JP4467384B2 - Thermoplastic resin composition - Google Patents

Description

  The present invention relates to a thermoplastic resin composition having excellent molding processability, extremely excellent heat resistance, and having both low temperature characteristics and oil resistance.

  Thermoplastic elastomers do not require a vulcanization process compared to vulcanized rubber, and can be processed on ordinary thermoplastic resin molding machines, making them useful in a wide range of fields including automotive parts and machine parts. Application development has been underway. Acrylic block copolymer is a polymer mainly composed of acrylate ester and is known as a thermoplastic elastomer material with excellent oil resistance. Molding of sealing materials such as oil seals, O-rings and packings. Can be used as material. However, generally, an acrylic elastomer having good oil resistance has a problem of embrittlement at low temperature, and a thermoplastic elastomer material having no crosslinked rubber has a problem of low elastic modulus at a high temperature as compared with the crosslinked rubber. Further improvement in low temperature and heat resistance has been desired (Non-Patent Document 1).

  In order to improve low-temperature properties, acrylic elastomers have also been developed with acrylic ester having a low glass transition temperature added as a monomer component, but the effects of deteriorating various physical properties such as oil resistance and mechanical strength cannot be ignored. Further improvement measures are desired.

  In order to increase the elastic modulus at high temperature, which is an index of heat resistance, a technique such as crosslinking of the elastomer part is generally performed. However, a composition obtained by dynamically crosslinking a crystalline resin and rubber. For example, when a molded article having a bellows such as a constant velocity joint boot for automobiles is injection-molded, the size of the bellows part becomes large after mold removal, that is, before and after mold removal. There is a problem with dimensionality.

In general, oil resistance and low-temperature characteristics are contradictory properties (Patent Document 2), and it has been desired to develop a thermoplastic elastomer material that has both oil resistance and low-temperature characteristics and has a high elastic modulus at high temperatures.
Development of automotive polymer materials, CMC Publishing, 1989, p219 JP-A-6-306217 International Publication No. 02/064822 Pamphlet

  By including a polyorganosiloxane graft polymer and a resin containing an epoxy group in the acrylic block copolymer, the present invention is excellent in molding processability, extremely excellent in heat resistance, and low temperature characteristics and oil resistance. It aims at providing the thermoplastic resin composition which also has.

  As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.

  That is, the present invention includes a thermoplastic resin composition comprising an acrylic block copolymer (A), a polyorganosiloxane graft polymer (B), and a resin (C) containing an epoxy group. About.

  As a preferred embodiment, 10 to 100 parts by weight of the polyorganosiloxane graft polymer (B) and 0.5 parts of the resin (C) containing an epoxy group with respect to 100 parts by weight of the acrylic block copolymer (A). It is related with the thermoplastic resin composition characterized by being-30 weight part.

  In a preferred embodiment, the acrylic block copolymer (A) is an acrylic block copolymer comprising an acrylic polymer block (a) and a methacrylic polymer block (b). The thermoplastic resin composition characterized by these.

  A preferred embodiment relates to a thermoplastic resin composition wherein the resin (C) containing an epoxy group is an olefin resin.

  As a preferred embodiment, in the acrylic block copolymer (A), 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）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熱可塑性樹脂組成物に関する。

(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 a thermoplastic resin composition comprising a unit comprising (c1) and / or a unit (c2) containing a carboxyl group.

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

  In a preferred embodiment, the acrylic block copolymer (A) contains 40 to 90% by weight of the acrylic polymer block (a), and the methacrylic polymer block (b) is 60 to 10% by weight. The thermoplastic resin composition characterized by containing.

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

  As a preferred embodiment, 5 to 90% by weight of 2-methoxyethyl acrylate, 5 to 90% by weight of n-butyl acrylate, and ethyl acrylate in the whole acrylic polymer block (a) It is related with the thermoplastic resin composition characterized by containing 5 to 90 weight%.

  As a preferred embodiment, the present invention relates to a thermoplastic resin composition characterized in that an acrylic block copolymer is produced by atom transfer radical polymerization.

