JP3499646B2 - Polyolefin resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyolefin resin composition, and more particularly to a polyolefin resin composition having excellent impact resistance and blocking resistance.

[0002]

2. Description of the Related Art Polyolefin resins are used as various molding materials because of their excellent moldability, processability and chemical resistance. They also have a high softening point, good transparency and water vapor shielding properties. Therefore, it is used as various packaging materials. However, polyolefin resin has poor impact resistance, and it is unstretched or
There has been a problem that the film is apt to block during the production or processing of the axially stretched single-layer or multi-layer film. For this purpose, for example, a polyolefin resin composition blended with powdery polymethylsilsesquioxane (see JP-A-50-151949 and JP-A-54-57551) or a polyolefin blended with powdered silicone rubber. Resin composition (JP-A-60-1)
No. 27367 and Japanese Patent Laid-Open No. 4-366148) are proposed.

However, since powdery polymethylsilsesquioxane and powdery silicone rubber have a poor affinity with the polyolefin resin, it is difficult to uniformly disperse them in the polyolefin resin, and the obtained polyolefin resin composition has There is a problem that the impact resistance is not sufficiently satisfactory. Further, a film made of such a polyolefin resin has a problem that the powdery silicone cured product falls off from the surface thereof, and thus the blocking resistance is not sufficiently satisfactory. In particular, a film made of a polyolefin resin composition containing a powdery polymethylsilsesquioxane has a problem that the surface of the film tends to be scratched by sliding.

[0004]

The present inventors have arrived at the present invention as a result of extensive studies on the above problems. That is, an object of the present invention is to provide a polyolefin resin composition having excellent impact resistance and blocking resistance.

[0005]

Means for Solving the Problem and Its Action The present invention provides (I) 100 parts by weight of a polyolefin resin and (II) a silicon atom-bonded alkyl group having 5 or more carbon atoms and an average particle size of 0.1 to 200 μm. 0.01 to 100 parts by weight of a powdered silicone cured product or (III) a group consisting of a silicon atom-bonded alkyl group having 5 or more carbon atoms and an acryl group, an epoxy group, a mercapto group, an amino group, a chloroalkyl group and an alkenyl group. A polyolefin resin composition comprising 0.01 to 100 parts by weight of a powdery silicone cured product having an average particle diameter of 0.1 to 200 μm and having at least one group selected from

The polyolefin resin as the component (I) is not limited, and examples thereof include ethylene, propylene, 1-butene and 1-butene.
Homopolymers of α-olefins such as pentene, 1-hexene, 4-methyl-1-pentene, copolymers of these α-olefins, vinyl esters of these α-olefins,
Examples thereof include copolymers with monomers other than α-olefins such as methyl methacrylate and maleic acid, and mixtures of these polymers. Examples of the component (I) include polyethylene resin, polypropylene resin, ethylene / propylene copolymer, ethylene / vinyl acetate copolymer, ethylene / methyl methacrylate copolymer, ethylene / 1-butene copolymer, ethylene / propylene. Examples include 1-1 butene copolymers, ethylene / propylene / butadiene copolymers, hydrogenated products of these polymers, and mixtures of these polymers.

The powdery silicone cured product of the component (II) has a silicon atom-bonded alkyl group having 5 or more carbon atoms and has an average particle diameter of 0.1 to 200 μm. The silicon atom to which the alkyl group is bonded is, for example, a silicon atom of a siloxane unit constituting the component (II) or a silicon atom of an organosilicon compound contained in the component (II) in a free state. In particular, the silicon atom of the siloxane unit constituting the component (II) is preferable. As this alkyl group,
For example, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group,
Hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group and the like, particularly hexyl group, heptyl group,
An alkyl group having 6 to 30 carbon atoms such as an octyl group, a nonyl group and a decyl group is preferable.

The siloxane units constituting the component (II) are limited
Not particularly, but especially R¹R² _aSiO_{(3- a) / 2}Unit and R² ₂
SiO_2/2It is preferred to have units. R in the formula¹Is charcoal
An alkyl group having a prime number of 5 or more, and the above alkyl group is an example
Shown. Also, R in the formula²Is a phenyl group or carbon number
An alkyl group of 4 or less, R²As an alkyl group of
Is, for example, methyl group, ethyl group, propyl group, butyl group.
And a methyl group is particularly preferable. Also, in the formula
a is 0, 1 or 2. (II) component is rubbery
First, R² ₂SiO_2/2Units are connected continuously
And are preferred.

The method for producing the component (II) is not limited, and examples thereof include a method of pulverizing a silicone cured product having a silicon atom-bonded alkyl group having 5 or more carbon atoms with a crusher such as a grinder, or a method of producing 5 or more carbon atoms. A method of spraying a liquid curable silicone composition having a silicon atom-bonded alkyl group in hot air to cure, and a liquid curable silicone composition having a silicon atom-bonded alkyl group having 5 or more carbon atoms dispersed in water in a granular form. And a method of curing, especially,
Since a spherical silicone cured product can be efficiently produced, a method in which a liquid curable silicone composition having a silicon atom-bonded alkyl group having 5 or more carbon atoms is granularly dispersed in water and cured is preferable.

Examples of the curable silicone composition for forming the component (II) include (A) 100 parts by weight of organopolysiloxane having at least two silicon-bonded hydroxyl groups in one molecule, (B) ) Organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule 0.1 to 1000 parts by weight, (C) General formula: R ¹ R ² _a Si (OR ³ ) _(3-a) (formula R ¹ is an alkyl group having 5 or more carbon atoms, R ² is a phenyl group or an alkyl group having 4 or less carbon atoms, R ³ is an alkyl group having 4 or less carbon atoms, and a is 0, 1 or 2.) A liquid curable silicone comprising 0.05 to 50 parts by weight of an organosilicon compound represented by the formula (2) or 0.0001 to 20 parts by weight of (D) a catalyst for condensation reaction. The composition includes It

The organopolysiloxane as the component (A) is the main component of the above composition and has at least two silicon-bonded hydroxyl groups in one molecule. The position of the silicon atom to which the hydroxyl group is bonded is not limited, but it is preferably at the end of the molecular chain because of its good reactivity. Examples of the silicon atom-bonded organic group in the component (A) include alkyl groups such as methyl group, ethyl group, propyl group and butyl group; alkenyl groups such as vinyl group, allyl group and butenyl group; phenyl group and tolyl group. , An aryl group such as a xylyl group; an aralkyl group such as a benzyl group and a phenethyl group; and a fluoroalkyl group such as a 3,3,3-trifluoropropyl group. A methyl group and a phenyl group are particularly preferable. The molecular structure of the component (A) is not limited, and examples thereof include linear, cyclic, net-like, and partially branched linear, with linear being particularly preferred. Examples of the component (A) include polymers having these molecular structures and mixtures of polymers having these molecular structures. The viscosity of the component (A) is not limited, but the viscosity at 25 ° C. is 20 to 10 because the workability of the obtained composition is good.
It is preferably 10,000 centipoise, and especially 2
It is preferably from 0 to 10,000 centipoise.

