WO2005030819A1 - エンジニアリングプラスチック用流動性向上剤およびこれを含有する熱可塑性樹脂組成物ならびにその成形品 - Google Patents
エンジニアリングプラスチック用流動性向上剤およびこれを含有する熱可塑性樹脂組成物ならびにその成形品 Download PDFInfo
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- WO2005030819A1 WO2005030819A1 PCT/JP2004/014393 JP2004014393W WO2005030819A1 WO 2005030819 A1 WO2005030819 A1 WO 2005030819A1 JP 2004014393 W JP2004014393 W JP 2004014393W WO 2005030819 A1 WO2005030819 A1 WO 2005030819A1
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- fluidity improver
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
Definitions
- Fluidity improver for engineering plastics thermoplastic resin composition containing the same, and molded article thereof
- the present invention relates to a flow improver for engineering plastics and resin, which exhibits excellent flow property improving properties and chemical resistance improving properties, and a fluidity, peeling resistance, heat resistance and chemical resistance using the same.
- TECHNICAL FIELD The present invention relates to a thermoplastic resin composition having excellent heat resistance and transparency, and to molded articles, automobile members and lamp covers using the same.
- Patent Document 4 a method of adding a polyester oligomer (for example, Patent Document 4), a method of adding a polycarbonate oligomer (for example, Patent Document 5), and a method of adding a low-molecular-weight styrene-based copolymer (Eg Patent Documents 6-8) proposed Has been.
- Patent Documents 9 and 10 and the like disclose, as lamp covers having excellent heat resistance, (2) 9,9-bis (4-oxyphenyl) fluorene structural unit and 1,1-bis (4-hydroxyphenyl) -3 A lamp cover comprising an aromatic polycarbonate resin having a 3,3,5-trimethylcyclohexane structural unit has been proposed.
- Patent Document 1 Japanese Patent Publication No. 59-42024
- Patent Document 2 JP-A-62-138514
- Patent Document 3 Japanese Patent No. 2622152
- Patent Document 4 Japanese Patent Publication No. 54 37977
- Patent Document 5 JP-A-3-24501
- Patent Document 6 Japanese Patent Publication No. 52-784
- Patent Document 7 JP-A-11-181197
- Patent Document 8 JP-A-2000-239477
- Patent Document 1 JP-A-6-65362
- Patent Document 2 JP-A-7-90073
- the method of reducing the molecular weight of the polycarbonate resin greatly improves the flowability, the excessive reduction in the molecular weight impairs the excellent heat resistance and chemical resistance of the polycarbonate. Also, since the impact resistance is remarkably reduced, there is a limit to improving the melt fluidity by low molecular weight filtration while maintaining the excellent properties of the polycarbonate resin.
- the balance between peel resistance and fluidity is still insufficient.
- the method using a specific styrene-based copolymer is excellent in melt fluidity, but the compatibility is still insufficient, so that the surface of the molded product is peeled off, and the appearance and mechanical properties are greatly reduced immediately.
- the specific acrylic copolymer has excellent compatibility and good transparency, but the effect of improving the melt fluidity is small. It is necessary to increase the amount of the ril copolymer, and there is a limit to improving the fluidity while maintaining the excellent characteristics of polycarbonate such as heat resistance and impact resistance.
- the method of adding a polyester oligomer or the method of adding a polycarbonate oligomer is effective in improving fluidity, but has a problem that the excellent heat resistance and impact resistance of polycarbonate are significantly reduced.
- the product has the following problems: the surface peeling occurs immediately after the product is peeled off, and the resulting impact strength, the weld appearance, which is important for practical use, and the surface impact are not sufficient.
- the molecular weight of the aromatic polycarbonate resin itself is reduced to a lower molecular weight.
- the melt viscosity is reduced and the melt fluidity is greatly improved, as the molecular weight is reduced, heat resistance and impact resistance are reduced.
- the mechanical properties such as gas resistance are reduced, and the chemical resistance such as gasoline resistance required for lamp power bars of automobiles is also impaired. Therefore, there is a limit in improving the moldability while maintaining the excellent characteristics of the aromatic polycarbonate resin by the low molecular weight resin, and at present, the aromatic compound having the low molecular weight resin has a low molecular weight. Molding is carried out using an aromatic polycarbonate resin and raising the molding temperature to near limit. If the molding temperature is excessively increased while applying force, appearance defects such as silver are generated, and molding defects are increased.
