JP2009079119A - Molded product and modifier comprising resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a molded product and a modifier each comprising a resin composition with excellent flexibility, molding workability, recyclability, rubber properties, permanent compression set properties, heat resistance, oil resistance, weatherproofness, transparency, adhesion with a base material, and the like. <P>SOLUTION: The resin composition comprises at least one kind of substance selected among a group consisting of an acrylic block copolymer A consisting of a methacrylic polymer block (a) and an acrylic polymer blocks (b), a thermoplastic resin B, a thermoplastic elastomer C, rubber D, and a thermosetting resin (E). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a molded article and a modifier containing a specific acrylic block copolymer.

  Thermoplastic resins, thermosetting resins, rubbers, and thermoplastic elastomers are useful industrial products widely used in various fields. These thermoplastic resins, thermosetting resins, rubbers, and thermoplastic elastomers can be used alone, but if a single unit does not meet the required performance, combine multiple resins, rubbers, and thermoplastic elastomers. Attempts have been made to use them. For example, for the purpose of improving the impact resistance of a resin, it is a common practice to add a rubber-based resin or a thermoplastic elastomer to a thermoplastic resin.

Examples of the technology using a thermoplastic elastomer composed of a block copolymer include: general-purpose resins such as polyolefin and polystyrene; engineering plastics such as polyphenylene ether and polycarbonate; and thermoplastic elastomers, particularly styrene-butadiene-styrene (SBS), hydrogen A blend with a styrenic thermoplastic elastomer such as additive type SBS (SEBS) is disclosed (for example, see Non-Patent Document 1 or 2). However, in Non-Patent Document 1 or 2, the acrylic block copolymer is not mentioned, and since the additives and fillers added to the resin composition are hardly disclosed, the resin composition is At present, it is not sufficiently known what kind of molded body can be used and what kind of modifier can be used.
Mitsuo Akiba "Manufacture and application of polymer blends" CM Publishing, 1988 Mitsuo Akiba “All about Thermoplastic Elastomers” Industrial Research Committee, 2003

  The present invention relates to a molded article and a modifier comprising a resin composition excellent in moldability, recyclability, impact resistance, heat resistance, oil resistance, weather resistance, and the like. In addition, the present invention relates to a molded body and a modifier made of a resin composition excellent in molding processability, recyclability, flexibility, rubber properties, heat resistance, oil resistance, weather resistance, transparency, adhesion to a substrate, and the like.

  As a result of intensive studies in order to solve the above problems, the present inventors have found that a molded article and a modifier comprising a resin composition containing a specific acrylic block copolymer solve the above problems. The present invention has been completed.

That is, the present invention
(I). Acrylic block copolymer (A) comprising methacrylic polymer block (a) and acrylic polymer block (b), thermoplastic resin (B), thermoplastic elastomer (C), rubber (D) and a resin composition comprising at least one selected from the group consisting of thermosetting resins (E),
(II). The thermoplastic resin (B) is a thermoplastic resin selected from the group consisting of polyvinyl chloride resin, polymethyl methacrylate resin, acrylonitrile-styrene copolymer resin, methyl methacrylate-styrene copolymer resin, and polycarbonate resin. (I) resin composition according to,
(III). The resin composition according to (I), wherein the thermoplastic resin (B) is a crystalline thermoplastic resin,
(IV). The resin composition according to (III), wherein the thermoplastic resin (B) is a crystalline polyester resin or a crystalline polyamide resin,
(V). The thermoplastic elastomer (C) is at least one thermoplastic elastomer selected from the group consisting of a styrene elastomer, an olefin elastomer, a urethane elastomer, a vinyl chloride elastomer, an amide elastomer, and an ester elastomer (I) to ( IV) the resin composition according to any one of
(VI). From (I), rubber (D) is at least one rubber selected from the group consisting of natural rubber, diene polymer rubber, olefin polymer rubber, acrylic rubber, silicone rubber, and fluororubber. (V) the resin composition according to any one of the above,
(VII). From the group in which the thermosetting resin (E) is composed of an epoxy resin, a phenol resin, a melamine resin, a urea resin, an unsaturated polyester resin, an alkyd resin, a thermosetting polyimide resin, a hydrosilylation cross-linked resin and a urea resin. The resin composition according to any one of (I) to (VI), which is at least one thermosetting resin selected;
(VIII). The resin composition according to (VII), wherein the thermosetting resin (E) is an epoxy resin,
(IX). Acrylic block copolymer (A) _{(a-b) n} type, b- _{(a-b) n} type and _(a-b) at least one selected from the group consisting of n -a type The resin composition according to any one of (I) to (VIII) having a seed structure,
(X) The resin according to any one of (I) and (IX), wherein the number average molecular weight of the acrylic block copolymer (A) measured by gel permeation chromatography is 15,000 to 300,000. Composition,
(XI). The acrylic block copolymer (A) is a methacrylic polymer block (a) containing 5 to 70% by weight of a methacrylic polymer as a main component, and the acrylic polymer as a main component. The resin composition according to any one of (I) to (XI), comprising 95 to 30% by weight of an acrylic polymer block (b),
(XII) The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography of the acrylic block copolymer (A) is 1.8 or less ( The resin composition according to any one of (I) to (XI),
(XIII). The acrylic polymer block (b) is at least one selected from the group consisting of acrylate-n-butyl, ethyl acrylate, 2-methoxyethyl acrylate, and 2-ethylhexyl acrylate. 50 to 100% by weight of monomers, acrylic acid esters other than -n-butyl acrylate, ethyl acrylate and 2-methoxyethyl acrylate, 2-ethylhexyl acrylate, / Or the resin composition according to any one of (I) to (XII), comprising 50 to 0% by weight of a vinyl monomer,
(XIV). The resin composition according to any one of (I) to (XIII), wherein the acrylic polymer block (b) is composed of n-butyl acrylate,
(XV). The methacrylic polymer block (a) comprises 50 to 100% by weight of methyl methacrylate and 0 to 50% by weight of a vinyl monomer copolymerizable therewith. Any of the resin compositions,
(XVI). The resin composition according to any one of (I) to (XV), wherein the acrylic block copolymer (A) has at least one functional group (X) in one molecule. ,
(XVII). The functional group (X) is at least one selected from the group consisting of an epoxy group, a hydrolyzable silyl group, a hydroxyl group, an amino group, a carboxyl group, an acid anhydride group, an alkenyl group, an active chlorine group and an oxazoline group. Resin composition according to (XVI), which is a functional group of the species,
(XVIII). The resin composition according to (XVII), wherein the functional group (X) is at least one functional group selected from the group consisting of an epoxy group, a hydroxyl group, and a carboxyl group,
(XIX). The resin composition according to any one of (XVI) to (XVIII), wherein the functional group (X) is contained in the methacrylic polymer block (a),
(XX). The resin composition according to any one of (XVI) to (XVIII), wherein the functional group (X) is contained in the acrylic polymer block (b),
(XXI) .A molded article comprising the resin composition according to any one of (I) to (XX),
(XXII) .A modifier comprising the resin composition according to any one of (I) to (XX),
(XXIII) .A pressure-sensitive adhesive comprising the resin composition according to any one of (I) to (XX),
(XXIV). A coating agent comprising the resin composition according to any one of (I) to (XX),
(XXV) .A pigment dispersant comprising the resin composition according to any one of (I) to (XX),
(XXVI) .A binder comprising the resin composition according to any one of (I) to (XX),
(XXVII) A vibration damping material, a vibration damping material, or a cushioning material comprising the resin composition according to any one of (I) to (XX),
About.

  ADVANTAGE OF THE INVENTION According to this invention, the molded object and modifier which consist of a resin composition excellent in molding processability, recyclability, impact resistance, heat resistance, oil resistance, weather resistance, etc. can be provided. Also provided are molded products and modifiers made of resin compositions with excellent moldability, recyclability, flexibility, rubber properties, heat resistance, oil resistance, weather resistance, transparency, adhesion to substrates, etc. can do.

Hereinafter, each component of the present invention will be described in detail.
<Acrylic block copolymer (A)>
The structure of the acrylic block copolymer (A) of the present invention is not particularly limited, and may be a linear block copolymer, a branched (star) block copolymer, or a mixture thereof. The structure of such a block copolymer may be appropriately selected according to the required physical properties of the acrylic block copolymer (A). However, from the viewpoint of cost and ease of polymerization, the linear block copolymer is selected. Polymers are preferred. The linear block copolymer may have any structure (arrangement). From the viewpoint of the physical properties of the linear block copolymer or the physical properties of the composition, the methacrylic polymer block (a ) Is expressed as a, and the acrylic polymer block (b) is expressed as b, (ab) _n- type, b- (ab) _n- type and (ab) _n- a-type (n is 1 An acrylic block copolymer having at least one structure selected from the group consisting of the above integers (for example, an integer of 1 to 3) is preferred. Among these, a diblock copolymer represented by ab, a triblock copolymer represented by abb, or a mixture thereof from the viewpoint of easy handling during processing and physical properties of the composition. preferable.

  The molecular weight of the acrylic block copolymer (A) is not particularly limited, and may be determined from the molecular weights required for the methacrylic polymer block (a) and the acrylic polymer block (b). In addition, when the molecular weight is small, the obtained resin composition may not exhibit sufficient mechanical properties and impact resistance, and conversely, if the molecular weight is larger than necessary, the processing characteristics may deteriorate. . From such a viewpoint, the molecular weight of the acrylic block copolymer (A) is preferably 15,000 to 300,000 in terms of number average molecular weight, more preferably 35,000 to 150,000, and still more preferably 50,000 to 50,000. 130,000.

  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 not particularly limited, but is 1.8 or less. It is preferable that it is 1.5 or less. When the Mw / Mn exceeds 1.8, the uniformity of the acrylic block copolymer is deteriorated, and when the obtained resin composition is used for a modifier, there are effects such as improvement of impact strength and reduction of strain stress. When used for molded products, the impact resistance of the resulting resin composition and the mechanical properties such as mechanical strength and elongation are reduced, and the moldability is deteriorated by increasing the viscosity. When the resin composition is used for a soft molded article, compression set characteristics and the like are also deteriorated. Furthermore, when used for applications such as coating agents and pressure-sensitive adhesives, the meltability and holding power at high temperatures decrease, and when used for dispersant applications, the dispersibility may deteriorate.

  The composition ratio of the methacrylic polymer block (a) and the acrylic polymer block (b) constituting the acrylic block copolymer (A) is 5 to 90% by weight of the methacrylic polymer block (a). The acrylic polymer block (b) is preferably set to 95 to 10% by weight. When the obtained resin composition is used for a modifier or a molded product, from the viewpoint of impact strength improvement, strain stress reduction, and the like, impact resistance and heat resistance of the resin composition, and the resin obtained When the composition is used for a soft molded article, the methacrylic polymer block (a) is 5 to 70% by weight and the acrylic polymer block (b) from the viewpoint of flexibility and compression set. Is more preferably set to 95 to 30% by weight, more preferably 15 to 50% by weight of the methacrylic polymer block (a) and 85 to 50% by weight of the acrylic polymer block (b). preferable. When the proportion of the methacrylic polymer block (a) is less than 5% by weight, the effect of improving the impact strength is deteriorated when used for a modifier, and the heat resistance when used for a molded product. And mechanical strength and the like tend to deteriorate. Moreover, when using the obtained resin composition for a soft molded object use, there exists a tendency for shape retainability and heat resistance to deteriorate. When the proportion of the acrylic polymer block (b) is less than 10% by weight, the effect of improving impact strength or reducing distortion stress is deteriorated when used for a modifier, and when used for a molded product. There is a tendency for impact resistance and the like to deteriorate. Moreover, when using the obtained resin composition for a soft molded object use, there exists a tendency for a softness | flexibility to deteriorate.

  Furthermore, when using the obtained resin composition for a coating agent or a pressure-sensitive adhesive, the methacrylic polymer block (a) is 5 to 40% by weight and acrylic from the viewpoint of the pressure-sensitive adhesive strength and holding power. The polymer polymer block (b) is more preferably set to 95 to 60% by weight, the methacrylic polymer block (a) is 5 to 30% by weight, and the acrylic polymer block (b) is 95 to 70% by weight. More preferably, it is set to%. When the proportion of the methacrylic polymer block (a) is less than 5% by weight, the holding power at a high temperature of the resulting resin composition tends to decrease, and the proportion of the acrylic polymer block (b) is 60. When the amount is less than% by weight, the adhesive strength of the resulting resin composition tends to decrease.

  From the viewpoint of the hardness of the acrylic block copolymer, the hardness is low when the proportion of the methacrylic polymer block (a) is small, and the hardness is high when the proportion of the acrylic polymer block (b) is small. The composition is appropriately set according to the hardness required for the obtained resin composition. Further, from the viewpoint of processing, when the proportion of (a) is small, the viscosity tends to be low, and when the proportion of (b) is small, the viscosity tends to be high, and the composition is appropriately set according to the required processing characteristics. .

When the relationship between the glass transition temperature of the methacrylic polymer block (a) and the acrylic polymer block (b) constituting the acrylic block copolymer (A) is used for a modifier or a molded product, In terms of imparting elastomeric properties and rubber elasticity, when used in coating materials and adhesives, the glass transition temperature of one polymer block is the other polymer block in terms of imparting adhesive strength and holding power. The glass transition temperature is preferably higher than the glass transition temperature of the glass transition temperature, and from the viewpoint of easy adjustment of the glass transition temperature, the glass transition temperature of each block (the glass transition temperature of the methacrylic polymer block (a) is Tg _a , the acrylic polymer block ( It is more preferable that the glass transition temperature of _b ) be Tg _b ) satisfies the following relationship.
Tg _a > Tg _b

The glass transition temperature (Tg) of the polymer (the methacrylic polymer block (a) and the acrylic polymer block (b)) is set according to the following Fox formula. This can be done by setting.
_{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 portion, and Tg ₁ , Tg ₂ ,..., Tg _m represent the glass transition temperature of each polymerization monomer. W ₁ , W ₂ ,..., W _m represent the weight ratio of each polymerization monomer.

  As the glass transition temperature of each polymerization monomer in the Fox formula, for example, a value described in Polymer Handbook Third Edition (Wiley-Interscience 1989) may be used.

  The glass transition temperature can be measured by DSC (differential scanning calorimetry) or tan δ peak of dynamic viscoelasticity, but the polarities of the methacrylic polymer block (a) and the acrylic polymer block (b). If they are too close, or if the number of monomer chains in the block is too small, the measured values and the calculation formula based on the Fox formula may be different from each other.

<Methacrylic polymer block (a)>
The methacrylic polymer block (a) is a block obtained by polymerizing a monomer having a methacrylic acid ester as a main component, and is 50 to 100% by weight of the methacrylic acid ester and a vinyl type copolymerizable therewith. It is preferably composed of 0 to 50% by weight of monomer. When the proportion of the methacrylic acid ester is less than 50% by weight, the weather resistance, transparency, etc., which are characteristics of the methacrylic acid ester, may be impaired.

