JP2017088763A - Resin composition and molded body consisting of resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition containing a specific reinforcement agent for providing a molded body excellent in impact resistance performance, especially impact resistance under a low temperature condition while maintaining physical properties or optical performance.SOLUTION: The problem is solved by a resin composition by blending a reinforcement agent (Y) such as a silicone rubber of 5 to 40 pts.mass based on 100 pts.mass of a copolymer (X) obtained by polymerizing a (meth)acrylic macromonomer having a terminal double bond (a) and a polymerizable monomer (b) which is polymerizable with the macromonomer.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition containing a reinforcing agent and a molded article comprising the reinforcing agent-containing resin composition.

  An acrylic resin typified by polymethyl methacrylate (PMMA) is excellent in transparency and weather resistance and is preferred as a material for articles exposed to the outdoor environment. However, because of poor heat resistance, low water absorption, flexibility, impact resistance, etc., there are cases where applications are limited.

  Various properties such as mechanical properties, optical properties, and chemical properties vary depending on the type of polymer, but homopolymers using a single monomer cannot meet the various requirements of materials, so random properties using various monomers A method using a copolymer or a method of mixing different types of polymers is used. However, when a random copolymer is used, the characteristics of each copolymerized monomer unit tend to be averaged. Further, when two or more kinds of polymers are simply mixed, the polymers are separated without being mixed (called macrophase separation), and often inferior to the characteristics of each monomer unit.

  In order to solve the above problems, block copolymers in which two or more polymer segments are chemically bonded are known. Since the polymers are difficult to mix with each other, phase separation occurs. However, since the polymers are connected to each other by chemical bonds, the phase separation structure becomes nanometer size (called microphase separation). Therefore, the characteristics of each polymer segment can be exhibited without impairing the characteristics of each polymer segment.

  As a method for producing a (meth) acryl block copolymer, the following methods (for example, Patent Document 1 and Patent Document 2) are known. The macromonomer is prepared in advance using a cobalt chain transfer agent having an extremely high chain transfer constant. The resulting macromonomer is then copolymerized with other (meth) acrylic monomers. Using this technique, an acrylic resin having excellent flexibility can be obtained by suspension polymerization of PMMA macromonomer and MMA / BA.

  However, in the method described in Patent Document 2, the impact resistance performance is not always sufficient, and the usage application may be limited.

JP 2000-355605 A International Publication No. 2015/056668 Pamphlet

  An object of the present invention is to improve the impact resistance of a copolymer of a macromonomer and a monomer.

[1] The reinforcing agent (Y) is used in an amount of 5 to 40 masses per 100 mass parts of the copolymer (X) of the macromonomer (a) represented by the following formula (1) and the monomer (b). A reinforcing agent-containing resin composition formulated in part.
(In Formula (1), R and R ^{1 to} R ⁿ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. An alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. The cyclic group may have a substituent, X _{1 to} X _n are each a hydrogen atom or a methyl group, Z is a terminal group of the macromonomer (a), and n is an integer of 2 or more and 1000 or less. .)

[2] The reinforcing agent (Y) is a graft copolymer of a rubber selected from silicone, butadiene, and acrylic, or a composite rubber thereof and one or more kinds of vinyl monomers. [1] ] The resin composition.
[3] The resin composition according to [1] or [2], wherein the reinforcing agent (Y) is a graft copolymer of silicone rubber and one or more vinyl monomers.
[4] The resin composition according to any one of [1] to [3], wherein the copolymer (X) has a molecular weight distribution (PDI) of 2.0 to 25.0.
[5] The resin composition according to any one of [1] to [4], wherein the copolymer (X) has a mass average molecular weight of 30,000 or more.
[6] The resin composition according to any one of [1] to [5], which has a flexural modulus of 2000 MPa or less when the copolymer (X) is formed into a molded product having a width of 10 mm, a length of 80 mm, and a thickness of 4 mm. .
[7] A molded article obtained by molding the reinforcing agent-containing resin composition according to any one of [1] to [6].

  The reinforcing agent-containing resin composition of the present invention is excellent in impact resistance at room temperature and below freezing point.

[Macromonomer (a)]
The macromonomer (a) is obtained by adding a radically polymerizable group having an unsaturated double bond to one end of a poly (meth) acrylate segment. Here, the macromonomer is a polymer having a polymerizable functional group, and is also called a macromer. In the present invention, “(meth) acrylic acid” means “acrylic acid” or “methacrylic acid”.

In the general formula (1), R and R ^{1 to} R ⁿ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. The alkyl group, cycloalkyl group, aryl group or heterocyclic group can have a substituent. n is 2 or more and 1000 or less, and preferably 3 or more and 500 or less.