- the present invention has been made in order to solve the above-mentioned problems, and has been made to solve the problems of heat resistance, exfoliation resistance, and transparency of an engineering plastic without impairing its transparency and the like.
- An object of the present invention is to provide a fluidity improver capable of improving fluidity, a resin composition using the same, and a product using the same.
- Another object of the present invention is to provide a lamp cover having improved moldability and chemical resistance without impairing the excellent characteristics of the conventional aromatic polycarbonate resin.
- the lamp cover in the present invention includes a lens and a cover used for an illumination lamp such as a head lamp lens and a cover of an automobile. Means for solving the problem
- the gist of the first invention is that (meth) acrylic acid in which the aromatic vinyl monomer unit (a1) is 0.5 to 99.5% by mass and the ester group is a phenyl group or a substituted phenyl group. 0.5 to 99.5% by mass of the ester monomer unit (a2) and 0 to 40% by mass of the other monomer units (a3) (the total of al-a3 is 100% by mass).
- a fluidity improver for engineering plastics comprising a polymer (A) having a weight average molecular weight of 5,000 to 1500,000.
- the gist of the second invention resides in a thermoplastic resin composition obtained by mixing the engineering plastics) with the fluidity improver for engineering plastics.
- the gist of the third invention resides in a molded product, an automobile member, and a lamp cover obtained by injection-molding the thermoplastic resin composition.
- the fluidity improver for engineering plastics of the present invention has a phase separation behavior at the time of melt molding with engineering plastics represented by polycarbonate resin, and has good peeling resistance in the use temperature range of molded products. It has a level of compatibility (affinity).
- affinity affinity
- the polycarbonate resin-based alloy lamp cover of the present invention provides the chemical resistance such as gasoline resistance required for automobile headlamps, etc., and the melt fluidity which do not impair the excellent transparency and heat resistance of conventional products. (Moldability) is remarkably excellent, so that it can be suitably used for a large-sized, thin-walled headlamp cover for an automobile, which has been increasingly required in recent years.
- Engineering plastics fluidity improver of the present invention include aromatic Bulle monomer unit (al) O. 5- 99. 5 mass 0/0, ester groups Hue - Le (Meth) acrylic acid ester monomer unit (a2) which is a group or a substituted phenol group (a2) 0.5 to 99.5% by mass, other monomer unit (a3) 0 to 40% by mass (al- a3 is 100% by mass), and has a weight average molecular weight of 5,000 to 150,000.
- Such a fluidity improver has a phase separation behavior at the time of melt molding with engineering plastics represented by polycarbonate resin, and has a good level of compatibility (affinity ), Exhibiting unprecedented remarkable melt flowability (molding processability) and chemical resistance improvement effects that do not impair the characteristics (heat resistance, peeling resistance, etc.) of engineering plastics.
- the copolymer contains a predetermined amount of the aromatic butyl monomer unit (al), it becomes a fluidity improver exhibiting excellent fluidity and chemical resistance improving effect.
- aromatic vinyl monomer constituting the aromatic vinyl monomer unit (al) examples include styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, ⁇ -t-butylstyrene, p-methoxystyrene, and o-methoxystyrene. , 2,4-dimethylstyrene, chlorostyrene, bromostyrene, vinyltoluene, vinylnaphthalene, vinylanthracene and the like, and these can be used alone or in combination of two or more. Among them, styrene, ⁇ -methylstyrene and ⁇ -t-butylstyrene are preferred.
- the content of the aromatic vinyl monomer unit (al) in the copolymer is 0.5 to 99.5% by mass. If the content of the aromatic vinyl monomer unit (al) exceeds 99.5% by mass, the compatibility with the engineering plastic becomes insufficient, so that the molded article of the mixture causes layer delamination. In some cases, appearance and mechanical properties may be impaired. On the other hand, if the aromatic vinyl monomer unit (al) content is less than 0.5% by mass, the compatibility with engineering plastics is too good. In some cases, it cannot be formed sufficiently, and the effect of improving chemical resistance tends to decrease.
- the content of the aromatic vinyl monomer unit (al) in the copolymer is preferably 98% by mass or less, more preferably 96% by mass or less, and further preferably 93% by mass or less. Or less, and most preferably 90% by mass or less.
- the content is preferably at least 10% by mass, more preferably at least 20% by mass, further preferably at least 50% by mass, and most preferably at least 75% by mass.
- the copolymer used in the fluidity improver of the present invention contains a (meth) acrylate monomer unit (a2) having an ester group having a phenyl group or a substituted phenyl group.
