[Mutual citations and related applications;
[2]
The invention claims the benefit of priority based on the Korea Patent Application No. 10-2017-0148529, filed on 9/11/2017, and includes all the information described in the literature of the Korea patent application as a part of this specification.
[3]
[Technology]
[4]
The present invention relates to a thermoplastic resin composition, and more particularly to the bleaching to improve the thermoplastic resin composition.
BACKGROUND
[5]
In general, alkyl (meth) acrylonitrile-containing acrylate-based polymer unit derived from styrene-acrylate copolymer is a representative example of a thermoplastic resin having excellent weather resistance and aging resistance. Thermoplastic resins are used in various fields such as automobile, marine, leisure goods, building materials, gardening has been rapidly increasing their usage.
[6]
Meanwhile, As high levels of emotional quality requirements of users, there is ongoing research to implements a luxurious appearance, good colorability and weatherability by finishing substrates such as ABS, PVC, steel plate with a thermoplastic resin. However, the whitening phenomenon occurs on the surface of the product when finishing in the properties of the thermoplastic resin at room temperature is the original color disappears and spoiled the appearance. This whitening phenomenon occurs because the air gap due to the cracks present in the inner thermoplastic resin. By adjusting the rubber content in the thermoplastic resin, or mixing a thermoplastic resin with the elastomer to improve this chlorosis, the softening of the thermoplastic resin has been proposed a method of improving the bleaching.
[7]
However, as improved bleaching mechanical property, coloring property, surface gloss is good for the development of both the thermoplastic resin composition is insufficient situation.
Detailed Description of the Invention
SUMMARY
[8]
An object of the present invention, while improving the bleaching, coloring property, surface gloss, to both the mechanical properties and processability offers excellent thermoplastic resin composition.
Problem solving means
[9]
A first graft copolymer in order to achieve the foregoing object, the present invention comprises a (meth) acrylate-based polymer unit derived from the aromatic vinyl-based monomer-derived unit and a vinyl cyanide-based monomer-derived units; Aromatic copolymer comprising a vinyl-based monomer-derived unit and a vinyl cyanide-based monomer-derived units; Polyester-based elastomers; Provides a thermoplastic resin composition and the plasticizer comprises a phthalate.
Effects of the Invention
[10]
The thermoplastic resin composition of the present invention is excellent both, as well as to improve the bleaching, coloring property, surface gloss, mechanical properties and processability.
Best Mode for Carrying Out the Invention
[11]
Hereinafter, the present invention will be described in more detail to aid the understanding of the present invention.
[12]
Herein and in the terms or words used in the claims is general and not be construed as limited to the dictionary meanings are not, the inventor can adequately define terms to describe his own invention in the best way on the basis of the principle that the interpreted based on the meanings and concepts corresponding to technical aspects of the present invention.
[13]
[14]
The weight average molecular weight and number average molecular weight in the present invention can be by using THF (tetrahydrofuran) as the eluent to measure the relative values ​​of the standard PS (standard polystyrene) sample through GPC (Gel Permeation Chromatography, waters breeze).
[15]
[16]
The average particle diameter of the first graft copolymer, a second graft copolymer, the alkyl (meth) acrylate copolymer in the present invention can be measured by the Particle Size Analyzer (NICOM 380).
[17]
[18]
Shore D hardness (shore D) of the polyester-based elastomer in the present invention can be measured according to ASTM D2240.
[19]
[20]
The thermoplastic resin composition according to an embodiment of the present invention: 1. alkyl (meth) acrylate-based polymer of claim 1 a graft copolymer derived from components comprising the aromatic vinyl-based monomer-derived unit and a vinyl cyanide-based monomer-derived units; 2. The copolymer containing the aromatic vinyl-based monomer-derived unit and a vinyl cyanide-based monomer-derived units; 3. The polyester-based elastomer; And 4. include phthalate plasticizers.
[21]
[22]
Further, the thermoplastic resin composition according to an embodiment of the present invention is that the first graft copolymer and the average particle diameter to the other 5. In a second graft copolymer.
[23]
[24]
It describes the following, each component in the thermoplastic resin composition of the present invention in detail.
[25]
[26]
1. The first graft copolymer
[27]
The first graft copolymer is included to improve the weather resistance, whitening, surface gloss, colorability and the mechanical properties of the thermoplastic resin composition according to an embodiment of the present invention.
[28]
[29]
The first graft and copolymer comprises alkyl (meth) acrylate copolymer derived from units of aromatic vinyl-based monomer-derived unit and a vinyl cyanide-based monomer-derived units.
[30]
[31]
The alkyl (meth) acrylate-based polymer derived from units of alkyl (meth) acrylate monomer is produced (meth) acrylates are acrylate-based polymer aromatic vinyl monomer and vinyl cyanide monomer and a graft-polymerization polymerization by being denatured It may be.
[32]
The alkyl (meth) acrylate-based monomers include C 1 to C 10 alkyl (meth) acrylate monomers one can, wherein the C 1 to C 10 alkyl (meth) acrylate monomers include methyl acrylate, ethyl acrylate, the butyl acrylate and ethylhexyl may be at least one selected from the group consisting of acrylate, of which butyl acrylate is preferred.
[33]
The alkyl (meth) acrylate-based polymer may be a mean particle diameter of 30 to 150 ㎚, 40 to 140 or 80 to 130 ㎚ ㎚, it is preferred that 80 to 130 of the ㎚.
[34]
When it satisfies the above-mentioned range, the effect of weather resistance, surface gloss, colorability, and become a more excellent thermoplastic resin composition.
[35]
The alkyl (meth) acrylate-based polymer derived from units of the first graft copolymer, based on the total weight, may contain from 30 to 70% by weight, 35 to 65% by weight, or 40 to 60% by weight, of 40 to be included in to 60% by weight.
[36]
When it satisfies the above-mentioned range, the first graft can be improved in mechanical properties and weatherability of the copolymer.
