JP2009167352A - Surface physical property improver for resin molding, production method and use thereof - Google Patents

Abstract

The present invention provides a surface property improving agent for a resin molded article having a good appearance of the resin molded article, capable of suppressing bleeding, odor and fogging, and improving the scratch resistance, a method for producing the same, and a use thereof. To do.
A surface property improving agent for a resin molding is a polymer obtained by emulsion polymerization or suspension polymerization of a mixed solution containing a nonpolar wax having a melting point of 50 to 100 ° C., a vinyl monomer and a radical polymerization initiator. contains. It is preferable that the mixed liquid further contains an oxidized wax having a melting point of 40 to 100 ° C. The surface property improving agent is produced through the following first and second steps. 1st process: The process of obtaining the polymer by emulsion polymerization or suspension polymerization of the liquid mixture containing the said nonpolar wax, a vinyl monomer, and a radical polymerization initiator. Second step: In the case of emulsion polymerization, the polymer of the first step is salted out, filtered and dried and purified. In the case of suspension polymerization, the polymer is filtered, dried and purified, and the surface physical properties of the resin molded body A step of obtaining an improving agent.
[Selection figure] None

Description

  The present invention improves the surface physical properties of a resin molded body that has a good appearance of a resin molded body used for, for example, automobile interior parts, can suppress bleeding, odor, and fogging, and can improve scratch resistance. The present invention relates to an agent, its production method and use.

  Conventionally, soft vinyl chloride resin has been the mainstream for automotive interior parts such as automotive instrument panels and door trims. However, in recent years, it is lightweight, easy to recycle, has high cost performance, and does not generate gas during combustion. Because of the advantages, replacement with polyolefin resins is being promoted. As the polyolefin resin, polypropylene, polyethylene, olefin thermoplastic elastomer, and the like are used. However, these automobile interior parts made of polyolefin resin have the disadvantages of being inferior in scratch resistance, abrasion resistance and wrinkle residue compared to automobile interior parts made of vinyl chloride resin as a raw material. There are some suggestions for improvement. Specifically, a composition composed of a propylene-based block copolymer and a higher fatty acid amide has been proposed as a propylene polymer composition for automobile interior parts (see, for example, Patent Document 1). This composition is excellent in fluidity and excellent in the balance of mechanical properties such as impact resistance and rigidity.

Further, an olefinic thermoplastic elastomer composition has been proposed as a skin layer of automobile interior and exterior parts (see, for example, Patent Document 2). Such an olefinic thermoplastic elastomer composition comprises at least one selected from (1) crystalline polyolefin resin, (2) styrene thermoplastic elastomer, (3) silicone oil, aliphatic ester, fluoropolymer and higher fatty acid amide. It contains components and may be partially crosslinked. According to this automotive interior / exterior component, it is excellent in scratch resistance, is lightweight and easy to recycle.
Japanese Patent No. 3472980 (first page and fifth page) Japanese Patent Laid-Open No. 9-156053 (pages 2 and 4)

  However, in the propylene polymer composition described in Patent Document 1, it is difficult for the higher fatty acid amide, which is a lubricant component, to migrate to the surface by simply blending a higher fatty acid amide with polypropylene, and the effect of the lubricant is long-lasting. Since it was not sustained, there was a drawback that satisfactory scratch resistance could not be obtained. Furthermore, there is a problem that odor and fogging are generated due to the fatty acid amide, which makes it difficult to use as an automobile interior part.

  On the other hand, in the olefinic thermoplastic elastomer composition described in Patent Document 2, among the component (3), silicone oil is incompatible with crystalline polyolefin resin and styrene thermoplastic elastomer. There was a problem of bleeding on the surface. Further, since the fluoropolymer is also incompatible with the crystalline polyolefin resin and the styrene thermoplastic elastomer, there is a problem that it is inferior in terms of scratch resistance and wear resistance. Furthermore, fatty acid esters and higher fatty acid amides have a problem that they cannot sufficiently exhibit scratch resistance and wear resistance by simply blending with component (1) and component (2).

  Therefore, the object of the present invention is that the appearance of the resin molded body is good, can suppress bleeding, odor and fogging, and can improve the surface property of the resin molded body, which can improve the scratch resistance, It is in providing the manufacturing method and use.

  The surface physical property improver of the resin molded body of the first invention is a polymer obtained by emulsion polymerization or suspension polymerization of a mixed solution containing a nonpolar wax having a melting point of 50 to 100 ° C., a vinyl monomer and a radical polymerization initiator. It is characterized by containing.

The surface physical property improving agent for a resin molded body of the second invention is characterized in that, in the first invention, the mixed solution further contains an oxidized wax having a melting point of 40 to 100 ° C.
The method for producing a surface physical property improving agent for a resin molded article according to a third invention is a method for producing a surface physical property improving agent for a resin molded article according to the first invention, and is subjected to the following first and second steps. A method for producing a surface physical property improving agent for a resin molded product, comprising producing a surface physical property improving agent for a resin molded product.

1st process: The process of obtaining the polymer by emulsion polymerization or suspension polymerization of the liquid mixture containing the nonpolar wax of melting | fusing point 50-100 degreeC, a vinyl monomer, and a radical polymerization initiator.
Second step: The polymer obtained in the first step is salted out in the case of emulsion polymerization, filtered and then dried and purified. In the case of suspension polymerization, the polymer is filtered and dried and purified. A step of obtaining a surface property improving agent for a molded article.

  The thermoplastic resin composition of the fourth invention comprises a polyolefin resin as a main component, contains the surface physical property improver of the resin molded article of the first invention, and the vinyl monomer has a polarity different from that of the polyolefin resin. It is characterized by that.

  A resin molded body of a fifth invention is a thermoplastic resin comprising a polyolefin resin as a main component and containing a surface physical property improver of the resin molded body of the first invention, wherein the vinyl monomer has a polarity different from that of the polyolefin resin. It is obtained by molding a resin composition.

According to the present invention, the following effects can be exhibited.
The surface property improving agent for a resin molded body in the first invention is a polymer obtained by emulsion polymerization or suspension polymerization of a mixed solution containing a nonpolar wax having a melting point of 50 to 100 ° C., a vinyl monomer and a radical polymerization initiator. It contains. Thus, by performing polymerization using a radical polymerization initiator in the presence of a nonpolar wax, a hydrogen abstraction reaction occurs from the nonpolar wax, and the polymer is formed from the nonpolar wax and the vinyl monomer. It is considered that a graft copolymer with (or copolymer) is formed. This graft copolymer does not show affinity with, for example, a polyolefin resin that forms a resin molded body, and is easily polarized on the surface of the resin molded body, and is harder than the polyolefin resin and has a polarity different from that of the polyolefin resin. And a polymer formed from a vinyl monomer.

  Therefore, when a thermoplastic resin composition is prepared by blending a surface property improver with a polyolefin resin and molded to obtain a resin molded body, it is formed from the surface orientation by nonpolar wax and a vinyl monomer. It is presumed that the surface property improving agent is oriented in the vicinity of the surface of the resin molding due to the exclusion effect due to the difference in polarity of the polymer. Therefore, the polymer of nonpolar wax and vinyl monomer is produced by the synergistic effect of nonpolar wax which has the effect of sliding the surface with a low coefficient of friction and a polymer formed from vinyl monomer harder than polyolefin resin. It is considered that high scratch resistance, which cannot be obtained by simply blending, is expressed.

  In addition, since the nonpolar wax forms a graft copolymer with a polymer of vinyl monomer, the graft copolymer exhibits affinity due to intermolecular force and the like with the polyolefin resin, and is contained in the resin molded body. Holds well. For this reason, the resin molded body is suppressed from bleeding, the appearance is kept good, and fogging is also suppressed. Further, since the nonpolar wax has no odor and the polymer of the vinyl monomer is polymerized and does not have a low molecular weight such as fatty acid amide, the odor of the resin molded product can be suppressed.