- a2 acrylate monomer unit having an ester group having a phenyl group or a substituted phenyl group.
- the monomers constituting the (meth) acrylic acid ester monomer unit (a2) in which the ester group has a phenyl group or a substituted phenyl group include phenyl (meth) acrylate, 4 t-butyl phenol ( (Meth) acrylate, bromophenyl (meth) acrylate, dibromophenyl (meth) T) acrylate, 2,4,6-tribromophenyl (meth) acrylate, monochlorophenol (meth) acrylate, dichlorophenyl (meth) acrylate, trichlorophenyl (meth) acrylate, etc. These can be used alone or in combination of two or more. Of these, phenol (meta) acrylate is particularly preferred.
- the content of the (meth) acrylic acid ester monomer unit ( a2 ) in which the ester group has a fluorine group or a substituted fluorine group in the copolymer is 0.5 to 99%. It must be 5% by mass.
- ester group has a phenyl or substituted phenyl group-containing (meth) acrylate monomer (a2) content of less than 0.5% by mass, the compatibility with engineering plastics is insufficient. For this reason, a molded article obtained by molding a resin composition containing a fluidity improver and an engineering plastic may cause delamination, resulting in impaired appearance and mechanical properties.
- ester groups Hue - group or a substituted phenylene Le having a group (meth) acrylic Sane ester monomer (a2) content of force 99.5 mass 0/0 exceeds the engineering plus nitride click and compatibility, In some cases, the phase separation behavior, which brings about a remarkable fluidity improving effect at the time of melting, cannot be sufficiently formed.
- the amount of the (meth) acrylate monomer (a2) in which the ester group has a phenol group or a substituted phenol group is preferably 90% by mass or less. It is preferably at most 80% by mass, more preferably at most 50% by mass, most preferably at most 25% by mass.
- the use amount is preferably 2% by mass or more, more preferably 4% by mass or more, still more preferably 7% by mass or more, and most preferably 10% by mass or more.
- the polymer used in the fluidity improver of the present invention may contain an aromatic vinyl monomer, a fluor group or a substituted fluor group, if necessary, as long as the above-mentioned characteristics are not impaired. It may contain 0 to 40% by mass of another monomer unit (a3) derived from another monomer copolymerizable with the (meth) acrylic ester monomer.
- the monomer constituting the other monomer unit (a3) is an a, j8-unsaturated monomer, specifically, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) ) Atarilate, 2 —Ethylhexyl acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, t-butyl (meth) acrylate, isopropyl (meta) ) Acrylates, alkyl (meth) acrylates such as t-butylcyclohexyl (meth) acrylate, (meth) acrylic acid, 2-hydroxyethyl (meth) atalylate, glycidyl (meth) atalylate, aryl (meta) ) (Meth) acrylates having a reactive functional group such as
- One or more copolymerizable components of the above can be used within the range of 0 to 40% by mass in the polymer. If the content of the monomer exceeds 40% by mass, the effect of improving the fluidity and chemical resistance of a thermoplastic resin composition obtained by blending a fluidity improver with an engineering plastic tends to decrease.
- the preferable content of the other monomer unit (a3) in the copolymer is 30% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, and most preferably. Or less than 5% by mass.
- the fluidity improver of the present invention is characterized in that it is excellent in compatibility with engineering plastics represented by polycarbonate, and therefore, the mixture is excellent in transparency.
- the (meth) acrylic acid ester monomer (a2) having the unit (a1) and the ester group having a phenol group or a substituted phenyl group is a two-component system, and the content thereof is within a specific range. By doing so, it becomes possible to express a very high degree of transparency. In this range, the (meth) acrylate ester in which the aromatic vinyl monomer unit (al) in the copolymer is 0.5 to 40% by mass and the ester group has a phenyl group or a substituted phenyl group.
- Monomer unit (a2) force 0-99.5% by mass (the total amount of both is 100% by mass) and the case where the aromatic vinyl monomer unit (al) in the copolymer is 60-99% 0.5% by mass, and when the (meth) acrylic acid ester monomer unit (a2) having a ester group or a substituted phenyl group as the ester group is 0.5 to 40% by mass. There are two.
- the weight average molecular weight of the copolymer used for the fluidity improver for engineering plastics of the present invention is 5,000 to 150,000.
- the weight average molecular weight is less than 5,000, the amount of low molecular weight substances increases relatively, There is a possibility that various functions such as properties and rigidity are reduced. In addition, there is a possibility that problems such as smoke during melt molding, mist, mechanical contamination, and poor appearance of molded products such as fish eyes and silver may occur.
