JP2003192909A - Thermoplastic resin composition and production method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition having improved properties such as improved sliding properties, and showing little silicone oil bleed-out, and to provide a production method therefor. <P>SOLUTION: This thermoplastic resin composition comprises (A) 100 pts.wt. of a thermoplastic resin, and (B) 0.01-300 pts.wt. of a silicone gel cross-linked by a hydrosilylation reaction, and having a 1/4 worked penetration (defined in JIS K 2220) of 5-200. The composition is manufactured by blending component (A) and component (B) in a heat-melted state. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition containing a silicone gel and a method for producing the same.
Further, the present invention relates to a thermoplastic resin composition containing a silicone gel, having no bleed-out of silicone oil, and excellent in slidability, and a method for producing the same.

[0002]

2. Description of the Related Art Silicone has been added to thermoplastic resins for the purpose of improving the slidability and impact resistance of thermoplastic resins, and preventing blocking. However, when polydimethylsiloxane or the like is simply added to the thermoplastic resin, it is difficult to mix it with the thermoplastic resin because the compatibility between the two is poor, or when the thermoplastic resin composition is molded or processed. Later, there was a problem that the uniformity of the surface was lost and the silicone component bleeded out. On the other hand, a method of blending cured silicone rubber particles with a thermoplastic resin (Japanese Patent Laid-Open No. 60-1273).
No. 67, JP-A-1-204959) are also proposed, but it is difficult to finely and uniformly disperse the silicone rubber particles in the thermoplastic resin by these methods, and kneading for a long time. There are problems that it takes time and that the properties such as mechanical properties and slidability of the resulting thermoplastic resin composition are not sufficiently improved.

In order to eliminate these drawbacks, for example,
A method in which a hydrosilylation-curable polyorganosiloxane composition is blended with a thermoplastic resin and cured in the thermoplastic resin (JP-A-58-189257, JP-A-3-189257).
(See Japanese Patent No. 41138 and Japanese Patent Laid-Open No. 3-41139)
A method of blending a polyorganosiloxane with a thermoplastic resin and a thermoplastic resin, and kneading by heating in the presence of a radical generating catalyst (Japanese Patent Publication No.
Japanese Patent Laid-Open No. 2-36898 and Japanese Patent Laid-Open No. 6-16824) have been proposed. However, as a result of the present inventor's study on the above technique, when the hydrosilylation reaction-curable polyorganosiloxane composition is blended into the thermoplastic resin composition, the polyorganosiloxane composition is heated by heating to melt the thermoplastic resin. It was found that the curing reaction of the product preferentially proceeded, and then the kneading started the dispersion of the polyorganosiloxane cured product in the thermoplastic resin. Therefore, in order to prepare a thermoplastic resin composition in which silicone cured particles having a sufficiently small particle size are dispersed, delicate temperature control, a strong kneading ability and a kneading step with a long residence time are required, which is economically difficult. Met. Since improvement of characteristics such as slidability strongly depends on this manufacturing condition, a simpler and more effective method has been demanded.

[0004]

The present inventors have completed the present invention as a result of intensive research to solve the above problems. That is, an object of the present invention is to provide a thermoplastic resin composition having improved properties such as slidability and free from bleed-out of silicone oil, and a method for producing the same.

[0005]

