JP3519746B2 - Manufacturing method of thermoplastic resin molded product - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates is intended appearance, mechanical strength, heat resistance, a method of manufacturing impact resistance and chemical resistance superior thermoplastic resin molded product, automotive parts,
Specifically, spoiler, door handle, wheel cover, fender panel, door panel, garnish,
Installation panel, console pox, electrical parts, specifically home appliances, office machines, office automation equipment, F
Provided is a method for producing a thermoplastic resin molded product suitable for equipment A, electric tools, communication devices and the like.

[0002]

2. Description of the Related Art In recent industrial fields, weight saving has been an important issue from the viewpoint of resource saving and energy saving, and resin parts, which were conventionally metal parts, are being actively promoted. Above all, the thermoplastic resin has excellent moldability,
It is widely used in various industrial fields, especially in the fields of automobiles and electric appliances, because it has a great degree of freedom in design, is lightweight, and has excellent durability. In addition, the market demand for these thermoplastic resins has diversified, and a single thermoplastic resin cannot be used. Therefore, a method of polymer alloy combining a plurality of thermoplastic resins is also widely used. Furthermore, in order to substitute for metals, various attempts have been made to increase strength and rigidity by adding various reinforcing agents to thermoplastic resins. Molded products of these thermoplastic resins are obtained by injection molding, but in the conventional technique, thermoplastic resins are mixed with impact modifiers, reinforcing agents, additives, etc., if necessary, and kneaded in an extruder or the like. It was melt-kneaded with a machine, pelletized and used for injection molding. It is possible to uniformly disperse the thermoplastic resin, impact modifier, toughening agent, additive, etc. by extrusion, melt-kneading, but due to thermal history, thermal deterioration, thermal decomposition, etc. occur.

For example, aromatic polycarbonate is widely used for automobile parts and electric parts because it has particularly excellent impact strength among mechanical strength, heat resistance and dimensional stability. However, since aromatic polycarbonate is inferior in chemical resistance, when it comes into contact with gasoline, oil, wax remover, etc. used in the automobile field,
Swelling or cracks may occur. Attempts have been made to compound polyester resins in order to improve the chemical resistance of aromatic polycarbonates. Although the chemical resistance of polycarbonate is improved by blending a polyester resin, the impact resistance may be lowered depending on the blending amount.
A material comprising an aromatic polycarbonate / polyester / impact modifier blended with an impact modifier to prevent such defects is widely used in automobile parts because it has excellent impact resistance, heat resistance, chemical resistance and dimensional stability. There is.

However, the aromatic polycarbonate and the polyester have the drawback that the performance, particularly the heat resistance, is lowered by the transesterification reaction during melt-kneading. That is, the extrusion melt-kneading process for obtaining a composition comprising an aromatic polycarbonate and a polyester, and the transesterification reaction is promoted when the residence time becomes long during the melt-kneading at the time of injection molding, and the heat resistance deteriorates and cannot be practically used.
As a material for automobile parts, it has a very narrow range of molding conditions. In addition, SBR is added to improve the impact resistance of polyphenylene ether, but the butadiene component in SBR is thermally decomposed during extrusion melt kneading, and the impact strength of the molded product after injection molding decreases, and yellowing occurs. Defective.

Further, polyethylene terephthalate, polybutylene terephthalate, polycarbonate and the like are
When extrusion-melting and kneading with glass fiber, there is a disadvantage that decomposition occurs due to an alkali component contained in the glass fiber and the mechanical strength is lowered due to a decrease in molecular weight. As described above, the extrusion melt-kneading step is a step necessary to uniformly disperse a plurality of materials in producing a polymer alloy or a fiber reinforced material. Not preferable.

[0006]

As described above, the thermoplastic resin injection-molded through the conventional extrusion melt-kneading process is subjected to a heat history, and the appearance, mechanical strength, heat resistance, impact resistance and chemical resistance are improved. Inferior in sex. Therefore, the present invention has solved such conventional problems, and is a thermoplastic resin molded article excellent in appearance, mechanical strength, heat resistance, impact resistance and chemical resistance.
It aims at providing the manufacturing method of.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned drawbacks, the present inventors have shown that a resin mixture consisting of a thermoplastic resin, an impact modifier, a reinforcing agent and an additive is extruded, melted and kneaded. It was found that by directly molding using an injection molding machine without undergoing heat treatment, a decrease in heat resistance can be prevented, and a thermoplastic resin molded product with excellent impact resistance, heat resistance, and dimensional stability can be obtained. Completed the invention. In injection molding, a thermoplastic resin molded product having excellent characteristics could be obtained by molding under a specific injection molding condition using a specific injection molding machine.

[0008]

The present invention comprises (a) a thermoplastic resin as an essential component, and (b) an impact modifier, (c) a reinforcing agent (excluding glass fiber) and / or (d) a resin containing an additive. A screw kneading section is directly used without a melt-kneading step of extruding a mixture obtained by mixing with a blender, and the screw kneading section is a Maddock type, dullage type, or with a pin, and the screw rotation speed is 30. ~ 120r
mp, melt-kneading and molding, and removing water and low molecular weight substances in the mixture from the vent section of the injection molding machine with a vent suction degree of 300 mmHg or more, and the resin mixture is (a) a thermoplastic resin. , 100 parts by weight, (b) more than 0 and 20 parts by weight of impact modifier, (c) more than 0 and not more than 70 parts by weight of reinforcing agent (excluding glass fiber), and / or (d) ) Provided is a method for producing a thermoplastic resin molded article, which comprises more than 0 and 15 parts by weight or less of an additive.

