WO2007132657A1

WO2007132657A1 - Polyorganosiloxane-containing graft copolymer, flame retardant composed of the same, and resin composition containing the same

Info

Publication number: WO2007132657A1
Application number: PCT/JP2007/059015
Authority: WO
Inventors: Kazunori Saegusa; Hiroshi Tone
Original assignee: Kaneka Corporation
Priority date: 2006-05-12
Filing date: 2007-04-26
Publication date: 2007-11-22
Also published as: TW200745182A; JPWO2007132657A1

Abstract

Disclosed is a resin composition having excellent impact resistance at low temperatures wherein the contents of halogens and phosphorus are reduced and the balance between flame retardance and impact resistance is excellent. Further disclosed is a halogen-free, phosphorus-free resin composition having excellent impact resistance at low temperatures wherein the balance between flame retardance and impact resistance is excellent. Also disclosed is a graft copolymer as a modifier which enables to obtain such a resin composition. Specifically disclosed is a polyorganosiloxane-containing graft copolymer containing a polyorganosiloxane moiety (A) and a polymer moiety (B) having at least a unit derived from a radical reactive group-containing ultraviolet absorbent (B'). Also specifically disclosed are a flame retardant composed of such a graft copolymer and a resin composition containing such a graft copolymer.

Description

Specification

Polyorganosiloxane-containing graft copolymer, flame retardant comprising the same, and resin composition containing the same

Technical field

The present invention relates to a polyorganosiloxane-containing graft copolymer, a flame retardant comprising the same, and a resin composition containing the same.

Background art

[0002] Flame retardant and excellent mechanical properties of a resin composition are in great demand, particularly in the electrical and electronic markets, and high performance is required.

[0003] In recent years, phosphorus-based flame retardants are often used as non-halogen-based flame retardants for imparting flame retardancy to rosin. Since phosphorus-based flame retardants have many points to be improved, such as the heat resistance and impact resistance of the final molded product, which are not only in terms of toxicity, there are many reductions in the amount of phosphorus-based flame retardants used. Furthermore, conversion to a non-halogen non-phosphorus flame retardant is required. The use of metal compounds as non-halogen and non-phosphorous flame retardants has been proposed, but these too may cause deterioration in mechanical properties if used in an amount necessary to obtain sufficient flame retardancy. Even when used, it was necessary to reduce the amount.

[0004] With regard to imparting mechanical properties, polymers having a low glass transition temperature such as polyorganosiloxane, polyalkyl (meth) acrylate (low glass transition temperature), polybutadiene, polyisobutylene and the like are thermoplastic. There are widely used methods to improve the impact resistance, bow I tension characteristics, and characteristics of these oils, which are mixed with and dispersed in a matrix resin such as oil, thermosetting oil, and elastomer. Yes. However, since polymers other than polyorganosiloxane have a problem of reducing the flame retardancy of the resin composition due to the addition of the polymer, it is difficult to achieve both flame retardancy and mechanical properties. There are many cases. When the polymer having the low glass transition temperature is blended for the purpose of recovering the deterioration of the mechanical properties due to the addition of the flame retardant, the flame retardancy is lowered. Therefore, when the amount of the flame retardant is increased, the mechanical properties are lowered. I often faced problems.

[0005] On the other hand, polyorganosiloxane is particularly advantageous due to its excellent low-temperature impact strength. It is known that when blended with the matrix rosin, it is effective for improving low-temperature mechanical properties. Polyorganosiloxane itself is a combustible material. Less heat of combustion compared to other low glass transition temperature polymers such as polyalkyl (meth) acrylate (low glass transition temperature) and polybutadiene. As a result, the molded body of the resin composition obtained by blending the polyorganosiloxane has less reduction in flame retardancy compared to the case of blending other polymers. In some cases, flame retardancy itself can be simultaneously imparted by utilizing the unique reaction of polyorganosiloxane.

[0006] However, polyorganosiloxane is blended into the above-mentioned matrix resin, which is poorly compatible with general resin components, and can be made sufficiently fine and uniform even if a molded product is obtained. Therefore, when it is used in a large amount, it often causes problems such as poor appearance of the molded body and delamination of layers to reduce mechanical strength.

[0007] Therefore, by using a resin composition having compatibility with the matrix resin and chemically bonding with a polyorganosiloxane component to form a block copolymer or a graft copolymer, Many attempts have been made to overcome the challenges. In particular, a graft copolymer obtained by graft-bonding the coconut resin component to a polyorganosiloxane component is advantageous in that the dispersion state of the polyorganosiloxane in the matrix cocoon resin can be controlled.

[0008] Since the reactivity between the polyorganosiloxane itself and the bulle monomer that forms the resin component is poor, the efficiency is improved by using polyorganosiloxane modified with a so-called graft-crosslinking unit having radical polymerization reactivity. Methods for forming graft copolymers are well known. For example, Patent Documents 1 and 2 show examples using a graft crossing agent having a (meth) attalyloyl group. Patent Document 1 discloses a method for improving the impact strength of a molded product obtained by molding the obtained graft copolymer by increasing the graft efficiency by using this specific graft crossing agent, Patent Document 2 Discloses a method of increasing the impact strength of the final molded body by blending the graft copolymer with a thermoplastic resin.

[0009] Even when the graft crossing agent is specified and the polyorganosiloxane-containing graft copolymer is efficiently obtained as described above, a considerable amount of the vinyl monomer is still required, and this may cause an adverse effect depending on physical properties. There is. For example, as described above, a polyorganosiloxane-containing graft copolymer was used to improve the flame retardancy and impact resistance with good tolerance. In some cases, even if the dispersion state of the polyorganosiloxane component in the matrix resin is good and impact resistance is exhibited, the flame retardancy may be deteriorated due to the excessive amount of the vinyl monomer component. .

[0010] Patent Documents 3 and 4 describe the presence of (modified) polyorganosiloxane in the presence of (modified) polyorganosiloxane for the purpose of simultaneously improving the flame retardancy while maintaining or improving the impact resistance with the least amount of bulle monomer used. A method of using a graft copolymer obtained by first polymerizing a polyfunctional monomer and then polymerizing the vinyl monomer is disclosed.

[0011] In these prior arts, the amount of introduction of the polyorganosiloxane component can be made extremely high while maintaining a well-dispersed state of the polyorganosiloxane component. Therefore, flame retardancy and impact resistance can be improved in a well-balanced manner. Further, Patent Document 5 discloses a method of further improving the flame retardancy and impact resistance in a balanced manner by using a polyfunctional monomer having a specific molecular structure, preferably a polyfunctional monomer.

However, even if these prior arts are used, there is still room for improvement in characteristics such as flame retardancy and impact resistance, focusing on the resin component derived from the vinyl monomer. Reference 1: JP-A-60-252613

Patent Document 2: Japanese Patent Laid-Open No. 61-235462

Patent Document 3: Japanese Patent Laid-Open No. 2003-238639

Patent Document 4: Pamphlet of International Publication No. 2005Z080460

Patent Document 5: International Publication No. 2005Z108450 Pamphlet

Disclosure of the invention

Problems to be solved by the invention

[0013] The problem of the present invention is that it has excellent impact resistance particularly at low temperatures, has a reduced halogen 'phosphorus content, and is also non-halogen' non-phosphorus flame retardant 'impact resistance. It is an object of the present invention to provide a graft copolymer as an improving agent capable of providing an excellent resin composition, which can provide an excellent resin composition.

Means for solving the problem [0014] As a result of intensive studies to solve the above-mentioned problems, the present inventors are excellent in the effect of improving the impact resistance without impairing the flame retardancy of the specific graft copolymer, or flame retardant. The resin composition having excellent impact resistance while maintaining or improving flame retardancy is obtained by simultaneously improving the properties and blending the graft copolymer with a resin such as a thermoplastic resin. The present invention has been completed.

That is, the present invention relates to a polyorganosiloxane-containing graft copolymer comprising a polyorganosiloxane (A) moiety and a polymer (Β) moiety having at least a unit derived from a radical reactive group-containing ultraviolet absorber (Β ′). Regarding coalescence.

[0016] Preferably, the embodiment further comprises a polyorganosiloxane-containing graph copolymer containing a polymer (C) site, wherein the polymer (C) is a polyfunctional monomer (C '). 50-: a polymer obtained by polymerizing a monomer containing LOO wt% and a radical-reactive monomer (C ") 50-0 wt% copolymerizable therewith, the polyfunctionality The monomer (C ′) is a polyorganosiloxane-containing graft copolymer that is a polyfunctional monomer () having two or more radical reactive groups in the molecule.

[0017] Preferably, in the embodiment, the polyfunctional monomer () force is a polyorganosiloxane-containing graft copolymer which is at least one selected from the group consisting of a cyanuric acid derivative, an isocyanuric acid derivative, and a biphenyl derivative. It is a polymer.

[0018] Preferably, an embodiment is a polyorganosiloxane-containing graft copolymer in which the ultraviolet absorber (Β ') is a benzotriazole-based compound.

[0019] Preferably, the embodiment is a polyorganosiloxane-containing graft copolymer characterized by having a benzotriazole-based compound power phenolic hydroxyl group.

[0020] Preferably, an embodiment is a polyorganosiloxane-containing graft copolymer characterized by having a glass transition temperature force of 40 ° C or higher of the polymer (i).

[0021] The present invention also relates to a flame retardant having a polyorganosiloxane-containing graft copolymer power.

[0022] Further, the present invention includes one or more selected from the group consisting of thermoplastic resin, thermosetting resin, and elastomer, and the polyorganosiloxane-containing graft copolymer. The present invention relates to a resin composition containing a graft copolymer.

[0023] Preferably, in the embodiment, the thermoplastic resin is a polycarbonate resin, a polyester resin, a polyester carbonate resin, a polyphenylene ether resin, a polyphenylene sulfide resin, a polysulfone resin, a polyether. Sulphone resin, polyarylene resin

Polyamide resin, polyetherimide resin, polyacetal resin, polyvinylacetal resin, polyketone resin, polyetherketone resin, polyetheretherketone resin, polyarylketone resin, polyether-tolyl resin, liquid crystal resin Selected from the group consisting of fat, polybenzimidazole resin, polyparabanic acid resin, Jeny compound, maleimide compound, aromatic alkellui compound, methacrylate ester, acrylate ester, and cyanide butyl compound A polymer obtained by polymerizing or copolymerizing one or more monomers, or a copolymer resin, a polyolefin resin, a salt resin resin, and a salt resin vinyl resin. It is a graft copolymer-containing resin composition characterized by being one or more selected.

[0024] Preferably, in the embodiment, the thermosetting resin is phenol resin, epoxy resin, urea resin, melamine resin, polyimide resin, polyamideimide resin, thermosetting polyester resin, alkyd. Resin, silicone resin, urethane resin, polybulle ester resin, diaryl polyphthalate resin, bismaleimide-triazine resin, furan resin, xylene resin, guanamine resin, maleic resin, and dicyclopenta A graft copolymer-containing resin composition characterized in that it is at least one selected from Jen resin.

[0025] Preferably, an embodiment is a graft copolymer-containing resin composition, wherein the elastomer is at least one selected from the group consisting of natural rubber and synthetic rubber. It is.

[0026] A preferred embodiment is a graft copolymer-containing resin composition, wherein the thermoplastic resin is an aromatic polycarbonate resin, in which case In addition, a graft copolymer-containing resin composition characterized by containing a sulfur-containing organometallic salt is preferable.

The invention's effect

[0027] By blending the graft copolymer of the present invention with a resin such as a thermoplastic resin. It has low halogen 'low phosphorus content and non-halogen' non-phosphorus, and has excellent impact resistance at low temperatures, etc. without reducing flame retardancy or improving flame retardancy. A fat composition can be provided.

BEST MODE FOR CARRYING OUT THE INVENTION

[0028] Hereinafter, preferred embodiments of the present invention will be described.

[0029] The graft copolymer of the present invention comprises a polyorganosiloxane (A) moiety and a polymer (B) moiety having at least a unit derived from a radical reactive group-containing ultraviolet absorber (Β '). This is a polyorganosiloxane-containing graft copolymer. In order to improve the flame retardancy and impact resistance in a well-balanced manner by reducing the amount of the polymer (Β) component, which is a flammable component, the polyorganosiloxane-containing graft copolymer of the present invention is: Preferably, the polymer further comprises a polymer (C) site having at least a unit derived from a polyfunctional monomer (C ′) having two or more radical reactive groups in the molecule.

[0030] The strong graft copolymer is obtained, for example, by polymerizing one or more stages of the monomer containing the polyfunctional monomer (C) as necessary in the presence of polyorganosiloxane (Α). The polyorganosiloxane-containing graft copolymer of the present invention can be obtained by polymerizing one or more monomers containing a radical reactive group-containing ultraviolet absorber (Β ′).

