JP2005232307A - Polyolefin resin composition modifier, polyolefin resin composition, and molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a PTFE addition technique which enhances uniform dispersibility of polytetrafluoroethylene into a thermoplastic resin composition and improves flame retardancy and mechanical strength by only a small amount of addition thereof. <P>SOLUTION: The polyolefin resin composition modifier comprises polytetrafluoroethylene (A) which is a homopolymer or a copolymer of tetrafluoroethylene and a (meth)acrylate polymer (B) comprising 30 mass% or more of (meth)acrylate monomer units having a 5-30C alkyl group or a cycloaliphatic alkyl group, wherein the content of the component (A) is 40-70 pts.mass relative to 100 pts.mass of the sum of the component (A) and component (B) and at least a part of the component (A) is covered with the component (B). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a modifier for a polyolefin resin composition using polytetrafluoroethylene, and a polyolefin resin composition and a molded article using the same.

  Polytetrafluoroethylene (PTFE) has high crystallinity, small intermolecular force, and has a property of forming fibers with a slight stress, and is widely used as an additive for thermoplastic resin compositions.

By adding PTFE, properties such as molding processability, mechanical properties, and dispersibility of the filler can be improved.
Regarding moldability, it is disclosed that the melting rate of a polyvinyl chloride resin composition or the like can be improved by adding PTFE encapsulated with a styrene / acrylonitrile copolymer (Patent Document 1). In addition, PTFE is made into a fiber in the resin composition to increase the melt tension of the composition, prevent blowdown in blow molding, prevent jetting in injection molding, reduce specific gravity in foam molding, It is known to exhibit effects such as appearance improvement.

  In addition, it is known that by spreading PTFE into a resin composition, the ability to suppress the spread of fire by suppressing dripping of flame drops (preventing drip) is expressed. Housings for OA equipment such as computers and printers and home appliances such as televisions and audio equipment have been required to have higher flame resistance as the equipment becomes smaller and lighter and the shape becomes more complicated. PTFE is expected as an additive for flame retardant resin compositions for housing materials.

  However, PTFE has poor compatibility with most thermoplastic resins, and it is difficult to uniformly disperse it simply by blending it into the resin composition. Therefore, agglomerates are easily generated in the composition, and appearance defects of the molded product are easily caused. Furthermore, in order to obtain desired characteristics (such as flame retardancy), the amount of PTFE may be increased, or mechanical characteristics such as impact resistance may be deteriorated.

Under such circumstances, an attempt to improve the uniform dispersibility and flame retardancy of PTFE by preparing a powder containing PTFE and another organic polymer and adding this to a resin composition as a modifier. Has been made.
As PTFE-containing modifiers, (1) powder obtained by mixing and co-solidifying a PTFE dispersion and an aromatic vinyl polymer dispersion (Patent Document 2), (2) Presence of PTFE dispersion Powder obtained by polymerizing acrylonitrile monomer and styrene monomer (Patent Document 3), (3) PTFE particle dispersion and alkyl (meth) acrylate having 5 to 30 carbon atoms in the alkyl group The powder (patent document 4) etc. which superpose | polymerize a vinyl-type monomer in the liquid mixture with the dispersion liquid of the organic type polymer particle which consists of ester monomer units are indicated.

In addition, (4) a technique of separately adding PTFE and (meth) acrylic acid alkyl ester polymer to a resin composition is disclosed, and it is said that it exhibits improved drawdown resistance and flame resistance (patent) Reference 5).
Japanese Patent Laid-Open No. 9-25420 Japanese Patent Publication No. 5-8749 Japanese Patent Laid-Open No. 9-95583 Japanese Patent No. 2942888 JP 2000-63652 A

  In the prior art (1) in which the PTFE dispersion and the aromatic vinyl polymer dispersion are co-coagulated, it is said that an effect of improving flame retardancy is obtained. However, if the temperature at the time of co-coagulation is too low, it becomes difficult to coat PTFE with an aromatic vinyl polymer, and a mixture of PTFE self-adhesives and fine particles of the aromatic vinyl polymer alone is produced and obtained. The powder has poor handleability and fluidity, and the dispersibility when added to the thermoplastic resin composition becomes insufficient. For this reason, it is difficult to stably impart the effect of improving flame retardancy to the thermoplastic resin composition, and there is a risk of causing a poor appearance of the molded product. Therefore, it is necessary to carry out the co-solidification temperature at a temperature close to the boiling point of water, which is not practical from the viewpoint of workability and productivity.

  In the prior art (2) in which an acrylonitrile-styrene polymer is polymerized in the presence of a PTFE dispersion, the obtained powder is said to be excellent in handleability. However, in practice, as the amount of PTFE increases, the particle size of the obtained powder increases, and the fluidity, that is, the handleability tends to decrease. For this reason, poor dispersion in the thermoplastic resin composition may be caused and the surface appearance of the molded product may be affected. In addition, acrylonitrile-styrene-based polymers require a great amount of labor and cost to remove monomers remaining at the end of polymerization, and may generate a gas with a large environmental load when discarded by incineration.

  Prior art (3), in which a vinyl monomer is polymerized in a mixture of a PTFE particle dispersion and a (meth) acrylic ester polymer particle dispersion, improves the dispersibility of PTFE in a polyolefin resin composition. The PTFE content in the modifier is insufficient for improving the flame retardancy. Moreover, there is no disclosure about a specific technique for increasing the PTFE content. Even if a large amount of such a low PTFE content modifier is added in order to improve flame retardancy, the amount of (meth) acrylic acid ester polymer added also increases, so a good flame retardancy improvement effect is obtained. I can't.

  Prior art (4) involves adding PTFE and a (meth) acrylic acid ester polymer separately to a resin composition, followed by melting and kneading. It does not eliminate appearance defects.

  The present invention has been made in view of the above circumstances. It improves the uniform dispersibility of polytetrafluoroethylene (PTFE) in a thermoplastic resin composition, and even when added in a small amount, it is flame retardant (anti-drip) and mechanical. An object of the present invention is to provide a PTFE addition technique for improving characteristics, a thermoplastic resin composition to which the PTFE addition technique is applied, and a molded product thereof.