The present invention comprises (A) 100 parts by weight of a thermoplastic resin, (B) is crosslinked by a hydrosilation reaction, and has a 1/4 consistency (specified in JIS K2220) of 5 to 200. Production of a thermoplastic resin composition comprising 0.01 to 300 parts by weight of a certain silicone gel, and the above-mentioned thermoplastic resin composition characterized by kneading the heat-melted component (A) and component (B). Regarding the method.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic resin as the component (A) is
Although not particularly limited, for example, ethylene, propylene,
Polyethylene, a low density polyethylene, a high density polyethylene, an ultra high molecular weight polyethylene, a polypropylene, which is composed of a homopolymer or a copolymer of α-olefin such as 1-butene, 1-pentene, 1-hexene, and 4-methyl-1pentene. Ethylene / propylene copolymers, ethylene / vinyl acetate copolymers comprising these α-olefins and monomers other than α-olefins such as vinyl acetate, methyl methacrylate and maleic acid, ethylene / acrylic acid esters Olefin resins such as copolymers and ethylene / methacrylic acid ester copolymers; acrylic acid, methacrylic acid, methyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylcyclohexyl acrylate, phenyl acrylate, acrylic acid Benzyl, acrylic acid 2-hydro Acrylic esters such as cyethyl, glycidyl acrylate, diethylaminoethyl acrylate, etc., polyfunctional acrylates such as ethylene glycol diacrylate, trimethylolpropane triacrylate, neopentyl glycol diacrylate, methyl methacrylate, butyl methacrylate, methacrylic acid Methacrylic acid esters such as cyclohexyl, 2-ethylcyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, diethylaminoethyl methacrylate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, Homopolymerization of acrylic monomers such as polyfunctional methacrylates such as neopentyl glycol dimethacrylate Or copolymers, these acrylic monomers and styrene, styrene monomers such as α-methylstyrene, vinyl acetate, vinyl chloride, vinyl monomers such as vinylidene chloride, phenylmaleimide, cyclohexylmaleimide, anhydrous Acrylic resins such as copolymers with maleimide monomers such as maleimide; vinyl halide resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride; polystyrene, high impact polystyrene, acrylonitrile / Styrene resins such as butadiene / styrene copolymer (ABS resin), acrylonitrile / styrene copolymer, acrylonitrile / acrylic rubber / styrene copolymer, acrylonitrile / ethylene propylene rubber / styrene copolymer; polyethylene terephthalate, polybutyle Terephthalate, polyethylene naphthalate, polyethylene terephthalate / isophthalate, polybutylene terephthalate / isophthalate polyester resin; nylon 6, nylon 66, nylon 6
/ 66, nylon 6/12, nylon 610, nylon 612, nylon 11, nylon 12 and other polyamide resins; polyvinyl alcohol resins; polyacetal and other polyoxyalkylene resins; polycarbonate resins; polyvinyl acetate resins; polysulfone -Based resin; polyether sulfone-based resin; polyarylene sulfide-based resin such as polyphenylene sulfide; polyarylate-based resin; polyimide-based resin; polyamide-imide-based resin; polyetherimide-based resin; polyether-ether-ketone-based resin; liquid crystal polyester-based Resin: Fluorine-based resin such as polytetrafluoroethylene, ethylene / tetrafluoroethylene copolymer; Styrene-based elastomer,
Olefin-based elastomer, urethane-based elastomer,
Examples include thermoplastic elastomer resins such as fluorine-based elastomers, vinyl chloride-based elastomers, polyamide-based elastomers, polyester-based elastomers; and mixtures or copolymers of two or more of these thermoplastic resins.

The preferred component (A) is a vinyl resin or a vinyl chloride thermoplastic elastomer. Here, the vinyl resin is a vinyl polymer or a vinyl copolymer obtained by an addition polymerization reaction of a vinyl compound, and is an olefin resin, an acrylic resin, a vinyl halide resin, a styrene resin, Examples are polyvinyl alcohol-based resins and polyvinyl acetate-based resins. Among them, particularly preferable vinyl resin is olefin resin or acrylic resin.

The component (B) is a silicone gel containing polyorganosiloxane as a main component, which is partially transformed into a three-dimensional network structure by cross-linking, and which is in a state of being deformed and having a limited fluidity due to the application of stress. It is prepared by crosslinking a silicone gel composition that is crosslinkable. The hydrosilylation reaction crosslinkable silicone gel composition comprises (b-1) 100 parts by weight of an alkenyl group-containing polyorganosiloxane, (b-2) a silicon atom-bonded hydrogen atom-containing polyorganosiloxane, and {(b-2) Amount in which the ratio of the number of moles of silicon-bonded hydrogen atoms to the number of moles of alkenyl groups in component (b-1) is (20: 1) to (1:20)} and (b-3) hydrosilylation reaction A composition comprising at least a catalyst (catalyst amount) for use.

The alkenyl group-containing polyorganosiloxane (b-1) is a main component for preparing the component (B), and its molecular structure is linear, partially branched linear, or branched. Examples of the ones, annular ones, resin-like ones,
In particular, a straight chain or a straight chain having a partially branched chain is preferable. Examples of the alkenyl group in this polyorganosiloxane include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group.
It is preferably a vinyl group. Examples of the silicon atom-bonded group other than the alkenyl group in this polyorganosiloxane include alkyl groups such as methyl group, ethyl group, and propyl group; aryl groups such as phenyl group, tolyl group, and xylyl group; benzyl group, phenethyl group. Aralkyl groups such as groups;
Substituted or unsubstituted monovalent hydrocarbon groups such as halogenated alkyl groups such as 3,3,3-trifluoropropyl group; alkoxy groups such as methoxy group, ethoxy group and propoxy group; Group, phenyl group,
It is preferably a 3,3,3-trifluoropropyl group. Specific examples of this component include polydimethylsiloxane capped with dimethylvinylsiloxy groups at both ends, dimethylsiloxane-methylvinylsiloxane copolymer capped with dimethylvinylsiloxy groups at both ends, and dimethylsiloxane-methylvinylsiloxane capped with trimethylsiloxy groups at both ends. Polymer, dimethylvinylsiloxy group-blocked dimethylsiloxane / methylphenylsiloxane copolymer at both ends,
Examples thereof include polyorganosiloxane resins composed of trimethylsiloxy groups or dimethylvinylsiloxy units and SiO4 / 2 units.

The component (b-1) preferably contains two or more alkenyl groups in one molecule, and repeats of an alkenyl group-free organosiloxane unit existing between the alkenyl group-containing organosiloxane units. The number is preferably in the range of 1 to 800, particularly 1 to 4
It is preferably in the range of 00. This is because the dispersibility of the component (B) in the thermoplastic resin becomes good.