  As an alkyl group, a C1-C20 branched or linear alkyl group is mentioned, for example. Specific examples include a methyl group, an ethyl group, an n-propyl group, and an i-propyl group.

  As a cycloalkyl group, a C3-C20 cycloalkyl group is mentioned, for example. Specific examples include a cyclopropyl group, a cyclobutyl group, and an adamantyl group.

  As an aryl group, a C6-C18 aryl group is mentioned, for example. Specific examples include a phenyl group and a naphthyl group.

  As a heterocyclic group, a C5-C18 heterocyclic group is mentioned, for example. Specific examples include a γ-lactone group and an ε-caprolactone group.

As the substituent for R or R ^{1 to} R ⁿ , each independently represents an alkyl group, an aryl group, a carboxyl group, an alkoxycarbonyl group (—COOR ′), a carbamoyl group (—CONR′R ″), a cyano group, A group selected from the group consisting of a hydroxyl group, an amino group, an amide group (—NR′R ″), a halogen, an allyl group, an epoxy group, an alkoxy group (—OR ′), and a group exhibiting hydrophilicity or ionicity. Or an atom is mentioned. R ′ and R ″ are each independently the same group as R except for a heterocyclic group.

Examples of the alkoxycarbonyl group as a substituent include a methoxycarbonyl group.
Examples of the carbamoyl group as a substituent include an N-methylcarbamoyl group and an N, N-dimethylcarbamoyl group.
Examples of the amide group as a substituent include a dimethylamide group.
Examples of the halogen as the substituent include fluorine, chlorine, bromine and iodine.
As an alkoxy group as a substituent, a C1-C12 alkoxy group is mentioned, for example. Specific examples include a methoxy group.
Examples of the hydrophilic or ionic group as the substituent include alkali salts of carboxyl groups or alkali salts of sulfoxyl groups, poly (alkylene oxide) groups such as polyethylene oxide groups and polypropylene oxide groups, and quaternary ammonium bases. Of the cationic substituent.

R and R ^{1 to} R ⁿ are preferably at least one selected from an alkyl group and a cycloalkyl group, and more preferably an alkyl group.

  As the alkyl group, a methyl group, an ethyl group, an n-propyl group or an i-propyl group is preferable, and a methyl group is more preferable from the viewpoint of availability.

In the general formula (1), X _{1 to} X _n are each a hydrogen atom or a methyl group, and a methyl group is preferable. Furthermore, from the viewpoint of easy synthesis of the macromonomer (a), it is preferable that at least half of X _{1 to} X _n are methyl groups.

  In the general formula (1), Z is a terminal group of the macromonomer (a). Examples of the terminal group of the macromonomer (a) include a group derived from a hydrogen atom and a radical polymerization initiator, similarly to the terminal group of a polymer obtained by known radical polymerization.

  The molecular weight Mw of the macromonomer (a) is preferably 1,000 or more and 1,000,000 or less from the viewpoint of mechanical properties of the molded article of the copolymer (X). The lower limit of Mw of the macromonomer (a) is more preferably 3,000 or more, and further preferably 5,000 or more. Further, the upper limit value of Mw of the macromonomer (a) is more preferably 500,000 or less, and further preferably 300,000 or less.

As monomers for obtaining the macromonomer (a), methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, n-dodecyl (meth) acrylate, n-stearyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, 2-methoxy (Meth) acrylic acid esters such as ethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate Hydroxyl group-containing (meth) acrylic acid esters such as rate, 4-hydroxybutyl (meth) acrylate, glycerol (meth) acrylate; (meth) acrylic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) ) Acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxypropyl Carboxyl group-containing vinyl such as maleic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxypropyl succinic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, monomethyl maleate, monomethyl itaconate Monomer; Acid anhydride group-containing vinyl monomers such as maleic anhydride and itaconic anhydride; glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, 3,4-epoxybutyl (meth) acrylate, etc. Epoxy group-containing vinyl monomers; amino group-containing (meth) acrylic acid esters such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; (meth) acrylamide, Nt-butyl (meth) acrylamide , Vinyl monomers containing amide groups such as N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, diacetone acrylamide, maleic acid amide, maleimide; , Α-methylstyrene, vinyltoluene, (meth) Vinyl monomers such as acrylonitrile, vinyl chloride, vinyl acetate, vinyl propionate; divinylbenzene, ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (Meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, allyl (meth) acrylate, N, N And polyfunctional vinyl monomers such as' -methylenebis (meth) acrylamide; One or more of these can be appropriately selected and used.
Among these, methacrylic acid esters are preferable from the viewpoint of easy availability of monomers.

  As the methacrylic acid ester, methyl methacrylate, n-butyl methacrylate, dodecyl methacrylate, stearyl methacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate and 4-hydroxybutyl methacrylate are preferable. More preferred are methyl methacrylate, n-butyl methacrylate and 2-ethylhexyl methacrylate.

