JP2005320443A - Acrylic block copolymer composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an acrylic block copolymer composition excellent in wear resistance, and to provide a composition for powder-slush molding excellent in wear resistance and a powder-slush molded article using the composition. <P>SOLUTION: This acrylic block copolymer composition comprises an acrylic block copolymer and when the composition is press-molded in a sheet form by using leather-like embossing of grain C, at least either of a coefficient of static friction and a coefficient of dynamic friction of the sheet surface is ≤0.25. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an acrylic block copolymer composition having excellent wear resistance. The present invention also relates to a composition for powder slush molding having excellent wear resistance, and a powder slush molding product using the composition.

  It is known that an acrylic block copolymer having methyl methacrylate as a hard segment and butyl acrylate as a soft segment has characteristics as a thermoplastic elastomer. For example, mechanical properties of an acrylic block copolymer having a methacryl block and an acrylic block produced by an iniferter method are disclosed (Patent Document 1).

  Acrylic block copolymers are characterized by excellent weather resistance, heat resistance, durability and oil resistance. Moreover, it is possible to give a very flexible elastomer compared with other thermoplastic elastomers, such as a styrene-type block body, by selecting suitably the component which comprises a block body.

  As an application utilizing the characteristics of such an acrylic block copolymer, it is expected to be developed as a material for various skin materials, interior materials, and other members that can be directly touched by human hands. In addition to mechanical properties, scratch resistance, heat resistance, strain recovery, etc., the physical properties required for these skin materials, etc., resistance to drugs that can be contacted, and when directly bonding the skin to the substrate Adhesiveness between the skin and the base material, and when a buffer material is provided between the skin and the base material, mention may be made of adhesiveness between the skin and the base material. As a method for molding the skin material, for example, there is powder slush molding, which is preferable from the balance of productivity, touch feeling, and texture transfer. 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 is taken out after a certain period of time.

  However, the abrasion resistance is often influenced by the hardness and strength design of the acrylic block copolymer, and it is expected that it is difficult to improve it by a normal method. Specifically, even if an acrylic block copolymer with poor wear resistance is blended with a filler or an acrylic block copolymer polymer with excellent wear resistance, dramatic improvement is difficult. Is expected.

Furthermore, in these methods, since the hardness and elastic modulus change greatly depending on the formulation, it is a problem that the design must be changed.
Japanese Patent No. 2553134

  An object of the present invention is to provide an acrylic block copolymer composition having excellent wear resistance. Another object of the present invention is to provide a composition for powder slush molding and a powder slush molded product using the composition.

  As a result of intensive studies on an acrylic block copolymer composition having excellent wear resistance, the present inventors have determined that the surface friction coefficient such as a static friction coefficient and a dynamic friction coefficient is a key parameter, and these parameters are controlled. Therefore, techniques such as addition of a lubricant are useful, and it has been found that the wear resistance can be dramatically improved by controlling them, and the present invention has been completed.

  That is, the present invention is a composition containing an acrylic block copolymer, and when the composition is press-molded into a sheet shape with grain C leather grain, at least a static friction coefficient and a dynamic friction coefficient of the sheet surface. One of them relates to an acrylic block copolymer composition, which is 0.25 or less.

  Furthermore, the present invention is a composition containing an acrylic block copolymer, and when the composition is press-molded into a sheet shape with grain C leather grain, both the static friction coefficient and the dynamic friction coefficient of the sheet surface Is an acryl-type block copolymer composition characterized by being 0.25 or less.

  A preferred embodiment is a composition containing an acrylic block copolymer, and when the composition is press-molded into a sheet shape with grain C leather, the relationship between the static friction coefficient and the dynamic friction coefficient of the sheet surface However, the present invention relates to an acrylic block copolymer composition characterized by satisfying (static friction coefficient> dynamic friction coefficient).

  As a preferred embodiment, the present invention relates to an acrylic block copolymer composition having a number average molecular weight of 30,000 to 500,000 as measured by gel permeation chromatography of the acrylic block copolymer.

