WO2022201977A1 - Master batch, resin composition and resin molded body - Google Patents
Master batch, resin composition and resin molded body Download PDFInfo
- Publication number
- WO2022201977A1 WO2022201977A1 PCT/JP2022/005987 JP2022005987W WO2022201977A1 WO 2022201977 A1 WO2022201977 A1 WO 2022201977A1 JP 2022005987 W JP2022005987 W JP 2022005987W WO 2022201977 A1 WO2022201977 A1 WO 2022201977A1
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- WIPO (PCT)
- Prior art keywords
- resin
- masterbatch
- polyester
- filler
- resin composition
- Prior art date
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- 229920005989 resin Polymers 0.000 title claims abstract description 55
- 239000011347 resin Substances 0.000 title claims abstract description 55
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 48
- 239000011342 resin composition Substances 0.000 title claims abstract description 47
- 239000000945 filler Substances 0.000 claims abstract description 38
- 229920001225 polyester resin Polymers 0.000 claims abstract description 30
- 239000004645 polyester resin Substances 0.000 claims abstract description 25
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000001007 phthalocyanine dye Substances 0.000 claims abstract description 20
- 229920000728 polyester Polymers 0.000 claims abstract description 14
- -1 inorganic acid salts Chemical class 0.000 claims description 19
- 238000000465 moulding Methods 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 11
- 229920001634 Copolyester Polymers 0.000 claims description 10
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000006229 carbon black Substances 0.000 claims description 9
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 229920008790 Amorphous Polyethylene terephthalate Polymers 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- 239000002734 clay mineral Substances 0.000 claims description 4
- WTIFIAZWCCBCGE-UUOKFMHZSA-N guanosine 2'-monophosphate Chemical compound C1=2NC(N)=NC(=O)C=2N=CN1[C@@H]1O[C@H](CO)[C@@H](O)[C@H]1OP(O)(O)=O WTIFIAZWCCBCGE-UUOKFMHZSA-N 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 3
- 150000002009 diols Chemical class 0.000 claims description 3
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 abstract description 36
- 230000008025 crystallization Effects 0.000 abstract description 36
- 230000003111 delayed effect Effects 0.000 abstract description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 26
- 239000005020 polyethylene terephthalate Substances 0.000 description 26
- 238000004898 kneading Methods 0.000 description 8
- 239000000975 dye Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000001000 anthraquinone dye Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 229920006038 crystalline resin Polymers 0.000 description 3
- 229920006122 polyamide resin Polymers 0.000 description 3
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 3
- 230000000979 retarding effect Effects 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- NIDFGXDXQKPZMA-UHFFFAOYSA-N 14h-benz[4,5]isoquino[2,1-a]perimidin-14-one Chemical compound C1=CC(N2C(=O)C=3C4=C(C2=N2)C=CC=C4C=CC=3)=C3C2=CC=CC3=C1 NIDFGXDXQKPZMA-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012770 industrial material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- IBABXJRXGSAJLQ-UHFFFAOYSA-N 1,4-bis(2,6-diethyl-4-methylanilino)anthracene-9,10-dione Chemical compound CCC1=CC(C)=CC(CC)=C1NC(C=1C(=O)C2=CC=CC=C2C(=O)C=11)=CC=C1NC1=C(CC)C=C(C)C=C1CC IBABXJRXGSAJLQ-UHFFFAOYSA-N 0.000 description 1
- VJUKWPOWHJITTP-UHFFFAOYSA-N 81-39-0 Chemical compound C1=CC(C)=CC=C1NC1=CC=C2C3=C1C(=O)C1=CC=CC=C1C3=CC(=O)N2C VJUKWPOWHJITTP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- LJFWQNJLLOFIJK-UHFFFAOYSA-N solvent violet 13 Chemical compound C1=CC(C)=CC=C1NC1=CC=C(O)C2=C1C(=O)C1=CC=CC=C1C2=O LJFWQNJLLOFIJK-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XRASPMIURGNCCH-UHFFFAOYSA-N zoledronic acid Chemical compound OP(=O)(O)C(P(O)(O)=O)(O)CN1C=CN=C1 XRASPMIURGNCCH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Definitions
- the present invention relates to masterbatches, resin compositions, and resin moldings.
- polyester resins such as polyethylene terephthalate have excellent chemical and physical properties, they have been widely used as industrial materials for manufacturing various molded products such as films and sheets.
- resin compositions containing thermoplastic resins such as polyethylene terephthalate and polybutylene terephthalate and fillers such as carbon black, and molded articles obtained by molding these resin compositions are known (Patent Documents 1).
- Patent document 2 As a technique for delaying the crystallization of crystalline resins (lowering the crystallization temperature), for example, a resin composition in which a nigrosine compound, which is a type of dye, is blended with a crystalline resin such as a polyamide resin has been proposed ( Patent document 2).
- JP 2006-305926 A Japanese Patent Application Laid-Open No. 2001-011055
- Patent Document 2 can delay the crystallization of polyamide resins, it is not possible to delay the crystallization of resins other than polyamide resins. proved difficult.
- the present invention has been made in view of the problems of the prior art, and the object thereof is to delay the crystallization of the polyester resin while containing a filler, thereby improving the appearance and surface of the resin.
- the object of the present invention is to provide a masterbatch capable of producing a resin composition capable of producing a polyester resin molded article having excellent quality such as gloss.
- the subject of the present invention is that the crystallization of the polyester resin is delayed even though it contains a filler, and it is possible to produce a resin molded product made of a polyester resin having excellent quality such as appearance and surface gloss.
- An object of the present invention is to provide a resin composition and a resin molded article that is a molded product of the resin composition.
- a masterbatch that is used for producing a resin molding mainly composed of polyester resin contains a polyester base resin and a filler, and satisfies the following condition (1).
- Condition (1) A copper phthalocyanine dye is further contained, and the content of the copper phthalocyanine dye is 3 to 200 parts by mass with respect to 100 parts by mass of the filler.
- the base resin contains at least one selected from the group consisting of amorphous polyethylene terephthalate and copolyester.
- the copper phthalocyanine dye is C.I. I.
- Solvent Blue 67 C.I. I. Solvent Blue 70, and C.I. I.
- the filler is at least one selected from the group consisting of carbon black, clay minerals, metal oxides, inorganic acid salts, and organic acid salts. masterbatch.
- the copolymer polyester is selected from the group consisting of a dicarboxylic acid component containing terephthalic acid and isophthalic acid, and ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,4-cyclohexanedimethanol
- the masterbatch according to any one of the above [2] to [4] which is a copolymer of at least one selected diol component.
- a resin molded product which is a molded product of the resin composition according to [7].
- a resin composition is produced in which crystallization of a polyester resin is delayed while a filler is contained, and a resin molded article made of a polyester resin having excellent quality such as appearance and surface gloss can be produced. It is possible to provide a masterbatch that can be
- the resin composition has a retarded crystallization of the polyester resin even though it contains a filler, and can produce a resin molded article made of a polyester resin having excellent quality such as appearance and surface gloss. , and a resin molding that is a molding of this resin composition.
- One embodiment of the masterbatch of the present invention is a masterbatch that is used for producing a resin molded article mainly composed of a polyester resin, and contains a polyester-based base resin and a filler. And the masterbatch of this embodiment satisfies at least one of the following conditions (1) and (2). Details of the masterbatch of the present embodiment will be described below.
- Condition (1) A copper phthalocyanine dye is further contained, and the content of the copper phthalocyanine dye is 3 to 200 parts by mass with respect to 100 parts by mass of the filler.
- a polyester-based resin is used as the base resin.
- a polyester-based resin is generally a resin having structural units derived from an aromatic dicarboxylic acid and structural units derived from an alkylenediol.
- Specific examples of polyester-based resins used as base resins include polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and polybutylene naphthalate (PBN). etc. can be mentioned.
- PET polyethylene terephthalate
- PET homo PET
- filler A filler that can function as a crystal nucleus that raises the crystallization temperature of the base resin is usually used as the filler.
- fillers include pigments such as carbon black and titanium oxide, as well as inorganic substances and inorganic compounds that are blended in general resin compositions.
- fillers include carbon black, clay minerals, metal oxides, inorganic acid salts, and organic acid salts. These fillers can be used individually by 1 type or in combination of 2 or more types.
- clay minerals include talc and clay.
- metal oxides include titanium oxide, zinc oxide, and alumina.
- inorganic acid salts include carbonates, silicates, and sulfates of various metals.
- organic acid salts include carboxylates of various metals and organic phosphates.
- carbon black is preferable as the filler.
- Commercially available carbon black can be used. Furnace black, channel black, acetylene black, and thermal black, which have different characteristics depending on the manufacturing method, can be used.
- the content of the filler in the masterbatch is preferably 3 to 40% by mass, more preferably 4 to 30% by mass, more preferably 4.5 to 25% by mass, based on the total mass of the masterbatch. It is particularly preferred to have
- the masterbatch of this embodiment satisfies at least one of the following conditions (1) and (2).
- the masterbatch of the present embodiment preferably satisfies both the following conditions (1) and (2).
- a synergistic effect is exhibited, so the crystallization of the polyester resin is further delayed, and a resin molded product made of polyester resin with improved quality is produced.
- a resin composition that can be manufactured can be produced.
- Condition (1) A copper phthalocyanine dye is further contained, and the content of the copper phthalocyanine dye is 3 to 200 parts by mass with respect to 100 parts by mass of the filler.
- Copper phthalocyanine-based dyes are dyes that can be dissolved in polyester-based resins. Copper phthalocyanine dyes include C.I. I. Solvent Blue 67, C.I. I. Solvent Blue 70, and C.I. I. Solvent Blue 44 and the like can be mentioned. These copper phthalocyanine dyes can be used singly or in combination of two or more. Among them, C.I. I. Solvent Blue 67 is preferably used because it can further delay the crystallization of the polyester resin.
- the content of the copper phthalocyanine dye in the masterbatch is preferably 3 to 200 parts by mass, preferably 10 to 100 parts by mass, relative to 100 parts by mass of the filler. is more preferable, and 30 to 100 parts by mass is particularly preferable. If the content of the copper phthalocyanine dye is too small, the crystallization retarding effect may be insufficient. On the other hand, if the content of the copper phthalocyanine-based dye is excessive, the effect of retarding crystallization reaches a ceiling, and the cost may be disadvantageous.
- Amorphous polyethylene terephthalate is polyethylene terephthalate (PET) that does not substantially have a crystallization temperature, and there is so-called "PET-G".
- PET-G is amorphous PET in which part of the ethylene glycol units (for example, about 30 to 40 mol %) in PET are replaced with cycloehexanedimethanol units.
- Copolyester is a resin in which at least some of the structural units (terephthalic acid units and ethylene glycol units) in polyethylene terephthalate (PET) are replaced with other structural units.
- the copolymer polyester is selected from the group consisting of dicarboxylic acid components including terephthalic acid and isophthalic acid, and ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,4-cyclohexanedimethanol. It is preferred to use a copolymer with at least one diol component. By using this copolyester, it is possible to delay the crystallization of the base resin (lower the crystallization temperature) while containing the filler.
