JP2000264935A - Fire-resistant resin and fire-resistant resin composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject resin having low environmental load without generating any harmful gas at the burning by using a graft copolymer obtained by graft polymerizing a vinyl-based monomer in the presence of a polyorganosiloxane-based particle having a specific rang of average particle diameter. SOLUTION: This fire-resistant resin is composed of a polyorganosiloxane- based graft copolymer obtained by graft polymerizing (B) a vinyl-based monomer (e.g. an aromatic vinyl-based monomer, a vinyl cyanide-based monomer, a halogenated vinyl-based monomer, a (meth)acrylate-based monomer, a carboxylic group-containing vinyl-based monomer, or the like) in the presence of (A) a polyorganosiloxane-based particle having 0.008-0.2 μm, preferably 0.01-0.1 μm average particle diameter (e.g. the one obtained by polymerizing a polyorganosiloxane-forming component comprising organosiloxane and/or a bifunctional or more than trifunctional silane compound, or the like), and preferably is composed of 5-99 pts.wt. of the component A and 95-1 pts.wt. of the component B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant resin and a flame-retardant resin composition containing the same.

[0002]

2. Description of the Related Art Thermoplastic resins are used for electric and electronic parts, OA.
Widely used as equipment, household goods or building materials. However, thermoplastic resins generally have the drawback of being easily flammable, and improvements have been attempted by adding various flame retardants. For example, addition of an organic halogen compound or an organic phosphorus compound has hitherto been widely performed. However, many of the organic halogen compounds and the organic phosphorus compounds have a problem in terms of toxicity, and in particular, the organic halogen compounds have a problem that they generate corrosive gas during combustion.

In order to solve these problems, studies have been made to develop flame retardancy by adding a polyorganosiloxane compound (also referred to as silicone). For example, JP-A-54-36365 describes that a flame-retardant resin can be obtained by kneading a silicone resin composed of a monoorganopolysiloxane with a non-silicone polymer.

JP-B-3-48947 describes that a mixture of a silicone resin and a Group IIA metal salt imparts flame retardancy to a thermoplastic resin.

JP-A-8-113712 discloses that 100 parts by weight of a polyorganosiloxane and a silica filler 10 to 10 parts by weight are used.
A method of obtaining a flame-retardant resin composition by dispersing a silicone resin prepared by mixing 150 parts by weight with a thermoplastic resin is described.

JP-A-10-139964 discloses a flame-retardant resin composition obtained by adding a silicone resin soluble in a solvent having a weight-average molecular weight of 10,000 to 270,000 to a non-silicone resin containing an aromatic ring. It states that a product is obtained.

[0007]

However, the silicone resin described in the above-mentioned publication has some degree of flame retardancy, but if added too much, the impact resistance of the resin composition is deteriorated. It was difficult to obtain a flame-retardant resin composition having a good balance of impact properties.

[0008] The gist of the present invention is to provide a flame-retardant resin with low environmental load that does not generate harmful gas during combustion, and to improve the impact resistance by blending the flame-retardant resin with a thermoplastic resin. An object of the present invention is to provide a flame-retardant resin composition which is excellent and does not generate harmful gas during combustion and has a low environmental load.

[0009]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that vinyl monomers can be polymerized in the presence of polyorganosiloxane particles having a specific average particle diameter. It is found that the polyorganosiloxane-based graft copolymer obtained can be used as a flame-retardant resin, and that a flame-retardant resin composition having excellent impact resistance can be obtained by blending the flame-retardant resin with a thermoplastic resin. The invention has been completed.

That is, according to the present invention, the average particle diameter is 0.0
Flame-retardant resin comprising a polyorganosiloxane-based graft copolymer obtained by graft-polymerizing a vinyl-based monomer (B) in the presence of polyorganosiloxane-based particles (A) having a thickness of from 08 to 0.2 µm (claim 1). ), 5 to 99 parts (parts by weight, the same applies hereinafter) of the polyorganosiloxane particles (A) and 95 to 1 part of the vinyl monomer (B) in a total amount of 100 parts.
The flame-retardant resin according to claim 1, which is obtained by graft polymerization so as to be a part, wherein the vinyl monomer (B) is an aromatic vinyl monomer and a vinyl cyanide monomer. 3. The flame retardant according to claim 1, wherein the flame retardant is at least one member selected from the group consisting of a monomer, a vinyl halide monomer, a (meth) acrylate monomer and a carboxyl group-containing vinyl monomer. 1 to 99 parts of the thermoplastic resin (Claim 3) and 1 to 99 parts of the thermoplastic resin, and 1 to 99 parts of the flame retardant resin according to claim 1, 2 or 3 so that the total amount is 100 parts. The flammable resin composition (Claim 4) and the thermoplastic resin are acrylonitrile-styrene copolymer, acrylonitrile-butadiene rubber-styrene copolymer (ABS
Resin), acrylonitrile-butadiene rubber-α-methylstyrene copolymer, styrene-butadiene rubber-acrylonitrile-N-phenylmaleimide copolymer, acrylonitrile-acryl rubber-styrene copolymer (AA)
S resin), acrylonitrile-acryl rubber-α-methylstyrene copolymer, styrene-acryl rubber-acrylonitrile-N-phenylmaleimide copolymer, acrylonitrile-acryl / silicone composite rubber-styrene copolymer, acrylonitrile-acryl / silicone Composite rubber-α-methylstyrene copolymer, styrene-acryl / silicone composite rubber-acrylonitrile-N-phenylmaleimide copolymer, acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin),
5. A thermoplastic resin selected from the group consisting of polycarbonate, polyester, polyvinyl chloride, polypropylene, polyphenylene ether, polystyrene, polymethyl methacrylate, methyl methacrylate-styrene copolymer and polyamide.
The present invention relates to the flame-retardant resin composition described in claim 5.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The flame retardant resin of the present invention is obtained by polymerizing a vinyl monomer (B) in the presence of polyorganosiloxane particles (A) having an average particle diameter of 0.008 to 0.2 μm. The polyorganosiloxane-based graft copolymer obtained is obtained.