[0031] Polyorganosiloxane (Α) used in the present invention, radical-reactive group-containing ultraviolet absorber

Specific examples of the polymer (Β) having at least units derived from (Β ′) and the polymer (C) having at least units derived from the polyfunctional monomer (C ′) are described below.

[0032] [Polyorganosiloxane (Α)]

The polyorganosiloxane (Α) used in the present invention is a component for improving impact resistance particularly at low temperatures without lowering flame retardancy, and in some cases, it is difficult for a resin composition containing itself. It is a component that improves flammability. As the polyorganosiloxane (Α), a polyorganosiloxane such as polydimethylsiloxane, polymethylphenylsiloxane, polydimethylsiloxane-diphenylsiloxane copolymer, etc., a part of the side chain alkyl group is substituted with a hydrogen atom. In addition, polyorganonoidogen siloxane can be used. Of these, polydimethylsiloxane, polymethylphenylsiloxane, and polydimethylsiloxane-diphenylsiloxane copolymer are preferred for imparting flame retardancy. Ridimethylsiloxane is most preferred because it is more economically available.

[0033] When polymethylphenol siloxane or polydimethylsiloxane-diphenylsiloxane copolymer is used, the low-temperature characteristics may be further improved, and the polymer (B) and if necessary If the refractive index of the graft copolymer of the present invention together with the polymer (C) is set to be close to that of the matrix resin, transparency and good colorability can be imparted to the resulting resin composition.

[0034] The polyorganosiloxane (A) preferably has a graft-crossing group because it can exhibit good impact resistance and flame retardancy. Among them, it is particularly preferable to have it in the side chain, among which it is more preferable to have it at the Z or molecular chain end.

[0035] A solution polymerization method, a suspension polymerization method, an emulsion polymerization method and the like are not particularly limited as a method for obtaining the polyorganosiloxane (A).

[0036] For example, a method of polymerizing a cyclic, linear or branched organosiloxane, preferably a cyclic organosiloxane, using a catalyst such as an acid, an alkali, a salt or a fluorine compound can be mentioned. The weight average molecular weight (Mw) of the organosiloxane used for the polymerization is preferably <20,000 or less, more preferably <10,000 or less, and even more preferably <5,000 or less, particularly preferably 2. 500 or less. In the above method, a method using a silane having a graft crossing group together with the organosiloxane and a cyclic, linear, or branched organosiloxane having the same weight average molecular weight (Mw) having a Z or graft crossing group. More preferably. Alternatively, in the above method, a method using a silane having a graft crossing group and a cyclic, linear or branched organosiloxane having the same weight average molecular weight (Mw) having a graft crossing group and Z or a graft crossing group without using the organosiloxane. Can be more preferable.

[0037] Alternatively, the weight average molecular weight (Mw) strength in solution, slurry, or emulsion is preferably <20,000 or more, more preferably <ί or more, 50, 000 or more, and even ί or 100, 000 or more. A silane having a graft crossover group and a cyclic, linear or branched organosiloxane having a graft crossover group having a weight average molecular weight (Mw) of preferably 20,000 or less. In the presence of the same catalyst as above A method of balancing can be given. Or in solution, slurry, or emulsion, a polyorganosiloxane having a weight average molecular weight (Mw) of preferably 20,000 or more and a graft crossover group having a weight average molecular weight (Mw) of preferably 20,000 or more. Examples thereof include a method of equilibrating a polyorganosiloxane having a hydrogen atom in the presence of a catalyst as described above.

[0038] The polyorganosiloxane (A) is preferably in the form of particles in order to develop the impact resistance of the final molded article satisfactorily. Powerful polyorganosiloxane (A) particles can also be produced by emulsion polymerization as described above. Instead of the emulsion polymerization method, the modified or non-modified polyorganosiloxane (A) obtained by the method of modifying the emulsion polyorganosiloxane as described above, the solution polymerization method, etc. is mechanically used using a high-pressure homogenizer. An emulsion containing polyorganosiloxane (A) particles can also be obtained by a method such as forced emulsification.

[0039] The particles of polyorganosiloxane (A) are described in detail in JP-A-2000-226420, JP-A-2000-834392, US Pat. Nos. 2891920, 3294725, etc. It can be obtained by a known emulsion polymerization method.

[0040] Specifically, for example, a cyclic siloxane represented by 1, 3, 5, 7-otatamethylcyclotetrasiloxane (D4), and a bifunctional group having a hydrolyzable group such as Z or dimethyldimethoxysilane. Silanes, trifunctional or higher functional alkoxysilanes such as methyltriethoxysilane and tetrapropyloxysilane, condensates of trifunctional or higher functional silanes such as methyl orthosilicate, and, if necessary, mercaptopropyldimethoxymethylsilane, Polyorganosiloxane (A) particles can be obtained using a grafting agent such as acryloyloxypropyldimethoxymethylsilane, methacryloyloxypropyldimethoxymethylsilane, vinyldimethoxymethylsilane, and vinylphenyldimethoxymethylsilane. . Preferably, the amount of the grafting agent used is 0.03 mol% or more in terms of siloxane units in the resulting polyorganosiloxane from the viewpoint of obtaining good impact resistance in the final molded product. Is not less than 0.06 mol%, more preferably not less than 0.15 mol%, particularly preferably not less than 0.5 mol%, not more than 5 mol%, more preferably not more than 3 mol%, further not more than lmol%. [0041] The conditions for the polymerization of the polyorganosiloxane (A) are preferably emulsified using a homogenizer or the like together with water and a surfactant, and mechanically emulsified and dispersed under high pressure as necessary, and then acid. PH is 4 or less, preferably 3 or less, more preferably 2 or less, or base is added and pH is 8 or more, preferably 9.5 or more, more preferably 11 or more. Thus, the polyorganosiloxane (A) particles can be obtained. The temperature during the polymerization is 0 ° C or higher, preferably 30 ° C or higher, more preferably 50 ° C or higher, further 60 ° C or higher, 150 ° C or lower, preferably 120 ° C or lower, more preferably A temperature of 95 ° C. or lower can be applied, and it can be preferably obtained by a hydrolysis and condensation reaction in an inert gas atmosphere such as nitrogen or in a vacuum degassed state.

[0042] Here, when polymerizing the cyclic siloxane and Z or silane, it is preferable to apply a seed polymerization method described below. For example, a method using an organic polymer as seed particles disclosed in JP-A-63-202630, JP-A-63-202631, and JP-A-4-258636, JP-A-60-088040 A method using the polyorganosiloxane latex disclosed in 1) as a seed latex, more preferably a method using an organic polymer having swelling properties with respect to a cyclic siloxane as disclosed in WO 03Z068835, or latex. A method of using a polymer having a particle size of 20 nm or less, preferably 15 nm or less, more preferably lOnm or less as seed particles can be employed. Further, a polymer (B) having at least a unit derived from a radical reactive group-containing ultraviolet absorber (Β ′) described later can be used as seed particles. The polymer (重合) at this time is preferably 20% by weight or less, more preferably 5% by weight or less, and further 2% by weight with respect to the total amount of the polyorganosiloxane (Α) and the polymer (Β). It is preferable to use less than U.

[0043] The emulsion of the polyorganosiloxane (Α) obtained by the above method usually contains a volatile low molecular weight cyclic siloxane. In the present invention, for the purpose of removing this volatile low-molecular-weight cyclic siloxane, steam stripping as disclosed in US Pat. No. 4,600,436, Japanese Patent Application Laid-Open No. 2002-249582 is applied. — Adsorption agent such as diatomaceous earth disclosed in No. 121284 is adsorbed to adsorb volatile low molecular weight cyclic siloxane, and the resulting polyorganosiloxane (シロキサン) is adsorbed. For example, a filtering method can be applied.

[0044] As another method for obtaining the polyorganosiloxane (A) in the emulsion state, methods disclosed in JP-A-11-222554, JP-A-2001-288269, and the like can be used. For example, the content of volatile low molecular weight siloxane is preferably 5% by weight or less, more preferably 1% by weight or less, and the weight average molecular weight (Mw) is preferably 20,000 or less, more preferably 10,000 or less, More preferably, it is 5,000 or less, more preferably 2,500 or less, having a condensable group and a Z or hydrolyzable group at the terminal, and if necessary, a mercaptopropyl group, a methacryloyloxypropyl group, or an allyloyl group. A linear or branched modified or non-modified (poly) organosiloxane partially substituted with a radical reactive group such as an oxypropyl group, a butyl group, a vinylphenyl group, or an aryl group can be used. Examples of the condensable group include a hydroxyl group, an amino group, and examples of the hydrolyzable group include an alkoxyl group, an acyloxy group, a ketoxime group, an alkenoxy group, an amide group, and an aminoxy group.

[0045] The modified or non-modified (poly) organosiloxane may be used together with a graft crossing agent such as silane having a radical reactive group as described above, and may be added with water, a surfactant, etc. It can be mechanically forcedly emulsified to a desired particle size with a homogenizer, an ultrasonic generator, a hyde mouth share, a membrane emulsifier or a colloidal mill. The polymerization temperature of the modified or non-modified (poly) organosiloxane is 0 ° C or higher, preferably 100 ° C or lower, more preferably 50 ° C or lower, and further 30 ° C or lower, and the pH is preferably In the same manner as described above, the polyorganosiloxane (A) can be obtained by applying the same range method using an acid or a base. When ヽ (poly) organosiloxane with a low content of volatile low molecular weight siloxane is used as a raw material, the polyorganosiloxane described above can be reduced in volatile low molecular weight siloxane by selecting the polymerization conditions. Siloxane (A) can be obtained.

[0046] Polymerization of the cyclic siloxane and Z or silane, or modified or non-modified

When acidic polymerization conditions are used in the forced emulsion polymerization of (poly) organosiloxane, it is preferable to use a surfactant that exhibits surface activity even under acidic conditions. As such a surfactant, for example, a metal salt of an alkyl sulfate ester And anionic surfactants such as metal salts of alkyl sulfonic acids and metal salts of alkyl aryl sulfonic acids.

[0047] The metal salt is preferably an alkali metal salt, particularly a sodium salt or potassium salt. Of these, sodium salt is preferred, and sodium dodecylbenzenesulfonate is most preferred. In addition, polyoxyalkylene alkyl ethers typified by polyoxyethylene dodecyl ether, polyoxyalkylene alkyl aryl ethers typified by polyoxyethylene norphe ether, and polyoxyalkylene higher grades typified by polyoxyethylene stearate ester. Nonionic surfactants such as fatty acid esters and sorbitan monolaurate can be used. Alternatively, they can be used in combination with the anionic surfactant.

[0048] As the acid for making the acidic condition, inorganic acids such as sulfuric acid, hydrochloric acid and nitric acid and organic acids such as dodecylbenzenesulfonic acid, dodecylsulfuric acid and trifluoroacetic acid can be used. Alkylaryl sulfonic acid represented by dodecylbenzene sulfonic acid has a function not only as an acid component but also as a surfactant. In some cases, it may be used alone, and can be preferably used. However, these acids and surfactants are not limited to these and may be either a single component or a combination of multiple components.

[0049] After the polymerization is completed under acidic conditions, the latex is aged at a temperature near or below room temperature for several hours or more as necessary, and after the polyorganosiloxane has a high molecular weight, sodium hydroxide, Neutralize the system to pH 5-8 by adding inorganic bases such as potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, ammonia, and organic bases such as alkylamines and alkyl ammonium hydroxides. By doing so, the polymerization of siloxane can be stopped.

[0050] Similarly, when basic polymerization conditions are used, it is preferable to use a surfactant that is basic but exhibits surface-active performance. Examples of such surfactants include alkyltrimethylammonium salts such as dodecyltrimethylammonium bromide and stearyltrimethylammonium bromide, and dialkyldimethylammonium such as didodecyldimethylammonium bromide. Salt, stearyldimethylbenzyl Examples thereof include cationic surfactants such as alkyl aralkyl ammonium salts such as ammonium chloride. Further, a nonionic surfactant as described above may be used or used in combination. As the base for the basic condition, an inorganic base such as lithium hydroxide, potassium hydroxide, sodium hydroxide, cesium hydroxide, or an organic base such as alkyl ammonium hydroxide is used. it can.

[0051] Tetraorganoammoum hydroxides such as cetyltrimethylammonium hydroxide described in JP-A-2001-106787 have the functions of both a cationic surfactant and a base. May be used preferably because it may be used alone. However, these bases and surfactants are not limited to these and may be either a single component or a combination of a plurality of components. After the polymerization is completed under basic conditions, the latex is aged as necessary, and the system is neutralized with an inorganic acid such as sulfuric acid or an organic acid such as acetic acid or dodecylbenzenesulfonic acid as described above. Thus, the polymerization of siloxane can be stopped.

