CN103228686B - Thermoplastic resin processing aid, and thermoplastic resin composition containing same - Google Patents
Thermoplastic resin processing aid, and thermoplastic resin composition containing same Download PDFInfo
- Publication number
- CN103228686B CN103228686B CN201180043825.6A CN201180043825A CN103228686B CN 103228686 B CN103228686 B CN 103228686B CN 201180043825 A CN201180043825 A CN 201180043825A CN 103228686 B CN103228686 B CN 103228686B
- Authority
- CN
- China
- Prior art keywords
- weight
- multipolymer
- thermoplastic resin
- monomer
- processing aid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—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 a halogen; Compositions of derivatives of such polymers
- C08L27/02—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
Abstract
[Problem] To provide a thermoplastic resin processing aid that can effectively increase molding/processing properties of a thermoplastic resin or a composition containing same without detracting from the intrinsic properties of the thermoplastic resin. [Solution] The processing aid for being combined with a thermoplastic resin is characterized by (1) the processing aid containing a copolymer (A) obtained by copolymerizing a) 50-95 wt% of an aromatic vinyl monomer, b) 5-50 wt% of a vinyl cyanide monomer, and d) 0-45 wt% of another vinyl monomer that can copolymerize with the aromatic vinyl monomer and the vinyl cyanide monomer (however, the total of the monomers used in the copolymer (A) is 100 wt%), (2) the peak molecular weight (Mp) of the copolymer (A) being at least one million, and (3) the copolymer being a particulate, wherein 1-50 wt% of particles with a particle size of at least 355 [mu]m are contained in every 100 wt% of the copolymer (A).
Description
Technical field
The present invention relates to suitable conduct for improving the thermoplastic resin processing aid thermoplastic resin of processing aid of the shaping processability of thermoplastic resin.Further relate to the thermoplastic resin composition who comprises above-mentioned processing aid.
Background technology
Thermoplastic resins such as phenylethylene resin series, vinyl chloride resin is because shaping processability is excellent, and excellent rigidity, so be widely used as the shaped material such as vehicle articles for use, household supplies, electrochemical product etc.
Conventionally, in the moulding methodes such as extrusion molding, foaming and molding, vacuum forming, the empty shaping of pressure, blow molding, require can maintain good viscoelastic shaped material in wide temperature range.More specifically, when melting occurs shaped material (resinous principle), can bring into play in the elastic situation of high melting, can access excellent shaping processability, the excellent molding such as result is can quality bills of materials, outward appearance.
Therefore the melting elasticity that, particularly improves thermoplastic resin is obtaining becoming important factor aspect excellent molding.For example, in the situation that manufacturing the resin forming products such as foam sheet, also must suitably improve the melting elasticity as the thermoplastic resin of shaped material (raw material).In this case, also considered to improve melting elasticity by increasing the molecular weight of thermoplastic resin self, if but there is the large significantly reduced shortcoming of the mobility of molten resin correspondingly of molecule quantitative change.Therefore, in order to improve the balance of mobility and shock strength, also propose to make to contain in thermoplastic resin the method for these two kinds of compositions of composition that composition that molecular weight is large and molecular weight are little, adjust the method etc. of the molecular weight distribution of thermoplastic resin, but had further room for improvement in order to make the shaped material of the various manufacturing process such as applicable extrusion molding, foaming and molding, vacuum forming, the empty shaping of pressure, blow molding.
On the other hand, even use in the situation of identical thermoplastic resin as shaped material, owing to carrying out the desired melting elasticity of requirement according to applicable manufacturing process, molding condition etc., so urgent expectation exploitation can be in the situation that do not damage the elastic processing aid of melting that the original characteristic of thermoplastic resin is at random adjusted thermoplastic resin.
On the other hand, proposed to use the styrene based copolymer that molecular weight ratio is higher as the processibility of thermoplastic resin, to improve (patent documentations 1～3) such as methods of auxiliary agent.Yet, even the processing aid of these prior aries, the viewpoint of the shaping processability in the time of from the composition that is coupled to thermoplastic resin or comprises it, also residual further room for improvement.
Prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 10-168131
Patent documentation 2: Japanese kokai publication hei 02-302412
Patent documentation 3: Japanese kokai publication hei 11-92528
Summary of the invention
Invent problem to be solved
Therefore, main purpose of the present invention is to provide a kind of thermoplastic resin processing aid, and it can be in the situation that do not damage the shaping processability of the composition that the original characteristic of thermoplastic resin effectively improves thermoplastic resin or comprise it.Further the object of the present invention is to provide the thermoplastic resin composition who comprises above-mentioned processing aid.
For the method for dealing with problems
The present inventors, in view of the problem of above-mentioned prior art conducts in-depth research repeatedly, found that, by the processing aid that uses specific multipolymer to use as thermoplastic resin, reach above-mentioned purpose, thereby complete the present invention.
That is, the present invention relates to following thermoplastic resin with processing aid and the thermoplastic resin composition that comprises it.
1. a thermoplastic resin processing aid, is characterized in that, it is for being coupled to the processing used additives of thermoplastic resin,
(1) above-mentioned processing aid comprises a) aromatic vinyl base system monomer 50～95 % by weight, b) vinyl cyanide is monomer 5～50 % by weight and d) (wherein, the total metering for the monomer of multipolymer (A) is 100 % by weight for the multipolymer (A) that can obtain with other ethene base system monomer 0～45 % by weight copolymerization of their copolymerization.)，
(2) highest weight (Mp) of above-mentioned multipolymer (A) is more than 1,000,000,
(3) above-mentioned multipolymer is particle shape, and the particle diameter that contains 1～50 % by weight in above-mentioned multipolymer (A) 100 % by weight is particle more than 355 μ m.
2. according to the thermoplastic resin processing aid described in above-mentioned 1, wherein, above-mentioned multipolymer is for by a) aromatic vinyl base system monomer 50～70 % by weight, b) vinyl cyanide is monomer 9～40 % by weight, c) (methyl) acrylic ester monomer 21～35 % by weight and d) (the total metering for the monomer of multipolymer (A) is 100 % by weight for the multipolymer (A) that can obtain with other ethene base system monomer 0～20 % by weight copolymerization of their copolymerization.)。
3. according to the thermoplastic resin processing aid described in above-mentioned 1 or 2, wherein, the highest weight (Mp) of multipolymer (A) is more than 2,000,000.
4. according to the thermoplastic resin processing aid described in any one in above-mentioned 1～3, wherein, the ultimate compression strength of the particles more than 850 μ m that comprise in multipolymer (A) is 250～900g/mm
2.
5. according to the thermoplastic resin processing aid described in above-mentioned 1, wherein, multipolymer (A) be from above-mentioned monomer to utilize the reaction product that letex polymerization obtains be to reclaim latex.
6. according to the thermoplastic resin processing aid described in above-mentioned 5, wherein, the weight average particle diameter of the latex particle of multipolymer (A) is below 160nm.
7. according to the thermoplastic resin processing aid described in above-mentioned 5, wherein, in latex, total metering of residual unreacted component is below 2.0 % by weight.
8. a thermoplastic resin composition, it comprises processing aid 0.1～15 weight part described in any one in thermoplastic resin 100 weight parts and above-mentioned 1～7.
