JP2009203397A - Resin composition for powder molding and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a resin composition for powder molding, which includes excellent powder fluidity, is excellent in antiblocking properties, hot-melt properties when molded, and the molding of which is excellent in scratch resistance and wear resistance. <P>SOLUTION: The resin composition for powder molding is obtained by sticking 0.01-5 parts weight spherical inorganic particle (E) to 100 parts weight acrylic polymer powder (C) composed of: an acrylic block copolymer (A) which is composed of a methacrylic polymer block (a) based on a methacrylic monomer and an acrylic polymer block (b) based on an acrylic monomer and in which at least one of the methacrylic polymer block (a) and the acrylic polymer block (b) includes an acid anhydride group and/or a carboxy group; and an acrylic polymer (B) having average 1.1 or more reactive functional groups (D) at the least in one molecule. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a resin composition for powder molding. The present invention also relates to a composition suitable for powder slush molding and a powder slush molded article using the composition.

  An example of a method for molding a skin material constituting an interior material or the like is a powder slush molding method which is a molding method using a powder resin. In this method, i) a soft tactile product can be obtained, ii) leather texture and stitches can be provided on the product, iii) a high-quality skin material with a high degree of design freedom and high designability can be formed. , Etc., and is widely used for the skin molding of automobile interior parts such as instrument panels, console boxes and door rims.

  Conventionally, vinyl chloride (PVC) has been used as a powder resin for powder slush molding. However, since PVC contains halogen, there is a problem that the load on the environment is large. Therefore, in recent years, a powder resin mainly composed of a thermoplastic polyurethane elastomer (TPU) has been used as a material not containing halogen. However, TPU has problems in weather resistance and flexibility.

  As a material for overcoming the above problems, a powder resin made of an acrylic thermoplastic elastomer has been proposed. Molded products obtained from this resin contain almost no halogen and are the properties required for skin materials, such as weather resistance, flexibility, mechanical properties, heat resistance, low temperature properties, strain recovery, and resistance to contactable drugs. Etc.

  The powder slush molding method is a method in which a powder resin is poured into a heated mold, and after being melt-molded, a molded body cooled and solidified into a desired shape is taken out. Unlike other molding methods such as injection molding, this method does not apply shaping pressure at the time of molding, so the powder resin has a powder flowability for quickly filling a mold having a complicated shape, Good heat-meltability is required for forming into a desired shape under no pressure. Furthermore, if the resins block during storage, the molded body will be uneven and the appearance will be impaired, so blocking resistance is also required.

Known methods for improving powder flowability and blocking resistance include a method of adding amorphous silica fine powder to a powder resin and a method of adding amorphous inorganic particles to a powder resin.
as well as . However, these methods sometimes have insufficient effects for improving powder flowability and blocking resistance.

Furthermore, as another method for improving powder flowability and blocking resistance, a method of adding an organic resin powder having an average particle size smaller than that of the powder resin to the powder resin is also known.
. However, the organic resin powder has insufficient heat resistance, and blocking resistance at high temperatures may not be sufficient.

As described above, the resin compositions for powder molding known so far sometimes leave room for improvement in the balance of heat melting property, powder fluidity and blocking property.
JP 2006-28319 A JP 2006-274080 A JP 2007-246616 A

  An object of the present invention is to obtain a resin composition for powder molding that exhibits good powder flowability, excellent blocking resistance and heat-melting property during molding, and has a molded body excellent in scratch resistance and abrasion resistance. It is.

  As a result of intensive studies, the present inventors have solved the above problems.

    That is, the present invention comprises a methacrylic polymer block (a) whose main component is a methacrylic monomer and an acrylic polymer block (b) whose main component is an acrylic monomer. An acrylic block copolymer (A) having an acid anhydride group and / or a carboxyl group in at least one of the polymer block (a) and the acrylic polymer block (b), and in one molecule With respect to 100 parts by weight of the acrylic polymer powder (C) comprising the acrylic polymer (B) having at least an average of 1.1 or more reactive functional groups (D), spherical inorganic particles (E) The present invention relates to a resin composition for powder molding characterized in that 01 to 5 parts by weight are adhered.

  A preferred embodiment includes a resin composition for powder molding, wherein the spherical inorganic particles as the component (E) have an average particle size of 0.01 μm to 50 μm.

  A preferred embodiment includes a resin composition for powder molding, wherein the spherical inorganic particles as component (E) are at least one selected from silica and alumina.

  A preferable embodiment includes a resin composition for powder molding, wherein the spherical inorganic particles as component (E) are silica.

  A preferred embodiment includes a resin composition for powder molding in which the reactive functional group (D) is at least one selected from an epoxy group, a hydroxyl group, and an amino group.

  A preferred embodiment includes a resin composition for powder molding in which the reactive functional group (D) is an epoxy group.

  A preferable embodiment includes a resin composition for powder molding, wherein the acrylic polymer powder (C) further contains an inorganic zinc compound (F).

  A preferable embodiment includes a resin composition for powder molding, wherein the inorganic zinc compound (F) is zinc oxide or zinc carbonate.

As a preferred embodiment, the acrylic block copolymer (A) has a methacrylic monomer as a main component and a methacrylic polymer block (a) 15 to 50 having a glass transition temperature of 50 to 130 ° C. Acrylic weight mainly composed of at least one monomer selected from the group consisting of wt% and acrylic acid-n-butyl, ethyl acrylate, acrylic acid-2-ethylhexyl and acrylic acid-2-methoxyethyl. An acid anhydride represented by the carboxyl group and / or the general formula (1), which comprises 85 to 50% by weight of the combined block (b), and at least one of the block (a) and the block (b). General formula (1):

（式中、Ｒ１はそれぞれ独立に水素またはメチル基を表わす。ｎは０〜３の整数、ｍは０または１の整数を表わす。）を有し、ゲルパーミエーションクロマトグラフィーで測定した数平均分子量が３０，０００〜２００，０００であるアクリル系ブロック共重合体である粉末成形用樹脂組成物挙げられる。

(Wherein R1 independently represents hydrogen or a methyl group, n represents an integer of 0 to 3, m represents an integer of 0 or 1), and the number average molecular weight measured by gel permeation chromatography Is a resin composition for molding a powder, which is an acrylic block copolymer having a molecular weight of 30,000 to 200,000.

  As a preferred embodiment, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography of the acrylic block copolymer as the component (A) is 1 And a resin composition for powder molding characterized by being 8 or less.

  A preferred embodiment includes a resin composition for powder molding, wherein the acrylic block copolymer as component (A) is a block copolymer produced by atom transfer radical polymerization.

  A preferred embodiment includes a resin composition for powder molding, wherein the acrylic polymer as the component (B) has a weight average molecular weight of 30,000 or less.

  As a preferred embodiment, there is a resin composition for powder molding characterized in that the acrylic polymer powder (C) has an average particle diameter of 1 μm or more and less than 1000 μm.

  As a preferred embodiment, there is a resin composition for powder molding characterized in that the spherical inorganic particles (E) are silica gel.

  A preferred embodiment includes a resin composition for powder molding, wherein the spherical inorganic particles (E) have an average particle size of 1 μm to 10 μm.

  As a preferred embodiment, the present invention relates to a powder slush molding composition comprising the above powder molding resin composition.

  As another embodiment, the present invention relates to a powder slush molded article obtained by powder slush molding the above powder molding resin composition.

  As another embodiment, the present invention relates to an automobile interior skin characterized by powder slush molding of the above powder molding resin composition.

According to the present invention, it is possible to obtain a resin composition for powder molding that exhibits good powder fluidity, is excellent in blocking resistance and heat melting property at the time of molding, and has a molded body having excellent scratch resistance and abrasion resistance. Is possible. The composition according to the present invention can be suitably used for powder slush molding, press molding, and other various molding methods. For example, the composition according to the present invention is suitably used for an automobile interior skin having excellent appearance. be able to

  Hereinafter, the present invention will be described in more detail.

    The present invention provides a resin composition for powder molding that exhibits good powder flowability, excellent blocking resistance and heat-melting property during molding, and has excellent scratch resistance and abrasion resistance. A methacrylic polymer block comprising a methacrylic polymer block (a) mainly composed of a methacrylic monomer and an acrylic polymer block (b) mainly composed of an acryl monomer. An acrylic block copolymer (A) having an acid anhydride group and / or a carboxyl group in at least one of the block (a) and the acrylic polymer block (b), and at least an average in one molecule 1.1 spherical inorganic particles (E) 0.01 to 100 parts by weight of acrylic polymer powder (C) composed of acrylic polymer (B) having at least one reactive functional group (D) 5 layers Parts wherein the is attached.

  Here, the acid anhydride group and / or carboxyl group in the acrylic block copolymer (A) and the reactive functional group (D) in the acrylic polymer (B) usually react at the time of molding, and acrylic The system block copolymer (A) is increased in molecular weight or crosslinked. As a result, the resulting molded article has improved heat resistance.

In the present invention, an acid anhydride derived from a carboxyl group is defined as an acid anhydride group, specifically a group represented by the general formula (1).
General formula (1):

（式中、Ｒ１はそれぞれ独立に水素またはメチル基を表わす。ｎは０〜３の整数、ｍは０または１の整数を表わす。）

＜アクリル系ブロック共重合体（Ａ）＞
ブロック共重合体（Ａ）の構造は、線状であっても、分岐状（星状）であってもよく、これらの混合物であってもよく、必要とされるブロック共重合体（Ａ）の物性に応じて適宜選択すればよいが、コスト面や重合容易性の点から、線状ブロック共重合体であるのが好ましい。

(In the formula, each R1 independently represents hydrogen or a methyl group. N represents an integer of 0 to 3, and m represents an integer of 0 or 1.)

<Acrylic block copolymer (A)>
The structure of the block copolymer (A) may be linear, branched (star), or a mixture thereof, and the required block copolymer (A). The linear block copolymer is preferable from the viewpoints of cost and ease of polymerization.

