CN104114635A - Thermoplastic resin composition and molded article of same - Google Patents
Thermoplastic resin composition and molded article of same Download PDFInfo
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- CN104114635A CN104114635A CN201380009742.4A CN201380009742A CN104114635A CN 104114635 A CN104114635 A CN 104114635A CN 201380009742 A CN201380009742 A CN 201380009742A CN 104114635 A CN104114635 A CN 104114635A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
- C08L25/12—Copolymers of styrene with unsaturated nitriles
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The thermoplastic resin composition and molded article of the same according to the present invention have excellent mechanical characteristics and surface luster, the thermoplastic resin composition including 0.01-1 part by weight of an acrylic/styrene-based copolymer (III) containing an epoxy group with respect to 100 parts by weight of a resin composition comprising a styrene-based resin (I) and polyethylene terephthalate resin (II).
Description
Technical field
The present invention relates to the thermoplastic resin composition and the products formed thereof that contain phenylethylene resin series and pet resin.
Background technology
Phenylethylene resin series taking ABS resin as representative is owing to having excellent mechanical properties, forming process and electrical insulating property, and is used in the field widely taking the various parts of household electric appliances, OA equipment and automobile etc. as representative.
On the other hand, as polyethylene terephthalate (PET) resin of polyester based resin because of physical strength, the transparency, excellent various bottles, food trays, the sheet material etc. of being widely used in of gas barrier property.
The present situation of PET resin is: owing to having following characteristic,, if the shock-resistance that stretches uprises, if crystallization thermotolerance also uprises, so the usage ratio in such use is high, but, in injection moulding, manifest significantly the shortcomings such as shock-resistance is low, extremely low as the usage ratio of injection molded article.
In addition, in recent years, due to the raising of the concern to environmental problem, so no matter all formulated Green Purchasing method, U.S.'s electronics standard (EPEAT) etc. both at home and abroad in order to effectively to utilize the standard of regenerating resin, from this background, to regenerating resin or effectively utilized the demand of the resin combination of regenerating resin to raise just gradually.Wherein, the discarded amount of PET resin is also stably increasing always year by year, and recovery, the recycling of these wastes receive publicity.
Therefore, if can eliminate the above-mentioned deficiency as injection molded article of PET resin, not only former green material (virgin materials) utilizes purposes to expand, and recycling purposes also expands, and can expect the increase of usage quantity.
As the one of modification method of shock-resistance that becomes problem, can list the polymer alloy with aforementioned ABS resin.In patent documentation 1, disclose in order to by coordinating ABS resin to improve composition and the preparation condition of shock-resistance in regenerative PET resin.But the consistency of known PET resin and ABS resin bad, in the composition obtaining, might not obtain good shock-resistance in the method for recording by patent document all the time.
Therefore, carried out a very long time about the research of consistency of the alloy composite that improves PET resin and ABS resin.In patent documentation 2, disclose and will there is the vinyl cyanide/styrol copolymer of epoxy group(ing) as the example of properties-correcting agent; Following methods is proposed in patent documentation 3: except vinyl cyanide and vinylbenzene, carry out graft copolymerization and realize the raising of consistency by making to have the vinyl monomer of epoxy group(ing) and diene series rubber.But, in these methods, although can realize the raising of physical strength,, have following situation: in forcing machine or in forming machine, generate cross-linking agent and damage surface luster property.
On the other hand, although there is the vinylformic acid/styrene based copolymer that contains epoxy group(ing) to be added the example in following composition, described composition is formed (patent documentation 4) or is formed (patent documentation 5) by polylactic resin and ABS resin by regenerative PET resin and straight chain shape ldpe resin, but, be not added on the example in the composition being formed by PET resin and ABS resin in order to realize the raising of consistency and good surface luster property.
Patent documentation 1: TOHKEMY 2004-67728 communique
Patent documentation 2: TOHKEMY 2003-286382 communique
Patent documentation 3: Japanese kokai publication hei 2-16145 communique
Patent documentation 4: TOHKEMY 2005-200534 communique
Patent documentation 5: TOHKEMY 2008-106091 communique
Summary of the invention
The object of the invention is to, eliminate the shortcoming of above-mentioned prior art, thermoplastic resin composition and products formed thereof that mechanical characteristics, surface luster property excellence are provided, described thermoplastic resin composition is contained phenylethylene resin series and pet resin.
The inventor conducts in-depth research repeatedly in order to solve above-mentioned problem, found that, with respect to the resin combination being formed by phenylethylene resin series (I) and pet resin (II) of 100 weight parts, vinylformic acid/the styrene based copolymer that contains epoxy group(ing) (III) that coordinates 0.01～1 weight part, can solve above-mentioned problem thus.
, the present invention relates to thermoplastic resin composition and the products formed thereof as described in following (1)～(7).
(1) a kind of thermoplastic resin composition, with respect to the resin combination being formed by phenylethylene resin series (I) and pet resin (II) of 100 weight parts, the vinylformic acid/styrene based copolymer that contains epoxy group(ing) (III) that contains 0.01～1 weight part.
(2) thermoplastic resin composition as described in (1), wherein, the weight-average molecular weight of the vinylformic acid/styrene based copolymer (III) that contains epoxy group(ing) is 2,000～20,000.
