JP2023143798A - Polymer-containing composition and resin composition - Google Patents

Abstract

To provide a polymer-containing composition which improves impact resistant properties.SOLUTION: There is provided a composition which comprises a polymer (A) having a core portion containing a rubbery polymer and a graft portion, which is a diene-based rubber, an acrylic rubber, a silicone-based rubber or a composite rubber combining these rubbers, and a polyorganosiloxane (B).SELECTED DRAWING: None

Description

The present invention relates to polymer-containing compositions and resin compositions.

Thermoplastic resins are used in various fields, but it is often difficult to obtain desired performance using only one type of resin. In such cases, it is known to use rubber-containing polymers such as acrylic and diene polymers together with the resin in order to modify the properties of the resin and obtain desired performance. For example, Patent Document 1 discloses that a rubber-modified thermoplastic resin having specific physical properties obtained by graft polymerizing a specific amount of a vinyl monomer in the presence of a specific ethylene-α-olefin rubber is blended. A rubber-modified styrenic thermoplastic resin composition is described that has an excellent balance of sliding properties, impact resistance, molded product surface appearance, scratch resistance, and flame retardancy, and molded products made from the composition are It is disclosed that it has a beautiful shiny appearance and excellent weather resistance.

Japanese Patent Application Publication No. 2000-119477

Generally, when such resin compositions are used for applications such as vehicle parts, further improvement in impact resistance properties is required. However, according to studies conducted by the present inventors, it has been found that the molded article obtained using the resin composition described in Patent Document 1 may have insufficient impact resistance properties. Therefore, an object of the present invention is to provide a composition containing a polymer that improves impact resistance properties.

As a result of intensive studies aimed at solving the above problems, the present inventors discovered that the impact resistance properties of molded articles obtained by adding a specific composition containing a polymer to a thermoplastic resin improved, and the present invention The invention was achieved. That is, the gist of the present invention is as follows.

[1] Polymer (A) having a core portion containing a rubbery polymer and a graft portion, which is a diene rubber, an acrylic rubber, a silicone rubber, or a composite rubber that is a combination of these rubbers.
and a polyorganosiloxane (B).
[2] The graft portion has a structural unit derived from methyl methacrylate, and the graft portion 10
The composition according to [1], wherein the proportion of the structural unit derived from methyl methacrylate in 0 parts by mass is 10 parts by mass or more.
[3] The rubbery polymer is a composite rubber containing an acrylic component and a silicone component containing an organosiloxane unit as a constitutional unit, and the amount of the organosiloxane constitutional unit based on 100 parts by mass of the rubbery polymer is The proportion is 1 part by mass or more and 20 parts by mass or less, [1
] or the composition according to [2].
[4] The weight average molecular weight of the polyorganosiloxane (B) is 250 or more and 1,000.0
00 or less, the composition according to any one of [1] to [3].
[5] The composition according to any one of [1] to [4], wherein the polyorganosiloxane (B) is silicone oil.
[6] The polyorganosiloxane (B) is silicone oil and has a viscosity of 10 to 5.
000,000 cSt, the composition according to any one of [1] to [5].
[7] The ratio of polyorganosiloxane (B) to 100 parts by mass of the polymer (A) is 1
The composition according to any one of [1] to [6], which contains 200 parts by mass or more and 200 parts by mass or less.
[8] A resin composition comprising a thermoplastic resin and the composition according to any one of [1] to [7].
[9] The resin composition according to [8], wherein the thermoplastic resin is a styrene resin.
[10] The resin composition according to [9], wherein the styrenic resin is an acrylonitrile-styrene copolymer.
[11] The ratio of the composition to 100 parts by mass of the thermoplastic resin is 1 part by mass or more 100 parts by mass
The resin composition according to any one of [8] to [10], which is not more than parts by mass.
[12] A molded article obtained by molding the resin composition according to any one of [8] to [11].

According to the present invention, it is possible to provide a composition for a resin additive containing a polymer for improving impact resistance properties. Furthermore, it is possible to provide a resin composition for obtaining a molded article having high impact resistance properties.

This embodiment will be described in detail below. Note that what is described below is one embodiment of the present invention, and the present invention is not limited to the following configuration.

<1. Polymer-containing composition>
The composition according to the present embodiment includes a polymer (A) having a core portion containing a rubbery polymer and a graft portion, and a polyorganosiloxane (B). The composition can be used as an additive composition for resin modification in order to improve the impact resistance properties of the molded product obtained. Although the mechanism by which the impact resistance of the resulting molded article is improved by adding the composition to the thermoplastic resin is not clear, the following reasons are considered.

When molding a molded article such as a sheet or film using a thermoplastic resin, it is preferable to add a specific polymer as a resin modifier for imparting elasticity, but polyorganosiloxane (B) may also be added. It is thought that by adding it, the polyorganosiloxane (B) takes a fluid state and impregnates or adheres to the polymer (A) to form a composite state during film forming. It is thought that the impact resistance of the molded product obtained by forming this composite state is dramatically improved.

<1-1. Polymer (A)>
The polymer (A) is a graft polymer having a core portion containing a rubbery polymer and a graft portion. That is, the polymer (A) is a graft polymer having a core-shell structure consisting of a core portion containing a rubbery polymer and a graft portion forming a shell structure. In addition, polymer (
A) can be produced by graft polymerizing monomers of the structural units constituting the graft portion in the presence of a rubbery polymer. In addition, in the present invention, the rubbery polymer means a polymer having a glass transition temperature of 0° C. or lower. The glass transition temperature of the polymer can be measured using differential scanning calorimetry (DSC) in accordance with JIS K-7121-1987. In order to have rubber elasticity, it is sufficient that the polymer has a rubber structure having a crosslinked structure. There is no particular limitation on the crosslinked structure, and it may be a chemical crosslink or a physical crosslink. Among these, chemical crosslinking is preferred from the viewpoint of stability during molding. In order to have a chemically crosslinked structure, the polymer preferably contains a crosslinkable monomer constituting the polymer, and is preferably contained in an amount of 0.01 part by mass or more in 100 parts by mass of the polymer.

The rubbery polymer is selected from conjugated diene rubber, acrylic rubber, silicone rubber, or a composite rubber that is a combination of these rubbers. Note that the conjugated diene rubber is a rubber containing a conjugated diene component, the acrylic rubber is a rubber containing an acrylic component, and the silicone rubber is a rubber containing a silicone component. These rubbery polymers have good compatibility with polyorganosiloxane (B) and can improve the impact resistance of the resulting molded product.

The conjugated diene rubber is not particularly limited, but is preferably a polymer containing alkylene as a constituent unit. Examples of the polymer containing alkylene as a structural unit include butadiene rubber, isopropylene rubber, chloroprene rubber, butyl rubber, and among them, butadiene rubber is preferred. There are no particular restrictions on the butadiene rubber, but preferably,
Examples include polybutadiene, acrylonitrile-butadiene rubber, and styrene-butadiene rubber.