  Moreover, as a monomer for obtaining the macromonomer (a), from the viewpoint of the heat resistance of the product copolymer (X) and this molded product, a monomer composition containing the above methacrylic acid ester or acrylic acid ester Things are preferred.

  Examples of the acrylate ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, and t-butyl acrylate. Among these, methyl acrylate is preferable in terms of availability.

  The content of the methacrylic acid ester in the monomer composition for obtaining the macromonomer (a) is 80% by mass or more and 99.99% from the viewpoint of the heat resistance of the product copolymer (X) and this molded article. 5 mass% or less is preferable. The content of the methacrylic acid ester is more preferably 82% by mass or more and 99% by mass or less, and still more preferably 84% by mass or more and 98% by mass or less. The content of the acrylic ester in the monomer composition for obtaining the macromonomer (a) is preferably 0.5% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 18% by mass or less, and 2% by mass. % To 16% by mass is more preferable.

[Method for Producing Macromonomer (a)]
The macromonomer (a) can be produced by a known method. As a method for producing a macromonomer, for example, a method using a cobalt chain transfer agent (US Pat. No. 4,680,352), an α-substituted unsaturated compound such as α-bromomethylstyrene is used as a chain transfer agent. Used as a method (International Publication No. 88/04304 pamphlet), a method of chemically bonding a polymerizable group (Japanese Patent Laid-Open No. 60-133007, US Pat. No. 5,147,952) and thermal decomposition And a method (Japanese Patent Laid-Open No. 11-240854).

  Among these, the production method of the macromonomer (a) is preferably a method using a cobalt chain transfer agent in that the number of production steps is small and a catalyst having a high chain transfer constant is used.

Examples of the method for producing the macromonomer (a) using a cobalt chain transfer agent include an aqueous dispersion polymerization method such as a bulk polymerization method; a solution polymerization method; a suspension polymerization method and an emulsion polymerization method.
Among these, the aqueous dispersion polymerization method is preferable from the viewpoint of simplifying the recovery step of the macromonomer (a).

  As the cobalt chain transfer agent used in the present invention, a cobalt chain transfer agent represented by the formula (2) can be used. For example, Japanese Patent No. 3585730, Japanese Patent Publication No. 6-23209, Japanese Patent Publication No. 7-35411 Gazette, U.S. Pat. Nos. 4,269,945, 4,694,054, 4,837,326, 4,886,861, 5,324,879, International Publication No. 95/17435, Hei 9 -510499 gazette etc. can be used.

(In Formula (2), R _{1 to} R ₄ are each independently an alkyl group, a cycloalkyl group, and an aryl group; X is each independently an F atom, Cl atom, Br atom, OH group, alkoxy group; Group, aryloxy group, alkyl group and aryl group.)

Specific examples of the cobalt chain transfer agent include bis (borondifluorodimethyldioxyiminocyclohexane) cobalt (II), bis (borondifluorodimethylglyoxymate) cobalt (II), and bis (borondifluorodiphenylglyoxymate). Cobalt (II), cobalt (II) complex of bicinalimino hydroxyimino compound, cobalt (II) complex of tetraazatetraalkylcyclotetradecatetraene, N, N′-bis (salicylidene) ethylenediaminocobalt (II) complex And cobalt (II) complexes of dialkyldiazadioxodialkyldodecadiene, cobalt (II) porphyrin complexes, and the like. Among these, bis (borondifluorodiphenylglyoxymate) cobalt (II) (R _{1 to} R ₄ : phenyl group, X: F atom) which is stably present in an aqueous medium and has a high chain transfer effect is preferable. One or more of these can be appropriately selected and used.

  As for the usage-amount of a cobalt chain transfer agent, 20-350 ppm is preferable with respect to 100 g of monomers for obtaining a macromonomer (a). If the amount of cobalt chain transfer agent used is less than 20 ppm, the molecular weight tends to be insufficiently reduced, and if it exceeds 350 ppm, the resulting macromonomer (a) tends to be colored.

  Examples of the solvent used when the macromonomer (a) is obtained by the solution polymerization method include hydrocarbons such as toluene; ethers such as diethyl ether and tetrahydrofuran; halogenated hydrocarbons such as dichloromethane and chloroform; ketones such as acetone. Alcohols such as methanol; nitriles such as acetonitrile; ester compounds that are liquid at room temperature such as ethyl acetate; carbonates such as ethylene carbonate; and supercritical carbon dioxide. These may be used alone or in combination of two or more.

