JPH021760A - Polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition consisting of polyphenylene ether resin having excellent impact resistance, heat resistance, mechanical strength and flame retardance by forming the composition from a polyphenylene ether resin, polystyrene resin, specific composite rubber based graft copolymer, specific flame retardant and/or specific inorganic fiber. CONSTITUTION:The aimed composition obtained by blending 100 pts.wt. resin blend consisting of (A) 20-80wt.% polyphenylene ether resin, (B) 19-75wt.% polystyrene resin, (C) 1-40wt.% composite rubber based graft copolymer obtained by subjecting a composite rubber having structure interwining C1: 10-90wt.% polyorganosiloxane rubber component with 10-90wt.% polyalkyl(meth)acrylate and 0.08-0.6mum average particle size to graft polymerization with C2: one or more kind of vinyl based monomers with (D) 0.5-35 pts.wt. phosphoric acid ester based flame retardant (preferably triphenyl phosphate) and/or (E) 5-100 pts.wt. inorganic fiber selected from glass fiber and carbon fiber.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polyphenylene ether resin composition having excellent impact resistance, heat resistance, mechanical strength, flame retardance, etc.

[Summary of the invention]

The present invention provides a polyphenylene ether resin composition in which the polyphenylene ether resin composition is a polyphenylene ether resin composition. Consists of N-styrene resin and a composite rubber graft copolymer obtained by highly efficient graft polymerization of a vinyl monomer to a composite rubber consisting of a polyorganosiloxane rubber component and a polyalkyl (meth)acrylate rubber component. By blending a phosphate ester flame retardant and/or at least one type of inorganic fiber selected from the group consisting of glass fiber and carbon fiber into the resin compound, it has excellent impact resistance, heat resistance, mechanical strength, flame retardance, etc. This makes it possible to provide a composition that has the following properties.

[Prior art and problems to be solved by the invention] Polyphenylene ether resins are increasingly being used as engineering plastics because they provide molded products with excellent heat resistance and rigidity. Its use is limited due to its slightly inferior properties.

As a method of improving the impact resistance of polyphenylene ether resin molded products, a method of blending a polybutadiene elastomer is disclosed in Japanese Patent Publication No. 47-32731 and Japanese Patent Application Laid-Open No. 1973-1989.
This is disclosed in Japanese Patent No.-2345 and the like. however,
When such a method is used, unsaturated bonds remain in the polybutadiene elastomer, making it thermally unstable, making it impossible to obtain a material with excellent thermal stability that is useful for practical purposes.

Furthermore, a method of improving impact resistance by blending a polyorganosiloxane-modified alkenyl aromatic resin with a polyphenylene ether resin is disclosed in JP-A-55-75444.
Japanese Patent Publication No. 49-6579 discloses a method for improving the strength of resin molded products by blending acrylates. However, the current situation is that even with these methods with deviations from b, it is not possible to obtain satisfactory molded appearance and impact resistance.

Therefore, as a result of intensive study on the resin composition to improve impact resistance and surface appearance while maintaining the excellent heat resistance and mechanical strength inherent to polyphenylene ether resin moldings, we found that polyorganosiloxane rubber components and polyalkyl ( By combining a composite rubber-based graft copolymer obtained by highly efficient graft polymerization of a vinyl monomer onto a composite rubber consisting of a meth)acrylate rubber component, a polyphenylene ether resin, and a polystyrene resin, each of these resins can be produced. The compatibility between the materials is good, and when molded, delamination does not occur, and the impact resistance and surface appearance are significantly improved, as well as excellent heat resistance and mechanical strength, as well as excellent moldability and fluidity. I applied for a patent after discovering that a resin composition with high flame retardance could be obtained.
It was not possible to provide sufficiently excellent mechanical strength.

[Means to solve the problem]

The present inventors conducted intensive studies in view of the current situation as described above, and found that a phosphate ester flame retardant imparts flame retardancy to a resin compound that combines the composite rubber graft copolymer and polyphenylene ether resin and tobolystyrene resin. In addition, at least one type of inorganic fiber such as glass #& fiber and carbon I fiber can provide excellent mechanical strength, and furthermore, the combination use of these phosphate ester flame retardants and inorganic fiber is preferred. The present invention was achieved by discovering that it is possible to impart excellent mechanical strength and flame retardancy to the material.

That is, the present invention is based on (A) rt! Lifuenylene ether resin, (B)
Polystyrene resin, (C) polyorganosiloxane rubber component 10-90
Heavy lubricant and polyalkyl (meth)acrylate rubber component 1
0 to qo7Ir have a structure in which they are intertwined with each other so that they cannot be separated, and the total amount of the polyorganosiloxane rubber component and the polyalkyl (meth)acrylate rubber component is 100 parts by weight. 08-0.6
A composite rubber-based graft copolymer obtained by graft-polymerizing one or more vinyl monomers to a μm-sized composite rubber, and (D) a polyphenylene ether resin composition containing a phosphate ester flame retardant as a constituent component. It is a thing.

