JP4455256B2 - Polyphenylene ether resin composition having excellent oil resistance - Google Patents

Description

  The present invention relates to a resin composition comprising a resin component comprising a combination of polyphenylene ether and a styrene resin, and a hydrogenated block copolymer.

  Depending on the mixing ratio of polyphenylene ether and styrene resin, any mixed resin containing polyphenylene ether or styrene resin as a basic component (hereinafter referred to as modified PPE resin) can be selected from styrene resin alone to polyphenylene ether alone. And has excellent properties such as electrical properties, dimensional stability, impact resistance, acid resistance, alkali resistance, low water absorption, and low specific gravity. Examples include electrical / electronic related parts, office equipment parts, various exterior materials, and industrial products. Further, the modified PPE resin can be made flame retardant without using halogen compounds and antimony trioxide, which are said to be harmful, and is excellent in terms of environment and safety and health. Phosphate ester flame retardants used as flame retardants for modified PPE resins include monophosphate esters such as triphenyl phosphate, cresyl diphenyl phosphate and tricresyl phosphate, bifunctional phenols such as resorcinol and bisphenol A, and polyfunctional phenols The condensed phosphate ester etc. which used this as a raw material are mentioned. Among them, the resin composition using the condensed phosphate ester flame retardant is superior in heat resistance compared to the resin composition using the monophosphate ester flame retardant, and is suitable for fuming and molds during injection molding. There are few problems such as adhesion of flame retardants, and it is said that demand is expanding.

  However, condensed phosphate ester flame retardants have improved rigidity, typified by physical properties such as tensile strength, bending strength, and elastic modulus, compared with monophosphate ester flame retardants, but reduced the inherent impact resistance of the resin. Let Moreover, since the flame retardant effect is inferior, it is necessary to add a larger amount. Therefore, since the impact resistance inherent in the resin is further reduced, it is necessary to improve the impact such as adding a large amount of elastomer. To improve the impact resistance of the modified PPE resin, it has been conventionally known to add a thermoplastic elastomer, but because the processing temperature is high, an elastomer having excellent thermal stability (thermal degradation) should be used. There are many. From such a point of view, means for blending a block copolymer of a hydrogenated styrene-conjugated diene compound that has almost no unsaturated bond and is excellent in heat deterioration resistance is generally used. It is also known to blend a block copolymer in which a double bond portion of a conjugated diene compound polymer block is partially hydrogenated in a block copolymer of an aromatic vinyl compound-conjugated diene compound (for example, , See Patent Document 1).

On the other hand, the modified PPE resin does not have sufficient chemical resistance to hydrocarbon compounds contained in lubricating oils or adhesives for various application parts, and the range of use may be limited. Further, the modified PPE resin is often processed by an injection molding method, but at that time, there is often a problem of bad mold separation from the mold. Improvement of these chemical resistance and releasability is a problem that has been conventionally demanded. In response to such demands for improving chemical resistance and releasability, conventional means such as blending polyolefin resin have been taken, but the compatibility with modified PPE resin is inferior, and impact resistance is reduced. There was a need for further improvements.
Japanese Examined Patent Publication No. 4-68343

  The present invention is a polyphenylene ether that improves the chemical resistance and mold releasability while maintaining the properties of the conventional modified PPE resin, and also has flame resistance excellent in impact resistance, molding fluidity and heat deterioration resistance. It aims at providing a resin composition.

  As a result of intensive studies to solve the above problems, the present inventors have determined the hydrogenation rate of a block copolymer of a vinyl aromatic hydrocarbon having a specific vinyl bond amount and a butadiene compound within a specific range. A modified PPE resin composition comprising a controlled hydrogenated block copolymer A, and a hydrogenated block copolymer B of a vinyl aromatic hydrocarbon and a butadiene compound in which a specific range of amounts of vinyl aromatic hydrocarbon blocks are combined. The inventors have found that the above problems can be effectively solved, and have completed the present invention.

