KR100486944B1 - Flame retardantion polyethylen terephalate use of phoshorus flame retardants and a manufacturing proecess - Google Patents
Flame retardantion polyethylen terephalate use of phoshorus flame retardants and a manufacturing proecess Download PDFInfo
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- KR100486944B1 KR100486944B1 KR10-2002-0048246A KR20020048246A KR100486944B1 KR 100486944 B1 KR100486944 B1 KR 100486944B1 KR 20020048246 A KR20020048246 A KR 20020048246A KR 100486944 B1 KR100486944 B1 KR 100486944B1
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- flame retardant
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- polyethylene terephthalate
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 62
- -1 polyethylen Polymers 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 241000430093 Proeces Species 0.000 title 1
- 229920000573 polyethylene Polymers 0.000 title 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 38
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 38
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 239000011347 resin Substances 0.000 claims abstract description 37
- 229920001038 ethylene copolymer Polymers 0.000 claims abstract description 10
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000005909 Kieselgur Substances 0.000 claims description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 15
- 239000011574 phosphorus Substances 0.000 claims description 15
- 238000000465 moulding Methods 0.000 claims description 12
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 238000001746 injection moulding Methods 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- KUKLSWLXUCSXIB-UHFFFAOYSA-N but-1-ene;prop-2-enoic acid Chemical compound CCC=C.OC(=O)C=C KUKLSWLXUCSXIB-UHFFFAOYSA-N 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 239000007970 homogeneous dispersion Substances 0.000 claims description 2
- 229940057995 liquid paraffin Drugs 0.000 claims description 2
- 238000004040 coloring Methods 0.000 claims 2
- 239000000975 dye Substances 0.000 claims 2
- 238000004898 kneading Methods 0.000 claims 2
- 239000000049 pigment Substances 0.000 claims 2
- 239000000843 powder Substances 0.000 claims 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 abstract 1
- 238000002845 discoloration Methods 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 21
- 238000002844 melting Methods 0.000 description 12
- 230000008018 melting Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920006038 crystalline resin Polymers 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- QLZJUIZVJLSNDD-UHFFFAOYSA-N 2-(2-methylidenebutanoyloxy)ethyl 2-methylidenebutanoate Chemical compound CCC(=C)C(=O)OCCOC(=O)C(=C)CC QLZJUIZVJLSNDD-UHFFFAOYSA-N 0.000 description 2
- 241000282341 Mustela putorius furo Species 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 2
- 239000005042 ethylene-ethyl acrylate Substances 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- QRIMLDXJAPZHJE-UHFFFAOYSA-N 2,3-dihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CO QRIMLDXJAPZHJE-UHFFFAOYSA-N 0.000 description 1
- MAKGFLSFGVUWJR-UHFFFAOYSA-N C(C=C)(=O)OCC.C(C)C=C Chemical compound C(C=C)(=O)OCC.C(C)C=C MAKGFLSFGVUWJR-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
Classifications
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- 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
- C08K3/34—Silicon-containing compounds
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0066—Flame-proofing or flame-retarding additives
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/01—Hydrocarbons
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
폴리에틸렌 테레프타레이트수지(이하 PET수지라 칭함)의 비할로겐계 난연제를 사용할때에 있어서 난연제의 용해에 의해 표면에 변색이나 끈적거림을 방지하고 수지에서 난연제로 변화를 용이하도록 하는 방법으로써 규조토나 에칠렌 아크릴산에틸과 그리시질메타그리레이트가 결합된 에틸렌코 폴리머를 단지체로써 첨가하는 것에서 외관품질이 우수한 난연성PET수지를 제공가능하다.When using non-halogen flame retardant of polyethylene terephthalate resin (hereinafter referred to as PET resin), it is a method to prevent discoloration or stickiness on the surface by dissolving the flame retardant and to facilitate change from resin to flame retardant. It is possible to provide a flame-retardant PET resin having excellent appearance quality by adding ethylene copolymers combined with ethyl acrylate and glycidyl methacrylate as a complex.