  In the surface physical property improving agent for a resin molded body according to the second aspect of the invention, the mixed solution further contains an oxidized wax having a melting point of 40 to 100 ° C. For this reason, in addition to the effect of the first invention, the oxidized wax exhibits a surface active action, and can improve the stability of the emulsion liquid by emulsion polymerization or the suspension liquid by suspension polymerization. A small amount of the surface property improving agent is obtained, and the appearance of the resin molding obtained by blending the surface property improving agent can be further improved.

The manufacturing method of the surface physical property improving agent of the resin molding in 3rd invention is performed through the 1st process and the 2nd process which are shown below.
1st process: The process of obtaining the polymer by emulsion polymerization or suspension polymerization of the liquid mixture containing the nonpolar wax of melting | fusing point 50-100 degreeC, a vinyl monomer, and a radical polymerization initiator.

  Second step: The polymer obtained in the first step is salted out in the case of emulsion polymerization, filtered and then dried and purified. In the case of suspension polymerization, the polymer is filtered and dried and purified. A step of obtaining a surface property improving agent for a molded article.

  For this reason, when emulsifying or suspending a nonpolar wax alone, it is generally carried out under high temperature and pressure, whereas the nonpolar wax is emulsified or suspended in a state of being dissolved in a vinyl monomer. Thus, an emulsion or suspension can be obtained in a stable state, and a surface property improving agent with few aggregates can be obtained. Therefore, the surface property improving agent having the effect of the first invention can be easily obtained by a simple operation.

  The thermoplastic resin composition of the fourth invention comprises a polyolefin resin as a main component, contains the surface physical property improver of the resin molded article of the first invention, and the vinyl monomer has a polarity different from that of the polyolefin resin. Is. Therefore, the effect of the first invention can be exhibited based on the surface property improving agent contained in the thermoplastic resin composition.

  A resin molded body according to a fifth aspect of the present invention is a thermoplastic resin comprising a polyolefin resin as a main component and containing a surface physical property improver of the resin molded body according to the first aspect, wherein the vinyl monomer has a polarity different from that of the polyolefin resin. It is obtained by molding a composition. For this reason, the surface property improving agent moves to the surface side of the resin molding mainly due to the difference in polarity. Therefore, the effect of the first invention can be effectively exhibited for the resin molded body.

In the following, embodiments that are considered to be the best of the present invention will be described in detail.
[Surface property improving agent for resin moldings]
The surface physical property improver (hereinafter also simply referred to as surface physical property improver) of the resin molded body of the present embodiment emulsifies a mixed solution containing a nonpolar wax having a melting point of 50 to 100 ° C., a vinyl monomer, and a radical polymerization initiator. It contains a polymer formed by polymerization or suspension polymerization. Such a polymer is considered to be a graft copolymer obtained by graft polymerizing a vinyl monomer polymer (branch component) to a nonpolar wax (trunk component), and based on the properties of the graft copolymer. Thus, the scratch resistance of the resin molded body is improved, the appearance thereof is good, and bleeding, odor and fogging can be suppressed. Therefore, the resin molded body molded from the thermoplastic resin composition containing the surface physical property improving agent is suitably used as automobile interior parts such as automobile instrument panels and door trims.
(Non-polar wax)
The nonpolar wax is a compound that can exhibit properties such as low friction, and includes all known waxes having a melting point of 50 to 100 ° C., preferably 60 to 100 ° C. When the melting point is lower than 50 ° C., it has tackiness (adhesiveness) at room temperature, so that workability is poor, there are many bleeds on the surface of the resin molded body, and scratch resistance is also lowered. On the other hand, when the melting point is higher than 100 ° C., stable emulsions and suspensions cannot be obtained at the time of polymerization, and the final surface property improving agent has a large particle size, which deteriorates the appearance of the resin molding. In addition, the scratch resistance also decreases. Nonpolar waxes include petroleum-derived natural waxes such as paraffin wax and microcrystalline wax, and synthetic waxes such as Fischer-Tropsch wax and polyethylene wax. Of these, paraffin wax, microcrystalline wax, and Fischer-Tropsch wax are preferred because they can exhibit excellent scratch resistance when a surface property improving agent is added to the polyolefin resin.

The paraffin wax, microcrystalline wax and Fischer-Tropsch wax are generally commercially available. As the paraffin wax, trade names of Nippon Seiwa Co., Ltd .: Paraffin wax 155, Paraffin wax 150, Paraffin wax 140, Paraffin wax 135, Paraffin wax 130, Paraffin wax 1251, Paraffin wax 120, HNP-3, HNP- 5, HNP-9, HNP-10, HNP-311, HNP-12, HNP-51, LUVAX-1266, LUVAX-2191, LUVAX-1151, LUVAX-1211 and the like. Also, as the microcrystalline wax, trade names manufactured by Nippon Seiwa Co., Ltd .: Hi-Mic-2095, Hi-Mic-1090, Hi-Mic-1080, Hi-Mic-1070, Hi-Mic-2065, Hi -Mic-1045, Hi-Mic-2045, etc. are mentioned. Examples of Fischer-Tropsch wax include trade names: FT-0070, FT100, FT-0165, and FT-5165 manufactured by Nippon Seiwa Co., Ltd.
(Vinyl monomer)
As the vinyl monomer, the polymer is harder than, for example, a polyolefin resin, and is oriented on the surface of the polyolefin resin molded article due to the exclusion (exclusion) effect due to the difference in polarity from the polyolefin resin. Monomers that increase the effect of sex are preferably used.

  Examples of such monomers include (meth) acrylic acid alkyl esters having an alkyl chain length of 1 to 20 carbon atoms, vinyl monomers having acid groups, vinyl monomers having hydroxyl groups, and epoxy groups. Examples thereof include a vinyl monomer, a vinyl monomer having a cyano group, and styrene. At least one monomer selected from these is used. In this specification, acrylic and methacryl are collectively referred to as (meth) acrylic.

More specific vinyl monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth ) Lauryl acrylate, stearyl (meth) acrylate, (meth) acrylic acid, maleic acid, maleic anhydride, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid Examples include glycidyl, (meth) acrylonitrile, and styrene. Of these, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate are highly effective in scratch resistance. Particularly preferred are 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylonitrile, styrene and the like.
(Radical polymerization initiator)
A radical polymerization initiator is a compound capable of initiating radical polymerization of vinyl monomers. Generally known azo polymerization initiators, organic peroxides, persulfates, hydrogen peroxide water, redox polymerization initiation An agent (polymerization initiator in which an oxidizing agent and a reducing agent are combined) can be used.

  Examples of the azo polymerization initiator include azobisisobutyronitrile, azobisisovaleronitrile, azobisdimethylvaleronitrile, azobis (4-methoxy-2,4-dimethylvaleronitrile), 1-phenylethylazodiphenylmethane, and the like. Can be mentioned.

  Examples of the organic peroxide include peroxyketals such as 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, p -Hydroperoxides such as menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, di (3.5 , 5-trimethylhexanoyl) peroxide, diacyl peroxides such as dibenzoyl peroxide, and peroxyesters such as cumyl peroxyl neodecanoate and t-butyl peroxyl neodecanoate. Examples of the persulfate include potassium persulfate and ammonium persulfate.

  Among these, a redox polymerization initiator is more preferable because of easy control of polymerization. As the oxidizing agent used in the redox polymerization initiator, hydroperoxide or persulfate is used. For example, as hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, p- Menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide and the like, and examples of persulfate include potassium persulfate and ammonium persulfate. Examples of the reducing agent include glucose, dextrose, formaldehyde sodium sulfoxylate (Longalite), sodium thiosulfate, ferrous sulfate, copper sulfate and potassium hexacyanoiron (III).

  Among these, organic peroxyesters typified by tertiary butyl peroxyacetate, tertiary hexyl peroxybenzoate, and tertiary butyl peroxybenzoate are used as the oxidizing agent, and glucose and sulfuric acid as the reducing agent. When iron is used, the grafting reaction by hydrogen abstraction can be promoted, which is preferable.