The arrangement of the linear block copolymer is not particularly limited. However, from the viewpoint of the physical properties or physical properties of the composition, a methacrylic polymer block (A) constituting the acrylic block copolymer (A) ( a) (hereinafter referred to as polymer block (a) or block (a)) and acrylic polymer block (b) (hereinafter referred to as polymer block (b) or block (b)) have the general formula: (Ab) _n , General formula: a- (ba) _n , General formula: (ba) From the group consisting of block copolymers represented by _n- b (n is an integer of 1 to 3). It is preferably at least one block copolymer selected. Among these, from the viewpoint of easy handling at the time of processing and physical properties in the case of a composition, an ab type diblock copolymer, an abb type triblock copolymer, or These mixtures are preferred.

  The number average molecular weight of the block copolymer (A) measured by gel permeation chromatography is not particularly limited, but is preferably 30,000 to 500,000, more preferably 50,000 to 400,000. If the number average molecular weight is small, the viscosity is low, and if the number average molecular weight is large, the viscosity tends to be high. Therefore, the viscosity is appropriately set according to the required processing characteristics.

  The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography of the block copolymer is not particularly limited, but is preferably 1.8 or less, more preferably 1 .5 or less. When Mw / Mn exceeds 1.8, the homogeneity of the block copolymer tends to decrease.

  The composition ratio of the methacrylic polymer block (a) and the acrylic polymer block (b) of the block copolymer (A) is 5 to 90% by weight of the methacrylic polymer block (a), and the acrylic weight The combined block (b) is desirably 95 to 10% by weight. When the proportion of the methacrylic polymer block (a) is less than 5% by weight, the shape tends to be difficult to be maintained at the time of molding, and when the proportion of the acrylic polymer block (b) is less than 10% by weight, an elastomer is obtained. There is a tendency that the elasticity and the meltability at the time of molding are lowered. From the viewpoint of maintaining the shape during molding and elasticity as an elastomer, the composition ratio is 10 to 60% by weight of the methacrylic polymer block (a) and 90 to 40% by weight of the acrylic polymer block (b). The methacrylic polymer block (a) is preferably 15 to 50% by weight, and the acrylic polymer block (b) is more preferably 85 to 50% by weight.

  The hardness of the elastomer composition tends to be low when the proportion of the methacrylic polymer block (a) is small and high when the proportion of the methacrylic polymer block (a) is large. For this reason, the proportion of the methacrylic polymer block (a) may be appropriately set according to the required hardness. Further, the viscosity tends to be low when the proportion of the methacrylic polymer block (a) is small and high when the proportion of the methacrylic polymer block (a) is large. For this reason, the proportion of the methacrylic polymer block (a) may be appropriately set according to required processing characteristics.

The relationship between the glass transition temperatures of the methacrylic polymer block (a) and the acrylic polymer block (b) constituting the acrylic block copolymer (A) is the glass transition of the methacrylic polymer block (a). Assuming that the temperature is Tg _a and the glass transition temperature of the acrylic polymer block (b) is Tg _b , it is preferable to satisfy the relationship of the following formula in terms of mechanical strength and rubber elasticity expression.
Tg _a > Tg _b
The glass transition temperature (Tg) of the polymer (methacrylic polymer block (a) and acrylic polymer block (b)) is set according to the following Fox formula: This can be done by setting the ratio.
_{1 / Tg = (W 1 /} Tg 1) + (W 2 / Tg 2) + ... + (W m / Tg m)
W ₁ + W ₂ + ... + W _m = 1
(In the formula, Tg represents the glass transition temperature of the polymer portion, Tg ₁ , Tg ₂ ,..., Tg _m represents the glass transition temperature of each polymerization monomer. Also, W ₁ , W ₂ ,. _m represents the weight ratio of each polymerization monomer.)
As the glass transition temperature of each polymerization monomer in the Fox formula, for example, a value described in Polymer Handbook Third Edition (Wiley-Interscience 1989) may be used.

  The glass transition temperature can be measured by DSC (differential scanning calorimetry) or tan δ peak of dynamic viscoelasticity, but the methacrylic polymer block (a) and the acrylic polymer block (b). If the polarity is too close or the number of block monomer chains is too small, the measured values may deviate from the calculation formula based on the Fox equation.

<Methacrylic polymer block (a)>
The methacrylic polymer block (a) is a block obtained by polymerizing a monomer having a methacrylic acid ester as a main component. From the viewpoint of processability, the methacrylic acid ester is 50 to 100% by weight and It is preferable that it consists of 0-50 weight% of vinyl-type monomers copolymerizable with.

  Examples of the methacrylic acid ester constituting the methacrylic polymer block (a) include, for example, methyl methacrylate, ethyl methacrylate, methacrylate-n-propyl, isopropyl methacrylate, and methacrylate-n-. Butyl, isobutyl methacrylate, methacrylate-n-pentyl, methacrylate-n-hexyl, cyclohexyl methacrylate, methacrylate-n-heptyl, methacrylate-n-octyl, methacrylate-2- Ethylhexyl, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, phenyl methacrylate, toluyl methacrylate, benzyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methacrylate 3-methoxybutyl 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, stearyl methacrylate, glycidyl methacrylate, 2-aminoethyl methacrylate, γ- (methacryloyloxypropyl) trimethoxysilane, γ- (Methacryloyloxypropyl) dimethoxymethylsilane, ethylene oxide adduct of methacrylic acid, trifluoromethylmethyl methacrylate, methacrylic acid-2-trifluoromethylethyl, methacrylic acid-2-perfluoroethylethyl, methacrylic Acid-2-perfluoroethyl-2-perfluorobutylethyl, methacrylic acid-2-perfluoroethyl, perfluoromethyl methacrylate, diperfluoromethylmethyl methacrylate, -2-acrylic methacrylate Oromechiru 2-perfluoroethyl methyl, methacrylic acid-2-perfluorohexylethyl, methacrylic acid-2-perfluorodecyl ethyl, and the like methacrylic acid-2-perfluoroalkyl-hexadecyl ethyl.

  These can be used alone or in combination of two or more. Among these, methyl methacrylate is preferable in terms of processability, cost, and availability. Further, the glass transition point can be increased by copolymerizing isobornyl methacrylate and cyclohexyl methacrylate. Furthermore, methacrylic acid-t-butyl is preferable as a precursor for introducing an acid anhydride to improve heat resistance.

  Examples of vinyl monomers copolymerizable with the methacrylic acid ester constituting the methacrylic polymer block (a) include acrylic acid esters, aromatic alkenyl compounds, conjugated diene compounds, and halogen-containing unsaturated compounds. And silicon-containing unsaturated compounds, unsaturated dicarboxylic acid compounds, vinyl ester compounds, maleimide compounds, and the like.

  Examples of the acrylate ester include methyl acrylate, ethyl acrylate, acrylic acid-n-propyl, isopropyl acrylate, acrylic acid-n-butyl, acrylic acid isobutyl, acrylic acid-t-butyl, and acrylic acid-n-. Pentyl, acrylate-n-hexyl, cyclohexyl acrylate, acrylate-n-heptyl, acrylate-n-octyl, acrylate-2-ethylhexyl, nonyl acrylate, decyl acrylate, dodecyl acrylate, phenyl acrylate, Toluyl acrylate, benzyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, stearyl acrylate, acrylic acid Guri Ziryl, 2-aminoethyl acrylate, ethylene oxide adduct of acrylic acid, trifluoromethyl methyl acrylate, 2-trifluoromethyl ethyl acrylate, 2-perfluoroethyl ethyl acrylate, 2-acrylic acid-2- Perfluoroethyl-2-perfluorobutylethyl, 2-perfluoroethyl acrylate, perfluoromethyl acrylate, diperfluoromethyl methyl acrylate, 2-perfluoromethyl-2-perfluoroethyl methyl acrylate, acrylic Examples include acid-2-perfluorohexylethyl, 2-perfluorodecylethyl acrylate, and 2-perfluorohexadecylethyl acrylate.

  Examples of the aromatic alkenyl compound include styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene, and the like. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. Examples of the conjugated diene compound include butadiene and isoprene. Examples of the halogen-containing unsaturated compound include vinyl chloride, vinylidene chloride, perfluoroethylene, perfluoropropylene, and vinylidene fluoride. Examples of the silicon-containing unsaturated compound include vinyltrimethoxysilane and vinyltriethoxysilane. Examples of the unsaturated dicarboxylic acid compound include maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid, fumaric acid, monoalkyl esters and dialkyl esters of fumaric acid, and the like. Examples of the vinyl ester compound include vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate, and the like. Examples of the maleimide compound include maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide and the like.

  These can be used alone or in combination of two or more. These vinyl monomers are appropriately selected from the viewpoints of adjusting the glass transition temperature required for the methacrylic polymer block (a) and compatibility with the acrylic polymer block (b). .

  From the viewpoint of thermal deformation of the elastomer composition, the methacrylic polymer block (a) is preferably designed so that the glass transition temperature is 25 ° C. or higher, more preferably 40 ° C. or higher. More preferably, the temperature is 50 ° C. or higher. When the glass transition temperature of (a) is lower than the temperature of the environment in which the elastomer composition is used, thermal deformation may easily occur due to a decrease in cohesive force.

  From the viewpoints described above, the methacrylic polymer block (a) is mainly composed of methyl methacrylate and for the purpose of controlling the glass transition point, ethyl acrylate, acrylic acid-n-butyl, acrylic acid. A block obtained by polymerizing at least one monomer selected from the group consisting of 2-methoxyethyl and 2-ethylhexyl acrylate is preferable.

<Acrylic polymer block (b)>
The acrylic polymer block (b) is a block formed by polymerizing a monomer having an acrylic ester as a main component. From the viewpoint of rubber elasticity and the like, the acrylic ester is 50 to 100% by weight and copolymerized therewith. It is preferably composed of 0 to 50% by weight of a possible vinyl monomer.

