JP4451691B2 - Acrylic polymer composition - Google Patents

Description

  The present invention is an acrylic polymer comprising an acrylic block copolymer and a polyorganosiloxane graft polymer which are rich in flexibility, excellent in moldability, very excellent in mechanical properties, and have both low temperature characteristics and oil resistance. Relates to the composition.

In recent years, thermoplastic elastomers have been used in place of vulcanized rubbers that are excellent in flexibility and rubber elasticity in terms of moldability (molding cycle) and recyclability. Among various types of thermoplastic elastomers, the amount of olefinic thermoplastic elastomers used has increased due to lightness, environmental pollution resistance, and economic efficiency. However, olefinic thermoplastic elastomers are more resistant to weathering than vulcanized rubbers. , Oil resistance and ozone resistance are not sufficient, and it is difficult to use for parts that require the required characteristics. Therefore, a composition comprising an acrylic block copolymer has been proposed as a thermoplastic elastomer that satisfies the above-mentioned required characteristics. (For example, refer to Patent Document 1). However, although the composition comprising the acrylic block copolymer has oil resistance, the low temperature characteristics are not sufficient. On the other hand, a composition in which an acrylic rubber-based or butadiene rubber-based core / shell type graft copolymer is added to a polyvinyl chloride resin (Patent Document 2) or an Si rubber-based core / shell type graft copolymer is added to a polybutylene terephthalic resin. A composition added to a tarate resin (Patent Document 3) has been proposed, but these have improved low-temperature characteristics, but their oil resistance is not sufficient. Automotive parts and the like are required to have oil resistance, low temperature characteristics, heat resistance, etc., but generally oil resistance and low temperature characteristics are contradictory properties (see Patent Document 4). Oil resistance and low temperature There has been a demand for development of a thermoplastic elastomer having both properties.
JP 2002-60584 A JP-A-7-188493 JP 2002-226661 A WO02 / 68482

  The present invention is an acrylic polymer comprising an acrylic block copolymer and a polyorganosiloxane graft polymer which are rich in flexibility, excellent in moldability, very excellent in mechanical properties, and have both low temperature characteristics and oil resistance. The aim is to develop a composition.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that, in the entire composition, (A) 50 to 90% by weight of an acrylic block copolymer and (B) a polyorganosiloxane graft weight. Found by forming a composition consisting of 50 to 10% by weight of a coalescence into a product, it is rich in flexibility, excellent in processability, very excellent in mechanical properties, and has both low temperature characteristics and oil resistance. The invention was completed.

  That is, the present invention relates to an acrylic polymer composition comprising (A) 50 to 90% by weight of an acrylic block copolymer and (B) 50 to 10% by weight of a polyorganosiloxane graft polymer in the entire composition. .

  In a preferred embodiment, the acrylic block copolymer (A) comprises (a) an acrylic polymer block and (b) a methacrylic polymer block, and in the main chain of at least one polymer block, (C) General formula (1):

（式中、Ｒ¹は水素原子またはメチル基で、互いに同一でも異なっていてもよい、ｐは０または１の整数、ｑは０〜３の整数）で表わされる酸無水物基を含有する単位（ｃ１）および／又はカルボキシル基を含有する単位（ｃ２）からなる単位を有することを特徴とするアクリル系重合体組成物に関する。

(Wherein R ¹ is a hydrogen atom or a methyl group, and may be the same or different, p is an integer of 0 or 1, q is an integer of 0 to 3) The present invention relates to an acrylic polymer composition comprising a unit comprising (c1) and / or a unit (c2) containing a carboxyl group.

  As a preferred embodiment, the present invention relates to an acrylic polymer composition comprising 0.1 to 50% by weight of a unit (c2) containing a carboxyl group in the entire acrylic block copolymer (A). .

  As a preferred embodiment, the whole acrylic block copolymer (A) comprises (a) 40 to 90% by weight of an acrylic polymer block and (b) 60 to 10% by weight of a methacrylic polymer block. The present invention relates to an acrylic polymer composition.

  As a preferred embodiment, at least one monomer selected from the group consisting of n-butyl acrylate, ethyl acrylate and 2-methoxyethyl acrylate in the entire acrylic polymer block (a) 50 to 100 The present invention relates to an acrylic polymer composition comprising 0% by weight to 50% by weight and another acrylic ester and / or other vinyl monomer copolymerizable therewith.

  As a preferred embodiment, 10 to 90% by weight of 2-methoxyethyl acrylate and 10 to 90% by weight of n-butyl acrylate in the entire acrylic polymer block (a), and further ethyl acrylate 0 as an optional component It is related with the acrylic polymer composition characterized by containing -80weight%.

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

  In a preferred embodiment, (B) the polyorganosiloxane graft polymer is a polyorganosiloxane graft polymer having a graft component content of 5 to 40% by weight and a polyorganosiloxane content of 95 to 60% by weight. The present invention relates to an acrylic polymer composition.

  As a preferred embodiment, (B) the content of the alkyl graft acrylate in the entire graft component of the polyorganosiloxane-based graft polymer is 5 to 99.5% by weight, and the alkyl acrylate content is 95 to 0.5% by weight. The present invention relates to an acrylic polymer composition which is a certain polyorganosiloxane graft polymer.

  A preferred embodiment is characterized in that (B) the alkyl methacrylate component in the entire graft component of the polyorganosiloxane-based graft polymer requires 0.5 to 50% by weight of n-butyl methacrylate. The present invention relates to an acrylic polymer composition.

  As a preferred embodiment, the present invention relates to (B) an acrylic polymer composition characterized in that 0.5 to 10% by weight of methacrylic acid or acrylic acid is contained in the entire graft of the polyorganosiloxane graft polymer.

  The present invention also provides an acrylic block copolymer (A), a polyorganosiloxane graft polymer (B), (C) a lubricant, (D) an inorganic filler, and / or (E) a thermoplastic resin. The present invention relates to a polymer composition.

  As a preferred embodiment, 15 to 100 parts by weight of the polyorganosiloxane-based graft polymer (B), (C) 0.1 to 10 parts by weight of a lubricant, with respect to 100 parts by weight of the acrylic block copolymer (A), The present invention relates to an acrylic polymer composition comprising (D) 0.1 to 100 parts by weight of an inorganic filler and / or (E) 0.1 to 100 parts by weight of a thermoplastic resin.

  The present invention also relates to a molded article for automobiles, household electric appliances or office electric appliances using an acrylic polymer composition.

  The acrylic polymer composition comprising an acrylic block copolymer and a polyorganosiloxane graft polymer used in the present invention is rich in flexibility, compression set, molding processability, oil resistance, low temperature characteristics and mechanical properties. It turns out that it is very excellent. In addition, by combining the acrylic block copolymer of the present invention with a polyorganosiloxane graft polymer, a lubricant, an inorganic filler and a thermoplastic resin, it is rich in flexibility, oil resistance, mechanical properties, molding processability, A novel acrylic polymer composition having excellent low-temperature characteristics and particularly remarkably good tensile modulus is obtained. Furthermore, since the acrylic polymer composition used in the present invention is particularly excellent in oil resistance, low temperature characteristics and mechanical characteristics, it should be suitably used for molded products for automobiles, household electrical appliances or office electrical appliances. Can do.

  Below, the composition of this invention is demonstrated in detail.

<Acrylic block copolymer (A)>
The structure of the acrylic block copolymer (A) may be a linear block copolymer, a branched (star) block copolymer, or a mixture thereof. The structure of the acrylic block copolymer (A) is to improve the required physical properties of the acrylic block copolymer (A) and the low temperature embrittlement of the acrylic block copolymer (A). It may be used depending on the processing characteristics and mechanical characteristics required for the composition with the polyorganosiloxane-based graft polymer (B) which may be used, but the cost and ease of polymerization From the viewpoint, a linear block copolymer is preferable.

The linear block copolymer may be of any linear block structure, but it constitutes the acrylic block copolymer (A) from the viewpoint of its physical properties or physical properties when made into a composition. Acrylic polymer block (a) (hereinafter also referred to as polymer block (a) or block (a)) and methacrylic polymer block (b) (hereinafter referred to as polymer block (b) or block ( b)) is represented by the general formula: (ab) _n , general formula: b- (ab) _n , general formula: (ab) _n -a (n is an integer of 1 to 3) The block copolymer is preferably at least one block copolymer selected from the group consisting of the represented block copolymers. Among these, an ab type diblock copolymer, a bab type triblock copolymer, or a mixture thereof from the viewpoint of easy handling during processing and physical properties in the case of a composition. Is preferred.

  General formula (1):

（式中、Ｒ¹は水素原子またはメチル基で、互いに同一でも異なっていてもよい、ｐは０または１の整数、ｑは０〜３の整数）で表わされる単位（ｃ）は、アクリル系重合体ブロック（ａ）及びメタアクリル系重合体ブロック（ｂ）の少なくとも一方の重合体ブロックあたりに１個以上含まれていればよく、その数が２個以上の場合には、その単量体が重合されている様式はランダム共重合であってもよくブロック共重合であってもよい。

Wherein R ¹ is a hydrogen atom or a methyl group and may be the same or different from each other, p is an integer of 0 or 1, q is an integer of 0 to 3, and the unit (c) is an acrylic group It is sufficient that at least one polymer block (a) and at least one polymer block of the methacrylic polymer block (b) are contained, and when the number is two or more, the monomer The manner in which is polymerized may be random copolymerization or block copolymerization.

  The manner in which the unit (c) is contained in the block copolymer is expressed by taking a b-b-type triblock copolymer as an example, and (b / c) -ab type, (b / c) -a -(B / c) type, cb-a-b type, c-b-a-b-c type, b- (a / c) -b-type, b-a-c-b type, b- It is represented by a c-a-b type, and any of these may be used. Here, (a / c) means that the unit (c) is contained in the block (a), and (b / c) means that the unit (c) is contained in the block (b). C−a− and a−c− indicate that the unit (c) is bonded to the end of the block (a). Expressions are (a / c), (b / c), c-a-, a-c-, etc., all of which belong to block (a) or block (b).

  The number average molecular weight of the acrylic block copolymer (A) is preferably 30000 to 500000, more preferably 40000 to 400000, and further preferably 50000 to 300000. If the molecular weight is less than 30,000, sufficient mechanical properties as an elastomer may not be exhibited, and if it exceeds 500,000, processing properties may be deteriorated.

  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 (A) is preferably 1 to 2, More preferably, it is 1-1.8. When Mw / Mn exceeds 2, the uniformity of the acrylic block copolymer (A) may be lowered. In the present invention, the number average molecular weight and the weight average molecular weight were measured by gel permeation chromatography using chloroform as a mobile phase and determining the molecular weight in terms of polystyrene.

  The composition ratio between the acrylic polymer block (a) and the methacrylic polymer block (b) constituting the acrylic block copolymer (A) is the required physical properties and molding required during processing of the composition. And the molecular weight required for each of the acrylic polymer block (a) and the methacrylic polymer block (b). When the range of the composition ratio of a preferable acrylic polymer block (a) and a methacrylic polymer block (b) is illustrated, the acrylic polymer block (a) is 40 to 90% by weight, and further 45 to 80% by weight. In particular, 50 to 70% by weight, methacrylic polymer block (b) is preferably 60 to 10% by weight, more preferably 55 to 20% by weight, and particularly preferably 50 to 30% by weight. When the proportion of the acrylic polymer block (a) is less than 40% by weight, the mechanical properties as an elastomer, particularly the elongation at break may be lowered or the flexibility may be lowered. In some cases, rubber elasticity at high temperatures may be reduced.

The relationship between the glass transition temperatures of the acrylic polymer block (a) and the methacrylic polymer block (b) constituting the acrylic block copolymer (A) is the glass transition of the acrylic polymer block (a). When the temperature is Tg _a and that of the methacrylic polymer block (b) is Tg _b , the relationship of the following formula is preferably satisfied.
Tg _a <Tg _b
The glass transition temperature (Tg) of the polymer block (acrylic polymer block (a) and methacrylic polymer block (b)) is roughly in accordance with the following Fox formula, and the monomer block in the polymer block: It can be determined using the weight ratio.
_{1 / Tg = (W 1 /} Tg 1) + (W 2 / Tg 2) + ... + (W m / Tg m)
W ₁ + W ₂ + ... + W _m = 1
(In the formula, Tg represents the glass transition temperature of the polymer block, and Tg ₁ , Tg ₂ ,..., Tg _m represent the glass transition temperatures of the polymerized monomers (homopolymers), and W ₁ , W ₂ ,..., W _m represent the weight ratio of the polymerized monomers.

  The glass transition temperature of each polymerized monomer in the Fox equation is described, for example, in Polymer Handbook Third Edition (Wiley-Interscience, 1989), and is described herein. So this value is used.

  As a specific example of the acrylic block copolymer (A), for example, a mixture of the acrylic block copolymer produced in Production Example 1-2 and the polyorganosiloxane graft polymer produced in Production Example 5 was used. Example 3 using a mixture of the acrylic block copolymer obtained in Example 1, the acrylic block copolymer obtained in Production Example 3-2 and the polyorganosiloxane graft polymer produced in Production Example 5 And acrylic block copolymers obtained in (1) above.

<Acrylic polymer block (a)>
The acrylic polymer block (a) is the acrylic polymer block (a) in the acrylic block copolymer (A), and the relationship between the glass transition temperature and the methacrylic polymer block (b). , satisfies the Tg _a <Tg _b. Single unit having a functional group that contains 50 to 100% by weight, preferably 60 to 100% by weight of a unit containing an acrylic ester in the entire acrylic polymer block (a), and serves as a precursor of the unit (c). 0 to 50% by weight, preferably 0 to 40% by weight, and other vinyl monomers copolymerizable therewith 0 to 50% by weight, preferably 0 to 25% by weight. preferable. If the unit containing the proportion of the acrylate ester is less than 50% by weight, the physical properties, particularly the elongation of the tensile properties, which are characteristics when using the acrylate ester may be reduced.

  The molecular weight required for the acrylic polymer block (a) may be determined from the elastic modulus and rubber elasticity required for the acrylic polymer block (a), the time required for the polymerization, and the like.

When the number average molecular weight required for the acrylic polymer block (a) is exemplified by M _A , the range is preferably M _A > 3000, more preferably M _A > 5000, still more preferably M _A > 10000, especially Preferably M _A > 20000, most preferably M _A > 40000. However, since the polymerization time tends to be longer when the number average molecular weight is large, the polymerization time may be set according to the required productivity, but is preferably 500,000 or less, more preferably 300,000 or less.