The content of the radical polymerization initiator is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the total amount of vinyl monomers. When the content is less than 0.001 part by mass, not only a long reaction time is required to complete the polymerization, but also the reaction is not completed, which is not preferable. On the other hand, when it exceeds 5 parts by mass, the heat generation becomes large and the polymerization reaction tends to be difficult to control.
(Oxidized wax)
The oxidized wax is obtained by oxidizing the nonpolar wax with chemicals or oxygen in the air, and has a melting point of 40 to 100 ° C. By using this oxidized wax together with a nonpolar wax, there is an effect of making the emulsion or suspension more stable by the surface active action, and as a result, the particle diameter of the polymer can be easily controlled. When the melting point of the oxidized wax is lower than 40 ° C., the workability is poor because it has tackiness like the nonpolar wax, the amount of bleeding on the surface of the resin molded body is increased, and the scratch resistance is also lowered. On the other hand, when the melting point is higher than 100 ° C., stable emulsions and suspensions cannot be obtained at the time of polymerization, and the particle size of the surface property improving agent is increased to deteriorate the appearance of the resin molded product. Abrasion is also reduced.

  The acid value, saponification value and hydroxyl value of the oxidized wax are preferably an acid value of 1 to 100 mgKOH / g, a saponification value of 0 to 250 mgKOH / g and a hydroxyl value of 0 to 120 mgKOH / g, respectively, and an acid value of 5 to 80 mgKOH. / G, a saponification value of 0 to 200 mgKOH / g, and a hydroxyl value of 0 to 100 mgKOH / g are more preferable.

  As representative examples of such oxidized wax, NPS series made by Nippon Seiwa Co., Ltd., which oxidized petroleum wax, LUVAX series and OX series, Licowax series made by Clariant Japan Co., Ltd. which oxidized polyethylene wax, Mitsui Chemicals Co., Ltd. Mitsui High Wax series and so on. Of these, NPS-8070, NPS-9210, NPS-9125, LUVAX-0321, OX-1949, and OX-020T are more preferable. The content of these oxidized waxes is preferably 0 to 200% by mass and more preferably 0 to 100% by mass with respect to the nonpolar wax.

The ratio of the nonpolar wax or the nonpolar wax and the oxidized wax to the polymer formed from the vinyl monomer is preferably 10 to 90% by mass of the wax and 90% of the polymer formed from the vinyl monomer. -10 mass%. The term “wax” means both nonpolar wax and oxidized wax. More preferably, the wax is 20 to 80% by mass and the polymer formed from the vinyl monomer is 80 to 20% by mass, and still more preferably the wax is 30 to 70% by mass and the weight formed from the vinyl monomer. The coalescence is 70 to 30% by mass. When the amount of the wax is less than 10% by mass, the resin scratch resistance is lowered, which is not preferable. When the amount is more than 90% by mass, the wax is bleed on the surface of the resin molded body, and the appearance is deteriorated.
[Method for producing surface property improving agent]
The surface property improving agent can be produced through the following first and second steps.

1st process: The process of obtaining the polymer by emulsion polymerization or suspension polymerization of the liquid mixture containing the wax of melting | fusing point 50-100 degreeC, a vinyl monomer, and a radical polymerization initiator.
2nd process: The 2nd process which obtains the surface physical property improvement agent of a resin molding by drying and refine | purifying the polymer obtained at the 1st process after salting out or filtering.

Next, typical production methods will be described below according to embodiments.
First, a method for producing a surface property improving agent by an emulsion polymerization method will be described.
Emulsion polymerization method (1):
A surface property improving agent is manufactured through the following first to fourth steps.

  1st process: The process of mixing a wax, a vinyl monomer, and surfactant, and heating to the melting | fusing point or more of a wax, and obtaining an oil phase. 2nd process: The process of adding the water heated more than the melting | fusing point of a wax in an oil phase, stirring, and obtaining an emulsion. Third step: A step of adding a radical polymerization initiator to the emulsion and polymerizing it to obtain a polymer. Fourth step: A step of purifying the polymer.

Emulsion polymerization method (2):
A surface property improving agent is manufactured through the following first to third steps.
1st process: The process which mixes wax, a vinyl monomer, surfactant, and water, and stirs, heating up to the melting | fusing point or more of a wax, and obtaining an emulsion. Second step: A step of adding a radical polymerization initiator to the emulsion and polymerizing it to obtain a polymer. Third step: a step of purifying the polymer.

Emulsion polymerization method (3):
A surface property improving agent is produced through the following first to fifth steps.
1st process: The process of mixing a wax, a vinyl monomer, and surfactant, and heating to the melting | fusing point or more of a wax, and obtaining an oil phase. Second step: A step of adding water heated to the melting point of the wax to the oil phase and stirring to obtain an emulsion. 3rd process: The process of heating the liquid mixture which consists of water and surfactant, and obtaining an aqueous phase. 4th process: The process of adding an emulsion and a radical polymerization initiator in an aqueous phase, and making it polymerize and obtaining a polymer. Fifth step: a step of purifying the polymer.

  As the surfactant used in the emulsion polymerization, known nonionic, anionic or cationic surfactants can be used, but anionic surfactants are preferred in consideration of taking out the polymer by salting out. . Examples of anionic surfactants include fatty acid salts, sodium alkylbenzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphates, naphthalene sulfonate formalin condensates, polyoxyethylene alkyl sulfates, etc. Can be mentioned. One or more kinds of these surfactants are appropriately selected and used, and usually 0.1 to 10 parts by weight, preferably 1 to 5% by weight, based on 100 parts by weight of the wax and vinyl monomer. Used in.

  In the emulsion polymerization, known pH adjusters, chelating agents, polymerization regulators, polymerization stabilizers and the like can be added as necessary. For example, pH regulators such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium bicarbonate, sodium carbonate, disodium hydrogen phosphate, chelating agents such as sodium ethylenediaminetetraacetate, sodium pyrophosphate, inorganic electrolytes, organic electrolytes , A viscosity modifier made of a polymer electrolyte, or a polymerization stabilizer. Furthermore, in order to control the degree of polymerization, a known crosslinking agent, chain transfer agent, polymerization inhibitor and the like can be added.

  The polymerization temperature is preferably appropriately changed depending on the melting point of the wax to be used and the kind of the polymerization initiator, and is, for example, 50 to 100 ° C, more preferably 60 to 100 ° C. In such a temperature range, a temperature at which temperature control is easy and polymerization is completed is appropriately selected.

  After the polymerization is completed, the emulsion obtained by emulsion polymerization is purified according to a usual method. Examples of the purification method include acids such as hydrochloric acid, sulfuric acid, and nitric acid, and electrolytes such as sodium chloride, potassium chloride, sodium sulfate, calcium chloride, magnesium sulfate, copper sulfate, and calcium nitrate. The method of filtering and drying after analyzing is mentioned.

Next, a method for producing a surface property improving agent by suspension polymerization will be described.
A surface property improving agent is manufactured through the following first to third steps.
1st process: The process of mixing water, a suspension agent, wax, and a vinyl monomer, and heating up more than melting | fusing point of wax. Second step: A step of adding a radical polymerization initiator to the suspension and performing a polymerization reaction to obtain a polymer. Third step: a step of purifying the polymer.

The radical polymerization initiator used here includes all of the radical polymerization initiators used in the emulsion polymerization method.
Examples of the dispersant used in the suspension polymerization method include inorganic compounds such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, and water. Examples thereof include aluminum oxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina, magnetic substance, and ferrite. Examples of the organic compound include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, starch, and the like, which are used by being dispersed or dissolved in an aqueous phase.

  The content of these dispersants is preferably 0.01 to 10.0 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the total amount of wax and vinyl monomer. In addition, commercially available nonionic, anionic and cationic surfactants can also be used as the dispersant. Examples of such surfactants include sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate and the like. After suspension polymerization is complete, the resulting polymer is purified according to conventional methods. Examples of the purification method include a method of filtering and drying the suspension.