[37]
[38]
The aromatic vinyl-based monomer-derived units of styrene, α- methyl styrene, p- methyl styrene may be, and 2,4-dimethyl-derived units of at least one member selected from the group consisting of styrene, a styrene-derived units of the preferred Do.
[39]
The aromatic vinyl-based monomer-derived units of the first graft, based on the total weight of the copolymer, may be included in a 20 to 60% by weight, 20 to 50% or from 20 to 40% by weight, with 20 to 40% by weight of is contained is preferable.
[40]
When it satisfies the above-mentioned range, the first graft can be improved in impact resistance and weather resistance than that of the copolymer.
[41]
[42]
The vinyl cyanide-based monomer-derived units of acrylonitrile, can be a methacrylate and acrylonitrile units derived from 1 or more kinds selected from the group consisting of acrylonitrile, from ethacrylic to, this is derived units in the acrylonitrile is preferred.
[43]
The vinyl cyanide-based monomer-derived units of the first graft relative to the copolymer total weight, may contain from 5 to 40% by weight, 10 to 30% by weight or 15 to 25% by weight, with 15 to 25% by weight of is contained is preferable.
[44]
When it satisfies the above-mentioned range, the first graft can be improved in impact resistance and weather resistance than that of the copolymer.
[45]
[46]
The first graft copolymer may be a mean particle diameter of 50 to 170 ㎚, 60 to 160 or 100 to 150 ㎚ ㎚, preferably from 100 to 150 of the ㎚.
[47]
When it satisfies the above-mentioned range, the appearance characteristics are excellent and at the same time excellent mechanical properties benefits such as surface gloss and colorability.
[48]
[49]
The first graft copolymer is the first graft copolymer, a copolymer and a polyester-based, based on the total weight of elastomer, 30 to 80% by weight, may contain from 40 to 75% by weight, or 45 to 75% by weight and, it is preferably included in the 45 to 75% by weight. When it satisfies the above-mentioned range, excellent in fluidity during processing of the thermoplastic resin composition, and it is the impact strength can be more excellent after forming.
[50]
[51]
On the other hand, the method comprising: the first graft copolymer is prepared 1) alkyl (meth) acrylate-based monomer by polymerizing an emulsion (meth) acrylate-based polymer; And 2) can be prepared by the method comprising the step of producing a first graft copolymer by emulsion polymerization of the alkyl (meth) acrylate-based polymer, an aromatic vinyl monomer and vinyl cyanide-based monomer.
[52]
[53]
Will be described below, each step of the manufacturing method of the first graft copolymer in detail.
[54]
[55]
1) preparing the polymer (meth) acrylate
[56]
First, the emulsion polymerization of alkyl (meth) acrylate-based monomers can be produced a polymer-based (meth) acrylate.
[57]
The alkyl (meth) acrylate monomer is preferably methyl acrylate, ethyl acrylate, butyl acrylate and ethyl hexyl may be at least one selected from the group consisting of acrylate, of butyl acrylate.
[58]
[59]
The emulsion polymerization may be carried out in the presence at least one member selected from an emulsifier, an initiator, a crosslinking agent, a graft teuje, electrolytes, and the group consisting of water.
[60]
The emulsifiers are C 12 to C 18 alkyl sulfosuccinate metal salt derivatives, and C 12 to C 20 can be at least one selected from the group consisting of a metal salt derivative of alkyl sulfuric acid ester.
[61]
The C 12 to C 18 of a metal salt derivative of alkyl sulfosuccinate is sodium dicyclohexyl sulfosuccinate, dihexyl sulfosuccinate sodium salt, di-2-ethylhexyl sulfosuccinate sodium salt, di-2-ethylhexyl sulfosuccinate and potassium salt one member selected from the group consisting of di-2-ethylhexyl sulfo succinate lithium salt may be at least.
[62]
The C 12 to C 20 of a metal salt derivative of alkyl sulfuric acid esters are sodium laurate rigs sulfate, sodium dodecyl sulfate, sodium dodecyl benzene sulfate, sodium octadecyl sulfate, sodium oleic sulfate, potassium dodecyl sulfate and potassium octadecyl sulfate It may be at least one selected from the group consisting of.
[63]
The emulsifier is to put the alkyl (meth) based on 100 parts by weight of acrylate monomer, it may be added an amount of 1 to 5 parts by weight, 1.5 to 4 parts by weight or 1.5 to 3 weight parts of the 1.5 to 3 parts by weight of desirable.
[64]
The emulsifier may be added to water and mixed state, in this case, it is preferable that a pH of 3 to 9. When satisfied with the above-mentioned range, the emulsifier is dissolved as it is possible to reliably to function, the activity of the initiator can be more improved.
[65]
[66]
The initiator may be an inorganic peroxide or an organic peroxide. The inorganic peroxide may be at least one in a water-soluble initiator, potassium persulfate, the group consisting of sodium persulfate and ammonium persulfate. The organic peroxide can be at least one selected from the group consisting of an oil-soluble initiator, cumene hydro peroxide, and benzoyl peroxide.
[67]
The initiator is preferably In the (meth) may be added acrylate monomer based on 100 parts by weight of 0.05 to 0.5 parts by weight of a portion of 0.05 to 0.3 part by weight or 0.05 to 0.2, 0.05 to 0.2 parts by weight of the portion Do.
[68]
[69]
The crosslinking agent is ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane may be at least one selected from the group consisting of propane trimethacrylate, and trimethylol methane triacrylate.
[70]
The cross-linking agent is to be added the alkyl (meth) acrylate monomer based on 100 parts by weight, 0.02 to 0.5 parts by weight, 0.02 to 0.4 may be added as part weight parts or 0.02 to 0.3 parts by weight, of 0.02 to 0.3 parts by weight desirable. When introduced into the above-mentioned range, the alkyl (meth) can be improved such as elasticity and the impact strength of the acrylate-based polymer.