That is, the present invention
[1] (1) 70-98.5 parts by weight of a resin component comprising polyphenylene ether or a combination of polyphenylene ether and a styrene resin,
(2) A hydrogenated block copolymer of a block copolymer having a polymer block mainly composed of at least one vinyl aromatic hydrocarbon and a polymer block mainly composed of at least one butadiene compound. ,
(A) The vinyl bond content based on the butadiene compound of the block copolymer before hydrogenation is 10 to 70%,
(B) the total hydrogenation rate of unsaturated double bonds based on butadiene compounds is 40 to 90%;
(C) the content of monomer units derived from vinyl aromatic hydrocarbon in the block copolymer before hydrogenation is 10 to 60% by weight,
1 to 15 parts by weight of hydrogenated block copolymer A
(3) A hydrogenated block copolymer of a block copolymer having a polymer block mainly composed of at least one vinyl aromatic hydrocarbon and a polymer block mainly composed of at least one butadiene compound. 0.5 to 15 parts by weight of hydrogenated block copolymer B having a vinyl aromatic hydrocarbon-derived monomer unit content in the block copolymer before hydrogenation of more than 60% by weight and less than 90% by weight, and ,
A chemical-resistant polyphenylene ether comprising (4) 0 to 40 parts by weight of a phosphate ester flame retardant with respect to 100 parts by weight of the total amount of (1), (2) and (3) Resin composition,
[2] (3) The hydrogenated block copolymer B has a total hydrogenation rate of 40 to 90% of unsaturated double bonds based on the butadiene compound, and is derived from the vinyl aromatic hydrocarbon of the block copolymer before hydrogenation. The chemical-resistant polyphenylene ether resin composition according to the above 1, wherein the monomer unit content is more than 60% by weight and less than 85% by weight,
It is.

  The present invention is a resin composition based on polyphenylene ether that improves the chemical resistance and release properties of the modified PPE resin, and also has excellent flame resistance with excellent impact resistance, molding fluidity, and heat deterioration resistance. Yes, it is very useful industrially.

The present invention is described in detail below.
The (1) polyphenylene ether used in the present invention has the general formula (I)

And / or general formula (II)

(In the above general formulas (I) and (II), R1, R2, R3, R4, R5, R6 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 9 carbon atoms, or a halogen atom) Represents an atom, provided that R5 and R6 are not hydrogen at the same time.) A homopolymer or copolymer having a repeating unit represented by:

  Representative examples of polyphenylene ether homopolymers include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2, 6-diethyl-1,4-phenylene) ether, poly (2-ethyl-6-n-propyl-1,4-phenylene) ether, poly (2,6-di-n-propyl-1,4-phenylene) Ether, poly (2-methyl-6-n-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-) 1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-1,4-phenyle) ) Include homopolymers such as ether.

Of these, poly (2,6-dimethyl-1,4-phenylene) ether is preferable, and 2- (dialkylaminomethyl) -6-methylphenylene ether described in JP-A-63-301222 and the like is preferable. A polyphenylene ether containing a unit or a 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether unit as a partial structure is particularly preferred.
Here, the polyphenylene ether copolymer is a copolymer having a phenylene ether structure as a main monomer unit. Examples thereof include a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, a copolymer of 2,6-dimethylphenol and o-cresol, or 2,6-dimethylphenol and 2 , 3,6-trimethylphenol and a copolymer with o-cresol.

Particularly preferred in practice, ηsp / c measured with a 30 ° C. chloroform solution is in the range of 0.3 to 0.7, preferably in the range of 0.4 to 0.6, and gel permeation chromatography ( Poly (2) in which the ratio of weight average molecular weight / number average molecular weight based on polystyrene-converted molecular weight measured by GPC) is in the range of 2.2 to 5.0, preferably 2.3 to 3.5. , 6-Dimethyl-1,4-phenylene) ether. Such polyphenylene ether is particularly preferable from the viewpoint of molding fluidity.
In the present invention, a functionalized polyphenylene ether resin in which a part or all of the polyphenylene ether is modified with an unsaturated carboxylic acid or a functional derivative thereof can be used. This functionalized polyphenylene ether is described in JP-A-2-276823, JP-A-63-108059, JP-A-59-59724, etc. For example, in the presence or absence of a radical initiator. In this method, an unsaturated carboxylic acid or a functional derivative thereof is melt-kneaded and reacted with polyphenylene ether. Alternatively, it is produced by dissolving polyphenylene ether and an unsaturated carboxylic acid or a functional derivative thereof in an organic solvent in the presence or absence of a radical initiator and reacting in a solution.

  Examples of unsaturated carboxylic acids or functional derivatives thereof include maleic acid, fumaric acid, itaconic acid, halogenated maleic acid, cis-4-cyclohexene 1,2-dicarboxylic acid, and endo-cis-bicyclo [2.2.1]. ] -5-heptene-2,3-dicarboxylic acid, acid anhydrides, esters, amides, imides, etc. of these dicarboxylic acids, acrylic acid, methacrylic acid, etc., esters of these monocarboxylic acids, amides, etc. Can be mentioned. In addition, a compound that is a saturated carboxylic acid but can be thermally decomposed itself at the reaction temperature when producing a functionalized polyphenylene ether to become a functional derivative used in the present invention can be used. Specifically, malic acid, Examples include citric acid. These may be used alone or in combination of two or more.