  Examples of the acrylic acid ester constituting the acrylic polymer block (a) include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, and acrylic acid. Acrylic aliphatic hydrocarbons such as n-hexyl, n-heptyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate, etc. -18 alkyl) esters; acrylic acid cycloaliphatic hydrocarbon esters such as cyclohexyl acrylate and isobornyl acrylate; aromatic acrylic hydrocarbon esters such as phenyl acrylate and toluyl acrylate; aralkyl acrylates such as benzyl acrylate Esters of esters, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, etc., and functional group-containing alcohols having etheric oxygen; trifluoromethyl methyl acrylate, 2-trifluoromethyl ethyl acrylate, acrylic 2-perfluoroethylethyl acid, 2-perfluoroethyl-2-perfluorobutylethyl acrylate, 2-perfluoroethyl acrylate, perfluoromethyl acrylate, diperfluoromethyl methyl acrylate, 2-peracrylate Fluorinated alkyl esters such as fluoromethyl-2-perfluoroethylmethyl, 2-perfluorohexylethyl acrylate, 2-perfluorodecylethyl acrylate, 2-perfluorohexadecylethyl acrylate, etc. That. These may be used alone or in combination of two or more. Among these acrylate esters, n-butyl acrylate is preferable from the viewpoint of low-temperature characteristics, compression set, cost, and availability. N-ethyl acrylate is preferred when oil resistance and mechanical properties are required. When low temperature characteristics, mechanical characteristics, and compression set are required, 2-ethylhexyl acrylate is preferred. From the standpoints of mechanical properties, oil resistance and low temperature properties, the entire acrylic polymer block (a) is 10 to 90% by weight of 2-methoxyethyl acrylate, 10 to 90% by weight of n-butyl acrylate, n-acrylate. Preferred is a mixture of 0 to 80% by weight of ethyl, and further preferred is a mixture of 15 to 85% by weight of 2-methoxyethyl acrylate, 15 to 85% by weight of n-butyl acrylate, and 0 to 70% by weight of n-ethyl acrylate. .

  Examples of vinyl monomers copolymerizable with the acrylate ester constituting the acrylic polymer block (a) include methacrylic acid esters, aromatic alkenyl compounds, vinyl cyanide compounds, conjugated diene compounds, and halongen. Examples thereof include an unsaturated compound, an unsaturated dicarboxylic acid compound, a vinyl ester compound, and a maleimide compound.

  Examples of the methacrylate ester include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-pentyl methacrylate, and n-methacrylate. Methacrylic acid aliphatic carbonization such as hexyl, n-heptyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, stearyl methacrylate Hydrogen (for example, alkyl having 1 to 18 carbon atoms); methacrylic acid alicyclic hydrocarbon ester such as cyclohexyl methacrylate, isobornyl methacrylate; methacrylic acid aralkyl ester such as benzyl methacrylate; And aromatic acrylic ester of methacrylic acid such as toluyl methacrylate; ester of methacrylic acid such as 2-methoxyethyl methacrylate and 3-methoxybutyl methacrylate and functional group-containing alcohol having etheric oxygen Trifluoromethyl methyl methacrylate, 2-trifluoromethyl ethyl methacrylate, 2-perfluoroethyl ethyl methacrylate, 2-perfluoroethyl-2-perfluorobutyl ethyl methacrylate, 2-methacrylic acid 2- Perfluoroethyl, perfluoromethyl methacrylate, diperfluoromethyl methyl methacrylate, 2-perfluoromethyl-2-perfluoroethyl methyl methacrylate, 2-perfluorohexyl ethyl methacrylate, methacrylic acid 2 -Perfect Rodeshiruechiru, such as methacrylic acid fluorinated alkyl esters such as meta 2-perfluoro-hexadecyl acrylate and the like.

  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 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, and vinyl cinnamate.

  Examples of the maleimide compound include maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide and the like.

  The copolymerizable monomers may be used alone or in combination of two or more. The vinyl monomer is required when the glass transition temperature, elastic modulus and polarity required for the acrylic polymer block (a) are used as the composition. Preferred ones can be selected depending on physical properties, compatibility with core / shell particles, and the like. For example, acrylonitrile can be copolymerized for the purpose of improving oil resistance.

  The glass transition temperature of the acrylic polymer block (a) is preferably 50 ° C. or lower, more preferably 0 ° C. or lower. When the glass transition temperature is higher than 50 ° C., the rubber elasticity of the block copolymer (A) may be lowered.

  The glass transition temperature (Tg) of the acrylic polymer block (a) can be determined by adjusting the weight ratio of the monomer constituting the polymer block according to the Fox formula.

  Here, the glass transition temperature is the value described in the aforementioned Polymer Handbook 3rd edition as the glass transition temperature of the homopolymer of each monomer constituting the polymer block, and the polymerization ratio of each monomer is used. , Fox's equation.

  Specific examples of the acrylic polymer block (a) include, for example, an acrylic polymer contained in the acrylic block copolymer obtained in Example 1 using the acrylic block copolymer produced in Production Example 1-2. Examples of the polymer block include an acrylic polymer block contained in the acrylic block copolymer obtained in Example 3 using the acrylic block copolymer produced in Production Example 3-2.

<Methacrylic polymer block (b)>
The methacrylic polymer block (b) is a methacrylic polymer block (b) in the acrylic block copolymer (A), and has a glass transition temperature with the acrylic polymer block (a). The relationship Tg _a <Tg _b is satisfied. From the viewpoint of easily obtaining a block copolymer (A) having desired physical properties, cost, and availability, the unit containing a methacrylic acid ester in the whole methacrylic polymer block (b) is 0 to 0. 100% by weight, preferably 0 to 85% by weight, 0 to 100% by weight, preferably 15 to 100% by weight, of monomers having a functional group as a precursor of the unit (c), and these It is preferable to contain 0 to 50% by weight, preferably 0 to 25% by weight, of other vinyl monomers copolymerizable with the polymer.

  The molecular weight required for the methacrylic polymer block (b) may be determined from the cohesive force required for the methacrylic polymer block (b) and the time required for the polymerization.

The cohesive force is said to depend on the interaction between molecules (in other words, polarity) and the degree of entanglement, and as the number average molecular weight increases, the entanglement point increases and the cohesive force increases. That is, the number-average molecular weight required for the methacrylic polymer block (b) and M _B, the the entanglement molecular weight of the polymer constituting the methacrylic polymer block (b) of M _B as Mc _B Exemplifying the range, when cohesive force is required, preferably M _B > Mc _B. As a further example, when a further cohesive force is required, preferably M _B > 2 × Mc _B. Conversely, when it is desired to achieve both a certain cohesive force and creep property, Mc _B <M _B <2 × Mc _B is preferred. The molecular weight between the entanglement points may be referred to Wu et al. (Polym. Eng. And Sci., 1990, Vol. 30, p. 753). For example, the range of the number average molecular weight of the methacrylic polymer block (b) when the cohesive force is required, assuming that the methacrylic polymer block (b) is entirely composed of methyl methacrylate. Then, it is preferable that it is 9200 or more. However, when the unit (c) is contained in the methacrylic polymer block (b), the cohesive force by the unit (c) is imparted, so the number average molecular weight can be set lower than this. When the number average molecular weight is increased, the polymerization time tends to be longer, so it may be set according to the required productivity, but is preferably 200000 or less, more preferably 100000 or less.

  Examples of the methacrylic acid ester constituting the methacrylic polymer block (b) include, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, meta N-pentyl acrylate, n-hexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, meta Methacrylic acid aliphatic hydrocarbon (e.g., alkyl having 1 to 18 carbon atoms) ester such as stearyl acrylate; Methacrylic acid alicyclic hydrocarbon ester such as cyclohexyl methacrylate and isobornyl methacrylate; Benzyl methacrylate, etc. Methacrylic Aralkyl esters; Methacrylic acid aromatic hydrocarbon esters such as phenyl methacrylate and toluyl methacrylate; Functionalities having methacrylic acid and etheric oxygen such as 2-methoxyethyl methacrylate and 3-methoxybutyl methacrylate Esters with group-containing alcohols: trifluoromethyl methyl methacrylate, 2-trifluoromethyl ethyl methacrylate, 2-perfluoroethyl ethyl methacrylate, 2-perfluoroethyl-2-perfluorobutyl ethyl methacrylate 2-perfluoroethyl methacrylate, perfluoromethyl methacrylate, diperfluoromethyl methyl methacrylate, 2-perfluoromethyl-2-perfluoroethyl methyl methacrylate, 2-perfluorohe methacrylate Shiruechiru, meta 2- perfluorodecyl acrylate, etc. methacrylic acid fluorinated alkyl esters such as meta 2-perfluoro-hexadecyl acrylate and the like. These may be used alone or in combination of two or more. Among these, methyl methacrylate is preferable from the viewpoint of compatibility when combined with a thermoplastic resin, cost, and availability.

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

  As said acrylic ester, the monomer similar to the structural monomer illustrated by description of the said acrylic polymer block (a) is mentioned.

  Examples of the aromatic alkenyl compound, vinyl cyanide compound, conjugated diene compound, halogen-containing unsaturated compound, unsaturated dicarboxylic acid compound, vinyl ester compound, and maleimide compound are exemplified in the description of the acrylic polymer block (a). Examples thereof include the same monomers as the constituent monomers.

  As the copolymerizable vinyl monomer, at least one of the above constituent monomers is used. From the viewpoint of compatibility when the block copolymer (A) is combined with the core-shell particles (B), the above vinyl-based monomer can be selected. In addition, methyl methacrylate polymer is almost quantitatively depolymerized by thermal decomposition. In order to suppress this, acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-methoxy acrylate are used. Ethyl or a mixture thereof or styrene can be copolymerized. Furthermore, acrylonitrile can be copolymerized for the purpose of improving oil resistance.

  The glass transition temperature of the methacrylic polymer block (b) is preferably 100 ° C. or higher, more preferably 110 ° C. or higher. When the glass transition temperature is less than 100 ° C., rubber elasticity at a high temperature may be lowered from a desired value.

  The setting of the glass transition temperature (Tg) of the methacrylic polymer block (b) can be adjusted by changing the ratio of the monomers constituting the polymer block according to the Fox equation. Here, the glass transition temperature is the value described in the aforementioned Polymer Handbook 3rd edition as the glass transition temperature of the homopolymer of each monomer constituting the polymer block, and the polymerization ratio of each monomer is used. , And Fox according to the formula.

  As a specific example of the methacrylic polymer block (b), for example, the methacrylic polymer contained in the acrylic block copolymer obtained in Example 1 using the acrylic block copolymer produced in Production Example 1-2. Examples thereof include an acrylic polymer block and a methacrylic polymer block contained in the acrylic block copolymer obtained in Example 3 using the acrylic block copolymer produced in Production Example 3-2.

<Unit (c)>
Since the unit (c) has reactivity with a compound having an amino group, a hydroxyl group, an epoxy group, etc., the reaction point, polyorganosiloxane-based graft polymer, thermoplastic resin and / or heat when the polymer is modified. It has characteristics that can be used as a compatibility improvement site when blended with a plastic elastomer, a crosslinking point when imparting further rubber elasticity to the soft segment, and the like. Moreover, since the unit (c) has a high glass transition temperature (Tg), when introduced into the hard segment, the heat resistance of the acrylic block copolymer (A) can be improved. The glass transition temperature of the polymer containing the unit (c) is, for example, as high as 159 ° C. in the case of polymethacrylic anhydride, and by introducing the unit (c), the acrylic block copolymer (A) Heat resistance can be improved, which is preferable.

  The unit (c) is represented by the general formula (1):

（式中、Ｒ¹は水素原子またはメチル基で、互いに同一でも異なっていてもよい、ｐは０または１の整数、ｑは０〜３の整数）で表わされる酸無水物基を含有する単位（ｃ１）とカルボキシル基を含有する単位（ｃ２）からなる。

(Wherein R ¹ is a hydrogen atom or a methyl group, and may be the same or different, p is an integer of 0 or 1, q is an integer of 0 to 3) It consists of (c1) and a unit (c2) containing a carboxyl group.

  Q in the general formula (1) is an integer of 0 to 3, preferably 0 or 1, and more preferably 1. When q exceeds 3, polymerization may become complicated or cyclization to an acid anhydride group may be difficult.

In general formula (1), p is an integer of 0 or 1. When q is 0, p is also 0. When q is 1 to 3, p is preferably 1. The unit (c) is contained in the acrylic polymer block (a) and / or the methacrylic polymer block (b). The introduction site of the unit (c) includes the reaction point of the block copolymer (A), the cohesive force and glass transition temperature of the block constituting the block copolymer (A), and the required block copolymer. It can be used according to the physical properties of (A). From the viewpoint of improving the heat resistance and heat decomposability of the block copolymer (A), the unit (c) may be introduced into the methacrylic polymer block (b), and the block copolymer (A) From the viewpoint of imparting rubber elasticity to the unit, the unit (c) may be introduced into the acrylic polymer block (a) as a crosslinkable reaction site (crosslinking point). From the viewpoint of control of the reaction point, heat resistance, rubber elasticity, etc., it is preferable to have the unit (c) in either the acrylic polymer block (a) or the methacrylic polymer block (b). When the unit (c) is contained in the methacrylic polymer block (b), R ^{1 in the} general formula (1) is preferably a methyl group, and is contained in the acrylic polymer block (a). In this case, R ¹ in the general formula (1) is preferably a hydrogen atom. When R ¹ is a hydrogen atom when the unit (c) is contained in the methacrylic polymer block (b), or when R ¹ is a methyl group when contained in the acrylic polymer block (a) The block copolymer (A) has a complicated polymerization operation, and the difference in glass transition temperature between the acrylic polymer block (a) and the methacrylic polymer block (b) is reduced. The rubber elasticity of (A) tends to decrease.

  The preferable range of the content of the unit (c) is the cohesive force, reactivity, the structure and composition of the acrylic block copolymer (A), and the block constituting the acrylic block copolymer (A). Depending on the number and the glass transition temperature and the site and mode of the acid anhydride group-containing unit (c1) and carboxyl group-containing unit (c2). Moreover, the preferable range of the said content changes also with the reactivity with a polyorganosiloxane type graft polymer (B), and a reaction point. 0.1-99.9 weight% is preferable in the whole acrylic block copolymer (A), 0.5-80 weight% is more preferable, 0.5-60 weight% is still more preferable. When the content of the unit (c) is less than 0.1% by weight, the reactivity of the acrylic block copolymer (A) and the compatibility with the polyorganosiloxane graft polymer may be insufficient. Further, when the unit (c) having a high Tg is introduced into the methacrylic polymer block (b), which is a hard segment, for the purpose of improving the heat resistance of the methacrylic polymer block (b), 0.1% by weight. If it is less, the improvement in heat resistance is insufficient and the expression of rubber elasticity at high temperatures may be reduced. On the other hand, if it exceeds 99.9% by weight, the cohesive force becomes too strong and the workability may be lowered.

