JP2007099987A - Acrylic block copolymer composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an acrylic block copolymer composition excellent in mold release characteristics. <P>SOLUTION: The acrylic block copolymer composition comprises (A) 100 pts.wt. acrylic block copolymer, (B) 0.01-10 pts.wt. modified polyorganosiloxane containing a carboxyl group, and (C) 0.01-10 pts.wt. modified polyorganosiloxane containing a carbinol group. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an acrylic block copolymer composition that is excellent in weather resistance, heat resistance, durability, and oil resistance, and further excellent in releasability.

  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. 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. Patent Document 1 describes that an acrylic block copolymer having a methacryl block and an acrylic block produced by an iniferter method has excellent mechanical properties.

  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 members that directly touch human hands by making use of tactile sensation.

  There are various methods for forming the skin material, and specific examples include press molding.

Japanese Unexamined Patent Publication No. 1-26619

  However, an acrylic block copolymer having a hardness range preferable as a skin material has adhesiveness to a metal or the like, and may be difficult to release from a mold during molding. Such properties often depend on the compositional design of the acrylic block copolymer and the composition, and it is difficult to improve them by a method usually employed for improving the releasability. Even if the releasability is improved, other characteristics often deteriorate. Specifically, when a silicone compound is blended in order to ensure releasability, bleed out occurs from the molded body and properties such as heat resistance are reduced, and it is difficult to achieve both of these properties.

  In addition, it has been found that silicone compounds generally have a possibility of lowering secondary processability such as adhesion and printing on a molded article using the same.

  The problem to be solved by the present invention is to provide an acrylic block copolymer composition excellent in releasability without deteriorating properties such as heat resistance. It is also preferable to provide an excellent composition from the viewpoint of not impairing secondary workability.

  As a result of intensive studies on an acrylic block copolymer composition excellent in releasability and other physical properties, the present inventors have found that an acrylic block copolymer composition containing a predetermined silicone compound is like this. The present inventors have found that various problems can be solved and have completed the present invention.

That is, the present invention
(A) 100 parts by weight of an acrylic block copolymer;
(B) 0.01 to 10 parts by weight of a modified polyorganosiloxane containing a carboxyl group;
(C) It is related with the acrylic block copolymer composition characterized by containing 0.01-10 weight part of modified polyorganosiloxane containing a carbinol group.

  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. An acrylic block copolymer composition comprising 90 to 40% by weight of an acrylic polymer block (A2) containing as a main component. Among these, the acrylic polymer block (A2) is at least one kind selected from the group consisting of acrylic acid-n-butyl, ethyl acrylate, acrylic acid-2-methoxyethyl, and acrylic acid-2-ethylhexyl. An acrylic block copolymer composition comprising 50 to 100% by weight of a polymer and 50 to 0% by weight of different acrylic esters and / or other vinyl monomers copolymerizable therewith Is more preferable.

In another preferred embodiment, the acrylic block copolymer having a number average molecular weight measured by gel permeation chromatography of the acrylic block copolymer as the component (A) is 30,000 to 500,000. 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. An acrylic block copolymer composition characterized by
(A) Acrylic block copolymer composition, wherein the acrylic block copolymer as a component is a block copolymer produced by atom transfer radical polymerization,
An acrylic block copolymer composition, wherein the modified polyorganosiloxane (B) and / or (C) is a modified polydimethylsiloxane;
An acrylic block copolymer composition, wherein the functional group equivalent weight of the modified polyorganosiloxane (B) is in the range of 1 to 10,000 g / mol;
An acrylic block copolymer composition, wherein the functional group of the modified polyorganosiloxane (C) has an OH value of 1 to 1000 mgKOH / g,
An acrylic copolymer composition characterized in that the modified polyorganosiloxane (B) and / or (C) has a viscosity at 25 ° C. of 10 to 100,000 mm ² / s.

  According to the present invention, it is possible to obtain an acrylic block copolymer composition excellent in releasability without deteriorating various properties such as heat resistance. Therefore, the composition according to the present invention can be suitably used for press molding and other molding. By such a method, various skin materials, interior materials and the like can be obtained.

Hereinafter, the present invention will be described in more detail.
The present invention
(A) 100 parts by weight of an acrylic block copolymer,
(B) 0.01 to 10 parts by weight of a modified polyorganosiloxane containing a carboxyl group,
(C) 0.01 to 10 parts by weight of a modified polyorganosiloxane containing a carbinol group,
It is characterized by the following. Thereby, it is possible to obtain an acrylic block copolymer composition excellent in releasability without deteriorating characteristics such as heat resistance.
In the present application, the releasability means the ease of releasing the molded body from the mold, and the molding method is not specified.