  Examples of the methacrylic acid ester constituting the methacrylic polymer block (a) include, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, N-pentyl methacrylate, n-hexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, Methacrylic acid aliphatic hydrocarbons (eg, alkyl having 1 to 18 carbon atoms) such as stearyl methacrylate; Methacrylic acid alicyclic hydrocarbon esters such as cyclohexyl methacrylate and isobornyl methacrylate; Benzyl methacrylate Etc. Acid aralkyl esters; methacrylic aromatic hydrocarbon esters such as phenyl methacrylate and toluyl methacrylate; methacrylic acid such as 2-methoxyethyl methacrylate and 3-methoxybutyl methacrylate and etheric oxygen Esters with functional group-containing alcohols; trifluoromethyl methacrylate, trifluoromethyl methyl methacrylate, 2-trifluoromethyl ethyl methacrylate, 2-trifluoroethyl methacrylate, 2-perfluoroethyl methacrylate Ethyl, 2-perfluoroethyl-2-perfluorobutyl ethyl methacrylate, 2-perfluoroethyl methacrylate, perfluoromethyl methacrylate, diperfluoromethyl methyl methacrylate, 2-perfluoro methacrylate Fluoroalkyl methacrylates such as romethyl-2-perfluoroethylmethyl, 2-perfluorohexylethyl methacrylate, 2-perfluorodecylethyl methacrylate, 2-perfluorohexadecylethyl methacrylate, etc. can give. These can be used alone or in combination of two or more. Among these, methyl methacrylate is preferable in terms of processability, cost, and availability.

  Examples of vinyl monomers copolymerizable with the methacrylic acid ester constituting the methacrylic polymer block (a) include, for example, acrylic acid esters, aromatic alkenyl compounds, vinyl cyanide compounds, conjugated diene compounds, Examples thereof include halogen-containing unsaturated compounds, vinyl ester compounds, maleimide compounds, and the like.

  Examples of the acrylate ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, N-octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate, and the like, acrylate aliphatic hydrocarbon (eg, alkyl having 1 to 18 carbon atoms) ester; cyclohexyl acrylate Acrylic acid cycloaliphatic hydrocarbon esters such as isobornyl acrylate; Acrylic aromatic hydrocarbon esters such as phenyl acrylate and toluyl acrylate; Aralkyl acrylates such as benzyl acrylate; 2-methoxyethyl acrylate , An ester of acrylic acid such as 3-methoxybutyl acrylate and a functional group-containing alcohol having etheric oxygen; trifluoromethyl methyl acrylate, 2-trifluoromethyl ethyl acrylate, 2-perfluoroethyl ethyl acrylate, 2-perfluoroethyl-2-perfluorobutylethyl acrylate, 2-perfluoroethyl acrylate, perfluoromethyl acrylate, diperfluoromethylmethyl acrylate, 2-perfluoromethyl-2-perfluoroethyl acrylate Examples thereof include fluorinated alkyl acrylates such as methyl, 2-perfluorohexylethyl acrylate, 2-perfluorodecylethyl acrylate, and 2-perfluorohexadecylethyl acrylate.

  Examples of the aromatic alkenyl compound include styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene, and the like.

  Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile.

  Examples of the conjugated diene compound include butadiene and isoprene.

  Examples of the halogen-containing unsaturated compound include vinyl chloride, vinylidene chloride, perfluoroethylene, perfluoropropylene, and vinylidene fluoride.

  Examples of the vinyl ester compound include vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate, and the like.

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

  These compounds can be used alone or in combination of two or more. These vinyl monomers are used for adjusting the glass transition temperature required for the methacrylic polymer block (a), acrylic block (b), thermoplastic resin (B), thermoplastic elastomer (C), A preferable one is selected from the viewpoint of compatibility with the rubber (D) and the thermosetting resin (E).

When using the resin composition obtained in the modifier and molding body applications, the cohesive force and glass transition temperature Tg _a of the methacrylic polymer block (a) is increased, the tendency for heat resistance and holding power is increased is there.

  The glass transition temperature of the methacrylic polymer block (a) is preferably from 25 to 200 ° C., more preferably from the viewpoint of the heat deformability (heat resistance and holding power) and moldability of the resin composition obtained. 50-150 ° C. When the glass transition temperature is higher than 200 ° C., the moldability tends to be lowered, and when it is lower than 50 ° C., the heat deformability tends to be deteriorated.

  From this point, it is desirable that the methacrylic polymer block (a) is mainly composed of methyl methacrylate, and ethyl acrylate is used for the purpose of adjusting the glass transition temperature of the methacrylic polymer block (a). It is preferable to polymerize at least one monomer selected from the group consisting of acrylic acid-n-butyl and acrylic acid-2-methoxyethyl. Of these, ethyl acrylate is particularly preferable from the viewpoint of compatibility with methyl methacrylate.

Tg _a configuration of the methacrylic polymer block (a) in accordance with said Fox equation, can be performed by setting the weight ratio of the monomers of each polymer portion.

<Acrylic polymer block (b)>
The acrylic polymer block (b) is a block obtained by polymerizing a monomer having an acrylic ester as a main component, and includes 50 to 100% by weight of the acrylic ester and a vinyl monomer copolymerizable therewith. It is preferably composed of 0 to 50% by weight. If the proportion of the acrylic ester is less than 50% by weight, the physical properties of the composition, particularly flexibility and oil resistance, which are characteristic when the acrylic ester is used, may be impaired.

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

  These can be used alone or in combination of two or more. Among these, acrylic acid-n-butyl is preferable in terms of balance between flexibility, rubber elasticity, low temperature characteristics, and cost. If oil resistance and mechanical properties are required, ethyl acrylate is preferred. Further, when it is necessary to impart low temperature characteristics and oil resistance and to improve the surface tackiness of the resin, 2-methoxyethyl acrylate is preferred. If low temperature properties and adhesive properties are required, 2-ethylhexyl acrylate is preferred. Further, when a balance between oil resistance and low-temperature characteristics is required, it is preferable to use a combination of ethyl acrylate, acrylic acid-n-butyl and acrylic acid-2-methoxyethyl. In the case of imparting adhesive properties, it is preferable to use acrylate-n-butyl and / or -2-ethylhexyl acrylate. Furthermore, at least one kind selected from the group consisting of acrylic acid-n-butyl, ethyl acrylate, 2-methoxyethyl acrylate, and 2-ethylhexyl acrylate, in terms of cost and physical property balance More preferably, it consists of 50 to 100% by weight of the body and 50 to 0% by weight of other acrylic ester and / or other vinyl monomer copolymerizable therewith.

  Examples of vinyl monomers copolymerizable with the acrylic ester constituting the acrylic polymer block (b) include methacrylic ester, aromatic alkenyl compound, vinyl cyanide compound, conjugated diene compound, halogen, and the like. -Containing unsaturated compounds, silicon-containing unsaturated compounds, unsaturated carboxylic acid compounds, unsaturated dicarboxylic acid compounds, vinyl ester compounds, maleimide compounds, etc., and specific examples thereof include methacrylic polymer blocks The thing similar to the said thing used for (a) can be mention | raise | lifted.

  These vinyl monomers can be used alone or in combination of two or more. These vinyl monomers include glass transition temperature and oil resistance required for acrylic polymer block (b), methacrylic polymer block (a), thermoplastic resin (B), and thermoplastic elastomer (C ), Rubber (D) and thermosetting resin (E), etc., and a preferable one is appropriately selected in consideration of the balance of compatibility. For example, acrylonitrile may be copolymerized for the purpose of improving the oil resistance of the composition.

  The glass transition temperature of the acrylic polymer block (b) is preferably 25 ° C. or less, more preferably 0, from the viewpoint of the flexibility, flexibility, rubber elasticity, and adhesive properties of the acrylic block copolymer. ° C or lower, more preferably -20 ° C or lower. When the glass transition temperature of the acrylic polymer block (b) is higher than the temperature of the environment in which the resin composition used is obtained, flexibility, rubber elasticity, and adhesive properties are hardly exhibited.

The Tg _b of the acrylic polymer block (b) can be set by setting the weight ratio of the monomers in each polymer portion according to the Fox formula.

  In the present invention, if necessary, the acrylic block copolymer (A) is an epoxy group, hydrolyzable silyl group, hydroxyl group, amino group, carboxyl group, acid anhydride group, alkenyl group, active chlorine group and At least one functional group (X) selected from oxazoline groups may be present in one molecule. By introducing a functional group, the compatibility with the thermoplastic resin (B), the thermoplastic elastomer (C), the rubber (D) and the thermosetting resin (E) is improved (by improving the compatibility) , Tend to improve the mechanical properties, impact resistance and wear properties of the resulting resin composition), and impart heat resistance, holding power, oil resistance, dispersant ability, etc. to the resulting molded product and adhesive Can do. Furthermore, the resin composition obtained using the functional group can be modified by reacting with other compounds. Furthermore, the acrylic polymer block is crosslinked in the thermoplastic resin (B), the thermoplastic elastomer (C), the rubber (D), and the thermosetting resin (E) by using as a crosslinking point. You can also.

  In the present invention, the functional group is compatible with the thermoplastic resin (B), the thermoplastic elastomer (C), the rubber (D), and the thermosetting resin (E), has reactivity, heat resistance, holding power, and adhesiveness. It is preferable that it is at least 1 type chosen from an acid anhydride group, a carboxyl group, a hydroxyl group, and an epoxy group from points, such as provision, the ease of introduction | transduction to an acryl-type block copolymer (A), and cost.

  These functional groups are introduced into the acrylic block copolymer (A) in a form in which the functional group is protected with an appropriate protective group, or in the form of a precursor of the functional group, and then a known chemical reaction is performed. Functional groups can also be generated.

  These functional groups can be used in combination of two or more, but when two or more types are used in combination, it is preferable to select functional groups that do not react with each other.

  The functional group may be contained only in one of the methacrylic polymer block (a) and the acrylic polymer block (b), or may be contained in both blocks. Reaction point and cross-linking point of block copolymer (A), aggregation of blocks (methacrylic polymer block (a) and acrylic polymer block (b)) constituting acrylic block copolymer (A) Depending on the purpose, such as force, glass transition temperature, and required physical properties of the resin composition, the conditions for introducing functional groups can be used appropriately.

  For example, functional groups are introduced into the methacrylic polymer block (a) in terms of improving the heat resistance and heat decomposability of the acrylic block copolymer (A), compression set properties, and increasing the molecular weight between crosslinking points. What is necessary is just to introduce a functional group into the acrylic polymer block (b) from the viewpoint of imparting oil resistance, rubber elasticity, creep properties, and adhesive properties to the acrylic block copolymer (A). Further, the thermoplastic resin (B), the thermoplastic elastomer (C), the rubber (D), and the thermosetting resin (E) to be used may be introduced according to the kind of the thermoplastic resin (B), the thermoplastic elastomer (C), the rubber (D), and the thermosetting resin (E). Although not particularly limited, either the methacrylic polymer block (a) or the acrylic polymer block (b) in terms of control of reaction points, heat resistance, rubber elasticity, mechanical strength, flexibility, and the like. It is preferable to introduce a functional group into the block.

  The content of the functional group includes the cohesive force of the functional group, the structure and composition of the acrylic block copolymer (A), the number of blocks constituting the acrylic block copolymer (A), the glass transition temperature, and Site and mode containing functional groups, when the acrylic block copolymer (A) is modified or crosslinked, the degree of modification or crosslinking, the acrylic block copolymer (A) is the thermoplastic resin (B), When making it react with a thermoplastic elastomer (C), rubber (D), and a thermosetting resin (E), it changes with compatibility or a reactivity. Therefore, what is necessary is just to set as needed, Preferably it is 1.0 or more per molecule | numerator of an acryl-type block copolymer (A), More preferably, it is 2.0 or more. When the number is less than 1.0, the acrylic block copolymer (A) tends to be insufficient in improving heat resistance and imparting adhesive properties.

  When the functional group is introduced into the methacrylic polymer block (a), it is preferably introduced within a range where the moldability of the acrylic block copolymer (A) is not lowered.

Specifically it is preferable to introduce such an extent that the glass transition temperature Tg _a of the methacrylic polymer block after introduction of the functional group (a) is 200 ° C. or less.

When the functional group is introduced into the acrylic polymer block (b), it is preferably introduced within a range in which the flexibility, rubber elasticity, and low temperature characteristics of the acrylic block copolymer (A) are not deteriorated. When the cohesive force of the acrylic polymer block (b) and the glass transition temperature Tg _b are improved by the introduction of the functional group, the flexibility, rubber elasticity, and low temperature characteristics tend to deteriorate. Specifically, the acrylic polymer block (b) after introduction of the functional group is introduced in such a range that the glass transition temperature Tg _b is 25 ° C. or lower, more preferably 0 ° C. or lower, and further preferably −20 ° C. or lower. It is preferable to do.

  Below, a hydroxyl group, a carboxyl group, an acid anhydride group, and an epoxy group will be described as preferred examples of the functional group (X).

<Hydroxyl group>
The hydroxyl group may be introduced into the main chain of the acrylic block copolymer (A) or may be introduced into the side chain, but from the ease of introduction into the acrylic block copolymer (A). It is preferably introduced into the side chain.

  The method for introducing the hydroxyl group into the block copolymer (A) is not particularly limited, but a (meth) acrylic monomer containing a hydroxyl group may be directly polymerized during the polymerization of the block copolymer (A). After the polymer (A) is polymerized, it may be introduced by using an esterification reaction or a transesterification reaction with a diol component, or may be hydrolyzed after the polymerization of a (meth) acrylic monomer containing an epoxy group. good. From the viewpoint of easy reaction, it is preferable to directly polymerize a (meth) acrylic monomer containing a hydroxyl group at the time of polymerization of the block copolymer (A). Here, in this application, (meth) acryl means acryl or methacryl.

  Specific (meth) acrylic monomers include (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid-3-hydroxypropyl, (meth) acrylic acid- 4-hydroxybutyl, Blemmer E series (Nippon Yushi Co., Ltd.), Blemmer PE series (Nippon Yushi Co., Ltd.), Blemmer AE series (Nippon Yushi Co., Ltd.), Blemmer P (Nippon Yushi Co., Ltd.), Blemmer PP Series (Nippon Yushi Co., Ltd.), Blemmer AP Series (Nippon Yushi Co., Ltd.), Blemmer PEP Series (Nippon Yushi Co., Ltd.), Blemmer AEP Series (Nippon Yushi Co., Ltd.), Blemmer PET Series (Nippon Yushi Co., Ltd.) )), Blemmer AET series (Nippon Yushi Co., Ltd.) )), Such as Blenmer APT series (NOF Corporation) are exemplified.

  These compounds can be used alone or in combination of two or more. Among these, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, and (meth) acrylic acid-4-hydroxybutyl are easily polymerized and easily available. Is preferable. Although not particularly limited, when it is contained in the methacrylic polymer block (a), it is preferably a hydroxyl group-containing methacrylic acid ester derivative, and when it is contained in the acrylic polymer block (b), it is a hydroxyl group-containing acrylic acid. An ester derivative is preferred. When introducing a hydroxyl group-containing acrylate derivative into the methacrylic polymer block (a), or when introducing a hydroxyl group-containing methacrylic ester derivative into the acrylic polymer block (b), the acrylic block copolymer The polymerization operation of the polymer (A) becomes complicated, the difference in glass transition temperature between the methacrylic polymer block (a) and the acrylic polymer block (b) becomes small, and the acrylic block copolymer (A ) Rubber elasticity and flexibility tend to decrease.