(B-2) The silicon atom-bonded hydrogen atom-containing polyorganosiloxane is a cross-linking agent obtained by the hydrosilylation reaction of the component (b-1), and its molecular structure is straight or partially branched. Examples thereof include chain-like, branched chain-like, cyclic, and resin-like ones, with straight-chain or partially-branched straight-chain ones being particularly preferable. (B-
The component 2) preferably has at least two silicon-bonded hydrogen atoms in one molecule. Examples of the silicon atom-bonded group other than hydrogen atom in component (b-2) include alkyl groups such as methyl group, ethyl group and propyl group; aryl groups such as phenyl group, tolyl group and xylyl group; benzyl group and phenethyl group. Groups such as aralkyl groups; substituted or unsubstituted monovalent hydrocarbon groups such as halogenated alkyl groups such as 3,3,3-trifluoropropyl group; alkoxy groups such as methoxy group, ethoxy group, propoxy group; Examples thereof are preferred, and a methyl group, a phenyl group, and a 3,3,3-trifluoropropyl group are particularly preferred. Specific examples of these components include polydimethylsiloxane capped with dimethylhydrogensiloxy groups at both ends, methylhydrogenpolysiloxane capped with trimethylsiloxy groups at both ends,
Both ends trimethylsiloxy-blocked dimethylsiloxane-methylhydrogensiloxane copolymer, both ends dimethylphenylsiloxy-blocked methylphenylsiloxane-
Examples thereof include methyl hydrogen siloxane copolymers, cyclic methyl hydrogen polysiloxanes, and copolymers composed of dimethyl hydrogen siloxane units and SiO4 / 2 units.

In the component (b-2), the ratio of the number of moles of silicon atom-bonded hydrogen atoms in the component (b-2) to the number of moles of the alkenyl group in the component (b-1) is (20: 1). ~ (1: 2
It is preferable to mix with the component (b-1) in a ratio of 0). In particular, the above ratio is (10: 1) to (1.1:
1) or (1: 1.1) to (1:10) is more preferable. By blending both components so that the alkenyl group in the component (b-1) and the silicon atom-bonded hydrogen atoms in the component (b-2) do not become equimolar, an alkenyl group or silicon as an unreacted residual group is obtained. (B) Silicone gel having an atom-bonded hydrogen atom can be prepared. In this case, the unreacted alkenyl group or silicon atom-bonded hydrogen atom in the component (B) is
Since it functions as a functional group that chemically bonds with the component (A),
It is suitable for preventing bleed-out of the silicone oil component.

Examples of the catalyst for hydrosilylation reaction (b-3) include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts, and in particular, platinum-based catalysts because the hydrosilylation reaction proceeds smoothly. It is preferable. As the platinum-based catalyst, chloroplatinic acid, an alcohol solution of chloroplatinic acid, and an olefin complex of platinum. An alkenyl siloxane complex of platinum is exemplified. The amount of the hydrosilylation reaction catalyst to be blended may be an amount sufficient to crosslink the hydrosilylation reaction-crosslinkable silicone gel composition. Specifically, as the hydrosilylation reaction catalyst, a platinum-based catalyst may be used. When used, the amount of platinum metal is preferably 0.1 to 100 ppm with respect to the total amount of the above-mentioned alkenyl group-containing polyorganosiloxane and silicon atom-bonded hydrogen atom-containing polyorganosiloxane, and particularly preferably Since the hydrosilylation reaction proceeds smoothly and the resulting silicone gel is less likely to be colored, the amount is preferably in the range of 1 to 50 ppm.

In order to improve the handling workability, the above-mentioned hydrosilylation-crosslinking silicone gel composition contains 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyne-3. -Ol, 3-phenyl-1
-Acetylenic compounds such as butyn-3-ol; 3-methyl-3-penten-1-yne, 3,5-dimethyl-3
-Enyne compounds such as hexen-1-yne; 1,3
Cycloalkenyl siloxanes such as 5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane and 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane A hydrosilylation reaction inhibitor such as a triazole compound such as benzotriazole may be blended. The blending amount of these hydrosilylation reaction inhibitors is preferably 0.001 to 5 parts by weight with respect to 100 parts by weight of the component (b-1).

The above hydrosilylation reaction-crosslinkable silicone gel composition may also contain other components such as dry silica fine powder, wet silica fine powder, quartz fine powder, and calcium carbonate, as long as the object of the present invention is not impaired. Fine powder, titanium dioxide fine powder, diatomaceous earth fine powder, aluminum oxide fine powder, aluminum hydroxide fine powder, zinc oxide fine powder,
Inorganic fillers such as zinc carbonate fine powder, or surfaces of these inorganic fillers such as methyltrimethoxysilane, vinyltrimethoxyethoxysilane and other organoalkoxysilanes; trimethylchlorosilane and other organohalosilanes;
Organosilazanes such as hexamethyldisilazane; siloxane oligomers such as dimethyl siloxane oligomers having hydroxyl groups blocked at both molecular chain ends, methylphenyl siloxane oligomers having hydroxyl groups blocked at both molecular chain terminals, higher fatty acids, or A surface-treated inorganic filler surface-treated with a metal salt or the like may be added.

