KR102593284B1 - Powder coating composition for electronic powder coating and manufacturing method thereof - Google Patents
Powder coating composition for electronic powder coating and manufacturing method thereof Download PDFInfo
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- KR102593284B1 KR102593284B1 KR1020210035748A KR20210035748A KR102593284B1 KR 102593284 B1 KR102593284 B1 KR 102593284B1 KR 1020210035748 A KR1020210035748 A KR 1020210035748A KR 20210035748 A KR20210035748 A KR 20210035748A KR 102593284 B1 KR102593284 B1 KR 102593284B1
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- rice straw
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- 239000000843 powder Substances 0.000 title claims abstract description 109
- 238000000576 coating method Methods 0.000 title claims abstract description 85
- 239000011248 coating agent Substances 0.000 title claims abstract description 70
- 239000008199 coating composition Substances 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 241000209094 Oryza Species 0.000 claims abstract description 48
- 235000007164 Oryza sativa Nutrition 0.000 claims abstract description 48
- 235000009566 rice Nutrition 0.000 claims abstract description 48
- 239000010902 straw Substances 0.000 claims abstract description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 32
- 238000011282 treatment Methods 0.000 claims abstract description 32
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 19
- 229920001225 polyester resin Polymers 0.000 claims abstract description 19
- 239000004645 polyester resin Substances 0.000 claims abstract description 19
- 239000006185 dispersion Substances 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 9
- MFIUDWFSVDFDDY-UHFFFAOYSA-M butyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 MFIUDWFSVDFDDY-UHFFFAOYSA-M 0.000 claims abstract description 6
- 239000000155 melt Substances 0.000 claims abstract description 4
- 238000002844 melting Methods 0.000 claims abstract description 3
- 230000008018 melting Effects 0.000 claims abstract description 3
- 238000010298 pulverizing process Methods 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 17
- 239000013067 intermediate product Substances 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 230000007062 hydrolysis Effects 0.000 claims description 14
- 238000006460 hydrolysis reaction Methods 0.000 claims description 14
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 8
- JESHZQPNPCJVNG-UHFFFAOYSA-L magnesium;sulfite Chemical compound [Mg+2].[O-]S([O-])=O JESHZQPNPCJVNG-UHFFFAOYSA-L 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 7
- 239000000920 calcium hydroxide Substances 0.000 claims description 7
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 239000003063 flame retardant Substances 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 239000000080 wetting agent Substances 0.000 claims description 3
- 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 description 2
- 238000011276 addition treatment Methods 0.000 claims description 2
- 238000004061 bleaching Methods 0.000 claims description 2
- 238000004040 coloring Methods 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- 238000000034 method Methods 0.000 description 23
- 230000000704 physical effect Effects 0.000 description 21
- 230000008569 process Effects 0.000 description 13
- 239000000203 mixture Substances 0.000 description 11
- 239000003973 paint Substances 0.000 description 9
- 230000006872 improvement Effects 0.000 description 8
- 230000003449 preventive effect Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000001913 cellulose Substances 0.000 description 5
- 229920002678 cellulose Polymers 0.000 description 5
- 238000007786 electrostatic charging Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 238000010128 melt processing Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000007665 sagging Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- -1 Butyltriphenylphosphonium chloride calcium carbonate Chemical compound 0.000 description 1
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
- C09D5/033—Powdery paints characterised by the additives
- C09D5/036—Stabilisers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
- B01J6/005—Fusing
-
- 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
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- 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
- C08K5/50—Phosphorus bound to carbon only
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/10—Greenhouse gas [GHG] capture, material saving, heat recovery or other energy efficient measures, e.g. motor control, characterised by manufacturing processes, e.g. for rolling metal or metal working
Abstract
본 발명은 정전 분체도장용 분체도료 조성물의 제조방법에 관한 것으로, 중량평균분자량 9500 내지 9700을 갖춘 카복실기(Carboxyl group) 함유 폴리에스테르 (Polyester) 수지 85 내지 89 중량부 및 β-hydroxyalkylamide (β-HAA) 6 중량부를 분쇄기에 넣어 분산 처리하는 A단계; 볏짚 유래 그래핀(Graphene)을 준비하는 B단계; 상기 A단계를 통해 마련된 분산 처리물에 상기 B단계를 통해 준비된 볏짚 유래 그래핀(Graphene) 1.2 내지 1.3 중량부, 염화 부틸트리페닐포스포늄(Butyltriphenylphosphonium chloride) 3 중량부 및 첨가제를 첨가하여 추가 분산 처리하는 C단계; 상기 C단계를 통해 마련된 2차 분산 처리물를 용융 압출기에 넣어 90℃의 온도 환경에서 용융 처리하는 D단계; 및 상기 D단계를 통해 마련된 용융 처리물을 냉각 처리 후 분쇄시켜 분체도료 조성물 제조하는 E단계;를 포함한다.The present invention relates to a method for producing a powder coating composition for electrostatic powder coating, comprising 85 to 89 parts by weight of a polyester resin containing a carboxyl group with a weight average molecular weight of 9500 to 9700 and β-hydroxyalkylamide (β- HAA) Step A of dispersing 6 parts by weight in a grinder; Step B, preparing rice straw-derived graphene; Additional dispersion treatment by adding 1.2 to 1.3 parts by weight of rice straw-derived graphene prepared through step B, 3 parts by weight of butyltriphenylphosphonium chloride, and additives to the dispersion treatment prepared through step A. Step C; Step D of melting the secondary dispersed product prepared through step C in a melt extruder in a temperature environment of 90°C; And a step E of producing a powder coating composition by cooling and pulverizing the molten product prepared through step D.
Description
본 발명은 정전 분체도장용 분체도료 조성물 및 이의 제조방법에 관한 것이다.The present invention relates to a powder coating composition for electrostatic powder coating and a method for manufacturing the same.
유기용제를 사용하는 도장 방법들은 톨루엔(Toluene, 휘발성 유기 화합물(VOC, Volatile Organic Compounds) 등의 유해성 물질을 배출시킴에 따라 환경오염에 영향을 주는 문제가 있어, 친환경적인 기술로서 자동차, 전력기기, 전자제품 등 다양한 분야에서 대기 중에 유해성 물질의 방출이 발생되지 않은 정전 분체도장(EPC, Electronic Powder Coating) 방법이 이용되고 있다.Painting methods that use organic solvents have the problem of affecting the environment by emitting harmful substances such as toluene (VOC), etc., and are used as an eco-friendly technology for automobiles, power equipment, etc. Electrostatic powder coating (EPC, Electronic Powder Coating), which does not emit harmful substances into the air, is being used in various fields, including electronic products.
이러한 정전 분체도장(EPC, Electronic Powder Coating) 방법은 분체도료를 압축공기와 일정 압력으로 혼합하여 도장관을 통해 분출시키고, 이 과정에서 고전압(60kV 내지 120kV) 하에서 부극성으로 대전된 분체도료를 접지된 피도물에 분사하여 정전기적으로 부착이 이루어지도록 한 뒤, 가열 및 용해 처리 과정을 거쳐 도막화가 완성되도록 한다.In this electrostatic powder coating (EPC, Electronic Powder Coating) method, powder coating is mixed with compressed air at a certain pressure and ejected through a paint pipe, and in this process, the negatively charged powder coating is grounded under high voltage (60kV to 120kV). It is sprayed on the coated object to ensure electrostatic adhesion, and then the coating is completed through a heating and dissolution process.
분체도료의 활용 형태는 액상도료와 크게 다르지 않으며, 미관 장식용 또는 보호용의 용도로 다양한 분야에서 광범위하게 사용되며, 특히 오버 스프레이(Over Spray)된 분체도료를 집진 회수하여 재사용이 가능하기 때문에 에너지 및 자원 절약 차원에서도 환경적이 이점을 갖추고 있다.The form of use of powder coating is not much different from liquid coating, and is widely used in various fields for aesthetic decoration or protection. In particular, oversprayed powder coating can be collected and reused, so it saves energy and resources. There are also environmental benefits in terms of savings.
이에 따라, 분체도료 조성물은 다양한 기능성 개선 혹은 부가를 통해 새롭게 개발되어 왔으며, 다양한 분체도료 조성물들이 출시되어 사용 대상 및 목적등에 맞추어 선별 사용되어 왔다.Accordingly, powder coating compositions have been newly developed through various functional improvements or additions, and various powder coating compositions have been released and used selectively according to the target and purpose of use.
이와 관련하여, 도막을 형성태는 대상 표면상에 특수한 질감 및 광택을 부여하고, 도막 내 다양한 물성적 개선을 제공하기 위해 마련된 종래기술에 대한 선행문헌에는 대한민국 등록특허공보 제10-1481316호의"통합형 분체도료 조성물과 그 제조방법"(이하, '종래기술'이라고 함)이 있다.In this regard, the form of the coating film gives a special texture and gloss to the target surface, and the prior literature on the prior art prepared to provide various improvements in physical properties within the coating film includes "Integrated Type" in Korean Patent Publication No. 10-1481316. “Powder coating composition and method for manufacturing the same” (hereinafter referred to as ‘prior art’).