9. a resin forming product, it is shaped the thermoplastic resin composition described in above-mentioned 8 to obtain.
The effect of invention
Processing aid of the present invention is owing to containing specific multipolymer, and is the powder consisting of specific granularity, so by being coupled in thermoplastic resin, can obtain excellent shaping processability when melt-shaping.Consequently, can provide more reliably the molding with the quality more excellent than prior art, outward appearance etc.
Embodiment
Below, the present invention is described in detail.
1. thermoplastic resin processing aid of the present invention
Processing aid (processing aid of the present invention) for thermoplastic resin of the present invention, is characterized in that, it is for being coupled to the processing used additives of thermoplastic resin,
(1) above-mentioned processing aid comprises a) aromatic vinyl base system monomer 50～95 % by weight, b) vinyl cyanide is monomer 5～50 % by weight and d) (wherein, the total metering for the monomer of multipolymer (A) is 100 % by weight for the multipolymer (A) that can obtain with other ethene base system monomer 0～45 % by weight copolymerization of their copolymerization.)，
(2) highest weight (Mp) of above-mentioned multipolymer (A) is more than 1,000,000,
(3) above-mentioned multipolymer is particle shape, and the particle diameter that contains 1～50 % by weight in above-mentioned multipolymer (A) 100 % by weight is particle more than 355 μ m.
(1) multipolymer (A)
Processing aid of the present invention is to using the material of multipolymer (A) as principal constituent.The content of the multipolymer in processing aid of the present invention (A) is generally 90～100 % by weight, is preferably 95～100 % by weight.Therefore, for example the content of multipolymer (A) is that the processing aid of 100 % by weight is also contained in the present invention.The 3rd composition (additive) comprising during lower than 100 % by weight about the content of multipolymer (A) is described in detail in aftermentioned (1-4).
(1-1) form the monomer of copolymerization (A)
Processing aid of the present invention must be used a) aromatic vinyl base system monomer and b) vinyl cyanide is monomer, also can use as required other ethene base system monomer.
A) aromatic vinyl base system monomer
As the aromatic vinyl base system monomer using in the present invention, be not particularly limited, can list for example vinylbenzene, t-butyl styrene, alpha-methyl styrene, p-methylstyrene, Vinylstyrene, 1,1-diphenyl benzene ethene, N, N-diethyl-to amino-ethyl vinylbenzene, N, N-diethyl-to amino methyl vinylbenzene, vinyl pyridine, vinyl-dimethyl benzene, monochloro vinylbenzene, dichlorostyrene, single bromstyrol, fluorostyrene, ethyl styrene, vinyl naphthalene etc.These aromatic vinyl base system monomers can be used one kind or two or more separately.In them, the present invention is at least a kind in vinylbenzene and alpha-methyl styrene particularly preferably.
In total metering 100 % by weight of the monomer that the content of the aromatic vinyl base system monomer using in the present invention is used in multipolymer (A), be necessary for 50～95 % by weight.Aromatic vinyl base system monomer during lower than 50 % by weight, coordinates the thermostability of the thermoplastic resin composition after processing aid to reduce, and easily produces xanthochromia.In addition, if surpass 95 % by weight, when the polymerization of multipolymer (A), polymerization rate reduces, and productivity worsens.Therefore, particularly from the viewpoint of productivity and tint permanence, be preferably 50～70 % by weight, especially more preferably 55～65 % by weight.
B) vinyl cyanide is monomer
As the vinyl cyanide using in the present invention, be monomer, do not limit, can list such as vinyl cyanide, methacrylonitrile, ethyl acrylonitrile, flumaronitrile etc., but preferred vinyl cyanide.It is one kind or two or more separately that these vinyl cyanides are that monomer can be used.In addition, the vinyl cyanide using in the present invention is except the monomer monomer that will use as above-mentioned a) aromatic vinyl base system monomer.
The vinyl cyanide using in the present invention is to be necessary for 5～50 % by weight in total 100 % by weight of the monomer that uses in multipolymer (A) of the content of monomer.Vinyl cyanide is monomer during lower than 5 % by weight, and when the polymerization of multipolymer (A), polymerization rate reduces, and productivity worsens.In addition, if surpass 50 % by weight, thermal control during polymerization becomes difficult, and the yellow chromaticity of the finished product uprises, so not preferred.Therefore, particularly, from the viewpoint of the tone (outward appearance) of productivity and the finished product, be preferably 9～40 % by weight, especially more preferably 10～30 % by weight.
D) other monomer
As in the present invention, use can be with copolymerization at multipolymer (A) time the aromatic vinyl base system monomer that uses and vinyl cyanide other the ethene base system monomer that is monomer copolymerization, can list such as (methyl) acrylic ester monomer, maleimide be monomer, unsaturated acid, containing the unsaturated monomer of acid anhydrides, containing the unsaturated monomer of epoxy group(ing), the unsaturated monomer of the unsaturated monomer of hydroxyl, amide-containing, containing amino unsaturated monomer, containing the unsaturated monomer of oxazolinyl etc.These monomers can be used one kind or two or more separately.In these monomers, from the viewpoint of conformability and thermostability, preferably use (methyl) acrylic ester monomer.The monomer of other use in the present invention in addition, will above-mentioned a) and b) in the monomer that uses all except.
As above-mentioned (methyl) acrylic ester monomer, can list for example (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, 2-EHA, (methyl) phenyl acrylate, (methyl) vinylformic acid 4-tert-butyl-phenyl ester, (methyl) vinylformic acid bromo phenylester, (methyl) vinylformic acid dibromo phenyl ester, (methyl) vinylformic acid 2, 4, 6-tribromo phenylester, (methyl) vinylformic acid monochloro phenylester, (methyl) vinylformic acid dichlorophenyl ester, (methyl) vinylformic acid trichlorophenyl ester etc., but preferable methyl methyl acrylate, in butyl acrylate etc. at least a kind.
As above-mentioned maleimide, it is monomer, can list such as at least a kind in maleimide, N-methyl maleimide, N-butyl maleimide, N-(p-methylphenyl) maleimide, N-phenylmaleimide, N-N-cyclohexylmaleimide etc., preferably can list at least a kind in N-phenylmaleimide and N-N-cyclohexylmaleimide.
As unsaturated acid, can list such as at least a kind in vinylformic acid, methacrylic acid etc.
Unsaturated monomer as containing anhydride group, can list such as at least a kind in maleic anhydride, itaconic anhydride, citraconic anhydride etc.Be preferably maleic anhydride.
Unsaturated monomer as containing epoxy group(ing), can list such as at least a kind in glycidyl methacrylate, glycidyl allyl ether etc.Be preferably glycidyl methacrylate.
Unsaturated monomer as hydroxyl, can list such as at least a kind in 3-hydroxyl-1-propylene, 4-hydroxyl-1-butene, cis-4-hydroxyl-2-butylene, trans-4-hydroxyl-2-butylene, 3-hydroxy-2-methyl-1-propylene, vinylformic acid 2-hydroxyethyl ester, methacrylic acid 2-hydroxyethyl ester etc., be preferably methacrylic acid 2-hydroxyethyl ester.
As the unsaturated monomer of amide-containing, can list such as at least a kind in acrylamide, Methacrylamide etc., be preferably acrylamide.