The polyorganosiloxane-based particles have an average particle size of from 0.008 to 0.2 μm, preferably from 0.01 to 0.2 μm, as determined by light scattering or electron microscopic observation.
０．１0.1 μm. It tends to be difficult to obtain particles having an average particle diameter of less than 0.008 μm, and if it exceeds 0.2 μm, the flame retardancy tends to deteriorate.

The polyorganosiloxane-based particles are obtained by polymerizing a polyorganosiloxane-forming component composed of, for example, an organosiloxane and / or a bifunctional silane compound, a trifunctional or higher silane compound, and a vinyl polymerizable group-containing silane compound. Can be obtained by

The above-mentioned organosiloxane and / or
The bifunctional silane compound is a component constituting the main skeleton of the polyorganosiloxane chain. Specific examples of the organosiloxane include, for example, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexene. Specific examples of bifunctional silane compounds such as cyclic siloxanes such as sasiloxane and trimethyltriphenylcyclosiloxane, and linear organosiloxane oligomers include diethoxydimethylsilane, dimethoxydimethylsilane, diphenyldimethoxysilane, diphenyldiethoxysilane, -Chloropropylmethyldimethoxysilane, 3-
Glycidoxypropylmethyldimethoxysilane, heptadecafluorodecylmethyldimethoxysilane, trifluoropropylmethyldimethoxysilane, octadecylmethyldimethoxysilane and the like can be mentioned. Of these, octamethylcyclotetrasiloxane or a mixture of two or more cyclic siloxanes is used in an amount of 30 to 99% (% by weight, hereinafter the same), and more preferably 50 to 99%, in terms of economy and flame retardancy. And the remaining components are preferably those containing 1 to 70%, more preferably 1 to 50%, of diphenyldimethoxysilane, diphenyldiethoxysilane and the like.

The trifunctional or higher functional silane compound is a component for imparting rubber elasticity by introducing a crosslinked structure into the polyorganosiloxane by copolymerizing with the organosiloxane and the bifunctional silane compound, that is, the polyorganosiloxane. Used as a crosslinking agent. Specific examples include tetraethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane,
Examples thereof include tetrafunctional and trifunctional alkoxysilane compounds such as heptadecafluorodecyltrimethoxysilane, trifluoropropyltrimethoxysilane, and octadecyltrimethoxysilane. Of these, tetraethoxysilane, methyltriethoxysilane, and methyltrimethoxysilane are preferably used from the viewpoint of high crosslinking efficiency.

The vinyl-based polymerizable group-containing silane compound includes the organosiloxane, the bifunctional silane compound,
It is a component for copolymerizing with a silane compound or the like having higher functionality to introduce a vinyl polymerizable group into a side chain or a terminal of the copolymer. The vinyl polymerizable group is a vinyl monomer (B ) Acts as a graft active site when chemically bonding with a vinyl (co) polymer formed from the polymer. Moreover,
It is also a component that can form a cross-link by a radical reaction between the graft active points by a radical polymerization initiator and can be used as a cross-linking agent. At this time, the same radical polymerization initiator that can be used in the later-described graft polymerization can be used. Even when cross-linked by a radical reaction, grafting is possible because a part remains as a graft active site.

Specific examples of the silane compound having a vinyl polymerizable group include, for example, a compound represented by the following general formula (I):

[0018]

Embedded image (Wherein, R ¹ is a hydrogen atom, a methyl group, and R ² is a C 1-6
X is an alkoxy group having 1 to 6 carbon atoms, a is 0, 1 or 2, and p is a number of 1 to 6), a silane compound represented by the general formula (II):

[0019]

Embedded image (Wherein R ² , X, a, and p are the same as those in the general formula (I)), and a general formula (III):

[0020]

Embedded image (Wherein R ² , X, a, and p are the same as those in the general formula (I)), and a silane compound represented by the general formula (IV):

[0021]

Embedded image (Wherein R ² , X, a, and p are the same as in the general formula (I), and R ³ is a divalent hydrocarbon group having 1 to 6 carbon atoms), a silane compound represented by the general formula (V) :

[0022]

Embedded image (Wherein R ² , X, a, and p are the same as those in the general formula (I), and R ⁴ is a divalent hydrocarbon group having 1 to 18 carbon atoms).

Specific examples of R ^{2 in} the general formulas (I) to (V) include, for example, an alkyl group such as a methyl group, an ethyl group and a propyl group, and a phenyl group. Examples thereof include an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Specific examples of R ^{3 in} the general formula (IV) include a methylene group, an ethylene group, a propylene group,
Examples of R ⁴ in the general formula (V) include a methylene group, an ethylene group, a propylene group, and a butylene group.
Butylene groups and the like.

Specific examples of the silane compound represented by the general formula (I) include, for example, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyl Oxypropyldimethylmethoxysilane, γ-methacryloyloxypropyltriethoxysilane, γ-methacryloyloxypropyldiethoxymethylsilane,
γ-methacryloyloxypropyltripropoxysilane, γ-methacryloyloxypropyldipropoxymethylsilane, γ-acryloyloxypropyldimethylmethoxysilane, γ-acryloyloxypropyltrimethoxysilane, etc. are silane compounds represented by the general formula (II). Specific examples include p-vinylphenyldimethoxymethylsilane, p-vinylphenyltrimethoxysilane, p-vinylphenyltriethoxysilane,
Specific examples of the silane compound represented by the general formula (III) include vinylphenyldiethoxymethylsilane and the like.
Specific examples of the silane compound represented by the general formula (IV) include, for example, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane. Allylmethyldimethoxysilane, allylmethyldiethoxysilane Specific examples of the silane compound represented by general formula (V) include allyltrimethoxysilane, allyltriethoxysilane, and the like include mercaptopropyltrimethoxysilane, mercaptopropyldimethoxymethylsilane, and the like.
Among them, the silane compounds represented by the general formulas (I), (II) and (V) are preferably used from the viewpoint of economy.