- the base resin preferably contains both amorphous polyethylene terephthalate and copolyester. Furthermore, it is preferable to use substantially only amorphous polyethylene terephthalate and copolyester as the base resin because the crystallization retarding effect can be further improved.
- the masterbatch of the present embodiment can contain other components other than the components described above, if necessary, as long as the object of the present invention is not impaired.
- Other components include, for example, antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, conductivity-imparting agents, release agents, lubricants, dyes (excluding the above-mentioned copper phthalocyanine dyes), and pigments. (excluding the above-mentioned fillers) and the like.
- the masterbatch of the present embodiment can be produced, for example, by melt-kneading the components described above.
- the melt-kneading method is not particularly limited, and conventionally known melt-kneading methods can be employed. Specifically, after pre-mixing each component using a high-speed mixer such as a Henschel mixer or various mixers such as a tumbler, a Banbury mixer, a roll, a plastograph, a single-screw extruder, a twin-screw extruder, and a kneader A method of melt-kneading with a kneading device such as the above can be mentioned.
- each component is melt-kneaded using an extruder because it can improve production efficiency.
- a twin-screw extruder as an extruder.
- Each component is melt-kneaded using a kneading device such as an extruder, and the kneaded product is extruded into a strand shape, and then the kneaded product extruded into a strand shape is processed into a desired shape such as pellets or flakes. can do.
- the temperature during melt-kneading is preferably 200 to 300°C, more preferably 260 to 280°C.
- One embodiment of the resin composition of the present invention is a resin composition for producing a resin molding mainly composed of a polyester resin, and contains a polyester-based raw material resin and the masterbatch described above. For this reason, when the resin composition of the present embodiment is melted and molded into a desired shape according to a conventionally known method, the crystallization of the raw material resin is delayed even though it contains a filler, so the appearance is improved. It is possible to produce a resin molding made of a polyester resin having excellent quality such as surface gloss and the like.
- polyester-based raw material resin for example, the same polyester-based resin that can be used as the base resin of the masterbatch can be used. That is, PET, PTT, PBT, PEN, PBN, etc. can be mentioned as raw material resin.
- the content of the filler in the resin composition is preferably 0.03 to 2% by mass, more preferably 0.05 to 1.5% by mass, based on the total mass of the resin composition. . That is, the content of the filler in the resin composition is preferably 0.03 to 2% by mass, more preferably 0.05 to 1.5% by mass, mixing (melting) the raw material resin and the masterbatch kneading) is preferred.
- the content of the amorphous PET in the resin composition is preferably 1 to 10% by mass based on the total mass of the resin composition. More preferably, it is up to 8% by mass. Further, when the resin composition contains a copolyester, the content of the copolyester in the resin composition is preferably 1 to 10% by mass based on the total mass of the resin composition. More preferably, it is up to 8% by mass.
- One embodiment of the resin molding of the present invention is a molding of the resin composition described above. Since the resin molded body of the present embodiment is formed of a resin composition obtained by diluting the above-described masterbatch with a polyester-based raw material resin, it crystallizes at a lower temperature, and has excellent appearance, surface gloss, etc. Excellent quality.
- the resin molded article of the present embodiment can be produced, for example, by molding the above resin composition into a desired shape according to a conventionally known molding method.
- resin moldings include blow moldings such as bottles and plastic tanks; injection moldings such as industrial materials, trays and housings.
- ⁇ Copolymer polyester A product name “TRN8084FB”, manufactured by Teijin, terephthalic acid/isophthalic acid/ethylene glycol
- ⁇ Copolymer polyester B Trade name “Kemit Q1500” manufactured by Toray Fine Chemicals Co., Ltd., terephthalic acid/isophthalic acid/1,4-butanediol/copper phthalocyanine dye A: C.I. I. Solvent Blue 67, trade name “ORAZOL 825”, manufactured by BASF ⁇ Copper phthalocyanine dye B: C.I. I. Solvent Blue 70, trade name "Oil Blue 5511-N", manufactured by Arimoto Chemical Industry Co., Ltd. Anthraquinone dye A: C.I. I.
- Solvent Red 52 trade name "Plast Red 8360", anthraquinone dye B: C.I. I. Solvent Blue 87, trade name "Plast Bule 8580", manufactured by Arimoto Chemical Industry Co., Ltd.
- Anthraquinone dye C C.I. I. Solvent Blue 97, trade name "Plast Bule 8590", manufactured by Arimoto Chemical Industry Co., Ltd.
- Anthraquinone dye D C.I. I. Solvent Violet 13
- trade name "Plast Vilet 8840 manufactured by Arimoto Chemical Industry Co., Ltd.
- Anthraquinone dye E C.I. I. Solvent Violet 36, trade name "Plast Vilet 8855", manufactured by Arimoto Chemical Co., Ltd.
- Perinone dye A C.I. I. Solvent Red 179, trade name “Plast Red 8370”, manufactured by Arimoto Chemical Industry Co., Ltd.
- Titanium oxide average primary particle size 0.15 ⁇ m, anatase type
- a masterbatch with a carbon black concentration of 5% is blended with PET (homo PET, trade name "MA-2103", manufactured by Unitika) at 20 times and 71.4 times (both based on mass), and biaxially. They were kneaded at 260 to 280° C. using an extruder to obtain resin compositions RC-1 to RC-16, 18 and 19 in the form of pellets.
- PET homo PET, trade name "MA-2103", manufactured by Unitika
- the masterbatch of the present invention is suitable as a material for easily producing a high-quality polyester resin molding.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention provides a master batch that is capable of producing a resin composition in which crystallization of a polyester resin is delayed even if a filler is contained therein, and which is capable of producing a polyester resin molded body that has excellent appearance and excellent appearance quality such as surface gloss. A master batch which is used for the purpose of producing a resin molded body that is mainly formed of a polyester resin. This master batch contains a polyester base resin and a filler, while satisfying the condition (1) described below. Condition (1): The master batch additionally contains a copper phthalocyanine dye; and the content of the copper phthalocyanine dye is from 3 to 200 parts by mass relative to 100 parts by mass of the filler.
Description
本発明は、マスターバッチ、樹脂組成物、及び樹脂成形体に関する。
The present invention relates to masterbatches, resin compositions, and resin moldings.
ポリエチレンテレフタレート等のポリエステル樹脂は、化学的及び物理的に優れた性質を有するため、従来、フィルム、シート等の各種成形体を製造するための工業材料として広く利用されている。例えば、ポリエチレンテレフタレートやポリブチレンテレフタレート等の熱可塑性樹脂及びカーボンブラック等の充填剤を含有する樹脂組成物、並びに、この樹脂組成物を成形して得られる成形体等が知られている（特許文献１）。
Because polyester resins such as polyethylene terephthalate have excellent chemical and physical properties, they have been widely used as industrial materials for manufacturing various molded products such as films and sheets. For example, resin compositions containing thermoplastic resins such as polyethylene terephthalate and polybutylene terephthalate and fillers such as carbon black, and molded articles obtained by molding these resin compositions are known (Patent Documents 1).
但し、一般的なポリエステル樹脂は結晶性を有するため、カーボンをはじめとする各種の充填剤を配合すると充填剤が結晶核として機能し、結晶化温度が上昇するといった現象（結晶化促進）が生じやすい。結晶化温度が上昇すると、溶融した樹脂組成物を所定形状に成形した後に速やかに固化させることができるので、製造効率の観点からは有用である場合もある。しかしながら、固化する速度が速すぎると、得られる成形体の外観や表面光沢が必ずしも良好にはならないといった課題があった。また、固化する速度が速いと、成形体の種類によっては想定通りのものが得られないといった懸念もある。例えば、成形体が複雑な構造を有する場合、溶融した樹脂組成物を型注入する途中で固化が開始しやすく、目的の成形体を得ることが困難になることが考えられる。これに対して、結晶化温度が低下すれば、固化する速度も遅くなって樹脂組成物の流動性を担保することができるので、成形体の構造が複雑であっても樹脂組成物が途中で固化しにくく、目的の成形体を得ることができる。このため、各種の充填剤を含有する結晶性樹脂の結晶化温度を低下させる、いわゆる結晶化遅延させたいとする要望があった。
However, since general polyester resins have crystallinity, when various fillers such as carbon are mixed, the fillers function as crystal nuclei, causing a phenomenon (crystallization acceleration) in which the crystallization temperature rises. Cheap. When the crystallization temperature rises, the molten resin composition can be molded into a predetermined shape and then rapidly solidified, which is sometimes useful from the viewpoint of production efficiency. However, if the solidification speed is too fast, there is a problem that the external appearance and surface gloss of the obtained molded article are not always good. Moreover, if the solidification speed is high, there is also a concern that depending on the type of molded product, the desired product cannot be obtained. For example, when the molded article has a complicated structure, solidification is likely to start during injection of the molten resin composition into the mold, which may make it difficult to obtain the intended molded article. On the other hand, when the crystallization temperature is lowered, the solidification speed is lowered and the fluidity of the resin composition can be ensured. It is hard to solidify, and the desired molded article can be obtained. Therefore, there has been a demand to lower the crystallization temperature of crystalline resins containing various fillers, that is, to delay crystallization.
結晶性樹脂の結晶化を遅延させる（結晶化温度を低下させる）技術として、例えば、染料の一種であるニグロシン系化合物をポリアミド樹脂等の結晶性樹脂に配合した樹脂組成物が提案されている（特許文献２）。
As a technique for delaying the crystallization of crystalline resins (lowering the crystallization temperature), for example, a resin composition in which a nigrosine compound, which is a type of dye, is blended with a crystalline resin such as a polyamide resin has been proposed ( Patent document 2).
しかしながら、本発明者が検討したところ、特許文献２で提案されたニグロシン系化合物はポリアミド樹脂の結晶化を遅延させることが可能である一方で、ポリアミド樹脂以外の樹脂の結晶化を遅延させることは困難であることがわかった。
However, as a result of examination by the present inventor, while the nigrosine compound proposed in Patent Document 2 can delay the crystallization of polyamide resins, it is not possible to delay the crystallization of resins other than polyamide resins. proved difficult.
本発明は、このような従来技術の有する問題点に鑑みてなされたものであり、その課題とするところは、充填剤を含有しながらもポリエステル樹脂の結晶化が遅延されており、外観や表面光沢等の品位に優れたポリエステル樹脂製の樹脂成形体を製造しうる樹脂組成物を製造することが可能なマスターバッチを提供することにある。
The present invention has been made in view of the problems of the prior art, and the object thereof is to delay the crystallization of the polyester resin while containing a filler, thereby improving the appearance and surface of the resin. The object of the present invention is to provide a masterbatch capable of producing a resin composition capable of producing a polyester resin molded article having excellent quality such as gloss.
また、本発明の課題とするところは、充填剤を含有しながらもポリエステル樹脂の結晶化が遅延されており、外観や表面光沢等の品位に優れたポリエステル樹脂製の樹脂成形体を製造しうる樹脂組成物、及びこの樹脂組成物の成形物である樹脂成形体を提供することにある。
In addition, the subject of the present invention is that the crystallization of the polyester resin is delayed even though it contains a filler, and it is possible to produce a resin molded product made of a polyester resin having excellent quality such as appearance and surface gloss. An object of the present invention is to provide a resin composition and a resin molded article that is a molded product of the resin composition.