  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 is 1.8 or less. The present invention relates to a characteristic acrylic block copolymer composition.

  In a preferred embodiment, the present invention relates to an acrylic block copolymer composition, wherein the acrylic block copolymer is a block copolymer produced by atom transfer radical polymerization.

  Furthermore, the present invention relates to an acrylic copolymer composition characterized by being used for powder slush molding.

  Furthermore, the present invention relates to a powder slush molded article using the above composition.

  As a preferred embodiment, the present invention relates to a powder slush molded product, which is used for an automobile interior skin.

  By using the present invention, it is possible to obtain an acrylic block copolymer composition excellent in wear resistance. Moreover, the composition of this invention can be used conveniently for powder slush molding.

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

  The present invention is an acrylic block copolymer composition excellent in abrasion resistance, and when the composition is press-molded into a sheet shape by using grain C leather wrinkles, the static friction coefficient of the sheet surface, and dynamic friction At least one of the coefficients is an acrylic block copolymer composition characterized by being 0.25 or less. Furthermore, an acrylic block copolymer composition characterized by having both a static friction coefficient and a dynamic friction coefficient being 0.25 or less is preferable. Further, it is preferable that the relationship between the static friction coefficient and the dynamic friction coefficient satisfies (static friction coefficient> dynamic friction coefficient).

  These friction coefficients are obtained by pressing the circumferential part of Kanakin No. 3 (gold cloth) wound around a semi-cylinder with a diameter of 2.5 cm and a width of 1 cm as a counterpart material. Contact is made and the load is 1 kg and the speed is 30 mm / min.

<Acrylic block copolymer>
The structure of the acrylic block copolymer may be a linear block copolymer, a branched (star) block copolymer, or a mixture thereof. The structure of the acrylic block copolymer may be selected depending on the required physical properties of the acrylic block copolymer, but is a linear block copolymer from the viewpoint of cost and ease of polymerization. Is preferred.

The linear block copolymer may be of any linear block structure, but from the viewpoint of its physical properties or physical properties when made into a composition, the methacrylic acid constituting the acrylic block copolymer. Polymer block (A1) (hereinafter also referred to as polymer block (A1) or block (A1)) and acrylic polymer block (A2) (hereinafter referred to as both polymer block (A2) or block (A2)) Are 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). It is preferably at least one block copolymer selected from the group consisting of 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 measured by gel permeation chromatography of the acrylic block copolymer is not particularly limited, but is preferably 30,000 to 500,000, more preferably 50,000 to 40,0000. When the number average molecular weight is small, the viscosity is low, and when the number average molecular weight is large, the viscosity tends to be high. Therefore, the viscosity is set according to 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 acrylic block copolymer is not particularly limited, but is preferably 1.8 or less, more preferably Is 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 (A1) to the acrylic polymer block (A2) of the acrylic block copolymer is 5 to 90% by weight for the block (A1) and 95 to 10% for the block (A2). %. 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. If the proportion of (A1) is less than 5% by weight, the shape tends to be difficult to be retained during molding, and if the proportion of (A2) is less than 10% by weight, the elasticity as an elastomer and the meltability during molding tend to decrease. is there.

  From the viewpoint of the hardness of the elastomer composition, if the proportion of (A1) is small, the hardness is low, and if the proportion of (A1) is large, the hardness tends to be high, so an elastomer composition is required. It can be set according to the hardness. Further, from the viewpoint of processing, when the proportion of (A1) is small, the viscosity tends to be low, and when the proportion of (A1) is large, the viscosity tends to be high, so that it can be set according to the required processing characteristics. it can.

<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. The methacrylic acid ester is 50 to 100% by weight and a vinyl copolymer 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 in order to raise heat resistance, acrylic acid-t-butyl is preferable as a precursor at the time of introducing an acid anhydride group.

  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.

  The glass transition temperature of the acrylic polymer block (A2) is preferably 25 ° C. or less, more preferably 0 ° C. or less, and further preferably −20 ° C. or less, from the viewpoint of rubber elasticity of the elastomer composition. If the glass transition temperature of the acrylic polymer block (A2) is higher than the temperature of the environment in which the elastomer composition is used, rubber elasticity is hardly exhibited, which is disadvantageous.