Furthermore, the present invention provides the above component (A), component (B), component (C), and at least one inorganic fiber component (E!1) selected from the group consisting of glass F fibers and carbon fibers, respectively. Containing polyphenylene ether fiber components and the above components (A), (B), and (
It contains a polyphenylene ether resin composition containing component (C), component (D), and component (c) as constituent components, respectively.

The polyphenylene ether resin (A) used in the present invention has the following formula: ) is a homopolymer or copolymer represented by

Specific examples of such polyphenylene ether resins include poly(2,15-dimethyl-1,4-7dinilene) ether, poly(2,6-ethyl-1,4-phenylene) ether, and poly(2,6-cyprobylene) ether. 1,4-phenylene)ether, poly(2-methyl-6-ethyl-1,4
-) unicine) ether, poly(2-methyl-6-propyl-1゜4-)unicine) ether, poly(2-ethyl-6-broby-1,4-phenylene) ether, (
2,6-dimethyl-1,4-phenylene)ether and (
Copolymer with 2,3,6-dolimethyl-1,4-phenylene)ether, (2,6-dinityl-1゜4-)unisine)nietelt(2,&6-)+7methyl-1
．． Copolymer with 4-phenylene) ether, (2,6-
dimethyl-1,4-phenylene)ether and (Z&6-
Examples include copolymers with dryethyl-1,4-phenylene) ether.

In particular, poly(2,6-dimethyl-1,4-phenylene) ether and copolymers of (2,6-dimethyl-1,4-)unicine) ether and (2,&6-drimethyl-t4-phenylene) ether is preferred, and poly(2,6-dimethyl-1,4-phenylene)ether is more preferred. Collaborif 22lene ether resin is compatible with polystyrene resin at all blending ratios.

The degree of polymerization of the polyphenylene ether resin used in the present invention is not particularly limited, but the reduced viscosity at 25° C. in a chloroform solvent is α3 to CL 7 dt/
f is preferably used. Those with a reduced viscosity of less than α5 dt/f tend to have poor thermal stability, while those with a reduced viscosity of more than [L7 dt/f tend to impair moldability. These polyphenylene ether resins may be used alone or in combination of two or more.

Moreover, polystyrene resin CB) used in the present invention
is the following formula (where Y is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, 2 is a halogen atom or an alkyl group having 1 to 4 carbon atoms,
L represents 0 or a number from 1 to 3. ) is a homopolymer composed of 50 to 84 or more aromatic vinyl monomer units, or a copolymer with other copolymerizable vinyl monomers.

Specific examples of such polystyrene resins include boriastyrene, polychlorstyrene, polybromstyrene,
Poly α-methylstyrene, styrene-acrylonitrile copolymer, styrene-methylmethacrylate copolymer,
Examples include styrene-maleic anhydride copolymer, styrene-maleimide copolymer, styrene-N-phenylmaleimide copolymer, styrene-acrylonitrile-α-methylstyrene ternary copolymer, and polystyrene is particularly preferred. Furthermore, the composite rubber-based graft copolymer (C) used in the present invention refers to the polyorganosiloxane rubber component 1.
0 to 90 parts by weight and 90 to 10 parts by weight of the polyalkyl (meth)acrylate rubber component (the total amount of each rubber component is 100 parts by weight)
(parts by weight), both rubber components are intertwined with each other and have a structure that is virtually inseparable, and the average particle size is α08.
It is a copolymer in which 11 types or 2 or more types of vinyl monomers are graft-polymerized on a composite rubber having a diameter of ~α6 μm.

Even if one of a polyorganosiloxane rubber component and a polyalkyl (meth)acrylate rubber component, or a simple mixture thereof, is used as a rubber source in place of the above-mentioned composite rubber, the characteristics of the resin composition of the present invention remain unchanged. Polyorganosiloxane rubber component topolyalkyl (
Only when the meth)acrylate rubber components are intertwined with each other and integrated into a composite body can a resin composition that provides a molded article with excellent impact resistance and molded surface appearance be obtained.

If the polyorganosiloxane rubber component constituting the mata composite rubber exceeds 90 parts by weight, the molded surface appearance of the molded product from the resulting resin composition will deteriorate, and the polyalkyl (meth)acrylate rubber component will exceed 90 parts by weight. If it exceeds this, the impact resistance of the molded product obtained from the resin composition will deteriorate. Therefore, the two rubber components constituting the composite rubber both have a weight of 10 to 90%81 (however, the total weight of both rubber components (i) J
-i 100 weight 84) is required, and it is particularly preferably in the range of 20 to 80 weight Fk4. Average particle diameter of the above composite ° rubber II''1108~α6
It is necessary to be in the μm range. The average particle diameter is Q,
If the average particle diameter is less than 0.8 μm, the impact resistance of the molded product obtained from the resin composition will deteriorate, and if the average particle size exceeds 16 μm, the impact resistance of the molded product obtained from the resin composition will deteriorate, and The surface appearance deteriorates.