As containing amino unsaturated monomer, can list such as at least a kind in allylamine, dimethylaminomethyl acrylate, diethylamino methyl acrylate, dimethylamino acrylate etc.
As containing the unsaturated monomer of oxazolinyl, can list such as second alkene oxazolin etc.
From the viewpoint of polymerization stability, in total 100 % by weight of the monomer that other monomer (while particularly using (methyl) acrylic ester monomer) is preferably used in multipolymer (A), contain 21～35 % by weight.
(1-2) multipolymer (A) is synthetic
Polymerization process about multipolymer of the present invention (A) is not particularly limited, and can be suitable for any known polymerization process, but preferably by letex polymerization, manufactures from the good aspect of the productivity of the extra high polymkeric substance of the polymerization degree.As long as the method for letex polymerization self is according to known method, for example, can utilize and comprise that to modulate reaction product be that the manufacture method of the operation of latex (suspension) is suitably manufactured by making monomer carry out polyreaction in the liquid phase that comprises water and emulsifying agent.Afterwards, as required, as long as reclaim copolymer particle according to known solid-liquid separating method etc. from resulting latex.
The emulsifying agent using when utilizing letex polymerization, can suitably be used at least a kind in an alkali metal salt such as sylvic acid, an alkali metal salt of lipid acid, an alkali metal salt of an alkali metal salt of glim, alkyl allyl sulphonic acid, an alkali metal salt of dialkyl sulfosuccinate succinate, the sulfuric ester an alkali metal salt of polyxyethylated (phenyl) ether, the phosphoric acid ester an alkali metal salt of polyxyethylated (ether) etc.With respect to total metering 100 % by weight of the monomer using in multipolymer (A), from aspects such as polymerization rate and reaction stability, suitable viscosity of latex, saltouing property, the usage quantity of emulsifying agent is preferably 1～5 % by weight.
In addition, when letex polymerization, preferably use polymerization starter.As polymerization starter, can suitably use known materials such as persulphate, organic hydroperoxide class.Particularly, from the aspect of the stability of latex, preferably use persulphate.From polyreaction, cause the viewpoint of the adjustment of behavior or highest weight, total metering 100 % by weight with respect to the monomer using in multipolymer (A), the usage quantity of polymerization starter is set as 0.01～0.5 % by weight conventionally, be preferably set to 0.03～0.3 % by weight, be further preferably set to 0.05～0.2 % by weight.
With respect to total metering 100 % by weight of the monomer using in multipolymer (A), the thermal control during from polyreaction and the viewpoint of productivity, the usage quantity of water during letex polymerization is preferably the scope of 100～200 % by weight conventionally.
Polymerization temperature during polymerization multipolymer (A) does not limit, but is preferably set to 50～75 ℃, is especially more preferably set as 55～70 ℃.During polymerization, can confirm to follow reaction heating during, preferred constant interior temperature within the scope of this polymerization temperature.Polymerization temperature during lower than 50 ℃, owing to being difficult to cause the decomposition of polymerization starter, easily becomes unstable so polymerization causes.On the other hand, if surpass 75 ℃, the formation speed due to free radical becomes too fast, so molecular weight can not become large sometimes.
The addition means of the monomer during as the manufacture of multipolymer (A), does not limit, and can adopt and the generally extensive known method such as add such as the multistage of adding in the lump, adding continuously, change the composition of each section.In them, the preferred method such as interpolation, continuous adding in the lump.In addition,, when utilizing the polymerization of adding continuously, the continuous adding time is preferably set to more than 3 hours.Under the polymerization time lower than 3 hours, due to because the thermogenetic heat release of polymerization is large, so there is the control of the polymerization temperature difficulty that becomes, result causes the tendency of reduction of the molecular weight of multipolymer.And then, comprise that the polymerization time of total metering of the polymerization time after continuous adding time and continuous adding is preferably set to 7～11 hours.
When polymerization multipolymer of the present invention (A), due to the molten impact of depositing oxygen because of in polymeric solution, and polymerization activity reduces, so nitrogen displacement is carried out in expectation fully.Oxygen concn before polymerization is preferably below 6.5mg/L, more preferably below 5.0mg/L.Further preferably by oxygen removers such as hydrosulphite, in fact fully remove the molten oxygen of depositing.
In utilizing the situation etc. of letex polymerization, the weight average particle diameter of the latex of multipolymer (A) is not particularly limited, but the weight average particle diameter of the latex of multipolymer (A) is preferably below 160nm.If weight average particle diameter is below 160nm, become and not only can reduce polymerization time, and the result that more improves of the shaping processability while using as processing aid.The control of the particle diameter of the latex of multipolymer (A) can be used for kind, its usage quantity of the emulsifying agent of polymerization, addition means of monomer etc. suitably carries out by adjustment.In addition, the weight average particle diameter of the latex of multipolymer (A) can be measured by carry out the observation of particle with transmission electron microscope.
To unreacted monomer residual in the latex of multipolymer of the present invention (A), become component to be not particularly limited, but take multipolymer (A) below benchmark is preferably 2.0 % by weight.The oligopolymer that the residual unreacted monomers composition of the latex of multipolymer (A) is 200～1000 by such weight-average molecular weight such as the dipolymer of each monomer using for multipolymer residual in the latex of multipolymer (A) is carried out to polymerization or each monomer, trimers forms.Conventionally, because unreacted monomer composition in the operation that copolymer emulsion is saltoutd is removed, so substantially there is no need to manage the residual unreacted monomers in copolymer emulsion.But, be not that the residual unreacted monomers comprising in the powder of multipolymer becomes component, but the residual unreacted monomers of copolymer emulsion becomes component, be in the situation below 2.0 % by weight, when the latex of multipolymer (A) is saltoutd, owing to can suppressing particle excessive hot sticky of multipolymer (A), so become the powder of the multipolymer (A) that forms excellent dispersion, the result that the shaping processability of the finished product improves more.Residual unreacted monomers becomes the control of component can be by regulating polymerization temperature etc. to carry out.The residual unreacted monomers of the latex of multipolymer (A) becomes the component can be by measuring with gc analysis device.
By letex polymerization, make after its reaction, multipolymer (A) can be by dry obtaining that this latex is saltoutd.As the peptizer of the middle use of saltouing, do not limit, can suitably use such as at least a kind in sulfuric acid, magnesium sulfate, calcium chloride, Tai-Ace S 150 etc.In addition, drying means is not particularly limited, and can adopt any in seasoning or forced drying.In addition, resulting multipolymer (A) also can carry out classification etc. as required.
(1-3) physical property of multipolymer (A)
The highest weight (Mp) of multipolymer of the present invention (A) is necessary for more than 1,000,000.Highest weight, lower than 1,000,000 o'clock, can not be given as the desired melting elasticity of processing aid thermoplastic resin.From the viewpoint of shaping processability, be preferably more than 2,000,000, more preferably more than 3,500,000.The upper limit of above-mentioned molecular weight (Mp) is not particularly limited, and for example also can be set as 8,000,000, and then be set as 6,000,000.Highest weight is the value of measuring by gel permeation chromatography (GPC), refers to the value that detects the apex that frequency is the highest in the molecular weight distribution detecting.In addition, from the viewpoint of thermostability etc., the molecular weight distribution of the multipolymer obtaining by the present invention (A), (wherein, Mw represents that weight-average molecular weight, Mn represent number-average molecular weight to utilize the Mw/Mn that gel permeation chromatography (GPC) obtains.) be preferably set to more than 5.0.