Description
본 발명은 인계 난연제를 이용한 난연화 폴리에틸렌 테레프타레이트(polyethylene terephthalate:PET)수지 및 그 제조방법에 관한 것으로, 특히 인산 축합에스테르를 베이스(Base)로 하는 난연제로써 난연제의 용해에 의해 표면에 변색이나 끈적거림을 방지하는 인계 난연제를 이용한 난연화 폴리에틸렌 테레프타레이트(polyethylene terephthalate:PET)수지및 제조방법에 관한 것이다.The present invention relates to a flame-retardant polyethylene terephthalate (PET) resin using a phosphorus-based flame retardant, and to a method of manufacturing the same. In particular, it is a flame retardant based on a phosphate condensation ester and is discolored on the surface by dissolution of the flame retardant. It relates to a flame-retardant polyethylene terephthalate (PET) resin and a manufacturing method using a phosphorus-based flame retardant to prevent sticking.
종래 PET수지의 난연제로써는 염소계, 산소계, 무기계의 난연제가 사용되어왔다. 또한 섬유제품에 있어서는 염색할때에는 방염가공하는 방법도 사용되었다.As flame retardants of conventional PET resins, chlorine-based, oxygen-based, and inorganic-based flame retardants have been used. In addition, for textile products, the method of flame retardant processing was used.
상기한 종래의 방법은 다음과 같이 문제점이 있었다.The conventional method described above has the following problems.
염소계에서는 설비나 금형부식의 문제와 더불어 폐기소각할때에 다이옥신발생등의 환경오염의 문제점이 있었으며, 또한 산소계에 있어서도 설비금형부식의 문제나 악취의 문제점이 있었고, 무기계에 있어서는 첨가량의 증대의 경향에서 생겨나는 가격적제약이나 기계적, 혹은 여러 물리적 성질의 영향에 의해 사용용도에 제약이 따르는 큰 문제점이 있었다.In the chlorine system, there were problems of equipment and mold corrosion as well as environmental pollution such as dioxin generation at the time of waste incineration. Also in the oxygen system, there was a problem of equipment mold corrosion and odor. There was a big problem that the usage restrictions were caused by the price constraint, mechanical or various physical properties.
또한 인산 축합에스테르계의 난연제는 융점이 96도 정도의 저융점이기 때문에 융점이 245도로 높은 융점과 고결정성 수지인 PET수지의 인산계 난연제를 삽입하는 것이 어려웠다. In addition, since the melting point of the phosphate condensation ester-based flame retardant has a low melting point of about 96 degrees, it was difficult to insert the phosphate flame retardant of a PET resin having a high melting point of 245 degrees and a highly crystalline resin.
또한 삽입후의 제품표면에 난연제 용출이 생겨 제품의 용도보다 외관 결점이 발생되는 것에 의해 사용상의 문제점이 있었다.In addition, there was a problem in use due to the appearance of flame retardants elution on the surface of the product after insertion, resulting in appearance defects than the use of the product.
본 발명은 융점이 낮은 인계 난연제를 고융점, 고결정성 수지로의 혼합가공 혹은 혼합성형가공을 실시하여 균질혼합과 성형체의 외관상에서 생기는 결점을 방지하는 수단으로 다공질로써 액체의 흡착성능을 높이고, 가격이 싼 규조토를 난연제의 단지체(다른 물질을 그 입자내에 흡착하고 목적으로 하는 위치까지 유지하는 성질을 갖는 물체)인 분산제로써 사용하여 유용성이 높은 외관이 우수하고 경제성이 좋은 난연성 PET수지를 제공하는 것을 목적으로 한다.The present invention is to improve the adsorption performance of the liquid by the porous as a means to prevent the defects in the homogeneous mixing and the appearance of the molded body by performing the mixing or mixing molding process of the phosphorus flame retardant with a low melting point to a high melting point, high crystalline resin This inexpensive diatomaceous earth is used as a dispersant that is a complex of flame retardant (an object having the property of adsorbing other substances into the particles and maintaining the desired position) to provide a flame retardant PET resin with excellent appearance and economical efficiency. For the purpose of
상기 목적을 달성하기 위해서 제안된 본 발명의 난연성 PET수지용 재료는 인산계 난연제를 PET수지에 배합하고 난연제의 흡착분산효과를 얻기 위해 규조토를 첨가하여 가열 혼합하여 조립(재 페렛트(pellet)화)하였다. In order to achieve the above object, the flame retardant PET resin material of the present invention is formulated by heating and mixing phosphoric acid-based flame retardant with PET resin and adding diatomaceous earth to obtain the adsorption and dispersing effect of the flame retardant. )
또한 상기 규조토는 2미크론이하의 미쇄화 한 것을 사용하여 섬유가공에도 사용 가능하도록 하였다.In addition, the diatomaceous earth can be used in the fiber processing using a finer than 2 micron.