  The acrylic block copolymer (A) may contain a unit (c2) containing a carboxyl group from the viewpoint of further improving heat resistance and cohesion. The unit (c2) containing a carboxyl group has a strong cohesive force, and the polymer of a monomer containing a carboxyl group has a high glass transition temperature (Tg). For example, the glass transition temperature (Tg) of polymethacrylic acid is As high as 228 ° C., the heat resistance of the block copolymer is improved. A functional group such as a hydroxyl group also has hydrogen bonding ability. However, compared with the monomer having the functional group, Tg is low and the effect of improving heat resistance is small. Therefore, if it contains the unit (c2) containing a carboxyl group, the heat resistance and cohesion of the block copolymer (A) can be further improved, which is preferable. It is preferable to contain 0.1 to 50% by weight of the carboxyl group-containing unit (c2) in the entire acrylic block copolymer because the heat resistance becomes high.

<Method for producing acrylic block copolymer (A)>
Although it does not specifically limit as a manufacturing method of an acryl-type block copolymer (A), It is preferable to use controlled polymerization. Examples of 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, as the organic halide or sulfonyl halide compound used as an initiator, a monofunctional, difunctional, or polyfunctional compound can be used. These can be used properly according to the purpose. When producing a diblock copolymer, a monofunctional compound is preferable. In the case of producing an aba type triblock copolymer or a babb 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. Further, a divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ), and a divalent nickel bistributylphosphine A complex (NiBr ₂ (PBu ₃ ) ₂ ) can also be used as a catalyst. The amount of the catalyst, ligand and activator used is not particularly limited, 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, 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.

  Furthermore, a method for introducing a unit (c) composed of a unit (c1) containing an acid anhydride group and / or a unit (c2) containing a carboxyl group into the acrylic block copolymer (A) is shown below. .

  The method for introducing the acid anhydride group-containing unit (c1) is not particularly limited, but a unit containing a group that serves as a precursor of the acid anhydride group is introduced into the block copolymer, and then the ring. It is preferable to make it. Details of the method will be described below.

  General formula (2):

（式中、Ｒ²は水素原子またはメチル基、Ｒ³は水素原子、メチル基またはフェニル基を表わし、少なくとも１個のメチル基を含むこと以外は互いに同一でも異なっていてもよい）で表わされる単位を少なくとも１個有するブロック共重合体、即ちアクリル系重合体ブロック（ａ）を構成するアクリル酸エステルとして下記に例示した単量体を用いたブロック共重合体組成物（Ａ）を、好ましくは１８０〜３００℃の温度で、溶融混練して環化させることにより導入することができる。１８０℃より低いと、酸無水物基の生成が不充分となる場合があり、３００℃より高くなると、アクリル系重合体ブロック（ａ）を構成するアクリル酸エステルとして下記に例示した単量体を用いたブロック共重合体組成物（Ａ）自体が分解する場合がある。

(Wherein R ² represents a hydrogen atom or a methyl group, R ³ represents a hydrogen atom, a methyl group or a phenyl group, and may be the same as or different from each other except that it contains at least one methyl group). A block copolymer composition (A) using the monomer exemplified below as a block copolymer having at least one unit, that is, an acrylic ester constituting the acrylic polymer block (a), preferably It can introduce | transduce by melt-kneading and making it cyclize at the temperature of 180-300 degreeC. When the temperature is lower than 180 ° C., the acid anhydride group may be insufficiently formed. When the temperature is higher than 300 ° C., the monomers exemplified below as the acrylic acid ester constituting the acrylic polymer block (a) are used. The used block copolymer composition (A) itself may decompose.

  The unit represented by the general formula (2) is eliminated and cyclized with an adjacent ester unit at a high temperature to generate, for example, a 6-membered cyclic acid anhydride group (for example, Hatada et al., J.M. Chemistry (JMS PURE APPL. CHEM.), A30 (9 & 10), PP.645-667 (1993)). According to these, in general, a polymer having a bulky ester unit and having β-hydrogen is decomposed at a high temperature to generate a carboxyl group, and then a cyclization occurs, for example, a 6-membered ring or the like. An acid anhydride group is formed. By utilizing these methods, an acid anhydride group can be easily introduced into the block copolymer (A). Specific examples of the monomer constituting the unit represented by the general formula (2) include t-butyl acrylate, isopropyl acrylate, α, α-dimethylbenzyl acrylate, α-methylbenzyl acrylate, meta Examples include, but are not limited to, t-butyl acrylate, isopropyl methacrylate, α, α-dimethylbenzyl methacrylate, and α-methylbenzyl methacrylate. Among these, t-butyl acrylate and t-butyl methacrylate are preferable from the viewpoint of availability, ease of polymerization, and ease of formation of acid anhydride groups.

  Various methods can be applied to the introduction of the carboxyl group-containing unit (c2), and there is no particular limitation. However, the process of introducing the acid anhydride group-containing unit (c1) into the block copolymer (A) is not limited. It is preferable to generate a unit (c2) containing a carboxyl group by appropriately adjusting the heating temperature and time according to the type and content of the unit represented by general formula (2). This is because it is easy to control the reaction point of the block copolymer (A) and to introduce the carboxyl group-containing unit (c2) into the block copolymer (A).

  Therefore, from the viewpoint of the introduction method, the carboxyl group-containing unit (c2) is preferably contained in the same block as the block containing the acid anhydride group-containing unit (c1). From the point of cohesive strength, it is more preferable that it is contained in the methacrylic polymer block (b). That is, by introducing a unit (c2) having a carboxyl group with high Tg and cohesive force into the methacrylic polymer block (b) which is a hard segment, it becomes possible to express rubber elasticity more at high temperatures. It is. Moreover, when the unit (c2) which has a carboxyl group is contained in an acrylic polymer block (a), it is preferable from a compatible point with a polyorganosiloxane graft polymer.

  The content of the carboxyl group-containing unit (c2) can be 1 or 2 or more per polymer block. When the number is 2 or more, the unit (c2) is The mode of polymerization may be random copolymerization or block copolymerization.

  The preferred range of the content of the carboxyl group-containing unit (c2) is the cohesive strength of the carboxyl group-containing unit (c2), the structure and composition of the block copolymer, the number of blocks constituting the block copolymer, In addition, it varies depending on the site and mode of the unit (c2) containing a carboxyl group.

  The content of the carboxyl group-containing unit (c2) is preferably 0.1 to 50% by weight, more preferably 0.5 to 50% by weight, and 1 to 40% by weight in the entire block copolymer (A). Further preferred. If the amount exceeds 50% by weight, the carboxyl group-containing unit (c2) tends to cyclize with the adjacent ester unit at high temperature, so that the physical properties after molding change, and stable physical properties are obtained. It may be difficult to make a product. In addition, when producing | generating the unit (c2) containing a carboxyl group in the introduction process of a unit (c), 0.1 weight% or more is normally produced | generated. When the production amount is less than 0.1% by weight, even if the unit (c2) containing a carboxyl group is introduced into the hard segment, the heat resistance and cohesion may not be improved sufficiently.

<Resin composition>
A composition in which the block copolymer (A) and the polyorganosiloxane graft polymer (B) are combined, and a lubricant (C), an inorganic filler (D), and / or a thermoplastic resin (E) are further combined. You may manufacture a product as an acrylic polymer composition.

  An acrylic block copolymer (A), a polyorganosiloxane graft polymer (B), a lubricant (C), an inorganic filler (D) and / or a thermoplastic resin (E) are blended to add acrylic. Not only the low temperature characteristics of the system block copolymer (A) but also physical properties such as tensile elongation, tensile elastic modulus, hardness, and tear strength can be improved.

  Further, by adding a lubricant (C), an inorganic filler (D) and / or a thermoplastic resin (E) to the block copolymer (A), the friction of the resin surface of the acrylic block copolymer (A) is achieved. It is also possible to improve the mechanical properties such as the method of reducing the property, the elastic modulus and the like, and further improve the workability.

  The acrylic block copolymer (A) and the polyorganosiloxane graft polymer (B) may be appropriately determined according to the characteristics of each product. For example, the low temperature characteristics of the acrylic block copolymer (A) are improved. In the case of seal products such as boots for constant velocity joints for automobiles, acrylic block copolymer (A) 50 to 90% by weight, polyorganosiloxane graft polymer (B) 50 in the entire composition It is preferably composed of 10 to 10% by weight. More preferably, the composition consists of 60 to 75% by weight and 40 to 25% by weight of the polyorganosiloxane graft polymer (B). When the acrylic block copolymer (A) is less than 50% by weight, the mechanical properties tend to deteriorate, and when the polyorganosiloxane graft polymer (B) is less than 10% by weight, the acrylic block copolymer The improvement of the low temperature characteristics of (A) may be insufficient.

  When the lubricant (C), the inorganic filler (D) and / or the thermoplastic resin (E) are added to the block copolymer (A) and the polyorganosiloxane graft polymer (B), an acrylic block copolymer ( A) When 100 parts by weight, the polyorganosiloxane-based graft polymer (B) is 15 to 100 parts by weight, the lubricant (C) is 0.1 to 10 parts by weight, and the inorganic filler (D) is 0.1 to 100 parts. It is preferable to blend 0.1 to 100 parts by weight of the thermoplastic resin (E) and / or 0.5 to 8 parts by weight of the lubricant (C) and / or 0.5 to 80 inorganic filler (D). More preferably, 0.1 part by weight and / or 0.1 part by weight of the thermoplastic resin (E) is blended. When the amount of the lubricant (C) is less than 0.1 parts by weight, the frictional property of the resin surface tends to increase, and when it is more than 10 parts by weight, bleeding out tends to occur. If the inorganic filler (D) is less than 0.1 parts by weight, the mechanical properties such as the elastic modulus may be insufficient. If more than 100 parts by weight, the elongation at the time of tension decreases or the compression set is reduced. May decrease.

  If the thermoplastic resin (E) is less than 0.1 parts by weight, mechanical properties such as elastic modulus at high temperatures may be insufficient. If it is more than 100 parts by weight, the elongation during tension may be reduced, Compression set may be reduced.

  These resin compositions are prepared by adding a block copolymer (A), a polyorganosiloxane-based graft polymer (B) to a lubricant (C), an inorganic filler (D) and / or a thermoplastic resin before actual molding. (E) may be weighed and put into a molding machine, but from the viewpoints of handling, uniformity of mixing, etc., it is preferable to pelletize before molding. Below, the pelletization is demonstrated.

  The method for pelletizing the resin composition of the present invention is not particularly limited, but it is possible to use a known apparatus such as a Banbury mixer, roll mill, kneader, single-screw or multi-screw extruder while heating at an appropriate temperature. It can be shaped into pellets by kneading in an automatic manner.

  The kneading temperature is the melting of the block copolymer (A) and the polyorganosiloxane graft polymer (B) to be used with the lubricant (C), the inorganic filler (D) and / or the thermoplastic resin (E). What is necessary is just to adjust according to temperature etc., for example, it can pelletize by melt-kneading at 20-300 degreeC.

  The composition of the present invention includes stabilizers (anti-aging agents, light stabilizers, ultraviolet absorbers, etc.), flexibility imparting agents, flame retardants, mold release agents, antistatic agents, antibacterial antifungal agents, depending on the required properties. An agent or the like may be added. These additives may be appropriately selected and used according to the required physical properties, workability, and the like.

  Examples of stabilizers (anti-aging agent, light stabilizer, ultraviolet absorber, etc.) include, but are not limited to, the following compounds.

  Anti-aging agents include phenyl α-naphthylamine (PAN), octyl diphenylamine, N, N′-diphenyl-p-phenylenediamine (DPPD), N, N′-di-β-naphthyl-p-phenylenediamine ( DNPD), N- (1,3-dimethyl-butyl) -N′-phenyl-p-phenylenediamine, N-phenyl-N′-isopropyl-p-phenylenediamine (IPPN), N, N′-diallyl-p -Phenylenediamine, phenothiazine derivative, diallyl-p-phenylenediamine mixture, alkylated phenylenediamine, 4,4'-α, α-dimethylbenzyldiphenylamine, p, p-toluenesulfonylaminodiphenylamine, N-phenyl-N '-( 3-methacryloyloxy-2-hydropropyl) -p-pheny Diamine, diallylphenylenediamine mixture, diallyl-p-phenylenediamine mixture, N- (1-methylheptyl) -phenyl-p-phenylenediamine, amine-based antioxidants such as diphenylamine derivatives, 2-mercaptobenzimidazole (MBI) ) Imidazole anti-aging agents, phenolic anti-aging agents such as 2,6-di-t-butyl-4-methylphenol, phosphate anti-aging agents such as nickel diethyl-dithiocarbamate, triphenyl phosphite Secondary anti-aging agents such as

  Examples of light stabilizers and ultraviolet absorbers include 4-t-butylphenyl salicylate, 2,4-dihydroxybenzophenone, 2,2′dihydroxy-4-methoxybenzophenone, ethyl-2-cyano-3,3′-diphenyl. Acrylate, 2-ethylhexyl-2-diano-3,3′-diphenyl acrylate, 2-hydroxy-5-chlorobenzophenone, 2-hydroxy-4-methoxybenzophenone-2-hydroxy-4-octoxybenzophenone, monoglycol salicy Rate, oxalic acid amide, 2,2 ′, 4,4′-tetrahydroxybenzophenone and the like. These stabilizers may be used alone or in combination of two or more.

  Examples of the flexibility-imparting agent include plasticizers, softeners, oligomers, oils (animal oil, vegetable oil, etc.) usually used in thermoplastic resins and rubbers, petroleum fractions (kerosene, light oil, heavy oil, naphtha, etc.). However, it is preferable to use those having excellent affinity with the block copolymer (A) and the core / shell particles (B). Among these, low-volatility plasticizers with low heat loss are adipic acid derivatives, phthalic acid derivatives, glutaric acid derivatives, trimellitic acid derivatives, pyromellitic acid derivatives, polyester plasticizers, glycerin derivatives, epoxy derivatives polyester polymerized plastics. An agent, a polyether polymerization type plasticizer and the like are preferably used.

  Examples of the softener include process oils such as petroleum process oils such as paraffinic oils, naphthenic process oils, and aromatic process oils.