すなわち、本発明によれば、以下に示すマスターバッチが提供される。
［１］ポリエステル樹脂を主体とする樹脂成形体を製造するために用いられるマスターバッチであって、ポリエステル系のベース樹脂及び充填剤を含有し、下記条件（１）を満たすマスターバッチ。
条件（１）：銅フタロシアニン系染料をさらに含有し、前記充填剤１００質量部に対する、前記銅フタロシアニン系染料の含有量が、３～２００質量部である。
［２］さらに、下記条件（２）を満たす前記［１］に記載のマスターバッチ。
条件（２）：前記ベース樹脂が、非晶性ポリエチレンテレフタレート及び共重合ポリエステルからなる群より選択される少なくとも一種を含む。
［３］前記銅フタロシアニン系染料が、Ｃ．Ｉ．ソルベントブルー６７、Ｃ．Ｉ．ソルベントブルー７０、及びＣ．Ｉ．ソルベントブルー４４からなる群より選択される少なくとも一種である前記［１］又は［２］に記載のマスターバッチ。
［４］前記充填剤が、カーボンブラック、粘土鉱物、金属酸化物、無機酸塩、及び有機酸塩からなる群より選択される少なくとも一種である前記［１］～［３］のいずれかに記載のマスターバッチ。
［５］前記共重合ポリエステルが、テレフタル酸及びイソフタル酸を含むジカルボン酸成分と、エチレングリコール、１，３－プロパンジオール、１，４－ブタンジオール、及び１，４－シクロヘキサンジメタノールからなる群より選択される少なくとも一種のジオール成分と、の共重合体である前記［２］～［４］のいずれかに記載のマスターバッチ。
［６］前記充填剤の含有量が、３～４０質量％である前記［１］～［５］のいずれかに記載のマスターバッチ。 That is, according to the present invention, the following masterbatch is provided.
[1] A masterbatch that is used for producing a resin molding mainly composed of polyester resin, contains a polyester base resin and a filler, and satisfies the following condition (1).
Condition (1): A copper phthalocyanine dye is further contained, and the content of the copper phthalocyanine dye is 3 to 200 parts by mass with respect to 100 parts by mass of the filler.
[2] The masterbatch according to [1], which further satisfies the following condition (2).
Condition (2): The base resin contains at least one selected from the group consisting of amorphous polyethylene terephthalate and copolyester.
[3] The copper phthalocyanine dye is C.I. I. Solvent Blue 67, C.I. I. Solvent Blue 70, and C.I. I. The masterbatch according to the above [1] or [2], which is at least one selected from the group consisting of Solvent Blue 44.
[4] Any one of [1] to [3] above, wherein the filler is at least one selected from the group consisting of carbon black, clay minerals, metal oxides, inorganic acid salts, and organic acid salts. masterbatch.
[5] The copolymer polyester is selected from the group consisting of a dicarboxylic acid component containing terephthalic acid and isophthalic acid, and ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,4-cyclohexanedimethanol The masterbatch according to any one of the above [2] to [4], which is a copolymer of at least one selected diol component.
[6] The masterbatch according to any one of [1] to [5], wherein the content of the filler is 3 to 40% by mass.
［１］ポリエステル樹脂を主体とする樹脂成形体を製造するために用いられるマスターバッチであって、ポリエステル系のベース樹脂及び充填剤を含有し、下記条件（１）を満たすマスターバッチ。
条件（１）：銅フタロシアニン系染料をさらに含有し、前記充填剤１００質量部に対する、前記銅フタロシアニン系染料の含有量が、３～２００質量部である。
［２］さらに、下記条件（２）を満たす前記［１］に記載のマスターバッチ。
条件（２）：前記ベース樹脂が、非晶性ポリエチレンテレフタレート及び共重合ポリエステルからなる群より選択される少なくとも一種を含む。
［３］前記銅フタロシアニン系染料が、Ｃ．Ｉ．ソルベントブルー６７、Ｃ．Ｉ．ソルベントブルー７０、及びＣ．Ｉ．ソルベントブルー４４からなる群より選択される少なくとも一種である前記［１］又は［２］に記載のマスターバッチ。
［４］前記充填剤が、カーボンブラック、粘土鉱物、金属酸化物、無機酸塩、及び有機酸塩からなる群より選択される少なくとも一種である前記［１］～［３］のいずれかに記載のマスターバッチ。
［５］前記共重合ポリエステルが、テレフタル酸及びイソフタル酸を含むジカルボン酸成分と、エチレングリコール、１，３－プロパンジオール、１，４－ブタンジオール、及び１，４－シクロヘキサンジメタノールからなる群より選択される少なくとも一種のジオール成分と、の共重合体である前記［２］～［４］のいずれかに記載のマスターバッチ。
［６］前記充填剤の含有量が、３～４０質量％である前記［１］～［５］のいずれかに記載のマスターバッチ。 That is, according to the present invention, the following masterbatch is provided.
[1] A masterbatch that is used for producing a resin molding mainly composed of polyester resin, contains a polyester base resin and a filler, and satisfies the following condition (1).
Condition (1): A copper phthalocyanine dye is further contained, and the content of the copper phthalocyanine dye is 3 to 200 parts by mass with respect to 100 parts by mass of the filler.
[2] The masterbatch according to [1], which further satisfies the following condition (2).
Condition (2): The base resin contains at least one selected from the group consisting of amorphous polyethylene terephthalate and copolyester.
[3] The copper phthalocyanine dye is C.I. I. Solvent Blue 67, C.I. I. Solvent Blue 70, and C.I. I. The masterbatch according to the above [1] or [2], which is at least one selected from the group consisting of Solvent Blue 44.
[4] Any one of [1] to [3] above, wherein the filler is at least one selected from the group consisting of carbon black, clay minerals, metal oxides, inorganic acid salts, and organic acid salts. masterbatch.
[5] The copolymer polyester is selected from the group consisting of a dicarboxylic acid component containing terephthalic acid and isophthalic acid, and ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,4-cyclohexanedimethanol The masterbatch according to any one of the above [2] to [4], which is a copolymer of at least one selected diol component.
[6] The masterbatch according to any one of [1] to [5], wherein the content of the filler is 3 to 40% by mass.
また、本発明によれば、以下に示す樹脂組成物が提供される。
［７］ポリエステル樹脂を主体とする樹脂成形体を製造するための樹脂組成物であって、ポリエステル系の原料樹脂と、前記［１］～［６］のいずれかに記載のマスターバッチと、を含有する樹脂組成物。 Moreover, according to this invention, the resin composition shown below is provided.
[7] A resin composition for producing a resin molding mainly composed of a polyester resin, comprising a polyester-based raw material resin and the masterbatch according to any one of [1] to [6] above. containing resin composition;
［７］ポリエステル樹脂を主体とする樹脂成形体を製造するための樹脂組成物であって、ポリエステル系の原料樹脂と、前記［１］～［６］のいずれかに記載のマスターバッチと、を含有する樹脂組成物。 Moreover, according to this invention, the resin composition shown below is provided.
[7] A resin composition for producing a resin molding mainly composed of a polyester resin, comprising a polyester-based raw material resin and the masterbatch according to any one of [1] to [6] above. containing resin composition;
さらに、本発明によれば、以下に示す樹脂成形体が提供される。
［８］前記［７］に記載の樹脂組成物の成形物である樹脂成形体。 Furthermore, according to the present invention, the following resin molding is provided.
[8] A resin molded product, which is a molded product of the resin composition according to [7].
［８］前記［７］に記載の樹脂組成物の成形物である樹脂成形体。 Furthermore, according to the present invention, the following resin molding is provided.
[8] A resin molded product, which is a molded product of the resin composition according to [7].
本発明によれば、充填剤を含有しながらもポリエステル樹脂の結晶化が遅延されており、外観や表面光沢等の品位に優れたポリエステル樹脂製の樹脂成形体を製造しうる樹脂組成物を製造することが可能なマスターバッチを提供することができる。
INDUSTRIAL APPLICABILITY According to the present invention, a resin composition is produced in which crystallization of a polyester resin is delayed while a filler is contained, and a resin molded article made of a polyester resin having excellent quality such as appearance and surface gloss can be produced. It is possible to provide a masterbatch that can be
また、本発明によれば、充填剤を含有しながらもポリエステル樹脂の結晶化が遅延されており、外観や表面光沢等の品位に優れたポリエステル樹脂製の樹脂成形体を製造しうる樹脂組成物、及びこの樹脂組成物の成形物である樹脂成形体を提供することができる。
In addition, according to the present invention, the resin composition has a retarded crystallization of the polyester resin even though it contains a filler, and can produce a resin molded article made of a polyester resin having excellent quality such as appearance and surface gloss. , and a resin molding that is a molding of this resin composition.
＜マスターバッチ＞
以下、本発明の実施の形態について説明するが、本発明は以下の実施の形態に限定されるものではない。本発明のマスターバッチの一実施形態は、ポリエステル樹脂を主体とする樹脂成形体を製造するために用いられるマスターバッチであり、ポリエステル系のベース樹脂及び充填剤を含有する。そして、本実施形態のマスターバッチは、下記条件（１）及び（２）の少なくともいずれかを満たす。以下、本実施形態のマスターバッチの詳細について説明する。
条件（１）：銅フタロシアニン系染料をさらに含有し、充填剤１００質量部に対する、銅フタロシアニン系染料の含有量が、３～２００質量部である。
条件（２）：ベース樹脂が、非晶性ポリエチレンテレフタレート及び共重合ポリエステルからなる群より選択される少なくとも一種を含む。 <Masterbatch>
Embodiments of the present invention will be described below, but the present invention is not limited to the following embodiments. One embodiment of the masterbatch of the present invention is a masterbatch that is used for producing a resin molded article mainly composed of a polyester resin, and contains a polyester-based base resin and a filler. And the masterbatch of this embodiment satisfies at least one of the following conditions (1) and (2). Details of the masterbatch of the present embodiment will be described below.
Condition (1): A copper phthalocyanine dye is further contained, and the content of the copper phthalocyanine dye is 3 to 200 parts by mass with respect to 100 parts by mass of the filler.
Condition (2): The base resin contains at least one selected from the group consisting of amorphous polyethylene terephthalate and copolyester.
以下、本発明の実施の形態について説明するが、本発明は以下の実施の形態に限定されるものではない。本発明のマスターバッチの一実施形態は、ポリエステル樹脂を主体とする樹脂成形体を製造するために用いられるマスターバッチであり、ポリエステル系のベース樹脂及び充填剤を含有する。そして、本実施形態のマスターバッチは、下記条件（１）及び（２）の少なくともいずれかを満たす。以下、本実施形態のマスターバッチの詳細について説明する。
条件（１）：銅フタロシアニン系染料をさらに含有し、充填剤１００質量部に対する、銅フタロシアニン系染料の含有量が、３～２００質量部である。
条件（２）：ベース樹脂が、非晶性ポリエチレンテレフタレート及び共重合ポリエステルからなる群より選択される少なくとも一種を含む。 <Masterbatch>
Embodiments of the present invention will be described below, but the present invention is not limited to the following embodiments. One embodiment of the masterbatch of the present invention is a masterbatch that is used for producing a resin molded article mainly composed of a polyester resin, and contains a polyester-based base resin and a filler. And the masterbatch of this embodiment satisfies at least one of the following conditions (1) and (2). Details of the masterbatch of the present embodiment will be described below.
