JP5708973B2 - Method for producing tablet of modifier for thermoplastic resin, thermoplastic resin composition and molded article - Google Patents

Description

  The present invention relates to a method for producing a thermoplastic resin modifier tablet for compression molding a powder containing a polytetrafluoroethylene-containing resin, a thermoplastic resin modifier tablet obtained by the production method, and a thermoplastic resin. The present invention relates to a thermoplastic resin composition obtained by mixing and a molded product obtained by molding the thermoplastic resin composition.

  Polytetrafluoroethylene has high crystallinity and low intermolecular force, so it has the property of forming fibers with a slight stress. When blended with thermoplastic resin, it forms as the polytetrafluoroethylene becomes fibrous. It is known that processability, mechanical properties and anti-dripping properties are improved.

  For example, Patent Document 1 proposes a method of blending unmodified polytetrafluoroethylene powder into a thermoplastic resin. Patent Document 2 proposes a method of blending a modified polytetrafluoroethylene powder with a thermoplastic resin.

JP-A-5-214184 Japanese Patent Laid-Open No. 11-124478

  However, in the methods of Patent Document 1 and Patent Document 2, since the powder of the polytetrafluoroethylene-containing resin is blended, the problem of classification when mixing with the pellets of the thermoplastic resin or in the thermoplastic resin It has the subject that it is inferior to the surface external appearance of the molded object which can be inferior to the dispersibility of polytetrafluoroethylene.

  An object of the present invention is to provide a thermoplastic resin modifier tablet having excellent handling properties, excellent molding processability of the obtained thermoplastic resin composition, and excellent surface appearance of the obtained molded article.

  This invention is a manufacturing method of the tablet (X) of the modifier for thermoplastic resins which compression-molds the powder containing polytetrafluoroethylene containing resin (A).

Moreover, this invention is a thermoplastic resin composition obtained by mixing the tablet (X) of the modifier for thermoplastic resins obtained by the said manufacturing method, and a thermoplastic resin (Y).
Furthermore, this invention is a molded object obtained by shape | molding the said thermoplastic resin composition.

  The thermoplastic resin modifier tablet (X) of the present invention has excellent handleability, excellent molding processability of the resulting thermoplastic resin composition, and the polytetrafluoroethylene in the thermoplastic resin (Y). It is excellent in the surface appearance of the molded product obtained from excellent dispersibility.

  The tablet (X) of the thermoplastic resin modifier of the present invention is obtained by compression molding a powder containing the polytetrafluoroethylene-containing resin (A).

  Polytetrafluoroethylene is obtained by polymerizing the monomer component (a) containing tetrafluoroethylene (a1).

The monomer component (a) may contain another monomer (a2) copolymerizable with tetrafluoroethylene (a1) within a range not impairing the original characteristics of polytetrafluoroethylene.
Examples of the other monomer (a2) include hexafluoropropylene, chlorotrifluoroethylene, fluoroalkylethylene, and perfluoroalkyl vinyl ether. These other monomers (a2) may be used alone or in combination of two or more.

  Since the composition ratio of the monomer component (a) is excellent in the molding processability of the resulting thermoplastic resin composition, the content of tetrafluoroethylene (a1) is 100% by mass in the monomer component (a). 80% by mass or more, and the content of other monomer (a2) is preferably 20% by mass or less, the content of tetrafluoroethylene (a1) is 90% by mass or more, and other monomer (a2) The content of is more preferably 10% by mass or less.

  The polymerization method of the monomer component (a) is not particularly limited, and a known polymerization method can be used.

The mass average molecular weight of polytetrafluoroethylene is preferably 1 million to 50 million, and more preferably 3 million to 30 million.
When the mass average molecular weight of polytetrafluoroethylene is 1,000,000 or more, the resulting thermoplastic resin composition is excellent in moldability. Moreover, when the mass average molecular weight of polytetrafluoroethylene is 50 million or less, the dispersibility of polytetrafluoroethylene in the thermoplastic resin (Y) is excellent, and the surface appearance of the resulting molded article is excellent.

  As the polytetrafluoroethylene-containing resin (A), unmodified polytetrafluoroethylene (A-1) may be used as it is without modifying polytetrafluoroethylene, or modified polytetrafluoroethylene obtained by modifying polytetrafluoroethylene. (A-2) may be used.

  Examples of commercially available powders of unmodified polytetrafluoroethylene (A-1) include “Teflon T5”, “Teflon T6”, “Teflon 6C”, “Teflon 6C-J”, “Teflon 6J”, “ Teflon 7A, Teflon 7J, Teflon 30, Teflon 30B, Teflon 30J, Teflon 30N, Teflon 100, Teflon 110, Teflon 120, Teflon 327, “Teflon 850” (trade name, manufactured by DuPont); “Fullon G201”, “Fullon G307”, “Fullon CD1”, “Fullon CD141”, “Fullon CD123”, “Fullon CD076”, “Fullon CD090”, "Full-on AD911L", "Full-on AD983L", "Full-on G163", "Full-on G192" "Full-on G307" (trade name, Asahi Glass Co., Ltd.); "Polyflon MPA FA-500C" (trade name, manufactured by Daikin Industries Co., Ltd.) and the like. These unmodified polytetrafluoroethylene (A-1) may be used individually by 1 type, and may use 2 or more types together.

  The modified polytetrafluoroethylene (A-2) can be obtained by a known production method. For example, an aqueous dispersion of polytetrafluoroethylene (A-2-1) and an aqueous dispersion of thermoplastic resin (A- 2-2) and then the coagulation or spray drying, the monomer component (a-2-3) in the presence of an aqueous dispersion of polytetrafluoroethylene (A-2-1). After polymerization, a method obtained by coagulation or spray drying, a mixed water dispersion of an aqueous dispersion of polytetrafluoroethylene (A-2-1) and an aqueous dispersion of thermoplastic resin (A-2-2) Examples thereof include a method obtained by polymerizing the monomer component (a-2-3) in the presence and then coagulating or spray drying.

  Examples of the coagulant in coagulation include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; organic acids such as formic acid and acetic acid; and inorganic salts such as aluminum sulfate, magnesium sulfate, calcium acetate, and calcium sulfate. . These coagulants may be used individually by 1 type, and may use 2 or more types together.