[0052] The volume average particle diameter of the polyorganosiloxane (A) particles is preferably from 0.008 to 0.6 μm, more preferably from 0.01 to 0.35 m force. In many cases, it is difficult to stably obtain a volume average particle size of less than 0.008 m. If it exceeds 0.6 m, the flame resistance and impact resistance of the final molded product may be deteriorated. The volume average particle diameter can be measured using, for example, MICROTRAC NPA150 manufactured by Nikkiso Co., Ltd.

[0053] The polyorganosiloxane (A) used in the present invention has a weight average molecular weight (Mw) of preferably 100,000 or more, more preferably <150,000 or more, preferably <is 1,000,000 or less, More preferably, it is 700,000 or less, and further 300,000 or less. If the weight average molecular weight (Mw) is too low, the flame resistance may deteriorate the impact resistance. In addition, if the weight average molecular weight (Mw) is too high, the productivity may decrease. As the weight average molecular weight (Mw), a standard polystyrene conversion value obtained by gel permeation 'chromatography (GPC) analysis can be used.

[0054] In the polyorganosiloxane-containing graft copolymer of the present invention (with the entire copolymer being 100% by weight), the polyorganosiloxane (A) moiety impairs the flame retardancy of the resulting resin composition. Therefore, it is preferable to contain 50% by weight or more, more preferably 6%. It is preferable to contain 5% by weight or more, further 75% by weight or more, particularly 82.5% by weight or more. The upper limit is preferably 99% by weight, more preferably 98% by weight, and even more preferably 95% by weight in order to improve the dispersion state of the polyorganosiloxane (A) component in the matrix resin.

[0055] [Polymer having at least units derived from radical-reactive group-containing ultraviolet absorber (Β ') (Β)]

The polymer (Β) component used in the present invention is a component that is introduced into the polyorganosiloxane-containing graft copolymer of the present invention in order to ensure compatibility with the matrix resin, and also has radical reactivity. It is characterized by having at least units derived from a group-containing ultraviolet absorber (Β ′).

[0056] The radical-reactive group-containing ultraviolet absorber (Β ') used in the present invention is a monomer component having both an ultraviolet-absorbing group and an ethylenically unsaturated group capable of radical reaction. The ultraviolet absorber (Β ′) is not limited, but preferably includes a benzotriazole derivative, a hinderdamine derivative, and the like. Although the mechanism of action is unknown, the use of the UV absorber (Β ′) tends to improve flame retardancy without degrading mechanical properties such as impact resistance.

[0057] The hindered amine derivative is not limited! /, But a hindered amine derivative represented by the following general formula (I) is preferably used. Specifically, 2, 2, 6, 6-tetramethyl-4- Examples include piperidylmetatalil®, 1, 2, 2, 6, 6-pentamethyl-4-piperidylmethacryla.

[0058] [Chemical 1]

(Wherein R ¹ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ² is a hydrogen atom or a methyl group.) The benzotriazole derivative is not particularly limited. The mechanism of action is unknown, but in particular Such benzotriazole derivatives are preferred because those having a phenolic hydroxyl group tend to improve flame retardancy. As a powerful compound, a benzotriazole derivative represented by the following general formula (Π) can be preferably used.

[0060] Specifically, 2- (2 'hydroxy 5'-methacryloyloxychetylphenol) 2H monobenzotriazole, 2- (2' hydroxy 5'-methacryloyloxychetyl phenyl) -5 2H benzotriazole, 2- (2'-hydroxy-5'-methacryloyloxypropyl phenol) 2H benzotriazole, 2- (2'-hydroxy-5'-methacryloyloxypropyl phenol) Examples thereof include 5) 2H benzotriazole, 2— (2′-hydroxy-5′-metatalyloxypropyl 3′-t-butylphenyl) 2H-benzotriazole, and the like.

[0061] [Chemical 2]

(Wherein X and R ¹ are a hydrogen atom, halogen or alkyl having 1 to 18 carbon atoms, R ² is an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 12 carbon atoms, or these And R ³ is a hydrogen atom or a methyl group.)

[0062] In particular, since the flame retardancy is remarkably improved, a benzotriazole derivative is more preferably used. 2- (2′-hydroxy 5′-methacryloyloxyethyl) represented by the following chemical formula (ΠΙ) — 2H-benzotriazole is particularly preferably used.

[0063] [Chemical 3]

(III) [0064] The ultraviolet absorber (Β ') may be used alone, but can preferably be used by copolymerization with an ethylenically unsaturated monomer. In order not to deteriorate the flame retardancy, the glass transition temperature of the polymer obtained by polymerizing only the ethylenically unsaturated monomer is preferably 40 ° C or higher, more preferably 60 ° C or higher. More preferably 90 ° C or more. In order to obtain better flame retardancy, the preferred glass transition temperature of the copolymer comprising the ultraviolet absorber (Β ′) and, if necessary, an ethylenically unsaturated monomer is the same as described above. The ultraviolet absorber (Β ') and the ethylenically unsaturated monomer can be polymerized in one stage or in two or more stages, even if they are polymerized in two or more stages. It is also preferable to adjust the monomer composition so that the glass transition temperature of the polymer satisfies the aforementioned range.

[0065] The ethylenically unsaturated monomer may be a single compound or a mixture of two or more compounds, but the glass transition temperature of the obtained polymer is set as described above. Is preferred. The glass transition temperature referred to in the present invention can be substituted by the one described in the fourth edition of the “Polymer Handbook” published by John Wiley & Son, 1999. In the case of a copolymer, the weight fraction in the copolymer can be used. Paying attention to the monomer unit with a ratio of 5% or more, it can be substituted by calculating from the glass transition temperature of the homopolymer of each monomer component and the weight fraction based on the Fox equation.

[0066] The amount of the ultraviolet absorber (Β ') used in the preparation of the polymer (B) according to the present invention is based on the total amount of the ultraviolet absorber (Β') and the ethylenically unsaturated monomer. It is particularly preferably 0.01% by weight or more, more preferably 1 to 33% by weight, and even more preferably 2 to 13% by weight. When the amount of the ultraviolet absorber (Β ′) is too large, the cost is increased and the polymerization may be difficult. When the amount is too small, the effect of improving flame retardancy may not be sufficient.

[0067] The ability to use various types of ethylenically unsaturated monomers includes, as specific examples thereof, styrene, a-methino styrene, vinyl retanolene, vinino naphthalene, vinino biphenyl, 1,1'-diphenylethylene, aromatic butyl monomers such as acenaphthylene, cyanuric butyl monomers such as acrylonitrile, methallyl-tolyl, methyl acrylate, ethyl acrylate, butyl acrylate, octyl Atalylate, 2-ethylhexyl Atalylate, lauryl atylate, stearyl atylate, benzyl atylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate Alkyl (meth) acrylates such as urylmethacrylate, myristylmethacrylate, stearylmethacrylate, behenylmethacrylate, benzylmethacrylate, acrylamide, methacrylate, dodecylmethacrylamide, cyclododecylmethacrylamide, adamantylmethacrylamide (Meth) acrylamides such as In the present invention, unless otherwise specified, for example, (meth) acryl means acryl and Z or methacryl.

[0068] Among these, in order to obtain good flame retardancy, aromatic styrene monomers such as styrene, (X-methyl styrene, butyl toluene, urnaphthalene, birbiphenyl, etc. Alkyl (meth) atalylates with 2 or less carbon atoms in alkyl groups such as cyanuric bur monomers such as ril, methyl metatalylate, ethyl metatalylate, methyl attalylate, and ethyl acrylate. More preferably, the homopolymer has a glass transition temperature of 40 ° C or higher, more preferably 60 ° C or higher, and even more preferably 90 ° C or higher. Specific examples of powerful monomers include styrene, a-methylenstyrene, vinyltoluene, vinylnaphthalene, vinylenobiphenol, acrylonitrile, metathalonitrile, Such as it is possible to increase the Rume Tatari rate.

[0069] If necessary, such as butyl monomers containing carboxyl groups such as itaconic acid, (meth) acrylic acid, fumaric acid, maleic acid, 4 styrene sulfonic acid, 2 acrylamide-2-methylpropane sulfonic acid, etc. Bulonic monomers containing sulfonic acid groups or sodium salts, potassium salts, calcium salts, magnesium salts, aluminum salts, organic phosphorous salts, organic sulfur salts, organic ammonium salts, glycidyl meta Use together with functional group-containing vinyl monomers such as epoxy group-containing butyl monomers such as talylate, hydroxyl group-containing vinyl monomers such as 2-hydroxyethyl methacrylate and 4-hydroxybutyl acrylate. I can do it.

[0070] In the polymerization of the ultraviolet absorber (Β ') with an ethylenically unsaturated monomer, the soot that is not essential is the heat resistance and thermal stability of the resulting polyorganosiloxane-containing graft copolymer. Since both flame retardancy and impact resistance of the molded article may be improved, it is preferable to use a chain transfer agent. Specific examples of chain transfer agents include unsaturated terpenes such as a-vinene, terpinolene and limonene, n-octyl mercaptan, and t-octylme Examples include mercaptans such as lucapbutane, n-dodecyl mercaptan, t-dodecyl mercaptan, 2-ethyl thiolglycolate, among which the mercaptans can be preferably used. Furthermore, since a polyorganosiloxane-containing graft copolymer or rosin composition having no odor is obtained, 2-ethylhexylthioglycolate can be preferably used.

[0071] The amount of the chain transfer agent used with respect to the total amount of the ultraviolet absorber (Β ') and the ethylenically unsaturated monomer is preferably 0.01 wt% or more, more preferably 0.05 wt% or more. Further, it is 0.1% by weight or more, preferably 10% by weight or less, more preferably 5% by weight or less, and further 2% by weight or less. Use of a chain transfer agent in excess of 10% by weight reduces the grafting efficiency of the resulting graft copolymer, which may reduce the dispersibility of the graft copolymer of the present invention in the matrix resin. Yes, there are cases where flame retardancy and mechanical properties are not good.

[0072] For example, in the emulsion polymerization of an ultraviolet absorber (Β ') and an ethylenically unsaturated monomer, a polymer (Β) can be obtained by polymerization using a known radical polymerization method. it can. When a (co) polymer containing a polymer (C) having at least a unit derived from the above-mentioned polyorganosiloxane (Α) site and, if necessary, a polyfunctional monomer () described later is obtained as an emulsion. The polymerization of the ultraviolet absorber (Β ′) and the ethylenically unsaturated monomer is preferably carried out by a emulsion polymerization method. As another preferred method, a slurry obtained by salting out the emulsion of the (co) polymer with sodium sulfate, sodium chloride calcium, magnesium sulfate or the like, and an ultraviolet absorber (Β ′) ) And an ethylenically unsaturated monomer, or a salt or the like is added to the mixture of the droplet-like ultraviolet absorber (Β ') and the ethylenically unsaturated monomer and the (co) polymer emulsion. A method of adsorbing the (co) polymer component to droplets of an ultraviolet absorber (Β ′) and an ethylenically unsaturated monomer, followed by polymerization (hereinafter referred to as a suspension seed polymerization method) is employed. be able to.

[0073] When the emulsion polymerization method is employed, a known polymerization initiator, that is, 2, 2'-azobisoxy-tolyl, hydrogen peroxide, potassium persulfate, ammonium persulfate, etc. is thermally decomposed. It can be used as a polymerization initiator. T-Butylperoxyisopropyl carbonate, paramentane hydride peroxide, cumene hydride peroxide, dicumyl Organic peroxides such as peroxides, t-butyl hydride peroxide, di-t-butyl peroxide, t-hexyl silver oxide, or inorganics such as hydrogen peroxide, persulfuric acid lithium and ammonium persulfate Peracids such as peracids and, if necessary, sodium formaldehyde sulfoxylate, reducing agents such as glucose, and transition metal salts such as iron (II) sulfate if necessary, and further Accordingly, it can be used as a redox-type polymerization initiator using a chelating agent such as ethylenediammine tetraacetate and a phosphorus-containing compound such as sodium pyrophosphate if necessary.

[0074] In the case of using a redox type polymerization initiator system, the peroxide does not substantially thermally decompose! Since the polymerization can be performed even at low temperature, the polymerization temperature can be widened in a range. This is preferable because it can be set. Among them, it is preferable to use an aromatic ring-containing peroxide such as cumene hydride peroxide and dicumyl peroxide as a redox polymerization initiator. The amount of the polymerization initiator used and the amount of the reducing agent / transition metal salt / chelating agent used when a redox type polymerization initiator is used can be used within a known range.

[0075] It should be noted that the ability to add a surfactant during or after the polymerization can be used within the publicly known range. Further, a buffering agent such as a pH buffer can be used as necessary, but this can also be used within a known range.