  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 acrylic block copolymer>
(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) or 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, 866, or Sawamoto et al., 28, 17).

  According to these methods, in general, the polymerization rate is very high, and the radical polymerization is likely to cause a termination reaction such as coupling between radicals, but the polymerization proceeds in a living manner and Mw / Mn = 1 having a narrow molecular weight distribution. A polymer having a molecular weight of about 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, a monofunctional, difunctional, or polyfunctional compound can be used as the organic halide or sulfonyl halide compound used as an initiator. These can be used properly according to the purpose. When producing a diblock copolymer, a monofunctional compound is preferable. When producing a xy-type triblock copolymer or a 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 that can be used as initiators, the carbon to which the halogen is bonded is bonded to the carbonyl group, phenyl group, etc., and the carbon-halogen bond is activated to initiate polymerization. To do. The amount of the initiator to be used may be determined from the ratio with 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 as a preferred one, a complex of monovalent and zerovalent copper, divalent ruthenium, divalent iron or divalent nickel is preferable. 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. Furthermore, 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, but can be 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 and 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 can be 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 can be performed preferably 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 a method of producing a 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, and polymerizing separately Examples thereof include a method of bonding a polymer by reaction. 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 that can 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. Further, if necessary, it may be possible to proceed to the next neutralization step without removing the metal salt. However, even in this case, the metal salt must be removed after the neutralization 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, or there may be adverse effects such as coloring of the molded product or deterioration of mechanical properties. is there.

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 step of neutralizing the system is required. As a method for neutralizing the system, a known method can be used, and there is no particular limitation. For example, a method using a basic solid can be mentioned. 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 500SH (manufactured by Kyowa Chemical). 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 basic anion exchange resin, and an acrylic weak base type anion exchange resin.

  The method for removing the adsorbent added during the neutralization 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 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)
A carboxyl group and an acid anhydride group can be introduced by subjecting the ester site of the monomer introduced into the polymer block by a polymerization reaction to a functional group conversion reaction as necessary.

  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 the above is synthesized, and known chemical reactions such as hydrolysis or acid decomposition, for example, JP-A-10-298248 and JP-A-2001-234146 are disclosed. There is a method of generating a carboxyl group by the method described in the above. 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. Then, by performing the dealcoholization reaction by heating as described above, the ester site of the adjacent monomer can be converted into a carboxylic acid anhydride.

  The block copolymer having an acid anhydride group derived by this 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 conditions are not particularly limited, and examples include 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.

<Friction coefficient>
The coefficient of friction is the ratio of the friction force to the vertical load. That is, when the friction coefficient is μ, the friction force is Ff, and the vertical load is Fn, the following equation is established.
μ = Ff / Fn
Generally, under the same conditions, it is considered that the wear resistance can be improved by reducing the frictional force in wear.

  The friction phenomenon is considered to have a so-called dual property including both the deformation process and the adhesion process of the object, and these two properties, the molecular-mechanical concept, are accepted as a general theory of friction. ing.

In sliding wear, Chicos can be expressed as the sum of microscopic frictional forces at the microcontact points, and the energy dissipated in the wear can be expressed as a dissipation process at each microcontact point. Kragelski gives the following equation from a microscopic viewpoint.
Ff = ΣF1 + ΣF2 + ΣF3 + ΣF4
Ff: Overall macroscopic friction force F1: Resistance due to elastic displacement of material F2: Resistance due to plastic displacement of material F3: Resistance caused by digging up soft material surface due to hard material F4: Shear of adhesion portion (film) between materials In other words, in order to reduce the frictional force, in each stage of the minute friction process, in the initial stage, it is difficult to be elastically deformed, difficult to plastically deform, and difficult to dig up, and in the intermediate stage In other words, it is difficult for adhesive bonding to occur, and it is difficult for shearing of the junction to occur in the final stage.