  In the production of the copolymer (X) described later, even if the synthesized macromonomer (a) is used as a powdered product recovered and purified, the suspension of the macromonomer (a) synthesized by suspension polymerization is used. May be used as they are. In the production of the copolymer (X), one type of the macromonomer (a) may be used alone, or two or more types may be used in combination.

[Monomer (b)]
The monomer (b) is not particularly limited as long as it can be polymerized with the macromonomer (a). Specifically, the thing similar to the monomer for obtaining a macromonomer (a) is mentioned. The monomer (b) is preferably a (meth) acrylic acid ester because of good copolymerizability with the macromonomer (a), and in particular, methyl (meth) acrylate, ethyl (meth) acrylate, N-propyl (meth) acrylate, n-butyl (meth) acrylate, dodecyl methacrylate, stearyl methacrylate, 2-ethylhexyl (meth) acrylate, glycidyl methacrylate, 2-hydroxyethyl (meth) acrylate and ( Meth) 4-hydroxybutyl acrylate is preferred.

  A monomer (b) may be used individually by 1 type, and may use 2 or more types together.

[Copolymer (X)]
Copolymer (X) is a polymer obtained by polymerizing macromonomer (a) and monomer (b).

  The copolymer (X) is composed of a block copolymer having a macromonomer (a) unit and a monomer (b) unit, and a graft copolymer of the monomer (b) having a macromonomer (a) unit in the side chain. Includes at least one selected.

  Further, the copolymer (X) is composed of a polymer consisting only of the macromonomer (a) unit, a polymer consisting only of the monomer (b) unit, an unreacted macromonomer (a), an unreacted monomer (b ) Can be contained.

  The Mw of the copolymer (X) is preferably from 30,000 to 5,000,000, from the viewpoint of mechanical strength and thermal stability of the molded body of the copolymer (X), preferably from 200,000 to 1, More preferably, it is less than 000,000.

  The molecular weight distribution of the copolymer (X) is preferably 2.0 or more and 25 or less, and more preferably 2.0 or more and 10 or less. When the molecular weight distribution is 2.0 or more, the moldability is good when the copolymer (X) is melt-molded. Moreover, if molecular weight distribution is 25 or less, the haze of a molded object will fall and an external appearance will become favorable.

  The flexural modulus of the copolymer (X) is preferably 50 or more and 2000 or less, more preferably 100 or more and 1900 or less, from the viewpoint of flexibility and strength of the molded body.

[Method for Producing Copolymer (X)]
The method for producing the copolymer (X) is not particularly limited, and various methods such as solution polymerization, suspension polymerization, emulsion polymerization, and bulk polymerization can be used. Aqueous polymerization such as suspension polymerization or emulsion polymerization is preferable because the polymerization heat generation is easily controlled and productivity is excellent, and suspension polymerization is more preferable because polymerization and recovery operations are simpler.

As a manufacturing method of copolymer (X) by suspension polymerization, the following [I] or [II] is mentioned, for example.
[I] The macromonomer (a) is dissolved in the monomer (b), and a radical polymerization initiator is added. This macromonomer (a) solution is dispersed in an aqueous solution in which a dispersant is dissolved to obtain a syrup dispersion. Then, the obtained syrup dispersion is subjected to suspension polymerization.
[II] Monomer in which the monomer (b) is added to an aqueous suspension obtained by synthesizing the macromonomer (a) by suspension polymerization, and the macromonomer (a) is dissolved as a syrup suspension A dispersion of body (b) is obtained. The obtained syrup suspension is subjected to suspension polymerization.

  The copolymer (X) obtained by the production method [I] tends to have excellent optical properties. Moreover, in the manufacturing method of [II], since the recovery process of macromonomer (a) can be omitted, the manufacturing process can be shortened.

  In any of the methods [I] and [II], it is preferable to warm the macromonomer (a) when it is dissolved in the monomer (b). The heating temperature is preferably 30 to 90 ° C. When the heating temperature is 30 ° C. or higher, the solubility of the macromonomer (a) can be improved. Moreover, volatilization of the monomer (b) can be suppressed at a heating temperature of 90 ° C. or lower. As for the lower limit of heating temperature, 35 degreeC or more is more preferable. Moreover, as for the upper limit of heating temperature, 75 degrees C or less is more preferable.

  In the method of [I], the radical polymerization initiator is added to the monomer (b) in which the macromonomer (a) is dissolved after the macromonomer (a) is dissolved in the monomer (b). It is preferable to do.

  The temperature at which the radical polymerization initiator is added is preferably 0 ° C. or higher and (10 hours half-life temperature of radical polymerization initiator + 15 ° C.) or lower. When the temperature at the time of adding the radical polymerization initiator is 0 ° C. or higher, the solubility of the radical polymerization initiator in the monomer becomes good. Moreover, stable polymerization can be performed when the temperature at the time of adding the radical polymerization initiator is equal to or lower than (the 10-hour half-life temperature of the radical polymerization initiator + 15 ° C.).