When the vinyl-based polymerizable group-containing silane compound is of the trialkoxysilane type, it also functions as a crosslinking agent.

The proportion of the organosiloxane, the bifunctional silane compound, the trifunctional or higher silane compound, and the vinyl-based polymerizable group-containing silane compound used in the polymerization is usually the ratio of the organosiloxane and / or the bifunctional silane compound (organosiloxane). And the bifunctional silane compound is usually in a weight ratio of 100/0 to 0/100, more preferably 9/0 to 0/100.
8/2 to 40/60) 50 to 100%, and even 60 to
98%, trifunctional or higher silane compound 0 to 50%, further 1 to 39%, vinyl type polymerizable group-containing silane compound 0 to 0%
It is preferably 40%, more preferably 1 to 30%.

When the use ratio of the organosiloxane and the bifunctional silane compound is less than 50%, the resin tends to become brittle. Further, a silane compound having three or more functional groups and a silane compound having a vinyl polymerizable group are optional components. However, if the use ratio is too large, the obtained resin tends to become brittle.

The polyorganosiloxane-based particles include, for example, a polyorganosiloxane-forming component comprising the organosiloxane and / or a bifunctional silane compound, a trifunctional or higher silane compound, and optionally a vinyl-based polymerizable group-containing silane compound. Is preferably produced by emulsion polymerization.

In the emulsion polymerization, for example, 1 to 50% of an emulsion composed of emulsified droplets of several μm or more obtained by emulsifying the polyorganosiloxane-forming component, water and an emulsifier by mechanical shearing is first used. It is preferable to carry out emulsion polymerization by heating in an acidic state, and then to carry out polymerization by adding the remaining emulsion in the presence of the obtained polyorganosiloxane.

The average particle size of the polyorganosiloxane-based particles obtained by such a method is 0.00 0.00% depending on the amount of the emulsifier.
It can be controlled in the range of 8 to 0.2 μm. Coefficient of variation of the particle size distribution of the polyorganosiloxane-based particles (100 ×
The standard deviation / average particle size (%)) is preferably controlled to 10 to 100%, more preferably 20 to 60%, from the viewpoint that the surface appearance of the resin molded article is good.

Incidentally, emulsion droplets of several μm or more can be prepared by using a high-speed stirrer such as a homomixer.

In the emulsion polymerization, an emulsifier that does not lose emulsifying ability under an acidic condition is used. Specific examples include alkylbenzenesulfonic acid, sodium alkylbenzenesulfonic acid, alkylsulfonic acid, sodium alkylsulfonic acid, sodium (di) alkylsulfosuccinate,
Examples thereof include sodium polyoxyethylene nonyl phenyl ether sulfonate and sodium alkyl sulfate. These may be used alone or in combination of two or more. Among these, alkyl benzene sulfonic acid, sodium alkyl benzene sulfonate, alkyl sulfonic acid, sodium alkyl sulfonate,
Sodium (di) alkyl sulfosuccinate is preferred because the emulsion has a relatively high emulsion stability. Further, alkylbenzene sulfonic acid and alkyl sulfonic acid are particularly preferred because they also act as polymerization catalysts for the polyorganosiloxane-forming component.

The acidic state may be determined by adding inorganic acids such as sulfuric acid and hydrochloric acid, alkylbenzenesulfonic acid, alkylsulfonic acid,
It is preferably obtained by adding an organic acid such as trifluoroacetic acid, and the pH is preferably adjusted to 1 to 3 from the viewpoint that the production equipment is not corroded and an appropriate polymerization rate can be obtained. It is more preferable to adjust to 0.5.

The heating for the polymerization is preferably from 60 to 120 ° C. from the viewpoint that an appropriate polymerization rate can be obtained, and from 70 to 10 ° C.
0 ° C. is more preferred.

In an acidic condition, the Si—O—Si bond forming the skeleton of the polyorganosiloxane is in an equilibrium state of cleavage and formation, and this equilibrium changes with temperature. For
The neutralization is preferably performed by adding an aqueous alkali solution such as sodium hydroxide, potassium hydroxide and sodium carbonate. Furthermore, since the equilibrium is more likely to produce a high molecular weight or a high degree of cross-linking due to the generation side as the temperature decreases, in order to obtain a high molecular weight or a high degree of cross-linking,
The polymerization of the polyorganosiloxane-forming component is preferably carried out at 60 ° C. or higher, cooled to room temperature or lower and maintained for about 5 to 100 hours before neutralization.

Thus, when the obtained polyorganosiloxane-based particles are formed from, for example, an organosiloxane and / or a bifunctional silane compound or a trifunctional or higher silane compound, they are usually copolymerized at random and crosslinked. It has a mesh structure. When a silane compound containing a vinyl polymerizable group is copolymerized, a silane compound having a vinyl polymerizable group has a crosslinked structure. Further, when the vinyl-based polymerizable groups are cross-linked by a radical reaction with a radical polymerization initiator used at the time of the graft polymerization described later, the vinyl-based polymerizable groups have a cross-linked structure in which they are chemically bonded, and Part of the unreacted vinyl polymerizable group remains. The amount of toluene-insoluble matter in the polyorganosiloxane-based particles (the amount of toluene-insoluble matter when 0.5 g of the particles is immersed in 80 ml of toluene at room temperature for 24 hours) is preferably 20 to 95% from the viewpoint of the flame retardant effect. 30-95% is more preferred.