  Examples of the acrylic acid ester constituting the acrylic polymer block (b) include the same monomers as the acrylic acid ester exemplified as the monomer constituting the methacrylic polymer block (b). it can.

  These may be used alone or in combination of two or more. Among these, acrylic acid-n-butyl is preferable from the viewpoint of rubber elasticity, low temperature characteristics and cost balance. Furthermore, when low temperature characteristics, mechanical characteristics, and compression set are required, 2-ethylhexyl acrylate may be copolymerized. If oil resistance and mechanical properties are required, ethyl acrylate is preferred. Further, when it is necessary to impart low temperature characteristics and oil resistance and to improve the surface tackiness of the resin, 2-methoxyethyl acrylate is preferable. When a balance between oil resistance and low-temperature characteristics is required, a combination of ethyl acrylate, acrylic acid-n-butyl and acrylic acid-2-methoxyethyl is preferred. Furthermore, when introducing an acid anhydride group in order to improve heat resistance, the precursor is preferably tert-butyl acrylate.

  Examples of vinyl monomers copolymerizable with the acrylic ester constituting the acrylic polymer block (b) include methacrylic ester, aromatic alkenyl compound, vinyl cyanide compound, conjugated diene compound, halogen, and the like. Examples thereof include an unsaturated compound containing silicon, an unsaturated compound containing silicon, an unsaturated dicarboxylic acid compound, a vinyl ester compound, and a maleimide compound.

  Methacrylic acid ester, aromatic alkenyl compound, vinyl cyanide compound, conjugated diene compound, halogen-containing unsaturated compound, silicon-containing unsaturated compound, unsaturated dicarboxylic acid compound, vinyl ester compound, maleimide compound The monomer similar to what was illustrated as a monomer which comprises a system polymer block (a) can be mention | raise | lifted.

  These can be used alone or in combination of two or more. These vinyl monomers are appropriately selected in consideration of the balance of the glass transition temperature and oil resistance required for the acrylic polymer block (b), compatibility with the methacrylic polymer block (a), and the like. Choose the preferred one.

  The acrylic polymer block (b) preferably has a glass transition temperature of 25 ° C. or lower, more preferably 0 ° C. or lower, and further preferably −20 ° C., from the viewpoint of rubber elasticity of the elastomer composition. It is as follows. If the glass transition temperature of the acrylic polymer block (b) is lower than the temperature of the environment in which the elastomer composition is used, rubber elasticity is easily developed.

  From the viewpoints described above, the acrylic polymer block (b) is at least one selected from the group consisting of -n-butyl acrylate, ethyl acrylate, 2-methoxyethyl acrylate, and 2-ethylhexyl acrylate. In addition, a block obtained by polymerizing 50 to 100% by weight of different acrylates copolymerizable with these and 50 to 0% by weight of vinyl monomers copolymerizable with these is preferable.

  From the viewpoint of rubber elasticity of the elastomer composition, the glass transition temperature of the acrylic polymer block (b) is preferably 25 ° C. or less, more preferably 0 ° C. or less, and further preferably −20 ° C. or less. When the glass transition temperature of the acrylic polymer block (b) is higher than the temperature of the environment in which the elastomer composition is used, flexibility and rubber elasticity are hardly exhibited.

  From the viewpoints described above, the acrylic polymer block (b) comprises an acid anhydride group, a carboxyl group or an acid anhydride group, a monomer having a carboxyl group precursor, and acrylic acid-n-butyl, acrylic acid. A block obtained by polymerizing a monomer having at least one selected from the group consisting of ethyl and 2-methoxyethyl acrylate as a main component is preferable.

The Tg _b of the acrylic polymer block (b) can be set by setting the weight ratio of the monomers in each polymer portion according to the Fox formula.

<Acid anhydride group and carboxyl group>
An acid anhydride group and a carboxyl group are methacrylic in order to retain mechanical properties at high temperatures while imparting chemical resistance and rubber elasticity to a molded product obtained from the resin composition for powder molding according to the present invention. One or more molecules per block copolymer are introduced into the polymer block (a) and / or the acrylic polymer block (b). An acid anhydride group and a carboxyl group are the reactivity of an acrylic block copolymer (A) and an acrylic polymer (B), a methacrylic polymer block (a), and an acrylic polymer block (b). Either an acid anhydride group or a carboxyl group may be introduced depending on the cohesive strength and glass transition temperature of the acrylic block copolymer, the required physical properties of the acrylic block copolymer (A), ease of introduction, etc. It is good or may be introduced together.

  In the present invention, the acid anhydride group and the carboxyl group may act as a reaction point with the acrylic polymer (B), and as a reaction point or a crosslinking point for the block copolymer to have a high molecular weight or to be crosslinked. It is preferable to act. The acid anhydride group and the carboxyl group are introduced into the block copolymer in a form in which the acid anhydride group and the carboxyl group are protected with an appropriate protecting group, or in the form of a precursor of the acid anhydride group and the carboxyl group. Later, it can be introduced by generating an acid anhydride group and a carboxyl group by a known chemical reaction.

  The content of the acid anhydride group and the carboxyl group is the cohesive force of the acid anhydride group and the carboxyl group, the reactivity, the structure and composition of the acrylic block copolymer (A), and the acrylic block copolymer (A). The number of blocks constituting the glass transition temperature varies depending on the necessity, and the number needs to be appropriately set as necessary. Preferably, the average number per block copolymer is 1.0 or more, more preferably 2.0 or more. This is because when the number is less than 1.0, there is a tendency that the high molecular weight due to the bimolecular reaction of the block copolymer and the heat resistance improvement due to crosslinking tend to be insufficient.

Note that when improved cohesive force and glass transition temperature Tg _b of the acrylic polymer block (b) by introducing an acid anhydride group or a carboxyl group, there is a tendency that flexibility, rubber elasticity, low temperature characteristics deteriorate. For this reason, when an acid anhydride group and / or a carboxyl group are introduced into the acrylic polymer block (b), the acrylic block copolymer (A) is introduced in a range that does not deteriorate the flexibility, rubber elasticity, and low temperature characteristics. It is preferable to do. Specifically, it is preferably introduced so that the glass transition temperature Tg _b of the acrylic polymer block (b) after introduction of the acid anhydride group or carboxyl group is 25 ° C. or less, more preferably 0 ° C. or less, More preferably, the temperature is set to −20 ° C. or lower.

  Below, an acid anhydride group and a carboxyl group are demonstrated.

<Acid anhydride group>
When the composition contains a compound having active protons, the acid anhydride groups in the methacrylic polymer block (a) and the acrylic polymer block (b) are heated at a predetermined temperature described below. By this, it reacts easily with the reactive functional group (D) in the compound (B). The introduction position of the acid anhydride group is not particularly limited, and the acid anhydride group is introduced into the main chain in the methacrylic polymer block (a) and the acrylic polymer block (b). It may be introduced to the side chain. The acid anhydride group is an anhydride of a carboxyl group, and is introduced into the main chain for ease of introduction into the methacrylic polymer block (a) and the acrylic polymer block (b). Is specifically represented by the general formula (1). General formula (1):

（式中、Ｒ^１は水素またはメチル基で、２つのＲ^１は互いに同一でも異なっていてもよい。ｎは０〜３の整数、ｍは０または１の整数）で表される形で含有される。

(Wherein R ¹ is hydrogen or a methyl group, two R ^{1 s} may be the same or different from each other, n is an integer of 0 to 3, and m is an integer of 0 or 1) Is done.

  N in General formula (1) is an integer of 0-3, Preferably it is 0 or 1, More preferably, it is 1. When n is 4 or more, polymerization tends to be complicated, and cyclization of the acid anhydride group tends to be difficult.

  As a method for introducing the acid anhydride group, it is preferable that the acid anhydride group is introduced into the acrylic block copolymer in the form of a precursor of the acid anhydride group and then cyclized. In particular, the general formula (2):

（式中、Ｒ^２は水素またはメチル基を表わす。Ｒ^３は水素、メチル基またはフェニル基を表わし、３つのＲ^３のうち少なくとも２つはメチル基および／またはフェニル基から選ばれ、３つのＲ^３は互いに同一でも異なっていてもよい。）で表される単位を少なくとも１つ有するアクリル系ブロック共重合体を溶融混練して、環化導入することが好ましい。

(Wherein R ² represents hydrogen or a methyl group; R ³ represents hydrogen, a methyl group or a phenyl group; at least two of the three R ³ are selected from a methyl group and / or a phenyl group; R ³ may be the same or different from each other. It is preferable to melt-knead an acrylic block copolymer having at least one unit represented by cyclization and introduce cyclization.

  The introduction of the unit represented by the general formula (2) into the acrylic polymer block (b) is obtained by copolymerizing an acrylate or methacrylic acid ester monomer derived from the general formula (2). Can be done. Examples of the monomer include t-butyl (meth) acrylate, isopropyl (meth) acrylate, α, α-dimethylbenzyl (meth) acrylate, α-methylbenzyl (meth) acrylate, It is not limited to these. Among these, (meth) acrylic acid-t-butyl is preferable from the standpoints of availability, ease of polymerization, and ease of acid anhydride group formation. In the present application, (meth) acrylic acid means acrylic acid or methacrylic acid.

  The formation of the acid anhydride group is preferably performed by heating the acrylic block copolymer having a precursor of the acid anhydride group at a high temperature, and more preferably by heating at 180 to 300 ° C. . When the temperature is lower than 180 ° C., the acid anhydride group is likely to be insufficiently generated. When the temperature is higher than 300 ° C., the acrylic block copolymer itself having a precursor of the acid anhydride group may be decomposed.

<Carboxyl group>
The carboxyl group in the acrylic block copolymer (A) easily reacts with the reactive functional group (D) in the compound (B). The introduction position of the carboxyl group is not particularly limited, and the carboxyl group may be introduced into the main chain in the methacrylic polymer block (a) and the acrylic polymer block (b). Although it may be introduced into the side chain, it is preferably introduced into the main chain from the viewpoint of ease of introduction.

