JP3812833B2 - Environmental coating agent - Google Patents
Environmental coating agent Download PDFInfo
- Publication number
- JP3812833B2 JP3812833B2 JP2002335460A JP2002335460A JP3812833B2 JP 3812833 B2 JP3812833 B2 JP 3812833B2 JP 2002335460 A JP2002335460 A JP 2002335460A JP 2002335460 A JP2002335460 A JP 2002335460A JP 3812833 B2 JP3812833 B2 JP 3812833B2
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- Prior art keywords
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- paint
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- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000011248 coating agent Substances 0.000 title description 19
- 230000007613 environmental effect Effects 0.000 title 1
- 239000003973 paint Substances 0.000 claims description 54
- 239000004814 polyurethane Substances 0.000 claims description 30
- 229920002635 polyurethane Polymers 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 22
- 239000002023 wood Substances 0.000 claims description 11
- 150000001934 cyclohexanes Chemical class 0.000 claims description 9
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical group CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 8
- GWESVXSMPKAFAS-UHFFFAOYSA-N Isopropylcyclohexane Chemical compound CC(C)C1CCCCC1 GWESVXSMPKAFAS-UHFFFAOYSA-N 0.000 claims description 7
- KVZJLSYJROEPSQ-UHFFFAOYSA-N 1,2-dimethylcyclohexane Chemical compound CC1CCCCC1C KVZJLSYJROEPSQ-UHFFFAOYSA-N 0.000 claims description 6
- ODNRTOSCFYDTKF-UHFFFAOYSA-N 1,3,5-trimethylcyclohexane Chemical compound CC1CC(C)CC(C)C1 ODNRTOSCFYDTKF-UHFFFAOYSA-N 0.000 claims description 6
- SGVUHPSBDNVHKL-UHFFFAOYSA-N 1,3-dimethylcyclohexane Chemical compound CC1CCCC(C)C1 SGVUHPSBDNVHKL-UHFFFAOYSA-N 0.000 claims description 6
- QRMPKOFEUHIBNM-UHFFFAOYSA-N 1,4-dimethylcyclohexane Chemical compound CC1CCC(C)CC1 QRMPKOFEUHIBNM-UHFFFAOYSA-N 0.000 claims description 6
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 claims description 6
- DEDZSLCZHWTGOR-UHFFFAOYSA-N propylcyclohexane Chemical compound CCCC1CCCCC1 DEDZSLCZHWTGOR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- DQTVJLHNWPRPPH-UHFFFAOYSA-N 1,2,3-trimethylcyclohexane Chemical compound CC1CCCC(C)C1C DQTVJLHNWPRPPH-UHFFFAOYSA-N 0.000 claims description 4
- VCJPCEVERINRSG-UHFFFAOYSA-N 1,2,4-trimethylcyclohexane Chemical compound CC1CCC(C)C(C)C1 VCJPCEVERINRSG-UHFFFAOYSA-N 0.000 claims description 4
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 4
- 238000009472 formulation Methods 0.000 claims description 3
- YPJRYQGOKHKNKZ-UHFFFAOYSA-N 1-ethyl-1-methylcyclohexane Chemical compound CCC1(C)CCCCC1 YPJRYQGOKHKNKZ-UHFFFAOYSA-N 0.000 claims 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 78
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 66
- 239000003795 chemical substances by application Substances 0.000 description 42
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 28
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 28
- 238000003756 stirring Methods 0.000 description 27
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 25
- 239000008096 xylene Substances 0.000 description 25
- 239000005056 polyisocyanate Substances 0.000 description 24
- 229920001228 polyisocyanate Polymers 0.000 description 24
- 229920005989 resin Polymers 0.000 description 24
- 239000011347 resin Substances 0.000 description 24
- QEGNUYASOUJEHD-UHFFFAOYSA-N 1,1-dimethylcyclohexane Chemical compound CC1(C)CCCCC1 QEGNUYASOUJEHD-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 20
- 239000003085 diluting agent Substances 0.000 description 20
