JP2001261919A - Sliding property modifier and sliding property resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a slidability modifier capable of imparting excellent slidability, surface appearance and impact resistance to a thermoplastic resin or a thermoplastic elastomer, and to provide such a modifier. Provided is a slidable resin composition used. A composite rubber-based graft copolymer (A) in which at least one vinyl monomer is graft-polymerized to a composite rubber comprising a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate component. A slidability modifier obtained by mixing a silicone-based oil or an olefin-based oil (B), and a slidable resin composition containing the slidability modifier, a thermoplastic resin and / or a thermoplastic elastomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a slidability modifier and a thermoplastic resin and / or a thermoplastic elastomer composition having improved slidability.

[0002]

2. Description of the Related Art AV equipment such as VTRs and OA such as printers.
Molded articles made of thermoplastic resins are widely used in various fields such as equipment, and one of the required physical properties of these molded articles is slidability. However,
If the thermoplastic resin is used alone, the sliding life is unsatisfactory or further improvement is desired, and as a countermeasure, the thermoplastic resin or the thermoplastic elastomer is chemically and physically used. A method of adding a silicone oil, olefin oil, etc., which are lubricants and release agents excellent in chemical stability, has been proposed ("Silicone Handbook", Kunio Ito, Nikkan Kogyo, P153, "Plastics and Rubber Handbook, Practical Handbook of Chemicals, P949, etc.), which easily oozes out near the surface of molded products and is easily consumed, not only impairing the surface appearance but also maintaining long-term sliding characteristics. Is also insufficient.

Further, there is a problem that the mechanical properties, particularly the impact resistance when they are added to a thermoplastic resin, are remarkably reduced. Also, a method of adding silicone powder (Japanese Patent Publication No. 7-5808) has been proposed.
This is a non-crosslinked polyorganosiloxane having a specific structure, which is obtained by graft polymerization of (meth) acrylic acid ester. The molded product obtained here has the effect of imparting slidability but has the problem of poor surface appearance. And are also known to be expensive.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned disadvantages of the prior art and to provide excellent sliding properties, surface appearance and impact resistance to thermoplastic resins and thermoplastic elastomers. An object of the present invention is to provide a slidability modifier which can be used and a slidability resin composition using such a modifier.

[0005]

Means for Solving the Problems The inventors of the present invention have heretofore described one or more types of vinyl-based monomers in a composite rubber comprising a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate component in a thermoplastic resin or the like. When a compound rubber-based graft copolymer whose main component is a graft-polymerized compound rubber-based graft copolymer is blended, a resin composition having excellent processability can be obtained without delaying kneading and melting and dispersion. And that the product obtained by processing has excellent slidability such as low tackiness and high gloss, and excellent impact strength (Japanese Patent Application Laid-Open No. 9-309935, JP-A-10-237266, JP-A-10-237266
No. 212387).

The inventors of the present invention have made intensive studies to solve the above problems, and as a result, the slidability modifier of the present invention comprises a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate component. Composition obtained by blending a silicone rubber or olefin oil with a composite rubber-based graft copolymer whose main component is a composite rubber-based graft copolymer in which one or more vinyl monomers are graft-polymerized to a composite rubber By adding the material to a thermoplastic resin or a thermoplastic elastomer as a slidability modifier, the slidability, impact resistance, and The present inventors have found that a resin composition having excellent surface appearance can be obtained, and have accomplished the present invention.

That is, the present invention relates to a composite rubber-based graft copolymer (A) in which at least one vinyl monomer is graft-polymerized to a composite rubber comprising a polyorganosiloxane and an alkyl (meth) acrylate rubber. On the other hand, there is provided a slidability modifier comprising a mixture of a silicone oil or an olefin oil (B). The present invention also provides
A slidable resin composition comprising the slidability modifier and a thermoplastic resin and / or a thermoplastic elastomer is provided.

[0008]

DETAILED DESCRIPTION OF THE INVENTION The polyorganosiloxane used in the composite rubber-based graft copolymer of the component (A) in the present invention is not particularly limited, but is preferably a polyorganosiloxane containing a vinyl polymerizable functional group. Siloxane. Such a polyorganosiloxane is, for example, by polymerizing a mixture of a diorganosiloxane and a vinyl polymerizable functional group-containing siloxane or, if necessary, a latex containing a siloxane-based crosslinking agent at a high temperature using an acid catalyst. Can be manufactured.