The organopolysiloxane as the component (B) is a curing agent for the above composition and has at least two silicon-bonded hydrogen atoms in one molecule. The silicon atom-bonded organic group in the component (B) is not limited, and examples thereof include an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group; an aryl group such as a phenyl group, a tolyl group and a xylyl group; a benzyl group; An aralkyl group such as a phenethyl group; and a fluoroalkyl group such as a 3,3,3-trifluoropropyl group.
A methyl group and a phenyl group are particularly preferable. The molecular structure of the component (B) is not limited, and examples thereof include linear, cyclic, network, and partially branched linear. As the component (B),
Examples thereof include polymers having these molecular structures and mixtures of polymers having these molecular structures.

The blending amount of the component (B) is 0.1 to 1000 parts by weight, preferably 0.1 to 50 parts by weight, relative to 100 parts by weight of the component (A). . This is because if the amount of the component (B) blended is less than 0.1 parts by weight relative to 100 parts by weight of the component (A), the resulting composition will not cure sufficiently, and this is 1000 parts by weight. This is because the mechanical strength of the obtained powdery silicone cured product becomes poor when it exceeds.

Component (C) is an organosilicon compound represented by the general formula: R ¹ R ² _a Si (OR ³ ) _(3-a) , or a partially hydrolyzed condensate thereof, which is a powdery silicone obtained. It is a component for imparting affinity to a polyolefin resin to a cured product. R ¹ in the formula is an alkyl group having 5 or more carbon atoms and is the same as the above. R ² in the formula is a phenyl group or an alkyl group having 4 or less carbon atoms and is the same as the above.
R ³ in the formula is an alkyl group having 4 or less carbon atoms,
Examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group, and a methyl group is particularly preferable. Further, a in the formula is 0, 1 or 2. As such a component (C),
For example, pentyltrimethoxysilane, pentylmethyldimethoxysilane, pentyltriethoxysilane, pentylmethyldiethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexylmethyldimethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, heptylmethylethoxysilane. Dimethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, octylmethyldimethoxysilane, nonyltrimethoxysilane, nonyltriethoxysilane, nonylmethyldimethoxysilane, decyltrimethoxysilane,
Examples thereof include decyltriethoxysilane, decylmethyldimethoxysilane, and partially hydrolyzed condensates thereof, and hexyltrimethoxysilane, decyltrimethoxysilane, and partially hydrolyzed condensates thereof are particularly preferable. These components (C) can be blended alone or in combination of two or more.

The blending amount of the component (C) is in the range of 0.05 to 50 parts by weight, preferably 0.05 to 15 parts by weight, based on 100 parts by weight of the component (A). .
This is because if the blending amount of the component (C) is less than 0.05 parts by weight relative to 100 parts by weight of the component (A), the resulting powdery silicone cured product will have a poor affinity with the polyolefin resin. If the amount exceeds 50 parts by weight, the mechanical strength of the obtained powdery silicone cured product becomes poor.

The catalyst for the condensation reaction of the component (D) is a catalyst for accelerating the curing of the above composition, and is, for example, di-n-butyltin diacetate or di-n-butyltin di-2-ethylhexyl. Xoate, n-butyltin tri-2-ethylhexoate, di-n-butyltin dilaurate, di-n-butyltin dioctoate, tin octenoate, tin laurate, stannous caprylate, tin naphthenate, Tin-based catalysts such as tin oleate; organic titanate compounds such as tetra-n-butyl titanate, tetraisopropyl titanate, tetra-2-ethylhexyl titanate, ethylene glycol titanate; diisopropoxybis (acetylacetone) titanium, diisopropoxy Bis (ethyl acetoacetate) titanium, diisopropoxy bis (methyl acetoacetate) titanium, dimethoxy Scan (methyl acetoacetate) titanium, dibutoxybis (ethyl acetoacetate) titanium, titanium-based catalysts such as naphthenate titanium; Sutanookuten acid second
Organic acid salt catalysts of metals such as iron, lead octenoate, lead laurate, zinc aurate, cobalt naphthenate, iron naphthenate, zinc naphthenate, zinc stearate, iron octenoate, lead octenoate; n-hexyl Amine-based catalysts such as amines and guanidines; chloroplatinic acid, alcohol solutions of chloroplatinic acid, complexes of chloroplatinic acid with olefins, complexes of chloroplatinic acid with alkenylsiloxanes, platinum black, platinum-supported platinum such as silica Examples include system catalysts. These components (D) can be blended alone or in admixture of two or more.

The blending amount of the component (D) is within the range of 0.0001 to 20 parts by weight, and particularly preferably within the range of 0.0001 to 10 parts by weight, relative to 100 parts by weight of the component (A). . When the component (D) is a tin-based catalyst, a titanium-based catalyst, a metal organic acid salt-based catalyst or an amine-based catalyst, the compounding amount is 0.01 to 10 parts by weight with respect to 100 parts by weight of the (A) component. It is preferably within the range. Further, when the component (D) is a platinum-based catalyst, the blending amount is preferably in the range of 0.0001 to 1 part by weight with respect to 100 parts by weight of the component (A).