  When the monomer having a carboxyl group does not poison the catalyst under the polymerization conditions, the introduction of the carboxyl group is preferably carried out by introducing it directly by polymerization. When the catalyst is deactivated during the polymerization, it is preferably carried out by a method of introducing a carboxyl group by functional group conversion.

  As a method for introducing a carboxyl group by functional group conversion, the carboxyl group is introduced into an acrylic block copolymer in the form of protecting the carboxyl group with an appropriate protecting group or in the form of a functional group that is a precursor of the carboxyl group. A method of generating a functional group by a predetermined chemical reaction known later is mentioned.

  As a synthesis method of the acrylic block copolymer (A) having a carboxyl group, for example, a functional group that becomes a precursor of a carboxyl group, such as t-butyl (meth) acrylate, trimethylsilyl (meth) acrylate, and the like. A method of synthesizing an acrylic block copolymer containing a monomer having a carboxyl group and generating a carboxyl group by a known chemical reaction such as hydrolysis or acid decomposition (Japanese Patent Laid-Open Nos. 10-298248 and 2001-234146) ) And general formula (2):

（式中、Ｒ^２は水素またはメチル基を表わす。Ｒ^３は水素、メチル基またはフェニル基を表わし、３つのＲ^３のうち少なくとも２つはメチル基および／またはフェニル基から選ばれ、３つのＲ^３は互いに同一でも異なっていてもよい。）で表わされる単位を少なくとも１つ有するアクリル系ブロック共重合体を、溶融混練して導入する方法がある。

(Wherein R ² represents hydrogen or a methyl group; R ³ represents hydrogen, a methyl group or a phenyl group; at least two of the three R ³ are selected from a methyl group and / or a phenyl group; R ³ may be the same or different from each other.) There is a method of introducing an acrylic block copolymer having at least one unit represented by melting and kneading.

  Moreover, a carboxyl group can also be introduce | transduced by hydrolyzing the said acid anhydride group.

<Method for producing acrylic block copolymer (A)>
A method for producing the acrylic block copolymer (A) is not particularly limited, but a controlled polymerization method using an initiator is preferably used. Examples of the controlled polymerization method include a living anion polymerization method, a radical polymerization method using a chain transfer agent, and a recently developed living radical polymerization method. Especially, it is preferable to manufacture by the living radical polymerization method from the point of control of the molecular weight and structure of an acryl-type block copolymer.

  The living radical polymerization method is a radical polymerization method in which the activity at the polymerization terminal is maintained without being lost. In the narrow sense, living polymerization refers to polymerization in which the terminal always has activity, but generally includes pseudo-living polymerization in which the terminal is inactivated and the terminal is in equilibrium. . The definition here is also the latter.

  As the living radical polymerization method, a method using a chain transfer agent such as polysulfide, cobalt porphyrin complex (J. Am. Chem. Soc., 1994, 116, 7943). ) And nitroxide compounds (Macromolecules, 1994, 27, 7228), atom transfer radicals using organic halides as initiators and transition metal complexes as catalysts Examples thereof include a polymerization method (Atom Transfer Radical Polymerization: ATRP). In the present invention, there is no particular limitation as to which of these methods is used, but from the viewpoint of ease of control, etc., a method using the atom transfer radical polymerization method described in International Publication No. 2004/13192 pamphlet or the like Is preferred.

<Acrylic polymer (B)>
The acrylic polymer (B) constituting the thermoplastic elastomer composition according to the present invention needs to have 1.1 or more reactive functional groups (D) in one molecule. The acrylic polymer (B) improves molding fluidity as a plasticizer during molding of the composition, and at the same time, reacts with an acid anhydride group or carboxyl group in the acrylic block copolymer (A) during molding. It reacts with the group (D) and plays a role of increasing the molecular weight or crosslinking of the acrylic block copolymer (A). In addition, the number of reactive functional groups (D) here represents the average number of reactive functional groups (D) present in one molecule of the acrylic polymer (B).

  The number of reactive functional groups (D) in the acrylic polymer (B) needs to be 1.1 or more, preferably 1.5 or more, and more preferably 2.0 or more. The number is the reactivity of the reactive functional group (D), the site and mode of the reactive functional group (D), the acid anhydride group and / or the carboxyl group in the acrylic block copolymer (A). Vary depending on the number, location, and mode of the contained. When the content of the reactive functional group (D) is less than 1.1, the effect of the block copolymer as a high molecular weight reaction agent or a crosslinking agent is reduced, and the heat resistance of the acrylic block copolymer (A) is reduced. The effect of improving the property may be insufficient.

  The acrylic polymer (B) is obtained by polymerizing one or more acrylic monomers, or one or two or more acrylic monomers and a monomer other than the acrylic monomer. It is preferable that it is obtained by polymerizing.

  Examples of the acrylic monomer include acrylic acid esters and methacrylic acid esters described in the section of the methacrylic polymer block (a). Among these, it is preferable from the point of availability to use either acrylic acid-n-butyl, ethyl acrylate and -2-methoxyethyl acrylate, or a combination of two or more thereof.

  The monomer other than the acrylic monomer is not particularly limited as long as it is a monomer copolymerizable with the acrylic monomer, and for example, vinyl acetate, styrene and the like can be used.

  In addition, it is preferable that the ratio of the monomer component which has an acryloyl group with respect to all the monomer components which comprise an acryl-type polymer (B) is 70 weight% or more. When the proportion is less than 70% by weight, the weather resistance is lowered and the compatibility with the acrylic block copolymer (A) tends to be lowered. Moreover, discoloration tends to occur in the molded product.

  The molecular weight of the acrylic polymer (B) is not particularly limited, but is preferably a low molecular weight having a weight average molecular weight of 30,000 or less, more preferably 500 to 30,000, and more preferably 500 to 10,000. Those are particularly preferred. When the weight average molecular weight is less than 500, the molded product tends to be sticky. On the other hand, when the weight average molecular weight exceeds 30,000, plasticization of the molded product tends to be insufficient.

  The viscosity of the acrylic polymer (B) is preferably 35,000 mPa · s or less when measured with a cone-plate type rotational viscometer (E-type viscometer) at 25 ° C., and 10,000 mPa · s. More preferably, it is 5,000 mPa · s or less. When the viscosity is higher than 35,000 mPa · s, the plasticizing effect of the composition tends to decrease. Although there is no particular lower limit of the preferred viscosity, the normal viscosity of the acrylic polymer is 10 mPa · s or more.

  The glass transition temperature Tg of the acrylic polymer (B) is preferably 100 ° C. or less, more preferably 25 ° C. or less, and more preferably 0 ° C. or less when measured by differential scanning calorimetry (DSC). More preferably, it is particularly preferably -30 ° C or lower. When glass transition temperature Tg exceeds 100 degreeC, there exists a tendency for the effect which improves a moldability as a plasticizer to become inadequate, and it exists in the tendency for the softness | flexibility of the molded object obtained to fall.

  The acrylic polymer (B) can be obtained by polymerizing by a conventionally known method. The polymerization method may be appropriately selected as necessary. For example, suspension polymerization method, emulsion polymerization method, bulk polymerization method, living anion polymerization method, polymerization using chain transfer agent, and control polymerization method such as living radical polymerization method, etc. However, it is preferable to use a controlled polymerization method in which a polymer having good weather resistance and heat resistance and having a relatively low molecular weight and a small molecular weight distribution is obtained, and it is costly to use the high-temperature continuous polymerization method described below. It is more preferable in terms of surface.

  The acrylic polymer (B) is preferably obtained by a polymerization reaction at a temperature of 180 to 350 ° C. At this polymerization temperature, an acrylic polymer having a relatively low molecular weight can be obtained without using a polymerization initiator or a chain transfer agent. For this reason, the acrylic polymer is an excellent plasticizer and has good weather resistance. Specifically, the high-temperature continuous polymerization method described in JP-T-57-502171, JP-A-59-6207, JP-A-60-215007 and WO 01/083619, An example is a method in which a mixture of the above monomers is continuously supplied into a reactor set at a predetermined temperature and pressure at a constant supply rate, and an amount of the reaction liquid corresponding to the supply amount is withdrawn.

<Reactive functional group (D)>
Examples of the reactive functional group (D) include an epoxy group, a hydroxyl group, and an amino group, and it is desirable to use at least one functional group selected from the group consisting of an epoxy group, a carboxyl group, a hydroxyl group, and an amino group. Among these functional groups, from the reactivity with the acid anhydride group and carboxyl group contained in the acrylic block copolymer (A) and the ease of introduction of the functional group into the acrylic polymer (B), An epoxy group is more preferable.

  Introduction of the reactive functional group (D) into the acrylic polymer (B) is, for example, a vinyl monomer having a reactive functional group (D) copolymerizable with the monomer constituting the acrylic polymer. It can be carried out by copolymerizing the body.

  Specific examples of the acrylic polymer (B) having a reactive functional group (D) include ARUFON (registered trademark) XG4000, ARUFON UG4000, ARUFON XG4010, ARUFON UG4010, ARUFON UG4012, ARUFON XD945 of Toagosei Co., Ltd. ARUFON XD950, ARUFON UG4030, ARUFON UG4070, etc. can be used preferably. These are acrylic polymers such as all acrylic and acrylate / styrene, and are polymers containing 1.1 or more epoxy groups in one molecule.

<Composition for acrylic polymer powder (C)>
The composition for acrylic polymer powder (C) has an acrylic block copolymer (A) having an acid anhydride group and / or a carboxyl group and an average of 1.1 or more epoxy groups per molecule. A thermoplastic elastomer composition comprising an acrylic polymer (B).

  Although the ratio of the blend amount of the acrylic block copolymer (A) and the acrylic polymer (B) contained in the composition for the acrylic polymer powder (C) is not particularly limited, the acrylic polymer (B ) Is preferably 0.1 to 100 parts by weight, more preferably 1 to 50 parts by weight with respect to 100 parts by weight of the acrylic block copolymer (A). When the blending amount of the acrylic polymer (B) is less than 0.1 parts by weight, the crosslinking reaction with the acrylic block copolymer (A) does not proceed sufficiently, and the heat resistance of the molded product becomes insufficient. If the amount is more than 100 parts by weight, the crosslinking reaction may proceed excessively, and the elongation and flexibility of the molded product may be impaired.