하지만 종래기술을 비롯한 기존의 분체도료 조성물과 관련한 기술들의 경우, 정전분체 도장법을 통해 도막형성을 실시하는 과정에서 분체도료가 관을 이동하거나 외부 요인으로 인해 영향을 받게 되는 과정에서 정전기 대전 현상을 수반하게 되고, 이로 인해 정전기 방전에 의한 점화 위험성을 일정 부분 가지고 있어 사용 환경 내 화재 혹은 폭발 사고의 발생에 대한 우려가 분명히 존재하고 있었다.However, in the case of technologies related to existing powder coating compositions, including the prior art, electrostatic charging occurs when the powder coating moves through the tube or is affected by external factors in the process of forming a coating film through the electrostatic powder coating method. As a result, there is a certain risk of ignition due to electrostatic discharge, so there was a clear concern about the occurrence of a fire or explosion in the use environment.
이에 더해, 종래기술을 비롯한 기존의 분체도료 조성물과 관련한 기술들의 경우, 정전기 방전에 의한 점화 위험성을 고려하여 분체도료의 전기적 물성에 대한 변화를 제조 방법 혹은 조성적 측면에서 변화시키려 하더라도 이러한 시도가 분체도료가 기본적으로 갖추어야할 피도물에 대한 정전기적 부착 성능에 영향을 주어 결국 형성되는 도막의 상태 불량으로까지 이어질 수 있는 문제점이 있었다.In addition, in the case of technologies related to existing powder coating compositions, including prior art, even if attempts are made to change the electrical properties of the powder coating in terms of manufacturing method or composition in consideration of the risk of ignition due to electrostatic discharge, such attempts are not effective in changing the powder coating composition. There was a problem in that it affected the electrostatic adhesion performance of the paint to the object, which is a basic requirement of the paint, and could eventually lead to poor condition of the formed paint film.
본 발명은 상기 문제점을 해결하기 위해 창작된 것으로써, 본 발명의 목적은 분체도료가 기본적으로 갖추어야할 피도물에 대한 정전기적 부착과 관련한 물성과 정전기 방전에 의한 점화 위험성에 관한 예방 효과를 제공하는 물성간의 균형적 개선을 통해 두 기능 모두가 유의하게 발현될 수 있는 정전 분체도장용 분체도료 조성물을 제조하기 위한 기술을 제공하는데 있다.The present invention was created to solve the above problems, and the purpose of the present invention is to provide the basic properties of powder coatings related to electrostatic adhesion to the object and the properties that provide a preventive effect regarding the risk of ignition due to electrostatic discharge. The aim is to provide a technology for manufacturing a powder coating composition for electrostatic powder coating that can significantly express both functions through balanced improvement between the two functions.
상기 목적을 달성하기 위하여 본 발명의 정전 분체도장용 분체도료 조성물 제조방법은, 중량평균분자량 9500 내지 9700을 갖춘 카복실기(Carboxyl group) 함유 폴리에스테르 (Polyester) 수지 85 내지 89 중량부 및 β-hydroxyalkylamide (β-HAA) 6 중량부를 분쇄기에 넣어 분산 처리하는 A단계; 볏짚 유래 그래핀(Graphene)을 준비하는 B단계; 상기 A단계를 통해 마련된 분산 처리물에 상기 B단계를 통해 준비된 볏짚 유래 그래핀(Graphene) 1.2 내지 1.3 중량부, 염화 부틸트리페닐포스포늄(Butyltriphenylphosphonium chloride) 3 중량부 및 첨가제를 첨가하여 추가 분산 처리하는 C단계; 상기 C단계를 통해 마련된 2차 분산 처리물를 용융 압출기에 넣어 90℃의 온도 환경에서 용융 처리하는 D단계; 및 상기 D단계를 통해 마련된 용융 처리물을 냉각 처리 후 분쇄시켜 분체도료 조성물 제조하는 E단계;를 포함하며, 상기 B단계는, 볏짚을 85℃의 온도 환경 내에서 황산을 이용해 8분 내지 10분간 가수분해시키는 B-1단계; 상기 B-1단계를 통해 마련된 가수분해 결과물에 110℃의 온도 환경 내에서 수산화칼슘 및 아황산 마그네슘을 포함하는 혼합 처리제를 첨가 처리한 후, 과산화수소를 이용해 80℃의 온도 환경 내에서 3시간 동안 표백 처리하는 B-2단계; 상기 B-2단계를 통해 마련된 표백 처리물에 염화 니켈을 이용해 촉매화 및 건조 처리하여 볏짚 유래 중간산물을 수득하는 B-3단계; 상기 B-3 단계를 통해 마련된 볏짚 유래 중간산물을 무산소 환경에서 400℃ 내지 450℃ 온도로 6시간동안 1차 열처리한 후, 600℃ 내지 650℃ 온도로 3시간동안 2차 열처리하고 난 뒤, 40℃ 미만으로 냉각 처리하는 B-4단계; 상기 B-4단계를 통해 열 처리 및 냉각 처리를 거친 볏짚 유래 중간산물을 세척 후 건조시켜 볏짚 유래 그래핀(Graphene)을 마련하는 B-5단계;를 포함한다.In order to achieve the above object, the method for producing a powder coating composition for electrostatic powder coating of the present invention includes 85 to 89 parts by weight of polyester resin containing a carboxyl group having a weight average molecular weight of 9500 to 9700 and β-hydroxyalkylamide. Step A of dispersing 6 parts by weight of (β-HAA) in a grinder; Step B, preparing rice straw-derived graphene; Additional dispersion treatment by adding 1.2 to 1.3 parts by weight of rice straw-derived graphene prepared through step B, 3 parts by weight of butyltriphenylphosphonium chloride, and additives to the dispersion treatment prepared through step A. Step C; Step D of melting the secondary dispersed product prepared through step C in a melt extruder in a temperature environment of 90°C; And a step E of producing a powder coating composition by cooling and pulverizing the molten product prepared through step D. In step B, the rice straw is treated with sulfuric acid in a temperature environment of 85° C. for 8 to 10 minutes. B-1 step of hydrolysis; A mixed treatment agent containing calcium hydroxide and magnesium sulfite is added to the hydrolysis result prepared through step B-1 in a temperature environment of 110°C, and then bleached using hydrogen peroxide for 3 hours in a temperature environment of 80°C. B-2 stage; Step B-3 of obtaining a rice straw-derived intermediate product by catalyzing and drying the bleached product prepared through step B-2 using nickel chloride; The rice straw-derived intermediate product prepared through step B-3 was first heat-treated in an oxygen-free environment at a temperature of 400 ℃ to 450 ℃ for 6 hours, and then secondary heat treatment was performed at 600 ℃ to 650 ℃ for 3 hours, and then 40 Step B-4 of cooling to less than ℃; It includes step B-5 of preparing rice straw-derived graphene by washing and drying the intermediate product derived from rice straw that has undergone heat treatment and cooling treatment through step B-4.
여기서, 상기 B-1단계는 볏짚 100 중량부에 황산 2.3 내지 2.5 중량부를 이용하여 가수분해 처리를 수행하는 단계이며, 상기 B-2단계는 가수분해 결과물 100 중량부에 수산화칼슘 3중량부 및 아황산 마그네슘 1.8 중량부를 포함하는 혼합 처리제를 이용하여 첨가 처리한 후, 과산화수소 4.2 중량부를 이용해 표백 처리를 수행하는 단계이다.Here, step B-1 is a step of performing hydrolysis treatment using 2.3 to 2.5 parts by weight of sulfuric acid per 100 parts by weight of rice straw, and step B-2 is a step of performing hydrolysis treatment using 3 parts by weight of calcium hydroxide and magnesium sulfite for 100 parts by weight of the hydrolysis result. After addition treatment using a mixed treatment agent containing 1.8 parts by weight, bleaching treatment is performed using 4.2 parts by weight of hydrogen peroxide.
또한, 상기 B-3단계는 상기 B-2단계를 통해 마련된 표백 처리물 100 중량부와 염화 니켈 1.5 중량부를 15℃의 온도환경 내에서 3시간동안 교반하여 촉매화 처리 후, 80℃의 온도 환경에서 건조 처리하여 6중량% 미만의 함수량을 갖춘 볏짚 유래 중간산물을 수득하는 단계이다.In addition, in step B-3, 100 parts by weight of the bleached material prepared through step B-2 and 1.5 parts by weight of nickel chloride are stirred for 3 hours in a temperature environment of 15°C, followed by catalytic treatment, and then catalyzed in a temperature environment of 80°C. This is the step of obtaining a rice straw-derived intermediate product with a water content of less than 6% by weight through drying treatment.
아울러, 상기 C단계를 통해 첨가되는 첨가제는 탄산칼슘(CaCO3) 5 중량부, 레벨링제 0.36 중량부를 포함하며, 상기 첨가제는 분산제, 핀홀 방지제, 광택 조절제, 난연제, 크래터링 방지제, 습윤제 및 착색 안료 중 적어도 하나 이상을 더 포함한다.In addition, the additive added through step C includes 5 parts by weight of calcium carbonate (CaCO 3 ) and 0.36 parts by weight of a leveling agent, and the additives include a dispersant, pinhole prevention agent, gloss control agent, flame retardant, anti-cratting agent, wetting agent, and color pigment. Includes at least one more of
그리고 상기 E단계를 통해 제조되는 분체도료 조성물은 35㎛ 내지 40㎛의 평균입자, 1.0×106Ω 내지 1.0×108Ω의 표면 전기 저항성 및 26mJ 내지 30mJ의 최소 점화 에너지(MIE, Minimum Ignition Energy)를 갖춘다.And the powder coating composition prepared through step E has an average particle size of 35㎛ to 40㎛, a surface electrical resistance of 1.0×10 6 Ω to 1.0×10 8 Ω, and a minimum ignition energy (MIE) of 26mJ to 30mJ. ) is equipped with
한편, 상기 목적을 달성하기 위하여 다른 일례로써 본 발명은 앞 서 설명한 정전 분체도장용 분체도료 조성물 제조방법에 의하여 제조된 정전 분체도장용 분체도료 조성물을 포함한다.Meanwhile, in order to achieve the above object, as another example, the present invention includes a powder coating composition for electrostatic powder coating manufactured by the method for producing a powder coating composition for electrostatic powder coating described above.