  When the material and its hardness are determined, it is often difficult to control the ease of elastic deformation and plastic deformation and the ease of shearing independently of them. Accordingly, attention was paid to digging (digging wear: abrasive wear) and adhesive bonding (adhesive wear). Further, in the case of a material having unevenness such as a skin, it is said that digging and abrasion are important.

  In order to improve these microscopic wear, it was considered useful to form a film that is less susceptible to digging and adhesive wear on the surface layer. As the means, there are a method of forming a film by a method such as direct application to the skin, and a method of forming a film at the time of molding by blending a material for forming a film into the composition of the skin material.

  In the present invention, although not particularly limited, a method of forming a film at the time of molding by mixing a substance that forms a film into the composition from the viewpoint of cost, ease of handling, etc. was considered.

  The substance for forming the film is not particularly limited, but a substance that has a polarity different from that of the acrylic block copolymer or has a melting point of room temperature or higher and becomes a solid state in the use environment has been considered. This is designated as additive (B).

  This technique was verified, and it was found that it is useful to add an additive to control the coefficient of friction even in the composition of an acrylic block copolymer. A detailed analysis of the friction coefficient of the sample that receives and does not receive the wear indicates that at least one of the static friction coefficient and the dynamic friction coefficient measured under specific conditions must be 0.25 or less. I understood. Furthermore, it is preferable that both a static friction coefficient and a dynamic friction coefficient are 0.25 or less. Furthermore, when the coefficient of static friction was compared with the coefficient of dynamic friction, it was found that the coefficient of dynamic friction was preferably small.

  The specific conditions mentioned here are: a sheet formed by pressing the composition and transferring grain C leather wrinkles, and a kanakin No. 3 (gold) wound around a semi-cylinder having a diameter of 2.5 cm and a width of 1 cm as a counterpart material. Cloth) is brought into contact with the circumference, and the load is 1 kg and the speed is 30 mm / min.

<Additive (B)>
The additive (B) is not particularly limited as long as it is effective, and examples thereof include ester lubricants, polyethylene lubricants, polypropylene lubricants, hydrocarbon lubricants, and silicone oils.

  The polyethylene lubricant and the polypropylene lubricant herein include an oxidized polyethylene lubricant and an oxidized polypropylene lubricant, respectively.

  The blending ratio of the acrylic block copolymer to the additive (B) is as follows: ester lubricant, polyethylene lubricant, polypropylene lubricant, hydrocarbon lubricant, and silicone with respect to 100 parts by weight of the acrylic block copolymer. It is 0.01-20 weight part of additive (B) which is at least 1 sort (s) chosen from the group which consists of oil. When the amount is less than 0.01 parts by weight, the improvement effect may be inferior, and when the amount is more than 20 parts by weight, molding failure may be caused.

  Although the mechanism of physical properties is not yet known in detail, it is presumed that these blended lubricants form a protective film by leaching onto the surface of the molded body. Therefore, which of these lubricants is preferred depends on the processing temperature, the composition and molecular weight of the acrylic block copolymer, and the polarity and viscosity relationship with the acrylic block copolymer. Ester lubricants are preferred because they can accommodate and have some affinity with acrylic block copolymers. Moreover, these compounding quantities are 0.05-5 weight part of ester activators with respect to 100 weight part of acrylic block copolymers in consideration of the effect and influence on other physical properties. preferable. If it is less than 0.05 parts by weight, the effect tends to be insufficient, although it depends on other conditions.

  Examples of lubricants and 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. The dropping point is a numerical value obtained by a measurement method different from the melting point, but can be interpreted as a similar numerical value. Among these, a lubricant having a melting point in the range of 50 to 90 ° C. is preferable. If the melting point is less than 50 ° C, bleeding during storage may be a problem, and if it exceeds 90 ° C, the effect may be inferior. Furthermore, in this, beef tallow extremely hardened oil and beef tallow 51 hardened oil are 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. Moreover, although there is no limitation in particular also about those viscosities, it is preferable that the viscosity in 25 degreeC exists in the range of 50-50,000 mm < ² > / s. When the viscosity is less than 50 mm ² / s, there may be a problem that the volatile matter is large or the flash point is low, and when the viscosity exceeds 50,000 mm ² / s, it may be difficult to handle. It can be a problem.