(3) thermoplastic resin composition as described in (1) or (2), wherein, the oxirane value of the vinylformic acid/styrene based copolymer (III) that contains epoxy group(ing) is 0.5～4.0 (meq/g).
(4) thermoplastic resin composition as described in any one in (1)～(3), wherein, phenylethylene resin series (I) is 50:50～99:1 with the weight ratio of pet resin (II).
(5) thermoplastic resin composition as described in any one in (1)～(4), wherein, phenylethylene resin series (I) is the composition that the ratio taking weight ratio as 10:90～50:50 contains graft copolymer (A) and ethylene-based polymer/multipolymer (B), described graft copolymer (A) is that to make to be selected from aromatic vinyl be monomer (b), vinyl cyanide is that more than a kind monomer and rubber polymer (a) graft copolymerization in monomer (c) and other vinyl monomer (d) that can copolymerization forms, described ethylene-based polymer/multipolymer (B) is to be monomer (b) by being selected from aromatic vinyl, vinyl cyanide is that the more than a kind monomer polymerization in monomer (c) and other vinyl monomer (d) that can copolymerization forms.
(6) thermoplastic resin composition as described in any one in (1)～(5), wherein, as pet resin (II), the recycled materials of all or part of use pet resin products formed.
(7) products formed, forms the thermoplastic resin composition's moulding described in any one in (1)～(6).
By the present invention, can obtain thermoplastic resin composition and the products formed thereof of mechanical characteristics, surface luster property excellence, described thermoplastic resin composition is contained phenylethylene resin series and pet resin.
Embodiment
Below illustrate to implement embodiments of the present invention.
Phenylethylene resin series of the present invention (I) refers to ethylene-based polymer/multipolymer (B), in ethylene-based polymer/multipolymer (B), add there the is rubber polymer resin of (a), described ethylene-based polymer/multipolymer (B) be by be selected from aromatic vinyl be monomer (b), vinyl cyanide be monomer (c) and can other vinyl monomer (d) of copolymerization in more than a kind monomer form.
In ethylene-based polymer/multipolymer (B), to add the have rubber polymer resin of (a) at phenylethylene resin series (I), viewpoint from ethylene-based polymer/multipolymer (B) with the consistency of rubber polymer (a), be preferably the composition that contains graft copolymer (A) and ethylene-based polymer/multipolymer (B), described graft copolymer (A) is that to make to be selected from aromatic vinyl be monomer (b), vinyl cyanide is that more than a kind monomer and rubber polymer (a) graft copolymerization in monomer (c) and other vinyl monomer (d) that can copolymerization forms, described ethylene-based polymer/multipolymer (B) is to be monomer (b) by being selected from aromatic vinyl, vinyl cyanide is that the more than a kind monomer in monomer (c) and other vinyl monomer (d) that can copolymerization forms.It should be noted that, be engaged in monomer mixture in graft copolymer (A) without whole graftings with rubber polymer (a) bonding, the monomer of monomer mixture each other can bonding, and is contained with the form of the polymkeric substance of grafting not.But percentage of grafting is preferably 10～100%, more preferably 20～50%.
The rubber polymer (a) using in graft copolymer (A) although use level without special stipulation, be preferably 10～80 weight parts, more preferably 20～70 weight parts, more preferably 35～65 weight parts.In addition, the use level of the monomer mixture in graft copolymer (A) is preferably 20～90 weight parts, more preferably 30～80 weight parts, more preferably 35～65 weight parts.By using rubber polymer (a) and monomer mixture with these ratios, can obtain good shock-resistance and forming process.In addition, for graft copolymer (A) although in the ratio of monomer mixture that coordinates without particular restriction, but preferably taking aromatic vinyl be monomer (b) as 20～99 % by weight, vinyl cyanide be monomer (c) as 1～40 % by weight, can, with other vinyl monomer (d) of their copolymerization as the ratio of 0～79 % by weight is used, can obtain good shock-resistance and forming process.
For ethylene-based polymer/multipolymer (B) although in the ratio of monomer mixture that coordinates without special stipulation, but preferably taking aromatic vinyl be monomer (b) as 20～99 % by weight, vinyl cyanide be monomer (c) as 1～40 % by weight, can, with other vinyl monomer (d) of their copolymerization as the ratio of 0～79 % by weight is used, can obtain good shock-resistance and forming process.
The ratio of mixture of graft copolymer (A) and ethylene-based polymer/multipolymer (B) is (A) preferably: the ratio that weight ratio (B) is 10:90～50:50, more preferably 20:80～40:60.If the ratio of graft copolymer (A) exceedes above-mentioned scope lower than the ratio of above-mentioned scope or ethylene-based polymer/multipolymer (B), form the trend that shock strength reduces.In addition, if the ratio of graft copolymer (A) exceedes above-mentioned scope, form the trend that mobility reduces.
Reduced viscosity (the η of the solvable composition of acetone of graft copolymer (A)
spalthough/c) without particular restriction, preferably 0.1～0.6dl/g.In addition in the situation that, shock-resistance reduces, or melt viscosity rises and the easy variation of formability, more preferably 0.3～0.5dl/g.