The powdered silicone cured product as the component (III) is selected from the group consisting of a silicon atom-bonded alkyl group having 5 or more carbon atoms, an acrylic group, an epoxy group, a mercapto group, an amino group, a chloroalkyl group and an alkenyl group. And at least one group having an average particle size of 0.1 to 200
μm. The silicon atom to which the alkyl group and the above groups are bonded is, for example, a silicon atom of a siloxane unit constituting the component (III), or a silicon atom of an organosilicon compound which is simply contained in the component (III) in a free state. Although it is an atom, it is particularly preferably a silicon atom of a siloxane unit constituting the component (III). This alkyl group is the same as above. Examples of the acryl group include 3-methacryloxypropyl group, 4-methacryloxybutyl group, 5-methacryloxypentyl group, 3-acryloxypropyl group, and 4-acryloxybutyl group, and particularly 3 A methacryloxypropyl group is preferred.
Examples of the epoxy group include 3-glycidoxypropyl group, 4-glycidoxybutyl group, 5-glycidoxypentyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3- (3,3 4-epoxycyclohexyl) propyl group is mentioned, and 3-glycidoxypropyl group and 2- (3,4-epoxycyclohexyl) ethyl group are particularly preferable. Examples of this mercapto group include:
2-mercaptoethyl group, 3-mercapropropyl group,
A 4-mercaptobutyl group is mentioned, and a 3-mercaptopropyl group is particularly preferable. Examples of the amino group include 2-aminoethyl group, 3-aminopropyl group, 4-
Aminobutyl group, 5-aminopentyl group, N- (2-aminoethyl) -3-aminopropyl group, N- (2-aminoethyl) -4-aminobutyl group are mentioned, and particularly 3-
Aminopropyl group and N- (2-aminoethyl) -3-aminopropyl group are preferable. Examples of the chloroalkyl group include a chloromethyl group, a 2-chloroethyl group,
A 3-chloroopropyl group is mentioned, and a chloromethyl group and a 3-chloropropyl group are particularly preferable. Examples of the alkenyl group include vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group,
Examples thereof include octenyl group, and vinyl group and allyl group are particularly preferable.

The siloxane unit constituting the component (III) is not limited, but especially R ¹ R ² _a SiO _{(3 -a) / 2} unit, R ² ₂ S
It is preferably composed of iO _2/2 units and R ⁴ R ² _b SiO _{(3-b) / 2} units. R ¹ in the formula is a silicon atom-bonded alkyl group having 5 or more carbon atoms and is the same as the above. R ² in the formula is a phenyl group or an alkyl group having 4 or less carbon atoms and is the same as the above. Further, R ⁴ in the formula is at least one group selected from the group consisting of an acrylic group, an epoxy group, a mercapto group, an amino group, a chloroalkyl group and an alkenyl group, and the aforementioned acrylic group, epoxy group, mercapto group , An amino group, a chloroalkyl group and an alkenyl group are exemplified. In the formula, a is 0, 1
Or 2, and b is 0, 1 or 2. Further, in order that the component (III) becomes rubbery, it is preferable that R ² ₂ SiO _2/2 units are continuously bonded.

The method for producing the component (III) is not limited,
For example, a silicone cured product having a silicon atom-bonded alkyl group having 5 or more carbon atoms and at least one group selected from the group consisting of an acrylic group, an epoxy group, a mercapto group, an amino group, a chloroalkyl group and an alkenyl group is grindered. Pulverizing with a crusher, carbon number 5
A liquid curable silicone composition having at least one group selected from the group consisting of the above silicon atom-bonded alkyl groups and acrylic groups, epoxy groups, mercapto groups, amino groups, chloroalkyl groups and alkenyl groups in hot air Method of spraying and curing, liquid having a silicon atom-bonded alkyl group having 5 or more carbon atoms and at least one group selected from the group consisting of acryl group, epoxy group, mercapto group, amino group, chloroalkyl group and alkenyl group The curable silicone composition may be dispersed in water in a granular form to be cured. In particular, since a spherical silicone cured product can be efficiently produced, a silicon atom-bonded alkyl group having 5 or more carbon atoms, an acrylic group, and an epoxy group can be used. Group consisting of groups, mercapto groups, amino groups, chloroalkyl groups and alkenyl groups Method of curing by dispersing granulated curable silicone liquid composition in water having at least one group are al selected preferred.

Examples of the curable silicone composition for forming the component (III) include (A) 100 parts by weight of organopolysiloxane having at least two silicon-bonded hydroxyl groups in one molecule, (B) ) Organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule 0.1 to 1000 parts by weight, (C) General formula: R ¹ R ² _a Si (OR ³ ) _(3-a) (formula R ¹ is an alkyl group having 5 or more carbon atoms, R ² is a phenyl group or an alkyl group having 4 or less carbon atoms, R ³ is an alkyl group having 4 or less carbon atoms, and a is 0, 1 or 2), or 0.05 to 50 parts by weight of a partially hydrolyzed condensate thereof, (D) a catalyst for condensation reaction 0.0001 to 20 parts by weight and (E) a general formula: _{^{R 4 R 2 b Si (OR}} 3) (3-b) ( Among, R ² is an alkyl group having 4 or less phenyl or carbon, R ³ is an alkyl group having 4 or less carbon atoms, R ⁴ is an acrylic group, an epoxy group, a mercapto group, an amino group, a chloroalkyl group and Is at least one group selected from the group consisting of alkenyl groups, and b is 0, 1 or 2, or an organic silicon compound represented by the formula: 0.05 to 50 parts by weight. A liquid curable silicone composition consisting of

The components (A) to (D) are the same as described above.
The component (E) is an organosilicon compound represented by the general formula: R ⁴ R ² _b Si (OR ³ ) _(3-b) , or a partially hydrolyzed condensate of the organosilicon compound. It is a component for imparting reactivity with polyolefin resins and other organic resins. R ² in the formula is a phenyl group or an alkyl group having 4 or less carbon atoms and is the same as described above. R ³ in the formula is an alkyl group having 4 or less carbon atoms and is the same as the above. R ⁴ in the formula is at least one group selected from the group consisting of an acrylic group, an epoxy group, a mercapto group, an amino group, a chloroalkyl group and an alkenyl group, and is the same as described above. Further, b in the formula is 0, 1 or 2. Examples of the organosilicon compound as the component (E) include 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 2- (3. 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-mercapto preparative propyl <br/> Le trimethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl methyl dimethoxysilane, 3- (2-aminoethyl) silane, 3-chloro-o trimethoxysilane, vinyl trimethoxysilane down, bi Nirutorisu (2-methoxyethoxy) silane, methyl vinyl dimethoxy silane, allyl trimethoxy silane, and partial hydrolytic condensates and the like . These components (E) can be blended alone or in combination of two or more.