- a higher mass average molecular weight is preferable.
- a preferable mass average molecular weight is 10,000 or more, more preferably 15,000. And more preferably 30,000 or more, and most preferably 40,000 or more.
- the mass average molecular weight exceeds 150,000, the melt viscosity of the resin composition to which the fluidity improver has been added becomes high, and a sufficient fluidity modifying effect may not be obtained.
- the mass average molecular weight is preferably 120,000 or less, and most preferably 100,000 or less.
- Examples of the polymerization method for obtaining the fluidity improver of the present invention include an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, and a bulk polymerization method.
- a turbid polymerization method and an emulsion polymerization method are preferred.
- a carboxylic acid salt emulsifier is used, and a phosphoric acid ester that recovers by acid precipitation coagulation etc. It is preferable to carry out salting out coagulation with a calcium acetate salt or the like using a non-aion type emulsifier or the like.
- the fluidity improver of the present invention when used together with an engineering plastic, the fluidity that the inherent properties of the engineering plastic, such as heat resistance, peel resistance, and transparency, are not impaired. (Forming workability) and chemical resistance can be improved.
- the engineering plastic (B) used in the thermoplastic resin composition of the present invention is not particularly limited as long as it is a conventionally known various thermoplastic engineering plastics, such as polyphenylene ether, polycarbonate, polyethylene terephthalate, and polycarbonate.
- Polyester polymers such as butylethylene terephthalate, nylon polymers such as syndiotactic polystyrene, 6-nylon, 6,6-nylon, polyarylate, polyphenylene sulfide, polyetherketone, polyetheretherketone, polysulfone, Examples include polyethersulfone, polyamideimide, polyetherimide, polyacetal, and the like. Wear.
- aromatic polycarbonate (C) examples include 4,4, dioxydiarylalkane-based polycarbonates such as 4,4'-dihydroxydiphenylene 2,2-propane (ie, bisphenol A) -based polycarbonate.
- the molecular weight of the engineering plastic (B) is not particularly limited in the present invention as long as it can be appropriately determined as desired.
- the engineering plastic is an aromatic polycarbonate resin (C)
- the viscosity average molecular weight is preferably 10,000 to 50,000, and more preferably 15,000 to 30,000! / ⁇ .
- Engineering plastics can be manufactured by various conventionally known methods. For example, when producing 4,4'-dihydroxydiphenylene 2,2-propane-based polycarbonate, 4,4'-dihydroxydiphenyl 2,2-propane is used as a raw material and an alkaline aqueous solution is used. And a method in which phosgene is blown in the presence of a solvent to cause a reaction, and a method in which 4,4, dihydroxydiphenyl 2,2-propane is transesterified with a carbonic acid diester in the presence of a catalyst.
- the engineering plastic (B) of the present invention has a range within which the excellent heat resistance, impact resistance, flame retardancy, etc. inherent to engineering plastics are not impaired, specifically, 100 parts by mass of engineering plastic.
- a thermoplastic resin other than engineering plastics such as styrene resin such as ABS, HIPS, PS, and PAS, acrylic resin, polyolefin resin, and elastomer is blended within 50 parts by mass. It is also possible to use engineering plastic polymer alloys that have been used.
- the mixing ratio of the fluidity improver (A) and the engineering plastic (B) is not particularly limited in the present invention as long as it can be appropriately determined according to desired physical properties and the like.
- a flow improver (A) O. 1-30 per 100 parts by mass of engineering plastic It is preferable to mix parts by mass. If the amount of the fluidity improver (A) is less than 0.1 part by mass, a sufficient improvement effect may not be obtained. If the amount of the fluidity improver (A) exceeds 30 parts by mass, the excellent mechanical properties of the engineering plastic may be impaired.
- the preferred amount of the fluidity improver (A) is at least 1 part by mass, more preferably at least 2 parts by mass, and even more preferably at least 3 parts by mass.
- the amount is preferably not more than 25 parts by mass, more preferably not more than 15 parts by mass, and most preferably not more than 10 parts by mass.
- the engineering plastic resin composition of the present invention may contain, if necessary, known stabilizers, reinforcing agents, inorganic fillers, impact resistance modifiers, flame retardants, fluorinated olefins, and the like. May be added.
- talc, myric, calcium carbonate, glass fiber, carbon fiber, potassium titanate fiber, and the like can be contained.