The adjustment of the highest weight of multipolymer of the present invention (A) also can be undertaken by interpolation such as chain-transfer agent etc.But during due to use chain-transfer agent, speed of response reduces sometimes, so the preferred addition means by the usage quantity such as polymerization starter, monomer etc. are adjusted.
The multipolymer of processing aid of the present invention (A) is generally particle shape (powder).And the particle of the above size of 355 μ m comprising in its powder contains 1～50 % by weight in multipolymer (A) 100 % by weight.Particle diameter is more than 355 μ m particle during lower than 1 % by weight, because the aggregation of particles of saltouing is insufficient, thus poor to nipping of screw rod when mixing, dispersed deterioration, thus the shaping processability of the finished product is poor.In addition, particle diameter is more than 355 μ m particle while surpassing 50 % by weight, so due to the too much dispersed variation of the ratio of oversize particle, the shaping processability of the finished product is poor.The ratio of above-mentioned particle is preferably the scope of 2～45 % by weight, more preferably the scope of 5～35 % by weight.And then, for thering is the particle of particle diameters more than 850 μ m in particles more than 355 μ m, from the size of the finished product or the aspect of shaping processability, be preferably lower than 18 % by weight, more preferably, lower than 10 % by weight, most further preferably be the particle not existing more than 850 μ m.
As the powder of multipolymer of the present invention (A), in the situation that there is particles more than 850 μ m, the ultimate compression strength of particles more than 850 μ m is not particularly limited, but is preferably 250～900g/mm
2.If ultimate compression strength is 250～900g/mm
2scope, there is corpusculed in the powder due to multipolymer (A) when carrying or take care of, can variation as the treatability of powder, there is appropriate recognition (original text: ほ ぐ れ や The い), so dispersiveness when mixing with other thermoplastic resin becomes well, shaping processability improves.According to described viewpoint, more preferably 300～850g/mm
2, most preferably be 350～800g/mm
2.
The particle diameter of the powder in multipolymer of the present invention (A) can be by modification the concentration etc. of the salt eutectoid temperature when saltoutd, slurry concentration, salting-out agent adjust.From preferred size of particles or suppress excessive bonding viewpoint, salt eutectoid temperature be preferably with respect to the second-order transition temperature of multipolymer (A) (℃) the low 10 ℃～temperature of 40 ℃.
(1-4) other composition of processing aid of the present invention
In processing aid of the present invention, in not hindering the scope of effect of the present invention, except multipolymer (A), also can contain as required following such additive.For example can list 1) 2,6-di-tert-butyl-4-methy phenol, 2-(1-methylcyclohexyl)-4,6-xylenol, 2, the antioxidants such as 2 '-methylene radical-bis--(4-ethyl-6-tert.-butyl phenol), 4,4 '-thiobis-(the 6-tertiary butyl-3-methylphenol), dilauryl thiodipropionate, three (two-nonyl phenyl) phosphoric acid ester; 2) for example, to tert-butyl-phenyl succinate, 2,2 '-dihydroxyl-4-methoxy benzophenone, 2-(2 '-hydroxyl-4 '-n-octyloxy phenyl) benzotriazole etc. UV light absorber; 3) lubricants such as wax, paraffin, stearic acid, winterized stearin, stearylamide, methylene-bis stearylamide, ethylenebisstearamide, normal-butyl stearate, ketone wax, octanol, lauryl alcohol, oxystearic acid Witepsol W-S 55; 4) such as the fire retardants such as condenses of ANTIMONY TRIOXIDE SB 203 99.8 PCT, aluminium hydroxide, zinc borate, Tritolyl Phosphate, tricresyl phosphate (two chloropropyls) ester, clorafin, tetrabromo-bisphenol, tetrabromo-bisphenol and epoxy chloropropane; 5) such as static inhibitor such as stearamide propyl dimethyl-beta-hydroxy ethyl ammonium nitrate; 6) tinting materials such as titanium oxide, carbon black; 7) weighting agents such as calcium carbonate, clay, silicon-dioxide, glass fibre, glass sphere, carbon fiber; 8) whipping agents such as halohydrocarbon, carbonic acid gas, nitrogen such as lower hydrocarbon such as propane, butane, pentane, hexane, methyl chloride, methylene dichloride, trichlorine list fluoromethane, Refrigerant 12.
2. the use of processing aid of the present invention
Processing aid of the present invention can be in the resin combination that improves or improve shaping processability etc. and be coupled to thermoplastic resin or comprise it.More specifically, in order to improve the physical property (particularly melting elasticity) of the thermoplastic resin of melting, can in this thermoplastic resin, add processing aid of the present invention.That is, processing aid of the present invention can be suitable for the improvement method of the melting elasticity (and then shaping processability) of thermoplastic resin.And, by processing aid of the present invention is added in thermoplastic resin, can access the resin forming product that quality, outward appearance etc. are excellent.
Thermoplastic resin that can be applicable as processing aid of the present invention (B), be not particularly limited, can list except for example ABS resin, AES resin, ASA resin, SAS resin, PS resin, HIPS resin, (rubber-reinforced) phenylethylene resin series such as AS resin, vinyl chloride resin, chlorinated polyethylene resin, ethylene-vinyl acetate resin, polypropylene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyacetal, polymeric amide, polyamide elastomer, epoxy resin, polyvinylidene difluoride (PVDF), polysulfones, polyisoprene, natural rubber, chlorinated butyl rubber, PPE resin, PPS resin, polyether-ether-ketone, outside styrene-maleic anhydride copolymer etc., the mixture that comprises two or more these resin, alloy resin etc.At least a kind in (rubber-reinforced) phenylethylene resin series, vinyl chloride resin, chlorinated polyethylene resin, the ethylene-vinyl acetate resin etc. such as ABS resin, AES resin, ASA resin, SAS resin, PS resin, HIPS resin, AS resin particularly preferably.
The addition of processing aid of the present invention can suitably be set according to kind of applicable thermoplastic resin etc., but conventionally with respect to thermoplastic resin 100 weight parts, preferably coordinates 0.1～15 weight part, especially more preferably coordinates 0.5～12 weight part.
3. thermoplastic resin composition and molding thereof
The present invention comprises the thermoplastic resin composition of containing thermoplastic resin 100 weight parts and processing aid of the present invention 0.1～15 weight part.In addition, the present invention also comprises the resin forming product that above-mentioned thermoplastic resin composition is shaped and obtains.
As above-mentioned thermoplastic resin, can use the material of enumerating in above-mentioned 2..In addition,, as processing aid of the present invention, can use the material of enumerating in above-mentioned 1..
