JP2005344075A - Polylactic acid-based thermoplastic resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition that has excellent heat resistance and impact resistance and comprises a polylactic acid-based polymer. <P>SOLUTION: The polylactic acid-based polymer thermoplastic resin composition comprises a polylactic acid-based polymer (A), an aromatic alkenyl-containing polymer (B) and a rubber-like polymer (C) in the composition ratio (mass ratio) of the polylactic acid-based polymer (A) to the alkenyl-containing polymer (B) of 1/99-99/1. A copolymer of a monomer containing an aromatic group and a copolymerizable vinyl group and another monomer is used as the polymer (B). A graft copolymer obtained by grafting a vinyl-based monomer onto a rubber component or a thermoplastic elastomer is used as the rubber-like polymer (C). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a polylactic acid-based thermoplastic resin composition excellent in heat resistance and impact resistance.

The amount of plastic products made of polyethylene, polypropylene, polystyrene, polyethylene terephthalate, vinyl chloride, and the like is currently enormous, and waste disposal has been highlighted as one of the environmental problems. That is, the current waste treatment is incineration disposal or burying treatment. However, for example, incineration disposal of polyethylene or the like causes a high combustion calorie, which causes damage to the incinerator and shortens the life. In addition, when polyvinyl chloride is incinerated, harmful gases are generated.
On the other hand, land is limited for the disposal of plastic products. In addition, when discarded in the natural environment, these plastics have extremely high chemical stability, so that they are hardly decomposed by microorganisms and remain almost permanently. Therefore, it causes problems such as damage to the landscape and pollution of the living environment of marine life.

  Under such circumstances, recently, plastics that are biodegradable or decompose in a natural environment have been attracting attention. Biodegradable plastics are known to gradually disintegrate and decompose in soil and water by hydrolysis and biodegradation, and finally become harmless degradation products due to the action of microorganisms. Biodegradable plastics that are currently being put into practical use include natural raw materials such as biocellulose, starch-based plastics, aliphatic polyesters, modified PVA (polyvinyl alcohol), cellulose ester compounds, starch modified products, and blends thereof. It is roughly divided into bodies. Among these biodegradable plastics, aliphatic polyesters are mentioned as those that are relatively balanced in terms of processability, cost, mechanical properties, water resistance and the like and are easy to use for various applications.

As the aliphatic polyester, for example, poly (hydroxybutyric acid / valeric acid) is known as a microbial production polymer, and polycaprolactone or a condensation product of an aliphatic dicarboxylic acid and an aliphatic diol is known as a synthetic polymer. A polylactic acid polymer is known as a semi-synthetic polymer.
Polylactic acid polymers have been attracting attention as plant-based plastics that do not use petroleum resources because they are synthesized using raw materials such as non-petroleum raw materials, sweet potatoes, and corn. There is a lot of movement to replace polylactic acid-based polymers in the applications that used glycans.
In particular, polylactic acid-based polymers are mainly used for film and sheet applications, taking advantage of their transparency.

However, since the polylactic acid polymer itself has low heat resistance, it is difficult to replace conventional general-purpose plastics such as transparent polyvinyl chloride resin and polyethylene terephthalate.
In addition, studies have been made to add an acrylic resin to a polylactic acid polymer for the purpose of improving moldability (see Patent Document 1). However, even in a thermoplastic resin composition obtained by adding an acrylic resin to a polylactic acid polymer, sufficient impact resistance has not been obtained yet.
JP 2002-155207 A

  The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a thermoplastic resin composition containing a polylactic acid-based polymer having both heat resistance and impact resistance.

The polylactic acid-based thermoplastic resin composition of the present invention comprises a polylactic acid-based polymer (A), a polymer (B) containing an aromatic alkenyl having a methyl methacrylate monomer unit, and a rubbery polymer (C The composition ratio of the polylactic acid polymer (A) and the polymer (B) containing aromatic alkenyl is 1/99 to 99/1 (mass ratio). It is.
Here, as the rubber polymer (C), a vinyl monomer is graft-polymerized on a polyorganosiloxane / acrylic composite rubber containing (1) polyorganosiloxane and polyalkyl (meth) acrylate rubber. (2) A graft copolymer in which a vinyl monomer is graft-polymerized on an acrylic rubber containing a polyalkyl (meth) acrylate rubber, and (3) a vinyl-based monomer on a diene rubber. It is desirable that the monomer is a graft copolymer obtained by graft polymerization.
The vinyl monomer to be graft polymerized preferably contains a monomer having an epoxy group.

  The thermoplastic resin composition of the present invention is a resin composition containing a biomass material, and has both heat resistance and impact resistance.

Further, a graft copolymer obtained by grafting a vinyl monomer to a polyorganosiloxane / acrylic composite rubber containing a polyorganosiloxane and a polyalkyl (meth) acrylate rubber as a rubber polymer (C). If so, the impact resistance is further improved, and the moldability is also improved.
If the rubbery polymer (C) is a graft copolymer obtained by graft polymerization of a vinyl monomer to an acrylic rubber containing a polyalkyl (meth) acrylate rubber, transparency and impact resistance Is further improved and moldability is also improved.
If the rubber polymer (C) is a graft copolymer obtained by graft polymerization of a vinyl monomer to a diene rubber, impact resistance is further improved and moldability is also improved.

  Moreover, if the vinyl monomer to be graft-polymerized contains a monomer having an epoxy group, the pigment colorability and heat distortion resistance of the thermoplastic resin composition are further improved.

Hereinafter, the present invention will be described in detail.
<Polylactic acid polymer (A)>
As the polylactic acid polymer (A) in the present invention, polylactic acid; lactic acid copolymer which is a copolymer of lactic acid and other components copolymerizable therewith; or a mixture thereof can be used.

Polylactic acid can be synthesized by a conventionally known method. For example, direct dehydration condensation from lactic acid as described in JP-A-7-33861, JP-A-59-96123, Preliminary Proceedings of Vol. 44, 3198-3199, or cyclic lactic acid It can be synthesized by ring-opening polymerization of a monomeric lactide.
When performing direct dehydration condensation, any lactic acid of L-lactic acid, D-lactic acid, DL-lactic acid, or a mixture thereof may be used. Moreover, when performing ring-opening polymerization, you may use any lactide of L-lactide, D-lactide, DL-lactide, meso-lactide, or these mixtures.

For the synthesis, purification and polymerization operations of lactide, see, for example, U.S. Pat. No. 4,057,537, published European Patent Application No. 261572, Polymer Bulletin, 14,491-495 (1985), and Makromol Chem., 187,1611-1628. (1986).
The constituent molar ratio (L / D) of the L-lactic acid unit and the D-lactic acid unit in the polylactic acid may be 100/0 to 0/100. L / D is 100/0 to 60/40, more preferably 100/0 to 80/20.

The lactic acid copolymer is obtained by copolymerizing a lactic acid monomer or lactide and other components copolymerizable therewith. Examples of such other components include dicarboxylic acids having two or more ester bond-forming functional groups, polyhydric alcohols, hydroxycarboxylic acids, and lactones.
Examples of the dicarboxylic acid include succinic acid, azelaic acid, sebacic acid, terephthalic acid, and isophthalic acid.

  Examples of the polyhydric alcohol include aromatic polyhydric alcohols obtained by addition reaction of bisphenol with ethylene oxide; ethylene glycol, propylene glycol, butanediol, hexanediol, octanediol, glycerin, sorbitan, trimethylolpropane, neopentyl Examples include aliphatic polyhydric alcohols such as glycol; ether glycols such as diethylene glycol, triethylene glycol, polyethylene glycol, and polypropylene glycol.

Examples of the hydroxycarboxylic acid include glycolic acid, hydroxybutylcarboxylic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 3-hydroxyvaleric acid, 4-hydroxyvaleric acid, 6-hydroxycaproic acid, and other JP-A-6-184417. The thing etc. which are described in gazette gazette are mentioned.
Examples of the lactone include glycolide, ε-caprolactone glycolide, ε-caprolactone, β-propiolactone, δ-butyrolactone, β- or γ-butyrolactone, pivalolactone, δ-valerolactone, and the like.

  The biodegradability of lactic acid copolymers is affected by the content of lactic acid units in the copolymer. For this reason, the content of lactic acid units in the lactic acid copolymer is usually 50 mol% or more, preferably 70 mol% or more, although it depends on the copolymerization component used. The mechanical properties and biodegradability of the resulting product can be adjusted by the content of lactic acid units and copolymerization components.

The polylactic acid polymer (A) is not particularly limited, but in the case of crystallinity, the melting point is usually 60 to 200 ° C., and the mass average molecular weight is 50,000 to 500,000, preferably about 100,000 to 300,000. is there.
In addition, for the purpose of obtaining the same effect as the copolymer, polylactic acid and other aliphatic polyester may be simply blended. In this case, the content of the monomer constituting the other aliphatic polyester, the content of polylactic acid contained in the blend, and the like are the same as in the case of the copolymer.
As the polylactic acid-based polymer (A), commercially available products can be used, and examples thereof include Lacia “H-100”, “H-400”, and “H-100J” manufactured by Mitsui Chemicals, Inc.

<Polymer (B) containing aromatic alkenyl>
The polymer (B) containing an aromatic alkenyl is a copolymer of a monomer having an aromatic group and a copolymerizable vinyl group and another monomer.
Among them, a monomer in which methyl methacrylate is added as a vinyl group to an aromatic group is desirable. Moreover, what copolymerized cyclohexyl maleimide, phenyl maleimide, maleic acid anhydride, glutaric acid anhydride, etc. can also be used as another copolymerizable monomer.

  The production method of the polymer (B) containing an aromatic alkenyl is not particularly limited, and various methods such as known suspension polymerization, bulk polymerization, and emulsion polymerization are applied.