<Acrylic block copolymer (A)>
In the present invention, the acrylic block copolymer (A) means a polymer having two or more polymer blocks containing a (meth) acrylic monomer as a main component, and a (meth) acrylic monomer. Means an acrylic ester or a methacrylic ester.

  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 have any linear block structure, but from the point of view of its physical properties or physical properties when it is made into a composition, the block copolymer (A) is composed of a meta. Acrylic polymer block (A1) (hereinafter also referred to as polymer block (A1) or block (A1)) and acrylic polymer block (A2) (hereinafter, both polymer block (A2) or block (A2)) Are also 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 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.

  Although the molecular weight of a block copolymer (A) is not specifically limited, It is preferable that it is 30,000-500,000 in the number average molecular weight measured by the gel permeation chromatography, More preferably, it is 50,000-400,000. It is. If the number average molecular weight is small, the viscosity tends to be low, and if the number average molecular weight is large, the viscosity tends to be high. Therefore, it is necessary to set appropriately 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.
<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, heat resistance can be improved by introducing a carboxylic acid or an acid anhydride thereof. As a precursor for introducing a carboxylic acid or an acid anhydride thereof in order to increase heat resistance, tert-butyl methacrylate is preferable.

  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, methacrylic acid, methacrylic acid anhydrides, acrylic acid, acrylic acid anhydrides, and the like.

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

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

  These can be used alone or in combination of two or more. These vinyl monomers are preferably 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) preferably contains methyl methacrylate as a main component, and ethyl acrylate, acrylate-n-butyl acrylate for the purpose of controlling the glass transition point. A block obtained by polymerizing at least one monomer selected from the group consisting of 2-methoxyethyl acrylate and 2-ethylhexyl acrylate is preferable.

<Acrylic polymer block (A2)>
The acrylic polymer block (A2) is a block obtained by polymerizing a monomer mainly composed of an acrylate ester, and includes acrylic acid-n-butyl, ethyl acrylate, acrylic acid-2-methoxyethyl, and 50 to 100% by weight of at least one monomer selected from the group consisting of 2-ethylhexyl acrylate, and 0 to 50% by weight of different acrylates or other vinyl monomers copolymerizable therewith It is preferable to consist of. Thereby, it can be set as the block copolymer excellent in rubber elasticity, a low temperature characteristic, a mechanical characteristic, and a compression set.

  These can be used alone or in combination of two or more thereof. Among these, acrylate-n-butyl is preferable from the viewpoint of rubber elasticity, low temperature characteristics, and cost. 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.

  Examples of the acrylic ester constituting the acrylic polymer block (A2) (excluding n-butyl acrylate, ethyl acrylate, 2-methoxyethyl acrylate, and 2-ethylhexyl acrylate) include, for example, meta Monomers similar to the acrylic ester exemplified as the monomer constituting the acrylic polymer block (A1) (acrylic acid-n-butyl, ethyl acrylate, acrylic acid-2-methoxyethyl, and acrylic acid- (Excluding 2-ethylhexyl). Among them, tert-butyl acrylate is preferable as a precursor for introducing a carboxyl group or an acid anhydride group to increase heat resistance.

  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 suitably preferable from the viewpoint of balance such as glass transition temperature and oil resistance required for the acrylic polymer block (A2) and compatibility with the methacrylic polymer block (A1). You can choose one.

  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.

<Method for producing block copolymer (A)>
(polymerization)
Although the manufacturing method of the acrylic block copolymer composition concerning this invention is not specifically limited, It is preferable to use controlled polymerization from a viewpoint that molecular weight can be controlled. The controlled polymerization is not particularly limited, and examples thereof include living polymerization, polymerization that can be regarded as substantially living, and polymerization having a living character, such as living anion polymerization, coordination anion polymerization, and chain transfer agent. And radical polymerization, living radical polymerization, living cationic polymerization, ring-opening metathesis polymerization, and other various metal catalyst polymerizations. As an example of anionic polymerization, specifically, the method described in JP-A-11-335432 is used. As an example of living polymerization using a rare earth metal complex, the method described in JP-A-10-17633 is used. I can give you.

  Here, 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. It is. In the present invention, the living radical polymerization is preferably performed by a radical polymerization method in which the polymerization end is activated and the inactivation is maintained in an equilibrium state.

  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, which of these methods is used is not particularly limited, but atom transfer radical polymerization is preferable from the viewpoint of ease of control.

  Among them, for example, Matyjaszewski et al., Journal of American Chemical Society, 1995, 117, 5614, and Macromolecules, 1995, 28, 7901, further, Science, 1996, 27, 66. Further, the polymerization method disclosed in JP 2001-200026 A can be preferably used.

