Resin composition and molded body

Abstract

A resin composition is provided that yields molded articles exhibiting excellent flame retardancy without significantly reducing impact resistance. The resin composition of the present invention comprises a thermoplastic resin and a polymer containing a polyorganosiloxane, satisfying the following formula (1): Y-X≥20℃...(1), where X refers to the temperature at which the residual amount of the above-mentioned polyorganosiloxane-containing polymer reaches 1 part by mass when heated to 550℃ at a nitrogen flow rate of 200 mL / min and a nitrogen flow rate of 10℃ / min; and Y refers to the temperature at which the residual amount of the above-mentioned thermoplastic resin reaches 90 parts by mass when heated to 550℃ at a nitrogen flow rate of 200 mL / min and a nitrogen flow rate of 200 mL / min.

Description

Technical Field

[0001] This invention relates to resin compositions and molded articles.

[0002] This application claims priority based on Japanese Patent Application No. 2021-056874 filed on March 30, 2021, the contents of which are incorporated herein by reference. Background Technology

[0003] Rubber-containing polymers, which are polymerized from vinyl monomers and rubbery polymers, can be dispersed in a wide variety of resins while maintaining a specified rubber particle size and rubber structure, making them suitable for resins requiring impact strength.

[0004] Compared to butadiene rubber, silicone rubbers are less prone to curing and coloring caused by heat and ultraviolet radiation, exhibiting superior durability. Therefore, they are suitable for applications requiring long-term maintenance of mechanical properties, such as building materials and automotive components. Silicone rubbers utilize polyorganosiloxanes, such as polydimethylsiloxane, and various graft copolymers containing such polyorganosiloxanes are known.

[0005] Patent document 1 describes a graft copolymer containing polyorganosiloxane, which has a specific glass transition temperature (Tg), formed by grafting monofunctional vinyl monomers and polyfunctional vinyl monomers onto a rubber containing polyorganosiloxane in a specific ratio.

[0006] Patent document 2 describes a graft copolymer containing polyorganosiloxane with a volume average particle size of 300-2000 nm and a polyorganosiloxane content of 70-98% by mass.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: International Publication No. 2018 / 225582

[0010] Patent Document 2: International Publication No. 2013 / 162080 Summary of the Invention

[0011] The problem that the invention aims to solve

[0012] When polymers containing polyorganosiloxanes as described in Patent Document 1 or 2 are added to resins, the resulting molded articles sometimes exhibit flame retardancy issues. Furthermore, when polymers containing polyorganosiloxanes and flame retardants such as metal salts are added to thermoplastic resins to improve flame retardancy, the impact resistance is sometimes significantly reduced.

[0013] The object of the present invention is to provide a resin composition that can produce molded articles that exhibit excellent flame retardancy without significantly reducing impact resistance.

[0014] Methods for solving problems

[0015] The present invention has the following aspects.

[0016] [1] A resin composition comprising a thermoplastic resin and a polymer containing a polyorganosiloxane, satisfying the following formula (1).

[0017] YX≥20℃...(1)

[0018] (In formula (1), X refers to the temperature at which the residual amount of the above-mentioned polymer containing polyorganosiloxane reaches 1 part by mass when 100 parts by mass of the above-mentioned polymer containing polyorganosiloxane is heated to 550°C at a nitrogen flow rate of 200 mL / min and at a nitrogen flow rate of 10°C / min; Y refers to the temperature at which the residual amount of the above-mentioned thermoplastic resin reaches 90 parts by mass when 100 parts by mass of the above-mentioned thermoplastic resin is heated to 550°C at a nitrogen flow rate of 200 mL / min and at a nitrogen flow rate of 10°C / min.)

[0019] [2] The resin composition according to [1] satisfies the following formula (2).

[0020] XZ≤40℃...(2)

[0021] (In formula (2), X has the same meaning as X in formula (1), and Z refers to the temperature at which the residual amount of the above-mentioned polymer containing polyorganosiloxane reaches 70 parts by mass when 100 parts by mass of the above-mentioned polymer containing polyorganosiloxane is heated to 550°C at a nitrogen flow rate of 200 mL / min at a rate of 10°C / min).

[0022] [3] The resin composition according to [1] or [2], wherein the polymer containing polyorganosiloxane is a polymer having a composite and a graft portion, wherein the composite comprises polyorganosiloxane and a first vinyl polymer, and the graft portion comprises a second vinyl polymer.

[0023] [4] According to the resin composition of [3], the proportion of the polyorganosiloxane in 100% by mass of the above-mentioned polymer containing polyorganosiloxane is 70% by mass or more and 98% by mass or less.

[0024] [5] According to the resin composition of [3] or [4], the first vinyl polymer contains a constituent unit derived from a (meth)acrylate monomer.

[0025] [6] The resin composition according to any one of [3] to [5], wherein the polyorganosiloxane comprises constituent units from a siloxane-based crosslinking agent, and the proportion of constituent units from the siloxane-based crosslinking agent in 100% by mass of the polyorganosiloxane is 3% by mass or less.

[0026] [7] A molded body comprising any one of the resin compositions described in [1] to [6].

[0027] Invention Effects

[0028] According to the present invention, a resin composition is provided that yields a molded article exhibiting excellent flame retardancy without significantly reducing impact resistance. Detailed Implementation

[0029] The embodiments of the present invention will be described in detail below, but the present invention is not limited to these descriptions. In addition to the following examples, appropriate modifications may be made to the embodiments without affecting the spirit of the present invention.

[0030] In this invention, vinyl monomers refer to compounds having polymerizable double bonds.

[0031] In this invention, (meth)acrylic acid refers to one or both of acrylic acid and methacrylic acid, and (meth)acrylate refers to one or both of acrylate and methacrylate.

[0032] In this specification, "~" is used to indicate that the values ​​listed before and after it are lower and upper limits. That is, the values ​​represented by "A~B" refer to values ​​above A and below B.

[0033] The resin composition of this embodiment comprises a thermoplastic resin and a polymer containing a polyorganosiloxane, satisfying the following formula (1).

[0034] YX≥20℃...(1)

[0035] In formula (1), X refers to the temperature at which the residual amount of the polymer containing polyorganosiloxane reaches 1 part by mass when 100 parts by mass of the polymer is heated to 550°C at a nitrogen flow rate of 200 mL / min and at a nitrogen flow rate of 10°C / min, and Y refers to the temperature at which the residual amount of the thermoplastic resin reaches 90 parts by mass when 100 parts by mass of the thermoplastic resin is heated to 550°C at a nitrogen flow rate of 200 mL / min and at a nitrogen flow rate of 10°C / min.

[0036] <Polymers containing polyorganosiloxanes>

[0037] According to one aspect of the present invention, a polymer containing a polyorganosiloxane (hereinafter also referred to as "polymer (C)") comprises a polymer (A) and a second vinyl polymer (B) (hereinafter also referred to as "vinyl polymer (B)"). Polymer (A) is preferably a composite comprising at least a polyorganosiloxane (A1) and further comprising a first vinyl polymer (A2) (hereinafter also referred to as "vinyl polymer (A2)"). The polyorganosiloxane (A1) and the vinyl polymer (B) are preferably at least partially crosslinked. The polymer containing the polyorganosiloxane is preferably a graft copolymer having a composite of the polyorganosiloxane (A1) and the vinyl polymer (A2) (a composite rubber-like polymer) and a graft portion comprising the vinyl polymer (B1).

[0038] Polymer (C) is a polyorganosiloxane-containing polymer that satisfies formula (1) relative to the thermoplastic resin contained in the resin composition.

[0039] Therefore, when molded in combination with resin, it is possible to provide molded articles with high impact resistance, high flame retardancy, and excellent appearance.

[0040] By decomposing the polymer (C) at a lower temperature than at which the thermoplastic resin begins to decompose, the silicone component of the polymer containing polyorganosiloxane can form a carbonized layer on the surface of the molded body before the thermoplastic resin decomposes. This carbonized layer reduces heat transfer to the interior of the molded body, thereby inhibiting the decomposition of the thermoplastic resin and preventing combustible gases generated inside the molded body from flowing into the air. Therefore, the flame retardancy of the molded body is considered to be improved.

[0041] In formula (1), the value of "YX" is 20°C or higher, preferably 25°C or higher, more preferably 30°C or higher, even more preferably 35°C or higher, and particularly preferably 40°C or higher. When the values ​​of Y and X are less than specific values, the organosilicon component easily forms a carbonized layer, improving flame retardancy. Therefore, the value of "YX" in formula (1) is preferably 60°C or lower, more preferably 50°C or lower. The above upper and lower limits can be combined arbitrarily. For example, the value of "YX" in formula (1) is preferably 20°C to 60°C, more preferably 25°C to 60°C or higher, even more preferably 30°C to 60°C or higher, even more preferably 35°C to 50°C or higher, and particularly preferably 40°C to 50°C or higher.

[0042] The resin composition of this embodiment preferably satisfies the following formula (2) because the decomposition rate of the organosilicon component of the polymer containing polyorganosiloxane is fast, the formation of the carbonized layer becomes easier, and the flame retardancy is improved.

[0043] XZ≤40℃...(2)

[0044] In formula (2), X has the same meaning as X in formula (1), and Z refers to the temperature at which the residual amount of the above-mentioned polymer containing polyorganosiloxane reaches 70 parts by mass when 100 parts by mass of the above-mentioned polymer containing polyorganosiloxane is heated to 550°C at a nitrogen flow rate of 200 mL / min at a rate of 10°C / min.

[0045] In formula (2), the value of "XZ" is preferably below 39°C, more preferably below 30°C. From the perspective of improving impact strength, the value of "XZ" in formula (2) is preferably above 1°C, more preferably above 10°C. The above upper and lower limits can be combined arbitrarily. For example, the value of "XZ" in formula (2) is preferably 1–40°C, more preferably 1–39°C, and even more preferably 10–30°C.

[0046] There are no particular limitations on the methods for adjusting the temperatures X and Z in equations (1) and (2). For example, methods for adjusting the alkali metal content of polymer (C) and methods for adjusting the particle size of polymer (C) can be listed.