  Examples of the plasticizer include dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, di- (2-ethylhexyl) phthalate, diheptyl phthalate, diisodecyl phthalate, di-n-octyl phthalate, and phthalic acid. Phthalic acid derivatives such as diisononyl, ditridecyl phthalate, octyl decyl phthalate, butyl benzyl phthalate, dicyclohexyl phthalate; isophthalic acid derivatives such as dimethyl isophthalate; tetrahydrophthal such as di- (2-ethylhexyl) tetrahydrophthalic acid Acid derivatives: dimethyl adipate, dibutyl adipate, di-n-hexyl adipate, di- (2-ethylhexyl) adipate, dioctyl adipate, isononyl adipate, diisodecyl adipate, dibutyl diglycol adipate, etc. Adipic acid derivatives; azelaic acid derivatives such as di-2-ethylhexyl azelate; sebacic acid derivatives such as dibutyl sebacate; dodecanedioic acid derivatives; maleic acid derivatives such as dibutyl maleate and di-2-ethylhexyl maleate; fumaric acid Fumaric acid derivatives such as dibutyl; p-oxybenzoic acid derivatives such as 2-ethylhexyl p-oxybenzoate; trimellitic acid derivatives such as tris-2-ethylhexyl trimellitic acid; pyromellitic acid derivatives; citric acid derivatives such as acetyltributyl citrate Itaconic acid derivative; oleic acid derivative; ricinoleic acid derivative; stearic acid derivative; other fatty acid derivative; sulfonic acid derivative; phosphoric acid derivative; glutaric acid derivative; dibasic acid such as adipic acid, azelaic acid, phthalic acid and glycol Polyester plasticizers that are polymers with monohydric alcohol, etc., glycol derivatives, glycerin derivatives, paraffin derivatives such as chlorinated paraffins, epoxy derivatives polyester polymerized plasticizers, polyether polymerized plasticizers, ethylene carbonate, propylene Examples thereof include carbonate derivatives such as carbonate, benzenesulfonic acid derivatives such as N-butylbenzeneamide, and the like, but are not limited to these, such as those widely marketed as plasticizers for rubber or thermoplastic resins. Various plasticizers can be used.

  Commercially available plasticizers include Thiocol TP (manufactured by Morton), Adekasizer O-130P, C-79, UL-100, P-200, RS-735 (Asahi Denka Kogyo Co., Ltd.), Sunsosizer N-400 (manufactured by Shin Nippon Rika Co., Ltd.), BM-4 (manufactured by Daihachi Chemical Industry Co., Ltd.), EHPB (manufactured by Ueno Pharmaceutical Co., Ltd.), UP-1000 (manufactured by Toagosei Co., Ltd.), etc. Can be given.

  Examples of the oil include vegetable oils such as castor oil, cottonseed oil, sesame oil, rapeseed oil, soybean oil, palm oil, palm oil, peanut oil, pine oil, tall oil, sesame oil, and camellia oil.

  Examples of other flexibility imparting agents include polybutene oil, spindle oil, machine oil, tricresyl phosphate, and the like.

  Examples of the agent include process oils such as petroleum process oils such as paraffinic oils, naphthenic process oils, and aromatic process oils.

  Examples of the flame retardant include, but are not limited to, triphenyl phosphate, tricresyl phosphate, decabromobiphenyl, decabromobiphenyl ether, and antimony trioxide. These flame retardants may be used alone or in combination of two or more.

  In order to improve the compatibility between the block copolymer (A) and the polyorganosiloxane graft polymer (B), various graft polymers and block polymers may be added as a compatibilizing agent.

  Examples of the compatibilizer include the Kraton series (manufactured by Shell Japan Co., Ltd.), the Tuftec series (manufactured by Asahi Kasei Kogyo Co., Ltd.), Dynalon (manufactured by Nippon Synthetic Rubber Co., Ltd.), and Epofriend (manufactured by Daicel Chemical Industries, Ltd.). ), Septon (manufactured by Kuraray Co., Ltd.), Nofaloy (manufactured by Nippon Oil & Fats Co., Ltd.), Lexpearl (manufactured by Nippon Polyolefin Co., Ltd.), Bond First (manufactured by Sumitomo Chemical Co., Ltd.), Bondine (Sumitomo Chemical Industries ( Co., Ltd.), Admer (Mitsui Chemicals Co., Ltd.), Umex (Sanyo Kasei Kogyo Co., Ltd.), VMX (Mitsubishi Chemical Co., Ltd.), Modiper (Nippon Yushi Co., Ltd.), Staphyroid (Takeda) Examples include commercial products such as Yakuhin Kogyo Co., Ltd. and Reeta (Toagosei Co., Ltd.). These can be appropriately selected and used in accordance with the combination of the polyorganosiloxane-based graft polymer (B) used to supplement the physical properties of the block copolymer (A).

<Polyorganosiloxane-based graft polymer (B)>
The polyorganosiloxane graft polymer (B) that can be used in the present invention is such that it is crosslinked by adding a graft crossing agent or the like.

  The polyorganosiloxane graft polymer (B) in the present invention will be described. The polyorganosiloxane-based graft polymer is blended and dispersed in an acrylic elastomer that is a matrix resin of the present composition. Even when the temperature is not higher than the embrittlement temperature of the acrylic elastomer alone as the matrix resin, no breakage due to embrittlement occurs, and good low temperature characteristics can be expressed. In addition, low temperature properties such as elastic recovery characteristics at low temperatures (TR characteristics) and low temperature torsion characteristics (Geman torsion characteristics) can be improved, and low temperature elastic recovery temperature and tensile permanent strain characteristics at low temperatures can be achieved. It is possible to improve. Furthermore, various properties that can be inherently exhibited by polyorganosiloxane (molding property such as mold releasability, slidability, flame retardancy, etc.) can be imparted.

  The composition of the polyorganosiloxane-based graft polymer (B) is not particularly limited, but the monomer (d2) is polymerized in an amount of 0 to 10% by weight in the presence of 40 to 95% by weight of the polyorganosiloxane (d1). Furthermore, a copolymer obtained by polymerizing 5 to 60% by weight of the vinyl monomer (d3) (100% by weight in total of (d1), (d2) and (d3)) is preferable. The monomer (d2) is composed of 50 to 100% by weight of a polyfunctional monomer (x) containing two or more polymerizable unsaturated bonds in the molecule, and other copolymerizable vinyl monomers ( y) A monomer composed of 0 to 50% by weight.

  Furthermore, it is preferable that the content of the graft component combining the monomer (d2) and the vinyl monomer (d3) is 5 to 40% by weight and the polyorganosiloxane content is 95 to 60% by weight.

  The polyorganosiloxane (d1) used in the present invention is not particularly limited in its production method, and can be obtained by ordinary emulsion polymerization. However, seed polymerization is also used because of the advantage that the particle size distribution in the latex state can be narrowed. Can do. The seed polymer used for seed polymerization is not limited to rubber components such as butyl acrylate rubber, butadiene rubber, butadiene-styrene and butadiene-acrylonitrile rubber, but butyl acrylate-styrene copolymer, styrene-acrylonitrile copolymer, etc. There is no problem with the polymer. A chain transfer agent may be used for the polymerization of the seed polymer. In the polymerization of the polyorganosiloxane (d1), a graft crossing agent and, if necessary, a crosslinking agent can be used.

The organosiloxane specifically used is represented by the general formula R _m SiO _{(4-m) / 2} (wherein R is a substituted or unsubstituted monovalent hydrocarbon group, and m is an integer of 0 to 3). And has a linear, branched or cyclic structure, and an organosiloxane having a cyclic structure is preferred from the viewpoint of availability and cost. Examples of the substituted or unsubstituted monovalent hydrocarbon group of the organosiloxane include a methyl group, an ethyl group, a propyl group, a phenyl group, and a substituted hydrocarbon group obtained by substituting them with a cyano group. it can. Specific examples of the organosiloxane include hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), and trimethyltriphenylcyclotrisiloxane. In addition to cyclic compounds such as these, linear or branched organosiloxanes can be mentioned. At least one of these organosiloxanes can be used.

  Examples of the graft crossing agent that can be used in the present invention include p-vinylphenylmethyldimethoxysilane, p-vinylphenylethyldimethoxysilane, 2- (p-vinylphenyl) ethylmethyldimethoxysilane, and 3- (p-vinylbenzo Iloxy) propylmethyldimethoxysilane, p-vinylphenylmethyldimethoxysilane, vinylmethyldimethoxysilane, tetravinyltetramethylcyclosiloxane, allylmethyldimethoxysilane, mercaptopropylmethyldimethoxysilane, methacryloxypropylmethyldimethoxysilane and the like. The proportion of the grafting agent used is preferably 0.1 to 10% by weight based on the organosiloxane. If the amount of the grafting agent used is more than 10% by weight, the impact resistance of the final molded product may be lowered. If the amount of the grafting agent used is less than 0.1% by weight, a large lump is formed during solidification and heat treatment. A decent resin powder may not be obtained or the moldability of the final molded product may be reduced.

  In the synthesis of the polyorganosiloxane (d1) used in the present invention, a crosslinking agent can be added if necessary. Examples of the crosslinking agent include trifunctional crosslinking agents such as methyltrimethoxysilane, phenyltrimethoxysilane, and ethyltriethoxysilane, tetraethoxysilane, 1,3bis [2- (dimethoxymethylsilyl) ethyl] benzene, 1,4-bis [2- (dimethoxymethylsilyl) ethyl] benzene, 1,3-bis [1- (dimethoxymethylsilyl) ethyl] benzene, 1,4-bis [1- (dimethoxymethylsilyl) ethyl] benzene 1- [1- (dimethoxymethylsilyl) ethyl] -3- [2- (dimethoxymethylsilyl) ethyl] benzene, 1- [1- (dimethoxymethylsilyl) ethyl] -4- [2-dimethoxymethylsilyl] And tetrafunctional cross-linking agents such as ethyl] benzene. At least one kind of these crosslinking agents can be used. The addition amount of the crosslinking agent is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the organosiloxane. When the addition amount of the crosslinking agent is more than 10 parts by weight, the flexibility of the polyorganosiloxane (d1) is impaired, so that the impact resistance at low temperature of the rubber material obtained from the acrylic elastomer composition may be lowered. .

  The average particle diameter of the latex polyorganosiloxane (d1) is preferably 0.008 to 0.6 μm, and more preferably 0.08 to 0.4 μm. It is difficult to stably obtain those having an average particle diameter of less than 0.008 μm, and if it exceeds 0.6 μm, the impact resistance of the final molded product may be deteriorated.

  Specific examples of the polyfunctional monomer (x) include allyl methacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and divinylbenzene. At least one of these can be used.

  Specific examples of the copolymerizable monomer (y) include aromatic vinyl monomers such as styrene and α-methylstyrene, vinyl cyanide monomers such as acrylonitrile, methyl acrylate, and acrylic acid. Examples thereof include (meth) acrylic acid ester monomers such as ethyl, methyl methacrylate, ethyl methacrylate and butyl methacrylate, and vinyl monomers containing an epoxy group in the molecule such as glycidyl methacrylate. At least one of these can be used.

  The monomer (d2) composed of the monomer (y) copolymerizable with the polyfunctional monomer (x), particularly, contains the polysiloxane (d1) in the polyorganosiloxane-based graft polymer (B). When the amount is as high as 80% by weight or more, the graft polymer resin can be pulverized. As the monomer (d2), the polyfunctional monomer (x) is preferably 50 to 100% by weight, more preferably 90 to 100% by weight, and the copolymerizable monomer (y) is preferably 0 to 100% by weight. It is preferably 50% by weight, more preferably 0 to 10% by weight.

  The amount of the monomer (d2) used is preferably 0 to 10% by weight, more preferably 0.5 to 10% by weight in the polyorganosiloxane graft polymer (B). The larger the amount used, the better the state of the powder, but if it exceeds 10% by weight, the impact resistance of the final molded product may be reduced.

  The vinyl monomer (d3) used in the present invention ensures compatibility between the polyorganosiloxane graft polymer (B) and the acrylic elastomer (A), and the polyorganosiloxane graft polymer (B). A component used for uniform dispersion. Specific examples of the monomer include the same monomers as the other copolymerizable monomer (y). Specifically, aromatic vinyl monomers such as styrene and α-methylstyrene, vinyl cyanide monomers such as acrylonitrile, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methacrylic acid (Meth) acrylic acid ester monomers such as methyl, ethyl methacrylate and butyl methacrylate, vinyl monomers containing an epoxy group in the molecule such as glycidyl methacrylate, ethylenic unsaturation such as methacrylic acid and acrylic acid Examples thereof include carboxylic acids, and at least one of them can be used. Here, the vinyl monomer (d3) is such that the solubility parameter value of the polymer obtained by polymerizing the vinyl monomer (d3) is close to the solubility parameter value of the acrylic elastomer that is the matrix resin. It is preferable to select. By selecting so that the solubility parameter of the polymer obtained by polymerizing the vinyl monomer (d3) is close to the solubility parameter of the acrylic elastomer, the polyorganosiloxane in the acrylic elastomer The dispersion state of the graft copolymer is excellent, and the low temperature characteristics of the molded product can be greatly improved. On the other hand, if the solubility parameter value is too different, the dispersion state of the polyorganosiloxane graft copolymer is not excellent, and the polyorganosiloxane graft polymer once dispersed may be re-aggregated. It becomes difficult to impart excellent low-temperature characteristics by the siloxane-based graft copolymer.

  Further, (B) the polyorganosiloxane graft polymer as a whole has an alkyl methacrylate content of 5 to 99.5% by weight and an alkyl acrylate content of 95 to 95% in the entire graft component of the polyorganosiloxane graft polymer. It is preferably 0.5% by weight. When the alkyl methacrylate content is more than 99.5% by weight, the heat resistance may decrease due to thermal decomposability. When the acrylic elastomer is an acrylic block copolymer, the alkyl methacrylate component in the entire graft component of the polyorganosiloxane graft polymer is meta-metamorphic for reasons such as bringing the solubility parameter close to that of the acrylic block copolymer. It is preferable to use 0.5 to 50% by weight of n-butyl acrylate as an essential component. When heat resistance is required, it is preferable that 0.5 to 10% by weight of methacrylic acid or acrylic acid is contained in the entire graft component of the polyorganosiloxane graft polymer.

  Specific examples of the radical initiator used in the production of the polyorganosiloxane (d1) of the present invention include organic peroxides such as cumene hydroperoxide, t-butyl hydroperoxide, benzoyl peroxide, and t-butyl peroxyisopropyl carbonate. And inorganic peroxides such as potassium persulfate and ammonium persulfate, and azo compounds such as 2,2′-azobisisobutyronitrile and 2,2′-azobis-2,4-dimethylvaleronitrile. Redox such as ferrous sulfate-sodium formaldehydesulfoxylate-ethylenediaminetetraacetic acid 2Na salt, ferrous sulfate-glucose-sodium pyrophosphate, ferrous sulfate-sodium pyrophosphate-sodium phosphate When carried out in the system, the polymerization is completed even at a low polymerization temperature.