The blending amount of the component (E) is 0.05 to 50 parts by weight, preferably 0.05 to 15 parts by weight, based on 100 parts by weight of the component (A). .
This is because when the blending amount of the component (E) is less than 0.05 parts by weight with respect to 100 parts by weight of the component (A), reactivity of the obtained powdery silicone cured product with the polyolefin resin and other organic resins is high. This is because when the amount exceeds 50 parts by weight, the mechanical strength of the obtained powdery silicone cured product becomes poor.

In order to control the fluidity of these curable silicone compositions or to improve the mechanical strength of the powdery silicone cured product obtained by curing the curable silicone composition, various inorganic fillers are added as optional components. Can be blended. Examples of the inorganic filler include reinforcing inorganic fillers such as fumed silica, wet silica, calcined silica, and fumed titanium dioxide; ground quartz, diatomaceous earth, aluminum hydroxide, aluminum oxide, magnesium oxide, aluminosilicate, Iron oxide, zinc oxide, calcium carbonate, zinc carbonate, mica, non-reinforcing inorganic fillers such as magnesium carbonate, organoalkoxysilane compounds, organochlorosilane compounds, these inorganic fillers in advance,
An inorganic filler surface-treated with an organosilicon compound such as an organosilazane compound, an organosiloxane oligomer, or an organopolysiloxane can be used. These inorganic fillers can be blended alone or in combination of two or more.

In producing these powdery silicone cured products, first, the above-mentioned components (A) to (D) or the above-mentioned components (A) to (E), and any other optional components. A liquid curable silicone composition comprising the components is prepared. The method of preparing these curable silicone compositions is not limited, and examples thereof include a method of preparing the above components by mixing them with a mixing device such as a planetary mixer or a Ross mixer. It is preferable to prepare these curable silicone compositions under cooling.

Next, these curable silicone compositions are uniformly dispersed in water to give an average particle size of 0.1 to 20.
Form a granular composition as described above that is 0 μm. In order to uniformly and stably disperse these curable silicone compositions in water, it is preferable to use a surfactant. The type of the surfactant is not limited, and examples thereof include polyoxyalkylene alkyl ether, polyoxyalkylene alkylphenol, polyoxyalkylene alkyl ester, polyoxyalkylene sorbitan ester, polyethylene glycol, polypropylene glycol,
Nonionic surfactants such as ethylene oxide adducts of diethyleneglycol trimethylnonanol; hexylbenzenesulfonic acid, octylbenzenesulfonic acid,
Anionic surfactants such as decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, cetylbenzenesulfonic acid, myristylbenzenesulfonic acid and its sodium salt; octyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, Cationic surfactants such as octyldimethylbenzylammonium hydroxide, decyldimethylbenzylammonium hydroxide, dioctadecyldimethylammonium hydroxide, tallow trimethylammonium hydroxide, coconut oil trimethylammonium hydroxide and the like can be mentioned. These surfactants can be blended alone or in combination of two or more. Further, in the method for producing these powdery silicone cured products, it is preferable to use a nonionic surfactant in order to prevent the curability of these curable silicone compositions from decreasing. Since the average particle size of the product can be made smaller, a mixture of two or more of a nonionic surfactant having an HLB value of less than 10 and a nonionic surfactant having an HLB value of 10 or more is used. Preferably.

The method for uniformly dispersing these curable silicone compositions in water is not limited, and for example, a known emulsifying machine such as a colloid mill, a homogenizer, a propeller type agitator, a combimix, an ultrasonic agitator or the like is used. be able to. In this way, a powdery silicone cured product can be prepared by curing the granular curable silicone composition uniformly dispersed in water. The method of curing the curable silicone composition is not limited, and examples thereof include a method of leaving it sufficiently at room temperature and a method of heating it. Further, these powdery silicone cured products are obtained as an aqueous suspension, and as a method of recovering the powdery silicone cured product from this suspension, for example, a method of leaving this in an oven, cold air, warm Examples thereof include a method of drying with air or hot air, a method of drying with vacuum, and a method of replacing water with a volatile organic solvent such as alcohol and then drying with the above method.

Further, in order to further improve the dispersibility of these powdery silicone cured products in the polyolefin resin, the surface thereof is a metal oxide sol such as colloidal silica;
It is preferable to coat with fine particles of metal oxide such as fumed silica and fumed titanium oxide. The method for coating the surface of the powdery silicone cured product with the metal oxide sol or the metal oxide fine particles is as follows: Examples thereof include a method of removing water from this suspension by the above method, and a method of rubbing the powdery silicone cured product with the metal oxide sol or the metal oxide fine particles.

The average particle size of these powdery silicone cured products is in the range of 0.1 to 200 μm. It is very difficult to produce a powdery silicone cured product having an average particle size of less than 0.1 μm, and this is 200
This is because a powdery silicone cured product having a size of more than μm cannot be uniformly dispersed in the polyolefin resin. The curing properties of these powdery silicone cured products are not limited, and examples thereof include gel, rubber, and resin. The handling workability thereof is good, and the polyolefin resin is particularly excellent in impact resistance and blocking resistance. From the viewpoint of imparting properties, it is preferably rubbery. The shape of these powdery silicone cured products is not limited, and examples thereof include spheres, flat spheres, and indefinite shapes, and the spheres are spherical because they are particularly excellent in dispersibility in various organic resins including polyolefin resins. Is preferable, and particularly spherical is preferable. Further, the hardness of these powdery silicone cured products is not limited, and those having a low hardness to a high hardness can be used, but it is possible to impart excellent impact resistance and blocking resistance to the polyolefin resin. In order that the film made of the polyolefin resin composition containing the powdery silicone cured product of No. 1 does not cause scratches on the surface due to sliding, it is preferably a rubber having a JIS A hardness within the range of 20 to 90. , Especially JIS A hardness of 30 ~
It is preferably rubbery within the range of 80.

The compounding amount of these powdery silicone cured products is
It is in the range of 0.01 to 100 parts by weight with respect to 100 parts by weight of the component (I). This is because when the amount of these powdery silicone cured products is less than 0.01 parts by weight per 100 parts by weight of component (I), the resulting polyolefin resin composition has improved impact resistance and blocking resistance. If it exceeds 100 parts by weight, the fluidity of the obtained polyolefin resin composition is significantly lowered,
This is because the moldability and processability of this composition are significantly reduced.