Examples of the radical polymerization initiator include organic peroxides and azo compounds.
Specific examples of the organic peroxide include 2,4-dichlorobenzoyl peroxide, t-butyl peroxypivalate, o-methylbenzoyl peroxide, bis-3,5,5-trimethylhexanoyl peroxide, octanoyl Peroxide, t-butylperoxy-2-ethylhexanoate, cyclohexanone peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, lauroyl peroxide, diisopropylbenzene hydroperoxide, t-butyl hydroperoxide and A di-t-butyl peroxide is mentioned.
Specific examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile). And 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile).
In terms of availability, benzoyl peroxide, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4- Dimethylvaleronitrile) and 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile) are preferred.

A radical polymerization initiator may be used individually by 1 type, and may use 2 or more types together.
The addition amount of the radical polymerization initiator is preferably 0.0001 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the total amount of the macromonomer (a) and the monomer (b) in terms of controlling the heat generation of polymerization.

  There is no restriction | limiting in particular as superposition | polymerization temperature in suspension polymerization, Generally it is 50-120 degreeC. In suspension polymerization, a chain transfer agent can be used depending on the purpose. Examples of chain transfer agents include mercaptans, α-methylstyrene dimers, and terpenoids.

[Strengthening agent (Y)]
The reinforcing agent (Y) of the present invention is a graft copolymer of rubber and one or more kinds of vinyl monomers. In this specification, rubber is a polymer having a crosslinked structure that behaves as an elastic body at room temperature or lower. The Tg of the rubber is preferably 10 ° C. or less, and more preferably 0 ° C. or less.

Specific examples of the rubber include any of the group consisting of silicone rubber, butadiene rubber and acrylic rubber, or composite rubbers such as butadiene / acrylic composite rubber and silicone / acrylic composite rubber.
From the viewpoint of improving the dispersibility of the rubber in the resin composition, a graft copolymer obtained by grafting one or more kinds of vinyl monomers onto the rubber can be used.

  In order to improve the impact resistance of the resin composition as a reinforcing agent, the graft copolymer preferably comprises 40 to 95% by mass of rubber in 100% by mass of the graft copolymer. In view of performance as a reinforcing agent and good dispersibility obtained by grafting, the rubber is more preferably 50 to 93% by mass, and 60 to 90% by mass in 100% by mass of the graft copolymer. More preferably.

  The mass average particle diameter of the rubber graft copolymer is preferably 300 to 2000 nm. Here, the mass average particle diameter is a value measured by a capillary particle size distribution meter using a rubber graft copolymer in a latex state as a measurement sample.

If the particle size is 300 nm or more, the impact resistance improving effect is sufficiently exhibited. When the particle diameter is 2000 nm or less, the appearance of the reinforcing agent-containing resin composition is hardly damaged.
The mass average particle diameter of the rubber graft copolymer is more preferably 300 to 1000 nm.

  The reinforcing agent (Y) may be synthesized by polymerization, or a commercially available one may be used. In the case of synthesizing by polymerization, emulsion polymerization is preferable from the viewpoint of particle size control and multistage polymerization.

  Examples of commercially available reinforcing agents (Y) include butadiene rubber, acrylic rubber, silicone rubber, or butadiene / acrylic composite rubber, for example, Metablene C type (for example, C233A, etc.) manufactured by Mitsubishi Rayon Co., Ltd. ), W type (for example, W450A), Kaneka Corporation B series (for example, B-561), FM series (for example, FM-40), M series (for example, M-701), Dow Chemical Co., Ltd. Examples include Paraloid EXL series (for example, EXL-2314) and BTA series (for example, BTA-730). Moreover, as what contains a silicone / acryl composite rubber | gum on the market, the Metabrene S type (for example, S2001 etc.) by Mitsubishi Rayon Co., Ltd. is mentioned, for example.

  Silicone rubber or silicone / acrylic composite rubber is preferred because the effect of improving impact resistance at low temperatures is sufficiently exhibited.

[Reinforcing agent-containing resin composition]
The reinforcing agent-containing resin composition of the present invention is a blend of copolymer (X) and reinforcing agent (Y).

  The reinforcing agent-containing resin composition has improved impact resistance even under freezing point where the resin composition becomes brittle. Here, the impact resistance can be compared by a notched Charpy impact strength measured according to JISK7111, using a test piece obtained by molding a reinforcing agent-containing resin composition.

  When comparing the notched Charpy impact strength at −3 ° C. between the resin composition and the reinforcing agent-containing resin composition, it is preferable that the Charpy impact value of the reinforcing agent-containing resin composition is three times or more that of the resin composition. , More preferably 7 times or more, still more preferably 15 times or more.