(Removal of polymerization catalyst, etc.)
The reaction liquid obtained by polymerization is a mixture of a polymer and a metal complex, and it is necessary to remove the metal complex. The removal method is not particularly limited, but for example, a treatment method using an organic acid as disclosed in JP-A No. 2003-147015 is preferably used.

(Functional group conversion)
In the present invention, an acrylic block copolymer having a carboxyl group or an acid anhydride group introduced by a functional group conversion reaction of the ester portion 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 the above 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 a publication. In addition, there is a method in which an acid anhydride group is hydrolyzed to generate a carboxyl group, such as the method described below.

  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, or the like 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 obtained 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.

<Modified polyorganosiloxane (B) containing a carboxyl group>
The modified polyorganosiloxane (B) containing a carboxyl group is a polyorganosiloxane having a carboxyl group at the side chain and / or terminal.

The carboxyl group may be bonded to the polyorganosiloxane main chain via an appropriate organic group. The organic group is not particularly limited as long as it is a bifunctional hydrocarbon group such as a methylene group or an oxygen-containing hydrocarbon group such as polyether. As such an organic group, for example,
—CH ₂ —
—CH ₂ —CH ₂ —
—CH ₂ —CH ₂ —CH ₂ —
_{-CH 2 -CH 2 -CH 2 -CH 2} -
_{-CH 2 -CH 2 -CH 2 -CH 2} -CH 2 -
-CHX-
—CH ₂ —CHX—
-CH ₂ -CH ₂ -CHX-
-CH ₂ -CH ₂ -CH ₂ -CHX-
_{-CH 2 -CH 2 -CH 2 -CH 2} -CH 2 -CHX-
—CH (CH ₃ ) —
—CH ₂ —CH (CH ₃ ) —
_{-CH 2 -CH 2 -CH (CH 3} ) -
_{-CH (CH 3) -CH 2 -CH} (CH 3) -
_{-CH 2 -CH 2 -CH 2 -CH (} CH 3) -
_{-CH 2 -CH (CH 3) -CH} 2 -CH (CH 3) -
_{-CH 2 -CH 2 -CH 2 -CH 2} -CH (CH 3) -
_{-CH (CH 3) -CH 2 -CH} (CH 3) -CH 2 -CH (CH 3) -
—C (CH ₃ ) ₂ —
—CH ₂ —C (CH ₃ ) ₂ —
_{-CH 2 -CH 2 -C (CH 3} ) 2 -
_{-C (CH 3) 2 -CH 2} -C (CH 3) 2 -
_{-CH 2 -CH 2 -CH 2 -C (} CH 3) 2 -
_{-CH 2 -C (CH 3) 2} -CH 2 -C (CH 3) 2 -
_{-CH 2 -CH 2 -CH 2 -CH 2} -C (CH 3) 2 -
_{-C (CH 3) 2 -CH 2} -C (CH 3) 2 -CH 2 -C (CH 3) 2 -
-C (CH ₃₎ X-
-CO-CH ₂ -
—CH ₂ —CO—CH ₂ —
_{-CH 2 -CH 2 -CO-CH 2} -
_{-CO-CH 2 -CO-CH 2} -
Is raised,
When the above bifunctional functional group is represented by N, or N1 and N2 (N1 and N2 may be the same or different),
-C ₆ H ₄ -N-
-N1-C ₆ H ₄ -N2-
What is represented,
When all the bifunctional functional groups listed above are expressed as M, or M1 and M2 (M1 and M2 may be the same or different),
_{- (CH 2 -CH 2 -O)} n -M-
_{- (O-CH 2 -CH 2} ) n -M-
_{- (CH 2 -CH 2 -CH 2} -O) n -M-
_{- (O-CH 2 -CH 2} -CH 2) n -M-
_{- (CH 2 -CH 2 -O)} n (CH 2 -CH 2 -CH 2 -O) m -M-
_{- (O-CH 2 -CH 2} ) n (O-CH 2 -CH 2 -CH 2) m -M-
_{-M1- (CH 2 -CH 2 -O)} n -M2-
_{-M1- (O-CH 2 -CH 2} ) n -M2-
_{-M1- (CH 2 -CH 2 -CH 2} -O) n -M2-
_{-M1- (O-CH 2 -CH 2} -CH 2) n -M2-
_{-M1- (CH 2 -CH 2 -O)} n (CH 2 -CH 2 -CH 2 -O) m -M2-
_{-M1- (O-CH 2 -CH 2} ) n (O-CH 2 -CH 2 -CH 2) m -M2-
What is represented.
(In the formula, C ₆ H ₄ represents a phenylene group. The phenylene group may be ortho-substituted, meta-substituted, or para-substituted. R ¹ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and 6 to 6 carbon atoms. 20 represents an aryl group or an aralkyl group having 7 to 20 carbon atoms, X represents chlorine, bromine or iodine, and n and m are each independently an integer of 1 to 1000.