  As the polymer (B) containing an aromatic alkenyl, a commercially available polymer can be used. For example, “LyTac-A 100PCF”, “Atrete MM-60” of Nippon A & L Co., Ltd. Rex SAN-C ”, Daicel Polymer Co., Ltd.“ Sebian MS10 ”, A & M Polystyrene Co., Ltd.“ GPPS HF ”and the like.

<Rubber polymer (C)>
Examples of the rubbery polymer (C) in the present invention include a graft copolymer in which a vinyl monomer is graft-polymerized on a rubber component, and a thermoplastic elastomer.
Here, examples of the thermoplastic elastomer include chlorinated polyolefin and ethylene / vinyl acetate copolymer.

Rubber components used in the graft copolymer include polybutadiene rubber, diene rubber such as styrene-butadiene rubber, acrylic rubber such as polyalkyl (meth) acrylate rubber, polyorganosiloxane rubber, and polyorganosiloxane. Examples include polyorganosiloxane / acrylic composite rubber containing polyalkyl (meth) acrylate rubber. The method for producing these rubber components is not particularly limited, but the emulsion polymerization method is optimal.
The vinyl monomer used for graft polymerization is preferably at least one selected from aromatic alkenyl compounds, methacrylic acid esters, acrylic acid esters, and vinyl cyanide compounds.

As the rubbery polymer (C) in the present invention, (1) a polyorganosiloxane and polyalkyl (meth) acrylate rubber containing polyorganosiloxane and polyalkyl (meth) acrylate rubber are particularly preferable in terms of the balance between the development of impact strength and optical properties. A graft copolymer in which a vinyl monomer is graft-polymerized to an organosiloxane / acrylic composite rubber, and (2) a vinyl monomer is graft-polymerized to an acrylic rubber containing a polyalkyl (meth) acrylate rubber. Any of the graft copolymer obtained and (3) a graft copolymer obtained by graft-polymerizing a vinyl monomer to a diene rubber is preferable.
Hereinafter, these graft copolymers will be described in detail.

(1) Polyorganosiloxane / acrylic composite rubber graft copolymer The polyorganosiloxane / acrylic composite rubber containing polyorganosiloxane and polyalkyl (meth) acrylate rubber has a polyorganosiloxane component of 1 to 99% by mass. The alkyl (meth) acrylate rubber component is preferably in the range of 99 to 1% by mass (the total amount of both components is 100% by mass).

  The method for producing the polyorganosiloxane / acrylic composite rubber is not particularly limited. First, a latex of polyorganosiloxane is prepared by emulsion polymerization, and then the monomer constituting the polyalkyl (meth) acrylate rubber is polymerized. A method is preferred in which the organosiloxane latex particles are impregnated and then polymerized.

The polyorganosiloxane component can be prepared by emulsion polymerization using an organosiloxane and a crosslinking agent (CI). In that case, a graft crossing agent (GI) can also be used together.
Examples of the organosiloxane include various cyclic members having three or more members, such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and trimethyltriphenylcyclotrisiloxane. , Tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, and the like. Among these, those having 3 to 6 membered rings are preferably used. These may be used alone or in admixture of two or more. The amount of the organosiloxane used in the polyorganosiloxane component is preferably 50% by mass or more, more preferably 70% by mass or more.

  As the crosslinking agent (CI), a trifunctional or tetrafunctional silane-based crosslinking agent, for example, trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetrabutoxy Silane etc. are mentioned. In particular, tetrafunctional crosslinking agents are preferred, and tetraethoxysilane is particularly preferred among these. The amount of the crosslinking agent used is preferably 0.1 to 30% by mass in the polyorganosiloxane component.

Examples of the graft crossing agent (GI) include a compound that can form a unit represented by the following formula.
^{_{CH 2 = C (R 2)}} -COO- (CH 2) p -SiR 1 n O (3-n) / 2 (GI-1)
^{_{CH 2 = C (R 2)}} -C 6 H 4 -SiR 1 n O (3-n) / 2 (GI-2)
_{^{CH 2 = CH-SiR 1 n}} O (3-n) / 2 (GI-3)
^{_{HS- (CH 2) p -SiR 1}} n O (3-n) / 2 (GI-4)
Wherein R ¹ is a methyl group, an ethyl group, a propyl group, or a phenyl group, R ² is a hydrogen atom or a methyl group, n is 0, 1 or 2, and p is 1-6. Indicates the number.)
The (meth) acryloyloxysiloxane capable of forming the unit of the above formula (GI-1) can form an effective graft chain because of its high grafting efficiency, which is advantageous in terms of impact strength development. .

  As the compound capable of forming the unit of the above formula (GI-1), methacryloyloxysiloxane is particularly preferable. Specific examples of methacryloyloxysiloxane include β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-methacryloyloxypropyl. Examples include ethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane, and γ-methacryloyloxybutyldiethoxymethylsilane.

Examples of the compound capable of forming the unit of the above formula (GI-2) include vinyl siloxane, and specific examples thereof include tetramethyltetravinylcyclotetrasiloxane.
Examples of the compound that can form the unit of the above formula (GI-3) include p-vinylphenyldimethoxymethylsilane.
Examples of the compound that can form the unit of the above formula (GI-4) include γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropylmethoxydimethylsilane, γ-mercaptopropyldiethoxymethylsilane, and the like.
The amount of the grafting agent used is preferably 0 to 10% by mass, more preferably 0.5 to 5% by mass in the polyorganosiloxane component.

  For example, US Pat. No. 2,891,920, US Pat. No. 3,294,725, and the like can be used for producing the latex of the polyorganosiloxane component. In the present invention, for example, a mixed solution of an organosiloxane, a cross-linking agent (CI) and, if desired, a graft crossing agent (GI) is used in the presence of a sulfonic acid-based emulsifier such as alkylbenzene sulfonic acid or alkyl sulfonic acid, for example, a homogenizer or the like. It is preferable to manufacture by the method of carrying out shear mixing with water using. Alkylbenzenesulfonic acid is suitable because it acts as an emulsifier for organosiloxane and at the same time serves as a polymerization initiator. In this case, it is preferable to use an alkylbenzene sulfonic acid metal salt, an alkyl sulfonic acid metal salt, or the like in combination because it has an effect of maintaining a stable polymer during graft polymerization.

The polyalkyl (meth) acrylate rubber component can be synthesized using an alkyl (meth) acrylate, a crosslinking agent (CII), and a graft crossing agent (GII).
Examples of the alkyl (meth) acrylate include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate; alkyls such as hexyl methacrylate, 2-ethylhexyl methacrylate, and n-lauryl methacrylate. Examples thereof include methacrylate, and n-butyl acrylate is particularly preferable.

Examples of the crosslinking agent (CII) include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, and the like.
Examples of the graft crossing agent (GII) include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate and the like. Allyl methacrylate can also be used as a crosslinking agent. These crosslinking agents and graft crossing agents may be used alone or in combination of two or more. The total amount of the crosslinking agent and the grafting agent used is preferably 0.1 to 20% by mass in the polyalkyl (meth) acrylate rubber component.

Manufacture of a polyalkyl (meth) acrylate rubber component is performed as follows, for example.
Into the latex of the polyorganosiloxane component neutralized by the addition of an aqueous alkali solution such as sodium hydroxide, potassium hydroxide or sodium carbonate, the above alkyl (meth) acrylate, crosslinking agent (CII) and graft crossing agent (GII) Is added to impregnate the polyorganosiloxane particles, and then an ordinary radical polymerization initiator is allowed to act. As the polymerization proceeds, a latex of a composite rubber of a polyorganosiloxane component and a polyalkyl (meth) acrylate rubber component is obtained.
The polyorganosiloxane / acrylic composite rubber thus produced by emulsion polymerization can be graft copolymerized with a vinyl monomer.

The polyorganosiloxane / acrylic composite rubber preferably has a gel content of 80% by mass or more measured by extraction with toluene at 90 ° C. for 4 hours.
In the present invention, as this composite rubber, the main skeleton of the polyorganosiloxane rubber component has a repeating unit of dimethylsiloxane, and the main skeleton of the polyalkyl (meth) acrylate rubber component has a repeating unit of n-butyl acrylate. Rubber is preferably used.

A polyorganosiloxane composed of a polyorganosiloxane / acrylic composite rubber and a graft portion is obtained by graft polymerization of one or more vinyl monomers in the presence of the polyorganosiloxane / acrylic composite rubber described above. A siloxane / acrylic composite rubber graft copolymer can be obtained.
The vinyl monomer constituting the graft portion is not particularly limited. Specific examples thereof include aromatic alkenyl compounds such as styrene, α-methylstyrene and vinyltoluene; methacrylic acid esters such as methyl methacrylate and 2-ethylhexyl methacrylate; acrylic acid esters such as methyl acrylate, ethyl acrylate and n-butyl acrylate. Various vinyl monomers such as vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; These vinyl monomers can be used alone or in combination of two or more.

(2) Acrylic rubber graft copolymer An acrylic rubber containing a polyalkyl (meth) acrylate rubber is an acrylic polymer obtained by polymerizing a (meth) acrylate monomer or a mixture containing the same as a main component. Rubber.
Although it does not restrict | limit especially as a (meth) acrylic-type monomer, Usually, (meth) acrylate is used. Specific examples thereof include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tridecyl acrylate, ethoxyethoxyethyl acrylate, methoxytripropylene glycol acrylate, and 4-hydroxybutyl acrylate. , Lauryl acrylate, lauryl methacrylate, stearyl methacrylate and the like. These can be used alone or in combination of two or more.

  Since the acrylic rubber is preferably a polymer having a glass transition temperature of 0 ° C. or less in terms of impact strength development, the (meth) acrylic monomer is particularly preferably n-butyl acrylate, 2- Alkyl (meth) acrylates such as ethylhexyl acrylate, octyl acrylate, lauryl acrylate, tridecyl acrylate, lauryl methacrylate, and tridecyl methacrylate are preferred. Moreover, when using (meth) acrylate (for example, stearyl methacrylate etc.) which has crystallinity near room temperature, it is good to mix and use the monomer which melt | dissolves this.

