CN102918104A - Resin composition and molded product thereof - Google Patents
Resin composition and molded product thereof Download PDFInfo
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- CN102918104A CN102918104A CN201180026826XA CN201180026826A CN102918104A CN 102918104 A CN102918104 A CN 102918104A CN 201180026826X A CN201180026826X A CN 201180026826XA CN 201180026826 A CN201180026826 A CN 201180026826A CN 102918104 A CN102918104 A CN 102918104A
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- 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
- C08L33/04—Homopolymers or copolymers of esters
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08K5/10—Esters; Ether-esters
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K2201/00—Specific properties of additives
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Abstract
Provided are: a molded resin product which exhibits excellent pitch-blackness, weather resistance, processability in molding, boss strength, wear resistance, smokiness, and so on; and a resin composition for producing the same. The resin composition comprises (A) an acrylic resin and (B) a carbon black having a number-average particle diameter of 10 to 40nm.
Description
Technical field
The present invention relates to contain resin combination and the molding thereof of carbon black.
Background technology
Have weathering resistance, gloss and the transparency of excellence as the acrylic resin of main component with polymethylmethacrylate, but can not satisfy simultaneously weathering resistance, shock-resistance and pitch-dark property, use range is limited.
As in order to have the method for pitch-dark property, the acrylic resin laminate film is disclosed in patent documentation 1, good delustring outward appearance and pitch-dark property, printing suitability are excellent as having for it, the acrylic resin laminate film of simultaneously surface hardness, anti-shaping albefaction and the whole edge excellent in workability when being shaped, and acrylic resin layer (A) and acrylic resin layer (B) are carried out laminated forming.The acrylic resin laminate film that uses with stay material as automobile is disclosed, its manufacture method and with its laminated laminate that forms, described acrylic resin laminate film is characterised in that, it is more than the 0.01 μ m that the acrylic resin layer (A) of this film not laminated has the arithmetic average roughness of the face of acrylic resin layer (B) side, be lower than 0.1 μ m, the not laminated of acrylic resin layer (B) has 60 ° of surface glosses of the face of acrylic resin layer (A) side to be lower than 60%, the rubber containing ratio that consists of the acrylic resin composition of acrylic resin layer (A) is more than the 25 quality %, be lower than 40 quality %, and the gel containing ratio is more than the 45 quality %, be lower than 70 quality %.But there is following problem in disclosed film in the patent documentation 1: in order to obtain having the stay material of pitch-dark outward appearance, carry out rete is combined in that structure resin etc. is processed and high price, and damaged during the tapping when digging threaded hole is processed.
As making material originally as pitch-dark method, known have the heat radiation screening plate (patent documentation 2) that has added infrared absorbent and carbon black in the metha crylic resin to reach the heat radiation screening methacrylic acid based resin composition (patent documentation 3) that has added specific carbon black in the metha crylic resin.In addition, as the skin material of ethylene series ester moulding base material, the also known making (patent documentation 4) that the film of the black transparent (smog) of sneaking into dyestuff etc. is arranged.But, in patent documentation 2 and 3, used the great carbon black of particle diameter, the degraded appearance of molding, and then in the shielding slab of patent documentation 2, the photostabilization of infrared absorbent also has problems.In addition, in patent documentation 4, because the particle diameter of the dyestuff that uses is little, therefore, the weathering resistance of dyestuff itself is very low, and therefore, the weathering resistance with film is low problem also.
On the other hand, as the method for improving shock-resistance, the transparent plastics molding is disclosed in patent documentation 5, wherein, as the first layer, it is resin that at least one surface layer on transparent plastic substrate surfaces such as acrylic resins closes the acid of hydroxyl co-polypropylene, laminated acrylic resin layer, the laminated colloid silica that comprises on this first layer, the thermofixation film layer of the organosiloxane resins composition of the hydrolytic condensate of trialkoxy silane, form therefrom described plastics forming body, described acrylic resin layer is to make to comprise the isocyanate group content of counting 0.7～5 equivalent take the total amount of isocyanate group with respect to this hydroxyl 1 equivalent as the polyisocyanate compound of 5.0～60 % by weight and/or be coated with film resin 100 weight parts with respect to the polyisocyanate compound precursor to form as the coating composition of the UV light absorber of 10～50 weight parts carries out thermofixation.But, for disclosed molding in the patent documentation 5, although weather resistance significantly improves, also have excellent performance aspect wear resistance, the hot water resistance, have the many and problem at high price of the worker ordinal number of wear resistance plastics forming body.
In addition, as the method for under the state of the weathering resistance of the excellence that keeps acrylic resin, giving shock-resistance, proposed to have the method that the graft copolymer of various multilayered structures mixes.But, although the method can be improved shock-resistance, owing to cooperating the material of xenogenesis, therefore, resin produces the result of gonorrhoea, has the large macrolesion transparency and pitch-dark property or the mobile problem that reduces.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2009-255555 communique
Patent documentation 2: Japanese kokai publication hei 7-173358 communique
Patent documentation 3: Japanese kokai publication hei 7-62189 communique
Patent documentation 4: TOHKEMY 2006-224459 communique
Patent documentation 5: TOHKEMY 2003-342403 communique
Summary of the invention
The problem that invention will solve
Problem of the present invention is, be provided for obtaining the resin combination of molding, described molding is easy and low-cost, has weathering resistance and gloss, even the black that also has even and excellent for large-scale injection forming parts, shock-resistance is excellent when namely having excellent appearance of black, and has high protruding hub intensity.
Particularly problem of the present invention is particularly in providing resin combination, and described resin combination is provided at equal excellent molding on weathering resistance, wear resistance and the pitch-dark property.
And then problem of the present invention is to be provided for obtaining being used as for example resin combination of the molding with excellent appearance of black and mist of trolley part.
Be used for solving the means of problem
The inventor concentrates on studies in order to solve above-mentioned problem, find, by in thermoplastic resin, containing the carbon black of number average bead diameter in certain scope, can obtain not only black, have excellent weather resistance, and the resin combination of shaping processability, protruding hub intensity, wear resistance and mist excellence, thereby finished the present invention.
That is, the present invention relates to resin combination, it is characterized in that, it contains acrylic resin (A) and number average bead diameter is the carbon black (B) of 10～40nm.
Described carbon black (B) the preferably state take number average bead diameter as 10～40nm disperses.
The state of the preferred described carbon black of described carbon black (B) (B) take number average bead diameter as 10～40nm is separated into primary particle.
It is that 120～250 ℃ organophosphorus is stablizer that described resin combination preferably also contains fusing point.
Described resin combination preferably also contains the lubricant more than a kind that is selected from the group that the acid amides by the lipid acid of the ester of the lipid acid of C10～C30 and C10～C30 consists of.
The specific absorbance of the molding that preferably described resin combination is shaped and obtains is 0.02～0.04ppm
-1Cm
-1
The full light transmittance that described acrylic resin (A) is preferably the thick molding of the 3mm that obtained by this acrylic resin is the acrylic resin more than 85%.
Described acrylic resin (A) preferably comprises the modified rubber acrylic resin.
In addition, the present invention relates to resin molded body, it forms resin combination of the present invention and obtains.
In addition, the present invention relates to trolley part, it has used resin molded body of the present invention.
The invention effect
The state of resin combination of the present invention take number average bead diameter as 10～40nm disperses, the organophosphorus that also contains fusing point and be 120～250 ℃ is the acid amides of the lipid acid of the ester of lipid acid of stablizer and C10～C30 or C10～C30, therefore, can obtain the resin molded body of the excellences such as pitch-dark property, weathering resistance, shaping processability, protruding hub intensity, wear resistance, mist and be used for obtaining the resin combination of this molding.
Description of drawings
Fig. 1 is electron microscope (TEM) photo of the molding of making among the embodiment 4;
Fig. 2 is electron microscope (TEM) photo of sample that has cooperated the composition (CB-4) of black masterbatch (CB-3);
Fig. 3 is electron microscope (TEM) photo of the sample of composition (CB-5).
Embodiment
(resin combination)
Resin combination of the present invention contains acrylic resin (A) and number average bead diameter is the carbon black (B) of 10～40nm.
(acrylic resin)
In the present application, use the acrylic resin (A) as thermoplastic resin.Acrylic resin has the excellent especially transparency, and shock-resistance is excellent, in addition, resin molded body can be made the molding with excellent especially appearance of black.Acrylic resin can contain some acrylic resin that has carried out modification, is that resin contains like that and utilizes the imide-modified resin that forms etc. such as containing just like the maleimide modified acroleic acid.
Considering from the viewpoint of giving excellent pitch-dark property or excellent mist, is that the full light transmittance of the molding of the 3mm thickness that obtains of resin (A) is preferably more than 85% by aforesaid propylene acid, more preferably more than 90%.At this, the light wavelength that is used for full light transmittance mensuration is 380～780nm.
As acrylic resin, consider from the viewpoint that shows excellent shock-resistance etc., preferably contain the modified rubber acrylic resin.
(modified rubber acrylic resin)
Consider from the viewpoint that obtains excellent shock strength, acrylic resin preferably is made as 100 % by weight with its total scale of construction, contains rubber acrylic acid series graft copolymer (A1) 5～100 % by weight and acrylic resin (A2) 95～0 % by weight.The content that contains rubber acrylic acid series graft copolymer (A1) and acrylic resin (A2) is distinguished more preferably 10～50 % by weight and 90～50 % by weight.