The diorganosiloxane used in the production of the polyorganosiloxane includes a diorganosiloxane cyclic body having three or more member rings, and a three to seven member ring is preferred. Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like, and these can be used alone or in combination of two or more.

The siloxane containing a vinyl polymerizable functional group may be a siloxane containing a vinyl polymerizable functional group and capable of bonding to a diorganosiloxane via a siloxane bond. Considering the properties, various alkoxysilane compounds containing a vinyl polymerizable functional group are preferred. Specifically, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-
Methacryloyloxysilanes such as methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropylethoxydiethoxymethylsilane and δ-methacryloyloxybutyldiethoxymethylsilane A vinylsiloxane such as tetramethyltetravinylcyclotetrasiloxane, vinylphenylsilane such as p-vinylphenyldimethoxymethylsilane, and further γ-mercaptopropyldimethoxymethylsilane;
and mercaptosiloxanes such as γ-mercaptopropyltrimethoxysilane. These vinyl polymerizable functional group-containing siloxanes can be used alone or as a mixture of two or more.

As the siloxane-based crosslinking agent, a trifunctional or tetrafunctional silane-based crosslinking agent, for example, trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane or the like is used. Can be. In the production of the polyorganosiloxane, specifically, for example, a mixture of a diorganosiloxane and a vinyl-polymerizable functional group-containing siloxane or, if necessary, a mixture containing a siloxane-based crosslinking agent was emulsified with an emulsifier and water. After the latex is atomized using a homomixer that atomizes by shearing force due to high-speed rotation or a homogenizer that atomizes by jet force from a high-pressure generator, the latex is polymerized at a high temperature using an acid catalyst, and then alkaline. This can be done by neutralizing the acid with a substance.

As a method for adding the acid catalyst used in the polymerization,
There are a method of mixing a siloxane mixture, an emulsifier, and water together, and a method of dropping a latex in which the siloxane mixture is finely divided into a high-temperature acid aqueous solution at a constant speed, etc., but the control of the particle diameter of the polyorganosiloxane is easy. In consideration of the above, a method of dropping a latex in which the siloxane mixture is finely divided into a high-temperature acid aqueous solution at a constant rate is preferable.

As the emulsifier used in the production of the polyorganosiloxane, an anionic emulsifier is preferable, and an emulsifier selected from sodium alkylbenzenesulfonate, sodium polyoxyethylene nonylphenyl ether sulfate and the like is used. Particularly, sodium alkylbenzenesulfonate, sodium lauryl sulfate and the like are preferable.

Methods for mixing a siloxane mixture, an emulsifier, water and / or an acid catalyst include mixing by high-speed stirring and mixing by a high-pressure emulsifying device such as a homogenizer. A method using a homogenizer is a method of mixing polyorganosiloxane latex particles. This is a preferable method because the diameter distribution is reduced. Examples of the acid catalyst used for the polymerization of the polyorganosiloxane include sulfonic acids such as aliphatic sulfonic acids, aliphatic substituted benzenesulfonic acids, and aliphatic substituted naphthalenesulfonic acids, and mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid. These acid catalysts can be used alone or in combination of two or more. Among them, aliphatic substituted benzenesulfonic acid is preferable because of excellent stabilizing action of the polyorganosiloxane latex, and n-dodecylbenzenesulfonic acid is particularly preferable. Further, when n-dodecylbenzenesulfonic acid and a mineral acid such as sulfuric acid are used in combination, it is possible to reduce the appearance defect of the resin composition caused by the emulsifier component of the polyorganosiloxane latex.

The polymerization temperature of the polyorganosiloxane is 5
0 ° C. or higher is preferable, and 80 ° C. or higher is more preferable. In addition, the polymerization time of the polyorganosiloxane is preferably 2 hours or more, more preferably 5 hours or more when the acid catalyst is mixed with the siloxane mixture, the emulsifier, and water to form fine particles and polymerized. In the method of dropping the latex in which the siloxane mixture is finely divided into the aqueous solution, it is preferable to hold the latex for about 1 hour after the dropping of the latex.

The termination of the polymerization can be carried out by cooling the reaction solution and neutralizing the latex with an alkaline substance such as caustic soda, caustic potash and sodium carbonate. The alkyl (meth) acrylate rubber constituting the composite rubber-based graft copolymer (A) is a polymer of an alkyl (meth) acrylate and a polyfunctional alkyl (meth) acrylate. The amount of the alkyl (meth) acrylate rubber in the composite rubber-based graft copolymer is not particularly limited.