Reduced viscosity (the η of ethylene-based polymer/multipolymer (B)
spalthough/c) without particular restriction, preferably 0.1～0.6dl/g.In addition in the situation that, shock-resistance reduces, or melt viscosity rises and the easy variation of formability.More preferably 0.3～0.5dl/g.
Rubber polymer (a) is without particular restriction, and can use diene series rubber, acrylic rubber, ethene is rubber etc.As concrete example, can list polyhutadiene, poly-(butadiene-styrene), poly-(butadiene-acrylonitrile), polyisoprene, poly-(butadiene-propylene acid butyl ester), poly-(divinyl-methyl methacrylate), poly-(butyl acrylate-methyl methacrylate), poly-(butadiene-propylene acetoacetic ester), ethylene-propylene rubber, ethylene-propylene-elastoprene, poly-(ethene-isoprene), poly-(ethylene-methyl acrylate) etc.These rubber polymers (a) can use with one kind or two or more mixture.In these rubber polymers (a), aspect shock-resistance, preferably use polyhutadiene, poly-(butadiene-styrene), poly-(butadiene-acrylonitrile), ethylene-propylene rubber.
Rubber polymer (a) although weight average particle diameter without particular restriction, from the harmony of the physical strengths such as shock-resistance, products formed outward appearance, preferably 0.1～0.5 μ m.If lower than 0.1 μ m, the shock strength of the thermoplastic compounds obtaining reduces sometimes, if exceed 0.5 μ m, the situation that products formed outward appearance reduces becomes many.More preferably 0.15～0.4 μ m.
The aromatic vinyl using in graft copolymer (A) and ethylene-based polymer/multipolymer (B) is that monomer (b) is without particular restriction, as concrete example, can list vinylbenzene, alpha-methyl styrene, o-methyl styrene, p-methylstyrene, p-tert-butylstyrene and halogenated styrenes etc., can use one kind or two or more.Wherein optimization styrene, alpha-methyl styrene, be particularly preferably vinylbenzene.
The vinyl cyanide using in graft copolymer (A) and ethylene-based polymer/multipolymer (B) is that monomer (c) is without particular restriction, as concrete example, can list vinyl cyanide, methacrylonitrile etc., can use one kind or two or more.Wherein preferred vinyl cyanide aspect shock-resistance.
Other vinyl monomer (d) of the energy copolymerization using in graft copolymer (A) and ethylene-based polymer/multipolymer (B) is without particular restriction, as concrete example, can list with (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, the just own ester of (methyl) vinylformic acid, (methyl) cyclohexyl acrylate, the esters of unsaturated carboxylic acids such as (methyl) vinylformic acid chloromethyl ester and (methyl) vinylformic acid 2-chloroethene ester, N-methyl maleimide, N-N-cyclohexylmaleimide, the maleimide compounds such as N-phenylmaleimide, the unsaturated dicarboxylic acids such as toxilic acid, the unsaturated dicarboxylic acid acid anhydrides such as maleic anhydride, with the unsaturated acyl amine compound such as acrylamide be representative can copolymerization vinyl compound etc., they can use separately or use two or more.It should be noted that, ethylene-based polymer/multipolymer (B) can use multiple kinds.
The preparation method of graft copolymer (A) or ethylene-based polymer/multipolymer (B) is without particular restriction, can be any in mass polymerization, solution polymerization, suspension polymerization, letex polymerization etc.The feeding method of monomer is also without particular restriction, can adopt the initial stage feed intake in the lump, by part or all continuous dosing of monomer or by any method of part or all step feeding of monomer.
As the concrete example of phenylethylene resin series used in the present invention (I), for example, can list polystyrene, shock-resistance vinylbenzene (high-impact polystyrenes; HIPS), hotchpotch (alloys) of AS resin, AAS resin, AES resin, ABS resin, MAS resin, MABS resin, MBS resin, these resins and other resin etc.
Pet resin of the present invention (II) refers to terephthalic acid for sour composition, by ethylene glycol for diol component, main chain has the thermoplastic polyester of the high molecular of ester bond, in addition, also can use 20 % by mole of following following compositions: m-phthalic acid, hexanodioic acid, oxalic acid etc. are as sour composition, propylene glycol, 1, 4-butyleneglycol, neopentyl glycol, 1, 5-pentanediol, 1, 6-hexylene glycol, 1, 10-decanediol, cyclohexanedimethanol, cyclohexanediols etc. or molecular weight are that 400～6000 long chain diol (is polyoxyethylene glycol, poly--1, ammediol, polytetramethylene glycol etc.) as diol component.
In addition, pet resin of the present invention (II) can be without the former green material that is subject to the thermal histories such as forming process, in addition, also can (be designated hereinafter simply as recycled materials for the recycled materials of pet resin products formed.), still, from the viewpoint of reserved resource, preferably contain recycled materials as all or part of.As the concrete example of recycled materials; can list following waste material, scrap stock; described waste material reclaims the products formed that is shaped to PET bottle etc. at least 1 time to obtain; described scrap stock are to produce in deburring (trimming) operation in the time of flap moulding; as the concrete example of the shape of recycled materials, can list thin slice (flake) shape, Powdered or in order to remove foreign matter again the shape of granulation as concrete example.In addition, recycled materials is not preferably sneaked into the material of the strongtheners such as glass fibre.