The styrene resin used in combination with polyphenylene ether in the present invention is a polymer obtained by polymerizing a styrene compound or a compound copolymerizable with the styrene compound in the presence or absence of a rubbery polymer.
Specific examples of the styrenic compound include styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, ethylstyrene, and the most preferable is styrene. It is. Examples of the compound copolymerizable with the styrene compound include methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile; and acid anhydrides such as maleic anhydride. And used with styrenic compounds. The amount of the copolymerizable compound used is preferably 20% by weight or less, more preferably 15% by weight or less, based on the total amount with the styrene compound.

  Examples of the rubbery polymer include conjugated diene rubbers, copolymers of conjugated dienes and aromatic vinyl compounds, and ethylene-propylene copolymer rubbers. Specifically, polybutadiene and styrene-butadiene copolymer are particularly preferable. As the rubbery polymer, it is preferable to use partially hydrogenated polybutadiene having an unsaturation degree of 80 to 20% or polybutadiene containing 90% or more of 1,4-cis bonds. Specific examples of the styrene resin include polystyrene and rubber-reinforced polystyrene, styrene-acrylonitrile copolymer (AS resin), rubber-reinforced styrene-acrylonitrile copolymer (ABS resin), other styrene copolymers, and the like. It is done. Preference is given to polystyrene and rubber-modified polystyrene.

In the present invention, the weight ratio of the polyphenylene ether and the styrene resin can be arbitrarily selected within a range of 100/0 to 1/99 in consideration of desired heat resistance and flame retardancy. The range as the molding material is in the range of 10/90 to 90/10, and the most practical range is in the range of 20/80 to 80/20.
The hydrogenated block copolymer of components (2) and (3) used in the present invention is at least one, preferably a polymer block mainly composed of two or more vinyl aromatic hydrocarbons, and at least one polymer block. A hydrogenated product of a block copolymer having a polymer block mainly composed of a butadiene compound. As the vinyl aromatic hydrocarbon, one or more selected from alkyl styrene such as styrene, α-methyl styrene, p-methyl styrene, p-tert-butyl styrene, paramethoxy styrene, vinyl naphthalene and the like. Of these, styrene is preferred.

Regarding the hydrogenated block copolymers of the components (2) and (3) used in the present invention, as a method for producing a block copolymer before hydrogenation, for example, Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43- 17979, JP-B 46-32415, JP-B 49-36957, JP-B 56-28925, JP-A 59-166518, and the like. By these methods, the block copolymer is obtained as a block copolymer represented by the following general formula.
(AB) _n , A- (BA) _n , B- (AB) _n
(In the above formula, A is a polymer block mainly composed of a vinyl aromatic hydrocarbon, and B is a polymer mainly composed of a butadiene compound. The boundary between the A block and the B block is always clearly distinguished. (N is not less than 1 and is generally an integer of 1 to 5.)

Alternatively the general formula _{[(B-A) n]} m + 1 -X, [(A-B) n] m + 1 -X, [(B-A) n -B] m + 1 -X, [(A -B) _n- A] _{m + 1-} X,
(In the above formula, A, B and n are the same as described above, and X is, for example, silicon tetrachloride, tin tetrachloride, epoxidized soybean oil, 2-6 functional epoxy group-containing compound, polyhalogenated hydrocarbon, carvone A residue of a coupling agent such as an acid ester or a polyvinyl compound such as divinylbenzene, or a residue of an initiator such as a polyfunctional organolithium compound, etc. m is 1 or more and generally an integer of 1 to 10.)

In the above, the polymer block mainly composed of vinyl aromatic hydrocarbon is a vinyl aromatic hydrocarbon containing 50 wt% or more, preferably 70 wt% or more of a monomer unit derived from vinyl aromatic hydrocarbon. A copolymer block with a butadiene compound and a vinyl aromatic hydrocarbon homopolymer block are shown, and the polymer block mainly composed of a butadiene compound is preferably an amount in which the monomer unit derived from the butadiene compound exceeds 50% by weight. Represents a copolymer block of butadiene compound and vinyl aromatic hydrocarbon and a butadiene compound homopolymer block containing 70% by weight or more.
The monomer units derived from vinyl aromatic hydrocarbons in the copolymer block may be distributed uniformly or in a tapered shape. In the copolymer portion, a plurality of portions where the monomer units derived from the vinyl aromatic hydrocarbon are uniformly distributed and a portion where the monomer units are distributed in a tapered shape may coexist. In the hydrogenated block copolymer used in the present invention, the hydrogenated product of the block copolymer represented by the above general formula can be used in any proportion.