The acrylic rubber may be a (co) polymer obtained by simply polymerizing one or more of the monomers, and is particularly a composite rubber that exhibits higher physical properties at low temperature impact strength. Preferably there is.
Preferable examples of the composite rubber include a (meth) acrylic acid ester of an alcohol having a branched side chain or an alcohol having an alkyl group having 13 or more carbon atoms, or a hydroxyl group, a methoxy group or an ethoxy group (meta ) A composite rubber composed mainly of an acrylic rubber (AR1) component containing a unit derived from at least one acrylic ester and an acrylic rubber (AR2) component containing a unit derived from n-butyl acrylate. The glass transition temperature (Tg1) derived from the rubber (AR1) component is lower than the glass transition temperature (Tg2) derived from the acrylic rubber (AR2) component. Such a composite rubber can impart higher low temperature impact resistance as compared with a simple copolymer type rubber.

As the (meth) acrylic acid ester constituting the acrylic rubber (AR1) component, in particular, 2-ethylhexyl acrylate, ethoxyethyl acrylate, methoxytripropylene glycol acrylate, 4-hydroxybutyl acrylate, tridecyl methacrylate, tridecyl acrylate, stearyl Methacrylate and stearyl acrylate are preferred.
The composite rubber usually contains 5 to 95% by mass of an acrylic rubber (AR1) component and 95 to 5% by mass of an acrylic rubber (AR2) component, preferably 10 to 90% by mass of an acrylic rubber (AR1) component and acrylic. It contains 90 to 10% by mass of rubber (AR2) component, more preferably 10 to 80% by mass of acrylic rubber (AR1) component and 90 to 20% by mass of acrylic rubber (AR2) component. These ranges are significant in terms of superiority over copolymer type rubber.

The monomer used to obtain the acrylic rubber usually contains a monomer having two or more unsaturated bonds in the molecule, and its content is preferably 2% by mass or less, and 1.5% by mass. The following is more preferable. A monomer having two or more unsaturated bonds in the molecule functions as a crosslinking agent or a graft crossing agent. Examples of the crosslinking agent include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, divinylbenzene, polyfunctional methacrylic group-modified silicone, and the like. Examples of the graft crossing agent include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate and the like. Allyl methacrylate can also be used as a crosslinking agent. These crosslinking agents and graft crossing agents can be used alone or in combination of two or more.
When the composite rubber is used as an acrylic rubber, the use amount of the crosslinking agent or graft crossing agent for the acrylic rubber (AR1) component and the acrylic rubber (AR2) component is based on the use amount (% by mass) for each component. It is preferable that the amount used for the (AR2) component is larger than the (AR1) component.

  The acrylic rubber may have two or more glass transition temperatures at 10 ° C. or lower. In that case, the glass transition temperature (Tg1) derived from the acrylic rubber (AR1) component is preferably lower than the glass transition temperature (Tg2) derived from the acrylic rubber (AR2) component. When the glass transition temperature satisfies such conditions, the obtained graft copolymer (rubber polymer (C)) exhibits higher impact resistance. This is a feature of being a composite rubber, and is different from a simple copolymer.

  Here, the glass transition temperature of the acrylic rubber is measured as a Tan δ transition point by a dynamic mechanical property analyzer (hereinafter referred to as “DMA”). In general, a polymer obtained from a monomer has an inherent glass transition temperature, and a single transition point is observed alone (single component or multiple component random copolymer), but a mixture of multiple components, Alternatively, a unique transition point is observed in each of the composite polymers. For example, in the case of two components, two transition points are observed by measurement. Two peaks are observed in the Tan δ curve measured by DMA. When the composition ratio is uneven or when the transition temperature is close, each peak may approach and may be observed as a peak having a shoulder portion, but it is a simple 1 seen in the case of a single component. It can be distinguished because it is different from the peak curve.

When a mixture of a (meth) acrylic monomer and another monomer is copolymerized, examples of the other monomer include aromatic alkenyl compounds such as styrene, α-methylstyrene and vinyltoluene, acrylonitrile, Various vinyl monomers such as vinyl cyanide compounds such as methacrylonitrile, methacrylic acid-modified silicone, and fluorine-containing vinyl compounds may be included as copolymerization components. The amount of other monomers used is preferably 30% by mass or less.
In producing an acrylic rubber, various conventionally known surfactants such as anionic, nonionic and cationic can be used as an emulsifier or a dispersion stabilizer. Moreover, 2 or more types of surfactant can also be mixed and used as needed.

An acrylic rubber graft copolymer comprising an acrylic rubber and a graft portion can be obtained by graft polymerization of one or more vinyl monomers in the presence of the acrylic rubber described above. .
The vinyl monomer constituting the graft portion is not particularly limited. Specific examples thereof include aromatic alkenyl compounds such as styrene, α-methylstyrene and vinyltoluene; methacrylic acid esters such as methyl methacrylate and 2-ethylhexyl methacrylate; acrylic acid esters such as methyl acrylate, ethyl acrylate and n-butyl acrylate. Various vinyl monomers such as vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; These vinyl monomers can be used alone or in combination of two or more.

  The vinyl monomer preferably contains a vinyl monomer having two or more unsaturated bonds in the molecule from the viewpoint of impact resistance and heat resistance. Specific examples thereof include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, divinylbenzene, polyfunctional methacrylic group-modified silicone, and the like, which function as a crosslinking agent. Monomer; Examples include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, and the like, a monomer that functions as a crosslinking agent and / or a graft crossing agent. The amount of these monomers used is preferably 20% by mass or less.

  The graft part can be produced by single stage or multistage polymerization. Depending on how you want to set the dispersibility of the graft copolymer (rubber polymer (C)) in the matrix, interfacial strength, etc., the effect of improving impact resistance by making the graft part multi-stage There is. For example, when the graft part contains a reactive monomer unit such as glycidyl methacrylate, it is effective to produce by multi-stage polymerization as a method for maintaining good dispersibility while maintaining the reactivity of glycidyl methacrylate. Means. However, an unnecessarily large number of stages increases the number of manufacturing steps and decreases the productivity, so it is not preferable to increase more than necessary. Therefore, the polymerization is preferably 5 stages or less, more preferably 3 stages or less.

  As a polymerization method for producing the graft portion, general dropping polymerization can be used. When the first stage of the acrylic rubber is produced in the absence of an emulsifier, the components constituting the graft portion are charged all at once in the presence of the acrylic rubber, and then polymerized by adding a catalyst. . According to this method, the agglomerated particles are difficult to fuse during powder recovery. In the case of multistage polymerization, the second and subsequent stages may be charged all at once or by dropping.

  The ratio of the acrylic rubber and the graft part in the graft copolymer is preferably 80 to 99 parts by mass, and 80 to 95 parts by mass based on the total of 100 parts by mass of both. Is more preferable, and 80 to 90 parts by mass is particularly preferable. When the amount of the graft part is 1 part by mass or more, the dispersibility of the obtained graft copolymer in the thermoplastic resin composition becomes good, and the processability of the thermoplastic resin composition is improved. On the other hand, when the amount of the graft portion is 20 parts by mass or less, the impact strength development of the graft copolymer is improved.

  Furthermore, in the present invention, the acrylic rubber and / or the graft part has one or more kinds derived from a vinyl monomer containing a functional group selected from the group consisting of an epoxy group, a hydroxyl group and an isobornyl group. It is preferable to include a monomer unit, and more preferable to include a unit derived from a monomer having an epoxy group. Thereby, the effect which further improves the physical properties, such as pigment coloring property and heat-resistant deformation property which are originally favorable, compared with the case where these are not included is recognized. Therefore, these functional groups can be introduced according to the required physical properties. The content of the unit derived from the vinyl monomer containing the functional group differs depending on the target matrix resin, but from the viewpoint of impact resistance, 50% in the acrylic rubber or the graft part. The mass% or less is preferable. Moreover, 0.01 mass% or more is preferable from the point of pigment coloring property or heat-resistant deformation property, and 0.05 mass% or more is more preferable.

  The acrylic rubber graft copolymer is usually obtained as a latex. In the present invention, the graft copolymer obtained as the latex is preferably recovered as powder or granules by spray recovery or wet coagulation with a coagulant such as acid or salt. However, when a functional group is included, wet coagulation with an acid is not preferable. This is because when an acid is used, the functional group may be deactivated or adversely affected. When wet coagulation using salts is performed, it is preferable to use an alkaline earth metal salt such as calcium acetate, calcium chloride, magnesium sulfate or the like. If alkaline earth metal is used, deterioration such as decomposition of the matrix resin due to moisture and heat can be suppressed as much as possible. If the deterioration of the matrix resin can be suppressed, the moisture and heat resistance of the molded article made of the thermoplastic resin composition is improved. Since the heat and humidity resistance affects the impact strength development of the molded product, it greatly affects the recyclability of the molded product.

  Further, as a recovery method considering recyclability, a spray recovery method that does not include the salt for the coagulant itself is effective. In spray recovery, in addition to the graft copolymer, fillers or other polymers can be co-sprayed at the same time and recovered as a powder in which both are combined. By selecting the type of co-spraying, a more preferable handling property of the powder property can be realized. Examples of the components to be co-sprayed include a calcium component described in the present specification, silica, and a hard vinyl copolymer.