The structure of the present invention will be described in detail below. The thermoplastic resin of the present invention means polyethylene (PE), polypropylene (PP), polybutene, polyisobutylene,
Olefin resins exemplified by polymethylpentene-1, ethylene-propylene copolymer, etc., ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl acetate-vinyl chloride copolymer, polyvinyl acetal, polyvinyl acetate, vinyl alcohol- Vinyl acetate copolymer, substituted olefin polymer such as polyvinyl chloride (PVC), chlorinated polyethylene, chlorinated polypropylene, chlorinated polyolefin polymer such as chlorinated polyvinyl chloride, polytetrafluoroethylene (PTFE), Fluororesin such as polytetrafluoroethylene-propylene copolymer, vinylidene fluoride resin, polytetrafluoroethylene-hexafluoropropylene copolymer, polymethylmethacrylate (PMMA), ethylacrylate containing methylmethacrylate as a main component Over DOO, a copolymer of n- butyl acrylate, polyethyl acrylate, acrylate copolymers such as butyl polyacrylate, polystyrene (P
S), high impact polystyrene (HIPS), methyl methacrylate-styrene copolymer (MS), acrylonitrile-styrene copolymer (AS), acrylonitrile-butadiene-styrene copolymer (ABS), methyl methacrylate butadiene-styrene copolymer Polymer (M
BS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), methyl methacrylate-alkyl acrylate rubber-styrene copolymer (MAS), and other acrylonitrile-acrylic rubber-styrene disclosed in JP-A-48-48547. Copolymers, styrene polymers represented by acrylonitrile-chlorinated polyolefin-styrene copolymers disclosed in JP-A-48-42452, and nylon-6.
(PA6), Nylon-66 (PA66), Nylon-12 (PA12), Nylon-6, 12 (PA6,1
2), Nylon-11 (PA11), Nylon-46
(PA46), polyamide resin represented by nylon-MXD6 (PAMXD6), polyethylene terephthalate (PET), polybutylene terephthalate (PB)
T), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), cyclohexanedimethanol as a diol component or a polyester with phthalic acid using ethylene glycol or the like (PCTA,
PCTG) and other saturated polyester resins, liquid crystal polymers such as copolymers of polyhydroxybenzoic acid and polyethylene terephthalate, polyacetals (PO
M), polyvinyl acetal, polyester imide, polyamide imide, polyarylate, polyether ketone, polyester carbonate, polysulfone, polyether sulfone, polycarbonate (PC), polyphenylene ether (PPE), polyphenylene sulfide, etc. Etc. and a mixture of one or more selected from the above, for example, PC / styrene-based copolymer compositions such as PC / ABS, PC / MBS, PC / PET, PC / PBT,
PC / polyester resin compositions such as PC / PCTG, PC / PCTA, PPE / PS, PPE / HIPS, PP
E / PA6, PPE / PA66, PPE / PBT, PP
Examples thereof include polyphenylene ether resin compositions such as E / PA / PP and other thermoplastic resins. Among these thermoplastic resins, general-purpose engineering plastics such as PC, PET, PBT, polyamide, POM, PPE and their compositions are preferable, and PC and PPE and their compositions are particularly preferable.

Impact modifiers used in the present invention include polyester elastomers, MBS resins, MAS resins,
Acrylic ester-based core-shell graft copolymer, polyolefin and polyolefin-based elastomer Styrene-based core-shell graft copolymer, S
One or more soft resins selected from the group consisting of BRSEBS-1 polyurethane elastomers. Here, as the polyester elastomer, a usual polyester elastomer containing 30 to 70% by weight of a soft segment can be used, but in the present invention, (1) a dicarboxylic acid containing 70 mol% or more of terephthalic acid or an ester thereof. Formable derivative, (2)
The component (3) is a polyester in which the component (3) is a low-molecular-weight glycol containing 70 mol% or more of tetramethylene glycol or an ester-forming derivative thereof, and (3) a poly (oxyalkylene) glycol having an average molecular weight of 500 to 5000 or an ester-forming derivative thereof. 70-9 in elastomer
Those obtained by polycondensation at a ratio of 0% by weight are preferable.

As the dicarboxylic acid containing 70 mol% or more of terephthalic acid or the ester-forming derivative thereof in the above (1), which is used as a dicarboxylic acid component other than terephthalic acid, aliphatic, alicyclic and aromatic compounds can be used. It may be any of the above groups and usually has a molecular weight of 300 or less, and examples thereof include adipic acid, sebacic acid, cyclohexyldicarboxylic acid, isophthalic acid and naphthalenedicarboxylic acid. As the glycol (2), the same diols as those used for the component (b) are exemplified. The poly (oxyalkylene) glycol of (3) is
The average molecular weight is 500 to 5000, and the number ratio of carbon atoms and oxygen atoms contained in this glycol is 2.0 to
4.3 is preferable, and examples thereof include poly (tetramethylene oxide) glycol, poly (ethylene oxide) glycol, poly (propylene oxide) glycol, and copolymers thereof. Particularly, poly (tetramethylene oxide) glycol is preferable. .

The polycondensation of the above (1), (2) and (3) is carried out by the component (3) in the obtained polyester elastomer.
Is 70 to 90% by weight. Furthermore, the polymerization degree of the polyester elastomer is chlorophenol 1.2.
The reduced viscosity of a solution having a concentration of g / dl at 35 ° C. is 0.5
Those in the range of to 5.0 are preferable. As such a polyester elastomer, one commercially available under the trade name “Perprene P30B” from Toyobo Co., Ltd. is preferably used.