[71]
[72]
The graft tingje is allyl methacrylate, it may be at least one selected from the group consisting of triallyl isocyanurate, triallylamine, and diallylamine.
[73]
The graft tingje is being introduced the alkyl (meth) with respect to the acrylate-based monomer of 100 parts by weight, 0.01 to 0.15 parts by weight, 0.01 to 0.1 may be added as part parts by weight or 0.01 to 0.07 parts by weight, 0.01 to 0.07 parts by weight of the portion it is desirable. When introduced into the above-mentioned range, the alkyl (meth) can be improved such as elasticity and the impact strength of the acrylate-based polymer.
[74]
[75]
The electrolyte is NaHCO 3 , Na 2 S 2 O 7 and K 2 CO 3 may be at least one selected from the group consisting of.
[76]
The electrolyte is to be added the alkyl (meth) acrylate monomer based on 100 parts by weight, 0.02 to 0.1 part by weight, 0.04 to 0.06 may be added as part parts by weight or 0.04 to 0.05, of which 0.04 to 0.05 parts by weight desirable.
[77]
[78]
The water may be a number, and performs a role in the emulsion polymerization medium, ion-exchanged water.
[79]
[80]
2) preparing the first graft copolymer
[81]
Then, the emulsion polymerization of the alkyl (meth) acrylate-based polymer, an aromatic vinyl monomer and vinyl cyanide-based monomers can be produced a first graft copolymer.
[82]
[83]
The alkyl (meth) acrylate-based polymer may be a colloidal alkyl (meth) acrylate-based polymer latex form and dispersed in water.
[84]
The alkyl (meth) acrylate-based polymer is a (meth) acrylate-based polymer, an aromatic vinyl monomer and vinyl cyanide-based with respect to the monomer total weight, 30 to 70% by weight based on solids, 35 to 65% by weight or 40 It can be included as to 60% by weight, and preferably contained in 40 to 60% by weight of. When it satisfies the above-mentioned range, the first graft can be improved in impact resistance and weather resistance than that of the copolymer.
[85]
[86]
The aromatic vinyl monomers are styrene, α- methyl styrene, p- methyl styrene, and may be at least one selected from the group consisting of 2,4-dimethyl styrene, and styrene is preferred among.
[87]
The aromatic vinyl monomers include the alkyl (meth) acrylate-based polymer, an aromatic vinyl monomer and vinyl cyanide-based with respect to the monomer total weight, 20 to 60% by weight, 20 to 50% by weight or may contain from 20 to 40% by weight and, it is preferably included in the 20 to 40% by weight of. When it satisfies the above-mentioned range, the first graft can be improved in impact resistance and weather resistance than that of the copolymer.
[88]
[89]
The vinyl cyanide monomer is an acrylonitrile, can be at least one selected from the group consisting of acrylonitrile and methacrylonitrile ethacrylic, it is preferred that of the acrylonitrile.
[90]
The vinyl cyanide-based monomer is a (meth) acrylate-based polymer, an aromatic vinyl monomer and vinyl cyanide-based with respect to the monomer total weight, from 5 to 40% by weight, 10 to 30% by weight or may contain 15 to 25% by weight and, it is preferably included in the 15 to 25% by weight. When it satisfies the above-mentioned range, the first graft can be improved in impact resistance and weather resistance than that of the copolymer.
[91]
The emulsion polymerization may be carried out in the presence at least one member selected from an emulsifier, initiator, chain transfer agent and water in the group consisting of.
[92]
The emulsifier may be a carboxylic acid metal salt derivative, the carboxylic acid metal salt derivative is C 12 to C 20 can be at least one selected from the group consisting of metal salts of fatty acids and rosin acid metal salts. The C 12 to C 20 fatty acid metal salts may be at least one selected from the group consisting of fatty acids, sodium lauryl acid, sodium oleate, sodium oleate and potassium. The rosin acid metal salt may be at least one selected from the group consisting of rosin acid, sodium rosin acid, and potassium.
[93]
The emulsifiers are the alkyl (meth) acrylate-based polymer, an aromatic vinyl monomer and vinyl cyanide-based respect to the sum of 100 parts by weight of monomer, 0.5 to 3 parts by weight, 0.5 to 2 parts by weight or 1 to be input portion 2 weight and, it is preferable that the input portion is 1 to 2 parts by weight of.
[94]
[95]
The initiators are alkyl (meth) acrylate may be used is the production of polymers using the same initiator as the initiator, of which it is preferable to use an organic peroxide.
[96]
The initiators are the alkyl (meth) acrylate-based polymer, an aromatic vinyl monomer and vinyl cyanide-based sum, based on 100 parts by weight of the monomer, from 0.05 to 0.5 part by weight, 0.05 to 0.4 weight parts or 0.05 to 0.3 may be added parts by weight and, it is preferred that the input of 0.05 to 0.3 parts by weight.
[97]
[98]
The chain transfer agent may be at least one selected from the group consisting of t- dodecyl mercaptan and n- meoreu meoreu octyl mercaptan, t- dodecyl meoreu of this mercaptan is preferred.
[99]
The chain transfer agent is the alkyl (meth) acrylate-based polymer, an aromatic vinyl monomer and vinyl cyanide-based sum, based on 100 parts by weight of the monomer, from 0.02 to 0.4 part by weight, 0.02 to 0.3 parts by weight or 0.02 to 0.2 to be added parts by weight number, and it is preferred that the input of 0.02 to 0.2 parts by weight.
[100]
[101]
The emulsion polymerization is preferably carried out while continuously added the reaction mixture containing the alkyl (meth) acrylate-based polymer, an aromatic vinyl monomer, vinyl cyanide-based monomer, an emulsifier, initiator, chain transfer agent, water and the like. When the emulsion polymerization is carried out while continuously added, pH is kept constant, and facilitating the graft polymerization, as well as excellent in stability of the graft copolymer particles, the interiors of the particles can be uniformly prepared.