The acrylic rubber is not particularly limited, but is preferably a polymer containing (meth)acrylate alkyl ester units as constituent units. Examples of the (meth)acrylate alkyl ester unit include methyl acrylate, ethyl acrylate, n-
Propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n
- Alkyl acrylates such as octyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl A rubbery polymer having an alkyl methacrylate such as methacrylate as a constituent unit is preferable. Among them, ethyl acrylate, n
It is preferable to contain at least one monomer selected from the group consisting of -butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate, and more preferably to contain n-butyl acrylate. These monomers can be used alone or in combination of two or more.

The silicone rubber is not particularly limited, but includes polymers containing organosiloxane units as constituent units. Examples of organosiloxanes include chain organosiloxanes, alkoxysilane compounds, and cyclic organosiloxanes. Among these, alkoxysilane compounds or cyclic organosiloxanes are preferred, and cyclic organosiloxanes are particularly preferred because of their high polymerization stability and high polymerization rate.

The alkoxysilane compound is not particularly limited, but bifunctional alkoxysilane compounds are preferred, such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethoxydiethylsilane, dipropoxydimethylsilane, diphenyldimethoxysilane, diphenyldiethoxysilane, etc. Examples include silane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, and the like. These can be used alone or in combination of two or more.

The cyclic organosiloxane is preferably a 3- to 7-membered ring, such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethylcyclotrisiloxane, etc. Examples include methyltetraphenylcyclotetrasiloxane and octaphenylcyclotetrasiloxane. These can be used alone or in combination of two or more. Among these, octamethylcyclotetrasiloxane is preferred because the particle size distribution can be easily controlled.

As the organosiloxane, at least one selected from the group consisting of cyclic dimethylsiloxane and bifunctional dialkylsilane compounds is preferable from the viewpoint of obtaining a polymer (A) that can further increase the impact strength of the molded article.
Cyclic dimethylsiloxane is a cyclic siloxane having two methyl groups on a silicon atom, and includes hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like. These can be used alone or in combination of two or more.

The bifunctional dialkylsilane compound is a silane compound having two alkoxy groups and two alkyl groups on a silicon atom, and examples include dimethyldimethoxysilane, dimethyldiethoxysilane, diethoxydiethylsilane, and dipropoxydimethylsilane. These can be used alone or in combination of two or more.
As the siloxane crosslinking agent, one having a siloxy group is preferable. Examples of the siloxane crosslinking agent include trifunctional or tetrafunctional silane crosslinking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, and tetrabutoxysilane. Examples include agents. Among these, tetrafunctional crosslinking agents are preferred, and tetraethoxysilane is more preferred.

Among these rubbery polymers, acrylic rubber, silicone rubber, or composite rubber of acrylic rubber and silicone rubber are preferred because they have good weather resistance and impact resistance when added to thermoplastic resins. are preferred, and among them, composite rubber of acrylic rubber and silicone rubber is more preferred.
When the rubbery polymer is a composite rubber of acrylic rubber and silicone rubber, that is, the rubbery polymer is a composite rubber containing an acrylic component and a silicone component containing organosiloxane units as constituent units. In this case, the ratio of organosiloxane structural units to 100 parts by mass of the rubbery polymer is not particularly limited;
It is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and particularly preferably 3 parts by mass or more. In addition, from the viewpoint of the appearance of the molded article, the amount is preferably 90 parts by mass or less, more preferably 70 parts by mass or less, particularly preferably 50 parts by mass or less, and preferably 20 parts by mass or less. Most preferred.

There are no particular restrictions on the method for producing the rubbery polymer, and it can be produced by any known method. In particular, methods such as emulsion polymerization or suspension polymerization of monomers in water in the presence of an emulsifier, solution polymerization in an organic solvent, and interfacial polymerization between two phases can be used. Emulsion polymerization is preferred from the viewpoint of easy introduction of the graft portion following the rubbery polymer. In addition, when producing a rubbery polymer by combining two or more types of monomer components, in addition to the method of polymerizing two or more types of monomer components at the same time, it is also possible to polymerize some of the monomer components. There is also a stepwise method in which other monomer components are subsequently polymerized.

The graft portion of the polymer (A), that is, the shell portion of the core-shell structure is not particularly limited, but preferably contains a structural unit derived from methyl methacrylate. In particular, the proportion of the structural units derived from methyl methacrylate in 100 parts by mass of all the structural units constituting the graft part is not particularly limited, but in order to improve the composite with polyorganosiloxane (B), The amount is preferably at least 15 parts by weight, more preferably at least 15 parts by weight, particularly preferably at least 20 parts by weight, even more preferably at least 30 parts by weight, and most preferably at least 50 parts by weight.

In addition to the structural unit derived from methyl methacrylate, the graft portion may contain a structural unit derived from other vinyl monomers. There are no particular restrictions on other vinyl monomers, but
(meth)acrylic acid alkyl esters other than methyl methacrylate, aromatic vinyl monomers,
Examples include vinyl cyanide monomers and (meth)acrylic group-modified silicone monomers. The graft portion of the polymer (A) may contain two or more types of structural units derived from other vinyl monomers.

There are no particular restrictions on the (meth)acrylic acid alkyl ester other than methyl methacrylate, but examples include ethyl methacrylate, n-butyl methacrylate, methyl acrylate,
Examples include butyl acrylate and n-butyl acrylate.
The aromatic vinyl monomer is not particularly limited, but includes styrene, alkyl-substituted styrene (p-methylstyrene, m-methylstyrene, о-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene). , 3,4-dimethylstyrene, 3,5-dimethylstyrene, p-ethylstyrene, m-ethylstyrene, о-ethylstyrene, etc.), alkyl-substituted isopropenylbenzene (isopropenylbenzene (α-methylstyrene), isopropenyl Examples include toluene, isopropenylethylbenzene, isopropenylpropylbenzene, isopropenylbutylbenzene, isopropenylpentylbenzene, isopropenylhexylbenzene, isopropenioctylbenzene, etc.), 1,1-diphenylethylene, and the like.

The vinyl cyanide monomer unit is not particularly limited, but examples include acrylonitrile and methacrylonitrile.
These can be used alone or in combination of two or more.
The graft portion can be produced by graft polymerizing a monomer component containing methyl methacrylate in the presence of a rubbery polymer (core portion). Graft polymerization can be carried out by a known method, and examples of the emulsifier used include alkali metal salts such as fatty acids, sulfonic acids, sulfuric acids, and phosphoric acids.