  The present inventor has intensively studied to solve the above-mentioned problems, and invented the following modifiers for polyolefin resin compositions, and polyolefin resin compositions and molded articles.

  The modifier for polyolefin resin composition of the present invention comprises polytetrafluoroethylene (A), which is a homopolymer or copolymer of tetrafluoroethylene, and an alkyl group or alicyclic alkyl group having 5 to 30 carbon atoms. (Meth) acrylate ester-containing polymer (B) containing 30% by mass or more of (meth) acrylic acid ester monomer unit and having a total of 100 parts by mass of component (A) and component (B) The content of the component (A) is 40 to 70 parts by mass, and at least a part of the component (A) is covered with the component (B).

  The polyolefin resin composition of the present invention is obtained by adding the above modifier for a polyolefin resin composition of the present invention to the polyolefin resin (C), and the polytetrafluoroethylene (A) is converted into the polyolefin resin (C). ) To 0.001 to 20% by mass.

  The molded article of the present invention is formed by molding the above-described polyolefin resin composition of the present invention.

According to the modifier for polyolefin resin composition of the present invention, since the uniform dispersibility of polytetrafluoroethylene (PTFE) in the polyolefin resin composition is good, even if the amount of PTFE added is small, flame retardancy ( (Drip prevention) and mechanical properties can be improved satisfactorily. According to the modifier of the present invention, a small amount of PTFE may be added and the uniform dispersibility thereof is good, so that there is no possibility of reducing the impact resistance of the resin composition.
The polyolefin resin composition of the present invention using the modifier of the present invention and a molded product thereof are excellent in flame retardancy (anti-drip property) and mechanical properties, and excellent in surface appearance.

Hereinafter, the present invention will be described in detail.
"Modifier for polyolefin resin composition"
The modifier for polyolefin resin composition of the present invention includes polytetrafluoroethylene (hereinafter abbreviated as “PTFE”) (A) and a specific (meth) acrylic acid ester polymer (hereinafter referred to as “PMMA heavy polymer”). Abbreviated as “union.”) (B), and at least a part of PTFE (A) is coated with a PMMA polymer (B).
In the modifier of the present invention, since at least a part of PTFE (A) is not exposed on the powder surface, the powder properties such as fluidity are good, and the dispersibility in the resin composition is excellent.

PTFE (A) is a homopolymer of tetrafluoroethylene or a copolymer of tetrafluoroethylene and another monomer, and can be used alone or in combination of two or more.
There are no particular restrictions on the copolymerization component, but fluorine-containing olefins such as hexafluoropropylene, chlorotrifluoroethylene, fluoroalkylethylene, and perfluoroalkyl vinyl ether; fluorine-containing (meth) such as (meth) acrylic acid perfluoroalkyl ester Examples include alkyl acrylates. The amount of the copolymerization component is not particularly limited, but is preferably 10% by mass or less based on the total of tetrafluoroethylene and the copolymerization component from the viewpoint of flame retardancy and mechanical properties.

In the present invention, as the PMMA polymer (B), a (meth) acrylic acid ester monomer having an alkyl group having 5 to 30 carbon atoms (which may be linear or branched) or an alicyclic alkyl group ( (M) A (meth) acrylic acid ester-based polymer containing units is used.
By using the (meth) acrylic acid ester monomer (M) having an ester group having such a chain length, the inventor can obtain a PMMA polymer (B) excellent in compatibility with an olefin resin. It has been found that the dispersibility of the modifier in the resin composition is good.
If the chain length of the ester group of the (meth) acrylic acid ester monomer (M) is less than the above lower limit, the dispersibility of the modifier in the polyolefin resin composition is lowered, and the flame retardancy improving effect (drip Prevention effect) may be insufficient, and if it exceeds the upper limit, it is not preferable from the viewpoint of mechanical properties.

  The (meth) acrylic acid ester monomer (M) is not particularly limited as long as it has an alkyl group having 5 to 30 carbon atoms or an alicyclic alkyl group, but has an alkyl group having 5 to 30 carbon atoms. Examples thereof include (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid dodecyl, (meth) acrylic acid tridecyl, (meth) acrylic acid octadecyl, etc., and an alicyclic alkyl group having 5 to 30 carbon atoms. Examples of the compound include cyclohexyl (meth) acrylate and 4-t-butylcyclohexyl (meth) acrylate. These can be used alone or in combination of two or more.

As the PMMA polymer (B), in addition to a homopolymer of (meth) acrylate monomer (M) units, (meth) acrylate monomer (M) units and other monomers These copolymers can be used. However, the content of the (meth) acrylic acid ester monomer (M) unit is 30% by mass or more, preferably 50% by mass or more.
If the unit amount of the (meth) acrylic acid ester monomer (M) in the PMMA polymer (B) is less than the above lower limit, the dispersibility of the modifier in the polyolefin resin composition is lowered and the flame retardancy is improved. The effect (drip prevention effect) tends to decrease.

  Although there is no restriction | limiting in particular as a copolymerization component, (meth) acrylic acid alkyl ester which has a C1-C4 alkyl group; (meth) acrylic acid ester, such as allyl methacrylate, hydroxyethyl methacrylate, glycidyl methacrylate; Fluorine-containing (meth) acrylic acid alkyl esters such as perfluoroalkyl acrylate; vinyl ether monomers such as vinyl methyl ether and vinyl ethyl ether; vinyl carboxylates such as vinyl acetate and vinyl butyrate; ethylene, Examples thereof include olefin monomers such as propylene and isobutylene; diene monomers such as butadiene, isoprene and dimethylbutadiene.

In the modifier of this invention, content of PTFE (A) shall be 40-70 mass parts with respect to a total of 100 mass parts of PTFE (A) and a PMMA polymer (B). By containing PTFE (A) within such a range, the effect of improving flame retardancy (drip prevention effect) when added to the resin composition is improved.
If the PTFE (A) content is less than the above lower limit, the flame retardancy improving effect (drip prevention effect) when added to the resin composition may not be sufficiently exhibited. Dispersibility and workability may be poor.