  The composition for the acrylic polymer powder (C) has a low melt viscosity when molding and is excellent in moldability (thermal meltability), while an acid anhydride group in the block copolymer (A) is heated. It is preferable that the acrylic block copolymer (A) has a high molecular weight or is cross-linked by reacting the carboxyl group and the reactive functional group (D) in the acrylic polymer (B). In terms of improving heat resistance, crosslinking is more preferable.

  In order to accelerate the reaction during molding, a catalyst may be added to the composition for acrylic polymer powder (C) as necessary. For example, curing agents commonly used for epoxy resins such as acid anhydrides such as acid dianhydrides, amines, and imidazoles, and metal compounds such as zinc tert-butylbenzoate, zinc laurate, and zinc oxide Can be used. Among these, the inorganic zinc compound (F) which is a metal compound is preferable.

  In addition, the composition for acrylic polymer powder (C) according to the present invention includes a filler, a lubricant, a stabilizer, a plasticizer, a flexibility-imparting agent, a flame retardant, a pigment, a charge as necessary. You may mix | blend an inhibitor, an antibacterial antifungal agent, etc.

  The filler is not particularly limited as long as it does not affect the effects of the present invention. From the viewpoint of improving mechanical properties, reinforcing effect, cost, etc., inorganic fillers are more preferable, and carbon black, silica, and talc are more preferable. preferable. When using a filler, the addition amount thereof may be added within a range that does not affect the effects of the present invention. In addition, a filler can be used 1 type or in combination of 2 or more types.

  Examples of the lubricant include fatty acids such as stearic acid and palmitic acid, fatty acid metal salts such as calcium stearate, zinc stearate, magnesium stearate, potassium palmitate, and sodium palmitate, polyethylene wax, polypropylene wax, and montanic acid. Waxes and other waxes, low molecular weight polyolefins such as low molecular weight polyethylene and low molecular weight polypropylene, polyorganosiloxanes such as dimethylpolysiloxane, amide-based lubricants such as octadecylamine, alkyl phosphates, fatty acid esters, and ethylene bisstearyl amide. Fluorine resin powder such as fluorinated ethylene resin, molybdenum disulfide powder, silicone resin powder, silicone rubber powder, silica, silicone oil and the like can be used. These can be used alone or in combination of two or more. Among these, stearic acid, zinc stearate, calcium stearate, fatty acid ester, and ethylene bisstearyl amide are preferable because of excellent cost and moldability. These lubricants can be expected to release from the mold and reduce the friction of the surface of the resulting molded body.

  When using a lubricant, the addition amount thereof is preferably in the range of 0.1 to 20 parts by weight, and in the range of 0.2 to 10 parts by weight with respect to 100 parts by weight of the acrylic block copolymer (A). Is more preferable. When the addition amount is less than 0.1 parts by weight, the effect of improving the releasability and the low friction of the obtained molded product may be insufficient. Mechanical properties and chemical resistance tend to deteriorate. A lubricant can be used alone or in combination of two or more.

  Examples of the stabilizer include an anti-aging agent, a light stabilizer, and an ultraviolet absorber. Industrial products include Irganox 1010 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Sanol LS770 (Sankyo Life Tech Co., Ltd.), ADK STAB LA-57 (Asahi Denka Kogyo Co., Ltd.), ADK STAB LA-68 (Asahi Denka Kogyo Co., Ltd.), Chimassorb 944 (Ciba Specialty Chemicals Co., Ltd.), Sanol LS765 (Sankyo Lifetech Co., Ltd.), ADK STAB LA -62 (Asahi Denka Kogyo Co., Ltd.), TINUVIN 144 (Ciba Specialty Chemicals Co., Ltd.), ADK STAB LA-63 (Asahi Denka Kogyo Co., Ltd.), TINUVIN 622 (Ciba Specialty Chemicals Co., Ltd.), Adekas LA-32 (Asahi Denka Kogyo Co., Ltd.), Adekastab LA-36 (Asahi Denka Kogyo Co., Ltd.), TINUVIN571 (Ciba Specialty Chemicals Co., Ltd.), TINUVIN234 (Ciba Specialty Chemicals Co., Ltd.), ADK STAB LA-31 (Asahi Denka Kogyo Co., Ltd.), TINUVIN 1130 (Ciba Specialty Chemicals Co., Ltd.), ADK STAB AO-20 (Asahi Denka Kogyo Co., Ltd.), ADK STAB AO-50 (Asahi Denka Kogyo Co., Ltd.) , Adeka Stub 2112 (Asahi Denka Kogyo Co., Ltd.), Adeka Stub PEP-36 Asahi Denka Kogyo Co., Ltd., Sumilyzer GM (Sumitomo Chemical Co., Ltd.), Sumilyzer GS (Sumitomo Chemical Co., Ltd.), Sumilyzer TP-D (Sumitomo) Chemical Industry Co., Ltd.) It is below. These may be used alone or in combination of two or more. Among them, Sanol LS770, Irganox 1010, Sumilizer GS, and TINUVIN234 are preferable because they are an effect of preventing deterioration and cost of acrylic block bodies due to heat and light.

Examples of the plasticizer include dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, di- (2-ethylhexyl) phthalate, diheptyl phthalate, diisodecyl phthalate, and di-n-octyl phthalate. Phthalic acid derivatives such as diisononyl phthalate, ditridecyl phthalate, octyl decyl phthalate, butyl benzyl phthalate and dicyclohexyl phthalate; isophthalic acid derivatives such as dimethyl isophthalate; di- (2-ethylhexyl) tetrahydrophthalic acid Tetrahydrophthalic acid derivatives; adipic acid derivatives such as dimethyl adipate, dibutyl adipate, di-n-hexyl adipate, di- (2-ethylhexyl) adipate, isononyl adipate, diisodecyl adipate, dibutyl diglycol adipate, etc. ; Azelaic acid derivatives such as di-2-ethylhexyl xylate; sebacic acid derivatives such as dibutyl sebacate; dodecane-2-acid derivatives; maleic acid derivatives such as dibutyl maleate and di-2-ethylhexyl maleate; dibutyl fumarate etc. Fumaric acid derivatives; trimellitic acid derivatives such as tris-2-ethylhexyl trimellitic acid; pyromellitic acid derivatives; citric acid derivatives such as acetyltributyl citrate; itaconic acid derivatives; oleic acid derivatives; ricinoleic acid derivatives; stearic acid derivatives; Derivatives; sulfonic acid derivatives; phosphoric acid derivatives; glutaric acid derivatives; polyester plasticizers that are polymers of dibasic acids such as adipic acid, azelaic acid, and phthalic acid and glycols and monohydric alcohols, glycol derivatives, glycerin derivatives, Paraffin derivatives of fluorinated paraffin, epoxy derivatives polyester polymerization type plasticizers, polyether polymerization type plasticizers, ethylene carbonate, or the like carbonate derivatives such as propylene carbonate. In the present invention, the plasticizer is not limited to these, and various plasticizers can be used, and those commercially available as rubber plasticizers can also be used. These compounds can be expected to lower the viscosity of the acrylic block copolymer (A). Commercially available plasticizers include Thiocol TP (Morton), Adekasizer O-130P, C-79, UL-100, P-200, RS-735 (Asahi Denka). Examples of other high molecular weight plasticizers include acrylic polymers, polypropylene glycol polymers, polytetrahydrofuran polymers, polyisobutylene polymers, and the like. Although not particularly limited, adipic acid derivatives, phthalic acid derivatives, glutaric acid derivatives, trimellitic acid derivatives, pyromellitic acid derivatives, polyester plasticizers, glycerin derivatives, epoxies, which are low volatility and low weight loss due to heating, are not particularly limited. Derivative polyester polymerization plasticizers, polyether polymerization plasticizers, and the like are preferable.
<Inorganic zinc compound (F)>
The resin composition for powder molding of the present invention can further contain an inorganic zinc compound (F).

  The inorganic zinc compound (F) comprises an acid anhydride group and / or a carboxyl group in the acrylic block copolymer (A) and a reactive functional group (D) in the acrylic polymer (B) at the time of molding. It plays a role as a catalyst for promoting the crosslinking reaction. In addition, the heat resistance of the molded object obtained by introduce | transducing a crosslinked structure improves, and it becomes possible to use it suitably for the use as which heat resistance is required, such as a vehicle interior member.

  An inorganic zinc compound (F) means the group which consists of a zinc compound which does not contain a carbon atom, and zinc carbonate, zinc hydrogencarbonate, zinc thiocyanate, and zinc cyanide. Zinc carboxylates such as zinc formate and zinc acetate and zinc compounds containing other carbon atoms are excluded.

  The inorganic zinc compound (F) is not particularly limited, but zinc oxide, zinc carbonate, zinc borate, zinc hydroxide, zinc phosphite, zinc phosphate, zinc diphosphate, zinc nitrate, zinc sulfate, sulfide Zinc, zinc perchlorate, zinc thiocyanate, zinc fluoride, zinc chloride, zinc bromide, zinc iodide, zinc cyanide, zinc oxide, zinc oxide molybdenum, zinc titanate, zinc telluride, zinc antimonide, etc. Is exemplified.

  The inorganic zinc compound (F) may be used alone or in combination.

  Among these, zinc oxide and zinc carbonate are preferable from the viewpoint of reactivity and availability. Specific examples include fine zinc oxide, one type of zinc oxide (above, zinc oxide, manufactured by Sakai Chemical Industry Co., Ltd.), zinc carbonate, (Zinc carbonate, manufactured by Shodo Chemical Industry Co., Ltd.).

