based resin is most preferable. The mechanical strength is further improved by combining such two kinds of olefin-based resins.

Compounding the master batch of the present invention (C)
And 100 parts by weight of a resin composition comprising (D)
(C) is used in a composition ratio of 1 to 99 parts by weight. Preferably it is 5-90 parts by weight, more preferably 20-80 parts by weight. If the amount is less than 1 part by weight, the fluidity and processability of the composition are reduced, and if it exceeds 99 parts by weight, the flexibility of the composition is insufficient, which is not desirable. The resin composition comprising (C) and (D) in which the masterbatch of the present invention is blended may optionally use (E) a crosslinking agent. Such a crosslinking agent comprises (E-1) a crosslinking initiator or (E-1) a crosslinking initiator and (E-2) a crosslinking assistant.

Here, the (E-1) crosslinking initiator preferably used includes a radical initiator such as an organic peroxide and an organic azo compound. Specific examples of 1,1-1-
Bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane,
1-bis (t-hexylperoxy) cyclohexane,
1,1-bis (t-butylperoxy) cyclododecane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl-4,4 Peroxy ketals such as -bis (t-butylperoxy) butane and n-butyl-4,4-bis (t-butylperoxy) valerate;
t-butyl peroxide, dicumyl peroxide,
t-butylcumyl peroxide, α, α′-bis (t
-Butylperoxy-m-isopropyl) benzene,
α, α'-bis (t-butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane and 2,5-dimethyl-
Dialkyl peroxides such as 2,5-bis (t-butylperoxy) hexine-3; acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5 Diacyl peroxides such as trimethylhexanoyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide and m-trioil peroxide; t-butylperoxyacetate, t-butylperoxyisobutyrate, t -Butylperoxy-2-ethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-di (benzoyl Peroxy Peroxyesters such as hexane, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, and cumylperoxyoctate; and t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide And 2,5-dimethylhexane-2,5-dihydroperoxide and 1,1,3,3-tetramethylbutyl peroxide.

Among these compounds, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl -2,5-bis (t-butylperoxy) hexane and 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 are preferred. These radical initiators are used in an amount of 0.02 to 3 based on 100 parts by weight of the composition comprising (C) and (D).
It is used in an amount of part by weight, preferably 0.05 to 1 part by weight. If the amount is less than 0.02 parts by weight, the crosslinking is insufficient, and if it exceeds 3 parts by weight, the physical properties of the composition are not improved, which is not preferable.

In the present invention, one of the crosslinking agents (E-2) of the crosslinking agent (E-2) includes divinylbenzene, triallyl isocyanurate, triallyl cyanurate, diacetone diacrylamide, polyethylene glycol diacrylate, and polyethylene. Glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, diisopropenylbenzene, P-quinone dioxime, P, P'-dibenzoylquinone Dioxime, phenylmaleimide, allyl methacrylate, N, N'-m-
Phenylene bismaleimide, diallyl phthalate, tetraallyloxyethane, 1,2-polybutadiene and the like are preferably used. These crosslinking aids may be used in combination of two or more.

These (E-2) crosslinking aids are used in an amount of 0.1 to 5 parts by weight, preferably 0.5 to 2 parts by weight, per 100 parts by weight of the composition comprising (C) and (D). Used in
If the amount is less than 0.1 part by weight, crosslinking is insufficient, and if it exceeds 5 parts by weight, the physical properties of the composition are not improved, and an excessive amount of a crosslinking aid remains, which is not preferable. The composition comprising (C) and (D), in which the masterbatch of the present invention is blended, may be blended with (F) a softening agent, if necessary, in order to improve workability.

The above (F) is preferably a paraffinic or naphthenic process oil. These are used for adjusting the hardness and flexibility of the composition in an amount of 5 to 500 parts by weight, preferably 1 to 500 parts by weight.
Use 0 to 150 parts by weight. If the amount is less than 5 parts by weight, flexibility and workability are insufficient, and if it exceeds 500 parts by weight, oil bleeding becomes remarkable, which is not desirable. Further, in order to produce a partially or completely crosslinked resin composition, a conventional resin composition, a Banbury mixer, a kneader, a single-screw extruder, a twin-screw extruder used for the production of an elastomer composition,
It is possible to adopt a general method such as In particular, a twin-screw extruder is preferably used to achieve dynamic crosslinking efficiently. The twin-screw extruder is used to uniformly and finely disperse an olefin-based elastomer and a propylene-based resin, and to add another component to cause a crosslinking reaction, thereby continuously producing the composition of the present invention. , More suitable.