(3) Diene rubber graft copolymer The diene rubber graft copolymer used in the present invention is obtained by graft polymerization of a vinyl monomer on a diene rubber.
Examples of the diene rubber include polybutadiene, polyisoprene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, and polychloroprene.
Preferably, the monomer used for rubber polymerization is a diene monomer such as 1,3-butadiene (sometimes referred to as Bd), isoprene, chloroprene, etc., when the total amount of the monomers is 100% by mass. It consists of one or two or more vinyl monomers that can be copolymerized with the diene monomer.
Examples of vinyl monomers copolymerizable with diene monomers include styrene (sometimes referred to as St), aromatic vinyl such as α-methylstyrene, alkyl methacrylates such as methyl methacrylate and ethyl methacrylate, Acrylic acid alkyl esters such as ethyl acrylate and n-butyl acrylate, unsaturated nitriles such as acrylonitrile and methacrylonitrile, vinyl ethers such as methyl vinyl ether and butyl vinyl ether, vinyl halides such as vinyl chloride and vinyl bromide, vinylidene chloride, odor Vinylidene halides such as vinylidene halide, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, ethylene glycol glycidyl ether and other vinyl monomers having a glycidyl group, divinylbenzene, ethyl Glycol dimethacrylate, polyfunctional monomers such as 1,3-butylene glycol dimethacrylate may be used. These vinyl monomers can be used alone or in combination of two or more.
As a polymerization method for the diene rubber, an emulsion polymerization method is usually used.
In the emulsion polymerization of the diene rubber in the present invention, a known emulsifier such as an alkali metal salt of a higher fatty acid such as disproportionated rosin acid, oleic acid or stearic acid, and / or a sulfonic acid type or sulfuric acid type alkali metal salt. Selected emulsifiers can be used. Among these, it is preferable to use a sulfonic acid-based or sulfuric acid-based alkali metal salt.
Specific examples of the sulfonic acid-based or sulfuric acid-based alkali metal salts include, for example, alkylbenzene sulfonic acid alkali metal salts such as sodium dodecylbenzene sulfonate, alkyl diphenyl ether disulfonic acid alkali metal salts such as sodium alkyldiphenyl ether disulfonate, and sodium lauryl sulfate. Examples thereof include primary alkyl alkali metal salts of sulfuric acid and secondary alkyl alkali metal salts of sulfuric acid. These emulsifiers can be used alone or in combination of two or more. By using the emulsifier, when molding a thermoplastic resin composition obtained by blending the rubber polymer-containing material of the present invention with a thermoplastic resin, the lubricity becomes good and long-term without causing plate-out and the like. Production stability can be ensured.
In addition, an emulsifying dispersant can be used for the purpose of improving the polymerization stability. Specific examples of the emulsifying dispersant include, for example, a sodium salt of β-naphthalenesulfonic acid formalin condensate.
As a polymerization method of the diene rubber, a multistage polymerization method of one stage or two stages or more can be adopted. In the case of multi-stage polymerization, a part of the monomer used for the polymerization is previously charged into the reaction system, and after the start of polymerization, the remaining monomer is added all at once or dividedly or continuously. It is preferable. By adopting such a polymerization method, the polymerization stability is improved, and a diene rubber latex having a desired particle size and particle size distribution can be stably prepared.
The average particle diameter of the diene rubber latex is generally 50 to 400 nm, preferably 70 to 300 nm in terms of weight average particle diameter (dw). When the weight average particle diameter (dw) is 50 nm or more, the impact resistance of the thermoplastic resin composition obtained by blending the rubbery polymer-containing material of the present invention with the thermoplastic resin is sufficiently improved, and the weight average particle diameter is increased. When the thickness is 400 nm or less, a molded product having a good surface appearance can be obtained, and a balance between impact resistance and transparency when added to a polyvinyl chloride resin can be achieved.
(Preparation of rubbery polymer based on diene rubber)
The rubbery polymer mainly composed of the diene rubber in the present invention can be prepared by graft copolymerizing a vinyl monomer to such a diene rubber.
For example, in the presence of the diene rubber latex, a monomer having an alkyl methacrylate as a main component, for example, one or more alkyl methacrylates can be copolymerized with the monomer, if desired. A rubbery polymer can be prepared by subjecting a monomer mixture comprising a vinyl monomer to multistage graft polymerization of one or more stages.
The graft polymerization is preferably a three-stage graft polymerization. Impact resistance of a thermoplastic resin composition obtained by blending a rubber polymer-containing material of the present invention with a thermoplastic resin when a monomer mainly composed of alkyl methacrylate is used in the first stage of graft polymerization The compatibility between the rubbery polymer-containing material and the thermoplastic resin is improved. It is preferable to use a monomer mainly composed of an aromatic vinyl compound in the second stage of the graft polymerization because the fluidity of the rubbery polymer is improved. In the third stage of the graft polymerization, the surface of the thermoplastic resin composition obtained by blending the rubber polymer-containing material of the present invention with the thermoplastic resin when a monomer mainly composed of alkyl methacrylate is used. The gloss of can be improved.
Specific examples of vinyl monomers copolymerizable with methacrylic acid alkyl esters include, for example, aromatic vinyl such as styrene, α-methylstyrene, halogen-substituted products thereof, and alkyl-substituted styrene, ethyl acrylate, and n-butyl. Acrylic acid alkyl esters such as acrylate, unsaturated nitriles such as acrylonitrile and methacrylonitrile, vinyl monomers having a glycidyl group such as glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, and ethylene glycol glycidyl ether. . These monomers can be used alone or in combination of two or more.
The content of the diene rubber component of the rubber polymer is usually preferably 50 to 90% by mass, more preferably 55 to 85% by mass. When the content of the diene rubber component is 50% by mass or more, the impact resistance of the thermoplastic resin composition obtained by blending the rubbery polymer-containing material of the present invention with the thermoplastic resin is improved, and the diene rubber component When the content of is 90% by mass or less, the dispersibility of the rubber polymer-containing material of the present invention in the thermoplastic resin is improved, and physical properties such as impact resistance are maintained while maintaining the excellent properties of the thermoplastic resin. Can be improved.
As the method of graft polymerization, an emulsion polymerization method is usually used as in the case of rubber polymerization. In the present invention, as in the case of rubber polymerization, a known emulsifier such as an alkali metal salt of a higher fatty acid such as disproportionated rosin acid, oleic acid or stearic acid and / or a sulfonic acid-based or sulfuric acid-based alkali metal salt. Selected emulsifiers can be used. These emulsifiers can be used alone or in combination of two or more. Of these, sulfonic acid-based and sulfuric acid-based alkali metal salts are preferable. Specific examples of the sulfonic acid-based or sulfuric acid-based alkali metal salts include alkylbenzene sulfonic acid alkali metal salts such as sodium dodecylbenzene sulfonate (sometimes referred to as DBSNa), and alkyl diphenyl ether disulfonic acid alkali metals such as sodium alkyldiphenyl ether disulfonate. Examples thereof include primary alkyl alkali metal sulfates such as salts and sodium lauryl sulfate (sometimes referred to as SLS) and secondary alkyl alkali metal sulfates.
In addition, an emulsifying dispersant can be used for the purpose of improving the polymerization stability. Specific examples of the emulsifying dispersant include a sodium salt of β-naphthalenesulfonic acid formalin condensate. These emulsifiers or emulsifying dispersants can be used alone or in combination of two or more.
The sulfonic acid-based or sulfuric acid-based alkali metal salt is preferably contained in an amount of 1-10 parts by mass, more preferably 1-8 parts by mass, with respect to 100 parts by mass of the finally obtained rubbery polymer. As described above, the amount used at the time of polymerization of the diene rubber or at the time of preparation of the rubbery polymer mainly composed of the diene rubber is determined.
As described above, the sulfonic acid-based or sulfuric acid-based alkali metal salt can be used at the time of polymerization of the diene rubber, or at the time of preparation of the rubbery polymer containing the diene rubber as a main component. Although it may be used, it is preferable to add the sulfonic acid-based or sulfuric acid-based alkali metal salt at a predetermined amount during polymerization of the diene rubber.
When the amount of the emulsifier is 1 part by mass or more, aggregates are not generated during polymerization, which is preferable.

<Thermoplastic resin composition>
The thermoplastic resin composition of the present invention contains at least a polylactic acid polymer (A), a polymer (B) containing an aromatic alkenyl, and a rubbery polymer (C).

The composition ratio of the polylactic acid polymer (A) and the polymer (B) containing aromatic alkenyl is 1/99 to 99/1 (mass ratio), preferably 5/95 to 95/5 ( Mass ratio). If the amount of the polylactic acid polymer (A) is too small, the effect of reducing the environmental load is small, and if the amount of the polymer (B) containing aromatic alkenyl is too small, the effect of improving heat resistance is small.
The blending amount of the rubber polymer (C) is not particularly limited, but is usually 1 to 50 mass with respect to 100 mass parts in total of the polylactic acid polymer (A) and the polymer (B) containing aromatic alkenyl. Part is preferable, and 1 to 30 parts by mass is more preferable.

(Other ingredients)
When the thermoplastic resin composition of the present invention requires flame retardancy, a flame retardant can be added. In particular, a halogen-based flame retardant, a phosphoric acid-based flame retardant, and a silicone-based flame retardant are preferable because they can exhibit high flame resistance without impairing the intended impact resistance and the like. Examples of such flame retardants include halogen-containing compounds, phosphoric acid compounds, silicone compounds, and halogen-containing organometallic salt compounds.
Specific examples of the flame retardant include phosphoric acid compounds such as phosphate compounds, phosphite compounds, and condensed phosphate compounds; aluminum hydroxide; antimony acids such as antimony trioxide and antimony pentoxide; Halogen-containing compounds such as halogenated phosphoric acid ester compounds, halogenated condensed phosphoric acid ester compounds, chlorinated paraffins, brominated aromatic triazines, brominated aromatic compounds such as brominated phenyl alkyl ethers; sulfone or sulfate compounds; epoxy System reaction type flame retardants; and the like.

  When preparing the thermoplastic resin composition of the present invention, as long as the physical properties are not impaired, various stabilizers conventionally known at a desired stage such as compounding, kneading, molding, etc. of the thermoplastic resin, Fillers and the like can be added.