  The functional group (B) may be introduced into a part of the side chain of the polyorganosiloxane, or may be introduced into one of the main chain ends of the polyorganosiloxane. The siloxane may be introduced at both ends of the main chain, or may be introduced at a part of the side chain of the polyorganosiloxane and the end of the main chain.

  The site where the functional group is not introduced at the end of (B) is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a terminal that is not It is preferably blocked with a non-reactive functional group such as a polyether group blocked with a reactive hydrocarbon group.

  The organic group directly bonded to the silicon atom of the main chain structure (B) is preferably a methyl group except for a modified functional group or terminal portion from the viewpoint of availability and cost. That is, the modified polyorganosiloxane is preferably a modified polydimethylsiloxane.

  The blending ratio of (A) to (B) is 0.01 to 10 parts by weight of (B) modified polyorganosiloxane with respect to 100 parts by weight of (A) acrylic block copolymer. When the amount is less than 0.01 parts by weight, the releasability may be inferior. When the amount is more than 10 parts by weight, mechanical properties may be deteriorated, molding defects may be caused. This blending ratio is appropriately set according to the weight ratio of (A1) and (A2), the molecular weight of (A), the viscosity of (B), and the like. The blending ratio of (A) and (B) is preferably 0.02 to 8 parts by weight of (B) relative to 100 parts by weight of (A), more preferably 100 parts by weight of (A). (B) 0.03 to 6 parts by weight with respect to parts.

  The number of functional groups in (B) is preferably 1 to 10,000 g / mol, more preferably 300 to 10,000 g / mol, when expressed in terms of functional group equivalents. When the functional group equivalent is less than 1 g / mol, the storage stability of the modified polyorganosiloxane may become a problem. If the functional group equivalent is greater than 10,000 g / mol, there may be a problem that the effect of functional group modification is small.

The viscosity of (B) is not particularly limited, is preferably 10~100,000mm ² / s, further preferably 25~70,000mm ² / s. When the viscosity is lower than 10 mm ² / s, thermal stability due to volatile matter may be a problem. When the viscosity is higher than 100,000 mm ² / s, handleability may be a problem.

Although the specific example of (B) is given below, it is not limited to them.
X-22-3701E (above, side chain type, made by Shin-Etsu Silicone), X-22-162C (above, made by terminal type, made by Shin-Etsu Silicone), FZ-3703 (above, made by terminal type, made by Nippon Unicar Co., Ltd.) can give.

<Modified polyorganosiloxane (C) containing carbinol group>
The modified polyorganosiloxane (C) containing a carbinol group has a carbinol group in the side chain and / or terminal of the polyorganosiloxane.

The carbinol group is bonded to the polyorganosiloxane main chain through a suitable organic group. The organic group is not particularly limited as long as it is a bifunctional hydrocarbon group such as a methylene group or an oxygen-containing hydrocarbon group such as polyether. As such an organic group, for example,
—CH ₂ —
—CH ₂ —CH ₂ —
—CH ₂ —CH ₂ —CH ₂ —
_{-CH 2 -CH 2 -CH 2 -CH 2} -
_{-CH 2 -CH 2 -CH 2 -CH 2} -CH 2 -
—CH (CH ₃ ) —
—CH ₂ —CH (CH ₃ ) —
_{-CH 2 -CH 2 -CH (CH 3} ) -
_{-CH (CH 3) -CH 2 -CH} (CH 3) -
_{-CH 2 -CH 2 -CH 2 -CH (} CH 3) -
_{-CH 2 -CH (CH 3) -CH} 2 -CH (CH 3) -
_{-CH 2 -CH 2 -CH 2 -CH 2} -CH (CH 3) -
_{-CH (CH 3) -CH 2 -CH} (CH 3) -CH 2 -CH (CH 3) -
—C (CH ₃ ) ₂ —
—CH ₂ —C (CH ₃ ) ₂ —
_{-CH 2 -CH 2 -C (CH 3} ) 2 -
_{-C (CH 3) 2 -CH 2} -C (CH 3) 2 -
_{-CH 2 -CH 2 -CH 2 -C (} CH 3) 2 -
_{-CH 2 -C (CH 3) 2} -CH 2 -C (CH 3) 2 -
_{-CH 2 -CH 2 -CH 2 -CH 2} -C (CH 3) 2 -
_{-C (CH 3) 2 -CH 2} -C (CH 3) 2 -CH 2 -C (CH 3) 2 -
-CO-CH ₂ -
—CH ₂ —CO—CH ₂ —
_{-CH 2 -CH 2 -CO-CH 2} -
_{-CO-CH 2 -CO-CH 2} -
Is raised,
When the above bifunctional functional group is represented by N, or N1 and N2 (N1 and N2 may be the same or different),
-C ₆ H ₄ -N-
-N1-C ₆ H ₄ -N2-
What is represented,
When all the bifunctional functional groups listed above are expressed as M, or M1 and M2 (M1 and M2 may be the same or different),
_{- (CH 2 -CH 2 -O)} n -M-
_{- (O-CH 2 -CH 2} ) n -M-
_{- (CH 2 -CH 2 -CH 2} -O) n -M-
_{- (O-CH 2 -CH 2} -CH 2) n -M-
_{- (CH 2 -CH 2 -O)} n (CH 2 -CH 2 -CH 2 -O) m -M-
_{- (O-CH 2 -CH 2} ) n (O-CH 2 -CH 2 -CH 2) m -M-
_{-M1- (CH 2 -CH 2 -O)} n -M2-
_{-M1- (O-CH 2 -CH 2} ) n -M2-
_{-M1- (CH 2 -CH 2 -CH 2} -O) n -M2-
_{-M1- (O-CH 2 -CH 2} -CH 2) n -M2-
_{-M1- (CH 2 -CH 2 -O)} n (CH 2 -CH 2 -CH 2 -O) m -M2-
_{-M1- (O-CH 2 -CH 2} ) n (O-CH 2 -CH 2 -CH 2) m -M2-
What is represented.
(In the formula, C ₆ H ₄ represents a phenylene group. The phenylene group may be ortho-substituted, meta-substituted, or para-substituted. R ¹ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and 6 to 6 carbon atoms. 20 represents an aryl group or an aralkyl group having 7 to 20 carbon atoms, X represents chlorine, bromine or iodine, and n and m independently represent an integer of 1 to 1000.)