In addition, in the situation of making the molding with specific specific absorbance described later, preferably the composition of modified rubber acrylic resin is made as and contains rubber acrylic acid series graft copolymer (A1) 10～40 % by weight, acrylic resin (A2) 60～90 % by weight and other material 0～5 % by weight.As other material, can use UV light absorber described later and photostabilizer, various antioxidant, carbon black tinting material in addition etc.
(containing rubber acrylic acid series graft copolymer (A1))
Consider from the viewpoint that obtains excellent shock strength and the transparency, make preferably that to contain rubber acrylic acid series graft copolymer (A1) be the multilayered structure graft copolymer, grafting composition (A1s) skin that its mode take the weight ratio of A1c:A1s as 5:95～85:15 contains rubbery copolymer (A1c) internal layer and covers this internal layer.Consider from the viewpoint of further raising shock strength, the weight ratio of above-mentioned A1c:A1s is 25:75～80:20 more preferably.
In addition, consider from the viewpoint that obtains excellent shock strength and the transparency especially, further more preferably has at least multilayered structure graft copolymer of 3-tier architecture, it is take the total amount of A1a:(A1c and A1s) weight ratio contain innermost layer polymkeric substance (A1a) and be in the presence of this innermost layer polymkeric substance (A1a) as the mode of 10:90～40:60, the monomer of the above-mentioned rubbery copolymer of polymerization (A1c) forms.
(rubbery copolymer (A1c))
Consider from the viewpoint that obtains excellent shock strength and the transparency, above-mentioned rubbery copolymer (A1c) but be preferably by vinyl monomer 0～49.9 % by weight of the copolymerization beyond alkyl acrylate 50～99.9 % by weight, alkyl acrylate and rubbery copolymer that multi-functional monomer 0.1～10 % by weight the consists of polymkeric substance with monomer, but more preferably by vinyl monomer 0～29 % by weight of the copolymerization beyond alkyl acrylate 70～99 % by weight, the alkyl acrylate and rubbery copolymer that multi-functional monomer 0.1～5 % by weight the consists of polymkeric substance with monomer.
The number-average molecular weight of rubbery copolymer (A1c) is generally 500～100000.
Above-mentioned rubbery copolymer (A1c) is for to utilize its caoutchouc elasticity mainly to bear the integrant of shock-resistance improved effect.In addition, the specific refractory power of rubbery copolymer (A1c) more close to the specific refractory power of grafting composition (A1s) or acrylic resin (A2), in addition, its particle diameter is less, more easily is transparent.
As the aforesaid propylene acid alkyl ester, the viewpoint of the speed of response during from polymerization is considered, the carbonatoms of its alkyl is preferably 1～8, such as enumerating: methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate (BA), ethyl acrylate (2EHA), vinylformic acid-n-octyl (nOA) etc., consider from the viewpoint that improves shock-resistance, be preferably selected from the group that is consisted of by BA, 2EHA and nOA more than a kind, be particularly preferably BA.They can use separately, and also two or more kinds may be used.The alkyl of alkyl acrylate can be the straight chain shape, also can be the side chain shape.
But as the vinyl monomer of the copolymerization beyond the aforesaid propylene acid alkyl ester, can enumerate: the non-alkyl ester of (methyl) vinylformic acid, (methyl) vinyl cyanide, (methyl) vinylformic acid etc. such as the alkyl methacrylates such as aromatic vinyl ester, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate such as vinylbenzene, alpha-methyl styrene, Vinyl toluene, (methyl) phenyl acrylate, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate.
Above-mentioned multi-functional monomer is the monomer that per 1 molecule has 2 above unconjugated double bonds, be the composition that works as linking agent or graft crosslinking agent, consider from the viewpoint of bridging property, be preferably selected from by aklylene glycol two (methyl) esters of acrylic acid, contain the multi-functional monomer class of vinyl and contain in the group that the multi-functional monomer class of allyl group consists of more than a kind.
As above-mentioned aklylene glycol two (methyl) esters of acrylic acid, can enumerate: ethylene glycol bisthioglycolate (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, dibutylene glycol two (methyl) acrylate etc.As the above-mentioned multi-functional monomer class of vinyl that contains, can enumerate: Vinylstyrene, divinyl adipic acid ester etc.As the above-mentioned multi-functional monomer class of allyl group that contains, can enumerate: (methyl) allyl acrylate, Phthalic acid, diallyl ester, triallyl cyanate, triallyl isocyanate etc.
(grafting composition (A1s))
Consider from the viewpoint that obtains excellent shock strength, the transparency and shaping processability, above-mentioned grafting composition (A1s) but be preferably grafting composition that vinyl monomer 0～50 % by weight by the copolymerization beyond alkyl methacrylate 50～100 % by weight and the alkyl methacrylate consists of with the polymkeric substance of monomer, but the grafting composition that more preferably is made of vinyl monomer 20～0 % by weight of the copolymerization beyond alkyl methacrylate 80～100 % by weight and the alkyl methacrylate is with the polymkeric substance of monomer.The viewpoint that from the flowability that improves resin combination of the present invention, further improves shaping processability is considered, preferably further adds mercaptan compound 0.01～5 weight parts such as lauryl mercaptan, octyl mercaptan with respect to the grafting composition with monomer 100 weight parts.
This grafting composition (A1s) can be made multilayered structure with himself as required.
As above-mentioned alkyl methacrylate, the viewpoint of the speed of response during from polymerization is considered, the carbonatoms of preferred its alkyl is 1～4, such as enumerating: methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate etc., but consider from the viewpoint that improves processibility, be preferably methyl methacrylate.The alkyl of alkyl methacrylate can be the straight chain shape, also can be the side chain shape.
But as the vinyl monomer of the copolymerization beyond the alkyl methacrylate, can enumerate: the non-alkyl ester of (methyl) vinylformic acid, (methyl) vinyl cyanide, (methyl) vinylformic acid etc. such as the alkyl acrylates such as aromatic vinyl ester, methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate such as vinylbenzene, alpha-methyl styrene, Vinyl toluene, (methyl) phenyl acrylate, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid benzyl ester.
(innermost layer polymkeric substance (A1a))
Above-mentioned innermost layer polymkeric substance (A1a) is preferably by 40～99.9 % by weight of the monomer more than a kind that are selected from the group that is made of alkyl methacrylate and aromatic ethenyl compound, but other vinyl monomer 59.9～0 % by weight of copolymerization, and the innermost layer polymkeric substance of multi-functional monomer 0.1～5 % by weight formation is with the polymkeric substance of monomer, more preferably by 55～90 % by weight more than a kind that are selected from the group that is made of alkyl methacrylate and aromatic ethenyl, other vinyl monomer 45～10 % by weight that can copolymerization, and the innermost layer polymkeric substance of multi-functional monomer 0.1～5 % by weight formation polymkeric substance of monomer.
In the presence of this innermost layer polymkeric substance (A1a), by the above-mentioned rubbery copolymer of polymerization monomer, innermost layer polymkeric substance (A1a) becomes the layer that probably is distributed in its central part in above-mentioned containing in the rubber acrylic acid series graft copolymer (A1).
As aromatic ethenyl compound, be preferably selected from the group that is consisted of by vinylbenzene, alpha-methyl styrene and Vinyl toluene more than a kind, vinylbenzene more preferably.
But other vinyl monomer and the multi-functional monomer as the alkyl methacrylate copolymerization can use respectively above-mentioned material.
Be explained, " (methyl) acrylate " refers to acrylate and/or methacrylic ester." (methyl) vinyl cyanide " refers to vinyl cyanide and/or methacrylonitrile, and in addition, " (methyl) vinylformic acid " refers to vinylformic acid and/or methacrylic acid.
Consider from the viewpoint of shock-resistance and the balance of the transparency, such number average bead diameter that contains rubber acrylic acid series graft copolymer (A1) preferably is made as 30～400nm, more preferably is made as 40～300nm.
The manufacture method that contains rubber acrylic acid series graft copolymer (A1) like this is not particularly limited, such as using suspension polymerization, emulsion polymerization etc., consistent by the particle diameter that makes copolymer particle, can bring into play more excellent effect, therefore, preferably make with emulsion polymerization.
As such rubber acrylic acid series graft copolymer (A1) that contains, from can significantly improving while the transparency of keeping acrylic resin the aspect consideration of shock-resistance, the acrylic acid series graft copolymer that contains acrylic rubber that for example can use Kanegafuchi Chemical Ind to make.
(acrylic resin (A2))
Acrylic resin (A2) is as the substrate resin of resin combination of the present invention, as containing the described successive layers resin that contains rubber acrylic acid series graft copolymer (A1) and carbon black of the present invention (B), being that matrix resin works.Consider from the viewpoint that obtains the excellent transparency, be preferably the polymkeric substance that the acrylic resin that is made of alkyl acrylate 0～50 % by weight and alkyl methacrylate 100～50 % by weight is used monomer.
The number-average molecular weight of acrylic resin (A2) is preferably 5000～150000, and more preferably 9000～120000.
The manufacture method of such acrylic resin (A2) is not particularly limited, such as using suspension polymerization, emulsion polymerization etc., but from making the effectively viewpoint consideration of copolymerization of alkyl methacrylate and alkyl acrylate, preferred suspension polymerization.