[0076] The polymerization temperature, pressure, deoxygenation, concentration, stirring, and other conditions for the above polymerization can be in a known range. The ultraviolet absorption is incorporated into the emulsion of the (co) polymer containing the polymer (C) having at least the unit derived from the polyorganosiloxane (A) and the polyfunctional monomer () described below, if necessary. Agent (Β ') and ethylenically unsaturated monomer are added at once, continuously added, or a single unit containing the ultraviolet absorber (Β') and an ethylenically unsaturated monomer. A method in which the polymerization of the polymer (C) is carried out by adding the polymer (C) emulsion to the reactor charged with the polymer can be appropriately employed.

[0077] In the polymerization by the suspension seed polymerization method, preferably a peroxide such as lauryl peroxide or benzoyl peroxide, an azo compound such as azobisisobutyrate-tolyl, and the like, preferably thermally decomposable. In advance, the polymerization initiator is dissolved in a monomer containing an ultraviolet absorber (Β ') and, if necessary, an ethylenically unsaturated monomer, and then the suspension is put into a suspended state and the reaction temperature is increased. Is preferably 60 ° C or more, more preferably The polymerization can be started by raising the temperature to 70 ° C or higher, and further to 80 ° C or higher.

[0078] At this time, a protective colloid agent such as polyvinyl alcohol, polyethylene oxide and calcium phosphate can be used to prevent the suspended particles from becoming unstable and coarsening. Known conditions can be applied to the initiator, the amount of the protective colloid agent used, and the conditions such as pressure, deoxygenation, and stirring.

[0079] Before and after polymerization of the monomer containing the radical-reactive group-containing UV absorber (Β '), only a single amount without the radical-reactive group-containing UV absorber (Β'). The body can also be polymerized. As the strong monomer, those similar to the ethylenically unsaturated monomer described above can be used. The same applies to chain transfer agents and initiators that can be used in the polymerization. The polymerization temperature, pressure, deoxygenation, additional method, etc. can be applied within a known range.

[0080] [Polymer (C) having at least units derived from polyfunctional monomer ()]

In the present invention, the use of the polymer (C) having at least a unit derived from the polyfunctional monomer () can be expected to improve the following characteristics.

[0081] For example, it is considered that the grafting efficiency to the polyorganosiloxane (Α) can be increased when the above-mentioned ultraviolet absorber (Β ') and, if necessary, the ethylenically unsaturated monomer are combined. This makes it possible to ensure the dispersibility of the graft copolymer of the present invention in the matrix resin even if the amount of the polymer (Β) site is kept to a minimum, and relatively polyorgano The proportion of the siloxane (Α) component can be increased. Can be burned! /, Can reduce the amount of polymer (Β) part used as a component, and at the same time increase the amount of polyorganosiloxane (Α) component effective for imparting impact resistance. The flame retardancy of the resin composition can be suppressed or improved, and at the same time the impact resistance can be improved. Furthermore, if the polyfunctional monomer (C ′) is appropriately selected, the heat resistance of the polymer (C) site is increased, and the heat resistance of the graft copolymer of the present invention itself is improved. There is a tendency that the heat resistance of the finally obtained resin composition can be maintained or improved.

[0082] [Polyfunctional monomer (C ')]

Examples of the polyfunctional monomer () used in the present invention include (meth) alkyl such as aryl (meth) acrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate. Relate-based polyfunctional monomers; gens such as butadiene and isoprene; aromatic bur-based polyfunctional monomers such as divinylbenzene, diisopropenebenzene, divinylnaphthalene, and divinylanthracene; Aromatic polyvalent carboxylic acid esters such as triallylbenzene tricarboxylate and diallyl phthalate; Tertiary amines such as triallylamine

Isocyanuric acid derivatives such as diallyl isocyanurate, diallyl n-propyl isocyanurate, triallyl isocyanurate, trimethallyl isocyanurate, tris ((meth) atari mouth kichetil) isocyanurate; Cyanuric acid derivatives typified by: tri (meth) ataryllohexahydrotriazine; 2,2'-divinylbiphenyl, 2,4'-divinylbiphenyl, 3,3 'divinylbiphenyl, 4,4' divinylbif Enil, 2, 4'-bi (2-probe) biphenyl, 4, 4'-di (2-probe) biphenyl, 2, 2 'divinyl 4-ethyl -4'-propyl Biphenyl derivatives such as biphenyl and 3,5,4'-trivinylbiphenyl. Of these, at least one selected from the group consisting of isocyanuric acid derivatives, cyanuric acid derivatives, and biphenyl derivatives is preferable. Particularly, triallyl isocyanurate, 2, 2'-dibibibiphenyl, 2, 4 '-Divinyl biphenyl, 3, 3'-dibi bibiphenyl, 4, 4' dibibi biphenyl can be most preferably used.

[0083] In the present invention, the polyfunctional monomer (C ') is also used as a mixture with another radical reactive monomer (C ") copolymerizable with the monomer (C'). Furthermore, a radically reactive group-containing ultraviolet absorber (Β ′) can also be used in combination with the polyfunctional monomer (C) and the above-mentioned copolymerizable radical reactive monomer. The ratio of the polyfunctional monomer (C ′) to the total weight with (C ″) increases the flame retardancy as the ratio of the polyfunctional monomer (C ′) increases, and conversely as the ratio decreases. Impact resistance may be improved. However, since the flame retardancy may be significantly impaired depending on the type of monomer to be copolymerized, the proportion of the polyfunctional monomer (C) is preferably 50% by weight or more, and more preferably 80% by weight. The use of the polyfunctional monomer (C) alone, which is particularly preferred, is most preferable in terms of flame retardancy. Similarly, the proportion of the copolymerizable radical reactive monomer (C ") is preferably 50% by weight or less, more preferably 20% by weight or less, and even more preferably not used! / Favored ,.

[0084] [Radically reactive monomer (C ")] Specific examples of the copolymerizable radical-reactive monomer (C ") include copolymerization with a radical-reactive group-containing ultraviolet absorber (Β ') that can be used as the polymer (B) component V. The same as the possible ethically unsaturated monomers can be mentioned, where the radical reactive monomer (C ") has a low glass transition temperature of a homopolymer, such as butyl acrylate. When 2-ethylhexyl acrylate is used, a graft copolymer having an excellent impact resistance improving effect can be obtained. However, in order to improve the impact resistance without impairing the flame retardancy, it is preferable to polymerize only the copolymerizable radical reactive monomer (C ") to be used, like the polymer (重合) component. It is preferable to select such that the glass transition temperature of the polymer obtained is 40 ° C or higher, more preferably 60 ° C or higher, particularly 90 ° C or higher. Preferred when polymerizing radically reactive monomers (C ") that can be copolymerized with C ') in two or more stages U, glass transition temperature in each stage, and ethylenically unsaturated monomers in two or more stages The copolymer when used as a mixture of compounds preferably has the same glass transition temperature as that of the polymer (B) component. Among them, it is preferable that the homopolymer has a glass transition temperature of only the same monomer as that described for the polymer (B) component, since it is possible to obtain better flame retardancy. Specific examples of the monomer to be used are the same as those exemplified for the polymer (B) component. Note that the glass transition temperature described for the polymer) is the glass transition temperature of the (co) polymer that is also a component force excluding the polyfunctional monomer (C ') among the monomers constituting the polymer (C). It shall refer to temperature.

[0085] A polymer (C) can be obtained by polymerizing a monomer or monomer mixture containing such a polyfunctional monomer (C) using a known radical polymerization method. When the polyorganosiloxane (A) is obtained as an emulsion, the polymerization of the monomer containing the polyfunctional monomer () is preferably carried out by an emulsion polymerization method.

[0086] Polymerization initiator used in the case of employing an emulsion polymerization method, reducing agent in the case of using a redox type polymerization initiator · transition metal salt 'chelating agent, chain transfer agent, additional surfactant, buffer agent, and The amount of their use, as well as the polymerization temperature, pressure, deoxygenation, concentration, addition method of the monomer or monomer mixture containing the polyfunctional monomer (C), and other conditions such as stirring are as follows. ) The same as described for the component.

[0087] The polyorganosiloxane-containing graft copolymer of the present invention (the copolymer constituting the copolymer) The content of the polymer (C) part having at least units derived from the polyfunctional monomer (C) is the flame retardant of the obtained resin composition. In order not to impair the properties, preferably 0.1% by weight or more, more preferably 0.5% by weight or more, further 1% by weight or more, preferably 94% by weight or less, more preferably 30% by weight or less. Furthermore, it is 20% by weight or less, further 10% by weight or less, and the most preferable range is 1 to 5% by weight.

[0088] Similarly, the content of the polymer (少なくとも) having at least units derived from the radical-reactive group-containing UV absorber (Β ') does not impair the flame retardancy of the obtained resin composition. Preferably, it is 0.5% by weight or more, more preferably 3% by weight or more, further 5% by weight or more, preferably 34.9% by weight or less, more preferably 24.5% by weight or less, Is less than 15% by weight.

[0089] When the polyorganosiloxane-containing graft copolymer of the present invention is obtained by emulsion polymerization, the latex of the graft copolymer and salt-calcium, salt-magnesium, magnesium sulfate, saltグラフト After solidifying by mixing a divalent or higher metal salt such as aluminum or calcium acetate, the graft copolymer is separated from the aqueous medium by heat treatment 'dehydration', 'washing' and drying according to a known method. (Coagulation method) As the above-mentioned divalent or higher metal salt, calcium chloride and magnesium chloride are preferred because they are economically available at low cost and are easy to handle.

[0090] When it is desired not to contain a trace amount of halogen, magnesium sulfate can be suitably used as the above-mentioned divalent or higher metal salt. In the process after salt coagulation, the slurry can be diluted to 20 times, more preferably 30 times, and even 50 times or more of the solid content of the graft copolymer before dehydration. The solid content of the graft copolymer is preferably 3 times, more preferably 5 times, and even 10 times or more. The dehydrated resin is preferably re-dispersed after being redispersed in the above-mentioned solvent having a solid content of 5 times or more, preferably water, to reduce problems such as burning and decomposition during the formation of the matrix resin. A better balance between flammability and mechanical properties.

[0091] Or alcohol such as methanol, ethanol and propanol, water such as acetone A soluble organic solvent can be added to the latex to precipitate the copolymer, separated from the solvent by centrifugation or filtration, and then dried and isolated. As another method, a slightly water-soluble organic solvent such as methylethylketone is added to the latex containing the draft copolymer of the present invention, and the copolymer in the latex is extracted into an organic solvent layer. For example, the solvent layer may be separated and then mixed with water to precipitate the copolymer component.

[0092] The latex can also be directly powdered by spray drying. In this case, the same effect can be obtained by washing the obtained powder with a solvent in the same manner as in the solidification method described above. Alternatively, the same effect can be obtained by adding calcium chloride, magnesium chloride, magnesium sulfate, aluminum chloride, etc. to the obtained powder, preferably in a solution such as an aqueous solution, and re-drying as necessary. Obtainable.

[0093] When the graft copolymer of the present invention is obtained by the suspension seed polymerization method, the aqueous medium force can also be separated by dehydration-washing-drying. In this case as well, the same effect can be obtained by diluting or washing with a solvent as in the above solidification method.

[0094] When a powdered resin is used as the matrix resin when the resin composition is obtained by blending the graft copolymer of the present invention, the volume average of the graft copolymer of the present invention is used. The particle size is preferably 1 μm or more, more preferably 10 μm or more, further 50 μm or more, particularly 100 μm or more, preferably 1 mm or less, more preferably 500 μm or less, further 200 μm or less. It is preferable to collect as a lower powder. In particular, it is preferable that the average particle size of the powder of the graft copolymer is close to the average particle size of the powder of the matrix resin, or the same volume average particle size, because it is easily classified. The graft copolymer powder is such that the graft copolymer of the present invention is in a state of gently agglomerating, so that the primary particles of the graft copolymer are easily dispersed in the matrix resin. This is preferable from the viewpoint.

[0095] [Graft Rate 'Free Polymer Molecular Weight]

The graft ratio of the graft copolymer of the present invention obtained as described above is preferably 1.001 or more, more preferably 1.01 or more, so as not to impair the flame retardancy of the obtained resin composition. Furthermore, it is 1.04 or more, particularly 1.08 or more, preferably 2 or less, more preferably Is 1. 4 or less, even 1.28 or less, especially 1.15 or less. A specific method for calculating the draft rate referred to in the present invention will be described later in [Graft rate] Method for obtaining free polymer molecular weight].