[0047] Increasing the alkali metal content of polymer (C) tends to decrease X and Z. By drying the polymer (C) obtained using the method described later, polymer (C) powder can be obtained. Then, by treating it with an alkali metal salt solution, the amount of alkali metal atoms in the polymer (C) powder can be increased, thereby decreasing X and Z. Specifically, after adding deionized water and stirring the polymer (C) powder, an aqueous solution of alkali metal salt is added and stirred, followed by filtration, washing, dehydration, and drying. This yields polymer (C) powder containing more alkali metal atoms. Increasing the alkali metal salt concentration in the alkali metal salt solution tends to increase the amount of alkali metal atoms in the polymer (C) powder, and decrease X and Z.

[0048] To improve flame retardancy and resistance to damp heat, the polymer containing polyorganosiloxane has an alkali metal atomic weight of 100 ppm by mass or more, preferably 150 ppm by mass or more, and more preferably 200 ppm by mass or more. To improve impact resistance, the polymer containing polyorganosiloxane preferably has an alkali metal atomic weight of 1000 ppm by mass or less, more preferably 800 ppm by mass or less, further preferably 600 ppm by mass or less, and particularly preferably 400 ppm by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 100 to 1000 ppm by mass, more preferably 100 to 800 ppm by mass, further preferably 150 to 600 ppm by mass, and particularly preferably 200 to 400 ppm by mass.

[0049] There are no particular restrictions on the alkali metals used; examples include lithium atoms, sodium atoms, potassium atoms, rubidium atoms, and cesium atoms. Polymers containing polyorganosiloxanes may contain one type of alkali metal atom or two or more types of alkali metal atoms. When a polymer containing polyorganosiloxanes contains two or more types of alkali metal atoms, the amount of alkali metal atoms in the polymer refers to the total mass of the alkali metal atoms. Lithium atoms, sodium atoms, and potassium atoms are preferred, with sodium atoms being particularly preferred.

[0050] The atomic weight of alkali metals can be determined as follows: Measure approximately 0.25 g of the sample, add 8 mL of nitric acid and 2 mL of hydrogen fluoride water, decompose the sample using microwave (wet decomposition), and dilute to 50 mL with distilled water. Use the resulting solution as the test solution and determine the atomic weight using an ICP luminescence analyzer (Thermo iCAP 7400Duo).

[0051] By increasing the particle size of polymer (C), there is a tendency for X and Z to decrease. Specifically, for example, by reducing the amount of emulsifier used in the manufacture of polyorganosiloxane (A), the particle size of polymers containing polyorganosiloxane (polymer (C)) tends to increase, thereby reducing X and Z.

[0052] The mass-average particle size (Dw) of the polymer containing polyorganosiloxane is not particularly limited. From the viewpoint of improving appearance and resistance to damp heat, it is preferably 350 nm or more, more preferably 375 nm or more, and even more preferably 400 nm or more. From the viewpoint of improving productivity, the mass-average particle size (Dw) of the polymer containing polyorganosiloxane is preferably 1000 nm or less, more preferably 800 nm or less, even more preferably 600 nm or less, and particularly preferably 500 nm or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 350-1000 nm, more preferably 350-800 nm, even more preferably 375-600 nm, and particularly preferably 400-500 nm.

[0053] Polymers containing polyorganosiloxanes sometimes contain alkaline earth metals and aluminum from the manufacturing process. Since alkaline earth metals and aluminum are impurities, it is preferable that the content of alkaline earth metals and aluminum in the polymer containing polyorganosiloxanes is low, but the content of alkaline earth metals and aluminum has little impact on the present invention. On the other hand, if it is desired to remove alkaline earth metals and aluminum from the polymer containing polyorganosiloxanes, the process can sometimes become complicated. Therefore, from the viewpoint of improving productivity, the content of alkaline earth metals and aluminum in the polymer containing polyorganosiloxanes can be 150 ppm or more, 100 ppm or more, 50 ppm or more, 0 ppm or more, or even 0 ppm, respectively.

[0054] (Polyorganosiloxane (A1))

[0055] Polyorganosiloxanes (Al) are polymers containing organosiloxane units. An organosiloxane unit is a Si-O unit bonded with an organic group. Polyorganosiloxanes have the structure shown in formula (1).

[0056] [Chemistry 1]

[0057]

[0058] In equation (1), R 1 and R 2 Each can independently represent a hydrogen atom, a halogen atom, or a monovalent organic group, R 1 and R 2 At least one of them is a monovalent organic group. n represents an integer greater than 2.

[0059] Polyorganosiloxanes (A1) can be obtained by polymerizing an organosiloxane mixture containing organosiloxanes. The organosiloxane mixture may further contain ingredients as needed.

[0060] Examples of components that can be used as needed include siloxane crosslinking agents, siloxane cross-linking agents, and siloxane oligomers with end-capping groups.

[0061] Examples of organosiloxanes include chain-like organosiloxanes, alkoxysilane compounds, and cyclic organosiloxanes. Alkoxysilane compounds and cyclic organosiloxanes are preferred, and cyclic organosiloxanes are more preferred from the perspective of high polymerization stability and fast polymerization rate.

[0062] As an alkoxysilane compound, a difunctional alkoxysilane compound is preferred. Examples include: dimethyldimethoxysilane, dimethyldiethoxysilane, diethoxydiethylsilane, dipropoxydimethylsilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, and methylphenyldiethoxysilane. Alkoxysilane compounds can be used alone or in combination of two or more.

[0063] As cyclic organosiloxanes, cyclic organosiloxanes with 3- to 7-membered rings are preferred. Examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, and octaphenylcyclotetrasiloxane. Cyclic organosiloxanes can be used alone or in combination of two or more. From the perspective of easy control of particle size distribution, octamethylcyclotetrasiloxane is preferred.

[0064] From the perspective of obtaining a polymer (C) that can further improve the impact strength of the molded article, the organosiloxane is preferably selected from at least one of the groups consisting of cyclic dimethylsiloxane and difunctional dialkylsilane compounds.

[0065] Cyclic dimethylsiloxanes are cyclic siloxanes having two methyl groups on a silicon atom. Examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecylcyclohexasiloxane. Cyclic dimethylsiloxanes can be used alone or in combination of two or more.

[0066] Difunctional dialkylsilane compounds are silane compounds having two alkoxy groups and two alkyl groups on a silicon atom. Examples include dimethyldimethoxysilane, dimethyldiethoxysilane, diethoxydiethylsilane, and dipropoxydimethylsilane. Difunctional dialkylsilane compounds can be used alone or in combination of two or more.

[0067] As a siloxane-based crosslinking agent, a crosslinking agent having a siloxane group is preferred. Examples of siloxane-based crosslinking agents include trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetrabutoxysilane, and other trifunctional or tetrafunctional silane crosslinking agents. Quadrifunctional crosslinking agents are preferred, and tetraethoxysilane is more preferred.

[0068] There is no particular limitation on the proportion of the siloxane-based crosslinking agent in 100% by mass of the organosiloxane mixture, i.e., the proportion of the constituent units from the siloxane-based crosslinking agent in 100% by mass of the polyorganosiloxane. However, to improve flame retardancy, it is preferably 10% by mass or less, more preferably 3% by mass or less, and even more preferably 0.5% by mass or less, or it can be 0% by mass. If the proportion of the siloxane-based crosslinking agent is below the above-mentioned upper limit, it is easier to obtain a molded article with good impact strength.

[0069] Siloxane-based crosslinkers have a silanoxy group (-Si-O-) and functional groups capable of polymerizing with vinyl monomers. Examples of siloxane-based crosslinkers include siloxanes represented by the following formula (I).

[0070] R-Si(R 1 ) n (OR 2 ) (3 -n)...(I)

[0071] In equation (I), R 1 Indicates methyl, ethyl, propyl, or phenyl. R 2This represents an organic group such as a hydrocarbon group, preferably methyl, ethyl, propyl, or phenyl. n represents 0, 1, or 2. R represents a functional group represented by any of the formulas (I-1) to (I-4) below.

[0072] CH2=C(R 3 )-COO-(CH2) p -...(I-1)

[0073] CH2=C(R 4 )-C6H4-...(I-2)

[0074] CH2=CH-...(I-3)

[0075] HS-(CH2) p -...(I-4)

[0076] In these formulas, R 3 and R 4 Each can be used to represent a hydrogen atom or a methyl group independently, and p represents an integer from 1 to 6.

[0077] As the functional group shown in formula (I-1), examples include methacryloyloxyalkyl. As a siloxane having the group shown in formula (I-1), examples include β-methacryloyloxyethyl dimethoxymethylsilane, γ-methacryloyloxypropyl methoxydimethylsilane, γ-methacryloyloxypropyl dimethoxymethylsilane, γ-methacryloyloxypropyl trimethoxysilane, γ-methacryloyloxypropyl ethoxydiethylsilane, γ-methacryloyloxypropyl diethoxymethylsilane, and δ-methacryloyloxybutyl diethoxymethylsilane.

[0078] Examples of functional groups represented by formula (I-2) include vinylphenyl. Examples of siloxanes having groups represented by formula (I-2) include vinylphenylethyldimethoxysilane.

[0079] Examples of siloxanes having the functional group shown in formula (I-3) include vinyltrimethoxysilane and vinyltriethoxysilane.

[0080] Mercaptoalkyl groups can be listed as functional groups represented by formula (I-4). Examples of siloxanes having groups represented by formula (I-4) include γ-mercaptopropyl dimethoxymethylsilane, γ-mercaptopropyl methoxydimethylsilane, γ-mercaptopropyl diethoxymethylsilane, γ-mercaptopropyl ethoxydimethylsilane, and γ-mercaptopropyl trimethoxysilane.

[0081] Siloxane cross-linking agents can be used alone or in combination of two or more.

[0082] As a siloxane crosslinking agent, γ-methacryloyloxypropylmethyldimethoxysilane is preferred because it is easy to form an island structure when polyorganosiloxane (A1) is compounded with vinyl polymer (A2).

