JP2019044120A - Method for producing thermoplastic resin composition and method for producing graft copolymer composition - Google Patents

Abstract

To provide a method for producing a thermoplastic resin composition having good workability in the production, for an additive usable for an automobile interior material.SOLUTION: A grafted precursor composition is obtained by impregnating (a1) one or more pellets selected from the group consisting of polyethylene, an ethylene-α-olefin copolymer rubber, an ethylene-α-olefin-non-conjugated diene copolymer ruber, and an ethylene-vinyl copolymer of ethylene and one or more vinyl monomers with (a2) a vinyl copolymer and (a3) t-butyl peroxy-methacryloyloxy ethyl carbonate, and progressing a polymerization reaction in the pellet. The grafted precursor composition is dried at 50-80°C for 2-10 hours. By melt-kneading the grafted precursor composition at a cylinder temperature of 120-250°C, (A) a graft copolymer composition is obtained. The (A) graft copolymer composition is dried at 50-80°C for 6-12 hours. By melt-kneading (A) the graft copolymer composition, (B) an ethylene-α-olefin copolymer rubber or ethylene-α-olefin-non-conjugated diene copolymer rubber, (C) an ethylene-vinyl copolymer of ethylene and one or more vinyl monomers and (D) fatty amide, at a cylinder temperature of 120-250°C, a thermoplastic resin composition is obtained.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a thermoplastic resin composition and a method for producing a graft copolymer composition.

  In recent years, interior materials for automobiles are required to have a design property in accordance with a variety of designs, and further, interior materials for automobiles have been made resinous for the purpose of reducing weight and cost. In making the resin, it is required to use a material excellent in scratch resistance, slidability, noise prevention, dimensional stability, color developability and the like.

  As resin additives for improving scratch resistance, thermoplastic resin compositions comprising a graft copolymer composition, a fatty acid amide, and other thermoplastic resins have been disclosed (Patent Documents 1 and 2).

JP2002-338778 JP2015-131949

  However, the thermoplastic resin compositions of Patent Document 1 and Patent Document 2 have a problem that the grafting precursor composition is blocked and the workability is lowered when the graft copolymer composition is melt-kneaded. Further, the graft copolymer composition after melt-kneading also has a problem that blocking occurs depending on the drying conditions, and the workability is lowered during the production of the thermoplastic resin composition.

  In view of the above situation, an object of the present invention is to provide a method for producing a thermoplastic resin composition having good workability at the time of production of additives that can be used for automobile interior materials and the like.

The present invention is as follows.
(1) (a1) Polyethylene, ethylene / α-olefin copolymer rubber, ethylene / α-olefin / non-conjugated diene copolymer rubber, and ethylene / vinyl copolymer of ethylene and one or more vinyl monomers One or more pellets selected from the group consisting of coalesce are impregnated with (a2) vinyl copolymer and (a3) t-butylperoxy-methacryloyloxyethyl carbonate, and the polymerization reaction proceeds in the pellets to graft. Obtaining a pre-cured precursor composition;
A drying step of drying the grafted precursor composition at 50 to 80 ° C. for 2 to 10 hours;
Next, (A) a step of obtaining a graft copolymer composition by melt-kneading the grafted precursor composition at a cylinder temperature of 120 to 250 ° C .;
Next, (A) a drying step of drying the graft copolymer composition at 50 ° C. to 80 ° C. for 6 to 12 hours;
Then
(A) a graft copolymer composition;
(B) ethylene / α-olefin copolymer rubber or ethylene / α-olefin / non-conjugated diene copolymer rubber;
(C) an ethylene-vinyl copolymer comprising ethylene and one or more vinyl monomers;
(D) A method for producing a thermoplastic resin composition, comprising a step of producing a thermoplastic resin composition by melt-kneading a fatty acid amide at a cylinder temperature of 120 to 250 ° C. to obtain a thermoplastic resin composition. .

(2) In the thermoplastic resin composition production step,
(A) Graft copolymer composition, (B) ethylene / α-olefin copolymer rubber or ethylene / α-olefin / non-conjugated diene copolymer rubber, and (C) ethylene and one or more vinyl monomers An ethylene / vinyl copolymer comprising a monomer is put into an extruder having a cylinder temperature of 120 to 250 ° C. and degassed by a degassing apparatus having a degree of vacuum of 0.001 to 0.05 MPa. The method of (1), wherein the thermoplastic resin composition is obtained by supplying from the middle of the extruder and melt-kneading.