더욱이 PET수지 100중량부에 대하여 인산계 난연제를 4∼6중량부와 상기 규조토 1∼6중량부를 배합하여 되는 것이다. Furthermore, 4-6 weight part of phosphate flame retardants and 1-6 weight part of said diatomaceous earths are mix | blended with respect to 100 weight part of PET resins.
또한 동시에 제한되는 난연화 열가소성 폴리에스테르의 제조방법으로써는 상기한 배합재료를 일반적인 단축 혼합조립기에서 가열 용융 혼합하여 조립하던지 용융온도가 낮은 인산계 난연제는 용융과 동시에 규조토에 흡착되기 때문에 혼합조립기의 반넬내에서 스립현상이 생기지 않고 수지에 분산혼합이 균일하게 이루어지는 것을 특징으로 한다.In addition, the method of manufacturing a flame-retardant thermoplastic polyester, which is limited at the same time, is to assemble by mixing the above-mentioned material by heat melt mixing in a general uniaxial mixing granulator, or a phosphate flame retardant having a low melting temperature is adsorbed on diatomaceous earth at the same time as the melting granulator. Slip phenomenon does not occur in the panel, it is characterized in that the dispersion and mixing in the resin is uniform.
또한 가공 최종상품이 헤어피스등의 섬유상제품의 경우 규조토의 함량을 낮게 하고 대신에 에틸렌 아크릴산 에틸(Ethylene-Ethylacrylata Copoiymar)과 그리시질메타크리레이트(Glycidyl Mathacrylata:GMA)와의 에칠렌코폴리머를 배합하는 것에 의해 혼합가공성을 확보하여 제품의 난연제 용출을 방지하는 제조방법이다.In addition, the processed final product is to reduce the content of diatomaceous earth in the case of fibrous products such as hairpieces, and instead to mix the ethylene copolymer of ethyl ethylene (Ethylene-Ethylacrylata Copoiymar) and glycidyl methacrylate (Glycidyl Mathacrylata: GMA) It is a manufacturing method for preventing the elution of the flame retardant of the product by ensuring mixing processability.
다음은 본 발명의 구체적 구성을 설명한다.The following describes the specific configuration of the present invention.
[1] 본 발명은 난연성PET수지는 인계 난연제의 균질 분산과 성형가공후에 용출방지를 목적으로 하여 규조토를 배합하고 용도에 따라 기계적 강도를 필요로 하는 경우는 에틸렌아크릴산 에틸(Ethylene-ethylacrylata copolymar)과 그리시질메타 크리레이트(glycidyl mathacrylata)로 형성되는 에틸렌코 폴리머를 삽입하는 것을 특징으로 한다.[1] The present invention relates to flame retardant PET resins, which contain diatomaceous earth for the purpose of homogeneous dispersion of phosphorus-based flame retardants and for elution prevention after molding and, if mechanical strength is required depending on the application, ethyl ethylene-ethylacrylata copolymar and Characterized by inserting an ethylene copolymer formed of glycidyl methacrylate (glycidyl mathacrylata).