Emulsion polymerization is the most suitable method for producing composite rubber having such an average particle size. First, a latex of polyorganosiloxane rubber is prepared, and then a monomer for synthesis of alkyl (meth)acrylate rubber is prepared. Preferably, the body is impregnated with rubber particles of polyorganosiloxane rubber latex before polymerization of the synthetic monomer.

The polyorganosiloxane rubber components constituting the above composite rubber include the organosiloxane and crosslinking agent (I) shown below.
It can be prepared by emulsion polymerization using
Furthermore, a grafting agent (I) can also be used in combination.

The organosiloxane includes various cyclic bodies having 3 or more membered rings, and 3- to 6-membered rings are preferably used. For example, hexamethylcyclotrisiloxane, octamethylcyclotetranoxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane,
Examples include trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, and octaphenylcyclotetrasiloxane, which may be used alone or in combination of two or more. The amount of these used is 50 parts by weight or more, preferably 70 parts by weight or more in the polyorganosiloxane rubber component.

As the crosslinking agent (I), a penta-functional or Fi4-functional silane thread crosslinking agent such as trimethoxymethylsilane, triethoxyphenylsilane, tetraethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetrabutoxysilane can be used. etc. are used. Particularly preferred are tetrafunctional crosslinking agents, and among these, tetraethoxysilane is particularly preferred. The amount of the crosslinking agent used is α1 to 30% by weight in the polyorganone loxane rubber component.

The graft crossover agent (I) is the following formula 0%) (In each formula, R1 is a methyl group, ethyl group, propyl group, or phenyl group, H1 is a hydrogen atom or a methyl group, n is 0.1 or 2, and p is A compound or the like that can form a unit represented by (indicates a number from 1 to 6) is used. (Meth)acryloyloxysiloxane that can form the unit of formula (I-1) has a high grafting efficiency, so it is possible to form an effective graft chain and is advantageous in terms of impact resistance.

Note that methacryloyloxysiloxane is particularly preferred as a unit capable of forming the unit of formula (li). Specific examples of methacryloyloxysiloxane include β-methacryloyloxyethyldimethoxymethylsilane, r-methacryloyloxypropylmethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylyran,
Examples include γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropyljethoxymethylsilane, δ-methacryloyloxybutyldiethoxymethylsilane, and the like. The amount of the kraft cross-agent used is D to 10 parts by weight in the polyorganosiloxane rubber component.

The latex of this polyorganosiloxane rubber component can be produced using, for example, the methods described in US Pat. No. 2,891,920 and US Pat. No. 3,294,725. In the practice of the present invention, for example, an organosiloxane and a crosslinking agent (I) and optionally a grafting agent (
I) in the presence of a sulfonic acid emulsifier such as alkylbenzenesulfonic acid or alkylsulfonic acid,
For example, it is preferably produced by a method of shear mixing with water using a homogenizer or the like, since it acts as an emulsifier for the b0 alkylbenzenesulfonic acid haorganosiloxane and at the same time serves as a polymerization initiator. At this time, it is preferable to use an alkylbenzenesulfonic acid metal salt, an alkylsulfonic acid metal salt, or the like in combination, since this is effective in maintaining the polymer stably during graft polymerization.

Next, the polyalkyl (meth)acrylate rubber component constituting the composite rubber can be synthesized using the alkyl (meth)acrylate, crosslinking agent (II), and grafting agent (n) shown below.

Examples of alkyl (meth)acrylates include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and other fulkyl acrylates, hexyl methacrylate, 2-ethylhexyl methacrylate,
Alkyl methacrylates such as n-lauryl methacrylate can be mentioned, with n-butyl acrylate being particularly preferred.

Examples of the crosslinking agent (...) include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1.3-butylene glycol dimethacrylate, 1.
Examples include 4-butylene glycol dimethacrylate.

Graft cross-linking agents (I0 include, for example, allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, etc. Allyl methacrylate can also be used as a cross-linking agent. These cross-linking agents and graft cross-agents may be used alone or in combination of two or more. The total amount of these crosslinking agents and grafting agents used is 0.1 to 20% by weight in the polyalkyl (meth)acrylate rubber component.

The polymerization of the polyalkyl (meth)acrylate rubber component is
The above alkyl (meth)acrylate, crosslinking agent and grafting agent are added to the latex of the polyorganosiloxane rubber component which has been neutralized by the addition of an aqueous alkali solution such as sodium hydroxide, potassium hydroxide, carbonate, etc. After impregnating polyorganosiloxane rubber particles, a conventional radical polymerization initiator is applied. As the polymerization progresses, a crosslinked network of polyalkyl (meth)acrylate rubber is formed that is intertwined with the crosslinked network of polyorganosiloxane rubber, and the polyorganosiloxane rubber component and polyalkyl (meth)acrylate rubber component are virtually inseparable. A composite rubber latex is obtained. In carrying out the present invention, this composite rubber is used in which the main skeleton of the polyorganosiloxane rubber component has repeating units of dimethylsiloxane, and the main skeleton of the polyalkyl (meth)acrylate rubber component has repeating units of n-butyl acrylate. Composite rubber is preferably used.