(3) (a1) Polyethylene, ethylene / α-olefin copolymer rubber, ethylene / α-olefin / non-conjugated diene copolymer rubber, and ethylene / vinyl copolymer of ethylene and one or more vinyl monomers One or more pellets selected from the group consisting of coalesce are impregnated with (a2) vinyl copolymer and (a3) t-butylperoxy-methacryloyloxyethyl carbonate, and the polymerization reaction proceeds in the pellets to graft. Obtaining a pre-cured precursor composition;
A drying step of drying the grafted precursor composition at 50 to 80 ° C. for 2 to 10 hours;
Next, (A) a step of obtaining a graft copolymer composition by melt-kneading the grafted precursor composition at a cylinder temperature of 120 to 250 ° C; and then (A) the graft copolymer composition at 50 ° C. A method for producing a graft copolymer composition, comprising a drying step of drying at -80 ° C for 6 to 12 hours.

  According to the present invention, after the grafting precursor composition is manufactured and the graft copolymer composition is manufactured separately by performing a drying treatment under the predetermined conditions, respectively, at the time of melt-kneading the graft copolymer composition, When melt-kneading the thermoplastic resin composition, blocking was prevented and workability was greatly improved.

  In addition, depending on each drying condition, blocking may occur, resulting in insufficient drying and an increase in VOC (volatile organic compounds, particularly toluene and styrene). If a thermoplastic resin composition in which VOC is not sufficiently reduced is used for an automobile interior material, not only VOC is released into the vehicle, but also because there are many impurities in the material, the dimensions of the parts change and dimensional stability is improved. Deteriorate. Further, during molding, a large amount of VOC gas is generated, and the high temperature gas is burned to deteriorate the appearance of the part. However, according to the present invention, when the graft copolymer composition is melt-kneaded and blocking at the time of melt-kneading the thermoplastic resin composition can be sufficiently suppressed, it is possible to prevent VOC from remaining in the thermoplastic resin composition.

<Method for producing thermoplastic resin composition>
The thermoplastic resin composition of the present invention comprises (A) a graft copolymer composition, (B) an ethylene / α-olefin copolymer rubber or an ethylene / α-olefin / non-conjugated diene copolymer rubber, C) An ethylene-vinyl copolymer composed of ethylene and at least one vinyl monomer, and (D) a fatty acid amide are mixed at a cylinder temperature of 120 to 250 using a melt kneader, for example, a twin screw extruder. It can be obtained by melt-kneading at 0 ° C.

  By setting the cylinder temperature to 120 ° C. or higher, each component can be melted satisfactorily, and the melt viscosity can be reduced to sufficiently knead. Thereby, phase separation and delamination can be prevented. From such a viewpoint, the cylinder temperature is preferably 150 ° C. or higher, and more preferably 170 ° C. or higher. Moreover, decomposition | disassembly of each component can be prevented by making cylinder temperature into 250 degrees C or less. From such a viewpoint, the cylinder temperature is preferably 230 ° C. or lower, and more preferably 210 ° C. or lower.

  Moreover, when producing a thermoplastic resin composition, it is preferable to perform deaeration with a deaerator because the drying efficiency is improved and the productivity can be improved. First, the component (A), the component (B), and the component (C) are put into an extruder having a cylinder temperature of 120 to 250 ° C. and degassed by a degassing apparatus having a degree of vacuum of 0.001 to 0.05 MPa. A thermoplastic resin composition can be obtained by supplying D) from the middle of the extruder and melt-kneading.

  In this embodiment, the component (D) has a remarkably low viscosity at the time of melting as compared with the component (A), the component (B), and the component (C), and the component (D) is charged into the extruder. When degassing, the melted component (D) is sucked up by the degassing device and closes the degassing port, which causes a problem that the degassing cannot be performed sufficiently. Moreover, in order to eliminate this malfunction, it is necessary to frequently clean the deaeration port, and productivity is lowered. Therefore, after only component (A), component (B) and component (C) are melt-kneaded and degassed first, component (D) is introduced from the middle of the extruder to perform melt-kneading. preferable.

  In addition, after obtaining the melt-kneaded product of component (A), component (B), and component (C), it is possible to perform melt-kneading with component (D) again, but productivity increases by increasing the number of times of melt-kneading. Tends to decrease.

  The method of melt kneading the thermoplastic resin composition is not particularly limited. For example, a known kneading method such as a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader, or a roll can be used. In view of ease of kneading and ease of degassing and component (D) addition during melt kneading, it is preferable to use a twin screw extruder.

Next, each component of the thermoplastic resin composition will be described.
<(A) Graft copolymer composition>
(A) Graft copolymer composition comprises (a1) polyethylene, ethylene / α-olefin copolymer rubber, ethylene / α-olefin / nonconjugated diene copolymer rubber, and ethylene and one or more vinyl monomers. And (a2) a vinyl copolymer obtained by polymerizing at least one vinyl monomer as a side chain, and (a3) t -Butylperoxy-methacryloyloxyethyl carbonate is used as a grafting agent.

  For this reason, at the time of manufacture, the grafting precursor composition is obtained by impregnating the component (a2) and the component (a3) into the pellet of the component (a1) and polymerizing in the pellet. This “impregnation” means a method of impregnating thermoplastic resin pellets with a liquid such as a vinyl monomer, a radical polymerization initiator, or an organic solvent.