The MBS resin is a bulk polymerization of one or more of a methacrylic acid ester, an aromatic monovinyl compound, and a vinyl cyanide compound in a butadiene rubber polymer such as polybutadiene or butadiene-styrene copolymer.
Graft polymerization is carried out by a method such as suspension polymerization, bulk suspension polymerization, solution polymerization or emulsion polymerization, particularly emulsion polymerization. Here, the amount of the butadiene-based polymer used is 1
0-85% by weight, preferably 30-70% by weight,
When the butadiene-based polymer is a copolymer, it is preferable to use one having a butadiene component in the copolymer of 50% by weight or more. When the amount of the butadiene component is less than 10% by weight, the resulting composition has low impact resistance, and when it exceeds 85% by weight, the moldability of the obtained composition is deteriorated, which is not preferable.
As the methacrylic acid ester, an alkyl ester having 1 to 4 carbon atoms, particularly methyl methacrylate is preferable.
Examples of the aromatic monovinyl compound include styrene, halogenated styrene, vinyltoluene, α-methylstyrene, vinylnaphthalene and the like, and styrene is particularly preferable. Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, and α-halogenated acrylonitrile, and acrylonitrile is particularly preferable.

The MAS resin of (1) is a rubber (I) mainly composed of an alkyl ester of acrylic acid or methacrylic acid having an alkyl group having 1 to 18 carbon atoms, and an aromatic hydrocarbon polymer or aromatic hydrocarbon. A copolymer (II) comprising a monomer and one or more vinyl or vinylidene monomers, and a part or all of the monomer (II) is polymerized in the presence of (I). It is preferable that the obtained rubber has a rubber content of 5 to 40% by weight. Rubber (I)
Contains 70% by weight or more, preferably 80% by weight, of one or more components of an alkyl ester of acrylic acid or methacrylic acid having 1 to 18 carbon atoms, and a vinyl aromatic monomer, cyan which is copolymerizable therewith It contains 30% by weight or less of vinyl chloride and an aliphatic vinyl ester component, and is cross-linked so that the second-order transition temperature is 0 ° C. or less and the swelling degree measured at 30 ° C. in methyl ethyl ketone is 4 to 12. Those are preferable. The crosslinking is carried out by reacting a polyfunctional monomer such as benzoyl peroxide or other peroxide, divinylbenzene, ethylene dimethacrylate, allyl cyanurate, triallyl phosphate or the like in an amount of 10% by weight or less. Further, (II) is a homopolymer or copolymer composed of 40 to 100% by weight of a vinyl aromatic monomer and 60 to 0% by weight of vinyl cyanide and an aliphatic vinyl ester.

The acrylic ester type core-shell graft copolymer of (1) means (1) an alkyl group having 2 to 1 carbon atoms.
2 to 70% by weight of an alkyl ester of acrylic acid of 2 and 30 to 5% by weight of a polyfunctional polymerizable monomer having a conjugated diene type double bond represented by butadiene as essential components,
(II) -1.50 to 80% by weight, to 50 to 75% by weight of a core made of a crosslinked rubber copolymer obtained by copolymerization by an emulsion polymerization method by adding 0.01 to 3% by weight of a crosslinking agent. Of styrene and 50 to 20% by weight of methyl methacrylate in the presence of 0.01 to 2% by weight of a crosslinking agent, or (II) -2.10.
Intermediate layer 45 obtained by graft-polymerizing a monomer mixture of 50% by weight of acrylonitrile, 10 to 80% by weight of styrene and 10 to 50% by weight of methyl methacrylate in the presence of 0.01 to 2% by weight of a crosslinking agent. 10% by weight, then added (III) methyl methacrylate to 0.0
The shell is formed by graft polymerization in the presence of 1 to 2% by weight of a cross-linking agent and forms 5 to 25% by weight of the shell. Such an acrylic acid ester-based core-shell graft copolymer is available from Kureha Chemical Industry Co., Ltd. under the trade name "HIA-1".
Resins commercially available as "5", "HIA-28", and "HIA-30" are preferably used.

Polyolefin is polyethylene,
Polypropylene, polybutene-1, ethylene-propylene copolymer, ethylene-propylene-non-conjugated diene copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, etc., having a low glass transition temperature, especially It is preferably 40 ° C. or lower.

The crosslinked polyolefin-based elastomer of (1) is one in which an ethylene-propylene copolymer is the main constituent component, and this is crosslinked with a diene compound using a peroxide as a catalyst. As such a cross-linked olefin elastomer, one commercially available from Mitsui Petrochemical Co., Ltd. under the trade name of "MILASTOMER" is preferably used.

The styrene-based core-shell graft copolymer of can be obtained by a continuous multi-stage seed emulsion polymerization method in which the polymer of the previous stage is sequentially coated with the polymer of the latter stage. In the invention, three-step emulsion polymerization is carried out. The first-stage polymerization is formed by polymerizing a vinyl aromatic compound. Examples of vinyl aromatic compounds include styrene, vinyltoluene, α-methylstyrene, chlorostyrene and the like. Particularly, styrene is preferably used. A vinyl aromatic compound and a conjugated diene that can be copolymerized can be copolymerized in the first-stage polymerization. When the first stage polymerization does not contain a conjugated diene, the low temperature impact resistance can be improved by using a small amount of a crosslinkable monomer. In the first stage polymerization, a non-aromatic monomer that can be copolymerized with the aromatic vinyl monomer can be used. The amount used is preferably in the range of 50% by weight or less, and more preferably in the range of 20% by weight or less, based on the total amount of the monomers used for the first-stage polymerization. Examples of such non-aromatic monomers include ethyl acrylate, alkyl acrylates such as butyl acrylate,
Examples thereof include alkyl methacrylate such as methyl methacrylate and butyl methacrylate, vinyl cyanide such as acrylonitrile and methacrylonitrile, and vinylidene cyanide. The core layer obtained in the first-stage polymerization may be crosslinked with a crosslinkable monomer. The amount of the crosslinkable monomer used is based on the total amount of the monomers used for the first-stage polymerization,
Usually, it is in the range of 30% by weight or less, preferably 0.5.
To 20% by weight, more preferably 5 to 15
It is in the range of% by weight. As such a monomer, a monomer having two or more polymerizable ethylenic unsaturated bonds in the molecule is preferably used. Specific examples include aromatic divinyl monomers and polyfunctional (meth) acrylates. Particularly, divinylbenzene is preferably used. Grafted monomers can also be used in the first-stage polymerization. The amount used is usually in the range of 5% by weight or less, and preferably in the range of 0.1 to 2% by weight, based on the total amount of the monomers used in the first-stage polymerization. As such a graft monomer, a monomer having two or more ethylenically unsaturated bonds having different reactivity in the molecule is used. Specific examples include allyl (meth) acrylate, diallyl maleate, diallyl fumarate,
Examples include unsaturated carboxylic acid allyl esters such as diallyl itaconate. Of these, allyl methacrylate is particularly preferably used.