  In the present invention, the vinyl bond content based on the butadiene compound in the block copolymer before hydrogenation is 10 to 70%, preferably 15 to 60%, and more preferably 25 to 50%. Here, the amount of vinyl bonds refers to 1,2-bonds among butadiene compounds incorporated in the block copolymer in 1,2-bond, 3,4-bond and 1,4-bond bond modes. And the ratio of those incorporated by 3,4-bonds. When the vinyl bond amount is less than 10% or exceeds 70%, the affinity between the hydrogenated block copolymer, polyphenylene ether and styrene resin is inferior, which is not preferable. The vinyl bond amount can be selected from ether compounds such as dimethyl ether, diethyl ether, diphenyl ether, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, trimethylamine, triethylamine, N, N, N ′, N′-tetramethylethylenediamine, diazabicyclo [2] 2.2.2] A tertiary amine such as octane can be used during the production of the block copolymer.

  The hydrogenated block copolymer used in the present invention is obtained by hydrogenating the above block copolymer (hydrogenation reaction). The catalyst used in the hydrogenation reaction includes (1) a supported heterogeneous catalyst in which a metal such as Ni, Pt, Pd, Ru is supported on carbon, silica, alumina, diatomaceous earth, etc., (2) Ni, So-called Ziegler type catalysts using transition metal salts such as organic acid salts such as Co, Fe and Cr or acetylacetone salts and reducing agents such as organic aluminum, (3) organometallic compounds such as Ti, Ru, Rh and Zr Homogeneous catalysts such as so-called organometallic complexes are known. Specific methods for the hydrogenation reaction include Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-337970, Japanese Patent Publication No. 1-53851. The method described in Japanese Patent Publication No. 2-9041 is mentioned, It can hydrogenate in the presence of a hydrogenation catalyst in a hydrocarbon solvent, and a hydrogenated substance can be obtained. At that time, the hydrogenation rate of the block copolymer can be controlled by adjusting the reaction temperature, reaction time, hydrogen supply amount, catalyst amount and the like.

(2) Hydrogenated block copolymer A used in the present invention has a total hydrogenation rate of unsaturated double bonds based on butadiene compounds of 40 to 90%, preferably 45 to 85%, more preferably 55 to 55%. The range is 80%. If the total hydrogenation rate is less than 40%, the thermal stability is inferior, and if it is 90% or more, the chemical resistance, fluidity and impact resistance are inferior.
Furthermore, in the present invention, in the hydrogenated block copolymers A and B, the hydrogenation rate of the vinyl bond portion based on the butadiene compound before hydrogenation should be 90% or more, preferably 95% or more. When the hydrogenation rate of the vinyl bond is less than 90%, the thermal stability is inferior, which is not preferable. Here, the hydrogenation rate of the vinyl bond portion refers to the ratio of the amount of vinyl bonds hydrogenated to the amount of vinyl bonds based on the butadiene compound incorporated in the block copolymer before hydrogenation.

The hydrogenation rate of the aromatic double bond based on the vinyl aromatic hydrocarbon in the block copolymer is not particularly limited, but the hydrogenation rate is 50% or less, preferably 30% or less, more preferably 20 % Or less is preferable. The hydrogenation rate can be known by an infrared spectrophotometer, a nuclear magnetic resonance apparatus (NMR) or the like.
The content of the monomer unit derived from vinyl aromatic hydrocarbon in the block copolymer before hydrogenation of (2) hydrogenated block copolymer A used in the present invention is 10 to 60% by weight, preferably 15 It is -55 weight%, More preferably, it is the range of 20-45 weight%. When the content of the monomer unit derived from vinyl aromatic hydrocarbon is less than 10% by weight or more than 60% by weight, chemical resistance and impact resistance are inferior.

The melt flow rate (according to ASTM D1238: 230 ° C., 2.16 kg load) of (2) hydrogenated block copolymer A used in the present invention is 10 g / 10 min or less, preferably 2 g / 10 min or less. When the MFR exceeds 10 g / 10 minutes, the impact resistance is poor. As for the lower limit of the melt flow rate, 0.1 g / 10 min or less is difficult to express as a numerical value because there is no measurement accuracy, but 0.1 g / 10 min or less is also used in the present invention.
(3) The content of the monomer unit derived from the vinyl aromatic hydrocarbon in the block copolymer before hydrogenation of the hydrogenated block copolymer B used in the present invention is more than 60% by weight and less than 90% by weight. , Preferably more than 60 wt% and less than 85 wt%, particularly preferably more than 65 wt% and less than 75 wt%. When the content of the monomer unit derived from vinyl aromatic hydrocarbon is less than 60% by weight or more than 90% by weight, the combined use effect with the hydrogenated block copolymer A is hardly exhibited, and the chemical resistance, Impact improvement effect is not enough. The (3) hydrogenated block copolymer B used in the present invention has a total hydrogenation rate of unsaturated double bonds based on a butadiene compound of 40% or more, preferably in the range of 40 to 90%, more preferably Is in the range of 50-80%. If the total hydrogenation rate is less than 40%, the thermal stability is inferior, and the chemical resistance, fluidity and impact resistance are inferior.