  The grafted precursor composition is then dried at 50-80 ° C. for 2-10 hours.

  By drying and drying the grafted precursor composition at 50 to 80 ° C. for 2 to 10 hours, blocking during storage can be prevented until melt-kneading. When the grafted precursor composition is stored in an undried state, the pellet surface becomes sticky and blocking occurs due to the low molecular weight of water, toluene, residual vinyl monomer and vinyl copolymer adhering to the pellet surface. . When blocking occurs, the product cannot be taken out from the bag during melt-kneading or cannot be stably supplied to the feeder of the extruder, resulting in a decrease in productivity. By drying the grafted precursor composition, the pellet surface is not sticky and blocking does not occur, so that workability during melt-kneading is improved.

  The grafted precursor composition is dried at 50 to 80 ° C. for 2 to 10 hours. When the drying temperature is lower than 50 ° C., stickiness is not improved and blocking occurs. When the drying temperature is higher than 80 ° C., the grafting precursor composition is softened and blocking occurs. Further, if the drying time is shorter than 2 hours, the stickiness is not improved and blocking occurs. If the drying time is longer than 10 hours, the equipment occupation time becomes longer, and the productivity is lowered. When blocking occurs in the dryer, the discharge workability decreases.

  Equipment for drying the grafted precursor composition is not particularly limited, and a shelf-type air dryer, a hopper dryer, a conical dryer, a nauter mixer, a pressure filtration dryer (WD filter), or the like can be used. Among these, a conical dryer, a nauter mixer, and a pressure filtration dryer that can be depressurized during drying are preferable.

  Next, the grafting precursor composition is melt-kneaded at a cylinder temperature of 120 to 250 ° C., whereby the main chain and the side chain are bonded by radicals generated from the grafting agent, and (A) the graft copolymer composition Is obtained. By setting the cylinder temperature to 120 ° C. or higher, each component can be melted satisfactorily, and the melt viscosity can be reduced to sufficiently knead, thereby preventing phase separation and delamination. From such a viewpoint, the cylinder temperature is preferably 150 ° C. or higher, and more preferably 170 ° C. or higher. Moreover, decomposition | disassembly of each component can be prevented by making cylinder temperature into 250 degrees C or less. From such a viewpoint, the cylinder temperature is preferably 230 ° C. or lower, and more preferably 210 ° C. or lower.

  (A) The method of melt-kneading the graft copolymer composition is not particularly limited. For example, a known kneading method such as a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader, or a roll can be used. In view of good productivity, it is preferable to use a single screw extruder or a twin screw extruder.

  The obtained (A) graft copolymer composition needs to be further dried at 50 to 80 ° C. for 6 to 12 hours. When this drying temperature is lower than 50 ° C., drying becomes insufficient, and when the drying temperature is higher than 80 ° C., (A) the graft copolymer composition is softened and blocking occurs. Further, when the drying time is shorter than 6 hours, the drying becomes insufficient, and when the drying time is longer than 12 hours, the equipment occupation time becomes longer, so that the productivity is lowered. When blocking occurs in the dryer, not only the discharge workability is lowered, but also the inside of the blocking is not dried, resulting in insufficient drying.

  (A) Equipment for drying the graft copolymer composition is not particularly limited, and a shelf-type air dryer, a hopper dryer, a conical dryer, a nauter mixer, a pressure filtration dryer (WD filter), or the like can be used. Of these, a hopper dryer, a conical dryer, and a nauter mixer are preferable.

  By obtaining (A) the graft copolymer composition by such a production method, there is also an advantage that the VOC of the thermoplastic resin composition can be greatly reduced.

<Component (a1)>
Component (a1) is the main chain of the (A) graft copolymer composition. Examples of polyethylene include high density polyethylene (HDPE), low density polyethylene (LDPE), and linear low density polyethylene (L-LDPE).

  Examples of the ethylene / α-olefin copolymer rubber include ethylene / propylene copolymer rubber (EPR), ethylene / 1-butene copolymer rubber (EBR), ethylene / 1-octene copolymer rubber (EOR), ethylene -Propylene / 1-butene copolymer rubber etc. are mentioned.

  Examples of the ethylene / α-olefin / non-conjugated diene copolymer rubber include ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber (EPDM), ethylene / propylene / dicyclopentadiene copolymer rubber, and the like. .