  The blending amount of the reinforcing agent (Y) is preferably 5 to 40 parts by mass with respect to 100 parts by mass of the copolymer (X). If the amount is 5 parts by mass or more, the impact resistance is sufficiently improved. If the blending amount is 40 parts by mass or less, it has good fluidity. From the viewpoint of achieving both impact resistance and fluidity, the blending amount of the reinforcing agent (Y) is more preferably 7 to 40 parts by mass, and still more preferably 10 to 30 parts by mass.

  The reinforcing agent-containing resin composition of the present invention can contain various additives as long as the transparency and mechanical properties of the molded article using the reinforcing agent-containing resin composition are not impaired. The smaller the amount of the additive, the better. The amount of the additive is preferably 0 to 20 parts by mass, more preferably 0 to 10 parts by mass, and 0 to 5 parts by mass with respect to 100 parts by mass of the reinforcing agent-containing resin composition. Further preferred.

  Examples of additives include ultraviolet absorbers, light stabilizers, heat stabilizers, anti-blocking agents such as synthetic silica and silicone resin powder, flow modifiers, plasticizers, antibacterial agents, antifungal agents, bluing agents, An antistatic agent is mentioned.

  A predetermined amount of the above essential components and optional components may be blended, and kneaded with a conventional kneader such as a roll, a Banbury mixer, a single screw extruder, or a twin screw extruder to prepare a reinforcing agent-containing resin composition. it can.

[Molded body]
The molded product of the present invention is obtained by molding the reinforcing agent-containing resin composition of the present invention.

  Examples of the processing method of the reinforcing agent-containing resin composition include injection molding, calendar molding, blow molding, extrusion molding, press molding, thermoforming, and melt spinning.

  Examples of the molded body obtained using the reinforcing agent-containing resin composition include films, sheets, injection molded bodies, hollow molded bodies, pipes, square bars, thermoformed bodies, and fibers.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.

In the examples, “parts” and “%” indicate “parts by mass” and “% by mass”.
[Evaluation method]
Each evaluation in an Example and a comparative example was implemented with the following method.

(Evaluation method of resin composition)
(1) Molecular weight and molecular weight distribution Mass average molecular weight (also referred to as Mw) and number average molecular weight (also referred to as Mn) use gel permeation chromatography (GPC) (trade name: HLC-8220, manufactured by Tosoh Corporation). The measurement was performed under the following conditions.
Column: TSK GUARD COLUMN HHR (30) and TSK-GEL GMH HR-H (7.8φ × 300 mm) connected in series Eluent: Tetrahydrofuran Measurement temperature: 40 ° C.
Flow rate: 0.6 mL / min

  Mw and Mn are calibration curves prepared using four types of polymethylmethacrylates having peak top molecular weights (also referred to as Mp) of 141,500, 55,600, 10,290 and 1,590 manufactured by Polymer Laboratories. Sought using.

(Method for evaluating molded product)
(2) Bending test Extrusion was performed at a maximum temperature of 220 ° C. using a φ30 mm twin-screw kneading extruder (manufactured by Werner & Pfleiderer) to obtain a pellet-shaped copolymer (X).

  Using the pellet-shaped copolymer (X), molding is performed with an injection molding machine IS100 (manufactured by Toshiba Machine) at a machine temperature of 220 ° C. and a mold temperature of 40 ° C., and is molded with a width of 10 mm, a length of 80 mm, and a thickness of 4 mm. Got the body. The obtained molded body was subjected to a bending test with a Tensilon universal testing machine RTC-1250A (manufactured by Orientec) according to JIS-K7171. The test was conducted at a bending speed of 1 mm / min, and the flexural modulus was obtained from the stress strain curve at that time.

(3) Charpy impact strength Using a pellet-form reinforcing agent-containing resin composition, molded with an injection molding machine IS100 (manufactured by Toshiba Machine) at a stand temperature of 220 ° C and a mold temperature of 40 ° C, with an A notch ( Two Charpy test pieces (see JIS K7111-2) were obtained.

  A test piece obtained by allowing the obtained test piece to stand at room temperature (25 ° C.) for 4 hours or longer and a room temperature constant temperature and humidity chamber (manufactured by ESPEC Corporation, trade name: MC811) for 4 hours at −3 ° C. Each piece was tested using a Charpy impact tester (trade name IMPACT TESTER, manufactured by Toyo Seiki Seisakusho), and the Charpy impact strength was measured. With reference to JIS K7111-2, it measured 5 times edgewise with the test piece with A notch, and made the average value Charpy impact strength.