  As a preferred embodiment, the polyorganosiloxane-based graft polymer (B) is a polyfunctional monomer having two or more polymerizable unsaturated bonds in the presence of 40 to 95% by weight of the polyorganosiloxane (d1). The vinyl monomer (d2) consisting of 50 to 100% by weight of the body (x) and other copolymerizable monomer (y) 0 to 50% by weight is polymerized, and further vinyl It is a polyorganosiloxane graft polymer obtained by polymerizing 5 to 60% by weight of a monomer (d3) (100% by weight in total of (d1), (d2) and (d3)) The present invention relates to a thermoplastic resin composition.

  Furthermore, the present invention relates to an automobile / electric / electronic component comprising a molded article of the thermoplastic resin composition described above.

  Furthermore, the present invention relates to automotive seals comprising a molded product of the thermoplastic resin composition described above.

  Furthermore, this invention relates to the constant velocity joint boot for motor vehicles which consists of a molded object of the said thermoplastic resin composition.

  According to the present invention, it is possible to obtain a thermoplastic resin composition having excellent molding processability, extremely excellent heat resistance, and having both low temperature characteristics and oil resistance.

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

The linear acrylic block copolymer may have any linear block structure, but constitutes an acrylic block copolymer 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 acrylic block copolymer is preferably at least one selected from the group consisting of acrylic 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.

  In the acrylic block copolymer of the present invention, 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）で表わされる単位（ｃ）を有することが好ましい。単位（ｃ）は、酸無水物基を含有する単位（ｃ１）及び／又はカルボキシル基を含有する単位（ｃ２）からなる単位であり、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, which 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) preferable. The unit (c) is a unit composed of a unit (c1) containing an acid anhydride group and / or a unit (c2) containing a carboxyl group, and an acrylic polymer block (a) and a methacrylic polymer block. It is sufficient that at least one polymer block in (b) is contained, and when the number is two or more, the mode in which the monomers are polymerized is 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) measured by gel permeation chromatography is preferably 30,000 to 500,000, more preferably 40,000 to 400,000, and 50,000 to 30,000. 0000 is more preferable. 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, the processing properties may deteriorate.

  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. If Mw / Mn exceeds 2, the uniformity of the acrylic block copolymer 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. May decrease the mechanical strength.

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.

Specific examples of the acrylic block copolymer (A) include the acrylic block copolymers produced in Production Examples 1-2 and 2-2, for example.
<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 the range M _A , the range is preferably M _A > 3,000, more preferably M _A > 5,000, and still more preferably M _A. > 10,000, particularly preferably M _A > 20,000, most preferably M _A > 40,000. However, since the polymerization time tends to be long when the number average molecular weight is large, it 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.

  50 to 100% by weight of units in which the acrylic polymer block (a) contains at least one monomer selected from the group consisting of n-butyl acrylate, ethyl acrylate, and 2-methoxyethyl acrylate, and What consists of 0 to 50 weight% of the unit containing the other acrylic ester and / or other vinyl monomer copolymerizable with these is preferable.

  Among these acrylate esters, n-butyl acrylate is preferable from the viewpoint of low-temperature characteristics, compression set, cost, and availability. If oil resistance and mechanical properties are required, ethyl acrylate is preferred. When low temperature characteristics, mechanical characteristics, and compression set are required, 2-ethylhexyl acrylate is preferred. From the viewpoint of mechanical properties, oil resistance, and low temperature properties, 2-methoxyethyl acrylate 5 to 90% by weight, n-butyl acrylate 5 to 90% by weight, ethyl acrylate 5 in the whole acrylic polymer block (a) A mixture of ˜90% by weight is preferable, and a mixture of 2-methoxyethyl acrylate 15 to 85% by weight, n-butyl acrylate 15 to 85% by weight, and ethyl acrylate 5 to 70% by weight is more preferable.

  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 has the glass transition temperature, elastic modulus and polarity required for the acrylic polymer block (a), and physical properties required when the acrylic block copolymer is used as a composition. The preferred one can be selected depending on the compatibility with the polyorganosiloxane-based graft polymer. 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. If the glass transition temperature is higher than 50 ° C., the rubber elasticity of the acrylic block copolymer may decrease.