  Examples of the ethylene / vinyl copolymer comprising ethylene and one or more vinyl monomers include ethylene / methyl acrylate copolymer (EMA), ethylene / ethyl acrylate copolymer (EEA), and ethylene / glycidyl methacrylate copolymer. Copolymer (EGMA), ethylene / vinyl acetate copolymer (EVA), ethylene / methyl acrylate / glycidyl methacrylate copolymer (EMA-GMA), ethylene / ethyl acrylate / glycidyl methacrylate copolymer (EEA-GMA), ethylene / Butyl acrylate / glycidyl methacrylate copolymer (EBA-GMA), maleic anhydride modified polyethylene, maleic anhydride modified ethylene / ethyl acrylate copolymer (EEA-MAN), maleic anhydride modified ethylene / vinyl acetate copolymer EVA-MAN), and the like.

These can use a commercial item. Examples of commercially available polyethylene products include Sumitomo Chemical Co., Ltd. product names: Sumikasen G201, Sumikasen G401, Sumikasen G701, Sumikasen G801, Excellen VL200, Excellen VL700, and NUC Corporation product names: NUC-8346, NUC- 8350, NUC-8360, NUC-8008, Nippon Polyethylene Corporation product name: Novatec HD
HJ360, Novatec HD HJ560, Novatec LD LJ802, Novatec LD LJ803, Novatec LD LJ902, Novatec LL UJ960, Novatec LL
UJ370, Novatec LL UJ580, etc. are mentioned.

  Examples of commercially available ethylene / α-olefin copolymer rubber and ethylene / α-olefin / non-conjugated diene copolymer rubber include product names manufactured by Sumitomo Chemical Co., Ltd .: Esprene SPO V0111, Esprene SPO V0131, Esprene. SPO V0132, Esplen SPO V0141, Esplen EPDM 502, Esplen EPDM 512F, Esplen EPDM 552, Esplen EPDM 553, Dow Chemical Japan Co., Ltd. Product names: Engage 7270, Engage 7447, Engage 7467, Engage 8003, Engage 8100, Engage 8200, Engage 8452, Prime Polymer Co., Ltd. product names: Prime TPO M142E, Prime TPO R110E, Prime TPO R1 0MP, product names manufactured by AES Japan KK: Santplane 201-55, Santplane 201-64, Santplane 201-73, Santplane 201-80, Santplane 201-87, Santplane 203-40, Santplane Plane 203-50, product names manufactured by Mitsui Chemicals, Inc .: Miralastomer 5030N, Miralastomer 6030N, Miralastomer 7030N, Miralastomer 8030N, Miralastomer 8032N, Miralastomer 9020N, manufactured by JSR Corporation: JSR EP21, JSR EP22, JSR EP24, JSR EP25, JSR EP27, JSR EP33, JSR EP35, JSR EP43, JSR EP51, JSR EP57F, JSR EP57C, JSR EP65, JSR E 93, JSR EP96, JSR EP98, JSR EP103AF, and the like.

Examples of commercially available ethylene / vinyl copolymers comprising ethylene and one or more vinyl monomers include product names manufactured by NUC Corporation: DPDJ-6169, DPDJ-6182, DPDJ-9169, NUC-6070. , NUC-6170, NUC-6220, NUC-6520, NUC-6520, NUC-6570, NUC-6940, DQDJ-1868, DQDJ-3269, NUC-3195, NUC-3461, NUC-3660, NUC-3810, NUC -3830, NUC-3888, manufactured by Nippon Polyethylene Co., Ltd. Product names: Lexpearl EMA EB050S, Lexpearl EMA EB140F, Lexpearl EMA EB230X, Lexparle EMA EB240H, Lexparle EMA EB330H, Lexpearl MA EB440H, Lexpearl EEA A1100, Lexpearl EEA A1150, Lexpearl EEA A3100, Lexpearl EEA A4200, Lexpearl EEA A4250, Lexpearl EEA A6200, manufactured by Sumitomo Chemical Co., Ltd .: Bond Fast 2C, Bond Fast E, Bond Fast 2B, Bond Fast 7B, Bond Fast 7L, Bond Fast 7M, Tosoh Corporation product names: Ultrasen 633, Ultrasen 680, Ultrasen 681, Ultrasen 635, Ultrasen 640, Ultrasen 634, Ultrasen 751, Ultrasen 710, Ultrasen 720, Ultrasen 722, Ultrasen 726, Ultrasen 750, product name manufactured by Arkema Co., Ltd .: LOTADER
AX8840, LOTADER AX8900, LOTADER 3430, LOTADER 6200, LOTADER 4210, BONDINE TX8030, BONDINE
HX8210 etc. are mentioned.

  Among those exemplified above, ethylene / propylene copolymer rubber, ethylene / octene copolymer rubber, ethylene / methyl acrylate copolymer, and ethylene / ethyl acrylate copolymer are preferable.