The silicone gel composition is prepared by uniformly mixing the above-mentioned components (b-1) to (b-3). The silicone gel composition of the present invention has the above (b-1)
Having a component and a component (b-3) and not having the component (b-2) described above, and the component (b-1) and the component (b-2) described above, Two-component type comprising the composition (II) having no component (b-3) above (the component (b-1) above may be incorporated in any composition. }, And uniformly mix just before use. The above hydrosilylation reaction crosslinkable silicone gel composition,
It is also possible to store it as a one-pack type, but by making it a two-pack type as described above, it is possible to prevent unintended progress of crosslinking, and it is also possible to prevent a decrease in crosslinkability that occurs during storage. is there.

The component (B) is a 1/4 consistency (JIS
K 2220) is 5 to 200, preferably 5 to 100, and more preferably 10 to 100. Below the lower limit of the above range, the component (B) cannot be sufficiently miniaturized in the component (A), and therefore the dispersed particle size of the component (B) in the component (A) becomes large, and the thermoplastic resin of the present invention This is because the physical properties of the composition are deteriorated or the properties such as slidability are not sufficiently improved. On the other hand, when the content exceeds the upper limit of the above range, it becomes difficult to blend the component (B) into the component (A), the dispersed particle size of the component (B) in the component (A) becomes large, and the silicone oil There are disadvantages such as increased bleed-out of the components and loss of surface uniformity of the resin composition.

The mixing ratio of the component (A) and the component (B) is
The component (B) is 0.01 to 100 parts by weight of the component (A).
The amount is 300 parts by weight, preferably 0.01 to 100 parts by weight, and more preferably 0.1 to 50 parts by weight.
If the blending amount of the component (B) is less than the lower limit of the above range, the effect of improving the desired properties is small, while if the blending amount exceeds the upper limit of the above range, the mechanical properties inherent to the thermoplastic resin (A) deteriorate. It is not preferable because such problems occur. When using the thermoplastic resin composition of the present invention as a masterbatch,
The amount of component (B) compounded is preferably 5 parts by weight or more. The mixing ratio of the (A) component and the (B) component is
It is appropriately selected depending on the type of the thermoplastic resin as the component (A). That is, in consideration of the compatibility between the component (A) and the component (B) and the like, there is an optimum range according to the type of the thermoplastic resin as the component (A).

In the present invention, if necessary,
A known radical generator such as an organic peroxide may be added during the kneading of the components (A) and (B). In particular,
t-butyl peroxyisopropyl carbonate, t-
Butyl peroxylaurate, 2,5-dimethyl-2,
5-di (benzoylperoxy) hexane, t-butylperoxyacetate, di-t-butyldiperoxyphthalate, t-butylperoxymaleic acid, cyclohexanone peroxide, t-butylperoxybenzoate, dicumyl peroxide, 2,5-dimethyl- Two
5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, t-butylhydroperoxide,
Di-t-butyl peroxide, 2,5-dimethyl-2,
5-di (t-butylperoxy) hexyne-3, di-isopropylbenzene hydroperoxide, p-menthane hydroperoxide, 2,5-dimethylhexane-2,
Examples thereof include organic peroxides such as 5-dihydroperoxide; azo compounds such as azobisisobutyronitrile.

The method for preparing the thermoplastic resin composition of the present invention is not particularly limited. For example, after the components (A) and (B) are mixed in advance by a mixing device such as a Henschel mixer, A method of kneading the mixture while melting the component (A) with a kneading device such as a kneader mixer, a Banbury mixer, a single-screw kneading extruder, or a twin-screw kneading extruder, and supplying both components to the kneading device at the same time (A)
Examples include a method of kneading while melting the components, and a method of supplying the component (B) to the component (A) heated and melted in the above kneading device and kneading. In some cases, the solvent may be removed after the component (A) and / or the component (B) are dissolved and mixed in an appropriate solvent.

A uniaxial extruder, a gear pump or the like can be used to supply the component (B) to the above kneading apparatus, but the hydrosilylation-crosslinking silicone gel composition is continuously kneaded by such a uniaxial kneading extruder. It is also possible to supply the silicone gel (B) to the above kneading apparatus while continuously forming it by heating and kneading in a machine. At this time,
If a continuous kneading machine such as a single-screw kneading extruder or a twin-screw kneading extruder is used for kneading with the component (A), the thermoplastic resin composition of the present invention can be continuously produced, which is efficient.