  The mass average molecular weight of the polymer formed from the vinyl monomer (measured by gel permeation chromatograph (GPC) in terms of styrene in tetrahydrofuran (THF)) is usually 1,000 to 6,000,000, preferably Is 1,000 to 4,000,000. If the mass average molecular weight is less than 1,000, the heat resistance of the polymer tends to decrease, and if the mass average molecular weight exceeds 6,000,000, the fluidity when the polymer is melted deteriorates. There exists a tendency for a moldability to fall.

  Further, in order to increase the grafting efficiency, a radical polymerizable organic peroxide represented by the following general formula (1) or general formula (2) may be copolymerized when producing the surface property improving agent. . By using these radically polymerizable organic peroxides, it is possible to easily obtain a high grafting efficiency.

式中、Ｒ^１は水素原子、メチル基又はエチル基、Ｒ^２は水素原子又はメチル基、Ｒ^３及びＲ^４はそれぞれ炭素数１〜４のアルキル基、Ｒ^５は炭素数１〜１２のアルキル基、フェニル基、アルキル置換フェニル基又は炭素数３〜１２のシクロアルキル基を表す。ｍは１又は２である。

In the formula, R ¹ is a hydrogen atom, methyl group or ethyl group, R ² is a hydrogen atom or methyl group, R ³ and R ⁴ are each an alkyl group having 1 to 4 carbon atoms, and R ⁵ is an alkyl group having 1 to 12 carbon atoms. Represents a group, a phenyl group, an alkyl-substituted phenyl group or a cycloalkyl group having 3 to 12 carbon atoms. m is 1 or 2.

式中、Ｒ^６は水素原子又は炭素数１〜４のアルキル基、Ｒ^７は水素原子又はメチル基、Ｒ^８及びＲ^９はそれぞれ炭素数１〜４のアルキル基、Ｒ^１０は炭素数１〜１２のアルキル基、フェニル基、アルキル置換フェニル基又は炭素数３〜１２のシクロアルキル基を表す。ｎは０、１又は２である。

In the formula, R ⁶ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁷ is a hydrogen atom or a methyl group, R ⁸ and R ⁹ are each an alkyl group having 1 to 4 carbon atoms, and R ¹⁰ is an alkyl group having 1 to 1 carbon atoms. 12 represents an alkyl group, a phenyl group, an alkyl-substituted phenyl group, or a cycloalkyl group having 3 to 12 carbon atoms. n is 0, 1 or 2.

  Here, the radical polymerizable organic peroxide refers to a compound having a peroxide bond and a radical polymerizable functional group in one molecule. As this radically polymerizable organic peroxide, for example, one or a mixture of two or more compounds represented by the general formula (1) or the general formula (2) is used. The content of the radical polymerizable organic peroxide is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the vinyl monomer.

  Examples of the radical polymerizable organic peroxide represented by the general formula (1) or the general formula (2) include, for example, t-butylperoxyacryloyloxyethyl carbonate, t-butylperoxymethacryloyloxyethyl carbonate, t-butyl. Peroxyallyl carbonate and t-butyl peroxymethacryloyl carbonate are preferred.

The surface property improving agent thus obtained is in the form of fine particles, and the average particle diameter of the particles is preferably 0.1 to 100 μm, more preferably 0.3 to 20 μm. When the average particle size is less than 0.1 μm, the surface property improving agent particles become too fine, resulting in poor handling and difficulty in production. On the other hand, when it exceeds 100 μm, the dispersibility is lowered when the surface property improving agent is blended with the polyolefin resin, the function of the surface property improving agent cannot be sufficiently exhibited, and the appearance of the resin molded article is deteriorated.
[Thermoplastic resin composition]
The thermoplastic resin composition contains a polyolefin resin as a main component and contains the aforementioned surface property improving agent, and the vinyl monomer has a polarity different from that of the polyolefin resin. Examples of polyolefin resins include α-olefin resins and thermoplastic elastomers.

  Specific examples of the α-olefin forming the α-olefin resin include ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 1-decene and 3-methyl-1- Examples include pentene, 4-methyl-1-pentene, 1-octene, and a mixture thereof. Specific examples of the α-olefin resin include polyethylene and polypropylene.

  Examples of the thermoplastic elastomer include olefin-based thermoplastic elastomers, and may include styrene-based thermoplastic elastomers. Specific examples of the olefinic thermoplastic elastomer include a blend of polypropylene and ethylene / propylene copolymer rubber or a crosslinked product thereof; a blend of polyethylene and ethylene / propylene copolymer rubber or a crosslinked product thereof; polypropylene and ethylene.・ Propylene / non-conjugated polyene copolymer rubber blend or cross-linked product thereof; polyethylene and ethylene / propylene / non-conjugated polyene copolymer rubber blend or cross-linked product; polypropylene and styrene / butadiene block copolymer rubber Blended product of hydrogenated product (SEBS) or cross-linked product thereof; Blended product of polypropylene and ethylene / 1-octene copolymer rubber or cross-linked product thereof; Blended product of polyethylene and ethylene / 1-octene copolymer rubber Or a cross-linked product thereof

  Such olefin-based thermoplastic elastomers are commercially available, for example, trade name: Miralastomer (manufactured by Mitsui Chemicals), trade name: Santoprene (manufactured by AES Japan Ltd.), trade name: Sumitomo Examples include TPE [manufactured by Sumitomo Chemical Co., Ltd.], trade name: Engage [manufactured by DuPont Dow Elastomer Co., Ltd.], and trade name: Thermoran [manufactured by Mitsubishi Chemical Corporation].

  Specific examples of the styrenic thermoplastic elastomer include styrene / butadiene copolymer rubber (SBR) or its hydrogenated product (H-SBR), styrene / butadiene block copolymer rubber (SBS) or its hydrogenated product (SEBS). ); Styrene / isoprene block copolymer rubber (SIS) or hydrogenated product thereof (SEPS, HV-SIS).

  Such styrenic thermoplastic elastomers are commercially available, for example, trade name: Tuftec [Asahi Kasei Co., Ltd.], trade name: Elastomer AR [Aron Kasei Co., Ltd.], trade name: Septon [Kuraray Co., Ltd.] Product name: Clayton [manufactured by Clayton Polymer Japan Co., Ltd.], product name: JSR TR [manufactured by JSR Corporation], and the like.

  The α-olefin resin and the thermoplastic elastomer may be used alone or in combination of two or more. The crosslinking is performed by a known method, and among them, crosslinking with an organic peroxide is preferable.

  0.1-20 mass% is preferable and, as for content of the surface physical property modifier in a thermoplastic resin composition, 1-10 mass% is more preferable. That is, the proportion of the polyolefin resin is preferably 80 to 99.9% by mass, and more preferably 90 to 99% by mass. If the surface property improving agent is less than 0.1% by mass, the expression of characteristics by the surface property improving agent tends to be insufficient. , Because the fluidity is lowered.

  Moreover, you may mix | blend another resin, rubber | gum, or an inorganic filler with the thermoplastic resin composition in the range which does not impair the objective of this invention. Examples of such resins and rubbers include ethylene / acrylic acid copolymers, ethylene / methyl acrylate copolymers, ethylene / methyl methacrylate copolymers, ethylene / ethyl acrylate copolymers, and ethylene / acrylic acid. Isobutyl copolymer, ethylene / n-butyl acrylate copolymer, ethylene / 2-ethylhexyl acrylate copolymer, ethylene / ethyl acrylate / maleic anhydride copolymer, ethylene / ethyl acrylate / glycidyl methacrylate copolymer Polymers, ethylene / glycidyl methacrylate copolymers, ethylene / vinyl acetate copolymers or saponified ethylene copolymers; ethylene / propylene copolymer rubbers, ethylene / propylene / non-conjugated polyene copolymer rubbers, Ethylene / butene copolymer rubber, ethylene / butene / non-conjugated polymer Ethylene copolymer rubbers such as ene copolymer rubber, ethylene / hexene copolymer rubber, ethylene / octene copolymer rubber; butyl rubber, polyisobutylene rubber, nitrile rubber (NBR), natural rubber (NR), acrylic rubber (ACM) and silicone rubber.