<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.

  It is desirable to add a stabilizer in consideration of the thermal stability during the molding process, the oxidation deterioration resistance during the molding process and during long-term use.

  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, a similarizer GM, a similarizer GS (manufactured by Sumitomo Chemical Co., Ltd.) can be exemplified.

  Examples of the primary oxidation stabilizer include phenol and amine. For example, as a phenol type, Sumilizer BHT, Sumilizer MDP-S, Sumilizer GA-80 (above, manufactured by Sumitomo Chemical Co., Ltd.), Irganox 1010 (manufactured by Ciba Specialty Chemicals Co., Ltd.), and as an amine type , Sumilyzer 9A (above, manufactured by Sumitomo Chemical Co., Ltd.) can be exemplified.

  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 the following additives as needed.

  Examples of the additive include various polymers, plasticizers, flexibility imparting agents, lubricants, flame retardants, pigments, fillers, mold release agents, antistatic agents, antibacterial and antifungal agents. What is necessary is just to select an optimal thing suitably for these additives according to the use etc. 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 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, and polyisobutylene polymers. 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 the following compounds other than the additive (B), but are not particularly limited as long as they are other than the additive (B). Organic fatty acids such as montanic acid wax and stearic acid, stearic acid amide Examples include organic acid amides such as organic acid metal salts such as magnesium stearate and calcium stearate, and these may be used alone or in combination.

  Examples of the flame retardant include the following compounds, but are not particularly limited, and examples thereof include triphenyl phosphate, tricresyl phosphate, decabromobiphenyl, decabromobiphenyl ether, antimony trioxide, and the like. You may use, and you may use combining several.

  Examples of the pigment include the following compounds, but are not particularly limited, and examples thereof include carbon black, titanium oxide, zinc sulfide, and zinc oxide. These may be used alone or in combination. Also good.

  Examples of the filler include the following compounds, but are not particularly limited, and examples include an amorphous filler, a plate-like filler, a needle-like filler, a spherical filler, a functional filler, a fibrous filler, and a metal powder. These may be used alone or in combination.

  Amorphous fillers include heavy calcium carbonate, light calcium carbonate, natural silica, synthetic silica, kaolin, clay, titanium oxide, barium sulfate, zinc oxide (zinc white), aluminum hydroxide, aluminum oxide (alumina), hydroxide Magnesium, etc. Plate-like fillers such as talc, mica, glass flake, synthetic hydrotalcite, etc. Needle-like fillers such as wollastonite, potassium titanate, basic magnesium sulfate, sepiolite, zonotlite, aluminum borate, etc. Glass beads, silica beads, glass (silica) balloons, etc., functional fillers such as metallic conductive fillers, nonmetallic conductive fillers, carbon conductive fillers, magnetic fillers, piezoelectrics, pyroelectric fillers, slidability Filler, etc. Glass fibers as fibrous fillers, metal fibers, asbestos, organic, such as milled fibers, inorganic, such as metal various fibers can be exemplified. Among these, calcium carbonate and silica are preferable from the viewpoints 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.

<Method for producing composition>
The production method of the composition is not particularly limited. For example, a mixing roll, a Banbury mixer, a pressure kneader, or a high shear mixer can be used as a batch-type kneading apparatus. An extruder, a KCK extrusion kneader, or the like may 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 depends on the acrylic block copolymer and additive (B) to be used, and, in the case of using other blends, their melting temperature and their melt viscosity. For example, it can be produced by melt-kneading at 100 to 300 ° C.

<Use and usage of molded body>
As a molding method of the composition of the present invention, powder slush molding is exemplified, 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 a sheet, flat plate, film as a material having a purpose such as skin material, tactile material, appearance material, wear resistant material, oil resistant material, vibration damping material, adhesive material, It can be used as a small molded article, a large molded article or any other arbitrary shape, as a part such as a panel, a handle, a grip, or a switch, and as a sealing member. Although it does not restrict | limit especially as a use, The object for motor vehicles, household electrical appliances, or office 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.