<Production Example 1>
[Dispersant]
In a 1200 L reaction vessel equipped with a stirrer, a condenser and a thermometer, 61.6 parts of a 17% potassium hydroxide aqueous solution, methyl methacrylate (Mitsubishi Rayon Co., Ltd., trade name: Acryester M, the same applies hereinafter) 19.1 parts and 19.3 parts deionized water were charged. Subsequently, the liquid in the reaction apparatus was stirred at room temperature, and after confirming an exothermic peak, it was further stirred for 4 hours. Thereafter, the reaction solution in the reaction apparatus was cooled to room temperature to obtain an aqueous potassium methacrylate solution.

  Next, in a reaction vessel having a capacity of 1050 L equipped with a stirrer, a condenser tube and a thermometer, 900 parts of deionized water, sodium 2- (methacryloyloxy) ethanesulfonate (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Acryester) 60 parts of SEM-Na), 10 parts of the aqueous potassium methacrylate solution and 12 parts of methyl methacrylate were added and stirred, and the temperature was raised to 50 ° C. while replacing the inside of the polymerization apparatus with nitrogen. In addition, 0.08 part of 2,2′-azobis (2-methylpropionamidine) dihydrochloride (manufactured by Wako Pure Chemical Industries, Ltd., trade name: V-50) is added as a polymerization initiator, The temperature was raised to 60 ° C. After raising the temperature, methyl methacrylate was continuously added dropwise at a rate of 0.24 parts / minute for 75 minutes using a dropping pump. The reaction solution was held at 60 ° C. for 6 hours and then cooled to room temperature to obtain a dispersant having a solid content of 10% as a transparent aqueous solution.

<Production Example 2>
[Macromonomer (a1)]
(Synthesis of cobalt complex)
In a synthesizer equipped with a stirrer, 2.00 g (8.03 mmol) of cobalt (II) acetate tetrahydrate (manufactured by Wako Pure Chemical Industries, Ltd., Wako Special Grade) and diphenylglyoxime (Tokyo) were added in a nitrogen atmosphere. Kasei Chemical Co., Ltd., EP grade) 3.86 g (16.1 mmol) and 100 ml of diethyl ether previously deoxygenated by nitrogen bubbling were added and stirred at room temperature for 2 hours.

  Next, 20 ml of boron trifluoride diethyl ether complex (manufactured by Tokyo Chemical Industry Co., Ltd., EP grade) was added, and the mixture was further stirred for 6 hours. The obtained product was filtered, and the solid was washed with diethyl ether and vacuum-dried at 20 ° C. for 12 hours to obtain 5.02 g (7.93 mmol, yield 99%) of a brown complex cobalt complex.

(Synthesis of macromonomer)
In a three-necked separable flask equipped with a stirrer, a condenser tube and a thermometer, 145 parts of deionized water, 0.1 part of sodium sulfate and 0.02 part of the dispersant produced in Production Example 1 (solid content 10%) are placed. And stirred to obtain a uniform aqueous solution. Next, 95 parts of methyl methacrylate (MMA), 5 parts of methyl acrylate (MA) (manufactured by Mitsubishi Chemical Co., Ltd.), 0.0032 parts of the cobalt complex produced by the above method, and perocta O (NOF Corporation) 1) 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, trade name) 0.1 part was added to obtain an aqueous dispersion. Next, the inside of the flask was sufficiently purged with nitrogen, and the aqueous dispersion was heated to 80 ° C. and held for 6 hours, and then heated to 95 ° C. and held for 1 hour. Thereafter, the reaction solution was cooled to 40 ° C. to obtain an aqueous suspension of macromonomer. This aqueous suspension was filtered through a filter cloth, and the filtrate was washed with deionized water and dried at 40 ° C. for 12 hours to obtain a macromonomer (a1). As a result of analysis by GPC, Mw of the macromonomer (a1) was 31500, Mn was 14000, and molecular weight distribution (PDI) was 2.3.

The results are shown in Table 1.

<Production Example 3>
[Copolymer (X1)]
An aqueous solution of the dispersant was prepared by mixing 145 parts of deionized water, 0.1 part of sodium sulfate and 0.02 part of the dispersant produced in Production Example 1.

  In a separable flask with a cooling tube, 40 parts of the macromonomer (a1) synthesized in Production Example 2, 24 parts of methyl methacrylate, 36 parts of n-butyl acrylate (BA) (trade name, manufactured by Mitsubishi Chemical Corporation) and 1 -0.1 part of octanethiol was mixed, and it heated at 50 degreeC, stirring, and obtained the raw material syrup.

  After cooling the raw syrup to 40 ° C. or less, 0.3 parts of AMBN (2,2′-azobis (2-methylbutyronitrile), trade name) manufactured by Otsuka Chemical Co., Ltd.) is dissolved in the raw syrup, Obtained.