The composite rubber thus prepared by emulsion polymerization is
It can be graft copolymerized with vinyl monomers, and since the polyorganosiloxane rubber component and polyalkyl (meth)acrylate rubber component are tightly intertwined, they cannot be extracted and separated using ordinary organic solvents such as acetone and toluene.

The gel content measured by extracting this composite rubber with toluene at 90° C. for 12 hours is 80 weight-f41 or more.

Examples of vinyl compounds to be graft-polymerized to this composite rubber include aromatic alkenyl compounds such as styrene, α-methylstyrene, and vinyltoluene; methyl methacrylate;
Examples include various vinyl monomers such as methacrylic acid esters such as 2-ethylhexyl methacrylate; acrylic acid esters such as methyl acrylate, ethyl acrylate, and butyl acrylate; and vinyl cyanide compounds such as acrylonitrile and methacrylaterile; may be used alone or in combination of two or more. Among these vinyl monomers, aromatic alkenyl compounds and methacrylic acid esters are preferred, and styrene and methyl methacrylate are particularly preferred.

The ratio of the composite rubber and the vinyl monomer in the composite rubber graft copolymer (C) is 30 to 95% by weight of the composite rubber based on the weight of the graft copolymer (C).
, preferably 40 to 90% by weight and full width monomer 5 to 90%
The amount is preferably 70'M, preferably 10 to 60 weight + Xl. If the vinyl monomer content is less than 5 weight %, the graft copolymer (C) will not be sufficiently dispersed in the resin composition, and if it exceeds 70 weight i%, impact strength development will decrease, so this is not preferred. 0 Composite rubber-based graft copolymer (C) is a composite rubber-based graft copolymer latex obtained by adding the above-mentioned vinyl monomer to composite rubber latex and polymerizing it in one step or in multiple stages using radical polymerization technology. It can be separated and recovered by pouring it into hot water in which a metal salt such as calcium chloride or magnesium sulfate is dissolved, and salting out and coagulating it.

The resin composition of the present invention contains a polyphenylene ether resin (A) (hereinafter referred to as component (A)), a polystyrene/resin (B) (hereinafter referred to as component (B)), and a composite rubber-based graft copolymer (hereinafter referred to as component (B)). C) (hereinafter referred to as component (C)) can be combined in a wide range of proportions.The resin formulation in the present invention contains 20 to 80 parts by weight of component (A) based on the weight of the entire resin formulation. It is preferable that component (I3) weighs 19 to 75 weights, and component (C) weighs 1 to 40 weights!4.

If the weight of the component is less than 20 parts by weight, heat resistance tends to be insufficient, and if it exceeds 80 parts by weight, the flow characteristics tend to deteriorate and moldability tends to deteriorate.

In addition, if component (B) is less than 19 kg by weight, it tends to be difficult to balance moldability and heat resistance;
When the amount exceeds 5yx, it tends to be difficult to maintain a balance between impact resistance and heat resistance. Furthermore, if component <C) is less than 1 part by weight, the impact resistance performance improvement effect tends to be insufficient, and if it exceeds 40 parts by weight, the content of composite rubber tends to increase and mechanical strength tends to decrease. It becomes difficult to withstand use.

The resin compound itself in the present invention has heat resistance, impact resistance,
A super heat-resistant resin that provides molded products with excellent impact resistance especially at low temperatures, and also has excellent fluidity, and by changing the blending ratio of component (A) and component (B), the level of heat resistance can be adjusted. It is possible to design freely up to the level of ordinary heat-resistant resin.

In the present invention, by blending a flame retardant in an amount capable of imparting flame retardance to a resin compound containing the above-mentioned components (A) to (C) as constituent components, flame retardance that can meet the UL-94 flame test is achieved. It can be made into a resin composition of. Specific examples of such flame retardants include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, triphthyl phosphate, tribenzyl phosphate, trihexyl phosphate, triphenyl phosphate, tricresyl phosphate, tricylyl phosphate, tris(chloroethyl) phosphate, Phosphate ester flame retardants such as tris(chlorophenyl) phosphate and tris(dibromopropyl) phosphate may be mentioned, and these may be used alone or in combination, with triphenyl phosphate being particularly preferred. When carrying out the present invention, decabromo biphenyl ether, brominated epoxy compounds,
It is preferable to use brominated polystyrene or the like in combination.

In particular, it is preferable to use brominated polystyrene in combination.

The amount of phosphate ester flame retardant used varies depending on the type of flame retardant, the composition ratio of the components (from component (A) to (C), etc.)
15 to 100 parts by weight of the resin compound consisting of (C)
A range of 35 parts by weight is preferred.