The polyolefin resin composition of the present invention comprises
As long as it does not impair the object of the present invention, as other optional components, for example, the above-mentioned inorganic filler, oleic acid amide,
Organic compounds such as erucic acid amide, stearic acid amide, stearic acid monoglyceride, stearic acid triglyceride, hydroish fatty acid amine, amino fatty acid sodium salt, betaine compound, N, N-bishydroxydiethylalkylamine, lubricant, antistatic agent, antioxidant Agents, antibacterial agents, heat stabilizers, and ultraviolet absorbers can be added.

The method for preparing the polyolefin resin composition of the present invention is not limited. For example, the component (I) and the component (II) or the component (III) and other optional components may be added to a Henschel mixer, a planetary mixer or a kneader mixer. ,
Examples of the method include melt-mixing with a stirring device such as a uniaxial continuous kneader or a biaxial continuous kneader.

The polyolefin resin composition of the present invention can be molded into various shapes. For example, when it is formed into a film, it is melted to form a sheet, and then the sheet is uniaxially or monoaxially shaped. A film can be obtained by biaxial stretching. The thickness of this film is preferably in the range of 0.1 μm to 1 mm, and particularly preferably in the range of 0.5 to 200 μm.
This film may be a single layer or a multi-layer such as two layers or three layers. Furthermore, the surface of this film can be plasma treated or metal evaporated.

[0034]

EXAMPLES The polyolefin resin composition of the present invention will be described in detail with reference to Examples. The viscosity in the examples is 25 ° C.
It is the value measured in. The characteristics of the powdery silicone cured product were measured by the following methods. [Hardness of powdered silicone cured product] The curable silicone composition was allowed to stand at 25 ° C for about 1 day to prepare a silicone cured product sheet having a thickness of about 1 mm. The JIS A hardness of this silicone cured product sheet was measured by Wallace micro hardness tester (H.
W. (Made by Wallace) and used as the hardness of the powdery silicone cured product. [Average particle size of powdered silicone cured product] The average particle size of the powdered silicone cured product was determined by an image processing device linked to an optical microscope at a magnification of 600 times. [Siloxane unit constituting powdered silicone cured product] The powdered silicone cured product was decomposed with tetraethoxysilane and an alkali catalyst, and the product was quantified by gas chromatography to obtain the siloxane unit constituting this. .

The characteristics of the polyolefin resin composition were measured by the following methods. [Impact resistance of polyolefin resin composition] The polyolefin resin composition was injection-molded to prepare a No. 1 test piece specified in JIS K7110. JIS K 7110
The impact fracture strength of this test piece was measured by the Izod impact test method specified in. [Dispersibility of Powdered Silicone Cured Product in Polyolefin Resin Composition] A film is prepared from the polyolefin resin composition and is fogged when two sheets of this film are stacked by a method according to ASTM-D-1003 ( The haze) was measured. [Blocking Property of Polyolefin Resin Composition] A film is prepared from the polyolefin resin composition, two films are stacked so that the overlapping area is 1 cm × 1 cm, and a load of 1 kgf is applied to the film and left for 1 day. did. The films were then peel tested to determine this maximum peel strength.

[Reference Example 1] Block of dimethylhydroxysiloxy groups at both ends of a molecular chain: 100 parts by weight of dimethylpolysiloxane (the number of bonds of dimethylsiloxane units is 11 on average), and a block of trimethylsiloxy groups at both ends of a molecular chain having a viscosity of 20 centipoise. 10 parts by weight of methyl hydrogen polysiloxane (equivalent of hydrogen atoms bonded to silicon atoms = 67) and 10 parts by weight of hexyltrimethoxysilane were uniformly mixed at -5 ° C. Then, 0.8 part by weight of tin octylate was rapidly mixed with this to prepare a liquid silicone rubber composition. This silicone rubber composition was added to an aqueous solution (about 5 ° C.) of 3 parts by weight of polyoxyethylene nonylphenyl ether (HLB = 13.1) and 120 parts by weight of pure water to give an average particle size of 0. The mixture was uniformly emulsified with a homogenizer so as to have a particle size of 1 to 200 μm. afterwards,
To this was added 240 parts by weight of pure water to prepare an emulsion of the silicone rubber composition. After leaving this emulsion at room temperature for 1 day to cure the silicone rubber composition,
Water was removed by a hot air dryer at 300 ° C. to prepare spherical powdery silicone rubber (A). Various properties of this powdery silicone rubber (A) are shown in Table 1.

[Reference Example 2] Block of dimethylhydroxysiloxy groups at both ends of the molecular chain Block of dimethylpolysiloxane (bonding number of dimethylsiloxane units is 11 on average) 100 parts by weight, trimethylsiloxy group at both ends of the molecular chain having a viscosity of 20 centipoise 10 parts by weight of methyl hydrogen polysiloxane (silicon atom-bonded hydrogen atom equivalent = 67) and 5 parts by weight of decyltrimethoxysilane were uniformly mixed at -5 ° C. Next, 1 part by weight of dibutyltin dilaurate was rapidly mixed with this to prepare a liquid silicone rubber composition. This silicone rubber composition was treated with polyoxyethylene nonylphenyl ether (HLB = 13.1) 3
It was put into an aqueous solution (about 5 ° C.) of 120 parts by weight of pure water and about 120 parts by weight of pure water, and the composition was uniformly emulsified by a homogenizer so that the average particle size of the composition was 0.1 to 200 μm. Thereafter, 240 parts by weight of pure water was added thereto to prepare an emulsion of the silicone rubber composition. This emulsion was allowed to stand at room temperature for 1 day to cure the silicone rubber composition, and then water was removed by a hot air dryer at 300 ° C. to prepare spherical powdery silicone rubber (B). Various properties of this powdery silicone rubber (B) are shown in Table 1.