<Carboxyl group>
The carboxyl group may be introduced into the main chain of the acrylic block copolymer (A) or may be introduced into the side chain, but is easy to introduce into the acrylic block copolymer (A). Therefore, it is preferably introduced into the main chain.

  When the monomer having a carboxyl group does not deactivate the catalyst under the polymerization conditions, the introduction of the carboxyl group is preferably introduced by direct polymerization. In the case of deactivation, it is preferable to introduce a carboxyl group by functional group conversion.

  In the method of introducing a carboxyl group by functional group conversion, the carboxyl group is introduced into the acrylic block copolymer in a form protected with an appropriate protective group or in the form of a functional group that is a precursor of the carboxyl group. A functional group can be generated by a known chemical reaction, and a carboxyl group can be introduced by this method.

  For example, an acrylic block copolymer containing a monomer having a functional group that becomes a precursor of a carboxyl group such as t-butyl (meth) acrylate and trimethylsilyl (meth) acrylate is synthesized and hydrolyzed. Alternatively, a method of generating a carboxyl group by a known chemical reaction such as acid decomposition (JP-A-10-298248, JP-A-2001-234146), for example, (meth) acrylic acid-t-butyl, (meth) acrylic A method of synthesizing and melt-kneading an acrylic block copolymer containing unit amounts such as isopropyl acid, α, α-dimethylbenzyl (meth) acrylate, and α-methylbenzyl (meth) acrylate (JP 2006-104419 A) No.).

<Acid anhydride group>
The acid anhydride group is not particularly limited, but may be introduced into the main chain of the acrylic block copolymer (A) or may be introduced into the side chain. The acid anhydride group is an anhydride group of a carboxyl group, and is preferably introduced into the main chain from the viewpoint of easy introduction into the acrylic block copolymer (A). It is preferably introduced in the form represented by General formula (1):

（式中、Ｒ^１は水素またはメチル基で、互いに同一でも異なっていてもよい。ｎは０〜３の整数、ｍは０または１の整数）
ここで、一般式（１）中のｎは、好ましくは０または１であり、より好ましくは１である。ｎが４以上の場合は、重合が煩雑になったり、酸無水物基の環化が困難になる傾向にある。

(In the formula, R ¹ is hydrogen or a methyl group, and may be the same or different. N is an integer of 0 to 3, and m is an integer of 0 or 1.)
Here, n in the general formula (1) is preferably 0 or 1, more preferably 1. When n is 4 or more, polymerization tends to be complicated, and cyclization of the acid anhydride group tends to be difficult.

  Regarding the method of introducing an acid anhydride group, when the monomer having an acid anhydride group does not deactivate the catalyst under the polymerization conditions, it is preferably introduced by direct polymerization and has an acid anhydride group. When the monomer deactivates the catalyst during polymerization, a method of introducing an acid anhydride group by functional group conversion is preferred. The introduction method is not particularly limited, but is introduced into the acrylic block copolymer in the form of a precursor of an acid anhydride group such as (meth) acrylic acid-t-butyl, and then melt-kneaded. It can be introduced by the method (WO 2004/013192).

<Epoxy group>
The epoxy group is not particularly limited as long as it is an organic group containing an epoxy ring. For example, 1,2-epoxyethyl group, 2,3-epoxypropyl group (that is, glycidyl group), 2,3-epoxy-2- Examples thereof include an aliphatic hydrocarbon (eg, alkyl) group having an epoxy ring such as a methylpropyl group; an alicyclic hydrocarbon group having an epoxy ring such as a 3,4-epoxycyclohexyl group. These may be selected from the reactivity, reaction rate, availability, cost, etc. as necessary. Although it does not restrict | limit in particular, A glycidyl group is preferable in these in view of availability.

  Regarding the method for introducing an epoxy group, it is preferable to introduce a monomer having an epoxy group by direct polymerization. Examples of the monomer having an epoxy group include glycidyl (meth) acrylate, 2,3-epoxy-2-methylpropyl (meth) acrylate, and (3,4-epoxycyclohexyl) methyl (meth) acrylate ( Examples thereof include esters of (meth) acrylic acid and an organic group-containing alcohol containing an epoxy ring; and epoxy group-containing unsaturated compounds such as 4-vinyl-1-cyclohexene 1 and 2 epoxides. These may be selected from reactivity, reaction rate, availability, cost, etc., if necessary, and are not particularly limited, but among these, glycidyl (meth) acrylate is easy to obtain. Is preferred.

<Thermoplastic resin (B)>
Examples of the thermoplastic resin (B) that can be used in the present invention include polyvinyl chloride resins, polyethylene resins, polypropylene resins, cyclic olefin copolymer resins, polymethyl methacrylate resins, polystyrene resins; aromatic alkenyls. 70 to 100% by weight of at least one vinyl monomer selected from the group consisting of a compound, a vinyl cyanide compound and a (meth) acrylic acid ester, and copolymerizable with these vinyl monomers, for example, Homopolymers or copolymers obtained by polymerizing 0 to 30% by weight of other vinyl monomers such as ethylene, propylene and vinyl acetate and / or diene monomers such as butadiene and isoprene; polyphenylene ether Resin, polycarbonate resin, polyester resin, polyamide resin, poly Acetal resins, polyphenylene sulfide resins, polysulfone resins, polyimide resins, polyether imide resins, polyether ketone resins, polyether ether ketone resin, and a polyamide-imide resin. These can be used alone or in admixture of two or more.

  Examples of the polyvinyl chloride resin include polyvinyl chloride homopolymers having various degrees of polymerization, vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinyl acetate-maleic anhydride copolymers, vinyl chloride-ethylene copolymers. Polyvinyl chloride copolymers such as polymers, vinyl chloride-propylene copolymers; alloys of polyvinyl chloride and ethylene-vinyl acetate copolymers, alloys of polyvinyl chloride and acrylonitrile-butadiene-styrene copolymers, poly Alloy of vinyl chloride and methyl methacrylate-butadiene-styrene copolymer, Alloy of polyvinyl chloride and chlorinated polyethylene, Alloy of polyvinyl chloride and acrylic copolymer, Alloy of polyvinyl chloride and polyurethane , Polyvinyl chloride alloys such as alloys of polyvinyl chloride and NBR; polyvinyl chloride Filler composite, functionalized polyvinyl chloride such as post-chlorinated polyvinyl chloride, polyvinylidene chloride homopolymer, vinylidene chloride-vinyl chloride copolymer, vinylidene chloride-acrylonitrile copolymer, vinylidene chloride-acrylic acid ester copolymer Examples thereof include polyvinylidene chloride copolymers such as coalescence. Any of the polyvinyl chloride resins can be suitably used from the viewpoint of compatibility.

  Examples of the polyethylene resin include polyethylene resins such as low density polyethylene, high density polyethylene, linear low density polyethylene, and ultrahigh molecular weight polyethylene; ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene- Ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate-glycidyl methacrylate copolymer, ethylene-vinyl acetate-glycidyl methacrylate copolymer, ethylene-acrylic acid copolymer, ethylene and acrylic acid or Copolymers with metal salts of methacrylic acid, maleic anhydride-modified polyethylene, maleic anhydride-modified ethylene-ethyl acrylate copolymer, ethylene-dimethylaminomethyl methacrylate copolymer, ethylene-vinyl Alcohol copolymers, ethylene - can be exemplified a copolymer of ethylene and a polar monomer such as ethylene oxide adducts of vinyl alcohol copolymer. Among these, a copolymer of ethylene and a polar monomer is preferable from the viewpoint of compatibility, and a copolymer having a glycidyl group, a carboxylic acid group, or an alcoholic hydroxyl group is preferable from the viewpoint of reactivity. .

Examples of the polypropylene resin include homoisotactic polypropylene, isotactic polypropylene random copolymer containing ethylene or 1-butene, isotactic polypropylene block copolymer containing ethylene propylene, and Ziegler-Natta catalyst isotactic. Polypropylene, polypropylene such as metallocene-catalyzed isotactic polypropylene, metallocene-catalyzed syndiotactic polypropylene, atactic polypropylene; polymer alloy of polypropylene and rubber, polypropylene / filler composite, chlorinated polypropylene, maleic acid modified polypropylene, etc. Examples include functionalized polypropylene. Among these, chlorinated polypropylene and maleic acid-modified polypropylene are preferable from the viewpoint of compatibility.
The cyclic olefin copolymer resin is not particularly limited as long as it contains a cyclic olefin, for example, cyclopentadiene, dicyclopentadiene, etc. For example, ARTON (manufactured by JSR Corporation), ZEONEX (manufactured by Nippon Zeon Co., Ltd.) It can be a copolymer of a cyclic olefin and ethylene or propylene. Among these, ARTON is preferable from the viewpoint of compatibility.

  The polymethyl methacrylate resin is not particularly limited as long as it is a resin mainly composed of methyl methacrylate, and examples thereof include polymethyl methacrylate resin in which α-methylstyrene, maleic anhydride, and the like are copolymerized. Since the said polymethylmethacrylate-type resin has an ester group in a side chain, all can be used suitably from a compatible and / or reactive viewpoint.

  Examples of the polystyrene resin include high-impact polystyrene such as polystyrene homopolymer, polystyrene-polybutadiene polymer alloy, polystyrene-acrylic rubber polymer alloy, and syndiotactic polystyrene.

  70-100% by weight of at least one vinyl monomer selected from the group consisting of aromatic alkenyl compounds, vinyl cyanide compounds, and (meth) acrylic acid esters, and copolymerization with these vinyl monomers For example, homopolymers or copolymers obtained by polymerizing 0 to 30% by weight with other vinyl monomers such as ethylene, propylene and vinyl acetate and / or diene monomers such as butadiene and isoprene. Examples of the polymer include acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene-α-methylstyrene copolymer, maleimide-modified acrylonitrile-butadiene-styrene copolymer, acrylonitrile- Butyl acrylate-styrene copolymer, acrylic Ronitoriru - ethylene-propylene - styrene copolymer, acrylonitrile - chlorinated polyethylene - acrylonitrile styrene copolymer - styrene copolymer resin; methyl methacrylate - styrene copolymer resin. Examples include acrylonitrile-styrene (based) copolymer resins and methyl methacrylate-styrene copolymer resins, and these can be preferably used from the viewpoint of compatibility / reactivity.

  Examples of the polyphenylene ether-based resin include polyphenylene ether homopolymers; alloys of polyphenylene ether and polystyrene, alloys of polyphenylene ether and polyamide, and alloys of polyphenylene ether and polybutylene terephthalate.

  Polycarbonate resins include polycarbonates such as bisphenol A type aromatic polycarbonates; alloys of polycarbonate and acrylonitrile-butadiene-styrene copolymers, alloys of polycarbonate and polybutylene terephthalate, alloys of polycarbonate and polyarylate, polycarbonate and poly Examples thereof include polycarbonate alloys such as alloys with methyl methacrylate. The polycarbonate resin is excellent in compatibility with the acrylic block copolymer (A), and the carbonate bond of the main chain, the carboxyl group at the terminal, and the hydroxyl group are reactive, so that any of them is preferably used. Can do.

Examples of polyester resins include aliphatic polyesters such as polyglycolic acid, polylactic acid, polycaprolactone, and polyethylene succinate; polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycyclohexanedimethylene terephthalate, and ethylene. Semi-aromatic polyesters such as terephthalate / cyclohexanedimethylene terephthalate copolymer and thermotropic liquid crystal polymer type 2; fully aromatics such as amorphous polyarylate, thermotropic liquid crystal polymer type 1 and thermotropic liquid crystal polymer type 2 Examples include polyester.
Moreover, the ester-type elastomer which is a block copolymer which has a polyester segment is mention | raise | lifted. The polyester-based resin is excellent in compatibility with the acrylic block copolymer (A), and the ester bond of the main chain, the terminal carboxyl group and the hydroxyl group are reactive, and therefore all are preferably used. Can do.

  Examples of polyamide resins include ring-opening polymerization type aliphatic polyamides such as PA6 (polycaproamide) and PA12 (polydodecanamide); PA66 (polyhexamethylene adipamide), PA46 (polytetramethylene adipamide) Polycondensation polyamides such as PA610, PA612, PA11; semi-aromatic polyamides such as MXD6, PA6T, PA9T, PA6T / 66, PA6T / 6, and amorphous PA; poly (p-phenylene terephthalamide), poly (m-phenylene) Terephthalamide) and wholly aromatic polyamides such as poly (m-phenyleneisophthalamide). Moreover, the amide-type elastomer which is a block copolymer which has a polyamide segment is also mentioned. The polyamide-based resin is excellent in compatibility with the acrylic block copolymer (A), and the amide bond in the main chain, the carboxyl group at the terminal, and the amino group are reactive, so that any of them is preferably used. be able to.

  Examples of the polyacetal resin include a polyacetal homopolymer and a copolymer of formaldehyde and trioxane.

  Polyphenylene sulfide resin, polysulfone resin, polyimide resin, polyetherimide resin, polyetherketone resin, polyetheretherketone resin, and polyamideimide resin are excellent in compatibility with the acrylic block copolymer (A). Since a reactive group exists in the main chain and the terminal, both can be preferably used.

  In the present invention, the thermoplastic resin (B) is not limited to these, and various other thermoplastic resins can be widely used. Among them, those having good compatibility and / or reactivity with the acrylic block copolymer (A) are preferable from the viewpoint that desired physical properties are easily obtained. Moreover, even if it is resin which cannot be said that compatibility with an acrylic block copolymer (A) is favorable and does not show the reactivity with an acrylic block copolymer (A), it is used for this invention. However, more preferable physical properties can be obtained by known means, for example, a method in which a silane coupling agent, an organic acid anhydride, or the like is allowed to act on a resin to perform chemical modification, or a method using a compatibilizer. A composition can be obtained. Even if the resin does not have a site that reacts with the acrylic block copolymer (A), the acrylic block copolymer (A) dispersed in the resin can be crosslinked to crosslink the acrylic block copolymer. The chemical stability and heat resistance of the coalesced (A) can be improved, and the dispersion diameter of the acrylic block copolymer (A) in the resin can be controlled by crosslinking during kneading with the resin. can do.

  When two or more types of the thermoplastic resins are mixed and used, the combination is not particularly limited, but a resin group having good compatibility and reactivity with the acrylic block copolymer (A) ( a1) Compatibility with the acrylic block copolymer (A) is good, but the resin group (a2) not having reactivity and compatibility with the acrylic block copolymer (A) are not good When a combination is illustrated by taking as an example the resin group (a3) having a reactivity, the resin group (a4) not having good compatibility with the acrylic block copolymer (A) and having no reactivity, , (A1), (a1) and (a2), (a1) and (a3), (a1) and (a4), (a2), (a2) and (a3), (a2) and (a4) , (A3), (a3) and (a4). When the acrylic block copolymer (A) has a functional group (X) and the functional group (X) is an epoxy group, specific examples of combinations thereof include, for example, (a1) PC / PBT, PET / PBT, (a1) and (a2) include PC / ABS, and (a2) includes PVC / ABS. Moreover, an acrylic block copolymer (A) can also be used as the compatibilizer for the purpose of improving the compatibility of the resins to be combined.