The latex polymer obtained by polymerization can be obtained as a powder by coagulating, washing, and drying, or by spraying and collecting. When recovering by coagulation, coagulants include various inorganic or organic acids and their salts, such as sulfuric acid, nitric acid,
Examples include hydrochloric acid, phosphoric acid, phosphorous acid, acetic acid, aluminum sulfate, magnesium sulfate, sodium sulfate, sodium nitrate, aluminum chloride, calcium chloride, sodium chloride, calcium acetate, sodium acetate, and the like. These coagulants may be used alone or in combination of two or more.

The proportion of the core portion, that is, the rubbery polymer, in 100 parts by mass of the polymer (A) is not particularly limited, but in order to improve the impact resistance of the resulting molded product, it is preferably 30 parts by mass or more. The amount is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, and on the other hand, in order to improve the dispersibility in the thermoplastic resin, the amount is preferably 99 parts by mass or less, and 95 parts by mass. It is more preferably at most 90 parts by mass, particularly preferably at most 90 parts by mass.

The proportion of the graft part, that is, the shell part, in 100 parts by mass of the polymer (A) is not particularly limited, but is preferably 1 part by mass or more in order to improve dispersibility in the thermoplastic resin.
It is more preferably 5 parts by mass or more, particularly preferably 10 parts by mass or more,
On the other hand, in order to improve the impact resistance of the molded product obtained, the amount is preferably 70 parts by mass or less, more preferably 60 parts by mass or less, and particularly preferably 50 parts by mass or less.

As mentioned above, the glass transition temperature of the rubbery polymer constituting the core part is not particularly limited as long as it is 0°C or lower; The temperature is preferably −20° C. or lower, particularly preferably −20° C. or lower. In addition, when the rubbery polymer has two or more glass transition temperatures, it is preferable that all the glass transition temperatures are within the above range.

There is no particular restriction on the glass transition temperature of the polymer that constitutes the graft part, that is, the shell part, which constitutes the polymer (A), but from the viewpoint of improving dispersibility in the thermoplastic resin and preventing blocking, it should be 30°C or higher. The temperature is preferably 50°C or higher, more preferably 60°C or higher.
It is particularly preferable that the temperature is 0°C or higher, and on the other hand, in order to improve the impact resistance of the molded product obtained,
The temperature is preferably 150°C or lower, more preferably 140°C or lower, and 120°C or lower.
It is particularly preferable that the temperature is below ℃. Note that in the present invention, the glass transition temperature can be measured by the DSC method.

The weight average molecular weight of the polymer constituting the graft part, that is, the shell part, is not particularly limited, but from the viewpoint of improving dispersibility in the thermoplastic resin, it is preferably 5000 or more, and 10
It is more preferably 000 or more, particularly preferably 20,000 or more, and on the other hand, it is preferably 2,000,000 or less from the viewpoint of a decrease in impact resistance due to a decrease in the density of the polymer constituting the graft part, that is, the shell part. , more preferably 1,000,000 or less, particularly preferably 500,000 or less. In the present invention, the weight average molecular weight of the polymer constituting the graft portion can be measured by gel permeation chromatography (GPC) using a soluble portion in an organic solvent such as THF.

The number average particle diameter of the polymer (A) is not particularly limited, but from the viewpoint of improving dispersibility in thermoplastic resins, it is preferably 10 nm or more, more preferably 30 nm or more, and 50 nm or more. It is particularly preferable that the particle diameter is 70 nm or more, and most preferably 70 nm or more. On the other hand, from the viewpoint of good compounding with the compound, it is preferably 1000 nm or less,
It is more preferably 800 nm or less, particularly preferably 600 nm or less. Although the method for measuring the particle size is not particularly limited, it is measured, for example, by the following method.

Using a sample obtained by diluting the latex of polymer (A) with deionized water to a concentration of approximately 3%, measure the number-based particle size distribution using a capillary type particle size distribution meter (CHDF2000 type particle size distribution meter manufactured by MATEC, USA). The median diameter is taken as the number average particle diameter.
The solvent-insoluble content of the polymer (A) is not particularly limited, but from the viewpoint of improving the impact resistance of the resulting molded product, it is preferably 90% by mass or more, more preferably 92% by mass or more. , 95% by mass or more is particularly preferred. The organic solvent that can be used as the solvent here is one that does not chemically alter the polymer (A) and has sufficient solubility in the case of non-crosslinking of each polymer constituting the polymer (A). If so, there are no particular limitations. From the viewpoint of workability, acetone is preferred because it has high volatility and is easy to distill off the solvent. However, since acetone has low solubility in polymers containing styrene as a main component, tetrahydrofuran (THF) is preferred when the polymer (A) contains styrene. A specific method for measuring the solvent-soluble content and the solvent-free content will be described below.

(Measurement method for solvent soluble and insoluble components)
The solvent-insoluble content is measured by preparing a solution consisting of 1% by mass of polymer (A) and 99% by mass of solvent, and performing the operations (1) to (4) below.
(1) The solution is subjected to centrifugation and centrifuged at 20,000 rpm for 30 minutes.
(2) Extract the supernatant liquid and put it into the flask.
(3) The flask containing the supernatant liquid from (2) is set in a constant temperature bath at 56°C, and volatile components are distilled off from the liquid using an evaporator.
(4) Dry the residue in the flask at a temperature of 120° C. for 3 hours to obtain a “dry sample”.
Measure the mass of the dry sample (solvent soluble content) and calculate the solvent insoluble content using the following formula.
wais=(wc1-was)/wc1×100
wc1: Mass of polymer (A) subjected to measurement was: Mass of solvent-soluble portion Wais: Mass of solvent-insoluble portion.
In the above operation, the "free polymer Pf" is extracted as a solvent-soluble component.

The degree of swelling of the polymer (A) in toluene solvent is not particularly limited, but from the viewpoint of improving the impact resistance due to the crosslinked structure, it is preferably 3 times or more, and more preferably 5 times or more. Preferably, it is particularly preferably 10 times or more. On the other hand, if it is too high, the impact resistance decreases, so it is preferably 50 times or less, more preferably 40 times or less, and 30 times or less. It is particularly preferable that there be. In the present invention, the swelling degree of the polymer (A) in a toluene solvent is a value calculated by the following method.