As alkyl acrylate and alkyl methacrylate, can use respectively above-mentioned alkyl acrylate and alkyl methacrylate.
(carbon black)
Resin combination of the present invention contains the carbon black that number average bead diameter is 10～40nm (B).
In the situation of the molding that obtains pitch-dark property, consider from the viewpoint of modified rubber acrylic resin composition of the present invention being given sufficient pitch-dark property, more preferably number average bead diameter is 10～30nm, more preferably 10～25nm most preferably is 10～20nm.The carbon black that number average bead diameter surpasses 40nm might not show sufficient pitch-dark degree, in addition, although number average bead diameter is lower than the ability excellence that the carbon black of 10nm is given pitch-dark degree, has the problem of easily cohesion or usually is difficult to the problem that particle diameter separates and is difficult to obtain.
In addition, in the situation of the resin molded body that obtains having specific specific absorbance of the present invention, from the viewpoint of resin combination being given excellent appearance of black, namely carbon black (B) is disperseed so that molding has the viewpoint of specific specific absorbance considers, its number average bead diameter is 10～30nm more preferably, more preferably 10～20nm.The carbon black that number average bead diameter surpasses 40nm is difficult to make molding to have specific specific absorbance sometimes, in addition, sometimes is difficult to obtain having the resin molded body that does not have anisochromatic black or mist.In addition, although number average bead diameter is lower than the ability excellence that the carbon black of 10nm is given mist, usually be difficult to obtain.
In addition, carbon black (B) preferably in resin combination the state take number average bead diameter as 10～40nm disperse.Consider from the aspect that makes the black colour developing, the dispersion state of carbon black is more preferably once disperseed.At this, once disperse to refer to that the particle of carbon black is primary particle, i.e. the unit cell state that can not disperse with other particle coacervation.In the situation that carbon black, particle itself is not spherical completely, can be confirmed whether by the observation that utilizes TEM once to disperse.
In the situation of the molding that obtains pitch-dark property, the number average bead diameter when carbon black disperses in resin combination, disperse particle diameter since with above-mentioned same reason, 10～30nm more preferably, more preferably 10～25nm most preferably is 10～20nm.
In addition, in the situation of the molding that obtains having specific specific absorbance of the present invention, the dispersion particle diameter of carbon black since with above-mentioned same reason, more preferably 10～30nm, more preferably 10～20nm.
Be explained, in the present invention, above-mentioned number average bead diameter is measured the size of the composition that has profile and can't separate for electron microscope observation carbon black aggregate, carries out arithmetical mean and the value that obtains under N=50 condition.
As carbon black, be preferably MCF (the Medium Colour Furnace that has as the generic name of color black, middle pigment furnace black) carbon black (the HCF:High Colour Furnace of above degree of blackness, high pigment furnace black or HCC:High Colour Channnel, high pigment channel black), can enumerate: Mitsubishi's カ ー ボ Application Block ラ ッ Network (registered trademark) #2600, #980, #960 (Mitsubishi chemical Co., Ltd's system) ト ー カ Block ラ ッ Network (registered trademark) #8500, #7400, #7350, #7100 (East Sea カ ー ボ Application Co., Ltd. system), ColourBlack (registered trademark) FW200, FW2, S170, Printex (registered trademark) 90,80 (エ ボ ニ ッ Network デ グ サ company systems), Raven (registered trademark) 7000,5750,3500 (コ ロ Application PVC ヤ Application ケ ミ カ Le ス company systems), Monarch (registered trademark) 1400,1300,900,800, Black Pearls (registered trademark) 1400,1300,900,800, Vulcan (registered trademark) P (キ ャ ボ ッ ト company system) etc., but be not limited to them.
In addition, supply form as carbon black has Powdered or granular form, compares with direct interpolation, consider from the viewpoint of the dispersiveness of carbon black, for example preferably use carbon black with acrylic resin and high density to carry out pre-mixing and pulverize the pigment of the so-called masterbatch that forms.The molecular weight of the acrylic resin that uses in the making of masterbatch is preferred 50000～150000, and more preferably 90000～120000.Be lower than at 50000 o'clock, exist easily to produce the tendency that the molecular weight in masterbatch manufacturing process, the granule manufacture operation reduces.Surpass at 150000 o'clock, the mobile reduction has the tendency that is difficult to injection forming.
In addition, in order to make the resin molded body with particular absorption that the present invention relates to, consider from the viewpoint of the dispersiveness of the quality stability of mist, carbon black, metering, quality stability, preference as through 2 stages with on reduce carbon black concentration, namely by carry out in advance mixing, then repeat the operation pulverized, the masterbatch that carbon black concentration is low is used for final shaping.
Consider from the viewpoint of giving sufficient pitch-dark property, the addition of carbon black is 0.05～10 weight part with respect to acrylic resin (A) 100 weight parts preferably, more preferably 0.1～5 weight part.When surpassing 10 weight part, pitch-dark degree is saturated, and is therefore uneconomical.
In the situation of the resin molded body that obtains having specific specific absorbance, consider from the viewpoint of giving black, be 0.001～0.1 weight part with respect to acrylic resin (A) 100 weight parts preferably, and then, consider from the viewpoint of giving mist, more preferably 0.001～0.05 weight part, i.e. 10～500 ppm by weight, further preferred 20～300 ppm by weight, further more preferably 40～250 ppm by weight, particularly preferably 40～100 ppm by weight.
In the present invention, in order to obtain the resin molded body of excellent appearance of black, preferably only use carbon black (B) to carry out painted, (Exposure to Sunlight weather colour fastness instrument is (rainy using but in the scope that can keep necessary weathering resistance, 63 ℃ of black panel temperature) under 2000 hours the condition of exposure, can keep Δ E and be lower than 3 scope) in, can further use pigment or dyestuff to carry out painted.But, when excessively adding pigment or dyestuff, because the reduction of the weathering resistance of the substrate resin that the existence of the weathering resistance of pigment or dyestuff self and pigment or dyestuff causes might can not get the long-term excellent resin molded body of appearance of black.
(organophosphorus is stablizer)
It is that 120～250 ℃ organophosphorus is stablizer that resin combination preferred resin composition of the present invention also contains fusing point (mp).This is because when obtaining resin molded body of the present invention by resin combination, in order to improve processibility, at high temperature form or owing to using large-scale forming mill, the residence time of resin combination prolongs, therefore, particularly can further improve the thermostability that adds man-hour, obtain the molding of the outward appearance of pitch-dark property excellence.In addition, from considering in the viewpoint that adds the viewpoint of bringing into play above-mentioned effect man-hour and prevent from oozing out, more preferably organophosphorus is that the fusing point of stablizer is 140 ℃～200 ℃.
Be stablizer as such organophosphorus, can preferably use 2,2 '-methylene-bis (4,6-two-tert-butyl-phenyl) octyl group phosphorous acid ester (mp146～152 ℃, the ア of Co., Ltd. デ カ HP-10 processed for example), three (2,4-two-tert-butyl-phenyl) phosphorous acid ester (mp180～190 ℃, the イ Le ガ Off ォ ス 168 that makes of BASF AG for example, the ア デ カ ス タ Block 2112 that the ア デ カ of Co., Ltd. makes), two (2,6-two-tertiary butyl-4-aminomethyl phenyl) pentaerythritol diphosphites (mp234～240 ℃, the PEP-36 that makes of the ア of Co., Ltd. デ カ for example), 2-[[2,4,8,10-four (1,1-dimethyl ethyl) dibenzo [d, f] [1,3,2] dioxathion suberene-6-yl] oxygen]-N, N-two [2-[[2,4,8,10-four (1,1-dimethyl ethyl) dibenzo [d, f] [1,3,2] dioxathion suberene-6-yl] oxygen]-ethyl] ethamine (mp190～210 ℃, イ Le ガ Off ォ ス 12 such as BASF AG's manufacturing) etc.
Preferably adding above-mentioned organophosphorus with respect to acrylic resin (A) 100 weight parts is stablizer 0.01～3 weight part, more preferably adds 0.05～1 weight part, further preferred 0.1～0.5 weight part that adds.
(lubricant)
Be maintained in the pitch-dark property of body and the viewpoint of the molding of excellent in abrasion resistance is considered from formation, in addition, from considering with the consistency of the suitable degree of acrylic resin (A) and the viewpoint of the balance that also shows external lubrication to a certain degree, resin combination of the present invention preferably also contains the lubricant more than a kind that is selected from the group that the acid amides by the lipid acid of the ester of the lipid acid of C10～C30 and C10～C30 consists of.
As fatty acid ester (the fatty acid part ester that contains polyvalent alcohol), can enumerate: montanate, butyl oleate, butyl stearate, hardened castor oil, ethylene glycol monostearate, XU 61518.10, Zerol, Span-20 etc.
As fatty amide, can enumerate: oleylamide, stearylamide, palmitic amide, methylene-bis stearylamide, ethylenebisstearamide etc.
In above-mentioned, more preferably be selected from the group that the alcohol ester by the C10～C30 of the lipid acid of the glycol ester of the lipid acid of C10～C30 and C10～C30 consists of more than a kind, the glycol ester of the lipid acid of further preferred C10～C30.As the glycol ester of the lipid acid of C10～C30, can enumerate the glycol ester of montanic acid, stearic glycol ester etc., more preferably the glycol ester of montanic acid.