As a flame-retardant resin composition, component (A) is 20 to 80%
The flame retardant is blended with 0.5 to 35 parts by weight to 100 parts by weight of a resin compound having a weight range of 19 to 75 parts by weight and a complete width B) of 1 to 40 parts by weight of component (C). preferable.

Furthermore, in the present invention, the strength reinforcing effect is achieved by blending at least one type of inorganic fiber selected from the group consisting of glass fiber and carbon fiber into the resin compound containing the above components (A) to (C) as constituent components. At the same time, the linear expansion coefficient of the resin composition can be significantly lowered. Glass fiber is 5-50μm
It is preferable that the fiber has a diameter of 2W or more. Furthermore, as the surface treatment agent used when blending glass fibers, it is preferable to use aminosilane, vinylsilane, epoxysilane, other silane type treatment agents, chromium type treatment agents, etc. Examples of the glass fiber sizing agent include polyester, epoxy, urethane, acrylic urethane, and ethylene-vinyl acetate. In addition, carbon fibers such as polyacrylonitrile type and pitch type can be used, and those having a diameter of 3 to 30 μm and a fiber length of 50 μm or more are preferable. These glass fibers and carbon ma can be used alone or in combination of two or more.

The amount of inorganic fibers selected from glass fibers and carbon fibers used is 5 to 100 parts by weight, based on 100 parts by weight of the resin compound consisting of components (A) to (C). It is 10 to 70 parts by weight. If the amount of inorganic fiber used is less than 5 parts by weight, it is difficult to impart a strength reinforcing effect to the resin composition;
If it exceeds 100 parts by weight, it will be difficult to exhibit the characteristics of the present invention.

As a resin composition that provides a strength reinforcing effect, component (A)
is 20-800-80 parts by weight B) is 19-759-75
Resin blend 100 consisting of weight part c3 of 1 to 40 weight
Preferably, the above-mentioned at least one type of inorganic fiber is contained in 5 to 100 parts by weight.Furthermore, in the present invention, a resin compound containing the above-mentioned components (A) to (C) as constituent components is preferably used. By blending the above-mentioned phosphate ester flame retardant and at least one kind of inorganic fiber together, a resin composition can be obtained which has flame retardancy and strength reinforcing effect that can meet the UL-94 combustion test. In this case, the amount of the phosphate ester flame retardant and at least one inorganic fiber used is 15 to 35 parts by weight based on 100 parts by weight of the resin compound consisting of components (A) to (C). Preferably, the amount of at least one type of inorganic fiber is 5 to 100 parts by weight.

As a method for preparing the resin composition of the present invention, component (A)
(C), the flame retardant (D) and/or the inorganic fiber (D) may be mechanically mixed using a known device such as a Banbury mixer roll mill or a twin screw extruder, and then shaped into a pellet.

Furthermore, stabilizers, plasticizers, lubricants, pigments, fillers, etc. may be added to the resin composition of the present invention, if necessary. Specifically, stabilizers such as triphenyl phosphite; lubricants such as polyethylene wax and polypropylene wax; pigments such as titanium oxide, zinc sulfide, and zinc oxide; fillers such as asbestos, wollastonite, mica, and talc. It will be done.

〔Example〕

The present invention will be specifically explained below with reference to Examples. In the following description, all "parts" mean parts by weight.

The various physical properties in each Example and Comparative Example were measured using the following methods.

Bending strength: According to the method of ASTM D790.

Izotsu impact strength: According to the method of As'I'M D256.

(I/4" with notch) Vicat softening temperature: 1130 According to the method of R306.

Melt index: By a method based on ASTM D1238 method.

(Measured value at 275℃ under 5kg load) Flammability: According to UL-94 test method.

Linear expansion coefficient: By a method based on ASTM D-696 method.

Reference Example 1 Production of composite rubber-based graft copolymer (s-1): 2 parts of tetraethoxysilane, 15 parts of r-methacryloyloxypropyldimethoxymethylsilane and 97.5 parts of octamethylcyclotetrasiloxane were mixed to form a siloxane mixture. I got 100 copies. 100 parts of the above mixed cloxane was added to 200 parts of distilled water in which 1 part each of sodium dodecylbenzenesulfonate and dodecylbenzenesulfonic acid were dissolved.
After pre-stirring with a homogenizer at 1000 rpm, 500 kg/1 with a homogenizer.
The mixture was emulsified and dispersed at a pressure of yn2 to obtain an organosiloxane latex. This mixed solution was transferred to a separable flask equipped with a condenser and stirring blades, heated at 80°C for 5 hours while stirring and mixed, and then left at 20°C.After 48 hours, the pH of this latex was adjusted with an aqueous sodium hydroxide solution.
-&? The polymerization was completed and polyorganosiloxane rubber latex-1 was obtained.