The molecular weights of the practical hydrogenated block copolymers A and B are such that the peak molecular weight is 40,000 to 300,000, preferably 50,000 to 250,000, more preferably 60,000 in terms of standard polystyrene as measured by GPC. ~ 200,000.
The hydrogenated block copolymer of the present invention can be obtained by removing the solvent from the hydrogenated block copolymer solution obtained as described above by an ordinary method. If necessary, a step of deashing metals can be employed. Moreover, you may use reaction terminator, antioxidant, neutralizing agent, surfactant, etc. as needed.
The hydrogenated block copolymer used in the present invention is a functionalized polymer or hydrogenated block copolymer in which a polar group-containing functional group selected from nitrogen, oxygen, silicon, phosphorus, sulfur, and tin is bonded to the polymer. Also included are functionalized block copolymers modified with a modifier such as maleic anhydride.

The hydrogenated block copolymer of the present invention can be blended with known naphthenic and paraffinic process oils and mixed oils thereof as softeners or processing aids.
In the present invention, a block copolymer of a hydrogenated or non-hydrogenated vinyl aromatic hydrocarbon outside the scope of the present invention and a conjugated diene compound can be used in an amount of less than 50%.
(2) If the hydrogenated block copolymer A is less than 1 part by weight, the properties of the present invention such as chemical resistance and impact resistance cannot be exerted, and if it exceeds 15 parts by weight, mechanical strength such as rigidity decreases. It is not preferable. Preferably, it is used in the range of 2 to 10 parts by weight.

If necessary, the composition of the present invention includes polyolefin-based or low-molecular-weight vinyl aromatic thermoplastic resins such as amorphous polyolefin and ethylene-ethyl acrylate copolymer; natural rubber; polyisoprene rubber, polybutadiene rubber, styrene-butadiene. Synthetic rubbers such as rubber, ethylene-propylene rubber, chloroprene rubber, acrylic rubber, isoprene-isobutylene rubber, polypentenamer rubber, and styrene-isoprene block copolymers other than the present invention may be added.
The phosphoric ester-based flame retardant component (4) used as necessary in the present invention is added to improve flame retardancy, and is an organic material generally used as a flame retardant for modified PPE resins. Any phosphoric acid ester can be used. More preferably, the following formula (III)

Or the following formula (IV)

(Wherein Q1, Q2, Q3 and Q4 are each a substituent and each independently represents an alkyl group having 1 to 6 carbon atoms, R1 and R2 are each a substituent and each represents a methyl group, R3, R4 each independently represents a hydrogen atom or a methyl group, n has an average value of 1 or more, n1 and n2 each independently represents an integer of 0 to 2, and m1, m2, m3 and m4 each independently It is an integer of 0 to 3. The main component is at least one selected from the group consisting of condensed phosphate esters represented by:
The condensed phosphate ester represented by the above formulas (III) and (IV) is composed of a plurality of molecular chains, and for each molecule, n is an integer of 1 or more, preferably an integer of 1 to 3. As a whole, n has an average value of 1 or more.

Among these, preferred condensed phosphate esters are those in which m1, m2, m3, m4, n1, and n2 in formula (III) are zero and R3 and R4 are methyl groups, and in formula (III) Q1, Q2, Q3, Q4, R3, R4 in the formula (1) are methyl groups, n1, n2 are zero, and m1, m2, m3, m4 are integer condensed phosphate esters of 1 to 3, Is preferably 1 to 3, particularly preferably containing 50 wt% or more of phosphoric acid ester in which n is 1.
These flame retardants are generally commercially available, and examples thereof include trade names CR-741, CR733S, and PX-200 (registered trademark) manufactured by Daihachi Chemical Co., Ltd.