By graft-polymerizing the vinyl monomer (B) to the polyorganosiloxane particles obtained in the above process, a flame-retardant resin comprising a polyorganosiloxane graft copolymer can be obtained.

The flame-retardant resin has a structure in which a vinyl-based monomer (B) is grafted to the polyorganosiloxane-based particles, and has a graft ratio of 1 to 500%, and more preferably 5 to 300%. However, it is preferable in terms of a good balance between flame retardancy and impact resistance.

The vinyl monomer (B) is a component used to obtain a flame-retardant resin comprising a polyorganosiloxane-based graft copolymer, and the flame-retardant resin is further converted into a thermoplastic resin. When adding flame retardancy by blending,
It is also a component used to ensure compatibility between the flame-retardant resin and the thermoplastic resin and to uniformly disperse the flame-retardant resin in the thermoplastic resin.

The amount of the vinyl monomer (B) used is 5 to 99 parts of the polyorganosiloxane particles, and
95-1 so that the total amount becomes 100 parts for 99 parts
Parts, more preferably 90 to 1 part.

If the amount of the vinyl monomer (B) is too large, the flame retardancy will not be sufficiently exhibited, and if the amount is too small, the surface appearance or impact resistance of the molded article tends to deteriorate. It is in.

Examples of the vinyl monomer (B) include aromatic vinyl monomers such as styrene, α-methylstyrene, paramethylstyrene, and parabutylstyrene.
Acrylonitrile, vinyl cyanide monomers such as methacrylonitrile, vinyl chloride, vinylidene chloride, vinyl halide monomers such as vinylidene fluoride, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, (Meth) acrylic acid esters such as 2-ethylhexyl acrylate, glycidyl acrylate, hydroxyethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, lauryl methacrylate, glycidyl methacrylate, and hydroxyethyl methacrylate And carboxyl group-containing vinyl monomers such as isomers, itaconic acid, (meth) acrylic acid, fumaric acid, and maleic acid. These may be used alone or in combination of two or more.

For the graft polymerization, ordinary seed emulsion polymerization can be applied, and the radical polymerization of the vinyl monomer (B) may be performed in an emulsion of the polyorganosiloxane particles (A). Further, the vinyl monomer (B) is
The polymerization may be carried out in one stage or in two or more stages.

The radical polymerization can be carried out by a method in which the reaction proceeds by thermally decomposing a radical polymerization initiator, or in a redox system using a reducing agent without any particular limitation.

Examples of the radical polymerization initiator include cumene hydroperoxide, t-butyl hydroperoxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, di-t-butyl peroxide, t-butylperoxylaurate, Organic peroxides such as lauroyl peroxide, potassium persulfate,
Inorganic peroxides such as ammonium persulfate, 2,2′-azobisisobutyronitrile, 2,2′-azobis-2,
Examples include azo compounds such as 4-dimethylvaleronitrile. Among these, organic peroxides or inorganic peroxides are preferably used because they have high reactivity.

As the reducing agent used in the redox system, ferrous sulfate / glucose / sodium pyrophosphate, ferrous sulfate / dextrose / sodium pyrophosphate, or ferrous sulfate / sodium formaldehyde sulfoxylate / A mixture of ethylenediamine acetate and the like can be mentioned.

The amount of the radical polymerization initiator used is based on 100 parts of the polyorganosiloxane component used.
Usually, it is 0.005 to 20 parts, more preferably 0.01 to 10 parts, and particularly preferably 0.03 to 5 parts.
When the amount of the radical polymerization initiator is less than 0.005 parts, the reaction rate tends to be low and the production efficiency tends to be poor. When the amount exceeds 20 parts, the heat generation during the reaction tends to increase and the production tends to be difficult. is there.

Further, a chain transfer agent can be used if necessary at the time of radical polymerization. The chain transfer agent is not particularly limited as long as it is one used in ordinary emulsion polymerization.

Specific examples of the chain transfer agent include t-dodecyl mercaptan, n-octyl mercaptan, and n-octyl mercaptan.
Examples include tetradecyl mercaptan and n-hexyl mercaptan.

The chain transfer agent is an optional component. When used, the amount of the chain transfer agent is preferably 0.01 to 5 parts based on 100 parts of the vinyl monomer (B). When the amount of the chain transfer agent is less than 0.01 part, the effect obtained is not obtained. When the amount exceeds 5 parts, the polymerization rate tends to be slow and the production efficiency tends to be low.

The reaction temperature during the polymerization is usually 30 to 1
Preferably it is 20 ° C.

In the above polymerization, when the polyorganosiloxane-based particles (A) contain a vinyl-based polymerizable group, the polyorganosiloxane-based particles (B) are polymerized by a radical polymerization initiator. The graft is formed by reacting with the vinyl polymerizable group of the system particles (A). When a vinyl polymerizable group is not present in the polyorganosiloxane-based particles (A), a specific radical initiator such as t-butylperoxylaurate can be used to convert an organic group such as a methyl group bonded to a silicon atom. Withdrawing hydrogen, the vinyl-based monomer (B) is polymerized by the generated radical to form a graft.

Further, 0.1% of the vinyl monomer (B) is used.
Even when 1 to 30%, preferably 0.5 to 20% is polymerized using a vinyl-based polymerizable group-containing silane compound, and a redistribution reaction is performed under an acidic condition of pH 5 or less, a graft is formed. This is because the Si-O-Si bond of the main skeleton of the polyorganosiloxane is in an equilibrium state of cleavage and formation in an acidic state, and in this equilibrium state, the vinyl-based monomer and the vinyl-based polymerizable group-containing silane compound are separated. Upon copolymerization, the silane in the side chain of the vinyl copolymer being produced or produced by the polymerization reacts with the polyorganosiloxane chain to produce a graft. The vinyl-based polymerizable group-containing silane compound may be the same as that used if necessary at the time of producing the polyorganosiloxane-based particles (A), and the amount of the vinyl-based polymerizable group-containing silane compound is 0.1%. If the percentage is less than
The rate of grafting of the vinyl monomer (B) decreases, and 3
If it exceeds 0%, the stability of the emulsion tends to decrease.