Polymerization rate Ir of the obtained polyorganosiloxane rubber!
a q and y 4, and the average particle diameter of the polyorganosiloxane rubber was 116 μm.

11 of the above polyorganosiloxane rubber latex-1
Collect 7 parts, put in a separable flask equipped with a stirrer, add 57.5 parts of distilled water, replace with nitrogen, and heat at 50°C.
A mixture of 3595 parts of n-butyl acrylate, 1.05 parts of allyl methacrylate and 26 parts of tert-butyl hydroperoxide (I) was charged and stirred for 30 minutes. Next, a mixture of 002 parts of ferrous sulfate Q, 006 parts of ethylenediaminetetraacetic acid disodium salt α, 26 parts of Rongalit (lk) and 5 parts of distilled water was charged to start radical polymerization, and then the internal The polymerization was completed by holding at a temperature of 70C for 2 hours to obtain a composite rubber latex.A portion of this latex was sampled and the average particle size of the composite rubber was measured and found to be α19μm.Also, this latex was dried to form a solid The product was extracted with toluene at 90°C for 12 hours, and the gel content was measured to be 97.5% by weight.To this composite rubber latex, 0.12 parts of tart-butyl hydroperoxide and 30 parts of styrene were added. The mixed solution was added dropwise at 70°C for 15 minutes, and then maintained at 70°C for 4 hours to complete the graft polymerization to the composite rubber.The polymerization rate of styrene was 9t54.The resulting graft copolymerization Mix the combined latex with hot water containing 1.5% calcium chloride (2)
00 parts, solidified, separated, washed, and dried at 75°C for 16 hours to form a composite rubber-based graft copolymer (hereinafter referred to as
Reference Example 2 264 parts of the composite rubber latex obtained in Reference Example 1 was placed in a separable flask equipped with a stirrer, and after purging with nitrogen, the temperature was raised to 60C. , then 30 parts of methyl methacrylate,
A mixture of 108 parts of cumene hydroperoxide was added dropwise over 1 hour, and the latex temperature was maintained at 60° C. for 2 hours to complete the polymerization. The polymerization rate of methyl methacrylate was 9aO%. The obtained graft copolymer latex was poured into 200 parts of hot water containing 1.5% calcium chloride by weight, coagulated, separated, washed, and then dried at 80°C for 16 hours to form a composite rubber graft copolymer (hereinafter referred to as , referred to as S-2) was obtained in 9 parts and 2 parts.

Examples 1 to 4 Composite rubber-based graft copolymer El obtained in Reference Examples 1 and 2
Flame-retardant polyphenylene/ether resin compositions using -1 and S-2 were produced as follows. That is, the composite rubber graft copolymers E+-1 and S-2 each have 8
4% by weight, poly(2,6-dimethyl-1,4-phenylene) ether in 5 8-in and 200°C load t5ki
Polystyrene strength 2q, sft, t% and IJ phenyl phosphate having a melt index of 51,710 minutes at 9 was mixed to prepare two types of resin compositions. Examples 1-2).

Furthermore, composite rubber-based graft copolymers S-1 and E3-
2 each have a weight width of 8%, the above poly(2゜6-dimethyl-1,4-phenylene) ether is 60@34, polystyrene is 222% by weight, and triphenyl phosphate is 10% by weight.
Two types of resin compositions were prepared by blending each resin composition in such a manner that the weight of the resin compositions increased (Examples 3 and 4).

Each of these four types of resin compositions was
The mixture was supplied to a Z8-130 (manufactured by Faudler Co., Ltd.), melted and kneaded at a cylinder temperature of 280°C, and shaped into a pellet shape.

After drying each of the obtained pellets, they were fed to an injection molding machine (Model 8J-35, manufactured by Keisyo Seisakusho) and the cylinder temperature was 2.
Various test pieces were obtained by injection molding at 80°C and a mold temperature of 60°C. Table 1 shows the results of evaluating various physical properties using each of these test pieces.

From the results in Table 1, the composite rubber graft copolymer, poly(
The composition of 2,6-dimethyl-1,4-phenylene) ether, polystyrene, and triphenyl phosphate provides excellent impact resistance and UL-94 test results of V-0 and V-1 at 1/16' thickness. It can be seen that it is possible to impart flame retardancy that meets the class.

Example 5 A flame-retardant polyphenylene ether resin composition using the composite rubber graft copolymerization holiday-1 obtained in Reference Example 1 was produced as follows. That is, 8% by weight of the composite rubber-based graft copolymer 8-1 and 8% by weight of the composite rubber-based graft copolymer 8-1,
-Simethyl-1゜4-)Unilene) ether is 60tf
%, Jllized polystyrene (Pyrocheck FB (trade name), manufactured by Nissan Fellow ■) was 100% by weight, the polystyrene used in Example 1 was 177% by weight, and triphenyl phosphate was 5% by weight. A resin composition was prepared.