<Component (a2)>
Component (a2) is a vinyl copolymer obtained by polymerizing one or more kinds of vinyl monomers in the side chain of the graft copolymer composition (A). Any vinyl monomer may be used as long as it has a radical polymerizable vinyl group. For example, aromatic vinyl monomers such as styrene and α-methylstyrene, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, stearyl (meth) acrylate, 2-ethylhexyl (Meth) acrylic acid alkyl esters such as (meth) acrylate and cyclohexyl (meth) acrylate, (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, (meta ) Acrylonitrile, glycidyl (meth) acrylate, vinyl alcohol, vinyl acetate, fluorinated (meth) acrylate and the like. Moreover, other functional vinyl monomers, such as macromonomers, such as polyalkylene oxide and the (meth) acrylate of polyorganosiloxane, divinylbenzene, and allyl (meth) acrylate, can be included. Among the vinyl monomers exemplified above, a vinyl copolymer containing (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate is preferable. These vinyl monomers may be used alone or in combination of two or more.

  The radical polymerization initiator used for polymerizing the vinyl monomer is not particularly limited, and generally known azo polymerization initiators, organic peroxides, persulfates, hydrogen peroxide water, A redox polymerization initiator (a polymerization initiator in which an oxidizing agent and a reducing agent are combined) or the like can be used.

  Examples of the azo polymerization initiator include azobisisobutyronitrile, azobisisovaleronitrile, azobisdimethylvaleronitrile, azobis (4-methoxy-2,4-dimethylvaleronitrile), 1-phenylethylazodiphenylmethane, and the like. Is mentioned.

  Examples of the organic peroxide polymerization initiator include peroxyketals such as 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, Hydroperoxides such as p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, di (3,5,5-trimethylhexa Noyl) peroxides, diacyl peroxides such as dibenzoyl peroxide, and peroxyesters such as cumyl peroxyl neodecanoate and t-butyl peroxyne neodecanoate.

  As the oxidizing agent used for the redox polymerization initiator, hydroperoxide or persulfate can be used. Examples of the hydroperoxide include cumene hydroperoxide, t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and the like. Examples of the persulfate include potassium persulfate and ammonium persulfate. Examples of the reducing agent include glucose, dextrose, formaldehyde sodium sulfoxylate (Longalite), sodium thiosulfate, ferrous sulfate, copper sulfate, and potassium hexacyanoiron (III).

  Among the radical polymerization initiators exemplified above, di (3,5,5-trimethylhexanoyl) peroxide or dibenzoyl peroxide is preferable.

  Further, when polymerizing the (a2) vinyl copolymer, a chain transfer agent may be added for the purpose of adjusting the molecular weight.

<Component (a3)>
Component (a3) is a grafting agent and has a vinyl group and a peroxide bond in one molecule. After the component (a3) is copolymerized with the component (a2), radicals are generated by cleaving the peroxide bond, and the component (a1) and the vinyl copolymer are grafted. T-Butylperoxy-methacryloyloxyethyl carbonate is used because of the copolymerizability of the component (a2) with the vinyl monomer and the ease of the grafting reaction.

  However, t-butylperoxy-methacryloyloxyethyl carbonate has very high reactivity, and is diluted with toluene or styrene from the viewpoint of safety during production or storage. This toluene and styrene cause VOC. When the diluent is styrene, a part thereof is polymerized with another vinyl monomer to form a vinyl copolymer, but there is no particular influence. However, since styrene is introduced into the vinyl copolymer, it is necessary to use a toluene diluted product when it is not desired to contain styrene.

  The following forms are mentioned as a polymerization method of a vinyl copolymer. That is, a component (a3) diluted with pelletized component (a1), vinyl monomer of component (a2), toluene, and / or styrene in a reaction vessel containing water, a suspending agent, and a dispersing agent. And the component (a1) is impregnated with the component (a2) and the component (a3), and then a radical polymerization initiator is added to perform polymerization. By this method, a structure in which the vinyl copolymer is finely dispersed in the component (a1) can be easily obtained, and a graft copolymer composition (A) having high graft efficiency can be obtained by subsequent grafting reaction. it can.

<(B) Ethylene / α-olefin copolymer rubber or ethylene / α-olefin / non-conjugated diene copolymer rubber>
Component (B) is an ethylene / α-olefin copolymer rubber or an ethylene / α-olefin / non-conjugated diene copolymer rubber. These are equivalent to the ethylene / α-olefin copolymer rubber exemplified in the component (a1) or the ethylene / α-olefin / non-conjugated diene copolymer rubber.

<(C) Ethylene / Vinyl Copolymer Composed of Ethylene and One or More Kinds of Vinyl Monomers>
Component (C) is an ethylene / vinyl copolymer composed of ethylene and one or more vinyl monomers. These are equivalent to an ethylene / vinyl copolymer comprising ethylene exemplified in the component (a1) and one or more vinyl monomers.

<(D) Fatty acid amide>
Component (D) is a fatty acid amide. Although the carbon atom number of the fatty acid part of a component (D) is not specifically limited, The carbon atom number of the said part becomes like this. Preferably it is 12-24, More preferably, it is 18-22. When the number of carbon atoms in the fatty acid moiety is 12 or more, good lubricity can be obtained, and sufficient scratch resistance and abrasion resistance can be imparted.