- 229920005862 polyol Polymers 0.000 description 20
- 238000000576 coating method Methods 0.000 description 19
- 150000003077 polyols Chemical class 0.000 description 19
- 229920000180 alkyd Polymers 0.000 description 17
- 239000008199 coating composition Substances 0.000 description 12
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 10
- 229920000742 Cotton Polymers 0.000 description 9
- CCTFMNIEFHGTDU-UHFFFAOYSA-N 3-methoxypropyl acetate Chemical compound COCCCOC(C)=O CCTFMNIEFHGTDU-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000004606 Fillers/Extenders Substances 0.000 description 7
- 238000005187 foaming Methods 0.000 description 7
- 229910002012 Aerosil® Inorganic materials 0.000 description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- 239000000454 talc Substances 0.000 description 6
- 229910052623 talc Inorganic materials 0.000 description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000006224 matting agent Substances 0.000 description 5
- 239000000344 soap Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 102100032812 HIG1 domain family member 1A, mitochondrial Human genes 0.000 description 4
- 101001066429 Homo sapiens HIG1 domain family member 1A, mitochondrial Proteins 0.000 description 4
- 235000010724 Wisteria floribunda Nutrition 0.000 description 4
- 230000003111 delayed effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 4
- 239000000391 magnesium silicate Substances 0.000 description 4
- 229910052919 magnesium silicate Inorganic materials 0.000 description 4
- 235000019792 magnesium silicate Nutrition 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 4
- 235000018185 Betula X alpestris Nutrition 0.000 description 3
- 235000018212 Betula X uliginosa Nutrition 0.000 description 3
- 241000218691 Cupressaceae Species 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 240000000731 Fagus sylvatica Species 0.000 description 2
- 235000010099 Fagus sylvatica Nutrition 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- -1 acrylic polyol Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- DGVMNQYBHPSIJS-UHFFFAOYSA-N dimagnesium;2,2,6,6-tetraoxido-1,3,5,7-tetraoxa-2,4,6-trisilaspiro[3.3]heptane;hydrate Chemical compound O.[Mg+2].[Mg+2].O1[Si]([O-])([O-])O[Si]21O[Si]([O-])([O-])O2 DGVMNQYBHPSIJS-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000002648 laminated material Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 235000013372 meat Nutrition 0.000 description 2
- 239000011527 polyurethane coating Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- UDDVMPHNQKRNNS-UHFFFAOYSA-N 1-ethyl-3-methylcyclohexane Chemical compound CCC1CCCC(C)C1 UDDVMPHNQKRNNS-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 240000005020 Acaciella glauca Species 0.000 description 1
- 241001337993 Agathis <wasp> Species 0.000 description 1
- JLUQTCXCAFSSLD-NXEZZACHSA-N Anemonin Chemical compound C1=CC(=O)O[C@]11[C@@]2(C=CC(=O)O2)CC1 JLUQTCXCAFSSLD-NXEZZACHSA-N 0.000 description 1
- 244000178400 Araucaria cunninghamii Species 0.000 description 1
- 241000218645 Cedrus Species 0.000 description 1
- 241000422842 Chamaecyparis pisifera Species 0.000 description 1
- 235000018782 Dacrydium cupressinum Nutrition 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 241000221017 Euphorbiaceae Species 0.000 description 1
- 101000652359 Homo sapiens Spermatogenesis-associated protein 2 Proteins 0.000 description 1
- 101000642464 Homo sapiens Spermatogenesis-associated protein 2-like protein Proteins 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 241000218652 Larix Species 0.000 description 1
