KR102234608B1 - UV curable composition having excellent flexibility and hardness, and method of manufacturing - Google Patents
UV curable composition having excellent flexibility and hardness, and method of manufacturing Download PDFInfo
- Publication number
- KR102234608B1 KR102234608B1 KR1020200111674A KR20200111674A KR102234608B1 KR 102234608 B1 KR102234608 B1 KR 102234608B1 KR 1020200111674 A KR1020200111674 A KR 1020200111674A KR 20200111674 A KR20200111674 A KR 20200111674A KR 102234608 B1 KR102234608 B1 KR 102234608B1
- Authority
- KR
- South Korea
- Prior art keywords
- weight
- parts
- coating
- peg
- reaction solution
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 37
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 37
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 claims abstract description 31
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims abstract description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008119 colloidal silica Substances 0.000 claims abstract description 12
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 11
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 9
- 235000019253 formic acid Nutrition 0.000 claims description 9
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 7
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 abstract description 2
- 150000007524 organic acids Chemical class 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 description 25
- 239000011248 coating agent Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 21
- 238000001723 curing Methods 0.000 description 8
- 239000008199 coating composition Substances 0.000 description 7
- 239000011247 coating layer Substances 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 239000012855 volatile organic compound Substances 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 238000003848 UV Light-Curing Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 125000004386 diacrylate group Chemical group 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- ILBBNQMSDGAAPF-UHFFFAOYSA-N 1-(6-hydroxy-6-methylcyclohexa-2,4-dien-1-yl)propan-1-one Chemical compound CCC(=O)C1C=CC=CC1(C)O ILBBNQMSDGAAPF-UHFFFAOYSA-N 0.000 description 1
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 1
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 1
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 1
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- KNSXNCFKSZZHEA-UHFFFAOYSA-N [3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical class C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C KNSXNCFKSZZHEA-UHFFFAOYSA-N 0.000 description 1
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical class C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Images
Classifications
-
- 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/71—Monoisocyanates or monoisothiocyanates
- C08G18/718—Monoisocyanates or monoisothiocyanates containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- 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
- C08K3/36—Silica
-
- 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
- C09D7/65—Additives macromolecular
-
- 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
- C09D7/80—Processes for incorporating ingredients
Abstract
Description
본 발명은 UV 경화형 조성물 및 제조방법에 관한 것으로, 보다 상세하게는 PCM 강판에 코팅할 시 굴곡성을 유지하면서 경도와 가시광투과율 등 표면 물성을 향상시킬 수 있는 굴곡성 및 표면 경도가 우수한 UV 경화형 유기-무기 복합체 조성물 및 제조방법에 관한 것이다.The present invention relates to a UV-curable composition and a manufacturing method, and more particularly, to improve surface properties such as hardness and visible light transmittance while maintaining flexibility when coated on a PCM steel sheet UV-curable organic-inorganic It relates to a composite composition and manufacturing method.
가전 및 산업용으로 광범위하게 사용되고 있는 PCM 강판은 일반적으로 표면에 무늬 및 색상을 갖는 도장층을 구비하고 있으며, 이러한 도장층은 외부에 노출되어 있고 기계적, 화학적 물성이 좋지 않아 가공 시 혹은 가공 후 쉽게 도막 손상으로 이어져 상품성과 내구성이 저하된다.PCM steel sheets, which are widely used in home appliances and industries, generally have a coating layer with patterns and colors on the surface, and these coating layers are exposed to the outside and have poor mechanical and chemical properties, so they are easily coated during or after processing. This leads to damage and deteriorates marketability and durability.
한편 세계적으로 친환경적인 공정 방법으로의 전환이 진행되고 있는 가운데 기존의 열경화 방식의 경화 방법은 휘발성 유기화합물이 발생할 뿐만 아니라 고에너지를 사용해야 하는 단점이 있다.Meanwhile, while the transition to an eco-friendly process method is in progress around the world, the conventional thermal curing method has a disadvantage that not only volatile organic compounds are generated, but also high energy is used.
따라서 최근에는 친환경적인 코팅제에 대한 관심이 높아져 이들과 관련된 연구가 활발히 진행되고 있으며, 현재 주목받고 있는 친환경적인 코팅 시스템은 파우더 코팅 시스템, 수성타입의 시스템, UHS 시스템, 광경화형 시스템 등 4가지 시스템이며, 이 중에서도 광경화형 시스템이 가장 유명한 코팅기술로 주목받고 있다. Therefore, in recent years, interest in eco-friendly coatings has increased, and studies related to them are being actively conducted. Currently, the eco-friendly coating systems that are drawing attention are four systems, including powder coating systems, water-based systems, UHS systems, and photocurable systems. Among them, the light-curable system is drawing attention as the most famous coating technology.
광경화형 시스템은 광중합이라고 불리는 화학반응으로 UV영역 광원에 의해 모노머 및 올리고머를 폴리머로 변화시키는 기술이다. 이러한 광경화형 시스템은 열을 이용한 경화가 아니라 UV광원에 의한 경화이기 때문에, 유기용제(휘발성 유기화합물)를 사용하던 기존 코팅제와는 달리 유기용제를 첨가하지 않아 경화시에도 휘발성 유기화합물이 발생하지 않는다.The photocurable system is a technology that converts monomers and oligomers into polymers by a UV light source through a chemical reaction called photopolymerization. Unlike conventional coatings that used organic solvents (volatile organic compounds), unlike conventional coatings that used organic solvents (volatile organic compounds), these photocurable systems do not generate volatile organic compounds even during curing. .
이에 따라 PCM(Pre-Coated Metal)제조에 광경화형 코팅제를 도입하고자 하는 연구와 개발이 활발히 진행되고 있다. 광경화형 코팅제는 UV영역에 민감한 합성물(광개시제)을 포함하고 있으며, 코팅제 내의 광개시제가 신속한 반응을 시작하여 조성물을 가교시켜 망상고분자의 형태로 도막을 형성하게 된다. Accordingly, research and development to introduce a photocurable coating agent to the manufacture of PCM (Pre-Coated Metal) are actively progressing. The photocurable coating agent contains a compound (photoinitiator) sensitive to the UV region, and the photoinitiator in the coating agent initiates a rapid reaction to crosslink the composition to form a coating film in the form of a network polymer.