Condition (1): A copper phthalocyanine dye is further contained, and the content of the copper phthalocyanine dye is 3 to 200 parts by mass with respect to 100 parts by mass of the filler.
Condition (2): The base resin contains at least one selected from the group consisting of amorphous polyethylene terephthalate and copolyester.
（ベース樹脂）
ベース樹脂としては、ポリエステル系の樹脂を用いる。ポリエステル系の樹脂は、通常、芳香族ジカルボン酸に由来する構成単位、及びアルキレンジオールに由来する構成単位を有する樹脂である。ベース樹脂として用いるポリエステル系の樹脂の具体例としては、ポリエチレンテレフタレート（ＰＥＴ）、ポリトリメチレンテレフタレート（ＰＴＴ）、ポリブチレンテレフタレート（ＰＢＴ）、ポリエチレンナフタレート（ＰＥＮ）、及びポリブチレンナフタレート（ＰＢＮ）等を挙げることができる。なかでも、ポリエチレンテレフタレート（ＰＥＴ（ホモＰＥＴ））が好ましい。 (base resin)
A polyester-based resin is used as the base resin. A polyester-based resin is generally a resin having structural units derived from an aromatic dicarboxylic acid and structural units derived from an alkylenediol. Specific examples of polyester-based resins used as base resins include polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and polybutylene naphthalate (PBN). etc. can be mentioned. Among them, polyethylene terephthalate (PET (homo PET)) is preferable.
ベース樹脂としては、ポリエステル系の樹脂を用いる。ポリエステル系の樹脂は、通常、芳香族ジカルボン酸に由来する構成単位、及びアルキレンジオールに由来する構成単位を有する樹脂である。ベース樹脂として用いるポリエステル系の樹脂の具体例としては、ポリエチレンテレフタレート（ＰＥＴ）、ポリトリメチレンテレフタレート（ＰＴＴ）、ポリブチレンテレフタレート（ＰＢＴ）、ポリエチレンナフタレート（ＰＥＮ）、及びポリブチレンナフタレート（ＰＢＮ）等を挙げることができる。なかでも、ポリエチレンテレフタレート（ＰＥＴ（ホモＰＥＴ））が好ましい。 (base resin)
A polyester-based resin is used as the base resin. A polyester-based resin is generally a resin having structural units derived from an aromatic dicarboxylic acid and structural units derived from an alkylenediol. Specific examples of polyester-based resins used as base resins include polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and polybutylene naphthalate (PBN). etc. can be mentioned. Among them, polyethylene terephthalate (PET (homo PET)) is preferable.
（充填剤）
充填剤としては、通常、ベース樹脂の結晶化温度を上昇させる結晶核として機能しうるものを用いる。このような充填剤としては、カーボンブラック、酸化チタン等の顔料の他、一般的な樹脂組成物に配合される無機物質や無機化合物等を用いることができる。充填剤としては、カーボンブラック、粘土鉱物、金属酸化物、無機酸塩、及び有機酸塩等を挙げることができる。これらの充填剤は、１種単独で又は２種以上を組み合わせて用いることができる。粘土鉱物としては、タルク、クレー等を挙げることができる。金属酸化物としては、酸化チタン、酸化亜鉛、アルミナ等を挙げることができる。無機酸塩としては、各種金属の炭酸塩、ケイ酸塩、硫酸塩等を挙げることができる。また、有機酸塩としては、各種金属のカルボン酸塩、有機リン酸塩等を挙げることができる。なかでも、充填剤としてはカーボンブラックが好ましい。カーボンブラックは、市販品として入手可能なものを用いることができる。製法によって異なる特徴を有する、ファーネスブラック、チャンネルブラック、アセチレンブラック、及びサーマルブラックのいずれであっても用いることができる。 (filler)
A filler that can function as a crystal nucleus that raises the crystallization temperature of the base resin is usually used as the filler. Examples of such fillers include pigments such as carbon black and titanium oxide, as well as inorganic substances and inorganic compounds that are blended in general resin compositions. Examples of fillers include carbon black, clay minerals, metal oxides, inorganic acid salts, and organic acid salts. These fillers can be used individually by 1 type or in combination of 2 or more types. Examples of clay minerals include talc and clay. Examples of metal oxides include titanium oxide, zinc oxide, and alumina. Examples of inorganic acid salts include carbonates, silicates, and sulfates of various metals. Examples of organic acid salts include carboxylates of various metals and organic phosphates. Among them, carbon black is preferable as the filler. Commercially available carbon black can be used. Furnace black, channel black, acetylene black, and thermal black, which have different characteristics depending on the manufacturing method, can be used.
充填剤としては、通常、ベース樹脂の結晶化温度を上昇させる結晶核として機能しうるものを用いる。このような充填剤としては、カーボンブラック、酸化チタン等の顔料の他、一般的な樹脂組成物に配合される無機物質や無機化合物等を用いることができる。充填剤としては、カーボンブラック、粘土鉱物、金属酸化物、無機酸塩、及び有機酸塩等を挙げることができる。これらの充填剤は、１種単独で又は２種以上を組み合わせて用いることができる。粘土鉱物としては、タルク、クレー等を挙げることができる。金属酸化物としては、酸化チタン、酸化亜鉛、アルミナ等を挙げることができる。無機酸塩としては、各種金属の炭酸塩、ケイ酸塩、硫酸塩等を挙げることができる。また、有機酸塩としては、各種金属のカルボン酸塩、有機リン酸塩等を挙げることができる。なかでも、充填剤としてはカーボンブラックが好ましい。カーボンブラックは、市販品として入手可能なものを用いることができる。製法によって異なる特徴を有する、ファーネスブラック、チャンネルブラック、アセチレンブラック、及びサーマルブラックのいずれであっても用いることができる。 (filler)
A filler that can function as a crystal nucleus that raises the crystallization temperature of the base resin is usually used as the filler. Examples of such fillers include pigments such as carbon black and titanium oxide, as well as inorganic substances and inorganic compounds that are blended in general resin compositions. Examples of fillers include carbon black, clay minerals, metal oxides, inorganic acid salts, and organic acid salts. These fillers can be used individually by 1 type or in combination of 2 or more types. Examples of clay minerals include talc and clay. Examples of metal oxides include titanium oxide, zinc oxide, and alumina. Examples of inorganic acid salts include carbonates, silicates, and sulfates of various metals. Examples of organic acid salts include carboxylates of various metals and organic phosphates. Among them, carbon black is preferable as the filler. Commercially available carbon black can be used. Furnace black, channel black, acetylene black, and thermal black, which have different characteristics depending on the manufacturing method, can be used.
マスターバッチ中の充填剤の含有量は、マスターバッチ全質量を基準として、３～４０質量％であることが好ましく、４～３０質量％であることがさらに好ましく、４．５～２５質量％であることが特に好ましい。
The content of the filler in the masterbatch is preferably 3 to 40% by mass, more preferably 4 to 30% by mass, more preferably 4.5 to 25% by mass, based on the total mass of the masterbatch. It is particularly preferred to have
（条件（１）及び（２））
本実施形態のマスターバッチは、下記条件（１）及び（２）の少なくともいずれかを満たす。なお、本実施形態のマスターバッチは、下記条件（１）及び（２）の両方を満たすことが好ましい。下記条件（１）及び（２）の両方を満たすことで、相乗的な効果が発揮されるため、ポリエステル樹脂の結晶化がさらに遅延され、より品位が向上したポリエステル樹脂製の樹脂成形体を製造しうる樹脂組成物を製造することができる。
条件（１）：銅フタロシアニン系染料をさらに含有し、充填剤１００質量部に対する、銅フタロシアニン系染料の含有量が、３～２００質量部である。
条件（２）：ベース樹脂が、非晶性ポリエチレンテレフタレート及び共重合ポリエステルからなる群より選択される少なくとも一種を含む。 (Conditions (1) and (2))
The masterbatch of this embodiment satisfies at least one of the following conditions (1) and (2). The masterbatch of the present embodiment preferably satisfies both the following conditions (1) and (2). By satisfying both the following conditions (1) and (2), a synergistic effect is exhibited, so the crystallization of the polyester resin is further delayed, and a resin molded product made of polyester resin with improved quality is produced. A resin composition that can be manufactured can be produced.
Condition (1): A copper phthalocyanine dye is further contained, and the content of the copper phthalocyanine dye is 3 to 200 parts by mass with respect to 100 parts by mass of the filler.
Condition (2): The base resin contains at least one selected from the group consisting of amorphous polyethylene terephthalate and copolyester.
本実施形態のマスターバッチは、下記条件（１）及び（２）の少なくともいずれかを満たす。なお、本実施形態のマスターバッチは、下記条件（１）及び（２）の両方を満たすことが好ましい。下記条件（１）及び（２）の両方を満たすことで、相乗的な効果が発揮されるため、ポリエステル樹脂の結晶化がさらに遅延され、より品位が向上したポリエステル樹脂製の樹脂成形体を製造しうる樹脂組成物を製造することができる。
条件（１）：銅フタロシアニン系染料をさらに含有し、充填剤１００質量部に対する、銅フタロシアニン系染料の含有量が、３～２００質量部である。
条件（２）：ベース樹脂が、非晶性ポリエチレンテレフタレート及び共重合ポリエステルからなる群より選択される少なくとも一種を含む。 (Conditions (1) and (2))
The masterbatch of this embodiment satisfies at least one of the following conditions (1) and (2). The masterbatch of the present embodiment preferably satisfies both the following conditions (1) and (2). By satisfying both the following conditions (1) and (2), a synergistic effect is exhibited, so the crystallization of the polyester resin is further delayed, and a resin molded product made of polyester resin with improved quality is produced. A resin composition that can be manufactured can be produced.
Condition (1): A copper phthalocyanine dye is further contained, and the content of the copper phthalocyanine dye is 3 to 200 parts by mass with respect to 100 parts by mass of the filler.
Condition (2): The base resin contains at least one selected from the group consisting of amorphous polyethylene terephthalate and copolyester.
［条件（１）］
銅フタロシアニン系染料を含有させることで、充填剤を含有しながらも、ベース樹脂として用いるポリエステル樹脂の結晶化を遅延させる（結晶化温度を低下させる）ことができる。銅フタロシアニン系染料は、ポリエステル系の樹脂中に溶解しうる染料である。銅フタロシアニン系染料としては、Ｃ．Ｉ．ソルベントブルー６７、Ｃ．Ｉ．ソルベントブルー７０、及びＣ．Ｉ．ソルベントブルー４４等を挙げることができる。これらの銅フタロシアニン系染料は、１種単独で又は２種以上を組み合わせて用いることができる。なかでも、Ｃ．Ｉ．ソルベントブルー６７を用いることが、ポリエステル樹脂の結晶化をより遅延させることができるために好ましい。 [Condition (1)]
By containing the copper phthalocyanine-based dye, it is possible to delay the crystallization of the polyester resin used as the base resin (lower the crystallization temperature) while containing the filler. Copper phthalocyanine-based dyes are dyes that can be dissolved in polyester-based resins. Copper phthalocyanine dyes include C.I. I. Solvent Blue 67, C.I. I. Solvent Blue 70, and C.I. I. Solvent Blue 44 and the like can be mentioned. These copper phthalocyanine dyes can be used singly or in combination of two or more. Among them, C.I. I. Solvent Blue 67 is preferably used because it can further delay the crystallization of the polyester resin.