  Examples of inorganic fillers include calcium carbonate, calcium silicate, clay, kaolin, talc, silica, diatomaceous earth, mica powder, asbestos, alumina, barium sulfate, aluminum sulfate, calcium sulfate, basic magnesium carbonate, molybdenum disulfide, Examples thereof include graphite, glass fiber, glass sphere, shirasu balloon, basic magnesium sulfate whisker, calcium titanate whisker, and aluminum borate whisker.

  Moreover, you may mix | blend a lubricant with the thermoplastic resin composition in the range which does not impair the objective of this invention. Such lubricants include saturated aliphatic amides such as lauric acid amide, palmitic acid amide, stearic acid amide, and behemic acid amide; unsaturated fatty acids such as erucic acid amide, oleic acid amide, brassic acid amide, and elaidic acid amide. Amides; bis-fatty acid amides such as methylene bis-stearic acid amide, methylene bis-oleic acid amide, ethylene bis-stearic acid amide, ethylene bis-oleic acid amide; methyl laurate, methyl myristate, methyl palmitate, methyl stearate, olein Methyl acid, methyl erucate, methyl behenate, butyl laurate, butyl stearate, isopropyl myristate, isopropyl palmitate, octyl palmitate, coconut fatty acid octyl, octyl stearate, lauric laurate , Stearyl stearate, behenyl behenate, cetyl myristate, neopentyl polyol long chain fatty acid ester, neopentyl polyol fatty acid ester, neopentyl polyol fatty acid ester, pentaerythritol tetrapalinate, etc .; polyethylene wax, polypropylene wax Hydrocarbons such as stearic acid and 1,2-hydroxystearic acid; higher alcohols such as stearyl alcohol; metal soaps such as calcium stearate, zinc stearate and magnesium stearate; silicones such as silicone oil Fluorine resin such as polytetrafluoroethylene; polyethylene glycol, polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether Lubricants alkylene glycol such as ether can be mentioned.

  Furthermore, the thermoplastic resin composition includes known heat stabilizers, flame retardants, anti-aging agents, weathering stabilizers, antistatic agents, dispersants, foaming agents, ultraviolet light inhibitors, as long as the object of the present invention is not impaired. It is also possible to add a colorant, a plasticizer, a mineral oil softener and the like.

The thermoplastic resin composition is prepared by mixing, heating, melting, and mixing the components described above, and the heating temperature at that time is preferably 70 to 300 ° C. When this heating temperature is less than 70 ° C., the kneading of the polyolefin resin and the surface property improving agent is incomplete, or the melt viscosity is high, so that the mixing becomes insufficient, and phase separation or delamination tends to appear. It is not preferable. On the other hand, when it exceeds 300 ° C., the decomposition of the polyolefin resin and the surface property improving agent tends to be severe, which is not preferable. As the melting and mixing method, a known method such as a kneading method using a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader, or a roll is employed.
[Resin molding]
The resin molded body is obtained by molding the above thermoplastic resin composition into a predetermined shape, and the effect of the surface physical property improving agent contained in the thermoplastic resin composition is exhibited. Examples of the form of the resin molded body include a sheet, a film, a heat molded body, a hollow molded body, a foamed body, and an injection molded body. As a molding method, a method of molding by a generally adopted thermoplastic resin molding machine is adopted, and specifically, a calendering method, a pressure processing method, a heat molding method, a blow molding method, a foam molding method, an extrusion molding method. , Injection molding, vacuum molding, powder slush molding, and the like. The resin molded body can be used for various products and semi-finished products in a wide range of fields such as automobile parts, home appliance parts, and miscellaneous goods by taking advantage of the above-described excellent characteristics.

  Specifically, the automobile interior skin material is obtained by molding the resin molded body into the form of an automobile interior skin material. The automobile interior skin material is, for example, a laminate of a polyolefin foam layer and a skin layer formed by molding the thermoplastic resin composition provided on the surface thereof. A topcoat layer can also be formed by coating on this skin layer. A primer layer may be interposed between the skin layer and the top coat layer. The skin layer formed by molding the thermoplastic resin composition is obtained by supplying it to a plastic processing machine such as an extrusion molding machine with a T-die or a calendar molding machine and molding it into a desired shape such as a sheet according to a conventional method. It is done.

  Specifically, polyethylene, polypropylene and the like are preferable as the polyolefin used in the polyolefin foam layer, and these crosslinked foams are more preferable. The cross-linked foam can be obtained by mixing a foaming agent and a cross-linking agent (radical generator) with polyethylene or polypropylene, heating at a temperature equal to or higher than the softening point of the obtained mixture, and decomposing the cross-linking agent. As the crosslinking agent, dicumyl peroxide, benzoyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2, Organic peroxides such as 5-di (t-butylperoxy) hexyne, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane-3, lauroyl peroxide, t-butylperoxybenzoate Used. Examples of other crosslinking methods include a method using ionizing radiation irradiation and a method using ionizing radiation irradiation in the presence of a polyfunctional monomer. Ionizing radiation includes electron beams, γ-rays, X-rays, ion beams, etc., but those that are industrially easily used are electron beams and γ-rays. A suitable dose of ionizing radiation is about 30 to 500 kGy. As the irradiation amount increases, the degree of crosslinking increases, but the heat aging resistance deteriorates, so the range of 60 to 300 kGy is preferable.

  The laminate is molded according to a known molding method. For example, a method of extruding a thermoplastic resin composition with an extruder with a T-die, and passing the extruded thermoplastic resin composition in a molten state between a pair of rolls in a state of being laminated with a polyolefin foam sheet Molded with.

  Specific examples of the material for the top coat layer applied and formed on the skin layer include at least one selected from a polyurethane resin, a saturated polyester resin, an acrylate resin, a polyvinyl chloride resin, and an isocyanate resin. More specifically, examples of the saturated polyester resin include polyethylene terephthalate, polybutylene terephthalate and derivatives thereof, and examples of the acrylic ester resin include polymethyl (meth) acrylate, polyisobutyl (meth) acrylate, poly 2-ethylhexyl (meth) acrylate, and the like. Examples of the isocyanate resin include polyhexamethylene diisocyanate and polyisophorone diisocyanate. The thickness of the top coat layer is preferably 300 μm or less.

In addition, an automobile interior skin material is usually used with a textured surface. The embossing can be performed by a known method, for example, by passing between an embossing roll and a pinch roll during sheet forming. Such an automobile interior skin material is used as a skin layer of, for example, an instrument panel, a door trim, a shift lever, a handle, a console box, an airbag cover, an assist grip, a ceiling, a seat, and the like.
[Summary of Action and Effect of Embodiment]
-The surface property improving agent of this embodiment contains the polymer formed by emulsion-polymerizing or suspension-polymerizing the liquid mixture containing the said nonpolar wax, a vinyl monomer, and a radical polymerization initiator. By performing polymerization using a radical polymerization initiator in the presence of a non-polar wax, a hydrogen abstraction reaction occurs from the non-polar wax, and the graft co-polymerization between the non-polar wax and the polymer formed from the vinyl monomer occurs. It is believed that a polymer is formed. Such a graft copolymer is formed from a nonpolar wax that does not have an affinity for a polyolefin resin and is easily oriented on the surface of a resin molding, and a vinyl monomer that is harder than the polyolefin resin and has a polarity different from that of the polyolefin resin. And a polymer.

  Therefore, when a thermoplastic resin composition is prepared by blending a surface property improver with a polyolefin resin and molded to obtain a resin molded body, it is formed from the surface orientation by nonpolar wax and a vinyl monomer. It is presumed that the surface property improving agent is oriented in the vicinity of the surface of the resin molded product due to the exclusion effect due to the difference in polarity between the polymer and the polyolefin resin. Therefore, the synergistic effect of the nonpolar wax, which has low friction properties and has the effect of sliding the surface, and the polymer formed from the vinyl monomer harder than the polyolefin resin, the weight of the nonpolar wax and the vinyl monomer is increased. High scratch resistance that could not be obtained by simply blending the coalescence can be exhibited.