경화형 코팅제는 휘발성 유기화합물의 함유량이 0에 근접하며 코팅공정의 특성상 짧은 시간에 코팅도막을 형성하여 생산성 및 작업성의 증대를 기대할 수 있다. 또한 유성타입의 코팅제를 사용할 때보다 짧은 공정단계를 확보할 수 있으며 이에 동반되는 코팅라인의 최소화를 통해 코팅 설비비용과 설비공간을 절감할 수 있고, 게다가 코팅공정에서 사용되는 에너지효율에서도 큰 이점을 가지고 있다.The curable coating agent has a volatile organic compound content close to zero, and due to the nature of the coating process, a coating film can be formed in a short time, thereby increasing productivity and workability. In addition, it is possible to secure a shorter process step than when using an oil-based coating agent, and by minimizing the accompanying coating line, coating equipment cost and equipment space can be saved. In addition, it has a great advantage in energy efficiency used in the coating process. Have.
하지만 일반적으로 사용되는 광경화 코팅제는, 코팅막의 표면경도가 약하여 운반이나 가공단계, 실내 및 외부에 적용 시 충격이나 마찰 등으로 인해 손상을 받기 쉽고, 이는 작업의 효율과 제품의 사용 기간에 악영향을 끼치게 된다는 문제점이 있다. However, commonly used photocurable coatings have a weak surface hardness and are easily damaged by impact or friction when applied to transport or processing steps, indoors and outdoors, which adversely affects the efficiency of work and the life of the product. There is a problem that it will cause you.
본 발명은 상기한 바와 같은 문제점을 해결하기 위한 것으로서, 경화속도, 표면 경도, 가공성, 부착성 및 작업성이 우수한 코팅층을 형성시킬 수 있는 굴곡성 및 표면 경도가 우수한 UV 경화형 조성물 및 그 제조방법을 제공하는 것을 목적으로 한다.The present invention is to solve the above-described problems, and provides a UV-curable composition having excellent curing speed, surface hardness, workability, adhesion, and workability, and excellent in flexibility and surface hardness to form a coating layer. It aims to do.
상기 문제점을 해결하기 위한 본 발명에 따른 굴곡성 및 표면 경도가 우수한 UV 경화형 조성물의 제조방법은, Polyethyleneglycol(PEG) 16.44~16.94 중량부와 3-Isocyanatopropyltriethoxysilane(IPTES) 17.5~18 중량부를 혼합한 후 80℃에서 12시간 400rpm 조건에서 교반하여 제1 반응액을 준비하는 단계; 상기 제1 반응액에 Colloidal Silica 16~18 중량부, Vinyltrimethoxysilane(VTMS) 34~35 중량부 및 Formic Acid 0.06 중량부를 혼합한 후 80℃에서 1시간 400rpm 조건에서 교반하여 제2 반응액을 준비하는 단계; 상기 제2 반응액에 1,6-Hexanediol diacrylate(HDDA) 9 중량부를 첨가한 후 1시간동안 400rpm 조건에서 교반한 후, 수분을 제거하는 단계; 및 광개시제인 1-hydroxy-cyclohexylphenyl ketone 5 중량부를 첨가한 후 1시간 동안 교반하는 단계로 이루어진 것을 특징으로 한다.In order to solve the above problems, the method of preparing a UV curable composition having excellent flexibility and surface hardness according to the present invention is 80°C after mixing 16.44 to 16.94 parts by weight of Polyethyleneglycol (PEG) and 17.5 to 18 parts by weight of 3-Isocyanatopropyltriethoxysilane (IPTES). Preparing a first reaction solution by stirring at 400 rpm for 12 hours; Preparing a second reaction solution by mixing 16 to 18 parts by weight of Colloidal Silica, 34 to 35 parts by weight of Vinyltrimethoxysilane (VTMS), and 0.06 parts by weight of Formic Acid to the first reaction solution and then stirring at 80° C. for 1 hour at 400 rpm. ; Adding 9 parts by weight of 1,6-Hexanediol diacrylate (HDDA) to the second reaction solution, stirring at 400 rpm for 1 hour, and removing moisture; And adding 5 parts by weight of 1-hydroxy-cyclohexylphenyl ketone, which is a photoinitiator, and then stirring for 1 hour.
삭제delete
삭제delete
삭제delete
본 발명에 따른 UV 경화형 조성물은 경화속도가 빠를 뿐만 아니라 코팅층의 표면 경도가 우수하다는 장점이 있다.The UV-curable composition according to the present invention has an advantage in that the curing speed is fast and the surface hardness of the coating layer is excellent.
또한 본 발명에 따른 UV 경화형 조성물은 가공성, 부착성 및 작업성이 탁월하다는 이점이 있다. In addition, the UV curable composition according to the present invention has the advantage of excellent processability, adhesion and workability.
도 1은 본 발명의 바람직한 실시예에 따른 UV 경화형 코팅용 조성물의 제조방법을 설명하는 흐름도이다.
도 2는 도막 부착성의 평가방법이다.
도 3은 가공성 측정방법을 설명하기 위한 개념도이다.1 is a flowchart illustrating a method of preparing a composition for a UV curable coating according to a preferred embodiment of the present invention.
2 is a method for evaluating the adhesion of a coating film.
3 is a conceptual diagram illustrating a method of measuring processability.
본 출원에서 “포함한다”, “가지다” 또는 “구비하다” 등의 용어는 명세서 상에 기재된 특징, 숫자, 단계, 구성요소, 부분품 또는 이들을 조합한 것이 존재함을 지정하려는 것이지 하나 또는 그 이상의 다른 특징들이나 숫자, 단계, 동작, 구성요소, 부분품 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다.In the present application, terms such as "include", "have" or "have" are intended to designate the existence of features, numbers, steps, components, parts, or combinations thereof described in the specification. It is to be understood that it does not preclude the presence or addition of features, numbers, steps, actions, components, parts, or combinations thereof.