  The method for separating the polymer from the polyorganosiloxane graft copolymer (B) latex obtained by emulsion polymerization is not particularly limited. For example, a metal salt such as calcium chloride, magnesium chloride or magnesium sulfate is added to the latex. Examples of the method include coagulation, separation, water washing, dehydration, and drying of the latex. A spray drying method can also be used.

  As for the contents of the acrylic elastomer (A) and the polyorganosiloxane graft polymer (B), the acrylic elastomer (A) is 50 to 98% by weight in the whole acrylic elastomer composition, and the polyorganosiloxane graft weight. The coalescence (B) is 50 to 2% by weight. If the content of the polyorganosiloxane-based graft polymer (B) is more than 50% by weight, the oil resistance may be lowered. If the content is less than 2% by weight, the low-temperature characteristics may be insufficiently improved.

<Lubricant (C)>
Examples of the lubricant (C) that can be used in the present invention include fatty acids such as stearic acid and palmitic acid, fatty acid metal salts such as calcium stearate, zinc stearate, magnesium stearate, potassium palmitate, sodium palmitate, polyethylene wax, Waxes such as polypropylene wax and montanic acid wax, low molecular weight polyolefins such as low molecular weight polyethylene and low molecular weight polypropylene, polyorganosiloxanes such as dimethylpolysiloxane, kuctadecylamine, alkyl phosphate, fatty acid ester, ethylene bisstearamide Amide lubricants such as 4-fluoroethylene resin, molybdenum disulfide powder, silicone resin powder, silicone rubber powder, silica, etc. Not intended to be constant. These may be used alone or in combination of two or more. Of these, stearic acid, zinc stearate, calcium stearate, and magnesium stearate are preferred from the viewpoint of low friction and processability on the resin surface.

<Inorganic filler (D)>
Examples of the inorganic filler (D) that can be used in the present invention include titanium oxide, zinc sulfide, zinc oxide, carbon black, calcium carbonate, calcium silicate, clay, kaolin, silica, mica powder, alumina, glass fiber, Examples thereof include, but are not limited to, metal fibers, potassium titanate whiskers, asbestos, wollastonite, mica, talc, glass flakes, milled fibers, and metal powders. These may be used alone or in combination. Among these, carbon black and titanium oxide are preferable from the viewpoint of high elastic modulus and silica and weather resistance and pigment.

  The composition of the present invention is molded by subjecting the composition to any molding process such as extrusion molding, compression molding, blow molding, calendar molding, vacuum molding, foam molding, injection molding, injection blow, and the like. Can be done. Of these, injection molding is preferred because it is simple.

<Thermoplastic resin (E)>
Examples of the thermoplastic resin (E) that can be used in the present invention include polyvinyl chloride resin, polyethylene resin, polypropylene resin, cyclic olefin copolymer resin, polymethyl methacrylate resin, polystyrene resin, and polyphenylene ether resin. , Polycarbonate resin, polyester resin, polyamide resin, polyacetal resin, polyphenylene sulfide resin, polysulfone resin, polyimide resin, polyetherimide resin, polyetherketone resin, polyetheretherketone resin, polyamideimide resin and imidized polymethyl For example, methacrylate resin. These may be used alone or in combination of two or more. Among these, those having good compatibility with the acrylic block copolymer are preferably used, and those having a functional group capable of reacting with an acid anhydride group are more preferably used. Examples of the functional group capable of reacting with the acid anhydride group include an amino group and a hydroxyl group, and examples of the thermoplastic resin having these include polyester resins and polyamide resins. Thermoplastic resins containing functional groups that react with acid anhydride groups other than these can also be suitably used.

  As conditions for molding the molded article of the present invention from the resin composition, for example, in the case of an injection molding method, a cylinder temperature of 150 to 240 ° C., a nozzle temperature of 240 ° C., an injection speed: low speed, a mold temperature: 40 to Examples of molding conditions are 120 ° C.

  The product according to the present invention manufactured by the method as described above has excellent low temperature characteristics, oil resistance, heat resistance, weather resistance, mechanical characteristics, etc., and can be suitably used for weather strips, for example. Compared with conventional vulcanized rubber systems, the molding process is simplified and recyclable, and compared to olefinic thermoplastic elastomers, it can have better oil resistance and weather resistance.

  Examples of uses of the composition include molded products for automobiles, household electrical appliances, and office electrical appliances. Specifically, various oil seals such as oil seals and reciprocating oil seals, various packings such as gland packing, lip packing, squeeze packing, constant velocity joint boots, rack and opinion boots, strut boots, stelling rack boots, etc. Various boots, dust cover for suspension, dust cover for suspension and tie rod, dust cover for stabilizer and die rod, resin intake manifold gasket, gasket for throttle body, gasket for power steering vane pump, gasket for head cover, water heater self-supply Type pump gasket, filter gasket, piping joint (ABS & HBB) gasket, HDD top cover gasket, HDD connector Gaskets such as gaskets, cylinder head gaskets combined with metal, car cooler compressor gaskets, gaskets around engines, AT separate plates, general-purpose gaskets (industrial sewing machines, nailing machines, etc.), needle valves, plunger valves, water / Mainly cushioning performance for various valves such as gas valves, brake valves, drinking valves, safety valves for aluminum electrolytic capacitors, vacuum boosters, water / gas diaphragms, seal washers, bore plugs, high-precision stoppers, etc. These include various stoppers, plug tube seals, injection pipe seals, oil receivers, brake drum seals, light shielding seals, plug seals, connector seals, precision seal rubbers such as keyless entry covers. Also, various weather strips such as door weather strips for automobiles, molded articles such as trunk seals and glass run channels can be mentioned.

  Next, the composition of the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

  In the following, EA, BA, MEA, MMA, TBMA, TBA, and HEA are ethyl acrylate, butyl acrylate, 2-methoxyethyl acrylate, methyl methacrylate, t-butyl methacrylate, and acrylic acid, respectively. t-Butyl and 2-hydroxyethyl acrylate are meant.

  Moreover, the molecular weight in this specification is the molecular weight of polystyrene conversion calculated | required by performing the GPC measurement which used the GPC analyzer shown below and made chloroform a mobile phase and used the polystyrene gel column.

<Test method>
(Molecular weight)
The molecular weight of the block copolymer was measured with a GPC analyzer (system: GPC system manufactured by Waters, column: Shodex K-804 (polystyrene gel) manufactured by Showa Denko KK). The molecular weight in terms of polystyrene was determined using chloroform as the mobile phase.

(6-membered cyclic acid anhydride group conversion analysis)
Confirmation of the 6-membered cyclic anhydride group conversion reaction of the block copolymer was performed by infrared spectrum analysis (manufactured by Shimadzu Corporation, using FTIR-8100) and nuclear magnetic resonance analysis (manufactured by BRUKER, using AM400). Performed.

  As a nuclear magnetic resonance analysis solvent, a block body having a carboxylic acid ester structure was analyzed using deuterated chloroform as a measurement solvent together with a block body having a 6-membered cyclic acid anhydride structure.

(Acid group conversion analysis)
Confirmation of the decomposition reaction of the block copolymer into carboxylic acid group-containing units is performed by infrared spectrum analysis (manufactured by Shimadzu Corporation, using FTIR-8100) and nuclear magnetic resonance analysis (manufactured by BRUKER, using AM400). It was performed using. As the solvent for nuclear magnetic resonance analysis, the block body having a carboxylic acid ester structure was analyzed using deuterated chloroform, and the carboxylic acid-containing block body was analyzed using deuterated methanol as a measuring solvent.

(hardness)
In accordance with JIS K6301, the hardness at 23 ° C. (JIS A) was measured.

(Tensile properties (mechanical strength))
According to the method described in JIS K7113, measurement was performed using an autograph AG-10TB type manufactured by Shimadzu Corporation. The measurement was performed at n = 3, and the average values of strength (MPa) and elongation (%) when the test piece broke were adopted. A test piece having a shape of 2 (1/3) shape and a thickness of about 2 mm was used. The test was conducted at 23 ° C. and a test speed of 500 mm / min. In principle, the test piece was conditioned at a temperature of 23 ± 2 ° C. and a relative humidity of 50 ± 5% for 48 hours or more before the test.

  In the case of a press-molded sheet, the dumbbell punching direction is not a specific direction, and the dumbbell punching direction for tensile property evaluation is a direction perpendicular to the gate of the injection molded body.

(Compression set)
In accordance with JIS K6301, the cylindrical formed body was held at 100 ° C. for 22 hours under the condition of a compression rate of 25%, and allowed to stand at room temperature for 30 minutes. Then, the thickness of the molded body was measured, and the strain residual degree was calculated.

  It means that all of the distortion is recovered at a compression set of 0%, and no distortion is recovered at 100% of the compression set.

(Oil resistance)
In accordance with ASTM D638, ASTM Oil No. 1 maintained at 150 ° C. The molded product of the composition was immersed in 3 for 72 hours, and the weight change rate (% by weight) was determined. Moreover, the shape after immersion was evaluated according to the following criteria.
Shape: Retention = ○, Slightly Swell = ○ to △, Swell = △, Severely Swell or Partially Dissolve = ×, Completely Dissolve = XX
(Low temperature embrittlement)
In accordance with JIS K7216, a 2 mm thick molded product sheet was cut into 38 × 6 mm, and a low temperature embrittlement temperature measuring device “Standard Model S type (dry ice type)” (manufactured by Toyo Seiki Co., Ltd.) was used. The low temperature embrittlement temperature was measured using a methanol mixture as a refrigerant.

<Manufacture of block copolymer>
(Production Example 1-1) [Synthesis of 2A40AN6.5]
The following operation was performed to obtain 2A40AN6.5.

  After the inside of the polymerization vessel of a 500 L reactor equipped with a stirrer capable of heating and cooling was purged with nitrogen, 840.1 g (5.9 mol) of copper bromide was measured, and 12 L of acetonitrile (nitrogen bubbling) was added. After heating and stirring at 70 ° C. for 30 minutes, 421.7 g (1.17 mol) of diethyl 2,5-dibromoadipate initiator, 41.4 L (288.9 mol) BA, and 18.6 L (144.5 mol) MEA were added. It was. The mixture was heated and stirred at 85 ° C., and 0.1 L (0.59 mol) of ligand diethylenetriamine was added to initiate polymerization.

  About 0.2 ml of the polymerization solution was sampled from the polymerization solution at regular intervals from the start of polymerization, and the conversion rate of BA was determined by gas chromatogram analysis of the sampling solution. The polymerization rate was controlled by adding diethylenetriamine as needed. When the conversion rate of BA was 94% and the conversion rate of MEA was 96%, TBMA 24.9L (153.8 mol), MMA 24.7L (230.8 mol), copper chloride 580 g (5.9 mol), butyl acetate 1 2 L (9.1 mol) and 122.8 L of toluene (nitrogen bubbled) were added. Similarly, conversion rates of TBMA and MMA were determined. When the conversion rate of TBMA was 61% and the conversion rate of MMA was 56%, 80 L of toluene was added and the reactor was cooled in a water bath to complete the reaction.

The reaction solution was diluted with 115 L of toluene, 1337 g of p-toluenesulfonic acid monohydrate was added and stirred at room temperature for 3 hours, and then the solid was removed using a bag filter (manufactured by HAYWARD). To the resulting polymer solution, 1642 g of adsorbent Kyoward 500SH (manufactured by Kyowa Chemical Co., Ltd.) was added and stirred for another 3 hours at room temperature. The adsorbent was filtered using a bag filter to obtain a colorless and transparent polymer solution. This solution was dried using a horizontal evaporator (heat transfer area: 1 m ² ) to remove the solvent and residual monomer, thereby obtaining the target block copolymer 2A40AN6.5.

  When the GPC analysis of obtained block copolymer 2A40AN6.5 was conducted, the number average molecular weight (Mn) was 93700, and molecular weight distribution (Mw / Mn) was 1.36.

(Production Example 1-2) [Six-membered cyclic acid anhydride reaction and characteristic evaluation of block copolymer 2A40T6.5]
A pressure kneader (DS1 manufactured by Moriyama Co., Ltd.) in which 700 g of the block copolymer (2A40T6.5) obtained in Production Example 1-1 and 1.4 g of Irganox 1010 (manufactured by Ciba Geigy) were set at 240 ° C. The target 6-membered cyclic acid anhydride group-containing block copolymer (the resulting polymer is hereinafter referred to as 2A40T6.5) is melt-kneaded at 70 rpm for 20 minutes using a -5MHB-E type kneader). Obtained.
The conversion of the t-butyl ester moiety to a 6-membered cyclic acid anhydride group could be confirmed by IR (infrared absorption spectrum) analysis and ¹³ C-NMR (nuclear magnetic resonance spectrum) analysis.

That is, in the IR analysis, it was confirmed that an absorption spectrum derived from an acid anhydride group was observed around 1800 cm ⁻¹ after conversion. ^{In the 13} C-NMR analysis, it was confirmed that the 82 ppm signal derived from the methine carbon of the t-butyl group and the 28 ppm signal derived from the methyl carbon disappeared after the conversion.

(Production Example 2-1) [Synthesis of 3A20T6.8]
Using a 500 L reactor equipped with a stirrer capable of heating and cooling, 427 g (1.18 mol) of diethyl 2,5-dibromoadipate, 25.3 L (176.6 mol) of BA, 24.1 L (222 mol) of EA, 13.6 L of MEA ( 106 mol), the polymerization was carried out at a charging ratio of 95% for BA, 95% for EA, and 98% for MEA, and TBMA 12.3L (76.2 mol), MMA 32.6L. (304.8 mol) was added. The reaction was terminated when the conversion rate of TBMA was 67% and the conversion rate of MMA was 59%. Otherwise, the production was conducted in the same manner as in Production Example 1 to obtain the target block copolymer (3A20T6.8).

  When the GPC analysis of the obtained block copolymer (3A20T6.8) was conducted, the number average molecular weight (Mn) was 107400, and molecular weight distribution (Mw / Mn) was 1.28.

(Production Example 2-2) [Six-membered cyclic acid anhydride reaction and characteristic evaluation of block copolymer 3A20T6.8]
A pressure kneader (DS1 manufactured by Moriyama Co., Ltd.) in which 700 g of the block copolymer (3A20T6.8) obtained in Production Example 2-1 and 1.4 g of Irganox 1010 (manufactured by Ciba Geigy) were set at 240 ° C. The target 6-membered cyclic acid anhydride group-containing block copolymer (the obtained polymer is hereinafter referred to as 3A20T6.8) is melt-kneaded at 70 rpm for 20 minutes using a -5MHB-E type kneader). Obtained.