  In addition, since the nonpolar wax forms a graft copolymer with a polymer of vinyl monomer, the graft copolymer exhibits affinity due to intermolecular force and the like with the polyolefin resin, and is contained in the resin molded body. Holds well. For this reason, the resin molded body can be prevented from bleeding, can maintain an excellent appearance, and can also suppress fogging. In addition, since the nonpolar wax has no odor and the polymer of the vinyl monomer is polymerized and does not have a low molecular weight such as fatty acid amide, the odor of the resin molded product can be suppressed. Therefore, the resin molded body can be suitably used as an automobile interior part, an electrical part, a machine part, or the like.

  -It is considered that when the mixed solution further contains an oxidized wax having a melting point of 40 to 100 ° C., the oxidized wax and the nonpolar wax are graft-polymerized with a vinyl monomer to form a graft copolymer. . The oxidized wax exhibits a surface active action, can improve the stability of the emulsion by emulsion polymerization or the suspension by suspension polymerization, and can provide a surface property improving agent with few aggregates. Therefore, the appearance of the resin molded body can be further improved.

-A surface physical property improving agent is manufactured through the 1st process and the 2nd process which are shown below.
1st process: The process of obtaining the polymer by emulsion polymerization or suspension polymerization of the liquid mixture containing the nonpolar wax of melting | fusing point 50-100 degreeC, a vinyl monomer, and a radical polymerization initiator.

  Second step: The polymer obtained in the first step is salted out in the case of emulsion polymerization, filtered and then dried and purified. In the case of suspension polymerization, the polymer is filtered and dried and purified. A step of obtaining a surface property improving agent for a molded article.

  Therefore, the nonpolar wax can be emulsified or suspended in a state dissolved in the vinyl monomer, and an emulsion or suspension can be obtained in a stable state, and a surface property improving agent with few aggregates can be obtained. it can. Therefore, a surface property improving agent having the above effects can be easily obtained by a simple operation.

  The thermoplastic resin composition is mainly composed of a polyolefin resin, contains a surface physical property improver, and the vinyl monomer has a polarity different from that of the polyolefin resin, and is included in the surface of the thermoplastic resin composition. The effects described above can be exhibited based on the physical property improving agent.

  The resin molded body is obtained by molding a thermoplastic resin composition containing a polyolefin resin as a main component, containing a surface property improving agent, and the vinyl monomer having a polarity different from that of the polyolefin resin. Therefore, the surface property improving agent moves to the surface side of the resin molded body mainly due to the difference in polarity, and can effectively exhibit the above-described effects on the resin molded body.

Hereinafter, although the said embodiment is described further more concretely by giving an Example and a comparative example, this invention is not limited to the range of these Examples. Moreover, unless otherwise indicated, the part and% in each example show a mass part and mass%. In addition, the physical property test methods in these Examples and Comparative Examples are as follows.
(1) Measurement of particle diameter: Using a laser diffraction / scattering particle size distribution measuring apparatus LA-920 (manufactured by HORIBA, Ltd.), the average particle diameter (μm) of the obtained surface property improving agent particles was measured. .
(2) Appearance of resin molded body: Using an injection molding machine (manufactured by Tabata Machine Industry Co., Ltd.), a resin molded body (plate test piece) having a length of 90 mm, a width of 55 mm, and a thickness of 2 mm from the pellet of the thermoplastic resin composition. The appearance was evaluated according to the following evaluation criteria.

○: No difference from blank is recognized. ○ △: A small amount of fine particles is observed. Δ: A large amount of fine particles is observed. Δ: A small amount of large particles is observed. X: A lot of large particles are observed.
(3) Bleedability of resin molded product: The plate test piece is left in an oven at 70 ° C. for 72 hours, the components that bleed on the surface of the plate test piece are visually observed, and the appearance is evaluated according to the following evaluation criteria. evaluated.

○: No bleed. Δ: Slight bleeding. X: There is a bleed.
(4) Scratch resistance: Using a five finger scratch tester (manufactured by ROCKWOOD SYSTEMS AND EQUIPMENT, INC.), Whitening of the scratch was observed visually, and a load at which no whitening occurred was used as an evaluation point. The loads were tested at 3, 6, 10, 15 and 20N.
(5) Fogging test: Using a fogging tester manufactured by HAAKE, the mass change at 10 g of a thermoplastic resin composition pellet, a test temperature of 100 ° C., a test time of 16 hours, and a cooling plate of 21 ° C. is performed in accordance with a method based on ISO6452. It was measured.
(6) Odor: Ten plate test pieces obtained were placed in a mayonnaise bottle having a capacity of 477 ml, sealed, and allowed to stand in a dryer at 90 ° C. for 3 hours. Then, it cooled at room temperature for 2 hours. An odor test was conducted by 10 panelists comparing the sample with a blank. As the blank, plate test pieces corresponding to Comparative Example 2 and Comparative Example 6 were used. Evaluation was performed by the average point of the total of 10 people according to the following criteria. The smaller the score, the better the odor characteristics.

1 point: No difference from blank. 2 points: Slightly different from blanks. 3 points: Slight odor is observed. 4 points: A weak odor is felt. 5 points: Strong odor is recognized.
The abbreviations in the following examples, comparative examples and tables represent the following substances.

PW-1: Paraffin wax 155 (manufactured by Nippon Seiwa Co., Ltd., melting point 69 ° C.)
PW-2: FT-0070 [Nippon Seiwa Co., Ltd., melting point 72 ° C.]
PW-3: Paraffin wax 115 (manufactured by Nippon Seiwa Co., Ltd., melting point 47 ° C.)
PW-4: FT-115 [Nippon Seiwa Co., Ltd., melting point 114 ° C.]
mPW-1: NPS-9125 [Nippon Seiwa Co., Ltd., melting point 69 ° C.]
mPW-2: LUVAX0321 [Nippon Seiwa Co., Ltd., melting point 75 ° C.]
St: styrene, AN: acrylonitrile, MMA: methyl methacrylate, MAA: methacrylic acid, HEMA: 2-hydroxyethyl methacrylate, PP: polypropylene [trade name: Prime Polypro J708UG, manufactured by Prime Polymer Co., Ltd.]
TPO: Olefin-based thermoplastic elastomer [trade name: Miralastomer 8030, manufactured by Mitsui Chemicals, Inc.]
OA: oleic acid amide [trade name: Alfro E-10, manufactured by NOF Corporation]
Silicone oil [trade name: SH200-1000CS, manufactured by Toray Dow Corning Co., Ltd., molecular weight of about 20000]
[Example 1, production of surface property improving agent 1]
In a separable flask with a volume of 1 liter, 140 g of nonpolar wax [manufactured by Nippon Seiwa Co., Ltd., trade name: paraffin wax 155, melting point: 69 ° C.], 42 g of styrene, 18 g of acrylonitrile, sodium dodecylbenzenesulfonate as a surfactant 10 g, 0.04 g of 2,4-diphenyl-4-methyl-1-pentene [manufactured by NOF Corporation, NOFMER MSD] as a chain transfer agent was added, and the temperature was raised to 70 ° C. with stirring to obtain a substantially uniform oil. Got the phase. Next, while maintaining a temperature of 70 ° C. and stirring, 466.7 g of ion-exchanged water, 0.02 g of ferrous sulfate (II) heptahydrate as a reducing agent and 1 g of glucose, and sodium pyrophosphate as a chelating agent A 70 ° C. warm water phase in which 1 g of decahydrate was dissolved was dropped into the oil phase in 2 hours using a dropping pump to obtain an emulsion.