  The amount of addition of the inorganic zinc compound (F) to the resin composition for powder molding is not particularly limited, but it is 0.000 with respect to 100 parts by weight of the total of the acrylic block copolymer (A) and the acrylic polymer (B). The amount is preferably from 01 to 3 parts by weight. If the amount added is more than 3 parts by weight, the melt fluidity at the time of molding may be reduced, or the crosslinking reaction may be promoted in the composition at room temperature to reduce the storage stability. If it is less, sufficient reaction promoting ability may not be obtained.

<Method for Producing Acrylic Polymer Powder (C)>
Although it does not specifically limit as a manufacturing method of acrylic polymer powder (C) used by this invention, For example, the composition for block-shaped or pellet-shaped acrylic polymer powder (C) is freeze-pulverized, normal temperature grinding | pulverization There is a method of obtaining an acrylic polymer powder (C) by pulverizing by the method of the method.

Moreover, when obtaining acrylic polymer powder (C), it does not necessarily need to pass through a grinding | pulverization process. For example, when the acrylic polymer powder (C) composition is obtained with a continuous extruder, the acrylic polymer composition that can be used for powder slush molding is directly attached as a micropellet by attaching a special die. Obtainable. Further, after the acrylic polymer (B) is dissolved in an acrylic block copolymer solution in which the acrylic block copolymer (A) is melted in an organic solvent, it is mixed with water and stirred. By forming droplets of an acrylic block copolymer solution having a size and heating as it is, the organic solvent is evaporated, and a powder having an appropriate particle size distribution can be obtained. At this time, the acrylic block copolymer solution is preliminarily added with the above-mentioned crosslinking promoting additive, catalyst, filler, lubricant, stabilizer, plasticizer, flexibility imparting agent, flame retardant, pigment, antistatic agent, antibacterial agent. An anti-fungal agent, etc. may be dissolved and dispersed. Moreover, in order to stably obtain droplets of a predetermined size, polyvinyl alcohol, polyvinyl alcohol / polyvinyl acetate copolymer, methyl cellulose or the like may be added as an emulsifier.
The powder obtained as a result is preferably fractionated only with a particle size of 1 to 1000 μm, more preferably 10 to 710 μm, more preferably 30 to 710 μm, using a sieve or the like. It is more preferable to sort out only those having a thickness of 75 to 500 μm, and most preferably. Powder containing particles having a particle size smaller than 1 μm causes the aggregation of the powders, which reduces the handling properties and the powder flowability. For this reason, when used for powder slush molding, the powder does not sufficiently reach the end of the mold, and the design of the molded article is impaired. In addition, when a powder containing particles having a particle size larger than 1000 μm is used for powder slush molding, the powder having a large particle size is not sufficiently melted, so that the design of the molded product is impaired.

<Spherical inorganic particles (E)>
In the powder molding resin composition of the present invention, spherical inorganic particles (E) are adhered to the polymer powder (C). By adhering the spherical inorganic particles (E), the powder fluidity and the blocking resistance can be improved without reducing the heat melting property.

  When the spherical inorganic particles (E) are adhered, the spherical inorganic particles (E) are in direct contact with the acrylic polymer powder (C) or in contact with any binder or particles. That is.

  Although it does not specifically limit as a binder, For example, a silicone oil etc. can be illustrated. Further, the particles are not particularly limited as long as the effects of the present invention are not impaired, and examples thereof include inorganic particles such as calcium carbonate and titanium oxide, and organic particles such as olefin resin, acrylic resin, and amide resin.

  Here, the term “spherical” refers to particles having a circularity of 0.7 or more. Here, the circularity refers to a value obtained by calculating a ratio of each of a plurality of particles (the projected area of particles / the area of a circle having the maximum particle length as a diameter) and arithmetically averaging them. For this reason, when the particle is a true sphere, the value of the circularity generally converges to 1, and the value tends to decrease as the particle deviates from the true sphere. The circularity is an average of about 10 measurement particles. If the circularity is less than 0.7, sufficient powder flowability and blocking resistance improving effects tend not to be obtained. The circularity of the spherical inorganic particles (E) of the present invention is preferably 0.8 or more, and more preferably 0.9 or more.

  The amount of the spherical inorganic particles (E) is 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the acrylic polymer powder (C). 0.1-1 part by weight is more preferable, and 0.1-0.5 part by weight is particularly preferable. When the amount is less than 0.01 part by weight, the effect of improving the powder fluidity and blocking resistance may be insufficient, and when the amount is more than 5 parts by weight, the heat melting property may be insufficient.

  The average particle size of the spherical inorganic particles (E) is not particularly limited, but is preferably in the range of 0.01 μm to 50 μm, more preferably in the range of 0.1 μm to 30 μm, and 0.1 μm. More preferably, it is 10-10 micrometers, and it is especially preferable that it is 1-10 micrometers. If it is smaller than 0.01 μm, the effect of improving the blocking resistance tends to be insufficient, and if it is larger than 50 μm, the scratch resistance of the molded product tends to deteriorate. The average particle diameter of the spherical inorganic particles (E) is usually a value measured by a laser method.

  The spherical inorganic particles (E) are not particularly limited as long as they are inorganic compounds. For example, carbon allotropes such as carbon black, metal oxides such as silica, alumina, cerium oxide, titanium oxide, and calcium carbonate, silicon nitride, and aluminum nitride Examples of such materials generally used for inorganic fillers include metal nitrides such as talc and kaolin. Among these, silica and alumina are preferable from the viewpoint of cost and availability.

  The spherical inorganic particles (E) are not particularly limited as long as the appearance is spherical, and the inside may be homogeneous, porous, or hollow. Among these, silica gel having a porous interior is preferable from the viewpoint of cost and availability.

  The pore volume of the spherical inorganic particles (E) is not particularly limited, but is preferably 1.00 ml / g or more, more preferably 1.30 ml / g or more, 1.45 ml / g. More preferably, it is more preferably 1.50 ml / g or more. If it is less than 1.00 ml / g, the amount of addition necessary for obtaining sufficient blocking resistance increases, and the scratch resistance may decrease.

  The pore volume is determined by adding a predetermined amount of spherical inorganic particles (E) into a jar and adding water to the jar so that the spherical inorganic particles (E) become a gel and the bottle does not fall even when the bottle is inverted. From the amount, find the following formula.

Pore volume (ml / g) = amount of water added (ml) / spherical inorganic particles (g)
Specific product names of the spherical inorganic particles (E) include Cyrossphere C-1504 (manufactured by Fuji Silysia Chemical Co., Ltd.) and Cyrossphere C-1510 (manufactured by Fuji Silysia Chemical Co., Ltd.). However, it is not limited to these.

<Use and usage of molded body>
Examples of the molding method of the composition of the present invention include powder slush molding, but other than that, injection molding, injection blow molding, blow molding, extrusion blow molding, extrusion molding, calendar molding, vacuum molding, press molding, etc. It is applicable to.

  The obtained molded article can be suitably used as, for example, a skin material, a tactile sensation material, and an appearance material, and has other purposes such as an abrasion resistant material, an oil resistant material, a vibration damping material, and an adhesive material. It can be used as a material having. As a shape, it can be used as a sheet, flat plate, film, small molded product, large molded product or other arbitrary shape, as a part such as panels, handles, grips, switches, etc. be able to. Although it does not restrict | limit especially as a use, The object for motor vehicles, household electrical appliances, or office electrical appliances are illustrated. For example, automotive skin materials, automotive tactile materials, automotive exterior materials, automotive panels, automotive handles, automotive grips, automotive switches, and household or office electrical panels Examples thereof include switches for household or office electrical appliances. Among these, it is suitably used for an automobile interior skin.

  EXAMPLES Although this invention is demonstrated further in detail based on an Example, this invention is not limited only to these Examples.

  In the examples, BA, MMA, TBA, and EA represent acrylate-n-butyl, methyl methacrylate, tert-butyl acrylate, and ethyl acrylate, respectively.

<Molecular weight measurement method>
The molecular weight shown in this example was measured by the GPC analyzer shown below, and the molecular weight in terms of polystyrene was determined using chloroform as the mobile phase. A Waters GPC system was used as the system, and Shodex K-804 (polystyrene gel) manufactured by Showa Denko KK was used as the column.

<Method for measuring conversion rate of polymerization reaction>
The conversion rate of the polymerization reaction shown in this example was measured using the following analyzer and conditions.
Equipment used: Gas chromatography GC-14B manufactured by Shimadzu Corporation
Sample preparation: The sample was diluted about 3 times with ethyl acetate, and butyl acetate was used as an internal standard.

<Powder fluidity test>
200 g of the resin powder was put into a cylindrical measurement bottle of a rotary repose angle measuring instrument (manufactured by Tsutsui Riken Kikai Co., Ltd.) and rotated at 2.4 rpm. A line connecting the highest position just before the collapse of the powder in the bottle and the highest position just after the collapse was drawn, and the angle between this line and the horizontal line was measured as the angle of repose. The smaller this angle, the better the powder flowability.