  The conditions for the coagulation are not particularly limited. For example, the obtained aqueous dispersion is brought into contact with the coagulant at 30 to 90 ° C., coagulated with stirring to form a slurry, and recovered by filtration. The method of dehydrating and drying later is mentioned. The drying temperature is preferably 40 to 100 ° C. for 1 to 12 hours.

  Examples of commercially available aqueous dispersions of polytetrafluoroethylene (A-2-1) include “Fluon AD911L”, “Fullon AD912L”, “Fullon AD938L”, “Fullon AD939L” (trade name, Asahi Glass Co., Ltd.) Manufactured). These aqueous dispersions of polytetrafluoroethylene may be used alone or in combination of two or more.

  The aqueous dispersion (A-2-2) of the thermoplastic resin is obtained by polymerizing the monomer component (a-2-2).

Examples of the monomer constituting the monomer component (a-2-2) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n- Butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, (Meth) acrylate monomers such as 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate and stearyl (meth) acrylate; aromatic vinyl monomers such as styrene and α-methylstyrene; (meth) acrylonitrile and the like Of vinyl cyanide monomer; (meth) ac Le acid. These monomers may be used individually by 1 type, and may use 2 or more types together.
In the present specification, “(meth) acrylate” means “acrylate” or “methacrylate”.

As a polymerization method of the monomer component (a-2-2), a known polymerization method can be used, and examples thereof include emulsion polymerization, soap-free emulsion polymerization, fine suspension polymerization, and suspension polymerization.
Among these polymerization methods, since the mixing of the polytetrafluoroethylene aqueous dispersion (A-2-1) and the thermoplastic resin aqueous dispersion (A-2-2) is easy, emulsion polymerization, Soap-free emulsion polymerization is preferred, and emulsion polymerization is more preferred.

  When a polymerization method such as emulsion polymerization or soap-free emulsion polymerization is used as a polymerization method of the monomer component (a-2-2), the particle structure of the obtained thermoplastic resin is a single layer or a multilayer. However, from the viewpoint of production cost, it is preferably 3 layers or less.

  As the emulsifier used in emulsion polymerization of the monomer component (a-2-2), a known emulsifier can be used, for example, an anionic emulsifier, a nonionic emulsifier, a polymer emulsifier, a reactive anionic emulsifier, A reactive nonionic emulsifier is mentioned.

  As the polymerization initiator used in the polymerization of the monomer component (a-2-2), a known polymerization initiator can be used. For example, a persulfate compound such as potassium persulfate, sodium persulfate, ammonium persulfate; Bisisobutyronitrile, 2,2'-azobis- (2-methylbutyronitrile), 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy) -2,4-dimethylvaleronitrile), oil-soluble azo compounds such as 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile; 2,2′-azobis- {2-methyl-N- [1,1 -Bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2′-azobis- {2-methyl-N- [2- (1-hydroxyethyl)] propionamide}, 2,2 -Azobis- {2-methyl-N- [2- (1-hydroxybutyl)] propionamide}, 2,2'-azobis- [2- (5-methyl-2-imidazolin-2-yl) propane] and Its salt, 2,2'-azobis- [2- (2-imidazolin-2-yl) propane] and its salt, 2,2'-azobis- [2- (3,4,5,6-tetrahydropyrimidine- 2-yl) propane] and salts thereof, 2,2′-azobis- {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} and salts thereof, 2,2′-azobis -(2-methylpropionamidine) and its salt, 2,2'-azobis- (2-methylpropionamidine) and its salt, 2,2'-azobis- [N- (2-carboxyethyl) -2- Methyl propiona Zin] and water-soluble azo compounds such as salts thereof; benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyisobutyrate, etc. Of organic peroxides. When the monomer component (a-2-2) is polymerized by emulsion polymerization, a reducing agent such as sodium bisulfite, ferrous sulfate, ascorbate is used as the persulfate compound or the organic peroxide. It can also be used in combination. These polymerization initiators may be used alone or in combination of two or more.

  As a monomer which comprises a monomer component (a-2-3), what was illustrated as a monomer which comprises a monomer component (a-2-2) is mentioned, for example. These monomers may be used individually by 1 type, and may use 2 or more types together.

As a polymerization method of the monomer component (a-2-3), a known polymerization method can be used, and examples thereof include emulsion polymerization, soap-free emulsion polymerization, fine suspension polymerization, and suspension polymerization.
Among these polymerization methods, since the modified polytetrafluoroethylene (A-2) can be stably produced, emulsion polymerization and soap-free emulsion polymerization are preferable, and emulsion polymerization is more preferable.

  Examples of the emulsifier used for emulsion polymerization of the monomer component (a-2-3) include those exemplified as the emulsifier used for emulsion polymerization of the monomer component (a-2-2).

  Examples of the polymerization initiator used in the polymerization of the monomer component (a-2-3) include those exemplified as the polymerization initiator used in the polymerization of the monomer component (a-2-2).

  Examples of commercially available powders of modified polytetrafluoroethylene (A-2) include “methabrene A-3000”, “methabrene A-3800”, “methabrene A-3750”, “methabrene A-3700” (trade names, "Brendex 449" (trade name, manufactured by Chemtura); "AD-001", "CX-500" (trade name, manufactured by Pacific Interchem); "SN3300" , “SN3300B2”, “SN3300B3” (trade name, manufactured by Shine Polymer Co., Ltd.). These modified polytetrafluoroethylene (A-2) may be used individually by 1 type, and may use 2 or more types together.

  As the polytetrafluoroethylene-containing resin (A), unmodified polytetrafluoroethylene (A-1) or modified polytetrafluoroethylene (A-2) may be used alone, or unmodified polytetrafluoroethylene (A-) may be used. 1) and modified polytetrafluoroethylene (A-2) may be used in combination.

  The tablet (X) of the modifier for thermoplastic resins of the present invention may contain a thermoplastic resin (B) as necessary in addition to the polytetrafluoroethylene-containing resin (A).