[0083] When the organosiloxane mixture contains a siloxane-based cross-linking agent, the proportion of the siloxane-based cross-linking agent in 100% by mass of the organosiloxane mixture is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more. The proportion of the siloxane-based cross-linking agent in 100% by mass of the organosiloxane mixture is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 0.05 to 20% by mass, more preferably 0.1 to 10% by mass, and even more preferably 0.5 to 5% by mass. If the proportion of the siloxane-based grafting cross-linking agent is within the range of the above upper and lower limits, covalent bonds between the polyorganosiloxane (A1) and the vinyl polymer (A2) can be sufficiently formed, and a polymer (C) with good impact strength can be obtained.

[0084] The mass-average particle size of the polyorganosiloxane (A1) is preferably 100 nm or more, more preferably 200 nm or more, and even more preferably 300 nm or more. The mass-average particle size of the polyorganosiloxane (A1) is preferably 1000 nm or less, more preferably 800 nm or less, and even more preferably 600 nm or less. The above upper and lower limits can be combined arbitrarily. For example, 100–1000 nm is preferred, more preferably 200–800 nm, and even more preferably 300–600 nm. If the mass-average particle size of the polyorganosiloxane (A1) is within the range of the above upper and lower limits, it is easy to adjust the mass-average particle size of the polymer (C) to the range of the above preferred upper and lower limits.

[0085] <Method for manufacturing polyorganosiloxane (A1)>

[0086] There are no particular limitations on the manufacturing method of polyorganosiloxane (A1). For example, the following manufacturing method (M) can be used: an emulsion is prepared by emulsifying an organosiloxane mixture containing organosiloxane, a required siloxane crosslinking agent, a required siloxane crosslinking agent, and a required siloxane oligomer with end-capped groups using an emulsifier and water. In this emulsion, the organosiloxane mixture is polymerized at high temperature in the presence of an acid catalyst. Subsequently, the acid catalyst is neutralized using an alkaline substance to obtain a latex of polyorganosiloxane.

[0087] The following description addresses the use of "organosiloxane mixtures" as raw materials for polymerization. The same manufacturing process can be applied even when using "organosiloxanes" as raw materials for polymerization.

[0088] In the manufacturing method (M), examples of methods for preparing the emulsion include: methods that utilize shear force generated by high-speed rotation, such as using a homogenizer; and methods that utilize ejection force generated by a high-pressure generator, such as using a homogenizer and mixing by high-speed stirring. To facilitate narrowing the particle size distribution of the polyorganosiloxane latex, the method using a homogenizer is preferred.

[0089] Examples of methods for mixing the acid catalyst during polymerization include: a method of adding and mixing the acid catalyst, an organosiloxane mixture, an emulsifier, and water together in one step (Method 1); a method of adding an aqueous solution of the acid catalyst to an emulsion of the organosiloxane mixture in one step (Method 2); and a method of mixing the emulsion of the organosiloxane mixture by dropping it dropwise into a high-temperature aqueous solution of the acid catalyst at a certain rate (Method 3). From the perspective of easily controlling the particle size of the polyorganosiloxane, Method 3 is preferred.

[0090] The polymerization temperature is preferably 50°C or higher, more preferably 70°C or higher. The upper limit of the polymerization temperature is, for example, 100°C.

[0091] When using method 3 for polymerization, the polymerization time is usually more than 2 hours, preferably more than 5 hours.

[0092] The cross-linking reaction between silanols occurs at temperatures below 30°C. Therefore, in order to increase the cross-linking density of polyorganosiloxanes, the latex can be polymerized at temperatures above 50°C and then kept at temperatures below 30°C for about 5 to 100 hours.

[0093] The polymerization reaction of organosiloxane mixtures can be terminated by neutralizing the reaction system containing latex to a pH above 6 and below 8 using alkaline substances such as sodium hydroxide, potassium hydroxide, and ammonia solution.

[0094] As an emulsifier, there are no particular limitations as long as it can emulsify organosiloxane mixtures; anionic or nonionic emulsifiers are preferred.

[0095] Examples of anionic emulsifiers include sodium alkylbenzene sulfonate, sodium alkyl diphenyl ether disulfonate, sodium alkyl sulfate, sodium polyoxyethylene alkyl sulfate, and sodium polyoxyethylene nonylphenyl ether sulfate.

[0096] Examples of nonionic emulsifiers include polyoxyethylene alkyl ethers, polyoxyethylene alkylene alkyl ethers, polyoxyethylene styrene phenyl ethers, polyoxyethylene tribenzyl phenyl ethers, and polyoxyethylene polyoxypropylene glycol.

[0097] Emulsifiers can be used alone or in combination of two or more.

[0098] The amount of emulsifier used is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the organosiloxane mixture. The amount of emulsifier used is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, relative to 100 parts by mass of the organosiloxane mixture. The above upper and lower limits can be combined arbitrarily. For example, 0.05 to 20 parts by mass is preferred, more preferably 0.1 to 10 parts by mass. By adjusting the amount of emulsifier used, the particle size of the polyorganosiloxane latex can be adjusted to a desired value. Increasing the amount of emulsifier reduces the particle size, while decreasing the amount of emulsifier increases the particle size. If the amount of emulsifier used is above the lower limit, the emulsion stability of the organosiloxane mixture emulsion can be improved. If the amount of emulsifier used is below the upper limit, the heat resistance and surface appearance of the molded article are excellent.

[0099] Examples of acid catalysts used in the polymerization of organosiloxane mixtures include sulfonic acids such as aliphatic sulfonic acids, aliphatic substituted benzenesulfonic acids, and aliphatic substituted naphthalenesulfonic acids; and inorganic acids such as sulfuric acid, hydrochloric acid, and nitric acid. One acid catalyst can be used alone or in combination of two or more. Using inorganic acids tends to narrow the particle size distribution of the polyorganosiloxane latex, thereby making it easier to suppress adverse effects caused by the emulsifier components in the polyorganosiloxane latex (such as reduced heat resistance of the molded body and poor appearance).

[0100] The amount of acid catalyst used is preferably 0.005 parts by mass to 40 parts by mass relative to 100 parts by mass of organosiloxane. If the amount of acid catalyst used is 0.005 parts by mass or more, the organosiloxane mixture can be polymerized in a short time. If the amount of acid catalyst used is 40 parts by mass or less, the molded article has excellent heat resistance, color change, and surface appearance.

[0101] Since the amount of acid catalyst used is a factor determining the particle size of the polyorganosiloxane (A1), in order to obtain the polyorganosiloxane (A1) with the particle size described later, the amount of acid catalyst used is more preferably 1 part by mass or more and 30 parts by mass or less relative to 100 parts by mass of the organosiloxane. It should be noted that when the amount of acid catalyst used is small, there is a tendency for the particle size to increase.

[0102] To improve mechanical stability, an emulsifier may be added as needed to the polyorganosiloxane latex obtained by manufacturing method (M). Preferably, the emulsifier is an anionic or nonionic emulsifier, as exemplified above.

[0103] (Vinyl Polymer (A2))

[0104] Polymer (A) may contain vinyl polymer (A2). When polymer (A) contains vinyl polymer (A2), polymer (A) may be a polymer formed by crosslinking vinyl polymer (A2) and polyorganosiloxane (A1), or it may be a composite polymer in which polyorganosiloxane (A1) and vinyl polymer (A2) are not crosslinked, preferably vinyl polymer (A2) and polyorganosiloxane (A1) are crosslinked.

[0105] Vinyl polymer (A2) is a polymer formed by polymerizing vinyl monomer component (a2). That is, vinyl polymer (A2) contains vinyl monomer units derived from vinyl monomer component (a2).

[0106] The vinyl monomer component (a2) constituting the first vinyl polymer (A2) can be one vinyl monomer or two or more vinyl monomers.

[0107] From the viewpoint of the impact strength of the molded article, the vinyl monomer component (a2) preferably contains (meth)acrylate monomers (hereinafter also referred to as "monomer (a2-1)").

[0108] As monomers (a2-1), there are no particular limitations, but (meth)acrylates with alkyl groups having 1 or more and 20 or fewer carbon atoms are preferred. Examples include: alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate; and alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, tridecyl methacrylate, and stearyl methacrylate.

[0109] (Meth)acrylates are preferably alkyl acrylates with 1 or more and 20 or less carbon atoms. From the viewpoint of improving the impact strength of the molded article, the alkyl group of the alkyl acrylate preferably has 2 or more carbon atoms, more preferably 3 or more, further preferably 4 or more, preferably 16 or less, more preferably 12 or less, and even more preferably 8 or less. n-Butyl acrylate is particularly preferred.

[0110] The monomer (a2-1) can be used alone or in combination of two or more.

[0111] When the vinyl monomer component (a2) contains monomer (a2-1), it may also contain other monomers. Examples of other monomers include multifunctional monomers (hereinafter also referred to as "monomer (a2-2)") that can copolymerize with monomer (a2-1). From the viewpoint of the impact strength of the molded article, the vinyl monomer component (a2) preferably contains monomer (a2-1) and monomer (a2-2).

[0112] As monomers (a2-2), there are no particular limitations, and examples include (meth)acrylates and cyanurates. Examples of (meth)acrylates include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, and allyl methacrylate. Examples of cyanurates include triallyl cyanurate and triallyl isocyanurate.

[0113] From the perspective of improving the impact strength of the molded article, allyl methacrylate, triallyl cyanurate, and triallyl isocyanurate are preferred, and allyl methacrylate is more preferred.

[0114] The monomer (a2-2) can be used alone or in combination of two or more.

[0115] The proportion of monomer (a2-1) in 100% by mass of the vinyl monomer component (a2) is not particularly limited, but from the viewpoint of improving the impact strength of the molded article, it is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more. The proportion of monomer (a2-1) in 100% by mass of the vinyl monomer component (a2) is 100% by mass or less, preferably 99.9% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 60 to 100% by mass, more preferably 70 to 100% by mass, further preferably 80 to 99.9% by mass, and particularly preferably 90 to 99.9% by mass.

[0116] There is no particular limitation on the proportion of monomer (a2-2) in 100% by mass of vinyl monomer component (a2), but it is preferably 0.1% by mass or more, and more preferably 2% by mass or less, in order to improve impact strength.

[0117] The vinyl monomer component (a2) may contain monomers other than monomers (a2-1) and monomers (a2-2) (a2-3). There are no particular restrictions on other monomers (a2-3), for example, aromatic vinyl monomers, cyanide vinyl monomers, and (meth)acrylic acid modified silicones can be listed.