  The resin composition of the present invention comprises (1) 70-98.5 parts by weight of a resin component comprising a combination of polyphenylene ether and styrene resin, (2) 1-15 parts by weight of hydrogenated block copolymer A, (3 ) 0.5-4 parts by weight of hydrogenated block copolymer B and 100 parts by weight of the total amount of (1), (2), (3), (4) phosphate ester flame retardant 0 It is a chemical resistant resin composition characterized by containing 40 parts by weight, and is excellent by combining (2) hydrogenated block copolymer A and (3) hydrogenated block copolymer B. Composition characteristics can be obtained. The combined ratio is in the range of 9/1 to 1/9, preferably in the range of 8/2 to 3/7, more preferably in the range of 8/2 to 5/5. (2) The hydrogenated block copolymer A is preferably used in the range of 1 to 10 parts by weight, more preferably in the range of 2 to 8 parts by weight. If it is less than 1 part by weight, the chemical resistance, impact resistance, etc. The characteristics of the present invention cannot be exhibited, and if it exceeds 15 parts by weight, the mechanical strength such as rigidity is lowered, which is not preferable. (3) Hydrogenated block copolymer B is preferably used in the range of 1 to 10 parts by weight, more preferably in the range of 2 to 8 parts by weight. The effect of the present invention such as chemical resistance and impact resistance cannot be exerted due to the small combined effect with the hydrogenated block copolymer, and if it exceeds 15 parts by weight, no further effect can be expected in the combined effect with the hydrogenated block copolymer A. It is economically disadvantageous. (4) Phosphate ester flame retardants should be added in any amount depending on the required level of flame retardancy. However, at 40 parts by weight or more, heat resistance and impact resistance are remarkably inferior. It is used in the range of 1 to 35 parts by weight, more preferably in the range of 3 to 30 parts by weight.

The composition of the present invention may contain an anti-drip agent if necessary. This anti-drip agent is an additive having a function of suppressing drip (dripping) during combustion, and a known one can be used. The anti-drip agent is in the range of 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight with respect to 100 parts by weight of the total of polyphenylene ether and styrene resin (including recovered styrene resin and virgin material). Is added.
In the present invention, a polyphenylene ether resin typified by polytetrafluoroethylene (PTFE) or the like that forms a fibril structure is particularly suitable because it has a high drip suppression effect. A resin composition containing such an anti-drip agent is particularly excellent in flame retardancy. Among such polytetrafluoroethylenes (PTFE), those having excellent dispersibility, for example, those obtained by emulsifying and dispersing PTFE in a solution such as water, acrylic ester resins, methacrylic ester resins, styrene-acrylonitrile A product obtained by encapsulating PTFE with a copolymer resin or the like is preferable because it gives a molded article made of a modified PPE resin a good surface appearance.

In the case where PTFE is emulsified and dispersed in a solution such as water, there is no particular limitation. However, PTFE having an average particle diameter of 1 μm or less is preferable, and 0.5 μm or less is particularly preferable. Specific examples of such commercially available PTFE include Teflon (registered trademark) 30J (manufactured by Mitsui Dupont Fluorochemical Co., Ltd.), Polyflon D-2C (registered trademark) (manufactured by Daikin Chemical Industries, Ltd.), Examples include Aflon AD1 (registered trademark) (manufactured by Asahi ICI Corporation).
Such polytetrafluoroethylene can also be produced by a known method (see US Pat. No. 2,393,967). Specifically, using a free radical catalyst such as sodium peroxydisulfate, potassium or ammonium, in an aqueous solvent, at a pressure of 0.7 to 7 MPa, 0 to 200 ° C, preferably 20 to 100 ° C. Polytetrafluoroethylene can be obtained as a white solid by polymerizing tetrafluoroethylene under temperature conditions. Such polytetrafluoroethylene has a molecular weight of 100,000 or more, preferably about 200,000 to 3,000,000.

The resin composition containing polytetrafluoroethylene suppresses drip during combustion. Furthermore, when polytetrafluoroethylene and a silicone resin are used in combination, drip can be further suppressed and combustion time can be shortened as compared with the case where only polytetrafluoroethylene is added.
If necessary, stabilizers such as antioxidants, ultraviolet absorbers and light stabilizers can be added to the composition of the present invention to improve the thermal stability and light resistance of the composition.

  Examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propionate, 2 , 2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,4-bis [(octylthio) methyl] -o-cresol 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-di-t-amyl-6- [1- (3 , 5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate, hinders such as 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl)] acrylate Dophenol-based antioxidants; sulfur-based antioxidants such as dilauryl thiodipropionate, lauryl stearyl thiodipropionate, pentaerythritol-tetrakis (β-lauryl thiopropionate); tris (nonylphenyl) phosphite, Examples thereof include phosphorus antioxidants such as tris (2,4-di-t-butylphenyl) phosphite. Examples of ultraviolet absorbers and light stabilizers include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-3 ′, 5′-t-butylphenyl) benzoate. Benzotriazole ultraviolet absorbers such as triazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, and benzophenones such as 2-hydroxy-4-methoxybenzophenone An ultraviolet absorber, a hindered amine light stabilizer, etc. can be mentioned.