The weight of the second stage is a glass transition temperature of -3 by polymerizing a conjugated diene or an alkyl acrylate having an alkyl group having 2 to 8 carbon atoms or a mixture thereof.
It forms a rubbery polymer below 0 ° C. Examples of such conjugated dienes include butadiene, isoprene, and chloroprene. In particular, butadiene is preferably used. Examples of the alkyl acrylate having an alkyl group of 2 to 8 include ethyl acrylate, propyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate and the like, but butyl acrylate and 2-ethylhexyl acrylate are particularly preferably used. In the second-stage polymerization, a monomer copolymerizable with a conjugated diene and an alkyl acrylate, for example, styrene, vinyltoluene, aromatic vinyl such as α-methylstyrene, aromatic vinylidene, acrylonitrile, vinyl cyanide such as methacrylonitrile, It is also possible to copolymerize vinylidene cyanide, alkyl methacrylate such as methyl methacrylate and butyl methacrylate. In the second-stage polymerization, the intermediate layer of the rubber-like polymer may also be crosslinked with the above-mentioned crosslinkable monomer.

The polymerization for forming the outermost layer in the third step also uses an aromatic vinyl monomer and has a glass transition temperature of 5
A hard polymer at 0 ° C. or higher is formed so as to cover the rubber-like polymer. As the aromatic vinyl monomer,
For example, styrene, vinyltoluene, α-methylstyrene, monochlorostyrene, 3,4-dichlorostyrene,
Although bromostyrene and the like can be mentioned, styrene is particularly preferably used. Also in this third stage polymerization, a non-aromatic monomer that can be copolymerized with the aromatic vinyl monomer can be used. The amount used is preferably in the range of 50% by weight or less, and more preferably in the range of 30% by weight or less, based on the total amount of the monomers used in the third-stage polymerization. Examples of such non-aromatic monomers include alkyl acrylates such as ethyl acrylate and butyl acrylate, alkyl methacrylates such as methyl methacrylate and butyl methacrylate, cyanide such as acrylonitrile and methacrylonitrile. Examples thereof include vinyl and vinylidene cyanide. Further, the outermost layer obtained by the third-stage polymerization may also be crosslinked with the above-mentioned crosslinkable monomer. As such a styrene-based core-shell graft polymer, those commercially available under the trade name "STAPHYLOID" from Takeda Pharmaceutical Co., Ltd. are preferably used.

The SBR is composed of a non-elastomeric polymer block containing a vinyl aromatic hydrocarbon polymer and an elastomeric polymer block containing a conjugated diene compound polymer, and the composition ratio is 10/90 to 55 /. The range is 45. The vinyl aromatic hydrocarbon polymer is preferably polystyrene, and the conjugated diene compound polymer is preferably a polybutadiene block or a polyisoprene block. As such an elastomer, those commercially available under the trade name “Califlex” from Shell Kagaku are preferably used.

SEBS is a hydrogenated ABA block copolymer, and the central block B is a conjugated diene hydrocarbon compound, usually a butadiene block or a polyisoprene block, which should be hydrogenated. Is a block in which the double bond in polybutadiene or polyisoprene is converted to a saturated hydrocarbon, and the terminal block A is a polymer block of vinyl aromatic hydrocarbon, and is preferably a block made of polystyrene. The molecular weight of the terminal block A is 4,000 to 115,000.
0. Preferably, the molecular weight of the central block B is 5,000 to 30,000 and the molecular weight of the central block B is 20,000 to 450,000. It is preferably 25,000 to 150,000. Such hydrogenated ABA type block copolymers are commercially available from Shell Chemistry under the trade name of "Clayton G1650, G".
1651, G1657 "and those sold by Kuraray Co., Ltd. under the trade name" Septon 2002, 2003, 2023 "are preferably used.

The polyurethane elastomer of -1 is obtained by using diisocyanate and polyol as a base material, and combining this with various chain extenders or crosslinking agents. Examples of the diisocyanate include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, naphthylene-1,5-diisocyanate, hexamethylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate, isophorone diisocyanate, Examples include isopropylidene bis (4-cyclohexyl isocyanate) and the like. As the polyol component, polyester polyol, polyether polyol, acrylic polyol,
Halogen-containing polyols, phosphorus-containing polyols and the like are used. Examples of the polyether polyol include polyoxypropylene glycol, polyoxypropylene polyoxyethylene glycol and polyoxytetramethylene glycol, and examples of the polyester glycol include 1,2-ethanediol, 1,4-butanediol, diethylene glycol and hexamethylene. Those obtained by the condensation of glycol and the like with adipic acid, as the acid component, phthalic acid, terephthalic acid, maleic acid, sebacic acid, as the hydroxy compound, propylene glycol, neopentyl glycol, trimethylolpropane, hexanetriol,
Glycerin, pentaerythritol and the like are also used. Further, a polylactone ester polyol obtained by ring-opening caprolactone is also used.

Further, as a chain extender and a crosslinking agent, 1,2-
Ethylene glycol, 1,3-butanediol, 1,4
-Butylene glycol, 2,2-dimethyl-1,3-propanediol, 1,2-propylene glycol, hexamethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, trimethylolpropane , Glycerin, 1,2,6-hexanetriol, 4,4'-diaminodiphenylmethane, hydrogenated 4,4'-diaminodiphenylmethane, isophoronediamine, hexamethylenediamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane, Tolylenediamine, ethanolamine, triethanolamine, ethylenediamine and the like are used. These polyurethane elastomers are commercially available. Specific examples include Paraprene manufactured by Nippon Polyurethane Industry Co., Ltd. and Elastollan manufactured by Takeda Badish Co., Ltd.