(1) 본 발명에서 사용되는 난연제는 인계 난연제에서 인산 축합 에스텔 단독이나 혹은 산소 또는 염소계 난연제와 병용하여 이용할때에는 상기 효과가 기대 가능하다.(1) The flame retardant used in the present invention can be expected to be effective when used in the phosphorus flame retardant alone or in combination with oxygen or chlorine flame retardant.
또한 이 함유량은 얻고자 하는 난연화에 적합한 최적량이 결정된다.In addition, this content is determined to an optimum amount suitable for flame retardation to be obtained.
(2) PET수지(2) PET resin
본 발명에서 사용되는 PET수지는 고무성분을 포함하지 않는 PET수지 전부 응용 가능하다.PET resin used in the present invention is applicable to all PET resins that do not contain a rubber component.
(3) 규조토(3) diatomaceous earth
본 발명은 사용되는 규조토는 염수, 해수계 규조토 어느것이나 이용하는 것이 가능하다. 단지 크기에 대하여는 난연제의 균일 분산과 기계적물성의 저하방지와 착색 및 염색할때에 채도확보의 면에서 5미크론 이하의 크기의 것을 사용하는 것이 바람직하다.The diatomaceous earth to be used in the present invention can use any of brine and seawater diatomaceous earth. In terms of size, it is preferable to use a size of 5 microns or less in terms of securing saturation when preventing uniform dispersion of flame retardant, deterioration of mechanical properties, and securing color and dyeing.
(4) 에틸렌 아크릴산 에틸과 그리시질메타크리레이트로 형성되는 에틸렌코 포리머수지 (4) Ethylene copolymer polymer formed from ethyl ethylene acrylate and glycidyl methacrylate
본 발명에서 사용되는 상기 에틸렌코 폴리머는 에틸렌 아크릴산 에틸 함량이 18중량부이상의 것을 베이스로 그리시질메타크릴레이트를 12중량부이상 더한 것이 바람직하고 이것은 에틸렌 아크릴산 에틸이 PET수지와 부분적으로 서로 녹는것과 그리시질메타크리레이트의 에폭시드가 인산과의 결합이 강하기 때문의 결과로써 PET수지에의 포접효과를 얻으며, 더욱이 난연제의 용출을 방지할 뿐만 아니라, 함량이 많은 것이 바람직하다.In the ethylene copolymer used in the present invention, it is preferable that glyceryl methacrylate is added 12 parts by weight or more based on the ethylene acrylate ethyl content of 18 parts by weight or more, which is partially dissolved with the PET resin and the grease. As a result of epoxide of methacrylate having a strong bond with phosphoric acid, it is possible to obtain a clathrate effect on PET resin, and to prevent elution of the flame retardant, as well as to have a high content.
상기 에틸렌 아크릴산 에틸과 그리시질메타크리레이트에 의해 생성되는 에틸렌코폴리머의 화학식을 나타낸 것이다.The chemical formula of the ethylene copolymer produced by the ethylene ethyl acrylate and the glycidyl methacrylate is shown.
[난연성 PET수지의 제조방법][Production method of flame retardant PET resin]
본 발명의 난연화 PET수지는 인계 난연제를 PET수지에 배합하고 규조토 및 에칠렌 아크릴산 에틸과 그리시질 메타크리레이트로 이루어지는 에틸렌코 포리머를 배합하여 용융 혼합하는 것에 의해 난연제의 균일 분산과 PET수지내의 포접효과의 증대를 도모하는 것에 의해 외관품질이 우수한 난연성PET수지의 조립물(페렛트)을 얻을수 있다.The flame retardant PET resin of the present invention is blended with PET-based flame retardant, mixed with ethylene copolymers composed of diatomaceous earth, ethyl ethylene ethyl acrylate and glycidyl methacrylate, and melt-blended to uniformly disperse the flame retardant and the inclusion effect in the PET resin. By increasing the density, a granule (ferret) of flame-retardant PET resin having excellent appearance quality can be obtained.