[0118] As aromatic vinyl monomers, there are no particular limitations; examples include styrene and α-methylstyrene.

[0119] There are no particular limitations on the types of vinyl cyanide monomers that can be used, such as acrylonitrile and methacrylonitrile.

[0120] Other monomers (a2-3) can be used alone or in combination of two or more.

[0121] (Polymer(A))

[0122] Polymer (A) comprises a polyorganosiloxane (A1) and a vinyl polymer (A2). Polymer (A) preferably functions as a composite rubber of polyorganosiloxane (A1) and vinyl polymer (A2). For it to function as a composite rubber, the glass transition temperatures (hereinafter sometimes referred to as Tg) of polyorganosiloxane (A1) and vinyl polymer (A2) are preferably below 0°C.

[0123] From the viewpoint of impact strength and flame retardancy of the molded article, the mass ratio of polyorganosiloxane (A1) to vinyl polymer (A2) in polymer (A) is preferably 50 / 50 or more, more preferably 70 / 98 or more, preferably 99 / 1 or less, and more preferably 95 / 5 or less. The above upper and lower limits can be combined arbitrarily. For example, 50 / 50 to 99 / 1 is preferred, and 70 / 98 to 95 / 5 is more preferred.

[0124] <Method for manufacturing polymer (A)>

[0125] The manufacturing method of polymer (A) is not particularly limited, but from the perspective of excellent impact strength of the molded article, a method of polymerizing the vinyl monomer component (a2) constituting the vinyl polymer (A2) in the presence of a latex containing polyorganosiloxane (A1) is preferred.

[0126] There are no particular limitations on the method of polymerizing the vinyl monomer component (a2) in the presence of a latex containing polyorganosiloxane (A1). Examples include: a method of adding the vinyl monomer component (a2) dropwise to a latex containing polyorganosiloxane (A1) and then polymerizing it (method i); a method of adding a portion of the vinyl monomer component (a2) to a latex containing polyorganosiloxane (A1) under conditions that do not initiate polymerization, so that it is impregnated with the particles of polyorganosiloxane (A1), then initiating polymerization, and then adding or adding the remaining portion of the vinyl monomer component (a2) dropwise or all at once and then polymerizing it (method ii); a method of adding all the vinyl monomer component (a2) to a latex containing polyorganosiloxane (A1) under conditions that do not initiate polymerization, so that it is impregnated with the particles of polyorganosiloxane (A1), and then polymerizing it (method iii).

[0127] From the perspective of superior impact strength of the molded part, method iii is preferred.

[0128] There are no particular limitations on the method for manufacturing the vinyl polymer (A2). For example, methods for polymerizing the vinyl monomer (a2) by emulsion polymerization, suspension polymerization, and micro-suspension polymerization can be listed, with emulsion polymerization being preferred.

[0129] As a free radical polymerization initiator used in the polymerization of vinyl monomer (a2), azo initiators, peroxides, or redox initiators composed of peroxides and reducing agents can be used. One type of free radical polymerization initiator can be used alone or in combination of two or more. Azo initiators and redox initiators are preferred.

[0130] Examples of azo initiators include: oil-soluble azo initiators such as 2,2'-azobisisobutyronitrile, dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(2,4-dimethylpentanitrile), and 2,2'-azobis(2-butanitrile); and water-soluble azo initiators such as 4,4'-azobis(4-cyanopentanoic acid), 2,2'-azobis[N-(2-carboxymethyl)-2-methylpropylamidine] hydrate, 2,2'-azobis(N,N'-dimethyleneisobutylamidine) dihydrochloride, and 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride. These substances can be used alone or in combination of two or more.

[0131] Examples of peroxides include: inorganic peroxides such as hydrogen peroxide, potassium persulfate, and ammonium persulfate; and organic peroxides such as diisopropylbenzene hydrogen peroxide, terpene hydrogen peroxide, cumene hydrogen peroxide, tert-butyl hydrogen peroxide, succinate peroxide, tert-butyl peroxyneodecanate, tert-butyl peroxyneoheptanoate, tert-butyl peroxynepentanoate, 1,1,3,3-tetramethylbutylperoxide-2-ethylhexanoate, and tert-butylperoxide-2-ethylhexanoate. Peroxides can be used alone or in combination of two or more.

[0132] When a redox initiator is prepared by combining a peroxide with a reducing agent, it is preferable to use the aforementioned peroxide, sodium formaldehyde sulfoxylate, L-ascorbic acid, fructose, glucose, sorbitol, inositol, or other reducing agents in combination with ferrous sulfate-ethylenediaminetetraacetic acid disodium salt. One redox initiator can be used alone or in combination of two or more.

[0133] In order to easily obtain graft copolymers with excellent impact resistance, the free radical polymerization initiator used in the polymerization of vinyl monomer (a2) is preferably a free radical polymerization initiator with a solubility of less than 5% by mass in water at 20°C, and more preferably a free radical polymerization initiator with a solubility of less than 2% by mass.

[0134] Examples of free radical polymerization initiators with a solubility of less than 5% by mass in water at 20°C include: cumene hydroperoxide, diisopropylbenzene hydroperoxide, terpene hydroperoxide, tert-butyl peroxyneodecanate, tert-butyl peroxyneoheptanoate, tert-butyl peroxyneopentate, 1,1,3,3-tetramethylbutyl peroxide-2-ethylhexanoate, tert-butyl peroxide-2-ethylhexanoate, 2,2'-azobisisobutyronitrile, dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(2,4-dimethylpentanonitrile), and 2,2'-azobis(2-butyronitrile). Free radical polymerization initiators with a solubility of less than 5% by mass in water at 20°C can be used alone or in combination of two or more.

[0135] The solubility of free radical polymerization initiators in water at 20°C can be found in catalogs of various free radical polymerization initiators.

[0136] When using an azo initiator as a free radical polymerization initiator, the amount of azo initiator used is preferably 0.01 to 1 part by mass relative to 100 parts by mass of the total monomers.

[0137] When using a redox initiator as a free radical polymerization initiator, the amount of peroxide used is preferably 0.01-1 parts by mass relative to 100 parts by mass of the monomer. When using a redox initiator as a free radical polymerization initiator, the amount of reducing agent used is preferably 0.01-1 parts by mass relative to 100 parts by mass of the monomer.

[0138] (Vinyl Polymer (B))

[0139] Vinyl polymer (B) is a polymer formed by polymerizing vinyl monomer component (b), and is a polymer containing constituent units derived from vinyl monomers.

[0140] The vinyl monomer component (b) constituting the vinyl polymer (B) may be any one or more vinyl monomers.

[0141] The vinyl monomers constituting vinyl monomer component (b) are not particularly limited, but (meth)acrylate monomers are preferably listed.

[0142] There are no particular limitations on the monomers used for (meth)acrylates, and alkyl (meth)acrylates can be listed as examples. When one or more vinyl monomers include alkyl (meth)acrylates such as methyl (meth)acrylate, the resulting graft copolymer tends to exhibit excellent compatibility and dispersibility in thermoplastic resins such as polycarbonate resins. Examples of alkyl (meth)acrylates include, for instance, alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate, as well as methyl acrylate, ethyl acrylate, and n-butyl acrylate.

[0143] (Meth)acrylate monomers can be used alone or in combination of two or more. The number of carbon atoms in the alkyl group of the (meth)acrylate is not particularly limited, but is preferably 1 or more, more preferably 12 or less, more preferably 6 or less, and even more preferably 4 or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 12 is preferred, more preferably 1 to 6, and even more preferably 1 to 4. Methyl methacrylate is particularly preferred.

[0144] The vinyl monomer component (b) may further include one or more monomers selected from the group consisting of polyfunctional vinyl monomers, aromatic vinyl monomers and cyanide vinyl monomers.

[0145] Examples of multifunctional vinyl monomers include allyl methacrylate, triallyl cyanurate, divinylbenzene, diallyl phthalate, and ethylene glycol di(meth)acrylate. A single multifunctional vinyl monomer can be used alone, or two or more can be used in combination.

[0146] There are no particular restrictions on aromatic vinyl monomers; examples include styrene and α-methylstyrene. An aromatic vinyl monomer can be used alone or in combination with two or more.

[0147] There are no particular limitations on the types of vinyl cyanide monomers used; examples include acrylonitrile and methacrylonitrile. A single vinyl cyanide monomer can be used alone, or in combination with two or more monomers.

[0148] The proportion of (meth)acrylate monomer in 100% by mass of vinyl polymer (B) is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, particularly preferably 90% by mass or more, and can be 100% by mass.

[0149] The Tg of the vinyl polymer (B) is preferably 70°C or higher, more preferably 80°C or higher, even more preferably 90°C or higher, and preferably 105°C or lower. The above upper and lower limits can be combined arbitrarily. For example, 70°C to 105°C is preferred, more preferably 80°C to 105°C, and even more preferably 90°C to 105°C. If the Tg of the vinyl polymer (B) is above the above lower limit, the resulting polymer (C) powder exhibits good flowability and other properties.

[0150] The Tg of the vinyl polymer (B) can be adjusted by the type and ratio of the vinyl monomers that make up the vinyl monomer component (b).

[0151] The Tg of the vinyl polymer (B) is determined using the FOX formula. In this case, the Tg of the homopolymer of the vinyl monomers constituting the vinyl monomer component (b) can be, for example, used the values ​​described in the "Polymer Handbook" (Wiley Interscience, 1999). The Tg of the homopolymer of vinyl monomers not described in that literature can be calculated using Bicerano's method "Prediction of Polymer Properties" (MARCEL DEKKER, 2002).

[0152] (Method for manufacturing polymer (C))

[0153] Polymer (C) can be manufactured, for example, by polymerizing (grafting) the vinyl monomer component (b) in the presence of polymer (A). Thus, a polymer is obtained in which part or all of the vinyl polymer (B) is grafted onto polymer (A).

[0154] There are no particular limitations on the manufacturing method of polymer (C), but a preferred method is to add vinyl monomer component (b) to the latex of polymer (A) and polymerize vinyl monomer component (b) in the latex. The latex of polymer (A) is preferably manufactured by polymerizing vinyl monomer component (a2) in the presence of a latex containing polyorganosiloxane (A1).