  The functional group (C) may be introduced into a part of the side chain of the polyorganosiloxane, or may be introduced into one of the main chain ends of the polyorganosiloxane. The siloxane may be introduced at both ends of the main chain, or may be introduced at a part of the side chain of the polyorganosiloxane and the end of the main chain.

  (C) the site where the functional group is not introduced is 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, or a terminal that is not It is preferably blocked with a non-reactive functional group such as a polyether group blocked with a reactive hydrocarbon group.

  The organic group directly bonded to the silicon atom of the main chain structure of (C) is preferably a methyl group except for a modified functional group and a terminal site. That is, the modified polyorganosiloxane is preferably a modified polydimethylsiloxane from the viewpoint of availability and cost.

  The blending ratio of (A) and (C) is 0.01 to 10 parts by weight of (C) modified polyorganosiloxane with respect to 100 parts by weight of (A) acrylic block copolymer. When the amount is less than 0.01 parts by weight, the releasability may be inferior. When the amount is more than 10 parts by weight, mechanical properties may be deteriorated, molding defects may be caused. This blending ratio is appropriately set according to the weight ratio of (A1) and (A2), the molecular weight of (A), the viscosity of (C), and the like. The mixing ratio of (A) and (C) is preferably (C) 0.02 to 8 parts by weight, more preferably (A) 100 parts by weight with respect to (A) 100 parts by weight. (C) 0.03 to 6 parts by weight with respect to parts.

  The number of functional groups in (C) is preferably 1 to 1000 mgKOH / g, more preferably 5 to 500 mgKOH / g, and more preferably 10 to 250 mgKOH / g when expressed in terms of OH value. Most preferred. When the functional group equivalent is smaller than 1 mg KOH / g, there may be a problem that the effect of functional group modification is small. When the functional group equivalent is larger than 1000 mgKOH / g, the storage stability of the modified polyorganosiloxane may become a problem.

The viscosity of (C) is not particularly limited, is preferably 10~100,000mm ² / s, further preferably 25~10,000mm ² / s. When the viscosity is lower than 10 mm ² / s, thermal stability due to volatile matter may be a problem. When the viscosity is higher than 100,000 mm ² / s, handleability may be a problem.

  Specific examples of (C) include X-22-4015 (above, side chain type, manufactured by Shin-Etsu Silicone), X-22-160AS, KF-6001, KF-6002, KF-6003 (above, end type) , Manufactured by Shin-Etsu Silicone Co., Ltd.) and XF42-B0970 (above, terminal type, manufactured by GE Toshiba Silicone Co., Ltd.), but are not limited thereto.

<Crosslinking agent>
About the composition of this invention, in order to improve performance, such as a moldability, heat resistance, and a mechanical physical property, you may mix | blend a crosslinking agent. 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.

  As specific product names, for example, ARUFON UG4010, UG4000 (manufactured by Toagosei Co., Ltd.) and the like are exemplified.

<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, 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 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.

  As these additives, those suitable for the use in which the composition is used can be appropriately selected.

  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, 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.