[0038] [Reference Example 3] at both molecular chain terminals dimethylhydroxysiloxy group dimethylpolysiloxane (number of bonds dimethylcarbamoyl Resid Rokisan units are mean 33.) 100 parts by weight, a viscosity of 20 centipoise at both molecular terminals with trimethylsiloxy groups 10 parts by weight of the blocked methyl hydrogen polysiloxane (silicon atom-bonded hydrogen atom equivalent = 67) and 10 parts by weight of hexyltrimethoxysilane were uniformly mixed at -5 ° C. Then, 0.8 part by weight of tin octylate was rapidly mixed with this to prepare a liquid silicone rubber composition. This silicone rubber composition was mixed with an aqueous solution (about 5 ° C.) of 3 parts by weight of polyoxyethylene nonylphenyl ether (HLB = 13.1) and 120 parts by weight of pure water to give an average particle size of 0. The mixture was uniformly emulsified with a homogenizer so as to have a particle size of 1 to 200 μm. Thereafter, 240 parts by weight of pure water was added thereto to prepare an emulsion of the silicone rubber composition.
This emulsion was allowed to stand at room temperature for 1 day to cure the silicone rubber composition, and then water was removed by a hot air dryer at 300 ° C. to prepare spherical powdery silicone rubber (C). Various properties of this powdery silicone rubber (C) are shown in Table 1.

[Reference Example 4] Block of dimethylhydroxysiloxy groups on both ends of the molecular chain Block of dimethylpolysiloxane (bonding number of dimethylsiloxane units is 11 on average) 100 parts by weight, trimethylsiloxy group on both ends of the molecular chain having a viscosity of 20 centipoise 10 parts by weight of methyl hydrogen polysiloxane (silicon atom-bonded hydrogen atom equivalent = 67), 5 parts by weight of hexyltrimethoxysilane and 5 parts by weight of 3-methacryloxypropyltrimethoxysilane were uniformly mixed at -5 ° C. Then, 0.8 part by weight of tin octylate was rapidly mixed with this to prepare a liquid silicone rubber composition. This silicone rubber composition was treated with polyoxyethylene nonylphenyl ether (HLB = 13.1) 3
The mixture was mixed with an aqueous solution (about 5 ° C.) of 120 parts by weight of pure water and about 120 parts by weight of pure water, and the composition was uniformly emulsified by a homogenizer so that the average particle diameter was 0.1 to 200 μm. Thereafter, 240 parts by weight of pure water was added thereto to prepare an emulsion of the silicone rubber composition. The emulsion was left at room temperature for 1 day to cure the silicone rubber composition, and then water was removed by a hot air dryer at 300 ° C. to prepare spherical powdery silicone rubber (D). Various properties of this powdery silicone rubber (D) are shown in Table 1.

[Reference Example 5] Capping of dimethylhydroxysiloxy group at both ends of the molecular chain: 100 parts by weight of dimethylpolysiloxane (the number of dimethylsiloxane units bonded is 11 on average), and trimethylsiloxy group at both ends of the molecular chain having a viscosity of 20 centipoise is blocked. 10 parts by weight of methyl hydrogen polysiloxane (silicon atom-bonded hydrogen atom equivalent = 67), 9 parts by weight of decyltrimethoxysilane and 1 part by weight of 3-glycidoxypropyltrimethoxysilane were uniformly mixed at -5 ° C. Then, 0.8 part by weight of tin octylate was rapidly mixed with this to prepare a liquid silicone rubber composition. This silicone rubber composition was mixed with an aqueous solution (about 5 ° C.) of 3 parts by weight of polyoxyethylene nonylphenyl ether (HLB = 13.1) and 120 parts by weight of pure water to give an average particle size of 0. The mixture was uniformly emulsified with a homogenizer so as to have a particle size of 1 to 200 μm. afterwards,
To this was added 240 parts by weight of pure water to prepare an emulsion of the silicone rubber composition. After leaving this emulsion at room temperature for 1 day to cure the silicone rubber composition,
Water was removed by a hot air dryer at 300 ° C. to prepare spherical powdery silicone rubber (E). Various properties of this powdery silicone rubber (E) are shown in Table 1.

[Reference Example 6] Block of dimethylhydroxysiloxy groups on both ends of the molecular chain Block of dimethylpolysiloxane (bonding number of dimethylsiloxane units is 11 on average) 100 parts by weight, trimethylsiloxy group on both ends of the molecular chain having a viscosity of 20 centipoise 10 parts by weight of methyl hydrogen polysiloxane (silicon atom-bonded hydrogen atom equivalent = 67), 10 parts by weight of hexyltrimethoxysilane and 2 parts by weight of 3-methacryloxypropyltrimethoxysilane were added at -5 ° C.
And evenly mixed. Then add tin octylate 0.8
A liquid silicone rubber composition was prepared by rapidly mixing parts by weight. This silicone rubber composition was treated with polyoxyethylene nonylphenyl ether (HLB = 13.1).
3 parts by weight and 120 parts by weight of pure water were mixed in an aqueous solution (about 5 ° C.), and the composition was uniformly emulsified by a homogenizer so that the average particle size was 0.1 to 200 μm. Thereafter, 240 parts by weight of pure water was added thereto to prepare an emulsion of the silicone rubber composition. This emulsion was allowed to stand at room temperature for 1 day to cure the silicone rubber composition, and then water was removed by a hot air dryer at 300 ° C. to prepare spherical powdery silicone rubber (F). Various properties of this powdery silicone rubber (F) are shown in Table 1.

[Reference Example 7] Capping of dimethylhydroxysiloxy group at both ends of the molecular chain: 100 parts by weight of dimethylpolysiloxane (the number of dimethylsiloxane units bonded is 11 on average), and trimethylsiloxy group at both ends of the molecular chain having a viscosity of 20 centipoise. 10 parts by weight of methyl hydrogen polysiloxane (silicon atom-bonded hydrogen atom equivalent = 67), 2 parts by weight of hexyltrimethoxysilane, 10 parts by weight of 3-methacryloxypropyltrimethoxysilane and 3 parts by weight of vinyltrimethoxysilane were added at -5 ° C. And evenly mixed. Then, 0.8 part by weight of tin octylate was rapidly mixed with this to prepare a liquid silicone rubber composition. This silicone rubber composition was mixed with an aqueous solution (about 5 ° C.) of 3 parts by weight of polyoxyethylene nonylphenyl ether (HLB = 13.1) and 120 parts by weight of pure water, and the composition had an average particle size of 0. The mixture was uniformly emulsified with a homogenizer so as to have a particle size of 1 to 200 μm.
In addition to 40 parts by weight, an emulsion of silicone rubber composition was prepared. This emulsion was allowed to stand at room temperature for 1 day to cure the silicone rubber composition, and then water was removed by a hot air dryer at 300 ° C. to prepare spherical powdery silicone rubber (G). Various properties of this powdery silicone rubber (G) are shown in Table 1.