<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.

<Powder slash property test>
According to the example, a mass of the composition was made. A lump of the composition was put into a small pulverizer SK-M2 (manufactured by Kyoritsu Riko Co., Ltd.) cooled with dry ice, and pulverized while adding dry ice. The obtained powder was evaluated under the following conditions.
Equipment used: Grain C leather plate with wrinkles (plate thickness 4.5mm, wrinkle depth 80%)
Heating conditions: 250 ° C
Heating time: 1 minute Cooling time: 5 minutes (air cooling in air)
Evaluation index: Visually good texture transfer, no pinholes / bubbles: ◯, any one item is bad: △, imperfectly formed, with pinholes / bubbles: It evaluated as x.

<Abrasion evaluation test>
According to the example, a molded product for evaluation having a thickness of 1 mm to which a leather texture pattern was transferred was obtained. This was cut into 3 cm × 10 cm and subjected to an abrasion test with an abrasion tester.
Equipment used: Haydon-type wear tester 14DR (manufactured by Shinto Kagaku Co., Ltd.)
Movement speed: 6000 mm / min Movement length: 5 cm
Number of movements: 5 reciprocating load weight: 1 kg
Wear jig: An ASTM jig was fixed to the shaft so that it did not come into contact with the jig so that the jig was always parallel to the sample. A semi-cylinder obtained by cutting a cylinder made of aluminum and having a diameter of 2.5 cm and a length of 1 cm in half was bonded to the lower side of the ASTM jig. From above, the cloth of Kanakin No. 3 was attached by a quadruple roll, and fixed with an ASTM jig stopper.

<Friction coefficient evaluation test>
According to the example, a molded product for evaluation having a thickness of 1 mm to which a leather texture pattern was transferred was obtained. This was cut into 3 cm × 10 cm and measured with a friction coefficient measuring machine.
Equipment used: Haydon-type wear tester 14DR (manufactured by Shinto Kagaku Co., Ltd.)
Movement speed: 30mm / min Movement length: 3cm
Number of movements: Single load weight: 1kg
Sampling rate: 5ms
Wear jig: An ASTM jig was fixed to the shaft so that it did not come into contact with the jig so that the jig was always parallel to the sample. A semi-cylinder obtained by cutting a cylinder made of aluminum, having a diameter of 2.5 cm and a length of 1 cm into half, was bonded to the lower side of the ASTM jig. On top of that, a gold cloth of Kanakin No. 3 was attached in a quadruple roll and fixed with an ASTM jig stopper.

(Production Example 1: NBC)
A nitrogen-substituted 500 L reactor was charged with 80.5 kg of n-butyl acrylate and 0.648 kg of cuprous bromide, and stirring was started. Thereafter, a solution prepared by dissolving 0.904 kg of diethyl 2,5-dibromoadipate in 7.06 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., 94.4 mL of pentamethyldiethylenetriamine was added to start polymerization of the first block.

  When the conversion of n-butyl acrylate reached 90%, 80.0 kg of toluene, 0.447 kg of cuprous chloride, 43.2 kg of methyl methacrylate, and 94.4 mL of pentamethyldiethylenetriamine were added. Block polymerization started. When the MMA conversion rate reached 92% and the BA conversion rate reached 98%, 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 conducted, the number average molecular weight Mn was 68300, and molecular weight distribution Mw / Mn was 1.37.

To the resulting block copolymer solution, 60 kg of toluene was added to make the polymer concentration 25% by weight. 1.55 kg of p-toluenesulfonic acid was added to 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 2.39 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 1.79 kg was added to about 478 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 (filter area 0.45 m ² ) equipped with polyester felt as a filter medium to obtain a polymer solution. It was.