Phenylethylene resin series (I) in the resin combination being formed by phenylethylene resin series of the present invention (I) and pet resin (II) and pet resin (II) although weight ratio without particular determination, but, in order to bring into play effect of the present invention, be in this resin combination of 100 weight parts in total amount, phenylethylene resin series (I) and pet resin (II) weight ratio are preferably the ratio of 50:50～99:1, the more preferably ratio of 55:45～90:10.If the ratio of phenylethylene resin series (I) exceedes above-mentioned scope lower than the ratio of above-mentioned scope or pet resin (II), physical strength reduces sometimes.
About the vinylformic acid/styrene based copolymer that contains epoxy group(ing) of the present invention (III), as its preparation method, without particular restriction, for example, can list following methods: (methyl) acrylate monomer, (methyl) vinylformic acid etc. of making to have epoxy group(ing) do not have the monomer of epoxy group(ing) and styrene copolymerized method; Make (methyl) vinylformic acid etc. do not have epoxy group(ing) monomer and styrene copolymerized after, make to have the method for the carboxyl addition of (methyl) acrylic acid units in alcohols and this multipolymer of epoxy group(ing) by condensation reaction.
As operable (methyl) acrylate monomer with epoxy group(ing) when prepare the vinylformic acid/styrene based copolymer (III) with epoxy group(ing) by copolymerization, can list glycidyl methacrylate, glycidyl acrylate etc., preferable methyl glycidyl acrylate.
Do not there is the concrete example of the monomer of epoxy group(ing) as (methyl) vinylformic acid etc., can list (methyl) vinylformic acid, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, the just own ester of (methyl) vinylformic acid, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid chloromethyl ester and (methyl) vinylformic acid 2-chloroethene ester etc., wherein preferably use (methyl) vinylformic acid, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate.They can use separately or use two or more.
From mobility, suppress the viewpoint of oozing out, the weight-average molecular weight of the vinylformic acid/styrene based copolymer that contains epoxy group(ing) (III) is preferably 2,000～20,000, more preferably 5,000～15,000.It should be noted that, weight-average molecular weight is the value that is scaled polystyrene of measuring by gel permeation chromatography (GPC).
From the aspect of physical strength, surface luster property, the oxirane value of the vinylformic acid/styrene based copolymer (III) that contains epoxy group(ing) is preferably 0.5～4.0 (meq/g), more preferably 1.0～3.5 (meq/g).It should be noted that, so-called oxirane value is the value recording by hydrochloric acid-dioxane method herein.
The polymerization process of the vinylformic acid/styrene based copolymer (III) that contains epoxy group(ing) is without particular determination, can use the known polymerization processs such as mass polymerization, solution polymerization, suspension polymerization, letex polymerization, from the high aspect of percent polymerization, do not use the aspect that becomes the polymerization starter of the reason that contains impurity, sulphur, chain-transfer agent and solvent to set out, more preferably under the high temperature more than 150 DEG C and pressurized conditions (preferably more than 1MPa), carry out the method for continuous bulk polymerization with the short period of time (preferably 5 minutes～30 minutes).
With respect to the resin combination being formed by phenylethylene resin series (I) and pet resin (II) of 100 weight parts, the use level of the vinylformic acid/styrene based copolymer that contains epoxy group(ing) used in the present invention (III) is 0.01～1 weight part, be preferably 0.03～0.7 weight part, more preferably 0.05～0.5 weight part.If the addition of the vinylformic acid/styrene based copolymer that contains epoxy group(ing) (III) is lower than above-mentioned scope, physical strength deficiency, otherwise, if exceed above-mentioned scope, cause the thermoplastic resin composition's who obtains surface luster property to have the trend of deterioration, so undesirable.
Thermoplastic resin composition of the present invention is surface luster property excellence by coordinating (I)～(III) make one of its feature.So-called surface luster property is that numerical value by measuring according to the regulation of JIS Z8741 (1997) is evaluated herein, and evaluation content is different from the superficiality (evaluation of spot) of recording in patent documentation 4 (TOHKEMY 2005-200534 communique).In thermoplastic resin composition of the present invention owing to having more than 90, preferred more than 95 surface luster property, so can be preferably used as outward appearance goods.
In addition,, in thermoplastic resin composition of the present invention, in the scope of not damaging object of the present invention, can coordinate polyvinyl chloride; The polyolefine such as polyethylene, polypropylene; The polymeric amide such as nylon 6, nylon 66; The polyester such as polybutylene terephthalate and poly terephthalic acid cyclohexanedimethanoester ester; Polycarbonate; The fluorine resins such as tetrafluoroethylene; With various elastomerics classes etc.