[Reference Example 8] Block of dimethylhydroxysiloxy groups at both ends of the molecular chain Block of dimethylpolysiloxane (bonding number of dimethylsiloxane units is 11 on average) 100 parts by weight, trimethylsiloxy group at both ends of the molecular chain having a viscosity of 20 centipoise 10 parts by weight of methyl hydrogen polysiloxane (silicon atom-bonded hydrogen atom equivalent = 67), 3 parts by weight of decyltrimethoxysilane and 7 parts by weight of 3-glycidoxypropyltrimethoxysilane were uniformly mixed at -5 ° C. Then, 0.8 part by weight of tin octylate was rapidly mixed with this to prepare a liquid silicone rubber composition. This silicone rubber composition was mixed with an aqueous solution (about 5 ° C.) of 3 parts by weight of polyoxyethylene nonylphenyl ether (HLB = 13.1) and 120 parts by weight of pure water to give an average particle size of 0. The mixture was uniformly emulsified with a homogenizer so as to have a particle size of 1 to 200 μm. afterwards,
To this was added 240 parts by weight of pure water to prepare an emulsion of the silicone rubber composition. After leaving this emulsion at room temperature for 1 day to cure the silicone rubber composition,
Water was removed by a hot air dryer at 300 ° C. to prepare spherical powdery silicone rubber (H). Various properties of this powdery silicone rubber (H) are shown in Table 1.

[Reference Example 9] Block of dimethylhydroxysiloxy groups on both ends of the molecular chain Block of dimethylpolysiloxane (bonding number of dimethylsiloxane units is 11 on average) 100 parts by weight, trimethylsiloxy group on both ends of the molecular chain having a viscosity of 20 centipoise 10 parts by weight of methyl hydrogen polysiloxane (silicon atom-bonded hydrogen atom equivalent = 67), 5 parts by weight of decyltrimethoxysilane and 5 parts by weight of 3-aminopropyltrimethoxysilane were uniformly mixed at -5 ° C. Then, 0.8 part by weight of tin octylate was rapidly mixed with this to prepare a liquid silicone rubber composition.
This silicone rubber composition was mixed with an aqueous solution (about 5 ° C.) of 3 parts by weight of polyoxyethylene nonylphenyl ether (HLB = 13.1) and 120 parts by weight of pure water to give an average particle size of 0. The mixture was uniformly emulsified with a homogenizer so as to have a particle size of 1 to 200 μm. Thereafter, 240 parts by weight of pure water was added thereto to prepare an emulsion of the silicone rubber composition. This emulsion is allowed to stand at room temperature for 1 day to cure the silicone rubber composition, then at 300 ° C.
The spherical powdery silicone rubber (I) was prepared by removing water with a hot air dryer. Various properties of this powdery silicone rubber (I) are shown in Table 1.

[Reference Example 10] Dimethylpolysiloxane blocked with dimethylhydroxysiloxy groups at both ends of the molecular chain (the number of dimethylsiloxane unit bonds is 11 on average) 100
Parts by weight and 10 parts by weight of a methylhydrogenpolysiloxane endblocked by trimethylsiloxy groups at both molecular chain ends and having a viscosity of 20 centipoise (silicon atom-bonded hydrogen atom equivalent = 67) were uniformly mixed at -5 ° C. Then, 0.8 part by weight of tin octylate was rapidly mixed with this to prepare a liquid silicone rubber composition. This silicone rubber composition was treated with polyoxyethylene nonyl phenyl ether (HLB = 1).
3.1) An aqueous solution (about 5 parts) of 3 parts by weight and 120 parts by weight of pure water.
C.) and the average particle size of the composition is 0.1 to 20.
The mixture was uniformly emulsified with a homogenizer so that the particle size became 0 μm. Thereafter, 240 parts by weight of pure water was added thereto to prepare an emulsion of the silicone rubber composition. This emulsion was allowed to stand at room temperature for 1 day to cure the silicone rubber composition, and then water was removed by a hot air dryer at 300 ° C. to prepare spherical powdery silicone rubber (J). Various properties of this powdery silicone rubber (J) are shown in Table 1.

[Reference Example 11] 100 dimethylpolysiloxanes capped with dimethylhydroxysiloxy groups at both ends of the molecular chain (the number of dimethylsiloxane unit bonds is 11 on average) 100
Parts by weight, 10 parts by weight of methylhydrogenpolysiloxane endblocked by trimethylsiloxy groups at both ends of the molecular chain with a viscosity of 20 centipoise (silicon atom-bonded hydrogen atom equivalent = 67) and 2 parts by weight of 3-methacryloxypropyltrimethoxysilane at -5 ° C. Mix evenly. Then, 0.8 part by weight of tin octylate was rapidly mixed with this to prepare a liquid silicone rubber composition. This silicone rubber composition was treated with polyoxyethylene nonyl phenyl ether (HLB
= 13.1) 3 parts by weight and 120 parts by weight of pure water were mixed in an aqueous solution (about 5 ° C.) to give an average particle size of 0.1.
The mixture was uniformly emulsified with a homogenizer so as to have a particle size of ˜200 μm. Thereafter, 240 parts by weight of pure water was added thereto to prepare an emulsion of the silicone rubber composition. This emulsion was allowed to stand at room temperature for 1 day to cure the silicone rubber composition, and then water was removed by a hot air dryer at 300 ° C. to prepare spherical powdery silicone rubber (K). Various properties of this powdery silicone rubber (K) are shown in Table 1.

Reference Example 12 Methyltrimethoxysilane was hydrolyzed in aqueous ammonia, washed with water, and dried in the same manner as in Reference Example 1 to prepare spherical powdery polymethylsilsesquioxane (L). Properties of this powdery polymethylsilsesquioxane (L) are shown in Table 1. However, although the hardness could not be measured, the hardness was extremely high.

[0048]

[Table 1]

Example 1 100 parts by weight of polypropylene resin (Sumitomo Chemical Co., Ltd .; Sumitomo Noblen Y101), powdery silicone rubbers (A) to (K) and powdery polymethylsilsesquioxane (L) were added. After 10 parts by weight of each was uniformly mixed with a Henschel mixer, these were melt-kneaded at 210 ° C. to prepare 12 kinds of polypropylene resin compositions. 220 ° C. of these polypropylene resin compositions
Injection-molded in accordance with JIS K 7110 1
No. test piece was prepared. The impact strength of these test pieces was measured. For comparison, the impact strength of a test piece prepared by injection molding the above polypropylene resin alone was measured. The results are shown in Table 2.