In addition,, in thermoplastic resin composition of the present invention, also can contain as required other additive.That is, can use with processing aid of the present invention in the same material of the additive that can use.For example can list 1) 2,6-di-tert-butyl-4-methy phenol, 2-(1-methylcyclohexyl)-4,6-xylenol, 2, the antioxidants such as 2 '-methylene radical-bis--(4-ethyl-6-tert.-butyl phenol), 4,4 '-thiobis-(the 6-tertiary butyl-3-methylphenol), dilauryl thiodipropionate, three (dinonyl phenyl) phosphoric acid ester; 2) for example, to tert-butyl-phenyl succinate, 2,2 '-dihydroxyl-4-methoxy benzophenone, 2-(2 '-hydroxyl-4 '-n-octyloxy phenyl) benzotriazole etc. UV light absorber; 3) lubricants such as wax, paraffin, stearic acid, winterized stearin, stearylamide, methylene-bis stearylamide, ethylenebisstearamide, normal-butyl stearate, ketone wax, octanol, lauryl alcohol, oxystearic acid Witepsol W-S 55; 4) such as the fire retardants such as condenses of ANTIMONY TRIOXIDE SB 203 99.8 PCT, aluminium hydroxide, zinc borate, Tritolyl Phosphate, tricresyl phosphate (two chloropropyls) ester, clorafin, tetrabromo-bisphenol, tetrabromo-bisphenol and epoxy chloropropane; 5) such as static inhibitor such as stearamide propyl dimethyl-beta-hydroxy ethyl ammonium nitrate; 6) tinting materials such as titanium oxide, carbon black; 7) weighting agents such as calcium carbonate, clay, silicon-dioxide, glass fibre, glass sphere, carbon fiber; 8) whipping agents such as halohydrocarbon, carbonic acid gas, nitrogen such as lower hydrocarbon such as propane, butane, pentane, hexane, methyl chloride, methylene dichloride, trichlorine list fluoromethane, Refrigerant 12.
Thermoplastic resin composition of the present invention or its molding also can obtain according to the manufacture method of known thermoplastic resin or resin forming product.For example, can by by processing aid of the present invention (multipolymer (A)) and thermoplastic resin (B) (or the resin combination that comprises it) in the situation that not carrying out in advance melting heating and mixing, under by well-mixed states such as mixing tanks, directly drop into such as forming and obtain resin forming product in extrusion shaper, injection machine, sheet forming machine, vacuum former, special-shaped forming mill, foaming and molding machine, blow-moulding machine etc.In addition, also can be by using such as various forcing machines, Banbury, kneader, roller etc., after processing aid of the present invention and thermoplastic resin (B) (or the resin combination that comprises it) melting heating is mixed, use such as extrusion shaper, injection machine, sheet forming machine, vacuum former, special-shaped forming mill, foaming and molding machine, blow-moulding machine etc. to form and obtain resin forming product.Be preferably and each composition directly dropped in the situation that not carrying out in advance melting heating mixing to the method in forming mill.The various molding that obtain by above-mentioned manufacturing process can utilize its excellent character, for each parts such as household appliances, trolley part.
Embodiment
Below list embodiment, the present invention will be described in more detail.But scope of the present invention is not limited to embodiment.In addition, as long as no specifying, part and % in embodiment are weight part and % by weight.In addition, the various mensuration projects in embodiment are according to following measuring method.
the mensuration of highest weight (Mp), number-average molecular weight (Mn), weight-average molecular weight (Mw)
As analytical equipment, use Shimadzu Seisakusho Ltd.'s gel permeation chromatograph processed (LC-10Avp), post is used the GMH HR-H processed of TOSOH Co., Ltd (30).With polystyrene benchmark, proofread and correct, solvent is used tetrahydrofuran (THF), under flow velocity 0.5ml/min, temperature 50 C, measures.
Measure sample by determination object 0.01g and tetrahydrofuran (THF) 25ml are added in 50ml glass flask and sealing, at 25 ℃, flood after 12 hours, with the tetrafluoroethylene masking filter that aperture is 3.0 μ m, filter to modulate.
Highest weight (Mp) is quantitatively in the molecular weight distribution detecting, to detect the numerical value of the value of the apex that frequency is the highest.In addition, number-average molecular weight (Mn) and weight-average molecular weight (Mw) are carried out quantitative Analysis by detected value by following formula.The results are shown in table 1.
[mathematical expression 1]
In addition, described in the symbol in formula is defined as follows.
The high molecular gross weight of W=
Wi=i high molecular weight
Molecular weight during i dissolution time of Mi=
The number of Ni=molecular weight Mi
Height during i dissolution time of Hi=
the mensuration of size-grade distribution
After the about 50g of powder of accurate weighing multipolymer (A), use dry type sound wave screening measuring machine SONIC SIFTER L-200P (SEISHIN ENTERPRISE Co., Ltd. make), under the condition of using respectively the sieve of 20 orders (mesh 850 μ m) and the sieve of 42 orders (mesh 355 μ m), measure size-grade distribution.850 μ m are above and 355 μ m above and calculate by following formula lower than the particle content of the particle diameter of 850 μ m.The results are shown in table 1.
The particle content of particle diameters more than 850 μ m
=remain in powder weight * 100 (%) before the weight/mensuration of the particle on 20 mesh sieve
355 μ m are above and lower than the particle content of the particle diameter of 850 μ m
=remain in powder weight * 100 (%) before the weight/mensuration of the particle on 42 mesh sieve
the mensuration of the weight average particle diameter of the latex of multipolymer (A)
By perosmic anhydride (OsO for copolymer emulsion
4) dyeing, after being dried, with transmission electron microscope (NEC (strain) JEM-1400), take pictures.Use image analysis processing device (device name: the IP-1000PC processed of Asahi Chemical Industry's (strain)) measure the area of 100 particles, obtain its equivalent circle diameter (diameter), calculate the weight average particle diameter of copolymer emulsion.The results are shown in table 1.
the residual unreacted monomers of the latex of multipolymer (A) becomes the mensuration of component
By the about 20ml dilution of dimethyl formamide for the about 1.0g of copolymer emulsion, in this diluting soln, add the hexyl benzene solution 5.0ml that is diluted to 0.06% as interior target with dimethyl formamide, sample is measured in modulation.
Use gc analysis device (GC device: (strain) GC2010 of Shimadzu Seisakusho Ltd. capillary column: the Agilent J & W DB-5 of society) measure under following condition, by resulting spectrogram, by calculating the Area Ratio with hexyl benzene as reference material, obtain unreacted monomer residual in copolymer emulsion and become component.The results are shown in table 1.
Injection rate: 1.0 μ l
(sample evaporation chamber)
230 ℃ of carrier gas of sample gasification chambers temp: helium master mode: linear velocity
Pressure: 90.6kPa total flux: 44.2mL/min
Post flow: 1.00mL/min linear velocity: 26.4cm/sec
(column oven)
70 ℃ of starting time: 3.0min of column temperature
(detector FID)
330 ℃ of sampling rate: 40msec of detector temperature
Make-up gas: nitrogen replenish air gas flow: 30.0mL/min
Hydrogen flowing quantity: 40.0mL/min air flow quantity: 400.0mL/min
the mensuration of ultimate compression strength
Use dry type sound wave screening measuring machine SONIC SIFTER L-200P (SEISHIN ENTERPRISE Co., Ltd. system), obtain the powder over the multipolymer (A) of 20 orders (mesh 850 μ m).To this powder, use particle measurement of hardness device (SEISHIN ENTERPRISE Co., Ltd. BHT-500 processed), measure ultimate compression strength (load cell: 500g environment: 23 ℃).When measuring, select randomly and measure 20 points, obtain mean value.The results are shown in table 1.