본 발명에 의하면 다음과 같은 효과가 있다.According to the present invention, the following effects are achieved.
첫째, 볏짚 유래 그래핀(Graphene)의 조성적 특징 및 제조공정상의 조건에 관한 특징을 기반으로 정전 분체도장 진행 공정에서 분체도료의 정전기 방전에 의한 점화 위험성에 관한 예방 효과를 제공하는 물성이 부여되어 분체도료의 사용상의 점화 위험성을 최소화하고 이와 연계되어 발생 가능한 공정 환경 내 화재 혹은 폭발 사고가 예방될 수 있다.First, based on the compositional characteristics of rice straw-derived graphene and the characteristics of the manufacturing process conditions, it is given physical properties that provide a preventive effect on the risk of ignition due to electrostatic discharge of powder coating during the electrostatic powder coating process. The risk of ignition when using powder coating is minimized, and fire or explosion accidents that may occur in the process environment can be prevented.
둘째, 분체도료가 기본적으로 갖추어야할 피도물에 대한 정전기적 부착과 관련한 물성에 정전 분체도장 진행 공정에서 분체도료의 정전기 방전에 의한 점화 위험성에 관한 예방 효과를 제공하기 위해 발현되는 물성으로 인한 영향이 최소화되고 두 물성간의 균형적 개선을 이룰 수 있다.Second, the physical properties related to electrostatic adhesion to the object that powder coatings must have as a basic requirement are minimized to prevent the risk of ignition due to electrostatic discharge of powder coatings during the electrostatic powder coating process. and a balanced improvement between the two physical properties can be achieved.
셋째, 정전 분체도장 진행에 따라 분체도료를 이용해 피도물에 형성되는 도막의 내충격성, 비등수성, 음극박리성, 내후성 등 물리적 특성과 관련한 물성이 우수하게 갖춰진다.Third, as electrostatic powder coating progresses, the coating film formed on the object to be coated using powder coating has excellent physical properties such as impact resistance, boiling water resistance, cathodic peelability, and weather resistance.
도1은 본 발명의 정전 분체도장용 분체도료 조성물의 제조방법에 대한 순서도이다. Figure 1 is a flowchart of a method for manufacturing the powder coating composition for electrostatic powder coating of the present invention.
본 발명의 바람직한 실시예에 대하여 첨부된 도면을 참조하여 더 구체적으로 설명하되, 이미 주지된 기술적 부분에 대해서는 설명의 간결함을 위해 생략하거나 압축하기로 한다.Preferred embodiments of the present invention will be described in more detail with reference to the attached drawings, but already well-known technical parts will be omitted or compressed for brevity of explanation.
1. 정전 분체도장용 분체도료 조성물의 제조방법에 관한 설명1. Description of the manufacturing method of the powder coating composition for electrostatic powder coating
본 발명의 정전 분체도장용 분체도료 조성물은 도1에 도시된 바와 같이 정전 분체도장용 분체도료 조성물의 제조방법에 의해 제조되는 결과물로서, 이에 관해 아래에서 단계별로 자세히 설명하고자 한다.The powder coating composition for electrostatic powder coating of the present invention is a result of manufacturing a powder coating composition for electrostatic powder coating as shown in Figure 1, and this will be described in detail step by step below.
(1) 제1분산 처리단계(A단계, S110)(1) First distributed processing step (Step A, S110)
본 단계는 우선적으로 카복실기(Carboxyl group) 함유 폴리에스테르 (Polyester) 수지와 β-HAA(β-hydroxyalkylamide)를 분쇄기(Henschel FM-10 Premixer)에 넣어 1분간 고르게 분쇄 및 분산 처리하는 과정을 진행한다.In this step, the carboxyl group-containing polyester resin and β-HAA (β-hydroxyalkylamide) are first placed in a grinder (Henschel FM-10 Premixer) and evenly pulverized and dispersed for 1 minute. .
여기서, 카복실기(Carboxyl group) 함유 폴리에스테르 (Polyester) 수지는 분체도료의 고전압(60kV 내지 120kV) 하에서 부극성으로 대전되어 피도물에 대한 정전기적 부착되기 위한 기본적 물성의 기저가 되는 주제이다. Here, polyester resin containing a carboxyl group is negatively charged under the high voltage (60 kV to 120 kV) of the powder coating and is the basis of the basic physical properties for electrostatic attachment to the object to be coated.
이러한 카복실기(Carboxyl group) 함유 폴리에스테르 (Polyester) 수지는 에스테르기(基)가 연결기가 된 고분자를 지칭하는 것으로, 말단에 카르복실기(Carboxyl)가 있는 폴리에스테르 수지로서, 일반적으로 옥외용 수지로 많이 사용된다.Polyester resin containing a carboxyl group refers to a polymer in which an ester group is a linking group. It is a polyester resin with a carboxyl group at the end, and is generally used as an outdoor resin. do.
제품예로서, 카복실기(Carboxyl group) 함유 폴리에스테르 (Polyester) 수지는 UCB그룹의 제품을 사용할 수 있으며, 구체적으로 중량평균분자량 9500 내지 9700을 갖추고 있으며, 7∼16 포아즈 (P)/200 ℃의 점도와 25 내지 40의 산가를 갖춤이 바람직히다.As a product example, polyester resin containing a carboxyl group can be used as a product of the UCB group, and specifically has a weight average molecular weight of 9500 to 9700, and 7 to 16 poise (P) / 200 ℃. It is desirable to have a viscosity of and an acid value of 25 to 40.
이러한 카복실기(Carboxyl group) 함유 폴리에스테르 (Polyester) 수지 물질 상태 조건들, 특히 중량평균분자량에 대한 조건은 앞 서 설명한 적정 범위를 벗어날 경우 도막 형성 전 도료의 흐름(Sagging)현상을 유발하거나, 도막 형성에 관한 분산성 및 레벨링성의 저하 혹은 불량으로 이어지게 된다.If these carboxyl group-containing polyester resin material state conditions, especially the weight average molecular weight conditions, are outside the appropriate range described above, it may cause sagging of the paint before forming the paint film or damage the paint film. This leads to a decrease or defect in dispersibility and leveling properties regarding formation.
이와 같은 구체적 조건을 갖춘 카복실기(Carboxyl group) 함유 폴리에스테르 (Polyester) 수지는 전체 조성물 내에서 85 내지 89 중량부로 마련됨이 바람직한데, 이는 카복실기(Carboxyl group) 함유 폴리에스테르 (Polyester) 수지가 85 중량부 미만으로 마련될 경우 추후 설명될 β-HAA(β-hydroxyalkylamide)와의 조성적 비율 변화로 인한 도막의 경화성 및 경화 후 도막에 갖춰지는 내충격성 및 내후성이 저해될 뿐만 아니라, 추후 설명될 볏짚 유래 그래핀(Graphene)과의 조성적 비율 변화로 인해 정전 분체도장 진행 공정에서 분체도료의 정전기 방전에 의한 점화 위험성에 관한 예방을 위한 표면 전기 저항성 및 최소 점화 에너지가 적정범위를 벗어나게 되기 때문이다.The polyester resin containing a carboxyl group that meets these specific conditions is preferably prepared in an amount of 85 to 89 parts by weight in the total composition, which means that the polyester resin containing a carboxyl group is 85 parts by weight. If prepared in less than parts by weight, the curability of the coating film and the impact resistance and weather resistance provided by the coating film after curing are impaired due to changes in the compositional ratio with β-HAA (β-hydroxyalkylamide), which will be explained later, as well as rice straw-derived This is because, due to changes in the compositional ratio with graphene, the surface electrical resistance and minimum ignition energy for preventing the risk of ignition due to electrostatic discharge of powder coating during the electrostatic powder coating process fall outside the appropriate range.
아울러, 카복실기(Carboxyl group) 함유 폴리에스테르 (Polyester) 수지가 89 중량부를 초과할 경우 추후 설명될 볏짚 유래 그래핀(Graphene)과의 조성적 비율 변화로 인해 정전 분체도장 진행 공정에서 분체도료의 정전기 방전에 의한 점화 위험성에 관한 예방을 위한 표면 전기 저항성 및 최소 점화 에너지가 낮아지며 관련 물성의 발현 자체가 제공되지 않게 된다.In addition, if the polyester resin containing a carboxyl group exceeds 89 parts by weight, static electricity of the powder coating may be generated during the electrostatic powder coating process due to a change in the compositional ratio with graphene derived from rice straw, which will be explained later. The surface electrical resistance and minimum ignition energy to prevent the risk of ignition due to discharge are lowered, and the expression of related physical properties itself is not provided.
이와 연계되어 β-HAA(β-hydroxyalkylamide)은 TGIC(Triglycidyl isocyanurate)에 비해 독성이 낮으며, 제조공정이 비교적 단순하고 제조원가가 저렴한 장점을 가진 경화제로서 카복실기(Carboxyl group) 함유 폴리에스테르 (Polyester) 수지는 전체 조성물 내에서 85 내지 89 중량부에 대해 6 중량부의 함량 수준을 갖춤이 바람직하다.In connection with this, β-HAA (β-hydroxyalkylamide) is a curing agent that has lower toxicity than TGIC (Triglycidyl isocyanurate), has a relatively simple manufacturing process, and has low manufacturing costs. It is a polyester containing a carboxyl group. The resin preferably has a content level of 6 parts by weight relative to 85 to 89 parts by weight in the total composition.