With respect to acrylic resin 100 weight parts, preferred 0.1～10 weight part of the addition of lubricant, more preferably 0.5～5 weight part.When being lower than 0.1 weight part, be difficult to show additive effect, when surpassing 10 weight part, show the reduction of pitch-dark property of molding or the reduction of physical property.
In addition, as other lubricant, such as may be used aliphatic hydrocarbon, fatty family alcohol, lipid acid, metallic soap, silicone oil etc.
As aliphatic hydrocarbon, can enumerate: Liquid Paraffin, native paraffin, synthetic paraffin, little wax (Microcrystalline Wax), polyethylene wax and their partial oxide, fluorochemical, muriate etc.As fatty family alcohol, can enumerate: hexadecanol, lauryl alcohol, stearyl alcohol, oleyl alcohol, mixing-in fat family alcohol etc.As lipid acid, can enumerate: lauric acid, stearic acid, mixed fatty acid (from the lipid acid of tallow, fish oil, Oleum Cocois, soybean oil, rapeseed oil, rice bran wet goods) etc.As metallic soap, can enumerate: barium stearate, Zinic stearas, calcium stearate, lead stearate, aluminum stearate, Magnesium Stearate etc.As silicone oil, can enumerate with the silicone oil of polydimethylsiloxane as main component, and then, in this silicone oil, can enumerate the silicone oil that contains the carboxylic acid group, the modified silicon oils such as silicone oil that contain hydroxyl.
(other additive)
In resin combination of the present invention, can further add as required various UV light absorber, photostabilizer, antioxidant, carbon black tinting material, organophosphorus in addition is stablizer in addition etc.
(UV light absorber)
From its ultraviolet radiation absorption can viewpoint consider, UV light absorber be preferably selected from the group that the UV light absorber by benzotriazole system, triazine system and benzophenone series consists of more than a kind.Example as the UV light absorber of benzotriazole system, can enumerate: 2-(2-hydroxy-5-methyl base phenyl) benzotriazole, 2-[2-hydroxyl-5-(1,1,3, the 3-tetramethyl butyl) phenyl] benzotriazole, 2-[2-hydroxyl-3, two (the α of 5-, α-dimethylbenzyl) phenyl] benzotriazole, 2-(the 2 '-hydroxyl-3-tertiary butyl-5 '-aminomethyl phenyl)-5-chlorobenzotriazole, 2-(2-hydroxyl-3,5-two-tert-pentyl phenyl) benzotriazole, 2-(2-hydroxyl-3-sec-butyl-5-tert-butyl-phenyl) benzotriazole, 2,2 '-methylene-bis [6-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethyl butyl) phenol], 2-(2-hydroxy-5-methyl base-3-dodecylphenyl) benzotriazole etc.As the UV light absorber of triazine system, can enumerate 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-5-[(hexyl) the oxygen base]-phenol etc.As the example example of the UV light absorber of benzophenone series, can enumerate: 2-hydroxy-4-phenyl methoxy benzophenone, ESCALOL 567-5-thionyl trihydrate benzophenone, 2-hydroxy-4-phenyl propoxy-benzophenone etc.
Consider from the viewpoint that weathering resistance is further improved, preferably in resin combination, add the UV light absorber of the amount that can not exert an influence to the full light transmittance of its molding.For example preferably add 0.1～15 weight part, more preferably 0.2～5 weight part with respect to acrylic resin (A) 100 weight parts.
(photostabilizer)
As photostabilizer, be not particularly limited, can use known photostabilizer, for example can enumerate: 2,2,6,6-tetramethyl--4-piperidyl stearate, 2,2,6,6-tetramethyl--4-piperidyl benzoic ether, 1,2,2,6,6-pentamethyl--4-piperidyl stearate, N-(2,2,6,6-tetramethyl--4-piperidyl) dodecyl succinate imide, 1,2,2,6,6-pentamethyl--4-piperidyl benzoic ether, 1,2,2,6,6-pentamethyl--4-piperidino methyl acrylate, two (2,2,6,6-tetramethyl--4-piperidyl) sebate, two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate, two (1-octyloxies-2,2,6,6-tetramethyl--4-piperidyl) sebate, two (2,2,6,6-tetramethyl--4-piperidyl) two (tridecyl)-1,2,3,4-ethylene-dimalonic acid ester, two (1,2,2,6,6-pentamethyl--4-piperidyl) two (tridecyl)-1,2,3,4-ethylene-dimalonic acid ester, two (1,2,2,6,6-pentamethyl--4-piperidyl)-2-butyl-2-(3,5-di-tert-butyl-hydroxy phenyl methyl) malonic ester, four (2,2,6,6-tetramethyl--4-piperidyl)-1,2,3,4-ethylene-dimalonic acid ester, four (1,2,2,6,6-pentamethyl--4-piperidyl)-1,2,3,4-ethylene-dimalonic acid ester, 3,9-two [1,1-dimethyl-2-[three (2,2,6,6-tetramethyl--4-piperidines oxygen base carbonyl oxygen base) butyl carbonyl oxygen base] ethyl]-2,4,8,10-four dislikes spiral shell [5.5] undecane, 3,9-two [1,1-dimethyl-2-[three (1,2,2,6,6-pentamethyl--4-piperidines oxygen base carbonyl oxygen base) butyl carbonyl oxygen base] ethyl]-2,4,8,10-four dislikes spiral shell [5.5] undecane, 1-[(3,5-two-tert-butyl-hydroxy phenyl) propionyloxy ethyl]-2,2,6,6-tetramethyl--4-piperidyl-(3,5-two-tert-butyl-hydroxy phenyl) propionic ester, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl--4-piperidine alcohols/Succinic acid dimethylester condenses, uncle's 2-octyl group amino-4,6-two chloro-s-triazine/N, N '-two (2,2,6,6-tetramethyl--4-piperidyl) hexamethylene-diamine condenses, N, N '-two (2,2,6,6-tetramethyl--4-piperidyl) hexamethylene-diamine/ethylene dibromide condenses, 2,2,6,6-tetramethyl--4-hydroxy piperidine-N-oxide compound, 1,6-two (2,2,6,6-tetramethyl--4-piperidyl amino) hexane/ethylene dibromide polycondensate, 1,6-two (2,2,6,6-tetramethyl--4-piperidyl amino) hexane/2,4-two chloro-uncle 6-octyl group amino-s-triazine polycondensates, 1,6-two (2,2,6,6-tetramethyl--4-piperidyl amino) hexane/2,4-two chloro-6-morpholino-s-triazine polycondensates etc.
Consider from the viewpoint that weathering resistance is further improved, with respect to acrylic resin (A) 100 weight parts, preferably in resin combination, add photostabilizer 0.1～3 weight part.
(resin molded body)
Resin molded body of the present invention forms resin combination of the present invention and obtain, and has excellent black, the i.e. appearance of black of excellence.
In the present invention, the molding of pitch-dark property excellence refers to that the L value of defined among the JISZ-8729 is the molding below 6.5.The L value is more preferably below 6.The L value by to the mensuration face of resin molded body from directly over (90 °) irradiation light, measure from measuring towards the light of 45 ° direction reflection and estimate.
In addition, form and the specific absorbance of the resin molded body that obtains is 0.02～0.04ppm at the resin combination with the present application
-1Cm
-1Situation under, resin molded body presents excellent appearance of black and excellent mist.
Above-mentioned specific absorbance defines with following mathematical expression 1.
Specific absorbance={ log
10(I
0/ I) }/(C * L) (mathematical expression 1)
In mathematical expression 1, C is the weight concentration (ppm) of the carbon black (B) in the resin (A), and I is the parallel rays transmissivity of this resin molded body, I
0For with the same shape of this resin molded body and do not contain the parallel rays transmissivity of the resin molded body of carbon black (B), L is to the thickness of this resin molded body of the incident direction of this parallel rays of this resin molded body (cm).
In addition, in the situation that acrylic resin (A) is the modified rubber acrylic resin, by aesthetic appearance, for example transparency and the gloss such as the distinctive excellence as glass of acrylic resin, not only help the appearance of black with the collaborative excellence of the carbon black that disperses in the mode with above-mentioned specific specific absorbance (B), and, can give weathering resistance, gloss and the shock-resistance of resin molded body excellence of the present invention.
In addition, have the resin molded body of above-mentioned specific specific absorbance, from having excellent light half transmitting, i.e. excellent mist and become the viewpoint consideration of the outward appearance with degree of depth, its full light transmittance is preferably 1%～80%, and more preferably 30%～80%.
In addition, has the resin molded body of above-mentioned specific specific absorbance by adopting by 2 principal planes and 4 flat boards that side plane consists of, and form this interarea and be minute surface, other this interarea and 4 these side planes have the shape on pears skin shape surface, can make thus the little molding of L value.
Resin combination of the present invention has excellent appearance of black, shaping processability is excellent, therefore, can utilize the manufacturing process of known thermoplastic resin, such as injection molding method, extrusion molding method etc. can be preferred for residential building material purposes, trolley part, electrical and electronic parts, groceries, film etc.This molding is weathering resistance, shock-resistance, outward appearance excellence not only, and black and gloss are also excellent, therefore, be suitable as the appearance part that for example needs senior outward appearance, as such appearance part, be suitable for vehicle part and household electrical appliances article component, furniture parts, OA framework purposes, film purposes.