  Specific examples of component (D) include lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, oleic acid amide, erucic acid amide, ethylene bis stearic acid amide, ethylene bis behenic acid amide, Examples thereof include ethylene bisoleic acid amide and ethylene biserucic acid amide. In particular, oleic acid amide, erucic acid amide, ethylene bis stearic acid amide, ethylene bis oleic acid amide, and ethylene biserucic acid amide are preferable. These fatty acid amides may be used alone or in combination of two or more.

  In addition, the thermoplastic resin composition includes known heat stabilizers, anti-aging agents, weathering stabilizers, ultraviolet absorbers, antistatic agents, colorants, lubricants, dispersants, foams as long as the object of the present invention is not impaired. You may mix | blend additives, such as an agent, a plasticizer, and an impact modifier.

  The thermoplastic resin composition thus obtained has no occurrence of VOC, and as a resin additive having excellent scratch resistance, noise prevention, dimensional stability, and color developability of a resin molded article, automotive parts, It can be used for various products and semi-finished products in a wide range of fields such as electrical appliances, building materials and general merchandise.

  Hereinafter, embodiments of the present invention will be described more specifically with reference to examples and comparative examples. Table 1 shows the abbreviations of substances used in the following Examples, Comparative Examples and Tables, substance names, components containing the substances, product names, and manufacturers.

(Blocking evaluation method)
A grafting precursor immediately before melt kneading, a grafting precursor after the drying step, and (A) 1 kg of the graft copolymer composition are arranged on a white paper so that the pellets do not overlap, and 10 or more pellets are fused. In the case where it is, blocking “NG” is judged as blocking “OK” if there is no fusion or if there is less than 10 grains even if there is fusion.

(Measurement method of VOC)
1 g of pellets of the thermoplastic resin composition or (A) graft copolymer composition were placed in a 20 ml capacity odor vial and heated at 90 ° C. for 30 minutes. Thereafter, 0.1 ml was weighed using a gas tight syringe and measured with GC-2014 manufactured by Shimadzu Corporation set to injection 200 ° C., detector 250 ° C., and column temperature 40 ° C. The temperature was raised to 250 ° C. at 15 ° C./min after holding at 40 ° C. for 25 minutes.

  The calibration curve was obtained by accurately measuring 0.1 g of toluene and 0.1 g of styrene in a 10 ml volumetric flask, measuring up with acetone, and then placing 1 μl in a 20 ml capacity odor vial with a microsyringe. Measured with From the area ratio of the obtained peak, the amount of VOC was quantified.

  In the production examples, if the residual toluene amount and the residual styrene amount are each 40 ppm or less, the residual toluene amount and the residual styrene amount are each 8 ppm or less in the examples. When 3 phr of this thermoplastic resin composition is added to the resin molding, the final VOC evaluation result is 1 ppm or less.

(Production example)
<Production of (A) Graft Copolymer Composition>
[Production Example 1]
In a 5 L reaction tank, 2000 g of water was added, 2.0 g of polyvinyl alcohol was dissolved therein as a suspending agent, and 20 g of tricalcium phosphate was further dispersed as a dispersing agent. In this, 700 g of EPR as (a1), 100 g of St as vinyl monomer (d2), 100 g of BA, 100 g of HPMA, and (a3) 40% toluene solution of t-butylperoxymethacryloyloxyethyl carbonate as a grafting agent 7 0.5 g was added and the temperature was raised to 70 ° C. with stirring. After the temperature in the reaction vessel reached 70 ° C, stirring was continued for another hour, and then 4.5 g of di-3,5,5-trimethylhexanoyl peroxide was added as a radical polymerization initiator. The polymerization reaction was performed for 5 hours. Thereafter, the mixture was cooled to room temperature, washed with water, filtered, and dried with a WD filter at 50 ° C. for 2 hours to obtain a grafted precursor composition.

  The obtained graft precursor composition is melt kneaded at 120 ° C. using a single screw extruder (VSK type vent type 50 mm extruder manufactured by Nippon Placon) and dried at 50 ° C. for 6 hours with a hopper dryer. As a result, (A) the graft copolymer composition of Production Example 1 was obtained. The VOC amount of the obtained (A) graft copolymer composition was a residual toluene amount of 40 ppm and a residual styrene amount of 15 ppm.

[Production Examples 2 to 13 and Comparative Production Examples 1 to 9]
The used resin (a1), the vinyl monomer (a2), the drying conditions for the grafting precursor composition, the melt-kneading conditions, and the drying conditions for the (A) graft copolymer composition are shown in Table 2, Table 2. The components and conditions shown in 3 were changed. Otherwise, the same operations as in Production Example 1 were performed to obtain (A) graft copolymer compositions of Production Examples 2 to 13 and Comparative Production Examples 1 to 9.