[102]
[103]
A first graft copolymer also, completion of the emulsion polymerization may be in the form of latices. The first graft copolymer latex may be pH 8 to 11 or from pH 9 to 10.5. When it satisfies the above-mentioned range has an excellent advantage that the stability of the latex.
[104]
[105]
The first graft copolymer latex can be prepared in powder form by performing the aggregation, aging, washing, dehydrating and drying.
[106]
The aggregation may be carried out by charging a flocculant to the latex of the first graft copolymer, is preferably carried out at normal pressure, 80 to 95 ℃. The coagulant may be an aqueous calcium chloride solution.
[107]
The fermentation may be performed after the aggregation may be performed for 90 to 95 ℃, 10 to 30 minutes.
[108]
The drying is in the 85 to 95 ℃ hot air may be conducted for 10 to 60 minutes.
[109]
[110]
2. Copolymer
[111]
The copolymer matrix is ​​a copolymer, is included to improve the bleaching and coloring property of the thermoplastic resin composition according to an embodiment of the present invention.
[112]
[113]
And wherein the copolymer comprises units derived from an aromatic vinyl monomer and vinyl cyanide-based monomer-derived units.
[114]
The aromatic vinyl-based monomer-derived units of styrene, α- methyl styrene, p- methyl styrene, and 2,4-dimethyl styrene may be derived from one or more units selected from the group consisting, of styrene and α- methyl styrene that the units derived from at least one member selected from the group consisting of is preferred.
[115]
The vinyl cyanide-based monomer-derived units of acrylonitrile, can be a methacrylate and acrylonitrile units derived from 1 or more kinds selected from the group consisting of acrylonitrile, from ethacrylic to, this is derived units in the acrylonitrile is preferred.
[116]
The copolymer may contain as the aromatic vinyl-based monomer-derived units and the vinyl cyanide-based monomer weight ratio of 60: 40 to 90:10, the resulting unit, 65:35 to 85:15 or 70:30 to 80:20, and it is preferable that a weight ratio of from 70:30 to 80:20. When it satisfies the above-described range, it is possible to have chemical resistance, and formability becomes more excellent.
[117]
[118]
The copolymer is a copolymer containing units derived from acrylonitrile in the styrene-derived units and acrylic; Copolymers comprising units derived from a nitrile with α- methylstyrene derived units, and acrylic; And acrylonitrile, α- methylstyrene derived units and units derived from styrene and acrylic may be at least one selected from the group consisting of a copolymer comprising a unit derived.
[119]
The copolymer preferably has a weight average molecular weight of 50,000 to 250,000g / mol, 80,000 to 220,000 g / mol, or from 110,000 to 190,000 g / mol it may be, of from 110,000 to 190,000 g / mol.
[120]
When it satisfies the above-mentioned range, it is possible to improve whitening of the thermoplastic resin composition and the coloring property is more.
[121]
[122]
The copolymer based on the total weight of the thermoplastic resin composition within the first graft copolymer, a copolymer and a polyester-based elastomer according to one embodiment of the present invention, 10 to 50% by weight, 15 to 45% by weight, or It may be included in a 20 to 40% by weight, preferably included in the 20 to 40% by weight of. When it satisfies the above-mentioned range, excellent in fluidity during processing of the thermoplastic resin composition, and it is the impact strength can be more excellent after forming.
[123]
[124]
3. The polyester-based elastomer
[125]
The polyester elastomer is contained in order to improve the bleaching, coloring, workability, aging resistance and chemical resistance of the thermoplastic resin composition according to an embodiment of the present invention.
[126]
[127]
The polyester-based elastomer may comprise room hangjok or aliphatic dicarboxylic acid or its ester-derived units, and a rigid portion comprising an aliphatic diol-derived units, and the soft parts of a polyalkyl containing alkylene oxide-derived units.
[128]
[129]
The aromatic or aliphatic dicarboxylic acid unit is derived from terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid and 1,4- cycloalkyl may be hexane dicarboxylic the units derived from at least one member selected from the group consisting of acid.
[130]
The aromatic or aliphatic dicarboxylic ester-derived units of the acid include dimethyl terephthalate, dimethyl isophthalate, dimethyl 2,6-naphthalene dicarboxylate, dimethyl 1,5-naphthalene dicarboxylate, dimethyl 1,4-naphthalenedicarboxylate Le carboxylate and dimethyl 1,4-cyclohexane dicarboxylic may be derived from one or more units selected from the group consisting of carboxylate, it is preferred that the units derived from the dimethyl terephthalate.
[131]
The room hangjok or aliphatic dicarboxylic acid or its ester-derived units, based on the total weight of the polyester-based elastomer, and may contain from 25 to 65% by weight or 30 to 60% by weight, is from 30 to 60% by weight of the preferred Do.
[132]
[133]
The aliphatic diol-derived unit can be a molecular weight of 300 g / mol of units derived from an aliphatic diol or less.
[134]
The aliphatic diol-derived units of ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-penta, 1,6-hexanediol and 1,4- cyclohexanedimethanol may be in one or more units derived from species selected from the group consisting of methanol, it is a unit derived from 1,4-butanediol in this preferred.
[135]
The aliphatic diol-derived units, based on the total weight of the polyester-based elastomer, and may contain from 20 to 45% by weight or 25 to 40% by weight, this is the 25 to 40% by weight is preferred.
[136]
The polyalkylene oxide-derived units may be a unit derived from the aliphatic polyether.
[137]
The polyalkylene oxide-derived units in the polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, ethylene oxide and propylene copolymers, ethylene oxide adducts of polypropylene glycol polymers, and ethylene oxide and tetrahydrofuran of oxide it may be a unit derived from at least one member selected from the group consisting of a copolymer, the addition of the polytetramethylene glycol or polypropylene glycol ethylene oxide in the units derived from the polymer is preferred.
[138]
[139]
The polytetramethylene glycol has a number-average molecular weight and the number of days from 600 to 3,000g / mol, 1,000 to 2,500 g / mol, or 1,800 to 2,200 g / mol, it is preferred that the of 1,800 to 2,200 g / mol.