  Among the thermoplastic resins, the compatibility and / or reactivity with the acrylic block copolymer (A) used in the present invention is good, and it is easy to obtain excellent physical properties, particularly impact resistance. Therefore, it is preferably at least one of polyvinyl chloride resin, polymethyl methacrylate resin, acrylonitrile-styrene copolymer resin, methyl methacrylate-styrene copolymer resin, polycarbonate resin, polyester resin, and polyamide resin. Moreover, these can mix and use 2 or more types, There is no restriction | limiting in particular in the combination.

The thermoplastic resin (B) is preferably a crystalline thermoplastic resin.
In the thermoplastic resin composition, the crystalline thermoplastic resin is preferably a thermoplastic resin selected from the group consisting of a crystalline polyester resin and a crystalline polyamide resin. These can be used alone or in admixture of two or more.

  Examples of crystalline polyester resins include aliphatic polyesters such as polyglycolic acid, polylactic acid, polycaprolactone, and polyethylene succinate; polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, And semi-aromatic polyesters such as polycyclohexanedimethylene terephthalate and ester elastomers. Among these, polybutylene terephthalate is preferable from the viewpoint of crystallization speed and physical property balance.

  Examples of crystalline polyamide resins include ring-opening polymerization aliphatic polyamides such as PA6 (polycaproamide) and PA12 (polydodecanamide); PA66 (polyhexamethylene adipamide), PA46 (polytetramethylene adipa) (Mid), polycondensation polyamides such as PA610, PA612, PA11; semi-aromatic polyamides such as PA6T / 66, amide elastomers, and the like. Among these, PA6 is preferable from the balance of physical properties and cost.

  When the thermoplastic resin (B) and the acrylic block copolymer (A) are blended, there is no particular limitation on the composition ratio of both, but from the viewpoint of a better balance between flexibility and heat resistance, It is preferably composed of 99 to 1% by weight of the plastic resin (B) and 1 to 99% by weight of the acrylic block copolymer (A), and 90 to 10% by weight of the thermoplastic resin (B) and the acrylic block copolymer. (A) It is preferably composed of 10 to 90% by weight, more preferably the thermoplastic resin (B) is composed of 80 to 20% by weight and the acrylic block copolymer (A) is composed of 20 to 80% by weight, More preferably, the thermoplastic resin (B) is 70 to 30% by weight and the acrylic block copolymer (A) is 30 to 70% by weight. In particular, when imparting oil resistance, flexibility, impact resistance, wear resistance, etc. while maintaining the characteristics of the thermoplastic resin (B), the thermoplastic resin (B) is 99 to 50% by weight and More preferably, the acrylic block copolymer (A) comprises 1 to 50% by weight, and the soft block resin improves the mechanical properties of the acrylic block copolymer (A) with emphasis on flexibility. When obtaining a composition, it is more preferable that the thermoplastic resin (B) is 1 to 50% by weight and the acrylic block copolymer (A) is 99 to 50% by weight.

  If the blending amount of the acrylic block copolymer (A) is less than 1% by weight, the effect of imparting flexibility and oil resistance tends to be insufficient, and if it exceeds 99% by weight, the thermoplastic resin (B) There is a tendency that the characteristics of the physical properties it has are difficult to produce.

<Thermoplastic elastomer (C)>
The thermoplastic elastomer (D) that can be used in the present invention is not particularly limited. For example, thermoplastic elastomers such as styrene elastomers, olefin elastomers, urethane elastomers, vinyl chloride elastomers, ester elastomers, and amide elastomers can be used. . At least one of these can be used.

  When the thermoplastic elastomer (C) and the acrylic block copolymer (A) are blended, there is no particular limitation on the composition ratio of both, but from the viewpoint of a better balance between flexibility and heat resistance, the thermoplastic elastomer (C) It preferably consists of 99 to 1% by weight and acrylic block copolymer (A) 1 to 99% by weight, thermoplastic elastomer (C) 90 to 10% by weight and acrylic block copolymer (A) The thermoplastic elastomer (C) is preferably 80 to 20% by weight and the acrylic block copolymer (A) is more preferably 20 to 80% by weight. More preferably, C) is 70 to 30% by weight and the acrylic block copolymer (A) is 30 to 70% by weight. In particular, when oil resistance and flexibility are imparted while maintaining the characteristics of the thermoplastic elastomer (C), 99 to 50% by weight of the thermoplastic elastomer (C) and the acrylic block copolymer (A) are provided. Is more preferably 1 to 50% by weight. When emphasizing flexibility or obtaining a soft resin composition, the thermoplastic elastomer (C) is 1 to 50% by weight and an acrylic block copolymer ( More preferably, A) consists of 99 to 50% by weight.

  If the blending amount of the acrylic block copolymer (A) is less than 1% by weight, the effect of imparting flexibility and oil resistance tends to be insufficient, and if it exceeds 99% by weight, the thermoplastic elastomer (C) There is a tendency that the characteristics of the property of is difficult to come out.

<Rubber (D)>
The rubber (D) that can be used in the present invention is at least one rubber selected from natural rubber, diene polymer rubber, olefin polymer rubber, acrylic rubber, silicone rubber, and fluororubber. These rubber components may be used alone or in combination.

  In the present invention, examples of the natural rubber include those obtained by solidifying a latex liquid collected from a rubber tree represented by heve brasiliensis into a sheet shape, a block shape, and the like. For example, it may be smoked and dried, or may be dried without being smoked. Ribbed smoked sheet (RSS), white crepe, pale crepe, estate brown crepe, component crepe, thin blank crepe, thick brown crepe, flat bar crepe, pure smoked blanket crepe Etc. RSS includes various grades visually graded according to the so-called Green Book (International Standards of Quality and Packing for Natural Rubber Grades). Examples of the block-like natural rubber include technically graded rubber (TSR) called crumb rubber or block rubber. Among them, SMR (Standard Malaysian Rubber) from Malaysia and SSR (Standard) from Singapore Singapore Rubber), Indonesian SIR (Standard Indonesian Rubber), Thailand STR (Standard Thai Rubber), and the like. Among these, a ribbed smoke sheet (RSS) is preferable in view of economy. Examples of natural rubber include deproteinized natural rubber and epoxidized natural rubber.

  Epoxidized natural rubber is a modified form of natural rubber in which the unsaturated bond of natural rubber is substituted with an epoxy group, and can be obtained by epoxy-modifying natural rubber latex. For example, (trade name) ENR50 (Gutherie) , Inc.) and (trade name) ENR25 (Gutherie, Inc.) are on the market and are generally available. In the resin composition of the present invention, a mixture of natural rubber and epoxidized natural rubber may be used.

  In the above-mentioned natural rubber, epoxidized natural rubber is preferable in terms of compatibility with the acrylic block copolymer (A) and mechanical properties of the resulting resin composition, and in terms of cost and availability, ribbed smoke. A sheet (RSS) is preferred.

  Examples of the diene polymer rubber include isoprene polymer rubber (IR), styrene / butadiene copolymer rubber (SBR), butadiene polymer rubber (BR), and acrylonitrile / butadiene copolymer rubber (NBR). And chloroprene polymer rubber (CR).

  Examples of the olefin polymer rubber include ethylene / propylene / diene copolymer rubber (EPDM), isobutylene / isoprene copolymer rubber (IIR), and halogenated isobutylene / isoprene copolymer rubber (CIIR, BIIR). And isobutylene / halogenated methylstyrene copolymer rubber, chlorosulfonated polyethylene, isobutylene polymer rubber, and ethylene / vinyl acetate copolymer rubber.

  As the acrylic rubber, any conventionally known acrylic rubber can be used. For example, 2-chloroethyl vinyl ether, methyl vinyl ketone, acrylic acid, acrylonitrile is added to a monomer composed of ethyl acrylate and / or butyl acrylate. An acrylic rubber obtained by copolymerizing a small amount of one or more other monomers such as butadiene.

  Further, as the silicone rubber, any conventionally known silicone rubber can be used, and examples thereof include dimethylsiloxane polymer rubber and methylphenylsiloxane polymer rubber.

  Furthermore, as the fluoro rubber, any conventionally known fluoro rubber can be used.

  In the thermoplastic elastomer composition of the present invention, the rubber (B) may be appropriately selected in consideration of required physical properties, cost, availability, and the like. For example, it is preferable to use acrylic rubber in terms of compatibility with the acrylic block copolymer (A) and the mechanical properties of the resulting resin composition. Moreover, it is preferable to use a silicone rubber from the point of the low temperature characteristic and weather resistance of the resin composition obtained. Furthermore, it is preferable to use diene polymer rubber and olefin polymer rubber in terms of cost. Natural rubber is preferably used in that it can be produced from plant-derived raw materials that do not depend on petroleum resources.

  In the present invention, the rubber (D) may be blended in advance with the acrylic block copolymer (A), or may be crosslinked after blending the acrylic block copolymer. The rubber (D) is melt-kneaded in the presence of the copolymer (A). At this time, the crosslinking agent (C) is added, and the rubber (D) is dynamically crosslinked simultaneously with the melt-kneading (dynamic crosslinking). You may do it.

  Here, the dynamic cross-linking means W.I. of Uniroyal. M.M. Fischer et al., Monsanto A.M. Y. This is a method developed by Coran et al. (US104210, All of thermoplastic elastomers, Mitsuo Akiba, Industrial Research Council, 2003 (first edition)). Here, rubber is blended into the matrix of the acrylic block copolymer (A), the rubber is highly crosslinked while kneading at a temperature higher than the crosslinking agent and the crosslinking agent, and the rubber is finely dispersed. It is a process. The composition obtained by this dynamic crosslinking is in a state in which the crosslinked rubber (D) phase that becomes a discontinuous phase is finely dispersed in the acrylic block copolymer (A) that becomes a continuous phase. While imparting the physical properties of D), the molding can be processed according to the acrylic block copolymer (A).

  In addition, even when the blending amount of the acrylic block copolymer (A) <the blending amount of the crosslinked rubber, the crosslinked rubber phase serving as a discontinuous phase is finely formed in the acrylic block copolymer (A) serving as a continuous phase. It becomes a distributed state.

  As a crosslinking agent for obtaining a crosslinked product of rubber (D), any crosslinking agent conventionally used in each rubber can be used and is not particularly limited. Examples of the crosslinking agent used to obtain a crosslinked product of rubber (D) include sulfur; organic sulfur compounds; organic nitroso compounds such as aromatic nitroso compounds; oxime compounds; metal oxides such as zinc oxide and magnesium oxide. Polyamines; selenium, tellurium and / or their compounds; various organic peroxides; resin crosslinking agents such as alkylphenol formaldehyde resins and brominated alkylphenol formaldehyde resins; organic organosiloxanes having two or more SiH groups in the molecule Examples of the compound include one or two or more crosslinking agents depending on the type of rubber. In obtaining a crosslinked product of rubber (D), a crosslinking agent is added to 100 parts by weight of rubber (D) in terms of crosslinking efficiency of rubber, imparting rubber elasticity to the resulting crosslinked product, odor, and the like. It is preferably used in a proportion of 3 to 30 parts by weight, more preferably in a proportion of 0.5 to 15 parts by weight, and particularly preferably in a proportion of 0.5 to 5 parts by weight. When the amount of the crosslinking agent is less than 0.3 parts by weight, the crosslinking becomes insufficient and rubber elasticity tends to deteriorate. When the amount is more than 30 parts by weight, the resulting composition has a tendency to increase odor or color. It is in.

  Moreover, when obtaining the crosslinked material of rubber | gum (D), 1 type, or 2 or more types of crosslinking adjuvants can be used with the above-mentioned crosslinking agent as needed. Examples of the crosslinking aid include guanidine compounds such as diphenylguanidine, aldehyde amine compounds, aldehyde ammonium compounds, thiazole compounds, sulfenamide compounds, thiourea compounds, thiuram compounds, dithiocarbamate compounds; palladium And hydrosilylation catalysts such as group transition metals such as rhodium and platinum, or compounds and complexes thereof.

  Further, in obtaining a crosslinked product of rubber (D), together with the above-mentioned crosslinking agent and crosslinking aid, etc., if necessary, divinylbenzene, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, zinc white, N, N- Compounds such as m-phenylene bismaleimide, metal halide, organic halide, maleic anhydride, glycidyl methacrylate, hydroxypropyl methacrylate, stearic acid and the like can also be used. By adding these, the crosslinking efficiency by a crosslinking agent can be raised and rubber elasticity can be provided.

  In addition to the rubber, a core-shell type cross-linked rubber characterized by excellent compatibility with other resins may be added. The core-shell type crosslinked rubber is not particularly limited, and examples thereof include methyl methacrylate-butadiene-styrene copolymer (MBS resin), acrylic graft copolymer, acrylic-silicone composite rubber-based graft copolymer, and the like. As MBS resin, Kane Ace B series and Kane Ace M series (both manufactured by Kaneka Co., Ltd.), As acrylic graft copolymer, Kane Ace FM series (manufactured by Kaneka Co., Ltd.), acrylic-silicone composite rubber-based graft copolymer As the coalescence, Metablen S-2001 (manufactured by Mitsubishi Rayon Co., Ltd.) and the like are available as industrial products.

  When the rubber (D) and the acrylic block copolymer (A) are blended, there is no particular limitation on the composition ratio between them, but from the viewpoint of a better balance between flexibility and heat resistance, the rubber (D) 99 Preferably 1 to 99% by weight and 1 to 99% by weight of the acrylic block copolymer (A), and 90 to 10% by weight of the rubber (D) and 10 to 90% by weight of the acrylic block copolymer (A). More preferably, the rubber (D) comprises 80 to 20% by weight and the acrylic block copolymer (A) comprises 20 to 80% by weight, and the rubber (D) comprises 70 to 30% by weight and acrylic. More preferably, the system block copolymer (A) comprises 30 to 70% by weight. In particular, when oil resistance and flexibility are imparted while maintaining the characteristics of the rubber (D), or when both thermoplasticity and rubber elasticity are achieved by dynamic crosslinking, the rubber (D) is 99 to 50% by weight. % And the acrylic block copolymer (A) are more preferably 1 to 50% by weight.

  When the blending amount of the acrylic block copolymer (A) is less than 1% by weight, the effect of imparting flexibility and oil resistance tends to be insufficient, and when it exceeds 99% by weight, the rubber (D) has. There is a tendency that characteristics of physical properties are not easily produced.

<Thermosetting resin (E)>
The thermosetting resin (E) that can be used in the present invention is not particularly limited. For example, epoxy resin, phenol resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, thermosetting polyimide, hydrosilylation can be used. Thermosetting resins such as cross-linked resins and urea resins can be used. At least one of these can be used. Especially, an epoxy resin and a phenol resin are preferable at points, such as oil resistance, heat resistance, compatibility, impact resistance improvement, and elastic modulus adjustment, and an epoxy resin is more preferable. In particular, when the acrylic block copolymer (A) has a functional group that reacts with an epoxy group, the compatibility and impact resistance can be further improved, and further, when used as an elastic adhesive or coating agent The coating property to the epoxy resin and the adhesiveness, adhesion and fluidity of the epoxy resin can be improved.