銅フタロシアニン系染料を含有させることで、充填剤を含有しながらも、ベース樹脂として用いるポリエステル樹脂の結晶化を遅延させる（結晶化温度を低下させる）ことができる。銅フタロシアニン系染料は、ポリエステル系の樹脂中に溶解しうる染料である。銅フタロシアニン系染料としては、Ｃ．Ｉ．ソルベントブルー６７、Ｃ．Ｉ．ソルベントブルー７０、及びＣ．Ｉ．ソルベントブルー４４等を挙げることができる。これらの銅フタロシアニン系染料は、１種単独で又は２種以上を組み合わせて用いることができる。なかでも、Ｃ．Ｉ．ソルベントブルー６７を用いることが、ポリエステル樹脂の結晶化をより遅延させることができるために好ましい。 [Condition (1)]
By containing the copper phthalocyanine-based dye, it is possible to delay the crystallization of the polyester resin used as the base resin (lower the crystallization temperature) while containing the filler. Copper phthalocyanine-based dyes are dyes that can be dissolved in polyester-based resins. Copper phthalocyanine dyes include C.I. I. Solvent Blue 67, C.I. I. Solvent Blue 70, and C.I. I. Solvent Blue 44 and the like can be mentioned. These copper phthalocyanine dyes can be used singly or in combination of two or more. Among them, C.I. I. Solvent Blue 67 is preferably used because it can further delay the crystallization of the polyester resin.
マスターバッチが銅フタロシアニン系染料を含有する場合、マスターバッチ中の銅フタロシアニン系染料の含有量は、充填剤１００質量部に対して、３～２００質量部であることが好ましく、１０～１００質量部であることがさらに好ましく、３０～１００質量部であることが特に好ましい。銅フタロシアニン系染料の含有量が少なすぎると、結晶化遅延効果が不十分になることがある。一方、銅フタロシアニン系染料の含有量を過剰にすると、結晶化遅延効果が頭打ちになるとともに、コスト面で不利になる場合がある。
When the masterbatch contains a copper phthalocyanine dye, the content of the copper phthalocyanine dye in the masterbatch is preferably 3 to 200 parts by mass, preferably 10 to 100 parts by mass, relative to 100 parts by mass of the filler. is more preferable, and 30 to 100 parts by mass is particularly preferable. If the content of the copper phthalocyanine dye is too small, the crystallization retarding effect may be insufficient. On the other hand, if the content of the copper phthalocyanine-based dye is excessive, the effect of retarding crystallization reaches a ceiling, and the cost may be disadvantageous.
［条件（２）］
非晶性ポリエチレンテレフタレート（非晶性ＰＥＴ）は、結晶化温度を実質的に有しないポリエチレンテレフタレート（ＰＥＴ）であり、いわゆる「ＰＥＴ－Ｇ」がある。ＰＥＴ－Ｇは、ＰＥＴ中のエチレングリコール単位の一部（例えば、３０～４０モル％程度）をシクロエヘキサンンジメタノール単位で置き換えた非晶性ＰＥＴである。このような非晶性ＰＥＴを用いることで、充填剤を含有しながらも、ベース樹脂の結晶化を遅延させる（結晶化温度を低下させる）ことができる。 [Condition (2)]
Amorphous polyethylene terephthalate (amorphous PET) is polyethylene terephthalate (PET) that does not substantially have a crystallization temperature, and there is so-called "PET-G". PET-G is amorphous PET in which part of the ethylene glycol units (for example, about 30 to 40 mol %) in PET are replaced with cycloehexanedimethanol units. By using such amorphous PET, it is possible to delay the crystallization of the base resin (lower the crystallization temperature) while containing the filler.
非晶性ポリエチレンテレフタレート（非晶性ＰＥＴ）は、結晶化温度を実質的に有しないポリエチレンテレフタレート（ＰＥＴ）であり、いわゆる「ＰＥＴ－Ｇ」がある。ＰＥＴ－Ｇは、ＰＥＴ中のエチレングリコール単位の一部（例えば、３０～４０モル％程度）をシクロエヘキサンンジメタノール単位で置き換えた非晶性ＰＥＴである。このような非晶性ＰＥＴを用いることで、充填剤を含有しながらも、ベース樹脂の結晶化を遅延させる（結晶化温度を低下させる）ことができる。 [Condition (2)]
Amorphous polyethylene terephthalate (amorphous PET) is polyethylene terephthalate (PET) that does not substantially have a crystallization temperature, and there is so-called "PET-G". PET-G is amorphous PET in which part of the ethylene glycol units (for example, about 30 to 40 mol %) in PET are replaced with cycloehexanedimethanol units. By using such amorphous PET, it is possible to delay the crystallization of the base resin (lower the crystallization temperature) while containing the filler.
共重合ポリエステルは、ポリエチレンテレフタレート（ＰＥＴ）中の構成単位（テレフタル酸単位及びエチレングリコール単位）の少なくとも一部を、他の構成単位に置き換えた樹脂である。共重合ポリエステルとしては、テレフタル酸及びイソフタル酸を含むジカルボン酸成分と、エチレングリコール、１，３－プロパンジオール、１，４－ブタンジオール、及び１，４－シクロヘキサンジメタノールからなる群より選択される少なくとも一種のジオール成分との共重合体を用いることが好ましい。この共重合ポリエステルを用いることで、充填剤を含有しながらも、ベース樹脂の結晶化を遅延させる（結晶化温度を低下させる）ことができる。
Copolyester is a resin in which at least some of the structural units (terephthalic acid units and ethylene glycol units) in polyethylene terephthalate (PET) are replaced with other structural units. The copolymer polyester is selected from the group consisting of dicarboxylic acid components including terephthalic acid and isophthalic acid, and ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,4-cyclohexanedimethanol. It is preferred to use a copolymer with at least one diol component. By using this copolyester, it is possible to delay the crystallization of the base resin (lower the crystallization temperature) while containing the filler.
ベース樹脂は、非晶性ポリエチレンテレフタレート及び共重合ポリエステルの両方を含むことが好ましい。さらに、非晶性ポリエチレンテレフタレート及び共重合ポリエステルのみを実質的にベース樹脂とすることが、結晶化遅延効果をより向上させることができるために好ましい。
The base resin preferably contains both amorphous polyethylene terephthalate and copolyester. Furthermore, it is preferable to use substantially only amorphous polyethylene terephthalate and copolyester as the base resin because the crystallization retarding effect can be further improved.
（その他の成分）
本実施形態のマスターバッチには、本発明の目的を損なわない限り、必要に応じて、上述の各成分以外のその他の成分を含有させることができる。その他の成分としては、例えば、酸化防止剤、紫外線吸収剤、光安定剤、帯電防止剤、導電性付与剤、離型剤、潤滑剤、染料（前述の銅フタロシアニン系染料を除く）、及び顔料（前述の充填剤を除く）等を挙げることができる。 (other ingredients)
The masterbatch of the present embodiment can contain other components other than the components described above, if necessary, as long as the object of the present invention is not impaired. Other components include, for example, antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, conductivity-imparting agents, release agents, lubricants, dyes (excluding the above-mentioned copper phthalocyanine dyes), and pigments. (excluding the above-mentioned fillers) and the like.
本実施形態のマスターバッチには、本発明の目的を損なわない限り、必要に応じて、上述の各成分以外のその他の成分を含有させることができる。その他の成分としては、例えば、酸化防止剤、紫外線吸収剤、光安定剤、帯電防止剤、導電性付与剤、離型剤、潤滑剤、染料（前述の銅フタロシアニン系染料を除く）、及び顔料（前述の充填剤を除く）等を挙げることができる。 (other ingredients)
The masterbatch of the present embodiment can contain other components other than the components described above, if necessary, as long as the object of the present invention is not impaired. Other components include, for example, antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, conductivity-imparting agents, release agents, lubricants, dyes (excluding the above-mentioned copper phthalocyanine dyes), and pigments. (excluding the above-mentioned fillers) and the like.
（マスターバッチの製造方法）
本実施形態のマスターバッチは、例えば、前述の各成分を溶融混練して製造することができる。溶融混練の方法は特に限定されず、従来公知の溶融混練方法を採用することができる。具体的には、ヘンシェルミキサー等の高速ミキサーやタンブラー等の各種混合機を使用して各成分を予め混合した後、バンバリーミキサー、ロール、プラストグラフ、単軸押出機、二軸押出機、及びニーダー等の混練装置で溶融混練する方法を挙げることができる。なかでも、押出機を使用して各成分を溶融混練することが、生産効率を高めることができるために好ましい。また、押出機としては二軸押出機を用いることが好ましい。押出機などの混練装置を使用して各成分を溶融混練するとともに、混練物をストランド状に押し出した後、ストランド状に押し出された混練物をペレット状やフレーク状等の所望とする形態に加工することができる。溶融混練時の温度は２００～３００℃とすることが好ましく、２６０～２８０℃とすることがさらに好ましい。 (Manufacturing method of masterbatch)
The masterbatch of the present embodiment can be produced, for example, by melt-kneading the components described above. The melt-kneading method is not particularly limited, and conventionally known melt-kneading methods can be employed. Specifically, after pre-mixing each component using a high-speed mixer such as a Henschel mixer or various mixers such as a tumbler, a Banbury mixer, a roll, a plastograph, a single-screw extruder, a twin-screw extruder, and a kneader A method of melt-kneading with a kneading device such as the above can be mentioned. Among them, it is preferable to melt-knead each component using an extruder because it can improve production efficiency. Moreover, it is preferable to use a twin-screw extruder as an extruder. Each component is melt-kneaded using a kneading device such as an extruder, and the kneaded product is extruded into a strand shape, and then the kneaded product extruded into a strand shape is processed into a desired shape such as pellets or flakes. can do. The temperature during melt-kneading is preferably 200 to 300°C, more preferably 260 to 280°C.