(Production Example 3-1) [Synthesis of 3A50T6]
In order to obtain 3A50T6, the following operation was performed. Using a 500 L reactor equipped with a stirrer capable of heating and cooling, 424.9 g (1.18 mol) of diethyl 2,5-dibromoadipate, 22.5 L (157 mol), 21.4 L of EA (197 mol), 12.1 L of MEA ( Polymerization was carried out at a charging ratio of 94.2 mol). When the conversion rate of BA was 95%, the conversion rate of EA was 95%, and the conversion rate of MEA was 98%, TBMA 34.8L (215 mol), MMA 23L (215 mol) ) Was added. The reaction was terminated when the conversion rate of TBMA was 67% and the conversion rate of MMA was 59%. Other than that was manufactured similarly to manufacture example 1, and obtained the target block copolymer (3A50T6).

  When the GPC analysis of the obtained block copolymer (3A50T6) was conducted, the number average molecular weight (Mn) was 101200, and molecular weight distribution (Mw / Mn) was 1.28.

(Production Example 3-2) [Six-membered cyclic acid anhydride reaction and property evaluation of block copolymer 3A50T6]
A pressure kneader (DS1-5MHB, manufactured by Moriyama Co., Ltd.) in which 700 g of the block copolymer (3A50T6) obtained in Production Example 3-1 and 1.4 g of Irganox 1010 (manufactured by Ciba Geigy) were set at 240 ° C. -E type kneader) was melt-kneaded at 70 rpm for 20 minutes to obtain a target 6-membered cyclic acid anhydride group-containing block copolymer (the obtained polymer is hereinafter referred to as 3A50AN6).

(Production Example 4-1) [Synthesis of 3A50T6.5]
The following operation was performed to obtain 3A50T6.5. Using a 500 L reactor equipped with a stirrer capable of heating and cooling, 483 g (1.34 mol) of diethyl 2,5-dibromoadipate, 27.3 L of BA (190.6 mol), 26.0 L of EA (239.6 mol), MEA 14. Polymerization was conducted at a charging ratio of 7 L (114.4 mol). When the conversion rate of BA was 95%, the conversion rate of EA was 95%, and the conversion rate of MEA was 98%, TBMA 34.0L (210 mol), MMA 22 .5 L (210 mol) was added. The reaction was terminated when the conversion rate of TBMA was 67% and the conversion rate of MMA was 59%. Otherwise, the production was carried out in the same manner as in Production Example 1 to obtain the target block copolymer (3A50T6.5).

  When the GPC analysis of the obtained block copolymer (3A50T6.5) was conducted, the number average molecular weight (Mn) was 98900, and molecular weight distribution (Mw / Mn) was 1.28.

(Production Example 4-2) [Six-membered cyclic acid anhydride reaction and characteristic evaluation of block copolymer 3A50T6.5]
A pressure kneader (DS1 manufactured by Moriyama Co., Ltd.) in which 700 g of the block copolymer (3A50T6.5) obtained in Production Example 4-1 and 1.4 g of Irganox 1010 (manufactured by Ciba Geigy) were set at 240 ° C. The target 6-membered cyclic acid anhydride group-containing block copolymer (the resulting polymer is hereinafter referred to as 3A50AN6.5) is melt-kneaded at 70 rpm for 20 minutes using a -5MHB-E type kneader). Obtained.
(Production Example 5-1) [Synthesis of 3A50T6.1]
Using a 500 L reactor equipped with a stirrer capable of heating and cooling, 634 g (1.76 mol) diethyl 2,5-dibromoadipate, 33.8 L (235.5 mol), 32.1 L (296 mol) EA, 18.2 L MEA (18.2 L) 141.3 mol) at a feed ratio, and when the conversion rate of BA is 96%, the conversion rate of EA is 95%, and the conversion rate of MEA is 97%, TBMA 33.4L (206 mol), MMA 22.0L (206.1 mol) was added. The reaction was terminated when the conversion rate of TBMA was 91% and the conversion rate of MMA was 94%. Otherwise, the production was carried out in the same manner as in Production Example 1 to obtain the intended acrylic block copolymer (3A50T6.1).

  When the GPC analysis of the obtained acrylic block copolymer (3A50T6.1) was performed, the number average molecular weight (Mn) was 104400, and molecular weight distribution (Mw / Mn) was 1.31.

(Production Example 5-2) [Six-membered cyclic acid anhydride reaction and characteristic evaluation of block copolymer 3A50T6.1]
Irganox 1010 (manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.6 weight with respect to 100 parts by weight of the obtained acrylic block copolymer (3A50T6.1) obtained in Production Example 5-1. Parts were mixed and extruded and kneaded using a twin screw extruder with a vent (44 mm, L / D = 42.25) (manufactured by Nippon Steel Works) at a rotation speed of 300 rpm and a set temperature of 240 ° C. An acid anhydride group-containing acrylic block copolymer was obtained. At this time, an underwater cut pelletizer (CLS-6-8.1 COMPACT LAB SYSTEM manufactured by GALA INDUSTRIES INC.) Is connected to the tip of the twin screw extruder, and Alfflow H- is used as an anti-adhesive agent in the circulating water of the underwater cut pelletizer. By adding 50ES (manufactured by NOF Corporation), spherical pellets (hereinafter referred to as 3A50AN6.1) having no adhesion resistance were obtained.

(Production Example 6-1) [Synthesis of 3A60T6]
Using a 500 L reactor equipped with a stirrer capable of heating and cooling, 634 g (1.76 mol) diethyl 2,5-dibromoadipate, 33.8 L (235.5 mol), 32.1 L (296 mol) EA, 18.2 L MEA (18.2 L) 141.3 mol) at a feed ratio, when the conversion rate of BA is 96%, the conversion rate of EA is 95%, and the conversion rate of MEA is 96%, TBMA 40.5L (249.9 mol), MMA 17 .8 L (166.6 mol) was added. The reaction was terminated when the conversion rate of TBMA was 95% and the conversion rate of MMA was 92%. Otherwise, the production was carried out in the same manner as in Production Example 1 to obtain the intended acrylic block copolymer (3A60T6).

  When the GPC analysis of the obtained acrylic block copolymer (3A60T6) was performed, the number average molecular weight (Mn) was 102100, and molecular weight distribution (Mw / Mn) was 1.30.

(Production Example 6-2) [6-membered cyclic acid anhydride reaction and characterization of acrylic block copolymer 3A60T6]
With respect to 100 parts by weight of the obtained acrylic block copolymer (3A60T6) obtained in Production Example 6-1, 0.3 part by weight of Irganox 1010 (manufactured by Ciba Specialty Chemicals) was added. Compounding and extrusion kneading using a vented twin screw extruder (44 mm, L / D = 42.25) (manufactured by Nippon Steel Works) at a rotation speed of 300 rpm and a set temperature of 240 ° C. An anhydride group-containing acrylic block copolymer was obtained. At this time, an underwater cut pelletizer (CLS-6-8.1 COMPACT LAB SYSTEM manufactured by GALA INDUSTRIES INC.) Is connected to the tip of the twin screw extruder, and Alfflow H- is used as an anti-adhesive agent in the circulating water of the underwater cut pelletizer. By adding 50ES (manufactured by Nippon Oil & Fats Co., Ltd.), a spherical pellet having no adhesion property (hereinafter referred to as 3A60AN6) was obtained.

(Production Example 7-1) [Synthesis of 3A70T6]
Using a 500 L reactor equipped with a stirrer capable of heating and cooling, 634 g (1.76 mol) diethyl 2,5-dibromoadipate, 33.8 L (235.5 mol), 32.1 L (296 mol) EA, 18.2 L MEA (18.2 L) 141.3 mol) at a charging ratio, and when the conversion rate of BA is 96%, the conversion rate of EA is 95%, and the conversion rate of MEA is 96%, TBMA 45.5L (281 mol), MMA 12.9L (120 mol) was added. The reaction was terminated when the conversion rate of TBMA was 93% and the conversion rate of MMA was 91%. Otherwise, the same production as in Production Example 1 was carried out to obtain the intended acrylic block copolymer (3A70T6).

  When the GPC analysis of the obtained acrylic block copolymer (3A70T6) was conducted, the number average molecular weight (Mn) was 95600, and molecular weight distribution (Mw / Mn) was 1.31.

(Production Example 7-2) [Acrylic block copolymer 3A70T6 6-membered cyclic acid anhydride reaction and evaluation]
With respect to 100 parts by weight of the obtained acrylic block copolymer (3A70T6) obtained in Production Example 7-1, 0.3 part by weight of Irganox 1010 (manufactured by Ciba Specialty Chemicals) was added. Compounding and extrusion kneading using a vented twin screw extruder (44 mm, L / D = 42.25) (manufactured by Nippon Steel Works) at a rotation speed of 300 rpm and a set temperature of 240 ° C. An anhydride group-containing acrylic block copolymer was obtained. At this time, an underwater cut pelletizer (CLS-6-8.1 COMPACT LAB SYSTEM manufactured by GALA INDUSTRIES INC.) Is connected to the tip of the twin screw extruder, and Alfflow H- is used as an anti-adhesive agent in the circulating water of the underwater cut pelletizer. By adding 50ES (Nippon Yushi Co., Ltd.), a spherical pellet having no adhesion (hereinafter referred to as 3A70AN6) was obtained.

(Production Example 8) [Synthesis of polyorganosiloxane-based graft polymer PM122]
In a 5-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port, and thermometer, 400 parts by weight of water and 12 parts of 10% sodium dodecylbenzenesulfonate aqueous solution (solid content) are mixed. Then, the temperature was raised to 50 ° C., and after the liquid temperature reached 50 ° C., nitrogen substitution was performed. Thereafter, 10 parts of butyl acrylate and 3 parts of t-dodecyl mercaptan were added. After 30 minutes, 0.01 part (solid content) of paramentane hydroperoxide, 0.3 part of sodium formaldehyde sulfoxylate (SFS), 0.01 part of disodium ethylenediaminetetraacetate (EDTA), 0.1 part of ferrous sulfate. 0025 parts were added and stirred for 1 hour. A mixed solution of 90 parts of butyl acrylate, 27 parts of t-dodecyl mercaptan and 0.09 part (solid content) of paramentane hydroperoxide was continuously added over 3 hours. Thereafter, post-polymerization was performed for 2 hours to obtain a latex containing a seed polymer.

Next, 2 parts (solid content) of the above-mentioned seed polymer were charged into a 5-neck flask equipped with a stirrer, reflux condenser, nitrogen blowing port, monomer addition port, and thermometer. Thereafter, 300 parts of pure water (including the amount brought in from the latex containing the seed polymer), 0.5 parts of 5% sodium dodecylbenzenesulfonate aqueous solution (solid content), 98 parts of octamethylcyclotetrasiloxane, mercaptopropylmethyldimethoxy A mixture of 2.9 parts of silane was stirred with a homomixer at 7000 rpm for 5 minutes to prepare a polyorganosiloxane-forming component emulsion, which was added all at once.
Next, after adding 1 part (solid content) of 10% dodecylbenzenesulfonic acid aqueous solution, the temperature was raised to 80 ° C. under a nitrogen stream while stirring the system. After reaching 80 ° C., stirring was continued at 80 ° C. for 10 hours, then cooled to 25 ° C. and left for 20 hours. Thereafter, the pH was adjusted to 6.5 with sodium hydroxide to complete the polymerization, and a latex containing polyorganosiloxane particles was obtained.

  Subsequently, in a 5-neck flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a monomer addition port and a thermometer, 240 parts of pure water (including the carry-in from latex containing organosiloxane particles), and the above 70 parts (solid content) of polyorganosiloxane particles were charged, and the temperature was raised to 40 ° C. under a nitrogen stream while stirring the system. After reaching 40 ° C., 0.2 part of sodium formaldehyde sulfoxylate (SFS), 0.01 part of ethylenediaminetetraacetic acid disodium (EDTA), and 0.0025 part of ferrous sulfate were added. A mixture of cumene hydroperoxide (0.01 parts, solid content) was added all at once, and stirring was continued at 40 ° C. for 1 hour. Thereafter, a mixture of 24 parts of methyl methacrylate, 6 parts of butyl acrylate and 0.06 part of cumene hydroperoxide (solid content) was added dropwise over 1.5 hours. After the addition was completed, the mixture was further stirred for 1 hour. A latex of graft copolymer was obtained by continuing.

Subsequently, the latex was diluted with pure water to a solid content concentration of 15%, and then 4 parts of a 25% calcium chloride aqueous solution (solid content) was added to obtain a coagulated slurry. The coagulated slurry was heated to 85 ° C., cooled to 50 ° C., dehydrated, and dried to obtain a polyorganosiloxane graft copolymer powder.
(Production Example 9) [Synthesis of polyorganosiloxane-based graft polymer NM015]
In a 5-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port, and thermometer, 400 parts by weight of water and 12 parts of 10% sodium dodecylbenzenesulfonate aqueous solution (solid content) are mixed. Then, the temperature was raised to 50 ° C., and after the liquid temperature reached 50 ° C., nitrogen substitution was performed. Thereafter, 10 parts of BA and 3 parts of t-dodecyl mercaptan were added. After 30 minutes, 0.01 part (solid content) of paramentane hydroperoxide, 0.3 part of sodium formaldehyde sulfoxylate (SFS), 0.01 part of disodium ethylenediaminetetraacetate (EDTA), 0.1 part of ferrous sulfate. 0025 parts were added and stirred for 1 hour. A mixed solution of 90 parts of BA, 27 parts of t-dodecyl mercaptan and 0.09 part (solid content) of paramentane hydroperoxide was continuously added over 3 hours. Thereafter, post-polymerization was performed for 2 hours to obtain a latex containing a seed polymer.

  Next, 2 parts (solid content) of the above-mentioned seed polymer were charged into a 5-neck flask equipped with a stirrer, reflux condenser, nitrogen blowing port, monomer addition port, and thermometer. Separately, 300 parts of pure water (including the carry-in from the latex containing the seed polymer), 0.5 parts of 5% aqueous sodium dodecylbenzenesulfonate (solid content), 98 parts of octamethylcyclotetrasiloxane, mercaptopropylmethyldimethoxy A mixture of 2.9 parts of silane was stirred with a homomixer at 7000 rpm for 5 minutes to prepare a polyorganosiloxane-forming component emulsion, which was added all at once.

  Next, after adding 1 part (solid content) of 10% dodecylbenzenesulfonic acid aqueous solution, the temperature was raised to 80 ° C. under a nitrogen stream while stirring the system. After reaching 80 ° C., stirring was continued at 80 ° C. for 10 hours, then cooled to 25 ° C. and left for 20 hours. Thereafter, the pH was adjusted to 6.2 with sodium hydroxide to complete the polymerization, and a latex containing polyorganosiloxane particles was obtained.