이는 앞 서 설명한 바와 같이 카복실기(Carboxyl group) 함유 폴리에스테르 (Polyester) 수지와의 적정 함량 수준에 관한 범위를 설정하여, 도막의 경화성 및 경화 후 도막에 갖춰지는 내충격성 및 내후성의 저해를 막고, TGIC에 비해서 기계적 강도 및 내열성(overbake resistance)이 떨어진다는 단점을 최대한 보안하기 위함이다.As explained previously, this sets the range for the appropriate content level of polyester resin containing a carboxyl group, preventing the curing of the coating film and the impact resistance and weather resistance provided by the coating film after curing from being impaired. This is to minimize the disadvantage of lower mechanical strength and heat resistance (overbake resistance) compared to TGIC.
더욱 구체적으로, 카복실기(Carboxyl group) 함유 폴리에스테르 (Polyester) 수지와의 관계를 고려하여 경화제로서 역할을 수행하는 β-HAA(β-hydroxyalkylamide)는 Dimethyl adipate 14중량부 (0.1404 mmol)와 diethanolamine 36 중량부(0.2784 mmol)를 증류장치와 교반기에 넣고 0.1 wt%에 해당하는 소듐메틸레이트(NaOCH3)를 추가한 뒤 90 ℃의 온도 환경에서 교반하고, 1시간이 경과된 후 증류장치에 감압을 걸어주어 메탄올을 제거하면서 반응을 진행 시킨 후, 반응물이 굳게 되면 반응을 종결하고 얻어진 고체생성물을 막자사발을 이용해서 잘게 부순 후 클로로포름(CHCl3)로 세척하고 진공에서 건조하여 마련한다.More specifically, considering its relationship with polyester resin containing a carboxyl group, β-HAA (β-hydroxyalkylamide), which acts as a curing agent, is composed of 14 parts by weight (0.1404 mmol) of dimethyl adipate and 36 parts by weight of diethanolamine. Add parts by weight (0.2784 mmol) to the distillation device and stirrer, add 0.1 wt% of sodium methylate (NaOCH 3 ), stir in a temperature environment of 90°C, and after 1 hour, reduce the pressure in the distillation device. After the reaction proceeds while removing methanol by walking, the reaction is terminated when the reactant solidifies, and the obtained solid product is crushed into small pieces using a mortar, washed with chloroform (CHCl 3 ), and dried in vacuum.
결과적으로, 9500 내지 9700의 중량평균분자량, 7∼16 포아즈 (P)/200 ℃의 점도 및 25 내지 40의 산가를 갖춘 카복실기(Carboxyl group) 함유 폴리에스테르 (Polyester) 수지 85 내지 89 중량부(가장 바람직하게는 88 중량부) 와 β-HAA(β-hydroxyalkylamide) 6중량부를 분쇄기(Henschel FM-10 Premixer)에 넣어 1분간 고르게 분쇄 및 분산 처리하여 1차 분산 처리물을 마련한다.As a result, 85 to 89 parts by weight of a polyester resin containing a carboxyl group with a weight average molecular weight of 9500 to 9700, a viscosity of 7 to 16 poise (P) / 200 ° C., and an acid value of 25 to 40. (Most preferably 88 parts by weight) and 6 parts by weight of β-HAA (β-hydroxyalkylamide) in a grinder (Henschel FM-10 Premixer) and evenly pulverized and dispersed for 1 minute to prepare a first dispersed product.
(2) 그래핀 준비단계(B단계, S120)(2) Graphene preparation step (step B, S120)
본 단계에서는 볏짚 유래 그래핀(Graphene)을 준비하는 과정이 진행된다.In this step, the process of preparing rice straw-derived graphene is carried out.
이러한 그래핀 준비단계(S120)는 쉽게 버려지고 활용되지 않은 볏짚을 이용하여 비산화형 그래핀을 제조하는 과정으로, 이를 통해 마련되는 볏짚 유래 그래핀(Graphene)은 다공성 구조 및 큰 비표면적을 갖추고 있다.This graphene preparation step (S120) is a process of manufacturing non-oxidized graphene using easily discarded and unused rice straw, and the rice straw-derived graphene prepared through this process has a porous structure and a large specific surface area. .
이를 위해, 우선 볏짚을 85℃의 온도 환경 내에서 황산을 이용해 8분 내지 10분간 가수분해시키는 제1전처리 단계(B-1단계)가 진행된다.To this end, a first pretreatment step (step B-1) is performed in which rice straw is hydrolyzed using sulfuric acid for 8 to 10 minutes in a temperature environment of 85°C.
구체적으로, 제1전처리 단계(B-1단계)에서는 볏짚 100 중량부에 황산 2.3 내지 2.5 중량부를 이용하여 85℃의 온도 환경 내에서 8분 내지 10분간 가수분해가 진행됨에 따라 가수분해 결과물로서 리그노셀룰로오스(Ligno-cellulose)가 생성된다.Specifically, in the first pretreatment step (step B-1), 2.3 to 2.5 parts by weight of sulfuric acid is used per 100 parts by weight of rice straw, and hydrolysis proceeds for 8 to 10 minutes in a temperature environment of 85°C, producing league as a result of hydrolysis. Ligno-cellulose is produced.
다음으로, 제1전처리 단계(B-1단계)를 통해 마련된 가수분해 결과물인 리그노셀룰로오스에 110℃의 온도 환경 내에서 수산화칼슘 및 아황산 마그네슘을 포함하는 혼합 처리제를 첨가 처리하여 다공성 셀룰로오스를 마련한 뒤, 과산화수소를 이용해 80℃의 온도 환경 내에서 3시간 동안 다공성 셀룰로오스를 표백 처리하는 제2전처리 단계(B-2단계)가 진행된다.Next, porous cellulose is prepared by adding a mixed treatment agent containing calcium hydroxide and magnesium sulfite to the lignocellulose, which is the hydrolysis result prepared through the first pretreatment step (step B-1), in a temperature environment of 110°C. A second pretreatment step (step B-2) is performed in which porous cellulose is bleached using hydrogen peroxide in a temperature environment of 80°C for 3 hours.
더욱 구체적으로, 제2전처리 단계(B-2단계)에서는 가수분해 결과물로서 리그노셀룰로오스 100 중량부에 수산화칼슘 3중량부 및 아황산 마그네슘 1.8 중량부를 포함하는 혼합 처리제를 이용하여 첨가 처리하여 다공성 셀룰로오스가 생산되도록 한다.More specifically, in the second pretreatment step (step B-2), porous cellulose is produced by adding a mixed treatment agent containing 3 parts by weight of calcium hydroxide and 1.8 parts by weight of magnesium sulfite to 100 parts by weight of lignocellulose as a result of hydrolysis. Make it possible.
그 후 다공성 셀룰로오스에 과산화수소 4.2 중량부를 이용해 80℃의 온도 환경 내에서 3시간 동안 다공성 셀룰로오스를 표백 처리하여 표백 처리물을 제공한다.Thereafter, the porous cellulose is bleached using 4.2 parts by weight of hydrogen peroxide in a temperature environment of 80° C. for 3 hours to provide a bleached product.
다음으로, 제2전처리 단계(B-2단계)를 통해 마련된 표백 처리물에 염화 니켈을 이용해 촉매화 및 건조 처리하여 볏짚 유래 중간산물을 수득하는 제3전처리 단계(B-3단계)가 진행된다.Next, the third pretreatment step (B-3 step) is performed in which the bleached material prepared through the second pretreatment step (B-2 step) is catalyzed and dried using nickel chloride to obtain a rice straw-derived intermediate product. .
여기서, 제2전처리 단계(B-2단계)를 통해 마련된 표백 처리물은 100 중량부를 기준으로 먼저 염화 니켈 1.5 중량부를 15℃의 온도환경 내에서 3시간동안 교반하여 촉매화 처리를 진행하게 된다.Here, the bleached product prepared through the second pretreatment step (step B-2) is first subjected to catalytic treatment by stirring 1.5 parts by weight of nickel chloride for 3 hours in a temperature environment of 15°C, based on 100 parts by weight.
그 후, 촉매화 처리를 마친 표백 처리물은 80℃의 온도 환경에서 건조 처리하여 6중량% 미만의 함수량을 갖춘 볏짚 유래 중간산물로 수득이 이루어지게 된다.Afterwards, the bleached product that has completed the catalytic treatment is dried in a temperature environment of 80°C to obtain a rice straw-derived intermediate product with a moisture content of less than 6% by weight.
다음으로, 제3전처리 단계(B-3단계)를 통해 마련된 볏짚 유래 중간산물을 무산소 환경에서 400℃ 내지 450℃ 온도로 6시간동안 1차 열처리한 후, 600℃ 내지 650℃ 온도로 3시간동안 2차 열처리하고 난 뒤, 40℃ 미만으로 냉각 처리하는 제4전처리 단계(B-4단계)가 진행된다.Next, the rice straw-derived intermediate product prepared through the third pretreatment step (step B-3) was first heat-treated in an oxygen-free environment at a temperature of 400°C to 450°C for 6 hours, and then at a temperature of 600°C to 650°C for 3 hours. After the secondary heat treatment, the fourth pretreatment step (step B-4) of cooling to less than 40°C is performed.