本実施形態のマスターバッチは、例えば、前述の各成分を溶融混練して製造することができる。溶融混練の方法は特に限定されず、従来公知の溶融混練方法を採用することができる。具体的には、ヘンシェルミキサー等の高速ミキサーやタンブラー等の各種混合機を使用して各成分を予め混合した後、バンバリーミキサー、ロール、プラストグラフ、単軸押出機、二軸押出機、及びニーダー等の混練装置で溶融混練する方法を挙げることができる。なかでも、押出機を使用して各成分を溶融混練することが、生産効率を高めることができるために好ましい。また、押出機としては二軸押出機を用いることが好ましい。押出機などの混練装置を使用して各成分を溶融混練するとともに、混練物をストランド状に押し出した後、ストランド状に押し出された混練物をペレット状やフレーク状等の所望とする形態に加工することができる。溶融混練時の温度は２００～３００℃とすることが好ましく、２６０～２８０℃とすることがさらに好ましい。 (Manufacturing method of masterbatch)
The masterbatch of the present embodiment can be produced, for example, by melt-kneading the components described above. The melt-kneading method is not particularly limited, and conventionally known melt-kneading methods can be employed. Specifically, after pre-mixing each component using a high-speed mixer such as a Henschel mixer or various mixers such as a tumbler, a Banbury mixer, a roll, a plastograph, a single-screw extruder, a twin-screw extruder, and a kneader A method of melt-kneading with a kneading device such as the above can be mentioned. Among them, it is preferable to melt-knead each component using an extruder because it can improve production efficiency. Moreover, it is preferable to use a twin-screw extruder as an extruder. Each component is melt-kneaded using a kneading device such as an extruder, and the kneaded product is extruded into a strand shape, and then the kneaded product extruded into a strand shape is processed into a desired shape such as pellets or flakes. can do. The temperature during melt-kneading is preferably 200 to 300°C, more preferably 260 to 280°C.
＜樹脂組成物＞
本発明の樹脂組成物の一実施形態は、ポリエステル樹脂を主体とする樹脂成形体を製造するための樹脂組成物であり、ポリエステル系の原料樹脂と、前述のマスターバッチとを含有する。このため、従来公知の方法にしたがって本実施形態の樹脂組成物を溶融させて所望とする形状に成形する場合に、充填剤を含有しながらも原料樹脂の結晶化が遅延されているので、外観や表面光沢等の品位に優れたポリエステル樹脂製の樹脂成形体を製造することができる。 <Resin composition>
One embodiment of the resin composition of the present invention is a resin composition for producing a resin molding mainly composed of a polyester resin, and contains a polyester-based raw material resin and the masterbatch described above. For this reason, when the resin composition of the present embodiment is melted and molded into a desired shape according to a conventionally known method, the crystallization of the raw material resin is delayed even though it contains a filler, so the appearance is improved. It is possible to produce a resin molding made of a polyester resin having excellent quality such as surface gloss and the like.
本発明の樹脂組成物の一実施形態は、ポリエステル樹脂を主体とする樹脂成形体を製造するための樹脂組成物であり、ポリエステル系の原料樹脂と、前述のマスターバッチとを含有する。このため、従来公知の方法にしたがって本実施形態の樹脂組成物を溶融させて所望とする形状に成形する場合に、充填剤を含有しながらも原料樹脂の結晶化が遅延されているので、外観や表面光沢等の品位に優れたポリエステル樹脂製の樹脂成形体を製造することができる。 <Resin composition>
One embodiment of the resin composition of the present invention is a resin composition for producing a resin molding mainly composed of a polyester resin, and contains a polyester-based raw material resin and the masterbatch described above. For this reason, when the resin composition of the present embodiment is melted and molded into a desired shape according to a conventionally known method, the crystallization of the raw material resin is delayed even though it contains a filler, so the appearance is improved. It is possible to produce a resin molding made of a polyester resin having excellent quality such as surface gloss and the like.
ポリエステル系の原料樹脂（希釈樹脂）としては、例えば、マスターバッチのベース樹脂として用いることができるポリエステル系の樹脂と同様のものを用いることができる。すなわち、原料樹脂としては、ＰＥＴ、ＰＴＴ、ＰＢＴ、ＰＥＮ、及びＰＢＮ等を挙げることができる。
As the polyester-based raw material resin (dilution resin), for example, the same polyester-based resin that can be used as the base resin of the masterbatch can be used. That is, PET, PTT, PBT, PEN, PBN, etc. can be mentioned as raw material resin.
樹脂組成物中の充填剤の含有量は、樹脂組成物の全質量を基準として、０．０３～２質量％であることが好ましく、０．０５～１．５質量％であることがさらに好ましい。すなわち、樹脂組成物中の充填剤の含有量が、好ましくは０．０３～２質量％、さらに好ましくは０．０５～１．５質量％となるように、原料樹脂とマスターバッチを混合（溶融混練）することが好ましい。
The content of the filler in the resin composition is preferably 0.03 to 2% by mass, more preferably 0.05 to 1.5% by mass, based on the total mass of the resin composition. . That is, the content of the filler in the resin composition is preferably 0.03 to 2% by mass, more preferably 0.05 to 1.5% by mass, mixing (melting) the raw material resin and the masterbatch kneading) is preferred.
樹脂組成物が非晶性ＰＥＴを含有する場合に、樹脂組成物中の非晶性ＰＥＴの含有量は、樹脂組成物の全質量を基準として、１～１０質量％であることが好ましく、２～８質量％であることがさらに好ましい。また、樹脂組成物が共重合ポリエステルを含有する場合に、樹脂組成物中の共重合ポリエステルの含有量は、樹脂組成物の全質量を基準として、１～１０質量％であることが好ましく、２～８質量％であることがさらに好ましい。
When the resin composition contains amorphous PET, the content of the amorphous PET in the resin composition is preferably 1 to 10% by mass based on the total mass of the resin composition. More preferably, it is up to 8% by mass. Further, when the resin composition contains a copolyester, the content of the copolyester in the resin composition is preferably 1 to 10% by mass based on the total mass of the resin composition. More preferably, it is up to 8% by mass.
＜樹脂成形体＞
本発明の樹脂成形体の一実施形態は、前述の樹脂組成物の成形物である。本実施形態の樹脂成形体は、前述のマスターバッチをポリエステル系の原料樹脂で希釈して得られる樹脂組成物によって形成されているため、より低い温度で結晶化しており、外観や表面光沢等の品位に優れている。 <Resin molding>
One embodiment of the resin molding of the present invention is a molding of the resin composition described above. Since the resin molded body of the present embodiment is formed of a resin composition obtained by diluting the above-described masterbatch with a polyester-based raw material resin, it crystallizes at a lower temperature, and has excellent appearance, surface gloss, etc. Excellent quality.
本発明の樹脂成形体の一実施形態は、前述の樹脂組成物の成形物である。本実施形態の樹脂成形体は、前述のマスターバッチをポリエステル系の原料樹脂で希釈して得られる樹脂組成物によって形成されているため、より低い温度で結晶化しており、外観や表面光沢等の品位に優れている。 <Resin molding>
One embodiment of the resin molding of the present invention is a molding of the resin composition described above. Since the resin molded body of the present embodiment is formed of a resin composition obtained by diluting the above-described masterbatch with a polyester-based raw material resin, it crystallizes at a lower temperature, and has excellent appearance, surface gloss, etc. Excellent quality.
本実施形態の樹脂成形体は、例えば、従来公知の成形方法にしたがって前述の樹脂組成物を所望とする形状に成形することで製造することができる。樹脂成形体としては、例えば、ボトル、ポリタンク等のブロー成形物；産業資材、トレイ、筐体等の射出成形物等を挙げることができる。
The resin molded article of the present embodiment can be produced, for example, by molding the above resin composition into a desired shape according to a conventionally known molding method. Examples of resin moldings include blow moldings such as bottles and plastic tanks; injection moldings such as industrial materials, trays and housings.
以下、本発明を実施例に基づいて具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、実施例、比較例中の「部」及び「％」は、特に断らない限り質量基準である。
The present invention will be specifically described below based on examples, but the present invention is not limited to these examples. "Parts" and "%" in Examples and Comparative Examples are based on mass unless otherwise specified.
＜マスターバッチの製造＞
表１－１、１－２、２－１、２－２、及び３に示す各成分を配合し、ヘンシェルミキサーを使用して十分に混合して混合物を得た。得られた混合物を、二軸押出機を使用して２６０～２８０℃で混練し、ペレット状のマスターバッチＭＢ－１～２７を得た。また、ＰＥＴ（ホモＰＥＴ）のみを「参考例１」とした。各成分の詳細を以下に示す。
・ＰＥＴ：ポリエチレンテレフタレート（ホモＰＥＴ）、商品名「ＭＡ－２１０３」、ユニチカ社製
・カーボンブラック：平均一次粒子径２５ｎｍ
・非晶性ＰＥＴ：商品名「ケイダンスＧＳ－１」、イーストマンケミカル社製
・共重合ポリエステルＡ：商品名「ＴＲＮ８０８４ＦＢ」、帝人社製、テレフタル酸／イソフタル酸／エチレングリコール
・共重合ポリエステルＢ：商品名「ケミットＱ１５００」、東レ・ファインケミカル社製、テレフタル酸／イソフタル酸／１，４－ブタンジオール
・銅フタロシアニン系染料Ａ：Ｃ．Ｉ．ソルベントブルー６７、商品名「オラゾール８２５」、ＢＡＳＦ社製
・銅フタロシアニン系染料Ｂ：Ｃ．Ｉ．ソルベントブルー７０、商品名「Ｏｉｌ Ｂｌｕｅ ５５１１－Ｎ」、有本化学工業社製
・アントラキノン系染料Ａ：Ｃ．Ｉ．ソルベントレッド５２、商品名「Ｐｌａｓｔ Ｒｅｄ ８３６０」、有本化学工業社製
アントラキノン系染料Ｂ：Ｃ．Ｉ．ソルベントブルー８７、商品名「Ｐｌａｓｔ Ｂｕｌｅ ８５８０」、有本化学工業社製
・アントラキノン系染料Ｃ：Ｃ．Ｉ．ソルベントブルー９７、商品名「Ｐｌａｓｔ Ｂｕｌｅ ８５９０」、有本化学工業社製
・アントラキノン系染料Ｄ：Ｃ．Ｉ．ソルベントバイオレット１３、商品名「Ｐｌａｓｔ Ｖｉｌｅｔ ８８４０」、有本化学工業社製
・アントラキノン系染料Ｅ：Ｃ．Ｉ．ソルベントバイオレット３６、商品名「Ｐｌａｓｔ Ｖｉｌｅｔ ８８５５」、有本化学工業社製
・ペリノン系染料Ａ：Ｃ．Ｉ．ソルベントレッド１７９、商品名「Ｐｌａｓｔ Ｒｅｄ ８３７０」、有本化学工業社製
・酸化チタン：平均一次粒子径０．１５μｍ、アナターゼ型 <Production of masterbatch>
Each component shown in Tables 1-1, 1-2, 2-1, 2-2, and 3 was blended and thoroughly mixed using a Henschel mixer to obtain a mixture. The resulting mixture was kneaded at 260-280° C. using a twin-screw extruder to obtain pellet-like masterbatches MB-1-27. In addition, only PET (homo PET) was designated as "Reference Example 1". Details of each component are shown below.
・ PET: polyethylene terephthalate (homo PET), trade name “MA-2103”, manufactured by Unitika ・ Carbon black: average primary particle size 25 nm
・Amorphous PET: product name “Kadance GS-1”, manufactured by Eastman Chemical Co. ・Copolymer polyester A: product name “TRN8084FB”, manufactured by Teijin, terephthalic acid/isophthalic acid/ethylene glycol ・Copolymer polyester B: Trade name “Kemit Q1500” manufactured by Toray Fine Chemicals Co., Ltd., terephthalic acid/isophthalic acid/1,4-butanediol/copper phthalocyanine dye A: C.I. I. Solvent Blue 67, trade name “ORAZOL 825”, manufactured by BASF ・Copper phthalocyanine dye B: C.I. I. Solvent Blue 70, trade name "Oil Blue 5511-N", manufactured by Arimoto Chemical Industry Co., Ltd. Anthraquinone dye A: C.I. I. Solvent Red 52, trade name "Plast Red 8360", anthraquinone dye B: C.I. I. Solvent Blue 87, trade name "Plast Bule 8580", manufactured by Arimoto Chemical Industry Co., Ltd. Anthraquinone dye C: C.I. I. Solvent Blue 97, trade name "Plast Bule 8590", manufactured by Arimoto Chemical Industry Co., Ltd. Anthraquinone dye D: C.I. I. Solvent Violet 13, trade name "Plast Vilet 8840", manufactured by Arimoto Chemical Industry Co., Ltd. Anthraquinone dye E: C.I. I. Solvent Violet 36, trade name "Plast Vilet 8855", manufactured by Arimoto Chemical Co., Ltd. Perinone dye A: C.I. I. Solvent Red 179, trade name “Plast Red 8370”, manufactured by Arimoto Chemical Industry Co., Ltd. Titanium oxide: average primary particle size 0.15 μm, anatase type
表１－１、１－２、２－１、２－２、及び３に示す各成分を配合し、ヘンシェルミキサーを使用して十分に混合して混合物を得た。得られた混合物を、二軸押出機を使用して２６０～２８０℃で混練し、ペレット状のマスターバッチＭＢ－１～２７を得た。また、ＰＥＴ（ホモＰＥＴ）のみを「参考例１」とした。各成分の詳細を以下に示す。
・ＰＥＴ：ポリエチレンテレフタレート（ホモＰＥＴ）、商品名「ＭＡ－２１０３」、ユニチカ社製
・カーボンブラック：平均一次粒子径２５ｎｍ
・非晶性ＰＥＴ：商品名「ケイダンスＧＳ－１」、イーストマンケミカル社製
・共重合ポリエステルＡ：商品名「ＴＲＮ８０８４ＦＢ」、帝人社製、テレフタル酸／イソフタル酸／エチレングリコール
・共重合ポリエステルＢ：商品名「ケミットＱ１５００」、東レ・ファインケミカル社製、テレフタル酸／イソフタル酸／１，４－ブタンジオール
・銅フタロシアニン系染料Ａ：Ｃ．Ｉ．ソルベントブルー６７、商品名「オラゾール８２５」、ＢＡＳＦ社製
・銅フタロシアニン系染料Ｂ：Ｃ．Ｉ．ソルベントブルー７０、商品名「Ｏｉｌ Ｂｌｕｅ ５５１１－Ｎ」、有本化学工業社製
・アントラキノン系染料Ａ：Ｃ．Ｉ．ソルベントレッド５２、商品名「Ｐｌａｓｔ Ｒｅｄ ８３６０」、有本化学工業社製
アントラキノン系染料Ｂ：Ｃ．Ｉ．ソルベントブルー８７、商品名「Ｐｌａｓｔ Ｂｕｌｅ ８５８０」、有本化学工業社製
・アントラキノン系染料Ｃ：Ｃ．Ｉ．ソルベントブルー９７、商品名「Ｐｌａｓｔ Ｂｕｌｅ ８５９０」、有本化学工業社製
・アントラキノン系染料Ｄ：Ｃ．Ｉ．ソルベントバイオレット１３、商品名「Ｐｌａｓｔ Ｖｉｌｅｔ ８８４０」、有本化学工業社製
・アントラキノン系染料Ｅ：Ｃ．Ｉ．ソルベントバイオレット３６、商品名「Ｐｌａｓｔ Ｖｉｌｅｔ ８８５５」、有本化学工業社製
・ペリノン系染料Ａ：Ｃ．Ｉ．ソルベントレッド１７９、商品名「Ｐｌａｓｔ Ｒｅｄ ８３７０」、有本化学工業社製
・酸化チタン：平均一次粒子径０．１５μｍ、アナターゼ型 <Production of masterbatch>
Each component shown in Tables 1-1, 1-2, 2-1, 2-2, and 3 was blended and thoroughly mixed using a Henschel mixer to obtain a mixture. The resulting mixture was kneaded at 260-280° C. using a twin-screw extruder to obtain pellet-like masterbatches MB-1-27. In addition, only PET (homo PET) was designated as "Reference Example 1". Details of each component are shown below.
・ PET: polyethylene terephthalate (homo PET), trade name “MA-2103”, manufactured by Unitika ・ Carbon black: average primary particle size 25 nm
・Amorphous PET: product name “Kadance GS-1”, manufactured by Eastman Chemical Co. ・Copolymer polyester A: product name “TRN8084FB”, manufactured by Teijin, terephthalic acid/isophthalic acid/ethylene glycol ・Copolymer polyester B: Trade name “Kemit Q1500” manufactured by Toray Fine Chemicals Co., Ltd., terephthalic acid/isophthalic acid/1,4-butanediol/copper phthalocyanine dye A: C.I. I. Solvent Blue 67, trade name “ORAZOL 825”, manufactured by BASF ・Copper phthalocyanine dye B: C.I. I. Solvent Blue 70, trade name "Oil Blue 5511-N", manufactured by Arimoto Chemical Industry Co., Ltd. Anthraquinone dye A: C.I. I. Solvent Red 52, trade name "Plast Red 8360", anthraquinone dye B: C.I. I. Solvent Blue 87, trade name "Plast Bule 8580", manufactured by Arimoto Chemical Industry Co., Ltd. Anthraquinone dye C: C.I. I. Solvent Blue 97, trade name "Plast Bule 8590", manufactured by Arimoto Chemical Industry Co., Ltd. Anthraquinone dye D: C.I. I. Solvent Violet 13, trade name "Plast Vilet 8840", manufactured by Arimoto Chemical Industry Co., Ltd. Anthraquinone dye E: C.I. I. Solvent Violet 36, trade name "Plast Vilet 8855", manufactured by Arimoto Chemical Co., Ltd. Perinone dye A: C.I. I. Solvent Red 179, trade name “Plast Red 8370”, manufactured by Arimoto Chemical Industry Co., Ltd. Titanium oxide: average primary particle size 0.15 μm, anatase type
＜評価（１）＞
（融点の測定）
示差熱分析計（ＴＧ－ＤＳＣ、商品名「ＴＧ－８１１０」、リガク社製）を使用し、室温（２５℃）から昇温速度１０℃／ｍｉｎで加熱する条件により各マスターバッチの融点を測定した。結果を表１－１、１－２、２－１、２－２、及び３に示す。 <Evaluation (1)>
(Measurement of melting point)
Using a differential thermal analyzer (TG-DSC, trade name "TG-8110", manufactured by Rigaku), the melting point of each masterbatch is measured under the conditions of heating from room temperature (25 ° C.) at a heating rate of 10 ° C./min. did. The results are shown in Tables 1-1, 1-2, 2-1, 2-2 and 3.
（融点の測定）
示差熱分析計（ＴＧ－ＤＳＣ、商品名「ＴＧ－８１１０」、リガク社製）を使用し、室温（２５℃）から昇温速度１０℃／ｍｉｎで加熱する条件により各マスターバッチの融点を測定した。結果を表１－１、１－２、２－１、２－２、及び３に示す。 <Evaluation (1)>
(Measurement of melting point)
Using a differential thermal analyzer (TG-DSC, trade name "TG-8110", manufactured by Rigaku), the melting point of each masterbatch is measured under the conditions of heating from room temperature (25 ° C.) at a heating rate of 10 ° C./min. did. The results are shown in Tables 1-1, 1-2, 2-1, 2-2 and 3.
（降温時の結晶化温度の測定）
示差熱分析計（ＴＧ－ＤＳＣ、商品名「ＴＧ－８１１０」、リガク社製）を使用し、窒素気流中、室温～３００℃～室温（昇温：１０℃／ｍｉｎ、降温：２０℃／ｍｉｎ）の条件で各マスターバッチの降温時の結晶化温度を測定した。また、基準となるマスターバッチの結晶化温度からの遅延（降下）温度を算出した。結果を表１－１、１－２、２－１、２－２、及び３に示す。 (Measurement of crystallization temperature during cooling)
Using a differential thermal analyzer (TG-DSC, trade name "TG-8110", manufactured by Rigaku), room temperature to 300 ° C. to room temperature (temperature increase: 10 ° C./min, temperature decrease: 20 ° C./min) in a nitrogen stream ), the crystallization temperature of each masterbatch was measured when the temperature was lowered. Also, the retarded (dropped) temperature from the crystallization temperature of the reference masterbatch was calculated. The results are shown in Tables 1-1, 1-2, 2-1, 2-2 and 3.
示差熱分析計（ＴＧ－ＤＳＣ、商品名「ＴＧ－８１１０」、リガク社製）を使用し、窒素気流中、室温～３００℃～室温（昇温：１０℃／ｍｉｎ、降温：２０℃／ｍｉｎ）の条件で各マスターバッチの降温時の結晶化温度を測定した。また、基準となるマスターバッチの結晶化温度からの遅延（降下）温度を算出した。結果を表１－１、１－２、２－１、２－２、及び３に示す。 (Measurement of crystallization temperature during cooling)
Using a differential thermal analyzer (TG-DSC, trade name "TG-8110", manufactured by Rigaku), room temperature to 300 ° C. to room temperature (temperature increase: 10 ° C./min, temperature decrease: 20 ° C./min) in a nitrogen stream ), the crystallization temperature of each masterbatch was measured when the temperature was lowered. Also, the retarded (dropped) temperature from the crystallization temperature of the reference masterbatch was calculated. The results are shown in Tables 1-1, 1-2, 2-1, 2-2 and 3.
＜樹脂組成物の製造＞
カーボンブラック５％濃度のマスターバッチをＰＥＴ（ホモＰＥＴ、商品名「ＭＡ－２１０３」、ユニチカ社製）で２０倍及び７１．４倍（いずれも質量基準）となるようにブレンドするとともに、二軸押出機を使用して２６０～２８０℃で混練し、ペレット状の樹脂組成物ＲＣ－１～１６、１８、及び１９を得た。なお、樹脂組成物ＲＣ－１７（参考例２）については、マスターバッチを希釈せず、表４－３に示す各成分をブレンドし、二軸押出機を使用して２６０～２８０℃で混練して得た。 <Production of resin composition>
A masterbatch with a carbon black concentration of 5% is blended with PET (homo PET, trade name "MA-2103", manufactured by Unitika) at 20 times and 71.4 times (both based on mass), and biaxially. They were kneaded at 260 to 280° C. using an extruder to obtain resin compositions RC-1 to RC-16, 18 and 19 in the form of pellets. For resin composition RC-17 (Reference Example 2), without diluting the masterbatch, each component shown in Table 4-3 was blended and kneaded at 260 to 280°C using a twin-screw extruder. I got it.
カーボンブラック５％濃度のマスターバッチをＰＥＴ（ホモＰＥＴ、商品名「ＭＡ－２１０３」、ユニチカ社製）で２０倍及び７１．４倍（いずれも質量基準）となるようにブレンドするとともに、二軸押出機を使用して２６０～２８０℃で混練し、ペレット状の樹脂組成物ＲＣ－１～１６、１８、及び１９を得た。なお、樹脂組成物ＲＣ－１７（参考例２）については、マスターバッチを希釈せず、表４－３に示す各成分をブレンドし、二軸押出機を使用して２６０～２８０℃で混練して得た。 <Production of resin composition>
A masterbatch with a carbon black concentration of 5% is blended with PET (homo PET, trade name "MA-2103", manufactured by Unitika) at 20 times and 71.4 times (both based on mass), and biaxially. They were kneaded at 260 to 280° C. using an extruder to obtain resin compositions RC-1 to RC-16, 18 and 19 in the form of pellets. For resin composition RC-17 (Reference Example 2), without diluting the masterbatch, each component shown in Table 4-3 was blended and kneaded at 260 to 280°C using a twin-screw extruder. I got it.
＜評価（２）＞
（融点の測定）
示差熱分析計（ＴＧ－ＤＳＣ、商品名「ＴＧ－８１１０」、リガク社製）を使用し、室温（２５℃）から昇温速度１０℃／ｍｉｎで加熱する条件により各樹脂組成物の融点を測定した。結果を表４－１～４－３に示す。 <Evaluation (2)>
(Measurement of melting point)
Using a differential thermal analyzer (TG-DSC, trade name "TG-8110", manufactured by Rigaku Corporation), the melting point of each resin composition was determined by heating from room temperature (25 ° C.) at a heating rate of 10 ° C./min. It was measured. The results are shown in Tables 4-1 to 4-3.
（融点の測定）
示差熱分析計（ＴＧ－ＤＳＣ、商品名「ＴＧ－８１１０」、リガク社製）を使用し、室温（２５℃）から昇温速度１０℃／ｍｉｎで加熱する条件により各樹脂組成物の融点を測定した。結果を表４－１～４－３に示す。 <Evaluation (2)>
(Measurement of melting point)
Using a differential thermal analyzer (TG-DSC, trade name "TG-8110", manufactured by Rigaku Corporation), the melting point of each resin composition was determined by heating from room temperature (25 ° C.) at a heating rate of 10 ° C./min. It was measured. The results are shown in Tables 4-1 to 4-3.
（降温時の結晶化温度の測定）
示差熱分析計（ＴＧ－ＤＳＣ、商品名「ＴＧ－８１１０」、リガク社製）を使用し、窒素気流中、室温～３００℃～室温（昇温：１０℃／ｍｉｎ、降温：２０℃／ｍｉｎ）の条件で各樹脂組成物の降温時の結晶化温度を測定した。また、樹脂組成物ＲＣ－１（比較例１０）の結晶化温度を基準とする遅延（降下）温度（ＲＣ－２～１３）、及び樹脂組成物ＲＣ－１４（比較例１３）の結晶化温度を基準とする遅延（降下）温度（ＲＣ－１５～１９）をそれぞれ算出した。結果を表４－１～４－３に示す。 (Measurement of crystallization temperature during cooling)
Using a differential thermal analyzer (TG-DSC, trade name "TG-8110", manufactured by Rigaku), room temperature to 300 ° C. to room temperature (temperature increase: 10 ° C./min, temperature decrease: 20 ° C./min) in a nitrogen stream ), the crystallization temperature of each resin composition was measured when the temperature was lowered. In addition, the retardation (decrease) temperature (RC-2 to 13) based on the crystallization temperature of the resin composition RC-1 (Comparative Example 10), and the crystallization temperature of the resin composition RC-14 (Comparative Example 13) The lag (drop) temperature (RC-15 to 19) based on was calculated respectively. The results are shown in Tables 4-1 to 4-3.
示差熱分析計（ＴＧ－ＤＳＣ、商品名「ＴＧ－８１１０」、リガク社製）を使用し、窒素気流中、室温～３００℃～室温（昇温：１０℃／ｍｉｎ、降温：２０℃／ｍｉｎ）の条件で各樹脂組成物の降温時の結晶化温度を測定した。また、樹脂組成物ＲＣ－１（比較例１０）の結晶化温度を基準とする遅延（降下）温度（ＲＣ－２～１３）、及び樹脂組成物ＲＣ－１４（比較例１３）の結晶化温度を基準とする遅延（降下）温度（ＲＣ－１５～１９）をそれぞれ算出した。結果を表４－１～４－３に示す。 (Measurement of crystallization temperature during cooling)
Using a differential thermal analyzer (TG-DSC, trade name "TG-8110", manufactured by Rigaku), room temperature to 300 ° C. to room temperature (temperature increase: 10 ° C./min, temperature decrease: 20 ° C./min) in a nitrogen stream ), the crystallization temperature of each resin composition was measured when the temperature was lowered. In addition, the retardation (decrease) temperature (RC-2 to 13) based on the crystallization temperature of the resin composition RC-1 (Comparative Example 10), and the crystallization temperature of the resin composition RC-14 (Comparative Example 13) The lag (drop) temperature (RC-15 to 19) based on was calculated respectively. The results are shown in Tables 4-1 to 4-3.
本発明のマスターバッチは、ポリエステル製の高品質な樹脂成形体を簡便に製造するための材料として好適である。
The masterbatch of the present invention is suitable as a material for easily producing a high-quality polyester resin molding.
The masterbatch of the present invention is suitable as a material for easily producing a high-quality polyester resin molding.
Claims (8)
- ポリエステル樹脂を主体とする樹脂成形体を製造するために用いられるマスターバッチであって、
ポリエステル系のベース樹脂及び充填剤を含有し、
下記条件（１）を満たすマスターバッチ。
条件（１）：銅フタロシアニン系染料をさらに含有し、前記充填剤１００質量部に対する、前記銅フタロシアニン系染料の含有量が、３～２００質量部である。 A masterbatch used for producing a resin molding mainly composed of a polyester resin,
Contains a polyester-based base resin and filler,
A masterbatch that satisfies the following condition (1).
Condition (1): A copper phthalocyanine dye is further contained, and the content of the copper phthalocyanine dye is 3 to 200 parts by mass with respect to 100 parts by mass of the filler. - さらに、下記条件（２）を満たす請求項１に記載のマスターバッチ。
条件（２）：前記ベース樹脂が、非晶性ポリエチレンテレフタレート及び共重合ポリエステルからなる群より選択される少なくとも一種を含む。 Furthermore, the masterbatch according to claim 1, which satisfies the following condition (2).
Condition (2): The base resin contains at least one selected from the group consisting of amorphous polyethylene terephthalate and copolyester. - 前記銅フタロシアニン系染料が、Ｃ．Ｉ．ソルベントブルー６７、Ｃ．Ｉ．ソルベントブルー７０、及びＣ．Ｉ．ソルベントブルー４４からなる群より選択される少なくとも一種である請求項１又は２に記載のマスターバッチ。 The copper phthalocyanine dye is C.I. I. Solvent Blue 67, C.I. I. Solvent Blue 70, and C.I. I. The masterbatch according to claim 1 or 2, which is at least one selected from the group consisting of Solvent Blue 44.
- 前記充填剤が、カーボンブラック、粘土鉱物、金属酸化物、無機酸塩、及び有機酸塩からなる群より選択される少なくとも一種である請求項１～３のいずれか一項に記載のマスターバッチ。 The masterbatch according to any one of claims 1 to 3, wherein the filler is at least one selected from the group consisting of carbon black, clay minerals, metal oxides, inorganic acid salts, and organic acid salts.
- 前記共重合ポリエステルが、
テレフタル酸及びイソフタル酸を含むジカルボン酸成分と、
エチレングリコール、１，３－プロパンジオール、１，４－ブタンジオール、及び１，４－シクロヘキサンジメタノールからなる群より選択される少なくとも一種のジオール成分と、の共重合体である請求項２～４のいずれか一項に記載のマスターバッチ。 The copolymer polyester is
a dicarboxylic acid component including terephthalic acid and isophthalic acid;
and at least one diol component selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,4-cyclohexanedimethanol. The masterbatch according to any one of . - 前記充填剤の含有量が、３～４０質量％である請求項１～５のいずれか一項に記載のマスターバッチ。 The masterbatch according to any one of claims 1 to 5, wherein the content of the filler is 3 to 40% by mass.
- ポリエステル樹脂を主体とする樹脂成形体を製造するための樹脂組成物であって、
ポリエステル系の原料樹脂と、
請求項１～６のいずれか一項に記載のマスターバッチと、を含有する樹脂組成物。 A resin composition for producing a resin molding mainly composed of a polyester resin,
a polyester-based raw material resin;
A resin composition containing the masterbatch according to any one of claims 1 to 6. - 請求項７に記載の樹脂組成物の成形物である樹脂成形体。
A resin molded product, which is a molded product of the resin composition according to claim 7 .
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| JP2021141718A JP7022248B1 (en) | 2021-03-25 | 2021-08-31 | Masterbatch, resin composition, and resin molded article |
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Citations (5)
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|---|---|---|---|---|
| JP2001064491A (en) * | 1999-08-26 | 2001-03-13 | Sumika Color Kk | Polyester resin composition for coloring use |
| JP2014151478A (en) * | 2013-02-06 | 2014-08-25 | Dainichiseika Color & Chem Mfg Co Ltd | Resin coloring master batch and manufacturing method thereof |
| CN110804285A (en) * | 2019-11-29 | 2020-02-18 | 张家港市顺禾化纤原料有限公司 | PET color master batch and preparation method thereof |
| JP2020511585A (en) * | 2017-02-21 | 2020-04-16 | 李耀輝 | Color masterbatch composition for dark-colored fabric or engineering plastic and product thereof |
| JP2020176192A (en) * | 2019-04-17 | 2020-10-29 | Dic株式会社 | Masterbatch for resin coloration, aromatic polyester resin composition, molding and method for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08283422A (en) * | 1995-04-18 | 1996-10-29 | Sunstar Inc | Molding of pet resin and additive-containing resin pellet therefor |
| JP2004059811A (en) * | 2002-07-30 | 2004-02-26 | Kureha Chem Ind Co Ltd | Semiconducting sheet and polyester resin composition |
| JP2007045895A (en) * | 2005-08-09 | 2007-02-22 | Toray Ind Inc | Colored polyester film |
| PT3910007T (en) * | 2017-12-15 | 2022-10-20 | Holland Colours Nv | Concentrate for polyester-based materials |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001064491A (en) * | 1999-08-26 | 2001-03-13 | Sumika Color Kk | Polyester resin composition for coloring use |
| JP2014151478A (en) * | 2013-02-06 | 2014-08-25 | Dainichiseika Color & Chem Mfg Co Ltd | Resin coloring master batch and manufacturing method thereof |
| JP2020511585A (en) * | 2017-02-21 | 2020-04-16 | 李耀輝 | Color masterbatch composition for dark-colored fabric or engineering plastic and product thereof |
| JP2020176192A (en) * | 2019-04-17 | 2020-10-29 | Dic株式会社 | Masterbatch for resin coloration, aromatic polyester resin composition, molding and method for producing the same |
| CN110804285A (en) * | 2019-11-29 | 2020-02-18 | 张家港市顺禾化纤原料有限公司 | PET color master batch and preparation method thereof |
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| JP7022248B1 (en) | 2022-02-17 |
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