The reinforcing agent of the present invention is for improving various properties such as strength, rigidity and heat resistance of the thermoplastic resin molded product, and is usually used as an inorganic or organic filler. Specific examples of the inorganic filler include glass fibers, glass beads, glass flakes, glass-based reinforcing agents such as glass balloons, talc, clay, mica, wollastonite, montmorillonite, magnesium silicate, and aluminum silicate. Acid salt type strengthening agents, sulfate type strengthening agents such as barium sulfate, carbonate type strengthening agents such as calcium carbonate, magnesium carbonate and zinc carbonate,
Hydroxide strengthening agents such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, silica, alumina, titanium oxide, antimony oxide, zinc oxide, magnesium oxide,
Oxide reinforcing agents such as calcium oxide and silicon oxide, carbon-based reinforcing agents such as carbon black, graphite and carbon fiber,
Examples thereof include aluminum, copper, iron, boron, stainless steel fibers, metal-based reinforcing agents such as powder and flakes, silicon carbide, boron nitride, potassium titanate whiskers, aluminum borate whiskers, and the like. Specific examples of the organic filler include natural products such as wood powder, paper, bamboo and cloth, and synthetic fibers such as nylon fiber, polyester fiber and aromatic polyamide fiber. In the present invention, one kind or a mixture of two or more kinds of these inorganic or organic fillers can be used.

The additive of the present invention imparts moldability and thermal stability when molding a thermoplastic resin, and improves durability under the environment where the thermoplastic resin molded product is used. It is a thing. Specifically, stabilizers (antioxidants,
Heat deterioration inhibitor, hydrolysis inhibitor), light stabilizer, ultraviolet absorber, lubricant, release agent, plasticizer, slidability improver, flame retardant,
It is a foaming agent, an antistatic agent, a cross-linking agent, a curing agent, a vulcanizing agent, a dispersant, etc. These additives can be used alone or in combination of two or more.

In the thermoplastic resin molded article of the present invention, the components (a), (b), (c) and (d) of the present invention described above are contained in (b) per 100 parts by weight of the thermoplastic resin (a). Impact modifier 0 to 20 parts by weight (c) Reinforcing agent 0 to 70 parts by weight (d) Additive 0 to 15 parts by weight.

If the amount of the impact modifier (b) is more than 20 parts by weight, heat resistance, mechanical strength, etc. are deteriorated. If the amount of the reinforcing agent (c) exceeds 70 parts by weight, the fluidity is remarkably reduced, the moldability is deteriorated, and the screw and cylinder of the molding machine are worn. (D) Heat resistance when the additive amount exceeds 15 parts by weight,
The mechanical strength etc. is reduced.

As described above, the thermoplastic resin molded article of the present invention can be blended with pigments, dyes and the like as desired, and further, other resin components and fillers can be added within the range not impairing the characteristics of the present invention. An agent may be included.

The thermoplastic resin molded article of the present invention comprises (a) a thermoplastic resin, (b) an impact modifier, (c) a reinforcing agent, and (d).
It can be obtained by extruding a mixture consisting of additives and directly injection-molding it without going through the melt-kneading step.These mixtures contain water and low molecular weight compounds, and can be molded using a normal injection molding machine. Then, decomposition and foaming occur, which is inconvenient because of poor appearance and reduced mechanical strength. In the present invention, a vent type injection molding machine is used to remove water and low molecular weight substances. Furthermore, the suction degree of the vent part is set to 300
When it is at least mmHg, it is possible to obtain an excellent thermoplastic resin molded product which does not have the above-mentioned drawbacks. When the suction degree of the vent portion is 300 mmHg or less, the removal of water and low molecular weight substances becomes insufficient, resulting in poor appearance of the thermoplastic resin molded product and deterioration of mechanical strength.

Further, in the present invention, a mixture comprising (a) a thermoplastic resin, (b) an impact modifier, (c) a reinforcing agent, and (d) an additive is extruded and directly subjected to no melt-kneading step. Since injection molding is performed, it is necessary that these mixtures be sufficiently melt-kneaded during injection molding to form a uniform composition. With a full-flight type screw used in an ordinary injection molding machine, uniform melt-kneading is insufficient, and the resulting thermoplastic resin molded product has a poor appearance and mechanical strength is reduced. In order to obtain a thermoplastic resin molded product that is capable of uniform melt-kneading and has excellent appearance and mechanical strength, a high kneading zone where a maddock, dullage, or pins are used in the kneading part of the screw of a vent-type injection molding machine. It is necessary to use the screw installed in.

Regarding the molding conditions for molding the thermoplastic resin molded article of the present invention, the resin temperature at the time of injection molding is 10 ° C. or more and 70 ° C. or less, preferably 2 ° C. or more, from the melting point of the thermoplastic resin.
It is in the range of 0 ° C to 50 ° C. Melt-kneading is insufficient at a temperature lower than 10 ° C., and decomposition occurs at a temperature higher than 70 ° C., and in both cases, poor appearance and reduced mechanical strength,
Heat resistance is reduced. The screw rotation speed during injection molding is 30 to 120 rpm, preferably 50 to 100 rp.
m, particularly preferably in the range of 60 to 90 rpm. When the screw rotation speed is less than 30 rpm, melt-kneading is insufficient, and when it exceeds 120 rpm, decomposition occurs, which is not preferable.