Various test pieces were prepared using this resin composition in the same manner as in Example 1, and the physical properties and flame retardance of the resin were measured. The picker softening temperature was 143°C, and the Izot impact strength (
I/a' notched 23℃) is 1 a9 kg・cm/
In the UL-94 test, it had a flame retardancy of 1/16# thickness and an average burning time of 28 seconds, meeting the V-○ class.

Example 6 The procedure was carried out in the same manner as in Example 5, except that the same amount of brominated ebo-shi (F2400 (trade name), Hitachi Chemical ##) was used instead of brominated polystyrene. When the physical properties and flame retardance of the resin were measured, the picker softening temperature was 138°C, and the Izot impact strength (I/4"
(23℃ with notch) is 1 & 5 Yu・(7)/α, and UL
-94 test had an average burning time of 56 seconds at a thickness of 1/16', and had flame retardancy meeting the V-O class.

Examples 7 to 12 Composite rubber-based graft copolymer El obtained in Reference Examples 1 and 2
Glass fiber-reinforced polyphenylene ether resin compositions using Samples -1 and -2 were produced as follows.

That is, composite rubber-based graft copolymers S-1 and 8-
2 was 64% by weight, respectively, and the poly(2,
6-') methyl-1,4-phenylene) ether is 41
．． Polystyrene with a melt index of 69/10 at 6wt-i% and 2CIOC load of 5kg is 32wtn
96 and glass fiber (manufactured by Nippon Sheet Glass ■, chopped strand NGS O3-Tp 68 (product name)) are 2
Two types of resin compositions were prepared by blending them so that the oi amount was 4 (Examples 7 and 8).

Additionally, four types of resin compositions were prepared in which the amount of glass fiber added was varied as shown in Table 2 (Examples 9 to 12).

These various compositions were shaped into pellets using a twin-screw extruder in the same manner as in Example 1, and various test pieces were obtained using an injection molding machine. Table 2 shows the results of evaluating various physical properties using each of these test pieces.

From the results in Table 2, the composite rubber graft copolymer, poly(2,6-dimethyl-1,4-phenylene) ether,
It can be seen that by using a composition of polystyrene and glass fiber, excellent transport strength and high A heat resistance can be imparted.

Examples 13 to 15 Carbon fiber-reinforced polyphenylene ether resin compositions using the composite rubber-based graft copolymer B-1 obtained in Reference Example 1 were produced as follows.

That is, the composite rubber-based graft copolymer with the composition shown in Table 3, the poly-17 (2,6-dimethyl-1
, 4-phenylene) ether, the polystyrene used in Example 7, and carbon fiber (chopped strand manufactured by Mitsubishi Rayon ■) to prepare a resin composition. These various compositions were shaped into pellet-shaped buttons using a twin-screw extruder in the same manner as in Example 1, and various test pieces were obtained using an injection molding machine.

Table 3 shows the results of evaluating various physical properties using each of these test pieces.

From the results in Table 3, the composite rubber-based graft copolymer, poly(2,6-dimethyl-1,4-)unilene)ether,
It can be seen that excellent mechanical strength and high heat resistance can be imparted by using a composition of polystyrene and carbon fiber.

Examples 16-21 Composite rubber-based graft copolymer El obtained in Reference Examples 1 and 2
Flame-retardant glass fiber reinforced resin compositions using -1 and B-2 were manufactured as follows.

The composite rubber-based graft copolymers S-1 and 8-2 were each 52% by weight, the poly(2,6-dimethyl-1,4-phenylene) ether used in Example 1 was 56% by weight, and Example 7 The polystyrene used in Example 7 was 16% by weight, the triphenyl phosphate was 4.2 parts by weight, and the glass fiber used in Example 7 was 20% by weight.
C2 types of resin compositions were prepared (Examples 16 to 17)
.

Further, compositions were prepared in which the amount of triphenyl phosphate m and the amount of jf 5 fiber added were varied as shown in Table 4 (Examples 18 to 21).

These various compositions were shaped into civet shapes using a twin-screw extruder in the same manner as in Example 1, and various test pieces were obtained using an injection molding machine. Table 4 shows the results of evaluating various physical properties using these various test pieces.

From the results in Table 4, the composite rubber graft copolymer, poly(
It can be seen that excellent mechanical strength and flame retardance can be imparted by using a composition of 2,6-dimethyl-1,4-)unilene) ether, polystyrene, glass fiber, and triphenyl phosphate.

Examples 22 to 25 Flame-retardant carbon fiber-reinforced polyphenylene ether resin compositions using the composite rubber-based graft copolymer S-1 obtained in Reference Example 1 were manufactured as follows.

Composite rubber-based graft copolymerization holiday-1 and poly (2,6-cymethyl-1,4-)unilene) used in Example 1
A resin composition was prepared by blending ether, t-1 styrene used in Example 7, triphenyl phosphate, the carbon fiber used in Example 13, and the glass fiber used in Example 7 in the proportions shown in Table 5. was prepared.