  The thermoplastic resin (B) can be appropriately set according to the type of the thermoplastic resin (Y). For example, a polyolefin resin, a polystyrene resin, a polyvinyl chloride resin, an acrylic resin, a polyester resin, Known thermoplastic resins such as polyamide-based resins, polycarbonate-based resins, and thermoplastic elastomers can be used. These thermoplastic resins (B) may be used individually by 1 type, and may use 2 or more types together.

Among these thermoplastic resins (B), the dispersibility of polytetrafluoroethylene in the thermoplastic resin (Y) is excellent, and the surface appearance of the resulting molded article is excellent. A thermoplastic resin having high compatibility is preferred.
For example, when the thermoplastic resin (Y) is a polyolefin resin, examples of the thermoplastic resin (B) include a polypropylene resin, a polyethylene resin, a polyolefin elastomer resin, and an alkyl (meta) having an alkyl group having 2 or more carbon atoms. ) A thermoplastic resin having high compatibility with a polyolefin resin such as an alkyl (meth) acrylate polymer having an acrylate monomer unit as a main component is preferable. These thermoplastic resins (B) may be used individually by 1 type, and may use 2 or more types together.
When the thermoplastic resin (Y) is a polycarbonate resin, the thermoplastic resin (B) may be a thermoplastic resin having high compatibility with a polycarbonate resin such as a polycarbonate resin, an acrylic resin, or a polystyrene resin. preferable. These thermoplastic resins (B) may be used individually by 1 type, and may use 2 or more types together.
Furthermore, when the thermoplastic resin (Y) is a polyvinyl chloride resin, the thermoplastic resin (B) is highly compatible with polyvinyl chloride resins such as polyvinyl chloride resins and methyl methacrylate polymers. It is preferable to use a thermoplastic resin. These thermoplastic resins (B) may be used individually by 1 type, and may use 2 or more types together.

The content of polytetrafluoroethylene in the thermoplastic resin modifier tablet (X) is preferably 1 to 99 mass% in 100 mass% of the thermoplastic resin modifier tablet (X). 3 to 70 mass% is more preferable, 5 to 60 mass% is still more preferable, and 10 to 50 is particularly preferable.
When the content of polytetrafluoroethylene is 1% by mass or more, the molding processability of the resulting thermoplastic resin composition is excellent. Further, when the content of polytetrafluoroethylene is 99% by mass or less, the dispersibility of polytetrafluoroethylene in the thermoplastic resin (Y) is excellent, and the surface appearance of the obtained molded article is excellent.

  Tablets (X) of the thermoplastic resin modifier of the present invention are optionally antioxidants, ultraviolet absorbers, light stabilizers, plasticizers, flame retardants, nucleating agents, foaming agents, antibacterial agents, Additives such as preservatives, fillers, lubricants, impact strength modifiers, antistatic agents, metal deactivators, fluidity modifiers, matting agents, pigments and dyes may also be included. These additives may be used alone or in combination of two or more.

  Known antioxidants can be used as the antioxidant, and examples thereof include hindered phenol antioxidants, sulfur antioxidants, and phosphorus antioxidants. These antioxidants may be used alone or in combination of two or more.

Examples of the hindered phenol antioxidant include “Yoshinox BHT”, “Yoshinox BB”, “Yoshinox 2246G”, “Yoshinox 425”, “Yoshinox 250”, “Yoshinox 930”, “Tominox SS”, “Tominox SS”, Minox TT, Tominox 917, Tominox 314 (trade name, manufactured by API Corporation); Irganox 1010, Irganox 1010FF, Irganox 1035, Irganox 1035FF "Irganox 1076", "Irganox 1076FD", "Irganox 1076DWJ", "Irganox 1098", "Irganox 135", "Irganox 1330", "Irganox 1425WL", " “Irganox 1520L”, “Irganox 1520SE”, “Irganox 1726”, “Irganox 245”, “Irganox 245FF”, “Irganox 245DWJ”, “Irganox 259”, “Irganox 3114”, “Irganox” 3790 ”,“ Irganox 5057 ”,“ Irganox 565 ”,“ Irganox 565DD ”(trade name, manufactured by Ciba Japan Co., Ltd.);“ ADK STAB AO-20 ”,“ ADK STAB AO-30 ”,“ ADK STAB AO ” -40 "," ADK STAB AO-50 "," ADK STAB AO-50F "," ADK STAB AO-60 "," ADK STAB AO-60G "," ADK STAB AO-70 "," ADK STAB AO-80 "," ADK STAB AO-80 " 330 "," A “Akastab A-611”, “Akastab A-611RG”, “Akastab A-612”, “Akastab A-612RG”, “Akastab A-613”, “Akastab A-613RG”, “Akastab AO-51”, “Akastab” AO-15 "," Adeka Stub AO-18 "," Adeka Stub 328 "," Adeka Stub AO-37 "(trade name, manufactured by ADEKA Corporation). These hindered phenolic antioxidants may be used alone or in combination of two or more.
Examples of the sulfur-based antioxidant include “Irganox PS 800 FD”, “Irganox PS 802 FD” (trade name, manufactured by Ciba Japan Co., Ltd.); “Adekastab AO-412S”, “Adekastab AO-503” (Trade name, manufactured by ADEKA Corporation). These sulfur type antioxidants may be used individually by 1 type, and may use 2 or more types together.
Examples of the phosphorus-based antioxidant include “Irgaphos 168”, “Irgaphos 168FF”, “Irgaphos 12”, “Irgaphos 38”, “Irgaphos P-EPQ”, “Irgaphos P-EPQ FD” (trade name, Ciba “Adeka Stub PEP-4C”, “Adeka Stub PEP-8”, “Adeka Stub PEP-8W”, “Adeka Stub PEP-24G”, “Adeka Stub PEP-36”, “Adeka Stub PEP-36Z”, “ ADK STAB HP-10, ADK STAB 2112, ADK STAB 2112RG, ADK STAB 260, ADK STAB 522A, ADK STAB 1178, ADK STAB 1500, ADK STAB C, ADK STAB 135A, ADK STAB 3010 , " ADK STAB TPP "(trade name, manufactured by ADEKA Corporation). These phosphorus antioxidants may be used alone or in combination of two or more.