As a preferred specific example, it can be manufactured through the following processing steps. That is, the masterbatch, the olefin-based elastomer and the propylene-based resin are mixed well and then charged into a hopper of an extruder. A crosslinking agent and a crosslinking aid may be added together with the olefin-based elastomer and the propylene-based resin from the beginning, or may be added in the middle of an extruder. The oil may be added from the middle of the extruder, or may be added separately at the beginning and during the middle. Part of the olefin elastomer and the propylene resin may be added in the middle of the extruder.
When heated and melted and kneaded in an extruder, the elastomer and the crosslinking agent and the crosslinking auxiliary undergo a crosslinking reaction, and after the oil and the like are added and melt-kneaded, the crosslinking reaction and kneading dispersion are sufficiently performed. By taking out from the extruder, it can be obtained as pellets. The composition obtained by blending the masterbatch of the present invention with a polymer can be used to produce various molded articles by any molding method. Injection molding, extrusion molding, compression molding, blow molding, calender molding, foam molding and the like are preferably used.

[0049]

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In these examples and comparative examples, the test methods used for evaluating various physical properties are as follows. (1) Average Particle Diameter of Component (B) The number average particle diameter of each particle was determined by an electron microscope, and was defined as the average particle diameter. That is, each particle is assumed to be a sphere, and the arithmetic average of the major axis and the minor axis is defined as the average diameter of each particle. And 100
The number average particle diameter was determined by arithmetic mean of the average diameters of the individual particles. (2) Tensile breaking strength [kgf / cm ² ] Evaluated at 23 ° C. according to JIS K6251. (3) Tensile elongation at break [%] Evaluated at 23 ° C. according to JIS K6251. (4) Abrasion resistance A molded body of surface grain was produced by injection molding, and then the abrasion resistance was evaluated using a Gakushin type abrasion tester. The evaluation conditions are as follows.

Temperature condition: 23 ° C. atmosphere Stroke: 120 mm Frequency: 1 round trip / 2 seconds Load: 1 kg Friction material: 100% cotton cloth Kanakin No. 3 (JIS L
0803)) Fold in three and attach. Contact area: 1 square cm. Evaluation is the number of times of friction reciprocation until disappearance of grain on the surface of molded article. (5) Feeling of touch (sensory test). The touch was evaluated for its dry feel (no stickiness) and whether or not a fingerprint mark was left on the surface of the molded article.

A: The feel is very good and smooth, and no fingerprint is left. ：: Fingerprint marks remain on the surface of the molded product, but no stickiness is felt. ×: Fingerprint marks remain, and there is a sticky feeling and a slimy feeling. (7) Extrusion stability (quality stability) Using a melt extruder, the resin composition is continuously melt-extruded for 10 hours, and the tensile rupture strength is measured from the composition obtained every hour, and the strength change. And evaluated the continuous productivity (quality stability). The difference between the 10-hour maximum and minimum tensile strength at break was used as an index of extrusion stability.

The following components were used in Examples and Comparative Examples. (A) Additive for polymer: polyorganosiloxane Polydimethylsiloxane having different kinematic viscosities at 25 ° C specified by JIS-K2410 manufactured by Shin-Etsu Chemical Co., Ltd. (Me
(B) Powder that does not melt at 250 ° C. Silica Commercially available silica (SiO ₂ ) was pulverized by a ball mill. At that time, SiO ₂ having different average particle diameters was produced by controlling the pulverization time. The surface treatment was performed by adding stearic acid at the time of ball mill pulverization while pulverizing.