  Subsequently, in a 5-neck flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a monomer addition port and a thermometer, 240 parts of pure water (including the carry-in from latex containing organosiloxane particles), and the above 70 parts of polyorganosiloxane particles (solid content) were charged, and the temperature was raised to 40 ° C. under a nitrogen stream while stirring the system. After reaching 40 ° C., 0.2 parts of sodium formaldehyde sulfoxylate (SFS), 0.01 parts of disodium ethylenediaminetetraacetate (EDTA) and 0.0025 parts of ferrous sulfate were added, and then allyl methacrylate 1.5 And a mixture of cumene hydroperoxide 0.01 parts (solid content) were added all at once, and stirring was continued at 40 ° C. for 1 hour. Thereafter, a mixture of MMA 15.6 parts, n-butyl methacrylate 13.5 parts, EA 0.9 parts, and cumene hydroperoxide 0.06 parts (solid content) was added dropwise over 1.5 hours. After completion, the mixture was further stirred for 1 hour to obtain a latex of graft copolymer.

  Subsequently, the latex was diluted with pure water to a solid content concentration of 15%, and then 4 parts of a 25% calcium chloride aqueous solution (solid content) was added to obtain a coagulated slurry. The coagulated slurry was heated to 80 ° C., cooled to 50 ° C., dehydrated, and dried to obtain a polyorganosiloxane graft polymer.

(Production Example 10) [Synthesis of polyorganosiloxane-based graft polymer BTM026]
In a 5-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port, and thermometer, 400 parts by weight of water and 12 parts of 10% sodium dodecylbenzenesulfonate aqueous solution (solid content) are mixed. Then, the temperature was raised to 50 ° C., and after the liquid temperature reached 50 ° C., nitrogen substitution was performed. Thereafter, 10 parts of BA and 3 parts of t-dodecyl mercaptan were added. After 30 minutes, 0.01 part (solid content) of paramentane hydroperoxide, 0.3 part of sodium formaldehyde sulfoxylate (SFS), 0.01 part of disodium ethylenediaminetetraacetate (EDTA), 0.1 part of ferrous sulfate. 0025 parts were added and stirred for 1 hour. A mixed solution of 90 parts of BA, 27 parts of t-dodecyl mercaptan and 0.09 part (solid content) of paramentane hydroperoxide was continuously added over 3 hours. Thereafter, post-polymerization was performed for 2 hours to obtain a latex containing a seed polymer.

  Next, 2 parts (solid content) of the above-mentioned seed polymer were charged into a 5-neck flask equipped with a stirrer, reflux condenser, nitrogen blowing port, monomer addition port, and thermometer. Separately, 300 parts of pure water (including the carry-in from the latex containing the seed polymer), 0.5 parts of 5% aqueous sodium dodecylbenzenesulfonate (solid content), 98 parts of octamethylcyclotetrasiloxane, mercaptopropylmethyldimethoxy A mixture of 2.9 parts of silane was stirred with a homomixer at 7000 rpm for 5 minutes to prepare a polyorganosiloxane-forming component emulsion, which was added all at once.

  Next, after adding 1 part (solid content) of 10% dodecylbenzenesulfonic acid aqueous solution, the temperature was raised to 80 ° C. under a nitrogen stream while stirring the system. After reaching 80 ° C., stirring was continued at 80 ° C. for 10 hours, then cooled to 25 ° C. and left for 20 hours. Thereafter, the pH was adjusted to 6.2 with sodium hydroxide to complete the polymerization, and a latex containing polyorganosiloxane particles was obtained.

  Subsequently, in a 5-neck flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a monomer addition port and a thermometer, 240 parts of pure water (including the amount brought in from the latex containing organosiloxane particles) and the above 75 parts of polyorganosiloxane particles (solid content) were charged, and the system was heated to 40 ° C. under a nitrogen stream while stirring the system. After reaching 40 ° C., 0.2 parts of sodium formaldehyde sulfoxylate (SFS), 0.01 parts of ethylenediaminetetraacetic acid disodium (EDTA), and 0.0025 parts of ferrous sulfate were added. A mixture of cumene hydroperoxide 0.01 part (solid content) was added all at once, and stirring was continued at 40 ° C. for 1 hour. Thereafter, a mixture of MMA 18.75 parts, BA 5 parts, methacrylic acid 1.25 parts, and cumene hydroperoxide 0.06 parts (solid content) was added dropwise over 1.5 hours. A latex of graft copolymer was obtained by continuing stirring for a period of time.

  Subsequently, the latex was diluted with pure water to a solid content concentration of 15%, and then 4 parts of a 25% calcium chloride aqueous solution (solid content) was added to obtain a coagulated slurry. The coagulated slurry was heated to 80 ° C., cooled to 50 ° C., dehydrated, and dried to obtain a polyorganosiloxane graft polymer.

Example 1 [Physical Properties of Mixture of Block Copolymer (2A40AN6.5) and Polyorganosiloxane Graft Polymer (PM122)]
Plastomil “MODEL20C200” in which 36 g of the block copolymer (2A40AN6.5) obtained in Production Example 1-2 and 9 g of the polyorganosiloxane-based graft polymer (PM122) obtained in Production Example 8 were first set to 50 ° C. (Toyo Seiki Co., Ltd.) was used and melt kneaded at 150 rpm for 5 minutes. At that time, when the increase in the resin temperature due to the shear heat generation between the resins was finished, the preset temperature was set to 220 ° C. under the same rotational speed, and the mixture was melt-kneaded for 10 minutes. The obtained bulk sample was hot press molded at 220 ° C. to obtain a cylindrical molded body for evaluation of compression set having a diameter of 30 mm and a thickness of 12 mm, and the compression set and hardness of the obtained molded body were measured. .

  Moreover, it hot-press-molded similarly and obtained the sheet-like molded object of thickness 2mm, and measured the low temperature embrittlement temperature, oil resistance, and the tensile characteristic using the obtained sheet-like molded object.

Example 2 [Physical Properties of Mixture of Block Copolymer (2A40AN6.5) and Polyorganosiloxane Graft Polymer (PM122)]
First, 33.3 g of the block copolymer (2A40AN6.5) obtained in Production Example 1-2 and 11.7 g of the polyorganosiloxane-based graft polymer (PM122) obtained in Production Example 8 were set to 50 ° C. Using a plast mill “MODEL20C200” (manufactured by Toyo Seiki Co., Ltd.), the mixture was melt kneaded at 150 rpm for 5 minutes. At that time, when the increase in the resin temperature due to the shear heat generation between the resins was finished, the preset temperature was set to 220 ° C. under the same rotational speed, and the mixture was melt-kneaded for 10 minutes. The obtained massive sample was hot press molded at 220 ° C. to obtain a cylindrical molded body for evaluation of compression set having a diameter of 30 mm and a thickness of 12 mm, and the hardness of the obtained molded body was measured.

  Moreover, it hot-press-molded similarly and obtained the sheet-like molded object of thickness 2mm, and low-temperature embrittlement temperature, oil resistance, and the tensile characteristic were measured using the obtained sheet-like molded object.

Example 3 [Physical Properties of Mixture of Block Copolymer (3A50AN6.5) and Polyorganosiloxane Graft Polymer (PM122)]
First, 27.3 g of the block copolymer (3A50AN6.5) obtained in Production Example 4-2 and 17.7 g of the polyorganosiloxane-based graft polymer (PM122) obtained in Production Example 8 were set to 50 ° C. Using a plast mill “MODEL20C200” (manufactured by Toyo Seiki Co., Ltd.), the mixture was melt kneaded at 150 rpm for 5 minutes. At that time, when the increase in the resin temperature due to the shear heat generation between the resins was finished, the preset temperature was set to 220 ° C. under the same rotational speed, and the mixture was melt-kneaded for 10 minutes. The obtained massive sample was hot press molded at 220 ° C. to obtain a cylindrical molded body for evaluation of compression set having a diameter of 30 mm and a thickness of 12 mm, and the hardness of the obtained molded body was measured. Moreover, it hot-press-molded similarly and obtained the sheet-like molded object of thickness 2mm, and low-temperature embrittlement temperature, oil resistance, and the tensile characteristic were measured using the obtained sheet-like molded object.

Example 4 [Physical Properties of Block Copolymer 3A50AN6, 3A20AN6.8, 2A40AN6.5, Polyorganosiloxane Graft Polymer, and Mixture of Lubricant and Inorganic Filler]
5.5 g of the block copolymer (2A40AN6.5) obtained in Production Example 1-2, 10.9 g of the block copolymer (3A20AN6.8) obtained in Production Example 2-2, and Production Example 3-2 Plastomill “MODEL20C200” (Toyo Seiki Co., Ltd.) in which 10.9 g of the obtained block copolymer (3A50AN6) and 17.7 g of the polyorganosiloxane graft polymer (PM122) obtained in Production Example 8 were first set to 50 ° C. )) For 5 minutes at 150 rpm. At that time, when the increase in the resin temperature due to the shear heat generation between the resins is completed, the set temperature is set to 220 ° C. under the same rotation speed, and the lubricant is added to the rotation speed at 100 rpm (Alfro H-50ES manufactured by NOF Corporation) 0 .05 g and 2.2 g of inorganic filler (Aerosil R972 manufactured by Nippon Aerosil Co., Ltd.) were added, and after completion of the addition, the number of revolutions was again set to 150 rpm and melt-kneaded for 10 minutes. The obtained massive sample was hot press molded at 220 ° C. to obtain a cylindrical molded body for evaluation of compression set having a diameter of 30 mm and a thickness of 12 mm, and the hardness of the obtained molded body was measured.

  Moreover, it hot-press-molded similarly and obtained the sheet-like molded object of thickness 2mm, and low-temperature embrittlement temperature, oil resistance, and the tensile characteristic were measured using the obtained sheet-like molded object. The results are shown in Table 1.

(Comparative Example 1) [Physical properties of block copolymer 2A40AN6.5]
45 g of the block copolymer (2A40AN6.5) obtained in Production Example 1-2 was melt-kneaded at 100 rpm for 15 minutes using a plastmill “MODEL20C200” (manufactured by Toyo Seiki Co., Ltd.) set at 220 ° C. The obtained bulk sample was hot press molded at 220 ° C. to obtain a cylindrical molded body for evaluation of compression set having a diameter of 30 mm and a thickness of 12 mm, and the compression set and hardness of the obtained molded body were measured. . Moreover, it hot-press-molded similarly and obtained the sheet-like molded object of thickness 2mm, and low-temperature embrittlement temperature, oil resistance, and the tensile characteristic were measured using the obtained sheet-like molded object. The results are shown in Table 1.

(Comparative Example 2) [Physical properties of block copolymer 3A20AN6.8]
45 g of the block copolymer (3A20AN6.8) obtained in Production Example 2-2 was melt-kneaded at 100 rpm for 15 minutes using a plastmill “MODEL20C200” (manufactured by Toyo Seiki Co., Ltd.) set at 220 ° C. The obtained bulk sample was hot press molded at 220 ° C. to obtain a cylindrical molded body for evaluation of compression set having a diameter of 30 mm and a thickness of 12 mm, and the compression set and hardness of the obtained molded body were measured. . Moreover, it hot-press-molded similarly and obtained the sheet-like molded object of thickness 2mm, and low-temperature embrittlement temperature, oil resistance, and the tensile characteristic were measured using the obtained sheet-like molded object. The results are shown in Table 1.

(Comparative Example 3) [Physical properties of block copolymer 3A50AN6]
45 g of the block copolymer (3A50AN6) obtained in Production Example 3-2 was melt-kneaded at 100 rpm for 15 minutes using a plastmill “MODEL20C200” (manufactured by Toyo Seiki Co., Ltd.) set at 220 ° C. The obtained bulk sample was hot press molded at 220 ° C. to obtain a cylindrical molded body for evaluation of compression set having a diameter of 30 mm and a thickness of 12 mm, and the compression set and hardness of the obtained molded body were measured. . Moreover, it hot-press-molded similarly and obtained the sheet-like molded object of thickness 2mm, and low-temperature embrittlement temperature, oil resistance, and the tensile characteristic were measured using the obtained sheet-like molded object. The results are shown in Table 1.

(Comparative Example 4) [Physical properties of block copolymer 3A50AN6.5]
45 g of the block copolymer (3A50AN6.5) obtained in Production Example 3-2 was melt-kneaded at 100 rpm for 15 minutes using a plastmill “MODEL20C200” (manufactured by Toyo Seiki Co., Ltd.) set at 220 ° C. The obtained bulk sample was hot press molded at 220 ° C. to obtain a cylindrical molded body for evaluation of compression set having a diameter of 30 mm and a thickness of 12 mm, and the compression set and hardness of the obtained molded body were measured. . Moreover, it hot-press-molded similarly and obtained the sheet-like molded object of thickness 2mm, and low-temperature embrittlement temperature, oil resistance, and the tensile characteristic were measured using the obtained sheet-like molded object. The results are shown in Table 1.

(Comparative Example 5) [Physical Properties of Block Copolymer 3A50AN6, 3A20AN6.8, 2A40AN6.5 and Mixture of Lubricant and Inorganic Filler]
18 g of the block copolymer (3A50AN6) obtained in Production Example 1-2, 18 g of the block copolymer (3A20AN6.8) obtained in Production Example 2-2, and the block copolymer obtained in Production Example 3-2 First, 9 g of the union (2A40AN6.5) was melt kneaded at 100 rpm for 5 minutes using a plastmill “MODEL20C200” (manufactured by Toyo Seiki Co., Ltd.) set at 220 ° C. 0.05 g and 2.2 g of an inorganic filler (Aerosil R972 manufactured by Nippon Aerosil Co., Ltd.) were added and then melt-kneaded for 10 minutes. The obtained massive sample was hot press molded at 220 ° C. to obtain a cylindrical molded body for evaluation of compression set having a diameter of 30 mm and a thickness of 12 mm, and the hardness of the obtained molded body was measured. Moreover, it hot-press-molded similarly and obtained the sheet-like molded object of thickness 2mm, and low-temperature embrittlement temperature, oil resistance, and the tensile characteristic were measured using the obtained sheet-like molded object. The results are shown in Table 1.