  As the ultraviolet absorber, known ultraviolet absorbers can be used. For example, “Tinuvin P”, “Tinuvin P FL”, “Tinuvin 234”, “Tinuvin 326”, “Tinuvin 326FL”, “Tinuvin 329”, "Tinubin 329FL", "Tinubin 360", "Tinuvin 213", "Tinubin 571", "Tinubin 1577FF", "Tinubin 120", "Kimasorb 81", "Kimasorb 81FL" (trade names, manufactured by Ciba Japan Co., Ltd.) ); “ADK STAB LA-32”, “ADK STAB LA-36”, “ADK STAB LA-36RG”, “ADK STAB LA-31”, “ADK STAB LA-31RG”, “ADK STAB 1413”, “ADK STAB LA-51” (product) Name, manufactured by ADEKA Corporation). These ultraviolet absorbers may be used alone or in combination of two or more.

  As the light stabilizer, a known light stabilizer can be used. For example, “Tinuvin 770” (trade name, manufactured by Ciba Japan Co., Ltd.); “ADK STAB LA-57”, “ADK STAB LA-63P”, NH type hindered amine light stabilizers such as “ADEKA STAB LA-68P” (trade name, manufactured by ADEKA Co., Ltd.); “TINUVIN 292”, “TINUVIN 144”, “TINUVIN 765”, “KIMASORB 119FL” (trade name) NR type hindered amine light stabilizers such as “ADK STAB LA-52”, “ADK STAB LA-62”, “ADK STAB LA-67” (trade name, manufactured by ADEKA Co., Ltd.), etc. Agents: “Tinuvin 123”, “Tinuvin 494AR”, “Tinubin NOR371FF”, “Frame Stub NOR116FF” (trade name, Ciba N-O-R type hindered amine light stabilizers such as Yapan Ltd.) and the like. These light stabilizers may be used alone or in combination of two or more.

  As the plasticizer, known plasticizers can be used. For example, “B2714”, “B2714”, “P0288”, “B2715”, “P0279”, “P0304”, “P0291”, “P0292”, “ “P0293”, “P0296”, “P0298”, “P0299”, “P0300”, “P0301”, “P0302”, “P0303”, “P0305”, “P0306”, “P0307”, “D3248”, “E0164” , “I0157”, “P0657”, “P1344”, “P0468”, “P1021”, “P0265”, “P1331”, “P2069”, “P0266”, “P0273”, “P0270”, “P0271”, “P0271” “P0272”, “P0683”, “P0268”, “P1022”, “B0881”, “ 1308 ”,“ S0027 ”,“ O0054 ”,“ O0143 ”,“ F0116 ”,“ M0009 ”,“ O0055 ”,“ A1386 ”,“ A0931 ”,“ A1388 ”,“ B2716 ”,“ A0163 ”,“ A0653 ” , “A1473”, “F0117”, “M0011”, “S0025”, “S0028”, “A0655”, “S0023”, “A0162”, “M0010”, “S0024”, “S0103”, “A0706”, “A0706” "A0164", "A1387", "A0654", "A0166", "A1308", "M0027", "O0054", "O0143", "F0116", "M0009", "O0055", "D1230", "D1522" , “B0828”, “B0489”, “B0498”, “G0082 , “T0364”, “G0086”, “T0923”, “B0496”, “B0737”, “C0602”, “C0601”, “E0164”, “A0086”, “A0879”, “C0366”, “A0822”, “ C0367 "," C0368 "(trade name, manufactured by Tokyo Chemical Industry Co., Ltd.). These plasticizers may be used alone or in combination of two or more.

  As the flame retardant, a known flame retardant can be used. For example, “ADK STAB PFR”, “ADK STAB FP-600”, “ADK STAB FP-700”, “ADK STAB FP-2000”, “ADK STAB FP-2200” ( “Reophos 35”, “Leophos 65”, “Leophos 95”, “Leophos 110”, “Leophos TPP”, “Leophos RDP”, “Leophos BAPP”, “Leophos CDP”, “Leophos Chronitex TCP”, “Leophos TXP”, “Leomol TIBP”, “Leomol TOP”, “KP-140”, “Leorube HYD-110”, “Empara 40”, “Empara 70”, “Empara K-43” ”,“ Empara K-45 ”,“ Empara K-47 ”,“ D "Para K-50", "Empara AR-500", "Poly Safe 100", "Poly Safe 100-T", "Poly Safe 100-NDT", "Poly Safe FCP-5", "Poly Safe FCP-6", "Poly Safe NS-" “80A”, “Polysafe NS-80B”, “Polysafe NH-12”, “Polysafe MG-23X” (trade name, manufactured by Ajinomoto Fine Techno Co., Ltd.); “TMP”, “TEP”, “TPP”, “TCP” ”,“ TXP ”,“ CDP ”,“ PX-110 ”,“ CR-733S ”,“ CR-741 ”,“ PX-200 ”,“ die guard 580 ”,“ die guard 610 ”,“ die guard 540 ”,“ “TMCPP”, “CRP”, “CR-900”, “CR-504L”, “CR-570” (trade name, manufactured by Daihachi Chemical Industry Co., Ltd.); "NOR 116FF", "Merapool MC 25", "Merapool 200/70" (trade name, manufactured by Ciba Japan Co., Ltd.). These flame retardants may be used alone or in combination of two or more.

  As the nucleating agent, known nucleating agents can be used. For example, “ADK STAB NA-11”, “ADK STAB NA-27”, “ADK STAB NA-902”, “ADK STAB NA-21”, “ADK STAB NA” -71 "(trade name, manufactured by ADEKA Corporation);" Irga Clear D "," Irga Clear DM "(trade name, manufactured by Ciba Japan Co., Ltd.). These nucleating agents may be used individually by 1 type, and may use 2 or more types together.

As the foaming agent, known foaming agents can be used, and examples thereof include inorganic foaming agents, volatile foaming agents, and decomposable foaming agents.
Examples of the inorganic foaming agent include carbon dioxide, air, and nitrogen.
Examples of volatile blowing agents include aliphatic hydrocarbons such as propane, n-butane, i-butane, pentane and hexane; cyclic aliphatic hydrocarbons such as cyclobutane and cyclopentane; trichlorofluoromethane and dichlorodifluoromethane. Halogenated hydrocarbons such as dichlorotetrafluoroethane, methyl chloride, ethyl chloride, and methylene chloride.
Examples of the decomposable foaming agent include azodicarbonamide, dinitrosopentamethylenetetramine, azobisisobutyronitrile, and sodium bicarbonate.
These foaming agents may be used individually by 1 type, and may use 2 or more types together.