또한, 다르게 정의되지 않는 한 기술적이거나 과학적인 용어를 포함해서 여기서 사용되는 모든 용어들은 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에 의해 일반적으로 이해되는 것과 동일한 의미를 가지고 있다. 일반적으로 사용되는 사전에 정의되어 있는 것과 같은 용어들은 관련기술의 문맥상 가지는 의미와 일치하는 의미를 가지는 것으로 해석되어야 하며, 본 출원에서 명백하게 정의하지 않는 한, 이상적이거나 과도하게 형식적인 의미로 해석되지 않는다.In addition, unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. Terms such as those defined in a commonly used dictionary should be interpreted as having a meaning consistent with the meaning of the context of the related technology, and should not be interpreted as an ideal or excessively formal meaning unless explicitly defined in the present application. Does not.
이하 본 발명에 따른 굴곡성 및 표면 경도가 우수한 UV 경화형 조성물 및 그 제조방법에 관하여 설명하기로 한다.Hereinafter, a UV curable composition having excellent flexibility and surface hardness according to the present invention and a method of manufacturing the same will be described.
본 발명에 따른 UV 경화형 조성물은, Polyethyleneglycol(PEG) 또는 분자량이 200~800 g/mol 범위에 해당되는 polypropyleneglycol이며, 바람직하게는 Polyethyleneglycol(PEG); 3-Isocyanatopropyltriethoxysilane(IPTES) 또는 3-Isocyanatopropyltrimethoxysilane이며, 바람직하게는 3-Isocyanatopropyltriethoxysilane(IPTES); 100nm 이하 사이즈를 갖는 Colloidal silica; 비닐(Vinyl) 또는 아크릴(Acryl) 작용기를 갖는 trialkoxysilane 또는 Vinyltrimethoxysilane(VTMS)이며, 바람직하게는 Vinyltrimethoxysilane(VTMS); Formic acid, Acetic acid, HCl 등의 유기산 또는 무기산이며, 바람직하게는 Formic acid; 1,6-Hexanediol diacrylate(HDDA), Trimethylolpropane triacrylate, Ethoxylated bisphenol A diacrylate, Diethylene glycol diacrylate, Triethylene glycol diacrylate, Polyethylene glycol diacrylate, Ethoxylated 1,6-Hexanediol diacrylate, Polypropylated Neopentyl gylcol diacrylate, Tripropylene glycol diacrylate, Ethoxylated trimethylolpropane triacrylate, Propoxylated trimethylolpropane triacrylate, Pentaerythritol triacrylate, Ethoxylated pentaerythritol tetraacrylate, Dipentaerythritol pentaacrylate, Dipentaerythritol hexaacrylate, Ethoxylated dipentaerythritol hexaacrylate 등의 단관능, 다관능 아크릴레이트계 모노머 또는 그의 올리고머에서 선택된 1종 이상으로, 바람직하게는 1,6-Hexanediol diacrylate(HDDA); 및 1-hydroxy-cyclohexylphenyl ketone, 2-Hydroxy-2-methyl-phenyl-propane-1-one 및 2-Isopropylthioxanthone 중에서 선택된 어느 하나 이상의 광개시제를 포함하여 구성된다. The UV curable composition according to the present invention is polyethyleneglycol (PEG) or a polypropyleneglycol having a molecular weight of 200 to 800 g/mol, preferably polyethyleneglycol (PEG); 3-Isocyanatopropyltriethoxysilane (IPTES) or 3-Isocyanatopropyltrimethoxysilane, preferably 3-Isocyanatopropyltriethoxysilane (IPTES); Colloidal silica having a size of 100 nm or less; Trialkoxysilane or Vinyltrimethoxysilane (VTMS) having a vinyl or acrylic functional group, preferably Vinyltrimethoxysilane (VTMS); Organic or inorganic acids such as Formic acid, Acetic acid, and HCl, preferably Formic acid; 1,6-Hexanediol diacrylate (HDDA), Trimethylolpropane triacrylate, Ethoxylated bisphenol A diacrylate, Diethylene glycol diacrylate, Triethylene glycol diacrylate, Polyethylene glycol diacrylate, Ethoxylated 1,6-Hexanediol diacrylate, Polypropylated Neopentyl gylcol diacrylate, Tripropylene glycol diacrylate, Ethoxylated trimethylol diacrylate , Propoxylated trimethylolpropane triacrylate, Pentaerythritol triacrylate, Ethoxylated pentaerythritol tetraacrylate, Dipentaerythritol pentaacrylate, Dipentaerythritol hexaacrylate, Ethoxylated dipentaerythritol hexaacrylate, etc. diacrylate (HDDA); And 1-hydroxy-cyclohexylphenyl ketone, 2-Hydroxy-2-methyl-phenyl-propane-1-one, and 2-Isopropylthioxanthone.
도 1은 본 발명의 바람직한 실시예에 따른 UV 경화형 코팅용 조성물의 제조방법을 설명하는 흐름도이다.1 is a flowchart illustrating a method of preparing a composition for a UV curable coating according to a preferred embodiment of the present invention.
도 1을 참조하면서 UV 경화형 코팅용 조성물의 제조방법에 관해 설명하기로 한다.A method of preparing a composition for a UV curable coating will be described with reference to FIG. 1.
먼저 Polyethyleneglycol(PEG)과 3-Isocyanatopropyltriethoxysilane(IPTES)을 혼합하여 80℃에서 12시간 400rpm으로 교반하여 제1 반응액을 준비한다. 제1 반응액은 점도 50~100cP의 투명한 용액이다.First, polyethyleneglycol (PEG) and 3-Isocyanatopropyltriethoxysilane (IPTES) were mixed and stirred at 80°C for 12 hours at 400 rpm to prepare a first reaction solution. The first reaction solution is a transparent solution having a viscosity of 50-100 cP.