(trolley part)
Resin formation body and function of the present invention can be made trolley part of the present invention, also can be used in exterior member, the inside components any.For example, if the molding of pitch-dark property then can be preferably used as the engines such as decoration class, engine shield periphery part, the radiator grids etc. such as cover class, pillar decoration, rear plaque, rear spoiler, switch cover, near the employed indoor rear plaque of supervisory control desk such as pillar cover.In addition, if having the resin molded body of the light half transmitting of above-mentioned specific specific absorbance, then can be suitable as side visor and sun visor, skylight etc.
The resin molded body of the application of the invention, can make and not only have excellent weathering resistance, gloss, even the trolley part that also has the black of uniform excellence, i.e. excellent appearance of black, and shock-resistance excellence, has high protruding hub intensity for large-scale injection forming parts.In addition, resin molded body of the present invention can be suitable as needs senior outward appearance, and needs the automotive part of excellent wear resistance.
Embodiment
Below, enumerate embodiment the present invention is described in further detail, but the present invention not only is defined in these embodiment.
In embodiment 1～6 and comparative example 1～3, use the raw material of following record, method to make sample, implement various evaluations.To form and evaluation result gathers and is shown in table 1～3.
(raw material)
(containing rubber acrylic acid series graft copolymer (A1)): the acrylic acid series modifier カ ネ エ ー ス M210 that Kanegafuchi Chemical Ind makes (rubber particles of multilayered structure, core: the acrylic rubber of multilayered structure, shell: with methyl methacrylate as the acrylic acid polymer of main component, about particle diameter: 220nm)
(acrylic resin (A2))
Acrylic resin 1: ア Network リ ペ ッ ト VH001 (Directory Value: 100 ℃ of load deformation temperature (JIS K7191,1.80MPa), melt flow rate (MFR) (JIS K7210,230 ℃, 37.3N) 2.0g/10min) (the full light transmittance of the molding of 3mm thickness: 92.5%) that レ イ ヨ Application Co., Ltd. of Mitsubishi makes
Acrylic resin 2: パ ラ ペ ッ ト F1000 (the full light transmittance of the molding of 3mm thickness: 92.5%) that the Network ラ レ of Co., Ltd. makes
Acrylic resin 3: デ Le ペ ッ ト 80NE (Directory Value: 97 ℃ of load deformation temperature (ISO75-1,75-2), melt flow rate (MFR) (ISO1133cond13) 2.3g/10min) (the full light transmittance of the molding of 3mm thickness: 92%) that Asahi Chemical Corp makes
Acrylic resin 4: デ Le ペ ッ ト 720V (Directory Value: 93 ℃ of load deformation temperature (ISO75-1,75-2), melt flow rate (MFR) (ISO1133cond13) 21g/10min) (the full light transmittance of the molding of 3mm thickness: 92%) that Asahi Chemical Corp makes
(carbon black)
Carbon black (#2600 processed of Mitsubishi chemical Co., Ltd, utilize the actual measurement particle diameter 10nm of TEM)
The twin screw extruder of use 44mm carries out 2 granulations with carbon black 40 weight parts, acrylic resin 2:59 weight part, antioxidant (the イ Le processed ガ ノ ッ of BASF AG Network ス 1010) 0.5 weight part and dispersion agent 0.5 weight part and (mixture of carbon black and acrylic resin is carried out granulation under 260 ℃, in this particle, mix other composition and carry out the 2nd time granulation) after pulverize, make thus the masterbatch (CB-1) of carbon black, do not make resin combination with carbon black itself with masterbatch.
(phosphorus is stablizer)
The PEP-36 (two (2,6-, two-tertiary butyl-4-aminomethyl phenyl) pentaerythritol diphosphites) that the ア デ カ of Co., Ltd. makes
The HP-10 (2,2 '-methylene-bis (4,6-, two-tert-butyl-phenyl) octyl group phosphorous acid ester) that the ア デ カ of Co., Ltd. makes
(other Synergist S-421 95)
In each table, the gradation composition of record, use respectively the チ ヌ PVC Application 234 (benzotriazole is UV light absorber) of BASF AG's manufacturing, the ア デ カ ス タ Block LA-63 (hindered amine is photostabilizer) of the ア デ カ of Co., Ltd. manufacturing and each 0.5 weight part of イ Le ガ ノ ッ Network ス 1010 (hindered phenol is antioxidant) that BASF AG makes.
(method)
(single Screw Extrusion)
Use the single screw extrusion machine (ironworker is made in Co., Ltd.'s stone) of 40mm, die head temperature is set as 260 ℃, have the title complex of above-mentioned raw materials to extrude dry blending and make material strip, carry out granulation with tablets press.
(twin-screw extrusion)
Use the twin screw extruder JSW-TEX44 (Corporation Japan Steel Works's system) of 44mm, die head temperature is set as 260 ℃, similarly carry out granulation.
(injection forming)
Being produced as follows of sample of using in embodiment 1～3, the comparative example 1 carried out.That is, use FANUC オ ー ト シ ョ ッ ト FAS-150B (150 tons of mold clamping pressures) injection machine, with spray nozzle front end Temperature Setting each temperature for regulation, the large flat sample (minute surface precision work) of 150 * 150 * 3mm is formed.
The protruding hub strength detection that uses in embodiment 4～6, comparative example 2,3 uses FANUC オ ー ト シ ョ ッ ト FAS-150B (150 tons of mold clamping pressures) injection machine with in the making of sample, is 250 ℃ with the spray nozzle front end Temperature Setting.The protruding hub intensity evaluation of M5 that has an a plurality of protruding hub section along circumference to the toroidal of diameter 160mm, thickness 2.5mm forms with molding.
(embodiment 1～3, comparative example 1)
Composition according to shown in the table 1 cooperates, utilizes extruding, be shaped, estimate of forcing machine.
[table 1]
(evaluation)
(delay thermostability)
Delay thermostability when having estimated injection forming.In the situation that without the residence time, will be set as namely 18 seconds cooling time of standard cooling time, the time cycle is namely 37 seconds cycle standard times.Residence time during evaluation only is made as the form that the part-time set prolongs cooling time.For example in the situation that 60 seconds residence times will be set as namely 78 seconds standard cooling time+residence time cooling time, the time cycle is namely 97 seconds cycle+residence time standard times.In addition, be set as the forming mode that per 2 injections prolong the residence time.In brief, at each temperature, after not having to carry out under the residence time 2 injection formings, carry out dijection with 60 seconds residence times and be shaped, carried out injection forming 2 times with 120 seconds residence times, carried out injection forming 2 times with 180 seconds residence times.In the situation that the change forming temperature fully purges.
Visual molding according to the state of flash of light (pattern, the silver bar line seen in the moving mode of many linear flows), is followingly judged.
Zero: do not see flash of light, become clearly minute surface.
△: see small flash of light.
*: obviously confirm flash of light.
* *: resin in the purging of machine barrel foams, can't normally be shaped.
-: do not implement to be shaped.
[table 2]
Like this, be stablizer in the situation that added organophosphorus, observe the high thermostability of being detained.Particularly find using 2, in the situation of 2 '-methylene-bis (4,6-, two-tert-butyl-phenyl) octyl group phosphorous acid ester, even under 290 ℃ of high like this forming temperatures, also can stand so long delay in 3 minutes.As its one of the main reasons, can enumerate: organophosphorus be stablizer fusing point with the scope of the process zone of acrylic resin coupling, that is, in the processing temperature of this fusing point and resin, have sufficient width.That is, think in extruding both of mixing and injection forming, require phosphorus to be stablizer fully dissolving under processing temperature, fused with composition.Consider from this viewpoint, think, be that the fusing point of stablizer is with respect in the too high situation of processing temperature at phosphorus, thereby under processing temperature, fully do not dissolve and do not bring into play function, on the contrary, be in the excessively low situation of the fusing point of stablizer at phosphorus, when using the no problem molding of dissolving, cause and the bad phenomenon such as ooze out.
(embodiment 4～6, comparative example 2 and 3)
Composition according to shown in the table 3 cooperates, utilizes extruding, be shaped, estimate of forcing machine.In comparative example 2,3, the acrylic resin as raw material is directly formed.
(evaluation)
(protruding hub intensity)
The evaluation of protruding hub intensity (M5): in the protruding hub 2 of the protruding hub 1 of external diameter 8.0mm, internal diameter 4.5mm, degree of depth 10mm and external diameter 10.0mm, internal diameter 4.3mm, degree of depth 10mm, repeat respectively to be screwed into for 2 times the coiled hair thread cutting screw of M5.0 * 6mm, the having or not of the crackle that in protruding hub, produces by Visual Confirmation.Be screwed into condition and evaluation result is as described below.
Moment of torsion: 3Nm
Rotating speed: 1000rpm
Sample number: 3
Zero: do not have crackle, also idle running etc. is unusual
*: produce crack and significant crackle
[table 3]
As mentioned above, distinguish that the application's the practical intensity of molding of composition is also excellent.
(large-scale shaping)
Use the resin combination of embodiment 4, set the B-pillar of automobile, use 360 tons injection machine (Nissei Plastic Industrial Co., Ltd) roughly to be the コ font with the cross section under 280 ℃ the flat board of 600 * 100 * 10mm (thickness 3mm) is formed, the result obtains the non-defective unit molding of pitch-dark property.