[How to calculate degree of swelling]
Accurately weigh the dried polymer (A) and put it into a test tube. An excess amount of toluene (approximately 100 times the mass of the dried rubber-containing polymer (A)) is added to the test tube, and the test tube is allowed to stand at 30° C. for 48 hours in a constant temperature water bath. Next, the obtained toluene solution is filtered through a 100-mesh wire mesh, and the mass of the obtained filtrate is defined as W ₁ (g). Finally, the weight of the dried product obtained by drying the filtrate and completely removing toluene is calculated using the following formula (1) as W ₂ (g).
Swelling degree = (W ₁ - W ₂ )/W ₂ (times)...(1)

<1-2. Polyorganosiloxane (B)>
As described above, by containing the polyorganosiloxane (B) in the composition according to the present embodiment, the impact resistance properties of the obtained molded article can be improved. In the present invention, polyorganosiloxane refers to a polymer or oligomer having a (-Si-O-) repeating unit in its main chain and an organic group in its side chain. There are no particular restrictions on organic groups, but
Examples include alkyl groups including methyl groups, phenyl groups, cyclohexyl groups, alkylamino groups, polyether groups, epoxy groups, carboxyl groups, mercapto groups, etc., from the viewpoint of good compatibility with the polymer (A). , an alkyl group or an alkylamino group are preferred.
As for the organic group, a plurality of these may exist. Moreover, from the viewpoint of not interfering with compatibility with the polymer (A), it is preferable that the polyorganosiloxane (B) does not contain crosslinking or long chain branching. Examples of such polyorganosiloxane (B) include dimethyl silicone,
Methylhydrogen silicone, methylphenyl silicone, diphenyl silicone,
Examples include amino-modified silicone, carboxyl-modified silicone, and epoxy-modified silicone. From the above-mentioned viewpoint, dimethyl silicone and amino-modified silicone are preferred.

The weight average molecular weight of the polyorganosiloxane (B) is not particularly limited, but the weight average molecular weight of the polyorganosiloxane (B) is
It is preferable that the number is 200 or more, and 25
It is more preferably 0 or more, particularly preferably 280 or more. On the other hand, if it is too high, it may not be successfully composited with the polymer (A), so it is preferably 1,000,000 or less, and 750,000 or less It is more preferable that it is, it is especially preferable that it is 500,000 or less, it is even more preferable that it is 200,000 or less, and it is 1,000 or less.
00 or less is particularly preferable, and 60,000 or less is most preferable. The weight average molecular weight of polyorganosiloxane (B) was determined according to the conditions described in JISK7252-1.
It means a value determined from a standard polystyrene calibration curve using gel permeation chromatography (GPC) using an organic solvent such as THF.

There are no particular restrictions on the form of the polyorganosiloxane (B), but silicone oil is preferred in order to be difficult to exclude from the polymer (A) and to facilitate compounding. The silicone oil referred to here is a polymer whose main chain is connected by siloxane bonds at room temperature (2.
It is liquid at 3℃).
When the polyorganosiloxane (B) is a liquid, the kinematic viscosity is preferably 10 cSt or more at room temperature (23 ° C.), and 25 cSt or more, in order to make it difficult to exclude from the polymer (A) and to facilitate compounding. It is preferable that it is 40 cSt or more, and more preferably that it is 40 cSt or more. On the other hand, if it is too high, it may not be successfully composited with the polymer (A).
,000,000 cSt or less, more preferably 1,000,000 cSt or less, particularly preferably 500,000 cSt or less, 100,000 cSt or less,
000 cSt or less is most preferable.

The kinematic viscosity of polyorganosiloxane (B) shall mean the value measured by an Ubbelohde viscometer according to JIS Z 8803.
In addition, a commercially available product can also be used as the polyorganosiloxane (B). Examples of such commercially available products include the KF series silicone oil manufactured by Shin-Etsu Chemical Co., Ltd. and the TSF series manufactured by Momentive Performance Materials Japan LLC.

In the polymer-containing composition, polyorganosiloxane (B) is added to 100 parts by mass of polymer (A).
) is not particularly limited, but in order to improve impact resistance, it is preferably 1 part by mass or more, more preferably 3 parts by mass or more, particularly 5 parts by mass or more. Preferably, on the other hand, in order to better combine with the polymer (A), the amount is preferably 200 parts by mass or less, more preferably 160 parts by mass or less, and 120 parts by mass or less. It is more preferably 100 parts by mass, more preferably 80 parts by mass or less, and particularly preferably 50 parts by mass or less.

<1-3. Other ingredients>
The rubber-containing polymer polymer-containing composition includes a polymer (A) and a polyorganosiloxane (B).
It may also contain other components.
Other components that the composition may contain include, but are not particularly limited to, compounds remaining during the production of the composition and various additives.

Compounds remaining during the production of the composition include, for example, emulsifiers, polymerization initiators, chain transfer agents, catalysts, pH adjusters, coagulants, coagulation aids, residual monomer components produced by emulsion polymerization, etc. The preferred content ratio of these is 5 parts by mass or less, more preferably 3 parts by mass or less, and 1 part by mass or less based on 100 parts by mass of the polymer-containing composition in order to improve the physical properties and appearance of the molded article. is particularly preferred.

Additives that may be added in producing the composition are not particularly limited, but include antioxidants, powder fluidity improvers, and the like. There is no particular restriction on the preferred content ratio of these additives, but in order to maintain good physical properties and appearance properties of the molded product, the ratio of the additive to 100 parts by mass of the polymer-containing composition is preferably 5 parts by mass or less, It is more preferably 3 parts by mass or less, particularly preferably 1 part by mass or less.

The composition can be used as an additive composition for modifying resins to improve their impact resistance properties. Films, sheets, etc. can be obtained by molding a resin composition containing a resin and the composition.

<2. Resin composition>
As described above, the resin composition includes at least a thermoplastic resin and a composition containing a polymer (A) and a polyorganosiloxane (B).

<Thermoplastic resin>
Thermoplastic resins are not particularly limited, and include, for example, engineering plastics (aromatic polycarbonates, etc.), styrene resins, polyester resins, olefin resins, thermoplastic elastomers, biodegradable resins, halogen resins (vinyl chloride resins, etc.) ), acrylic resin, etc.

As the engineering plastic, various known thermoplastic engineering plastics can be used without particular limitation. As engineering plastics,
Polyphenylene ether, polycarbonate, polyester polymers (polyethylene terephthalate, polybutylene terephthalate, etc.), syndiotactic polystyrene, nylon polymers (6-nylon, 6,6-nylon, etc.), polyarylate, polyphenylene sulfide, polyether ketone , polyetheretherketone, polysulfone, polyethersulfone, polyamideimide, polyetherimide, and polyacetal.

In addition, special styrene resins such as heat-resistant ABS, heat-resistant acrylic resins, etc., which are highly heat resistant and require melt fluidity, can also be exemplified as engineering plastics in the present invention. Among these, aromatic polycarbonate and polybutylene terephthalate are more preferred when higher strength development is required. Examples of the aromatic polycarbonate include 4,4'-dioxydiarylalkane polycarbonates such as 4,4'-dihydroxydiphenyl-2,2-propane (ie, bisphenol A) polycarbonate.

Examples of olefin resins include high-density polyethylene, medium-density polyethylene, low-density polyethylene, copolymers of ethylene and other α-olefins; polypropylene, copolymers of propylene and other α-olefins; polybutene, poly- Examples include 4-methylpentene-1.
Examples of thermoplastic elastomers include styrene elastomers, urethane elastomers,
Examples include polyolefin elastomers, polyamide elastomers, fluorine elastomers, chlorinated PE elastomers, acrylic elastomers, and the like.