Subsequently, the solvent component was evaporated from the polymer solution. As an evaporator, SCP100 (heat transfer area 1 m ² ) 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 (polymer pellet 1).
Example 1
Polymer pellets 1 obtained in Production Example 1 were mixed with Softon 3200 (made by Bihoku Flourishing Co., Ltd.), calcium carbonate, beef fat extremely hardened oil (made by Nippon Oil & Fats Co., Ltd.), carbon black ( Asahi Carbon Co., Ltd., Asahi # 15) was compounded. The raw material is supplied at a ratio of 30 parts by weight of softon, 0.1 part by weight of beef tallow extremely hardened oil, and 0.5 parts by weight of carbon black to 70 parts by weight of pellets, using a lab plast mill (manufactured by Toyo Seiki Co., Ltd.) Were melt-kneaded at 180 ° C. to obtain a block sample. The obtained sample was hot press-molded at a set temperature of 180 ° C. to obtain a molded body for evaluation having a thickness of 1 mm onto which a leather texture pattern was transferred with a press plate modified with leather texture. About these molded objects, abrasion property and a friction coefficient were measured. The results are shown in Table 1. Further, when a powder slush test was performed on a part of the composition, the moldability was good.
(Example 2)
A molded body was produced in the same manner as in Example 1 except that 0.3 parts by weight of beef tallow extremely hardened oil (manufactured by Nippon Oil & Fats Co., Ltd.) was used, and physical properties were measured. The results are shown in Table 1. Further, when a powder slush test was performed on a part of the composition, the moldability was good.
Example 3
A molded body was prepared in the same manner as in Example 1 except that 0.6 parts by weight of beef tallow extremely hardened oil (manufactured by Nippon Oil & Fats Co., Ltd.) was used, and physical properties were measured. The results are shown in Table 1. Further, when a powder slush test was performed on a part of the composition, the moldability was good.
(Comparative Example 1)
Except that no beef tallow extremely hardened oil was used, a molded body was produced in the same manner as in Example 1, and the physical properties were measured. The results are shown in Table 1. Further, when a powder slush test was performed on a part of the composition, the moldability was good.

このように、エステル系滑剤である牛脂極度硬化油を添加することで、摩擦係数を制御することができ、そのことで耐磨耗性を飛躍的に改善することができることが明らかである。また、パウダースラッシュ成形性を損なうことがないことから、パウダースラッシュ用途の組成物としても有効であることが分かる。

Thus, it is clear that the friction coefficient can be controlled by adding the beef tallow extremely hardened oil which is an ester lubricant, and the wear resistance can be remarkably improved. Moreover, since powder slush moldability is not impaired, it turns out that it is effective also as a composition for powder slush use.

Claims (9)

  A composition containing an acrylic block copolymer, wherein when the composition is press-molded into a sheet shape with grain C leather texture, at least one of the static friction coefficient and the dynamic friction coefficient of the sheet surface is: An acrylic block copolymer composition characterized by being 0.25 or less.   A composition containing an acrylic block copolymer, and when the composition is press-molded into a sheet shape with grain C leather texture, both the static friction coefficient and the dynamic friction coefficient of the sheet surface are 0.25. The acrylic block copolymer composition according to claim 1, wherein:   A composition containing an acrylic block copolymer, and when the composition is press-molded into a sheet shape with grain C leather grain, the relationship between the static friction coefficient and the dynamic friction coefficient of the sheet surface is (static coefficient of friction> 3. The acrylic block copolymer composition according to claim 1, wherein a dynamic friction coefficient is satisfied.   The acrylic block copolymer according to any one of claims 1 to 3, wherein the acrylic block copolymer has a number average molecular weight measured by gel permeation chromatography of 30,000 to 500,000. 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 is 1.8 or less. To 4. The acrylic block copolymer composition according to any one of items 1 to 4.   The acrylic block copolymer composition according to any one of claims 1 to 5, wherein the acrylic block copolymer is a block copolymer produced by atom transfer radical polymerization.   The acrylic copolymer composition according to any one of claims 1 to 6, wherein the acrylic copolymer composition is used for powder slush molding.   A powder slush molding using the composition according to any one of claims 1 to 7.   The powder slush molded product according to claim 8, wherein the powder slush molded product is used for an automobile interior skin.