(tem observation)
On to the basis that cuts for example ultrathin section(ing) enforcement ruthenium dyeing of the part of the molding of embodiment 4 with slicing machine, carry out TEM (infiltration type electron microscope) and observe.As shown in Figure 1, confirming fine carbon black disperses in resin well.Be explained, observing in the continuous mode of the particle of carbon black is that particle for the particle that can observe the place ahead and rear overlaps.Consider from the aspect that shows pitch-dark property as can be known, need to use fine carbon black and carbon black not to condense and well dispersion.The resin molded body and the trolley part that are made of such resin combination have excellent outward appearance.
(embodiment 7～11, comparative example 4,5)
Use raw material, the method for following record to make sample, implement various evaluations.
(raw material)
(containing rubber acrylic acid series graft copolymer (A1)): the カ ネ エ ー ス M210 that Kanegafuchi Chemical Ind makes
(acrylic resin (A2))
(A2-1): the デ Le ペ ッ ト 80NE that Asahi Chemical Corp makes
(A2-2): the デ Le ペ ッ ト 720V that Asahi Chemical Corp makes
(lubricant)
WAXE: montanic acid wax (montanic acid glycol ester), Network ラ リ ア Application ト society system
The LOXIOLG47 of G47:C11-24 lipid acid C13-24 ester, エ メ リ ー オ レ オ ケ ミ カ Le ズ ジ ャ パ Application company system
WH255C: high fatty acid amide (ラ イ ト ア マ イ De), Kyoeisha Chemical Co., Ltd.'s system
EB-FF: ethylenebisstearamide, Kao Corp's system
FZ3703: silicone oil, Japanese ユ ニ カ ー Co., Ltd. system
(carbon black)
Carbon black (#2600 processed of Mitsubishi chemical Co., Ltd, utilize the actual measurement particle diameter of TEM to be 10nm)
In order to improve the dispersiveness of carbon black, with carbon black 40 weight parts, the acrylic acid series softening agent resin (multipolymer of methyl methacrylate 87 % by weight and methyl acrylate 13 % by weight, and being the resin of 15g/10min for melt flow rate (MFR) (JIS K7210,230 ℃, 37.3N)) 60 weight parts and antioxidant (the イ Le ガ ノ ッ Network ス 1010 that BASF AG makes) the 0.5 weight part twin screw extruder that uses 44mm pulverizes after 2 granulations carrying out under 240 ℃, makes thus the masterbatch (CB-2) of carbon black.
(method)
Containing rubber acrylic acid series graft copolymer (A1) 15 weight parts, (A2-1) 50 weight parts, (A2-2) 35 weight parts, (CB-2) チ ヌ PVC Application 234 (benzotriazole is UV light absorber) 0.5 weight part that dry blending BASF AG makes in the lubricant of the amount of record in 0.5 weight part and the table 4, イ Le ガ ノ ッ Network ス 1010 (hindered phenol is antioxidant) 0.5 weight part that ア デ カ ス タ Block LA-63 (hindered amine is photostabilizer) 0.5 weight part that the ア デ カ of Co., Ltd. makes and BASF AG make uses the twin screw extruder of 44mm to carry out granulation under 240 ℃.Use this particle that the bar of the flat board of 150 * 150 * 3mm, the autochromatic plate of 50 * 90 * 3mm (CP) and 63.5 * 12.7 * 6.3mm is formed and estimates.
(evaluation)
(mensuration of L value)
About flat samples and autochromatic plate sample, the SE2000 (according to light splitting mode behind JISZ8722, the 0-45 degree) that uses the Japanese electric look Industrial Co., Ltd as colour-difference meter to make measures the L value as the index of pitch-dark property.That is, to the mensuration face of resin molded body from directly over (90 °) irradiation light, measure from measuring towards the light of 45 ° direction reflection and also estimate.Be explained, the sample that the L pH-value determination pH is used uses the minute surface wax (compound) of using in advance #7000 to carry out the accurately machined mould of minute surface (NAK80 that steel use Daido Steel Co., Ltd to make) and makes.
(abradability test)
In the molding sample, the minute surface that the die face to by injection forming the time forms carries out wearing test with wear testing machine under following condition.
Use equipment: HEIDON(ヘ イ De Application) formula wear testing machine 14DR (new eastern science Co., Ltd. system)
Translational speed: 6000mm/ minute
Movable length: 5cm
Mobile number of times: 50 is reciprocal
Weighing load: 1kg
The wearing and tearing anchor clamps: ASTM formula anchor clamps are fixed with respect to axle with the not way of contact each other, and anchor clamps are generally parallel with respect to sample.In the lower side bonds rigid plastics 2cm * 2cm processed of ASTM anchor clamps, the compact board of thickness 2mm.The cloth of No. 3, canequim is installed by the side with 4 recoil groups from it, is fixed with the kayser of ASTM anchor clamps.Like this, cloth and sample are with about 4cm
2Area contact, and correctly be transmitted at load under the state of sample and carry out wearing test.
After the test, estimate by visual, to almost not be made as 4 with situation about damaging on the surface, with obvious damage with a plurality of muscle shapes, even (front refers to that viewer's head is positioned at flat board with respect to sample in vertical normal direction from positive, even exist from light behind, also become the viewer the head shadow and such condition that is blocked) see that situation about also bleaching is made as 1, the situation of will be between 4 and 1 and confirming damage from the front is made as 2, will be in the situation that be difficult to see damage between 4 and 2 and seeing from the front, but in situation about tilting, can see that the situation of damage is made as 3.
The kind of the lubricant of each embodiment, comparative example and composition and L value and cut resistance test result concluded be shown in table 4.
[table 4]
As shown in Table 4, as lubricant, in the situation of the ester of the lipid acid that has used C10～C30, particularly used in the situation of glycol ester of montanic acid, obtain well excellent molding as the L value of the index of pitch-dark property and both balances of wear resistance.
Particularly, in embodiment 7, although for carry out the wearing test of 50 reciprocal such very harsh conditions with 1kgf load, show good wear resistance, it is shocking, be lower than 1 with the difference of the L value of the pitch-dark degree of the comparative example 4 that does not have lubricant.And then, in embodiment 8, show the better wear resistance unlike embodiment 7, to one's surprise equally, be lower than 0.3 with the difference of the L value of the pitch-dark degree of the comparative example 4 that does not have lubricant.In addition, in embodiment 9, as can be known and since show to surpass embodiment 8 good wear resistance and with the pitch-dark degree of embodiment 8 with the excellence of degree, therefore, also preferred as the ester base lubricant beyond the montanate of lubricant.In embodiment 10,11, as can be known, although the kind of lubricant be acid amides system with embodiment 7～embodiment 9 in the ester base lubricant that uses have chemically visibly different character, have both the pitch-dark degree and the wear resistance that are equal to them, also preferred as the acid amides base lubricant of lubricant.Be explained, the result of the abradability test of embodiment 11 is between 3 and 4.Even use as can be known stearylamide, the variation of L value is also few, and wear resistance is good.
Yet in comparative example 5, although the lacquer density difference, wear resistance is not enhanced, and therefore, the selection of the kind of lubricant, particularly to be conceived to the selection of the fusing point of lubricant and polarity very important.
(reference example 1, embodiment 12～15, comparative example 6～9)
Use raw material, the method for following record to make sample, implement various evaluations.
(raw material)
(containing rubber acrylic acid series graft copolymer (A1)): the カ ネ エ ー ス M210 that Kanegafuchi Chemical Ind makes
(acrylic resin (A2))
(A2-3): the acrylic resin that is made of methyl methacrylate 97 % by weight and methyl acrylate 3 % by weight is with the multipolymer of monomer, and is that melt flow rate (MFR) (JIS K7210,230 ℃, 37.3N) is the acrylic resin of 2.0g/10min (the full light transmittance of the molding of 3mm thickness: 92%)
(A2-4): the acrylic resin that is made of methyl methacrylate 87 % by weight and methyl acrylate 13 % by weight is with the multipolymer of monomer, and is that melt flow rate (MFR) (JIS K7210,230 ℃, 37.3N) is the acrylic resin of 15g/10min (the full light transmittance of the molding of 3mm thickness: 92%)
(composition (CB-4))
In order to improve the dispersiveness of carbon black, the twin screw extruder that uses 44mm is pulverized carbon black (#2600 that Mitsubishi chemical Co., Ltd makes, utilize the actual measurement particle diameter of TEM to be 10nm) 40 weight parts, the above-mentioned A2-3 of 60 weight parts and antioxidant (the イ Le ガ ノ ッ Network ス 1010 that BASF AG makes) 0.5 weight part carrying out under 240 ℃ after 2 granulations, make thus the masterbatch (CB-3) of carbon black.In by the modified rubber acrylic resin (A) that contains rubber acrylic acid series graft copolymer (A1) and acrylic resin (A2) formation, cooperate black masterbatch (CB-3) with the composition shown in the table 5, further チ ヌ PVC Application 234 (benzotriazole is UV light absorber) 0.5 weight part that BASF AG makes will have been added, the title complex of イ Le ガ ノ ッ Network ス 1010 (hindered phenol is antioxidant) 0.5 weight part that ア デ カ ス タ Block LA-63 (hindered amine is photostabilizer) 0.5 weight part that the ア デ カ of Co., Ltd. makes and BASF AG make uses the twin screw extruder of 44mm to carry out granulation under 240 ℃, makes composition (CB-4).