[혼합 및 조립][Mixing and assembly]
본 발명의 제조방법에서는 난연제 PET수지 및 규조토나 상기 에치렌코 포리머를 배합하고 핸셀믹서, V브렌더, 탄브러등의 혼합기기를 사용하여 교반, 혼합한 후에 단축의 압출 조립기를 사용하여 가열, 용융, 혼합하여 조립(페렛트화)한다.In the production method of the present invention, after mixing the flame retardant PET resin and diatomaceous earth or the above-mentioned Echirenko polymer and stirring and mixing by using a mixing device such as a Hansel mixer, V blender, tangbrush, etc., it is heated and melted using a single-axis extrusion granulator. It is mixed and granulated (ferretized).
이때에 스크류의 피드(전송속도)량을 안정되게 보내기 위해 호퍼 하부의 설정온도를 인계 난연제의 융점이하 예를 들면 70℃ 정도로 하는 것이 바람직하다.At this time, in order to stably transmit the feed amount of the screw, it is preferable that the set temperature of the lower part of the hopper is set to about 70 ° C below the melting point of the phosphorus-based flame retardant.
[2] 난연성 PET수지 성형체[2] molded articles, flame retardant PET resin
본 발명에 의한 재료의 조합과 배합에 의하면 상기의 용융, 혼합, 조립의 공정을 거치지 않고 직접 성형가공할때에는 첨가, 배합하여 용융, 혼합하여 난연성 PET수지의 성형체를 얻는 것이 가능하다.According to the combination and compounding of the material according to the present invention, it is possible to obtain a molded body of a flame-retardant PET resin by adding, blending, melting, and mixing in the direct molding process without going through the melting, mixing, and granulation process described above.
상기에 의한 방법으로 재료를 배합하고 교반 혼합하는 경우에는 유동파라핀(liquid paraffin)등을 전체량의 0.5∼1중량부 첨가하는 것에 의해 교반 혼합후의 분산효과를 유효하게 갖도록 하는 것이 바람직하다.In the case of blending and stirring the materials by the above method, it is preferable to add the liquid paraffin or the like to 0.5 to 1 parts by weight of the total amount so as to effectively have a dispersion effect after the stirring and mixing.
또한 교반 혼합후의 브렌드(blend)재료의 성형은 열가소성수지의 성형에서 범용적으로 사용되는 각종성형기, 예를 들면 스크류타입 사출성형기, 압출성형기, 인프레이션성형기, 중공성형기등을 사용하여 행한다.In addition, the molding of the blended material after stirring and mixing is performed using various molding machines commonly used in molding thermoplastics, for example, screw type injection molding machines, extrusion molding machines, inflation molding machines, and blow molding machines.
실시예Example
이하에서 본 발명의 실시예를 비교예와 대비하여 설명한다.Hereinafter, an embodiment of the present invention will be described in comparison with a comparative example.
실시예1∼7, 비교예 1, 2) 표 1에 나타내는 바와 같이 실시예 1∼7, 비교예 1∼2로써 PET수지(일본 미쯔비시 다이야나이트 KR-461S)100중량부에 대하여 인계 난연제(일본 다이와화학 PX-200)를 4∼10중량부와 난연화 상태에 따라 변화시켜 그것과 대응하여 규조토(일본 쇼와화학 라지오나이트 F)를 표1의 비율로 하여 에틸렌 아크릴산 에틸과 그리시질 아크리레이트의 합성물 에틸렌코폴리머(일본 쓰미또모 노브렌 본드퍼스트 E)를 똑같이 표 1의 비율로 배합하고, 핸셀믹서에서 2분간 교반 혼합한 후에 이것을 구경40mm ,L/D36의 단축 압출조립기에서 255℃로 용융 혼합하여 입상(페렛트상)의 성형기 재료를 얻는다.Examples 1 to 7, Comparative Examples 1 and 2 As shown in Table 1, Examples 1 to 7 and Comparative Examples 1 to 2 were used as the phosphorus flame retardant based on 100 parts by weight of PET resin (Japan Mitsubishi Diamond Knight KR-461S). Daiwa Chemical PX-200) was changed according to 4 to 10 parts by weight and the flame retardant state, and correspondingly, diatomaceous earth (Japan Showa Chemical Lazionite F) was used in the ratio of Table 1 to ethylene ethyl acrylate and glycidyl acrylate. Compound ethylene copolymer (Tumitomo Nobren Bond First E of Japan) was similarly blended in the ratio of Table 1, stirred and mixed in a Hansel mixer for 2 minutes, and then melted at 255 ° C. in a single-axis extrusion granulator with a diameter of 40 mm and L / D36. By mixing, a granular (ferret) molding machine material is obtained.