구체적으로, 1차 열처리 방식은 400℃ 내지 450℃ 온도로 6시간에 걸쳐 점진적으로 승온시킨 뒤 보온을 진행하게 되고, 2차 열처리 방식은 600℃ 내지 650℃ 온도로 3시간에 걸쳐 점진적으로 승온시킨 뒤 보온을 진행하게 된다.Specifically, the first heat treatment method involves gradually raising the temperature to a temperature of 400°C to 450°C over 6 hours and then maintaining the temperature, and the second heat treatment method involves gradually raising the temperature to a temperature of 600°C to 650°C over 3 hours. Afterwards, warming is carried out.
그리고 2차 열처리를 마친 볏짚 유래 중간산물은 40℃ 미만으로 냉각시켜 그래핀 전구체가 마련된다.Then, the rice straw-derived intermediate product that has completed the secondary heat treatment is cooled to less than 40°C to prepare a graphene precursor.
최종적으로, 제4전처리 단계(B-4단계)를 통해 열 처리 및 냉각 처리를 거친 볏짚 유래 중간산물로서의 그래핀 전구체는 100 중량부를 기준으로 수산화나트륨 3 중량부에 4시간동안 1차 세척을 수행한 뒤, 다시 70℃의 온도환경에서 3.7 중량부의 염산 수용액에서 2시간동안 세척을 수행하고, 최종적으로 증류수로 중성이 될 때까지 세척을 수행한 뒤 건조시켜 세척 후 건조시켜 볏짚 유래 그래핀(Graphene)을 완성한다.Finally, the graphene precursor as an intermediate product derived from rice straw that has undergone heat treatment and cooling treatment through the fourth pretreatment step (step B-4) is first washed with 3 parts by weight of sodium hydroxide for 4 hours based on 100 parts by weight. Afterwards, washing was performed again in an aqueous solution of 3.7 parts by weight of hydrochloric acid for 2 hours in a temperature environment of 70°C, and finally washing was performed with distilled water until neutral, followed by drying, washing, and drying to obtain rice straw-derived graphene. ) to complete.
이와 같이 마련된 볏짚 유래 그래핀(Graphene)은 정전 분체도장 진행 공정에서 전체 분체도료 조성물의 정전기 방전에 의한 점화 위험성에 관한 예방 효과를 제공하는 물성의 부여를 이룸과 동시에, 앞 서 진행된 제1분산 처리단계(S110)를 통해 마련된 1차 분산 처리물 내 카복실기(Carboxyl group) 함유 폴리에스테르 (Polyester) 수지 및 β-HAA(β-hydroxyalkylamide)과의 상호 작용을 통해 분체도료가 기본적으로 갖추어야할 피도물에 대한 정전기적 부착과 관련한 물성과의 균형적 개선을 일으킨다.The rice straw-derived graphene prepared in this way provides physical properties that provide a preventive effect on the risk of ignition due to electrostatic discharge of the entire powder coating composition during the electrostatic powder coating process, and at the same time, it is used in the first dispersion treatment previously performed. Through interaction with the carboxyl group-containing polyester resin and β-HAA (β-hydroxyalkylamide) in the first dispersion treatment prepared through step (S110), powder coating is fundamentally required to be applied to the object to be coated. It causes a balanced improvement in physical properties related to electrostatic adhesion.
결과적으로, 볏짚 유래 그래핀(Graphene)은 전체 분체도료 조성물 내에서 표면 전기 저항성을 안정화시키고, 입자크기 대비 최소 점화 에너지 (MIE, Minimum Ignition Energy)의 수준을 높여 정전기 대전 현상의 발생 빈도를 급격히 낮추고 발생 되더라도 전화가 이루어질 수 있는 조건을 높임으로서, 정전분체 도장법을 통해 도막형성을 실시하는 과정에서 분체도료가 관을 이동하거나 외부 요인으로 인해 영향을 받게 되는 과정에서 정전기 대전 현상을 수반하게 되고, 이로 인해 정전기 방전에 의한 점화 위험성을 최대한 배제시키게 된다.As a result, rice straw-derived graphene stabilizes the surface electrical resistance within the entire powder coating composition and drastically reduces the frequency of electrostatic charging phenomenon by increasing the level of Minimum Ignition Energy (MIE) relative to particle size. By increasing the conditions for conversion to occur even if it occurs, in the process of forming a coating film through the electrostatic powder coating method, the phenomenon of electrostatic charging is accompanied when the powder coating moves through the pipe or is affected by external factors, and this leads to electrostatic charging. As a result, the risk of ignition due to electrostatic discharge is eliminated as much as possible.
하지만, 이러한 조성의 부가로 인해 도막 형성 전 분체도료를 접지된 피도물에 분사하여 정전기적으로 부착이 이루어지도록 하는 과정에 영향을 주어 결과적으로 도막의 물리적 물성의 수준에 영향을 줄 수 있기 때문에 균형적 물성 개선을 위해 적정 함량 수준과 제조 과정상의 방법전 조건을 정확히 갖춤과 함께, 나머지 조성간의 함량 수준 비율에 대한 조건이 지켜져야 한다.However, the addition of this composition may affect the process of electrostatically attaching the powder coating to the grounded object before forming the coating film, which can ultimately affect the level of physical properties of the coating film, so it is not balanced. In order to improve physical properties, the appropriate content level and pre-method conditions during the manufacturing process must be accurately met, and the conditions for the content level ratio between the remaining compositions must be maintained.
(3) 제2분산 처리단계(C단계, S130)(3) Second distributed processing step (C step, S130)
본 단계에서는 제1분산 처리단계(S110)를 통해 마련된 분산 처리물에 그래핀 준비단계(S120)를 통해 준비된 볏짚 유래 그래핀(Graphene), 염화 부틸트리페닐포스포늄(Butyltriphenylphosphonium chloride) 및 첨가제를 첨가하여 추가 분산 처리하는 과정이 진행된다.In this step, rice straw-derived graphene, butyltriphenylphosphonium chloride, and additives prepared through the graphene preparation step (S120) are added to the dispersion material prepared through the first dispersion treatment step (S110). Thus, the process of additional distributed processing proceeds.
여기서, 제1분산 처리단계(S110)를 통해 마련된 분산 처리물에 추가 첨가되는 볏짚 유래 그래핀(Graphene)은 1.2 내지 1.3 중량부의 함량 수준을 갖추고, 염화 부틸트리페닐포스포늄(Butyltriphenylphosphonium chloride)는 3 중량부의 함량 수준을 갖춤이 바람직하다.Here, rice straw-derived graphene, which is additionally added to the dispersed product prepared through the first dispersion treatment step (S110), has a content level of 1.2 to 1.3 parts by weight, and butyltriphenylphosphonium chloride has a content level of 3. It is desirable to have a content level of parts by weight.
이는 전체 분산도료 조성물 내 볏짚 유래 그래핀(Graphene)이 1.2 중량부 미만으로 마련될 경우 정전 분체도장 진행 공정에서 전체 분체도료 조성물의 정전기 방전에 의한 점화 위험성에 관한 예방 효과를 제공하는 물성과 관련하여 표면 전기 저항성이 급격히 저하되는 문제점이 있으며, 1.3 중량부를 초과할 경우 카복실기(Carboxyl group) 함유 폴리에스테르 (Polyester) 수지 및 β-HAA(β-hydroxyalkylamide)을 통해 도막을 형성하는 과정에서 갖춰져야 할 도막의 물리적 물성의 저해로 이어지는 악영향을 주는 문제점이 발생하기 때문이다.This is related to the physical properties that provide a preventive effect against the risk of ignition due to electrostatic discharge of the entire powder coating composition during the electrostatic powder coating process when the rice straw-derived graphene in the entire disperse coating composition is prepared in an amount of less than 1.2 parts by weight. There is a problem in that the surface electrical resistance decreases rapidly, and if it exceeds 1.3 parts by weight, the coating film that must be prepared in the process of forming a coating film through polyester resin containing a carboxyl group and β-hydroxyalkylamide (β-HAA) This is because problems that cause adverse effects that lead to the deterioration of the physical properties of the material occur.
또한, 염화 부틸트리페닐포스포늄(Butyltriphenylphosphonium chloride)는 3 중량부의 적정 함량 수준을 갖춤이 바람직한데, 이는 β-HAA(β-hydroxyalkylamide)이 TGIC에 비해서 기계적 강도 및 내열성(overbake resistance)이 떨어진다는 단점을 보완하고 경화 속성을 개선 및 촉진시키기 위함으로 해당 적정 함량 수준을 벗어날 경우 도막의 경화 과정에서 도료의 흐름(Sagging)현상이 유발되고 막의 은폐성능 저하로 이어질 뿐만 아니라 도막의 기계적 강도 및 내열성(overbake resistance)이 부족한 문제점이 나타난다.In addition, it is desirable to have an appropriate content level of 3 parts by weight of butyltriphenylphosphonium chloride, which has the disadvantage that β-HAA (β-hydroxyalkylamide) has lower mechanical strength and heat resistance (overbake resistance) than TGIC. In order to supplement and improve and promote curing properties, if the appropriate content level is exceeded, sagging of the paint occurs during the curing process of the paint film, which not only leads to a decrease in the hiding performance of the film, but also reduces the mechanical strength and heat resistance of the film (overbake). A problem of insufficient resistance appears.