  The silicone oil is not particularly limited except those listed in (B) and (C). TSF451 (dimethylsilicone 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), amino group modified silicone oil, epoxy group modified silicone oil, alkoxy Mention may be made of group-modified silicone oils. Amino group-modified silicone oils include TSF4700, TSF4701, TSF4702, TSF4703, TSF4704, TSF4705, TSF4706, TSF4707, TSF4708, TSF4709 (above GE Toshiba Silicone Co., Ltd.), KF-393, KF-859, KF-860 , KF-861, KF-867, KF-869, KF-880, KF-8002, KF-8004, KF-8005, KF-858, KF-864, KF-865, KF-868, KF-8003 (or above , Side chain type, Shin-Etsu silicone), KF-8010, X-22-161A, X-22-161B, X-22-1660B-3, KF-8008, KF-8012 (above, terminal type, Shin-Etsu silicone) ), FZ-3501, FZ-3504, FZ-3508, FZ-3705, FZ-3707, FZ-3710, FZ-3750, FZ-3760, FZ-3785, FZ-3789 (above, side chain type, Nippon Unicar) Product). As epoxy group-modified silicone oil, TSF4730 (above, manufactured by GE Toshiba Silicone Co., Ltd.), KF-1001, KF-101, KF-22-2000, KF-102 (above, side chain type, manufactured by Shin-Etsu Silicone), KF-105, X-22-163A, X-22-163B, X-22-163C, X-22-169AS, X-22-169B, X-22-173DX (End type, Shin-Etsu Silicone), L-9300, FZ-3720, FZ-3736, Y-7499 (above, side chain type, manufactured by Nippon Unicar Co., Ltd.). Examples of the alkoxy group-modified silicone oil include FZ-3704 (end type, manufactured by Nippon Unicar Co., Ltd.). 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.

  There is no limitation in particular as said filler, For example, an amorphous filler, a plate-like filler, an acicular filler, a spherical filler, a functional filler, a fibrous filler, a metal powder etc. can be used. 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, zonotrite, boron Examples include spherical acid fillers such as glass beads, silica beads, and glass (silica) balloons. Functional fillers include metallic conductive fillers, nonmetallic conductive fillers, and carbon conductive fillers. , Magnetic filler, piezoelectric, pyroelectric Filler, and the like sliding filler, and 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, light 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 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 (Shiraishi Calcium Co., Ltd., surface treatment product), Whiten 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.

  Light calcium carbonate includes colloidal calcium carbonate and light calcium carbonate.

  Examples of the above-mentioned colloidal calcium carbonate include, for example, Brilliant 15 (hereinafter, BRILLIANT is referred to as Brilliant), Brilliant S15, Brilliant 40, UNIBUR70, VIGOT15, VIGOT10, Brilliant 1500, UNIFANT15, UNIFANT15FR, VISCOLITE ), Obtained by continuous reaction method), white gloss flower 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 homoton DM, white gloss flower gelton 50, white gloss flower O, White Glossy DD, White Glossy TDD, White Glossy IGV (above, manufactured by Shiraishi Kogyo Co., Ltd., obtained by batch reaction method), MSK-C, MSK-G, MSK-K, MSK-P, MSK-P , Calfine 100, Calfine 200, Calfine 200M, Calfine 500, Carlex 100, Carlex 300, MT-100, MS-100M, MS-600, Sealets 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 product) and the like.

  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.

  As natural silica, IMSIL-A25, IMSIL-A15, IMSIL-A10, IMSIL-A8, Crystallite VX-S2, Crystallite VX-S, Crystallite VX-SR, Crystallite 5X (manufactured by Tatsumori) Is given.

  As synthetic silica, NIPSIL-VN3, NIPSIL-AQ, NIPSIL-LP, NIPSIL-NA, NIPSIL-ER, NIPSIL-RS150 (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.

<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, a high shear mixer can be used as a batch type kneader, and a single screw extruder, a twin screw extruder, a KCK extruder Etc. can be used. Furthermore, existing methods such as a method of mechanically mixing and shaping into pellets 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>
The method for molding the composition of the present invention is not particularly limited, and injection molding, injection blow molding, blow molding, extrusion blow molding, extrusion molding, calendar molding, vacuum molding, press molding, and the like can be used.

  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. In the following description, butyl acrylate is BA, t-butyl acrylate is TBA, ethyl acrylate is EA, methyl methacrylate is MMA, and t-butyl methacrylate is TBMA.

<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.