The composite rubber used in the present invention is produced by impregnating a polyorganosiloxane latex with an alkyl (meth) acrylate component comprising an alkyl (meth) acrylate and a polyfunctional alkyl (meth) acrylate, followed by polymerization. can do. Examples of the alkyl (meth) acrylate include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, and hexyl methacrylate, 2-ethylhexyl methacrylate, and n-
Examples thereof include alkyl methacrylates such as lauryl methacrylate, and these can be used alone or in combination of two or more. Further, in consideration of the impact resistance and the molded gloss of the resin composition containing the graft copolymer, it is particularly preferable to use n-butyl acrylate.

Examples of the polyfunctional alkyl (meth) acrylate include allyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate,
Triallyl cyanurate, triallyl isocyanurate and the like can be mentioned, and these can be used alone or in combination of two or more. Preferred examples of the polyfunctional alkyl (meth) acrylate include allyl methacrylate and 1,3-butylene glycol dimethacrylate in consideration of the graft structure of the graft copolymer (the acetone-insoluble content and the solution viscosity of the acetone-soluble component). Combinations.

The composite rubber comprising a polyorganosiloxane and an alkyl (meth) acrylate rubber used in the present invention is prepared by adding the above alkyl (meth) acrylate component to a latex of a polyorganosiloxane component, and adding a usual radical polymerization initiator. It can be prepared by acting and polymerizing. As a method of adding the alkyl (meth) acrylate, there are a method of mixing the poly (organosiloxane component) with the latex of the polyorganosiloxane component at a time and a method of dropping into the latex of the polyorganosiloxane component at a constant rate. In consideration of the impact resistance of the obtained resin composition containing the graft copolymer, a method in which the latex of the polyorganosiloxane component is mixed at a time is preferable. As the radical polymerization initiator used for the polymerization, a peroxide, an azo-based initiator, or a redox-based initiator obtained by combining an oxidizing agent and a reducing agent is used. Of these,
A redox-based initiator is preferred, and a system in which ferrous sulfate, disodium ethylenediaminetetraacetate, Rongalit, and hydroperoxide are combined is particularly preferred.

The average particle size of the composite rubber-based graft copolymer is not particularly limited, but may be from 0.01 to
It is preferably in the range of 0.6 μm. When the average particle size is less than 0.01 μm, the impact resistance of a molded product obtained from the resin composition may deteriorate, and when the average particle size exceeds 0.6 μm, the molded product obtained from the resin composition Of the molding surface may deteriorate and the appearance of the molding surface may deteriorate.

By subjecting one or more vinyl monomers to radical polymerization in the presence of the above composite rubber, a composite rubber graft copolymer (A) is obtained. The vinyl monomer is not particularly limited, for example, styrene, α-methylstyrene, aromatic alkenyl compounds such as vinyl toluene, methyl methacrylate, ethyl methacrylate,
Examples include methacrylates such as 2-ethylhexyl methacrylate, acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate, and vinyl cyanide compounds such as acrylonitrile and methacrylonitrile. These can be used alone or in combination of two or more.

The graft polymerization can be carried out in one stage or in multiple stages by a radical polymerization method by adding a vinyl monomer to the latex of the composite rubber. As the radical polymerization initiator used for the polymerization, a peroxide, an azo initiator, or a redox initiator obtained by combining an oxidizing agent and a reducing agent is used. Among them, a redox-based initiator is preferable, and a system in which ferrous sulfate, disodium ethylenediaminetetraacetate, Rongalit, and hydroperoxide are combined is particularly preferable.

Various chain transfer agents for adjusting the molecular weight and the graft ratio of the graft polymer can be added to the vinyl monomer used in the graft polymerization. In addition, at the time of graft polymerization, an emulsifier can be added to stabilize the polymerization latex and further control the average particle size of the graft copolymer. The emulsifier used is not particularly limited, but preferable examples thereof include a cationic emulsifier, an anionic emulsifier and a nonionic emulsifier, and more preferable examples thereof include a sulfonate emulsifier or a sulfate emulsifier and a carboxylate. There are combinations with emulsifiers.