아울러, 첨가제는 탄산칼슘(CaCO3) 5 중량부, 레벨링제 0.36 중량부를 기본적으로 포함하고, 실시에 따라 추가적으로 분산제, 핀홀 방지제, 광택 조절제, 난연제, 크래터링 방지제, 습윤제, 체질 안료(Extender) 및 착색 안료 중 적어도 하나 이상을 더 포함할 수 있다. In addition, the additive basically includes 5 parts by weight of calcium carbonate (CaCO 3 ) and 0.36 parts by weight of a leveling agent, and depending on the implementation, additional dispersants, pinhole preventers, gloss control agents, flame retardants, anti-cratting agents, wetting agents, extenders, and It may further include at least one coloring pigment.
특히, 탄산칼슘(CaCO3)은 충진제로서 볏짚 유래 그래핀(Graphene)에 의한 정전기 대전 현상의 발생 빈도를 급격히 낮추고 발생 되더라도 전화가 이루어질 수 있는 조건을 높이는 물성적 특징으로 인해 도막 형성 전 분체도료를 접지된 피도물에 분사하여 정전기적으로 부착이 이루어지도록 하는 물성적 특징에 영향을 줄 수 있는 사항을 최대한 보완하기 위한 것으로 도막의 기계적 특성 개선을 위해 5중량부의 정정 함량 수준을 갖춤이 바람직하다.In particular, calcium carbonate (CaCO 3 ), as a filler, drastically reduces the frequency of electrostatic charging caused by rice straw-derived graphene and increases the conditions for conversion even if it occurs, so it is used as a powder coating before forming a film. This is to compensate as much as possible for matters that may affect the physical properties of electrostatic attachment by spraying on a grounded object, and it is desirable to have a correction content level of 5 parts by weight to improve the mechanical properties of the coating film.
여기서, 탄산칼슘(CaCO3)이 5 중량부의 적정 함량 수준을 벗어날 경우 도막의 분산성 저하 및 점도 상승을 유발할 뿐만 아니라, 볏짚 유래 그래핀(Graphene)에 의해 제공하고자 하는 물성적 특성의 단점이 오히려 부각되게 되는 문제점이 있다. Here, if calcium carbonate (CaCO 3 ) exceeds the appropriate content level of 5 parts by weight, it not only causes a decrease in dispersibility and an increase in viscosity of the coating film, but also causes disadvantages in the physical properties intended to be provided by rice straw-derived graphene. There is a problem that stands out.
(4) 용융 처리단계(D단계, S140)(4) Melt processing step (step D, S140)
본 단계에서는 앞 서 진행된 제2분산 처리단계(S130)를 통해 마련된 2차 분산 처리물를 용융 압출기(Werner&Pfleiderer ZSK-30)에 넣어 90℃의 온도 환경에서 용융 처리하여 압출(Zone 1: 100 ℃, Zone 2:100 ℃, Screw Speed: 300 rpm, Torque: 30∼50 %)하는 과정이 진행된다. In this step, the secondary dispersion material prepared through the previous second dispersion treatment step (S130) is put into a melt extruder (Werner&Pfleiderer ZSK-30) and melted and extruded in a temperature environment of 90°C (Zone 1: 100°C, Zone). 2:100 ℃, Screw Speed: 300 rpm, Torque: 30∼50%) is carried out.
(5) 냉각 및 분쇄 처리단계(E단계, S150)(5) Cooling and grinding processing step (E stage, S150)
마지막으로, 본 단계에서는 용융 처리단계(S140)를 통해 마련된 용융 처리물을 상온에서 냉각 처리 후 분쇄시켜 분체도료 조성물 제조하는 과정이 진행된다.Finally, in this step, the molten product prepared through the melt processing step (S140) is cooled at room temperature and then pulverized to produce a powder coating composition.
구체적으로, 냉각 처리까지 마친 용융 처리물은 Paudal K2-1형 햄머밀로 3회 이상 분쇄하여 35㎛ 내지 40㎛의 평균입자(D50)를 갖춘 분체도료 조성물로 만듬이 바람직하다.Specifically, it is preferable to grind the molten product after cooling treatment three or more times with a Paudal K2-1 type hammer mill to make a powder coating composition with average particles (D50) of 35㎛ to 40㎛.
결과적으로 본 단계(S150)까지 모두 거쳐 제조되는 분체도료 조성물은 35㎛ 내지 40㎛의 평균입자, 1.0×106Ω 내지 1.0×108Ω의 표면 전기 저항성 및 26mJ 내지 30mJ의 최소 점화 에너지(MIE, Minimum Ignition Energy)을 갖추게 된다.As a result, the powder coating composition manufactured through all steps (S150) has an average particle size of 35㎛ to 40㎛, a surface electrical resistance of 1.0×10 6 Ω to 1.0×10 8 Ω, and a minimum ignition energy (MIE) of 26mJ to 30mJ. , Minimum Ignition Energy).
그리고 이를 통해, 앞서 설명한 바와 같은 분체도료가 기본적으로 갖추어야할 피도물에 대한 정전기적 부착과 관련한 물성과 정전기 방전에 의한 점화 위험성에 관한 예방 효과를 제공하는 물성간의 균형적 개선을 통해 두 기능 모두가 유의하게 발현될 수 있는 정전 분체도장용 분체도료 조성물이 완성된다.Through this, both functions are maintained through a balanced improvement between the properties related to electrostatic adhesion to the object, which powder coatings as described above must basically have, and the properties that provide a preventive effect regarding the risk of ignition due to electrostatic discharge. A powder coating composition for electrostatic powder coating that can be expressed effectively has been completed.
2. 정전 분체도장용 분체도료 조성물의 물성에 관한 설명2. Description of physical properties of powder coating composition for electrostatic powder coating
본 발명에 따른 정전 분체도장용 분체도료 조성물 제조방법에 의해 제조된 정전 분체도장용 분체도료 조성물을 다양한 실시예로 마련하여 아래와 같은 다양한 실험 방법들을 통해 피도물에 형성되는 도막의 내충격성, 비등수성, 음극박리성, 내후성 등 물리적 물성과 분체도료 조성물 자체가 갖추고 있는 표면 전기 저항성 및 최소 점화 에너지에 대한 전기적 물성에 관해 검사를 수행하였으며, 당업계의 기술자들에게 자명한 수단에 의한 성질 등을 정의하기 위한 목적으로 하기 실험 방법들을 이용하였다. The powder coating composition for electrostatic powder coating manufactured by the method for manufacturing the powder coating composition for electrostatic powder coating according to the present invention was prepared in various embodiments to determine the impact resistance, boiling water properties, and Tests were conducted on physical properties such as cathodic peelability and weather resistance, as well as electrical properties of the powder coating composition itself, such as surface electrical resistance and minimum ignition energy, and defining properties by means that are obvious to those skilled in the art. For this purpose, the following experimental methods were used.
(1) 정전 분체도장용 분체도료 조성물의 실시예 준비(1) Preparation of examples of powder coating compositions for electrostatic powder coating
우선, 실시예 1 내지 실시예 8는 9600의 중량평균분자량, 12 포아즈 (P)/200 ℃의 점도 및 30의 산가를 갖춘 카복실기(Carboxyl group) 함유 폴리에스테르 (Polyester) 수지를 이용하였다.First, Examples 1 to 8 used a polyester resin containing a carboxyl group with a weight average molecular weight of 9600, a viscosity of 12 poise (P)/200°C, and an acid value of 30.
또한, 볏짚 100 중량부에 황산 2.3 중량부를 이용하여 85℃의 온도 환경 내에서 10분간 가수분해가 진행한 뒤, 가수분해 결과물에 110℃의 온도 환경 내에서 가수분해 결과물 100 중량부를 기준으로 수산화칼슘 3중량부 및 아황산 마그네슘 1.8 중량부를 포함하는 혼합 처리제를 첨가 처리하고, 과산화수소 4.2 중량부를 이용해 80℃의 온도 환경 내에서 3시간 동안 표백 처리하였다.In addition, 100 parts by weight of rice straw was hydrolyzed using 2.3 parts by weight of sulfuric acid in a temperature environment of 85°C for 10 minutes, and then calcium hydroxide 3 was added to the hydrolysis product based on 100 parts by weight of the hydrolysis result in a temperature environment of 110°C. A mixed treatment agent containing 1.8 parts by weight of magnesium sulfite and 1.8 parts by weight of magnesium sulfite was added and bleached using 4.2 parts by weight of hydrogen peroxide in a temperature environment of 80° C. for 3 hours.
그 후, 표백 처리물에 표백 처리물 100 중량부를 기준으로 먼저 염화 니켈 1.5 중량부를 15℃의 온도환경 내에서 3시간동안 교반하여 촉매화 처리하고, 80℃의 온도 환경에서 건조 처리하여 6중량% 미만의 함수량을 갖춘 볏짚 유래 중간산물을 마련한다.Thereafter, based on 100 parts by weight of the bleached material, 1.5 parts by weight of nickel chloride was first catalyzed by stirring in a temperature environment of 15°C for 3 hours, and then dried in an environment of 80°C to obtain 6% by weight of nickel chloride. An intermediate product derived from rice straw with a moisture content of less than 100% is prepared.
그리고 볏짚 유래 중간산물을 무산소 환경에서 400℃에서 450℃ 온도로 6시간에 걸쳐 점진적으로 승온시킨 뒤 보온을 진행하게 되고, 600℃에서 650℃ 온도로 3시간에 걸쳐 점진적으로 승온시킨 뒤 보온을 진행한 뒤, 40℃ 미만으로 냉각시켜 그래핀 전구체를 마련한다.In addition, the temperature of the rice straw-derived intermediate product is gradually raised from 400℃ to 450℃ over 6 hours in an oxygen-free environment and then kept warm. The temperature is gradually raised from 600℃ to 650℃ over 3 hours and then kept warm. Then, it is cooled below 40°C to prepare a graphene precursor.