<Releasability test>
About 45 g of the composition obtained according to the examples was hot press-molded with a press plate having a width of 21 cm modified with a grain F leather texture pattern at a setting of a hot press set temperature of 200 ° C., a pressure of 5 MPa, and a thickness of 1 mm ( 200 degreeC, 5 MPa, 8 minutes) and the cooling press (room temperature, 5 MPa, 5 minutes) were performed. Then, the stress at the time of peeling from the press plate the evaluation molded body to which the leather texture pattern was transferred was measured.
Measurement method: The press plate with the molded body attached was vertically placed on the weighing scale, and the molded body was peeled off in the vertical direction at a speed of about 10 cm / 30 seconds. The stress at that time was read and used as a measured value. The unit of stress is kilogram weight (kgf).

<Secondary workability test>
According to the example, the composition was press-molded to prepare a skin material. A cartridge type polyurethane (manufactured by Air Tight Co., Ltd.) whose main component is 4,4′-diphenylmethane diisocyanate was applied on a metal plate, and a skin material was immediately placed on the foam and adhered. After 12 hours or more have passed (the foam is completely cured), peel the skin from the foamed urethane by hand and observe the state of failure. The case where fracture occurred at the interface between and urethane was evaluated as x.

<Heat resistance test>
A part of the obtained molded body was cut out, put into a 130 ° C. hot air oven, and taken out after 24 hours. Changes in the wrinkle pattern were observed, and there was no particular change: ◯, wrinkles of wrinkles disappeared due to shine: evaluated as x.

(Production Example 1)
<Synthesis of Acrylic Block Copolymer (A) Precursor>
The following operation was performed in order to obtain an acrylic block copolymer (A) precursor. After replacing the inside of the 500 L pressure-resistant reactor with nitrogen, 692 g (4.82 mol) of copper bromide, 77,820 g (607 mol) of BA and 3,470 g (27.1 mol) of TBA were charged, and stirring was started. Then, a solution prepared by dissolving 965.1 g (2.68 mol) of diethyl 2,5-dibromoadipate in 7140 g of acetonitrile (nitrogen bubbling) was charged, and the inner solution was heated to 75 ° C. for 30 minutes. Stir. When the internal temperature reached 75 ° C., 83.6 g (0.482 mol) of the ligand pentamethyldiethylenetriamine was added to start polymerization of the acrylic polymer block.

  About 100 mL of the polymerization solution was extracted from the polymerization solution for sampling at regular intervals from the start of polymerization, and the conversion rates of BA and TBA were determined by gas chromatogram analysis of the sampling solution. During polymerization, the polymerization rate was controlled by adding pentamethyldiethylenetriamine as needed. Pentamethyldiethylenetriamine was added a total of 2 times (167 g in total) during the acrylic polymer block polymerization.

  When the conversion rate of BA is 98.9% and the conversion rate of TBA is 99.0%, MMA 49,590 g (495 mol), EA 8,050 g (80.4 mol), copper chloride 477 g (4.82 mol) Then, 83.6 g (0.482 mol) of pentamethyldiethylenetriamine and 106,860 g of toluene (nitrogen bubbled) were added to initiate polymerization of the methacrylic polymer block.

Sampling was performed when MMA and EA were added, and conversion rates of MMA and EA were determined based on this. After adding MMA and EA, the internal temperature was set to 85 ° C. During polymerization, the polymerization rate was controlled by adding pentamethyldiethylenetriamine as needed. Pentamethyldiethylenetriamine was added a total of 6 times (502 g in total) during block polymerization of the methacrylic polymer. When the conversion rate of MMA was 95.9%, 250,000 g of toluene was added, and the reactor was cooled to complete the reaction. When the GPC analysis of the obtained block copolymer was performed, the number average molecular weight Mn was 77,400 and molecular weight distribution Mw / Mn was 1.44. Toluene was added to the resulting reaction solution to make the polymer concentration 25% by weight. 2,203 g 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 2,650 g 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.

(Production Example 2)
<Synthesis of acrylic block copolymer (A)>
790 g of Irganox 1010 (manufactured by Ciba Specialty Chemicals Co., Ltd.) was added to the obtained filtrate, and TBMA was added as an internal standard substance at 0.1 wt% with respect to 100 wt% of the filtrate. This solution was heated and stirred at 150 ° C. for 4 hours. After 4 hours, the solution was sampled, and it was confirmed that TBMA had disappeared by GC measurement.
Kyoward 500SH, 13,150 g, was added to the resulting solution, the inside of the reactor was purged with nitrogen, and the mixture was stirred at 30 ° C for 1 hour. The solution was sampled, and it was confirmed that the solution was neutral. 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. 790 g of Irganox 1010 (manufactured by Ciba Specialty Chemicals Co., Ltd.) and 1,315 g of hydrotalcite DHT-4A-2 (manufactured by Kyowa Chemical Industry Co., Ltd.) are added as an acid trapping agent to the resulting polymer solution. did.

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. In this way, pellets of the acrylic block copolymer (A) were produced.