The particle size of the composite rubber-based graft copolymer prepared as described above is not particularly limited, but the impact resistance of the resin composition containing the obtained graft copolymer is not limited. In consideration of the surface appearance of the molded product, the average particle size of the composite rubber is preferably in the range of 0.01 to 2 μm. When the average particle size is less than 0.01 μm,
The impact resistance of the molded product obtained from the resin composition may deteriorate, and when the average particle size exceeds 2 μm, the impact resistance of the molded product obtained from the resin composition decreases and the appearance of the molding surface deteriorates. May be.

In the present invention, the graft copolymer (A)
Is the graft copolymer latex produced as described above.
Calcium chloride, calcium acetate, aluminum sulfate
Into hot water in which metal salts such as
The graft copolymer is separated by solidification,
It is manufactured by collecting in a form. In the present invention,
The silicone-based oil of (B) is not particularly limited.
Rather, a wide range effective to achieve the purpose of the present invention
Can be used. Typical
As a suitable silicone oil, R_ThreeSiO_0.5, R _Two
SiO, RSiO_1.5, SiO_Two, R¹R_TwoSi
O_0.5, R¹RSiO, R¹ _TwoSiO units and their
A mixture wherein R is independently saturated or unsaturated
Represents a monovalent hydrocarbon group;¹Are independently paired with R
The same group (R¹And both R exist
In these cases, they may be the same or different)
Or hydrogen atom, hydroxyl, alkoxyl, aryl
Group selected from the group consisting of
Represents a chemically bonded white group selected from the group consisting of
Silicone oils composed of xy units are exemplified.

The olefin oil is not particularly limited, and a wide range of olefin oils can be used. Representative examples of olefin-based oils useful in the present invention include olefin-based oligomers, especially cooligomers of ethylene and α-olefins having 3 to 20 carbon atoms, and α-olefins having 3 to 20 carbon atoms. -As the olefin, for example, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-
Octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like can be mentioned. Furthermore, the olefin-based oligomer is 1
The kinematic viscosity at 00 ° C. is preferably from 15 to 1000 cSt from the viewpoints of slidability and moldability.

Examples of the thermoplastic resin useful in the present invention include polyethylene (PE) and polypropylene (PP).
Such as olefin resins, polystyrene (PS), high impact polystyrene (HIPS), (meth) acrylate / styrene copolymer (MS), styrene
Acrylonitrile copolymer (SAN), styrene / maleic anhydride copolymer (SMA), ABS, ASA, AE
S-based resins such as S, polymethyl methacrylate (P
MMA), polyester resins such as polycarbonate resins (PC), polyamide resins (PA), polyethylene terephthalate (PET), polybutylene terephthalate polycarbonate (PBT), and (modified) polyphenylene ether resins (PP
E), polyoxymethylene resin (POM), polysulfone resin (PSO), polyarylate resin (PA
r), engineering plastics such as polyphenylene sulfide resin (PPS) and thermoplastic polyurethane resin (PU), and polycarbonate resin / styrene resin alloys such as PC / ABS, PA / ABS
Such as polyamide resin / styrene resin alloy, PA
/ Polyamide resin such as PP / Polyolefin resin alloy, PC / Polycarbonate resin such as PBT /
Polyester resin alloy, alloy of olefin resins such as PP / PE, PPE / HIPS, PPE /
(Modified) polyphenylene ether-based resin alloys such as PBT and PPE / PA.

The thermoplastic elastomer useful in the present invention includes, for example, styrene-based elastomers, vinyl chloride-based elastomers, olefin-based elastomers, urethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, and acrylic-based elastomers. These can be used alone or in combination of two or more.

In the present invention, a composite rubber-based graft copolymer (A) in which one or more vinyl monomers are graft-polymerized on a composite rubber comprising a polyorganosiloxane and an alkyl (meth) acrylate rubber, and a silicone-based graft copolymer In the slidability modifier composed of oil or olefinic oil (B), component (A) / component (B) = 99/1 to 1
The ratio (weight ratio) is preferably 60/40. More preferably, component (A) / component (B) = 90/10
７０70/30. Component (A) / Component (B) is 99 /
If it is smaller than 1, the effect of improving the slidability of the molded product obtained from the resin composition may not be obtained. When the ratio of component (A) / component (B) exceeds 60/40,
Molding processability may decrease, and the molding surface appearance of a molded product obtained from the resin composition may deteriorate.