As the styrene elastomer, styrene-butadiene-styrene copolymer (SBS
), styrene-isoprene-styrene copolymer (SIS), styrene-ethylene-butene copolymer (SEB), styrene-ethylene-propylene copolymer (SEP), styrene-
Ethylene-butene-styrene copolymer (SEBS), styrene-ethylene-propylene
Styrene copolymer (SEPS), styrene-ethylene/ethylene/propylene-styrene copolymer (SEEPS), styrene-butadiene/butylene-styrene copolymer (partially hydrogenated styrene-butadiene-styrene copolymer: SBBS) ), styrene-isoprene-
Examples include partially hydrogenated styrene copolymers and partially hydrogenated styrene-isoprene/butadiene-styrene copolymers. "-" indicates that the monomers forming the units connected by "-" are copolymerized, and "・" indicates that they are randomly modified by hydrogenation etc. after copolymerization. Show that.

Examples of urethane-based elastomers include reaction products of polymeric diols, organic diisocyanates, and chain extenders.
Examples of the polymer diol include polyester diol, polyether diol, polyester ether diol, polycarbonate diol, and polyester polycarbonate diol.

Examples of the organic diisocyanate include 4,4'-diphenylmethane diisocyanate, toluene diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate (
4,4'-dicyclohexylmethane diisocyanate), isophorone diisocyanate,
Examples include hexamethylene diisocyanate. Among these organic diisocyanates, 4,4'-diphenylmethane diisocyanate is preferred.

As chain extenders, ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-1,3-propanediol, 1,6-hexanediol, neopentyl glycol, 1,9 -nonanediol, cyclohexanediol, 1,4-bis(β-hydroxyethoxy)benzene and the like.
Examples of the polyolefin elastomer include ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-vinyl acetate copolymer, butyl rubber, butadiene rubber, propylene-butene copolymer, ethylene-acrylic acid ester copolymer, and the like.

Styrene resins include polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-styrene-α-methylstyrene copolymer, acrylonitrile-methyl methacrylate-styrene-α-methylstyrene copolymer, ABS resin, AS resin, MABS.
Resin, MBS resin, AAS resin, AES resin, acrylonitrile-butadiene-styrene-α-methylstyrene copolymer, acrylonitrile-methyl methacrylate-butadiene-styrene-α-methylstyrene copolymer, styrene-maleic anhydride copolymer , styrene-maleimide copolymer, styrene-N-substituted maleimide copolymer, acrylonitrile-
Styrene-N-substituted maleimide copolymer, acrylonitrile-butadiene-styrene-β
-Isopropenylnaphthalene copolymer and acrylonitrile-methyl methacrylate-
Examples include butadiene-styrene-α-methylstyrene-maleimide copolymer.

The polyester resin is a polymer of a polybasic acid and a polyhydric alcohol, and is not particularly limited as long as it has thermoplasticity. Examples of polybasic acids include terephthalic acid, naphthaldicarboxylic acid, cyclohexyldicarboxylic acid, and esters thereof. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, butanediol, pentanediol, neopentyl glycol, hexanediol, octanediol, decanediol, cyclohexanedimethanol, hydroquinone, bisphenol A, 2,2-bis(4-hydroxyethoxy) phenyl)propane, 1,4-dimethyloltetrabromobenzene, tetrabromobisphenol A bis(2-hydroxyethyl)ether (TBA
-EO), etc.

The polyester resin may be a homopolymer, a copolymer, or a blend of two or more thereof.
As the polyester resin, commercially available products such as "PETG" manufactured by Eastman Chemical Co., Ltd. may be used.
Examples of biodegradable resins include microbial polymers, chemically synthesized polymers, and natural product polymers.

Examples of microbial polymers include biopolyesters such as polyhydroxybutyrate/valerate (PHB/V), bacterial cellulose, and microbial polysaccharides (pullulan, curdlan, etc.)
etc.
Examples of chemically synthesized polymers include aliphatic polyesters (polycaprolactone, polybutylene succinate, polyethylene succinate, polyglycolic acid, polylactic acid, etc.), polyvinyl alcohol, polyamino acids (PMLG, etc.), and the like.
Examples of natural polymers include chitosan, cellulose, starch, cellulose acetate, and the like.

As the halogen-based resin, for example, a homopolymer of vinyl chloride, 80% by mass of vinyl chloride
Examples include copolymers and vinyl chloride resins such as highly chlorinated polyvinyl chloride contained in the above proportions. In addition to vinyl chloride, examples of components of the copolymer include monovinylidene compounds such as ethylene, vinyl acetate, methyl methacrylate, and butyl acrylate. The copolymer may contain these compounds in a total amount of 20% by mass or less.
Examples of the halogen-based resin include vinyl chloride resins, as well as fluorinated polymers, brominated polymers, iodinated polymers, and the like.

Examples of the acrylic resin include a copolymer obtained by polymerizing methyl methacrylate and a copolymerizable vinyl monomer. Copolymerizable vinyl monomers include alkyl acrylates such as methyl acrylate, ethyl acrylate, i-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, ethyl methacrylate,
Examples include alkyl methacrylates such as propyl methacrylate and n-butyl methacrylate, and aromatic vinyl compounds such as styrene, α-methylstyrene and vinyltoluene.

Polyester resins such as polyphenylene ether, polycarbonate, polyethylene terephthalate and polybutylene terephthalate, syndiotactic polystyrene, 6-
Polyamide resins such as nylon and 6,6-nylon, engineering plastics such as polyarylate, polyphenylene sulfide, polyetherketone, polyetheretherketone, polysulfone, polyethersulfone, polyamideimide, polyetherimide, polyacetal, etc. Polymer alloys with thermoplastic resins are also included within the scope of thermoplastic resins in the present invention.

These thermoplastic resins may be used alone or in combination of two or more.
Among the above, the thermoplastic resin is preferably a styrene resin. In particular, when a styrene resin and the above polymer-containing composition are used together as a thermoplastic resin, the resulting resin has a higher resistance than when other thermoplastic resins and the polymer-containing composition are used together. Impact properties tend to be significantly improved. In particular, the impact resistance at low temperatures, which is generally difficult to improve, is significantly improved compared to when other resins are used. Among these, acrylonitrile-styrene copolymer is particularly preferred.

There is no particular restriction on the weight average molecular weight of the thermoplastic resin, but from the viewpoint of mechanical properties of the molded product,
It is preferably 1,000 or more, more preferably 10,000 or more, and 20
000 or more, and on the other hand, from the viewpoint of moldability, it is preferably 1,000,000 or less, more preferably 750,000 or less, and 500,000 or less.
The following is particularly preferable. Note that the weight average molecular weight means a value determined from a standard polystyrene calibration curve by gel permeation chromatography (GPC) using an organic solvent such as THF according to the conditions described in JIS K7252-1.