In addition, in thermoplastic resin composition of the present invention, can further as required, in the scope of not damaging object of the present invention, coordinate more than a kind following common additive: the inorganic filling materials such as glass fibre, glass powder, granulated glass sphere, glass flake, aluminum oxide, sapphire whisker, carbon fiber, graphite fibre, Stainless Steel Fibre, whisker, potassium titanate fiber, wollastonite, asbestos, flint clay (hard clay), calcined clay, talcum, kaolin, mica, calcium carbonate, magnesiumcarbonate, aluminum oxide and mineral; The antioxidants such as hindered phenol system, sulfocompound system or organic phosphorus compound system; The thermo-stabilizers such as phenol system, acrylic ester; The UV light absorber such as benzotriazole system, benzophenone series or salicylate system; Hindered amine is photostabilizer; Higher fatty acid, acid esters system and acid amides system, and lubricant and the softening agent such as higher alcohols; Montanic acid and its salt, its ester, its half ester, the releasing agents such as stearyl alcohol, stearylamide and ethylene waxes; Various fire retardants, flame retardant; The agent of the anti-coloring such as phosphite, hypophosphite; The neutralizing agents such as phosphoric acid, SODIUM PHOSPHATE, MONOBASIC, maleic anhydride, succinyl oxide; Nucleator; The static inhibitor such as amine system, sulfonic acid system, polyester system; The tinting materials such as carbon black, pigment, dyestuff etc.
About thermoplastic resin composition's of the present invention preparation method, without particular restriction, thermoplastic resin composition of the present invention can be the composition obtaining as follows: use V-type mixing tank such as, super mixing machine, the composition that the mixing machines such as vibrating mixer (super floater) and Henschel mixer obtain (I)～(III), aforementioned other composition pre-mixing that flows suspends, but, mostly conventionally be by above-mentioned premixture equably melting mixing and mixture.Such mixture can obtain by the following method: above-mentioned premixture is used to compounding process, for example preferably 230～300 DEG C, more preferably at the temperature of 250～285 DEG C of left and right, carry out melting mixing, and carry out granulation.As concrete melting mixing, the method for granulation, can list following methods: use various melting mixing machines (such as kneader, single screw rod and twin screw extruder etc.) that resin combination is melt extruded, carry out granulation by tablets press.
The thermoplastic resin composition of the present invention who obtains by aforesaid method can carry out moulding for thermoplastic resin molded known method at present by injection molding, extrusion moulding, blow molding, vacuum forming, compressed moulding and gas assistant formation etc., and itself there is no particular determination forming method.
Embodiment
Explain the present invention with comparative example by the following examples, still, and without they restriction the present invention.
(1) weight average rubber size
The sodium alginate method of recording by " Rubber Age Vol.88p.484～490 (1960) E.Schmidt, P.H.Biddison work " is tried to achieve.That is, the polyhutadiene particle diameter that utilizes emulsification because of the difference of the concentration of sodium alginate different, trying to achieve accumulating weight mark by the part by weight of emulsification and the accumulating weight mark of sodium alginate concentration is 50% particle diameter.
(2) percentage of grafting
In the graft copolymer of specified amount (m), add acetone, reflux 3 hours, after this solution centrifugal being separated to 40 minutes under 8800r/min (10000G), the insoluble composition of leaching, at 60 DEG C by this insoluble composition drying under reduced pressure 5 hours, gravimetry (n).Percentage of grafting calculates according to following formula.
Percentage of grafting (%)={ [(n)-(m) × L]/[(m) × L] } × 100
Herein, the rubber containing ratio that L is graft copolymer.
(3) reduced viscosity [η
sp/ c]
To the acetone that adds 200ml in the sample of 1g, reflux 3 hours, 8800r/min (10000G) is lower this solution centrifugal is separated to 40 minutes after, filter insoluble composition.With rotatory evaporator, filtrate is concentrated, at 60 DEG C, precipitate (the solvable composition of acetone) drying under reduced pressure, after 5 hours, is adjusted into 0.4g/100ml (methylethylketone, 30 DEG C), use determination of ubbelohde viscometer [η
sp/ c].
(4) intrinsic viscosity [η]
The sample of 1g is dissolved in to 100cm equably
3methylene dichloride in, use determination of ubbelohde viscometer specific viscosity [η
sp].And then change concentration and similarly measure specific viscosity, will be to concentration [c] and [η
sp/ c] curve of mapping gained to the value of zero-dose side extrapolation gained as intrinsic viscosity [η]., according to η=lim η
sp/ c (c → 0) calculates.
(5) tensile strength, tensile elongation
According to the regulation of ISO527 (1993), under being 50mm/min, 23 DEG C, the condition of 50%RH, speed measures.
(6) charpy impact intensity (charpy impact strength)
According to the regulation of ISO179 (2000), measure forming under V-type recess (residue width is 8.0mm), 23 DEG C, the condition of 50%RH.
(7) surface luster property
According to the regulation of JIS Z8741 (1997), be to measure under the condition of 60 ° at input angle and reflection angle.
The preparation method of [reference example 1] graft copolymer (A)
To drop in the reactor having replaced with nitrogen pure water, 0.5 weight part of 120 weight parts glucose, (weight average rubber size is 0.3 μ m to trisodium phosphate, the ferrous sulfate of 0.005 weight part and the polybutadiene latex of 60 weight parts (being scaled solids component) of 0.5 weight part, gel containing ratio is 85%), in stirring, the temperature in reactor is warming up to 65 DEG C.The time point that internal temperature is reached to 65 DEG C is counted the mixture that polymerization starts and formed by the tertiary lauryl mercaptan of monomer (vinyl cyanide of the vinylbenzene of 30 weight parts and 10 weight parts) and 0.3 weight part with continuous dropping in 5 hours.Dripped continuously with 7 hours the aqueous solution being formed by cumene hydroperoxide, the potassium oleate of 2.5 weight parts and the pure water of 25 weight parts of 0.25 weight part abreast simultaneously, make to have reacted., after neutralizing with sodium hydroxide, wash, filter, dry and obtain graft copolymer (A) the styrene based copolymer latex coagulation obtaining with sulfuric acid.The percentage of grafting of this styrenic graft copolymer (A) is 35%, the reduced viscosity η of the solvable composition of acetone
sp/ c is 0.35dl/g.