  Below, an epoxy resin is demonstrated as a preferable illustration as a thermosetting resin (E).

  The epoxy resin that can be used in the present invention is not particularly limited. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, polycyclic aromatic type epoxy resin, Biphenyl type epoxy resins, epoxy resins hydrogenated with these, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, alicyclic epoxy resins, novolac type epoxy resins (phenol novolac type epoxy resins, cresol novolak type epoxy resins), Urethane-modified epoxy resin having a urethane bond, fluorinated epoxy resin, rubber-modified epoxy resin containing polybutadiene or NBR, flame retardant epoxy resin such as glycidyl ether of tetrabromobisphenol A, Epoxy resins, liquid epoxy resins.

  When the thermosetting resin (E) and the acrylic block copolymer (A) are blended, there is no particular limitation on the composition ratio of both, but from the viewpoint of a better balance between flexibility and heat resistance, thermosetting It preferably comprises 99 to 1% by weight of the curable resin (E) and 1 to 99% by weight of the acrylic block copolymer (A), and 90 to 10% by weight of the thermosetting resin (E) and the acrylic block copolymer. (A) It preferably consists of 10 to 90% by weight, more preferably the thermosetting resin (E) consists of 80 to 20% by weight and the acrylic block copolymer (A) consists of 20 to 80% by weight, More preferably, the thermosetting resin (E) is 70 to 30% by weight and the acrylic block copolymer (A) is 30 to 70% by weight. In particular, when oil resistance, flexibility, impact resistance, etc. are imparted while maintaining the characteristics of the thermosetting resin (E), the thermosetting resin (E) is 99 to 50% by weight and the acrylic block. More preferably, the copolymer (A) consists of 1 to 50% by weight, and when the elastic modulus of the acrylic block copolymer (A) is improved, flexibility is important, or a soft resin composition is obtained. More preferably, the thermosetting resin (E) is 1 to 50% by weight and the acrylic block copolymer (A) is 99 to 50% by weight.

  If the blending amount of the acrylic block copolymer (A) is less than 1% by weight, the effect of imparting flexibility and oil resistance tends to be insufficient, and if it exceeds 99% by weight, the thermosetting resin (E ) Tend to be difficult to achieve the characteristics of physical properties. The thermosetting resin (E) may be blended with a cured product, or may be cured after blending with the acrylic block copolymer (A), from the viewpoint of utilizing the characteristics of the thermosetting resin (E). Therefore, it is preferable that the resin composition blended with the acrylic block copolymer (A) is cured during molding.

  Various additives and catalysts may be added to the thermosetting resin (E) used in the present invention, if necessary, in order to promote the reaction during molding. For example, it is possible to use a curing agent generally used for epoxy resins such as acid anhydrides such as acid dianhydrides, amines, and imidazoles.

  The thermoplastic resin (B), the thermoplastic elastomer (C), the rubber (D), and the thermosetting resin (E) can be used alone or in combination of two or more, and the resulting resin composition, What is necessary is just to select according to the physical property required for a modifier and a molded object.

<Method for producing acrylic block copolymer (A)>
The method for producing the acrylic block copolymer of the present invention is not particularly limited, but it is preferable to use a controlled polymerization method. Controlled polymerization methods include living anion polymerization (JP-A-11-335432), polymerization using an organic rare earth transition metal complex as a polymerization initiator (JP-A-6-93060), radical polymerization using a chain transfer agent (special Kaihei 2-45511), a living radical polymerization method and the like.

  Living radical polymerization methods include, for example, a polymerization method using a chain transfer agent such as polysulfide, a polymerization method using a cobalt porphyrin complex, a polymerization method using a nitroxide (WO 2004/014926), and a high-cycle heteroelement compound such as an organic tellurium compound. And the like. (Polymer No. 3839829), Reversible Addition / Desorption Chain Transfer Polymerization (RAFT) (Patent No. 3639859), Atom Transfer Radical Polymerization (ATRP) (Patent No. 3040172), and the like. In the present invention, any of these methods is not particularly limited, but the atom transfer radical polymerization method is preferable from the viewpoint of easy control.

  As a method for producing an acrylic block copolymer using the atom transfer radical polymerization method, for example, the method described in WO2004 / 013192 can be used.

<Other ingredients>
You may mix | blend a filler with the resin composition of this invention as needed. The filler is not particularly limited, but wood powder, pulp, cotton chips, asbestos, glass fiber, carbon fiber, mica, walnut shell powder, rice husk powder, graphite, diatomaceous earth, white clay, silica (fumed silica, sedimentation) Silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, etc.), reinforcing filler such as carbon black; heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, Fillers such as clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, red pepper, aluminum fine powder, flint powder, zinc oxide, activated zinc white, zinc dust, zinc carbonate and shirasu balloon; asbestos, Glass fiber and glass filament, carbon fiber, Kevlar fiber, polyethylene fiber And fibrous fillers such as and the like.

  Among these fillers, inorganic fillers are more preferable from the viewpoint of improving mechanical properties, reinforcing effect, cost, and the like, and titanium oxide, carbon black, calcium carbonate, silica, and talc are more preferable.

  In the case of silica, silica whose surface has been previously hydrophobically treated with an organosilicon compound such as organosilane, organosilazane, or diorganopolysiloxane may be used. Furthermore, calcium carbonate is surface-treated using surface treatment agents such as organic substances such as fatty acids, fatty acid soaps and fatty acid esters, various surfactants, and various coupling agents such as silane coupling agents and titanate coupling agents. You may use what has been given.

  When the filler is used, the addition amount is preferably in the range of 5 to 200 parts by weight, more preferably in the range of 10 to 100 parts by weight with respect to 100 parts by weight of the resin composition. If the blending amount is less than 5 parts by weight, the reinforcing effect of the resulting molded product may not be sufficient, and if it exceeds 200 parts by weight, the molding of the resulting composition tends to be reduced. A filler can be used 1 type or in combination of 2 or more types.

  If necessary, the resin composition of the present invention may be blended with various lubricants for moldability, mold releasability from the mold, and reduction of friction on the surface of the resulting molded body.

  Examples of the lubricant include fatty acids such as stearic acid and palmitic acid, fatty acid metal salts such as calcium stearate, zinc stearate, magnesium stearate, potassium palmitate and sodium palmitate, polyethylene wax, polypropylene wax, and montanic acid wax. Waxes, low molecular weight polyolefins such as low molecular weight polyethylene and low molecular weight polypropylene, polyorganosiloxanes such as dimethylpolysiloxane, amide-based lubricants such as octadecylamine, alkyl phosphate, fatty acid ester, ethylenebisstearylamide, tetrafluoroethylene Fluorine resin powder such as resin, molybdenum disulfide powder, silicone resin powder, silicone rubber powder, silica and the like can be used. These can be used alone or in combination of two or more. Among these, stearic acid, zinc stearate, calcium stearate, fatty acid ester, and ethylene bisstearyl amide are preferable because of excellent cost and moldability.

  When the lubricant is used, the addition amount is preferably in the range of 0.05 to 20 parts by weight and more preferably in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the resin composition. When the blending amount is less than 0.1 part by weight, the improvement effect of moldability and the reduction of friction of the resulting molded body may be insufficient. When the blending amount exceeds 20 parts by weight, the resulting molded body machine Characteristics and chemical resistance tend to deteriorate. The lubricants can be used alone or in combination of two or more.

  Various additives other than the above may be added to the resin composition of the present invention, if necessary, for the purpose of adjusting the physical properties of the resin composition and the obtained molded article and modifier. As such additives, stabilizers, plasticizers, flexibility imparting agents, flame retardants, pigments, antistatic agents, antibacterial antifungal agents, tackifiers, fluidity improvers, antiblocking agents, crosslinking agents, crosslinking aids , Modifiers, dyes, conductive fillers and the like may be added. These can be used alone or in combination of two or more. Moreover, a foaming agent, that is, various chemical foaming agents and physical foaming agents can be added.

  Examples of the stabilizer include an anti-aging agent, a light stabilizer, and an ultraviolet absorber. Antiaging agents include, for example, phenyl-α-naphthylamine (PAN), octyldiphenylamine, N, N′-diphenyl-p-phenylenediamine (DPPD), N, N′-di-β-naphthyl-p-phenylenediamine (DNPD), N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine, N-phenyl-N′-isopropyl-p-phenylenediamine (IPPN), N, N′-diallyl-p -Phenylenediamine, phenothiazine derivatives, diallyl-p-phenylenediamine mixture, alkylated phenylenediamine, 4,4'-bis (α, α-dimethylbenzyl) diphenylamine, N-phenyl-N '-(3-methacryloyloxy- 2-hydropropyl) -p-phenylenediamine, diallylphenylenedia Amine mixtures, diallyl-p-phenylenediamine mixtures, N- (1-methylheptyl) -N′-phenyl-p-phenylenediamine, amine-based antioxidants such as diphenylamine derivatives, 2-mercaptobenzimidazole (MBI), etc. Phenol-based aging such as imidazole-based anti-aging agent, 2,6-di-t-butyl-4-methylphenol, pentaerythrityltetrakis [3- (5-di-t-butyl-4-hydroxyphenol) -propinate] Inhibitors, phosphate anti-aging agents such as nickel diethyl-dithiocarbamate, secondary anti-aging agents such as triphenyl phosphite, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5 -Methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di Such as t- pentylphenyl) ethyl] -4,6-di -t- pentylphenyl acrylate. 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-cyano-3,3′-diphenyl acrylate, 2-hydroxy-5-chlorobenzophenone, 2-hydroxy-4-methoxybenzophenone-2-hydroxy-4-octoxybenzophenone, monoglycol sari Examples include tyrates, oxalic acid amides, 2,2 ′, 4,4′-tetrahydroxybenzophenone, and the like.

  Specific products of such stabilizers include Irganox (registered trademark) 1010 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Sanol (registered trademark) LS770 (Sankyo Lifetech Co., Ltd.), Adekastab (registered trademark) LA -57 (Asahi Denka Kogyo Co., Ltd.), Adeka Stub LA-68 (Asahi Denka Kogyo Co., Ltd.), Chimassorb (registered trademark) 944 (Ciba Specialty Chemicals Co., Ltd.), Sanol LS765 (Sankyo Lifetech Co., Ltd.) ADEKA STAB LA-62 (Asahi Denka Kogyo Co., Ltd.), TINUVIN (registered trademark) 144 (Ciba Specialty Chemicals Co., Ltd.), ADK STAB LA-63 (Asahi Denka Kogyo Co., Ltd.), TINUVIN 622 (Ciba Specialty KK) Chemicals Co., Ltd.) ADK STAB LA-32 (Asahi Denka Kogyo Co., Ltd.), ADK STAB LA-36 (Asahi Denka Kogyo Co., Ltd.), TINUVIN 571 (Ciba Specialty Chemicals Co., Ltd.), TINUVIN 234 (Ciba Specialty Chemicals Co., Ltd.), ADK STAB LA-31 (Asahi Denka Kogyo Co., Ltd.), TINUVIN 1130 (Ciba Specialty Chemicals Co., Ltd.), ADK STAB AO-20 (Asahi Denka Kogyo Co., Ltd.), ADK STAB AO-50 (Asahi Denka Kogyo Co., Ltd.) , Adeka Stub 2112 (Asahi Denka Kogyo Co., Ltd.), Adeka Stub PEP-36 Asahi Denka Kogyo Co., Ltd., Sumilyzer GM (Sumitomo Chemical Co., Ltd.), Sumilyzer GS (Sumitomo Chemical Co., Ltd.), Sumilyzer TP-D (Sumitomo) Chemical industry stock association ) It is and the like. These may be used alone or in combination of two or more. Among them, Sanol LS770, Irganox 1010, Sumilizer GS, and TINUVIN234 are preferable because they are an effect of preventing deterioration and cost due to heat and light of the acrylic block body.

When the stabilizer is used, the addition amount is preferably in the range of 0.05 to 20 parts by weight, more preferably in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the resin composition. . When the blending amount is less than 0.05 parts by weight, the effect of improving resistance to heat and light of the obtained molded product may be insufficient, and when it exceeds 20 parts by weight, the surface of the obtained molded product may be insufficient. There is a tendency to bleed out or mechanical properties deteriorate. The stabilizers can be used alone or in combination of two or more.

  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 phthalate. Phthalic acid derivatives such as diisononyl acid, ditridecyl phthalate, octyldecyl phthalate, butylbenzyl phthalate, dicyclohexyl phthalate; isophthalic acid derivatives such as dimethyl isophthalate; tetrahydro such as di- (2-ethylhexyl) tetrahydrophthalic acid Phthalic acid derivatives; adipic acid derivatives such as dimethyl adipate, dibutyl adipate, di-n-hexyl adipate, di- (2-ethylhexyl) adipate, isononyl adipate, diisodecyl adipate, dibutyldiglycol adipate; Azelaic acid derivatives such as di-2-ethylhexyl acid; sebacic acid derivatives such as dibutyl sebacate; dodecane-2-acid derivatives; maleic acid derivatives such as dibutyl maleate and di-2-ethylhexyl maleate; dibutyl fumarate etc. Fumaric acid derivatives; trimellitic acid derivatives such as tris-2-ethylhexyl trimellitic acid; pyromellitic acid derivatives; citric acid derivatives such as acetyltributyl citrate; itaconic acid derivatives; oleic acid derivatives; ricinoleic acid derivatives; stearic acid derivatives; Derivatives; sulfonic acid derivatives; phosphoric acid derivatives; glutaric acid derivatives; polyester plasticizers that are polymers of dibasic acids such as adipic acid, azelaic acid, and phthalic acid and glycols and monohydric alcohols, glycol derivatives, glycerin derivatives, Chlorination Paraffin derivatives such as paraffin, epoxy derivatives polyester polymerization type plasticizers, polyether polymerization type plasticizers, ethylene carbonate, or the like carbonate derivatives such as propylene carbonate. In the present invention, the plasticizer is not limited to these, and various plasticizers can be used, and those commercially available as rubber plasticizers can also be used. These compounds can be expected to lower the viscosity of the acrylic block copolymer (A). Commercially available plasticizers include Thiocol TP (Morton), Adekasizer (registered trademark) O-130P, C-79, UL-100, P-200, RS-735 (Asahi Denka). Can be mentioned. Examples of other high molecular weight plasticizers include acrylic polymers, polypropylene glycol polymers, polytetrahydrofuran polymers, polyisobutylene polymers, and the like. Among these, plasticizers that are low volatility and have little weight loss due to heating are adipic acid derivatives, phthalic acid derivatives, glutaric acid derivatives, trimellitic acid derivatives, pyromellitic acid derivatives, polyester plasticizers, glycerin derivatives, epoxy derivatives polyester polymerization type A plasticizer, a polyether polymerization type plasticizer, and the like are preferable.

  Examples of the flexibility-imparting agent include softeners such as process oils; oils such as animal oils and vegetable oils; petroleum fractions such as kerosene, light oil, heavy oil, and naphtha. Examples of the softening agent include process oil, and more specifically, paraffin oil; naphthenic process oil; petroleum process oil such as aromatic process oil, and the like. Examples of vegetable oils include castor oil, cottonseed oil, sesame oil, rapeseed oil, soybean oil, palm oil, coconut oil, peanut oil, pine oil, tall oil and the like, but are not limited thereto. These softening agents can be used alone or in combination of two or more.