[0096] Similarly, it is soluble in 2-butanone contained in the graft copolymer of the present invention and insoluble in methanol, which is obtained by the method described later in [Method of obtaining graft ratio 'free polymer molecular weight]. The weight average molecular weight in terms of polystyrene by gel 'permeation' chromatography (GPC) of a certain component (free polymer) is preferably 10,000 or more so as not to impair the flame retardancy of the obtained resin composition. More preferably 30,000 or more, more preferably ί or 50,000 or more, specially preferably ί or 80,000 or more, preferably ί or 1,00 0,000 or less, more preferably 450, 000 In the following, it is more preferably 200,000 or less, particularly preferably 150,000 or less. The method for separating the components is the same as the method for obtaining the free polymer component obtained by calculating the graft ratio described above. The weight average molecular weight of the free polymer component calculated in this way is the weight average molecular weight of the free polymer component that has not been grafted by those skilled in the art. It is clear that the molecular weight of the graft component of the luganosiloxane-containing graft copolymer is being evaluated.

[0097] [Matrix fat]

In the present invention, the graft copolymer of the present invention can be blended with a matrix resin such as a thermoplastic resin, a thermosetting resin or an elastomer, and used as a resin composition. The graft copolymer of the present invention is characterized in that the mechanical properties such as impact resistance are improved, but there are few bad flame retardances. It can also be used as a flame retardant for the matrix rosin by maintaining and further improving the properties. The resin composition can be used as a flame retardant resin composition capable of imparting high flame retardancy and impact resistance to the finally obtained molded article.

[0098] The use amount of the graft copolymer of the present invention with respect to the matrix resin gives flame retardancy and impact resistance to the matrix resin, and further improves the balance of mechanical properties represented by them. From the viewpoint, per 100 parts by weight of the matrix resin, 0.1 parts by weight or more is preferable, and 0.5 parts by weight or more is more preferable. Particularly preferably, 1 part by weight or more is blended. In addition, from the viewpoint of securing moldability and preventing deterioration of heat resistance of the resin composition after blending, 20 parts by weight or less is preferable, and further 10 parts by weight or less is preferable. More preferably, it is 6 parts by weight or less, and most preferably 4 parts by weight or less.

[0099] [Thermoplastic resin]

Preferred examples of the thermoplastic resin that can be used as the matrix resin include polycarbonate resin, polyester resin, polyester carbonate resin, polyphenylene ether resin, polyphenylene sulfide resin, and polyether resin. Sulphone resin, polysulfone resin, polyarylene resin, polyamide resin such as nylon, polyetherimide resin, polyacetal resin such as polyoxymethylene,

Polyburacetal resin, Polyketone resin, Polyetherketone resin, Polyether ketone resin, Polyaryl ketone resin, Polyether-tolyl resin, Liquid crystal resin, Polybenzimidazole resin, Polyparabanic acid resin, Geny Compound, maleimide compound, aromatic alkenyl compound, methacrylic acid ester, acrylate ester, cyanide vinyl compound, polymerized or copolymerized with at least one vinyl monomer selected from the group consisting of Examples thereof include bur polymer or copolymer resin, polyolefin resin, and salt resin resin. These can be used alone or in a blend of two or more.

[0100] [Aromatic polycarbonate-based resin]

Among these thermoplastic resins, the polyorganosiloxane-containing graft copolymer of the present invention exhibits an excellent flame retardant effect especially when used for aromatic polycarbonate-based resins. As such, an aromatic polycarbonate-based resin is preferable. Such an aromatic polycarbonate-based resin is a resin containing 50% by weight or more of aromatic polycarbonate resin with respect to the total amount of the aromatic polycarbonate resin and other resins, and has good flame retardancy. From the viewpoint of obtaining a good balance between impact resistance and the like, those containing 70% by weight or more are preferred. The case where the aromatic polycarbonate resin containing 95% by weight or more is substantially independent is most preferred.

[0101] As such aromatic polycarbonate-based resin, copolymers such as polyamide polycarbonate resin and polyester-polycarbonate resin can also be used. In this case, it is preferable that the ratio of the polycarbonate unit in the total resin is the same as described above. As other resins included in the aromatic polycarbonate-based resin, resins other than the aromatic polycarbonate resins listed in the above-mentioned thermoplastic resin can be used.

[0102] [Sulfur-containing organometallic salt]

When an aromatic polycarbonate-based resin is used, a sulfur-containing organometallic salt can be included for the purpose of synergistically enhancing flame retardancy. The sulfur-containing organometallic salt may be used alone or in combination of two or more. Preferred sulfur-containing organometallic salts include sulfonic acid metal salts, sulfuric monoester metal salts, sulfonamide metal salts, and the like. Of these, sulfonic acid metal salts are preferably used from the viewpoint of flame retardancy, and particularly preferably (alkyl) aromatic sulfonic acid metal salts, perfluoroalkane sulfonic acid metal salts, and aliphatic sulfonic acid metal salts. , Diallyl sulfone sulfonic acid metal salt and alkyl sulfate metal salt are used.

[0103] The metal of the metal salt is preferably sodium, potassium, lithium, rubidium, cesium, beryllium, magnesium, calcium, strontium, norium, aluminum, etc., more preferably sodium, potassium, Alkali metals such as lithium, rubidium and cesium, and sodium or potassium are preferably used.

[0104] Specific examples of the sulfonamide metal salt include sodium salt of saccharin, N- (p-tolylsulfol) -p-toluenesulfimide sodium salt, N- (Ν'-benzylaminocarbole) Sodium salt of sulfarimide, sodium salt of —- (phenol carboxyl) -sulfurimide, etc .; (alkyl) aromatic sulfonic acid metal salts include sodium dodecyl benzenesulfonate, sodium paratoluenesulfonate, di- Sodium chlorobenzene sulfonate, sodium benzene sulfonate, sodium xylene sulfonate, sodium tame sulfonate, etc .; perfluoroalkane sulfonic acid metal salts include potassium perfluorobutane sulfonate and perfluoromethyl butane sulfonic acid. Potassium, etc .; aliphatic sulfonic acid metal As sodium dodecyl sulfonate, sodium dioctyl sulfosuccinate, etc .; as diaryl sulfone sulfonic acid metal salt, diphenyl sulfonate-3-potassium sulfonate, 4,4'-dibromodiphenyl sulfonate, 3 -Sulfonic acid Potassium, 4—Black mouth 4 ′ —- Trodiphenyl sulfone 1—Potassium sulfonate, diphenyl sulfone-3,3′-potassium disulfonate, etc .; Examples of alkyl sulfate metal salts include sodium dodecyl sulfate. Of these, those not containing halogen are preferably used.

[0105] Among the above, the point that the flame retardancy is good with a small amount is also good because it does not contain potassium perfluorobutane sulfonate or halogen, and the flame retardancy is good with a small amount. Sulfone-3-potassium sulfonate, sodium dodecylbenzenesulfonate, sodium xylenesulfonate, and sodium cumenesulfonate are particularly preferably used. Sodium salts of (alkyl) aromatic sulfonic acids represented by dodecylbenzenesulfonic acid are most preferred because they can be obtained and used industrially at low cost.

[0106] When the sulfur-containing organometallic salt is used, 0.001 part by weight or more is preferable with respect to 100 parts by weight of the aromatic polycarbonate-based resin, more preferably 0.005 part by weight or more. Preferably it is 0.01 part weight or more. Further, 0.5 parts by weight or less is more preferable, 0.3 parts by weight or less, more preferably 0.019 parts by weight or less, particularly preferably 0.015 parts by weight or less, and even more preferably 0.012 parts by weight or less. Is most preferred. Depending on the presence of the sulfur-containing organometallic salt, a reduction in the strength of the resin composition may be observed in some cases, but the effect of improving flame retardancy is excellent, which is preferable for balancing strength and flame retardancy. The range is the above range. If it is less than the above range, the flammability improving effect is small, or if it is almost too much, flame retardancy may be adversely affected.

[0107] [Polycarbonate resin]

The polycarbonate resin used in the present invention is obtained by reacting a divalent phenol with phosgene or a power bonate precursor, and includes an aromatic polycarbonate and an aliphatic polycarbonate.

[0108] As the divalent phenol, bis (hydroxyaryl) alkane is preferred, for example, bis (hydroxyphenol) methane, 1,1-bis (4-hydroxyphenol) ethane, 1,2-bis. (4-hydroxyphenol) ethane, 2,2-bis (hydroxyphenol) propane, 2,2-bis (4-hydroxyphenol 3-methylphenol) propane, 2,2-bis (4 —Hydroxy-1,3,5-dibromophenol) propane, 2,2-bis (4-hydroxy-1,3,5-dichlorophenol) And propane, 2,2-bis (hydroxyphenol) hexafluoropropane, and the like.

[0109] Other divalent phenols include 1,1-bis (4 hydroxyphenol) cyclohexane; 1,1-bis (4hydroxy-1-methylphenol) cyclohexane; 1, 1- Bis (4hydroxyphenyl) 1,3,3,5 Trimethylcyclohexane; 1,1-bis (4hydroxyphenyl) cyclodecane and other bis (4-hydroxyphenyl) cycloalkanes, 1,1bis (4-hydroxyphenol) phenolic len; 1,1-biscresol fluorene; fluorene derivatives such as 1,1-bisphenoloxyethanol fluorene, phenol bis (hydroxyphenol) methane; diphenol-norelebis (hydroxy) Phenyl) methane; 1-Pheninole-1,1,1 Phenyl group-containing bis (hydroxyphenol) alkanes such as bis (4-hydroxyphenol) ethane, 4,4'-dihydroxydiphenyl- Le, screw (4- Droxyphenyl) oxide, bis (4-hydroxyphenol) sulfide, bis (4-hydroxyphenol) snorephone, bis (4-hydroxyphenol) sulfoxide, bis (4-hydroxyphenol) ketone, Hydroquinone, piperazine, dipiperidyl hydroquinone, resorcin, and the like.

[0110] These divalent phenols are used alone or in combination. Of these, divalent phenol containing no halogen is preferably used. Particularly preferred divalent phenols are bis (hydroxyphenol) methane, 2,2'-bis (hydroxyphenol) propan, 4,4'-dihydroxydiphenyl, 1,1-bis (4 hydroxy). Phenyl) fluorene.

[0111] Examples of the carbonate precursor include diaryl carbonates such as diphenyl carbonate, and dialkyl carbonates such as dimethyl carbonate and jetyl carbonate.

[0112] In addition to these aromatic polycarbonate resins, aliphatic polycarbonate resins such as polyethylene carbonate can also be used. These polycarbonate resins do not work even if dimethylsiloxane is copolymerized in the main chain.

[0113] [Polyester resin]

The polyester resin that can be used in the present invention is obtained by polycondensation of a dicarboxylic acid or a derivative such as an alkyl ester of a dicarboxylic acid with a diol, Alternatively, a monomer obtained by polycondensing a monomer having both a carboxylic acid or an alkyl ester of a carboxylic acid and a hydroxyl group in one molecule, or a monomer having a cyclic ester structure in one molecule is opened. Ring-polymerized.

[0114] Specific examples of such polyester resin include polymethylene terephthalate, polyethylene terephthalate, polypropylene terephthalate, polytetramethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexane dimethylene terephthalate (PCT). , Poly (ethylene cyclohexene dimethylene) terephthalate (PETG), polyethylene naphthalate, polytrimethylene naphthalate, polycyclohexanedimethylene naphthalate, polyarylate, polylactic acid, polyhydroxybutyric acid, poly (hydroxybutyric acid- Hydroxyhexanoic acid), ethylene polysuccinate, butylene polysuccinate, polybutylene adipate, poly ε-strength prolatatone, poly (α-oxyacid) and their copolymerization And polybutylene terephthalate in the force present invention these blends are exemplified, polyethylene terephthalate, PETG, polylactic acid are particularly preferred.

[0115] Examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, succinic acid, adipic acid, sebacic acid and the like. Examples of the diol include ethane diol, propane diol, butane diol, pentane diol, neopentyl glycol, hexane diol, and cyclohexane dimethanol. Examples of the monomer having both a carboxylic acid or a derivative such as an alkyl ester of carboxylic acid and a hydroxyl group in the molecule include hydroxy, such as lactic acid, hydroxypropionic acid, hydroxybutyric acid, and hydroxyhexanoic acid. Examples include alkanoic acids. Examples of the monomer having a cyclic ester structure in one molecule include force prolatatone.

[0116] [Polyphenylene ether oil]

In the present invention, poly (phenylene ether) resin that can be used in the present invention is represented by the following chemical formula (I

A homopolymer or copolymer having a repeating unit represented by V).

[0117] [Chemical 4]

(In the formula, Qi Q ⁴ is a group independently selected from the group consisting of hydrogen and hydrocarbon groups, and m is an integer of 30 or more.)

[0118] Specific examples of the polyphenylene ether resin include poly (2, 6 dimethyl-1, 4 phenol) ether, poly (2-methyl 6 propyl mono 1, 4 phenol) ether, poly ( 2, 6 Jetyl 1,4 Phenyl) ether, Poly (2 Ethyl-6 Propyl-1,4 Phylene) ether, Poly (2,6 Dipropyl mono 1,4 Phylene) ether, (2, 6 Copolymers of dimethyl-1,4-phenylene) and (2,3,6 trimethyl-1,4-phenolene) ether, (2,6 jetyl-1,4-phenylene) ether and (2, Copolymer of 3,6 trimethyl-1,4 phenol) ether, copolymer of (2,6 dimethyl-1,4 phenol) ether and (2,3,6 triethyl-1,4 phenol) ether Etc.