- other engineering plastic compositions such as polyethylene terephthalate for improving chemical resistance and the like, rubber-like elastic materials having a core-shell two-layer structure for improving impact resistance and the like may be blended.
- the blending of the engineering plastic (B) and the fluidity improver (A) is carried out by mixing the powder with the engineering plastic (B) and the fluidity improver (A) by heating and kneading. It may be obtained.
- Examples of such a compounding method include a method using a Henschel mixer, a Banbury mixer, a single screw extruder, a twin screw extruder, a two-roller, a kneader, a Brabender and the like.
- a masterbatch prepared by mixing the flowability improver (A) and the engineering plastic (B) so that the ratio of the flowability improver is large is prepared in advance, and then the masterbatch and the engineering plastic (B) are mixed. Can be mixed again to obtain a desired composition.
- the molded article of the present invention is obtained by injection molding the above-mentioned thermoplastic resin composition.
- the flowability Z that cannot be achieved with low molecular weight Because it is possible to improve the chemical resistance balance, it is extremely effective for automotive parts such as headlamps, etc., which require chemical resistance, OA equipment, and large-sized thin injection molded products of electric and electronic equipment. is there.
- the injection molding method is not particularly limited, and can be performed by a known method.
- the lamp cover of the present invention is obtained by mixing (kneading) the flow improver (A) and the polycarbonate resin (C).
- the content of (A) may be appropriately determined according to the desired physical properties and the like, and is not particularly limited in the present invention. However, the performance (heat resistance, impact strength, etc.) of the aromatic polycarbonate resin (C) is low. In order to obtain an effective moldability improvement effect and chemical resistance improvement effect without lowering, the aromatic polycarbonate resin (C) is 80-99.5% by mass, and the fluidity improver (A) Is preferably 0.5 to 20% by mass. If the content of the fluidity improver (A) is less than 0.5% by mass, a sufficient improvement effect may not be obtained. If the content of the fluidity improver (A) is more than 20% by mass, the excellent mechanical properties of the aromatic polycarbonate resin (C) may be impaired.
- the lower limit of the preferable content of the fluidity improver (A) is 1% by mass or more, more preferably 2% by mass or more, and further preferably 3% by mass or more.
- the upper limit of the preferred content of the fluidity improver (A) is 15% by mass or less, more preferably 10% by mass or less.
- a polycarbonate resin-based alloy may be used, for example, as necessary.
- the lamp cover of the present invention is manufactured by molding the above-mentioned polycarbonate resin-based alloy using various molding methods such as injection molding, compression molding, extrusion molding, blow molding, and casting. It can. Of these, injection molding is the simplest method and is preferred. In the injection molding, the alloy is preferably melted and processed at a processing temperature of 250 ° C to 350 ° C.
- the lamp cover of the present invention is excellent in melt fluidity (moldability), easy to perform large-scale and thin-wall molding that has not been achieved conventionally, and the obtained lamp cover impairs the excellent characteristics of aromatic polycarbonate. Excellent chemical resistance to solvents such as gasoline.
- a separable flask equipped with a condenser and a stirrer was charged with 0.4 part of calcium phosphate and 150 parts of distilled water, and then 80 parts of styrene, 20 parts of phenyl methacrylate, 1 part of AIBN, and 1 part of t-butinolemenolecabutane.
- the mixture obtained by dissolving 5 parts was dried, stirred for a while, and then subjected to nitrogen bubbling for 30 minutes. Under a nitrogen atmosphere, the mixture was stirred at 80 ° C for 4 hours, and further stirred at 90 ° C for 1 hour to complete the polymerization.
- the precipitate was separated and washed, and dried at 75 ° C for 24 hours to obtain a fluidity improver (A-1).
- the weight average molecular weight (Mw) was 92,000.
- a fluidity improver (A-3) was obtained in the same manner as in Production Example 2, except that the amount of n-octyl mercaptan was changed from 0.3 part to 0.5 part.
- Mass-average molecular weight (Mw) was 50,000 o
- a fluidity improver (A-4) was obtained in the same manner as in Production Example 2 except that the amount of n-octyl mercaptan was changed from 0.3 part to 1 part.
- the weight average molecular weight (Mw) was 27100.
- the fluidity improver (A-6) was prepared in the same manner as in Production Example 5 except that 80 parts of the monomer yarn styrene and 19 parts of phenol methacrylate were replaced with 60 parts of styrene and 39 parts of phenol methacrylate. Obtained.
- the weight average molecular weight (Mw) was 13,800.