(composition (CB-5))
In order to compare, with the composition shown in the table 5 by containing rubber acrylic acid series graft copolymer (A1), and the middle masterbatch of commercially available carbon black that cooperates of modified rubber acrylic resin (A) that acrylic resin (A2) consists of is namely firmly changed the SPAB-8K500 (carbon concentration 45 % by weight) that カ ラ ー Co., Ltd. makes, further チ ヌ PVC Application 234 (0.5 weight part) will have been added, the title complex of ア デ カ ス タ Block LA-63 (0.5 weight part) and イ Le ガ ノ ッ Network ス 1010 (0.45 weight parts) uses the twin screw extruder of 44mm to carry out granulation under 240 ℃, makes composition (CB-5).
[table 5]
(method)
(reference example 1)
Contain rubber acrylic acid series graft copolymer (A1) 15 weight parts and by (A2-3) 50 weight parts and (A2-4) add チ ヌ PVC Application 234 (0.5 weight parts), ア デ カ ス タ Block LA-63 (0.5 weight part) and イ Le ガ ノ ッ Network ス 1010 (0.5 weight parts) in modified rubber acrylic resin (A) 100 weight parts of acrylic resin (A2) 85 weight parts that consist of of 35 weight parts and carry out dry blending, using the twin screw extruder of 44mm under 240 ℃, to carry out granulation.Use this particle, the flat board of 150 * 150 * 3mm, the autochromatic plate of 50 * 90 * 3mm and the bar of 63.5 * 12.7 * 6.3mm are formed.
(embodiment 12～15)
In modified rubber acrylic resin composition 101.5 weight parts of reference example 1, add composition (CB-4), in embodiment 12, add respectively 2.5 weight parts, in embodiment 13, add 5 weight parts, in embodiment 14, add 10 weight parts, in embodiment 15, add 20 weight parts, said composition and reference example 1 are similarly formed, obtain thus flat board, autochromatic plate (CP) and bar.
(comparative example 6～9)
In embodiment 12～15, composition (CB-4) monomer is replaced with composition (CB-5), in addition, the sample of comparison example 6～9 and estimating similarly.
Namely, in modified rubber acrylic resin composition 101.5 weight parts of reference example 1, add composition (CB-5), in comparative example 6, add respectively 2.5 weight parts, in comparative example 7, add 5 weight parts, in comparative example 8, add 10 weight parts, in comparative example 9, add 20 weight parts, said composition and reference example 1 are similarly formed, obtain thus flat board, autochromatic plate and bar.
(evaluation)
(mensuration of L value)
For the L value, the SE2000 (according to light splitting mode behind JISZ8722, the 0-45 degree) that uses the Japanese electric look Industrial Co., Ltd as colour-difference meter to make measures flat samples and autochromatic plate (CP) sample.That is, by to the mensuration face of resin molded body from directly over (90 °) irradiation light, measure from measuring towards the light of 45 ° direction reflection and estimate.Be explained, the sample use that the L pH-value determination pH is used has been carried out the accurately machined mould of minute surface (NAK80 that steel use Daido Steel Co., Ltd to make) making with the minute surface wax of #7000 in advance.
(mensuration of full light transmittance and haze value)
The average value that sees through under wavelength 380～780nm that full light transmittance and haze value are measured for the NDH-300A that flat samples used Japanese electric look Industrial Co., Ltd make, according to JIS K7105.
(parallel rays transmissivity)
In addition, take these measurement results as the basis, utilize following mathematical expression 2 to obtain the parallel rays transmissivity.
Parallel rays transmissivity=0.01 * full light transmittance * (100-haze value) (mathematical expression 2)
(specific absorbance)
The value of the parallel rays transmissivity that use obtains uses following mathematical expression 1 to calculate the specific absorbance (ppm of each sample
-1Cm
-1).
Specific absorbance={ log
10(I
0/ I) }/(C * L) (mathematical expression 1)
In mathematical expression 1, C is the carbon black weight concentration (ppm) in the resin, and L is thickness (cm), the I with the direction of each sample tests light ray parallel
0Be the parallel rays transmissivity of the sample of the reference example 1 that do not contain carbon black, I is the parallel rays transmissivity that is dispersed with each sample of carbon black.
(Izod impact test)
Izod impact test uses the bar sample, according to ASTM D256, implements under 1/4 inch, non-notch, 23 ℃ condition.
(carbon black number average bead diameter)
Cut the part of flat samples with slicing machine, carry out tem observation on the basis of this ultrathin section(ing) having been implemented ruthenium dyeing.Number average bead diameter (dispersion particle diameter) is for being scattered in the carbon black aggregate in the molding and measuring size with composition that profile can't separate, carry out the value that arithmetical mean obtains with N=50 with tem observation.
(mist at initial stage)
Use flat samples, by the visual valuation mist, with 4: very excellent, 3: poor than 4, but very excellent, 2: excellence, 1: the 4 such stages of poor (having the tone inequality) are estimated.
(weathering resistance)
Evaluation for weathering resistance, the flat samples of 150 * 150 * 3mm is cut into 47 * 72 * 3mm, the WEL-SUN-HCHB type daylight carbon arc lamp formula atmospheric exposure test machine (daylight extra long life weather-meter) that uses ス ガ trier Co., Ltd. to make, be implemented under 63 ℃ of the black panel temperature, expose 2000 hours atmospheric exposure test under the such condition of the circulation of 12 minutes water sprays in the irradiation in 60 minutes, to be lower than 3 average evaluation be that weathering resistance is good with keeping Δ E.
(outward appearance)
Outward appearance by the visual valuation sample.If excellent appearance of black then is evaluated as zero, if not excellent outward appearance, then be evaluated as *.
The evaluation result of calculated value, L value, full light transmittance, haze value, specific absorbance, cantilever-type impact strength, carbon black number average bead diameter, weathering resistance and the outward appearance of the carbon concentration of each sample is shown in table 6.As shown in table 6, the black of resin molded body of the present invention, mist, shock-resistance, weathering resistance and outward appearance are excellent.
[table 6]
| ? | Reference example 1 | Embodiment 12 | Embodiment 13 | Embodiment 14 | Embodiment 15 | Comparative example 6 | Comparative example 7 | Comparative example 8 | Comparative example 9 |
| Carbon concentration (ppm by weight) | 0 | 48 | 94 | 179 | 329 | 49 | 95 | 181 | 332 |
| L value (CP) | 11.0 | 6.0 | 5.4 | 5.4 | 5.2 | 7.4 | 7.2 | 7.4 | 7.6 |
| L value (flat board) | 6.7 | 5.7 | 5.0 | 5.0 | 5.2 | 7.0 | 6.9 | 7.1 | 7.3 |
| Full light transmittance (flat board) (T%) | 92.5 | 29.60 | 11.50 | 1.90 | 0.10 | 16.68 | 3.46 | 0.18 | 0.00 |
| Haze value (%) | 2.23 | 3.49 | 2.67 | 3.72 | 4.74 | 3.49 | 4.74 | 6.78 | 100.00 |
| Parallel rays transmissivity (%) | 90.44 | 28.57 | 11.19 | 1.83 | 0.10 | 16.10 | 3.30 | 0.17 | 0.00 |
| Specific absorbance (ppm -1cm -1) | ? | 0.0348 | 0.0322 | 0.0315 | 0.0302 | 0.0510 | 0.0505 | 0.0503 | ? |
| Protruding hub intensity (J/m) | 460 | 460 | 460 | 460 | 460 | 460 | 460 | 460 | 460 |
| Carbon black number average bead diameter (nm) | Nothing | 10 | 10 | 10 | 10 | 30 | 30 | 30 | 30 |
| The mist at initial stage | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | - |
| Weathering resistance is estimated | Good | Good | Good | Good | Good | Good | Good | Good | Good |
| Outward appearance | - | ○ | ○ | ○ | ○ | × | × | × | × |
The sample of the embodiment 12～15 that obtains all has excellent appearance of black.The appearance of black of the sample of the comparative example 6～9 that obtains does not all have the degree of depth, with the appearance of black phase ratio of the sample of embodiment 12～15.
Carry out the tem observation of composition (CB-4) and sample (CB-5).
Fig. 2 represents the electron micrograph of the sample of composition (CB-4).Be under the state of primary particle at carbon black as can be known, as number average bead diameter, disperse equably with 10～15nm.Be explained, this is because observing in the continuous mode of the particle of carbon black is that particle for the particle of observing the place ahead and rear overlaps.The particle of particle diameter 220nm among the figure is for containing rubber acrylic acid series graft copolymer (A1).
Fig. 3 represents the electron micrograph of the sample of composition (CB-5).As can be known a plurality of cohesions of carbon black and disperseing with number average bead diameter 50nm.Be explained, the particle of the particle diameter 220nm among the figure is for containing rubber acrylic acid series graft copolymer (A1).
As shown in Table 6, in the embodiment 12～15 of the composition (CB-4) that has used carbon black once to disperse equably with number average bead diameter 10～15nm, the carbon black in each sample still once disperses with number average bead diameter 10～15nm.
Resin molded body of the present invention disperses to form in the mode that carbon black (B) has a specific specific absorbance in acrylic resin (A), therefore, compare with existing carbon black dispersion resin molded body, for absorbancy low, the light permeability is high, the resin molded body of black and mist excellence, appearance of black is excellent.
Claims (10)
1. resin combination is characterised in that, it contains acrylic resin (A) and number average bead diameter is the carbon black (B) of 10～40nm.