  Next, an aqueous solution of a dispersant was added to the syrup, and then the stirring rotation speed was increased while the atmosphere in the separable flask was replaced with nitrogen by nitrogen bubbling to obtain a syrup dispersion.

  The syrup dispersion was heated to 75 ° C., and the external temperature of the separable flask was maintained until a polymerization exothermic peak appeared. After the polymerization exothermic peak appeared, when the syrup dispersion reached 75 ° C., the syrup dispersion was heated to 85 ° C. and held for 30 minutes to complete the polymerization to obtain a suspension.

After the suspension was cooled to 40 ° C. or lower, the suspension was filtered with a filter cloth, the filtrate was washed with deionized water, and dried at 40 ° C. for 16 hours to obtain a copolymer (X1). Mw of the copolymer (X1) was 252000, Mn was 40500, and PDI was 6.2.
Table 2 shows the parameters again.

<Example 1>
[Reinforcing agent-containing resin composition]
100 parts of copolymer (X1) produced in Production Example 3 as copolymer (X) and a silicone / acrylic composite rubber graft copolymer (manufactured by Mitsubishi Rayon Co., Ltd., trade name: 25 parts of Metablen S2100) were pre-dried at 60 ° C. overnight.
After the copolymer (X) and the reinforcing agent (Y) were dry blended, they were extruded at a maximum temperature of 220 ° C. by a φ30 mm twin-screw kneading extruder (manufactured by Werner & Pfleiderer) to obtain a pellet-shaped reinforcing agent-containing resin composition.

<Examples 2 to 4>
A reinforcing agent-containing resin composition was obtained in the same manner as in Example 1 except that the reinforcing agent (Y) was used as shown in Table 3.
The results are shown in Table 3.

<Comparative Example 1>
A resin composition was obtained in the same manner as in Example 1 except that the reinforcing agent (Y) was not used.
The results are shown in Table 3.

<Comparative example 2>
A reinforcing agent-containing resin composition was obtained in the same manner as in Example 1 except that PMMA (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Acrypet VH001) was used instead of the polymer (2).
The results are shown in Table 3.

<Comparative Example 3>
A reinforcing agent-containing resin composition was obtained in the same manner as in Example 1 except that only PMMA (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Acrypet VH001) was used.
The results are shown in Table 3.

METABLEN S2100 (Mitsubishi Rayon Co., Ltd.) Silicone / acrylic composite rubber graft copolymer METABLEN S2001 (Mitsubishi Rayon Co., Ltd.) silicone / acrylic composite rubber graft copolymer METABLEN W450 (Mitsubishi Rayon Co., Ltd.) Acrylic rubber graft copolymer METABLEN W377 (Mitsubishi Rayon Co., Ltd.) butadiene / acrylic composite rubber graft copolymer

  As shown in Table 3, the Charpy impact strength of the test piece obtained in each example is ten times as large as that of the test piece of Comparative Example 1 at room temperature (25 ° C.) (for example, In the case of Example 2, it was about 27 times), and it was 2.5 times or more even at low temperature conditions (−3 ° C.). In particular, Example 1 and Example 2 using a silicone / acrylic composite rubber had Charpy impact strengths at low temperatures (−3 ° C.) of about 8.5 times and 6.0 times that of Comparative Example 1, respectively. It became.

Claims (7)

The reinforcing agent (Y) is blended in an amount of 5 to 40 parts by mass with respect to 100 parts by mass of the copolymer (X) of the macromonomer (a) represented by the following formula (1) and the monomer (b). Resin composition.

(In Formula (1), R and R ^{1 to} R ⁿ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. An alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. The cyclic group can have a substituent.
X _{1 to} X _n are each a hydrogen atom or a methyl group.
Z is a terminal group of the macromonomer (a).
n is an integer of 2 or more and 1000 or less. )   The reinforcing agent (Y) is a graft copolymer of a rubber selected from silicone, butadiene, and acrylic or a composite rubber thereof and one or more kinds of vinyl monomers. Strong resin composition.   The resin composition according to claim 1 or 2, wherein the reinforcing agent (Y) is a graft copolymer of silicone rubber and one or more types of vinyl monomers.   The resin composition of any one of Claims 1-3 whose molecular weight distribution (PDI) of the said copolymer (X) is 2.0-25.0.   The resin composition according to any one of claims 1 to 4, wherein the copolymer (X) has a mass average molecular weight of 30000 or more.   The strong resin composition according to any one of claims 1 to 5, wherein a bending elastic modulus when the copolymer (X) is formed into a molded body having a width of 10 mm, a length of 80 mm, and a thickness of 4 mm is 2000 MPa or less. .   The molded object which shape | molded the reinforcing agent containing resin composition of any one of Claims 1-6.