[0155] There are no particular limitations on the conditions for polymerizing the vinyl monomer component (b). Conventional conditions can be used, such as 45°C to 95°C and 0.1 to 10 hours.

[0156] There are no particular limitations on the method of adding vinyl monomer component (b) to the latex of polymer (A), but dropwise addition is preferred from the perspective of suppressing the generation of broken glass. The entire vinyl monomer component (b) can be added dropwise continuously, or it can be added dropwise in multiple times while setting a holding time during which vinyl monomer component (b) is not added dropwise.

[0157] After the vinyl monomer component (b) is polymerized, it is preferable to recover the polymer (C) from the latex of the resulting polymer (C) in the form of powder (or a group of powders or a group of powders containing inclusions).

[0158] When recovering polymer (C) in powder form, direct drying methods such as spray drying or coagulation methods can be used. In direct drying, the additives added during polymerization are largely retained in the resulting powder. In coagulation, the washing process after coagulation reduces the amount of polymerization additive residues in the resulting powder, such as emulsifiers, condensate salts, and initiators used during polymerization. The powder recovery method can be appropriately selected in a way that results in the desired residual state when the polymer (C) is added to the thermoplastic resin.

[0159] Spray drying, as a direct drying method, involves spraying polymer (C) latex into tiny droplets in a dryer and then drying it by blowing heated drying gas onto the droplets. Methods for generating these tiny droplets include, for example, rotating disc type, pressure nozzle type, two-fluid nozzle type, and pressurized two-fluid nozzle type. The capacity of the dryer can range from small-scale laboratory use to large-scale industrial use. The temperature of the heating gas for drying is preferably below 200°C, more preferably 120–180°C. Latexes of two or more graft copolymers manufactured separately can also be spray-dried together. To improve powder properties such as adhesion and specific gravity during spray drying, any component such as silica can be added to the polymer (C) latex before spray drying.

[0160] The coagulation method involves coagulating the latex of polymer (C), separating, recovering, and drying the polymer (C). The latex of polymer (C) is added to hot water containing a coagulant, causing salting out and coagulation, thereby separating the polymer (C). The separated, wet polymer (C) is then dehydrated to recover the polymer (C) with reduced moisture content. The recovered polymer (C) is then dried using a press dehydrator or a hot air dryer.

[0161] Examples of coagulants include inorganic salts such as aluminum chloride, aluminum sulfate, sodium sulfate, magnesium sulfate, sodium nitrate, and calcium acetate, as well as acids such as sulfuric acid, with calcium acetate being preferred. One coagulant can be used alone or in combination of two or more.

[0162] When using a coagulant in aqueous solution form, from the viewpoint of stably coagulating and recycling the polymer (C), the concentration of the coagulant aqueous solution is preferably 0.1% by mass or more, more preferably 1% by mass or more. From the viewpoint of preventing a decrease in the molded appearance of the molded article by reducing the amount of coagulant remaining in the recycled polymer (C), the concentration of the coagulant aqueous solution is preferably 20% by mass or less, more preferably 15% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, 0.1 to 20% by mass is preferred, more preferably 1 to 15% by mass.

[0163] The amount of the coagulant aqueous solution is not particularly limited, but is preferably 10 parts by mass or more and 500 parts by mass or less relative to 100 parts by mass of the latex of polymer (C).

[0164] There are no particular limitations on the method of contacting the latex of polymer (C) with the coagulant aqueous solution; the following methods can be listed.

[0165] (1) A method of continuously adding latex to a coagulant aqueous solution while stirring it and maintaining the solution for a certain period of time;

[0166] (2) A method of continuously injecting a coagulant aqueous solution and latex into a container equipped with a stirrer at a certain ratio and bringing them into contact, and continuously extracting a mixture of polymer and water containing coagulation from the container.

[0167] There is no particular limitation on the temperature at which the latex comes into contact with the coagulant aqueous solution, but it is preferably above 30°C and below 100°C. There is no particular limitation on the contact time.

[0168] The condensed polymer (C) is washed with approximately 1 to 100 times its weight of water and then filtered. The filtered, wet polymer (C) is dried using a flow dryer, press dehydrator, or similar method. The drying temperature and time are determined appropriately based on the desired polymer (C).

[0169] Alternatively, the polymer (C) discharged from the press dehydrator and extruder can be sent directly to the extruder and molding machine for manufacturing resin compositions without being recycled, and mixed with thermoplastic resin to obtain a molded body.

[0170] Polymer (C) powder can be obtained by drying the polymer (C), but the amount of alkali metal atoms in the polymer (C) powder can be increased by treating it with an alkali metal salt solution. Specifically, after adding deionized water to the polymer (C) powder and stirring, an aqueous solution of alkali metal salt is added and stirred, followed by filtration, washing, dehydration, and drying. This yields polymer (C) powder containing more alkali metal atoms. Increasing the concentration of the alkali metal salt in the solution tends to increase the amount of alkali metal atoms in the polymer (C) powder.

[0171] The proportion of polyorganosiloxane (A1) in 100% by mass of polymer (C) is preferably less than 100% by mass, more preferably 98% by mass or less. The proportion of polyorganosiloxane (A1) in 100% by mass of polymer (C) is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, and particularly preferably 95% by mass or more. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 50% by mass or more and less than 100% by mass, more preferably 70% by mass or more and less than 100% by mass, further preferably 70-98% by mass, further preferably 90-98% by mass or more, and particularly preferably 95-98% by mass or more. If the proportion of polyorganosiloxane (A1) is above the above lower limit, the impact strength of the molded article is excellent. If it is below the above upper limit, the color appearance of the molded article is excellent.

[0172] The proportion of polymer (A) in 100% by mass of polymer (C) is preferably 60% by mass or more, more preferably 70% by mass or more. The proportion of polymer (A) in 100% by mass of polymer (C) is preferably 95% by mass or less, more preferably 90% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, 60 to 95% by mass is preferred, more preferably 70 to 90% by mass. If the content of polymer (A) is above the above lower limit, the impact strength and flame retardancy of the molded article are excellent. If it is below the above upper limit, the dispersibility of polymer (C) in the thermoplastic resin is excellent, and the appearance of the obtained molded article is excellent.

[0173] The proportion of grafted portion in 100% by mass of polymer (C) is preferably 5% by mass or more, more preferably 7.5% by mass or more, and even more preferably 10% by mass or more. The proportion of grafted portion in 100% by mass of polymer (C) is preferably 20% by mass or less, more preferably 17.5% by mass or less, and even more preferably 15% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, 5 to 20% by mass is preferred, more preferably 7.5 to 17.5% by mass, and even more preferably 10 to 15% by mass. If the content of grafted portion is above the above lower limit, the dispersibility of polymer (C) in the thermoplastic resin is excellent, and the appearance of the resulting molded article is excellent. If it is below the above upper limit, the impact strength of the molded article is excellent.

[0174] The proportion of vinyl polymer (B) in 100% by mass of polymer (C) is preferably 5% by mass or more, more preferably 10% by mass or more. The proportion of vinyl polymer (B) in 100% by mass of polymer (C) is preferably 40% by mass or less, more preferably 35% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 5 to 40% by mass, more preferably 10 to 35% by mass. If the content of vinyl polymer (B) is above the above lower limit, the dispersibility of polymer (C) in thermoplastic resin is excellent, and the appearance of the resulting molded article is excellent. If it is below the above upper limit, the impact strength of the molded article is excellent.

[0175] <Resin Composition>

[0176] A resin composition of one embodiment of the present invention (hereinafter also referred to as "the resin composition") comprises a thermoplastic resin (hereinafter also referred to as "thermoplastic resin (D)") and a polymer containing a polyorganosiloxane. The polyorganosiloxane-containing polymer contained in the resin composition is preferably polymer (C).

[0177] As for thermoplastic resin (D), there is no particular limitation, for example, engineering plastics (aromatic polycarbonate, etc.), styrene resins, polyester resins, olefin resins (polyethylene, etc.), thermoplastic elastomers, biodegradable resins, halogen resins (vinyl chloride resin, etc.), and acrylic resins can be listed.

[0178] As an engineering plastic, various well-known thermoplastic engineering plastics can be used without particular restrictions.

[0179] Examples of engineering plastics include polyphenylene ether, polycarbonate, polyester polymers (polyethylene terephthalate, polybutylene terephthalate, etc.), syndiotactic polystyrene, nylon polymers (6-nylon, 6,6-nylon, etc.), polyarylate, polyphenylene sulfide, polyetherketone, polyetheretherketone, polysulfone, polyamide-imide, polyetherimide, and polyacetal.

[0180] For example, as engineering plastics in this invention, examples include special styrene-based resins such as heat-resistant ABS, which have excellent heat resistance and require melt flowability, and heat-resistant acrylic resins. When further strength performance is required, aromatic polycarbonate and polybutylene terephthalate are more preferred.

[0181] Examples of aromatic polycarbonates include 4,4'-dioxane-2,2-propane (bisphenol A) polycarbonates and other 4,4'-dioxane-based polycarbonates.

[0182] Examples of olefin-based 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, and poly-4-methylpentene-1.

[0183] Examples of thermoplastic elastomers include styrene-based elastomers, urethane-based elastomers, polyolefin-based elastomers, polyamide-based elastomers, fluorinated elastomers, chlorinated PE-based elastomers, and acrylic elastomers.

[0184] Examples of styrene-based elastomers include styrene-butadiene-styrene copolymers (SBS), styrene-isoprene-styrene copolymers (SIS), styrene-ethylene-butene copolymers (SEB), styrene-ethylene-propylene copolymers (SEP), styrene-ethylene-butene-styrene copolymers (SEBS), styrene-ethylene-propylene-styrene copolymers (SEPS), styrene-ethylene-ethylene-propylene-styrene copolymers (SEEPS), styrene-butadiene-butene-styrene copolymers (partially hydrogenated styrene-butadiene-styrene copolymers: SBBS), partially hydrogenated SIS copolymers, and partially hydrogenated styrene-isoprene-butadiene-styrene copolymers. "-" indicates copolymerization of monomers forming units connected by "-", and "·" indicates random modification after copolymerization, such as hydrogenation.