  As the antibacterial agent, known antibacterial agents can be used. For example, “Ilguard B1000”, “Ilguard B5000”, “Ilguard B5120”, “Ilguard B6000”, “Ilguard B7000”, “Ilguard B7250”, “Ilguard B7620” "," Ilguard B7920 "(trade name, manufactured by Ciba Japan Co., Ltd.). These antibacterial agents may be used alone or in combination of two or more.

  As the preservative, a known preservative can be used.

  As the filler, known fillers can be used, for example, calcium carbonate, talc, glass fiber, carbon fiber, magnesium carbonate, mica, kaolin, calcium sulfate, barium sulfate, titanium white, white carbon, carbon black. Can be mentioned. These fillers may be used individually by 1 type, and may use 2 or more types together.

  As the lubricant, a known lubricant can be used. For example, “Atomer SA1750”, “Atomer SA1753”, “Atomer SA1753FD”, “Atomer SA1756”, “Atomer 1759”, “Atomer SA1759FD” (Ciba Japan Co., Ltd.) ) ;; “Metabrene L-1000” (trade name, manufactured by Mitsubishi Rayon Co., Ltd.). These lubricants may be used individually by 1 type, and may use 2 or more types together.

  As the impact strength modifier, a known impact strength modifier can be used. For example, “methabrene C-223A”, “methabrene C-201A”, “methabrene C140A”, “methabrene S-2001”, “ METABLEN S-2006, “METABBRENE S-2030”, “METABBRENE S-2100”, “METABBRENE S-2200”, “METABBRENE SX-005”, “METABBRENE SX-006”, “METABBRENE SRK-200”, “METABBRENE W” -450A "," Metabrene W-300A "(trade name, manufactured by Mitsubishi Rayon Co., Ltd.);" Kane Ace B56 "," Kane Ace B564 "," Kane Ace M511 "," Kane Ace M600 "," Kane Ace M400 "," Kane Ace M580 " ”,“ Kane Ace MR01 ”,“ Kane Ace M300 ”,“ Kane A "B22", "Kaneace B52", "Kaneace B522", "Kaneace B521", "Kaneace FM21", "Kaneace FM22", "Kaneace FM25", "Kaneace FM40" (trade name, manufactured by Kaneka Corporation) . These impact strength modifiers may be used alone or in combination of two or more.

  As the antistatic agent, a known antistatic agent can be used. For example, “Irgastat P16”, “Irgastat P18”, “Irgastat P20”, “Irgastat P22” (trade name, Ciba Japan ( Co., Ltd.). These antistatic agents may be used alone or in combination of two or more.

  As the metal deactivator, a known metal deactivator can be used. For example, “ADK STAB CDA-1,” “ADK STAB CDA-1M,” “ADK STAB CDA-6,” “ADK STAB CDA-10” Is mentioned. These metal deactivators may be used individually by 1 type, and may use 2 or more types together.

  As the fluidity modifier, a known fluidity modifier can be used, and examples thereof include “Metablene TP-001” and “Metablene TP-003” (trade names, manufactured by Mitsubishi Rayon Co., Ltd.). . These fluidity modifiers may be used alone or in combination of two or more.

  As the matting agent, a known matting agent can be used, and examples thereof include “Metablene F-410” and “Metablene F-444” (trade name, manufactured by Mitsubishi Rayon Co., Ltd.). These matting agents may be used individually by 1 type, and may use 2 or more types together.

  As the pigment, known pigments can be used. For example, “Seika First Yellow”, “Seika First Orange”, “Seika First Red”, “Chromofine Blue”, “Chromofine Green”, “Chromofine Red”. , “Chromofine Black”, “Seikalite”, “Daipyrokiside Yellow”, “Daipyroxyside Brown”, “Daipyroxyside Green”, “Daipyroxyside Blue”, “Daipyroxyside Black”, “Miroli Blue” ”,“ Love Color Clear ”,“ Love Color Color ”,“ Daipromenade ”,“ New Lactimine Color ”(trade name, manufactured by Dainichi Seika Kogyo Co., Ltd.). These pigments may be used alone or in combination of two or more.

  Known dyes can be used as the dye.

  The thermoplastic resin modifier tablet (X) of the present invention is a compression molding of a polytetrafluoroethylene-containing resin (A), if necessary, a thermoplastic resin (B), a powder containing additives, and the like. Obtained.

  Since the polytetrafluoroethylene-containing resin (A), the thermoplastic resin (B), and the additive can be uniformly mixed, it is preferable that all of them are powder.

As the compression molding machine used for compression molding, a known compression molding machine can be used, and examples thereof include a tableting machine and a press machine.
Among these compression molding machines, a tableting machine is preferable because of excellent productivity.

  A known tableting machine can be used as the tableting machine. For example, “VIRGO 0512SS2AZ”, “VIRGO 0506SS”, “VIRGO 0512SS”, “VIRGO 0518SS”, “VIRGO 0524SS”, “VIRGO 05122L”, “LIBRA2” "0836SS2JZ", "LIBRA2 0845SS", "PEGASUS 1024SS4KZ", "PEGASUS 1030SS", "NEW GEMINI 0855DS", "NEW GEMINI 0867DS", "NEW GEMINI 067DS", "NEW GEMINI 1545L" 1529SS "(model name, manufactured by Kikusui Seisakusho Co., Ltd.);" X-SS type "," X-MS type "," X LD type, X-LS type, AP-SS type, AP-MS type, AP-LD type, AP-LS type, MS-C type, LS-3L "Type", "BX-SM type", "BX-NM type", "HX-LD type", "HT-EX-SS type", "HT-BEX-S type", "B-S type", " "BD type", "FXH type", "FX-D type" (model name, manufactured by Hata Seiko Co., Ltd.); "HANDSTAB-100" (model name, manufactured by Ichibashi Seiki Co., Ltd.) .