2. resin combination as claimed in claim 1 is characterised in that, the state of described carbon black (B) take number average bead diameter as 10～40nm disperses.
3. resin combination as claimed in claim 2 is characterised in that, the state of described carbon black (B) take number average bead diameter as 10～40nm is separated into primary particle.
4. such as each described resin combination in the claim 1～3, be characterised in that, it also contains fusing point is that 120～250 ℃ organophosphorus is stablizer.
5. such as each described resin combination in the claim 1～3, it is characterized in that, also contain the lubricant more than a kind that is selected from the group that the acid amides by the lipid acid of the ester of the lipid acid of C10～C30 and C10～C30 consists of.
6. such as each described resin combination in the claim 1～3, it is characterized in that, the specific absorbance of the molding that the resin combination shaping is obtained is 0.02～0.04ppm
-1Cm
-1
7. such as each described resin combination in the claim 1～6, it is characterized in that, the serve as reasons full light transmittance of the thick molding of 3mm that this acrylic resin obtains of described acrylic resin (A) is acrylic resin more than 85%.
8. resin combination as claimed in claim 7 is characterized in that, described acrylic resin (A) comprises the modified rubber acrylic resin.
9. resin molded body, it is shaped each described resin combination in the claim 1～8 and obtains.
10. trolley part, it has used resin molded body claimed in claim 9.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010126158 | 2010-06-01 | ||
| JP2010-126159 | 2010-06-01 | ||
| JP2010126159 | 2010-06-01 | ||
| JP2010-126157 | 2010-06-01 | ||
| JP2010-126158 | 2010-06-01 | ||
| JP2010126157 | 2010-06-01 | ||
| PCT/JP2011/062587 WO2011152449A1 (en) | 2010-06-01 | 2011-06-01 | Resin composition and molded product thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102918104A true CN102918104A (en) | 2013-02-06 |
Family
ID=45066807
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180026826XA Pending CN102918104A (en) | 2010-06-01 | 2011-06-01 | Resin composition and molded product thereof |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5898072B2 (en) |
| KR (1) | KR20130113316A (en) |
| CN (1) | CN102918104A (en) |
| WO (1) | WO2011152449A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107033512A (en) * | 2016-02-04 | 2017-08-11 | 旭化成株式会社 | Methacrylic resin composition and its formed body |
| CN109071908A (en) * | 2016-03-30 | 2018-12-21 | 日本瑞翁株式会社 | Acrylic polymer compositions |
| CN110494460A (en) * | 2017-02-03 | 2019-11-22 | 卢塞特英国国际有限公司 | Polymer composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2425471B1 (en) * | 2012-03-12 | 2014-07-25 | Iqap Masterbatch Group, S.L. | Concentrated polymeric composition ("masterbatch"), its manufacturing process, and its use for the aditivication of polyester fibers and filaments |
| JP2014234508A (en) * | 2013-06-05 | 2014-12-15 | 旭化成ケミカルズ株式会社 | Thermoplastic resin composition and enclosure |
| JP6356006B2 (en) * | 2014-08-05 | 2018-07-11 | 旭化成株式会社 | Molded product of methacrylic resin composition |
| WO2017170042A1 (en) * | 2016-03-30 | 2017-10-05 | 日本ゼオン株式会社 | Acrylic polymer composition |
| JP6597785B2 (en) * | 2016-07-21 | 2019-10-30 | 三菱ケミカル株式会社 | Thermoplastic resin composition, molded article and vehicle material |
| JP7110609B2 (en) * | 2018-02-05 | 2022-08-02 | テクノＵｍｇ株式会社 | Thermoplastic resin composition and molded article thereof |
| JP7082566B2 (en) * | 2018-12-28 | 2022-06-08 | 株式会社クラレ | Opaque resin substrate for ball game and its manufacturing method, and resin substrate for ball game with printing film |
| JP7000366B2 (en) * | 2019-02-01 | 2022-02-10 | 大日精化工業株式会社 | Resin composition, resin molded product, and method for manufacturing the resin composition. |
| KR20240113245A (en) | 2023-01-13 | 2024-07-22 | 현대자동차주식회사 | Resin composition |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09241474A (en) * | 1996-03-04 | 1997-09-16 | Mitsubishi Rayon Co Ltd | Thermoplastic resin composition |
| JP2003055527A (en) * | 2001-08-22 | 2003-02-26 | Techno Polymer Co Ltd | Thermoplastic resin composition for laser marking |
| CN1500835A (en) * | 2002-11-06 | 2004-06-02 | ������������ʽ���� | Master batch and toner for use in electrophotography |
| JP2006335849A (en) * | 2005-06-01 | 2006-12-14 | Daicel Polymer Ltd | Thermoplastic resin composition for white color marking use |
| CN101155874A (en) * | 2005-02-07 | 2008-04-02 | 纳幕尔杜邦公司 | Thermoplastic vulcanisate blend |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2555860B2 (en) * | 1993-12-20 | 1996-11-20 | 株式会社日本触媒 | Heat ray shield |
| JP3456301B2 (en) * | 1995-03-30 | 2003-10-14 | チッソ株式会社 | Fiber-reinforced thermoplastic composite containing fibers and specific carbon black uniformly |
| DE19523086A1 (en) * | 1995-06-26 | 1997-01-02 | Bayer Ag | Use of polymer molding compounds for partial color changes by laser energy to generate optical information with very good contrasts |
| JPH09111083A (en) * | 1995-10-19 | 1997-04-28 | Nok Corp | Acrylic rubber composition |
| JPH09227749A (en) * | 1996-02-20 | 1997-09-02 | Denki Kagaku Kogyo Kk | Elastomer composition and rubber hose |
| JP3892983B2 (en) * | 1999-01-25 | 2007-03-14 | ダイセル化学工業株式会社 | Resin composition for white marking |
| JP3507003B2 (en) * | 2000-04-21 | 2004-03-15 | 呉羽化学工業株式会社 | Polyvinylidene fluoride black monofilament and method for producing the same |
| JP4516196B2 (en) * | 2000-06-02 | 2010-08-04 | パナソニック株式会社 | Photosensitive black paste |
| JP3900834B2 (en) * | 2001-01-29 | 2007-04-04 | 東海ゴム工業株式会社 | Rubber composition and heat-resistant hose |
| JP2006137815A (en) * | 2004-11-10 | 2006-06-01 | Toray Ind Inc | Polyamide resin composition and molding consisting of the same |
| JP2006348082A (en) * | 2005-06-13 | 2006-12-28 | Kaneka Corp | Thermoplastic elastomer composition |
| WO2007005899A2 (en) * | 2005-06-30 | 2007-01-11 | E.I. Du Pont De Nemours And Company | Ethylene/alkyl acrylate copolymers, compounds and vulcanizates thereof |
| JP2008255145A (en) * | 2007-04-02 | 2008-10-23 | Nippon Carbide Ind Co Inc | Polyurethane-based master batch |
| JP5313135B2 (en) * | 2007-06-13 | 2013-10-09 | 電気化学工業株式会社 | Acrylic rubber composition and vulcanized rubber and use thereof |
| JP2009067981A (en) * | 2007-08-23 | 2009-04-02 | Sanyo Chem Ind Ltd | Transparent resin composition |
| JP5130163B2 (en) * | 2008-09-05 | 2013-01-30 | 三菱エンジニアリングプラスチックス株式会社 | Method for producing polyamide resin composition having excellent weather resistance |
-
2011
- 2011-06-01 JP JP2012518426A patent/JP5898072B2/en not_active Expired - Fee Related
- 2011-06-01 WO PCT/JP2011/062587 patent/WO2011152449A1/en active Application Filing
- 2011-06-01 CN CN201180026826XA patent/CN102918104A/en active Pending
- 2011-06-01 KR KR1020127031446A patent/KR20130113316A/en not_active Application Discontinuation
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09241474A (en) * | 1996-03-04 | 1997-09-16 | Mitsubishi Rayon Co Ltd | Thermoplastic resin composition |
| JP2003055527A (en) * | 2001-08-22 | 2003-02-26 | Techno Polymer Co Ltd | Thermoplastic resin composition for laser marking |
| CN1500835A (en) * | 2002-11-06 | 2004-06-02 | ������������ʽ���� | Master batch and toner for use in electrophotography |
| CN101155874A (en) * | 2005-02-07 | 2008-04-02 | 纳幕尔杜邦公司 | Thermoplastic vulcanisate blend |
| JP2006335849A (en) * | 2005-06-01 | 2006-12-14 | Daicel Polymer Ltd | Thermoplastic resin composition for white color marking use |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107033512A (en) * | 2016-02-04 | 2017-08-11 | 旭化成株式会社 | Methacrylic resin composition and its formed body |
| CN109071908A (en) * | 2016-03-30 | 2018-12-21 | 日本瑞翁株式会社 | Acrylic polymer compositions |
| CN110494460A (en) * | 2017-02-03 | 2019-11-22 | 卢塞特英国国际有限公司 | Polymer composition |
| CN110494460B (en) * | 2017-02-03 | 2022-06-07 | 三菱化学英国有限公司 | Polymer composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2011152449A1 (en) | 2013-08-01 |
| KR20130113316A (en) | 2013-10-15 |
| WO2011152449A1 (en) | 2011-12-08 |
| JP5898072B2 (en) | 2016-04-06 |
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