Next, 0.84 g of t-butyl hydroperoxide [manufactured by NOF Corporation, Perbutyl H] is added as a radical polymerization initiator, and the mixture is polymerized for 1 hour while stirring at 70 ° C. for 5 hours and after heating to 80 ° C. A polymer was obtained. After cooling, salting out was performed using calcium carbonate. The precipitated polymer was filtered and dried to obtain the surface property improving agent 1 of the present invention.
[Example 2, production of surface property improving agent 2]
A surface property improving agent 2 was obtained in the same manner as in Example 1 except that the paraffin wax 155 was changed to FT-0070 (Nippon Seiwa Co., Ltd., melting point 72 ° C.).
[Example 3, Production of surface property improving agent composition 3]
The same operation as in Example 1 except that 140 g of nonpolar wax (paraffin wax 155) was added to 100 g and 40 g of oxidized wax (manufactured by Nippon Seiwa Co., Ltd., trade name: NPS9125, melting point: 63 ° C.). A surface property improving agent 3 was obtained.
[Example 4, production of surface property improving agent 4]
100 g of the nonpolar wax (paraffin wax 155) of Example 3 is 80 g of wax (manufactured by Nippon Seiwa Co., Ltd., trade name: FT-0070, melting point: 72 ° C.), and 40 g of oxidized wax (NPS9125) is 20 g. , Vinyl monomer (42 g of styrene and 18 g of acrylonitrile) to 100 g of methyl methacrylate, chain transfer agent (Nofmer MSD 0.09 g) to 0.05 g of n-dodecyl mercaptan [NDM-1 manufactured by NOF Corporation] The surface property improving agent 4 was obtained in the same manner as in Example 3 except that the temperature for obtaining the oil phase was changed from 70 ° C to 72 ° C.
[Example 5, production of surface property improving agent 5]
40 g of nonpolar wax (paraffin wax 155) of Example 3 above, 40 g of oxidized wax (NPS9125) in LUVAX 0321 (manufactured by Nippon Seiwa Co., Ltd., melting point 75 ° C.), 96 g of styrene, and 24 g of acrylonitrile 18 g In addition, 0.09 g of 2,4-diphenyl-4-methyl-1-pentene (manufactured by NOF Corporation, NOFMER MSD) is changed to 0.36 g, and the temperature for obtaining the oil phase is changed from 70 ° C. to 75 ° C. Obtained the surface property improving agent 5 in the same manner as in Example 3.
[Comparative Example 1]
A polymer was obtained in the same manner as in Example 1 except that the paraffin wax 155 was changed to paraffin wax 115 (manufactured by Nippon Seiwa Co., Ltd., melting point 47 ° C.).
[Comparative Example 2]
A polymer was obtained in the same manner as in Example 1 except that the paraffin wax 155 was changed to FT-115 (manufactured by Nippon Seiwa Co., Ltd., melting point 114 ° C.).
[Example 6, production of surface property improving agent 6]
In a separable flask having a volume of 1 liter, 80 g of nonpolar wax [manufactured by Nippon Seiwa Co., Ltd., trade name: FT-0070, melting point: 72 ° C.], oxidized wax [manufactured by Nippon Seiwa Co., Ltd., trade name: LUVAX0321 , Melting point: 75 ° C.] 40 g, methyl methacrylate 60 g, methacrylic acid 20 g, surfactant sodium dodecylbenzenesulfonate 10 g, chain transfer agent n-dodecyl mercaptan [manufactured by NOF Corporation, NDM-1] 04 g, 466.7 g of ion-exchanged water, 0.02 g of ferrous sulfate (II) sulfate heptahydrate as a reducing agent and 1 g of glucose, and 1 g of sodium pyrophosphate decahydrate as a chelating agent were heated to 75 ° C. The mixture was stirred at 10,000 rpm for 10 minutes using a homomixer to obtain an emulsion.

Next, it is cooled to 70 ° C., 0.84 g of t-butyl hydroperoxide [manufactured by NOF Corporation, Perbutyl H] is added as a polymerization initiator, and the temperature is raised to 80 ° C. for 5 hours at 70 ° C. For 1 hour to obtain a polymer. After cooling, salting out was performed with calcium carbonate. The precipitated polymer was filtered and dried to obtain the surface property improving agent 6.
[Example 7, production method of surface property improving agent 7]
In a separable flask having a volume of 1 liter, 80 g of nonpolar wax [manufactured by Nippon Seiwa Co., Ltd., trade name: paraffin wax 155, melting point: 69 ° C.], oxidized wax [manufactured by Nippon Seiwa Co., Ltd., trade name: NPS9125 , Melting point: 63 ° C.] 20 g, methyl methacrylate 80 g, 2-hydroxyethyl methacrylate 20 g, sodium dodecylbenzenesulfonate 6 g as a surfactant, n-dodecyl mercaptan [manufactured by NOF Corporation, NDM- 1] 0.1 g was added and the temperature was raised to 70 ° C. with stirring to obtain a uniform oil phase.

Next, 200 g of ion-exchanged water at 70 ° C. was dropped into the oil phase with a dropping pump for 2 hours so as not to lower the temperature, thereby obtaining an emulsion. On the other hand, 266.7 g of ion exchange water in a 1 liter separable flask, 4 g of sodium dodecylbenzenesulfonate as a surfactant, 0.02 g of ferrous sulfate (II) sulfate heptahydrate as a reducing agent, 1 g of glucose, and a chelating agent 1 g of sodium pyrophosphate decahydrate was added and heated to 70 ° C. To this warm water phase, 0.84 g of the emulsion and t-butyl hydroperoxide [manufactured by NOF Corporation, Perbutyl H] as a polymerization initiator was dropped by a dropping pump for 2 hours, and 70 ° C. for 5 hours and 80 ° C. The temperature was raised to 1, and polymerization was performed for 1 hour to obtain a polymer. After cooling, salting out was performed with calcium carbonate. The precipitated polymer was filtered and dried to obtain the surface property improving agent 7.
[Example 8, production of surface property improving agent 8]
In a separable flask having a volume of 1 liter, 500 g of water was added, and 0.5 g of polyvinyl alcohol was further dissolved as a suspending agent. In this, 56 g of nonpolar wax [Nippon Seiwa Co., Ltd., brand name: Paraffin wax 155, melting | fusing point: 69 degreeC], oxidation wax [Nippon Seiwa Co., Ltd. brand name: LUVAX0321, melting | fusing point: 75 degreeC] ] 24 g, 100 g of styrene, 20 g of 2-hydroxyethyl methacrylate, 2,4-diphenyl-4-methyl-1-pentene [manufactured by NOF Corporation, NOFMER MSD] as a chain transfer agent was added and stirred. The temperature was raised to 80 ° C. As a polymerization initiator, 0.3 g of benzoyl peroxide [manufactured by NOF Corporation, Nyper BW] was added, and polymerization was carried out at 80 ° C. for 5 hours and at 90 ° C. for 1 hour to obtain a polymer. Next, the surface property improving agent 8 was obtained by washing with water and drying.

実施例１〜８及び比較例１では粉末状の重合体が得られたが、比較例２では重合時にワックスが溶解せず、均一な乳化液が得られなかったため、結果的に凝集物が多く平均粒子径の測定ができなかった。また、実施例１と３の比較において、実施例３の方が重合後の凝集物が少なく、平均粒子径も細かくなったことから酸化ワックスの併用の効果が観察された。
〔実施例９〜１６及び比較例３〜１０、熱可塑性樹脂組成物の製造及び樹脂成形体の評価〕
表２に示す成分及び配合割合でドライブレンドした後、シリンダー温度２００℃に設定されたスクリュー径３０ｍｍの同軸方向二軸押出機で溶融・混合して、熱可塑性樹脂組成物のペレットを得た。これらのペレットを用いて樹脂成形体としての試験片（縦９０ｍｍ、横５５ｍｍ及び厚さ２ｍｍ）を射出成形した。得られた樹脂成形体について前記の外観、ブリード性、耐擦傷性、フォギング及び臭気の試験を行った。それらの結果を表２に示した。なお、比較例３はポリプロピレンのブランク、比較例４はワックスのみ、比較例５はビニル共重合体としてのスチレン・アクリロにリル共重合体（ＡＳ）のみ、比較例６はワックスとスチレン・アクリロにリル共重合体（ＡＳ）をそれぞれ配合したもの、比較例７はオレフィン系熱可塑性エラストマー（ＴＰＯ）のブランク、比較例８はオレイン酸アミド（ＯＡ）添加系、比較例９はシリコーンオイル添加系、比較例１０は比較例１添加系であって、何れも本発明の範囲外となる例を示した。