Examples of the stabilizer include metal stabilizers and other stabilizers.
Examples of metal stabilizers include lead stabilizers such as tribasic lead sulfate, dibasic lead phosphite, basic lead sulfite, and lead silicate; potassium, magnesium, barium, zinc, cadmium, lead, etc. Soaps derived from 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, ricinoleic acid, linoleic acid, behenic acid, etc. Stabilizers; organotin stabilizers derived from alkyl groups, ester groups, etc., and fatty acid salts, maleates, sulfides, etc .; Ba—Zn, Ca—Zn, Ba—Ca—Sn, Composite metal soap stabilizers such as Ca—Mg—Sn, Ca—Zn—Sn, Pb—Sn, and Pb—Ba—Ca; metals such as barium and zinc, and 2-ethylhexa Aromatic acids such as branched fatty acids such as acids, isodecanoic acid and trialkylacetic acids, unsaturated fatty acids such as oleic acid, ricinoleic acid and linoleic acid, alicyclic acids such as naphthenic acid, coalic acid, benzoic acid, salicylic acid Metal salt stabilizers derived from usually two or more organic acids such as aliphatic acids; these stabilizers are dissolved in organic solvents such as petroleum hydrocarbons, alcohols, glycerin derivatives, phosphites and epoxy compounds , Color stabilizers, transparency improvers, light stabilizers, antioxidants, plate-out inhibitors, metal salt liquid stabilizers and the like which are blended with stabilizing aids such as lubricants.

Other stabilizers include epoxy resins, epoxidized soybean oil, epoxidized vegetable oil, epoxidized fatty acid alkyl esters, and the like; phosphorus is substituted with an alkyl group, aryl group, cycloalkyl group, alkoxyl group, etc., and propylene Organic phosphites containing aromatic compounds such as dihydric alcohols such as glycol, hydroquinone and bisphenol A; dimerized with 2,4-di-t-butyl-3-hydroxytoluene (BHT), sulfur or methylene groups, etc. UV absorbers such as hindered phenols such as bisphenol, salicylic acid ester, benzophenone and benzotriazole; light stabilizers of hindered amines or nickel complex salts; UV screening agents such as carbon black and rutile type titanium oxide; trimerol propane and penta Erythritol , Polyhydric alcohols such as sorbitol and mannitol, nitrogen-containing compounds such as β-aminocrotonate, 2-phenylindole, diphenylthiourea and dicyandiamide; sulfur-containing compounds such as dialkylthiodipropionate; acetoacetate and dehydro Keto compounds such as acetic acid and β-diketone; organosilicon compounds; borate esters;
These stabilizers can be used alone or in combination of two or more.

  Examples of the filler include carbonates such as heavy calcium carbonate, precipitated calcium carbonate, and colloidal calcium carbonate; titanium oxide, clay, talc, mica, silica, carbon black, graphite, glass beads, glass fiber, carbon fiber, Examples thereof include inorganic fillers such as metal fibers; organic fibers such as polyamide; organic fillers such as silicone; natural organic substances such as wood flour; In particular, a fiber reinforced resin composition containing a fibrous reinforcing material such as glass fiber or carbon fiber is very useful.

  The thermoplastic resin composition of the present invention includes other impact resistance modifiers, processing aids, plasticizers, lubricants, heat resistance improvers, mold release agents, crystal nucleating agents, fluidity improvers, colorants, charging agents. An inhibitor, a conductivity imparting agent, a surfactant, an antifogging agent, a foaming agent, an antibacterial agent, and the like can be added.

Examples of impact strength modifiers include MBS (methyl methacrylate-butadiene-styrene resin), ABS, AES, NBR (acrylonitrile-butadiene rubber), EVA (ethylene-vinyl acetate copolymer), chlorinated polyethylene, and acrylic. Examples thereof include impact modifiers other than the rubbery polymer (C) in the present invention, such as rubber, polyalkyl (meth) acrylate rubber-based graft copolymer, and thermoplastic elastomer.
Examples of processing aids include (meth) acrylic acid ester copolymers.

  Examples of the plasticizer include alkyl esters of aromatic polybasic acids such as dibutyl phthalate, dioctyl phthalate, diisodecyl phthalate, diisononyl phthalate, diundecyl phthalate, trioctyl trimellitate, triisooctyl trimellitate; dibutyl adipate, dioctyl Alkyl esters of fatty acid polybasic acids such as adipate, dithiononyl adipate, dibutyl azelate, dioctyl azelate, diisononyl azelate; phosphate esters such as tricresyl phosphate; adipic acid, azelaic acid, sebacic acid, phthalic acid, etc. And a polyhydric alcohol such as ethylene glycol, 1,2-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, and 1,4-butylene glycol. Polyester plasticizers such as compounds in which the end of a polycondensate having a molecular weight of about 600 to 8,000 is sealed with a monohydric alcohol or monovalent carboxylic acid; epoxidized soybean oil, epoxidized linseed oil, epoxidized tall oil Epoxy plasticizers such as fatty acid-2-ethylhexyl; chlorinated paraffin and the like.

Examples of the lubricant include liquid hydrocarbons such as liquid paraffin and low molecular weight polyethylene, halogenated hydrocarbons, fatty acids such as higher fatty acids and oxyfatty acids, fatty acid amides, polyhydric alcohol esters of fatty acids such as glycerides, and fatty alcohol esters of fatty acids. (Ester wax), metal soap, fatty alcohol, polyhydric alcohol, polyglycol, polyglycerol, fatty acid and polyhydric alcohol partial ester, fatty acid and polyglycol, polyglycerol partial ester, etc., (meth) acrylic acid ester Examples thereof include system copolymers.
Examples of the heat resistance improver include (meth) acrylic acid ester copolymers, imide copolymers, styrene-acrylonitrile copolymers, and the like.
The thermoplastic resin composition of the present invention may be mixed with another polymer material as long as it does not inhibit the effects of the present invention.

(Method for producing thermoplastic resin composition)
The method for producing the thermoplastic resin composition of the present invention is not particularly limited. Various conventionally known mixing methods can be used, and the melt mixing method is usually preferable. Moreover, you may use a small amount of solvent as needed. Examples of the apparatus used for mixing include an extruder, a Banbury mixer, a roller, and a kneader. These devices may be operated batchwise or continuously. The mixing order of the components is not particularly limited.

  The use of the thermoplastic resin composition of the present invention is not particularly limited. For example, it can be widely used for miscellaneous goods such as building materials, automobiles, toys, and stationery, as well as molded articles that require impact resistance, such as automobile parts, OA equipment, and home appliances.

  In the thermoplastic resin composition of the present invention, the heat resistance and impact resistance of the polylactic acid polymer (A) are added by adding the rubbery polymer (C) to the polylactic acid polymer (A). Can be improved. Furthermore, the transparency of the polylactic acid polymer (A) is maintained by using an acrylic rubber graft copolymer or a polyorganosiloxane / acrylic composite rubber graft copolymer as the rubber polymer (C). In addition, various moldings such as sheet / film molding, foam molding, profile molding, and injection molding can be easily performed.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited to these examples.

The average particle diameter and mass average molecular weight were measured as follows.
Average particle size:
The mass average particle diameter of the polyorganosiloxane in the latex and the mass average particle diameter of the graft copolymer in the polymerized latex were determined by a dynamic light scattering method using DLS-700 type manufactured by Otsuka Electronics Co., Ltd.
Mass average molecular weight measurement (GPC measurement):
The dried sample was dissolved in tetrahydrofuran (THF) at 40 ° C. over 1 hour, and then allowed to stand overnight at room temperature to obtain a GPC (HLC-8020) manufactured by Tosoh Corp. The mass average molecular weight was measured under the following conditions using TSK-GEL GMHXL × 2). Here, a GPC calibration curve was prepared using monodisperse polystyrene manufactured by the same company.
Sample concentration: 0.1 g / dl
・ Injection volume: 0.1ml
-Column temperature: 40 ° C

(Production Example 1) Production of polyorganosiloxane / acrylic composite rubber graft copolymer (M-1):
2 parts by mass of tetraethoxysilane, 0.5 part by mass of γ-methacryloyloxypropyldimethoxymethylsilane and 97.5 parts by mass of octamethylcyclotetrasiloxane were mixed to obtain 100 parts by mass of a siloxane mixture. After adding 100 parts by mass of a siloxane mixture to 200 parts by mass of distilled water in which 0.67 parts by mass of sodium dodecylbenzene sulfonate and 0.66 parts by mass of dodecylbenzene sulfonate were dissolved, the mixture was pre-stirred at 10,000 rpm with a homomixer, and then homogenizer. An organosiloxane emulsion was obtained by emulsifying and dispersing at a pressure of 200 kg / cm ² . This was transferred to a separable flask equipped with a condenser and a stirring blade, heated at 80 ° C. for 5 hours with mixing and stirring, left at 20 ° C., and after 48 hours, the pH of the emulsion was adjusted to 7.0 with an aqueous sodium hydroxide solution. Thus, the polymerization was completed to obtain a latex containing polyorganosiloxane.
The polymerization rate of the obtained polyorganosiloxane was 89.1%, and the average particle size of the polyorganosiloxane was 0.19 μm.

35 parts by mass of this polyorganosiloxane-containing latex was sampled as a solid content, placed in a separable flask equipped with a stirrer, 175 parts by mass of distilled water was added, the atmosphere was replaced with nitrogen, and the temperature was raised to 50 ° C. -A mixture of 78.4 parts by weight of butyl acrylate, 1.6 parts by weight of allyl methacrylate and 0.3 part by weight of tert-butyl hydroperoxide was charged, stirred for 30 minutes, and this mixture was infiltrated into the polyorganosiloxane. Next, a mixture of 0.002 part by mass of ferrous sulfate, 0.006 part by mass of disodium ethylenediaminetetraacetate, 0.3 part by mass of Rongalite and 10 parts by mass of distilled water was charged to start radical polymerization. The polymerization was completed at a temperature of 70 ° C. for 2 hours to obtain a polyorganosiloxane / acrylic composite rubber latex.
A part of this latex was sampled and the average particle size of the polyorganosiloxane / acrylic composite rubber was measured and found to be 0.22 μm.