상기 입상의 성형기 재료를 스크류 타입 사출성형기(일본 : 주식회사 山城精機VS-30-35형)로 250℃에서 2mm 두께의 성형기로 성형한다.The granular molding machine material is molded into a 2 mm thick molding machine at 250 ° C. using a screw type injection molding machine (Japan: Yamato Seiki VS-30-35).
얻어진 실시예 1∼7의 성형체는 표1에서 나타내는 외관상의 결점이 없는 광택이 나는 성형체를 나타낸다.The obtained molded articles of Examples 1 to 7 show a glossy molded article having no apparent defects shown in Table 1.
이상에서 설명한 바와 같이 본 발명의 난연성 PET수지의 제조방법에 의하면 융점이 낮은 인계 난연제를 고융점, 고결정성 수지로의 혼합가공 혹은 혼합성형가공을 실시하여 균질혼합과 성형체의 외관상에서 생기는 결점을 방지하는 수단으로 다공질로써 액체의 흡착성능을 높이고, 가격이 싼 규조토를 난연제의 단지체 분산제로써 사용됨으로써 유용성이 높은 인계 난연제의 열가소성 폴리에스테르와 응용성이 확대되어 PET수지가 갖는 여러 가지의 성질이 손실되는 것이 적은 경제성이 우수한 난연성 PET수지의 제공이 가능한 효과가 있다. As described above, according to the manufacturing method of the flame-retardant PET resin of the present invention, the phosphorus-based flame retardant having a low melting point is subjected to high melting point, mixed processing to a high crystalline resin or mixed molding processing to prevent defects in homogeneous mixing and appearance of the molded body As a means to improve the adsorption performance of liquids as a porous material, and inexpensive diatomaceous earth is used as a dispersant for flame retardants, the applicability of thermoplastic polyester of a highly useful phosphorus flame retardant is expanded, and various properties of PET resin are lost. It is possible to provide a flame retardant PET resin excellent in economical efficiency is less.
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| KR20010012533A (en) * | 1998-03-25 | 2001-02-15 | 야스이 쇼사꾸 | Resin composition |
| JP2001181490A (en) * | 1999-12-28 | 2001-07-03 | Polyplastics Co | Flame-retardant resin composition |
| JP2001226570A (en) * | 2000-02-18 | 2001-08-21 | Toray Ind Inc | Flame-retardant polyester resin composition |
| JP2002105334A (en) * | 2000-07-26 | 2002-04-10 | Polyplastics Co | Flame-retardant resin composition |
| JP2002105336A (en) * | 2000-07-26 | 2002-04-10 | Polyplastics Co | Flame-retardant resin composition |
| JP2002105335A (en) * | 2000-07-26 | 2002-04-10 | Polyplastics Co | Flame-retardant resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20010012533A (en) * | 1998-03-25 | 2001-02-15 | 야스이 쇼사꾸 | Resin composition |
| JP2001181490A (en) * | 1999-12-28 | 2001-07-03 | Polyplastics Co | Flame-retardant resin composition |
| JP2001226570A (en) * | 2000-02-18 | 2001-08-21 | Toray Ind Inc | Flame-retardant polyester resin composition |
| JP2002105334A (en) * | 2000-07-26 | 2002-04-10 | Polyplastics Co | Flame-retardant resin composition |
| JP2002105336A (en) * | 2000-07-26 | 2002-04-10 | Polyplastics Co | Flame-retardant resin composition |
| JP2002105335A (en) * | 2000-07-26 | 2002-04-10 | Polyplastics Co | Flame-retardant resin composition |
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