- the flowability improver (A—) was prepared in the same manner as in Production Example 5 except that 80 parts of the monomer yarn styrene and 19 parts of phenol methacrylate were replaced with 25 parts of styrene and 74 parts of phenol methacrylate. 7) was obtained.
- the weight average molecular weight (Mw) was 13,800.
- a flow improver (B-2) was obtained in the same manner as in Production Example 2 except that the part was changed to 0.4 part of kabutane.
- the weight average molecular weight (Mw) was 60,000.
- Table 1 shows the monomer composition for the copolymer produced in Production Example 119, the mass average molecular weight (Mw), and the polymerization mode of the obtained copolymer.
- St Styrene
- PhMA Feral methacrylate
- MA Methyl acrylate
- BA Butyla Tallylate
- MMA methyl methacrylate
- the obtained fluidity improver and polycarbonate resin were mixed at the mass ratio shown in Table 2, supplied to a twin-screw extruder (model name "TEM-35", manufactured by Toshiba Machine Co., Ltd.), and melt-kneaded at 280 ° C. Thus, an engineering plastic composition was obtained.
- thermoplastic resin composition was evaluated in the following (1)-(5). The results are shown in Table 2.
- the spiral flow length SFL of the obtained engineering plastic composition was evaluated using an injection molding machine (“IS-100”, manufactured by Toshiba Machine Co., Ltd.).
- the molding temperature was 280 ° C
- the mold temperature was 80 ° C
- the injection pressure was 98MPa.
- the molded product has a thickness of 2 mm and a width of 15 mm.
- a molded product having a wall thickness of 1Z4 inches was molded by an injection molding machine (“IS-100”, manufactured by Toshiba Machine Co., Ltd.).
- the deflection temperature under load of the molded article was measured according to ASTM D648. Note that annealing was not performed, and the load was 1.82 MPa.
- an injection molding machine (“IS-100”, manufactured by Toshiba Machine Co., Ltd.) was used to mold a 3 mm-thick, 5 cm square flat plate.
- the engineering plastic resin composition obtained in Comparative Example 2 had sufficient fluidity and chemical resistance because the fluidity improver did not contain the aromatic bead conjugate and had too good compatibility. I could't get the sex.
- the engineering plastic composition obtained in Comparative Example 3 did not contain a flowability improver, and thus did not have sufficient flowability and chemical resistance.
- a mixture of 12.5 parts, 0.2 part of t-butyl hydroperoxide and 0.5 part of n-octylmercaptan was added dropwise over 180 minutes. Thereafter, the mixture was stirred for 60 minutes to complete the polymerization.
- 300 parts of an aqueous solution in which sulfuric acid was dissolved at a rate of 0.7% was heated to 70 ° C and stirred.
- the obtained polymer emulsion was gradually dropped therein to coagulate.
- the precipitate was separated and washed, dried at 75 ° C for 24 hours, and dried for 24 hours to obtain a fluidity improver (A-8).
- the weight average molecular weight (Mw) was 49,000.
- a flow improver (A-9) was obtained in the same manner as in Production Example 10, except that the amount of n-octyl mercaptan was changed from 0.5 part to 0.2 part.
- Mass-average molecular weight (Mw) was 98000 o
- Table 3 shows the monomer composition for the copolymer produced in Production Examples 10 to 11, the weight average molecular weight (Mw), and the polymerization mode of the obtained copolymer. [Table 3]
- the obtained fluidity improver and polycarbonate resin were mixed at the mass ratio shown in Table 4, supplied to a twin-screw extruder (model name "TEM-35", manufactured by Toshiba Machine Co., Ltd.), and melt-kneaded at 280 ° C. Thus, an engineering plastic composition was obtained.
- thermoplastic resin composition was evaluated in the following (1)-(5). The results are shown in Table 4.
- PC2 polycarbonate resin
- Panlite L1225WS manufactured by Teijin Chemicals, viscosity average molecular weight 21,000
- PC3 Polycarbonate resin (“Panlite L1225ZL”, manufactured by Teijin Chemicals, viscosity average molecular weight: 190,000)
- the spiral flow length SFL of the obtained engineering plastic composition was evaluated using an injection molding machine (“IS-100”, manufactured by Toshiba Machine Co., Ltd.).
- the molding temperature was 280 ° C
- the mold temperature was 80 ° C
- the injection pressure was 98MPa.
- the molded product has a thickness of 2 mm and a width of 15 mm.