[Example 2] Polypropylene resin (Sumitomo Chemical Co., Ltd .; Sumitomo Noblen FK145) 100
2 parts by weight of powdery silicone rubbers (A) to (K) and powdery polymethylsilsesquioxane (L), 2, 6 parts by weight, respectively.
-0.1 parts by weight of di-t-butyl-p-cresol and 0.01 parts by weight of calcium stearate were uniformly mixed in a Henschel mixer, and then melt-kneaded at 210 ° C to prepare 12 polypropylene resin compositions. Was prepared.
These polypropylene resin compositions were molded into a film by rolls while being injected at 220 ° C. and biaxially stretched at 150 ° C. to prepare a film having a thickness of 30 μm. The haze and peel strength of these films were measured. Also,
For comparison, the haze and peel strength of the film prepared by molding only the above polypropylene resin were measured. The results are shown in Table 2.

[0051]

[Table 2]

[0052]

The polyolefin resin composition of the present invention is characterized by excellent impact resistance and blocking resistance.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C08L 83/08 C08L 83/08 (72) Inventor Haruhiko Furukawa 2-2 Chikusaigan, Ichihara-shi, Chiba Toray Dow Corning Silicone Co., Ltd. (56) Reference JP 62-215646 (JP, A) JP 7-179679 (JP, A) JP 1-129050 (JP, A) JP 3-292329 (JP, A) JP 63-308067 (JP, A) JP 50-151949 (JP, A) JP 54-57551 (JP, A) JP 60-127367 (JP, A) Kaihei 4-366148 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 23/00 C08L 83/00

Claims (7)

(57) [Claims] 1. (I) Polyolefin resin 100 parts by weight and (II) having a silicon atom-bonded alkyl group having 5 or more carbon atoms and having an average particle size of 0.1 to 0.1 Powdered silicone cured product having a size of 200 μm 0.01 to 100 parts by weight A polyolefin resin composition comprising: 2. The component (II) comprises R ¹ R ² _a SiO _{(3-a) / 2} units and R ² ₂ SiO _2/2 units (wherein R ¹ is an alkyl group having 5 or more carbon atoms, The polyolefin resin composition according to claim 1, wherein R ² is a phenyl group or an alkyl group having 4 or less carbon atoms, and a is 0, 1 or 2.). 3. The component (II) comprises (A) 100 parts by weight of an organopolysiloxane having at least two silicon atom-bonded hydroxyl groups in one molecule, and (B) at least two silicon atom bonds in one molecule. 0.1 to 1000 parts by weight of an organopolysiloxane having a hydrogen atom, (C) General formula: R ¹ R ² _a Si (OR ³ ) _(3-a) (In the formula, R ¹ is an alkyl group having 5 or more carbon atoms. And R ² is a phenyl group or an alkyl group having 4 or less carbon atoms, R ³ is an alkyl group having 4 or less carbon atoms, and a is 0, 1 or 2. Or, a liquid curable silicone composition comprising 0.05 to 50 parts by weight of this partial hydrolysis-condensation product and 0.0001 to 20 parts by weight of a catalyst for condensation reaction (D) is uniformly dispersed in water to obtain an average particle. Granules with a diameter of 0.1 to 200 μm , The polyolefin resin composition of claim 1 wherein the powder silicone cured product obtained by curing the composition of the particulate. 4. (I) Polyolefin resin 100 parts by weight and (III) A silicon atom-bonded alkyl group having 5 or more carbon atoms, an acrylic group, an epoxy group, a polymer Selected from the group consisting of a rucapto group, an amino group, a chloroalkyl group and an alkenyl group. Having at least one selected group and having an average particle size of 0.1 to 200 μm Powdered silicone cured product 0.01 to 100 parts by weight A polyolefin resin composition comprising: 5. The component (III) is R ¹ R ² _a SiO ² _{(3-a) / 2} unit,
R ² ₂ SiO _2/2 units and R ⁴ R ² _b SiO _{(3-b) / 2} units (wherein R ¹ is an alkyl group having 5 or more carbon atoms, R ² is a phenyl group or 4 or less carbon atoms) Is an alkyl group of R
⁴ is at least one group selected from the group consisting of an acrylic group, an epoxy group, a mercapto group, an amino group, a chloroalkyl group and an alkenyl group, a is 0, 1 or 2, and b is 0, 1 or It is 2. 5. The polyolefin resin composition according to claim 4, which is a powdery silicone cured product having a). 6. The component (III) comprises (A) 100 parts by weight of an organopolysiloxane having at least two silicon atom-bonded hydroxyl groups in one molecule, and (B) at least two silicon atom bonds in one molecule. 0.1 to 1000 parts by weight of an organopolysiloxane having a hydrogen atom, (C) General formula: R ¹ R ² _a Si (OR ³ ) _(3-a) (In the formula, R ¹ is an alkyl group having 5 or more carbon atoms. And R ² is a phenyl group or an alkyl group having 4 or less carbon atoms, R ³ is an alkyl group having 4 or less carbon atoms, and a is 0, 1 or 2. Or 50 to 50 parts by weight of this partially hydrolyzed condensate, (D) a catalyst for condensation reaction 0.0001 to 20 parts by weight and (E) a general formula: R ⁴ R ² _b Si (OR ³ ) _{(3 -b)} (wherein, R ² is der alkyl group having not more than 4 carbon phenyl group or a C , R ³ is an alkyl group having 4 or less carbon atoms, R ⁴ is at least one group selected from the group consisting of acrylic group, an epoxy group, a mercapto group, an amino group, a chloroalkyl group and alkenyl group, b Is 0, 1 or 2.) A liquid curable silicone composition comprising 0.05 to 50 parts by weight of an organosilicon compound represented by the formula: or a partially hydrolyzed condensate is uniformly dispersed in water. The polyolefin resin composition according to claim 4, which is a powdery silicone cured product obtained by curing the granular composition after being granulated with an average particle size of 0.1 to 200 µm. 7. The polyolefin resin composition according to any one of claims 1 to 6, wherein the component (I) is a polypropylene resin.