Examples of the composition contained in the resin composition include the compositions listed above, and the polymer (A) and polyorganosiloxane (B) may also be the same as those mentioned above.
In the resin composition, the ratio of the polymer-containing composition to 100 parts by mass of the thermoplastic resin is not particularly limited, but in order to improve impact resistance, it is preferably 1 part by mass or more, and 3 parts by mass or more. More preferably, the amount is at least 5 parts by mass, particularly preferably at least 5 parts by mass, and most preferably at least 10 parts by mass. On the other hand, in order to suppress a decrease in fluidity and heat deformation resistance temperature of the molded article, the amount is preferably 100 parts by mass or less, more preferably 90 parts by mass or less, and particularly preferably 80 parts by mass or less. , most preferably 70 parts by mass or less.

The resin composition may contain other components as long as they do not impair the effects of the present invention.
Such components include various well-known additives. Examples of such additives include stabilizers, flame retardants, flame retardant aids, hydrolysis inhibitors, antistatic agents, blowing agents, dyes, pigments, and the like. In addition, the resin composition may contain the additives and components derived from polymer production mentioned above for the polymer-containing composition. Note that the content ratio of these other components to 100 parts by mass of the resin composition is not particularly limited, but is preferably 0.01 parts by mass or more and 10 parts by mass or less.

There are no particular restrictions on the method of blending each component when producing a resin composition as long as a desired resin composition can be obtained, and examples include known blending methods. Examples include methods of mixing and kneading with a tumbler, V-type blender, super mixer, Nauta mixer, Banbury mixer, kneading roll, extruder, etc.
A molded article can be produced by molding the resin composition. There are no particular restrictions on the molding method, and known molding methods commonly used for molding thermoplastic resin compositions may be used, such as injection molding, extrusion molding, blow molding, calendar molding, etc. It will be done. The temperature during molding is not particularly limited, and is usually 150°C or higher and 500°C or lower.

This molded article can be applied to various uses. Specifically, it can be widely used industrially as a variety of materials in the automobile field, OA equipment field, home appliances, electric/electronic field, architecture field, lifestyle/cosmetics field, medical supplies field, etc. More specifically, it can be used as housings for electronic devices, various parts, covering materials, automobile structural members, automobile interior parts, light reflecting plates, building structural members, fittings, and the like. More specifically, our products include computer housings, mobile phone housings, mobile information terminal housings, mobile game machine housings, interior and exterior materials for printers, copiers, etc., conductive coating materials, automobile interior and exterior materials, and buildings. It can be used as exterior materials, resin window frame members, flooring materials, piping members, etc. In particular, the molded product obtained according to this embodiment has excellent impact resistance properties, and therefore can be suitably used as an automobile material.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. In addition, in the examples, various measurement methods used are as follows.

(Calculation of polymerization rate of polymer latex)
The polymerization rate is calculated as follows: X is the mass of an aluminum plate measured to the nearest 0.1 mg, Y is the mass of an aluminum plate on which a specific amount of polymer latex measured to the nearest 0.1 mg is placed, and the aluminum plate is After heating in a dryer at 180 ° C for 45 minutes and cooling to 24 ° C in a desiccator, the mass of the aluminum plate measured to the nearest 0.1 mg is defined as Z, and the solid content is calculated using the following formula (2). .
(Z-X)/(Y-X)×100[%]...(2)
The solid content obtained by the above formula (2) is divided by the solid content at the time of charging to calculate the polymerization rate of the polymer.

[Measurement of particle size]
Using a latex diluted with deionized water to a solid content concentration of approximately 3% as a sample, the number average particle diameter Dn and mass average particle The diameter Dw was measured. Cartridge: Dedicated capillary cartridge for particle separation (product name: C-202), Carrier liquid: Dedicated carrier liquid (product name: 2X
GR500),
Liquidity of carrier liquid: Neutral,
Carrier liquid flow rate: 1.4 mL/min,
Carrier liquid pressure: 4,000 psi (2,600 kPa),
Measurement temperature: 35℃,
Sample usage amount: 0.1 mL.

[Measurement of weight average molecular weight of THF soluble content]
The weight average molecular weight of the THF soluble component was measured by performing the following operations (2-1) to (2-3).

(2-1) THF is distilled off under reduced pressure using a rotary evaporator from the liquid containing the THF-soluble content collected in the previous section [Measurement of THF-insoluble content] to obtain the THF-soluble content.

(2-2) The THF-soluble content obtained in the above (2-1) is redissolved in THF to a sample concentration of 0.1 to 0.3% to obtain a THF solution of the THF-soluble content. .

(2-3) Gel permeation chromatography (GPC) is performed on the THF solution of the THF-soluble component obtained in (2-2) above, and the weight average molecular weight (Mw) is determined from a standard polystyrene calibration curve.
The GPC measurement conditions are as follows.
Equipment: “HLC8220” manufactured by Tosoh Corporation
Column: “TSKgel SuperMultiporeHZ-H” manufactured by Tosoh Corporation (inner diameter 4.6 mm x length 15 cm x 2, exclusion limit 4 x 107 (estimated))
Eluent: THF
Eluent flow rate: 0.35mL/min Measurement temperature: 40℃
Sample injection volume: 10μL

<Production Example 1: Production of polymer (A-1)>
98 parts of cyclic organosiloxane mixture (manufactured by Shin-Etsu Silicone Co., Ltd., product name: DMC, mixture of 3- to 6-membered cyclic organosiloxanes) and 3-methacryloxypropylmethyldimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., product name) :KBM-502) were mixed to obtain 100 parts of an organosiloxane mixture. An aqueous solution of 0.7 parts of sodium dodecylbenzenesulfonate (DBSNa, manufactured by Kao Corporation, product name: Neoperex G-15, solid content equivalent) dissolved in 300 parts of deionized water was added to the mixture. , 10 in homomixer
After stirring at ,000 rpm for 5 minutes, the mixture was passed through a homogenizer twice at a pressure of 20 MPa to obtain a stable premixed emulsion. Dodecylbenzenesulfonic acid (DBSH
After adding an aqueous solution containing 15 parts of Neoperex GS (manufactured by Kao Corporation, product name: Neoperex GS), the aqueous solution was heated to a temperature of 80°C, and then the above emulsion was continuously added for 240 minutes to initiate a polymerization reaction. After that, the reaction solution was cooled to 25° C., and a 5% aqueous sodium hydroxide solution was added to neutralize the reaction solution to pH 7.0 to obtain a polyorganosiloxane latex. The solids content of this latex was 20%. Further, the number average particle diameter (Dn) of this latex measured by a capillary particle size distribution meter was 26 nm, the mass average particle diameter (Dw) was 35 nm, and Dw/Dn was 1.35.