A polyolefin homopolymer or copolymer can be added to the resin composition of the present invention as an agent for improving releasability from a mold during injection molding. In particular, it can be further improved by adding polyethylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-octene copolymer or the like.
In the resin composition of the present invention, an inorganic filler such as glass fiber, glass flake, kaolin clay, talc, and other fibrous reinforcing agents are blended to obtain a high strength composite excellent in fluidity and heat resistance. be able to.
In addition, conventionally known various flame retardants, flame retardant aids, char promoters such as red phosphorus, various organic and inorganic phosphorus compounds other than the above, cyclic nitrogen compounds such as melamine and melon, derivatives thereof, and phosphazene compounds , Halogen compounds, hydroxides such as magnesium hydroxide and aluminum hydroxide, zinc borate compounds, zinc stannate compounds, metal oxides such as antimony trioxide and iron oxide, and inorganic silicon compounds such as silica and silica alumina Further, tetrafluoroethylene-based polymers, silicone compounds, phenol compounds, phenol resins, polyhydric alcohols, saccharides, and the like can be added.

Furthermore, various organic or inorganic dyes and pigments as commonly used colorants, waxes such as paraffin wax, microcristan wax, and low molecular weight polyethylene wax as lubricants, higher fatty acids, metal salts of higher fatty acids, higher fatty acids Various antistatic agents, conductive carbon, various plasticizers, and the like can be added.
The method for producing the resin composition of the present invention is not particularly specified, and can be kneaded and produced using a kneader such as an extruder, a heating roll, a kneader, or a Banbury mixer. Among these, kneading with an extruder is preferable in terms of productivity. The kneading temperature may be in accordance with the preferred processing temperature of the base resin, and is generally in the range of 200 to 360 ° C, preferably in the range of 240 to 320 ° C.

EXAMPLES Hereinafter, although an Example demonstrates this invention, these Examples do not limit this invention.
Each component used in the examples and comparative examples is as follows.
(1-a) Polyphenylene ether (PPE)
Poly-2,6-dimethyl-1,4-phenylene ether having a ηsp / c of 0.51 and a weight average molecular weight / number average molecular weight of 2.8 measured with a chloroform solution at 30 ° C.
(1-b) Rubber reinforced polystyrene (HIPS)
Rubber reinforced polystyrene having a rubber content of 9% by weight, 30 ° C., ηsp / c of the matrix polystyrene measured with a toluene solution is 0.70, and the volume average rubber particle diameter is 1.5 μm.
(2) and (3) Preparation of Hydrogenated Block Copolymer A 100 l autoclave with a stirrer and a jacket was washed, dried, purged with nitrogen, and charged with a cyclohexane solution containing 20 parts by weight of styrene purified in advance. Next, after adding n-butyllithium and tetramethylethylenediamine and polymerizing at 70 ° C. for 1 hour, a cyclohexane solution containing 60 parts by weight of pre-purified butadiene was added for 1 hour, and a cyclohexane solution containing 20 parts by weight of styrene was further added. For 1 hour.

A part of the resulting block copolymer solution was sampled, and octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added to 100 parts by weight of the block copolymer. .3 parts by weight were added, and then the solvent was removed by heating. The obtained polymer had a styrene content of 40% by weight and a 1,2-vinyl bond content of the polyptadiene part of 20% by weight. The styrene content was measured using infrared analysis (IR). The vinyl bond amount was measured using infrared analysis (IR) and calculated by the Hampton method.
Next, using the remaining block copolymer solution, hydrogenation was performed at a temperature of 70 ° C. using Polymer 1 as a hydrogenation catalyst using di-p-trisbis (1-cyclopentagenyl) titanium and n-butyllithium. Obtained. Polymer 1 had a hydrogenation rate of 65%. The hydrogenation rate was measured using a nuclear magnetic resonance apparatus (NMR). The hydrogenation rate was controlled by measuring the amount of hydrogen gas to be supplied with a flow meter and stopping the gas supply when the target hydrogenation rate was achieved.
The obtained polymer 1 was cut by removing the solvent by heating, and the melt flow rate was measured at 230 ° C. under 2.16 kg (according to ASTM D1238). As a result, it was 8 g / 10 minutes.
Furthermore, polymers 2 to 6 were prepared by controlling the weight ratio of styrene / butadiene, the addition amount of n-butyllithium and tetramethylethylenediamine, and the hydrogenation rate by the same operation as for polymer 1. The polymer structure of each prepared polymer is shown in Table 1.

The vinyl bond content after hydrogenation of each prepared polymer sample was almost 0%.
(4) Phosphoric acid ester A condensed phosphoric acid ester mainly composed of bisdiphenyl phosphate of bisphenol A. Product name CR-741 (registered trademark), manufactured by Daihachi Chemical Co., Ltd.