여기서 Polyethyleneglycol(PEG)은 14~20 중량부, 그리고 3-Isocyanatopropyltriethoxysilane(IPTES)은 15~21 중량부 비율로 혼합되는 것이 좋다. Polyethyleneglycol(PEG)이 14 중량부 미만이면 고분자량 사슬이 감소되어 유연성을 저하시킬 수 있고, 반면 20 중량부를 초과하면 고분자량 사슬이 과다하여 경도가 저하될 수 있도록 상기 범위로 혼합되는 것이 바람직하다. Here, polyethyleneglycol (PEG) is preferably mixed in a ratio of 14 to 20 parts by weight and 3-Isocyanatopropyltriethoxysilane (IPTES) is mixed in a ratio of 15 to 21 parts by weight. If the polyethyleneglycol (PEG) is less than 14 parts by weight, the high molecular weight chain may be reduced and thus the flexibility may be reduced, whereas if it exceeds 20 parts by weight, the high molecular weight chain is excessive and thus the hardness is preferably mixed in the above range.
또 3-Isocyanatopropyltriethoxysilane(IPTES) 첨가량이 15 중량부 미만이면 silica 입자와 PEG의 중합에 필요한 실란이 부족하여 silica와 PEG의 결합이 충분하지 못하게 되어 silica가 용액 내에 단독으로 존재하게 되고, 이는 silica 경화 시 주변의 실란들과 강하여 결합하게 되어 유연성을 저하시킬 수 있으며, 21 중량부를 초과하면 PEG와 결합에 필요한 양 이상으로 존재하게 되며 이로 인하여 실란 커플링이 증가하여 유연성을 저하시킬 수 있으므로, 상기 범위로 첨가되는 것이 바람직하다.In addition, if the amount of 3-Isocyanatopropyltriethoxysilane (IPTES) added is less than 15 parts by weight, the silane required for polymerization of silica particles and PEG is insufficient, so that the bonding between silica and PEG is insufficient, so that silica exists alone in the solution. Since it is strongly bonded with surrounding silanes, the flexibility may be reduced, and when it exceeds 21 parts by weight, it is present in an amount greater than necessary for bonding with PEG, and thus, silane coupling increases and thus flexibility may decrease. It is preferably added.
다음은 준비한 제1 반응액에 Colloidal Silica 14~18 중량부, Vinyltrimethoxysilane(VTMS) 30~38 중량부 및 Formic Acid 0.04~0.1 중량부를 혼합한 후 80℃에서 1시간 동안 400rpm으로 교반하여 가수분해와 중합을 유도하여 제2 반응액을 준비하는 단계이다. 반응 완료 시 점도 25~80의 투명한 용액이 합성되며, 제1 반응액에서 제조된 PEG사슬 양쪽에 존재하는 OH 혹은 OR 기에 Colloidal silica 및 VTMS가 커플링되어 경도 향상 및 부착에 관여하게 된다. Formic Acid는 반응물의 가수분해 및 중합을 유도한다. Next, 14 to 18 parts by weight of Colloidal Silica, 30 to 38 parts by weight of Vinyltrimethoxysilane (VTMS) and 0.04 to 0.1 parts by weight of Formic Acid were mixed in the prepared first reaction solution, and then stirred at 80° C. for 1 hour at 400 rpm for hydrolysis and polymerization. It is a step of preparing a second reaction solution by inducing. Upon completion of the reaction, a transparent solution having a viscosity of 25 to 80 is synthesized, and colloidal silica and VTMS are coupled to the OH or OR groups present on both sides of the PEG chain prepared in the first reaction solution to improve hardness and participate in adhesion. Formic Acid induces the hydrolysis and polymerization of the reactants.
여기서, Colloidal silica의 첨가량이 14 중량부 미만이면 코팅층의 표면 경도가 저하되고 반면 18 중량부를 초과하면 PEG와 결합하지 못하고 남은 silica가 농축 시 주변의 실란들과 결합하여 겔화가 진행되기 때문에 상기 범위인 것이 바람직하다.Here, if the amount of colloidal silica is less than 14 parts by weight, the surface hardness of the coating layer decreases, whereas if it exceeds 18 parts by weight, the remaining silica cannot be combined with PEG and the remaining silica binds with surrounding silanes and gelation proceeds. It is desirable.
또 Vinyltrimethoxysilane(VTMS)의 첨가량이 30 중량부 미만이면 이중결합 작용기의 부족으로 경화성과 부착력이 저하되고, 반면 38 중량부를 초과하면 실라놀의 과다로 실란 커플링이 증가하여 유연성이 낮아지므로 상기 범위인 것이 바람직하다.In addition, if the amount of vinyltrimethoxysilane (VTMS) is less than 30 parts by weight, the curability and adhesion decrease due to the lack of double bond functional groups, whereas if the amount exceeds 38 parts by weight, the silane coupling increases due to an excess of silanol and the flexibility decreases. It is desirable.
게다가 Formic Acid의 첨가량이 0.04 중량부 미만이면 가수분해와 중합이 부족하여 제대로 경화되지 못하고, 반면 0.1 중량부를 초과하면 중합 증가로 농축 시 겔화가 진행되므로 상기 범위인 것이 바람직하다.In addition, if the amount of Formic Acid is less than 0.04 parts by weight, hydrolysis and polymerization are insufficient, so that it cannot be cured properly. On the other hand, if it exceeds 0.1 parts by weight, gelation proceeds upon concentration due to increased polymerization, and thus the above range is preferable.
계속해서, 제2 반응액에 1,6-Hexanediol diacrylate(HDDA) 8~10 중량부를 첨가한 후, 1시간 동안 400rpm으로 교반하고, 이후 진공회전농축기를 사용하는 농축과정을 통해 수분을 제거한다.Subsequently, after adding 8 to 10 parts by weight of 1,6-Hexanediol diacrylate (HDDA) to the second reaction solution, the mixture is stirred at 400 rpm for 1 hour, and then moisture is removed through a concentration process using a vacuum rotary concentrator.