Ultimate compression strength is at 250～900g/mm
2scope in: zero
Ultimate compression strength is at 250～900g/mm
2scope outside: *
(1) multipolymer (A) is synthetic
About the copolymerization (A) of processing aid of the present invention, by method as following, synthesize respectively.
the manufacture of copolymer A-1
4 parts of monomer mixtures, 1.5 parts of Sodium dodecylbenzene sulfonate 20% aqueous solution of the ratio of recording in adding 150 parts of pure water, table 1 in the reactor after nitrogen displacement, be heated to 50 ℃.After heating, add 0.1 part of Potassium Persulphate, with the speed of 0.5 ℃/min, be warming up to 60 ℃, carry out slaking in 10 minutes after reaching 60 ℃.After slaking, respectively through within 6 hours, adding continuously 8.5 parts of 96 parts of monomer mixtures and Sodium dodecylbenzene sulfonate 20% aqueous solution.After interpolation finishes, by further carry out polymerization in 4 hours at 60 ℃, obtain copolymer emulsion A-1.
The solid component concentration of saltouing in groove after dropping is finished reaches the water of 15% condition and the magnesium sulfate that is 4 parts with respect to 100 parts of the solids components of copolymer emulsion A-1 adds and saltouts in groove, and the groove of saltouing is warming up to 85 ℃.After intensification, drip resulting copolymer emulsion A-1.After dropping finishes, the groove of saltouing is warming up to 95 ℃, in the moment that reaches 95 ℃, finishes to saltout.After saltouing, by using centrifuge to dewater, wash, use hot air dryer at the temperature of 90 ℃, to carry out being dried for 12 hours, obtain copolymer A-1.
the manufacture of copolymer A-2
Except the ratio to record in table 1 is used monomer mixture, the emulsifier aqueous solution that initial stage is added changes to 1.0 parts, the usage quantity of Potassium Persulphate is changed to 0.09 part, the emulsifier aqueous solution using during by continuous adding changes to 8.0 parts, by the continuous adding time change of monomer mixture and emulsifier aqueous solution, be beyond 4 hours, with the same condition of multipolymer A-1 under carry out polymerization, obtain copolymer emulsion A-2.Saltout, drying conditions is used carries out with the same method of multipolymer A-1, obtains copolymer A-2.
the manufacture of copolymer A-3
Except the ratio to record in table 1 is used monomer mixture, by more 0.04 part of Potassium Persulphate quantitative change, the curing time that reactor is reached after 60 ℃ changes to 40 minutes, by the continuous adding time change of monomer mixture and emulsifier aqueous solution, be beyond 3.5 hours, with the same condition of multipolymer A-2 under carry out polymerization, obtain copolymer emulsion A-3.Saltout, drying conditions is except changing to the temperature of the groove of saltouing 80 ℃, uses the method same with multipolymer A-1 to carry out, and obtains copolymer A-3.
the manufacture of copolymer A-4
Use copolymer emulsion A-2, saltout, drying conditions is except the temperature of the groove of saltouing is changed to 83 ℃, and the temperature heating up after dripping is changed to beyond 90 ℃, uses the method same with multipolymer A-2 to carry out, and obtains copolymer A-4.
the manufacture of copolymer A-5
3 parts of monomer mixtures, 1.5 parts of potassium stearate 20% aqueous solution of the ratio of recording in adding 130 parts of pure water, table 1 in the reactor after nitrogen displacement, be heated to 50 ℃.After heating, add 0.08 part of Potassium Persulphate, with the speed of 0.5 ℃/min, be warming up to 60 ℃, reach 60 ℃ of post curings 40 minutes.After slaking, respectively through within 4.25 hours, adding continuously 8.5 parts of 97 parts of monomer mixtures and potassium stearate 20% aqueous solution.After interpolation finishes, by further carry out polymerization in 4 hours at 60 ℃, obtain copolymer emulsion A-5.
The solid component concentration of saltouing in groove after dropping is finished reaches the water of 15% condition and 10% aqueous sulfuric acid that is the magnesium sulfate of 3 parts and 3 parts with respect to 100 parts of the solids components of copolymer emulsion A-5 adds and saltouts in groove, and the groove of saltouing is warming up to 80 ℃.After intensification, drip resulting copolymer emulsion A-5.After dropping finishes, the groove of saltouing is warming up to 95 ℃, in the moment that reaches 95 ℃, finishes to saltout.After saltouing, by using centrifuge to dewater, wash, use hot air dryer at the temperature of 90 ℃, to carry out being dried for 12 hours, obtain copolymer A-5.
the manufacture of copolymer A-6
4 parts of monomer mixtures, 1.5 parts of alkenyl succinic dipotassium 20% aqueous solution of the ratio of recording in adding 140 parts of pure water, table 1 in the reactor after nitrogen displacement, be heated to 50 ℃.After heating, add 0.06 part of Potassium Persulphate, with the speed of 0.5 ℃/min, be warming up to 60 ℃, carry out slaking in 10 minutes after reaching 60 ℃.After slaking, respectively through within 3.5 hours, adding continuously 8.5 parts of 96 parts of monomer mixtures and alkenyl succinic dipotassium 20% aqueous solution.After interpolation finishes, by further carry out polymerization in 4 hours at 60 ℃, obtain copolymer emulsion A-6.
The solid component concentration of saltouing in groove after dropping is finished reaches the water of 15% condition and 10% aqueous sulfuric acid that is the magnesium sulfate of 3 parts and 1.5 parts with respect to 100 parts of the solids components of copolymer emulsion A-6 adds and saltouts in groove, and the groove of saltouing is warming up to 75 ℃.After intensification, drip resulting copolymer emulsion A-6.After dropping finishes, the groove of saltouing is warming up to 90 ℃, in the moment that reaches 90 ℃, finishes to saltout.After saltouing, by using centrifuge to dewater, wash, use hot air dryer at the temperature of 85 ℃, to carry out being dried for 12 hours, obtain copolymer A-6.
the manufacture of copolymer A-7
Except the ratio to record in table 1 is used monomer mixture, with the same condition of multipolymer A-6 under carry out polymerization, obtain copolymer emulsion A-7.Saltout, drying conditions is used carries out with the same method of multipolymer A-6, obtains copolymer A-7.
the manufacture of copolymer A-8
Except the ratio to record in table 1 is used monomer mixture, by more 0.04 part of Potassium Persulphate quantitative change, reactor is reached beyond curing time after 60 ℃ changes to 40 minutes, with the same condition of multipolymer A-7 under carry out polymerization, obtain copolymer emulsion A-8.Saltout, drying conditions is used carries out with the same method of multipolymer A-7, obtains copolymer A-8.
the manufacture of copolymer A-9
Use copolymer emulsion A-7, saltout, drying conditions is except the temperature heating up after dripping is changed to 85 ℃, uses the method same with multipolymer A-6 to carry out, and obtains copolymer A-9.