<Melability test>
Powder slush molding:
The obtained powder was subjected to a molding melt test evaluation under the following conditions.
Equipment used: Metal plate with skin wrinkles (plate thickness 4.5mm, wrinkle depth 80%)
Heating conditions: 240 ° C
Heating time: The mold and powder are brought into contact at the first inversion, the mold is inverted after 6 seconds to separate the unmelted powder, the mold is removed after 1 minute, and the cooling start time is within 1 minute (water in the aquarium To contact with cooling)
Meltability evaluation index: The thickness of the molded product is uniform: ○, thickness unevenness in part: Δ, thickness unevenness in the whole, or pinholes: x
<Blocking resistance test>
30 g of the obtained powder was put into a cylindrical cell having a diameter of 5 cm, and 1350 g of a cylindrical weight having a diameter of 5 cm was placed thereon and allowed to stand at 50 ° C. for 24 hours. After 24 hours, the powder solidified in a columnar shape was taken out from the cell and placed on a scale. A 5.31 cm ² cylindrical rod was stabbed vertically into the solidified powder, and the force required to collapse the powder lump was measured. The smaller this force, the better the blocking resistance.
<Scratch resistance test>
A sample of 10 cm × 10 cm was cut out from the molded sheet obtained by the meltability test and attached to a mount to obtain a measurement sample. A scratch resistance test was performed under the following conditions.
Equipment used: Tabers Clutch Tester (Toyo Seiki Seisakusho Co., Ltd.)
Rotation speed: 0.5rpm
Cutter: Tungsten carbide, 4.8 mm square x 19 mm length, cutting edge radius 12.7 mm
Cutter orientation: A test was conducted with an attachment load of 2N so that the long side of the cutter was on the top so that the blade side of the cutter was on the bottom, and the test was visually observed and evaluated according to the following criteria.
Good scratches not seen from the front; ○
Slightly scratched when seen from the front;
Obvious scratches such as whitening and erosion; ×

(Production Example 1)
Synthesis of Acrylic Block Copolymer The following operation was performed to obtain an acrylic block copolymer. After replacing the inside of the pressure-resistant reactor with nitrogen, 0.89 parts by weight of copper bromide, 100 parts by weight of acrylate-n-butyl and 4.46 parts by weight of acrylate-t-butyl were charged, and stirring was started. Thereafter, a solution prepared by dissolving 1.24 parts by weight of diethyl 2,5-dibromoadipate in 9.18 parts by weight of acetonitrile (nitrogen bubbling) was charged as an initiator, and the temperature of the solution was increased to 75 ° C. Stir for minutes. When the solution temperature reached 75 ° C., 0.11 part by weight of pentamethyldiethylenetriamine was added as a ligand to initiate polymerization of the acrylic polymer block.

  The conversion rate of acrylic acid-n-butyl and acrylic acid-t-butyl was determined by gas chromatography analysis of the sampling solution at regular intervals from the initiation of polymerization. During polymerization, the polymerization rate was controlled by adding pentamethyldiethylenetriamine as needed. Pentamethyldiethylenetriamine was added twice (total 0.21 parts by weight) during the acrylic polymer block polymerization.

  When the conversion rate of acrylate-n-butyl was 99.0% and the conversion rate of tert-butyl acrylate was 99.1%, methyl methacrylate was 63.76 parts by weight, ethyl acrylate was 10.38% Part, 0.61 part by weight of copper chloride, 0.11 part by weight of pentamethyldiethylenetriamine and 137.41 parts by weight of toluene (nitrogen bubbled) were added to initiate polymerization of the methacrylic polymer block.

  Sampling was performed when methyl methacrylate and ethyl acrylate were added, and conversion rates of methyl methacrylate and ethyl acrylate were determined based on this sampling. After adding methyl methacrylate and ethyl acrylate, the internal temperature was set to 85 ° C. During polymerization, the polymerization rate was controlled by adding pentamethyldiethylenetriamine as needed. Pentamethyldiethylenetriamine was added a total of 6 times (0.64 parts by weight in total) during methacrylic polymer block polymerization. When the conversion rate of methyl methacrylate was 95.0%, 212.77 parts by weight of toluene was added, and the reactor was cooled to complete the reaction. When the GPC analysis of the obtained acrylic block copolymer was conducted, the number average molecular weight Mn was 72,100, and the molecular weight distribution Mw / Mn was 1.48.

  Toluene was added to the reaction solution containing the acrylic block copolymer to make the polymer concentration 25% by weight. 0.41 part by weight of p-toluenesulfonic acid was added to 100 parts by weight of this solution, the inside of the reactor was purged with nitrogen, and the mixture was stirred at 30 ° C. for 3 hours.

  The reaction solution was sampled to confirm that the solution was colorless and transparent, and 0.50 part by weight of Radiolite # 3000 manufactured by Showa Chemical Industry was added as a filter aid. Thereafter, the reactor was pressurized to 0.1 to 0.4 MPaG with nitrogen, and the solid content was separated using a pressure filter equipped with polyester felt as a filter medium.

  After adding 0.15 parts by weight of Irganox 1010 as an antioxidant to 100 parts by weight of the block copolymer-containing solution after filtration, the inside of the reactor was purged with nitrogen, and in a pressure resistant reactor at 150 ° C. for 4 hours. Stir. After adding 1.75 parts by weight of Kyward 500SH as a solid base to the reaction solution cooled to 30 ° C., the inside of the reactor was purged with nitrogen and stirred for 2 hours. The reaction solution was sampled to confirm that the solution was neutral, and the reaction was completed. Thereafter, the reactor is pressurized to 0.1 to 0.4 MPaG with nitrogen, the solid content is separated using the pressure filter shown above equipped with polyester felt as a filter medium, and an acrylic block copolymer is contained. A polymer solution was obtained.

  This polymer solution was vacuum-dried at 80 ° C. to obtain an acrylic block copolymer (hereinafter referred to as “polymer 1”). In addition, it was 101 degreeC when the glass transition temperature of the methacrylic polymer block (a) of the polymer 1 obtained by this manufacture example 1 was calculated according to the said Fox formula.

(Production Example 2)
Synthesis of emulsion polymerization latex (A-1) 200 parts of water, 0.16 part of sodium alkanesulfonate, and 0.25 part of potassium persulfate were charged into a reactor equipped with a stirring base, and the temperature was raised to 70 ° C. after purging with nitrogen. . A mixed solution of 95 parts of methyl methacrylate, 5 parts of butyl acrylate and 0.65 part of 2-ethylhexyl thioglycolate was added over 6 hours, and 0.1893 parts of sodium alkanesulfonate was added 2 hours after the start of the addition. 0.2007 parts were added after hours. After completion of addition, 0.05 part of potassium persulfate was added and polymerization was performed for 1 hour, and a polymer having a polymerization conversion rate of 99%, a glass transition temperature of 92 ° C., a weight average molecular weight of 64,000 and a solid content concentration of 33% Latex (A-1) was obtained.

(Production Example 3)
Production of acrylic block copolymer composition powder: 200 parts by weight of pure water and 0.7 parts by weight of polyvinyl alcohol (trade name KH-17, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) (3% aqueous solution) 23.3 parts by weight), 400 parts by weight of the polymer solution obtained in Production Example 1 (solid content concentration 25% by weight), ARUFON (registered trademark) UG4010 (Toagosei Co., Ltd.) which is an acrylic polymer having an epoxy group 10 parts by weight of RS800K which is a polyether ester plasticizer (manufactured by ADEKA Co., Ltd.), extremely hardened oil of beef tallow which is an ester lubricant (melting point 60 ° C .: manufactured by NOF Corporation) 0.1 parts by weight, 0.3 parts by weight of a black powder pigment mainly composed of carbon black, and 0.3 parts by weight of zinc p-t-butylbenzoate (manufactured by Sakai Chemical Industry Co., Ltd.) were added. Stirring was performed using a two-stage four-paddle paddle as a stirring blade, and steam was introduced from the bottom of the stirring tank. Solvent gas and vapor were condensed with a condenser connected to the upper part of the stirring tank, and the solvent and water were sequentially recovered outside the system. The steam flow rate was adjusted while paying attention to foaming, the steam was stopped 5 minutes after reaching 100 ° C., and cooling was performed using a jacket of a stirring tank to obtain a slurry containing polymer particles, water and a dispersant. The obtained polymer particles were sieved with a standard sieve, the weights of the fractions belonging to the respective particle size ranges were individually weighed, and the average value based on the weight was obtained. The average particle diameter of the obtained polymer particles was 200 μm.

  The slurry containing the polymer particles thus obtained, water and a dispersing agent is allowed to stand for 1 hour, and after removing the supernatant corresponding to 72% of the slurry weight, water is added until the slurry concentration reaches 20% by weight. Was added to a reactor equipped with a stirrer and heated to 60 ° C. The polymer latex (A-1) produced by the emulsion polymerization method of Production Example 2 was added in an amount of 3.7 parts by weight based on the solid content, followed by 5.6 parts by weight based on the solid content of 15% sodium sulfate solution over 5 minutes. Added continuously. Five minutes after the end of the addition, the dispersion was heated to 85 ° C., held at 85 ° C. for 5 minutes, and then cooled to obtain a polymer slurry in which the latex adhered to the surface of the polymer particles. This slurry was dehydrated with a batch centrifugal filter and dried with a batch fluid dryer at a resin temperature of 50 ° C. until the water content reached 0.4%. The obtained powder was passed through a sieve having an opening of 500 μm, and fine powder of less than 99 μm was removed with a filter having an opening of 99 μm to obtain an acrylic polymer powder.