여기서, 1,6-Hexanediol diacrylate(HDDA)의 첨가량이 8 중량부 미만이면 농축 후 점도가 높아 코팅이 어려울 뿐만 아니라 부착성이 저하되고, 반면 10 중량부를 초과하면 모노머 과다로 인해 표면 경도와 내화학성이 떨어지므로 상기 범위로 첨가되는 것이 바람직하다. HDDA는 코팅액의 점도 조절 및 합성된 고형분의 고른 분산, PCM 표면에 부착성 향상을 위하여 첨가된다. 농축 완료 시 점도 50~100cp의 투명한 용액으로 합성이 완료된다.Here, if the addition amount of 1,6-Hexanediol diacrylate (HDDA) is less than 8 parts by weight, the viscosity after concentration is high, making it difficult to coat as well as adhesion, whereas if it exceeds 10 parts by weight, surface hardness and chemical resistance due to an excess of monomers It is preferred to be added in the above range because this falls. HDDA is added to control the viscosity of the coating liquid, evenly disperse the synthesized solid, and improve adhesion to the PCM surface. Upon completion of concentration, the synthesis is completed with a clear solution with a viscosity of 50 to 100 cp.
마지막으로 광개시제를 4~6 중량부 첨가한 후, 1시간 교반하여 코팅용 조성물을 제조한다.Finally, after adding 4 to 6 parts by weight of the photoinitiator, it is stirred for 1 hour to prepare a coating composition.
여기서, 광개시제의 첨가량이 4 중량부 미만이면 경화성이 미흡하고, 반면 6 중량부를 초과하면 경화 후 황변발생과 함께, 부착성과 유연성이 저하되므로 상기 범위로 배합되는 것이 바람직하다.Here, when the amount of the photoinitiator added is less than 4 parts by weight, curability is insufficient, whereas when the amount exceeds 6 parts by weight, yellowing occurs after curing, and adhesion and flexibility are deteriorated. Therefore, it is preferable to be blended in the above range.
상기와 같은 방법으로 제조되는 본 발명의 조성물은 고분자량의 사슬 양 끝단에 이중 결합기를 포함하는 silica 입자가 부착된 형태의 사슬이 아크릴레이트계 모노머에 광경화제와 함께 분산되어 있는 형태로서, 광경화시 사슬의 이중 결합기가 아크릴레이트계 모노머 및 PCM 도장의 표면과 결합하는 형태로 코팅층이 형성된다. The composition of the present invention prepared by the above method is a form in which a chain in which silica particles including a double bond group are attached to both ends of a high molecular weight chain is dispersed in an acrylate monomer with a photocuring agent. The coating layer is formed in a form in which the double bond group of the city chain is bonded to the surface of the acrylate-based monomer and the PCM coating.
따라서 PCM 강판에 투명한 상도층을 형성할 수 있어, PCM의 색상을 그대로 유지하면서도 표면 물성을 향상시킬 수 있다. 즉, 100nm 이하 크기의 silica를 포함하는 고분자량으로 합성된 실란계 사슬을 아크릴레이트계 모노머와 혼합함으로써, PCM 강판의 부족한 물리적, 화학적 물성을 극복하는 동시에 강판 성형에 필수적인 유연성을 확보하는 것이 가능하고, 또 광경화형이므로 PCM 공정 시 에너지 효율을 향상시킴과 동시에 공정 시간 단축 등 생산성 증대에 기여할 수 있다. Therefore, a transparent top coat layer can be formed on the PCM steel sheet, so that the surface properties can be improved while maintaining the color of the PCM as it is. That is, by mixing a silane-based chain synthesized with a high molecular weight containing silica having a size of 100 nm or less with an acrylate-based monomer, it is possible to overcome the insufficient physical and chemical properties of the PCM steel sheet and at the same time secure the flexibility necessary for the steel sheet molding. In addition, since it is a photo-curing type, it can improve energy efficiency during the PCM process and at the same time contribute to increased productivity such as shortening process time.
이하 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나 하기의 실시예는 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐, 이에 의해 본 발명의 내용이 한정되는 것은 아니다.Hereinafter, a preferred embodiment is presented to aid the understanding of the present invention. However, the following examples are only provided to more easily understand the present invention, thereby not limiting the content of the present invention.
실시예 1Example 1
분자량 400 g/mol의 Polyethylene glycol(PEG) 16.94 중량부와 3-Isocyanatopropyltriethoxysilane(IPTES) 18 중량부를 80℃에서 12시간 400rpm으로 교반하여 제1 반응액을 준비하였다.A first reaction solution was prepared by stirring 16.94 parts by weight of polyethylene glycol (PEG) having a molecular weight of 400 g/mol and 18 parts by weight of 3-Isocyanatopropyltriethoxysilane (IPTES) at 80° C. for 12 hours at 400 rpm.
준비한 제1 반응액에 Colloidal Silica 16 중량부, Vinyltrimethoxysilane(VTMS) 35 중량부 및 Formic Acid 0.06 중량부를 혼합한 후 80℃에서 1시간 동안 400rpm으로 교반하여 가수분해와 중합을 유도하여 제2 반응액을 준비하였다.After mixing 16 parts by weight of Colloidal Silica, 35 parts by weight of Vinyltrimethoxysilane (VTMS), and 0.06 parts by weight of Formic Acid in the prepared first reaction solution, the mixture was stirred at 80°C for 1 hour at 400 rpm to induce hydrolysis and polymerization to prepare the second reaction solution. Ready.
이어서 제2 반응액에 1,6-Hexanediol diacrylate(HDDA) 9 중량부를 첨가한 후, 1시간 동안 400rpm으로 교반하였고, 이후 진공회전농축기를 사용하는 농축과정을 통해 수분을 제거하였다.Subsequently, 9 parts by weight of 1,6-Hexanediol diacrylate (HDDA) was added to the second reaction solution, followed by stirring at 400 rpm for 1 hour, and then moisture was removed through a concentration process using a vacuum rotary concentrator.