Next, 18 parts of the obtained rubbery polymer latex (3.0 parts in terms of polymer) was collected in a separable flask with a capacity of 5 liters, and 170 parts of deionized water was added and mixed. Next, in this separable flask, 76.6 parts of n-butyl acrylate (nBA), 0.4 parts of allyl methacrylate (AMA), and 0 parts of sodium dodecylbenzenesulfonate (DBSNa) were added.
．． 3 parts were added, the atmosphere inside the flask was replaced with nitrogen by passing a nitrogen stream, the liquid temperature was raised to 43° C., and the mixture was stirred for 1 hour. Radical polymerization was started by adding 0.15 parts of potassium persulfate (KPS), and after stirring for 10 hours and confirming the exothermic peak of polymerization, it was cooled to 25°C and
Polymerization was completed by holding for 5 hours, and a polymer latex was obtained.

This polymer latex was heated to 80°C, and 20 parts of methyl methacrylate (MMA) was added to 0.
．． It was added dropwise into this latex at a rate of 6 parts/min to initiate the graft polymerization reaction. After the dropwise addition was completed, the temperature was maintained at 80°C for 1 hour, and then cooled to 25°C to obtain a latex of polymer (A-1). The solid content of this latex was 35%, and the polymerization rate was 99.9% or more. This polymerization rate is the polymerization rate of the monomer components used in all steps from production of the rubbery polymer to graft polymerization. The number average particle diameter (Dn) of the polymer (A-1) latex measured by a capillary particle size distribution meter is 94 nm, the mass average particle diameter (Dw) is 105 nm, and Dw
/Dn was 1.12.

Next, 630 parts of an aqueous solution of calcium acetate having a concentration of 0.8% was heated to 50° C., and while stirring, the polymer (A-1) latex was gradually dropped into the aqueous solution and solidified. The obtained polymer (A-1) was filtered, washed, dehydrated, and then dried to obtain a powder of polymer (A-1). The ratio of THF-insoluble matter in polymer (A-1) was 95%. Further, the weight average molecular weight of the THF soluble portion was 230,000.

<Production Example 2: Production of polymer (A-2)>
98 parts of cyclic organosiloxane mixture (manufactured by Shin-Etsu Silicone Co., Ltd., product name: DMC, mixture of 3- to 6-membered cyclic organosiloxanes) and 3-methacryloxypropylmethyldimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., product name) :KBM-502) were mixed to obtain 100 parts of an organosiloxane mixture. An aqueous solution of 0.7 parts of sodium dodecylbenzenesulfonate (DBSNa, manufactured by Kao Corporation, product name: Neoperex G-15, solid content equivalent) dissolved in 300 parts of deionized water was added to the mixture. , 10 in homomixer
After stirring at ,000 rpm for 5 minutes, the mixture was passed through a homogenizer twice at a pressure of 20 MPa to obtain a stable premixed emulsion. Dodecylbenzenesulfonic acid (DBSH
After adding an aqueous solution containing 15 parts of Neoperex GS (manufactured by Kao Corporation, product name: Neoperex GS), the aqueous solution was heated to a temperature of 80°C, and then the above emulsion was continuously added for 240 minutes to initiate a polymerization reaction. After that, the reaction solution was cooled to 25° C., and a 5% aqueous sodium hydroxide solution was added to neutralize the reaction solution to pH 7.0 to obtain a polyorganosiloxane latex. The solids content of this latex was 20%. Further, the number average particle diameter (Dn) of this latex measured by a capillary particle size distribution meter was 26 nm, the mass average particle diameter (Dw) was 35 nm, and Dw/Dn was 1.35.

Next, 25 parts of the obtained rubbery polymer latex (5.0 parts in terms of polymer) was collected into a separable flask with a capacity of 5 liters, and 170 parts of deionized water was added and mixed. Next, in this separable flask, 62.5 parts of n-butyl acrylate (nBA), 2.5 parts of allyl methacrylate (AMA), and sodium dodecylbenzenesulfonate (DBSNa) were added.
), the atmosphere inside the flask was replaced with nitrogen by passing a nitrogen stream,
The liquid temperature was raised to 43°C and stirred for 1 hour. Radical polymerization was started by adding 0.15 parts of potassium persulfate (KPS), and after stirring for 10 hours and confirming the exothermic peak of polymerization, the polymerization was completed by cooling to 25°C and holding for 15 hours, resulting in a polymer latex. I got it.

This polymer latex was heated to 80°C, and 25.5 parts of styrene and 4.0 parts of acrylonitrile were added.
5 parts were dropped into this latex at a rate of 0.6 parts/min to initiate the graft polymerization reaction. After the dropwise addition was completed, the temperature was maintained at 80°C for 1 hour, and then cooled to 25°C to form the polymer (A-2).
of latex was obtained. The solid content of this latex was 35%, and the polymerization rate was 99.9% or more. This polymerization rate is the polymerization rate of the monomer components used in all steps from production of the rubbery polymer to graft polymerization. The number average particle diameter (Dn) of the polymer (A-2) latex measured by a capillary particle size distribution analyzer was 93 nm, the mass average particle diameter (Dw) was 99 nm, and Dw/Dn was 1.06.

Next, 630 parts of an aqueous solution of calcium acetate having a concentration of 0.8% was heated to 50° C., and while stirring, the polymer (A-2) latex was gradually dropped into the aqueous solution and solidified. The obtained polymer (A-2) was filtered, washed, dehydrated, and then dried to obtain a powder of polymer (A-2). The ratio of THF-insoluble matter in polymer (A-2) was 96%. Further, the weight average molecular weight of the THF-soluble portion was 160,000, and the proportion of the structural unit derived from methyl methacrylate in 100 parts by mass of the graft portion was 0 parts by mass.

<Production Example 3: Production of polymer (A-3)>
98 parts of cyclic organosiloxane mixture (manufactured by Shin-Etsu Silicone Co., Ltd., product name: DMC, mixture of 3- to 6-membered cyclic organosiloxanes) and 3-methacryloxypropylmethyldimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., product name) :KBM-502) were mixed to obtain 100 parts of an organosiloxane mixture. An aqueous solution of 0.7 parts of sodium dodecylbenzenesulfonate (DBSNa, manufactured by Kao Corporation, product name: Neoperex G-15, solid content equivalent) dissolved in 300 parts of deionized water was added to the mixture. , 10 in homomixer
After stirring at ,000 rpm for 5 minutes, the mixture was passed through a homogenizer twice at a pressure of 20 MPa to obtain a stable premixed emulsion. Dodecylbenzenesulfonic acid (DBSH
After adding an aqueous solution containing 15 parts of Neoperex GS (manufactured by Kao Corporation, product name: Neoperex GS), the aqueous solution was heated to a temperature of 80°C, and then the above emulsion was continuously added for 240 minutes to initiate a polymerization reaction. After that, the reaction solution was cooled to 25° C., and a 5% aqueous sodium hydroxide solution was added to neutralize the reaction solution to pH 7.0 to obtain a polyorganosiloxane latex. The solids content of this latex was 20%. Further, the number average particle diameter (Dn) of this latex measured by a capillary particle size distribution meter was 26 nm, the mass average particle diameter (Dw) was 35 nm, and Dw/Dn was 1.35.