Example 1
Acrylic polymer powder obtained in Production Example 3; with respect to 100 parts by weight, 0.05 part by weight of epoxy group-modified silicone oil X-22-4015 (manufactured by Shin-Etsu Chemical Co., Ltd.) is added, and the content is 2 liters. After hand blending for 1 minute in a cylindrical polypropylene container (manufactured by ASONE Co., Ltd.), spherical silica having an average particle diameter of 4.5 μm by laser method, Cyrossphere C-1504 (manufactured by Fuji Silysia Chemical Co., Ltd.) ) 0.5 part by weight was added and hand blended for 1 minute in a 40 cm × 28 cm polyethylene bag (manufactured by Nippon Shokubai Co., Ltd.). Then, stationary drying (room temperature, 24 hours) was performed, and the powdery sample was obtained. Using the samples obtained here, a powder fluidity test, a blocking resistance test, and an evaluation of meltability were performed. Moreover, it was 0.94 when the circularity of Cyrossphere C-1504 was measured. The results are shown in Table 1. Furthermore, when the scratch resistance was evaluated using the molded product obtained in the meltability test, good results were obtained.
(Example 2)
Acrylic polymer powder obtained in Production Example 3; with respect to 100 parts by weight, 0.05 part by weight of epoxy group-modified silicone oil X-22-4015 (manufactured by Shin-Etsu Chemical Co., Ltd.) is added, and the content is 2 liters. After hand blending for 1 minute in a cylindrical polypropylene container (manufactured by As One Co., Ltd.), spherical silica having an average particle diameter of 10 μm by laser method, Cyrossphere C-1510 (manufactured by Fuji Silysia Chemical Co., Ltd.) 1 0.0 part by weight was added, and hand blended for 1 minute in a 40 cm × 28 cm polyethylene bag (manufactured by Nippon Shokubai Co., Ltd.). Then, stationary drying (room temperature, 24 hours) was performed, and the powdery sample was obtained. Using the samples obtained here, a powder fluidity test, a blocking resistance test, and an evaluation of meltability were performed. Moreover, when the circularity of Cyrossphere C-1510 was measured, it was 0.90 to 0.94. The results are shown in Table 1. Furthermore, when the scratch resistance was evaluated using the molded product obtained in the meltability test, good results were obtained.
(Comparative Example 1)
Acrylic polymer powder obtained in Production Example 3; with respect to 100 parts by weight, 0.05 part by weight of epoxy group-modified silicone oil X-22-4015 (manufactured by Shin-Etsu Chemical Co., Ltd.) is added, and the content is 2 liters. In a cylindrical polypropylene container (manufactured by ASONE Co., Ltd.) for 1 minute. After 3 minutes, hand blending was similarly carried out for 1 minute in a 40 cm × 28 cm polyethylene bag (manufactured by Nippon Shokubai Co., Ltd.). Then, stationary drying (room temperature, 24 hours) was performed, and the powdery sample was obtained. Using the samples obtained here, a powder fluidity test, a blocking resistance test, and an evaluation of meltability were performed. The results are shown in Table 1.
(Comparative Example 2)
Acrylic polymer powder obtained in Production Example 3; with respect to 100 parts by weight, 0.05 part by weight of epoxy group-modified silicone oil X-22-4015 (manufactured by Shin-Etsu Chemical Co., Ltd.) is added, and the content is 2 liters. After hand blending for 1 minute in a cylindrical polypropylene container (manufactured by As One Co., Ltd.), an amorphous silica particle Silicia 530 (manufactured by Fuji Silysia Chemical Co., Ltd.) 0 having an average particle diameter of 2.7 μm by laser method .5 parts by weight was added and hand blended for 1 minute in a 40 cm × 28 cm polyethylene bag (manufactured by Nippon Shokubai Co., Ltd.). Then, stationary drying (room temperature, 24 hours) was performed, and the powdery sample was obtained. Using the samples obtained here, a powder fluidity test, a blocking resistance test, and an evaluation of meltability were performed. Moreover, it was 0.57 when the circularity of the silicia 530 was measured. The results are shown in Table 1.
(Comparative Example 3)
Acrylic polymer powder obtained in Production Example 3; with respect to 100 parts by weight, 0.05 part by weight of epoxy group-modified silicone oil X-22-4015 (manufactured by Shin-Etsu Chemical Co., Ltd.) is added, and the content is 2 liters. After hand blending for 1 minute in a cylindrical polypropylene container (manufactured by As One Co., Ltd.), amorphous silica particles Imsil A-10 having an average particle diameter of 2.4 μm (manufactured by unimin speciality minerals Co., Ltd.) 5 parts by weight was added and hand blended for 1 minute in a 40 cm x 28 cm polyethylene bag (manufactured by Nippon Shokubai Co., Ltd.). Then, stationary drying (room temperature, 24 hours) was performed, and the powdery sample was obtained. Using the samples obtained here, a powder fluidity test, a blocking resistance test, and an evaluation of meltability were performed. Moreover, when the circularity of Imsil A-10 was measured, it was less than 0.7. The results are shown in Table 1.
(Comparative Example 4)
Acrylic polymer powder obtained in Production Example 3; with respect to 100 parts by weight, 0.05 part by weight of epoxy group-modified silicone oil X-22-4015 (manufactured by Shin-Etsu Chemical Co., Ltd.) is added, and the content is 2 liters. After hand blending for 1 minute in a cylindrical polypropylene container (manufactured by As One Co., Ltd.), 1 part by weight of spherical crosslinked MMA particles MA1002 (manufactured by Nippon Shokubai Co., Ltd.) having an average particle diameter of 2 μm by a Coulter counter was added. Then, it was hand-blended for 1 minute in a 40 cm × 28 cm polyethylene bag (manufactured by Nihonsha Co., Ltd.). Then, stationary drying (room temperature, 24 hours) was performed, and the powdery sample was obtained. Using the samples obtained here, a powder fluidity test, a blocking resistance test, and an evaluation of meltability were performed. Further, the circularity of MA1002 was measured and found to be 0.92. The results are shown in Table 1.
(Comparative Example 5)
Acrylic polymer powder obtained in Production Example 3; with respect to 100 parts by weight, 0.05 part by weight of epoxy group-modified silicone oil X-22-4015 (manufactured by Shin-Etsu Chemical Co., Ltd.) is added, and the content is 2 liters. After hand blending for 1 minute in a cylindrical polypropylene container (manufactured by As One Co., Ltd.), 5 parts by weight of spherical cross-linked MMA particles MA1002 (manufactured by Nippon Shokubai Co., Ltd.) having an average particle diameter of 2 μm by a Coulter counter were added. Then, it was hand-blended for 1 minute in a 40 cm × 28 cm polyethylene bag (manufactured by Nippon Shokubai Co., Ltd.). Then, stationary drying (room temperature, 24 hours) was performed, and the powdery sample was obtained. Using the samples obtained here, a powder fluidity test, a blocking resistance test, and an evaluation of meltability were performed. Moreover, when the circularity of MA1002 was measured, it was 0.92. The results are shown in Table 1.

表１（実施例１〜２および比較例１〜４）からわかるように、実施例１〜２の粉体成形用樹脂組成物は、粉体流動性、耐ブロッキング性、溶融性および耐スクラッチ性において良好な結果が得られた。一方、比較例１〜４のサンプルでは、粉体流動性、耐ブロッキング性、溶融性のすべてを満たしていなかった。

As can be seen from Table 1 (Examples 1 and 2 and Comparative Examples 1 to 4), the powder molding resin compositions of Examples 1 and 2 have powder flowability, blocking resistance, meltability and scratch resistance. Good results were obtained. On the other hand, the samples of Comparative Examples 1 to 4 did not satisfy all of powder flowability, blocking resistance, and meltability.

From the above, the resin composition for powder molding of the present invention exhibits good powder flowability, excellent blocking resistance and heat melting property at the time of molding, and the molded body has scratch resistance and wear resistance. It was shown to be an excellent resin composition for powder molding.

Claims (18)

  A methacrylic polymer block (a) having a methacrylic monomer as a main component and an acryl polymer block (b) having an acrylic monomer as a main component, the methacrylic polymer block (a And an acrylic block copolymer (A) having an acid anhydride group and / or a carboxyl group in at least one of the polymer blocks (b) and the acrylic polymer block (b), and an average of at least 1.1 per molecule. 0.01-5 parts by weight of spherical inorganic particles (E) with respect to 100 parts by weight of the acrylic polymer powder (C) comprising the acrylic polymer (B) having at least one reactive functional group (D) A resin composition for powder molding characterized by comprising   2. The powder molding resin composition according to claim 1, wherein the spherical inorganic particles as component (E) have an average particle size of 0.01 μm to 50 μm.   3. The resin composition for powder molding according to claim 1 or 2, wherein the spherical inorganic particles (E) are at least one selected from silica and alumina.   4. The resin composition for powder molding according to claim 1, wherein the spherical inorganic particles (E) are silica.   The resin composition for powder molding according to claim 1, wherein the reactive functional group (D) is at least one selected from an epoxy group, a hydroxyl group, and an amino group.   The resin composition for powder molding according to claim 1, wherein the reactive functional group (D) is an epoxy group.   The resin composition for powder molding according to claim 1, wherein the acrylic polymer powder (C) further contains an inorganic zinc compound (F).   8. The resin composition for powder molding according to claim 1, wherein the inorganic zinc compound (F) is at least one selected from zinc oxide and zinc carbonate. The acrylic block copolymer (A) has a methacrylic monomer as a main component and a methacrylic polymer block (a) having a glass transition temperature of 50 to 130 ° C., 15 to 50% by weight, acrylic acid -Acrylic polymer block (b) 85 containing at least one monomer selected from the group consisting of -n-butyl, ethyl acrylate, 2-ethylhexyl acrylate and 2-methoxyethyl acrylate as a main component The acid anhydride group represented by the carboxyl group and / or the general formula (1) in at least one polymer block of the block (a) and the block (b). :

(Wherein R1 independently represents hydrogen or a methyl group, n represents an integer of 0 to 3, m represents an integer of 0 or 1), and the number average molecular weight measured by gel permeation chromatography The resin composition for powder molding according to claim 1, wherein the resin composition is an acrylic block copolymer having a viscosity of 30,000 to 200,000.   The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography of the acrylic block copolymer as the component (A) is 1.8 or less. The resin composition for powder molding according to claim 1, wherein:   11. The resin composition for powder molding according to claim 1, wherein the acrylic block copolymer (A) is a block copolymer produced by atom transfer radical polymerization.   12. The resin composition for powder molding according to claim 1, wherein the acrylic polymer as the component (B) has a weight average molecular weight of 30,000 or less.   13. The resin composition for powder molding according to claim 1, wherein the average particle size of the acrylic polymer powder (C) is 1 μm or more and less than 1000 μm.   The resin composition for powder molding according to claim 1, wherein the spherical inorganic particles (E) are silica gel.   The resin composition for powder molding according to claim 1, wherein the spherical inorganic particles (E) have an average particle diameter of 1 μm to 10 μm.   A powder slush molding composition comprising the powder molding resin composition according to any one of claims 1 to 15.   A powder slush molded article obtained by powder slush molding the powder molding resin composition according to any one of claims 1 to 16. A skin for automobile interior, wherein the powder molding resin composition according to any one of claims 1 to 16 is formed by powder slush molding.