No Surface treatment Average particle size (μm) SI-1 None 0.0005 SI-2 None 0.001 SI-3 None 0.15 SI-4 None 1.0 SI-5 None 10.0 SI-6 None 100.0 SI-7 None 100.0 SI-8 None 1050.0 SI-9 Existence 1.0

Calcium carbonate No commercial calcium carbonate surface treatment, average particle size 1.0
μm (referred to as CaCO ₃ ) (c) Ethylene / α-olefin copolymer Copolymer of ethylene and octene-1 (TPE-1) Produced by a method using a metallocene catalyst described in JP-A-3-1630088 did. The ethylene / octene-1 composition ratio of the copolymer is 72/28 (weight ratio).
(Referred to as TPE-1) Copolymer of ethylene and octene-1 (TPE-2) Produced by a method using a usual Ziegler catalyst. The ethylene / octene-1 composition ratio of the copolymer is 72/2.
8 (weight ratio). (Referred to as TPE-2)

Ethylene / propylene / dicyclopentadiene copolymer (TPE-3) This was produced by a method using a metallocene catalyst described in JP-A-3-1630088. The composition ratio of ethylene / propylene / dicyclopentadiene in the copolymer is 72/2.
4/4 (weight ratio). (D) Olefin resin polypropylene Nippon Polychem Co., Ltd., isotactic polypropylene (PP) (e) Paraffin oil Idemitsu Kosan Co., Ltd., Diana Process Oil PW-3
80 (referred to as MO) (f) Cross-linking agent: cross-linking initiator 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane (trade name: Perhexa 25B) manufactured by NOF Corporation (G) Cross-linking agent: cross-linking aid divinylbenzene (referred to as DVB) manufactured by Wako Pure Chemical Industries, Ltd.

[0056]

Examples 1 to 18 and Comparative Examples 1 to 7 The compositions shown in Tables 1 to 4 were mixed at 23 ° C. in a Henschel mixer to prepare a master batch (MB) (first stage), and then to the center of the barrel. Twin screw extruder (40mmφ, L / D
= 47) and the composition shown in Table 1 was melt-kneaded at a temperature of 200 ° C (second stage). As the screw, a double screw having a kneading portion before and after the injection port was used.
On the other hand, for comparison, all components were put into the twin-screw extruder without producing MB, and melt extrusion was performed under the same conditions.

From the composition thus obtained, 200
A sheet having a thickness of 2 mm was prepared by compression molding at ℃, and each mechanical property was evaluated. The results are shown in Tables 1 to 4.

[0058]

[Table 1]

[0059]

[Table 2]

[0060]

[Table 3]

[0061]

[Table 4]

According to Tables 1 to 4, the use of a powder that satisfies the requirements of the present application makes it possible to produce a high concentration MB because the polymer additive is absorbed or adsorbed at a high concentration. In addition, by using the MB of the present invention, not only excellent mechanical properties are exhibited, but also stable quality is maintained because the extrusion stability is improved. And especially as (C), produced using a metallocene-based catalyst,
It can be seen that the copolymer of ethylene and octene-1 imparts excellent mechanical strength.

[0063]

The masterbatch of the present invention allows for the inclusion of high viscosity additives, and such masterbatches are
Incorporation into a polymer not only allows for excellent mechanical strength, but also enables stabilization of quality in order to improve productivity. The composition obtained by using the masterbatch of the present invention has excellent mechanical properties, so that it is used for automobile parts, automobile interior materials, airbag covers, mechanical parts, electric parts, cables, and hoses. ,belt,
It can be widely used for toys, miscellaneous goods, daily necessities, building materials, sheets, films, and other applications, and plays a large role in the industrial world.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) C08L 101/16 C08L 101/00 F term (reference) 4F070 AA04 AA12 AA13 AA16 AC23 AC92 AE30 FA05 FA17 FB03 FC05 4J002 AC03W AC06W AC07W AC09W AC11W BB00X BB05W BB15W BC03X BD03X BG04W BG05X CF00X CG00X CH07X CL00X CN01X CP033 DJ016 FB236 FD173 FD206 GT00

Claims (5)

[Claims] (A) 25 ° C. specified in JIS-K2410
And a polymer additive having a kinematic viscosity of 5000 centistokes or more and (B) an average particle size of 0.001 to 1000
A master batch comprising a powder having a particle diameter of 250 μm and not melting at 250 ° C. 2. The masterbatch according to claim 1, wherein (A) is a polyorganosiloxane and (B) is silica. 3. A resin composition obtained by adding the masterbatch according to claim 1 to (C) a rubbery polymer and (D) a thermoplastic resin. 4. A method according to claim 1, wherein (C) is ethylene and α having 3 to 20 carbon atoms.
The resin composition according to claim 3, which is an ethylene / α-olefin copolymer composed of an olefin, wherein (D) is an olefin-based resin. 5. A resin composition obtained by partially or completely cross-linking the resin composition according to claim 3 or 4.