[140]
Ethylene oxide addition polymer of the polypropylene glycol is from the terminal may be a polypropylene glycol capped with ethylene oxide, it may be in the range of 2,000 to 3,000g / mol weight-average molecular weight.
[141]
Wherein the polyalkylene oxide units are derived, based on the total weight of the thermoplastic polyester-based elastomer, it may be contained in 10 to 50% by weight or from 15 to 45% by weight. When it satisfies the above-mentioned range, a polyester flexibility, heat resistance and usability of the elastomer may become superior.
[142]
[143]
On the other hand, the polyester-based elastomer may be of 2,000 to 3,000 g / mol average molecular weight.
[144]
[145]
The polyester-based elastomer may be in a Shore D hardness of 35 to 55 or 40 to 50, a is from 40 to 50 is preferred.
[146]
When it satisfies the above-mentioned range, the extrusion and molding of the thermoplastic resin composition can be easily and improve the chemical resistance. Further, the tensile strength of the thermoplastic resin composition, such as bending strength and impact strength can be remarkably improved, and the bleaching properties of the thermoplastic resin composition can be improved.
[147]
If it is less than the above range, the tensile strength, and flexural strength of the thermoplastic resin composition is remarkably reduced can be significantly reduced whitening properties.
[148]
If it exceeds the above range, the impact strength of the thermoplastic resin composition can be significantly reduced.
[149]
[150]
When on the basis of the polyester-based elastomer to the ASTM D1238 measures the weight for 10 minutes at a temperature 230 ℃, load 2.16 kg, may be a melt index of 0.1 to 10 g / min or 1 to 10 g / min.
[151]
When it satisfies the above-mentioned range, the extrusion and molding of the thermoplastic resin composition can be easily and improve the chemical resistance.
[152]
[153]
The polyester-based elastomer is against one embodiment the thermoplastic resin composition within the first graft copolymer, a copolymer and a polyester-based elastomer total weight according to the present invention, 3 to 20% by weight, 4 to 18% by weight, or it may contain from 5 to 15% by weight, preferably included in the 5 to 15% by weight of. When it satisfies the above-mentioned range, can be improved than the bleaching, coloring property and aging resistance.
[154]
[155]
On the other hand, the polyester-based elastomer 1) preparing an aromatic or aliphatic dicarboxylic acid or its ester-forming derivative, an aliphatic diol and a polyalkylene oxide by melt polymerization of the poly ester-based elastomer precursor; And 2) can be produced by a production method including the step of producing the polyester-based elastomer to the solid phase polymerizing the polyester-based elastomer precursor.
[156]
[157]
Will be described below, each step of the production method of the polyester-based elastomer in detail.
[158]
[159]
1) preparing the polyester-based elastomer precursor
[160]
First, it is possible to prepare the aromatic or aliphatic dicarboxylic acid or its ester, an aliphatic diol, and polyalkylene oxide as a starting material.
[161]
[162]
The aromatic or aliphatic dicarboxylic acid or its ester may be fed to the with respect to the total weight of the starting material, 25 to 65% or from 30 to 60% by weight, is from 30 to 60% by weight of the preferred. When it satisfies the above-mentioned range, the reaction balance is to be superior to the melt polymerization is carried out smoothly.
[163]
Specific examples of the aromatic or aliphatic dicarboxylic acid or its esters are as defined above.
[164]
[165]
The aliphatic diol may be fed to the with respect to the total weight of the starting material, 20 to 45% by weight, 25 to 40% by weight. When it satisfies the above-mentioned range, the reaction balance is to be superior to the melt polymerization is carried out smoothly.
[166]
Specific examples of the aliphatic diol are the same as described above.
[167]
[168]
The polyalkylene oxide is preferably that can be fed to the with respect to the total weight of the starting material, 10 to 50% or from 15 to 45% by weight, fed to a 15 to 45% by weight of. When it satisfies the above-mentioned range, a polyester flexibility, heat resistance and usability of the elastomer may become superior.
[169]
Specific examples of the polyalkylene oxides as described above.
[170]
[171]
Then, the catalyst primary input to the starting material, and can be a melt polymerization initiated after raising the temperature to 140 to 215 ℃.
[172]
The catalyst may be a titanium butoxide.
[173]
If the melt polymerization is initiated, there can be a transesterification performed between the starting material, whereby there is a oligomer, preferably bis (4-hydroxybutyl) terephthalate (BHBT) oligomers can be prepared. The transesterification reaction can be carried out for 1 to 3 hours or 1 hour for 30 minutes to 2 hours and 30 minutes.
[174]
[175]
Was then added a catalytic secondary to the oligomer, 215. The polycondensation reaction can be carried out as to after the temperature was raised to 245 ℃ reduced pressure at 760 torr to 0.3 torr, and the axis is produced due to polymerization of polyester-based elastomer precursor It can be.
[176]
The polycondensation reaction may be carried out for 1 to 3 hours or 1 hour for 30 minutes to 2 hours and 30 minutes.
[177]
When the polyester-based elastomer precursor to measure the melt index for 10 minutes at a temperature 230 ℃, load of 2.16 kg in accordance with ASTM D1238, a melt index of can be from 15 to 25g / 10 min or 18 to 22 g / 10 min .
[178]
[179]
Then, the polyester was discharged in a strand form the elastomer precursor to the nitrogen pressure, by this pellets palletizing, it is possible to manufacture a polyester-based elastomer precursor of the pellet form.
[180]
[181]
On the other hand, when the melting point of the melt polymerization, the polyester-based elastomer may be branched I be further introduced in order to improve the degree and melt tension.
[182]
The branching agent is glycerol, pentaerythritol, trimellitic tic anhydride, may be at least one selected from trimellitic acid, trimethylolpropane, and neopentyl group consisting of glycol, of which are preferable the trimellitic tic anhydride .