In Examples 1 to 8 and Comparative Example 1, a powdery polymer was obtained. However, in Comparative Example 2, the wax was not dissolved during polymerization, and a uniform emulsion was not obtained. The average particle size could not be measured. Further, in the comparison between Examples 1 and 3, the effect of the combined use of the oxidized wax was observed because Example 3 had fewer aggregates after polymerization and the average particle diameter became finer.
[Examples 9-16 and Comparative Examples 3-10, Production of Thermoplastic Resin Composition and Evaluation of Resin Molded Article]
After dry blending at the components and blending ratios shown in Table 2, the mixture was melted and mixed with a coaxial twin screw extruder having a screw diameter of 30 mm set at a cylinder temperature of 200 ° C. to obtain pellets of a thermoplastic resin composition. Using these pellets, test pieces (length 90 mm, width 55 mm, and thickness 2 mm) as resin molded bodies were injection molded. The obtained resin molded body was subjected to the above-mentioned appearance, bleedability, scratch resistance, fogging and odor tests. The results are shown in Table 2. Comparative Example 3 is a polypropylene blank, Comparative Example 4 is only a wax, Comparative Example 5 is a styrene acrylo as a vinyl copolymer and only a ril copolymer (AS), and Comparative Example 6 is a wax and styrene acrylo. Comparative Example 7 is a blank of olefinic thermoplastic elastomer (TPO), Comparative Example 8 is an oleic acid amide (OA) addition system, Comparative Example 9 is a silicone oil addition system, The comparative example 10 was a comparative example 1 addition system, and all showed the example which was outside the scope of the present invention.

実施例９〜１６の結果に見られる通り、本発明の樹脂成形体は、外観とブリード性と耐擦傷性に優れ、しかもフォギングと臭気はブランクと差異がない。従って、これらの樹脂成形体を自動車部品、家電部品、雑貨等の幅広い分野における多種の製品及び半製品に利用することができる。その中でも、自動車内装用の表皮材等に好適に使用することができる。

As seen in the results of Examples 9 to 16, the resin molded body of the present invention is excellent in appearance, bleedability and scratch resistance, and fogging and odor are not different from those of the blank. Therefore, these resin moldings can be used for various products and semi-finished products in a wide range of fields such as automobile parts, home appliance parts, and miscellaneous goods. Among them, it can be suitably used for a skin material for automobile interior.

  On the other hand, in Comparative Example 3, since it is a single polypropylene, which is a thermoplastic resin, the appearance and bleeding properties are excellent, the fogging amount and the odor are small, but the scratch resistance is inferior. In Comparative Example 4, a paraffin wax is blended with polypropylene, and the scratch resistance is better than Comparative Example 3, but it is inferior to Examples 9-14. Moreover, although the external appearance is good, it is inferior in bleeding property. In Comparative Example 5, a styrene / acrylonitrile copolymer, which is a copolymer formed from a vinyl monomer, is blended with polypropylene, and the bleeding property, fogging property and odor are excellent. Inferior in scratch resistance. In Comparative Example 6, styrene / acrylonitrile copolymer, which is a copolymer formed from wax and vinyl monomer, is blended with polypropylene, and fogging and odor are excellent, but appearance, bleed, Abrasion is poor.

  In Comparative Example 7, it is an olefinic thermoplastic elastomer alone, which is excellent in appearance, bleedability, fogging and odor, but inferior in scratch resistance. In Comparative Example 8, polypropylene is blended with oleic amide, the appearance is good, and the scratch resistance is improved as compared with Comparative Example 3, but it is inferior to Examples 9-16. Also inferior in bleed, fogging and odor. In Comparative Example 9, polypropylene is blended with silicone oil, the appearance is good, and the scratch resistance is improved as compared with Comparative Example 3, but it is inferior to Examples 9-16. Furthermore, it is inferior in bleeding property. In Comparative Example 10, the composition of Comparative Example 1 is blended with polypropylene, and the appearance, fogging and odor are good, but bleeding occurs. Although the scratch resistance is improved as compared with Comparative Example 3, it is inferior to Examples 9-16.

It should be noted that the embodiment described above can be modified and embodied as follows.
A plurality of nonpolar waxes or oxidized waxes having different melting points can be used.

-When a nonpolar wax and an oxidized wax are used in combination, those having a melting point close to each other can be used in combination so that the effects can be effectively exhibited.
A component that improves scratch resistance such as a lubricant can be added to the mixed solution, and a vinyl monomer can be graft polymerized by emulsion polymerization or suspension polymerization.

Furthermore, the technical idea grasped from the embodiment will be described below.
A method for producing a surface physical property improver for a resin molded article according to claim 1, wherein the surface physical property improver for the resin molded article is produced through the following first and second steps. A method for producing a surface property improving agent for a resin molded product.

  First step: A step of obtaining a polymer by emulsion polymerization or suspension polymerization of a nonpolar wax having a melting point of 50 to 100 ° C., an oxidized wax having a melting point of 40 to 100 ° C., a vinyl monomer and a radical polymerization initiator. .

  Second step: The polymer obtained in the first step is salted out in the case of emulsion polymerization, filtered and then dried and purified. In the case of suspension polymerization, the polymer is filtered and dried and purified. A step of obtaining a surface property improving agent for a molded article.

In this case, the stability of the emulsified liquid or suspension can be improved, and a surface property improving agent capable of further exerting the effect of the invention according to claim 1 can be easily obtained by a simple operation.
-A thermoplastic resin composition comprising a polyolefin resin as a main component and containing the surface physical property improver for a resin molded article according to claim 1, wherein the vinyl monomer has a polarity different from that of the polyolefin resin. A molded resin product, wherein the molded resin product is molded into the form of a skin material for automobile interior. In this case, the effect of the invention according to claim 1 can be effectively exhibited as an automobile interior skin material.

  The surface physical property improving agent for a resin molded product according to claim 1 or 2, wherein the surface physical property improving agent is formed into particles and has an average particle size of 0.1 to 100 µm. When comprised in this way, when a surface physical property improving agent is mix | blended with polyolefin resin, the outstanding dispersibility can be expressed and the effect of a surface physical property improving agent can fully be exhibited.

  The surface property improving agent for a resin molded article according to claim 1 or 2, wherein the radical polymerization initiator is a redox polymerization initiator. When comprised in this way, the grafting reaction by hydrogen extraction from wax can be promoted.

Claims (5)

Improvement of surface physical properties of resin molded article comprising a polymer obtained by emulsion polymerization or suspension polymerization of a mixed solution containing a nonpolar wax having a melting point of 50 to 100 ° C., a vinyl monomer and a radical polymerization initiator Agent. The surface property improving agent for a resin molded product according to claim 1, wherein the mixed solution further contains an oxidized wax having a melting point of 40 to 100 ° C. It is a manufacturing method of the surface physical property improvement agent of the resin molding of Claim 1, Comprising: The resin characterized by manufacturing the surface physical property improvement agent of a resin molding through the 1st process and 2nd process shown below. A method for producing a surface property improving agent for a molded article.
1st process: The process of obtaining the polymer by emulsion polymerization or suspension polymerization of the liquid mixture containing the nonpolar wax of melting | fusing point 50-100 degreeC, a vinyl monomer, and a radical polymerization initiator.
Second step: The polymer obtained in the first step is salted out in the case of emulsion polymerization, filtered and then dried and purified. In the case of suspension polymerization, the polymer is filtered and dried and purified. A step of obtaining a surface property improving agent for a molded article. A thermoplastic resin composition comprising a polyolefin resin as a main component, the surface physical property improving agent for a resin molded article according to claim 1, wherein the vinyl monomer has a polarity different from that of the polyolefin resin. It is obtained by molding a thermoplastic resin composition comprising a polyolefin resin as a main component and containing the surface physical property improving agent for a resin molded article according to claim 1, wherein the vinyl monomer has a polarity different from that of the polyolefin resin. A resin molded product characterized by that.