[0119] Especially with poly (2,6 dimethyl-1,4 phenylene) ether, and (2,6 dimethyl-1,4 phenylene) ether and (2,3,6 trimethyl-1,4 phenylene) ether Poly (2, 6 dimethyl-1, 4 phenylene) ether is most preferred, with the copolymer being preferred.

[0120] These poly (phenylene ether) resins are compatible with polystyrene resins at all blending ratios. In the present invention, the degree of polymerization of the polyphenylene ether resin used in the present invention is not particularly limited, but 0.2 g is dissolved in 100 cm ³ of black mouth form, and the reduced viscosity of the solution measured at 25 ° C. Those of 0.3 to 0.7 dlZg are preferably used. If the reduced viscosity is less than 0.3 dlZg, the thermal stability tends to be poor, and if it exceeds 0.7 dlZg, the moldability tends to be impaired. These poly (phenylene ether) resins are used alone or in admixture of two or more.

[0121] The polyphenylene ether resin can be used by mixing with other resins, and preferably can be used by mixing with polystyrene resin described later. Used by mixing with other resins The preferred mixing ratio between the polyphenylene ether resin and the other resin can be set within a known range.

[0122] [Polyphenol-Rensulfide oil]

Polyphenylene sulfide resin that can be used in the present invention is a degree of polymerization having a repeating unit represented by the following chemical formula (V) of 50 mol% or more, preferably 70 mol% or more.

~ 300 polymers.

[0123] [Chemical 5]

[0124] The unit represented by the chemical formula (VI) can be used as the copolymer component, but the content of these copolymer components is preferably 10 mol% or less.

[0125] [Chemical 6]

(Wherein R represents an alkyl group, a nitro group, a phenyl group, an alkoxy group, a carboxylic acid group or a metal salt thereof)

[Polyether sulfone resin, polysulfone resin]

The polysulfone-based resin is a polymer containing —SO— group, which is aromatic and oleoresin.

2

Forces roughly classified into fin systems Aromatic systems are preferred as the matrix resin of the present invention. For example, a polymer having a repeating unit represented by the following chemical formula (VII) obtained by polycondensation reaction of dichlorodiphenylsulfone, a repeating formula represented by the following chemical formula (VIII) obtained from dichlorodiphenylsulfone and bisphenol A. Polymerization with units The body is mentioned. In general, the former is called polyether sulfone resin and the latter is called polysulfone resin, and these are preferable as the matrix resin of the present invention.

[Chemical 7]

[0129] [Polyarylene resin]

Examples of the polyarylene resin used in the present invention include poly (p-phenylene), poly (2,5-chalene), poly (1,4-naphthalene diyl) and the like.

[0130] [Polyamide resin]

Examples of the polyamide resin that can be used in the present invention include aliphatic, alicyclic, or aromatic diamines, aliphatic, alicyclic, or aromatic dicarboxylic acids, and derived polyamides, _ε Polyamides obtained by ring-opening polymerization of ratatams such as prolatatam, _ω- dodecalactam, or polyamides obtained from 6-aminocaproic acid, 1,1-aminoundecanoic acid, 1,2-aminododecanoic acid, etc. Homopolymers such as these, copolymers of these polyamides, and blends, among which nylon 6, nylon 6, 6, nylon 11, nylon 12, nylon, which are industrially inexpensive and manufactured in large quantities 6,10, nylon 4,6, copolymers thereof, or blends thereof are preferred.

[0131] Examples of the aliphatic, alicyclic, or aromatic diamine include ethylene diamine, tetramethylenediamine, hexamethylene diamine, decamethylene diamine, dodecamethylene diamine, 2, 2, 4— and 2, 4, 4-trimethylhexamethylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, bis (ρ-aminocyclohexyl) methane , M-xylylenediamine, p-xylenediamine and the like. [0132] Examples of the aliphatic, alicyclic, or aromatic dicarboxylic acid include adipic acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, and isophthalic acid.

[0133] [Polyetherimide resin]

The polyetherimide resin that can be used in the present invention is a polymer having a repeating unit represented by the following chemical formula (IX) having an ether bond and an imide bond.

[0134] [Chemical 9]

(I X)

[0135] [Polyvinylacetal resin]

The polybutacetal rosin that can be used in the present invention is a product obtained by modifying polyvinyl alcohol with an aldehyde, and examples thereof include polybule formal and polyvinyl butyral.

[0136] [Polyketone resin]

Examples of the polyketone resin that can be used in the present invention include an alternating copolymer of ethylene and carbon monoxide, and an alternating copolymer of a-olefin and carbon monoxide-carbon.

[0137] [Polyolefin resin]

The polyolefin-based octopus essence that can be used in the present invention is a copolymer of olein and copolymer only from olefins typified by polyethylene, polypropylene, polymethylpentene, polybutene, cycloolefin polymers or copolymers. It can be a copolymer with a compound having at least one double bond. Examples of the copolymerizable compound include (meth) acrylic acid and its ester, maleic acid and its ester, maleic anhydride, and butyl acetate. These copolymerizable compounds are preferably used in a proportion of 10% by weight or less. Polyolefins that can be used in the present invention An ethylene-based resin is a copolymer obtained by hydrogenating a copolymer of a gen-based component and another vinyl monomer, such as acrylonitrile mono (ethylene gen-gen-propylene (EPDM))-styrene. This concept includes copolymer (AES) resin. Further, the degree of polymerization of polyolefin resin is preferably 300 to 6000.

[0138] [Salt-bulu oil]

The salt vinyl resin that can be used in the present invention is a vinyl chloride homopolymer, or other bulle monomer having at least one double bond that can be copolymerized with the salt vinyl. This refers to a copolymer with salt butyl, chlorinated salt vinyl vinyl resin, chlorinated polyethylene resin, and the other vinyl monomer in the copolymer is preferably 50% by weight or less, more preferably 45% by weight or less.

[0139] Examples of other vinyl monomers having at least one double bond include ethylene, propylene, butyl acetate, (meth) acrylic acid and esters thereof, maleic acid and esters thereof, and salt vinylidene. , Bromobromide and acrylonitrile.

[0140] These vinyl chloride resins are homopolymerized or copolymerized with vinyl chloride alone or with vinyl chloride and other vinyl monomers in the presence of a radical polymerization initiator. It is obtained by polymerization. The degree of polymerization of this salt-bulb resin is usually 400 to 4500, especially 400 to 1500 is preferred!

[0141] [Other Bull oil]

The matrix resin that can be used in the present invention is at least one selected from the group consisting of a gen compound, a maleimide compound, an aromatic alkenyl compound, a methacrylic acid ester, an acrylic acid ester, and a cyanurized vinyl compound. A polymer or copolymer resin obtained by polymerizing or copolymerizing these monomers can be used.

[0142] Examples of the polymer or copolymer resin include polystyrene resin, s polystyrene resin, polymethyl methacrylate resin, polychlorostyrene resin, polybromostyrene resin, poly a-methyl Styrene resin, styrene-acrylonitrile copolymer resin, styrene-methyl methacrylate copolymer resin, styrene-maleic anhydride copolymer resin, styrene-maleimide copolymer resin, styrene-N-phenol Rumaleimide copolymer resin, styrene-N N-phenolmaleimide-acrylonitrile copolymer resin, methyl methacrylate Tyl acrylate copolymer resin, Methyl methacrylate-ethyl acrylate copolymer resin, Styrene monoacrylonitrile one _a —Methyl styrene terpolymer resin resin, Butadiene styrene copolymer (HIPS) resin, Acrylonitrile Butadiene rubber Styrene copolymer (ABS) resin, Acrylonitrile-Butadiene rubber- _a —Methylstyrene copolymer resin, aromatic alkenyl compound, mono-cyanyl-bulle-N-phenolmaleimide copolymer resin Etc.

[0143] [Thermosetting resin]

Preferred examples of the thermosetting resin that can be used as the matrix resin include epoxy resin, phenol resin, urea resin, melamine resin, polyimide resin, polyamideimide resin, and thermosetting polyester. Resin (unsaturated polyester resin), alkyd resin, silicone resin, urethane resin, polybulle ester resin, diallyl polyphthalate resin, bismaleimide-triazine resin, furan resin, xylene resin, Examples include guanamine resin, maleic resin, and dicyclopentagen resin.

[0144] [Epoxy resin]

Known epoxy resins can be used in the present invention. For example, a novolac epoxy resin obtained by condensing a nopolac resin obtained by condensing phenols such as phenol novolac type epoxy resin, cresol novolac type epoxy resin, biphenols or naphthols with aldehydes, 2, 2 ', 6, 6'—Biphenol type epoxy resin such as tetramethylbiphenol diglycidyl ether, biphenol or aromatic nucleus-substituted biphenols or polyvalent such as bisphenol A, F, S, trimethylolpropane Polyglycidyl ethers of phenols or polyhydric alcohols, or their condensates, or cycloaliphatic epoxy resins containing a cycloolefin oxide structure skeleton in one molecule. A wide range of epoxy resins can be used.

[0145] Of these, diglycidyl ether of biphenol or aromatic nucleus-substituted biphenol or its condensate, novolac type epoxy resin, dicyclopentagel type epoxy resin, cycloolefin in one molecule One or more epoxy resins selected from alicyclic epoxy resins containing an inoxide structure skeleton, 50 times the total amount of thermosetting resins U, preferably containing more than%. These can be cured using phenolic resins such as phenol novolac, aliphatic amines, aromatic amines, or carboxylic acid derivatives such as acid anhydrides and blocked carboxylic acids. Among these, it is more preferable to use phenol resin from the viewpoint that the obtained cured product has high heat resistance.

[0146] [Elastomer]

Preferred elastomers that can be used as the matrix resin include natural rubber, acrylic rubber such as butyl acrylate, ethyl acrylate, octyl acrylate, butadiene monoacrylonitrile copolymers, and the like. -Tolyl rubber, chloroprene rubber, butadiene rubber, isoprene rubber, isobutylene rubber, styrene butadiene rubber, methyl methacrylate-butyl acrylate block copolymer, styrene isobutylene block copolymer, styrene butadiene block copolymer, hydrogenated styrene butadiene Block copolymer, ethylene propylene copolymer (EPR), hydrogenated ethylene butadiene copolymer (EPDM), polyurethane, chlorosulfonated polyethylene, silicone rubber (millable, room temperature vulcanizable, etc. ), Butyl rubber, Fluoro rubber, Olefin thermoplastic elastomer, Styrenic thermoplastic elastomer, PVC thermoplastic elastomer, Urethane thermoplastic elastomer, Polyamide thermoplastic elastomer, Polyester thermoplastic elastomer And synthetic rubbers such as fluorine-based thermoplastic elastomers, and various types can be used.

[0147] [mixed]

Mixing of the polyorganosiloxane-containing copolymer of the present invention and the matrix resin is carried out by an ordinary known kneading machine. Examples of such machines include Mixing Glore, Calender Ronore, Banbury mixer, Henschel mixer, ribbon blender, kneader, extruder, blow molding machine, and inflation molding machine.

[0148] [Antioxidant]

In the present invention, an antioxidant may be further added to the graft copolymer-containing resin composition. There are no restrictions on the antioxidants that can be used, such as phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like. These can be used alone or in combination. [0149] Specific examples of the phenolic antioxidant include 2,4 dimethyl-6- (1 methylpentadecyl) phenol, 2,6 di tert-butyl-p cresol, 4, 4'-butylidenebis (6- tert). —Butyl-3 methylphenol), 2, 2'-methylenebis (4-methyl-6-tertbutylphenol), 2,2'-methylenebis (4-ethyl-6-tertbutylphenol), 2,6 ditert-butyl-4-ethylphenol, 1, 1, 3 Tris (2-methyl-4-hydroxy-5-tertbutylphenyl) butane, Octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenol) propionate, tetrakis [methylene-3- (3,5-di-tert —Butyl-4-hydroxyphenol) propionate] methane, triethylene glycol bis [3- (3-tert-butyl 4-hydroxy-5-methyl -L) propionate], tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, butylidene-1,1-bis (2-methyl-4-hydroxy-1-5-butyl-phenol), and the like It is done. These can be used alone or in combination.

[0150] In particular, in order to improve the flame retardancy, it is preferable to use a combination of two or more phenolic acid oxidants. A particularly preferred combination is a combination of 2,4 dimethyl 6- (1-methylpentadecyl) phenol and octadecyl-3- (3,5 di-tert-butyl-4-hydroxyphenol) propionate, tris (3,5-di tert A combination of butyl 4-hydroxybenzyl) isocyanurate with other phenolic antioxidants, in particular a combination of 1,1,3 tris (2-methyl-4-hydroxy-5-tertbutylbutyl) butane.