[183]
The branching agent with respect to 100 parts by weight of the starting materials, can be incorporated from 0.05 to 0.1% by weight. When it satisfies the above-mentioned range, the polyester to the melt viscosity of the elastomer and also the degree of polymerization as appropriate, it is possible to easily control the reaction of the melt polymerization, and facilitate the ejection of the polyester-based elastomer precursor into the reactor outside.
[184]
[185]
2) a step for preparing a poly-ester-based elastomer
[186]
Then, it is possible by solid phase polymerizing the polyester-based elastomer precursor to manufacture a polyester-based elastomer.
[187]
The solid phase polymerization may be carried out during the polyester-based elastomer was charged into a precursor to the solid-phase polymerization reactor, under 140 to 200 ℃, an inert atmosphere, and gradually reduced pressure to a high vacuum for 10 to 24 hours.
[188]
The solid phase polymerization reactor may be a Rotatable high vacuum pump is connected to vessel (vessel) vacuum dryer, the inert atmosphere may be a nitrogen atmosphere.
[189]
[190]
On the other hand, the polyester-based elastomer may be used commercially available materials, preferably of LG Chemical KEYFLEX BT 2140D (DSC melting point 198 ℃, Shore A hardness: 43: 95, Shore D hardness) and the like.
[191]
[192]
4. phthalate plasticizer
[193]
The phthalate-based plasticizer is included in order to improve the bleaching and processability of the thermoplastic resin composition.
[194]
The phthalate-based plasticizer, diisopropyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, diisodecyl phthalate and butyl benzyl phthalate may be at least one selected from the group consisting of diisopropyl that the phthalate is preferred.
[195]
The phthalate-based plasticizers may be included as part of the first graft copolymer, a copolymer and a polyester-based sum, based on 100 parts by weight of an elastomer, 1 to 20 parts by weight, 2 to 15 parts by weight, or from 3 to 10 parts by weight, to be included from 3 to 10 parts by weight of the preferred.
[196]
When it satisfies the above range, the gloss processing to help the surface of the thermoplastic resin composition can be more excellent.
[197]
[198]
5. In the second graft copolymer
[199]
The second graft copolymer may be included in order to improve the bleaching properties and mechanical properties of the thermoplastic resin composition.
[200]
[201]
The second graft copolymer may include an alkyl (meth) acrylate-based polymer derived from units derived from an aromatic vinyl monomer unit and vinyl cyanide-based monomer-derived units.
[202]
The alkyl (meth) acrylate-based polymer derived from units of alkyl (meth) acrylate monomer is produced (meth) acrylates are acrylate-based polymer aromatic vinyl monomer and vinyl cyanide monomer and a graft-polymerization polymerization by being denatured It may be.
[203]
[204]
The alkyl (meth) average particle diameter of the acrylate-based polymer may be a 150 to 600 ㎚ ㎚ than or less, 250 to 550 or 350 to 500 ㎚ ㎚, this is 350 to 500 of ㎚ preferred.
[205]
When it satisfies the above-mentioned range, it can be improved in mechanical properties of the thermoplastic resin composition.
[206]
The alkyl (meth) acrylate and specific examples of the content of the polymer unit derived from the aromatic vinyl-based monomer-derived unit and a vinyl cyanide-based monomer-derived units is "1. The same as described in the first graft copolymer.
[207]
[208]
Wherein the second average particle size of the graft copolymer may be in excess to 250㎚ 750㎚ less, 350 to 700 or 450 to 650 ㎚ ㎚, this is 450 to 600 of ㎚ preferred. When it satisfies the above-mentioned range, it can be improved in mechanical properties of the thermoplastic resin composition.
[209]
[210]
The second graft copolymer is the first graft copolymer, a second graft copolymer, copolymer and a polyester-based elastomer, based on the total weight, from 5 to 40% by weight, 15 to 35 wt% or 25 - 30 may be included by weight%, it is preferably included in 25 to 30% by weight of. When it satisfies the above-mentioned range, the impact strength, surface hardness and scratch resistance can be further improved.
[211]
[212]
The weight ratio of the first graft copolymer and the second graft copolymer is from 1: 1 to 1: 8, 1: 1 to 1: 6, or from 1: 1 to 1: 1 may be 4, is of 1: 1 to 1: 4 is not preferred. When it satisfies the above-mentioned range has an excellent advantage that the surface gloss, colorability and weather resistance.
[213]
On the other hand, the second graft copolymer was prepared in the same way as that of the first graft copolymer, except that (meth) acrylate copolymer produced when (meth) acrylate-based monomers and the other input of emulsifier It can be.
[214]
[215]
The weight ratio of the second graft copolymer prepared when injected (meth) acrylate-based monomers of the first graft (meth) acrylate-based monomer injected during polymer manufacture is 1.6: 1 to 10: 1 il .
[216]
The second graft (meth) acrylate-based polymer emulsions injected in the manufacture of the agent copolymer may be an 0.1 to 1, based on the weight of 100 parts by weight of the alkyl (meth) acrylate-based monomer.
[217]
[218]
The second graft pH of the alkyl (meth) acrylate-based polymer latex is introduced in the preparation of the copolymer may be from 5 to 9, or 6 to 8, of which preferably has a pH of 6 to 8. When it satisfies the above-mentioned range has an excellent advantage that the stability of the latex
[219]
[220]
On the other hand, the thermoplastic resin composition according to an embodiment of the present invention may further include additives. The additive be at least one selected from a dropping preventing agent, flame retardant, hyanggyunje, antistatic agents, stabilizers, mold release agents, thermal stabilizers, UV stabilizers, mineral additive, a lubricant, an antioxidant, a light stabilizer, a pigment, a group consisting of a dye and an inorganic filler this, and the double lubricant, at least one element selected from the group consisting of from antioxidants and UV stabilizers is preferred.