As a method of blending the components (A) and (B), a method of impregnating the composite rubber graft copolymer (A) with a silicone oil or an olefin oil (B) is preferable. The slidability modifier of the present invention is preferably added in the range of 0.5 to 50 parts by weight based on 100 parts by weight of the thermoplastic resin and / or the thermoplastic elastomer. More preferably, it is 3 to 30 parts by weight.
When the amount of the slidability modifier of the present invention is less than 0.5 part by weight, sufficient slidability-imparting effect cannot be obtained, and strength may not be improved. . If the amount of the slidability modifier of the present invention exceeds 50 parts by weight, the molded product obtained from the resin composition may have poor molded surface appearance.

The slidability modifier of the present invention is mixed with a thermoplastic resin and / or a thermoplastic elastomer by a generally known kneading method, for example, a thermoplastic resin and / or a thermoplastic elastomer in the form of powder, beads or pellets. The slidable resin composition of the present invention can be obtained by, for example, a method of weighing and mixing a predetermined amount of the mixture and melting and kneading the obtained mixture. The method of mixing the slidability modifier with the thermoplastic resin and / or the thermoplastic elastomer is not particularly limited, and an ordinary method can be effectively used. However, generally the melt mixing method is preferred. In this case, a small amount of solvent may be used, but is generally unnecessary. Apparatuses useful for mixing include, in particular, extruders, Banbury mixers, rollers, kneaders, etc., which are preferably operated batchwise or continuously.
The order of mixing the components is not particularly limited.

The slidable resin composition of the present invention can be used as it is as a raw material for producing a molded article. Further, the slidable resin composition of the present invention, if necessary, a dye,
Pigments, flame retardants, flame retardant aids, stabilizers, reinforcing agents, fillers, heat resistance improvers, release agents, crystal nucleating agents, flow improvers, antistatic agents, conductivity imparting agents, surfactants, Fogging agents, foaming agents, antibacterial agents and the like can be added.

The slidable resin composition of the present invention is formed into a desired molded article by various molding methods such as injection molding, extrusion molding, blow molding, compression molding, calender molding, and inflation molding. . Applications of the slidable resin composition containing the slidability modifier of the present invention include, but are not particularly limited to, connectors, electric wire covering materials, various electric and electronic components such as sockets, personal computer housings, and batteries. Case, mobile phone housing, printer housing, copier housing,
OA equipment such as facsimile housing, communication equipment parts,
Various building material parts such as wall materials, floor materials, window frame materials, sheet materials, car interior parts such as instrument panel parts, tableware, household appliances parts such as vacuum cleaner housing, television housing, air conditioner housing, toys, stationery, etc. Can be

[0034]

The present invention will be further described with reference to the following examples. The “parts” in Reference Examples, Examples and Comparative Examples
And “%” are “parts by weight” unless otherwise specified.
And "% by weight". Various physical properties shown in the examples were measured by the following methods. (1) Particle size distribution, weight average particle size A sample solution was prepared by diluting a particle dispersion with water, and a dynamic light scattering method ("ELS800" manufactured by Otsuka Electronics Co., Ltd., temperature 25
° C, scattering angle 90 °). (2) Thrust-type friction and wear test A test piece was molded using a 75t injection molding machine, and JIS K7
A thrust-type friction and wear test was performed based on the 218A method.
The same material was used as the partner material. The outer diameter of the test piece was 25.6.
A hollow cylindrical member having a diameter of 20.0 mm and an inner diameter of 20.0 mm was used, and a counterpart material having the same shape was used.

The dynamic friction coefficient was measured at room temperature 23 ° C. and humidity 5
0% atmosphere, load 20N, running speed 10cm / s
ec. The dynamic friction coefficient is obtained by the following equation. μ = f × r / L × R (−) μ: Dynamic friction coefficient f: Friction force detected by load cell R: Average radius of sample r: Length of load cell at center of axis L: Load Specific wear was measured at room temperature 23 ° C. In a 50% humidity atmosphere, the load was 20 N, the running speed was 10 cm / sec, and the running distance was 8.64 km.

The specific wear amount is obtained by the following equation. A = △ W / P × 1 × α (mm ³ / N · m) A: Specific wear ΔW: Weight change of sample P: Load 1: Running distance α: Density of sample (3) Adhesion evaluation of sheet 5 sheets of 100 mm x 100 mm sheets
After sandwiching between acrylic plates having a thickness of 2 mm and pressing at 23 ° C. and 0.2 MPa for 6 hours, the stacked sheets were taken out, and the adhesion was evaluated.