A mixture of 10 parts by weight of methyl methacrylate and 0.024 parts by weight of tert-butyl hydroperoxide was dropped into the latex containing the polyorganosiloxane / acrylic composite rubber at 60 ° C. over 15 minutes, and then 60 ° C. For 2 hours to complete the graft polymerization to the polyorganosiloxane / acrylic composite rubber.
The polymerization rate of methyl methacrylate was 97.1%. The average particle size of the graft copolymer (M-1) was 0.23 μm.
The latex containing the obtained graft copolymer (M-1) was added to a calcium chloride aqueous solution having a concentration of 5% at 40 ° C. so that the ratio of the latex to the aqueous solution was 1: 2, and then to 90 ° C. The temperature is raised to solidify the graft copolymer (M-1), washing is repeated with water, the solid content is separated and dried at 80 ° C. for 24 hours, and the polyorganosiloxane / acrylic rubber composite rubber graft copolymer A powder of the polymer (M-1) was obtained.

(Production Example 2) Production of polyorganosiloxane / acrylic rubber-based composite rubber graft copolymer (M-2):
2 parts by mass of tetraethoxysilane, 0.5 part by mass of γ-methacryloyloxypropyldimethoxymethylsilane and 97.5 parts by mass of octamethylcyclotetrasiloxane were mixed to obtain 100 parts by mass of a siloxane mixture. 100 parts by mass of the above mixed siloxane was added to 200 parts by mass of distilled water in which 0.67 parts by mass of sodium dodecylbenzenesulfonate and dodecylbenzenesulfonic acid were dissolved, and the mixture was pre-stirred at 10,000 rpm with a homomixer, and then homogenizer. An organosiloxane latex was obtained by emulsifying and dispersing at a pressure of 200 kg / cm ² . This mixed solution was transferred to a separable flask equipped with a condenser and a stirring blade, heated at 80 ° C. for 5 hours with mixing and stirring, and then allowed to stand at 20 ° C. After 48 hours, the pH of the latex was adjusted to 7 with an aqueous sodium hydroxide solution. The mixture was neutralized to 0.0 to complete the polymerization to obtain a polyorganosiloxane latex (hereinafter referred to as PDMS-1).
The polymerization rate of the obtained polyorganosiloxane was 89.1%, and the average particle size of the polyorganosiloxane was 0.19 μm.

35 parts by mass of this PDMS-1 was collected as a solid content, placed in a separable flask equipped with a stirrer, 175 parts by mass of distilled water was added, and the temperature was raised to 50 ° C. after nitrogen substitution, and n-butyl acrylate 78 A mixed solution of .4 parts by mass, 1.6 parts by mass of allyl methacrylate and 0.3 parts by mass of tert-butyl hydroperoxide was charged and stirred for 30 minutes, and this mixed solution was infiltrated into the polyorganosiloxane particles. Next, a mixture of ferrous sulfate (0.002 parts by mass), ethylenediaminetetraacetic acid disodium salt (0.006 parts by mass), Rongalite (0.3 parts by mass) and distilled water (10 parts by mass) was charged to start radical polymerization. The polymerization was completed at a temperature of 70 ° C. for 2 hours to obtain a polyorganosiloxane / acrylic composite rubber latex.
A part of this latex was sampled and the average particle size of the polyorganosiloxane / acrylic composite rubber was measured and found to be 0.22 μm.

In the latex containing this polyorganosiloxane / acrylic composite rubber, 60 parts of a mixture of a monomer mixture of 3 parts by mass of glycidyl methacrylate and 7 parts by mass of methyl methacrylate and 0.024 parts by mass of tert-butyl hydroperoxide was added. The mixture was added dropwise at 15 ° C. for 15 minutes, and then maintained at 60 ° C. for 2 hours to complete the graft polymerization onto the polyorganosiloxane / acrylic composite rubber.
The polymerization rate of glycidyl methacrylate was 98.5%. The average particle size of the graft copolymer (M-2) was 0.24 μm.
The latex containing the obtained graft copolymer (M-2) is added to a calcium chloride aqueous solution having a concentration of 5% at 40 ° C. so that the ratio of latex to aqueous solution is 1: 2, and then to 90 ° C. The temperature is raised to solidify the graft copolymer (M-2), washing is repeated with water, the solid content is separated, dried at 80 ° C. for 24 hours, and the polyorganosiloxane / acrylic composite rubber graft copolymer A dry powder of coalescence (M-2) was obtained.

(Production Example 3) Production of polyorganosiloxane / acrylic rubber-based composite rubber graft copolymer (M-3):
Polyorganosiloxane / acrylic as in Production Example 1 except that 7.5 parts by mass of acrylonitrile and 2.5 parts by mass of styrene were used instead of 10 parts by mass of methyl methacrylate used in the graft polymerization in Production Example 1. A dry powder of the composite rubber graft copolymer (M-3) was obtained.

(Production Example 4) Production of butadiene-based graft copolymer (M-4):
As a first monomer mixture, the following substances were charged into a 70 L autoclave, and when the temperature was raised to 43 ° C., a redox initiator was added into the autoclave to start polymerization of the monomer, and then 60 The temperature was raised to ° C.
First monomer: 100 parts by mass of 1,3-butadiene, 0.4 parts by mass of t-dodecyl mercaptan, 0.75 parts by mass of potassium rosinate, 0.75 parts by mass of potassium oleate, 0.24 parts of diisopropylbenzene peroxide Part by mass, 70 parts by mass of deionized water.
Redox initiator: 0.003 parts by mass of ferrous sulfate, 0.3 parts by mass of dextrose, 0.3 parts by mass of sodium pyrophosphate, 5 parts by mass of deionized water.
The reaction was allowed to proceed for 8 hours from the start of polymerization to obtain a butadiene rubber polymer latex (r-1). The resulting butadiene rubber polymer latex (r-1) had a particle size of 90 nm.

By adding 2 parts by mass of methyl methacrylate-n-butyl acrylate copolymer as a solid content to 75 parts by mass (solid content) of butadiene-based rubber polymer latex (r-1) and stirring at room temperature for 30 minutes Then, 1.5 parts by mass of potassium oleate and 0.6 parts by mass of sodium formaldehyde sulfoxylate were charged into the flask and the internal temperature was maintained at 70 ° C., and 13 parts by mass of methyl methacrylate, n-butyl. A mixture of 2 parts by mass of acrylate and 0.03 parts by mass of cumene hydroxyperoxide was added dropwise over 1 hour and then held for 1 hour (first stage).
Thereafter, in the presence of the polymer obtained in the first stage, as a second stage, a mixture of 17 parts by mass of styrene and 0.034 parts by mass of cumene hydroxyperoxide was added dropwise over 1 hour, and then maintained for 3 hours. did.

Thereafter, in the presence of the polymer obtained in the first and second stages, a mixture of 3 parts by mass of methyl methacrylate and 0.003 parts by mass of cumene hydroxyperoxide was added as the third stage for 0.5 hour. After the dropwise addition, the mixture was held for 1 hour, and then the polymerization was terminated to obtain a latex of graft copolymer (M-4).
After adding 0.5 parts by weight of butylated hydroxytoluene to the latex containing the graft copolymer (M-4), 0.2% sulfuric acid aqueous solution is added to coagulate the graft copolymer (M-4). And solidified by heat treatment at 90 ° C. Thereafter, the solidified product was washed with warm water and further dried to obtain a butadiene-based graft copolymer (M-4).

(Production Example 5) Production of acrylic rubber graft copolymer (M-5):
99.5 parts by mass of 2-ethylhexyl acrylate and 0.5 parts by mass of allyl methacrylate were mixed to obtain 100 parts by mass of a (meth) acrylate monomer mixture. As alkyl diphenyl ether disulfonate sodium, 100 parts by mass of the above (meth) acrylate monomer mixture was added to 195 parts by mass of distilled water in which 1 part by mass of the registered trademark PELEX SS-L commercially available from Kao Corporation was dissolved. In addition, after pre-stirring at 10,000 rpm with a homomixer, it was emulsified and dispersed with a homogenizer at a pressure of 30 MPa to obtain a (meth) acrylate emulsion. This emulsion was transferred to a separable flask equipped with a condenser and a stirring blade, heated while being purged with nitrogen and mixed and stirred, and 0.5 parts by mass of tert-butyl hydroperoxide was added when the temperature reached 50 ° C. The temperature was raised, and a mixture of 0.002 parts by mass of ferrous sulfate, disodium ethylenediaminetetraacetic acid salt, 0.006 parts by mass, 0.26 parts by mass of Rongalite and 5 parts by mass of distilled water was added and left for 5 hours. Polymerization was completed to obtain an acrylic rubber (AR1) component latex.
The polymerization rate of the obtained acrylic rubber (AR1) component latex was 99.9%. Furthermore, 0.7 parts by mass of PELEX SS-L as a solid content was added to the obtained latex.

  The acrylic rubber (AR1) component latex is sampled to be 10 parts by mass as the solid content of poly-2-ethylhexyl acrylate containing allyl methacrylate units, placed in a separable flask equipped with a stirrer, and the amount of distilled water in the system Distilled water was added so as to be 195 parts by mass. At this time, PELEX SS-L is present in the latex in a solid content of 0.8 parts by mass. Next, a mixed liquid of 78 parts by mass of n-butyl acrylate containing 2.0% by mass of allyl methacrylate constituting the acrylic rubber (AR2) component and 0.32 parts by mass of tert-butyl hydroperoxide was charged and stirred for 10 minutes. The mixed solution was infiltrated into the acrylic rubber (AR1) component particles. After stirring for another 10 minutes, the atmosphere was replaced with nitrogen, and the temperature of the system was raised to 50 ° C. Ferrous sulfate 0.002 parts by mass, ethylenediaminetetraacetic acid disodium salt 0.006 parts by mass, Rongalite 0.26 parts by mass And 5 parts by mass of distilled water were charged to start radical polymerization, and then held at an internal temperature of 70 ° C. for 2 hours to complete the polymerization, and a polyalkyl comprising an acrylic rubber (AR1) component and an acrylic rubber (AR2) component A latex (ARL1) of (meth) acrylate composite rubber was obtained.