[0185] Examples of urethane-based elastomers include reaction products of high molecular weight diols, organic diisocyanates, and chain extenders.

[0186] Examples of high molecular weight diols include polyester diol, polyether diol, polyester ether diol, polycarbonate diol, and polyester polycarbonate diol.

[0187] Examples of organic diisocyanates include 4,4'-diphenylmethane diisocyanate, toluene diisocyanate, terephthalic diisocyanate, dimethyl phthalate diisocyanate, naphthalene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate (4,4'-dicyclohexylmethane diisocyanate), isophorone diisocyanate, and hexamethylene diisocyanate, with 4,4'-diphenylmethane diisocyanate being preferred.

[0188] Examples of chain extenders include ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-1,3-propanediol, 1,6-hexanediol, neopentanediol, 1,9-nonanediol, cyclohexanediol, and 1,4-bis(β-hydroxyethoxy)benzene.

[0189] Examples of polyolefin-based elastomers include ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-vinyl acetate copolymer, butyl rubber, butadiene rubber, propylene-butene copolymer, and ethylene-acrylate copolymer.

[0190] Examples of styrene-based 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-butadiene-styrene-α-methylstyrene-maleimide copolymer.

[0191] Polyester resin is a polymer of polybasic acids and polyols, with thermoplasticity as a condition, and is not particularly limited. Examples of polybasic acids include terephthalic acid, naphthalenedicarboxylic acid, cyclohexyl dicarboxylic acid, and their esters. Examples of polyols include ethylene glycol, propylene glycol, butanediol, pentanediol, neopentanediol, hexanediol, octanediol, decanediol, cyclohexanediol, hydroquinone, bisphenol A, 2,2-bis(4-hydroxyethoxyphenyl)propane, 1,4-dimethyloltetrabromobenzene, and tetrabromobisphenol A bis(2-hydroxyethyl) ether (TBA-EO).

[0192] Polyester resin can be a homopolymer, a copolymer, or a mixture of two or more of them.

[0193] As a polyester resin, commercially available products such as "PETG" manufactured by Eastman Chemical Co., Ltd. can be used.

[0194] Examples of biodegradable resins include microbial polymers, chemically synthesized polymers, and natural polymers.

[0195] Examples of microbial polymers include biopolyesters such as polyhydroxybutyrate / valerate (PHB / V), bacterial cellulose, and microbial polysaccharides (pullulan, gel polysaccharides, etc.).

[0196] Examples of chemically synthesized polymers include aliphatic polyesters (polycaprolactone, polybutylene succinate, polyethylene succinate, polyglycolic acid, polylactic acid, etc.), polyvinyl alcohol, and polyamino acids (PMLG, etc.).

[0197] Examples of natural polymers include chitosan, cellulose, starch, and cellulose acetate.

[0198] Examples of halogen-based resins include homopolymers of vinyl chloride, copolymers containing vinyl chloride in a proportion of 80% or more by mass, and vinyl chloride resins such as highly chlorinated polyvinyl chloride. In addition to vinyl chloride, components of copolymers may include monovinyl compounds such as ethylene, vinyl acetate, methyl methacrylate, and butyl acrylate. The proportion of constituent units from these compounds in the copolymer may be 20% or less by mass.

[0199] In addition to vinyl chloride resins, other examples of halogenated resins include fluorinated polymers, brominated polymers, and iodinated polymers.

[0200] Examples of acrylic resins include copolymers formed by polymerizing methyl methacrylate with copolymerizable vinyl monomers. Examples of copolymerizable vinyl monomers include alkyl acrylates such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate; alkyl methacrylates such as ethyl methacrylate, propyl methacrylate, and n-butyl methacrylate; and aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyltoluene.

[0201] Polyester resins such as polyphenylene ether, polycarbonate, polyethylene terephthalate and polybutylene terephthalate, polyamide resins such as syndiotactic polystyrene, 6-nylon and 6,6-nylon, polyarylate, polyphenylene sulfide, polyetherketone, polyetheretherketone, polysulfone, polyethersulfone, polyamide imide, polyetherimide, polyacetal and other engineering plastics are also included in the scope of thermoplastic resins (D).

[0202] Thermoplastic resin (D) can be used alone or in combination of two or more.

[0203] From the perspective of being readily available in industry and having an excellent balance between the impact strength and colorability of the molded article, the thermoplastic resin (D) preferably includes at least one selected from the group consisting of aromatic polycarbonate, polymethyl methacrylate, styrene-acrylonitrile copolymer, polyethylene terephthalate, polybutylene terephthalate, polyvinyl chloride, polyphenylene sulfide and polyacetal, and more preferably includes at least one selected from the group consisting of polymethyl methacrylate and styrene-acrylonitrile copolymer.

[0204] In addition to the substances described above, this resin composition may also contain various known additives within a scope that does not impair the purpose of the present invention.

[0205] Examples of additives include flame retardants (e.g., phosphorus-based, bromine-based, organosilicon-based, organometallic salt-based), anti-drip agents (e.g., fluorinated polyolefins, organosilicon, and aramid fibers), lubricants (e.g., long-chain fatty acid metal salts such as magnesium stearate), mold release agents (e.g., pentaerythritol tetrastearate), nucleating agents, antistatic agents, stabilizers (e.g., phenolic stabilizers, phosphorus stabilizers, UV absorbers, amine light stabilizers), fillers (e.g., titanium dioxide, talc, mica, kaolin, calcium carbonate, glass sheets), plasticizers, reinforcing agents (e.g., glass fibers, carbon fibers), pigments, and dyes. In this invention, the presence of the polymer (C) tends to improve the flame retardancy of the resin composition; therefore, high flame retardancy can be obtained even without or with only a small amount of flame retardant.

[0206] As pigments, examples of inorganic pigments include iron oxide, ultramarine, titanium dioxide, and carbon black. Examples of organic pigments include phthalocyanine and anthraquinone blue pigments, perylene and quinacridone red pigments, and isoindolineone yellow pigments. Examples of specialty pigments include fluorescent pigments, metallic pigments, and pearlescent pigments. Examples of dyes include aniline black, violet ketone, and anthraquinone dyes. Regarding pigments, various grades of pigments are commercially available to match the desired color; they can be used individually or in combination of two or more.

[0207] The proportion of polymer (C) in 100% by mass of this resin composition is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more. The proportion of polymer (C) in 100% by mass of this resin composition is preferably 30% by mass or less, more preferably 20% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 0.5-30% by mass, more preferably 1-30% by mass, and even more preferably 2-20% by mass. If the proportion of polymer (C) is above the above lower limit, the resulting molded article has excellent impact strength. If it is below the above upper limit, the decrease in the flowability and heat distortion temperature of the resin composition can be suppressed.

[0208] The proportion of thermoplastic resin (D) in 100% by mass of this resin composition is not particularly limited, but is preferably 40% by mass or more, more preferably 50% by mass or more. The proportion of thermoplastic resin (D) in 100% by mass of this resin composition is preferably 99.5% by mass or less, more preferably 99% by mass or less, and even more preferably 98% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, 40 to 99.5% by mass is preferred, more preferably 40 to 99% by mass, and even more preferably 50 to 98% by mass. If the proportion of thermoplastic resin (D) is above the above lower limit, the fluidity of the resin composition and the decrease in its heat distortion temperature can be suppressed. If it is below the above upper limit, the resulting molded article has excellent impact strength.

[0209] (Method for manufacturing the resin composition)

[0210] The resin composition can be manufactured by mixing a polymer containing a polyorganosiloxane, preferably a polymer (C), with a thermoplastic resin (D) and additives as needed.

[0211] As for methods of mixing various materials, well-known blending methods can be listed, without particular limitation. For example, methods of mixing and compounding using rollers, V-type mixers, super mixers, Nota mixers, Banbury internal mixers, mixing rollers, extruders, etc., can be listed.

[0212] As an example of a method for manufacturing the resin composition of the present invention, the following method can be described: A polymer (C), granular thermoplastic resin (D), and desired additives are mixed using an extruder, extruded into a filament, and then cut into granules using a rotary cutter or the like. By this method, a granular resin composition can be obtained.

[0213] <Molded Body>

[0214] A molded article of one embodiment of the present invention (hereinafter also referred to as "the molded article") comprises the resin composition. That is, the molded article preferably comprises a polymer (C) and a thermoplastic resin (D).

[0215] This molded article may further include other components. Examples of such other components include those that are already known.

[0216] This molded body can be manufactured, for example, by molding this resin composition.

[0217] Examples of molding methods used in the molding of thermoplastic resin compositions include injection molding, extrusion molding, blow molding, and calendering.

[0218] This molded material can be widely used in various industries, such as automotive, office automation (OA) equipment, home appliances, electrical / electronics, construction, consumer / cosmetics, and medical supplies. More specifically, it can be used as housings, various components, coating materials, automotive structural components, automotive interior components, light reflectors, building structural components, and doors and windows. Even more specifically, it can be used as internal / external components for personal computer housings, mobile phone housings, portable information terminal housings, portable game console housings, printers, copiers, etc., conductive coating materials, automotive interior / external components, building exterior materials, resin window frame components, flooring materials, and piping components.

[0219] Example

[0220] Hereinafter, the present invention will be specifically described through examples and comparative examples. Before the examples, various evaluation methods and manufacturing examples 1-1 to 1-6 of polyorganosiloxane latex will be described. Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-7 are examples concerning the manufacture and evaluation of graft copolymers, and Examples 2-1 to 2-9 and Comparative Examples 2-1 to 2-8 are examples concerning the manufacture and evaluation of thermoplastic resin compositions. In the manufacturing examples and examples, unless otherwise specified, "parts", "%", and "ppm" refer to "parts by mass", "% by mass", and "ppm by mass".

[0221] <Solid Composition>

[0222] A mass w1 of polyorganosiloxane latex was dried in a hot air dryer at 180°C for 30 minutes. The mass w2 of the residue after drying was measured, and the solid content [%] was calculated using the following formula.

[0223] Solid content [%]=w2 / w1×100

[0224] <Particle size>

[0225] The substance obtained by diluting "polyorganosiloxane (A1) latex" or "polymer (C) latex" with deionized water to a solid content concentration of about 3% was used as a sample. The number average particle size Dn and mass average particle size Dw were determined using a MATEC CHDF 2000 particle size analyzer under the following conditions.