the manufacture of copolymer A-10
Except the ratio to record in table 1 is used monomer mixture, the monomer mixture that initial stage is added changes to 2 parts, the monomer using during by continuous adding changes to 98 parts, the emulsifier aqueous solution that initial stage is used changes to 2.0 parts, the emulsifier aqueous solution using during by continuous adding changes to beyond 8.0 parts, use the condition common with multipolymer A-7, obtain copolymer emulsion A-10.Saltout, drying conditions is used carries out with the same method of multipolymer A-6, obtains copolymer A-10.
the manufacture of copolymer A-11
Except the ratio to record in table 1, use monomer mixture, the polymerization temperature after continuous adding is finished changes to beyond 73 ℃, with the same condition of multipolymer A-6 under carry out polymerization, obtain copolymer emulsion A-11.Saltout, drying conditions is used carries out with the same method of multipolymer A-6, obtains copolymer A-11.
the manufacture of copolymer A-12
Except the ratio to record in table 1 is used monomer mixture, the monomer mixture that initial stage is added changes to 3 parts, the monomer using during by continuous adding changes to 97 parts, the emulsifier aqueous solution that initial stage is used changes to 3.0 parts, the emulsifier aqueous solution using during by continuous adding changes to beyond 7.0 parts, with the same condition of multipolymer A-11 under carry out polymerization, obtain copolymer emulsion A-12.Saltout, drying conditions is used carries out with the same method of multipolymer A-6, obtains copolymer A-12.
the manufacture of multipolymer a-1
In the reactor of nitrogen displacement, add 150 parts of pure water, by the monomer of the ratio of recording in table 1 and 3 parts, 0.05 part of mixture forming of tertiary lauryl mercaptan, 1.0 parts of Sodium dodecylbenzene sulfonate 20% aqueous solution, be heated to 50 ℃.After heating, add 0.1 part of Potassium Persulphate, with the speed of 0.5 ℃/min, be warming up to 60 ℃, carry out slaking in 10 minutes after reaching 60 ℃.After slaking, respectively through within 6 hours, adding continuously 9.0 parts of 97 parts of monomer mixtures and Sodium dodecylbenzene sulfonate 20% aqueous solution.After interpolation finishes, by further carry out polymerization in 4 hours at 60 ℃, obtain copolymer emulsion a-1.Saltout, drying conditions is used carries out with the same method of multipolymer A-1, obtains multipolymer a-1.
the manufacture of multipolymer a-2
The solid component concentration of saltouing in groove after dropping is finished reaches the water of 7.5% condition and the magnesium sulfate that is 2.5 parts with respect to 100 parts of the solids components of copolymer emulsion A-2 adds and saltouts in groove, and the groove of saltouing is warming up to 65 ℃.After intensification, drip resulting copolymer emulsion A-2.In the moment that drips end, finish to saltout.After saltouing, by using centrifuge to dewater, wash, use hot air dryer at the temperature of 90 ℃, to carry out being dried for 12 hours, obtain multipolymer a-2.
the manufacture of multipolymer a-3
The solid component concentration of saltouing in groove after dropping is finished reaches the water of 20% condition and 10% aqueous sulfuric acid that is the magnesium sulfate of 3 parts and 3 parts with respect to 100 parts of the solids components of copolymer emulsion A-7 adds and saltouts in groove, and the groove of saltouing is warming up to 85 ℃.After intensification, drip resulting copolymer emulsion A-7.After dropping finishes, the groove of saltouing is warming up to 95 ℃, in the moment that reaches 95 ℃, finishes to saltout.After saltouing, by using centrifuge to dewater, wash, use hot air dryer at the temperature of 85 ℃, to carry out being dried for 12 hours, obtain copolymer A-5.
(2) physical property of multipolymer or latex
About multipolymer or latex, the content of the weight average particle diameter of highest weight, number-average molecular weight, weight-average molecular weight, molecular weight distribution, latex, residual unreacted monomers and compressive strength are studied.The results are shown in table 1.
(3) manufacture of the resin forming product that comprises thermoplastic resin composition
According to the mode that becomes the composition shown in table 2, use respectively each multipolymer, thermoplastic resin (B) and additive, after they are mixed equably, drop in the 40mm sheet extruder be set as 160 ℃, used thickness is that 2mm, the width punch die that is 200mm is by sheet forming.The thermoplastic resin (B) and the additive that in table 2, use are as described below.
thermoplastic resin (B)
Vinyl chloride resin: ProductName " TH-1000 " (the TAIYO VINYL CORPORATION polymerization degree 1000 processed)
ABS resin: the ABS resin of utilizing polyhutadiene 60%, vinylbenzene 30% and vinyl cyanide 10% to obtain by known letex polymerization
AS resin: the AS resin that utilizes vinylbenzene 75% and vinyl cyanide 25% to obtain by known letex polymerization
additive
Stablizer: tin alkyl sulfhydryl compound ProductName " TM-181FSJ " (Sheng Tian Chemical Co., Ltd system)
Lubricant: stearic acid based compound ProductName " L-27 " (Sheng Tian Chemical Co., Ltd system)
(4) evaluation of the shaping processability of resin forming product
In above-mentioned (3), the sample that cut-out length is 2m after 30 minutes from starting sheet forming, with the width of this sample of measuring space of 5cm, calculates the maximum width of sample and the difference of minimum width and width average.This evaluation result is shown in Table 2.The size of width average represents that, to the size of the modified effect of the thermoplastic resin that utilizes multipolymer (A) (B), numerical value more represents that modified effect is larger.
Evaluation in table 2 is carried out in the following way.
Width average is lower than 170mm=E
Width average is more than 170mm and lower than 174mm=D
Width average is more than 174mm and lower than 178mm=C
Width average is more than 178mm and lower than 182mm=B
Width average be 182mm above=A
In addition, the difference of maximum width and minimum width becomes multipolymer (A) is coupled in thermoplastic resin (B) and the standard of the thermoplastic resin composition's who obtains shaping processability, and this numerical value is less represents that shaping processability is higher.
Evaluation in table is carried out in the following way.
The difference of maximum width and minimum width be 7mm above=*
The difference of maximum width and minimum width is more than 5mm and lower than 7mm=△
The difference of maximum width and minimum width is more than 3mm and lower than 5mm=zero
The difference of maximum width and minimum width is lower than 3mm=◎
[table 1]
As shown in table 2, known embodiment 1～19 is thermoplastic resin composition of the present invention, and shaping processability is all excellent.Represent that highest weight is 3,500,000 when above, the weight average particle diameter of copolymer emulsion be 160nm when following and/or in copolymer emulsion the amount of residual volatile component be 0.2 % by weight when following, become the shaping processability result of excellence especially.
On the other hand, do not use the comparative example 1 of multipolymer of the present invention, the shaping processability of vinyl chloride resin is poor.Use highest weight lower than the comparative example 2 of 1,000,000 multipolymer and the particle that uses more than 355 μ m size lower than 1 % by weight or surpass in the comparative example 3～5 of multipolymer of 50 % by weight, all do not see the improved effect for the shaping processability of vinyl chloride resin or ABS resin.
Utilizability in industry
By coordinating processing used additives of the present invention, can improve thermoplastic resin composition's shaping processability, consequently, can produce the costly product of commodity.Therefore, industrial value of the present invention is large.