(Evaluation results of production examples)
Tables 2 and 3 show the blocking and VOC evaluation results of Production Examples 1 to 13 and Comparative Production Examples 1 to 9. However, the amount of residual toluene and residual styrene was determined to be “good” at 40 ppm or less.

  From the results of Tables 2 and 3, in Production Examples 1 to 13, there is no blocking, and the amount of residual toluene and the amount of residual styrene are each 40 ppm or less.

  On the other hand, when producing the graft copolymer composition (A), Comparative Production Example 1 in which the grafting precursor was not dried, melt-kneaded, and dried after melt-kneading, and the grafted precursor was dried. In Comparative Production Example 2 in which drying after melt kneading was not performed and in Comparative Production Example 3 in which the grafting precursor was not dried, blocking of the grafting precursor occurred. The amount of residual toluene and / or the amount of residual styrene was large.

  In Comparative Production Example 4 in which the drying temperature of the grafted precursor was less than 50 ° C., the amount of residual toluene and the amount of residual styrene were large. In Comparative Production Example 5 in which the drying temperature of the grafted precursor was higher than 80 ° C., the workability of discharging from the dryer deteriorated because the grafted precursor was blocked in the dryer. Furthermore, blocking occurred during drying of the precursor, and it could not be dried into the blocking portion, so the amount of residual toluene and the amount of residual styrene increased.

  In Comparative Production Example 6 in which the melt-kneading temperature of the grafted precursor was less than 120 ° C. and Comparative Production Example 7 in which the melt-kneading temperature was higher than 250 ° C., (A) the graft copolymer composition was not obtained. In Comparative Production Example 8 in which the drying temperature after melt kneading was less than 50 ° C., the amount of residual toluene and the amount of residual styrene were large. In Comparative Production Example 9 in which the drying temperature after the melt-kneading was higher than 80 ° C., the workability of discharging from the dryer was poor because of blocking in the dryer, the drying was insufficient, and the amount of residual toluene was increased.

<Manufacture of thermoplastic resin composition>
[Example 1-1]
240 g of the graft copolymer composition of Production Example 1 as component (A), 170 g of EPR as component (B), 390 g of EVA as component (C), and 200 g of OA as component (D) were dry blended. Then, the thermoplastic resin composition of Example 1-1 was obtained by melt-kneading and pelletizing with a coaxial twin screw extruder (manufactured by Ikegai Co., Ltd.) having a screw diameter of 30 mm set at a cylinder temperature of 120 ° C. It was. The obtained thermoplastic resin composition had a VOC content of 8 ppm residual toluene and 3 ppm residual styrene.

[Examples 1-2 to 2-2 and Comparative Examples 1-1 to 2-1]
The same operations as in Example 1 are performed except that the components (A), components (B), components (C), components (D), and melt-kneading conditions used are changed to the components and conditions shown in Table 3. Thus, thermoplastic resin compositions of Examples 1-2 to 13 and Comparative Production Examples 1-1 to 2-1 were obtained.

(Evaluation results)
Tables 4 and 5 show VOC evaluation results of Examples 1-1 to 2-2 and Comparative Examples 1-1 to 2-1.

* Residual toluene amount, residual styrene amount: 8ppm or less, good * Fatty acid amide notation OL: oleic acid amide ST: stearic acid amide ER: erucic acid amide BE: behenic acid amide LA: lauric acid amide ES: ethylenebisstearic acid amide : Ethylene bisoleic acid amide

  From the results of Tables 4 and 5, in Examples 1-1 to 2-2, the residual toluene amount and the residual styrene amount are each 8 ppm or less.

  On the other hand, a thermoplastic resin composition was not obtained in Comparative Example 1-1 having a melt-kneading temperature lower than 120 ° C. and Comparative Example 1-2 having a melt-kneading temperature higher than 250 ° C.

  In Comparative Examples 1-3 to 1-9 using the graft copolymer composition of Comparative Production Example, the amount of residual toluene and / or residual styrene in the thermoplastic resin composition was more than 8 ppm. Further, Comparative Example 2-1 using the graft copolymer composition of Comparative Production Example 4 had a residual toluene amount of more than 8 ppm despite degassing during melt kneading.

(Example of use)
The thermoplastic resin composition produced by the production method of the present invention can be finally used as an additive for improving scratch resistance, anti-noise properties, and slipperiness for various resins. The resulting resin molded body does not generate VOC, is excellent in dimensional stability, and does not cause color tone defects when it is continuously molded, so-called burns.

(Evaluation method of usage examples)
(Preparation of test piece)
3 parts by weight of the thermoplastic resin composition shown in Table 6 was blended with 100 parts by weight of each resin, and 55 mm × 80 mm × t 2 mm test pieces were produced by injection molding or foam molding.