◎: No adhesion ○: Almost no stickiness ×: Adhesion (4) Impact resistance A test piece was molded using a 75t injection molding machine, and JIS K7
Izod impact strength was evaluated based on the 110 method. (5) Surface appearance The surface appearance of the molded article was evaluated according to the following criteria.

：: Smooth and good appearance △: Slight surface roughness is observed X: Severe surface roughness and poor appearance Examples and Comparative Examples (A) Composite Rubber Graft Copolymer Reference Example 1: Composite Production of rubber-based graft copolymer (A-1) 2 parts of tetraethoxysilane, 0.5 part of γ-methacryloyloxypropyldimethoxymethylsilane and 97.5 parts of octamethylcyclotetrasiloxane were mixed, and 100 parts of a siloxane mixture was mixed. Obtained. 100 parts of the above mixed siloxane was added to 200 parts of distilled water in which 1 part of sodium dodecylbenzenesulfonate and 1 part of dodecylbenzenesulfonic acid were respectively dissolved, and the mixture was mixed at 10,000 rpm with a homomixer.
pm, then 30MP with a homogenizer.
The mixture was emulsified and dispersed at the pressure of a to obtain an organosiloxane latex. This mixed solution was transferred to a separable flask equipped with a condenser and a stirring blade, and mixed and stirred.
After heating at 0 ° C. for 5 hours, the mixture was allowed to stand at 20 ° C., and after 48 hours, the pH of this latex was adjusted to 7.0 with an aqueous sodium hydroxide solution.
The mixture was neutralized to 4 to complete D polymerization, and a polyorganosiloxane latex was obtained. The polymerization rate of the obtained polyorganosiloxane was 89.5%, and the average particle size of the polyorganosiloxane was 0.16 μm. The latex was coagulated and dried with isopropanol to obtain a solid, which was extracted with toluene at 90 ° C. for 12 hours. The gel content was measured and found to be 91.4%.

250 parts of the above-mentioned polyorganosiloxane latex was placed in a separable flask equipped with a stirrer, and 120 parts of distilled water was added.
C., and a mixed solution of 9.7 parts of n-butyl acrylate, 0.3 part of allyl methacrylate and 0.56 part of tert-butyl hydroperoxide was charged and stirred for 30 minutes, and the mixed solution was mixed with polyorganosiloxane particles. Infiltrated. Next, a mixed solution of 0.002 part of ferrous sulfate, 0.006 part of disodium ethylenediaminetetraacetate, 0.26 part of Rongalit and 5 parts of distilled water was charged, radical polymerization was started, and then at an internal temperature of 70 ° C. The polymerization was completed by holding for 2 hours to obtain a composite rubber latex. A part of this latex was collected, and the average particle diameter of the composite rubber was measured to be 0.22 μm. The latex was dried to obtain a solid, which was dissolved in toluene at 90 ° C. for 1 hour.
Extraction was performed for 2 hours, and the gel content was measured to be 97.3%
Met. To this composite rubber latex, a mixed solution of 0.06 part of tert-butyl hydroperoxide and 10 parts of methyl methacrylate was dropped at 70 ° C. for 15 minutes, and then kept at 70 ° C. for 4 hours to carry out graft polymerization onto the composite rubber. Completed. The polymerization rate of methyl methacrylate was 96.4%. The obtained graft copolymer latex was dropped into 200 parts of hot water containing 1.5% of calcium chloride, coagulated, separated, washed, and dried at 75 ° C. for 16 hours to obtain a powdery composite rubber graft copolymer. Polymer A-1 was obtained in an amount of 96.9 parts.