Claims (10)
1. a thermoplastic resin processing aid, is characterized in that, it is for being coupled to the processing used additives of thermoplastic resin,
(1) described processing aid comprises a) aromatic vinyl base system monomer 50～95 % by weight, b) vinyl cyanide is monomer 5～50 % by weight and d) multipolymer (A) that can obtain with other ethene base system monomer 0～45 % by weight copolymerization of their copolymerization, wherein, the total metering that is used for the monomer of multipolymer (A) is 100 % by weight
(2) the highest weight Mp of described multipolymer (A) is more than 1,000,000,
(3) described multipolymer is particle shape, and the particle diameter that contains 1～50 % by weight in described multipolymer (A) 100 % by weight is particle more than 355 μ m.
2. thermoplastic resin processing aid according to claim 1, wherein, described multipolymer is by a) aromatic vinyl base system monomer 50～70 % by weight, b) vinyl cyanide is monomer 9～40 % by weight, c) (methyl) acrylic ester monomer 21～35 % by weight and d) multipolymer (A) that can obtain with other ethene base system monomer 0～20 % by weight copolymerization of their copolymerization, wherein, the total metering for the monomer of multipolymer (A) is 100 % by weight.
3. thermoplastic resin processing aid according to claim 1 and 2, wherein, the highest weight Mp of multipolymer (A) is more than 2,000,000.
4. thermoplastic resin processing aid according to claim 1 and 2, wherein, the ultimate compression strength of the particles more than 850 μ m that comprise in multipolymer (A) is 250～900g/mm
2.
5. thermoplastic resin processing aid according to claim 3, wherein, the ultimate compression strength of the particles more than 850 μ m that comprise in multipolymer (A) is 250～900g/mm
2.
6. thermoplastic resin processing aid according to claim 1, wherein, multipolymer (A) is that the reaction product obtaining from the utilizing letex polymerization of described monomer is to reclaim latex.
7. thermoplastic resin processing aid according to claim 6, wherein, the weight average particle diameter of the latex particle of multipolymer (A) is below 160nm.
8. thermoplastic resin processing aid according to claim 6, wherein, in latex, total metering of residual unreacted component is below 2.0 % by weight.
9. a thermoplastic resin composition, wherein, comprises processing aid 0.1～15 weight part described in any one in thermoplastic resin 100 weight parts and claim 1～8.
10. a resin forming product, it is shaped thermoplastic resin composition claimed in claim 9 and obtain.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-207240 | 2010-09-15 | ||
| JP2010207240 | 2010-09-15 | ||
| PCT/JP2011/070907 WO2012036173A1 (en) | 2010-09-15 | 2011-09-13 | Thermoplastic resin processing aid, and thermoplastic resin composition containing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103228686A CN103228686A (en) | 2013-07-31 |
| CN103228686B true CN103228686B (en) | 2014-11-05 |
Family
ID=45831631
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180043825.6A Expired - Fee Related CN103228686B (en) | 2010-09-15 | 2011-09-13 | Thermoplastic resin processing aid, and thermoplastic resin composition containing same |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPWO2012036173A1 (en) |
| CN (1) | CN103228686B (en) |
| WO (1) | WO2012036173A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014065570A1 (en) * | 2012-10-26 | 2014-05-01 | 한화케미칼 주식회사 | Polyvinyl chloride-based paste resin, and preparation method therefor |
| CN110546200B (en) * | 2017-04-28 | 2021-11-02 | 韩华化学株式会社 | Vinyl chloride-based resin latex composition and method for preparing the same |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3256453B2 (en) * | 1996-12-10 | 2002-02-12 | テクノポリマー株式会社 | Modifier consisting of copolymer with good thermal stability |
| JPH10330425A (en) * | 1997-05-30 | 1998-12-15 | Mitsubishi Rayon Co Ltd | Processing auxiliary for styrene-based resin and styrene-based resin composition using the same |
| JP3187751B2 (en) * | 1997-08-28 | 2001-07-11 | テクノポリマー株式会社 | Thermoplastic resin |
| JP2000026543A (en) * | 1998-07-13 | 2000-01-25 | Techno Polymer Kk | Production of copolymer |
| JP3504215B2 (en) * | 1999-05-19 | 2004-03-08 | 三菱レイヨン株式会社 | Processing aid, vinyl chloride resin composition using the same, and method for producing molded article using the same |
-
2011
- 2011-09-13 WO PCT/JP2011/070907 patent/WO2012036173A1/en active Application Filing
- 2011-09-13 JP JP2012534022A patent/JPWO2012036173A1/en not_active Withdrawn
- 2011-09-13 CN CN201180043825.6A patent/CN103228686B/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| JP特开2000-26543A 2000.01.25 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103228686A (en) | 2013-07-31 |
| WO2012036173A1 (en) | 2012-03-22 |
| JPWO2012036173A1 (en) | 2014-02-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5599973B2 (en) | Bulk polymerized rubber modified monovinylidene aromatic copolymer composition exhibiting improved low gloss | |
| CN1237114C (en) | Preparation of multi-layer polyer composition and products thereby | |
| JP4582638B2 (en) | Core / shell particles for improving impact resistance of poly (meth) acrylate molding materials | |
| JP5022444B2 (en) | Thermoplastic resin with uniform composition and narrow molecular weight distribution and method for producing the same | |
| CN101754982B (en) | Method for producing enlarged rubber, graft copolymer, thermoplastic resin composition and molded article | |
| JP7383805B2 (en) | Thermoplastic resin and its manufacturing method | |
| JP7195444B2 (en) | ACRYLIC GRAFT COPOLYMER, METHOD FOR PRODUCING SAME, AND THERMOPLASTIC RESIN COMPOSITION CONTAINING THE SAME | |
| CN103228686B (en) | Thermoplastic resin processing aid, and thermoplastic resin composition containing same | |
| KR100870754B1 (en) | Thermoplastic resin composition having excellent low gloss characteristic and scratch resistance, and method for preparing the same | |
| JP5100483B2 (en) | Thermoplastic resin composition and molded body | |
| CA2941557C (en) | Thermoplastic resin composition and resin molded article | |
| JP5453511B2 (en) | Graft copolymer, thermoplastic resin composition, and method for producing graft copolymer | |
| JP2021520438A (en) | Method for producing graft copolymer powder | |
| CN110016195A (en) | Polymethacrylates constituent and its be formed by optical element and display equipment | |
| MX2011000606A (en) | Improved low gloss abs compositions. | |
| CN103910960B (en) | Rubber modified methacrylate resin composition | |
| CN103910962B (en) | Polymethacrylate composition | |
| CN103910957A (en) | Rubber modified methacrylate resin composition | |
| JP5547828B2 (en) | Thermoplastic resin composition and extruded product | |
| JP7342276B2 (en) | Thermoplastic resin composition, method for producing the same, and molded products containing the same | |
| US20230145425A1 (en) | Thermoplastic resin composition, method of preparing the same, and molded article including the same | |
| JP5547794B2 (en) | Thermoplastic resin composition and extruded product | |
| CN101809087B (en) | Transparent compositions based on high-impact vinyl aromatic copolymers | |
| JP2023517123A (en) | THERMOPLASTIC RESIN COMPOSITION, MANUFACTURING METHOD THEREOF AND MOLDED PRODUCT CONTAINING THE SAME | |
| WO2022102547A1 (en) | Resin composition for coating |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141105 Termination date: 20170913 |