  The conversion efficiency of the t-butyl ester moiety into an acid anhydride group and a carboxyl group was measured by quantifying the amount of isobutylene generated from the t-butyl group by a 280 ° C. thermal decomposition reaction. As a result of the measurement, the conversion efficiency of the obtained resin was 95% or more. The resulting acrylic block copolymer (A) had a Tg of 101 ° C. for the methacrylic polymer block (a).

Example 1
According to the composition of Table 1, the polymer pellet (A) obtained in Production Example 2, carbon black as a colorant (Asahi Carbon Co., Ltd., Asahi # 15), carboxy-modified silicone (B) FZ3703 (Nihon Unicar ( Co., Ltd., functional group equivalent 3600, viscosity 3000 mm ² / s), X22-4015 (manufactured by Shin-Etsu Silicone Co., Ltd.) as the carbinol-modified silicone (C), and Lab Plast Mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) Using a 1 mm thick molded product for evaluation with a leather wrinkle pattern transferred on a press plate modified with leather wrinkles, melt-kneaded at 100 ° C./100 rpm and heat press molded at a set temperature of 200 ° C. Obtained. Table 1 shows the results of evaluating this molded body.

(Comparative Example 1)
A molded body was obtained in the same manner as in Example 1 except that (B) was increased and (C) was not blended, so that the total amount of the modified silicone oil was the same. The results are shown in Table 1.

(Comparative Example 2)
A molded body was obtained in the same manner as in Example 1 except that (C) was increased and (B) was not added, so that the total amount of the modified silicone oil was the same. The results are shown in Table 1.

(Comparative Example 3)
A molded body was obtained in the same manner as in Example 1 except that (B) and (C) were not blended. The results are shown in Table 1.

(Example 2)
According to Table 1, polymer pellet (A) obtained in Production Example 2, UG4010 (manufactured by Toagosei Co., Ltd., epoxy group-containing) as a cross-linking agent, Adeka Sizer RS-700 (Asahi Denka Kogyo Co., Ltd.) as a plasticizer Carbon black (manufactured by Asahi Carbon Co., Ltd., Asahi # 15), carboxy-modified silicone (B) as FZ3703 (manufactured by Nihon Unicar), and carbinol-modified silicone (C) as X22-4015 (manufactured by Asahi Carbon Co., Ltd.) Shin-Etsu Silicone Co., Ltd.) is melt-kneaded at 100 ° C / 100rpm using Labo Plast Mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.). A molded product for evaluation having a thickness of 1 mm to which a leather texture pattern was transferred with a pressed plate was obtained. Table 1 shows the results of evaluating this molded body.

(Comparative Example 4)
A molded body was obtained in the same manner as in Example 2 except that (B) was increased and (C) was not blended, so that the total amount of the modified silicone oil was the same. The results are shown in Table 1.

(Comparative Example 5)
A molded body was obtained in the same manner as in Example 2 except that (C) was increased and (B) was not added, so that the total amount of the modified silicone oil was the same. The results are shown in Table 1.

(Comparative Example 6)
A molded body was obtained in the same manner as in Example 2 except that (B) and (C) were not blended. The results are shown in Table 1.

By comparing Example 1 and Comparative Examples 1 to 3, by using (B) and (C) in combination, the same amount of (B) alone or (C) is used more than when used alone. You can see that In addition, by comparing Example 2 and Comparative Examples 4 to 6, even when crosslinking is performed with a carboxyl group and a crosslinking agent contained in the block copolymer, (B) and (C) are used in combination. When the same amount of (B) alone or (C) alone is used, it can be seen that the releasability is superior to that of use.

Claims (10)

(A) 100 parts by weight of an acrylic block copolymer;
(B) 0.01 to 10 parts by weight of a modified polyorganosiloxane containing a carboxyl group;
(C) An acrylic block copolymer composition comprising 0.01 to 10 parts by weight of a modified polyorganosiloxane containing a carbinol group.   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 to The acrylic block copolymer according to claim 2, comprising 100% by weight and 50 to 0% by weight of different kinds of acrylic ester and / or other vinyl monomers copolymerizable therewith. Combined composition.   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. 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 modified polyorganosiloxane (B) and / or (C) is a modified polydimethylsiloxane.   The acrylic block copolymer composition according to any one of claims 1 to 7, wherein the functional group equivalent of the modified polyorganosiloxane (B) is in the range of 1 to 10,000 g / mol. .   The acrylic block copolymer composition according to any one of claims 1 to 8, wherein the functional group of the modified polyorganosiloxane (C) has an OH value in the range of 1 to 1000 mgKOH / g. 10. The acrylic copolymer according to claim 1, wherein the modified polyorganosiloxane (B) and / or (C) has a viscosity at 25 ° C. of 10 to 100,000 mm ² / s. Polymer composition.