[0151] Specific examples of the phosphorus-based antioxidation agent include cyclic neopentanetetraylbis (2,6 di-tert-butyl-4-methylphenol) phosphite, tris (2,4 di-). tert-butylphenyl) phosphite, bis (2,6 di-tert-butyl-4-methylphenol) pentaerythritol phosphite, 2,2-methylenebis (4,6 ditert-butylphenol) octyl phosphite, etc. Is given.

[0152] Specific examples of the sulfur-based antioxidant include dilauryl thiodipropionate, distearinolethiodipropionate, dimyristinoretiodipropionate, ditridecinoretiodipropionate, and the like. . Tris (3, 5- It is preferable to use di-tert-butyl 4-hydroxybenzyl) isocyanurate in combination with these because flame retardancy is good.

[0153] For example, 4, 4'-thiobis (6-tert-butyl-3-methylphenol) is used as an antioxidant having both the properties of the phenolic antioxidant and the sulfurous antioxidant. You can also

[0154] The amount of the anti-oxidation agent used is preferably 0. with respect to 100 parts by weight of the graphitic copolymer-containing resin composition of the present invention in consideration of the balance between the effect and the cost. 001 parts by weight or more, further 0.01 parts by weight or more, particularly preferably 0.015 parts by weight or more, preferably 1 part by weight or less, more preferably 0.4 parts by weight or less, and further 0.1 parts by weight. In particular, the amount is 0.075 parts by weight or less.

[0155] There is no restriction on the method of mixing the anti-oxidation agent with the graft copolymer-containing resin composition, and the graft copolymer of the present invention can be used with thermoplastic resin, thermosetting resin, elastomer. A method of simultaneously mixing an antioxidant when mixing with at least one resin selected from the group consisting of: a method of mixing the graft copolymer with a mixture of the resin and an antioxidant; A method of mixing the resin with a mixture of an anti-wetting agent and a graft copolymer, a method of mixing an anti-oxidation agent with a mixture of the graft copolymer and the resin in advance, and the like. .

[0156] Self-mixing]

At this time, if necessary, commonly used compounding agents, such as dripping (anti-drip) agents, flame retardants, impact modifiers, plasticizers, lubricants, high molecular weight polymethylmetatalate-based fats, etc. Melt viscosity (elasticity) modifiers, UV absorbers, pigments, fiber reinforcing agents such as glass fibers, antistatic agents, fillers, terpene resin 'Acryonitrile' Fluidity modifiers such as styrene copolymers, monoglycerides' silicone oil 'A mold release agent such as polyglycerin, a compatibilizing agent, and a coupling agent between a filler and a matrix resin can be appropriately blended.

[0157] The anti-dripping agent, particularly the anti-dripping agent in a combustion test such as UL-94 test, includes fluorine-based resins such as polytetrafluoroethylene and poly (vinylidene fluoride), or polytetrafluoro. Loethylene and (meth) acrylic acid ester, aromatic alcohol compound, cyanide It is possible to use powders, polyorganosiloxanes, etc., which are compounded with other polymers such as polymers obtained by polymerizing bismuth, and the amount is preferably per 100 parts by weight of matrix resin. 2 parts by weight or less, more preferably 1 part by weight or less, further 0.6 parts by weight or less, and preferably 0.1 parts by weight or more, when dripping causes a problem. An effect is acquired and it is preferable.

[0158] Examples of the flame retardant include phosphoric acid esters represented by red phosphorus, bisphenol monobis (diphenyl phosphate) and triphenyl phosphate, condensed phosphate esters, tetrabromobisphenol mono A, tris. (2, 3 dibromopropyl) isocyanurate, hexose, etc.

[0159] Examples of the impact resistance improver include butadiene-methyl methacrylate-styrene copolymer (MBS), alkyl (meth) acrylate rubber, or polyorganosiloxane and composite rubber that also has alkyl (meth) acrylate rubber strength. Examples thereof include those obtained by graft copolymerization of metatalylate, styrene, talli mouth-tolyl, and the like.

[0160] Examples of the filler include talc · my power · calcium carbonate · silica · polyorganosilsesquioxane 'titanium oxide' oxide and zinc nanoparticle · layered silicate · metal fine particle 'carbon nanotube. Examples of the antistatic agent include polyamide, polyether block, alkylene glycol, glycerin, and fatty acid ester.

Examples of the compatibilizer include functional group-containing polyorganosiloxane such as epoxy group-containing polyorganosiloxane, (epoxy-modified) styrene butadiene styrene block copolymer, and the like.

[0162] Examples of the coupling agent between the filler and the matrix resin include a polyol, a silane coupling agent, and a titanium coupling agent.

[0163] [Molding method]

As a molding method of the resin composition of the present invention, when it is obtained from the polyorganosiloxane copolymer of the present invention and a thermoplastic resin, a molding method used for molding an ordinary thermoplastic resin composition, that is, An injection molding method, an extrusion molding method, a blow molding method, a calendar molding method, an inflation molding method, a rotational molding method, and the like can be applied. Further, when obtained from a thermosetting resin, the resin composition of the present invention is introduced into a mold and then heated. For example, a curing method can be applied. When it is obtained from an elastomer, it is formed into a shape according to the molding purpose by a molding method such as slush molding, injection molding or hot press molding, and vulcanized as necessary to form a molded product.

[0164] [Use of molded products]

The molded product obtained from the resin composition of the present invention is particularly excellent in impact resistance at low temperatures and excellent in flame retardancy, and its use is not particularly limited. Computer's' notebook computer 'LCD · Plasma display · Field emission display · Projector ^ ~ · Projection TV • PDA' Printer 'Copier' Fax '(portable) audio device' (portable) video device · (Mobile) Phone · Lighting equipment 'Game machine' Digital video camera · Digital camera · Video recorder ^ ~. Hard disk video recorder ^ ~ · DVD recorder ^ ~ · Water heater · Rice cooker 'Microwave oven' Range 'Watches' Automatic ticket gates' Automatic ticketing machines' Heat pumps (air conditioners, etc.)' Office products such as co-generators 'Household appliances' Industrial equipment, benches' playground equipment, automotive batteries, etc.' Capacitor parts, LED video display devices' Display materials in power boxes · Telephone jacks · Terminal block covers · Coil bobbins · Electronics such as transformers · Electrical parts Products such as electrical and electronic materials such as sealants, adhesives, seal materials, glass vibration prevention materials, automotive parts such as heater fan 'handle' vibration insulation materials, etc. have impact resistance, flame resistance, cold resistance, etc. Necessary uses are listed.

Example

[0165] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The following measurements and tests were performed as follows.

[0166] [Polymerization conversion]

First, a part of the obtained latex was collected and precisely weighed and dried in a hot air dryer at 130 ° C. for 1 hour, and the weight after drying was precisely weighed as the solid content. Next, the ratio of the precision weighing results before and after drying was determined as the ratio of solid components in the latex. Finally, using this solid component ratio, the polymerization conversion rate was calculated by the following formula 1. In Formula 1, the chain transfer agent was handled as a charged monomer. [0167] [Equation 1]

Polymerization addition rate

= (Total weight of raw materials charged X ratio of solid components—total weight of raw materials other than water / monomer) Weight of raw monomers charged X 1 0 0 (%)

(Formula 1)

[0168] [Volume average particle diameter]

The volume average particle size of the seed polymer, polyorganosiloxane particles, and graft copolymer was measured in the latex state. The volume average particle size (μm) was measured using a MICRO TRAC NPA150 manufactured by Nikkiso Co., Ltd. as a measuring device.

[0169] [Graft rate. Determination of free polymer molecular weight]

About 2 g of the graft copolymer of the present invention is precisely weighed, then immersed in about 100 g of 2-butanone, a free polymer extraction solvent, for 12 hours, and then the gel content is precipitated by an ultracentrifuge. And separated into a supernatant and a gel. 2-butanone addition and ultracentrifugation were repeated twice more on the collected gel. The ultracentrifugation was carried out using a super centrifuge CP-60E manufactured by Hitachi, Ltd., equipped with a P70AT as a rotor, at 30, OOOrpm for 1 hour at a time. The gel part finally recovered in this way was dried under reduced pressure at 40 ° C., and the weight after drying was precisely weighed as the gel part residue weight. First, the gel part content was determined according to the following formula 2.

[0170] [Equation 2]

Gel content = gel residue weight / graft copolymer weight (Formula 2)

[0171] Next, all the supernatants of the 2-butanone soluble component are combined and concentrated until the solution is about 20 g, and this is dropped into 300 ml of methanol to form a free polymer as a methanol insoluble component. Then, the dried free polymer was recovered, and its weight was precisely weighed, and the free polymer content was determined by the following formula 3.

[0172] [Equation 3] Free polymer content

= Free polymer weight Graft copolymer weight (Formula 3)

[0173] Next, based on the values shown in Table 2, the siloxane usage rate was determined by the following formula 4.

[0174] [Equation 4] Siloxane usage rate

= Raw material weight of polyorganosiloxane component only Z Total weight of polyorganosiloxane component and monomer

(Formula 4)

[0175] Using the gel content, free polymer content, and siloxane usage rate obtained above, the graft ratio was determined according to the following formula 5.

[0176] [Equation 5] Graft rate

= Gel content Z ((gel content + free polymer content) X siloxane usage rate)

(Formula 5)

[0177] After obtaining a dried free polymer in the same manner as described above, this was converted to a chloroform solution of about 5 mgZ3 ml, and the solution was subjected to gel-permeation-chromatography (GPC) analysis to obtain a weight average. Molecular weight (Mw) was determined. For GPC analysis, a Waters GPC system was used, and polystyrene genore columns Shodex K-806 and K805 (manufactured by Showa Denko Co., Ltd.) were used as the column. .

[0178] [Shock resistance]

According to ASTM D-256, it was evaluated by an Izod test.

[0179] [Flame Retardancy]

The test was conducted according to the UL94 V test and expressed in terms of the total number of combustion seconds.

[0180] (Production Example 1) Production of polybutyl attalylate seed polymer (SD-1)

To a 5-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port, and thermometer, 400 parts by weight of water and 15% by weight sodium dodecylbenzenesulfonate aqueous solution (manufactured by Kao Corporation, After adding 12 parts by weight (solid content) of Neobelex G15), the temperature was raised to 50 ° C, and after the liquid temperature reached 50 ° C, nitrogen substitution was performed. Thereafter, 10 parts by weight of butyl acrylate and 3 parts by weight of tododecyl mercaptan were obtained. 30 minutes later, noramentane hydroperoxide 0.01 parts by weight (solids), sodium formaldehyde sulfoxylate (SFS) O. 3 parts by weight, disodium ethylenediamine tetraacetate (EDTA) O. 01 parts by weight, and Ferrous sulfate (FeSO · 7Η Ο) was added at 0.025 parts by weight and stirred for 1 hour.

4 2

[0181] Thereafter, 90 parts by weight of butyl acrylate, 27 parts by weight of tododecyl mercaptan, and A liquid mixture of 0.09 parts by weight (solid content) of ramentan nanodropperoxide was continuously added over 3 hours, followed by post-polymerization for 2 hours, and a volume average particle size of 0.03 ^ m, A latex containing seed polymer (SD-1) having a polymerization conversion rate of 90% (t-dodecyl mercaptan was regarded as a monomer raw material component) was obtained.

[0182] (Production Example 2) Seed polymer containing radically reactive group-containing UV absorber (Β ') (SD

2) Manufacture

To a 5-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port, and thermometer, 400 parts by weight of water and 15% by weight sodium dodecylbenzenesulfonate aqueous solution (manufactured by Kao Corporation, After charging 6 parts by weight (solid content) of Neo Belex G15), the temperature was raised to 50 ° C, and after the liquid temperature reached 50 ° C, nitrogen substitution was performed. Then, 9 parts by weight of methylmethalate, 2- (2'-hydroxy-1 5'-methacryloyloxychetylphenol) 2H benzotriazole (Otsuka Chemical Co., Ltd., trade name: RUVA-93) 1 part by weight and 3 parts by weight of t-dodecyl mercaptan were obtained. After 30 minutes, 0.01 parts by weight of paramenthanohydroperoxide (solid content), 3 parts by weight of sodium formaldehyde sulfoxylate (SFS) O., 1 part by weight of disodium ethylenediamine tetraacetate (EDTA), and sulfuric acid One iron (Fe SO · 7Η Η) was added at 0.200 parts by weight and stirred for 1 hour.