In the polymerization of the vinyl monomer (B) in the presence of the polyorganosiloxane particles, a portion corresponding to a branch of the graft copolymer (here, a polymer of the vinyl monomer (B)) is used. ) Does not graft onto the trunk component (here, polyorganosiloxane-based particles (A)), but also produces a so-called free polymer, which is obtained by polymerizing solely with the branch component alone, as a mixture of the graft copolymer and the free polymer. In the present invention, both are collectively referred to as a graft copolymer.

The flame-retardant resin comprising the graft copolymer obtained by emulsion polymerization may be used by separating the polymer from the emulsion or may be used as it is. As a method for separating the polymer, a usual method,
For example, there is a method in which a metal salt such as calcium chloride, magnesium chloride, and magnesium sulfate is added to the emulsion to coagulate, separate, wash, dehydrate, and dry the emulsion. Also, a spray drying method can be used.

The flame-retardant resin comprising the graft copolymer obtained in this manner is a resin having flame retardancy itself (a polymer separated or as an emulsion), and various heat-resistant resins. A flame-retardant resin composition which is blended with a plastic resin and has excellent impact resistance.

Preferred specific examples of the thermoplastic resin include acrylonitrile-styrene copolymer, acrylonitrile-butadiene rubber-styrene copolymer (ABS resin), acrylonitrile-butadiene rubber-α-methylstyrene copolymer, styrene- Butadiene rubber-acrylonitrile-N-phenylmaleimide copolymer, acrylonitrile-acryl rubber-styrene copolymer (AAS)
Resin), acrylonitrile-acryl rubber-α-methylstyrene copolymer, styrene-acryl rubber-acrylonitrile-N-phenylmaleimide copolymer, acrylonitrile-acryl / silicone composite rubber-styrene copolymer, acrylonitrile-acryl / silicone composite Rubber-α-methylstyrene copolymer, styrene-acryl / silicone composite rubber-acrylonitrile-N-phenylmaleimide copolymer, acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin), polycarbonate, polyethylene terephthalate and polybutylene Polyester such as terephthalate, polyvinyl chloride, polypropylene, polyphenylene ether, polystyrene, polymethyl methacrylate, methyl methacrylate-styrene copolymer Body and polyamide can also be used. These may be used alone or in combination of two or more.

Among them, acrylonitrile-butadiene rubber-styrene copolymer (ABS resin), acrylonitrile-butadiene rubber-α-methylstyrene copolymer,
Styrene-butadiene rubber-acrylonitrile-N-phenylmaleimide copolymer, acrylonitrile-acryl rubber-styrene copolymer (AAS resin), acrylonitrile-acryl rubber-α-methylstyrene copolymer,
Styrene-acrylic rubber-acrylonitrile-N-phenylmaleimide copolymer, acrylonitrile-acryl / silicone composite rubber-styrene copolymer, acrylonitrile-acryl / silicone composite rubber-α-methylstyrene copolymer, styrene-acryl / silicone composite Rubber-acrylonitrile-N-phenylmaleimide copolymer, acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin), polycarbonate, polyester such as polyethylene terephthalate and polybutylene terephthalate, polyvinyl chloride, and polystyrene are more preferable.

The amount of the flame-retardant resin comprising the polyorganosiloxane-based graft copolymer added to the thermoplastic resin is preferably from 1 to 99 parts from the viewpoint of a good balance between impact resistance and flame retardancy. , Preferably 1 to 9
It is desirable to mix 1 to 99 parts, preferably 5 to 99 parts, of the flame retardant resin with 5 parts so that the total amount becomes 100 parts.

The mixing of the thermoplastic resin with the flame-retardant resin powder comprising the polyorganosiloxane-based graft copolymer separated from the emulsion was carried out by a Henschel mixer.
After mixing with a ribbon blender or the like, the mixture can be melt-kneaded with a roll, extruder, kneader or the like.

At this time, the commonly used compounding agents, ie, plasticizer, stabilizer, lubricant, ultraviolet absorber, antioxidant,
Flame retardants, pigments, glass fibers, fillers, polymer processing aids,
A polymer lubricant, an impact resistance improver, and the like can be blended.

When the thermoplastic resin is produced by an emulsion polymerization method, both an emulsion of the thermoplastic resin and an emulsion of a flame-retardant resin comprising a polyorganosiloxane-based graft copolymer are prepared in an emulsion state. After blending, it is also possible to obtain a thermoplastic resin composition by co-coagulation.

As the molding method of the obtained thermoplastic resin composition, molding methods used for molding ordinary thermoplastic resin compositions, that is, injection molding method, extrusion molding method, blow molding method, calender molding method, etc. Can be applied.

The obtained molded article has excellent impact resistance and flame retardancy.

[0065]

EXAMPLES The present invention will be specifically described based on examples, but the present invention is not limited to these examples.

The measurements and tests in the following Examples and Comparative Examples were performed as follows. [Polymerization conversion] The emulsion was dried in a hot air drier at 120 ° C. for 1 hour to determine the amount of solid components, and was calculated as 100 × the amount of solid components / the amount of charged monomers (%). [Toluene-insoluble content] A solid of 0.5 g of polyorganosiloxane-based particles obtained by drying from the emulsion was immersed in 80 ml of toluene at room temperature for 24 hours.
After centrifugation at 60 rpm for 60 minutes, the weight fraction (%) of the toluene-insoluble portion of the polyorganosiloxane-based crosslinked particles was measured. [Graft ratio] 1 g of the graft copolymer was immersed in 80 ml of acetone at room temperature for 48 hours, and then 6 g at 12000 rpm.
The insoluble content (w) of the graft copolymer was determined by centrifugation for 0 minutes, and the graft ratio was calculated by the following equation.