마지막으로 광개시제로서 1-hydroxy-cyclohexylphenyl ketone 5 중량부를 첨가한 후, 1시간 교반하여 코팅용 조성물을 제조하였다.Finally, 5 parts by weight of 1-hydroxy-cyclohexylphenyl ketone was added as a photoinitiator, followed by stirring for 1 hour to prepare a coating composition.
실시예 2Example 2
Polyethylene glycol(PEG) 16.44 중량부, 3-Isocyanatopropyltriethoxysilane(IPTES) 17.5 중량부, Colloidal Silica 18 중량부, Vinyltrimethoxysilane(VTMS) 34 중량부로 변경한 것을 제외하고는 실시예 1과 동일한 방법으로 코팅용 조성물을 제조하였다.Polyethylene glycol (PEG) 16.44 parts by weight, 3-Isocyanatopropyltriethoxysilane (IPTES) 17.5 parts by weight, Colloidal Silica 18 parts by weight, Vinyltrimethoxysilane (VTMS) 34 parts by weight, except for the change to prepare a coating composition in the same manner as in Example 1 I did.
비교예 1Comparative Example 1
Polyethyleneglycol(PEG) 18.44 중량부, 3-Isocyanatopropyltriethoxysilane(IPTES) 19.5 중량부, Colloidal Silica를 12 중량부 및 Vinyltrimethoxysilane(VTMS) 36 중량부로 변경한 것을 제외하고는 실시예 1과 동일한 방법으로 코팅용 조성물을 제조하였다.A coating composition was prepared in the same manner as in Example 1, except that 18.44 parts by weight of polyethyleneglycol (PEG), 19.5 parts by weight of 3-Isocyanatopropyltriethoxysilane (IPTES), 12 parts by weight of Colloidal Silica, and 36 parts by weight of Vinyltrimethoxysilane (VTMS) were changed. I did.
비교예 2Comparative Example 2
Polyethyleneglycol(PEG) 18.44 중량부, 3-Isocyanatopropyltriethoxysilane(IPTES) 19 중량부, Vinyltrimethoxysilane(VTMS) 36.5 중량부 및 1,6-Hexanediol diacrylate(HDDA)를 5 중량부로 변경한 것을 제외하고는 실시예 1과 동일한 방법으로 코팅용 조성물을 제조하였다.Same as in Example 1, except that 18.44 parts by weight of polyethyleneglycol (PEG), 19 parts by weight of 3-Isocyanatopropyltriethoxysilane (IPTES), 36.5 parts by weight of Vinyltrimethoxysilane (VTMS) and 5 parts by weight of 1,6-Hexanediol diacrylate (HDDA) were changed. A coating composition was prepared by the method.
비교예 3Comparative Example 3
Polyethyleneglycol(PEG) 16 중량부, 3-Isocyanatopropyltriethoxysilane(IPTES) 17 중량부, Vinyltrimethoxysilane(VTMS) 33.94 중량부 및 1,6-Hexanediol diacrylate(HDDA)를 12 중량부로 변경한 것을 제외하고는 실시예 1과 동일한 방법으로 코팅용 조성물을 제조하였다.Same as in Example 1, except that 16 parts by weight of polyethyleneglycol (PEG), 17 parts by weight of 3-Isocyanatopropyltriethoxysilane (IPTES), 33.94 parts by weight of Vinyltrimethoxysilane (VTMS), and 12 parts by weight of 1,6-Hexanediol diacrylate (HDDA) were changed. A coating composition was prepared by the method.
비교예 4Comparative Example 4
Polyethyleneglycol(PEG) 17.94 중량부, 3-Isocyanatopropyltriethoxysilane(IPTES) 18.5 중량부, Vinyltrimethoxysilane(VTMS) 35.5 중량부 및 1-hydroxy-cyclohexylphenyl ketone을 3 중량부로 변경한 것을 제외하고는 실시예 1과 동일한 방법으로 코팅용 조성물을 제조하였다.Coating in the same manner as in Example 1, except that 17.94 parts by weight of polyethyleneglycol (PEG), 18.5 parts by weight of 3-Isocyanatopropyltriethoxysilane (IPTES), 35.5 parts by weight of Vinyltrimethoxysilane (VTMS), and 3 parts by weight of 1-hydroxy-cyclohexylphenyl ketone were changed. A composition for use was prepared.
비교예 5Comparative Example 5
Polyethyleneglycol(PEG) 16 중량부, 3-Isocyanatopropyltriethoxysilane(IPTES) 17 중량부, Vinyltrimethoxysilane(VTMS) 32.94 중량부 및 1-hydroxy-cyclohexylphenyl ketone을 9 중량부로 변경한 것을 제외하고는 실시예 1과 동일한 방법으로 코팅용 조성물을 제조하였다.Polyethyleneglycol (PEG) 16 parts by weight, 3-Isocyanatopropyltriethoxysilane (IPTES) 17 parts by weight, Vinyltrimethoxysilane (VTMS) 32.94 parts by weight, and 1-hydroxy-cyclohexylphenyl ketone were changed to 9 parts by weight. A composition for use was prepared.
(중량부)PEG
(Part by weight)
(중량부)IPTES
(Part by weight)
(중량부)Colloidal silica
(Part by weight)
(중량부)VTMS
(Part by weight)
(중량부)Formic acid
(Part by weight)
(중량부)HDDA
(Part by weight)
(중량부)Photoinitiator
(Part by weight)
실험예Experimental example
실시예 1, 2 및 비교예 1 내지 5의 방법으로 제조한 각 코팅용 조성물을 사용하여 PCM(Pre-Coated Metal)에 10㎛ 두께로 Bar 코팅하여 UV 경화속도, 연필경도, 가공성, 부착성, 및 작업성을 평가하였다. Using the respective coating compositions prepared by the methods of Examples 1 and 2 and Comparative Examples 1 to 5, Bar-coated with a thickness of 10 μm on PCM (Pre-Coated Metal), and UV curing speed, pencil hardness, workability, adhesion, And evaluating workability.