  The addition amount in the case of using a plasticizer or a flexibility imparting agent is preferably in the range of 1 to 200 parts by weight, more preferably in the range of 1 to 100 parts by weight with respect to 100 parts by weight of the resin composition. preferable. When the blending amount is less than 1 part by weight, the improvement effect of moldability and flexibility may be insufficient. When the blending amount exceeds 200 parts by weight, the surface of the resulting molded body may bleed out or mechanical properties may be obtained. Tend to get worse. The plasticizer and the flexibility-imparting agent can be used alone or in combination of two or more.

  Examples of the flame retardant include triphenyl phosphate, tricresyl phosphate, tris (chloropropyl) phosphate, polyphosphate, phosphate type polyol, decabromobiphenyl, decabromobiphenyl ether, antimony trioxide, ammonium phosphate, polyphosphoric acid Ammon, guanidine phosphate, perchlorocyclodecane, aluminum hydroxide, magnesium hydroxide, chlorinated paraffin, polyethylene chloride, perchlorocyclodecane, boron compounds, zirconium compounds, etc. Absent. These may be used alone or in combination of two or more.

  When the flame retardant is used, the addition amount is preferably in the range of 1 to 300 parts by weight and more preferably in the range of 10 to 100 parts by weight with respect to 100 parts by weight of the resin composition. When the blending amount is less than 1 part by weight, the effect of imparting flame retardancy to the obtained molded product tends to be insufficient, and when it exceeds 300 parts by weight, the moldability and mechanical properties of the obtained molded product are poor. It tends to get worse.

  As the pigment, for example, both organic pigments and inorganic pigments can be used. Organic pigments include, for example, azo pigments such as azo lakes, insoluble monoazo pigments, insoluble disazo pigments, condensed azo pigments, chelate azo pigments; phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, isoindigo pigments Polycyclic pigments such as linone pigments and quinophthalone pigments; dye chelates such as basic dye chelates and acid dye chelates; nitro pigments; nitroso pigments and the like.

  Examples of the inorganic pigment include titanium oxide, iron oxide, red pepper, chromium oxide, bitumen, ultramarine blue, molybdenum red, iron black, yellow lead, and carbon black. These can be used alone or in admixture of two or more.

  Specific examples of the organic pigment include, for example, Pigment Yellow 1 (Color Index (hereinafter referred to as CI) 11680), Pigment Yellow 3 (C.I. 11710), and Pigment Yellow 14 (C.I. Pigment Yellow 17 (C.I. 21105), Pigment Yellow 42 (C.I. 77492), Pigment Yellow 74 (C.I. 11741), Pigment Yellow 83 (C.I. 21108), Pigment Yellow 93 (C.I. 20710), Pigment Yellow 98 (C.I. 11727), Pigment Yellow 109 (C.I. 56284), Pigment Yellow 110 (C.I. 56280) Pigment Yellow 128 (C.I.20037), Pigment Yellow 138 (C.I. 56300), Pigment Yellow 139 (C.I. 56298), Pigment Yellow 147 (C.I. 60645), Pigment Yellow 154 (C.I. 117817), Pigment Yellow 155 Pigment Yellow 180 (C.I. 21290), Pigment Yellow 185, Pigment Orange 5 (C.I. 12075), Pigment Orange 13 (C.I. 21110), Pigment Orange 16 (C.I. Pigment Orange 34 (C.I. 21160), Pigment Orange 43 (C.I. 71105), Pigment Orange 61 (C.I. 11265), Pigment Orange 71 (C.I. 561200) ), Pigment Red 5 (C.I.124 0), Pigment Red 8 (C.I. 12335), Pigment Red 17 (C.I. 12390), Pigment Red 22 (C.I. 12315), Pigment Red 48: 2 (C.I. 15865: 2), Pigment Red 112 (C.I. 12370), Pigment Red 122 (C.I. 73915), Pigment Red 177 (C.I. 65300), Pigment Red 202 (C.I. 73907), Pigment Red 254 (C.I. 56110), Pigment Violet 19 (C.I. 46500), Pigment Violet 23 (C.I. 51319), Pigment Blue 15: 1 (C.I. 74160), Pigment Blue 15: 3 (C.I. 74160), Pigment Blue 15: 4 (C. I. 74160), Pigment Blue 60 (C.I. 69800), Pigment Green 7 (C.I. 74260), Pigment Green 36 (C.I. 74265), and the like.

  Specific examples of the inorganic pigment include, for example, Pigment Yellow 42 (C.I. 77492), Pigment White 6 (C.I. 777891), Pigment Blue 27 (C.I. 77510), and Pigment Blue 29 (C.I. 77007), pigment black 7 (C.I. 77266), and the like. When the pigment is used, the addition amount is preferably in the range of 0.01 to 100 parts by weight, and more preferably in the range of 1 to 50 parts by weight with respect to 100 parts by weight of the resin composition. If the blending amount is less than 0.01 parts by weight, color spots and glossy spots tend to occur in the resulting molded product, and if it exceeds 100 parts by weight, the moldability and mechanical properties of the resulting molded product deteriorate. Tend to. The pigments can be used alone or in combination of two or more.

  Examples of the tackifier include natural rosin derivatives, terpene, and synthetic coumarone indene resins, petroleum resins, and alkylphenol resins.

  Examples of natural rosin derivatives include rosin and tall oil-containing resins such as gum rosin, tall oil rosin, and wood rosin. Examples of natural terpene resins include polyterpenes obtained by polymerizing terpene oil obtained when rosin is taken from a pine tree, and those having a softening point of about 120 ° C. from a liquid. A terpene / phenol copolymer may also be mentioned.

  Examples of the synthetic coumarone indene resin include those obtained by polymerizing a mixture of coumarone, indene, styrene and the like in coal tar. Examples of synthetic petroleum resins include those obtained by decomposing naphtha or gas at high temperature. Specifically, aliphatic resins that polymerize C5 fraction (such as isoprene, piperine, 2-methylbutene-1, etc.). Copolymer), aromatic system for polymerizing C9 fraction (main components are styrene, vinyltoluene, α-methylstyrene), C5 / C9 copolymer system (copolymerization system for C5 fraction and C9 fraction), Examples thereof include an aliphatic system in which a cycloaliphatic dicyclopentadiene or a C9 system is hydrogenated. Synthetic alkylphenol resins include alkylphenol / acetylene resins and alkylphenol / formaldehyde resins. In addition, xylene, formaldehyde resin, oligomers such as polybutene, liquid rubber (IR, acrylic oligomer) and the like can be mentioned. Commercially available tackifiers include coumarone resin RG (made by Fuji Steel), coumarone resin NG4 (made by Nippon Steel Chemical Co., Ltd.), coumarone LC (made by Ouchi Shinsei), process resin A81 (made by Kobe Oil Chemical Co., Ltd.), process Resin AC5 (manufactured by Kobe Oil Chemical Industry), Process Resin TX (manufactured by Kobe Oil Chemical Industry), Hinotar 1501 (manufactured by Hitachi Chemical), Hinotar 1502 (manufactured by Hitachi Chemical), Tamanoru 510 (manufactured by Arakawa Chemical Industries), Tactrol 101 (Manufactured by Sumitomo Chemical Co., Ltd.), tack roll 160 (manufactured by Sumitomo Chemical Co., Ltd.), tack roll EP20 (manufactured by Sumitomo Chemical Co., Ltd.), tack roll EP30 (manufactured by Sumitomo Chemical Co., Ltd.), Sumilite Resin PR19900 (Sumitomo Durez), Nikanol HP70 (Mitsubishi Kawasaki Chemical) ), PP1521 (manufactured by Gunei Chemical Industry), Alcon P90 (manufactured by Arakawa Chemical Industries) Ester gum H (manufactured by Arakawa Chemical Industries), petrozine # 80 (manufactured by Mitsui Chemicals), petrozine # 120 (manufactured by Mitsui Chemicals), Hiretz G100X (manufactured by Mitsui Chemicals), Escorez 5280 (manufactured by Esso Chemicals), Koresin (manufactured by Bayer), Wing Tack95 (manufactured by Goodyear), Nikanol A70 (manufactured by Mitsubishi Kalashan Chemical), Lignol R70 (manufactured by Lignite), Staybelite Resin (manufactured by Hercules), YS resin Px (manufactured by Yashara Chemical), YS resin PxN (manufactured by Yashara Chemical), YS resin D (Yasuhara Chemical), YS Resin D (Yasuhara Chemical), YS Resin A (Yasuhara Chemical), Dimaron (Yasuhara Chemical), YS Polystar 2000 (Yasuhara Chemical), YS Polystar U ( Suhara Chemical), YS Polystar T (Yasuhara Chemical), YS Polystar S (Yasuhara Chemical), YS Polystar N (Yasuhara Chemical), Mighty Ace G (Yasuhara Chemical), Mighty Ace K (Yasuhara Chemical), YP-90L (Yasuhara Chemical) ), YP-902 (Yasuhara Chemical), YS Resin TO (Yasuhara Chemical), YS Resin TR (Yasuhara Chemical), YS Resin Z (Yasuhara Chemical), Clearon P (Yasuhara Chemical), Clearon M (Yasuhara Chemical), Clearon K (manufactured by Yasuhara Chemical), Clearon K4090 (manufactured by Yasuhara Chemical) and the like.

  When the tackifier is used, the addition amount is preferably 0.1 to 200 parts by weight, more preferably 1 to 100 parts by weight, based on 100 parts by weight of the resin composition. When the blending amount is less than 0.1 parts by weight, tackifying and curing to the resulting molded product tends to be insufficient, and when it exceeds 200 parts by weight, the mechanical properties of the resulting molded product tend to deteriorate. It is in. The tackifiers can be used alone or in combination of two or more.

  As a crosslinking agent or a crosslinking aid, the acrylic block copolymer (A) of the present invention can be added for crosslinking as necessary, and a functional group having reactivity with the functional group (X) is added. What is necessary is just to add the compound which has 2 or more in 1 molecule. What is necessary is just to select an appropriate thing according to the kind of functional group (X), but as a crosslinking agent or a crosslinking adjuvant, the thing similar to what was described in the term of rubber (D) may be illustrated, for example. it can. Furthermore, various additives and catalysts may be added to promote the crosslinking reaction. Depending on the beast of functional group (X), for example, curing agents generally used for acid anhydrides such as acid dianhydrides, amines, imidazoles, etc., divalent tin compounds, titanates, etc. It is possible to use a known esterification catalyst or a transesterification catalyst.

  Moreover, as described in the section of rubber (D), when the acrylic block copolymer (A) is crosslinked, the acrylic block copolymer (A) may be blended after the crosslinking, It may be crosslinked later or may be dynamically crosslinked.

  Specific examples of such additives are described, for example, in Mitsuo Akiba “Rubber / Elastomer Compounding Design Manual”, Industrial Science Systems Co., Ltd., 2000.

  There is no restriction | limiting in particular in the manufacturing method of the resin composition in this invention, A well-known method is applicable.

  For example, it can mix | blend by using a batch type kneading apparatus and a continuous kneading apparatus. As a batch type kneading apparatus, for example, a pressure-resistant reaction vessel, a mixing roll, a Banbury mixer, a pressure kneader, or a high shear mixer can be used. Moreover, as a continuous kneading apparatus, a single screw extruder, a twin screw extruder, a KCK extrusion kneader, etc. can be used. At this time, after the acrylic block copolymer (A) and the compound are mixed in a soluble solvent, the solvent may be removed, or the acrylic block copolymer (A) and the compound are mixed. You may mix | blend directly, knead | mixing at the temperature which a thing melts. The kneading order of the components is not particularly limited, and can be determined according to the apparatus used, workability, or physical properties of the resin composition to be obtained. Furthermore, an existing method such as a method of forming a pellet or powder can be used. Further, for example, the pellets can be subjected to an adhesion preventing process by the method described in JP-A-2003-253005.

  The processing method of the resin composition in the present invention is not particularly limited, and is an extrusion molding method, a profile extrusion method, an injection molding method, a multilayer molding method, a two-color molding method, an insert molding method, a sandwich molding method, and a foam molding method. , Press molding, blow molding, calendar molding, rotational molding, slush molding, dip molding, cast molding, and the like. Examples of the shape of the molded body obtained by such a processing method include films, sheets, tubes, bags, pipes, various atypical materials, containers and the like.

  The molded article and modifier of the present invention are rich in flexibility, moldability, recyclability, rubber properties, compression set properties, heat resistance, oil resistance, weather resistance, transparency, flexibility, base material Excellent adhesion and other properties.

  Therefore, as modifiers and molded products for resin modification, automobiles, home appliances / light electrical appliances, industrial parts, civil engineering / architecture, sporting goods / daily miscellaneous goods, packaging materials, medical / healthcare, etc. Is available.

(1) Modifier
Resin modifiers (impact modifiers for thermoplastic resins, fluidity modifiers, damping modifiers, softeners, impact modifiers for thermosetting resins, low stress modifiers, Viscosity modifiers), asphalt modifiers (asphalt modifiers for roads, asphalt modifiers for waterproof sheets, waterproof materials for bridge decks), tire modifiers (wet grip improvers for tires), rubber modification Pesticide.

(2) Adhesive or adhesive
Plywood, woodwork, packaging, textiles, rubber products, architectural civil engineering, automobiles, vehicles, electronics, aviation, space-use hot melt adhesives, water-based adhesives, solvent-based adhesives, reactive type (photocuring type, thermosetting type) ) Adhesives, solvent-based pressure-sensitive adhesives, hot-melt pressure-sensitive adhesives, water-based pressure-sensitive adhesives, reactive pressure-sensitive adhesives, pressure-sensitive adhesives, adhesives, base sheets and films for pressure-sensitive adhesives / adhesives.
For example, electrostatic flocking products for automobiles, adhesives for adhering tapes to automobile side protection moldings, etc., polar materials (PMMA, PC, ABS, COP, etc.), rubber products, and synthetic trees that are difficult to bond as automotive parts Adhesives for automobiles such as adhesives for trial products, adhesives for synthetic leather, adhesives for laminated inorganic boards, adhesives for optical disks, adhesives for vulcanized rubber, adhesives for fibers, plated steel sheets-edge materials for speakers Adhesives for propylene / PVC sheets, adhesives for metal parts, adhesives for foam sheets, adhesives for metal / polar resin laminates, adhesives for food packaging, hot melt adhesives, solventless adhesives , Ink adhesives, powder adhesives, primers and the like.

  Examples of adhesives include adhesive sheets and tapes, tack sheets, resins, adhesives for rubber surface coating, automobiles, displays, adhesives for surface protection sheets for precision devices, adhesives for automobile bodies and bumpers, and optical film bonding. Adhesives for LCD, Adhesives for bonding to LCD, Double-sided adhesive tape for fixing precision parts, Adhesives for Blue-ray discs, Adhesive tapes for electronic material processes, Tapes for back grinding, Dicing tape, etc. Applications are listed.