The compression pressure at the time of compression molding is preferably 0.1 to 100 MPa, more preferably 0.5 to 90 MPa, and further preferably 1 to 80 MPa.
When the compression pressure is 0.1 MPa or more, the shape stability of the resulting thermoplastic resin modifier tablet (X) is excellent. When the compression pressure is 100 MPa or less, decomposition of the thermoplastic resin (B) can be suppressed.

  The molding temperature at the time of compression molding is not particularly limited as long as the tablet (X) of the thermoplastic resin modifier is not melted, and is preferably 5 to 50 ° C, preferably 10 to 40 ° C. It is more preferable that

The shape of the thermoplastic resin modifier tablet (X) of the present invention is not particularly limited, but is preferably a columnar shape because it is easy to produce.
The size of the thermoplastic resin modifier tablet (X) in a cylindrical shape can be appropriately set according to the size of the thermoplastic resin (Y) pellets, and the diameter is 1 to 20 mm. It is preferably 1 to 30 mm, more preferably 2 to 10 mm in diameter and 2 to 15 mm in length.
When the size of the tablet (X) of the thermoplastic resin modifier is 1 mm or more in diameter and 1 mm or more in length, classification during mixing with the pellets of the thermoplastic resin (Y) is suppressed. Further, when the size of the tablet (X) of the modifier for thermoplastic resin is 20 mm or less in diameter and 30 mm or less in length, the dispersibility of polytetrafluoroethylene in the thermoplastic resin (Y) is excellent and obtained. Excellent surface appearance of the molded product.

  The thermoplastic resin composition of the present invention is obtained by mixing the thermoplastic resin modifier tablet (X) and thermoplastic resin (Y) of the present invention.

  As the thermoplastic resin (Y), a known thermoplastic resin can be used, for example, polyolefin resin, polystyrene resin, polyvinyl chloride resin, acrylic resin, polyester resin, polyamide resin, polycarbonate resin. And thermoplastic elastomers. These thermoplastic resins (Y) may be used individually by 1 type, and may use 2 or more types together.

The mixing ratio of the thermoplastic resin can be appropriately set according to the target performance of the obtained molded product, and the mixing ratio of the tablet (X) of the modifier for thermoplastic resin in 100% by mass of the thermoplastic resin composition. Is 0.1 to 40 mass%, the mixing ratio of the thermoplastic resin (Y) is preferably 60 to 99.9 mass%, and the mixing ratio of the tablet (X) of the thermoplastic resin modifier is 0.00. It is more preferable that the mixing ratio of 2 to 30% by mass and the thermoplastic resin (Y) is 70 to 99.8% by mass, and the mixing ratio of the tablet (X) of the thermoplastic resin modifier is 0.3 to 0.3%. More preferably, the mixing ratio of 20% by mass and the thermoplastic resin (Y) is 80 to 99.7% by mass.
When the mixing ratio of the modifier (X) for the thermoplastic resin modifier is 0.1% by mass or more, the molding processability of the resulting thermoplastic resin composition is excellent. Further, when the mixing ratio of the tablet (X) of the modifier for thermoplastic resin is 40% by mass or less, the dispersibility of polytetrafluoroethylene in the thermoplastic resin (Y) is excellent, and the resulting molded article It has excellent surface appearance and does not impair the original properties of the thermoplastic resin (Y).
When the mixing ratio of the thermoplastic resin (Y) is 60% by mass or more, the dispersibility of the polytetrafluoroethylene in the thermoplastic resin (Y) is excellent, the surface appearance of the resulting molded article is excellent, and the thermoplasticity The original characteristics of the resin (Y) are not impaired. Moreover, it is excellent in the moldability of the thermoplastic resin composition obtained as the mixing rate of a thermoplastic resin (Y) is 99.9 mass% or less.

The thermoplastic resin composition of the present invention comprises an antioxidant, an ultraviolet absorber, a light stabilizer, a plasticizer, a flame retardant, a nucleating agent, a foaming agent, an antibacterial agent, an antiseptic, a filler, and a lubricant as necessary. , Impact strength modifiers, antistatic agents, metal deactivators, fluidity modifiers, matting agents, pigments, dyes and other additives. These additives may be used alone or in combination of two or more.
Specific examples of these additives include those exemplified as additives that may be included in the tablet (X) of the thermoplastic resin modifier.

  As a method of mixing the thermoplastic resin modifier tablet (X), the thermoplastic resin (Y), and additives as required, a known method can be used, for example, extrusion kneading, roll kneading, etc. And a method by melt kneading.

  What is necessary is just to set suitably the kneading | mixing temperature in the case of melt-kneading according to the kind of thermoplastic resin (Y), and it is 150-350 degreeC generally.

  The molded article of the present invention is obtained by molding the thermoplastic resin composition of the present invention.

  A known method can be used as a molding method for obtaining the molded article of the present invention, and examples include molding methods such as extrusion molding, injection molding, calendar molding, blow molding, thermoforming, foam molding, and melt spinning. It is done.

  What is necessary is just to set the molding temperature for obtaining the molded object of this invention suitably according to the kind of thermoplastic resin (Y), and it is 150-350 degreeC generally.

  Since the molded body of the present invention has excellent surface appearance, it is a sheet material such as an optical sheet, a film material such as a food film, a material for home appliances, a material for OA equipment, a material for automobiles, a medical material, a building material, and a coating for electric wires. Suitable for materials and the like.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.
In the examples, “parts” and “%” indicate “parts by mass” and “% by mass”.

  Each evaluation in an Example and a comparative example was implemented with the following method.

(1) Solid content concentration After drying the obtained water dispersion for 30 minutes at 170 degreeC, mass was measured and solid content was computed.

(2) Polymerization rate The polymerization rate of the monomers in Production Examples 1 to 3 was calculated by measuring the amount of monomer remaining after polymerization using a gas chromatograph.
The gas chromatograph is “GC6890” (model name, manufactured by Agilent Technologies), and the separation column is “HP-5” (trade name, Agilent Technologies, Inc., inner diameter 0.25 mm, length 30 m, film thickness 0 .25 μm), butyl acetate was used as an internal standard substance, and measurement was performed by the internal standard method.