The preparation method of [reference example 2] ethylene-based polymer/multipolymer (B)
Use by 2m
3complete mixed type polymerization tank, single screw extrusion machine type preheating machine and the continous way mass polymerization device that forms of twin-screw extrusion type feeder (evaporation that described complete mixed type polymerization tank has monomer vapours refluxes with condenser and spiral shape impeller (Helical ribbon impeller), described twin-screw extrusion type feeder has twin-screw extrusion type demonomerization machine and is connected in series in the heating unit of the cylindrical portion of distance front end 1/3 length of demonomerization machine), implement as described below the mixing of copolymerization and resinous principle.
First, with 150kg/ hour by 1 of the octyl mercaptan of the vinyl cyanide of the vinylbenzene by 70.0 weight parts, 30.0 weight parts, 0.15 weight part and 0.01 weight part, the monomer mixture that 1-bis-(tert-butyl hydroperoxide) hexanaphthene forms is supplied to polymerization tank continuously, is to press under the condition for 0.08MPa and carry out continuous bulk polymerization in 130 DEG C, groove keeping polymerization temperature.The percent polymerization of the polymerization reaction mixture in polymerization tank is controlled to 74～76% scope.Utilize twin-screw extrusion type demonomerization machine to reclaim unreacted monomer from venting port underpressure distillation from the polyreaction resultant obtaining; it is more than 99% making apparent percent polymerization; be strand shape and discharge, carry out granulation by cutting unit and obtain ethylene-based polymer/multipolymer (B).The reduced viscosity η of this ethylene-based polymer/multipolymer (B)
sp/ c is 0.53dl/g.
[reference example 3] pet resin (II)
Pet resin (II)-1
Prepare the recirculation pellet (Xie Rong Industry Co., Ltd system) of pet resin.
Pet resin (II)-2
As the primary pellet (virgin pellet) of pet resin, prepare TSB900 (intrinsic viscosity that uses ortho chloro phenol solvent to measure is 0.90 for Toray Industries, Inc. system) at 25 DEG C.
Vinylformic acid/styrene based copolymer (III) that [reference example 4] contains epoxy group(ing)
Vinylformic acid/the styrene based copolymer (III)-1 that contains epoxy group(ing)
Vinylformic acid/styrene based copolymer (trade(brand)name: ARUFON UG-4035 that preparation contains epoxy group(ing), Toagosei Co., Ltd's system), described multipolymer contains glycidyl methacrylate, (methyl) vinylformic acid and vinylbenzene as monomeric unit, weight-average molecular weight is 11,000, oxirane value is 1.8meq/g.
Vinylformic acid/the styrene based copolymer (III)-2 that contains epoxy group(ing)
Vinylformic acid/styrene based copolymer (trade(brand)name: JONCRYL ADR-4368 that preparation contains epoxy group(ing), Johnson Polymers Ltd. system), described multipolymer contains glycidyl methacrylate, (methyl) vinylformic acid and vinylbenzene as monomeric unit, weight-average molecular weight is 7,000, oxirane value is 3.5meq/g.
Vinyl cyanide/styrol copolymer (IV) that [reference example 5] contains epoxy group(ing)
By the glycidyl methacrylate suspension polymerization of the vinyl cyanide of the vinylbenzene of 73 weight parts, 26 weight parts, 1 weight part, obtain the vinyl cyanide/styrol copolymer that contains epoxy group(ing) of pearl.
[embodiment 1～6]
With in table 1 show proportioning with reference to the graft copolymer shown in example (A), ethylene-based polymer/multipolymer (B), pet resin (II), vinylformic acid/the styrene based copolymer (III) that contains epoxy group(ing) mixes, use the 30mm twin screw extruder of subsidiary venting hole, be to carry out melting mixing under the condition of 260 DEG C at barrel design temperature, extrude, prepare thus granular thermoplastic resin composition, in 105 DEG C of hot air dryers by predrying the thermoplastic resin composition who obtains 5 hours, use the electric injection moulding machine SE50 processed of Sumitomo Heavy Industries, it is 260 DEG C at barrel temperature, die temperature is that under the condition of 60 DEG C, to many objects test film A shape of ISO3167 (2002) defined, (total length is 150mm, the width of test portion is 10mm, thickness is 4mm) carry out moulding, measure tensile strength, tensile elongation, charpy impact intensity.In addition, also the other side's sheet metal forming product (thickness is 3mm) carry out moulding, for the mensuration of surface luster property.
[comparative example 1～5]
Mix with reference to the graft copolymer shown in example (A), ethylene-based polymer/multipolymer (B), pet resin (II), vinylformic acid/styrene based copolymer (III) of containing epoxy group(ing) with the proportioning that shows in table 2, prepare granular thermoplastic resin composition by the method identical with embodiment.In addition, in comparative example 5, replace the vinylformic acid/styrene based copolymer (III) that contains epoxy group(ing), use with the proportioning of recording in table 2 vinyl cyanide/the styrol copolymer (IV) that contains epoxy group(ing).For the thermoplastic resin composition who obtains, measure various physical property according to embodiment 1～6.