To this polyalkyl (meth) acrylate composite rubber latex (ARL1), a mixed solution of 0.06 parts by mass of tert-butyl hydroperoxide and 12 parts by mass of methyl methacrylate was added dropwise at 70 ° C. over 15 minutes. Holding at 4 ° C. for 4 hours, graft polymerization onto the polyalkyl (meth) acrylate composite rubber was completed.
The polymerization rate of methyl methacrylate was 99.4%. The obtained latex of acrylic rubber graft copolymer (M-5) is dropped into 200 parts by mass of hot water of 1.5% calcium acetate, and the graft copolymer (M-5) is coagulated, separated and washed. And then dried at 75 ° C. for 16 hours to obtain a powdery acrylic rubber graft copolymer (M-5).

(Production Example 6) Production of acrylic rubber graft copolymer (M-6):
In a separable flask equipped with a condenser and a stirring blade, 1.275 parts by weight of n-butyl acrylate containing 1% by weight of allyl methacrylate and 0.051 part by weight of tert-butyl hydroperoxide were mixed and previously purged with nitrogen. While mixing and stirring, 128 parts by mass of distilled water in which 0.08 parts by mass of dipotassium alkenyl succinate substituted with nitrogen was dissolved was charged. Thereafter, the temperature was raised to 60 ° C., and a mixed solution of 0.002 parts by mass of ferrous sulfate, 0.006 parts by mass of disodium ethylenediaminetetraacetate, 0.26 parts by mass of Rongalite and 10 parts by mass of distilled water was added. The mixture was allowed to stand for a period of time to complete the emulsion polymerization, and poly (meth) acrylate latex seed particles were obtained.
The polymerization rate of this poly (meth) acrylate latex was 99.8%.

Subsequently, n-butyl acrylate containing 1% by mass of a mixed liquid of 1.02 parts by mass of dipotassium alkenyl succinate and 16 parts by mass of distilled water separately prepared, and seed particles of the poly (meth) acrylate latex. A (meth) acrylate mixed solution of 83.725 parts by mass and 0.33 parts by mass of tert-butyl hydroperoxide was added dropwise simultaneously over 3 hours, then held for 1 hour to complete the dropwise polymerization, and the latex of rubber component (AR3) Got.
A part of this latex was sampled and the average particle size of the rubber was measured and found to be 0.12 μm. In addition, as a result of measuring the particle size distribution with a particle size distribution measuring apparatus CHDF-2000 type (manufactured by MATEC APPLIED SCIENCE), particles in the range of 0.05 to 0.15 μm are 95 mass of the rubber component (AR3) as a whole. %Met.

  A mixture of 0.075 parts by mass of tert-butyl hydroperoxide and 15 parts by mass of methyl methacrylate was dropped into 85 parts by mass of the latex of the rubber component (AR3) at 60 ° C. over 15 minutes, and then 2 parts at 70 ° C. Holding for a time, the graft polymerization onto the rubber component was completed. The polymerization rate of methyl methacrylate was 99.4%. After the latex of the obtained graft copolymer (M-6) was dropped into 200 parts by mass of hot water containing 1.5% sulfuric acid, the graft copolymer (M-6) was coagulated, separated, washed, and then 75. Drying was carried out at 0 ° C. for 16 hours to obtain a powdery acrylic rubber graft copolymer (M-6).

(Production Example 7) Production of acrylic rubber graft copolymer (M-7):
In a separable flask equipped with a condenser and a stirring blade, 1.275 parts by weight of n-butyl acrylate containing 1% by weight of allyl methacrylate and 0.051 part by weight of tert-butyl hydroperoxide were mixed and previously purged with nitrogen. While mixing and stirring, 128 parts by mass of distilled water in which 0.08 part by mass of dipotassium alkenyl succinate was substituted with nitrogen was charged. Thereafter, the temperature was raised to 60 ° C., and a mixed solution of 0.002 parts by mass of ferrous sulfate, 0.006 parts by mass of disodium ethylenediaminetetraacetate, 0.26 parts by mass of Rongalite and 10 parts by mass of distilled water was added. The mixture was allowed to stand for a period of time to complete the emulsion polymerization, and poly (meth) acrylate latex seed particles were obtained.
The polymerization rate of this poly (meth) acrylate latex was 99.8%.

Subsequently, a mixed liquid of 0.34 parts by mass of dipotassium alkenyl succinate and 5 parts by mass of distilled water is added to the seed particles of the poly (meth) acrylate latex, and n-butyl acrylate 83 containing 1% by mass of allyl methacrylate is added. A (meth) acrylate mixed solution of .725 parts by mass and 0.33 parts by mass of tert-butyl hydroperoxide was added dropwise so that the addition was completed in 3 hours. One hour after the start of dropping, a mixed liquid of 0.34 parts by mass of dipotassium alkenyl succinate and 5 parts by mass of distilled water was added. Two hours after starting the above (meth) acrylate mixed droplets, a mixed solution of 0.34 parts by mass of dipotassium alkenyl succinate and 5 parts by mass of distilled water was further added. The (meth) acrylate mixed solution was dropped in 3 hours, and then held for 1 hour to complete the dropping polymerization to obtain a rubber component (AR4) latex.
A part of this latex was sampled and the average particle size of the rubber was measured and found to be 0.11 μm. The number of particles in the range of 0.05 to 0.15 μm was 87% of the total rubber component (AR4).

A mixture of 0.075 parts by mass of tert-butyl hydroperoxide and 15 parts by mass of methyl methacrylate is added dropwise to the latex of the rubber component (AR4) over 15 minutes at 60 ° C., and then maintained at 70 ° C. for 2 hours. The graft polymerization to the rubber component was completed.
The polymerization rate of methyl methacrylate was 99.7%. After the latex of the obtained graft copolymer (M-7) was dropped into 200 parts by mass of hot water containing 1.5% sulfuric acid, the graft copolymer (M-7) was coagulated, separated, washed, and then 75. Drying was carried out at 0 ° C. for 16 hours to obtain a powdery acrylic rubber graft copolymer (M-7).

(Production Example 8) Production of acrylic rubber graft copolymer (M-8):
In Production Example 6, the same operation as in Production Example 6 was performed except that 30 parts by mass of methyl methacrylate, which is a vinyl monomer, was grafted onto 70 parts by mass of the rubber component (AR3), and the average particle size was 0. A graft copolymer (M-8) containing a rubber component of .12 μm was obtained.

(Production Example 9) Production of acrylic rubber graft copolymer (M-9):
The n-butyl acrylate used in the synthesis of the seed particles in Production Example 7 is a mixture of n-butyl acrylate (BA) and 2-ethylhexyl acrylate (abbreviated as 2-EHA) (BA / 2-EHA = 80 by mass ratio). / 20), except that the emulsifier, water and monomers were mixed and processed at a homomixer of 10,000 rpm, the same operation as in Production Example 7 was performed, and the average particle diameter of the rubber component was 0.13 μm, 0.05- The particles in the range of 0.15 μm gave an acrylic rubber graft copolymer (M-9) that was 91% of the total rubber component.

(Production Example 10) Production of acrylic rubber graft copolymer (M-10):
The n-butyl acrylate used in the synthesis of the seed particles in Production Example 7 is a mixture of n-butyl acrylate (BA) and 2-ethylhexyl acrylate (abbreviated as 2-EHA) (mass ratio of BA / 2-EHA = 50). / 50), except that the emulsifier, water and monomers were mixed and processed at a homomixer of 10,000 rpm, the same operation as in Production Example 7 was performed, and the average particle diameter of the rubber component was 0.13 μm, 0.05- The particles in the range of 0.15 μm gave an acrylic rubber graft copolymer (M-10), which was 91% of the total rubber component.

(Production Example 11) Production of acrylic rubber graft copolymer (M-11):
195 masses of distilled water in which 0.8 parts by mass of sodium lauryl sulfate was dissolved in a mixture of 100 parts by mass of 2-ethylhexyl acrylate and allyl methacrylate in an amount corresponding to 1.0 mass% with respect to the amount of 2-ethylhexyl acrylate In addition to the part, it was pre-stirred at 10,000 rpm with a homomixer, and further emulsified and dispersed with a homogenizer at a pressure of 30 MPa to obtain a (meth) acrylate emulsion.
This emulsion was transferred to a separable flask equipped with a condenser and a stirring blade, heated with nitrogen substitution and mixing and stirring, and 0.5 parts by mass of tertiary butyl hydroperoxide was added when the temperature reached 50 ° C. Thereafter, the temperature was raised to 50 ° C., and a mixed liquid of ferrous sulfate 0.002 parts by mass, ethylenediaminetetraacetic acid disodium salt 0.006 parts by mass, Rongalite 0.26 parts by mass and distilled water 5 parts by mass was added. Holding for 5 hours, the first polymerization step was completed to obtain latex of acrylic rubber (AR5).

  To this acrylic rubber (AR5) latex, 0.06 parts by mass of tertiary butyl hydroperoxide, 13 parts by mass of methyl methacrylate and 2.0 parts by mass of butyl acrylate were dropped at 70 ° C. over 15 minutes. Thereafter, the temperature was maintained at 70 ° C. for 4 hours to complete the graft polymerization, and an acrylic rubber graft copolymer (ARL7) latex was obtained. The graft copolymer latex was dropped into 200 parts by mass of hot water in which 1.5% by mass of calcium chloride was dissolved, and the acrylic rubber graft copolymer (ARL7) was coagulated, separated, washed, and 75 ° C. And dried for 16 hours to obtain a powdery acrylic rubber-based graft copolymer (M-11).