(3) Handling property 10 parts of the resulting modifier for thermoplastic resin and polypropylene resin pellets (trade name “NOVATEC FY-4”, manufactured by Nippon Polypro Co., Ltd., 4 mm diameter, 2 mm long cylindrical pellets) ) 90 parts were thoroughly mixed by hand blending, the state of classification after standing for 3 minutes was visually confirmed, and judged according to the following criteria.
○: Classification is not seen.
X: Classification is seen.
The classifying property of the thermoplastic resin modifier is a criterion for determining whether or not the thermoplastic resin modifier can be mixed uniformly when blended with the thermoplastic resin (Y). It can be considered that the modifier for resin is excellent in handleability.

(4) Melt tension Using the obtained thermoplastic resin composition, a capillary type rheometer (model name “Twin Capillary Rheometer RH-7”, manufactured by ROSAND) was used, and the die was φ1.0 mm, L / D = 16. Extruded at a constant amount (0.54 cm ³ / min) under the conditions of a temperature of 190 ° C., and the strand was taken up at a constant speed (3 m / min).
The melt tension of the thermoplastic resin composition is a criterion for determining moldability such as thermoformability, blow moldability, and foam moldability, and improvement in melt tension can be regarded as improvement in moldability.

(5) Number of surface irregularities The number of foreign matters present in the obtained molded body (film having a thickness of 500 μm) was evaluated. As an evaluation procedure, the unevenness seen on the surface of the film 1 m ² (width 0.1 m, length 10 m) is visually marked, the marked unevenness is observed using a stereomicroscope, and polytetrafluoro Only irregularities derived from aggregates of the ethylene-containing resin (A) were counted. Whether the unevenness is derived from the aggregate of the polytetrafluoroethylene-containing resin (A) can be confirmed by infrared absorption spectrum measurement.
The number of surface irregularities of the molded body is a criterion for determining the dispersibility of the polytetrafluoroethylene-containing resin (A) in the thermoplastic resin (Y) and the surface appearance of the molded body to be obtained. The smaller the number of irregularities, the better the dispersibility of the polytetrafluoroethylene-containing resin (A) in the thermoplastic resin (Y) and the surface appearance of the resulting molded body.

[Production Example 1] Production of polytetrafluoroethylene-containing resin (1) 129 parts of distilled water was added to 100 parts of "Fluon AD939L" (trade name, manufactured by Asahi Glass Co., Ltd., solid content concentration 60%). An aqueous dispersion (Z-1) of fluoroethylene was obtained.
The resulting polytetrafluoroethylene aqueous dispersion (Z-1) had a solid content concentration of 26.2%.
0.1 part of 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved in a monomer mixed solution of 50 parts of dodecyl methacrylate and 50 parts of methyl methacrylate. A mixed solution of 2.0 parts of sodium dodecylbenzenesulfonate and 300 parts of distilled water was added to the resulting solution, and the mixture was stirred for 2 minutes at a rotation speed of 10,000 rpm with a homomixer. A stable preliminary dispersion was obtained through two passes. The obtained preliminary dispersion was charged into a separable flask equipped with a stirring blade, a condenser, a thermocouple, and a nitrogen inlet, and the internal temperature was raised to 80 ° C. under a nitrogen stream and maintained for 3 hours to perform radical polymerization. Upon completion, an aqueous dispersion (Z-2) of polymer particles was obtained. The solid content concentration of the aqueous dispersion (Z-2) of the obtained polymer particles was 25.1%.
A separable flask equipped with a stirrer, a condenser, a thermocouple, and a nitrogen inlet was charged with 76 parts of (Z-1) and 239 parts of (Z-2), and stirred at 25 ° C. for 1 hour under a nitrogen stream. Thereafter, the system was heated to 80 ° C. and held for 1 hour, and then 0.001 part of ferrous sulfate, 0.003 part of disodium ethylenediaminetetraacetate, 0.24 part of Rongalite salt, 60.8 parts of distilled water And a monomer mixture solution of 20 parts of methyl methacrylate and 0.4 part of t-butyl peroxide was added dropwise over 1 hour. After completion of the addition, the internal temperature was maintained at 80 ° C. for 1 hour, Polymerization was completed to obtain an aqueous dispersion of the polytetrafluoroethylene-containing resin (1). Through the series of operations, separation of solids and the like were not confirmed, and the obtained aqueous dispersion of the polytetrafluoroethylene-containing resin (1) was uniform. The polymerization rate of the monomer was 99% or more.
The obtained aqueous dispersion of polytetrafluoroethylene-containing resin (1) was put into 400 parts of 90 ° C. hot water containing 5 parts of calcium chloride, coagulated, and collected by filtration. The obtained recovered material was dried at 65 ° C. for 12 hours to obtain a polytetrafluoroethylene-containing resin (1) powder. The polytetrafluoroethylene concentration in the powder of the obtained polytetrafluoroethylene-containing resin (1) is 20% (calculated from preparation).

[Production Example 2] Production of polytetrafluoroethylene-containing resin (2) An aqueous dispersion of polytetrafluoroethylene obtained in Production Example 1 was placed in a separable flask equipped with a stirrer, a condenser, a thermocouple, and a nitrogen inlet ( Z-1) 191 parts, methyl methacrylate 40 parts, n-butyl acrylate 10 parts, alkenyl succinate dipotassium 3.0 parts, t-butyl hydroperoxide 0.2 parts, n-octyl mercaptan 0.5 parts, distilled water 35 parts were charged and stirred at 25 ° C. for 1 hour under a nitrogen stream. Thereafter, the temperature inside the system was raised to 60 ° C., and a mixed liquid of 0.0005 part of ferrous sulfate, 0.0015 part of disodium ethylenediaminetetraacetate, 0.3 part of Rongalite salt, and 5 parts of distilled water was added. Was held at 60 ° C. for 1.5 hours to complete radical polymerization, and an aqueous dispersion of a polytetrafluoroethylene-containing resin (2) was obtained. Through a series of operations, separation of solids and the like were not confirmed, and the obtained aqueous dispersion of the polytetrafluoroethylene-containing resin (2) was uniform. The polymerization rate of the monomer was 99% or more.
The obtained polytetrafluoroethylene-containing resin (2) aqueous dispersion is coagulated, filtered and dried in the same manner as in Production Example 1 to obtain a polytetrafluoroethylene-containing resin (2) powder. It was. The polytetrafluoroethylene concentration in the powder of the obtained polytetrafluoroethylene-containing resin (2) is 50% (calculated from preparation).