Each of these compositions was molded using a twin-screw extruder and an injection molding machine in the same manner as in Example 1 to obtain various test pieces.

Table 5 shows the results of evaluating each vegetable quality using these various test pieces. The results in Table 5 indicate that a resin composition that uses carbon fiber, and in some cases glass fiber in combination, can have a low coefficient of linear expansion and provide excellent mechanical strength and flame retardancy. Recognize.

〔Effect of the invention〕

The present invention provides an excellent flame-retardant polyphenylene ether resin composition by blending a specific flame retardant into a polyphenylene ether resin composition consisting of a polyphenylene ether resin, a polystyrene resin, and a composite rubber-based graft copolymer. A polyphenylene ether resin composition that has superior mechanical strength when blended with at least one type of inorganic fiber selected from fibers and carbon fibers, and a polyphenylene ether resin composition that has superior mechanical strength when blended with a specific flame retardant and the above-mentioned specific inorganic fibers. It has excellent effects such as being able to obtain a polyphenylene ether resin composition that is flammable and has excellent mechanical strength.

Patent applicant: Mitsubishi Rayon Co., Ltd. Agent: Patent Attorney Toshio Yoshizawa

Claims (1)

[Claims] 1. (A) polyphenylene ether resin, (B) polystyrene resin, (C) 10 to 90% by weight of a polyorganosiloxane rubber component and 10 to 90% by weight of a polyalkyl (meth)acrylate rubber component.
The polyorganosiloxane rubber component and the polyalkyl (meth)acrylate rubber component have a total amount of 1.
A composite rubber graft copolymer obtained by graft polymerizing one or more vinyl monomers to a composite rubber having an average particle diameter of 0.08 to 0.6 μm and (D) phosphoric acid. A polyphenylene ether resin composition containing an ester flame retardant as a constituent component. 2. Component (A) is 20-80% by weight, component (B) is 19% by weight.
The polyphenylene ether resin according to item 1, wherein 0.5 to 35 parts by weight of component (D) is blended to 100 parts by weight of a resin blend consisting of 1 to 40 parts by weight of component (C). Composition. 3. (A) polyphenylene ether resin, (B) polystyrene resin (C) 10 to 90% by weight of polyorganosiloxane rubber component and 10 to 90% by weight of polyalkyl (meth)acrylate rubber component
The polyorganosiloxane rubber component and the polyalkyl (meth)acrylate rubber component have a total amount of 1.
A composite rubber graft copolymer obtained by graft polymerizing one or more vinyl monomers to a composite rubber having an average particle diameter of 0.08 to 0.6 μm and (E) glass fiber. A polyphenylene ether resin composition containing as a constituent component at least one type of inorganic fiber selected from the group consisting of 4. Component (A) is 20-80% by weight, component (B) is 19% by weight.
6. The polyphenylene ether resin composition according to item 5, wherein 5 to 100 parts by weight of component (E) is blended to 100 parts by weight of a resin blend containing 1 to 40% by weight of component (C). 5. (A) polyphenylene ether resin, (B) polystyrene resin (C) 10 to 90 parts by weight of polyorganosiloxane rubber component and 10 to 90 parts by weight of polyalkyl (meth)acrylate rubber component
90 parts by weight are intertwined with each other so that they cannot be separated, and the total amount of the polyorganosiloxane rubber component and the polyalkyl (meth)acrylate rubber component is 1
A composite rubber graft copolymer obtained by graft polymerizing one or more vinyl monomers to a composite rubber having an average particle diameter of 0.08 to 0.6 μm and (D) phosphoric acid. Ester Flame Retardant (E) A polyphenylene ether resin composition containing as a constituent component at least one inorganic fiber selected from the group consisting of glass fibers and carbon fibers. 6. Component (A) is 20 to 80% by weight, component (B) is 19
~75% by weight, 0.5 to 35 parts by weight of component (D) and 5 to 100 parts by weight of component (E) are blended into 100 parts by weight of a resin blend consisting of 1 to 40 parts by weight of component (C). Naru no 5
The polyphenylene ether resin composition described in . 7. The composite rubber of component (C) is a polyorganosiloxane rubber component obtained by emulsion polymerization using an organosiloxane, a crosslinking agent (I), and optionally a grafting agent (I), and this polyorganosiloxane rubber component. a polyalkyl (meth)acrylate rubber component obtained by impregnating alkyl (meth)acrylate, a crosslinking agent (II), and a grafting agent (II) and then polymerizing the rubber component.
The polyphenylene ether resin composition according to item 1, 2, 3, 4, 5 or 6. 8. The first component (D) is triphenyl phosphate
The polyphenylene ether resin composition according to item 1, 2, 5 or 6. 9. The polyphenylene ether resin composition according to item 1, item 2, item 5, or item 6, wherein the phosphoric acid ester flame retardant of component (D) is used in combination with brominated polystyrene.