In particular, the modifier of the present invention obtained by preparing a dispersion (E) containing PTFE (A) and a PMMA polymer (B) and coagulating or spray-drying the liquid is PTFE (A). Most of them are coated with the PMMA polymer (B), and the fluidity and dispersibility are remarkably excellent.
The method for preparing the dispersion liquid (E) is not particularly limited, but each of the PTFE (A) dispersion liquid (PE1) and the PMMA polymer (B) dispersion liquid (PE2) is prepared and mixed. Is preferred.

  In the dispersion liquid (PE1), PTFE (A) is not an aggregate, and is preferably particles having an average particle diameter of 10 μm or less, particularly an average particle diameter of 0.05 to 1.0 μm. If the average particle size of PTFE (A) is too large, the dispersibility in the modifier may be poor. On the other hand, if it is too small, there is a high probability that PTFE (A) will appear on the powder surface of the modifier, resulting in poor powder properties such as fluidity and poor dispersibility in the resin composition. is there.

The dispersion (PE1) of PTFE (A) particles is obtained, for example, by emulsion polymerization of tetrafluoroethylene and a copolymerization component as necessary.
Known emulsifiers can be used for the polymerization. Specific examples include anionic surfactants such as fatty acid salts, alkyl sulfate esters, alkylbenzene sulfonates, alkyl phosphate esters, dialkyl sulfosuccinates; polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acids Nonionic surfactants such as esters and glycerin fatty acid esters; cationic surfactants such as alkylamine salts and the like can be mentioned, and these can be used alone or in combination of two or more.
The aqueous dispersion of PTFE (A) particles is “Fluon AD-1”, “AD-936”, “XAD-938” manufactured by Asahi Fluoropolymers; “Polyflon D-1” manufactured by Daikin Industries, Ltd. “Teflon (registered trademark) 30J” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., and the like are commercially available.

  The dispersion (PE2) of the PMMA polymer (B) is, for example, a radical polymerization or ion by emulsion polymerization or miniemulsion polymerization of (meth) acrylic acid ester monomer (M) and a copolymerization component as necessary. Obtained by polymerization. In the polymerization, multistage polymerization such as block copolymerization, graft copolymerization, and seed polymerization may be employed. When multistage polymerization is employed, if the unit amount of the (meth) acrylic acid ester monomer (M) in the finally obtained polymer is 30% by mass or more, the monomer (M ) The unit amount is not particularly limited.

As the emulsifier used for the polymerization, known ones mentioned in the dispersion (PE1) can be used. However, when the dispersion (E) is coagulated to obtain a modifier, it is possible to use a fatty acid salt, an alkyl phosphate ester salt, a dialkyl sulfosuccinate or the like as an emulsifier with the PTFE (A) dispersion (PE1). It is preferable in terms of co-coagulation properties.
Further, when the pH of the polymerization system becomes alkaline depending on the emulsifier used, in order to prevent hydrolysis of the (meth) acrylic acid ester (M), a pH adjuster may be used to make the pH near neutral. it can. Examples of the pH regulator include boric acid-potassium chloride-potassium hydroxide, potassium dihydrogen phosphate-disodium hydrogen phosphate, boric acid-potassium chloride-potassium carbonate, citric acid-potassium hydrogen citrate, diphosphate phosphate. Examples include potassium hydrogen-boric acid, disodium hydrogen phosphate-citric acid, and the like.

  Although it does not specifically limit as a polymerization initiator, The single system of a water-soluble initiator or an oil-soluble initiator, or a redox system etc. are mentioned. Examples of water-soluble initiators include inorganic initiators such as persulfates, and oil-soluble initiators include organic peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, and lauroyl peroxide. Oxides; azo compounds and the like. Examples of redox initiators include those in which the above inorganic initiators are combined with sulfites, hydrogen sulfites, thiosulfates, and the like, and those in which the above organic peroxides and azo compounds are combined with sodium formaldehyde sulfoxylate, etc. Is mentioned.

  In the dispersion (PE2), the PMMA polymer (B) is preferably not particles but particles having an average particle diameter of 0.05 to 0.25 μm. If the average particle size of the PMMA polymer (B) is too large, there is a high probability that PTFE (A) will appear on the powder surface of the modifier, resulting in poor powder properties such as fluidity. There is a risk that the dispersibility of the resin becomes poor. If it is too small, a large amount of emulsifier is required for the polymerization of the PMMA polymer (B), which is not preferable in terms of industrial productivity.

  In the present invention, a (meth) acrylic acid ester polymer containing a (meth) acrylic acid ester monomer (M) unit is polymerized, and a (meth) acrylic acid ester having a glass transition temperature Tg of 40 ° C. or higher. The polymerization is preferably performed by seed polymerization of the polymer, so that at least the glass transition temperature Tg of the surface layer of the PMMA polymer (B) particles is 40 ° C. or higher, preferably 50 ° C. or higher. If the Tg of the surface layer of the PMMA polymer (B) particles is too low, the storage stability of the modifier may be insufficient.

  The dispersion (E) can be prepared by mixing the dispersions (PE1) and (PE2), and this is solidified or spray-dried to obtain the modifier of the present invention. The coagulation of the dispersion (E) can be performed, for example, by putting the dispersion (E) into hot water in which a metal salt such as calcium chloride or magnesium sulfate is dissolved and salting out. The dispersion (E) can be carried out by spraying in a heated atmosphere.

  As described above, the modifier for polyolefin resin composition of the present invention is such that at least a part of PTFE (A) is coated with a PMMA polymer (B), and powder properties such as fluidity are good. Therefore, the uniform dispersibility of PTFE (A) in the resin composition is good, and even when added in a small amount, flame retardancy (anti-drip property) and mechanical properties can be improved. According to the modifier of the present invention, a small amount of PTFE may be added and the uniform dispersibility thereof is good, so that there is no possibility of reducing the impact resistance of the resin composition.

In the present invention, since the specific PMMA polymer (B) is used as a component for coating PTFE (A), the dispersibility of PTFE (A) in the polyolefin resin composition can be improved. . This is because the PMMA polymer (B) used in the present invention is excellent in compatibility with the polyolefin resin.
In addition, unlike the acrylonitrile-styrene polymer used in the prior art (2), the PMMA polymer (B) has a remarkably small amount of monomer remaining at the end of the polymerization, and is also environmentally friendly when discarded by incineration. It is suitable without generating a heavy load gas.