Reference Examples 2 and 3: Preparation of Composite Rubber Graft Copolymers (A-2 and A-3) Composite rubber grafts were prepared in the same manner as in Reference Example 1 except that the charged compositions shown in Table 1 were used. Copolymers A-2 and A-3
I got Reference Example 4: Production of Acrylic Graft Copolymer (A-4) To a separable flask equipped with a stirrer, 295 parts of distilled water and 0.1 part of sodium dodecylbenzenesulfonate were added. C., 87.3 parts of n-butyl acrylate, 1.7 allyl methacrylate
And a mixture of 0.4 parts of tert-butyl hydroperoxide was charged and stirred for 30 minutes. Next, a mixed solution of 0.002 part of ferrous sulfate, 0.006 part of disodium ethylenediaminetetraacetate, 0.26 part of Rongalit and 5 parts of distilled water was charged, radical polymerization was started, and then at an internal temperature of 70 ° C. The polymerization was completed by holding for 2 hours to obtain a latex. A part of this latex was collected, and the average particle diameter was measured to be 0.22 μm. Further, this latex was dried to obtain a solid, which was extracted with toluene at 90 ° C. for 12 hours, and the gel content was measured to be 97.3%. In this composite rubber latex,
A mixture of 0.06 parts of tert-butyl hydroperoxide and 10 parts of methyl methacrylate was added dropwise at 70 ° C. over 15 minutes, and then maintained at 70 ° C. for 4 hours to complete the graft polymerization onto the composite rubber. The polymerization rate of methyl methacrylate was 97.2%. The obtained graft copolymer latex was dropped into 200 parts of hot water containing 1.5% of calcium chloride, coagulated, separated, washed, and then dried.
It dried at 16 degreeC for 16 hours, and obtained the powdery acrylic-type graft copolymer A-4.

Reference Example 5: Production of polyorganosiloxane-based graft copolymer (A-5) Polyorganosiloxane latex 2 in Reference Example 1
85 parts of tert-butyl hydroperoxide 0.0
A mixture of 6 parts of methyl methacrylate and 10 parts of
For 15 minutes, and then kept at 70 ° C. for 4 hours to complete the graft polymerization to the composite rubber. The polymerization rate of methyl methacrylate was 97.4%. The obtained graft copolymer latex was treated with calcium chloride 1.
It was dropped into 200 parts of 5% hot water, coagulated, separated, washed, and dried at 75 ° C. for 16 hours to obtain a powdery polyorganosiloxane-based graft copolymer A-5.

The thus obtained graft copolymer A-
The compositions of 1 to A-5 are shown in Table 1 below.

[0043]

[Table 1]

The symbols in the table represent the following. PSi: polyorganosiloxane component BA: butyl acrylate AMA: allyl methacrylate MMA: methyl methacrylate (B) Silicone oil, olefin oil Silicone oil, olefin oil (B) used.

(B-1) Dimethyl silicone oil S
H-200 (manufactured by Toray Dow Corning Co., Ltd.) (B-2) Methylphenyl silicone oil SH-5
10 (manufactured by Toray Dow Corning Co., Ltd.) (B-3) Ethylene-α-olefin cooligomer Lucant HC-40 (manufactured by Mitsui Chemicals, Inc.) (B-4) Ethylene-α-olefin cooligomer Lucant HC-100 (Manufactured by Mitsui Chemicals, Inc.) Examples 1 to 16 As shown in Tables 2 and 3, a composite rubber graft copolymer (A-1 to A-3) was added to 100 parts of a thermoplastic resin.
And a silicone oil (B-1 or B-2) or an olefin oil (B-3 or B-4), and extruded with an extruder to prepare pellets. The pellets are molded using a 75-t injection molding machine (the molding temperature is the same as that of the pelletization and is described in the table), and a thrust-type friction and wear test, impact resistance, surface appearance and processing are performed. The sex was evaluated.

The evaluation results are shown in Tables 2 and 3.

[0047]

[Table 2]

[0048]

[Table 3]

Here, the following thermoplastic resins were used. Rigid PVC Shin-Etsu Chemical Co., Ltd. polyvinyl chloride resin "TK700" 1
00 parts, 3 parts of dioctyltin mercaptide as a stabilizer and a lubricant, "METABLEN P-55" manufactured by Mitsubishi Rayon Co., Ltd.
No. 0 "and 1 part of" METABLEN P-710 "manufactured by Mitsubishi Rayon Co., Ltd. were mixed with a Henschel mixer for 10 minutes until the temperature reached 110 ° C.

PC "NOVAREX 7022A" manufactured by Mitsubishi Engineering Plastics, Inc. HIPS "Sumibright E580" manufactured by Sumitomo Chemical Co., Ltd. ABS "Diapet 3001" manufactured by Mitsubishi Rayon Co., Ltd. PBT "Toughpet N1000" manufactured by Mitsubishi Rayon Co., Ltd. Comparative Examples 1 to 11 For comparison, as shown in Table 4, with respect to 100 parts by weight of the same thermoplastic resin used in Examples 1 to 16, a graft copolymer (A) which was not a composite rubber graft copolymer was used. -4
Or A-5) or a mixture of only the component (A),
Alternatively, molding was performed in the same manner as in Examples 1 to 16 using a product to which a commercially available silicone powder (“Charine R170” manufactured by Nissin Chemical Co., Ltd.) was added, and the performance was evaluated. "Charine R170" is obtained by graft-polymerizing a (meth) acrylic ester on a non-crosslinked polyorganosiloxane.