In the method for producing a thermoplastic resin composition of the present invention, it is preferable that the component (B) is supplied to the kneading device as a granule or agglomerate having an average particle diameter of 100 μm or more and kneaded with the component (A). This is because when the average particle diameter of the component (B) is less than 100 μm, the component (B) easily sticks and adheres to the kneading device or the conveying device, or particles are aggregated with each other, so that the thermoplastic resin composition This is because the handling workability during manufacturing may deteriorate.

(B) in the thermoplastic resin composition of the present invention
The dispersed particle size of the component is preferably 100 μm or less, more preferably 10 μm or less. This is because if the dispersed particle size exceeds this value, the adhesive property of the component (B) is likely to be exhibited on the surface of the molded product, and the slidability is likely to decrease. Also,
A part of the component (B) may be bonded to the component (A) by a graft reaction by a radical generated during melt-kneading of the component (A) or a radical derived from a radical generator separately blended.

In the preparation of the thermoplastic resin composition of the present invention, glass fibers, carbon fibers, thermoplastic resin fibers, graphite, mica, talc, silica fine powder or the like reinforcing agents or fillers, lubricants and the like are molded. Stabilizers such as processability improvers, weather resistance agents, light resistance agents, antioxidants, UV inhibitors, flame retardants,
Conventional additives such as antistatic agents, colorants such as pigments, surfactants, antibacterial agents and the like can be added within a range that does not impair the effects of the present invention.

The thermoplastic resin composition of the present invention can be applied to various molding means such as injection molding, extrusion molding, compression molding and blow molding, and the thermoplastic resin composition of the present invention can be used as a masterbatch. As the above, it is possible to use the above-mentioned various molding means together with the thermoplastic resin. The molded product thus obtained is excellent in various properties such as lubricity, slidability, moldability, and water repellency. Moreover, there is no bleed-out or separation of the silicone oil component, the surface uniformity is maintained, and the appearance is good. Since it has the feature of being present, it can be widely expected to be applied to various uses.

[0026]

EXAMPLES The present invention will be described in detail below with reference to examples.
In Examples and Comparative Examples, the viscosity is a measured value at 25 ° C. Various characteristics were measured by the following methods. [Williams Plasticity of Silicone Gum] Sample 4.2 g
Was sandwiched between two pieces of cellophane and set on a Williams plasticity meter (manufactured by Kamijima Seisakusho). A load of 5 kg was applied to this, and the thickness (mm) after 3 minutes elapsed was measured, and the "Williams plasticity" was determined by the following formula. Williams plasticity (mm × 100) = thickness of sample after 3 minutes (mm) × 100 [1/4 consistency of silicone gel] JIS K 22
The measurement was performed according to the method specified in 20. [Dispersion Particle Size of Silicone in Thermoplastic Resin Molded Product] The thermoplastic resin composition was cooled in liquid nitrogen and cut with a microtome, and the cut surface was analyzed by SEM-XMA,
The dispersed particle size of the silicone gel was measured. [Graft reaction rate] 2 g of a thermoplastic resin sample was cut into about 1 mm square, placed in a round bottom flask equipped with a reflux machine, 100 g of hexane was added thereto, and the mixture was heated under reflux for 1 hour. The hexane insoluble matter was filtered off, transferred to a glass dish and heated to 60 ° C. to remove hexane. Then, it was weighed to obtain the hexane extraction rate. From the hexane extraction rate and the total polyorganosiloxane content in the sample, the graft reaction rate was calculated as follows. Grafting reaction rate = (total polyorganosiloxane content in sample−hexane extraction rate) × 100 / content of total polyorganosiloxane in sample [surface condition of molded article] Thermoplastic resin composition is compression molded at 180 ° C. Then, a sheet having a thickness of 2 mm was prepared. The surface of this sheet was observed with the naked eye, and its uniformity and exudation of polyorganosiloxane were observed. The observation results are displayed as follows. ◯: The surface was uniform, and the polyorganosiloxane did not exude. Δ: Although the surface was uniform, exudation of polyorganosiloxane was observed. X: The surface was non-uniform, and exudation of polyorganosiloxane was observed. [Dynamic Friction Coefficient of Thermoplastic Resin Composition] A disk-shaped molded piece of a thermoplastic resin composition using an injection molding machine (manufactured by Yamashiro Seisakusho), and a cylindrical molded piece made of a base resin of the thermoplastic resin composition. Were produced respectively. The dynamic friction coefficient between the obtained disk-shaped molded piece and the end surface of the cylindrical molded piece was measured using a thrust friction wear tester (manufactured by Toyo Seiki Co., Ltd.).
At this time, the friction area was set to 2 cm ² , the load was set to 2 kg weight, and the friction coefficient was determined from the value at 5 minutes after the start of measurement at a speed of 10 cm / sec.