  In the present invention, in particular, the solid content is taken out from the dispersion liquid (E) containing PTFE (A) and the PMMA polymer (B) by co-coagulation or spray-drying, and used as a modifier. However, a modifier having good powder characteristics in which most of PTFE (A) is coated with the PMMA polymer (B) is stably obtained, which is preferable.

"Polyolefin resin composition"
The polyolefin resin composition of the present invention is obtained by adding the above modifier for a polyolefin resin composition of the present invention to the polyolefin resin (C).

A polyolefin resin (C) is not specifically limited, A well-known thing can be used. Specific examples include polypropylene, polyethylene, polypropylene / polyethylene copolymer, polyolefin resin alloy, (ultra) low density polyethylene, poly-α-olefins such as polybutene and poly-4-methylpentene, ethylene propylene rubber, ethylene butene. Copolymers, Copolymers of α-olefins such as ethylene butene terpolymer, ethylene vinyl acetate copolymer, ethylene / ethyl acrylate copolymer, ethylene / methyl methacrylate copolymer, ethylene / maleic anhydride Polyolefin resins such as copolymers of α-olefins and various monomers such as copolymers, ethylene / acrylic acid copolymers, ethylene / glycidyl methacrylate copolymers, 1,2-polybutadiene, trans 1,4 -Polyisoprene etc. are mentioned.
In the present specification, the “polyolefin resin” includes a polyolefin thermoplastic elastomer.
Polyolefin resin (C) can be used individually by 1 type or in combination of 2 or more types.

In this invention, the modifier for polyolefin resin compositions of this invention is added so that content of PTFE (A) may be 0.001-20 mass% with respect to polyolefin resin (C).
By adding the modifier of the present invention so that the amount of PTFE (A) falls within such a range, a resin composition in which PTFE (A) is dispersed uniformly and excellent in flame retardancy and mechanical properties can be obtained. can get. If the amount of PTFE (A) is less than the above lower limit, the flame retardancy improving effect may not be sufficiently exhibited, and if it exceeds the upper limit, the mechanical property improving effect may not be sufficiently exhibited.

  The polyolefin resin composition of the present invention includes a flame retardant (D), a filler (E), a foaming agent, a plasticizer, a stabilizer, an impact resistance modification, and the like within a range not departing from the effects of the present invention. Various additives such as a texture agent, a lubricant, a processing aid, a pigment, an antifogging agent, an antibacterial agent, an antistatic agent, a conductivity imparting agent, a surfactant, a crystal nucleating agent, and a heat resistance improver can be added. These can be used individually by 1 type or in combination of 2 or more types.

  The composition of the present invention containing PTFE (A) exhibits good flame retardancy, in particular, an effect of suppressing the spread of fire by preventing drip. Further, by adding a flame retardant (D), it is more flame retardant. An excellent resin composition can be obtained.

Examples of the flame retardant (D) include tricresyl phosphate, triallyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, tri (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (2,3-dibromo Propyl) phosphate, phosphate compounds such as phenylene bis (phenylglycidyl phosphate), phosphorous compounds such as red phosphorus, ammonium polyphosphate / pentaerythritol complex, phosphate polyols, halogen-containing polyols, Polyols such as phosphorus-containing polyols, aromatic halogen compounds such as hexabromobenzene and decabromodiphenyl oxide, halogenated epoxy resins such as brominated bisphenol epoxy resins, halogenated polycarbonates Bonate resin, brominated polystyrene resin, brominated bisphenol cyanurate resin, brominated polyphenylene oxide, decabromodiphenyl oxide bisphenol condensate, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, calcium aluminate, hydrotalcite and other metals Antimony compounds such as hydroxide, antimony trioxide, antimony pentoxide, triazine compounds such as melamine, cyanuric acid, melamine cyanurate, kaolin clay, dosonite, calcium carbonate borate, molybdenum compound, ferrocene, tin compound, Examples include inorganic complex salts.
Among them, phosphoric esters such as halogen-free tricresyl phosphate, triallyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, condensed phosphate esters such as phenylenebis (phenylglycidyl phosphate), etc. are preferable. .

  Although the addition amount of a flame retardant (D) is not specifically limited, 0.001-150 mass% is preferable with respect to polyolefin resin (C). If the amount added is too small, the effect of adding the flame retardant (D) may not be sufficiently exhibited. If the amount added is too large, the mechanical strength such as impact resistance of the resin composition tends to decrease.

  By adding the filler (E), mechanical strength such as rigidity and heat resistance can be improved. Since PTFE (A) exhibits the function of improving the dispersibility of the filler (E), the present invention can be preferably applied to a resin composition containing the filler (E), and the filler (E) is well dispersed. The obtained resin composition can be provided.

  Although it does not specifically limit as a filler (E), A metal powder, an oxide, a hydroxide, silicic acid or its salt, carbonate, silicon carbide, a vegetable fiber, an animal fiber, a synthetic fiber etc. are mentioned. Specific examples of these include aluminum powder, copper powder, iron powder, alumina, natural wood, paper, calcium carbonate, talc, magnesium carbonate, mica, kaolin, calcium sulfate, barium sulfate, aluminum hydroxide, magnesium hydroxide, silica , Clay, zeolite, talc, wollastonite, acetate powder, silk powder, aramid fiber, glass fiber, carbon fiber, metal fiber, carbon black, graphite, glass beads, and recycled filler using waste material as filler Can be mentioned.

  Among the examples of “recycled fillers”, rice husk, bran, rice bran, corn waste, rice bran, defatted soybeans, walnut husk, coconut coconut shell, sucrose, bagasse and other agricultural wastes, distilled spirits such as shochu Distilled rice cake, beer malt rice cake, wine grape rice cake, liquor rice cake, soy sauce cake and other brewed rice cakes, tea cakes, coffee cakes, citrus squeezed rice cakes, and other food processing waste such as okara and chlorella, oyster shells Wood waste such as shrimp shells, marine waste such as shrimp and carp shells, sawdust, waste wood, bark, felled bamboo, wood cutting at sawmills, and demolition of wooden houses Specific examples include waste, waste pulp generated from waste paper and paper industry, and waste such as paper pieces.