최종적으로, 열 처리 및 냉각 처리를 거친 볏짚 유래 중간산물로서의 그래핀 전구체 100 중량부에 수산화나트륨 3 중량부를 이용해 4시간동안 1차 세척을 수행한 뒤, 다시 70℃의 온도환경에서 3.7 중량부의 염산 수용액에서 2시간동안 세척을 수행하고, 최종적으로 증류수로 중성이 될 때까지 세척을 수행한 뒤 건조시켜 세척 후 건조시켜 볏짚 유래 그래핀(Graphene)을 완성하였다.Finally, 100 parts by weight of the graphene precursor, which is an intermediate product derived from rice straw that has undergone heat treatment and cooling, was first washed for 4 hours using 3 parts by weight of sodium hydroxide, and then again washed with 3.7 parts by weight of hydrochloric acid in a temperature environment of 70°C. Washing was performed in an aqueous solution for 2 hours, and finally washing was performed with distilled water until neutral, then dried, and rice straw-derived graphene was completed by washing and drying.
그리고 제조되는 모든 실시예에 따른 분체도료 조성물은 38㎛ 내지 40㎛의 평균입자(D50)을 갖추도록 하였다.And the powder coating composition according to all manufactured examples had an average particle size (D50) of 38㎛ to 40㎛.
이와 같이 마련된 조성들을 이용해 아래 표1과 같은 함량 수준을 달리하여 다양한 실시예들을 마련하였으며, 표1에 도시된 조성별 수치의 단위는 중량부이다.Using the compositions prepared in this way, various examples were prepared by varying the content levels as shown in Table 1 below, and the unit of the numerical value for each composition shown in Table 1 is parts by weight.
이와 같이 마련된 실시예1 내지 실시예8을 이용해 아래 설명될 물성 검사들을 진행하였다.Physical property tests described below were conducted using Examples 1 to 8 prepared as described above.
(2) 기계적 물성에 관한 검사(2) Inspection of mechanical properties
본 발명에 따른 정전 분체도장용 분체도료 조성물의 조성을 위 표1과 같이 구성하되, 38㎛ 내지 40㎛의 평균입자(D50)을 갖춘 실시예1 내지 실시예8을 스프레이 건(Nordson Versa-Spray 100, applied at 80 kV)으로 피도물(강판)에 분사시켜 건조된 도막의 두께가 400 내지 450㎛이 되게 하였다. 피도물을 오븐에서 200 ℃를 유지한 채 14 min 동안 굽는 과정을 거쳐 도막을 형성하였다.The composition of the powder coating composition for electrostatic powder coating according to the present invention is as shown in Table 1 above, and Examples 1 to 8 with average particles (D50) of 38 ㎛ to 40 ㎛ were sprayed with a spray gun (Nordson Versa-Spray 100). , applied at 80 kV) was sprayed on the object (steel plate) so that the thickness of the dried film was 400 to 450㎛. A coating film was formed by baking the object in an oven at 200°C for 14 min.
실시예1 내지 실시예8을 기반으로 만들어진 도막들의 내충격성, 밀착성, 비등수성(rating), 음극박리성 및 내후성 시험을 진행하였으며, 그 결과는 아래 표2와 같다. The impact resistance, adhesion, boiling water rating, cathodic peelability, and weather resistance of the coating films made based on Examples 1 to 8 were tested, and the results are shown in Table 2 below.
- 내충격성 :CAN/CSA 245.2 12.12
- 밀착성: KSD 4317
- 비등수성: CAN/CSA 245.2
- 음극박리성: CAN/CSA 245.2
-촉진 내후성 : 램프-UVB 318 LAMP /온도-60 ℃/습도-80%/CYCLE: WETTING-4시간/DRYING-8시간/기간-6일[Test Standard]
- Impact resistance: CAN/CSA 245.2 12.12
- Adhesion: KSD 4317
- Effervescent aqueous: CAN/CSA 245.2
- Cathodic peelability: CAN/CSA 245.2
-Accelerated weather resistance: Lamp - UVB 318 LAMP / Temperature - 60 ℃ / Humidity - 80% / CYCLE: WETTING - 4 hours / DRYING - 8 hours / Period - 6 days
표2에 나타난 바와 같이 실시예2, 실시예3 및 실시예7에 의해 만들어진 도막들의 물리적, 기계적 특성이 양호한 상태를 유지하고 있음을 알 수 있는데, 이는 실시예3과 같이 적정 함량 수준을 상호 갖추어 배합되거나, 실시예2와 같이 볏짚 유래 그래핀의 함량 수준이 다소 부족하거나 실시예7과 같이 탄산칼슘의 함량 수준이 다소 초과되는 경우에 상대적으로 물리적, 기계적 물성이 개선 유지되기 때문이다.As shown in Table 2, it can be seen that the physical and mechanical properties of the coating films made in Example 2, Example 3, and Example 7 are maintained in good condition. This is because the appropriate content level is maintained as in Example 3. This is because the physical and mechanical properties are relatively improved when blended, or when the content level of rice straw-derived graphene is somewhat insufficient as in Example 2 or when the content level of calcium carbonate is slightly exceeded as in Example 7.
하지만 실시예2 및 실시예7의 경우, 아래 설명될 전기적 물성 시험 검사 결가에서는 다소 부족하거나 두 물성 간의 균형적 개선이 깨질 수 있다.However, in the case of Examples 2 and 7, the electrical property test results described below may be somewhat insufficient or the balanced improvement between the two properties may be broken.
(3) 전기적 물성에 관한 검사(3) Inspection of electrical properties
본 발명에 따른 정전 분체도장용 분체도료 조성물의 조성을 위 표1과 같이 구성하여 마련된 38㎛ 내지 40㎛의 평균입자(D50)을 갖춘 실시예1 내지 실시예8에 대해 스위스의 Kuhner사에서 제작된 MIKE 3 측정 장치를 이용해 점화에 필요한 최소의 에너지를 측정하였다.The composition of the powder coating composition for electrostatic powder coating according to the present invention was prepared by Kuhner in Switzerland for Examples 1 to 8 with average particles (D50) of 38㎛ to 40㎛ prepared by configuring the composition as shown in Table 1 above. The minimum energy required for ignition was measured using the MIKE 3 measuring device.
구체적으로, 최소점화에너지 측정장치를 이용한 점화에너지 제공을 위한 스파크(spark) 발생 방법은 1 내지 3 mJ일 경우에는 High-Voltage Relay로 유발하며, 10 내지 1,000 mJ 경우에는 Electrode movement로 유발시켜 시험을 실시하며, 시험에 적용된 국제규격의 시험방법은 EN 13821(2002)에 따른다.Specifically, the spark generation method to provide ignition energy using a minimum ignition energy measuring device is triggered by High-Voltage Relay in the case of 1 to 3 mJ, and induced by electrode movement in the case of 10 to 1,000 mJ. The international standard test method applied to the test is in accordance with EN 13821 (2002).
다음으로, 본 발명에 따른 정전 분체도장용 분체도료 조성물의 조성을 위 표1과 같이 구성하여 마련된 38㎛ 내지 40㎛의 평균입자(D50)을 갖춘 실시예1 내지 실시예8을 인산아연으로 전처리 한 1.0mm 냉간압연강판에 100∼120㎛ 두께로 도장하고, 200℃에서 8분 경화시켜 시료를 제작하고, 이 시료에 대해 표면 전기저항을 가오사끼사의 모델 R-503을 사용하여 ASTM-D257에 의거하여 측정하였다.Next, the composition of the powder coating composition for electrostatic powder coating according to the present invention was prepared as shown in Table 1 above, and Examples 1 to 8 with average particles (D50) of 38㎛ to 40㎛ were pretreated with zinc phosphate. A sample was produced by coating a 1.0mm cold rolled steel sheet to a thickness of 100-120㎛ and curing at 200°C for 8 minutes. The surface electrical resistance of this sample was measured according to ASTM-D257 using Kaosaki's model R-503. It was measured.
그 결과는 아래 표3과 같다.The results are shown in Table 3 below.
표3에 나타난 바와 같이 실시예1, 실시예3, 실시예5는 최소점화에너지의 수준을 충분히 높이 표면 전기저항의 수준 또한 충분히 안정적으로 유지하여 정전기 방전에 의한 점화 위험성에 관한 예방 효과를 제공할 수 있음은 분명하나, 실시예1 및 실시예5의 경우 앞 서 설명한 표2의 결과와 같이 상대적으로 물리적 물성에 대한 수준에 영향을 주어 분체도료가 기본적으로 갖춰야할 도막 형성의 조건들을 충분히 제공하지 못하는 문제점이 있다.As shown in Table 3, Examples 1, 3, and 5 sufficiently increase the level of minimum ignition energy and maintain a sufficiently stable level of surface electrical resistance to provide a preventive effect on the risk of ignition due to electrostatic discharge. It is clear that it is possible, but in the case of Examples 1 and 5, as shown in the results in Table 2 described above, it relatively affects the level of physical properties and does not sufficiently provide the conditions for forming a film that powder coatings must basically have. There is a problem that I cannot do.