Graft ratio (%) = 100 × ｛(w−1 ×
Polyorganosiloxane component fraction in graft copolymer) / (1 × polyorganosiloxane component fraction in graft copolymer)｝ [average particle diameter] average particle diameter of polyorganosiloxane-based particles and graft copolymer Was measured in an emulsion state. Using a NICOMP MODEL370 particle size analyzer manufactured by PACIFIC SCIENTIFIC as a measuring device, the volume average particle diameter (μm) and the coefficient of variation of the particle diameter distribution (standard deviation / number average particle) are measured by a light scattering method. (Diameter (%)) was measured. [Impact resistance] According to ASTM D-256, a notched 1/4 inch bar or a notched 1/8 inch bar was used to evaluate by an Izod test at 23 ° C. [Flame retardancy] Evaluated by UL94 V test and UL94 HB test. [Surface Appearance] The test pieces used for the evaluation of flame retardancy were visually observed, and the surface appearance was evaluated according to the following criteria.

：: good surface appearance △: streak pattern is observed on the surface

×: Streaky pattern and peeling are observed on the surface.

The raw materials used are shown below. PC: polycarbonate Teflon A-2200 manufactured by Idemitsu Petrochemical Co., Ltd. AAS: AAS resin manufactured in Example 2 S-1: polyorganosiloxane-based particles manufactured in Reference Example 1 S-2: manufactured in Reference Example 2 Polyorganosiloxane-based particles SG-1: Polyorganosiloxane-based graft copolymer produced in Example 1 SG-2: Polyorganosiloxane-based graft copolymer produced in Example 2 SG-3: Implementation Polyorganosiloxane-based graft copolymer produced in Example 3 SG'-1: Polyorganosiloxane-based graft copolymer produced in Comparative Example 1 Reference Example 1 Production of polyorganosiloxane-based particles (S-1) Next The aqueous solution comprising the components of
The emulsion was prepared by stirring at 0 rpm for 5 minutes.

Component Amount (parts) Pure water 200 Sodium dodecylbenzenesulfonate (SDBS) 2.5 Octamethylcyclotetrasiloxane (D4) 20 This emulsion was stirred with a stirrer, a reflux condenser, a nitrogen inlet,
The mixture was charged all at once into a 5-neck flask equipped with a monomer addition port and a thermometer. After the temperature was raised to 90 ° C. over about 40 minutes while stirring the system, 2.0 parts of dodecylbenzenesulfonic acid (DBSA) was added and reacted at 90 ° C. for 3 hours to prepare an emulsion containing a polyorganosiloxane. . The polymerization conversion at this time was 84%. The average particle size of the polyorganosiloxane in the emulsion is 0.03 μm.
Met. The pH of the emulsion was 2.0.

Separately, a mixture comprising the following components was stirred with a homomixer at 10,000 rpm for 5 minutes to prepare a polyorganosiloxane-forming component-containing emulsion.

Component Amount (parts) Pure water 70 SDBS 0.5 D455 5 γ-acryloyloxypropyltrimethoxysilane (TSA) 5 Emulsion containing polyorganosiloxane-forming component prepared while stirring the emulsion containing polyorganosiloxane Was added all at once. One hour after the addition, 20 parts of diphenyldimethoxysilane was added dropwise over 2 hours, and the reaction was continued for another 3 hours. Thereafter, the system was cooled to 25 ° C., left for 20 hours, and then the pH of the system was returned to 8.2 with sodium hydroxide to terminate the polymerization, thereby obtaining an emulsion containing polyorganosiloxane-based particles. The polymerization conversion, the average particle size of the emulsion of the crosslinked polyorganosiloxane particles, and the amount of toluene-insoluble matter were measured. The results are shown in Table 1.

Reference Example 2 Production of polyorganosiloxane-based particles (S-2)
The emulsion was prepared by stirring at 0 rpm for 5 minutes.

Component Amount (parts) Pure water 200 DBSA 1 D4 75 TSA 5 Further, this emulsion was passed twice through a high-pressure homogenizer set to a pressure of 300 kg / cm ² . The obtained emulsion was charged into a 5-neck flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a monomer addition port, and a thermometer.
After raising the temperature over about 40 minutes, the mixture was reacted for 1 hour, 20 parts of diphenyldimethoxysilane was added dropwise over 2 hours, and the reaction was further performed for 3 hours. Then, after cooling to 25 ° C. and maintaining for 20 hours, the pH of the system was returned to 8.0 with sodium hydroxide to terminate the polymerization. Table 1 shows the results.

[0076]

[Table 1] Example 1 and Comparative Example 1 A five-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a monomer addition port, and a thermometer was charged with 250 parts of pure water, sodium formaldehyde sulfoxylate (SFS) 0.1 part, and water.
2 parts, disodium ethylenediaminetetraacetate (EDT
A) 0.01 part, 0.0025 part of ferrous sulfate and Table 2
Was charged and heated to 60 ° C. under a nitrogen stream while stirring the system. 6
After reaching 0 ° C., a mixture of the monomer and the radical polymerization initiator shown in Table 2 was added dropwise over 6 hours, and then stirring was continued at 60 ° C. for 1 hour to obtain an emulsion of the graft copolymer. Subsequently, 2 parts of calcium chloride was added to the emulsion, coagulated, dehydrated and dried to obtain a polyorganosiloxane-based graft copolymer (SG-1).
And SG′-1) powder. Table 2 shows the polymerization conversion, average particle size, and graft ratio.