구체적으로 먼저, UV 경화 조건은 벨트식 UV경화기를 이용하여 경화하였고, 벨트속도는 분당 2m(2m/min)이고 광량은 1890mJ, 조도는 672mW이며, 경화 속도는 30초간 경화하여 표면 tack free가 확인될 때까지의 횟수를 확인하였다. Specifically, first, the UV curing conditions were cured using a belt-type UV curing machine, the belt speed was 2m per minute (2m/min), the amount of light was 1890mJ, the illuminance was 672mW, and the curing speed was cured for 30 seconds to confirm surface tack free. The number of times until it was confirmed was checked.
표면경도는 KS M ISO 15184:2013 평가방법에 의한 연필경도로 측정하였고, 가공성은 도 3과 같이 코팅된 PCM 기판을 굽힐 시 접힌 부분의 내측 반경이 해당 두께를 갖도록 굽힌 후 도막의 손상 여부로 확인하였다.Surface hardness was measured by pencil hardness according to the KS M ISO 15184:2013 evaluation method, and workability was confirmed by whether the coating film was damaged after bending so that the inner radius of the folded portion had the corresponding thickness when the coated PCM substrate as shown in FIG. 3 is bent. I did.
부착성은 도 2와 같이 KS M ISO 2409:2013 평가 방법에 따라, 1mm 간격의 격자모양으로 도막을 절단하여 tape로 부착 및 제거를 반복하는 cross cut test로 확인하였고, 작업성은 Bar 코팅 시 Bar에 묻어 용액이 코팅을 원하지 않는 부분에 묻는 등의 작업 용이성으로 확인하였다.Adhesion was confirmed by a cross cut test in which the coating film was cut in a grid pattern at 1 mm intervals and attached and removed with tape according to the KS M ISO 2409:2013 evaluation method as shown in FIG. 2, and the workability was buried on the bar when coating the bar. The solution was confirmed by the ease of work, such as burying the coating on the unwanted part.
실시예 1 및 2의 경우, 경화속도 2회, 표면 경도 2H, 가공성 2~3mm, 부착성 0 그리고 작업성이 매우 우수한 것을 확인하였다.In the case of Examples 1 and 2, it was confirmed that the curing rate was 2 times, the surface hardness was 2H, the workability was 2 to 3 mm, the
이에 반해, Colloidal silica 함량이 부족한 비교예 1은 코팅층 내의 silica 함량이 부족하여 표면경도가 B에 불과하였다. On the other hand, Comparative Example 1, which lacked colloidal silica content, had a surface hardness of only B due to insufficient silica content in the coating layer.
또 1,6-Hexanediol diacrylate 함량이 부족한 비교예 2는 용액의 농도가 높아 작업성이 좋지 않을 뿐만 아니라, 상대적으로 silica 및 실록산 함량이 증가함으로 인해 가공성도 저하되는 것을 확인하였다. 게다가 1,6-Hexanediol diacrylate 함량이 과량일 시(비교예 3)에는, 표면 경도와 작업성에 좋지 않은 것을 알 수 있었다.In addition, it was confirmed that Comparative Example 2 in which the content of 1,6-Hexanediol diacrylate was insufficient was not only not good in workability due to the high concentration of the solution, but also decreased workability due to the relatively increased content of silica and siloxane. In addition, when the 1,6-Hexanediol diacrylate content was excessive (Comparative Example 3), it was found that the surface hardness and workability were not good.
광개시제인 1-hydroxy-cyclohexylphenyl ketone가 부족할 시(비교예 4)에는 경화 속도가 현저하게 저하될 뿐만 아니라 표면 경도가 낮고, 반면 과량으로 첨가될 시(비교예 5)에는 과경화로 인하여 가공성이 현저하게 떨어짐을 확인하였다. When the photoinitiator, 1-hydroxy-cyclohexylphenyl ketone, is insufficient (Comparative Example 4), the curing rate is significantly lowered and the surface hardness is low. On the other hand, when it is added in an excessive amount (Comparative Example 5), the processability is remarkable due to overcuring. It was confirmed to fall.
(UV경화 횟수) Curing speed
(Number of UV curing)
(H)Surface hardness
(H)
(mm)Processability
(mm)
(0~5)Adherence
(0~5)
(바코팅)Workability
(Bar coating)
이상으로 본 발명 내용의 특정한 부분을 상세히 기술하였는 바, 당업계의 통상의 지식을 가진 자에게, 이러한 구체적 기술은 단지 바람직한 실시 양태일 뿐이며, 이에 의해 본 발명의 범위가 제한되는 것은 아니며, 본 발명의 범주 및 기술사상 범위 내에서 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연하다.The specific parts of the present invention have been described in detail above, and for those of ordinary skill in the art, these specific techniques are only preferred embodiments, and the scope of the present invention is not limited thereby. It is obvious to those skilled in the art that various changes and modifications are possible within the scope and scope of the technical idea, and it is natural that such modifications and modifications fall within the appended claims.