[0034]

EXAMPLES The present invention will be described in detail below with reference to Examples and Comparative Examples, but "parts" are based on weight unless otherwise specified. Examples 1 to 12 and Comparative Examples 1 to 6 Aromatic polycarbonate using bisphenol A (BPA) as a raw material (Mitsubishi Gas Chemical Co., Ltd., trade name: Iupilon E-2000, referred to as PC), polyethylene terephthalate (Mitsubishi Rayon) Co., Ltd., trade name: Dyanite PA200, referred to as PET), polybutylene terephthalate (manufactured by Polyplastics Co., Ltd., trade name: Duranex 2002, referred to as PBT), aromatic polycarbonate oligomer (viscosity average degree of polymerization 7). No. 1), and an impact modifier described below are weighed in the ratios shown in Tables 1 to 3, placed in a blender and mixed for 30 minutes, and then a vent type injection molding machine (manufactured by Japan Steel Works, Ltd.). J220E
V) was used to mold a test piece for measuring physical properties, and physical properties were measured. The results are shown in Tables 1 to 3. The abbreviations in the table are as follows. Examples 10, 11, and 12 are
This is a modification of the type of impact modifier (ELA). Comparison
Examples 1 and 2 have the same composition as Examples 1 and 2
The oil temperature was changed from 250 ° C. and 300 ° C. of Examples 1 and 2 respectively.
In this case, the temperature is changed to 220 ° C and 340 ° C. Comparative Example 3
In the same composition as in Examples 3, 4, 5
The types of madok, dulmage, and pie of Examples 3, 4, and 5
In this case, the flight was changed to full flight. Comparative example
4 and 5 were the same composition as in Examples 6 and 7
Liu rotation speed is 40 rpm of Examples 6 and 7, 120 r
pm to 20 rpm and 150 rpm respectively
It is. Comparative Example 6 has the same composition as Example 8.
Vent suction degree was 20 against 400 mmHg of Example 8.
In this case, the value is changed to 0 mmHg. Comparative Examples 7 and 8
In the same composition as in Example 9 is the vent type of Example 9.
Full flight vinegar general of the injection molding machine for the injection molding machine
This is the case using clew.

Comparative Examples 7 to 8 PC, PBT and impact modifier were weighed in the ratios shown in Tables 1 to 3, placed in a blender and mixed for 30 minutes, and then an extruder with a vent (40 mm diameter, L / D =). No. 28, cylinder temperature 240 to 260 ° C.) and melt-kneading and extruding to form pellets. 120 with hot air dryer
Dry for 5 hours at ℃, and use a normal cylinder (injection without vent)
A tester for measuring physical properties was molded using a molding machine and the physical properties were measured. The results are shown in 1-3.

Impact modifier (described as ELA): Polyester elastomer (manufactured by Toyobo Co., Ltd., trade name: Perprene P30B, described as P30B) MBS resin (manufactured by Japan Synthetic Rubber Co., Ltd., trade name: JSR)
MBS67, referred to as MBS) MAS resin (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Metabrene W529, referred to as MAS) acrylic acid ester-based core-shell graft polymer (manufactured by Kureha Chemical Co., Ltd., trade names: HIA28, HIA) Polyolefin (manufactured by Nippon Unicar Co., Ltd., trade name: D
PDJ-6169, ethylene ethyl acrylate copolymer, referred to as EEA) Crosslinked olefin elastomer (Mitsui Petrochemical Co., Ltd.)
Product name: Mirastomer, CEPM) Styrene core-shell graft copolymer (Takeda Pharmaceutical Co., Ltd. product name: Staphyroid MG-101)
Abbreviation TS: Tensile strength Kg / cm ² TE: Tensile elongation at break% FS: Bending strength Kg / cm ² FM: Bending elastic modulus Kg / cm ² DTUL: Deflection temperature under load (° C. Load 18. 6 kg / c
m ² ) IZ: Izod impact strength kg-cm / cm Q: Flowability A part of the molded product was cut out and heated from 280 ° C. to a nozzle of 1 mm diameter and 10 mm length, 160 kg.
Outflow velocity when flowing under the load of 10 ^-2 cc / sec

Examples 13 to 15 Comparative Examples 9 to 10 An automobile spoiler (product thickness: 4 mm) was molded from the same composition as in Example 3 using a vent type injection molding machine, and a strength test was carried out. The results are shown in Table 4. In addition, Example 3
A blend similar to the above was put in a blender and mixed for 30 minutes, and then an extruder with a vent (40 mm diameter, L / D = 2)
8. Melt-kneading and extruding at a cylinder temperature of 240 to 260 ° C.) to obtain pellets. The pellets are dried in a hot air dryer at 120 ° C for 5 hours and then dried in a normal cylinder (without vent).
Then, a spoiler was molded with an injection molding machine) and a strength test was performed. The results are shown in Table 4. The strength of the spoiler is
Five 100 mm square test pieces were cut out from the spoiler molded product, and a weight of 4 kg was dropped from various heights onto the surface of the test piece to examine the presence or absence of breakage. Test temperature is room temperature (23 ℃)
And -40 ° C. Comparative Examples 9 and 10 are the same as Example 1.
Odor of the same composition as 3, 14, 15 (equivalent to Example 3)
As for the form of the material, powder mixture of Examples 13, 14 and 15
This is a case where pellets (P) are used instead of (F).

The molding the car door handle with a vented injection molding machine similar to formulation as Examples 16 to 18 Comparative Examples 11 to 12 Example 1 was conducted to a strength test.
The results are shown in Table 5. Further, the same composition as in Example 1 was put into a blender and mixed for 30 minutes, and then melt-kneaded and extruded by a extruder with a vent (40 mm diameter, L / D = 28, cylinder temperature 240 to 260 ° C.) to form pellets. And The pellets are heated in a hot air dryer at 120 ° C for 5
Dried for an hour, and then a normal cylinder (ventless injection molding machine)
A car door handle was molded at and a strength test was conducted. The results are shown in Table 5. The strength of the automobile door handle was the breaking strength when a case was fixed, a hook was hooked on the handle, and a tensile test was performed at a speed of 10 mm / min. Table 5 also shows the result when the destructive test was performed after being immersed in gasoline. Comparative Examples 11 and 12
Same composition as in Examples 16, 17 and 18 (same as Example 1)
Etc.), the form of the material is the powder of Examples 16, 17, and 18
Case where pellet (P) is changed to powder mixture (F)
Is.