[221]
The additive of the first graft copolymer, based on 100 parts by weight of the sum of the copolymer and a polyester-based elastomer, may be included in amount of 0.1 to 20 parts by weight, 0.1 to 15 parts by weight or 0.1 to 10 parts by weight, of 0.1 to be an amount of to 10 parts by weight is preferred.
[222]
The lubricant is the first graft copolymer, based on 100 parts by weight of the sum of the copolymer and a polyester-based elastomer, may be included in amount of 0.1 to 10 parts by weight, 0.1 to 5 parts by weight or 0.1 to 3 parts by weight, of 0.1 to be an amount to 3 parts by weight is preferred.
[223]
The antioxidant is the first graft copolymer, a copolymer and a polyester-based sum, based on 100 parts by weight of the elastomer, it may be included in amount of 0.1 to 2 parts by weight, 0.1 to 1.5 wt% or 0.1 to 1 parts by weight, of to be an amount of 0.1 to 1 by weight.
[224]
The UV stabilizer is the first graft copolymer, based on 100 parts by weight of the sum of the copolymer and a polyester-based elastomer, it may be included in amount of 0.1 to 4 parts by weight, 0.1 to 3 parts by weight or 0.1 to 2 parts by weight, of to be an amount of 0.1 to 2 parts by weight is preferred.
[225]
[226]
The thermoplastic resin composition according to an embodiment of the present invention may be made from a sheet, the sheet may be for a roof.
[227]
Mode for the Invention
[228]
Will be described in detail below, embodiments of the present to the invention can easily be made self-of ordinary skill in the art to practice invention belongs. However, the invention is not to be implemented in many different forms and limited to the embodiments set forth herein.
[229]
[230]
Example 1
[231]
A first graft copolymer (average particle size: 130 nm, core: butyl acrylate polymer derived from units of 50 wt%, shell: 30% by weight of styrene-derived units, acrylonitrile 20% by weight derived units) 70 parts by weight, SAN copolymer copolymer (manufacturer: LG chemical, product name: 90HR, the weight average molecular weight: 150,000 g / mol) 20 parts by weight of a polyester-based elastomer (Manufacturer: LG chemical, trade name: KEYFLEX BT2140D resin, the Shore D hardness: 43) 10 parts by weight , phthalate-based plasticizer with diisopropyl phthalate 5 parts by weight, EBS resin with a lubricant (manufacturer: precursor chemical), 3 parts by weight, Irgranox 1076 as an antioxidant (trade name, manufacturer: BASF) 0.4 parts by weight, Irgrafos 168 (trade name, manufacturer: BASF) 0.4 parts by weight, Tinuvin 770 (trade name of an ultraviolet stabilizer, Manufacturer: was prepared in the Sun Fine global) a thermoplastic resin composition by putting 0.6 parts by weight: BASF) 0.6 parts by weight, Sunsorb329 (trade name, manufacturer.
[232]
In the thermoplastic resin composition groups extrusion mixing, create a pellet form under conditions of a cylinder temperature of 230 ℃, was prepared by injection this specimen.
[233]
[234]
Example 2
[235]
A first graft copolymer to 60 parts by weight, was prepared and is the test piece in the same manner as in Example 1 except that In the SAN copolymer 30 parts by weight.
[236]
[237]
Example 3
[238]
A first graft copolymer to 35 parts by weight of a second graft copolymer (average particle size: 500 nm, core: butyl acrylate polymer derived from units of 50 wt%, shell: styrene-derived units 30% by weight, an acrylonitrile-derived units of 20 except that the input to% by weight) 35 parts by weight to prepare a specimen in the same manner as in example 1.
[239]
[240]
Example 4
[241]
The first grafting 15 parts by weight of a copolymer, a second graft copolymer (average particle size: 500 nm, core: butyl acrylate polymer derived from units of 50 wt%, shell: styrene-derived units 30% by weight, an acrylonitrile-derived units of 20 except that the input to% by weight) 55 parts by weight to prepare a specimen in the same manner as in example 1.
[242]
[243]
Comparative Example 1
[244]
A first graft does not supply the copolymer with phthalate-based plasticizer, a second graft copolymer (average particle size: 500 nm, core: butyl acrylate polymer derived from units of 50 wt%, shell: styrene-derived units 30% by weight, acrylic nitrile was prepared in the specimen in the same manner as in example 1 except that the turned-derived units 20% by weight) 70 parts by weight.
[245]
[246]
Comparative Example 2
[247]
A first graft copolymer, 20 parts by weight of a second graft copolymer (average particle size: 500 nm, core: butyl acrylate polymer derived from units of 50 wt%, shell: styrene-derived units 30% by weight, an acrylonitrile-derived units of 20 wt. %) a specimen was prepared in 30 parts by weight of a copolymer of 50 parts by weight of a phthalate-based plasticizer, 4 parts by weight of in, and the polyester-based elastomer with the exception that no in the example 1 in the same manner.
[248]
[249]
Comparative Example 3
[250]
A specimen was prepared in the same manner as in Example 1 except that no In the polyester-based elastomer.
[251]
[252]
Comparative Example 4
[253]
Except that the phthalate-based plasticizer is not added to thereby prepare a specimen in the same manner as in Example 1.
[254]
[255]
Examples 1 to 4, as compared to Examples 1 to clean up the composition of the comparative sample of Example 4 are shown in Table 1 and Table 2.
[256]
TABLE 1
division Example 1 (parts by weight) Example 2 (parts by weight) Example 3 (parts by weight) Example 4 (parts by weight)
A first graft copolymer 70 60 35 15
A second graft copolymer - - 35 55
Copolymer 20 30 20 20
Polyester-based elastomer 10 10 10 10
Phthalate plasticizer 5 5 5 5

[257]
TABLE 2
division Comparative Example 1 (parts by weight) Comparative Example 2 (parts by weight) Comparative Example 3 (parts by weight) Comparative Example 4 (parts by weight)
A first graft copolymer - 20 70 70
A second graft copolymer 70 30 - -
Copolymer 20 50 20 20
Polyester-based elastomer 10 - - 10
Phthalate plasticizer - 4 5 -

[258]
[259]
Experimental Example
[260]
Examples 1 to 4, comparison and measurement in the same way as to the characteristics of the specimens of Examples 1 to Comparative Example 4, are shown and the results are shown in Table 3 and 4.