Claims (4)
상기 제1 반응액에 Colloidal Silica 16~18 중량부, Vinyltrimethoxysilane(VTMS) 34~35 중량부 및 Formic Acid 0.06 중량부를 혼합한 후 80℃에서 1시간 400rpm 조건에서 교반하여 제2 반응액을 준비하는 단계;
상기 제2 반응액에 1,6-Hexanediol diacrylate(HDDA) 9 중량부를 첨가한 후 1시간동안 400rpm 조건에서 교반한 후, 수분을 제거하는 단계; 및
광개시제인 1-hydroxy-cyclohexylphenyl ketone 5 중량부를 첨가한 후 1시간 동안 교반하는 단계로 이루어진 것을 특징으로 하는 UV 경화형 조성물 제조방법.Preparing a first reaction solution by mixing 16.44 to 16.94 parts by weight of polyethyleneglycol (PEG) and 17.5 to 18 parts by weight of 3-Isocyanatopropyltriethoxysilane (IPTES) and then stirring at 80° C. for 12 hours at 400 rpm;
Preparing a second reaction solution by mixing 16 to 18 parts by weight of Colloidal Silica, 34 to 35 parts by weight of Vinyltrimethoxysilane (VTMS), and 0.06 parts by weight of Formic Acid to the first reaction solution, and then stirring at 80° C. for 1 hour at 400 rpm. ;
Adding 9 parts by weight of 1,6-Hexanediol diacrylate (HDDA) to the second reaction solution, stirring at 400 rpm for 1 hour, and removing moisture; And
A method for preparing a UV-curable composition comprising the step of stirring for 1 hour after adding 5 parts by weight of 1-hydroxy-cyclohexylphenyl ketone as a photoinitiator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020200111674A KR102234608B1 (en) | 2020-09-02 | 2020-09-02 | UV curable composition having excellent flexibility and hardness, and method of manufacturing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020200111674A KR102234608B1 (en) | 2020-09-02 | 2020-09-02 | UV curable composition having excellent flexibility and hardness, and method of manufacturing |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR102234608B1 true KR102234608B1 (en) | 2021-04-01 |
Family
ID=75441252
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020200111674A KR102234608B1 (en) | 2020-09-02 | 2020-09-02 | UV curable composition having excellent flexibility and hardness, and method of manufacturing |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR102234608B1 (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040007432A (en) * | 2001-01-08 | 2004-01-24 | 쓰리엠 이노베이티브 프로퍼티즈 캄파니 | Energy curable inks and other compositions incorporating surface modified, nanometer-sized particles |
| KR20110050952A (en) * | 2009-11-09 | 2011-05-17 | 주식회사 케이씨씨 | Resin and composition for ultraviolet curable coating and automobile head lamp lens comprising a coating layer thereof |
| KR101790491B1 (en) | 2017-09-08 | 2017-10-26 | (주)필스톤 | Ultraviolet Ray Hardening Type Oligomer Composition and Manufacturing method of Organic-Inorganic Hybrid Solution for Plastic Substrate thereof |
| KR20190052318A (en) * | 2017-11-08 | 2019-05-16 | 주식회사 이엔에프테크놀로지 | Photosensitive Resin Composition, Cured Film Prepared Therefrom, and Electronic Device Comprising the Cured Film |
| KR102014206B1 (en) * | 2019-03-29 | 2019-08-27 | (주)필스톤 | UV curable composition having excellent flexibility and hardness and method of manufacturing |
| KR102045325B1 (en) * | 2019-04-17 | 2019-12-04 | (주)필스톤 | UV-fast curable composition applicable to Optical Clear film and method of manufacturing thereof |
-
2020
- 2020-09-02 KR KR1020200111674A patent/KR102234608B1/en active IP Right Grant
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040007432A (en) * | 2001-01-08 | 2004-01-24 | 쓰리엠 이노베이티브 프로퍼티즈 캄파니 | Energy curable inks and other compositions incorporating surface modified, nanometer-sized particles |
| KR20110050952A (en) * | 2009-11-09 | 2011-05-17 | 주식회사 케이씨씨 | Resin and composition for ultraviolet curable coating and automobile head lamp lens comprising a coating layer thereof |
| KR101790491B1 (en) | 2017-09-08 | 2017-10-26 | (주)필스톤 | Ultraviolet Ray Hardening Type Oligomer Composition and Manufacturing method of Organic-Inorganic Hybrid Solution for Plastic Substrate thereof |
| KR20190052318A (en) * | 2017-11-08 | 2019-05-16 | 주식회사 이엔에프테크놀로지 | Photosensitive Resin Composition, Cured Film Prepared Therefrom, and Electronic Device Comprising the Cured Film |
| KR102014206B1 (en) * | 2019-03-29 | 2019-08-27 | (주)필스톤 | UV curable composition having excellent flexibility and hardness and method of manufacturing |
| KR102045325B1 (en) * | 2019-04-17 | 2019-12-04 | (주)필스톤 | UV-fast curable composition applicable to Optical Clear film and method of manufacturing thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5740893B2 (en) | Hard coat composition, hard coat film and display device | |
| CN1240787C (en) | Radiation-curable metal particles and curable resin compositions comprising these prrticles | |
| KR20070095894A (en) | Ultra-thin thiol-ene coatings | |
| WO2007034720A1 (en) | Syrup composition, resin mortar composition and application method | |
| TW201241020A (en) | Polymerizable compositions, cured products obtained therewith, and use of these materials | |
| JPWO2006019175A1 (en) | Photocurable composition for antifogging film formation | |
| KR101995378B1 (en) | Light-Curable Cohesive and Adhesive Composition | |
| KR20130087576A (en) | Curable resin composition | |
| CN104271623B (en) | Siliceous (methyl) acrylate compounds | |
| KR20120003429A (en) | Curable resin composition | |
| KR100344081B1 (en) | Radiation Curable Coating Compositon for PVC Floor Applications Having Excellent Heat Resistance and Stain Resistance and Use Thereof | |
| CN107532061B (en) | Pressure-sensitive adhesive | |
| US6951910B2 (en) | Coating compositions for plastic substrates | |
| CN102482486A (en) | Curable composition | |
| KR102234608B1 (en) | UV curable composition having excellent flexibility and hardness, and method of manufacturing | |
| CN104610537A (en) | Flame-retardant polyester | |
| CN106795389A (en) | Optical fiber coatings and composition | |
| JP2011202070A (en) | Curable resin composition and cured product thereof | |
| KR102014206B1 (en) | UV curable composition having excellent flexibility and hardness and method of manufacturing | |
| JP5495087B2 (en) | Active energy ray curable composition, active energy ray curable coating and active energy ray curable printing ink using the same | |
| JP2011026492A (en) | Active energy ray-curable resin composition and cured product thereof | |
| KR102045325B1 (en) | UV-fast curable composition applicable to Optical Clear film and method of manufacturing thereof | |
| JP2006106385A (en) | Curable composition for liquid crystal display device | |
| JP6701614B2 (en) | (Meth)acrylate compound, curable composition, cured product and article | |
| KR101999559B1 (en) | Organic-inorganic hybrid ultraviolet curable coating composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant |