JP2006111709A - Acrylic block copolymer composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an acrylic block copolymer composition excellent in grindability and scratch resistance, and to provide a composition for powder slush molding and a powder slush-molded product using the composition. <P>SOLUTION: The acrylic block copolymer composition contains (A) 100 pts.wt. acrylic block copolymer and (B) 10-100 pts.wt. precipitated calcium carbonate comprising colloidal calcium carbonate and/or light calcium carbonate. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an acrylic block copolymer composition excellent in grindability and mechanical properties. More specifically, the present invention relates to an acrylic block copolymer composition having excellent crushability and scratch resistance. The present invention also relates to a composition for powder slush molding and a powder slush molded product using the composition.

  An acrylic block copolymer having methyl methacrylate as a hard segment and butyl acrylate as a soft segment is known to have properties as a thermoplastic elastomer. For example, Patent Document 1 discloses an iniferter. The mechanical properties of acrylic block copolymers having a methacrylic block and an acrylic block produced by the method are disclosed. In such an acrylic block copolymer, it is possible to give an extremely flexible elastomer as compared with other thermoplastic elastomers such as a styrene block body by appropriately selecting components constituting the block body.

  In addition, the acrylic block copolymer has a feature that it is excellent in weather resistance, heat resistance, durability and oil resistance.

  Taking advantage of the characteristics of such an acrylic block copolymer, the acrylic block copolymer is used for various skin materials, interior materials and the like. In addition, it is expected to be developed as a material for a member that directly touches a human hand by making use of tactile sensation. In addition to mechanical properties such as breaking strength and breaking elongation, scratch resistance, heat resistance, strain recovery, etc., physical properties required for these skin materials, etc., resistance to drugs that can be contacted, and the skin and substrate In the case of directly bonding, the adhesiveness between the skin and the base material, and in the case of providing a buffer material between the skin and the base material, the adhesiveness between the skin and the buffer material can be mentioned.

  As a method for molding the skin material, for example, there is powder slush molding, and this molding method is an excellent method in which productivity, tactile sensation, and texture transferability are balanced. Here, powder slush molding is a method in which resin powder as a raw material is poured into a molding die, melt-molded, and a molded body cooled and solidified after a certain period of time is taken out. Powder slush powder can be produced by a method of pulverizing pellets and the like at room temperature.

Japanese Unexamined Patent Publication No. 1-26619

  However, an acrylic block copolymer having a hardness range preferable as a skin material, an interior material, or the like is sticky and may be difficult to grind at room temperature. Such pulverizability often depends on the composition design of the acrylic block copolymer or the composition, and it is difficult to improve the pulverizability by a method usually employed for improving the pulverizability. Even if the grindability is improved, other characteristics often deteriorate. Specifically, when a small amount of filler is blended to ensure grindability, properties such as scratch resistance are reduced, and it is difficult to achieve both of these properties.

  The problem to be solved by the present invention is to provide an acrylic block copolymer composition excellent in grindability and mechanical properties. More specifically, an object of the present invention is to provide an acrylic block copolymer composition excellent in grindability and scratch resistance. It is another object of the present invention to provide a composition for powder slush molding and a powder slush molded article using the composition.

  As a result of intensive studies on an acrylic block copolymer composition excellent in friability and mechanical properties, the acrylic block copolymer composition containing a predetermined filler has a pulverization property and mechanical properties, In particular, the present inventors have found that it is excellent in scratch resistance and have completed the present invention.

That is, the present invention
(A) 100 parts by weight of an acrylic block copolymer;
(B) 10-100 parts by weight of precipitated calcium carbonate comprising colloidal calcium carbonate and / or light calcium carbonate,
And an acrylic block copolymer composition characterized by comprising:

  As a preferred embodiment, the acrylic block copolymer as the component (A) is a methacrylic polymer block (A1) 10 to 60% by weight mainly composed of a methacrylic polymer, and the acrylic polymer. The present invention relates to an acrylic block copolymer composition comprising 90 to 40% by weight of an acrylic polymer block (A2) containing as a main component.

  As a preferred embodiment, the acrylic polymer block (A2) is at least one selected from the group consisting of n-butyl acrylate, ethyl acrylate, 2-methoxyethyl acrylate, and 2-ethylhexyl acrylate. Acrylic block copolymer composition comprising 50 to 100% by weight of monomers and 50 to 0% by weight of different acrylic esters and / or vinyl monomers copolymerizable therewith About.

  In a preferred embodiment, the acrylic block copolymer is characterized in that the number average molecular weight measured by gel permeation chromatography of the acrylic block copolymer as the component (A) is 30,000 to 500,000. It relates to a coalescence composition.

  As a preferred embodiment, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography of the acrylic block copolymer as the component (A) is 1. It is related with the acrylic block copolymer composition characterized by being 8 or less.

  As a preferred embodiment, the present invention relates to an acrylic block copolymer composition, wherein the acrylic block copolymer as component (A) is a block copolymer produced by atom transfer radical polymerization.

  As a preferred embodiment, the present invention relates to an acrylic block copolymer composition, wherein the precipitated calcium carbonate (B) is colloidal calcium carbonate.

  As a preferred embodiment, the present invention relates to an acrylic block copolymer composition characterized in that the average particle size in terms of BET specific surface area of precipitated calcium carbonate (B) is less than 0.40 μm.

  In a preferred embodiment, the present invention relates to an acrylic copolymer composition, wherein the precipitated calcium carbonate (B) is precipitated calcium carbonate that has not been surface-treated with a surface treatment agent.

  As a preferred embodiment, the present invention relates to a powder slush molding composition containing the acrylic copolymer composition.

  The present invention also relates to a powder slush molded article obtained by powder slush molding of the above composition.

  As a preferred embodiment, the present invention relates to an automotive interior skin characterized by powder slush molding of the above composition.

  According to the present invention, it is possible to obtain an acrylic block copolymer composition excellent in pulverization and scratch resistance. The composition according to the present invention can be suitably used for powder slush molding, and thereby, for example, an interior skin for an automobile or the like can be produced.

Hereinafter, the present invention will be described in more detail.
The present invention relates to an acrylic block copolymer composition excellent in grindability and scratch resistance, comprising (A) 100 parts by weight of an acrylic block copolymer, (B) colloidal calcium carbonate and light calcium carbonate And 10 to 100 parts by weight of at least one precipitated calcium carbonate selected from the group consisting of: In addition, in this application, scratch resistance means the scratch property of the molded object which consists of a composition concerning this invention.

<Acrylic block copolymer (A)>
The structure of the block copolymer (A) may be a linear block copolymer, a branched (star) block copolymer, or a mixture thereof. The structure of the block copolymer (A) may be appropriately selected according to the required physical properties of the block copolymer (A). From the viewpoint of cost and ease of polymerization, a linear block copolymer is used. Is preferred.

The linear block copolymer may be of any linear block structure, but it constitutes the acrylic block copolymer (A) from the viewpoint of its physical properties or physical properties when made into a composition. Methacrylic polymer block (A1) (hereinafter also referred to as polymer block (A1) or block (A1)) and acrylic polymer block (A2) (hereinafter referred to as polymer block (A2) or block ( A2)) is represented by the general formula: (A1-A2) _n , general formula: A1- (A2-A1) _n , general formula: (A2-A1) _n -A2 (n is an integer of 1 to 3). The block copolymer is preferably at least one block copolymer selected from the group consisting of the represented block copolymers. Among these, from the viewpoint of easy handling at the time of processing and physical properties in the case of a composition, A1-A2 type diblock copolymer, A1-A2-A1 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 40,0000. 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 block copolymer (A) to the methacrylic polymer block (A1) and the acrylic polymer block (A2) is 5 to 90% by weight for the block (A1) and 95 to 10 for the block (A2). It is desirable to set the weight%. When the proportion of (A1) is less than 5% by weight, the shape tends to be difficult to be retained during molding, and when the proportion of (A2) is less than 10% by weight, the elasticity as an elastomer and the meltability during molding tend to decrease. There is. From the viewpoint of maintaining the shape during molding and elasticity as an elastomer, the preferred range of the composition ratio is 10 to 60% by weight of (A1), 90 to 40% by weight of (A2), and more preferably (A1). ) Is 15 to 50% by weight, and (A2) is 85 to 50% by weight.

  From the viewpoint of the hardness of the elastomer composition, when the proportion of (A1) is small, the hardness tends to be low, and when the proportion of (A1) is large, the hardness tends to be high. For this reason, it sets suitably according to the required hardness of an elastomer composition. Further, from the viewpoint of processing, when the proportion of (A1) is small, the viscosity is low, and when the proportion of (A1) is large, the viscosity tends to be high. Therefore, it is appropriately set according to the required processing characteristics.

<Methacrylic polymer block (A1)>
The methacrylic polymer block (A1) is a block obtained by polymerizing a monomer having a methacrylic acid ester as a main component, and is 50 to 100% by weight of the methacrylic acid ester and a vinyl type copolymerizable therewith. It is preferably composed of 0 to 50% by weight of monomer.

  Examples of the methacrylic acid ester constituting the methacrylic polymer block (A1) include, for example, methyl methacrylate, ethyl methacrylate, methacrylate-n-propyl, isopropyl methacrylate, and methacrylate-n-. Butyl, isobutyl methacrylate, methacrylic acid-, methacrylic acid-n-pentyl, methacrylic acid-n-hexyl, cyclohexyl methacrylate, methacrylic acid-n-heptyl, methacrylic acid-n-octyl, meta 2-ethylhexyl acrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, phenyl methacrylate, toluyl methacrylate, benzyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate , Methacrylic acid 3-methoxybutyl, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, stearyl methacrylate, glycidyl methacrylate, 2-aminoethyl methacrylate, γ- (methacryloyloxypropyl) tri Methoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, ethylene oxide adduct of methacrylic acid, trifluoromethylmethyl methacrylate, methacrylic acid-2-trifluoromethylethyl, methacrylic acid-2-perfluoro Ethylethyl, 2-perfluoroethyl-2-perfluorobutylethyl methacrylate, 2-perfluoroethyl methacrylate, perfluoromethyl methacrylate, diperfluoromethyl methyl methacrylate, methacrylate 2-perfluoromethyl-2-perfluoromethyl methyl phosphate, 2-perfluorohexyl ethyl methacrylate, 2-perfluorodecyl ethyl methacrylate, 2-perfluorohexadecyl ethyl methacrylate, etc. Can give.

  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, in order to raise heat resistance, methacrylic acid-t-butyl is preferable as a precursor at the time of introducing an acid anhydride.

  Examples of vinyl monomers copolymerizable with the methacrylic acid ester constituting the methacrylic polymer block (A1) include, for example, 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 should be selected from the viewpoints of adjusting the glass transition temperature required for the methacrylic polymer block (A1) and compatibility with the acrylic polymer block (A2). Can do.

  The glass transition temperature of (A1) is preferably 25 ° C. or higher, more preferably 40 ° C. or higher, and further preferably 50 ° C. or higher, from the viewpoint of thermal deformation of the elastomer composition. If the glass transition temperature of (A1) is lower than the temperature of the environment in which the elastomer composition is used, thermal deformation may be likely due to a decrease in cohesive force.

  From the viewpoints described above, the methacrylic polymer block (A1) 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 (A2)>
The acrylic polymer block (A2) is a block obtained by polymerizing a monomer having an acrylic ester as a main component. The acrylic monomer is 50 to 100% by weight and a vinyl monomer copolymerizable therewith. It is preferably composed of 0 to 50% by weight.

  Examples of the acrylic ester constituting the acrylic polymer block (A2) include the same monomers as the acrylic ester exemplified as the monomer constituting the methacrylic polymer block (A1). it can.

  These can be used alone or in combination of two or more thereof. Among these, acrylic acid-n-butyl is preferable from the viewpoint of rubber elasticity, low temperature characteristics and cost balance. Further, 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. And as a precursor at the time of introduce | transducing an acid anhydride group for improving heat resistance, acrylate-t-butyl is preferable.

  Examples of the vinyl monomer copolymerizable with the acrylic ester constituting the acrylic polymer block (A2) include, for example, methacrylic ester, aromatic alkenyl compound, vinyl cyanide compound, conjugated diene compound, halogen 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 polymer block (A2) can be mention | raise | lifted.

  These can be used alone or in combination of two or more. These vinyl monomers are preferable from the viewpoint of balance such as glass transition temperature and oil resistance required for the acrylic polymer block (A2), compatibility with the methacrylic polymer block (A1), and the like. Can be selected.

  From the viewpoint of rubber elasticity of the elastomer composition, the acrylic polymer block (A2) preferably has a glass transition temperature of 25 ° C. or lower, more preferably 0 ° C. or lower, and further preferably −20 ° C. or lower. . By making the glass transition temperature of the acrylic polymer block (A2) 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 (A2) is at least one selected from the group consisting of -n-butyl acrylate, ethyl acrylate, 2-methoxyethyl acrylate, and 2-ethylhexyl acrylate. A block obtained by polymerizing a monomer mainly composed of is preferable.

<Method for producing block copolymer (A)>
(polymerization)
Although it does not specifically limit as a manufacturing method, It is preferable to use controlled polymerization. Examples of the controlled polymerization include living anion polymerization, radical polymerization using a chain transfer agent, and recently developed living radical polymerization. Living radical polymerization is preferable from the viewpoint of controlling the molecular weight and structure of the block copolymer and copolymerizing a monomer having a crosslinkable functional group.

  Living polymerisation, in the narrow sense, indicates that the terminal always has activity, but generally also includes pseudo-living polymerization where the terminal is inactive and the terminal is in equilibrium. The living radical polymerization in the present invention is a radical polymerization in which the polymerization terminal is activated and deactivated is maintained in an equilibrium state, and has been actively studied in various groups in recent years. .

  Examples thereof include those using a chain transfer agent such as polysulfide, those using a radical scavenger such as a cobalt porphyrin complex (Journal of American Chemical Society, 1994, 116, 7943) and a nitroxide compound (Macromolecules, 1994). 27, 7228), atom transfer radical polymerization (ATRP) using an organic halide as an initiator and a transition metal complex as a catalyst. In the present invention, there is no particular limitation as to which of these methods is used, but atom transfer radical polymerization is preferred from the viewpoint of ease of control.

  In the atom transfer radical polymerization, an organic halide or a sulfonyl halide compound is used as an initiator, and a metal complex having a group metal of group 8, 9, 10, or 11 as a central metal in the periodic table is used as a catalyst ( For example, Matyjaszewski et al., Journal of American Chemical Society, 1995, 117, 5614, Macromolecules, 1995, 28, 7901, Science, 1996, 272, amu es 1995, 28, 1721).

  According to these methods, the polymerization proceeds generally in a living manner with a very high polymerization rate and is likely to cause a termination reaction such as coupling between radicals, and Mw / Mn = narrow molecular weight distribution. A polymer having a molecular weight of about 1.1 to 1.5 is obtained, and the molecular weight can be freely controlled by the ratio of the monomer and the initiator when charged.

  In the atom transfer radical polymerization method, as the organic halide or sulfonyl halide compound used as an initiator, a monofunctional, difunctional, or polyfunctional compound can be used. These can be used properly according to the purpose. When producing a diblock copolymer, a monofunctional compound is preferable. In the case of producing an xy-type triblock copolymer and an xy-type triblock copolymer, it is preferable to use a bifunctional compound. In the case of producing a branched block copolymer, it is preferable to use a polyfunctional compound.

Examples of the monofunctional compound include compounds represented by the following chemical formulas.
C ₆ H ₅ —CH ₂ X
C ₆ H ₅ -CHX-CH _{3
C 6 H 5 -C (CH 3} ) 2 X
R ¹ —CHX—COOR ^{2
_{R 1 -C (CH 3) X}} -COOR 2
R ¹ —CHX—CO—R ²
R ¹ —C (CH ₃ ) X—CO—R ²
R ¹ —C ₆ H ₄ —SO ₂ X
In the formula, C ₆ H ₄ represents a phenylene group. The phenylene group may be any of ortho substitution, meta substitution and para substitution. R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. X represents chlorine, bromine or iodine. R ² represents a monovalent organic group having 1 to 20 carbon atoms.

Examples of the bifunctional compound include compounds represented by the following chemical formulas.
X—CH ₂ —C ₆ H ₄ —CH ₂ —X
_{X-CH (CH 3) -C} 6 H 4 -CH (CH 3) -X
_{X-C (CH 3) 2} -C 6 H 4 -C (CH 3) 2 -X
X—CH (COOR ³ ) — (CH ₂ ) _n —CH (COOR ³ ) —X
_{X-C (CH 3) (} COOR 3) - (CH 2) n -C (CH 3) (COOR 3) -X
X—CH (COR ³ ) — (CH ₂ ) _n —CH (COR ³ ) —X
_{X-C (CH 3) (} COR 3) - (CH 2) n -C (CH 3) (COR 3) -X
_{X-CH 2 -CO-CH 2} -X
_{X-CH (CH 3) -CO} -CH (CH 3) -X
_{X-C (CH 3) 2} -CO-C (CH 3) 2 X
_{X-CH (C 6 H 5} ) -CO-CH (C 6 H 5) -X
X—CH ₂ —COO— (CH ₂ ) _n —OCO—CH ₂ —X
_{X-CH (CH 3) -COO-} (CH 2) n -OCO-CH (CH 3) -X
_{X-C (CH 3) 2} -COO- (CH 2) n -OCO-C (CH 3) 2 -X
_{X-CH 2 -CO-CO-} CH 2 -X
_{X-CH (CH 3) -CO} -CO-CH (CH 3) -X
_{X-C (CH 3) 2} -CO-CO-C (CH 3) 2 -X
X—CH ₂ —COO—C ₆ H ₄ —OCO—CH ₂ —X
X—CH (CH ₃ ) —COO—C ₆ H ₄ —OCO—CH (CH ₃ ) —X
_{X-C (CH 3) 2} -COO-C 6 H 4 -OCO-C (CH 3) 2 -X
_{X-SO 2 -C 6 H 4} -SO 2 -X
In the formula, R ³ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. C ₆ H ₄ represents a phenylene group. The phenylene group may be any of ortho substitution, meta substitution and para substitution. C ₆ H ₅ represents a phenyl group. n represents an integer of 0 to 20. X represents chlorine, bromine or iodine.

Examples of the polyfunctional compound include compounds represented by the following chemical formulas.
C ₆ H ₃ (CH ₂ X) _{3
C 6 H 3 (CH (CH} 3) -X) 3
_{C 6 H 3 (C (CH} 3) 2 -X) 3
_{C 6 H 3 (OCO-CH} 2 X) 3
_{C 6 H 3 (OCO-CH} (CH 3) -X) 3
_{C 6 H 3 (OCO-C} (CH 3) 2 -X) 3
C ₆ H ₃ (SO ₂ X) ₃
In the formula, C ₆ H ₃ represents a trisubstituted phenyl group. In the trisubstituted phenyl group, the position of the substituent may be any of 1-position to 6-position. X represents chlorine, bromine or iodine.

  In these organic halides or sulfonyl halide compounds used as initiators, the carbon to which the halogen is bonded is bonded to a carbonyl group, a phenyl group, etc., and the carbon-halogen bond is activated to initiate polymerization. . The amount of the initiator to be used is determined from the ratio to the monomer in accordance with the required molecular weight of the block copolymer. That is, the molecular weight of the block copolymer can be controlled by the number of monomers used per molecule of the initiator.

  The transition metal complex used as the catalyst for the atom transfer radical polymerization is not particularly limited, but is preferably a monovalent and zerovalent copper, divalent ruthenium, divalent iron, or divalent nickel complex. I can give you. Among these, a copper complex is preferable from the viewpoint of cost and reaction control.

Examples of the monovalent copper compound include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, and the like. . In the case of using a copper compound, 2,2′-bipyridyl and its derivative, 1,10-phenanthroline and its derivative, tetramethylethylenediamine (TMEDA), pentamethyldiethylenetriamine, hexamethyl (2-aminoethyl) Polyamines such as amines can also be added as ligands. A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) can also be used as a catalyst.

When a ruthenium compound is used as a catalyst, aluminum alkoxides can also be added as an activator. Further, a divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ), and a divalent nickel bistributylphosphine A complex (NiBr ₂ (PBu ₃ ) ₂ ) can also be used as a catalyst. The amount of the catalyst, ligand and activator used is not particularly limited, and is appropriately determined from the relationship between the amount of initiator, monomer and solvent used and the required reaction rate.

  The atom transfer radical polymerization can be carried out without solvent (bulk polymerization) or in various solvents. Examples of the solvent include hydrocarbon solvents such as benzene and toluene, halogenated hydrocarbon solvents such as methylene chloride and chloroform, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, methanol, ethanol, propanol, and isopropanol. Alcohol solvents such as n-butanol and t-butanol, nitrile solvents such as acetonitrile, propionitrile, benzonitrile, ester solvents such as ethyl acetate and butyl acetate, carbonate solvents such as ethylene carbonate and propylene carbonate, etc. These can be used by mixing at least one of them. Moreover, when using a solvent, the usage-amount is suitably determined from the relationship between the viscosity of the whole system, and the required reaction rate (namely, stirring efficiency).

  The atom transfer radical polymerization is preferably performed in the range of room temperature to 200 ° C, more preferably 50 to 150 ° C. If the atom transfer radical polymerization temperature is lower than room temperature, the viscosity may be too high and the reaction rate may be slow, and if it exceeds 200 ° C., an inexpensive polymerization solvent may not be used.

  As the method for producing the block copolymer by the atom transfer radical polymerization, a method of sequentially adding monomers, a method of polymerizing the next block using a polymer synthesized in advance as a polymer initiator, For example, a method of binding the coalescence by reaction can be given. These methods can be used properly according to the purpose. From the viewpoint of simplicity of the production process, a method by sequential addition of monomers is preferred.

(Removal of polymerization catalyst, etc.)
The reaction liquid obtained by polymerization contains a mixture of a polymer and a metal complex, and an organic acid is added to remove the metal complex. Subsequently, an acrylic block copolymer solution can be obtained by removing impurities by adsorption treatment.

The organic acid to be used is not particularly limited, but preferably contains a carboxylic acid group or a sulfonic acid group.
Among them, benzenesulfonic acid or a derivative thereof is preferable from the viewpoint of easy dispersion in an organic solvent, properties of a product of reaction between an acid and a metal complex, availability, and the like. Among them, p-toluenesulfonic acid is preferable. Is more preferable.

  The amount of the organic acid used in the present invention is preferably 1 mol or more per 1 mol of copper contained in the metal complex centered on copper. The amount of the organic acid used is preferably 0.5 mol or more, more preferably 1.0 mol or more, per 1 mol of the ligand coordination site. However, although the reaction time is shortened as the amount of the organic acid is increased, it is desirable to suppress the reaction time to a necessary amount in consideration of the cost, the necessity of removing excess organic acid, and the like.

  The reaction of the present invention by addition of an organic acid can be carried out without solvent (polymer melt) or in various solvents.

  The method for removing the metal salt produced as a result of the reaction is not particularly limited, and known methods such as filtration using a filter press, decantation, and centrifugal sedimentation can be used as necessary. In some cases, it is possible to proceed to the next base treatment step without removing the metal salt. However, even in this case, the metal salt must be removed after the base treatment step. If the metal salt remains in the solid acrylic block copolymer, the polymer may deteriorate during the removal of volatile components by a vacuum extruder, and there is a risk of adverse effects such as coloring of the molded product and deterioration of mechanical properties. .

After removing the metal complex by adding an organic acid to a mixture containing a polymer and a metal complex with copper as the central metal, the system may approach the acidic side, which may be a problem. . In that case, a base treatment step is required. A known method can be used as the method for base treatment, and there is no particular limitation, but examples include a method using a basic solid. Examples of basic solids include basic activated alumina, basic adsorbent, solid inorganic acid, anion exchange resin, cellulose anion exchanger and the like. Examples of the basic adsorbent include KYOWARD (registered trademark) 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.). Examples of the solid inorganic acid include Na ₂ O, K ₂ O, MgO, and CaO. Examples of the anion exchange resin include a styrene strong basic anion exchange resin, a styrene weak base anion exchange resin, and an acrylic weak base type anion exchange resin.

  The method for removing the adsorbent added during the base treatment step is not particularly limited, and known methods such as filtration using a filter press, decantation, and centrifugal sedimentation can be used as necessary.

  The polymer solution thus obtained is then subjected to an evaporation operation to remove the polymerization solvent and unreacted monomers to isolate the acrylic block copolymer. As the evaporation method, a thin film evaporation method, a flash evaporation method, a horizontal evaporation method provided with an extrusion screw, or the like can be used. Since the acrylic block copolymer has adhesiveness, efficient evaporation is possible by combining the horizontal evaporation method with an extrusion screw alone or another evaporation method among the above evaporation methods.

(Functional group conversion)
In the present invention, an acrylic copolymer block having a carboxyl group or an acid anhydride group introduced by a functional group conversion reaction of the ester moiety of the monomer introduced into the polymer block may be used.

  The method for synthesizing the block copolymer having a carboxyl group is not particularly limited. For example, a carboxyl group such as t-butyl methacrylate, t-butyl acrylate, trimethylsilyl methacrylate, trimethylsilyl acrylate, etc. A block copolymer containing a monomer having a functional group serving as a precursor of is synthesized, and a known predetermined chemical reaction such as hydrolysis or acid decomposition, for example, JP-A-10-298248 and JP-A-2001-234146. There is a method of generating a carboxyl group by a method described in Japanese Patent Publication No. Gazette. There is also a method of hydrolyzing an acid anhydride group derived by the method shown below to generate a carboxyl group.

  As a method for synthesizing a block copolymer having an acid anhydride group, the block copolymer having a carboxyl group is subjected to a dehydration or dealcoholization reaction by heating, whereby an ester site of an adjacent monomer is obtained. Can be converted to carboxylic acid anhydrides. Alternatively, a block copolymer containing a monomer having a functional group that becomes a precursor of a carboxyl group, such as t-butyl methacrylate, t-butyl acrylate, trimethylsilyl methacrylate, trimethylsilyl acrylate, etc., is synthesized. In addition, there is a method of converting an ester site of an adjacent monomer into a carboxylic acid anhydride by performing a dealcoholization reaction by heating as described above.

  The block copolymer having an acid anhydride group derived by such a method can be hydrolyzed by heating with purified water in an autoclave, for example, and the acid anhydride group can be converted into a carboxyl group. . Hydrolysis can be performed, for example, by heating at 200 ° C. for 2 hours.

  When a t-butyl group is contained in the methacrylic polymer block (A1) or the methacrylic polymer block (A2), a carboxylic acid group, or a carboxylic acid group and an acid anhydride group are obtained by the above-described method. Can be converted into both.

<Precipitated calcium carbonate (B)>
Precipitated calcium carbonate used in the present invention, that is, light calcium carbonate includes colloidal calcium carbonate and light calcium carbonate, and these can be used alone or in combination of two or more.

  Examples of the colloidal calcium carbonate include BRILLIANT (registered trademark) 15 (hereinafter, “BRILLIANT” is referred to as “brilliant”), brilliant S15, brilliant 40, UNIBUR70, VIGOT (registered trademark) 15, VIGOT10, and brilliant 1500. , UNIFANT (registered trademark) 15, UNIFANT15FR, VISCOLITE (manufactured by Shiraishi Kogyo Co., Ltd., obtained by a continuous reaction method), white gloss flower (registered trademark) PZ, white gloss flower PX, white gloss flower tunex E, white gloss flower CC, white gloss flower CCR , White gloss flower Carmos, white gloss flower U, white gloss flower homocal D, white gloss flower homocal DM, white gloss flower gelton 50, white gloss flower O, white gloss flower DD, white gloss flower TDD, white gloss flower IGV (above, manufactured by Shiroishi Kogyo Co., Ltd., obtained by batch reaction method) , MSK-C, MSK-G, MSK-K, MSK-P, MSK-PO, Calfine 100, Calfine 200, Calfine 200M, Calfine 500, Carlex 100, Carlex 300, MT-100, MS -100M, MS-600, Sealet 200, N-2, MC-5, MC-K, MC-SII, MC-S5, MC-T, Unigloss 1000, Unigloss 3000, Luminous (Made by Maruo Calcium Co., Ltd.) , Colloidal products). However, it is not limited to these. The shape of the particles is often cubic.

  Examples of the light calcium carbonate include PC, PC-700, PCX, PCX-850, Silver W, Akadama (manufactured by Shiraishi Kogyo Co., Ltd., obtained by a batch reaction method) and the like. However, it is not limited to these. The shape of the particles is often spindle-shaped.

Among them, it is preferable to use colloidal calcium carbonate in order to improve the scratch resistance. The reason is not clear, but it is presumed to be derived from the shape of the calcium carbonate particles.
Further, the average particle size in terms of BET specific surface area is preferably less than 1.0 μm, and more preferably less than 0.40 μm. If it is larger than 1.0 μm, sufficient mechanical strength, particularly scratch resistance may not be obtained. This is considered to be because the larger the particle size, the easier it is to become a starting point of fracture in the molded body, and this is presumed to cause a decrease in mechanical properties, particularly a scratch resistance.

  Examples of the calcium carbonate having an average particle size in terms of BET specific surface area of less than 0.4 μm include, for example, Brilliant 15, Brilliant S15, UNIBUR70, VIGOT15, VIGOT10, Brilliant 1500, UNIFANT15, UNIFANT15FR, White Glossy PZ, White Glossy Px, White gloss flower tunex E, white gloss flower CC, white gloss flower CCR, white gloss flower Carmos, white gloss flower U, white gloss flower homocal D, white gloss flower homocal DM, white gloss flower gelton 50, white gloss flower O (manufactured by Shiraishi Kogyo Co., Ltd.). However, it is not limited to these.

  In addition, the precipitated calcium carbonate preferably has an average particle size of less than 3.0 μm, more preferably less than 1.0 μm, as observed by an electron microscope. If it is larger than 3.0 μm, sufficient mechanical strength, particularly scratch resistance may not be obtained. This is considered to be because the larger the particle size, the easier it is to start the fracture in the molded body, and it is assumed that this leads to a decrease in mechanical properties, particularly a scratch resistance. Yes.

  Examples of the calcium carbonate having an average particle size of less than 1.0 μm in observation with an electron microscope include, for example, Brilliant 15, Brilliant S15, VIGOT15, VIGOT10, UNIFANT15 (above, manufactured by Shiroishi Kogyo Co., Ltd., but 50% Med), MSK-C, MSK-G, MSK-K, MSK-P, MSK-PO, Calfine 100, Calfine 200, Calfine 200M, Calfine 500, Carlex 100, Carlex 300, MT-100, MS- 100M, MS-600, Sealet 200, N-2, MC-5, MC-K, MC-SII, MC-S5, MC-T, Unigros 1000, Unigros 3000, Luminous (above, manufactured by Maruo Calcium Co., Ltd., Colloidal products). However, it is not limited to these.

  The precipitated calcium carbonate is preferably not subjected to a surface treatment with a surface treatment agent, and more preferably not subjected to a surface treatment with a fatty acid. The reason is unknown in detail, but the acrylic block copolymer and the surface of calcium carbonate that has not been surface-treated interact with each other to provide good dispersibility and mechanical properties. It is considered a thing. Those whose surface is treated with a fatty acid or the like tends to deteriorate the dispersibility because the appropriate interaction tends to be impaired. Surface treatment agents include fatty acids such as stearic acid, rosin acid, ignin, quaternary ammonium salts, silicone compounds, silicone resins, waxes, fatty acid alcohols, modified fatty acids, sulfonic acids, polymers such as polyester and polyacrylic acid. , Etc. can be used. As an easily available commercial product, calcium carbonate surface-treated with a fatty acid can be used.

  Examples of the calcium carbonate not subjected to the surface treatment with the surface treating agent include brilliant 15, brilliant 1500, and silver W. However, it is not limited to these.

  The blending ratio of (A) and (B) is (B) 10-100 parts by weight of precipitated calcium carbonate with respect to 100 parts by weight of the acrylic block copolymer. When the amount is less than 10 parts by weight, the pulverization property may be inferior, and when the amount is more than 100 parts by weight, the mechanical properties may be deteriorated or the molding may be poor. This blending ratio is appropriately set according to the weight ratio of (A1) and (A2), the molecular weight of (A), and the like.

  The blending ratio of (A) and (B) is preferably 15 to 80 parts by weight with respect to 100 parts by weight of (A), more preferably 100 parts by weight of (A). On the other hand, (B) is 20 to 60 parts by weight.

<Crosslinking agent>
In the composition of the present invention, it may be necessary to add a crosslinking agent in order to satisfy necessary performance such as moldability, heat resistance and mechanical properties. As a crosslinking agent, what is used for crosslinked rubber etc. can be used, In addition, the polymer containing a reactive functional group is illustrated.

  The polymer containing such a reactive functional group may be liquid or solid at room temperature, and the composition, functional group content, molecular weight, etc. in consideration of the desired reaction rate and reaction conditions. Can be determined.

  Examples of the reactive functional group include an epoxy group, an amino group, a hydroxyl group, a vinyl group, a Si—H group, and an oxazolyl group. The form containing the reactive functional group may be located at the end of the polymer chain, or may be pendant or grafted at a place other than the end of the polymer chain.

  Examples of the polymer containing the reactive functional group include, for example, a polyacrylic acid ester containing an epoxy group, a polyacrylic acid ester containing an amino group, a polyacrylic acid ester containing a hydroxyl group, and a polyacrylate containing a vinyl group. Acrylic acid ester, polyacrylic acid ester containing Si-H group, polyacrylic acid ester containing oxazolyl group, polymethacrylic acid ester containing epoxy group, polymethacrylic acid ester containing amino group, hydroxyl group Polymethacrylic acid ester containing, polymethacrylic acid ester containing vinyl group, polymethacrylic acid ester containing Si-H group, polymethacrylic acid ester containing oxazolyl group, silicone containing epoxy group, Silicone containing amino groups, hydroxyl groups Silicone having a silicone containing vinyl groups, silicone containing Si-H groups, silicones containing oxazolyl groups, and the like are exemplified.

  Specific product names include, for example, ARUFON (registered trademark) UG4010, UG4000 (manufactured by Toagosei Co., Ltd.), and the like.

<Other compounds>
About the composition of this invention, in order to satisfy | fill performance required in the process of manufacture, processing, shaping | molding, distribution | circulation, use as a product, disposal, or recycling, it may be necessary to mix | blend various additives.
For example, it is desirable to add a stabilizer in consideration of thermal stability during molding, oxidation resistance during molding and long-term use, and the like.

  As the stabilizer, it is desirable to use a combination of a heat deterioration inhibitor, a primary oxidation stabilizer, and a secondary oxidation stabilizer. However, the use limited to the heat deterioration inhibitor and / or the primary oxidation stabilizer is also possible.

  Examples of the heat deterioration preventing agent include phenol acrylate. For example, Sumilyzer (registered trademark) GM and Sumilyzer GS (manufactured by Sumitomo Chemical Co., Ltd.) can be exemplified.

  Examples of the primary oxidation stabilizer include phenol and amine. For example, as the phenolic system, Sumilizer BHT, Sumilizer MDP-S, Sumilizer GA-80 (above, manufactured by Sumitomo Chemical Co., Ltd.), Irganox (registered trademark) 1010 (manufactured by Ciba Specialty Chemicals Co., Ltd.), An example of the amine-based material is a Sumilizer 9A (manufactured by Sumitomo Chemical Co., Ltd.).

  Secondary oxidation stabilizers include sulfur and phosphorus. For example, as a sulfur system, Sumilizer TPS, Sumilizer TP-D (above, manufactured by Sumitomo Chemical Co., Ltd.), and as a phosphorus system, Sandstab P-EPQ, Hostanox par24 (above, manufactured by Clariant Japan Co., Ltd.) Can be illustrated.

Moreover, you may mix | blend various polymers, a plasticizer, a softness | flexibility imparting agent, a lubricant, a flame retardant, a pigment, a filler, a mold release agent, an antistatic agent, an antibacterial antifungal agent, etc. as needed.
What is necessary is just to select suitably those additives suitable for the use for which a composition is used.

  Although it does not specifically limit as said polymer, Styrene-butadiene rubber (SBR), butadiene rubber (BR), isoprene rubber (IR), ethylene-propylene copolymer rubber (EPM), ethylene-propylene-diene copolymer rubber (EPDM), acrylonitrile-butadiene copolymer rubber (NBR), chloroprene rubber, butyl rubber (IIR), urethane rubber, silicone rubber, polysulfide rubber, hydrogenated nitrile rubber, fluoro rubber, tetrafluoroethylene-propylene rubber, tetrafluoro rubber Ethylene-propylene-vinylidene fluoride rubber, acrylic rubber (ACM), chlorosulfonated polyethylene rubber, epichlorohydrin rubber (CO), ethylene-acrylic rubber, norbornene rubber, styrenic thermoplastic elastomer (SBC), olefinic heat Plasticity Stomer (TPO), urethane-based thermoplastic elastomer (TPU), polyester-based thermoplastic elastomer (TPEE), polyamide-based thermoplastic elastomer (TPAE), 1,2-polybutadiene-based thermoplastic elastomer, vinyl chloride-based thermoplastic elastomer (TPVC) And fluorine-based thermoplastic elastomers can be exemplified, and these may be used alone or in combination.

  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, dicyclohexyl phthalate; isophthalic acid derivatives such as dimethyl isophthalate; and 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 ; 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 block copolymer (A). Commercially available plasticizers include Thiocol TP (Morton), Adekasizer (registered trademark) O-130P, C-79, UL-100, P-200, RS-735 (Asahi Denka Kogyo Co., Ltd.) ) And the like. 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.

  The flexibility imparting agent is not particularly limited, and examples thereof include softeners such as process oils; oils such as animal oils and vegetable oils; petroleum fractions such as kerosene, light oil, heavy oil, and naphtha. Examples of the softening agent include process oil, and more specifically, paraffin oil; naphthenic process oil; petroleum process oil such as aromatic process oil, and the like. Examples of vegetable oils include castor oil, cottonseed oil, linseed oil, rapeseed oil, soybean oil, palm oil, palm oil, peanut oil, pine oil, tall oil, etc., and at least one of these flexibility-imparting agents should be used. Can do.

  Examples of the lubricant include ester-based lubricants, polyethylene-based lubricants, polypropylene-based lubricants, hydrocarbon-based lubricants, and silicone oils. However, there is no particular limitation, and montanic acid-based wax, stearic acid, and the like are also included. Examples include organic fatty acid, organic acid amides such as stearamide, and organic acid metal salts such as magnesium stearate and calcium stearate. These may be used alone or in combination. The polyethylene lubricant and the polypropylene lubricant herein include an oxidized polyethylene lubricant and an oxidized polypropylene lubricant, respectively.

  Examples of lubricants and silicone oils are given below, but of course they can be used without being limited thereto.

  Examples of ester lubricants include beef tallow 45 hardened oil (melting point 45 ° C .; manufactured by Nippon Oil & Fats Co., Ltd., the same shall apply hereinafter), beef tallow 51 hardened oil (melting point 51 ° C.), beef tallow 54 hardened oil (melting point 54 ° C.), and beef tallow extremely hardened oil. (Melting point 60 ° C.), Licowax E (drop point 79-85 ° C .; manufactured by Clariant Japan Co., Ltd., the drop point is quoted from the company catalog, the same applies hereinafter), Licowax F (drop point 77-83 ° C.), Licowax KP (drop point 81- 87 ° C.), Licowax KP303 (drop point 86-92 ° C.), Licowax KPS (drop point 80-85 ° C.), Licowax KSL (drop point 79-85 ° C.), Licowax KFO (drop point 86-92 ° C.), Licowax KST (drop point 56- 63 ° C), Licowax WE4 (drop point 78-85 ° C), Licowax WE40 (drop point 73-79 ° C), Licow xBJ (drop point 72-78 ° C.), Licowax RT (drop point 77-83 ° C.), Licowax KPE (drop point 79-85 ° C.), Licowax KLE (drop point 82-88 ° C.), Licowax NE (drop point 74-82 ° C.), Licowax X102 (drop point 81-87 ° C.) and the like can be mentioned. Among these, beef tallow extremely hardened oil is preferable.

  As polyethylene-based lubricants, Licowax PE520 (manufactured by Clariant Japan Co., Ltd., the same shall apply hereinafter), LicowaxPE130, LicowaxPE190, LicowaxPE810, LicowaxPE820, LicowaxPE830, LicowaxPE840, Ceridust130, 15 Licoax PED521, Licowax PED522, Licowax PED121, Licowax PED136, Licowax PED153, Licowax PED191, LicowaxPED192, LicowaxPED1101, LicoaxPED821 LicowaxPED822, Ceridust3715, Ceridust3719, and the like.

  Examples of the polypropylene lubricant include Licowax PP230 (manufactured by Clariant Japan Co., Ltd., the same shall apply hereinafter), Licowax VP-PP220, Ceridust VP6071 and the like. Further, as an oxidized polypropylene lubricant, Limont AR504 can be exemplified.

  Examples of the hydrocarbon lubricant include Licowax R21 (manufactured by Clariant Japan Co., Ltd., the same shall apply hereinafter) and Licolub H4.

  As the silicone oil, TSF451 (dimethyl silicone oil; manufactured by GE Toshiba Silicone Co., Ltd., the same shall apply hereinafter), TSF410 (higher fatty acid-modified silicone oil), TSF4427 (alkyl aralkyl-modified silicone oil), TSF4421 (alkyl-modified silicone oil), TSF484 (Methyl hydrogen silicone oil), TSF431 (methylphenyl silicone oil), TSF4440 (polyether modified silicone oil), TSF4700 (amino modified silicone oil), XF42-B0970 (carbinol modified silicone oil), TSF4730 (epoxy modified silicone oil) ), TSF4770 (carboxyl-modified silicone oil), and the like. Of these, dimethyl silicone oil is preferred from the viewpoint of cost and ease of handling.

  The flame retardant is not particularly limited, and for example, triphenyl phosphate, tricresyl phosphate, decabromobiphenyl, decabromobiphenyl ether, antimony trioxide and the like can be used. These may be used alone or in combination.

  The pigment is not particularly limited, and for example, carbon black, titanium oxide, zinc sulfide, zinc oxide and the like can be used. These may be used alone or in combination.

  The filler is not particularly limited except for those mentioned in (B). For example, amorphous filler, plate filler, needle filler, spherical filler, functional filler, fibrous filler, metal powder, etc. Can be used. These may be used alone or in combination.

  Amorphous fillers include heavy calcium carbonate, natural silica, synthetic silica, kaolin, clay, titanium oxide, barium sulfate, zinc oxide (zinc white), aluminum hydroxide, aluminum oxide (alumina), magnesium hydroxide, etc. As the plate-like filler, talc, mica, glass flake, synthetic hydrotalcite, etc., and as the needle-like filler, wollastonite, potassium titanate, basic magnesium sulfate, sepiolite, zonotlite, aluminum borate, etc. Yes, spherical fillers include glass beads, silica beads, glass (silica) balloons, etc., and functional fillers include metallic conductive fillers, nonmetallic conductive fillers, carbon conductive fillers, magnetic fillers, Piezoelectric, pyroelectric filler, slidable film Chromatography and the like, As the fibrous filler, glass fiber, metal fiber, asbestos, organic, such as milled fibers, inorganic, such as metal of various fibers, can be exemplified. Among these, heavy calcium carbonate and silica are preferable in view of cost, dispersibility, ease of handling, and the like. In addition, when synthetic hydrotalcite, aluminum hydroxide, aluminum oxide (alumina) or magnesium hydroxide is used, the acid component derived from the acrylic block copolymer (A) and other components should be neutralized. Therefore, it is useful in applications where acid components from these components cause rust.

  As heavy calcium carbonate, Softon 3200, Softon 2600, Softon 2200, Softon 1800, Softon 1500, Softon 1200, Softon 1000, BF-100, BF-200, BF-300 Product), Ryton 32-X, Ryton 26-S, Ryton 26-A, Ryton BS-0, Ryton A, Ryton S-4, Ryton S-5 (above, manufactured by Bihoku Powdered Industry, surface treatment product), white (Registered trademark) SSB, Whiteon SB, Whiten B (above, manufactured by Shiraishi Calcium Co., Ltd., dry product), PO-320-B10, PO-220-B10, PO-180-B10, PO-150 -B10, PO-120-B10, PO-10-B10 (above, manufactured by Shiroishi Calcium Co., Ltd., surface treatment product), WH Ton 305, Whiton 306, Whiton 307, Whiton 310, ST Powder H50, Cloyster 500, RS-10, HG-10H (or, Shiraishi Central Laboratories Co., Ltd., surface-treated product), and the like.

  As natural silica, IMSIL-A25, IMSIL-A15, IMSIL-A10, IMSIL-A8, Crystallite (registered trademark) VX-S2, Crystallite VX-S, Crystallite VX-SR, Crystallite 5X (Co., Ltd.) Made by Tatsumori).

  As synthetic silica, NIPSIL (registered trademark) -VN3, NIPSIL-AQ, NIPSIL-LP, NIPSIL-NA, NIPSIL-ER, NIPSIL-RS150 (above, Nippon Silica Kogyo Co., Ltd., general silica), NIPSIL- SS10, NIPSIL-SS15, NIPSIL-SS30, NIPSIL-SS50, NIPSIL-SS70 (Nippon Silica Kogyo Co., Ltd., surface-treated silica) and the like can be mentioned.

<Method for producing composition>
There is no restriction | limiting in particular in the manufacturing method of a composition, An acrylic block copolymer composition can be manufactured by using a batch type kneading apparatus or a continuous kneading apparatus. As a batch type kneader, a mixing roll, a Banbury mixer, a pressure kneader, and a high shear mixer can be used as a batch type kneader, and a single screw extruder, a twin screw extruder, a KCK extrusion kneader as a continuous kneader. Etc. can be used. Furthermore, an existing method such as a method of mechanically mixing and shaping into a pellet can be used. The temperature at the time of kneading is the acrylic block copolymer (A) and additive (B) to be used, and when using other blends, their melting temperature, their melt viscosity, etc. For example, it can be manufactured by melt-kneading at 100 to 300 ° C.

<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 body is, for example, a skin material, a material that requires tactile sensation (hereinafter referred to as “tactile material”), or a material that requires good appearance and weather resistance (hereinafter referred to as “appearance material”). In addition, it can be used suitably, and it can be used as a material having a purpose such as an abrasion resistant material, an oil resistant material, a vibration damping material, and an adhesive material. 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 addition, the molecular weight described in the examples, the conversion rate of the polymerization reaction, and evaluation of each physical property were performed according to the following methods.

<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. As a system, a GPC system manufactured by Waters was used, and Shodex K-804 (polystyrene gel) manufactured by Showa Denko Co., Ltd. was used for 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
Separation column: manufactured by J & W SCIENTIFIC INC, capillary column Supercoux-10, 0.35 mmφ × 30 m
Separation conditions: Initial temperature 60 ° C, hold for 3.5 minutes
Temperature increase rate 40 ° C / min
Final temperature 140 ° C, hold for 1.5 minutes
Injection temperature 250 ° C
Detector temperature 250 ° C
Sample preparation: The sample was diluted about 3 times with ethyl acetate, and butyl acetate was used as an internal standard.

<Crushability test>
According to the example, pellets of the composition were made. The pellets were put into a room temperature pulverizer UCM150 (manufactured by Mitsui Mining Co., Ltd.), and pulverized while adding 6 parts by weight of silica (Immsil A-10) to 100 parts by weight of the pellets.
Evaluation index for grindability: Good grindability: ○, no grindability: x.

<Powder slash property test>
The obtained powder was evaluated by a powder slush test under the following conditions.
Equipment used: Metal plate with skin wrinkles (plate thickness 4.5mm, wrinkle depth 80%)
Heating conditions: 250 ° C
Heating time: 1 minute Cooling time: 5 minutes (cool by contacting with metal at room temperature)
Evaluation index: Visually good texture transferability, no pinhole / bubbles: ◯, any one item is defective: △, improper texture formation and pinhole / bubbles: It evaluated as x.

<Scratch test>
According to the example, the composition was press-molded to prepare a skin material. A sample was cut out from the sample and pasted on a mount to obtain a measurement sample. A scratch test was conducted under the following conditions.
Equipment used: Tabers clutch tester (Toyo Seiki)
Rotation speed: 0.5rpm
Cutter: Tungsten carbide, 4.8 mm square x 19 mm length, cutting edge radius 12.7 mm
Cutter orientation: The cutter was mounted so that the long side of the cutter was down so that the blade side of the cutter was up.
The load was changed from 1N to 3N.
Sample size: 10 cm square Evaluation index: Visually, 5 points: scars are hardly visible, 4 points: scratches are difficult to see when viewed from the front, but scratches are visible when viewed diagonally, 3 points: slight scratches The evaluation was carried out as a state where 2 is visible, 2 points: a state where scratches are visible, and 1 point: a state where severe scratches are present.

(Production Example 1)
A nitrogen-substituted 500 L reactor was charged with 70.19 kg of n-butyl acrylate, 4.81 kg of t-butyl acrylate, and 0.625 kg of cuprous bromide, and stirring was started. Thereafter, a solution prepared by dissolving 0.872 kg of diethyl 2,5-dibromoadipate in 6.59 kg of acetonitrile was charged, warm water was passed through the jacket, and the inner solution was stirred for 30 minutes while being heated to 75 ° C. When the internal temperature reached 75 ° C., 75.6 g of pentamethyldiethylenetriamine was added to start polymerization of the first block.

  When the conversion reached 97%, 101.6 kg of toluene, 0.432 kg of cuprous chloride, 45.54 kg of methyl methacrylate, 9.26 kg of ethyl acrylate, and 75.6 g of pentamethyldiethylenetriamine were added. Biblock polymerization was initiated. When the conversion rate reached 91%, 220 kg of toluene was added to dilute the reaction solution, and the reactor was cooled to terminate the polymerization. When the GPC analysis of the obtained block copolymer was performed, the number average molecular weight Mn was 73700, and molecular weight distribution Mw / Mn was 1.39.

To the obtained block copolymer solution, 30 kg of toluene was added to make the polymer concentration 25 wt%. To this solution, 1.74 kg of p-toluenesulfonic acid was added, 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 2.48 kg of Radiolite # 3000 manufactured by Showa Chemical Industry was added. Thereafter, the reactor was pressurized to 0.1 to 0.4 MPaG with nitrogen, and the solid content was separated using a pressure filter (filter area 0.45 m ² ) equipped with polyester felt as a filter medium.

  KYOWARD 500SH 1.86 kg was added to about 450 kg of the block copolymer solution after filtration, and the inside of the reactor was purged with nitrogen, followed by stirring at 30 ° C. for 1 hour. The reaction solution was sampled to confirm that the solution was neutral, and the reaction was completed. 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 (filtration area 0.45 m 2) to obtain a polymer solution. .

  Subsequently, the solvent component was evaporated from the polymer solution. As an evaporator, SCP100 (heat transfer area 1 m2) manufactured by Kurimoto Steel Corporation was used. The evaporation of the polymer solution was carried out by setting the heating medium oil at the evaporator inlet to 180 ° C., the evaporator vacuum to 90 Torr, the screw rotation speed to 60 rpm, and the polymer solution supply rate to 32 kg / h. The polymer is made into a strand with a φ4 mm die through a discharger, cooled in a water tank filled with 3% suspension of Alflow H50ES (main component: ethylenebisstearic acid amide, manufactured by Nippon Oil & Fats Co., Ltd.), and then by a pelletizer. A cylindrical pellet was obtained.

Furthermore, with respect to 100 parts by weight of the pellets, 0.2 part by weight of Irganox 1010 (manufactured by Ciba Specialty Chemicals Co., Ltd.) was blended, and TEX44 (manufactured by Nippon Steel Works, Ltd.) set at 260 ° C. Then, modification by extrusion at 100 rpm was performed to obtain pellets of the target acid anhydride group and carboxyl group-containing acrylic block copolymer (polymer pellet 1).
Conversion of the t-butyl ester moiety to an acid anhydride group and a carboxyl group could be confirmed by IR (infrared absorption spectrum) and ¹³ C ( ¹ H) -NMR (nuclear magnetic resonance spectrum). That is, it was confirmed by IR that an absorption spectrum derived from an acid anhydride group was observed around 1800 cm ⁻¹ after conversion. ^{In 13} C ( ¹ H) -NMR, after conversion, the 82 ppm signal derived from the quaternary carbon of the t-butyl group and the 28 ppm signal derived from the methyl carbon disappeared, and a new 172 derived from the carbonyl carbon of the acid anhydride group. It was confirmed from the appearance of a signal of ˜173 ppm (m) and a signal of 176 to 179 ppm (m) derived from the carbonyl carbon of the carboxyl group.

Example 1
According to Table 1, polymer pellet 1 obtained in Production Example 1, brilliant 1500 (manufactured by Shiroishi Kogyo Co., Ltd.) as calcium carbonate, UG4010 (manufactured by Toagosei Co., Ltd.) as a crosslinking agent, carbon black (Asahi Carbon Co., Ltd.) ), Asahi # 15), beef tallow extremely hardened oil (Nippon Yushi Co., Ltd.) was compounded. The raw material is supplied at a ratio of 30 parts by weight of calcium carbonate, 7 parts by weight of a crosslinking agent, 0.5 part by weight of carbon black, and 1 part by weight of beef tallow extremely hardened oil to 70 parts by weight of the pellets, and twin screw extruder TEX30HSS (Nippon Steel) Extrusion melt kneading at 80 ° C. using a Tokoro Co., Ltd. to obtain a pellet sample.
The obtained pellets are melt-kneaded at 100 ° C. using a Laboplast mill (manufactured by Toyo Seiki Co., Ltd.), further hot press-molded at a set temperature of 200 ° C., and leather is pressed with a press plate modified with leather wrinkles. A molded product for evaluation having a thickness of 1 mm to which the texture pattern was transferred was obtained. About this molded object, scratch property was measured.
Table 1 shows the results of the grindability, powder slush properties, and scratch properties of the molded product obtained as described above.

(Examples 2 to 4)
A molded body in the same manner as in Example 1 except that VIGOT15, CCR (both manufactured by Shiroishi Kogyo Co., Ltd.) and Softon 3200 (manufactured by Shiroishi Calcium Co., Ltd.) were used instead of brilliant 1500 as calcium carbonate. Were prepared and the physical properties were measured. Table 1 shows the results of the grindability, powder slush properties and scratch properties of the molded product.

(Comparative Example 1)
Compound treatment was performed in the same manner as in Example 1 except that the crosslinking agent and calcium carbonate were not used. However, it could not be crushed and the powder slush property could not be confirmed. The results are shown in Table 1.

(Comparative Example 2)
A molded body was produced in the same manner as in Example 1 except that silica (Immsil A-10) was used instead of calcium carbonate, and physical properties were measured. Table 1 shows the results of the grindability of the composition, the powder slush property, and the scratch property of the molded product.

(Comparative Example 3)
A molded body was produced in the same manner as in Example 1 except that talc (LMS400) was used instead of calcium carbonate, and the physical properties were measured. Table 1 shows the results of the grindability of the composition, the powder slush property, and the scratch property of the molded product.

Furthermore, the particle diameter of the filler by various measuring methods is shown.
Brilliant 1500: 0.20 μm (BET specific surface area converted value) from Shiroishi Kogyo catalog VIGOT15: 0.15 μm (electron micrograph), 0.20 μm (BET specific surface area converted value) Shiraishi Kogyo catalog CCR: 0.12 μm ( BET specific surface area conversion value) From Shiroishi Kogyo catalog Softon 3200: 1.1 μm (Cedigraph system) From Shiroishi calcium catalog Imsil A-10: 2.6 μm (Cedigraph system) From Tatsumori catalog LMS400: 3.8 μm (Shimadzu laser diffraction method) From the catalog of Fuji Talc Industry

From the above, it can be seen that the composition according to the present invention is excellent in grindability, powder slush property, and scratch resistance, and particularly excellent in scratch resistance as compared with conventional compositions. Among these, it is understood that calcium carbonate having a particle diameter of less than 0.40 μm and calcium carbonate not subjected to surface treatment with a fatty acid are excellent in terms of scratch resistance.

Claims (12)

(A) 100 parts by weight of an acrylic block copolymer;
(B) 10-100 parts by weight of precipitated calcium carbonate comprising colloidal calcium carbonate and / or light calcium carbonate,
And an acrylic block copolymer composition.   The acrylic block copolymer as the component (A) is 10 to 60% by weight of a methacrylic polymer block (A1) whose main component is a methacrylic polymer, and an acrylic whose main component is an acrylic polymer. The acrylic block copolymer composition according to claim 1, comprising 90 to 40% by weight of the polymer block (A2).   The acrylic polymer block (A2) is at least one monomer selected from the group consisting of n-butyl acrylate, ethyl acrylate, 2-methoxyethyl acrylate, and 2-ethylhexyl acrylate 50-100 3. The acrylic block copolymer composition according to claim 2, comprising 50% by weight and 50 to 0% by weight of different acrylates and / or vinyl monomers copolymerizable therewith. .   The number average molecular weight measured by gel permeation chromatography of the acrylic block copolymer as the component (A) is 30,000 to 100,000. An acrylic block copolymer composition.   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 acrylic block copolymer composition according to any one of claims 1 to 4, wherein:   The acrylic block copolymer according to any one of claims 1 to 5, wherein the acrylic block copolymer as the component (A) is a block copolymer produced by atom transfer radical polymerization. Composition.   The acrylic block copolymer composition according to any one of claims 1 to 6, wherein the precipitated calcium carbonate (B) is colloidal calcium carbonate.   The acrylic block copolymer composition according to any one of claims 1 to 7, wherein the average particle size of the precipitated calcium carbonate (B) in terms of a BET specific surface area is less than 0.40 µm.   The acrylic copolymer composition according to any one of claims 1 to 8, wherein the precipitated calcium carbonate (B) is precipitated calcium carbonate that has not been surface-treated with a surface treatment agent.   A composition for forming a powder slush comprising the acrylic copolymer composition according to any one of claims 1 to 9.   A powder slush molded article obtained by powder slush molding of the composition according to any one of claims 1 to 10. A skin for automobile interior, which is obtained by powder slush molding the composition according to any one of claims 1 to 10.