  As the filler (E), the surface of the above powder is a polybasic acid anhydride such as maleic anhydride, an organic peroxide such as dicumyl peroxide, acid-modified for the purpose of improving dispersibility in the resin composition. The modified polyolefin, polyester wax, fatty acid metal salt such as zinc stearate, and surface treated with fine particles such as metal oxide such as titanium oxide and calcium oxide can also be used.

  The shape and size of the filler (E) are not particularly limited, but if the particles are large, if the particles are large, if the fibers are too long, the dispersibility of the filler (E) is reduced and the appearance of the product Is less than 10 mesh path, more preferably 100 mesh path or less. When the particle diameter of the filler (E) is larger than this, it is preferable to use it after adjusting the particle diameter by pulverization or the like. Moreover, it is preferable that it is 10,000 meshon or more from a viewpoint of the handleability of powder.

  Although the moisture content of a filler (E) is not specifically limited, 20 mass% or less is preferable from the handleability as a powder. Since commercially available fillers tend to contain a lot of moisture, it is preferable to use them after heat treatment in a heating furnace or heating and stirring as necessary to adjust the water content within the above range. Moreover, when there exists a possibility that abnormal foaming etc. may arise in a molded article with the water | moisture content contained in a filler (E), it is especially preferable to make a moisture content into 1 mass% or less.

0-2000 mass% is preferable with respect to polyolefin resin (C), and, as for the compounding quantity of a filler (E), 5-100 mass% is especially preferable.
If the amount of the filler (E) added is too small relative to the polyolefin resin (C), the effect of adding the filler may not be sufficiently exhibited. There is a fear.

Examples of the foaming agent include inorganic foaming agents, volatile foaming agents, and decomposable foaming agents.
Here, specific examples of the inorganic foaming agent include carbon dioxide, air, and nitrogen. Volatile blowing agents include halogenated hydrocarbons such as propane, n-butane, isobutane, pentane, hexane, etc., trichlorofluoromethane, dichlorofluoromethane, dichlorotetrafluoroethane, methyl chloride, ethyl chloride, methylene chloride, etc. Specific examples include hydrocarbons. Examples of the decomposable foaming agent include azodicarbonamide, dinitrosopentamethylenetetramine, azobisisobutyronitrile, sodium bicarbonate and the like.

  When melt-kneading the resin composition, a foaming agent and a cell regulator can be used in combination. Examples of the air conditioner include inorganic powders such as talc and silica, acidic salts of polyvalent carboxylic acids, reaction mixtures of polyvalent carboxylic acids with sodium carbonate or sodium bicarbonate, citric acid and the like.

  Plasticizers include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dinormal octyl phthalate, 2-ethylhexyl phthalate, diisooctyl phthalate, dicapryl phthalate, dinonyl phthalate, diisononyl phthalate, didecyl phthalate, diisodecyl phthalate, diun Phthalic acid esters such as decyl phthalate, dilauryl phthalate, ditridecyl phthalate, dibenzyl phthalate, dicyclohexyl phthalate, butyl benzyl phthalate, octyl decyl phthalate, butyl octyl phthalate, octyl benzyl phthalate, normal hexyl normal decyl phthalate, normal octyl normal decyl phthalate Plasticizer; tricresyl phosphate, tri-2 Phosphate plasticizers such as ethylhexyl phosphate, triphenyl phosphate, 2-ethylhexyl diphenyl phosphate, cresyl diphenyl phosphate; di-2-ethylhexyl adipate, diisodecyl adipate, normal octyl-normal decyl adipate, normal heptyl-normal nonyl adipate, Adipic acid plasticizers such as diisooctyl adipate, diisonormal octyl adipate, dinormal octyl adipate, didecyl adipate; dibutyl sebacate, di-2-ethylhexyl sebacate, diisooctyl sebacate, butylbenzyl sebacate Sebacic acid ester plasticizers such as di-2-ethylhexyl azelate, dihexyl azelate, diisooctyl azelate, etc. Citric acid ester plasticizers such as triethyl citrate, triethyl acetyl citrate, tributyl citrate, tributyl acetyl citrate, tri-2-ethylhexyl citrate; methyl phthalyl ethyl glycolate, ethyl Glycolic ester plasticizers such as phthalyl ethyl glycolate and butyl phthalyl butyl glycolate; tributyl trimellitate, tri-normal hexyl trimellitate, tri-2-ethylhexyl trimellitate, tri-normal octyl trimellitate , Trimellitic acid ester plasticizers such as tri-isooctyl trimellitate and tri-isodecyl trimellitate; phthalic acid isomers such as di-2-ethylhexyl isophthalate and di-2-ethylhexyl terephthalate Plasticizers; ricinoleic acid ester plasticizers such as methyl acetyl ricinolate and butyl acetyl ricinolate; polyester plasticizers such as polypropylene adipate, polypropylene sebacate and modified polyesters thereof; epoxidized soybean oil, epoxy butyl stearate, Examples thereof include epoxy plasticizers such as epoxy (2-ethylhexyl) stearate, epoxidized linseed oil, and 2-ethylhexyl epoxy torate.