- a molded product having a wall thickness of 1Z4 inches was molded by an injection molding machine (“IS-100”, manufactured by Toshiba Machine Co., Ltd.). After annealing at 120 ° C for 2 hours, the deflection temperature under load of the molded article was measured in accordance with ASTM D648. The load was 1.82MPa.
- an injection molding machine (“IS-100”, manufactured by Toshiba Machine Co., Ltd.) was used to mold a flat plate having a thickness of 2 mm and a size of 5 cm ⁇ 10 cm.
- Example 9 Using the engineering plastic composition obtained in Example 9, a flat molded product having a thickness of 2 mm and a size of 10 cm ⁇ 10 cm was molded by an injection molding machine (“IS-100”, manufactured by Toshiba Machine Co., Ltd.). After performing a hard coat treatment by UV curing on this flat plate, an instrumented surface impact test (No. Mouth shot). The total absorbed energy is 30J and the fracture mode is ductile fracture.
- a flat molded product having a thickness of 2 mm and a size of 10 cm ⁇ 10 cm was molded in the same manner as in Example 10 except that the engineering plastic composition obtained in Comparative Example 5 was used. After performing a hard coat treatment by UV curing on this flat plate, an instrumented surface impact test (hide opening shot) was performed. The total absorbed energy was 5J and the fracture mode was brittle.
- a flow improver (A-10) was obtained in the same manner as in Production Example 10 except that the monomer composition was changed to 90 parts of styrene and 10 parts of phenol metathallate.
- the weight average molecular weight (Mw) was 51,000.
- a flow improver (B-3) was obtained in the same manner as in Production Example 10 except that the monomer composition was changed to 100 parts of styrene.
- the weight average molecular weight (Mw) was 55,000.
- Table 5 shows the monomer composition for the copolymers produced in Production Examples 12 and 13, the weight average molecular weight (Mw) of the obtained copolymers, and the polymerization mode.
- Production example 1 0 Production example 1 2 Production example 1 3
- Weight average molecular weight 49000 98000 55000 [0053] The abbreviations in the table are as follows.
- Polymer (A-8) (A-10) (A-3) and (B-3) and each component shown in Table 6 were mixed at the ratio (mass ratio) shown in Table 6 to obtain a biaxial polymer. It was supplied to an extruder (model name "TEM-35", manufactured by Toshiba Machine Co., Ltd.) and melt-kneaded at 280 ° C to obtain a polycarbonate resin alloy.
- PC-4 Polycarbonate resin (Panlite L 1225Z-100, manufactured by Teijin Chemicals, viscosity average molecular weight 220,000)
- PC-5 Polycarbonate resin (Panlite L 1225ZL-100, manufactured by Teijin Chemicals, viscosity average molecular weight: 19,000)
- the spiral flow length (SFL) of the obtained polycarbonate resin-based alloy was evaluated using an injection molding machine (“IS-100”, manufactured by Toshiba Machine Co., Ltd.).
- the molding temperature was 280 ° C
- the mold temperature was 80 ° C
- the injection pressure was 98MPa.
- the molded product had a thickness of 2 mm and a width of 15 mm.
- the above-mentioned SFL is within the range of 200 mm or more.
- a molded product having a wall thickness of 1Z4 inches was molded by an injection molding machine (“IS-100”, manufactured by Toshiba Machine Co., Ltd.).
- the deflection temperature under load of the molded article was measured according to ASTM D648. The annealing was not performed, and the load was 1.82 MPa.
- the above heat resistance is 120 ° C or more.
- the range of the above heat resistance is 120 ° C or more.
- the lamp cover preferably has a total light transmittance of 88% or more. Further, the haze is preferably within a range of 2% or less ⁇
- the molded product of the polycarbonate resin-based alloy obtained in Examples 11 to 15 has sufficient heat resistance and transparency, as well as melt fluidity and chemical resistance. The characteristics required for a large and thin lamp cover were extremely excellent.
- the molded product of the polycarbonate resin alloy obtained in Comparative Example 7 was the same as that of the polycarbonate resin of Example 11-15. Compared with the molded article obtained by using the alloy, the lens appearance with poor peelability and transparency was poor. This is thought to be due to insufficient compatibility between polymer B-1 and PC-4.
- Example 11-1 The molded product of the polycarbonate resin-based alloy obtained in Comparative Examples 8 and 9, which did not contain the copolymers (A-8), (A-10) and (A-3), was obtained in Example 11-1. Compared to the polycarbonate resin alloy molded product obtained in 15, the balance between the melt fluidity and the chemical resistance sufficient to make a large and thin lamp cover was not obtained.