(Measurement of VOC)
The obtained test piece was placed in a 1 liter Tedlar bag and heated at 90 ° C. for 30 minutes. Thereafter, 0.1 ml was weighed using a gas tight syringe and measured with GC-2014 manufactured by Shimadzu Corporation set to injection 200 ° C., detector 250 ° C., and column temperature 40 ° C. The temperature was raised to 250 ° C. at 15 ° C./min after holding at 40 ° C. for 25 minutes.

The calibration curve was obtained by accurately measuring 0.1 g of toluene and 0.1 g of styrene in a 10 ml volumetric flask, measuring up with acetone, and then placing 1 μl in a 1 liter Tedlar bag with a microsyringe under the same conditions as the above sample. It was measured. From the area ratio of the obtained peak, the amount of VOC was quantified.
When the total VOC amount of toluene and styrene was 1 ppm or less, it was judged as acceptable.

(Dimensional stability)
The molded test piece was stored for 48 hours in a constant temperature and humidity chamber having a temperature of 23 ° C. and a humidity of 50% after molding. Thereafter, the side length of 80 mm was measured with a caliper, and a value obtained by dividing the measured side length by the length of the mold (= 80 mm) was calculated as dimensional stability. The dimensional stability is 99.9% or more, which is acceptable.

(Yake)
When molding the above test piece, the same test piece was molded 20 times, and then the appearance of the test piece was visually observed. The test piece passes if no burns occur.

  As a specific example, Table 6 shows the results of evaluating VOC, dimensional stability, and the presence or absence of burns when 3 parts are added to each resin.

From the results of Table 6, the test pieces of each resin using Examples 1-1 to 2-2 all have a VOC amount of 1 ppm or less, have a dimensional stability of 99.9%, and are further repeatedly molded. There was no burn when I did it.
As for the use examples using Comparative Examples 1-3, 1-6, and 2-1 having a large amount of VOC as the thermoplastic resin composition, the VOC amount is more than 1 ppm, and the dimensional stability is 99.9%. Burns occurred when smaller and further molded.

Claims (3)

(A1) Polyethylene, ethylene / α-olefin copolymer rubber, ethylene / α-olefin / non-conjugated diene copolymer rubber, and ethylene / vinyl copolymer of ethylene and one or more vinyl monomers. One or more kinds of pellets selected from the group are impregnated with (a2) vinyl copolymer and (a3) t-butylperoxy-methacryloyloxyethyl carbonate, and a polymerization reaction is allowed to proceed in the pellet, thereby grafting precursor. Obtaining a composition;
A drying step of drying the grafted precursor composition at 50 to 80 ° C. for 2 to 10 hours;
Next, (A) a step of obtaining a graft copolymer composition by melt-kneading the grafted precursor composition at a cylinder temperature of 120 to 250 ° C .;
Next, (A) a drying step of drying the graft copolymer composition at 50 ° C. to 80 ° C. for 6 to 12 hours;
Then
(A) a graft copolymer composition;
(B) ethylene / α-olefin copolymer rubber or ethylene / α-olefin / non-conjugated diene copolymer rubber;
(C) an ethylene-vinyl copolymer comprising ethylene and one or more vinyl monomers;
(D) A method for producing a thermoplastic resin composition, comprising a step of producing a thermoplastic resin composition by melt-kneading a fatty acid amide at a cylinder temperature of 120 to 250 ° C. to obtain a thermoplastic resin composition. . In the thermoplastic resin composition production step,
(A) Graft copolymer composition, (B) ethylene / α-olefin copolymer rubber or ethylene / α-olefin / non-conjugated diene copolymer rubber, and (C) ethylene and one or more vinyl monomers An ethylene / vinyl copolymer comprising a monomer is put into an extruder having a cylinder temperature of 120 to 250 ° C. and degassed by a degassing apparatus having a degree of vacuum of 0.001 to 0.05 MPa. The method according to claim 1, wherein the thermoplastic resin composition is obtained by supplying from the middle of the extruder and melt-kneading. (A1) Polyethylene, ethylene / α-olefin copolymer rubber, ethylene / α-olefin / non-conjugated diene copolymer rubber, and ethylene / vinyl copolymer of ethylene and one or more vinyl monomers. One or more kinds of pellets selected from the group are impregnated with (a2) vinyl copolymer and (a3) t-butylperoxy-methacryloyloxyethyl carbonate, and a polymerization reaction is allowed to proceed in the pellet, thereby grafting precursor. Obtaining a composition;
A drying step of drying the grafted precursor composition at 50 to 80 ° C. for 2 to 10 hours;
Next, (A) a step of obtaining a graft copolymer composition by melt-kneading the grafted precursor composition at a cylinder temperature of 120 to 250 ° C; and then (A) the graft copolymer composition at 50 ° C. A method for producing a graft copolymer composition, comprising a drying step of drying at -80 ° C for 6 to 12 hours.