[261]
[262]
It was measured quantitatively in accordance with FT-IR: ※ rubber content (% by weight).
[263]
※ surface glossiness (%) was measured in accordance with ASTM D528 at a 45 ° angle.
[264]
※ impact strength (1/4 In, kgf · cm / cm): measured in accordance with STM D256.
[265]
※ flexural strength (kgf / ㎠): was measured according to ASTM D790.
[266]
※ tensile strength (kgf / ㎠): was measured according to ASTM D638.
[267]
※ low bleaching was measured based on ASTM D2176.
[268]
Was measured according to ASTM D785: ※ surface hardness.
[269]
※ coloring: using a color difference meter to measure the L value of the coloring property measurement specimen. At this time, the lower the L value is tinged with dark black brightness is low means that the good coloring property.
[270]
[271]
TABLE 3
division Example 1 Example 2 Example 3 Example 4
Low bleaching ◎ ○ ◎ ◎
Colorable 77.85 80.68 78.21 82.10
Rubber content 34.3 29.4 34.7 35.0
Surface gloss 72.5 84.2 24.8 29.6
Impact strength 39.13 42.29 37.07 38.07
Flexural strength 295 386 258 194
The tensile strength 190 220 167 156
Surface hardness 46.0 41.2 47.1 46.5

[272]
TABLE 4
division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4
Low bleaching △ × △ △
Colorable 83.59 84.60 80.98 81.42
Rubber content 35.0 25.0 34.3 34.3
Surface gloss 24.0 50.0 88.1 89.0
Impact strength 38.12 6.98 31.3 24.7
Flexural strength 271 502 435 518
The tensile strength 170 285 263 311
Surface hardness 47.2 74.4 53.4 68.5

[273]
[274]
Referring to Tables 3 and 4, an embodiment of the specimen 1 to the embodiment 4, it was confirmed that Comparative Examples 1 to 4 compared to that remarkably excellent bleaching properties and impact strength. On the other hand, in the case of Example 3 and Example 4, it was confirmed that to implement a large-diameter second graft embodiment, by further comprising the copolymer in Example 1 and conducting low gloss characteristics, unlike Example 2. In addition, in Example 1, a comparison of Comparative example 3 and Comparative example 4, example 1, it was confirmed that the polyester-based elastomer comparison does not contain the example 3 compared to low-whitening property, coloring resistance, impact strength, flexural strength, and a remarkably high tensile strength . Further, the embodiment 1 is phthalate-based plasticizer Comparative Example 4 which does not include the contrast, it was confirmed that a low-whitening property, coloring property and impact strength remarkably excellent.
[275]

WE Claims

[Claim 1]
Alkyl (meth) acrylate-based first graft copolymer comprising a polymer derived from units derived from an aromatic vinyl monomer unit and vinyl cyanide-based monomer-derived units; Aromatic copolymer comprising a vinyl-based monomer-derived unit and a vinyl cyanide-based monomer-derived units; Polyester-based elastomers; And phthalate-based thermoplastic resin composition containing a plasticizer.
[Claim 2]
The method according to claim 1, wherein the first graft copolymer, a copolymer and a polyester based on 100 parts by weight of the sum of the elastomer, the thermoplastic resin composition to an amount of the phthalate-based plasticizer from 1 to 20 wt.
[Claim 3]
The method according to claim 1, wherein the first graft copolymer, copolymer and polyester based on the total weight of the ester-based elastomer, wherein the first graft copolymer to 30 to 80% by weight; 10 to 50% by weight of the copolymer; And a thermoplastic resin composition comprising 3 to 20% by weight of the polyester-based elastomer.
[Claim 4]
The method according to claim 1, wherein the first graft copolymer is the (meth) acrylate-based polymer units derived from 30 to 70% by weight; The aromatic vinyl monomer-derived units of 20 to 60% by weight; And a thermoplastic resin composition containing the vinyl cyanide-based monomer-derived units of from 5 to 40% by weight.
[Claim 5]
The method according to claim 1, wherein the first graft copolymer has an average particle diameter of 50 to 170 ㎚ the graft copolymer to a thermoplastic resin composition.
[Claim 6]
The method according to claim 1, wherein the copolymer is a thermoplastic resin composition having a weight average molecular weight of from 50,000 to 250,000 g / mol.
[Claim 7]
The method according to claim 1, wherein the copolymer is a thermoplastic resin composition comprises a weight ratio of 60:40 to 90:10, the vinyl cyanide-based monomer-derived units and the aromatic vinyl-based monomer-derived units.
[Claim 8]
The method according to claim 1, wherein the polyester-based elastomer is a thermoplastic resin composition to a Shore D hardness of 35 to 55.
[Claim 9]
The method according to claim 1, wherein the phthalate-based plasticizer, diisopropyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, diisodecyl phthalate and butyl benzyl phthalate is at least one member selected from the group consisting of the thermoplastic resin composition.
[Claim 10]
The method according to claim 1, wherein the thermoplastic resin composition of the first graft copolymer and different from the mean particle diameter, (meth) acrylate-based polymer derived from units, aromatic vinyl-based monomer-derived units, and comprising a vinyl cyanide-based monomer-derived units a second graft of the thermoplastic resin composition further comprises a copolymer.
[Claim 11]
The method according to claim 10, wherein the second graft than the average particle diameter of 250 ㎚ copolymer 750 ㎚ than that of the thermoplastic resin composition.
[Claim 12]
The method according to claim 10, wherein the first graft copolymer and the second graft copolymer weight ratio of from 1: 1 to 1: 8, to the thermoplastic resin composition.