- the flowability improver of the present invention is remarkably added by adding a small amount to the engineering plastic without impairing the characteristics (transparency, heat resistance, peeling resistance, chemical resistance, etc.) of the engineering plastic, thereby improving the melt flowability ( An improvement effect can be obtained.
- Engineering plastics containing this fluidity improver have excellent physical properties and good melt fluidity (moldability), so that molded products of any shape, such as more complex, large, thin, etc. can be easily formed. It can be molded stably, and is extremely useful industrially as OA (office automation) equipment, information and communication equipment, electricity and electronic equipment, home appliances, automobile components, and building components.
- the lamp cover of the present invention is excellent in melt fluidity (moldability) and also has excellent polycarbonate resin alloy strength that is excellent in solvent resistance without impairing the excellent characteristics of aromatic polycarbonate.
- melt fluidity melt fluidity
- polycarbonate resin alloy strength that is excellent in solvent resistance without impairing the excellent characteristics of aromatic polycarbonate.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Non-Portable Lighting Devices Or Systems Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/573,831 US8729205B2 (en) | 2003-09-30 | 2004-09-30 | Flowability improver for engineering plastics, thermoplastic resin compositions containing the same and molded articles of the compositions |
EP04788421.8A EP1679324B1 (en) | 2003-09-30 | 2004-09-30 | Flowability improver for engineering plastics, thermoplastic resin compositions containing the same, and molded articles of the compositions |
CN200480034416XA CN1882621B (zh) | 2003-09-30 | 2004-09-30 | 工程塑料用流动性改进剂、含有它的热塑性树脂组合物及其成型品 |
KR1020067007980A KR101192949B1 (ko) | 2003-09-30 | 2004-09-30 | 엔지니어링 플라스틱용 유동성 향상제, 이것을 함유하는 열가소성 수지 조성물 및 그의 성형품 |
JP2005514282A JP4054042B2 (ja) | 2003-09-30 | 2004-09-30 | 熱可塑性樹脂組成物ならびにその成形品 |
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JP2003-340819 | 2003-09-30 | ||
JP2003340819 | 2003-09-30 | ||
JP2004-049320 | 2004-02-25 | ||
JP2004049320 | 2004-02-25 |
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US (1) | US8729205B2 (ja) |
EP (1) | EP1679324B1 (ja) |
JP (1) | JP4054042B2 (ja) |
KR (1) | KR101192949B1 (ja) |
CN (1) | CN1882621B (ja) |
WO (1) | WO2005030819A1 (ja) |
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KR20160111993A (ko) | 2014-03-20 | 2016-09-27 | 미쯔비시 레이온 가부시끼가이샤 | 비닐 중합체 분체, 열가소성 수지 조성물 및 그의 성형체 |
KR20180128081A (ko) | 2014-03-20 | 2018-11-30 | 미쯔비시 케미컬 주식회사 | 비닐 중합체 분체, 열가소성 수지 조성물 및 그의 성형체 |
US10221268B2 (en) | 2014-03-20 | 2019-03-05 | Mitsubishi Chemical Corporation | Vinyl polymer powder, thermoplastic resin composition, and molded body thereof |
US10787529B2 (en) | 2014-03-20 | 2020-09-29 | Mitsubishi Chemical Corporation | Vinyl polymer powder, thermoplastic resin composition, and molded body thereof |
JP2016041788A (ja) * | 2014-08-19 | 2016-03-31 | 三菱レイヨン株式会社 | 重合体の製造方法、重合体、及び、芳香族ポリカーボネート系樹脂用流動性向上剤 |
JP2021017545A (ja) * | 2019-07-22 | 2021-02-15 | 三菱ケミカル株式会社 | 流動性向上剤、熱可塑性樹脂組成物およびその成形品 |
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KR20060108624A (ko) | 2006-10-18 |
EP1679324A4 (en) | 2007-11-07 |
EP1679324B1 (en) | 2014-03-05 |
EP1679324A1 (en) | 2006-07-12 |
CN1882621A (zh) | 2006-12-20 |
US8729205B2 (en) | 2014-05-20 |
JP4054042B2 (ja) | 2008-02-27 |
KR101192949B1 (ko) | 2012-10-18 |
CN1882621B (zh) | 2013-05-15 |
JPWO2005030819A1 (ja) | 2006-12-07 |
US20070213451A1 (en) | 2007-09-13 |
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