By table 1,2 the clearly following situation of result.
About thermoplastic resin composition of the present invention (embodiment 1～6), physical strength and surface luster property are all balanced and excellent.
On the other hand, comparative example 1 does not add the vinylformic acid/styrene based copolymer (III) that contains epoxy group(ing), compares respectively physical strength inequality with embodiment 2,4 with 5.Otherwise vinylformic acid/styrene based copolymer (III) addition that contains epoxy group(ing) in comparative example 3 and 4 is many, with embodiment 2,6 respectively compared with, surface luster property inequality.
The proportioning of pet resin in comparative example 2 (II) is many, with embodiment 1～3 respectively compared with, physical strength inequality.In addition, used the vinyl cyanide/styrol copolymer (IV) that contains epoxy group(ing) to replace the vinylformic acid/styrene based copolymer (III) that contains epoxy group(ing) in comparative example 5, compared with 5 with embodiment 2,4, surface luster property is poor.
[embodiment 7 and 8, comparative example 6 and 7]
Mix with reference to the graft copolymer shown in example (A), ethylene-based polymer/multipolymer (B), pet resin (II), vinylformic acid/styrene based copolymer (III) of containing epoxy group(ing) with the proportioning that shows in table 3, prepare granular thermoplastic resin composition by method same as the previously described embodiments.In addition, in comparative example 7, use the vinyl cyanide/styrol copolymer (IV) that contains epoxy group(ing) to replace the vinylformic acid/styrene based copolymer (III) that contains epoxy group(ing) with the proportioning showing in table 3.For the thermoplastic resin composition who obtains, measure various physical property according to above-described embodiment.
By the clearly following situation of result of table 3.
About thermoplastic resin composition of the present invention (embodiment 7 and 8), physical strength and surface luster property are all balanced and excellent.
On the other hand, comparative example 6 does not add the vinylformic acid/styrene based copolymer (III) that contains epoxy group(ing), compares respectively physical strength inequality with embodiment 7 with 8.In addition, use the vinyl cyanide/styrol copolymer (IV) that contains epoxy group(ing) to replace the vinylformic acid/styrene based copolymer (III) that contains epoxy group(ing) in comparative example 7, compare with 8 with embodiment 7, surface luster property is poor.
utilizability in industry
Thermoplastic resin composition of the present invention is due to mechanical characteristics, surface luster property excellence, so can be for the various uses such as shell and their parts of electrical/electronic part, auto parts, mechanism part, OA equipment, home appliance etc.Particularly, for example can list the electrical/electronic part taking various gears, various case, sensor, LEP lamp, junctor, socket, resistor, relay1 box, switch, coil stand, electrical condenser, variable condenser case, optical pick-up, vibrator, various wiring board, umformer, plug, printing distributing board, tuner, loud speaker, speaker, earphone, micro-machine, head base, power module, shell, semi-conductor, liquid crystal, FDD slide, FDD chassis, motor brush rocker, parabolic antenna, computer correlated parts etc. as representative; Family, office electric product part taking the sound device parts such as the televisor parts such as VTR part, TV. frames, base, back of the body case, flatiron, blower, electric cooker part, microwave oven part, sound equipment part, Audio Laser Disks (registered trademark), CD, illumination part, refrigerator part, air-conditioning part, type-writer part, word processing machine part etc. as representative; With various bearings, motor parts such as office machine correlated parts, telephone set correlated parts, facsimile recorder correlated parts, duplicating machine correlated parts, cleaning fixture, oilless bearing, stern bearing, immersion bearings, lighter, the mechanical correlated parts that type-writer etc. are representative; Optical device, precision optical machinery correlated parts taking microscope, binoculars, photographic camera, clock and watch etc. as representative; Alternator terminal stud; Alternator junctor; IC setter; The various valves such as vent valve; The relevant exhaust system of fuel is air-breathing is various pipes; Nozzle of air supply ventpipe; Suction manifold; Petrolift; Engine coolant joint; Carburetor main body; Carburettor packing ring; Exhaust gas sensor; Cooling fluid sensor; Oil temperature sensor; Brake(-holder) block wear sensor; Throttle valve position sensor; Crankshaft position sensor; Anemometer; Idle call temperature controller base; Well heater hot air flow control valve; Scatterer motor motor brush rocker; Water pump impeller; Turbine blade; Wiper motor correlated parts; Divider; Starter motor switch; Starter motor rly.; Transmission wire harness; Window washer nozzle; Air-conditioning panel switch substrate; Fuel associated solenoid valve coil; Safety fuse junctor; Loudspeaker terminal stud; Denso part insulcrete; Stepper-motor roller; Lamp socket; Lamp reflector; Lamp housing; Brake piston; Solenoid coil bobbin; Engine oil filter; Portfire case etc., exceedingly useful for above-mentioned various uses.
Claims (7)
1. a thermoplastic resin composition, with respect to the resin combination being formed by phenylethylene resin series (I) and pet resin (II) of 100 weight parts, the vinylformic acid/styrene based copolymer that contains epoxy group(ing) (III) that contains 0.01～1 weight part.