Examples 19 to 21 Intrinsic viscosity of 0.45 measured in chloroform at 25 ° C.
dl / g, poly (2,6-dimethyl-1,4-o)
-Phenylene) ether powder, impact-resistant polystyrene (Dialex YH-478 manufactured by Mitsubishi Kasei Polytech), and hydrogenated ABA type block copolymer elastic body (Clayton G1650 manufactured by Shell Chemical), brominated as a heat-resistant agent Polystyrene and antimony trioxide were weighed in the ratios shown in Table 6, placed in a blender and mixed for 30 minutes.
Bent type injection molding machine (J220E manufactured by Japan Steel Works, Ltd.)
Table 6 shows the results of measuring the physical properties by molding a test piece for measuring physical properties using V). In the system to which the flame retardant was added, a combustion test was conducted according to UL94. The thickness of the test piece is 1.6 mm.

Comparative Examples 13 to 15 The materials used in Examples 19 to 21 were weighed in the ratios shown in Table 6, placed in a blender and mixed for 30 minutes, and then an extruder with a vent (diameter of 40 mm, L / D =). No. 28, cylinder temperature 240 to 260 ° C.) and melt-kneading and extruding to form pellets. The pellets are heated to 100 with a hot air dryer.
Table 6 shows the results of measuring the physical properties by drying at 5 ° C. for 5 hours, molding a test piece for measuring physical properties using a normal cylinder.

Examples 22 to 24 Comparative Examples 16 to 17 Polyphenylene ether powder 32 used in Example 19
Part, impact-resistant polystyrene 61 parts, hydrogenated ABA type block copolymer elastic body 6 parts, ethylene-α-olefin cooligomer (Mitsui Petrochemical Lucant HC-60
0) 1 part, titanium oxide 4 parts as a colorant and carbon black 0.05 part, and tetrakis (2,4-di.t-butylphenyl) 4,4 'biphenylene diphosphonate 0.5 part as a stabilizer. 0.3 part of zinc oxide was weighed, put in a blender and mixed for 30 minutes, and then an automobile wheel cover was molded using a vent type injection molding machine, and a strength test was carried out. The results are shown in Table 7. In addition, the same formulation,
The mixture was put in a blender and mixed for 30 minutes, and then melt-kneaded and extruded with a vented extruder (40 mm diameter, L / D = 28, cylinder temperature 240 to 260 ° C.) to obtain pellets. The pellets were dried with a hot air dryer at 100 ° C. for 5 hours, and an automobile wheel cover was molded with a normal cylinder (ventless injection molding machine) to carry out a strength test. The results are shown in Table 7. The strength of the car wheel cover is
A weight of 0.5 kg was dropped from various heights onto the center surface of the foil cover, and the presence or absence of breakage was examined. The test temperature is room temperature (2
3 ° C) and -40 ° C. Comparative Examples 16 and 17 are actually
Form of material in the same composition as in Examples 22, 23 and 24
To the powder mixture (F) of Examples 22, 23 and 24
In this case, the pellet (P) is used.

[0042]

[0043]

Examples 25 to 27 PC and impact modifier used in Example 1, ABS (Santac GT-10 manufactured by Mitsui Petrochemical Co., Ltd.), a carbonate oligomer mainly containing tetrabromobisphenol A as a flame retardant (Mitsubishi Gas Chemical Co., Ltd. FR-34 manufactured by Co., Ltd. and antimony trioxide, and tris (2,4 di, t- as a stabilizer.
Butylphenyl) phosphite was weighed in the ratio shown in Table 7, put in a blender and mixed for 30 minutes, and then a vent type injection molding machine (J220E manufactured by Japan Steel Works Ltd.).
Table 8 shows the results of measuring physical properties by molding test pieces for measuring physical properties using V). In the system to which the flame retardant was added, a combustion test was conducted according to UL94. The thickness of the test piece is 1.6 mm.

Comparative Examples 18 to 20 The materials used in Examples 25 to 27 were weighed in the ratios shown in Table 8 , placed in a blender and mixed for 30 minutes, and then a vented extruder (40 mm diameter, L / D =). No. 28, cylinder temperature 240 to 260 ° C.) and melt-kneading and extruding to form pellets. The pellets are heated in a hot air dryer at 100 ° C,
Dry for 5 hours, then use normal cylinder (vent molding without vent)
Table 8 shows the results of measurement of physical properties by molding a test piece for measuring physical properties using a machine .

Examples 28 to 30 Comparative Examples 21 to 22 Using the same composition as in Example 27 , a printer housing (product thickness: 2 mm) was molded using a vent type injection molding machine, and a strength test was carried out. The results are shown in Table 9 . Also, the same composition as in Example 27 was put in a blender and mixed for 30 minutes, and then the extruder with a vent (40 mm
(Diameter, L / D = 28, cylinder temperature 240-260 ° C)
The mixture was melt-kneaded and extruded into pellets. The pellets were dried with a hot air dryer at 100 ° C. for 5 hours, a printer housing was molded with a normal cylinder (ventless injection molding machine), and a strength test was performed. The results are shown in Table 9 . Regarding the strength of the housing, five 100 mm square test pieces were cut out from the molded product, and a weight of 1 kg was dropped from various heights onto the surface of the test piece to check for the presence or absence of breakage. The test temperatures are room temperature (23 ° C) and -40 ° C. Further, a test piece according to UL94 was cut out from the molded product and a combustion test was performed. Comparative Examples 21 and 22 are the same as Examples 28, 29 and 30.
Example of material morphology in the same composition (Example 27)
Pellets for powder mixture (F) of 28, 29, 30
This is the case where it is changed to (P).