The powder 100 of the graft copolymer (SG-1 or SG'-1) obtained in Example 1 or Comparative Example 1
Phenolic stabilizer (Asahi Denka Kogyo Co., Ltd.)
AO-20) and 0.2 parts of ethylene bisstearyl amide were mixed and heated to 230 ° C by a single screw extruder (HW-40-28 manufactured by Tabata Machine Co., Ltd.) to melt. The mixture was kneaded to prepare a pellet. Using these pellets, a FAS100B injection molding machine manufactured by FANUC, set at a cylinder temperature of 230 ° C.,
A test piece for evaluating / 8 inch flame retardancy was prepared. Using the obtained test pieces, evaluation was performed according to the above evaluation method.

Table 2 shows the results.

In Table 2, AN represents acrylonitrile, St represents styrene (above, monomer), and CHP represents cumene hydroperoxide (radical polymerization initiator).

[0080]

[Table 2] From the results of the flame retardancy test in Table 2, it can be seen that the graft copolymer of the present invention has flame retardancy and is effective as a flame retardant resin.

Example 2 Improvement of AAS (acrylonitrile-acryl rubber-styrene copolymer) resin (1) Polyorganosiloxane-based graft copolymer (S
Production of G-2) In Example 1, the polyorganosiloxane-based particles (S
-1) in 70 parts, St in 21 parts, AN in 9 parts, CHP
Was set to 0.06, and the mixed component of the graft monomer and the radical polymerization initiator was dropped over 3 hours, in the same manner as in Example 1 except that the polyorganosiloxane-based graft copolymer (SG-2) was used. ) Was prepared.
The polymerization conversion was 99%, the average particle diameter was 0.07 μm, and the graft ratio was 35%. (2) Production of AAS Resin Emulsion The following components were collectively charged into a 5-neck flask equipped with a stirrer, reflux condenser, nitrogen gas inlet, monomer addition port, and thermometer.

Component Amount (parts) Pure water 200 Dioctyl sodium sulfosuccinate 0.005 SFS 0.4 EDTA 0.01 Ferrous sulfate 0.0025 Next, the system was heated to 45 ° C. while stirring under a nitrogen gas stream. While keeping the same, 15% of the next monomer mixture was charged at once and stirred for 1 hour, and then 0.3 parts of sodium dioctylsulfosuccinate was added. Thereafter, the remaining monomer mixture was added dropwise over 4 hours. After completion of the dropwise addition, stirring was continued for 1 hour to complete the polymerization, and a polybutyl acrylate rubber emulsion was obtained.

Component Amount (parts) Butyl acrylate 60 CHP 0.1 The solid content of the obtained emulsion was 23%,
The average particle size was 0.30 μm. The polymerization conversion of the monomer mixture was 99%.

Subsequently, the system was maintained at 65 ° C., and the following monomer mixture was added dropwise over 4 hours. After the addition, stirring was continued for 2 hours to complete the polymerization, and an emulsion of a poly (butyl acrylate) rubber-based graft copolymer was obtained.

Component Amount (Parts) The solid content of the St 28 AN 12 CHP 0.1 emulsion was 33%, and the polymerization conversion of the monomer mixture was 99%.

Subsequently, separately, AN-
An emulsion of St copolymer was prepared. The following components were collectively charged into a 5-neck flask equipped with a stirrer, a reflux condenser, a nitrogen gas inlet, a monomer addition port, and a thermometer.

Component Amount (parts) Pure water 200 Dioctyl sodium sulfosuccinate 1.0 SFS 0.4 EDTA 0.01 Ferrous sulfate 0.0025 Next, the system was heated to 65 ° C. while stirring under a nitrogen gas stream. While keeping the same, the next monomer mixture was added dropwise over 6 hours. Also, 0.5 part of sodium dioctyl sulfosuccinate was added at the first hour of polymerization and 0.5 part at the third hour. After completion of the dropwise addition, stirring was continued for one hour to complete the polymerization, and an AN-St copolymer emulsion was obtained.

Component Amount (parts) St 70 AN 30 CHP 0.2 The solid content of the obtained emulsion was 33%,
The polymerization conversion of the monomer mixture was 99%.

The AN-St copolymer emulsion and the graft copolymer emulsion were mixed so that the amount of polybutyl acrylate rubber became 20% in terms of solid content,
An emulsion of AAS resin was obtained. (3) Production of AAS resin composition The AAS resin emulsion obtained and the polyorganosiloxane-based graft copolymer obtained in (1) (SG-2)
And an emulsion of the AAS resin composition was obtained by mixing so that the polyorganosiloxane became 15% in solid content conversion.

The obtained emulsion of the AAS resin composition was coagulated with 2 parts of calcium chloride, and then dehydrated and dried to prepare an AAS resin composition.

Resin powder 100 of AS resin composition obtained
Phenolic stabilizer (Asahi Denka Kogyo Co., Ltd.)
AO-20) and 0.2 parts of ethylene bisstearyl amide were mixed and heated to 240 ° C. by a single screw extruder (HW-40-28 manufactured by Tabata Machine Co., Ltd.) to melt. The mixture was kneaded to prepare a pellet. Using these pellets, a FAS100B injection molding machine manufactured by FANUC, set at a cylinder temperature of 240 ° C.,
/ 4 inch Izod test pieces and 1/8 inch test pieces for flame retardancy evaluation were prepared. Using the obtained test pieces, evaluation was performed according to the above evaluation method.

Table 3 shows the results.

Comparative Example 2 In Example 2, instead of the emulsion of the graft copolymer (SG-2), the emulsion of the polyorganosiloxane-based particles (S-1) produced in Reference Example 1 was used. Evaluation was carried out in the same manner as in Example 2 except that an emulsion of the AAS resin composition was obtained by mixing so as to have a solid content of 15%.

Table 3 shows the results.