Reference Example [Silicone Gels 1 to 4, Silicone Rubber] (a): Polydimethylsiloxane with a viscosity of 127 mPa · s and a dimethylhydrogensiloxy group blocked at both ends of the molecular chain.
(Content of silicon-bonded hydrogen atoms = 0.025% by weight,
Me ₂ SiO continuous repeating number: 100 on average) (b): A dimethylsiloxane / methylhydrogensiloxane copolymer with a trimethylsiloxy group blocked at both molecular chain ends with a viscosity of 50 mPa · s (content of hydrogen atoms bonded to silicon atom = 0. 31% by weight, the number of Me ₂ SiO continuous repeats: 3 on average), (c): Polydimethylsiloxane blocked with dimethylvinylsiloxy groups at both molecular chain terminals having a viscosity of 90 mPa · s (vinyl group content = 0.97% by weight, Me ₂ SiO continuous repetition number: mean 73 pieces), (d): at both molecular chain terminals by trimethylsiloxy viscosity 33 mPa · s siloxy group dimethylsiloxane-methylvinylsiloxane copolymer (vinyl group content = 8.0 wt%, Me ₂
The number of continuous repetitions of SiO: average 3) was blended in a blending amount shown in Table 1, and platinum of 1,3-divinyltetramethyldisiloxane of 5 ppm as platinum metal was added to all polyorganosiloxane. After mixing the isopropyl alcohol solution of the complex, 200
100 g of the mixture was placed in a ml beaker, deaerated, and then left at room temperature for 1 day to prepare Silicone gel 1 to Silicone gel 4 and silicone rubber. Table 1 shows the 1/4 consistency of each. The silicone rubber of Reference Example 5 was crushed and then granulated after curing. The particle size was 0.1 mm to 5 mm in diameter.

[0028]

[Table 1]

[0029]

Example 1 20 g of polypropylene (PP) resin [J-105P manufactured by Grand Polymer Co., Ltd.] was placed in a Labo Plastomill (manufactured by Toyo Seiki), and heated and kneaded at 210 ° C. and 100 rpm to be melted, and subsequently, Then, 10 g of the massive silicone gel 4 prepared in Reference Example 4 was added,
After kneading at 100 rpm for 10 minutes, the mixture was taken out and cooled to obtain a thermoplastic resin composition. Next, place Lapoplast Mill (made by Toyo Seiki) in polypropylene (P
P) Resin [Nobren Y101 manufactured by Sumitomo Chemical Co., Ltd.] 24
g and 6 g of the obtained thermoplastic resin composition were charged, and 210
The mixture was heated and kneaded for 5 minutes at a temperature of 100 rpm to prepare a diluted thermoplastic resin composition. With respect to the thermoplastic resin composition thus obtained and the diluted product of the thermoplastic resin composition, the above-mentioned various properties were examined, and the results are shown in Table 2.

[0030]

[Comparative Example 1] A polypropylene (PP) resin [J-made by Grand Polymer Co., Ltd.
105P] 30 g was charged and heated and kneaded at 210 ° C. and 100 rpm to melt. Further 210
After kneading for 10 minutes at a temperature of 100 rpm, the mixture was taken out and cooled. Various characteristics of the obtained thermoplastic resin were examined in the same manner as in Example 1. The results are shown in Table 2.

[0031]

Comparative Example 2 A thermoplastic resin composition and a thermoplastic resin composition were prepared in the same manner as in Example 1 except that 10 g of a silicone gum having a Williams plasticity of 160 (polydimethylsiloxane endcapped with trimethylsiloxy groups at both ends) was used in place of the silicone gel 4. , A dilution of the thermoplastic resin was prepared. For these, various characteristics were examined in the same manner as in Example 1, and the results are shown in Table 2.

[0032]

[Comparative Example 3] Instead of Silicone Gel 4, a vinyl group-containing silicone gum having a Williams plasticity of 160 (a dimethylvinylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer having both ends terminated with 0.14 mol% of methylvinylsiloxane units). )} Was used in the same manner as in Example 1 to prepare a thermoplastic resin composition and a diluted thermoplastic resin. Regarding these, Example 1
Various characteristics were examined in the same manner as in, and the results are shown in Table 2.

[0033]

Comparative Example 4 A thermoplastic resin composition and a diluent of the thermoplastic resin were prepared in the same manner as in Example 1 except that 10 g of the silicone rubber powder prepared in Reference Example 5 was used instead of the silicone gel 4. Prepared. For these, various characteristics were examined in the same manner as in Example 1, and the results are shown in Table 2.

[0034]

[Comparative Example 5] 20 g of polypropylene (PP) resin [J-105P manufactured by Grand Polymer Co., Ltd.] was put into a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) and melted by heating and kneading at 210 ° C. and 100 rpm. , (C) Viscosity 90m
Pa · s molecular chain both ends dimethylvinylsiloxy group-capped polydimethylsiloxane (vinyl group content = 0.97% by weight, Me ₂ SiO continuous repeating number: 73 on average) 9.5
g and (b) Copolymer of dimethylsiloxy-methylhydrogensiloxane with trimethylsiloxy groups blocked at both ends of the molecular chain with a viscosity of 50 mPa · s (content of silicon atom-bonded hydrogen atoms = 0.31% by weight, Me ₂ SiO continuous repeat number) :
0.5 g was added (average of 3 pieces). Even after 20 minutes of kneading, the polypropylene resin and the polyorganosiloxane component were not uniform. In addition, the amount of platinum metal, which is 5 ppm, of the blended polyorganosiloxane is 1.
When an isopropyl alcohol solution of a platinum complex of 3-divinyltetramethyldisiloxane was added, the polyorganosiloxane component rapidly hardened in a lump in Labo Plastomill, and a uniform thermoplastic resin composition sample could not be obtained. It was