  Stabilizers include lead-based stabilizers such as tribasic lead sulfate, dibasic lead phosphite, basic lead sulfite and lead silicate; metals such as potassium, magnesium, barium, zinc, cadmium and lead; Metal soap stabilizers derived from fatty acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, ricinoleic acid, linoleic acid, behenic acid; Organotin stabilizers derived from alkyl groups, ester groups and fatty acid salts, maleates, and sulfides; Ba—Zn, Ca—Zn, Ba—Ca, Ca—Mg—Sn, Ca— Composite metal soap stabilizers such as Zn-Sn, Pb-Sn, and Pb-Ba-Ca; metals such as barium and zinc, 2-ethylhexanoic acid, isodecanoic acid, trialkyl Usually two or more kinds of branched fatty acids such as acetic acid, unsaturated fatty acids such as oleic acid, ricinoleic acid and linoleic acid, alicyclic acids such as naphthenic acid, aromatic acids such as carboxylic acid, benzoic acid, salicylic acid and substituted derivatives thereof Metal salt stabilizers derived from organic acids of these; these stabilizers are dissolved in organic solvents such as petroleum hydrocarbons, alcohols, glycerin derivatives, and further phosphites, epoxy compounds, coloring inhibitors, Metal stabilizers such as metal salt liquid stabilizers that contain stabilizers such as transparency improvers, light stabilizers, antioxidants, and lubricants; epoxy resins, epoxidized soybean oil, epoxidized vegetable oils, epoxies Epoxy compounds such as alkylated fatty acid alkyl esters, phosphorus is substituted with alkyl groups, aryl groups, cycloalkyl groups, alkoxyl groups, etc., and propylene glycol, etc. UV light such as organic phosphites having aromatic compounds such as monohydric alcohol, hydroquinone, bisphenol A, hindered phenols such as bisphenol dimerized with BHT, sulfur or methylene groups, salicylic acid esters, benzophenone, benzotriazole, etc. Absorber, hindered amine or nickel complex light stabilizer, carbon black, UV shielding agent such as rutile type titanium oxide, polyhydric alcohol such as trimerolpropane, pentaerythritol, sorbitol, mannitol, β-aminocrotonic acid ester, 2- Nitrogen-containing compounds such as phenylindole, diphenylthiourea, dicyandiamide, sulfur-containing compounds such as dialkylthiodipropionic acid esters, ketone compounds such as acetoacetate ester, dehydroacetic acid, β-diketone, organic silicon Compound, non-metallic stabilizers, and the like such as boric acid ester.

  Impact modifiers include polybutadiene, polyisoprene, polychloroprene, fluororubber, styrene-butadiene copolymer rubber, methyl methacrylate-butadiene-styrene copolymer, methyl methacrylate-butadiene-styrene graft Copolymer, Acrylonitrile-styrene-butadiene copolymer rubber, Acrylonitrile-styrene-butadiene graft copolymer, Styrene-butadiene-styrene block copolymer rubber, Styrene-isoprene-styrene copolymer rubber, Styrene-ethylene -Butylene-styrene copolymer rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber (EPDM), silicone-containing acrylic rubber, silicone / acrylic composite rubber graft copolymer, silico Emissions-based rubber, and the like. Examples of the diene of the ethylene-propylene-diene copolymer rubber (EPDM) include 1,4-hexadiene, dicyclopentadiene, methylene norbornene, ethylidene norbornene, and propenyl norbornene.

  Lubricants include pure hydrocarbons such as liquid paraffin, natural paraffin, micro wax, synthetic paraffin, and low molecular weight polyethylene; halogenated hydrocarbons; fatty acids such as higher fatty acids and oxy fatty acids; fatty acid amides, bis fatty acid amides, etc. Fatty acid amides; fatty acid lower alcohol esters, fatty acid polyhydric alcohol esters such as glycerides, fatty acid polyglycol esters, fatty acid fatty alcohol esters (ester waxes) and other ester systems; metal soaps, fatty alcohols, polyhydric alcohols, Polyglycol, polyglycerol, partial ester of fatty acid and polyhydric alcohol, fatty acid and polyglycol, partial ester based lubricant of polyglycerol, and the like.

  Processing aids include (meth) acrylic acid ester copolymers, (meth) acrylic acid ester-styrene copolymers, (meth) acrylic acid ester-styrene-α-methylstyrene copolymers, acrylonitrile-styrene copolymers. Examples include a polymer, an acrylonitrile-styrene- (meth) acrylic acid ester copolymer, an acrylonitrile-styrene-α-styrene copolymer, and an acrylonitrile-styrene-maleimide copolymer.

  The method for preparing the resin composition of the present invention is not particularly limited. For example, the polyolefin resin (C), the modifier of the present invention, and other additives as necessary, such as extrusion kneading, roll kneading, and the like are known. It can be prepared by melt kneading with a technique. Also, instead of mixing all the components at once, a part of the polyolefin resin (C) and the modifier of the present invention are mixed to prepare a masterbatch, and then the remaining components are added and mixed, for example. There is no problem.

"Molding"
The molded article of the present invention is formed by molding the above-described polyolefin resin composition of the present invention.
The molding method is not particularly limited, and a known molding method such as calendar molding, thermoforming, foam molding, extrusion molding, extrusion blow molding, injection molding, melt spinning, etc. can be employed.
Specific examples of the molded article include a sheet, a film, and an odd-shaped molded article by extrusion molding; a hollow molded article by injection blow molding or injection molding, an injection molded article, and the like.

  Since the polyolefin resin composition of the present invention and the molded product thereof are those using the modifier of the present invention, the flame retardancy (anti-drip property) and mechanical properties are improved.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited by the following example. In the following examples, “%” and “part” are based on mass.

(Evaluation items and evaluation methods)
Evaluation items and evaluation methods were as follows.
(1) Solid content concentration of dispersion The solid content concentration of the dispersion prepared in the production of the modifier was determined by drying the dispersion at 180 ° C. for 30 minutes.
(2) Mass average particle diameter of PMMA polymer dispersion The mass average particle diameter of the PMMA polymer dispersion prepared in the production of the modifier was measured as follows.
The dispersion was diluted with distilled water as a sample and measured using a CHDF2000 particle size distribution meter manufactured by MATEC, USA. The measurement conditions were standard conditions recommended by MATEC. That is, using a dedicated cartridge cartridge for particle separation and carrier liquid, the liquidity is almost neutral, the flow rate is 1.4 ml / min, the pressure is about 4000 psi (2600 KPa), and the temperature is kept at 35 ° C., the concentration is about 3%. 0.1 ml of the diluted sample was used for the measurement. As the standard particle size substance, a total of 12 monodisperse polystyrenes having a known particle size manufactured by DUKE in the United States were used within a range of 0.02 to 0.8 μm.

(3) Glass transition temperature of the surface layer of the PMMA polymer The glass transition temperature based on the Fox equation was calculated from the charging ratio to obtain an approximate value. However, as for the modifier (X-4), a glass of tert-butyl cyclohexyl methacrylate homopolymer and MMA homopolymer calculated by Bicerano's method [Prediction of polymer properties, Marcel Dekker Inc, New York (1993)]. It calculated | required by the arithmetic mean from transition temperature.