The evaluation results are also shown in Table 4.

[0052]

[Table 4]

Examples 17 to 28 As shown in Tables 5 and 6, the thermoplastic elastomer 1
With respect to 00 parts, the composite rubber graft copolymer (A-1 to
A-3) and a silicone oil (B-1 or B-
2) or olefinic oil (B-3 or B-4)
Were melt-kneaded using a 6-inch roll machine (the molding temperature is described in the table), and sandwiched between glass plates to obtain a sheet. The adhesiveness and surface appearance of the obtained sheet were evaluated.

The evaluation results are shown in Tables 5 and 6.

[0055]

[Table 5]

[0056]

[Table 6]

Here, as the thermoplastic elastomer,
The following were used: Soft PVC Shin-Etsu Chemical Co., Ltd. polyvinyl chloride resin "TK1300"
100 parts, 3 parts of a composite metal soap as a stabilizer, 3 parts of "METABLEN P-530" manufactured by Mitsubishi Rayon Co., Ltd., and 80 parts of DOP (dioctyl phthalate) as a plasticizer are mixed with a Henschel mixer for 10 minutes until the temperature reaches 110 ° C. What you did.

Olefin-based thermoplastic elastomer "Santoprene 121-67" manufactured by AES Japan Ltd. Comparative Examples 12 to 19 For comparison, as shown in Table 7, the same thermoplastic elastomer 100 used in Examples 17 to 28 was used. For the department
A compound containing only a graft copolymer (A-4 or A-5) or a component (A) which is not a composite rubber graft copolymer, or a commercially available silicone powder ("Charine R170" manufactured by Nissin Chemical Co., Ltd.) Was added and molded in the same manner as in Examples 17 to 28, and the performance was evaluated.

The evaluation results are also shown in Table 7.

[0060]

[Table 7]

[0061]

According to the slidable resin composition using the slidability modifier of the present invention, excellent slidability is permanently maintained by various molding methods, and impact resistance is improved. Thus, a molded article having good surface appearance can be obtained.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C10M 107/50 C10M 107/50 143/00 143/00 145/14 145/14 145/16 145/16 145/22 145 / 22 145/24 145/24 147/02 147/02 149/18 149/18 151/04 151/04 169/04 169/04 // (C08L 51/00 (C08L 51/00 83:04 83:04 23:02) 23:02) C10N 40:02 C10N 40:02 (72) Inventor Koichi Shishido 20-1 Miyuki-cho, Otake City, Hiroshima Prefecture Inside Mitsubishi Rayon Co., Ltd. Otake Plant (72) Inventor Takashi Miura Hiroshima Prefecture 20-1 Miyukicho, Otake-shi Mitsubishi Rayon Co., Ltd. Otake Works F-term (reference) 4F071 AA02 AA10 AA15X AA21X AA33X AA67 AA67X AA76 AA77 AH03 AH07 AH12 EA01 4H104 BA08A CA01C CB08C CB09C13C04 C13C01 C03C02J 4J002 AA013 BB033 BB052 BB123 BC033 BC043 BC063 BC083 BG063 BH013 BN063 BN153 BN221 CB003 CF063 CF073 CF163 CG003 CH073 CK023 CL003 CN013 CN033 CP032 GC00 GL00 GN00 GQ00

Claims (4)

[Claims] 1. A composite rubber-based graft copolymer (A) obtained by graft-polymerizing a composite rubber comprising a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate component with at least one vinyl monomer. A slidability modifier obtained by mixing a silicone oil or an olefin oil (B). 2. The weight ratio of the composite rubber-based graft copolymer (A) to the silicone-based oil or olefin-based oil (B) is (A) / (B) = 99/1 to 60/40. The slidability modifier according to 1. 3. A slidable resin composition comprising the slidability modifier according to claim 1 and a thermoplastic resin and / or a thermoplastic elastomer. 4. The slidable resin according to claim 3, wherein the amount of the slidability modifier is 0.5 to 50 parts by weight based on 100 parts by weight of the thermoplastic resin and / or the thermoplastic elastomer. Composition.