[0035]

[Table 2]

[0036]

[Example 2] 20 g of polyethylene (LLDPE) resin [Sumikasen L-GA-701 manufactured by Sumitomo Chemical Co., Ltd.] was put into Labo Plastomill (manufactured by Toyo Seiki), and 220 ° C.
It was heated and kneaded under the condition of 100 rpm to be melted. Next, 10 g of the silicone gel 2 prepared in Reference Example 2 was added to this.
After blending and kneading at 220 ° C. and 100 rpm for 5 minutes, 0.01 g of a radical generator [Kayahexa AD-40C {2,5-dimethyl-2,5-bis (t-butyl) manufactured by Kayaku Akzo Co., Ltd.] [A mixture of peroxy) hexane] and calcium silicate powder] was added, and the mixture was further kneaded for 5 minutes under the same conditions, taken out, and cooled to prepare a thermoplastic resin composition. Next, 24 g of polyethylene (LLDPE) resin [Sumikasen L-GA-701 manufactured by Sumitomo Chemical Co., Ltd.] and 6 g of this thermoplastic resin composition were charged into a Labo Plastomill (manufactured by Toyo Seiki) and kneaded at 210 ° C. for 5 minutes Then, a dilution of the thermoplastic resin was prepared. Various properties of the thus obtained thermoplastic resin composition and the diluted thermoplastic resin composition were examined in the same manner as in Example 1, and the results are shown in Table 3.

[0037]

Example 3 A thermoplastic resin composition and a diluent for the thermoplastic resin composition were prepared in the same manner as in Example 2 except that 10 g of the silicone gel 3 prepared in Reference Example 3 was used in place of the silicone gel 2. Prepared. For these, various characteristics were examined in the same manner as in Example 1, and the results are shown in Table 3.

[0038]

Example 4 A thermoplastic resin composition and a dilution of the thermoplastic resin composition were prepared in the same manner as in Example 2 except that 10 g of the silicone gel 1 prepared in Reference Example 1 was used instead of the silicone gel 2. Prepared. For these, various characteristics were examined in the same manner as in Example 1, and the results are shown in Table 3.

[0039]

[Comparative Example 6] 30 g of polyethylene (LLDPE) resin [Sumikasen L-GA-701 manufactured by Sumitomo Chemical Co., Ltd.] was placed in Labo Plastomill (manufactured by Toyo Seiki) at 220 ° C.
It was heated and kneaded under the condition of 100 rpm to be melted. Further, this was kneaded at 220 ° C. and 100 rpm for 10 minutes, then taken out and cooled. Various properties of the obtained thermoplastic resin were examined in the same manner as in Example 1, and the results are shown in Table 3.

[0040]

[Comparative Example 7] Instead of the silicone gel 2, a vinyl group-containing silicone gum having a Williams plasticity of 160 (polydimethylsiloxane with both ends dimethylvinylsiloxy group-blocked polydimethylsiloxane.
A thermoplastic resin composition and a dilution of the thermoplastic resin were prepared in the same manner as in Example 2 except that 10 g of methylvinylsiloxane copolymer (0.14 mol% of methylvinylsiloxy units)} was used. For these, various characteristics were examined in the same manner as in Example 1, and the results are shown in Table 3.

[0041]

Comparative Example 8 A thermoplastic resin composition and a diluent of the thermoplastic resin were prepared in the same manner as in Example 2 except that 10 g of the silicone rubber powder prepared in Reference Example 5 was used instead of the silicone gel 2. . For these, various characteristics were examined in the same manner as in Example 1, and the results are shown in Table 3.

[0042]

[Table 3]

[0043]