(4) Fluidity of the modifier The fluidity of the modifier was measured using a bulk specific gravity meter (manufactured by Tsutsui Rika Instruments Co., Ltd.) in accordance with JIS K6721. In this method, a predetermined amount of modifier powder is filled in a funnel of a bulk density meter, and the fluidity is evaluated by the amount of powder outflow (g / 10 sec) when dropped from the funnel for 10 seconds. In addition, it means that fluidity | liquidity is so high that the amount of outflow powder is large, and it means that it is excellent in the handleability in actual work.

(5) Flame retardance The flame retardancy of the resin composition molded product was evaluated by a vertical combustion test in accordance with UL94 standard. The test piece was 1.6 mm thick. Each composition was tested with five test pieces, and the ratio of drip generation was determined from the number of drip generated during the test.
(6) Izod Impact Strength The Izod impact strength of the resin composition molded article was measured at 23 ° C. using a 3.2 mm thick, notched test piece in accordance with ASTM D256.
(7) Surface appearance The surface appearance of the resin composition molded article was evaluated by visual observation based on the following criteria.
Judgment criteria ○: No irregularities or streaks are observed on the surface.
X: Spots and streaks are observed on the surface.

[Modifier (X-1)]
<Preparation of PTFE dispersion>
116.7 parts of distilled water was added to 83.3 parts of PTFE particle dispersion “Fluon XAD938” (solid content concentration: 63.0%, containing 5% of surfactant relative to PTFE) manufactured by Asahi Fluoropolymers. This was added to obtain a PTFE (A-1) particle dispersion. The solid content concentration of this dispersion was 26.2% (PTFE concentration was 25%), and the average particle size was 290 nm.
<Preparation of PMMA polymer dispersion>
Separately, 280 parts of distilled water, 2.0 parts of dipotassium alkenyl succinate (“Latemul ASK” manufactured by Kao Corporation) as an emulsifier, 60 parts of 2-ethylhexyl acrylate, and 20 parts of methyl methacrylate were mixed in a homomixer with 10 parts. Preliminary dispersion was performed by stirring at 1,000 rpm for 5 minutes. Then, this dispersion was performed by passing twice through a homogenizer at a pressure of 20 MPa. This was charged into a separable flask equipped with a stirring blade, a condenser, a thermocouple, and a nitrogen inlet, and heated to 60 ° C. under a nitrogen stream.
Next, 0.8 parts of cumene hydroperoxide was added, and further a mixed solution of 0.001 part of iron (II) sulfate, 0.003 part of disodium ethylenediaminetetraacetate, 0.24 part of Rongalite salt, and 10 parts of distilled water was added. The radical polymerization was started. After the end of heat generation, the temperature inside the system was kept at 60 ° C. for 1 hour.
Thereafter, the temperature in the system was raised to 80 ° C., and a mixed liquid of 0.001 part of iron (II) sulfate, 0.003 part of disodium ethylenediaminetetraacetate, 0.24 part of Rongalite salt, and 10 parts of distilled water was added, While maintaining the same temperature, a mixed solution of 19 parts of methyl methacrylate, 1 part of ethyl acrylate and 0.2 part of tertiary butyl hydroperoxide was added dropwise over 30 minutes to carry out the second stage polymerization. After the heat generation was completed, the temperature in the system was maintained at 80 ° C. for 1 hour to obtain 400 parts of a PMMA polymer (B-1) dispersion. The liquid had a solid content concentration of 26% and a mass average particle size of 100 nm.
<Preparation of modifier>
A dispersion (E-1) was obtained by adding 200 parts of PTFE (A-1) dispersion to 200 parts of the PMMA polymer (B-1) dispersion and stirring for 30 minutes. 600 parts of a 1% calcium acetate aqueous solution was heated to 70 ° C. and stirred, and 400 parts of the dispersion (E-1) prepared in the liquid was gradually added dropwise to solidify and precipitate a solid. Finally, this precipitate was separated, filtered and dried to obtain the modifier (X-1) of the present invention.

[Modifier (X-2)]
The modifier (X-2) of the present invention was obtained in the same manner as the modifier (X-1) except that dodecyl methacrylate was used instead of 2-ethylhexyl acrylate.

[Modifier (X-3)]
A mixed solution of 290 parts of distilled water, 2.0 parts of dipotassium alkenyl succinate (“Latemul ASK” manufactured by Kao Corporation), 60 parts of 2-ethylhexyl acrylate, and 40 parts of methyl methacrylate as an emulsifier was mixed at 10,000 rpm with a homomixer. The mixture was stirred for 5 minutes and preliminarily dispersed. Then, this dispersion was performed by passing twice through a homogenizer at a pressure of 20 MPa. This was charged into a separable flask equipped with a stirring blade, a condenser, a thermocouple, and a nitrogen inlet, and heated to 60 ° C. under a nitrogen stream. Next, 1.0 part of cumene hydroperoxide was added, and a mixed solution of 0.001 part of iron (II) sulfate, 0.003 part of disodium ethylenediaminetetraacetate, 0.24 part of Rongalite salt and 10 parts of distilled water was then added. The radical polymerization was started. After the heat generation was completed, the temperature in the system was maintained at 60 ° C. for 1 hour to obtain 400 parts of a PMMA polymer (B-2) dispersion. The liquid had a solid content concentration of 25% and a mass average particle size of 100 nm.
The modification of the present invention was carried out in the same manner as the modifier (X-1) except that the PMMA polymer (B-2) dispersion was used instead of the PMMA polymer (B-1) dispersion. Agent (X-3) was obtained.

[Modifier (X-4)]
The modifying agent (X-4) of the present invention was obtained in the same manner as the modifying agent (X-3) except that tertiary butyl cyclohexyl methacrylate was used instead of 2-ethylhexyl acrylate.
[Modifier (X-5)]
In the same manner as the modifier (X-1) except that 240 parts of the PTFE (A-1) dispersion was added to 160 parts of the PMMA polymer (B-1) dispersion, the modifier ( X-5) was obtained.
[Modifier (X-6)]
The modifier (X-6) of the present invention was obtained in the same manner as the modifier (X-1) except that the modifier (X-1) was recovered by spray drying the dispersion (E-1).

[Modifier (Y-1)]
A comparative modifier (Y-1) was obtained in the same manner as the modifier (X-3) except that butyl acrylate was used instead of 2-ethylhexyl acrylate.
[Modifier (Y-2)]
Comparative modifier (Y-2) in the same manner as modifier (X-1) except that the amount of 2-ethylhexyl acrylate was changed to 10 parts and the amount of methyl methacrylate was changed to 70 parts in the first stage polymerization. Got.
[Modifier (Y-3)]
A comparative modifier (X-1) was added in the same manner as the modifier (X-1) except that 80 parts of PTFE (A-1) dispersion was added to 320 parts of the PMMA polymer (B-1) dispersion. Y-3) was obtained.
[Modifier (Y-4)]
The comparative modifier (X-1) is the same as the modifier (X-1) except that 80 parts of the PMMA polymer (B-1) dispersion is added with 320 parts of the PTFE (A-1) dispersion. Y-4) was obtained.
[Modifier (Y-5)]
Aflon PTFECD-1 manufactured by Asahi Glass Co., Ltd., which is a commercially available PTFE powder, was prepared and used as a comparative modifier (Y-5).

[Characteristics of modifier]
The properties of the above modifiers are summarized in Table 1. The table shows the monomer component and composition ratio used in preparing the PMMA polymer dispersion, the glass transition temperature (Tg) of the PMMA polymer particle surface layer, and the PTFE content (% ) And fluidity evaluation results are shown.
In the table, each abbreviation indicates the following monomer component. The arrows indicate that multistage polymerization was performed.
2EHA: 2-ethylhexyl acrylate MMA: methyl methacrylate EA: ethyl acrylate SLMA: dodecyl methacrylate tBCHMA: tertiary butyl cyclohexyl methacrylate BA: butyl acrylate

[Examples 1 to 10, Comparative Examples 1 to 9]
In the compositions shown in Tables 2 and 3, any of the above modifiers and appropriate flame retardants or fillers are added to the polyolefin resin, and the polyolefin resin is kneaded and pelletized with a 20φ co-directional twin screw extruder. A composition was prepared. This was injection molded to obtain a molded product.
The polyolefin resin, flame retardant, and filler used are as follows.
Polyolefin resin (C-1): PP (“Novatec FY-4” manufactured by Nippon Polychem Co., Ltd.)
Polyolefin resin (C-2): HDPE (“NOVATEC HY430” manufactured by Nippon Polychem Co., Ltd.)
Polyolefin resin (C-3): EPR (Mitsui Chemicals, Inc. “Toughmer P0680”)
Flame retardant (D-1): Magnesium hydroxide (“Kisuma 5A” manufactured by Kyowa Chemical)
Flame Retardant (D-2): Phosphate Ester (Daihachi Chemical "tricresyl phosphate")
Filler (E-1): Talc

[Example 11, Comparative Example 10]
As Example 11 and Comparative Example 10, pellets obtained in the same manner as in Example 1 and Comparative Example 1 were respectively extruded to obtain square bars, which were cut into test pieces.

(result)
The evaluation results of each example are shown in Tables 2 and 3.
As shown in Table 1, the modifiers (X-1) to (X-6) of the present invention all had high fluidity and excellent handling properties. Further, as shown in Table 2, in Examples 1 to 11 in which this was blended, a polyolefin resin composition and a molded article excellent in flame retardancy and drip prevention properties based on the UL94 standard were obtained. Further, the obtained molded product was excellent in impact resistance and surface appearance.

In contrast, the comparative modifiers (Y-4) and (Y-5) having a PTFE content of more than 70% had remarkably poor fluidity and poor handleability. Further, in Comparative Examples 4, 5, and 9 using this, the dispersibility of PTFE was poor, and the obtained resin composition and molded product had poor flame retardancy, anti-drip property, and surface appearance based on the UL94 standard. It was.
In Comparative Example 6 in which the flame retardant (D) was added based on Comparative Example 5, the flame retardancy and the drip prevention were good, but the PTFE dispersibility was poor and the surface appearance was still poor. In addition, as shown in Comparative Examples 7 and 8, when using a modifier having a high PTFE content, even if a flame retardant (D) is added depending on the type of polyolefin resin, good flame retardancy and drip It became clear that the preventive properties did not appear.

The comparative modifier (Y-3) having a PTFE content of less than 40% has good fluidity, and in Comparative Example 3 using this, a molded article having a good surface appearance was obtained. Flame retardancy and drip prevention were poor.
The PTFE content was the same as that of the modifiers (X-1) to (X-6) of the present invention, but the chain lengths of the alkyl groups of the monomer units in the PMMA polymer were all less than 5 The content of the modifier (Y-1) for comparison and the (meth) acrylic acid ester monomer unit having a chain length of 5 to 30 in the alkyl group in the PMMA polymer was less than 30% by mass. In Comparative Examples 1, 2, and 10 using the modifier (Y-2), the obtained resin compositions and molded articles are all flame retardant, anti-drip, and surface appearance based on the UL94 standard. It was bad.

  The polyolefin resin composition modifier of the present invention, the polyolefin resin composition to which the modifier is applied, and a molded product thereof are used for applications requiring flame retardancy and good mechanical properties, specifically OA equipment and home appliances. It can be preferably used for housings of products, automobile parts (bumpers, spoilers, side moldings, sealings, etc.), building materials (interior materials, window frames, shelf boards, flooring materials, wall materials, etc.).

Claims (3)

30 units of polytetrafluoroethylene (A) which is a homopolymer or copolymer of tetrafluoroethylene, and a (meth) acrylic acid ester monomer unit having an alkyl group or alicyclic alkyl group having 5 to 30 carbon atoms. The content of the component (A) is 40 to 70 with respect to a total of 100 parts by mass of the component (A) and the component (B). Mass part,
And the modifier for polyolefin resin compositions characterized by at least one part of a component (A) being coat | covered with the component (B).   The polyolefin resin composition modifier according to claim 1 is added to the polyolefin resin (C), and the polytetrafluoroethylene (A) is added to the polyolefin resin (C) from 0.001 to 0.001. A polyolefin resin composition containing 20% by mass.   A molded product obtained by molding the polyolefin resin composition according to claim 2.