Comparative Example 3 Evaluation was made in the same manner as in Example 2 except that the emulsion of the graft copolymer (SG-2) was not used.

Table 3 shows the results.

[0097]

[Table 3] From the results in Table 3, it can be seen that a flame-retardant resin composition having excellent impact resistance can be obtained by blending the polyorganosiloxane-based graft copolymer (SG-2) of the present invention with an AAS resin.

Example 3 Flame Retardancy of Polycarbonate Resin (1) Polyorganosiloxane Graft Copolymer (S
Production of G-3) The polyorganosiloxane-based particles in Example 1 were replaced with 9
In two parts, using 8 parts of methyl methacrylate instead of the graft monomer components St and AN, and using 0.02 parts of t-butyl hydroperoxide instead of CHP, and adding the methyl methacrylate. A powder of a polyorganosiloxane-based graft copolymer (SG-3) was obtained in the same manner as in Example 1, except for adding all at once. The polymerization conversion rate is 99%, the average particle diameter is 0.06 μm, and the graft rate is 8%.
Met. (2) Polycarbonate (PC) resin composition The powder of the polyorganosiloxane-based graft copolymer (SG-3) obtained in (1) was mixed with the powder of the polyorganosiloxane in 100 parts of the powder of the PC resin. It was blended so as to be 6% to obtain a PC composition.

The obtained mixture was melt-kneaded at 280 ° C. with a twin screw extruder (TEX44SS manufactured by Nippon Steel Works, Ltd.) to produce pellets. The pellets obtained were set at a cylinder temperature of 270 ° C.
A 1/8 inch Izod test piece and a 1/12 inch flame retardancy evaluation test piece were prepared using an FAS100B injection molding machine manufactured by C). Using the obtained test pieces, evaluation was performed according to the above evaluation method.

Table 4 shows the results.

Comparative Example 4 In place of the graft copolymer (SG-3) in Example 3, 2 parts of calcium chloride was added to the emulsion of polyorganosiloxane particles (S-1) obtained in Reference Example 1. The same procedure as in Example 3 was carried out except that a polyorganosiloxane rubber material obtained by coagulation, dehydration, and drying was used and the content of the polyorganosiloxane was blended so as to be 6% to obtain a PC resin composition. evaluated.

Table 4 shows the results.

Comparative Example 5 Evaluation was made in the same manner as in Example 3 except that the graft copolymer (SG-3) was not used and only the PC resin was used.

Table 4 shows the results.

[0105]

[Table 4] Table 4 shows that the composition comprising the graft copolymer and the PC resin of the present invention has an excellent balance of flame retardancy, surface appearance and impact resistance.

[0106]

According to the present invention, it is possible to obtain a flame-retardant resin of low environmental load which does not generate harmful gas during combustion, and has excellent impact resistance by blending the flame-retardant resin with a thermoplastic resin. A flame-retardant resin composition can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C08L 25/12 C08L 25/12 25/16 25/16 27/06 27/06 33/12 33/12 51 / 08 51/08 67/00 67/00 69/00 69/00 71/12 71/12 77/00 77/00 F term (reference) 4J002 BB12X BC03X BC06X BC07X BC09X BD04X BG06X BN06X BN12X BN15X BN17W CF00X CG00X CH07X CL00X GC00 GL00 GQ00 4J011 KA02 KB19 PA99 PB06 PB29 PC02 PC06 SA76 SA79 SA85 4J026 AB44 BA05 BA06 BA10 BA11 BA27 BA34 BB03 DA04 DA07 DA15 DB04 DB08 DB12 DB14 DB15 DB16 EA04 FA03 GA01 GA09

Claims (5)

[Claims] 1. A polyorganosiloxane graft copolymer obtained by graft polymerization of a vinyl monomer (B) in the presence of polyorganosiloxane particles (A) having an average particle diameter of 0.008 to 0.2 μm. Flame-retardant resin made of united. 2. Polyorganosiloxane particles (A) 5
The flame-retardant resin according to claim 1, which is obtained by graft-polymerizing 95 to 1 part by weight of a vinyl monomer (B) so that the total amount becomes 100 parts by weight with respect to 99 parts by weight. 3. The vinyl monomer (B) is an aromatic vinyl monomer, a vinyl cyanide monomer, a vinyl halide monomer, a (meth) acrylate monomer and a carboxyl monomer. 3. The flame-retardant resin according to claim 1, which is at least one monomer selected from the group consisting of group-containing vinyl monomers. 4. It is difficult to mix 1 to 99 parts by weight of the flame-retardant resin according to claim 1, 2 or 3 with respect to 1 to 99 parts by weight of the thermoplastic resin so that the total amount becomes 100 parts by weight. Flammable resin composition. 5. The thermoplastic resin is an acrylonitrile-styrene copolymer, acrylonitrile-butadiene rubber-
Styrene copolymer (ABS resin), acrylonitrile
Butadiene rubber-α-methylstyrene copolymer, styrene-butadiene rubber-acrylonitrile-N-phenylmaleimide copolymer, acrylonitrile-acryl rubber-styrene copolymer (AAS resin), acrylonitrile-acryl rubber-α-methylstyrene copolymer Polymer, styrene-acryl rubber-acrylonitrile-N-phenylmaleimide copolymer, acrylonitrile-acryl / silicone composite rubber-styrene copolymer, acrylonitrile-acryl / silicone composite rubber-α-methylstyrene copolymer, styrene-acryl / Silicone composite rubber
Acrylonitrile-N-phenylmaleimide copolymer,
Acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin), polycarbonate, polyester, polyvinyl chloride, polypropylene, polyphenylene ether, polystyrene, polymethyl methacrylate,
The flame-retardant resin composition according to claim 4, which is at least one kind of thermoplastic resin obtained from the group consisting of methyl methacrylate-styrene copolymer and polyamide.