2. thermoplastic resin composition as claimed in claim 1, wherein, the weight-average molecular weight of the vinylformic acid/styrene based copolymer (III) that contains epoxy group(ing) is 2,000～20,000.
3. thermoplastic resin composition as claimed in claim 1 or 2, wherein, the oxirane value of the vinylformic acid/styrene based copolymer (III) that contains epoxy group(ing) is 0.5～4.0 (meq/g).
4. the thermoplastic resin composition as described in any one in claim 1～3, wherein, the weight ratio of phenylethylene resin series (I) and pet resin (II) is 50:50～99:1.
5. the thermoplastic resin composition as described in any one in claim 1～4, wherein, phenylethylene resin series (I) is the composition that the ratio taking weight ratio as 10:90～50:50 contains graft copolymer (A) and ethylene-based polymer/multipolymer (B), described graft copolymer (A) is that to make to be selected from aromatic vinyl be monomer (b), vinyl cyanide is that more than a kind monomer and rubber polymer (a) graft copolymerization in monomer (c) and other vinyl monomer (d) that can copolymerization forms, described ethylene-based polymer/multipolymer (B) is to be monomer (b) by being selected from aromatic vinyl, vinyl cyanide is that the more than a kind monomer polymerization in monomer (c) and other vinyl monomer (d) that can copolymerization forms.
6. the thermoplastic resin composition as described in any one in claim 1～5, wherein, as polyethylene terephthalate (II), the recycled materials of all or part of use pet resin products formed.
7. a products formed, forms the thermoplastic resin composition's moulding described in any one in claim 1～6.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2012-043706 | 2012-02-29 | ||
| JP2012043706 | 2012-02-29 | ||
| PCT/JP2013/055329 WO2013129547A1 (en) | 2012-02-29 | 2013-02-28 | Thermoplastic resin composition and molded article of same |
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| CN104114635A true CN104114635A (en) | 2014-10-22 |
| CN104114635B CN104114635B (en) | 2015-09-09 |
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| CN201380009742.4A Active CN104114635B (en) | 2012-02-29 | 2013-02-28 | Thermoplastic resin composition and products formed thereof |
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| JP (1) | JP5565523B2 (en) |
| KR (1) | KR101949555B1 (en) |
| CN (1) | CN104114635B (en) |
| MY (1) | MY167375A (en) |
| PH (1) | PH12014501843B1 (en) |
| TW (1) | TW201343763A (en) |
| WO (1) | WO2013129547A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105802144A (en) * | 2015-01-19 | 2016-07-27 | 富士施乐株式会社 | Resin composition and resin molded article |
| CN109641993A (en) * | 2016-09-01 | 2019-04-16 | 大科能宇菱通株式会社 | Epoxy-modified vinyl based copolymer, the thermoplastic resin composition comprising the copolymer and its molded product |
| CN110382659A (en) * | 2017-03-02 | 2019-10-25 | 艾克伯有限责任公司 | Cooling liquid composition in cooling liquid cooling system is carried out to the thermogenesis element of setting on a printed circuit |
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| KR20190055573A (en) * | 2017-11-15 | 2019-05-23 | 에스케이케미칼 주식회사 | Polyamide Resin Composition and Resin Product Comprising the Same |
| WO2024010749A1 (en) * | 2022-07-06 | 2024-01-11 | Kaneka Americas Holding, Inc. | Modifiers for polyesters that improve viscosity in melt |
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- 2013-02-28 JP JP2013511430A patent/JP5565523B2/en active Active
- 2013-02-28 WO PCT/JP2013/055329 patent/WO2013129547A1/en active Application Filing
- 2013-02-28 CN CN201380009742.4A patent/CN104114635B/en active Active
- 2013-02-28 KR KR1020147018361A patent/KR101949555B1/en active IP Right Grant
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| JP2001139782A (en) * | 1999-11-11 | 2001-05-22 | Aron Kasei Co Ltd | Polyester resin composition |
| JP2003286382A (en) * | 2002-03-28 | 2003-10-10 | Toray Ind Inc | Sheetlike resin and molded article comprising the same |
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| CN105802144A (en) * | 2015-01-19 | 2016-07-27 | 富士施乐株式会社 | Resin composition and resin molded article |
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| CN109641993B (en) * | 2016-09-01 | 2021-06-22 | 大科能宇菱通株式会社 | Epoxy-modified vinyl copolymer, thermoplastic resin composition containing the same, and molded article thereof |
| CN110382659A (en) * | 2017-03-02 | 2019-10-25 | 艾克伯有限责任公司 | Cooling liquid composition in cooling liquid cooling system is carried out to the thermogenesis element of setting on a printed circuit |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101949555B1 (en) | 2019-02-18 |
| JP5565523B2 (en) | 2014-08-06 |
| PH12014501843A1 (en) | 2014-11-17 |
| WO2013129547A1 (en) | 2013-09-06 |
| CN104114635B (en) | 2015-09-09 |
| KR20140133498A (en) | 2014-11-19 |
| TW201343763A (en) | 2013-11-01 |
| JPWO2013129547A1 (en) | 2015-07-30 |
| PH12014501843B1 (en) | 2014-11-17 |
| MY167375A (en) | 2018-08-16 |
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