  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, acrylic polymer blocks contained in the acrylic block copolymer (A) produced in Production Example 1-2 and Production Example 2-2.
<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 an acrylic block copolymer having desired physical properties, cost, and easy availability, 0 to 100 units containing a methacrylic acid ester are contained in the entire methacrylic polymer block (b). Containing 0 to 85% by weight, preferably 0 to 85% by weight, containing 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 It is preferable to contain 0 to 50% by weight, preferably 0 to 25% by weight, of another copolymerizable vinyl monomer.

  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. (Polymer. Eng. And Sci., 1990, 30, 753) and the like. 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. Therefore, it may be set according to the required productivity, but it is preferably 200,000 or less, more preferably 100,000 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. The vinyl monomer can be selected from the viewpoint of compatibility when the acrylic block copolymer is combined with the polyorganosiloxane graft polymer (B). In addition, methyl methacrylate polymer is almost quantitatively depolymerized by thermal decomposition, but in order to suppress it, acrylic acid esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, acrylic acid 2 -Methoxyethyl 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.

Specific examples of the methacrylic polymer block (b) include, for example, the methacrylic polymer block contained in the acrylic block copolymer (A) produced in Production Example 1-2 and Production Example 2-2. It is done.
<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) is required for the reaction point of the acrylic block copolymer (A), the cohesive force and glass transition temperature of the block constituting the acrylic block copolymer (A), and further. Depending on the physical properties of the acrylic block copolymer (A), it can be used properly. From the viewpoint of improving the heat resistance and heat decomposability of the acrylic block copolymer (A), the unit (c) may be introduced into the methacrylic polymer block (b). From the viewpoint of imparting rubber elasticity to the coalescence, 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 polymerization operation of the acrylic block copolymer becomes complicated, and the difference in the glass transition temperature between the acrylic polymer block (a) and the methacrylic polymer block (b) is reduced. The rubber elasticity of the coalescence 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, 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 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 acrylic 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 acrylic block copolymer (A) can be further improved, which is preferable. In the whole acrylic block copolymer (A), it is preferable to contain 0.1 to 50% by weight of the unit (c2) containing a carboxyl group, since the heat resistance becomes high.

  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) will be described below.

  The method for introducing the unit (c1) containing an acid anhydride group is not particularly limited, but a unit containing a group that is a precursor of an acid anhydride group is introduced into the acrylic block copolymer (A). Thereafter, cyclization is preferred. 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アクリル系ブロック共重合体組成物を、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アクリル系ブロック共重合体組成物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 having at least one unit, that is, an acrylic block copolymer composition using the monomers exemplified below as an acrylic ester constituting the acrylic polymer block (a), preferably 180 It can introduce | transduce by melt-kneading and cyclizing at the temperature of -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 acrylic block copolymer composition 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 acrylic block copolymer. 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, in the process of introducing the acid anhydride group-containing unit (c1) into the acrylic block copolymer. 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 the general formula (2). This is because it is easy to control the reaction point of the acrylic block copolymer and to introduce the carboxyl group-containing unit (c2) into the acrylic block copolymer.
<Manufacture of acrylic block copolymer (A)>
Although it does not specifically limit as a manufacturing method, 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. When producing a b-a-b type triblock copolymer or an a-b-a 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.
<Polyorganosiloxane-based graft polymer (B)>
The polyorganosiloxane graft polymer (B) in the present invention will be described. The polyorganosiloxane graft polymer is blended and dispersed in an acrylic block copolymer which is a matrix resin of the present composition. Even when the temperature is not higher than the embrittlement temperature of the acrylic block copolymer alone, which is a matrix resin, no breakage due to embrittlement occurs, and it is possible to develop good low-temperature characteristics. In addition, low temperature properties such as low temperature elastic recovery characteristics (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 graft polymer (B) is not particularly limited, but in the presence of 40 to 95% by weight of the polyorganosiloxane (d1), the vinyl monomer (d2) is 0 to 10% by weight. And 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)). Here, the vinyl monomer (d2) is a polyfunctional monomer (x) 50 to 100% by weight containing two or more polymerizable unsaturated bonds, and other copolymerizable vinyl monomers. The body (y) refers to 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, it functions to enable the graft polymer resin to be powdered. Further, as the graft crossing agent used for the component (d1), generally, a graft crossing agent that is insufficient in grafting efficiency at the time of graft polymerization of the vinyl monomer (d3) described below, specifically, for example, In the case of using mercaptopropylmethyldimethoxysilane or the like described in JP-A-60-252613, the use of the component (d2) makes it possible to use a polymer component that does not participate in grafting among the vinyl monomers (d3) ( Free polymer component) can be reduced, and more efficient graft polymerization can be achieved. With such an effect, it is possible to effectively improve the physical properties of the molded product obtained from the thermoplastic resin composition according to the present invention. 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 the compatibility between the polyorganosiloxane graft polymer (B) and the acrylic block copolymer (A), and the polyorganosiloxane graft polymer ( It is a component used for uniformly dispersing B). 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) has a solubility parameter value of a polymer obtained by polymerizing the vinyl monomer (d3), and a solubility parameter value of an acrylic block copolymer that is a matrix resin. It is preferable to select to be close. By selecting so that the solubility parameter value of the polymer obtained by polymerizing the vinyl monomer (d3) is close to the solubility parameter of the acrylic block copolymer, in the thermoplastic resin composition The dispersion state of the polyorganosiloxane 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. For reasons such as bringing the solubility parameter close to the acrylic block copolymer, the alkyl methacrylate component in the entire graft component of the polyorganosiloxane graft polymer is 0.5 to 50% by weight of n-butyl methacrylate. It is preferable to make it 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.

The blending amount of the polyorganosiloxane graft polymer (B) with respect to 100 parts by weight of the acrylic block copolymer (A) is not particularly limited, but is preferably 10 to 100 parts by weight. If the blending amount of the polyorganosiloxane graft polymer (B) is larger than 100 parts by weight, the oil resistance may be lowered, and if it is smaller than 10% by weight, the low temperature characteristics may be insufficiently improved.
<Resin containing epoxy group (C)>
The resin (C) containing an epoxy group used in the present invention is not particularly limited as long as it is a resin that reacts with the unit (c) contained in the acrylic block copolymer (A). And a copolymer of ethylene and glycidyl methacrylate, a copolymer of ethylene and glycidyl methacrylate having methyl acrylate, a copolymer of ethylene and glycidyl methacrylate grafted with polymethyl methacrylate, etc. A copolymer of ethylene and glycidyl methacrylate grafted with polymethyl methacrylate having good compatibility with the methacrylic polymer block (b) of the acrylic block copolymer (A) is preferable. Although there is no restriction | limiting in particular in the compounding quantity of resin (C) containing an epoxy group with respect to 100 weight part of acrylic block copolymers (A), 0.5-30 weight part is preferable. When the compounding amount of the resin (C) containing an epoxy group is larger than 30 parts by weight, the cohesiveness of the acrylic block copolymer (A) becomes too strong, and the tensile elongation may be lowered. If it is less than% by weight, the improvement in elastic modulus at high temperatures may be insufficient. Resins (C) containing these epoxy groups are, for example, commercially available Modiper, Bond First, etc., and can be easily obtained from the market.
<Thermoplastic resin composition>
The thermoplastic resin composition of the present invention comprises an acrylic block copolymer (A), a polyorganosiloxane graft polymer (B), and an epoxy group-containing resin (C). However, the blending amount of each component may be appropriately determined according to the characteristics of each product. For example, in the case of seal products such as boots for constant velocity joints for automobiles, the acrylic block copolymer (A) is added to 100 parts by weight. On the other hand, it is preferably composed of 10 to 100 parts by weight of the polyorganosiloxane graft polymer (B) and 0.5 to 30 parts by weight of the epoxy group-containing resin (C). When the respective contents are within the above ranges, a molded article having good heat resistance, oil resistance and low temperature can be obtained, which is particularly preferable in the case of seal products such as boots for constant velocity joints for automobiles.

  The composition of the present invention further includes stabilizers (anti-aging agents, light stabilizers, UV absorbers, etc.), flexibility imparting agents, flame retardants, mold release agents, antistatic agents, antibacterial agents, depending on the required properties. A mold 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 acrylic polymer block (A) and the polyorganosiloxane graft polymer (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.

  The thermoplastic resin composition thus obtained is molded into a shape according to the molding purpose by a molding method such as injection molding or hot press molding. From the viewpoint of handling, uniformity of kneading, 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.

  What is necessary is just to adjust the temperature at the time of the said kneading | mixing according to the melting temperature etc. of the acrylic block copolymer (A) to be used, polyorganosiloxane type graft polymer (B), resin (C) containing an epoxy group. For example, it can be pelletized by melt-kneading at 20 to 300 ° C.

  The molding of the composition of the present invention can be exemplified by any molding method such as extrusion molding, compression molding, blow molding, calender molding, vacuum molding, foam molding, injection molding, injection blow and the like. Of these, injection molding is preferred because it is simple.

  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 moldability, low temperature property, oil resistance and heat resistance, and can be suitably used for boots for constant velocity joints for automobiles, For example, compared to conventional vulcanized rubber systems, the molding process is simplified and the recyclability is excellent.

  Examples of uses of the composition include molded products for automobiles, household electrical appliances, and office electrical appliances. Specifically, oil seals, various oil seals such as reciprocating oil seals, various packings such as gland packing, lip packing, squeeze packing, suspension dust cover, suspension / tie rod dust cover, stabilizer / die rod dust cover, etc. Various dust covers, resin intake manifold gaskets, gaskets for throttle bodies, gaskets for power steering vane pumps, gaskets for head covers, gaskets for water heater self-contained pumps, filter gaskets, gaskets for pipe fittings (ABS & HBB), top cover gaskets for HDDs, HDD connector gasket, cylinder head gasket combined with metal, car cooler compressor gasket, gasket around the engine , AT separate plates, various gaskets such as general-purpose gaskets (industrial sewing machines, nailing machines, etc.), needle valves, plunger valves, water / gas valves, brake valves, drinking valves, safety valves for aluminum electrolytic capacitors, etc. Valves, vacuum boosters, water / gas diaphragms, seal washers, bore plugs, high-precision stoppers and other stoppers mainly with buffer performance, plug tube seals, injection pipe seals, oil receivers, brake drum seals , Precision seal rubber such as shading seal, plug seal, connector seal, keyless entry cover and the like. Also, various weather strips such as door weather strips for automobiles, molded articles such as trunk seals and glass run channels can be mentioned. In particular, the molded product obtained by injection molding is useful as a molded product for automobiles, household electrical appliances, or office appliances, and particularly useful as automotive seals and constant velocity joint boots for automobiles.

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, and TBMA mean ethyl acrylate, butyl acrylate, 2-methoxyethyl acrylate, methyl methacrylate, and t-butyl methacrylate, respectively.

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

  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.

(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.

(High temperature tensile properties (elastic modulus))
In accordance with the method described in JIS K7113, the elastic modulus was measured using an autograph AG-10TB type manufactured by Shimadzu Corporation. 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 120 ° 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.

  The dumbbell punching direction was horizontal with respect to the gate of the injection molded body.

(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
<Production example of acrylic block copolymer>
(Production Example 1-1) [Synthesis of 3A20T6.5]
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, 1047 g (7.3 mol) of copper bromide was measured, and 14.8 L of acetonitrile (nitrogen bubbling) was added. After heating and stirring at 70 ° C. for 30 minutes, the initiators diethyl 2,5-dibromoadipate 525.6 g (1.46 mol) and BA 29.7 L (207.4 mol), EA 28.3 L (260.8 mol), MEA 16.0 L (124.5 mol) was added. The mixture was heated and stirred at 85 ° C., and 0.15 L (0.73 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%, the conversion rate of EA was 96%, and the conversion rate of MEA was 96%, TBMA 16.6L (102.4 mol), MMA 43.8L (409.6 mol), copper chloride 723 g ( 7.3 mol), 1.5 L (11.2 mol) of butyl acetate and 149.5 L of toluene (nitrogen bubbled). 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, 1666 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 obtained polymer solution, 1013.8 g of adsorbent Kyoward 500SH (manufactured by Kyowa Chemical Co., Ltd.) was added and stirred at room temperature for further 3 hours, and the adsorbent was filtered using a bag filter to obtain a colorless and transparent polymer solution. It was. This solution was dried using a horizontal evaporator (heat transfer area: 1 m ² ) to remove the solvent and residual monomers, thereby obtaining the target block copolymer 3A20T6.5.

  When the GPC analysis of obtained block copolymer 3A20T6.5 was performed, 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 characteristics evaluation of block copolymer 3A20T6.5]
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 (3A20T6.5) obtained in Production Example 1-1 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 Alfro H- By adding 50ES (Nippon Yushi Co., Ltd.), spherical pellets (hereinafter referred to as 3A20T6.5) having no adhesion were obtained.

(Production Example 2-1) [Synthesis of 3A50T5.5]
Using a 500 L reactor equipped with a stirrer capable of heating and cooling, 627.9 g (1.74 mol) of diethyl 2,5-dibromoadipate, 30.5 L (213.0 mol) of BA, 29.0 L (267.8 mol) of EA, MEA Polymerization was carried out at a charge ratio of 16.4 L (127.8 mol). When the conversion rate of BA was 96%, the conversion rate of EA was 95%, and the conversion rate of MEA was 96%, TBMA 38.7L (238.9 mol) ), 25.6 L (238.9 mol) of MMA were 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 1-1 to obtain the intended acrylic block copolymer (3A50T5.5).

  When the GPC analysis of the obtained acrylic block copolymer (3A50T5.5) was performed, the number average molecular weight (Mn) was 99900, and molecular weight distribution (Mw / Mn) was 1.37.

(Production Example 2-2) [6-membered cyclic acid anhydride reaction and characterization of acrylic block copolymer 3A50T5.5]
Irganox 1010 (manufactured by Ciba Specialty Chemicals) 0.3 weight with respect to 100 parts by weight of the obtained acrylic block copolymer (3A50T5.5) obtained in Production Example 2-1 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 Alfro H- By adding 50ES (manufactured by NOF Corporation), spherical pellets having no adhesion (hereinafter referred to as 3A50T5.5) were obtained.
<Production Example of Polyorganosiloxane Graft Polymer>
(Production Example 3) [Synthesis of 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.

Example 1
448.7 g of acrylic block copolymer (3A20AN6.5) obtained in Production Example 1-2, 1794.9 g of acrylic block copolymer (3A50AN5.5) obtained in Production Example 2-2, Production Example 3) 1009.6 g of the polyorganosiloxane graft polymer (NM15) obtained in Step 3 and 224.4 g of an epoxy group-containing resin (ethylene-glycidyl methacrylate grafted with polymethyl methacrylate) were dispersed uniformly. Mix well in blend. 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.) having 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 (120 ° C. elastic modulus) were measured. The results are shown in Table 1.

(Example 2)
596.6 g of acrylic block copolymer (3A20AN6.5) obtained in Production Example 1-2, 1392.0 g of acrylic block copolymer (3A50AN5.5) obtained in Production Example 2-2, Production Example The polyorganosiloxane-based graft polymer (NM15) 1292.6 g obtained in 3 and 198.9 g of an epoxy group-containing resin (ethylene-glycidyl methacrylate grafted with polymethyl methacrylate) were dispersed so as to be uniformly dispersed. Mix well in blend. Kneading and injection molding were performed under the same conditions as in Example 1 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. A low temperature embrittlement temperature, oil resistance and tensile properties (120 ° C. elastic modulus) were measured by punching into various shapes. The results are shown in Table 1.

(Comparative Example 1)
The acrylic block copolymer (3A50AN5.5) obtained in Production Example 2-2 was molded by injection molding under the same conditions as in Example 1 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 1.

(Comparative Example 2)
602.4 g of acrylic block copolymer (3A20AN6.5) obtained in Production Example 1-2, 2409.6 g of acrylic block copolymer (3A50AN5.5) obtained in Production Example 2-2, Production Example 1957.8 g of the polyorganosiloxane graft polymer (NM15) obtained in 3 was thoroughly mixed by hand blending so as to be uniformly dispersed. Kneading and injection molding were performed under the same conditions as in Example 1 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. A low temperature embrittlement temperature, oil resistance and tensile properties (120 ° C. elastic modulus) were measured by punching into various shapes. The results are shown in Table 1.

表１（実施例１、２および比較例１、２）の結果から明らかのように、実施例１、２で示した本発明のアクリル系ブロック共重合体とポリオルガノシロキサン系グラフト重合体およびエポキシ基を含有する樹脂からなる組成物の成形体は、アクリル系ブロック共重合体の耐油性、および高温の引張弾性率を維持したまま、優れた低温特性を示しており、比較例１、２に比べ、バランスのよい特性を示していることがわかる。

As is apparent from the results of Table 1 (Examples 1 and 2 and Comparative Examples 1 and 2), the acrylic block copolymer, polyorganosiloxane graft polymer and epoxy of the present invention shown in Examples 1 and 2 were used. The molded body of the composition comprising a group-containing resin exhibits excellent low-temperature characteristics while maintaining the oil resistance of the acrylic block copolymer and the high-temperature tensile elastic modulus. It can be seen that the characteristics are well balanced.

Claims (9)

An acrylic block copolymer (A);
A polyorganosiloxane-based graft polymer (B);
A thermoplastic resin composition comprising a resin (C) containing an epoxy group,
The acrylic block copolymer (A) comprises an acrylic polymer block (a) and a methacrylic polymer block (b).
In the acrylic block copolymer (A), the general formula (1):

(Wherein R1 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,
Polyorganosiloxane-based graft polymer (B) is a polyfunctional monomer (x) 50 to 100 containing two or more polymerizable unsaturated bonds in the presence of 40 to 95% by weight of polyorganosiloxane (d1). And 0 to 10% by weight of a vinyl monomer (d2) consisting of 0 to 50% by weight and other copolymerizable monomers (y), and further vinyl monomer (d3) A polyorganosiloxane-based graft polymer obtained by polymerizing 5 to 60 wt% (100 wt% in total of (d1), (d2), and (d3)),
The epoxy group-containing resin (C) is a copolymer of ethylene and glycidyl methacrylate, a copolymer of ethylene and glycidyl methacrylate having methyl acrylate, or ethylene and glycidyl methacrylate grafted with polymethyl methacrylate. copolymer der of is,
The polyorganosiloxane graft polymer (B) is 10 to 100 parts by weight and the epoxy group-containing resin (C) is 0.5 to 30 parts by weight with respect to 100 parts by weight of the acrylic block copolymer (A). A thermoplastic resin composition characterized by the above.   2. The thermoplastic resin composition according to claim 1, wherein the acrylic block copolymer (A) contains 0.1 to 50% by weight of the carboxyl group-containing unit (c2). The acrylic block copolymer (A) contains 40 to 90% by weight of the acrylic polymer block (a) and 60 to 10% by weight of the methacrylic polymer block (b). The thermoplastic resin composition according to claim 1 or 2 . 50 to 100% by weight of units in which the acrylic polymer block (a) contains at least one monomer selected from the group consisting of n-butyl acrylate, ethyl acrylate, and 2-methoxyethyl acrylate, and The heat according to any one of claims 1 to 3 , comprising 0 to 50% by weight of a unit containing other acrylic acid ester and / or other vinyl monomer copolymerizable therewith. Plastic resin composition. In the whole acrylic polymer block (a), 2-methoxyethyl acrylate 5% to 90% by weight, n-butyl acrylate 5% to 90% by weight, and ethyl acrylate 5% to 90% by weight. The thermoplastic resin composition according to any one of claims 1 to 4 , characterized by comprising: The thermoplastic resin composition according to any one of claims 1 to 5 , wherein the acrylic block copolymer is produced by atom transfer radical polymerization. Automobiles, electric and electronic parts comprising a molded article of the thermoplastic resin composition according to any one of claims 1 to 6. An automobile seal comprising a molded article of the thermoplastic resin composition according to any one of claims 1 to 6 . The constant velocity joint boot for motor vehicles consisting of the molded object of the thermoplastic resin composition in any one of Claim 1 to 6 .