결과적으로, 정전 분체도장 진행 공정에서 분체도료의 정전기 방전에 의한 점화 위험성에 관한 예방 효과를 제공하는 물성이 부여되어 분체도료의 사용상의 점화 위험성을 최소화하고 이와 연계되어 발생 가능한 공정 환경 내 화재 혹은 폭발 사고가 예방되도록 함과 동시에, 분체도료가 기본적으로 갖추어야할 피도물에 대한 정전기적 부착과 관련한 물성에 악영향을 주지 않고 균형적 개선을 이루기 위해서는 실시예3과 같은 조성적 특징을 갖추어야 한다.As a result, during the electrostatic powder coating process, physical properties are provided that provide a preventive effect on the risk of ignition due to electrostatic discharge of powder coating, thereby minimizing the risk of ignition when using powder coating, and fire or explosion in the process environment that may occur in connection with this. In order to prevent accidents and at the same time achieve balanced improvement without adversely affecting the physical properties related to electrostatic adhesion to the coated object, which powder coatings must have as a basic feature, it must have the same compositional characteristics as in Example 3.
본 발명에 개시된 실시예는 본 발명의 기술 사상을 한정하기 위한 것이 아니라 설명하기 위한 것이고, 이러한 실시예에 의해서 본 발명의 기술 사상의 범위가 한정되는 것은 아니다. 보호범위는 아래 청구범위에 의하여 해석되어야 하며, 그와 동등한 범위 내에 있는 모든 기술 사상은 본 발명의 권리 범위에 포함되는 것으로 해석되어야 할 것이다. The embodiments disclosed in the present invention are not intended to limit but illustrate the technical idea of the present invention, and the scope of the technical idea of the present invention is not limited by these examples. The scope of protection should be interpreted in accordance with the claims below, and all technical ideas within the equivalent scope should be interpreted as being included in the scope of rights of the present invention.
Claims (6)
볏짚 유래 그래핀(Graphene)을 준비하는 B단계;
상기 A단계를 통해 마련된 분산 처리물에 상기 B단계를 통해 준비된 볏짚 유래 그래핀(Graphene) 1.2 내지 1.3 중량부, 염화 부틸트리페닐포스포늄(Butyltriphenylphosphonium chloride) 3 중량부 및 첨가제를 첨가하여 추가 분산 처리하는 C단계;
상기 C단계를 통해 마련된 2차 분산 처리물를 용융 압출기에 넣어 90℃의 온도 환경에서 용융 처리하는 D단계; 및
상기 D단계를 통해 마련된 용융 처리물을 냉각 처리 후 분쇄시켜 분체도료 조성물 제조하는 E단계;를 포함하며,
상기 B단계는,
볏짚을 85℃의 온도 환경 내에서 황산을 이용해 8분 내지 10분간 가수분해시키는 B-1단계;
상기 B-1단계를 통해 마련된 가수분해 결과물에 110℃의 온도 환경 내에서 수산화칼슘 및 아황산 마그네슘을 포함하는 혼합 처리제를 첨가 처리한 후, 과산화수소를 이용해 80℃의 온도 환경 내에서 3시간 동안 표백 처리하는 B-2단계;
상기 B-2단계를 통해 마련된 표백 처리물에 염화 니켈을 이용해 촉매화 및 건조 처리하여 볏짚 유래 중간산물을 수득하는 B-3단계;
상기 B-3 단계를 통해 마련된 볏짚 유래 중간산물을 무산소 환경에서 400℃ 내지 450℃ 온도로 6시간동안 1차 열처리한 후, 600℃ 내지 650℃ 온도로 3시간동안 2차 열처리하고 난 뒤, 40℃ 미만으로 냉각 처리하는 B-4단계; 및
상기 B-4단계를 통해 열 처리 및 냉각 처리를 거친 볏짚 유래 중간산물을 세척 후 건조시켜 볏짚 유래 그래핀(Graphene)을 마련하는 B-5단계;를 포함하는 것을 특징으로 하는
정전 분체도장용 분체도료 조성물의 제조방법.
Step A of dispersing 85 to 89 parts by weight of polyester resin containing a carboxyl group having a weight average molecular weight of 9500 to 9700 and 6 parts by weight of β-hydroxyalkylamide (β-HAA) in a grinder;
Step B, preparing rice straw-derived graphene;
Additional dispersion treatment by adding 1.2 to 1.3 parts by weight of rice straw-derived graphene prepared through step B, 3 parts by weight of butyltriphenylphosphonium chloride, and additives to the dispersion treatment prepared through step A. Step C;
Step D of melting the secondary dispersed product prepared through step C in a melt extruder in a temperature environment of 90°C; and
It includes step E of producing a powder coating composition by cooling and pulverizing the molten product prepared through step D,
In step B,
Step B-1 of hydrolyzing rice straw using sulfuric acid for 8 to 10 minutes in a temperature environment of 85°C;
A mixed treatment agent containing calcium hydroxide and magnesium sulfite is added to the hydrolysis result prepared through step B-1 in a temperature environment of 110°C, and then bleached using hydrogen peroxide for 3 hours in a temperature environment of 80°C. Step B-2;
Step B-3 of obtaining a rice straw-derived intermediate product by catalyzing and drying the bleached product prepared through step B-2 using nickel chloride;
The rice straw-derived intermediate product prepared through step B-3 was first heat-treated in an oxygen-free environment at a temperature of 400 ℃ to 450 ℃ for 6 hours, and then secondary heat treatment was performed at 600 ℃ to 650 ℃ for 3 hours, and then 40 Step B-4 of cooling to less than ℃; and
A step B-5 of preparing rice straw-derived graphene by washing and drying the intermediate product derived from rice straw that has undergone heat treatment and cooling treatment through step B-4.
Method for producing a powder coating composition for electrostatic powder coating.
상기 B-1단계는 볏짚 100 중량부에 황산 2.3 내지 2.5 중량부를 이용하여 가수분해 처리를 수행하는 단계이며,
상기 B-2단계는 가수분해 결과물 100 중량부에 수산화칼슘 3중량부 및 아황산 마그네슘 1.8 중량부를 포함하는 혼합 처리제를 이용하여 첨가 처리한 후, 과산화수소 4.2 중량부를 이용해 표백 처리를 수행하는 단계인 것을 특징으로 하는
정전 분체도장용 분체도료 조성물의 제조방법.
According to paragraph 1,
Step B-1 is a step of performing hydrolysis treatment using 2.3 to 2.5 parts by weight of sulfuric acid per 100 parts by weight of rice straw,
The B-2 step is characterized in that 100 parts by weight of the hydrolysis result is subjected to addition treatment using a mixed treatment agent containing 3 parts by weight of calcium hydroxide and 1.8 parts by weight of magnesium sulfite, followed by bleaching treatment using 4.2 parts by weight of hydrogen peroxide. doing
Method for producing a powder coating composition for electrostatic powder coating.
상기 B-3단계는 상기 B-2단계를 통해 마련된 표백 처리물 100 중량부와 염화 니켈 1.5 중량부를 15℃의 온도환경 내에서 3시간동안 교반하여 촉매화 처리 후, 80℃의 온도 환경에서 건조 처리하여 6중량% 미만의 함수량을 갖춘 볏짚 유래 중간산물을 수득하는 단계인 것을 특징으로 하는
정전 분체도장용 분체도료 조성물의 제조방법.
According to paragraph 2,
In step B-3, 100 parts by weight of the bleached material prepared through step B-2 and 1.5 parts by weight of nickel chloride are stirred for 3 hours in a temperature environment of 15°C to catalyze treatment, and then dried in a temperature environment of 80°C. Characterized by the step of processing to obtain an intermediate product derived from rice straw with a water content of less than 6% by weight.
Method for producing a powder coating composition for electrostatic powder coating.
상기 C단계를 통해 첨가되는 첨가제는 탄산칼슘(CaCO3) 5 중량부, 레벨링제 0.36 중량부를 포함하며,
상기 첨가제는 분산제, 핀홀 방지제, 광택 조절제, 난연제, 크래터링 방지제, 습윤제 및 착색 안료 중 적어도 하나 이상을 더 포함하는 것을 특징으로 하는
정전 분체도장용 분체도료 조성물의 제조방법.
According to paragraph 3,
The additive added through step C includes 5 parts by weight of calcium carbonate (CaCO 3 ) and 0.36 parts by weight of a leveling agent,
The additive further comprises at least one of a dispersing agent, a pinhole preventing agent, a gloss control agent, a flame retardant, an anti-cratting agent, a wetting agent, and a coloring pigment.
Method for producing a powder coating composition for electrostatic powder coating.
상기 E단계를 통해 제조되는 분체도료 조성물은 35㎛ 내지 40㎛의 평균입자, 1.0×106Ω 내지 1.0×108Ω의 표면 전기 저항성 및 26mJ 내지 30mJ의 최소 점화 에너지 (MIE, Minimum Ignition Energy)를 갖추는 것을 특징으로 하는
정전 분체도장용 분체도료 조성물의 제조방법.
According to paragraph 4,
The powder coating composition prepared through step E has average particles of 35㎛ to 40㎛, surface electrical resistance of 1.0×10 6 Ω to 1.0×10 8 Ω, and Minimum Ignition Energy (MIE) of 26mJ to 30mJ. Characterized by having
Method for producing a powder coating composition for electrostatic powder coating.
A powder coating composition for electrostatic powder coating, characterized in that it is manufactured by the method for producing the powder coating composition for electrostatic powder coating according to any one of claims 1 to 5.
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| KR102042203B1 (en) | 2017-11-10 | 2019-11-07 | 주식회사 케이씨씨 | Powder coating composition |
| CN110511367A (en) | 2019-08-20 | 2019-11-29 | 安徽神剑新材料股份有限公司 | A kind of polyester resin for powder coating of containing graphene |
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