[0226] Cartridge: A dedicated capillary cartridge for particle separation (trade name: C-202).

[0227] Carrier fluid: Dedicated carrier fluid (trade name: 2XGR 500),

[0228] Liquidity of carrier liquid: neutral,

[0229] Flow rate of the carrier fluid: 1.4 mL / min

[0230] Carrier fluid pressure: 4,000 psi (2,600 kPa),

[0231] Measurement temperature: 35℃

[0232] Sample volume used: 0.1 mL.

[0233] <Thermal decomposition>

[0234] Thermogravimetric analysis was performed on the graft copolymer using TG / DTA 6200 (manufactured by Seiko Instruments), and the thermal decomposability was evaluated using the following method.

[0235] Under a nitrogen flow rate of 200 mL / min, 100 parts by mass of a polymer containing polyorganosiloxane were heated to 550°C at a rate of 10°C / min. The temperature at which the residual amount of the polyorganosiloxane-containing polymer reached 1 part by mass was designated as X, and the temperature at which the residual amount reached 70 parts by mass was designated as Z. Samples with a residual amount of less than 1% at the end of the test were designated as having thermal decomposability A, and samples with a residual amount of more than 1% at the end of the test were designated as having thermal decomposability B. For samples with thermal decomposability A, the thermal decomposability was calculated using "XZ". The smaller the value of "XZ", the shorter the time required from the start to the end of thermal decomposition, and the better the thermal decomposability.

[0236] <y-x>

[0237] The temperature at which 90 parts by mass of 100 parts by mass of thermoplastic resin are obtained when heated to 550°C at a nitrogen flow rate of 200 mL / min and a rate of 10°C / min is defined as Y, and X is the temperature used in the thermal decomposition evaluation. For samples that are confirmed to reach the temperature of X, the thermal decomposition is calculated using "YX". When the value of "YX" is above 20, the polymer containing polyorganosiloxanes makes an excellent contribution to the formation of the carbonized layer, thus exhibiting excellent flame retardancy. Samples that cannot be confirmed to reach the temperature of X are designated as B. When the value is B, it is difficult to form a carbonized layer using polymers containing polyorganosiloxanes, resulting in a lack of effect on flame retardancy.

[0238] (Methods for manufacturing polymers)

[0239] [Manufacturing Example 1-1: Manufacturing of Polyorganosiloxane Latex (S-1)]

[0240] Two parts of γ-methacryloxypropyl dimethoxymethylsilane (DSMA) and 98 parts of octamethylcyclotetrasiloxane (manufactured by Momentive Performance Materials Japan, product name: TSF 404) were mixed to obtain 100 parts of an organosiloxane mixture. An aqueous solution containing 1 part of sodium dodecylbenzenesulfonate (DBSNa) dissolved in 150 parts of deionized water was added to the organosiloxane mixture. The mixture was stirred at 10,000 rpm for 5 minutes using a homogenizer, and then passed through a homogenizer twice at a pressure of 20 MPa to obtain a stable premixed emulsion.

[0241] The obtained emulsion was added to a 5-liter separable flask equipped with a cooling condenser. The emulsion was heated to 80°C, and a mixture of 0.20 parts sulfuric acid and 49.8 parts distilled water was continuously added over 3 minutes. The polymerization reaction was carried out at 80°C for 7 hours, then cooled to room temperature (25°C), and the resulting reactant was kept at room temperature for 6 hours. A 5% sodium hydroxide aqueous solution was added to the resulting reactant to neutralize the reaction solution to pH 7.0, yielding polyorganosiloxane latex (S-1).

[0242] The solids content of the polyorganosiloxane latex (S-1) is 30.2% by mass. The number-average particle size (Dn) is 384 nm, the mass-average particle size (Dw) is 403 nm, and the Dw / Dn ratio is 1.05.

[0243] [Manufacturing Example 1-2: Manufacturing of Polyorganosiloxane Latex (S-2)]

[0244] Except for changing the composition of the organosiloxane mixture to the composition shown in Table 1, the same operation as in Manufacturing Example 1-1 was performed to obtain polyorganosiloxane latex (S-2).

[0245] The solids content of the polyorganosiloxane latex (S-2) is 30.4% by mass. The number-average particle size (Dn) is 384 nm, the mass-average particle size (Dw) is 403 nm, and the Dw / Dn ratio is 1.05.

[0246] [Manufacturing Examples 1-3: Manufacturing of Polyorganosiloxane Latex (S-3)]

[0247] Except for changing the composition of the organosiloxane mixture to the composition shown in Table 1, the same operation as in Manufacturing Example 1-1 was performed to obtain polyorganosiloxane latex (S-3).

[0248] The solids content of the polyorganosiloxane latex (S-3) is 30.6% by mass. The number-average particle size (Dn) is 384 nm, the mass-average particle size (Dw) is 403 nm, and the Dw / Dn ratio is 1.05.

[0249] [Manufacturing Examples 1-4: Manufacturing of Polyorganosiloxane Latex (S-4)]

[0250] Except for changing the composition of the organosiloxane mixture to the composition shown in Table 1, the same operation as in Manufacturing Example 1-1 was performed to obtain polyorganosiloxane latex (S-4).

[0251] The solids content of the polyorganosiloxane latex (S-4) is 30.8% by mass. The number-average particle size (Dn) is 384 nm, the mass-average particle size (Dw) is 403 nm, and the Dw / Dn ratio is 1.05.

[0252] [Manufacturing Examples 1-5: Manufacturing of Polyorganosiloxane Latex (S-5)]

[0253] 0.5 parts of γ-methacryloxypropyl dimethoxymethylsilane (DSMA), 2 parts of tetraethoxysilane (TEOS), and 97.5 parts of octamethylcyclotetrasiloxane (manufactured by Shin-Etsu Silicon Co., Ltd., product name: DMC, a mixture of 3- to 6-membered ring cyclic organosiloxanes) were mixed to obtain 100 parts of organosiloxane mixture. An aqueous solution containing 0.68 parts of sodium dodecylbenzenesulfonate (DBSNa) and 0.68 parts of dodecylbenzenesulfonic acid (DBSH) dissolved in 150 parts of deionized water was added to the organosiloxane mixture. The mixture was stirred at 10,000 rpm for 5 minutes using a homogenizer, and then passed through a homogenizer twice at a pressure of 20 MPa to obtain a stable premixed emulsion.

[0254] The obtained emulsion was added to a 5-liter separable flask equipped with a cooling condenser. The emulsion was heated to 80°C and maintained for 5 hours for polymerization. After cooling to room temperature (25°C), the resulting reactant was kept at room temperature for 6 hours. A 5% sodium hydroxide aqueous solution was added to the resulting reactant to neutralize the reaction solution to pH 7.0, yielding polyorganosiloxane latex (S-5).

[0255] The solids content of the polyorganosiloxane latex (S-5) is 33.0% by mass. The number-average particle size (Dn) is 64 nm, the mass-average particle size (Dw) is 248 nm, and the Dw / Dn ratio is 3.88.

[0256] [Manufacturing Examples 1-6: Manufacturing of Polyorganosiloxane Latex (S-6)]

[0257] The composition of the organosiloxane mixture was changed to the composition shown in Table 1, and the amount of sodium dodecylbenzenesulfonate (DBSNa) was increased to 1.5 parts. Otherwise, the same operation as in Manufacturing Example 1-1 was performed to obtain polyorganosiloxane latex (S-6).

[0258] The solids content of the polyorganosiloxane latex (S-6) is 30.8% by mass. The number-average particle size (Dn) is 38 nm, the mass-average particle size (Dw) is 276 nm, and the Dw / Dn ratio is 7.26.

[0259] The components of manufacturing examples 1-1 to 1-6 are shown in Table 1.

[0260] The abbreviations in Table 1 are as follows.

[0261] TSF 404: Octamethylcyclotetrasiloxane

[0262] DMC: A mixture of cyclic organosiloxanes with 3- to 6-membered rings.

[0263] DSMA: γ-Methacryloxypropyldimethoxymethylsilane

[0264] TEOS: Tetraethoxysilane

[0265] [Table 1]

[0266]

[0267] [Example 1-1]

[0268] 80 parts (10.0 parts in polymer terms) of the polyorganosiloxane latex (S-1) obtained in Manufacturing Example 1-1 were collected into a 5-liter detachable flask, and a mixture of 8.82 parts of butyl acrylate (BA), 0.18 parts of allyl methacrylate (AMA), and 0.16 parts of cumene hydroperoxide (CB) was added. The mixture was stirred continuously at room temperature for 1 hour to allow it to impregnate the polyorganosiloxane.

[0269] The liquid temperature was raised to 50°C by purging the flask with nitrogen. At 50°C, an aqueous solution containing 0.001 parts ferrous sulfate (Fe), 0.003 parts disodium ethylenediaminetetraacetate (EDTA), and 0.24 parts sodium formaldehyde sulfoxylate (SFS) dissolved in 10 parts deionized water was added to initiate free radical polymerization. After the addition was complete, the liquid temperature was maintained at 65°C for 1 hour to complete the polymerization of the acrylate component, yielding a latex of a composite rubber of polyorganosiloxane and n-butyl acrylate.

[0270] The latex of the resulting composite rubber was heated to 65°C. A mixture of 11.0 parts methyl methacrylate (MMA) and 0.24 parts cumene peroxide (CB) was added dropwise to the latex over one hour to initiate the graft polymerization reaction. After the addition was complete, the mixture was maintained at 65°C for one hour, then cooled to room temperature to obtain a latex containing a graft copolymer (G-1) of polyorganosiloxane.

[0271] 500 parts of a 1% (w / w) aqueous solution of calcium acetate were heated to 85°C, and 340 parts of latex of graft copolymer (G-1) were slowly added dropwise while stirring until it solidified. The resulting graft copolymer (G-1) was filtered, washed, dehydrated, and dried to obtain graft copolymer (G-1).