From the above examples and comparative examples, the following is considered. Examples 9 to 36 and Comparative Examples for appearance and physical property values of a molded product using a direct injection molding machine without the extrusion melt-kneading step of the present invention and a conventional molded product molded by extrusion melt-kneading 7 to 26 were compared. When there is no retention in the molding machine cylinder for both the product of the present invention and the conventional product,
The physical properties of the product of the present invention are superior to those of the conventional product. For example, comparison between Examples 13 and 15 and Comparative Example 9 and Example 19
The comparison between Comparative Example 13 and Comparative Example 13 clearly shows the difference, and the other Examples and Comparative Examples also clearly show the difference. Further, when retention occurs in the cylinder of the molding machine for some reason, as a result of comparison between the product of the present invention and the conventional product, even when retention occurs, the physical properties of the product of the present invention are higher than those of the conventional product. Are better. For example, the difference is clear in the comparison between Example 9 and Comparative Example 8 and the comparison between Example 14 and Comparative Example 10. The difference is clear also in the other examples and comparative examples. As a result of comparing the effects of the resin temperature during injection molding with Examples 1 and 2 and Comparative Examples 1 and 2, it was found that there is an optimum range (10 ° C to 70 ° C below the melting point). Regarding the type of screw of the injection molding machine, Example 3 to
As a result of examination in Example 5 and Comparative Example 3, it was found that the mudock, dulmage and pin showed better results than the conventional full flight. Rotational Speed of Screw of Injection Molding Machine Example 6-
7 and Comparative Examples 4 to 5, the optimum range (30
~ 120 rpm). As a result of examining the suction degree of the vent part of the injection molding machine in Example 8 and Comparative Example 6, a certain value or more (300 mmH
It has been found necessary.

[0048]

INDUSTRIAL APPLICABILITY The thermoplastic resin molded article of the present invention is produced by directly using an injection molding machine without extruding a resin mixture consisting of a thermoplastic resin, an impact modifier, a reinforcing agent, and an additive and performing a melt-kneading step. Since it is obtained by molding, it is excellent in appearance, mechanical strength, heat resistance, impact resistance, and chemical resistance, and a molded product suitable for automobile parts, electrical parts, etc. is provided.

[0049]

[Table 1]

[0050]

[Table 2]

[0051]

[Table 3]

[0052]

[Table 4]

[0053]

[Table 5]

[0054]

[Table 6]

[0055]

[Table 7]

[0056]

[0057]

[0058]

[Table 8]

[0059]

[Table 9]

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Tsutomu Miyoshi 5-6-2 Higashi-Hachiman, Hiratsuka-shi, Kanagawa Mitsubishi Gas Chemical Co., Ltd. Plastic Center (72) Goro Shimaoka 5-6, Higashi-Hachiman, Hiratsuka-shi, Kanagawa No. 2 Mitsubishi Gas Chemical Co., Ltd. Plastics Center (72) Inventor Daisuke Sanada 5-6-2 Higashiyawata, Hiratsuka City, Kanagawa Prefecture Mitsubishi Gas Chemical Co., Ltd. (72) Tokuzo Hirabayashi Asahi Kariya City, Aichi Prefecture 2-chome, Aishin Seiki Co., Ltd. (72) Inventor Tadahiko Obama 2-chome, Asahi-cho, Kariya City, Aichi Prefecture In-house Aisin Seiki Co., Ltd. (72) Yoshiro Hattori 2-chome, Asahi-cho, Kariya City, Aichi Prefecture Address Aisin Seiki Co., Ltd. (72) Inventor Atsushi Teraoka Hiroshima City, Hiroshima Prefecture 1-6-1, Funakoshi-Minami, Gei-ku, Japan Steel Works, Ltd. (72) Masashi Kato 1-6-1, Funakoshi-Minami, Aki-ku, Hiroshima City, Hiroshima Prefecture (56) Reference: Japanese Patent Laid-Open No. 4 -163013 (JP, A) JP 59-194821 (JP, A) JP 52-66569 (JP, A) JP 58-183230 (JP, A) JP 63-265613 (JP, A) ) JP-A-6-8278 (JP, A) JP-A-59-169826 (JP, A) Actually opened 62-70913 (JP, U) Actually opened 58-64420 (JP, U) JP-B 56- 47847 (JP, B2) On-site manual XI roll Kneading processing of plastic and its equipment (thermoplastic resin), Japan, Institute for Chemical Research, April 1972, pp. 84-85 (58) Fields investigated (Int.Cl. ⁷ , DB name) B29C 45/00-45/84

Claims (2)

(57) [Claims] 1. A blender comprising a resin containing (a) a thermoplastic resin as an essential component, and further containing (b) an impact modifier, (c) a reinforcing agent (excluding glass fiber) and / or (d) an additive. Extruding the mixture obtained by mixing in the above, without directly going through the melt-kneading step, the screw kneading section directly uses a vent-type injection molding machine having a Maddock type, a dullage type or a pin, and the screw rotation speed is 30 to 30. At 120 rpm,
Melt-kneading and molding are performed, and water and low molecular weight substances in the mixture are discharged and removed from the vent section of the injection molding machine at a vent suction degree of 300 mmHg or more, and the resin mixture is (a) thermoplastic resin, 100 parts by weight. (B) impact modifier to more than 0 and 20 parts by weight or less, (c) reinforcing agent (excluding glass fiber) to more than 0 and 70 parts by weight or less, and / or (d) additive. Of more than 0 and 15 parts by weight or less is included. Temperature wherein the resin during the vent type injection molding, the manufacture of the thermoplastic resin molded article according to claim 1, wherein in the range of 10 ° C. or higher 70 ° C. less than the melting point of the thermoplastic resin Method.