In the examples and comparative examples, the composition was evaluated by the following method.
1. Izod impact strength Measured at 23 ° C. using an injection molded test piece having a thickness of 1/4 inch in accordance with ASTM D256.
2. Fluidity Using an injection molding machine set to a heating cylinder of 260 ° C and a mold temperature of 60 ° C, injection molding is performed with a molded product mold of 4 inches long x 1/2 inches wide x 1/16 inch thick. Do. At that time, the injection pressure immediately before full filling was read from the gauge. The lower the injection pressure, the better the fluidity.
3. Chemical resistance An arc formed by cutting out about 100 mm of the center of a 1/8 inch thick tensile test specimen injection molded according to ASTM D638 so that the strain on the specimen surface is about 0.5%. The shape jig was fixed so that there was no gap. Next, a cotton gauze containing salad oil (Nisshin Oillio Group Co., Ltd., Nisshin Salad Oil (registered trademark)) was placed on the entire test piece surface and left at 23 ° C., and the state after 120 hours was observed. According to the visual judgment, the broken ones were indicated as x, the ones with cracks but not broken were indicated as Δ, the fine cracks were indicated as ○, and the ones with almost no change were indicated as ◎.

4). Flame retardance Based on the UL-94 vertical combustion test, measurement was performed using an injection molded test piece having a thickness of 1/16 inch, and the total combustion time at the 10th flame contact and the presence or absence of drops during combustion were evaluated.
5). Heat resistance (deflection temperature under load)
Based on ASTM D648, it was measured under 1.82 MPa.
6). Releasability When a 1/16 inch thick test piece was formed by injection molding, the degree of ease of mold release from the test piece and runner mold was visually determined. Those with good mold release are indicated with Δ when the mold is not good, and those with poor release are indicated with x.
7). Layer peelability Using a 1/8 inch-thick tensile test piece injection-molded based on ASTM D638, the test piece was repeatedly bent 180 degrees alternately on the front and back, and peeling of the surface layer was visually observed. X indicates that there is no surface layer adhesion and is severely peeled, X indicates surface layer adhesion but is peeled, △ indicates that there is a sign of peeling but does not cause a problem, ○ indicates almost no sign of peeling Those that were not allowed were marked as ◎.

[Examples 1-6, Comparative Examples 1-5]
Each component was blended in the proportions shown in Table 1. In addition, 0.3 parts by weight of tris (2,4-di-t-butylphenyl) phosphite was added to the composition as a stabilizer. These blended compositions are supplied to a twin screw extruder with a screw diameter of 25 mm with the maximum temperature of the heating cylinder set to 300 ° C., melt kneaded at a screw rotation speed of 300 rpm, and the strand is cooled and cut to give a resin composition Product pellets were obtained. Next, the obtained resin composition pellets were molded by an injection molding machine set at a heating cylinder of 260 ° C. and a mold temperature of 60 ° C., and evaluated by the above test method, and the results shown in Table 2 were obtained.

  The resin composition of the present invention is excellent in chemical resistance, heat resistance, fluidity, impact resistance, flame retardancy, and electrical properties, and particularly in chemical resistance and fluidity. It is suitable for internal and external parts, office equipment-related internal and external parts, various exterior materials and industrial products.

Claims (2)

(1) 70-98.5 parts by weight of a resin component composed of polyphenylene ether or a combination of polyphenylene ether and a styrene resin,
(2) A hydrogenated block copolymer of a block copolymer having a polymer block mainly composed of at least one vinyl aromatic hydrocarbon and a polymer block mainly composed of at least one butadiene compound. ,
(A) The vinyl bond content based on the butadiene compound of the block copolymer before hydrogenation is 10 to 70%,
(B) the total hydrogenation rate of unsaturated double bonds based on butadiene compounds is 40 to 90%;
(C) the content of monomer units derived from vinyl aromatic hydrocarbon in the block copolymer before hydrogenation is 10 to 60% by weight,
1 to 15 parts by weight of hydrogenated block copolymer A
(3) A hydrogenated block copolymer of a block copolymer having a polymer block mainly composed of at least one vinyl aromatic hydrocarbon and a polymer block mainly composed of at least one butadiene compound. , 0.5 to 15 parts by weight of hydrogenated block copolymer B having a vinyl aromatic hydrocarbon-derived monomer unit content in the block copolymer before hydrogenation of more than 60% by weight and less than 90% by weight,
And (4) phosphate ester flame retardant containing 0 to 40 parts by weight with respect to 100 parts by weight of the total amount of (1), (2) and (3) Polyphenylene ether resin composition.   (3) Hydrogenated block copolymer B has a total hydrogenation rate of 40 to 90% of unsaturated double bonds based on a butadiene compound, a monomer derived from a vinyl aromatic hydrocarbon of the block copolymer before hydrogenation The chemical-resistant polyphenylene ether resin composition according to claim 1, wherein the unit content is more than 60% by weight and less than 85% by weight.