4 2

[0183] Thereafter, 81 parts by weight of methylmethacrylate, 2- (2'hydroxy 5'-methacryloyloxychetylphenol), 2 parts 9 parts by weight of benzotriazole, 7 parts by weight of tododecyl mercaptan, and paramenthano, id A liquid mixture of 0.09 parts by weight (solid content) of mouth peroxide was continuously added over 3 hours, followed by post-polymerization for 2 hours, a volume average particle size of 0.05 m, and a polymerization conversion rate. A latex containing 90% of the seed polymer (SD-2) (90% t-dodecyl mercaptan was regarded as a monomer raw material component) was obtained.

[0184] (Production Examples 3 and 4) Production of polyorganosiloxane particles (S-1 and 2)

First, a mixture obtained by mixing the compositions shown in the respective columns of Production Example 3 and Production Example 4 in Table 1 with stirring was stirred at 7500 rpm for 5 minutes with a homomixer to prepare a siloxane emulsion.

[0185] Separately, the seed polymer (SD-1, 2) latex produced by the above-described method was added in an amount corresponding to the solid content shown in Table 1, a stirrer, a reflux condenser, a nitrogen blowing port, and a monomer addition port. And warm A five-necked flask equipped with a dynamometer was charged.

[0186] Next, the siloxane emulsion prepared as described above was added all at once to this 5-necked flask, and then the system was stirred at 35 ° C to 80 ° C over 1 hour under nitrogen flow. The temperature rose to.

[0187] Next, 1 part by weight (solid content) of 10 wt% dodecylbenzenesulfonic acid (DBSA, manufactured by Kao Corporation, trade name: Neobelex GS) was added, and allowed to react for 15 hours.

[0188] Finally, the system was cooled to 25 ° C and allowed to stand for 20 hours, then the pH was adjusted to 6.5 with a 3 wt% aqueous sodium hydrogen carbonate solution to terminate the polymerization, and polyorganosiloxane particles (S-l, A latex including 2) was obtained. Table 1 shows the results of measurement of polymerization conversion and volume average particle diameter of polyorganosiloxane latex.

[0189] (Production Example 5) Production of polyorganosiloxane particles (S-3)

Production Example of Siloxane Emulsion in Table 1 A mixture mixed with the composition shown in the column 5 is stirred for 5 minutes at lOOOOrpm with a homomixer, and then passed through a high-pressure homogenizer three times under a pressure of 500 bar to obtain a siloxane emulsion. And immediately charge it into a 5-necked flask equipped with a stirrer, return cooler, nitrogen inlet, additional monomer port, and thermometer. The reaction was performed at ° C for 16 hours.

[0190] Thereafter, the system was cooled to 23 ° C and allowed to stand for 20 hours, after which the polymerization was terminated by setting the pH to 6.8 with a 3 wt% aqueous sodium hydrogen carbonate solution, and polyorganosiloxane particles (S-3) were obtained. Latex containing was obtained. Table 1 shows the results of measurement of polymerization conversion and volume average particle diameter of latex of polyorganosiloxane particles.

[0191] [Table 1]

Polyorganosiloxane particles S-1 S-2 S-3 Seed polymer SD-1 parts by weight 2-1 SD-2 parts by weight-5-Siloxane ion-exchanged water 280 280 200 Emulsion SDBS parts by weight 0.5 0.5 1

DBSA parts by weight--1

D4 Weight part 93 91-

DHPDMS parts by weight-1 97.5

DSMA Emperor ^ 5 4 2.5 Polymerization catalyst DBSA parts by weight 1 1-Polymerization conversion 86% 87% 97% Volume average particle size II m 0.23 0.22 0.28

SDBS: Sodium dodecylbenzene sulfonate

DBSA: dodecylbenzene sulfonic acid

D4: Talented Kutamethylcyclotetrasiloxane

DHPDMS: terminal dihydroxypolydimethylsiloxane with an average molecular weight of 2000

DSMA: T-methacryloyl-aged xylpropylmethyldimethylsilane

(Example 1 to: L 1, Comparative Examples 1 to 3) Polyorganosiloxane-containing graft copolymer (SG — 1 to 11, SG′— 1 to 3)

240 parts by weight of ion-exchanged water in a 5-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet, additional monomer port, and thermometer (including the amount of latex power including organosiloxane particles) ), And the amount of polyorganosiloxane particles (S-1 to 3) obtained in Production Examples 3 to 5 as shown in Table 2 (however, Table 2 corresponds to the solid content), and a nitrogen stream while stirring the system The temperature was raised to the temperature shown in Table 2 below. One hour after reaching the temperature shown in Table 2, sodium formaldehyde sulfoxylate (SFS) O. 25 parts by weight, ethylenediamine tetrasodium acetate 2 (EDTA) O. 002 parts by weight, ferrous sulfate 0.005 parts by weight After mixing, a mixture of graft monomers (MG-1) having the composition shown in Table 2 was added all at once, and stirring was continued for 30 minutes.

[0193] Then, 0.04 part by weight of tamenoid oxide was added and stirred for 90 minutes. Thereafter, a mixture of graft monomers (MG-2) having the composition shown in Table 2 was added dropwise at a follow-up acceleration of 20 parts by weight Z hours. Further, when there was an additional component, 1 hour after the completion of the addition, a mixture of graft monomers (MG-3) having the composition shown in Table 2 was added dropwise at a follow-up calorie rate of 20 parts by weight Z hours. After addition of MG-2 or MG-3, stirring was continued for another 2 hours, and 0.05 parts by weight of cumene hydride peroxide was added, and 30 minutes later, 0.025 part by weight of sodium formaldehydesulfoxylate was added. Then, the mixture was further stirred for 30 minutes to obtain a latex of a polyorganosiloxane-containing graft copolymer (SG-1 to 11, SG′-1 to 3). Table 2 shows the results of measuring the polymerization conversion rate of all graft components and the volume average particle diameter of latex.

[0194] Separately, 700 parts by weight of ion-exchanged water in which 4 parts by weight of calcium chloride (solid content) was melted was heated to 80 ° C, and the above-mentioned latex was added thereto at once with stirring to obtain a coagulated slurry. It was. The obtained coagulated slurry was heated to 125 ° C and held at 125 ° C for 2 minutes, then cooled to 70 ° C, dehydrated, washed with 15 times the amount of oil, dried, and then polyorgano A powder of siloxane-containing graft copolymer was obtained. Table 2 shows the results of analysis of the graft ratio and weight average molecular weight.

[0195] [Table 2]

(Example 12 20, Comparative Example 4 7) Flame retardant

0 or 3 parts by weight of the polyorganosiloxane-containing graft copolymer powder shown in Table 3 is added to polytetrafluoroethylene (trade name: Polyflon FA-500, manufactured by Daikin Industries, Ltd.). Sulfur-containing organometallic salt of the indicated amount (sodium alkylbenzenesulfonate (average chain length of alkyl group is 12), manufactured by Kao Corporation, trade name: Neoperex G-15) was added to 100 parts by weight of polycarbonate resin (manufactured by Teijin Chemicals Ltd., trade name: Panlite L1 225WX). The obtained blend was melted and kneaded at 260 ° C. with a twin-screw extruder (Nihon Steel Works TEX44SS) to produce pellets.

[0197] Using the pellets obtained, FASIOOB injection molding machine manufactured by FANUC Corporation with a cylinder temperature set to 290 ° C, 1Z20 inch flame retardant test piece and 1 Z4 inch impact resistance An evaluation test piece was prepared. The obtained test piece was used for evaluation according to the evaluation method. Table 3 shows the results of impact resistance (30 ° C) and flame retardancy of the compacts.

[0198] [Table 3]

As can be seen in Table 3, when using the copolymer of the example, compared with the comparative example, both flame retardancy and impact resistance are superior ^).

(Examples 21 and 22 and Comparative Example 8) Phosphorus flame retardant polycarbonate ABS resin flame retardant 3 parts by weight of polyorganosiloxane-containing graft copolymer powder shown in Table 4 was added to polytetrafluoroethylene (Daikin Industries Ltd.) Made by company, product name: Polyflon FA-500) 0.5 parts by weight, aromatic condensed phosphate ester (made by Daihachi Chemical Industry Co., Ltd., product name: PX-200) Both were blended with 80 parts by weight of polycarbonate resin (made by Idemitsu Kosan Co., Ltd., trade name: Toughlon A1900) and 20 parts by weight of ABS resin (Japan A & L Co., Ltd., trade name: Santac AT-08).

[0200] The obtained blend was melt kneaded at 250 ° C with a twin-screw extruder (TEX44SS manufactured by Nippon Steel Works, Ltd.) to produce pellets. Using the obtained pellets, a FASIOOB injection molding machine manufactured by FANUC Co., Ltd., set to a cylinder temperature of 280 ° C, 1Z16 inch flame retardant evaluation test piece and 1Z4 inch impact resistance evaluation test A piece was made. It evaluated according to the said evaluation method using the obtained test piece. Table 4 shows the impact resistance (30 ° C) and flame retardancy results of the compacts.

[0201] [Table 4]

PTFE: Polytetrafluoroethylene

PX-200: Aromatic condensed phosphate I Stell

[0202] As shown in Table 4, in comparison with the comparative example, when the copolymer of the example was used, the flame retardancy and It can be seen that both impact properties are excellent.

Industrial applicability

By blending the polyorganosiloxane-containing graft copolymer of the present invention with a resin such as a thermoplastic resin, it is non-halogen and non-phosphorus and does not decrease or improve the flame retardancy. Thus, it is possible to provide a resin composition having excellent impact resistance.

Claims

The scope of the claims

[1] A polyorganosiloxane-containing graph copolymer containing a polyorganosiloxane (A) moiety and a polymer (Β) moiety having at least a unit derived from a radical reactive group-containing ultraviolet absorber () ′).

[2] The polyorganosiloxane-containing graft copolymer according to claim 1, further comprising a polymer (C) site,

The polymer (C) contains 50% by weight of a polyfunctional monomer (C ′): 50% by weight of LOO and a radical reactive monomer (C ″) copolymerizable therewith. It is a polymer obtained by polymerizing monomers,

The polyorganosiloxane-containing graft copolymer according to claim 1, wherein the polyfunctional monomer (C ') is a polyfunctional monomer (C') having two or more radical reactive groups in the molecule. Polymer.

[3] The polyfunctional monomer (C) is at least one selected from the group consisting of cyanuric acid derivatives, isocyanuric acid derivatives, and biphenyl derivatives. Polyorganosiloxane-containing graft copolymer.

[4] The polyorganosiloxane-containing graft copolymer according to claim 1 or 2, wherein the ultraviolet absorber (Β ') is a benzotriazole-based compound.

[5] The benzotriazole-based compound has a phenolic hydroxyl group

5. A polyorganosiloxane-containing graft copolymer according to claim 4.

[6] The glass transition temperature force of the polymer (Β) is 40 ° C or more.

Or a polyorganosiloxane-containing graft copolymer according to 2,

[7] A flame retardant comprising a polyorganosiloxane-containing graft copolymer according to claim 1 or 2.

[8] One or more selected from the group consisting of thermoplastic resin, thermosetting resin, and elastomer, and the polyorganosiloxane-containing graft copolymer according to claim 1 or 2. A graft copolymer-containing resin composition characterized by that.

[9] The thermoplastic resin is polycarbonate resin, polyester resin, polyester carbonate resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfur resin, Phon resin, Polyether sulfone resin, Polyarylene resin, Polyamide resin, Polyetherimide resin, Polyacetal resin, Polyvinylacetal resin, Polyketone resin, Polyether ketone resin, Polyether ether ketone resin, Poly Aryl ketone resin, polyether-tolyl resin, liquid crystal resin, polybenzimidazole resin, polyparabanic acid resin, Jeny compound, maleimide compound, aromatic alkenyl compound, methacrylate ester, acrylic acid A polymer obtained by polymerizing or copolymerizing one or more monomers selected from the group consisting of an ester and a cyanide vinyl compound, or a copolymer resin and a polyolefin-based polymer; 9. One or more selected from fat, salt-based vinyl sebum, and powerful group power Graft copolymer-containing 榭脂 composition.

[10] The thermosetting resin is phenol resin, epoxy resin, urea resin, melamine resin, polyimide resin, polyamideimide resin, thermosetting polyester resin, alkyd resin, silicone. Select from resin, urethane resin, polybulle ester resin, diaryl polyphthalate resin, bismaleimide-triazine resin, furan resin, xylene resin, guanamine resin, malein resin, and dicyclopentagen resin The graft copolymer-containing resin composition according to claim 8, wherein the composition is at least one selected from the group consisting of:

[11] The graft copolymer-containing resin composition according to claim 8, wherein the elastomer is at least one selected from the group consisting of natural rubber and synthetic rubber.

[12] The graft copolymer-containing resin composition according to claim 9, wherein the thermoplastic resin is an aromatic polycarbonate resin.

[13] The graft copolymer-containing resin composition according to claim 12, further comprising a sulfur-containing organometallic salt.