[0272] Ten parts of the obtained graft copolymer (G-1) were added to 141 parts of deionized water and stirred for 3 minutes. Then, 10 parts of a 10% sodium chloride aqueous solution were added and stirred for 3 minutes. The graft copolymer (A-1) was filtered, washed, dehydrated, and dried to obtain sodium-containing graft copolymer powder (A-1).

[0273] The mass-average particle size and thermal decomposability of the graft copolymer powder (A-1) obtained were determined using the method described above. The results are shown in Table 2.

[0274] [Examples 1-2 to 1-4]

[0275] Except that the composition of each raw material used in Examples 1-1 was changed to the conditions shown in Table 2, graft copolymers (G-2 to G-4) containing polyorganosiloxane were prepared in the same manner as in Examples 1-1, and graft copolymer powders (A-2-A-4) were obtained and subjected to the same measurements. The results are shown in Table 2.

[0276] [Examples 1-5]

[0277] The graft copolymer containing polyorganosiloxane (G-1) was prepared in the same manner as in Example 1-1, except that the amount of the 10% by mass aqueous solution of sodium chloride was changed to 20 parts. Otherwise, the graft copolymer powder (A-5) was obtained using the same method as in Example 1-1, and the same measurements were performed. The results are shown in Table 2.

[0278] [Examples 1-6]

[0279] The graft copolymer containing polyorganosiloxane (G-1) was prepared in the same manner as in Example 1-1, except that the amount of the 10% by mass aqueous solution of sodium chloride was changed to 50 parts. Otherwise, the graft copolymer powder (A-6) was obtained using the same method as in Example 1-1, and the same measurements were performed. The results are shown in Table 2.

[0280] [Comparative Example 1-1]

[0281] After obtaining the graft copolymer containing polyorganosiloxane (G-1), without treatment with sodium chloride solution, the graft copolymer powder containing polyorganosiloxane (A-7) was obtained using the same method as in Example 1-1, and the same measurements were performed. The results are shown in Table 2.

[0282] [Comparative Examples 1-2]

[0283] After obtaining the graft copolymer containing polyorganosiloxane (G-2), without treating it with sodium chloride solution, the graft copolymer powder containing polyorganosiloxane (A-8) was obtained using the same method as in Examples 1-2, and the same measurements were performed. The results are shown in Table 2.

[0284] [Comparative Examples 1-3]

[0285] After obtaining the graft copolymer containing polyorganosiloxane (G-3), without treating it with sodium chloride solution, the graft copolymer powder containing polyorganosiloxane (A-9) was obtained using the same method as in Examples 1-3, and the same measurements were performed. The results are shown in Table 2.

[0286] [Comparative Examples 1-4]

[0287] After obtaining the graft copolymer containing polyorganosiloxane (G-4), without treatment with sodium chloride solution, the graft copolymer powder containing polyorganosiloxane (A-10) was obtained using the same method as in Examples 1-4, and the same measurements were performed. The results are shown in Table 2.

[0288] [Comparative Examples 1-5]

[0289] Except that the composition of each raw material used in Examples 1-1 was changed to the conditions shown in Table 2, the graft copolymer containing polyorganosiloxane (G-5) was prepared in the same manner as in Examples 1-1, and the graft copolymer powder (A-11) was obtained and the same measurements were performed. The results are shown in Table 2.

[0290] [Comparative Examples 1-6]

[0291] After obtaining the graft copolymer (G-5) containing polyorganosiloxane using the method described in Comparative Examples 1-5, 10 parts of the obtained graft copolymer (G-5) were added to 141 parts of deionized water and stirred for 3 minutes. Then, 10 parts of a 10% by mass aqueous solution of sodium chloride were added and stirred for 3 minutes. After filtration, washing, dehydration, and drying, sodium-containing graft copolymer powder (A-12) was obtained and subjected to the same determination. The results are shown in Table 2.

[0292] [Comparative Examples 1-7]

[0293] The raw material composition used in Examples 1-1 was changed to the conditions shown in Table 2. Otherwise, the procedure was the same as in Examples 1-1 to obtain a graft copolymer (G-6) containing polyorganosiloxane. Ten parts of the obtained graft copolymer (G-6) were added to 141 parts of deionized water and stirred for 3 minutes. Then, 10 parts of a 10% by mass sodium chloride aqueous solution were added and stirred for 3 minutes. After filtration, washing, and dehydration, the product was dried to obtain a sodium-containing graft copolymer powder (A-13). The same measurements were performed. The results are shown in Table 2.

[0294] [Table 2]

[0295]

[0296] The abbreviations in Table 2 are as follows.

[0297] nBA: n-Butyl acrylate

[0298] AMA: Allyl Methacrylate

[0299] MMA: Methyl methacrylate

[0300] Na: Sodium

[0301] K: Potassium

[0302] Compared to the graft copolymers of Comparative Examples 1-1 to 1-7, the graft copolymers of Examples 1-1 to 1-6 exhibit improved thermal decomposability.

[0303] [Examples 2-1 to 2-9, Comparative Examples 2-1 to 2-8]

[0304] The polymer powder containing polyorganosiloxane, additives, and thermoplastic resin were blended according to the ratios in Table 3 to obtain a mixture. The mixture was fed into a devolatilization twin-screw extruder (manufactured by Ikebe Corporation, PCM-30 (trade name)) for compounding to produce granules of each resin composition.

[0305] The following substances are used as thermoplastic resins.

[0306] PC: Polycarbonate resin (Iupilon S-2000F, manufactured by Mitsubishi Engineering Plastics, with a viscosity-average molecular weight of 24,000).

[0307] The thermal decomposition of PC was determined, and the result showed that the temperature at which the residual content reached 90% was 506℃.

[0308] The following substances are used as additives.

[0309] A-3750: Acrylic acid modified PTFE (METABLEN A-3750, manufactured by Mitsubishi Chemical Corporation).

[0310] The resin composition was injection molded into particles using an injection molding machine (Sumitomo Heavy Industries, SE 100DU (trade name)) to produce test pieces for evaluation.

[0311] Specifications of the test piece:

[0312] Test piece A: 80mm long × 10mm wide × 4mm thick

[0313] Test piece B: 100mm long × 50mm wide × 2mm thick

[0314] Test piece C: 125mm long × 13mm wide × 1.6mm thick

[0315] The extrusion and injection molding conditions are as follows.

[0316] Extrusion barrel temperature: 280℃

[0317] Injection barrel temperature: 280℃

[0318] Mold temperature: 60℃.

[0319] For test piece A, the notched Charpy impact strength of TYPE A according to ISO 179-1 was determined. A higher Charpy impact strength indicates higher impact resistance. The results are shown in Table 3.

[0320] For test piece B, visually observe the flow marks (striped patterns observed near the gate of the molded part) that appear near the gate of test piece B.

[0321] The "judgment method" involves visually assessing the appearance of the gate (A: flow marks are not obvious; B: flow marks are obvious). The evaluation results are shown in Table 3.

[0322] Using test piece C, the total burning time and whether dripping occurred during ignition were determined for five test pieces using the vertical burning test method according to UL94V. The shorter the total burning time, the higher the flame retardancy; no dripping is preferred. The evaluation results are shown in Table 3.

[0323] [Table 3]

[0324]

[0325] The resin composition of Comparative Example 2-1 does not contain graft copolymers, and therefore has low low-temperature impact strength and flame retardancy.

[0326] The molded articles of Examples 2-1 to 2-9, with specific values ​​of 90% thermoplastic resin residue and 1% polymer residue containing polyorganosiloxane, exhibit good flame retardancy compared to the molded articles of Comparative Examples 2-1 to 2-8. If the graft copolymer (A) does not decompose, the flame retardancy improvement effect cannot be obtained. When the decomposition temperature of the graft copolymer (A) is too close to that of the matrix resin, the matrix resin decomposes before the graft copolymer forms a carbonized layer, thus failing to achieve the flame retardancy improvement effect.

[0327] Compared with the graft copolymers of Examples 2-1 to 2-9, the graft copolymers of Comparative Examples 2-6 to 2-7 have poor appearance.

Claims

1. A resin composition comprising a thermoplastic resin and a polyorganosiloxane-containing polymer, the thermoplastic resin being an engineering plastic, the resin composition satisfying the following formula (1), Y - X > 20°C...(1) in formula (1), X means the temperature at which the residual amount of the polyorganosiloxane-containing polymer becomes 1 part by mass when 100 parts by mass of the polyorganosiloxane-containing polymer is warmed at 10°C / minute to 550°C under a nitrogen flow rate of 200 mL / minute, and Y means the temperature at which the residual amount of the thermoplastic resin becomes 90 parts by mass when 100 parts by mass of the thermoplastic resin is warmed at 10°C / minute to 550°C under a nitrogen flow rate of 200 mL / minute, the polyorganosiloxane-containing polymer contains an alkali metal atom in an amount of 100 mass ppm or more and 1000 mass ppm or less, the polyorganosiloxane-containing polymer has a mass average particle diameter Dw of 375 nm or more and 1000 nm or less.

2. The resin composition according to claim 1, satisfying the following formula (2), X - Z < 40°C...(2) in formula (2), X has the same meaning as X in formula (1), and Z means the temperature at which the residual amount of the polyorganosiloxane-containing polymer becomes 70 parts by mass when 100 parts by mass of the polyorganosiloxane-containing polymer is warmed at 10°C / minute to 550°C under a nitrogen flow rate of 200 mL / minute.

3. The resin composition according to claim 1 or 2, the polyorganosiloxane-containing polymer being a polymer having a complex and a grafted portion, the complex containing a polyorganosiloxane and a first vinyl polymer, and the grafted portion containing a second vinyl polymer.

4. The resin composition according to claim 3, the proportion of the polyorganosiloxane in 100 mass% of the polyorganosiloxane-containing polymer being 70 mass% or more and 98 mass% or less.

5. The resin composition according to claim 3, the first vinyl polymer containing a constitutional unit derived from a (meth)acrylate monomer.

6. The resin composition according to claim 3, the polyorganosiloxane containing a constitutional unit derived from a siloxane crosslinking agent, the proportion of the constitutional unit derived from the siloxane crosslinking agent in 100 mass% of the polyorganosiloxane being 3 mass% or less.

7. A molded body containing the resin composition according to any one of claims 1 to 6. ​ ​ ​ ​

Images