Next, 35 parts of the obtained rubbery polymer latex (7.0 parts in terms of polymer) was collected into a separable flask with a capacity of 5 liters, and 170 parts of deionized water was added and mixed. Next, in this separable flask, 43 parts of n-butyl acrylate (nBA), 0.26 parts of allyl methacrylate (AMA), and sodium dodecylbenzenesulfonate (DBSNa) were added.
0.3 part of the flask was added, the atmosphere inside the flask was replaced with nitrogen by passing a nitrogen stream through the flask, the liquid temperature was raised to 43° C., and the mixture was stirred for 1 hour. Radical polymerization was started by adding 0.15 parts of potassium persulfate (KPS), and after stirring for 10 hours and confirming the exothermic peak of polymerization, the polymerization was completed by cooling to 25°C and holding for 15 hours, resulting in a polymer latex. I got it.

This polymer latex was heated to 80°C, and 37.5 parts of styrene and 12 parts of acrylonitrile were added.
．． 5 parts were dropped into this latex at a rate of 0.6 parts/min to initiate the graft polymerization reaction. After the dropwise addition was completed, the temperature was maintained at 80°C for 1 hour, and then cooled to 25°C to form the polymer (A-3
) latex was obtained. The solid content of this latex was 30%, and the polymerization rate was 99.9% or more. This polymerization rate is the polymerization rate of the monomer components used in all steps from production of the rubbery polymer to graft polymerization. The number average particle diameter (Dn) of the polymer (A-3) latex measured by a capillary particle size distribution meter is 108 nm, and the mass average particle diameter (Dw) is 112 nm.
and Dw/Dn was 1.04.

Next, 630 parts of an aqueous solution of calcium acetate having a concentration of 0.8% was heated to 50° C., and while stirring, the polymer (A-3) latex was gradually dropped into the aqueous solution and solidified. The obtained polymer (A-3) was filtered, washed, dehydrated, and then dried to obtain a powder of polymer (A-3). The ratio of THF-insoluble matter in polymer (A-3) was 70%. Further, the weight average molecular weight of the THF-soluble portion was 170,000, and the proportion of the structural unit derived from methyl methacrylate in 100 parts by mass of the graft portion was 0 parts by mass.

As the polyorganosiloxane (B), the compounds listed in Table 1 were used.
(B-1) Amino-modified silicone oil: TSF-4700 (Momentive Performance Ma
terials Inc.)
(B-2) Amino-modified silicone oil: KF-8002 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(B-3) Silicone oil: KF-96-1000 (manufactured by Shin-Etsu Chemical Co., Ltd.)

(Manufacture of polymer-containing composition)
100 parts by mass of the polymer (A) and 10 parts by mass of the polyorganosiloxane (B) were placed in a Henschel mixer and mixed for 10 minutes at a rotational speed of 300 rpm to obtain a polymer-containing composition.

<Examples 1 to 13 and Comparative Examples 1 to 6>
As the thermoplastic resin, styrene-acrylonitrile copolymer (manufactured by Techno UMG Co., Ltd.,
Product name: AP-H) and the polymer-containing composition were blended in the proportions shown in Table 2, and the mixture was heated using a twin-screw extruder ((
PCM-30) manufactured by Ikegai Co., Ltd., and melted and kneaded at 240°C to obtain a resin composition.
The obtained resin composition was injection molded under the following conditions to produce a molded article.
Injection molding machine: manufactured by Sumitomo Heavy Industries, Ltd., SE100DU (product name)
Cylinder temperature: 240℃, mold temperature: 80℃
Specimen specifications: length 80mm x width 10mm x thickness 4mm

The following evaluations were performed using the molded bodies obtained in Examples 1 to 13 and Comparative Examples 1 to 6.
(Charpy impact test)
A notch of TYPE A in accordance with ISO 179-1 was cut on the test piece A, and the temperature was 23°C.
Charpy impact strength was measured at -30°C. The higher the numerical value, the better the impact resistance, which is preferable. The results obtained are shown in Tables 2 and 3.

As is clear from Tables 2 and 3, the molded bodies of the resin compositions obtained in Examples 1 to 13 had dramatically improved impact resistance. This can be said to be an effect due to the polymer composition. On the other hand, comparative example 1~
6, when the polymer (A) and/or polyorganosiloxane (B) is not included, the impact resistance is poor.

Claims (12)

A polymer (A) having a core part containing a rubbery polymer and a graft part, which is a diene rubber, an acrylic rubber, a silicone rubber, or a composite rubber made of a combination of these rubbers;
A composition comprising a polyorganosiloxane (B). The composition according to claim 1, wherein the graft portion has a structural unit derived from methyl methacrylate, and the proportion of the structural unit derived from methyl methacrylate in 100 parts by mass of the graft portion is 10 parts by mass or more. The rubbery polymer is a composite rubber containing an acrylic component and a silicone component containing an organosiloxane unit as a constitutional unit, and the ratio of the organosiloxane constitutional unit to 100 parts by mass of the rubbery polymer is 1. Claim 1, wherein the amount is not less than 20 parts by mass and not more than 20 parts by mass.
Or the composition according to 2. The weight average molecular weight of the polyorganosiloxane (B) is 250 or more and 1,000,000
The composition according to any one of claims 1 to 3, which is: The composition according to any one of claims 1 to 4, wherein the polyorganosiloxane (B) is a silicone oil. The polyorganosiloxane (B) is silicone oil and has a viscosity of 10 to 5,000
A composition according to any one of claims 1 to 5, which has a hardness of 0,000 cSt. The composition according to any one of claims 1 to 6, wherein the ratio of the polyorganosiloxane (B) to 100 parts by mass of the polymer (A) is 1 part by mass or more and 200 parts by mass or less. A resin composition comprising a thermoplastic resin and the composition according to any one of claims 1 to 7. The resin composition according to claim 8, wherein the thermoplastic resin is a styrene resin. The resin composition according to claim 9, wherein the styrenic resin is an acrylonitrile-styrene copolymer. The resin composition according to any one of claims 8 to 10, wherein the ratio of the composition to 100 parts by mass of the thermoplastic resin is 1 part by mass or more and 100 parts by mass or less. A molded article obtained by molding the resin composition according to any one of claims 8 to 11.