(3) Viscosity modifier
Viscosity modifier added to oil, lubricant, solvent, etc.

(4) Coating agent
Base resins and sealants used in paints, etc. For example, topcoat paints, automobile repair paints, automotive intermediate coating type anti-pitching paints, automotive electrostatic flocking product paints, polar resin paints for automobiles, etc. Automotive paints such as difficult-to-paint plastic paints for parts and automotive inserts, and polar resin paints for home appliances, difficult-to-paint plastic paints for home appliances, etc., plants, thick slate, outer walls Buildings and building exterior paints such as spray materials, railroad cars, aircraft, specially equipped vehicles, industrial equipment and appliances, aluminum sashes, metal pipes and other metals, FRP products such as helmets and skis, various plastic molded products, Rubber products such as golf balls, rubbers such as leather including synthetic leather, plastics and leather, varnishes for electric wires, thermosetting paints such as one-component baking paints, and For heavy corrosion protection of vessels such as balance tanks, plant towers, etc., and for priming and rust prevention of cationic electrodeposition paints, corrosion-inhibiting conductive paints for automobiles and electrical equipment, and powder paints and printing inks , Primer, fiber, leather, metal, various resin coating agents, dip coating agents, surface modifiers, and the like.

(5) Materials used for PVC replacement
Cable covering materials such as cables, connectors, and plugs, toys such as dolls, curing tapes, logo marks (for sportswear and sports shoes), carry bags, clothing packaging materials, truck hoods, agricultural films (for house cultivation) ), Eraser, commercial apron (tarpaulin), interior materials for buildings such as flooring and ceiling materials, raincoats, umbrellas, shopping bags, skin materials such as chairs and sofas, skin materials such as belts and bags, garden hoses, Gaskets (packing) for refrigerators, flexible hoses for washing machines and vacuum cleaners, automotive interior materials.

(6) Damping material, anti-vibration material, cushioning material
Damping material, especially damping material laminated in multiple layers with aluminum and steel plate, damping material, cushioning material (for building use, automobile use, floor damping use, flooring use, play equipment use, precision equipment use, electronic equipment use Use) Machine / industrial for vibration-absorbing composite materials for various equipment / equipment / vehicles, etc. Grips for shoe soles, stationery / toy supplies, grips for daily goods / carpenter supplies, grips and heartwood for golf clubs / bats, etc. Rubber and grips such as tennis rackets and table tennis rackets.

(7) Soundproof material, sound absorbing material
Automotive interior and exterior materials, automotive ceiling materials, railcar materials, piping materials.

(8) Sealing materials such as packing materials and sealing materials, packaging materials
Gaskets, gaskets for construction, plugs Glass sealing materials for laminated glass and multilayer glass Packaging materials, sheets, multilayer sheets, containers, sealing agents for multilayer containers, etc., waterproof sheets, waterproof sheets, packaging and transport materials, Sealant.

(9) Foam
Foaming agent carrier in bead foaming, slow pressure foaming, foams by extrusion foaming (pipe coating materials, synthetic wood, wood flour foams, etc.), chemical foaming and physical foaming.

(10) Dispersant Dispersant for various pigments. For example, paints, inks, lacquers, color filters, automotive paints, coating agents, toners, colored plastics, and pigment dispersants for cosmetics. Ingredient dispersant for cosmetics and medical use.

(11) Binder
Binder for various inorganic and organic substances. For example, various binders such as magnetic tape binders, printing ink / paint binders, fiber binders and ceramic binders.

(12) Leather materials For shoe uppers, for sports equipment such as balls, baseball gloves and gloves, for automotive parts such as handle covers, seats and interior materials, for clothing such as coats, blazers, skirts, trousers, dresses, blousons, Applications include interiors such as furniture and wall coverings.

(13) Gels For example, uses such as automobile fragrances, mattresses, mattress inserts, wheelchair cushions, bicycle saddles, car seats, padded furniture pads, biocompatible hydrogels, drug retaining agents and the like.

(14) Related to electronic parts For example, charging rolls and developing rolls of copying machines and printers, cleaning blades for electrophotographic copying machines, potting of electronic parts in the engine room of automobiles, electrophotographic toners, electrophotographic apparatuses and electrostatic recording printers Applications such as charging / developing / transfer / fixing / feeding / conveying members, charge control agents, charge transport agents, etching mask materials for integrated circuits, battery electrolyte solution solidifying agents, and the like.

(15) Insulation materials For example, hybrid IC, mounting on alumina base, mounting on diode, IC regulator for four-wheeled vehicles, CDI unit for two-wheeled vehicles, igniter, wiper motor, winker canceller, door light sensor, noise filter, outboard motor Control equipment, control equipment for farm equipment, office equipment, office equipment, space equipment, aerospace electronic equipment, washing machine, toilet washlet, water heater, dishwasher, rice cooker pot, home bakery・ Moisture-proofing of automotive electronic component control boards ・ Robots, sensors, vending machines ・ Moisture-proof insulation of printed circuit boards for outdoor environment investigation equipment, capacitors and noise filters, TVs, VTR cameras, various adapters, and enamels for office equipment Coil-related parts for electric wires, transformers, electric cables Interlayer insulation for wire coils for joint waterproof insulation.

(16) Cosmetics Foam stabilizers such as moisturizing agents, hair setting agents, nail polish binders, hair mousses, dispersants such as hair dyes and light shielding agents, cosmetic medicinal component dispersants.

(17) Others ・ Flame retardant use ・ Foaming fireproof sheet
・ Airbag covers, bumpers, interior parts (skin materials such as instrument panels and shift knobs), weather strips, roof moldings, door moldings, hoses, meter hoods, mudguards, boots, air hoses, glass run channels, rack & pinion boots, CVJ Boots, shock absorbers, dash insulators, mats, bushes, dust covers, gaskets, ball joints, spring stops, spring covers, ball seats, pedal stoppers, door locks, bearing covers, gears, bellows, doubt seals, timing belts, bearings , Automotive parts such as anti-vibration parts, exterior parts, snow chains, refrigerator parts, solid tires, various containers, etc.
・ Food trays for microwave ovens, food containers for potions, laminated films for food containers, polystyrene sheets for food containers (sashimi containers / chicken egg packs), cup ramen containers, polystyrene mesh foam, frozen dessert cups, transparent beverage cups, etc. Food containers
・ Adhesives for paper diapers, syringes, syringes, toothbrush patterns, grommets, hair brushes, medical tubes, etc. ・ Healthcare products ・ IC trays, CD-ROM chassis, wheel caps, elastic threads, non-woven fabrics, wire harnesses, paper diaper bags Sheet, 2-color molding compound material, underwater goggles, PC mouse, cushion, stopper, various gears, casters, rolls, pickers, bushes, caps, bags, gaskets, connectors, printing drums, rubber screens, lawn mower plates, hands Fir pump, shoe sole, point, women's shoe heel top, goggle band, stock grip, roller, sports / stationery / tool grip, aqualung, film, toys, figurine, doll, watch band, in ball Bag, air array Sports goods such as tubes, daily goods, medical and food conveyor belts, various keyboard sheets, air mats, diaphragms, laminates, antistatic belts, hot melt films, overflow tanks, tarpaulins, various packaging, clothing, stair slides Films and sheets such as stoppers, high-pressure resin hoses, paint hoses, fire hoses, agricultural spray hoses, hydraulic tubes, fuel tubes, pneumatic tubes, medical tubes, etc., power and communication cables, concrete Wiring, automotive wiring, sheath pipe, high pressure hose, various belt slip stoppers, oil resistance of ropes, gloves, wires, etc., impact resistant coating for automobiles, protection of aircraft acrylic canopy, coating for microbial resistant articles, etc. Mitsugen, base polymer for water development photoresist Photoresist base polymer, rubber switch, a waterproof packing of cable joints, vibration-proof, moisture-proof potting material, optical cable waterproofing agents include applications such as a surfactant.

  Therefore, the molded body and the modifier made of the resin composition of the present invention can be widely used for various applications and have a great industrial value.

  EXAMPLES Although this invention is demonstrated further in detail based on an Example, this invention is not limited only to these Examples. In the examples, BA, AA, MMA, and TBA represent acrylic acid-n-butyl, acrylic acid, methyl methacrylate, and acrylic acid-t-butyl, respectively. Moreover, the molecular weight described in the examples, the conversion rate of the polymerization reaction, and the evaluation of each physical property were performed according to the following methods.

<Molecular weight measurement method>
The molecular weight shown in this example was measured by the GPC analyzer shown below, and the molecular weight in terms of polystyrene was determined using chloroform as the mobile phase. As a system, a GPC system manufactured by Waters was used, and Shodex K-804 (polystyrene gel) manufactured by Showa Denko Co., Ltd. was used for the column.

<Method for measuring conversion rate of polymerization reaction>
The conversion rate of the polymerization reaction shown in this example was measured using the following analyzer and conditions.
Equipment used: Gas chromatography GC-14B manufactured by Shimadzu Corporation
Separation column: manufactured by J & W SCIENTIFIC INC, capillary column Supercoux-10, 0.35 mmφ × 30 m
Separation conditions: Initial temperature 60 ° C, hold for 3.5 minutes
Temperature increase rate 40 ° C / min
Final temperature 140 ° C, hold for 1.5 minutes
Injection temperature 250 ° C
Detector temperature 250 ° C
Sample preparation: The sample was diluted about 10 times with ethyl acetate, and butyl acetate or acetonitrile was used as an internal standard substance.

Evaluation <Functional group content>
The content of the functional group (carboxyl group) in the acrylic block copolymer (A) is such that the acrylic block copolymer (A) is treated with diazomethane to convert the carboxyl group to methyl ester, and then diazomethane at 350 ° C. It determined by performing the thermal decomposition reaction of the processed acrylic block copolymer (A), and quantifying the amount of generated methyl acrylates by gas chromatography.

<Injection molding>
For the injection molding shown in this example, Toshiba's injection molding machine IS80EPN was used. The mold was a center gate plate (length 120 mm * width 120 mm * thickness 2 mm). The measurement position was 55 mm, the molding cycle was 2 seconds for injection, and 30 seconds for cooling, and the molded body was taken out from the mold in a semi-automatic mode. Further, the dumbbell described below was punched out in the TD direction (perpendicular to the injection direction) and the mechanical strength of the molded body taken out was measured.

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

<Hardness>
According to JIS K6253, the hardness at 23 ° C. (immediately after, JIS A) was measured with a type A durometer.

<Oil resistance>
In accordance with ASTM D638, ASTM Oil No. 1 in which the molded product of the composition was kept at room temperature or 100 ° C. 3 was immersed for 72 hours, and the weight change rate (% by weight) was determined.

<Scratch resistance test>
The molded bodies prepared in Examples and Comparative Examples were cut out and pasted on a mount to obtain a measurement sample. The scratch resistance test (scratch test) shown in FIG. 1 was performed under the following conditions. Equipment used: Tabers Clutch Tester (Toyo Seiki Seisakusho Co., Ltd.)
Rotation speed: 0.5rpm
Cutter: Tungsten carbide, 4.8 mm square x 19 mm length, cutting edge radius 12.7 mm
Load: 3N
Sample dimensions: a sheet having a thickness of 2.0 mm, a length of 10 cm and a width of 10 cm. The obtained molded sheet was visually evaluated and evaluated according to the following criteria.
A sheet that looks white when viewed from an angle but does not appear white when viewed from the front: ○
What looks white when the sheet is viewed from the front:
The surface is cut off: ×

(Production Example 1)
<Synthesis of block copolymer (A)>
In a 500-liter reactor purged with nitrogen, 87.1 kg of n-butyl acrylate (nBA) and 2.23 kg of t-butyl acrylate (tBA) were charged, and then 625 g of cuprous bromide was charged and stirring was started. Thereafter, a solution prepared by dissolving 628 g of diethyl 2,5-dibromoadipate in 7.84 kg of acetonitrile was charged, and the jacket was heated and held at an internal temperature of 75 ° C. for 30 minutes. Thereafter, 76 g of pentamethyldiethylenetriamine was added to initiate polymerization of the acrylic polymer block. A small amount of the polymerization solution was withdrawn at regular intervals from the start of polymerization, and the conversion of butyl acrylate was determined by gas chromatogram analysis. The polymerization rate was controlled by adding pentamethyldiethylenetriamine as needed.

  When the conversion rate of butyl acrylate (nBA) reached 95%, 106.5 kg of toluene, 431 g of cuprous chloride, 76 g of pentamethyldiethylenetriamine and 38.4 kg of methyl methacrylate (MMA) were added, Polymerization of the polymer block was started. When the conversion rate of methyl methacrylate (MMA) reached 90%, 220 kg of toluene was added to dilute the reaction solution and the reactor was cooled to stop the polymerization.

  When the GPC analysis of the obtained acrylic block copolymer was conducted, the number average molecular weight (Mn) was 108,900 and the molecular weight distribution (Mw / Mn) was 1.34.

  Moreover, the obtained block copolymer is an aba type triblock structure, and the composition ratio (a / b) of the methacrylic polymer block (a) and the acrylic polymer block (b) is It was 30% by weight / 70% by weight. The composition of the methacrylic polymer block (a) was MMA 28% by weight + nBA 2% by weight, and the composition of the acrylic polymer block (b) was nBA 69% by weight + tBA 1% by weight.

  Moreover, the glass transition temperature of each polymer block calculated from the Fox equation is that the glass transition temperature of the acrylic polymer block (b) is −53 ° C., and the glass transition temperature of the methacrylic polymer block (a) is 81. ° C.

  Toluene was added to the obtained block copolymer solution to adjust the polymer concentration to 22% by weight. To this solution, 1.49 kg of p-toluenesulfonic acid monohydrate was added and stirred at 30 ° C. for 3 hours. This converted t-butyl acrylate (tBA) units to acrylic acid (AA) units. The content of acrylic acid units in the entire block copolymer was 1.0% by weight.

  The reaction solution was sampled, it was confirmed that the solution was colorless and transparent, and 2.47 kg of Radiolite # 3000 manufactured by Showa Chemical Industry, which is a filter aid, was added. Thereafter, pressure filtration was performed at 0.1 to 0.4 MPaG using a pressure filter equipped with polyester felt as a filter medium to separate a solid content.

  The filtered block copolymer solution was charged into a 500 L reactor and heated at 150 ° C. for 4 hours. After cooling, 6.18 kg of Kyowa Chemical Kyoward 500SH, which is a basic adsorbent, was added for the purpose of removing the remaining organic acid, followed by stirring for 1 hour. The reaction solution was sampled to confirm that the solution was neutral, and the reaction was completed. Then, using a pressure filter equipped with polyester felt as a filter medium, pressure filtration was performed at 0.1 to 0.4 MPaG to separate a solid content, and a polymer solution was obtained.

After adding 0.6 parts by weight of Irganox 1010 (manufactured by Ciba Specialty Chemicals Co., Ltd.) to 100 parts by weight of the polymer to the obtained polymer solution, SCP100 (Kurimoto Corporation) The solvent component was evaporated using a heat transfer area of 1 m ² ). The heating medium oil at the evaporator inlet was 180 ° C., the evaporator vacuum was 0.01 MPa or less, the screw rotation speed was 60 rpm, and the polymer solution supply rate was 32 kg / h. The polymer was made into a strand through a φ4 mm die, cooled in a water bath, and polymer pellets were obtained by a pelletizer.