表１（実施例１〜４および比較例１〜５）の結果から明らかのように、実施例１、２、３で示した本発明のブロック共重合体にポリオルガノシロキサン系グラフト重合体を導入された組成物からなる成形体は、比較例１、４に示したブロック共重合体単独だけの成形体よりも良好な引張特性、圧縮永久歪、耐油性を維持して、引張特性の弾性率と低温特性が非常に良好であることがわかる。加えて、実施例４で示したポリオルガノシロキサン系グラフト重合体、滑剤および無機充填剤を導入することで、比較例１〜５よりも引張特性の弾性率と低温特性が著しく良好な材料であることがわかる。

As is apparent from the results of Table 1 (Examples 1 to 4 and Comparative Examples 1 to 5), the polyorganosiloxane graft polymer was introduced into the block copolymers of the present invention shown in Examples 1, 2, and 3. The molded product comprising the composition thus obtained maintained the tensile properties, compression set and oil resistance better than the molded products of the block copolymer alone shown in Comparative Examples 1 and 4, and the elastic modulus of the tensile properties. It can be seen that the low-temperature characteristics are very good. In addition, by introducing the polyorganosiloxane-based graft polymer, lubricant and inorganic filler shown in Example 4, the material has significantly higher elastic modulus and low-temperature characteristics than those of Comparative Examples 1 to 5. I understand that.

(Example 5)
2.7 g of the acrylic block copolymer (3A50AN6.1) obtained in Production Example 5-2 and 472.7 g of the polyorganosiloxane graft polymer (PM122) obtained in Production Example 8 were uniformly dispersed. Mix thoroughly by hand blending. The kneading conditions are C1-C4: 50 ° C., C5: 100 ° C., C6: 150 ° C., C7: 200 ° C., die head: 220 ° C., rotation speed: 100 rpm, 100 mesh, 150 mesh, 100 mesh stainless steel wire mesh at the die part. Were melt-kneaded with a vented twin-screw extruder “TEX30HSS-25.5PW-2V” (manufactured by Nippon Steel). The extruded strand was pelletized with a pelletizer “SCF-100” (manufactured by Isuzu Chemical Co., Ltd.) so as to facilitate injection molding. The pellets obtained by drying at 80 ° C. for 3 hours or more were obtained by using an injection molding machine “IS-80EPN” (manufactured by Toshiba Machine Co., Ltd.) with a clamping pressure of 80 TON, a nozzle temperature of 240 ° C., an injection pressure of 50%, and an injection speed of 50%. Then, injection molding is performed at a mold temperature of 80 ° C., a 120 × 120 × 2 mm flat plate is obtained, the obtained molded bodies are stacked three times, the hardness is measured, and the 2 mm flat plate is punched into a shape necessary for each evaluation at a low temperature. The embrittlement temperature, oil resistance and tensile properties were measured. The results are shown in Table 2.

(Example 6)
Acrylic block copolymer (3A60AN6) 1515.2 g obtained in Production Example 6-2 and polyorganosiloxane graft polymer (NM15) 984.8 g obtained in Production Example 9 were uniformly dispersed. Mix thoroughly by hand blending. Kneading and injection molding were performed under the same conditions as in Example 5 to obtain a 120 × 120 × 2 mm flat plate, and three molded products were stacked to measure the hardness. A 2 mm flat plate was required for each evaluation. Punched into various shapes, the low temperature embrittlement temperature, oil resistance and tensile properties were measured. The results are shown in Table 2.

(Example 7)
Hand blend so that 727 g of the acrylic block copolymer (3A70AN6) obtained in Production Example 7-2 and 472.7 g of the polyorganosiloxane graft polymer (NM15) obtained in Production Example 9 are uniformly dispersed. Mix thoroughly. Kneading and injection molding were performed under the same conditions as in Example 5 to obtain a 120 × 120 × 2 mm flat plate, and three molded products were stacked to measure the hardness. A 2 mm flat plate was required for each evaluation. Punched into various shapes, the low temperature embrittlement temperature, oil resistance and tensile properties were measured. The results are shown in Table 2.

(Example 8)
536.7 g of the acrylic block copolymer (3A70AN6) obtained in Production Example 7-2 and 266.7 g of the polyorganosiloxane graft polymer (BMT26) obtained in Production Example 10 were uniformly dispersed. Mix thoroughly by hand blending. The kneading and injection molding were performed under the same conditions as in Example 5 to obtain a 120 × 120 × 2 mm flat plate, the obtained molded bodies were stacked three times, the hardness was measured, and a 2 mm flat plate was necessary for each evaluation. The shape was punched and the low temperature embrittlement temperature, oil resistance and tensile properties were measured. The results are shown in Table 2.

Example 9
1466.3 g of the acrylic block copolymer (3A70AN6) obtained in Production Example 7-2, 953.1 g of the polyorganosiloxane graft polymer (NM15) obtained in Production Example 9 and a thermoplastic resin (Nylon 6 Ube) 73.3 g manufactured by Kosan Co., Ltd. 1013B) was sufficiently mixed by hand blending so as to be uniformly dispersed. The kneading conditions are C1-C4: 50 ° C., C5: 80 ° C., C6: 100 ° C., C7: 240 ° C., die head: 240 ° C., rotation speed: 100 rpm, 100 mesh, 150 mesh, 100 mesh stainless steel wire mesh at the die part. Were melt-kneaded with a vented twin-screw extruder “TEX30HSS-25.5PW-2V” (manufactured by Nippon Steel). The extruded strand was pelletized with a pelletizer “SCF-100” (manufactured by Isuzu Chemical Co., Ltd.) so as to facilitate injection molding. Injection molding is performed under the same conditions as in Example 5 to obtain a 120 × 120 × 2 mm flat plate, the obtained three molded bodies are stacked, the hardness is measured, and the 2 mm flat plate is formed into a shape necessary for each evaluation. Punching was performed to measure the low temperature embrittlement temperature, oil resistance and tensile properties. The results are shown in Table 2.

Example 10 [Physical Properties of Injection Molded Body of Mixture of Acrylic Block Copolymer (3A50AN6.1), Polyorganosiloxane Graft Polymer (NM15), and Lubricant (Amino-Modified Silicone)]
1918.6 g of the acrylic block copolymer (3A50AN6.1) obtained in Production Example 5-2, 575.6 g of the polyorganosiloxane graft polymer (NM15) obtained in Production Example 9, and a lubricant (amino-modified silicone) 5.8 g of Nippon Unicar Co., Ltd. FZ-3508) was sufficiently mixed by hand blending so as to be uniformly dispersed. The kneading and injection molding were performed under the same conditions as in Example 5 to obtain a 120 × 120 × 2 mm flat plate, the obtained molded bodies were stacked three times, the hardness was measured, and a 2 mm flat plate was necessary for each evaluation. The shape was punched and the low temperature embrittlement temperature, oil resistance and tensile properties were measured. The results are shown in Table 2.

Example 11 [Physical Properties of Injection Molded Body of Mixture of Acrylic Block Copolymer (3A70AN6), Polyorganosiloxane Graft Polymer (NM15), and Inorganic Filler (Carbon Black)]
604.2 g of the acrylic block copolymer (3A70AN6) obtained in Production Example 7-2, 392.7 g of the polyorganosiloxane graft polymer (NM15) obtained in Production Example 9 and an inorganic filler (Asahi Carbon Black) 3.0 g of Asahi # 15 manufactured by Carbon Co., Ltd. was thoroughly mixed by hand blending so as to be uniformly dispersed. The kneading and injection molding were performed under the same conditions as in Example 5 to obtain a 120 × 120 × 2 mm flat plate, the obtained molded bodies were stacked three times, the hardness was measured, and a 2 mm flat plate was necessary for each evaluation. The shape was punched and the low temperature embrittlement temperature, oil resistance and tensile properties were measured. The results are shown in Table 2.

(Comparative Example 6) [Physical Properties of Injection Molded Body of Acrylic Block Copolymer (3A50AN6.1)]
The acrylic block copolymer (3A50AN6.1) obtained in Production Example 5-2 was molded by injection molding under the same conditions as in Example 5 to obtain a 120 × 120 × 2 mm flat plate, and the resulting molded product 3 were stacked and the hardness was measured. A 2 mm flat plate was punched into a shape necessary for each evaluation, and the low temperature embrittlement temperature, oil resistance and tensile properties were measured. The results are shown in Table 2.

(Comparative Example 7) [Physical Properties of Injection Molded Body of Acrylic Block Copolymer (3A60AN6)]
The acrylic block copolymer (3A60AN6) obtained in Production Example 6-2 was molded by injection molding under the same conditions as in Example 5 to obtain a 120 × 120 × 2 mm flat plate. The hardness was measured by stacking the sheets, and a 2 mm flat plate was punched into a shape necessary for each evaluation to measure the low temperature embrittlement temperature, oil resistance and tensile properties. The results are shown in Table 2.

(Comparative Example 8) [Physical Properties of Injection Molded Body of Acrylic Block Copolymer (3A70AN6)]
The acrylic block copolymer (3A70AN6) obtained in Production Example 7-2 was molded by injection molding under the same conditions as in Example 5 to obtain a 120 × 120 × 2 mm flat plate. The hardness was measured by stacking the sheets, and a 2 mm flat plate was punched into a shape necessary for each evaluation to measure the low temperature embrittlement temperature, oil resistance and tensile properties. The results are shown in Table 2.

表２（実施例５〜１１および比較例６〜８）の結果から明らかのように、実施例５、６、７、８で示した本発明のアクリル系ブロック共重合体にポリオルガノシロキサン系グラフト重合体を導入された組成物からなる成形体は、比較例６，７，８に示したアクリル系ブロック共重合体単独だけの成形体よりも良好な引張特性、耐油性を維持して、引張特性の弾性率と低温特性が非常に良好であることがわかる。加えて、実施例９、１０、１１で示したポリオルガノシロキサン系グラフト重合体、熱可塑性樹脂、滑剤および無機充填剤を導入することでも、比較例６〜８よりも引張特性の弾性率と低温特性が著しく良好な材料であることがわかる。

As is apparent from the results of Table 2 (Examples 5 to 11 and Comparative Examples 6 to 8), the polyorganosiloxane grafts were applied to the acrylic block copolymers of the present invention shown in Examples 5, 6, 7, and 8. The molded body made of the composition into which the polymer was introduced maintained a better tensile property and oil resistance than the molded body of the acrylic block copolymer alone shown in Comparative Examples 6, 7, and 8. It can be seen that the elastic modulus and low-temperature characteristics are very good. In addition, even when the polyorganosiloxane graft polymer, thermoplastic resin, lubricant and inorganic filler shown in Examples 9, 10, and 11 are introduced, the elastic modulus and the low temperature of tensile properties are higher than those of Comparative Examples 6-8. It can be seen that the material has remarkably good characteristics.

Claims (16)

In the whole composition, an acrylic polymer composition comprising (A) 50 to 90% by weight of an acrylic block copolymer and (B) 50 to 10% by weight of a polyorganosiloxane graft polymer,
The acrylic block copolymer (A) comprises (a) an acrylic polymer block and (b) a methacrylic polymer block. In the main chain of at least one polymer block, (c) the general formula (1 ):

(Wherein R ¹ is a hydrogen atom or a methyl group, and may be the same or different, p is an integer of 0 or 1, q is an integer of 0 to 3) Having a unit consisting of (c1) and / or a unit (c2) containing a carboxyl group,
In the whole acrylic block copolymer (A), 0.1 to 50% by weight of a unit (c2) containing a carboxyl group is contained ,
The polyorganosiloxane graft polymer (B) is a polyfunctional monomer containing two or more polymerizable unsaturated bonds in the molecule, an aromatic vinyl monomer, and cyanide. At least one monomer selected from the group consisting of vinyl monomers, (meth) acrylic acid ester monomers, vinyl monomers containing an epoxy group in the molecule, and ethylenically unsaturated carboxylic acids An acrylic polymer composition characterized by being a polymer obtained by graft polymerization . 2. The acrylic block copolymer (A) as a whole comprises (a) 40 to 90% by weight of an acrylic polymer block and (b) 60 to 10% by weight of a methacrylic polymer block. The acrylic polymer composition according to 1. In the entire acrylic polymer block (a), at least one monomer selected from the group consisting of n-butyl acrylate, ethyl acrylate and 2-methoxyethyl acrylate, and copolymerized therewith. The acrylic polymer composition according to claim 1 or 2, comprising 0 to 50% by weight of another possible acrylic ester and / or other vinyl monomer. The whole acrylic polymer block (a) contains 10 to 90% by weight of 2-methoxyethyl acrylate and 10 to 90% by weight of n-butyl acrylate, and further contains 0 to 80% by weight of ethyl acrylate as an optional component. The acrylic polymer composition according to any one of claims 1 to 3. The acrylic polymer composition according to any one of claims 1 to 4, wherein the acrylic block copolymer (A) is a block copolymer produced by atom transfer radical polymerization. (B) The polyorganosiloxane graft polymer is a polyorganosiloxane graft polymer having a graft component content of 5 to 40% by weight and a polyorganosiloxane content of 95 to 60% by weight. The acrylic polymer composition according to any one of 1 to 5. (B) A polyorganosiloxane-based graft polymer having an alkyl methacrylate content of 5 to 99.5% by weight and an alkyl acrylate content of 95 to 0.5% by weight in the entire graft component of the polyorganosiloxane-based graft polymer. The acrylic polymer composition according to any one of claims 1 to 6, which is a coalescence. (B) The alkyl methacrylate component in the entire graft component of the polyorganosiloxane-based graft polymer essentially comprises 0.5 to 50% by weight of n-butyl methacrylate. Acrylic polymer composition. (B) The acrylic polymer composition according to claim 8, wherein 0.5 to 10% by weight of methacrylic acid or acrylic acid is contained in the entire graft of the polyorganosiloxane graft polymer. Further, the acrylic polymer composition according to any one of claims 1 to 9 blended with (C) Lubricant. Furthermore, (D) The acrylic polymer composition in any one of Claims 1-10 which mix | blended the inorganic filler. Furthermore, the acrylic polymer composition in any one of Claims 1-11 which mix | blended (E) thermoplastic resin. For 100 parts by weight of the acrylic block copolymer (A), 15 to 100 parts by weight of the polyorganosiloxane graft polymer (B) is blended,
The acrylic polymer composition according to claim 10, further comprising (C) 0.1 to 10 parts by weight of a lubricant. For 100 parts by weight of the acrylic block copolymer (A), 15 to 100 parts by weight of the polyorganosiloxane graft polymer (B) is blended,
The acrylic polymer composition according to claim 11, further comprising (D) 0.1 to 100 parts by weight of an inorganic filler. For 100 parts by weight of the acrylic block copolymer (A), 15 to 100 parts by weight of the polyorganosiloxane graft polymer (B) is blended,
The acrylic polymer composition according to claim 12, further comprising (E) 0.1 to 100 parts by weight of a thermoplastic resin. A molded article for automobiles, household electric appliances or office electric appliances using the acrylic polymer composition according to any one of claims 1 to 15 .