[Example 5] (c) Polydimethylsiloxane capped with dimethylvinylsiloxy groups at both ends of a molecular chain having a viscosity of 90 mPa · s
(Vinyl group content = 0.97% by weight, Me ₂ SiO continuous repetition number: 73 on average) 100 parts of an isopropyl alcohol solution of a platinum complex of 1,3-divinyltetramethyldisiloxane gives 10 ppm as platinum metal. Silicone gel composition (I)
Was prepared. Next, (c) a polydimethylsiloxane endblocked by dimethylvinylsiloxy groups at both molecular chain ends having a viscosity of 90 mPa · s (vinyl group content = 0.97% by weight, Me ₂ Si
O repeat number: 73 on average) (b) Viscosity of 50 mPa · s Molecular chain both ends trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer (content of silicon-bonded hydrogen atom = 0.3
1% by weight, continuous number of Me ₂ SiO repeated: average of 3) 9.
Silicone gel composition (II) was prepared by mixing 7 parts with 7 parts until uniform. Next, the silicone gel composition (I)
And a silicone gel composition (II) were mixed at a mixing ratio of 1: 1 using a static mixer and heated to 150 ° C., a single-screw extruder (UT-25-T manufactured by Japan Plastics Engineering Laboratory Co., Ltd.). Was fed at a rate of 12 kg / hr. Since the mixture of the silicone gel composition is cross-linked in a single-screw extruder to form a silicone gel, it is formed into an amorphous lump in a twin-screw kneading extruder {manufactured by Toshiba Machine Co., Ltd., TEM.
It had a barrel portion of 48; 12 and L / D (length / caliber) of 48} was supplied to a third barrel at a rate of 12 kg / hr. From the first barrel of the twin-screw kneading extruder, polypropylene (PP) resin [J-105 manufactured by Grand Polymer Co., Ltd.
P] was supplied at a rate of 24 kg / hr. The barrel temperature of the twin-screw kneading extruder was adjusted so that the first barrel part, the second barrel part, and the third barrel part were 100 ° C., and the fourth barrel part to the twelfth barrel part were 210 ± 4 ° C. As for the screw arrangement, the first barrel portion, the third barrel portion, and the twelfth barrel portion had a feed screw arrangement, and the other barrel portions all had a kneading screw arrangement. The obtained mixture was extruded from a die having 6 holes with a diameter of 4.5 mm installed at the discharge port, and this was left to cool at room temperature to obtain a thermoplastic resin composition.
The dispersed particle size of the silicone gel in the obtained thermoplastic resin composition is 5 to 20 μm, and the graft reaction rate is 40.
%, The surface condition of the thermoplastic resin composition was smooth, and the exudation of the silicone component was not observed, and the coefficient of dynamic friction was 0.10.

Continued front page    (72) Inventor Koji Shiromoto             2-2 Chikusaigan, Ichihara-shi, Chiba Toray Dow             Corning Silicone Co., Ltd. R & D             In headquarters F-term (reference) 4F070 AA12 AB09 AC92 AE09 FA03                       FA17 FB06 FC06 GA01 GA05                       GB10                 4J002 AA01W BB02W BB06W BB07W                       BB11W BB15W BB17W BC02W                       BC06W BC09W BD03W BD10W                       BD13W BD14W BD15W BE02W                       BF02W BG01W BG04W BG05W                       BG07W BH02W BN15W CB00W                       CF06W CF07W CF08W CF16W                       CG00W CH09W CL01W CL03W                       CL05W CM04W CN01W CN03W                       CP03X CP04X CP12X DA116                       DD076 EK017 EK037 EK057                       EK067 EK087 ET007 FA08X                       FD010 FD147 FD156

Claims (10)

[Claims] 1. (A) 100 parts by weight of a thermoplastic resin, (B) 1/4 Consistency (JIS K 22) crosslinked by hydrosilylation reaction 20 to 50) Silicone gel 0.01 to 300 parts by weight A thermoplastic resin composition comprising: 2. The component (B) is (b-1) 100 parts by weight of an alkenyl group-containing polyorganosiloxane, (b-2) a silicon atom-bonded hydrogen atom-containing polyorganosiloxane {the silicon atom in the component (b-2). Amount in which the ratio of the number of moles of bonded hydrogen atoms to the number of moles of alkenyl groups in the component (b-1) is (20: 1) to (1:20)} and (b-3) catalyst for hydrosilylation reaction The thermoplastic resin composition according to claim 1, which is a cross-linked product of a silicone gel composition comprising (amount of catalyst). 3. The component (B) is a silicone gel having a hydrogen atom bonded to an unreacted silicon atom, or an unreacted alkenyl group-containing organic group.
The thermoplastic resin composition according to claim 1 or 2. 4. The thermoplastic resin composition according to claim 1, wherein the component (A) is a vinyl resin. 5. The heat according to claim 1, wherein the component (B) in the component (A) has a dispersed average particle diameter of 0.01 to 100 μm. Plastic resin composition 6. The method for producing a thermoplastic resin composition according to claim 1, wherein the heat-melted component (A) and component (B) are kneaded. 7. The method for producing a thermoplastic resin composition according to claim 6, wherein the component (B) is a granular material or an agglomerate having an average particle diameter of 100 μm or more. 8. The method for producing a thermoplastic resin composition according to claim 6 or 7, wherein a radical generator is further added when the components (A) and (B) are kneaded. 9. A hydrosilylation-reactive crosslinkable silicone gel composition is continuously crosslinked, and this is continuously supplied as a component (B) to a kneading machine and kneaded with the component (A). A method for producing the thermoplastic resin composition according to any one of claims 6 to 8. 10. The method for producing a thermoplastic resin organism according to claim 9, wherein the kneading device is a twin-screw kneading extruder.