(Examples 1-2)
Acrylic block copolymer prepared in Production Example 1, thermoplastic polyurethane resin (Elastollan C60D: manufactured by BASF Japan) and Irganox 1010 as a stabilizer were hand-blended in the proportions shown in Table 1, and 200 ° C. (8 cylinder portions). (C1 to C8, in order of C1 to C8 from the bottom of the hopper to the die side))) (32 mmφ, L / D = 22.5, manufactured by Nippon Steel Works, product name TEX30HSS) Used and melt-kneaded at 300 rpm. The obtained sample was injection-molded to obtain a sheet of 120 mm square and 2 mm thickness. Using this sheet, hardness measurement and oil resistance test were performed. The evaluation results are shown in Table 1.

(Comparative Example 1)
An ester-based thermoplastic polyurethane-based resin (Elastollan C60D: manufactured by BASF Japan) was injection molded to obtain a sheet of 120 mm square and 2 mm thickness. Using this sheet, hardness measurement and oil resistance test were performed. The evaluation results are shown in Table 1.

(Comparative Examples 2-3)
Styrene elastomer (Septon 2063: manufactured by Kuraray) and thermoplastic polyurethane resin (Elastollan C60D: manufactured by BASF Japan) were hand-blended at the ratio shown in Table 1, and 200 ° C. (cylinder part 8 points (C1-C8, hopper). Using a twin screw extruder (32 mmφ, L / D = 22.5, manufactured by Nippon Steel Works Co., Ltd., product name TEX30HSS) from bottom to die side in the order of C1 to C8) Melt kneaded. Moreover, the obtained sample was injection-molded to obtain a sheet of 120 mm square and 2 mm thickness. Using this sheet, hardness measurement and oil resistance test were performed. The evaluation results are shown in Table 1.

実施例１、２と比較例１の対比から、熱可塑性ポリウレタン系樹脂にアクリル系ブロック共重合体を添加したものは、熱可塑性ポリウレタン系樹脂単体に対して柔軟性が改善されていることがわかる。また、実施例１と比較例２の対比、および実施例２と比較例３の対比から、樹脂種が同一で樹脂と改質剤の配合比が同一の場合、改質剤としてアクリルブロック共重合体を使用したものは、スチレン系エラストマーを使用したものに比べ、良好な耐油性有している事がわかる。

From the comparison between Examples 1 and 2 and Comparative Example 1, it is understood that the thermoplastic polyurethane resin added with the acrylic block copolymer has improved flexibility relative to the thermoplastic polyurethane resin alone. . Further, from the comparison between Example 1 and Comparative Example 2 and the comparison between Example 2 and Comparative Example 3, when the resin type is the same and the compounding ratio of the resin and the modifier is the same, the acrylic block co-polymer is used as the modifier. It can be seen that those using coalescence have better oil resistance than those using styrene elastomer.

(Example 3)
The polymer pellets obtained in Production Example 1, the polyether-based thermoplastic polyurethane resin (PANDEX T-8180N: manufactured by DIC Bayer Polymer Co., Ltd.) and the stabilizer: Irganox 1010 in the proportions shown in Table 1 Using a mill (manufactured by Toyo Seiki Co., Ltd.), melt-kneading was performed at 200 ° C. to obtain a block sample. The obtained sample was hot press molded at a set temperature of 200 ° C. to obtain a molded body for evaluation having a thickness of 2 mm. This molded body was used for hardness measurement, mechanical strength, and oil resistance test. The evaluation results are shown in Table 2.

Example 4
Labo plast mill with the polymer pellets obtained in Production Example 1, polyester thermoplastic polyurethane resin (PANDEX T-1180: manufactured by DIC Bayer Polymer Co., Ltd.) and stabilizer: Irganox 1010 in the proportions shown in Table 1. Using a Toyo Seiki Co., Ltd. melt kneaded at 200 ° C., a block sample was obtained. The obtained sample was hot press molded at a set temperature of 200 ° C. to obtain a molded body for evaluation having a thickness of 2 mm. This molded body was used for hardness measurement, mechanical strength, and oil resistance test. The evaluation results are shown in Table 2.

(Comparative Example 4)
Polyether-based thermoplastic polyurethane resin (PANDEX T-8180N: manufactured by DIC Bayer Polymer Co., Ltd.) and stabilizer: Irganox 1010 in the ratio shown in Table 1, using Labo Plast Mill (manufactured by Toyo Seiki Co., Ltd.) Were melt-kneaded at 200 ° C. to obtain block samples. The obtained sample was hot press molded at a set temperature of 200 ° C. to obtain a molded body for evaluation having a thickness of 2 mm. This molded body was used for hardness measurement, mechanical strength, and oil resistance test. The evaluation results are shown in Table 2.

(Comparative Example 5)
Polyester-based thermoplastic polyurethane-based resin (PANDEX T-1180: manufactured by DIC Bayer Polymer Co., Ltd.) and stabilizer: Irganox 1010 in the ratio shown in Table 1, using Labo Plast Mill (manufactured by Toyo Seiki Co., Ltd.) It melt-kneaded at 200 degreeC and the block-shaped sample was obtained. The obtained sample was hot press molded at a set temperature of 200 ° C. to obtain a molded body for evaluation having a thickness of 2 mm. This molded body was used for hardness measurement, mechanical strength, and oil resistance test. The evaluation results are shown in Table 2.

(Comparative Example 6)
Styrene elastomer (Septon 2063: manufactured by Kuraray Co., Ltd.) and polyether thermoplastic polyurethane resin (PANDEX T-8180N: manufactured by DIC Bayer Polymer Co., Ltd.) and stabilizer: Irganox 1010 in the ratios shown in Table 1. Using a Laboplast mill (manufactured by Toyo Seiki Co., Ltd.), it was melt kneaded at 200 ° C. to obtain a block sample. The obtained sample was hot press molded at a set temperature of 200 ° C. to obtain a molded body for evaluation having a thickness of 2 mm. This molded body was used for hardness measurement, mechanical strength, and oil resistance test. The evaluation results are shown in Table 2.

(Comparative Example 7)
Styrene-based elastomer (Septon 2063: manufactured by Kuraray Co., Ltd.), polyester-based thermoplastic polyurethane resin (PANDEX T-1180: manufactured by DIC Bayer Polymer Co., Ltd.) and stabilizer: Irganox 1010 in the ratios shown in Table 1, Using a Laboplast mill (manufactured by Toyo Seiki Co., Ltd.), melt-kneading was performed at 200 ° C. to obtain a block sample. The obtained sample was hot press molded at a set temperature of 200 ° C. to obtain a molded body for evaluation having a thickness of 2 mm. This molded body was used for hardness measurement, mechanical strength, and oil resistance test. The evaluation results are shown in Table 2.

実施例３，４と比較例４、５の対比から、熱可塑性ポリウレタン系樹脂にアクリルブロック共重合体を添加した樹脂組成物は、熱可塑性ポリウレタン系樹脂単体に対して柔軟性が改善されていることがわかる。

From the comparison between Examples 3 and 4 and Comparative Examples 4 and 5, the resin composition obtained by adding the acrylic block copolymer to the thermoplastic polyurethane resin has improved flexibility relative to the thermoplastic polyurethane resin alone. I understand that.

Further, from the comparison between Example 3 and Comparative Example 6 and the comparison between Example 4 and Comparative Example 7, when the resin type is the same and the compounding ratio of the resin and the modifier is the same, the acrylic block co-polymer is used as the modifier. It can be seen that the resin composition using the coalescence has better oil resistance and mechanical properties than the resin composition using the styrene elastomer.
(Examples 5 to 8)
The acrylic block copolymer prepared in Production Example 1, PA6 (UBESTA 1013B (manufactured by Ube Industries, Ltd.), number average molecular weight: 13000), and Irganox 1010 (manufactured by Ciba Specialty Chemicals). Hand blended at the ratio shown in Table 1 and set at 260 ° C. (cylinder portion 8 points (C1 to C8: C1 to C8 in order from the bottom of the hopper to the die side) (32 mmφ, L / D = 22) .5, manufactured by Nippon Steel Works, Ltd., product name TEX30HSS) and melt kneaded at a rotation speed of 300 rpm, and the obtained sample was used for 120 mm square (thickness 2.0 mm, length 120 mm, width 120 mm). As a result of injection molding into a sheet shape and a gear shape, it was possible to obtain a molded article with good moldability, of which a 120 mm square sheet was used and the hardness was Constant, oil resistance test was conducted scratch resistance test. The evaluation results are shown in Table 3.
(Comparative Example 8)
PA6 (UBESTA 1013B: manufactured by Ube Industries, Ltd.) was injection-molded to obtain a 120 mm square sheet (thickness 2.0 mm, length 120 mm, width 120 mm). Using this sheet, hardness measurement, oil resistance test, and scratch resistance test were performed. The evaluation results are shown in Table 3.
(Comparative Examples 9 to 10)
Styrene elastomer (Septon 2063: manufactured by Kuraray), PA6 (UBESTA 1013B: manufactured by Ube Industries, Ltd.) and Irganox 1010 (manufactured by Ciba Specialty Chemicals) were hand blended at a ratio shown in Table 1, and 240 ° C. (Cylinder part 8 points (C1 to C8, in order of C1 to C8 from the bottom of the hopper to the die side))) (32 mmφ, L / D = 22.5, manufactured by Nippon Steel Works, Using a product name TEX30HSS), the mixture was melt kneaded at a rotation speed of 300 rpm. The obtained sample was injection molded to obtain a 120 mm square sheet (thickness 2.0 mm, length 120 mm, width 120 mm). Using this sheet, hardness measurement, oil resistance test, and scratch resistance test were performed. The evaluation results are shown in Table 3.

実施例５〜８と、比較例８〜１０の評価結果の比較から、本発明にかかる成形体は、柔軟性を有し、加えて、良好な耐油性、耐傷付き性を示すことがわかる。また、成形性が良好であるので、例えば、その成形体をギア類やベアリング類等の耐傷つき性や耐摩耗性、耐衝撃性等が必要とされる成形品に好適に適用できることも確認できた。

From comparison of the evaluation results of Examples 5 to 8 and Comparative Examples 8 to 10, it can be seen that the molded body according to the present invention has flexibility and, in addition, exhibits good oil resistance and scratch resistance. In addition, since the moldability is good, it can be confirmed that the molded body can be suitably applied to molded products that require scratch resistance, wear resistance, impact resistance, etc., such as gears and bearings. It was.

It is a schematic diagram of a scratch resistance evaluation test

Explanation of symbols

1 Cutter blade 2 Sample for measurement a Movement direction of sample for measurement

Claims (27)

 An acrylic block copolymer (A) comprising a methacrylic polymer block (a) and an acrylic polymer block (b), a thermoplastic resin (B), a thermoplastic elastomer (C), a rubber (D), And a resin composition comprising at least one selected from the group consisting of thermosetting resins (E).   2. The thermoplastic resin (B) is a thermoplastic resin selected from the group consisting of polyvinyl chloride resin, polymethyl methacrylate resin, acrylonitrile-styrene copolymer resin, methyl methacrylate-styrene copolymer resin, and polycarbonate resin. Resin composition.   The resin composition according to claim 1, wherein the thermoplastic resin (B) is a crystalline thermoplastic resin.   The resin composition according to claim 3, wherein the thermoplastic resin (B) is a crystalline polyester resin or a crystalline polyamide resin.   The thermoplastic elastomer (C) is at least one thermoplastic elastomer selected from the group consisting of styrene elastomers, olefin elastomers, urethane elastomers, vinyl chloride elastomers, amide elastomers, and ester elastomers. The resin composition as described.   The rubber (D) is at least one rubber selected from the group consisting of natural rubber, diene polymer rubber, olefin polymer rubber, acrylic rubber, silicone rubber, and fluororubber. The resin composition described in 1.   The thermosetting resin (E) is at least one selected from the group consisting of epoxy resins, phenol resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, thermosetting polyimide resins, hydrosilylated crosslinked resins, and urea resins. The resin composition according to claim 1, which is a seed thermosetting resin.   The resin composition according to claim 7, wherein the thermosetting resin (E) is an epoxy resin. Acrylic block copolymer (A) _{(a-b) n} type, b-a _{(a-b) n} type and _(a-b) at least one structure selected from the group consisting of n -a type The resin composition according to any one of claims 1 to 8.   10. The resin composition according to claim 1, wherein the number average molecular weight of the acrylic block copolymer (A) measured by gel permeation chromatography is 15,000 to 300,000.   The acrylic block copolymer (A) is a methacrylic polymer block (a) having a methacrylic polymer as a main component and 5 to 70% by weight of the acrylacrylic polymer and the acrylic polymer having a main component of the acrylic polymer. The resin composition according to claim 1, comprising 95 to 30% by weight of the block (b).   The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography of the acrylic block copolymer (A) is 1.8 or less. The resin composition in any one of.   The acrylic polymer block (b) comprises at least one monomer selected from the group consisting of acrylic acid-n-butyl, ethyl acrylate, acrylic acid-2-methoxyethyl, and acrylic acid-2-ethylhexyl. Acrylic acid ester and / or vinyl type other than 50 to 100% by weight and copolymerizable with -n-butyl acrylate, ethyl acrylate, and 2-methoxyethyl acrylate and 2-ethylhexyl acrylate The resin composition according to any one of claims 1 to 12, comprising 50 to 0% by weight of monomer.   The resin composition according to any one of claims 1 to 13, wherein the acrylic polymer block (b) comprises n-butyl acrylate.   The resin according to any one of claims 1 to 14, wherein the methacrylic polymer block (a) comprises 50 to 100% by weight of methyl methacrylate and 0 to 50% by weight of a vinyl monomer copolymerizable therewith. Composition.   The resin composition according to any one of claims 1 to 15, wherein the acrylic block copolymer (A) has at least one functional group (X) in one molecule.   The functional group (X) is at least one functional group selected from the group consisting of epoxy groups, hydrolyzable silyl groups, hydroxyl groups, amino groups, carboxyl groups, acid anhydride groups, alkenyl groups, active chlorine groups, and oxazoline groups. The resin composition according to claim 16.   The resin composition according to claim 17, wherein the functional group (X) is at least one functional group selected from the group consisting of an epoxy group, a hydroxyl group, and a carboxyl group.   The resin composition according to any one of claims 16 to 18, wherein the functional group (X) is contained in the methacrylic polymer block (a).   The resin composition according to any one of claims 16 to 18, wherein the functional group (X) is contained in the acrylic polymer block (b).   The molded object which consists of a resin composition in any one of Claim 1 to 20.   A modifier comprising the resin composition according to any one of claims 1 to 20.   A pressure-sensitive adhesive comprising the resin composition according to claim 1.   A coating agent comprising the resin composition according to any one of claims 1 to 20.   A dispersant comprising the resin composition according to any one of claims 1 to 20.   A binder comprising the resin composition according to any one of claims 1 to 20.   A vibration damping material, a vibration damping material, or a cushioning material comprising the resin composition according to claim 1.

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