(Production Example 12) Production of butadiene rubber-based graft copolymer (M-12)
To 75 parts by mass (solid content) of the butadiene-based rubber polymer latex (r-1) used in Production Example 4, 2 parts by mass of a methyl methacrylate-n-butyl acrylate copolymer as a solid content was added at room temperature. It was enlarged by stirring for 30 minutes.
50 parts by mass (solid content) of enlarged diene rubber latex was taken in a reaction kettle, diluted by adding 140 parts by mass of ion-exchanged water, and heated to 70 ° C. Separately, 50 parts by mass of a graft monomer mixture composed of acrylonitrile / styrene = 29/71 (mass ratio) was adjusted, 0.35 parts by mass of benzoyl peroxide was dissolved, and then purged with nitrogen. This monomer mixture was added into the reaction system at a rate of 15 parts by mass / hour using a metering pump. After completion of the injection of all the monomers, the system temperature was raised to 80 ° C., and stirring was continued for 30 minutes to obtain a latex of graft copolymer (M-12).
The latex produced as described above was poured into a 0.5% aqueous solution of sulfuric acid (90 ° C.) in an amount three times that of the total latex while stirring to coagulate. After the addition of all the latex, the temperature in the coagulation tank was raised to 93 ° C. and left for 5 minutes. After cooling, the solution was removed by a centrifuge, washed and dried to obtain a butadiene-based graft copolymer (M-12).

(Production Example 13) Production of acrylic rubber-based graft copolymer (M-13) Instead of 15 parts by mass of methyl methacrylate used in the graft polymerization in Production Example 6, 11.25 parts by mass of acrylonitrile and 3.75 of styrene A dry powder of an acrylic rubber-based graft copolymer (M-13) was obtained in the same manner as in Production Example 6 except that the parts by mass were used.

Production Example 14 Production of Butadiene Rubber / Acrylic Rubber Graft Copolymer (M-14) A graft copolymer of a composite rubber such as polybutadiene / polybutyl acrylate was synthesized as follows. 20 parts by mass (as solids) of polybutadiene latex having a solid content of 35% by mass and an average particle size of 0.08 μm were combined with an average particle size of 0.10 μm consisting of 82% n-butyl acrylate units and 18% methacrylic acid units. 0.4 parts by mass of polymerization latex (as solid content) was added with stirring, and stirring was continued for 30 minutes to obtain an enlarged diene rubber latex having an average particle size of 0.36 μm. Transfer 20 parts by mass (solid content) of the resulting enlarged diene rubber latex to a reaction kettle, add 1 part by mass of disproportionated potassium rosinate, 150 parts by mass of ion-exchanged water, and the following monomer mixture, and replace with nitrogen. The temperature was raised to 50 ° C. (internal temperature). To this was added a solution prepared by dissolving 0.0002 parts by mass of ferrous sulfate, 0.0006 parts by mass of disodium ethylenediaminetetraacetate and 0.25 parts by mass of Rongalite in 10 parts by mass of ion exchange water.
n-Butyl acrylate 80 parts by weight Allyl methacrylate 0.32 parts by weight Ethylene glycol dimethacrylate 0.16 parts by weight The internal temperature at the end of the reaction is 75 ° C, but when the temperature is further raised to 80 ° C and the reaction is continued for 1 hour The polymerization rate reached 98.8%, and a composite rubber of an enlarged diene rubber and a polyalkyl acrylate rubber was obtained. 50 parts by mass (solid content) of a composite rubber latex of enlarged diene rubber and polyalkyl acrylate rubber was taken in a reaction kettle, diluted by adding 140 parts by mass of ion-exchanged water, and heated to 70 ° C. Separately, 50 parts by mass of a graft monomer mixture composed of acrylonitrile / styrene = 29/71 (mass ratio) was adjusted, 0.35 parts by mass of benzoyl peroxide was dissolved, and then purged with nitrogen. This monomer mixture was added into the reaction system at a rate of 15 parts by mass / hour using a metering pump. After the injection of all the monomers was completed, the system temperature was raised to 80 ° C., and stirring was continued for 30 minutes to obtain a graft copolymer latex. The polymerization rate was 99%.
The latex produced as described above was poured into a 0.5% aqueous solution of sulfuric acid (90 ° C.) in an amount three times that of the total latex while stirring to coagulate. After the addition of all the latex, the temperature in the coagulation tank was raised to 93 ° C. and left for 5 minutes. After cooling this, the solution was removed by a centrifuge, washed and dried to obtain a dry powder of the graft copolymer (M-14).

(Production Example 15) Production of butadiene rubber-based graft copolymer (M-15) Methyl methacrylate-n with respect to 75 parts by mass (solid content) of butadiene-based rubber polymer latex (r-1) used in Production Example 4 -2 parts by mass of a butyl acrylate copolymer as a solid content was added, and the mixture was stirred for 30 minutes at room temperature to enlarge.
50 parts by mass (solid content) of enlarged diene rubber latex was taken in a reaction kettle, diluted by adding 140 parts by mass of ion-exchanged water, and heated to 70 ° C. Separately, 50 parts by mass of a graft monomer mixture composed of acrylonitrile / styrene = 29/71 (mass ratio) was adjusted, and after dissolving 3 parts by mass of glycidyl methacrylate and 0.35 parts by mass of benzoyl peroxide, nitrogen substitution was performed. This monomer mixture was added into the reaction system at a rate of 15 parts by mass / hour using a metering pump. After the injection of all the monomers was completed, the system temperature was raised to 80 ° C., and stirring was continued for 30 minutes to obtain a latex of a graft copolymer (M-15).
The latex produced as described above was added to a calcium chloride aqueous solution having a concentration of 5% at 40 ° C. so that the ratio of the latex to the aqueous solution was 1: 2, and then the temperature was raised to 90 ° C. for graft copolymerization. The coalescence (M-15) was solidified. The temperature in the coagulation tank was raised to 93 ° C. and left for 5 minutes. After cooling this, the solution was removed by a centrifuge, washed and dried to obtain a butadiene-based graft copolymer (M-15).

(Production Example 16) Production of AS (acrylonitrile-styrene copolymer) resin (AS-1) Acrylonitrile 30 parts by mass Styrene monomer 70 parts by mass
Azobisisobutyronitrile 0.15 parts by weight t-dodecyl mercaptan 0.40 parts by weight Calcium phosphate 0.50 parts by weight Distilled water 150 parts by weight The above composition was charged into a 100 liter autoclave and stirred vigorously. After confirming dispersion in the system, the temperature was raised to 75 ° C., and polymerization was carried out over 3 hours.
Then, it heated up to 110 degreeC and aged for 30 minutes. After cooling, dehydration, washing, and drying were performed to obtain a powdery copolymer having a reduced viscosity of 0.55 dl / g.

[Examples 1 to 45, Comparative Examples 1 to 24]
As the polylactic acid polymer (A), Laissia H-100 (manufactured by Mitsui Chemicals) and Lacia H-400 (manufactured by Mitsui Chemicals) are used, and the polymer (B) containing an aromatic alkenyl is prepared as the AS resin. AS-1, manufactured by Litec-A 100PCF (Nippon A & L Co., Ltd.), manufactured by Sanrex SAN-C (Technopolymer Co., Ltd.), MS resin, manufactured by Sebian MS10 (Daicel Polymer Co., Ltd.), Atrete MM -60 (Nippon A & L Co., Ltd.), GPPS HF (A & M Polystyrene Co., Ltd.) is used as the PS resin, and the graft copolymer (M-1) to (M) is used as the rubbery polymer (C). M-15) and using “Plamate PD-150” of Dainippon Ink & Chemicals, Inc. as a biodegradable reinforcing agent, at the ratios shown in Tables 1 to 8. After blending, the pellets were melt kneaded at a barrel temperature of 200 ° C. and a screw rotation speed of 150 rpm using a same-direction twin screw extruder (φ30 mm, L / D = 28, PCM30-28.5 manufactured by Ikegai Co., Ltd.). It was shaped into a shape.
Each pellet obtained was measured for Charpy impact strength, total light transmittance, HAZE, deflection temperature under load, melt flow rate (MFR), bending stress and bending elastic modulus. The results are shown in Tables 1-8.

Charpy impact strength:
A test piece having a width of 10 mm, a height of 4 mm, and a length of 12.7 mm was molded by the injection molding method using the thermoplastic resin composition pellets, and the Charpy impact strength was measured at 23 ° C. according to JIS K-7111.
Total light transmittance:
Using the thermoplastic resin composition pellets, a 10 cm square plate was molded by an injection molding method and measured according to ASTM D1003.
HAZE:
Using the thermoplastic resin composition pellets, a 10 cm square plate was molded by an injection molding method and measured according to ASTM D1003.
Deflection temperature under load:
A test piece having a width of 10 mm, a height of 4 mm, and a length of 12.7 mm was molded by an injection molding method and measured under a load of 1.80 MPa according to ISO75.
Melt flow rate (MFR):
The MFR of the thermoplastic resin composition pellets was measured under the conditions of a load of 37.3 N and 200 ° C. according to ASTM D1238.
Bending stress / flexural modulus:
Measurement was performed according to ASTM D-790 using a test piece having a width of 10 mm, a height of 4 mm, and a length of 12.7 mm by an injection molding method.

  The thermoplastic resin composition of the present invention improves the heat resistance and impact resistance of the polylactic acid polymer while maintaining the transparency of the polylactic acid polymer. Therefore, it becomes possible to use polylactic acid polymers as substitutes for conventional petroleum-based general-purpose plastics such as transparent polyvinyl chloride resin and polyethylene terephthalate, as well as miscellaneous goods such as building materials, automobiles, toys, and stationery, and automobile parts. It can be widely used for molded products that require impact resistance, such as office automation equipment and home appliances.

Claims (1)

Contains a polylactic acid polymer (A), a polymer (B) containing an aromatic alkenyl, and a rubbery polymer (C), and contains a polylactic acid polymer (A) and an aromatic alkenyl. A polylactic acid-based thermoplastic resin composition having a composition ratio (mass ratio) to the polymer (B) of 1/99 to 99/1.