[Production Example 3] Production of thermoplastic resin (B-2) In a separable flask equipped with a stirrer, condenser, thermocouple, nitrogen inlet, 225 parts of distilled water, 2.5 parts of sodium dodecylbenzenesulfonate, sulfuric acid 0.0002 part of ferrous iron, 0.0006 part of disodium ethylenediaminetetraacetate and 0.48 part of ascorbic acid were charged and stirred at 25 ° C. for 1 hour under a nitrogen stream. Thereafter, the temperature in the system was raised to 73 ° C., and a monomer mixture of 98 parts of isobutyl methacrylate, 2 parts of n-butyl acrylate, 1 part of n-octyl mercaptan and 0.2 part of cumene hydroperoxide was added dropwise over 1 hour. And after completion | finish of dripping, internal temperature was hold | maintained at 73 degreeC for 1 hour, radical polymerization was completed, and the aqueous dispersion of the thermoplastic resin (B-2) was obtained. Through a series of operations, separation of solids or the like was not confirmed, and the obtained aqueous dispersion of the thermoplastic resin (B-2) was uniform. The polymerization rate of the monomer was 99% or more.
The obtained aqueous dispersion of the thermoplastic resin (B-2) was put into 500 parts of hot water of 70 ° C. containing 5 parts of calcium acetate, heated to 90 ° C., coagulated, and collected by filtration. The obtained recovered material was dried at 60 ° C. for 12 hours to obtain a thermoplastic resin (B-2) powder. The mass average molecular weight measured by gel permeation chromatography of the obtained thermoplastic resin (B-2) was 30,000.

[Examples 1 to 8]
A polytetrafluoroethylene-containing resin (A) and a thermoplastic resin (B) are blended in the ratios shown in Table 1, mixed by hand blending, and a tabletop simple tablet molding machine “HANDSTAB-100” (model name, Ichibashi Seiki) (Made by Co., Ltd.), and compression molding is performed under the conditions of a compression pressure of 10 MPa and a temperature of 25 ° C., and the modifiers (T-1) to (T) for a cylindrical tablet having a diameter of 5 mm and a length of 6 mm. -8) was obtained.

[Comparative Examples 1-8]
Polytetrafluoroethylene-containing resin (A) and thermoplastic resin (B) are blended at the ratios shown in Table 2, mixed by hand blending, and powdered thermoplastic resin modifier (P-1) to (P-8) was obtained.

  Tables 1 and 2 show the handling properties of the resulting thermoplastic resin modifier.

The abbreviations in the table indicate the following compounds.
(1): Polytetrafluoroethylene-containing resin powder produced in Production Example 1 (2): Polytetrafluoroethylene-containing resin powder produced in Production Example 2 (3): Modified polytetrafluoroethylene powder (Product name “Brendex 449”, manufactured by Chemtura, polytetrafluoroethylene concentration 50%)
(4): Unmodified polytetrafluoroethylene powder (trade name “Fluon CD-1”, manufactured by Asahi Glass Co., Ltd.)
(B-1): Polypropylene resin powder (trade name “PPW-5”, manufactured by Seishin Corporation)
(B-2): Thermoplastic resin powder produced in Production Example 3

[Examples 9 to 16, Comparative Examples 9 to 17]
A thermoplastic resin modifier and a thermoplastic resin (Y) are blended in the ratios shown in Tables 3 to 5, mixed by hand blending, and a φ30 mm co-directional twin screw extruder (Plastic Engineering Laboratory Co., Ltd.) Manufactured, L / D = 30), and extrusion molding was performed under the conditions of a screw rotational speed of 200 rpm and a cylinder temperature of 200 ° C. to obtain a thermoplastic resin composition.
The obtained thermoplastic resin composition was dried at 80 ° C. for 12 hours, and using a single screw extruder (manufactured by GM Engineering, L / D = 30) equipped with a T die, the screw rotation speed was 20 rpm. Then, the film was formed to have a thickness of 500 μm and a width of 10 cm under the conditions of a cylinder temperature of 200 ° C. and a T-die temperature of 210 ° C. to obtain a molded body (film).

  Tables 3 to 5 show the melt tension of the obtained thermoplastic resin composition and the number of surface irregularities of the obtained molded body.

The abbreviations in the table indicate the following compounds.
(Y-1): Polypropylene resin pellets (trade name “NOVATEC PP FY-4”, manufactured by Nippon Polypro Co., Ltd., melt flow rate 5 g / 10 min, diameter 4 mm, length 2 mm columnar pellets)

As is apparent from Tables 3 to 5, Examples 9 to 16 used the tablet (X) of the thermoplastic resin modifier of the present invention, and therefore, the molding processability of the obtained thermoplastic resin composition. And the surface appearance of the obtained molded body was excellent.
On the other hand, Comparative Example 12 was inferior in molding processability of the obtained thermoplastic resin composition because the thermoplastic resin modifier was not used. In Comparative Examples 9 to 11 and 13 to 17, since the shape of the modifier for thermoplastic resin was powder, the resulting thermoplastic resin composition was excellent in molding processability, but was obtained. The surface appearance of the molded body was inferior.

The thermoplastic resin modifier tablet (X) of the present invention has excellent handleability, excellent molding processability of the resulting thermoplastic resin composition, and the polytetrafluoroethylene in the thermoplastic resin (Y). It is excellent in the surface appearance of the molded product obtained from excellent dispersibility.
Since the molded body of the present invention has excellent surface appearance, it is a sheet material such as an optical sheet, a film material such as a food film, a material for home appliances, a material for OA equipment, a material for automobiles, a medical material, a building material, and a coating for electric wires. Suitable for materials and the like.

Claims (3)

  The manufacturing method of the tablet (X) of the modifier for thermoplastic resins which compression-molds the powder containing polytetrafluoroethylene containing resin (A) using a tableting machine.   The production method according to claim 1, wherein the polytetrafluoroethylene-containing resin (A) is a modified polytetrafluoroethylene (A-2). The manufacturing method according to claim 1, wherein the thermoplastic resin modifier tablet (X) further contains a thermoplastic resin (B).