- 235000005590 Larix decidua Nutrition 0.000 description 1
- 241000218657 Picea Species 0.000 description 1
- 241000218641 Pinaceae Species 0.000 description 1
- 235000013697 Pinus resinosa Nutrition 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 241000219492 Quercus Species 0.000 description 1
- 235000015392 Sesbania grandiflora Nutrition 0.000 description 1
- 102100030254 Spermatogenesis-associated protein 2 Human genes 0.000 description 1
- 241000736892 Thujopsis dolabrata Species 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical class OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000010685 fatty oil Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002987 primer (paints) Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/01—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
【0001】
【発明の属する技術分野】
本発明は、2液型ポリウレタン塗料において、溶媒としてシクロヘキサン誘導体を使用する木材塗料に関するものである。
【0002】
【従来の技術】
従来より、木材用塗料として2液型ポリウレタン塗料は広く使用されてきた。その主たる組成は樹脂、機能を高めるための体質顔料などであって、溶媒としてはエステル類、ケトン類、芳香族系のトルエン、キシレンなどで構成されてきた(例えば、特許文献1参照。)。
【0003】
近年、住空間において発生する揮発性有機化合物の人体に与える影響が問題視されるようになってきたため、厚生労働省では、その検出量と有害性を加味し、室内濃度指針値を策定した。この対象物質にトルエンおよびキシレンが含まれた(2000年6月)ので、屋内で使用される木材製品の塗装に供する塗料は、その組成から揮発性有機化合物発生の原因となるこれらの物質を含有しない設計を行う必要が生じてきた。初期の設計では、トルエンおよびキシレンを排除することに注力されたが、トルエンおよびキシレンを含有しない塗料は得られたものの、結果として樹脂と溶媒の親和度が過度に増し、本来塗料がもつ機能のバランスにずれが生じやすいことがわかってきた。
【0004】
このバランスのずれによって、塗料の根本的な性能に様々な問題を発生するが、特に木材用2液型ポリウレタン塗料の下塗り塗料においては、重要視されている目詰まり性および発泡性が、トルエンおよびキシレンを排除することにより、塗料の樹脂成分が木材内部に浸透しやすくなり、塗膜底部の乾燥が表面部分に比べ大幅に遅れることにより、従来発生しなかった導管部分の発泡が起こりやすくなり、さらに重要な目詰まり性も悪くなった。また、下中塗りに汎用的に配合される金属石鹸類の塗膜中での均一性が欠如し、塗り重ねられる塗膜間の密着性を大きく阻害することが判明した。さらに、溶媒の親和度が向上することにより、2液型ポリウレタン塗料の上塗りにおいては、従来発生しなかった導管部からの発泡や部分的な乾燥遅れによる光沢ムラが発生することもわかった。
【0005】
下中塗り塗料の場合、最終的な塗装物の表面平滑性を出すために、サンドペーパーなどにより研磨することが多く、このとき研磨により発生した塗膜の粉がサンドペーパー表面に付着しにくくするなどの目的で、ステアリン酸亜鉛などの金属石鹸を配合することが多い。前述のように、塗料中からトルエンおよびキシレンを排除するだけの設計により、樹脂と溶媒の親和性が過度に増した場合、この金属石鹸と樹脂のヌレ合い(化学的引き合い)が悪くなること、さらに段階的に研磨された塗膜表面の成分分析により、塗料の樹脂成分が木材内部に浸透しやすくなることなどにより、塗膜の表面付近に比べ塗膜内部、特に木地界面付近での金属石鹸量が極端に増大することがわかった。このような状態の塗膜を研磨し、同じ塗料あるいは別の塗料を塗り重ねた場合には、研磨された塗膜表面の金属石鹸の性質により、塗膜間の密着性が大きく低下し、必要な性能が得られないことがある。また、樹脂と溶媒の親和度が過度に向上することにより、塗装された塗膜からの溶媒の蒸発が遅れることになるが、2液型ポリウレタン塗料の上塗りにおいては、特に塗膜底部の乾燥が表面部分に比べ大幅に遅れることにより、従来発生しなかった、導管部からの発泡および、部分的な乾燥の遅れによる光沢ムラ、が発生する。これらは表面の乾燥に比べ塗膜底部の乾燥が大幅に遅れることにより、塗膜底部の溶媒が気化することで塗膜が押し上げられ、発泡するのである。また、艶消し型の上塗りでは、塗料に含まれる溶媒が蒸発し、樹脂から離脱することで、配合されている艶消し剤の量に合わせて表面の光沢が消えるが、塗膜底部の溶媒の蒸発が遅れている部分では光沢が消えきらない状態で硬化するため光沢ムラが発生するのである。一方、前記の密着性低下と同様に、これらの現象は従来のトルエンおよびキシレンなどの芳香族系溶媒を含む塗料では発生しないこともわかった。
【0006】
【特許文献1】
特開平7−305026号公報(第4頁右欄第25〜31頁)
【0007】
【発明が解決しようとする課題】
このような状況に鑑みて、溶媒としてトルエンおよびキシレンを使用しない2液型ポリウレタン塗料において、上記の問題を発生しない塗料の開発が当業界における課題となってきた。
【0008】
【課題を解決するための手段】
本発明者は、これらの課題を解決するために鋭意検討した結果、溶媒としてトルエンおよびキシレンを使用しない2液型ポリウレタン塗料を提供するにいたった。すなわち、2液型ポリウレタン塗料において、溶媒としてシクロヘキサン誘導体を使用することを特徴とする木材用塗料であって、上記シクロヘキサン誘導体の塗装配合全量中に占める含有量が1〜50重量%であることが好ましい。また、上記シクロヘキサン誘導体が、メチルシクロヘキサン、エチルシクロヘキサン、1,2−ジメチルシクロヘキサン、1,3−ジメチルシクロヘキサン、1,4−ジメチルシクロヘキサン、プロピルシクロヘキサン、イソプロピルシクロヘキサン、1,2−メチルエチルシクロヘキサン、1,3−メチルエチルシクロヘキサン、1,4−メチルエチルシクロヘキサン、1,2,3−トリメチルシクロヘキサン、1,2,4−トリメチルシクロヘキサンおよび1,3,5−トリメチルシクロヘキサンのいずれか1種または2種以上であることが好ましい。
【0009】
【発明の実施の形態】
本発明で用いられるポリウレタン系塗料は、ポリエステルポリオール、脂肪酸もしくは油脂変性アルキッド、アクリルポリオール、エポキシエステル、ポリエーテルポリオールなどのポリオール(好ましい水酸基価は樹脂固形分で20〜400KOHmg/gである。)またはこれらのポリオール樹脂に加え、硝化綿やセルロースアセテートブチレートなどの繊維素類が配合された主剤、ポリイソシアネート化合物とを混合したいわゆる2液型のものである。ポリイソシアネート化合物としては具体的にはトリレンジイソシアネート、キシリレンジイソシアネート、ヘキサメチレンジイソシアネート、ジフェニルメタンジイソシアネート、1,5−ナフチレンジイソシアネート、4,4−メチレンビスシクロヘキシルジイソシアネート、2,4−メチレンビスシクロヘキシルジイソシアネート、イソホロンジイソシアネートなどの多官能芳香族ポリイソシアネート、多官能脂肪族ポリイソシアンエートおよびそのアダクト体、誘導体があげられる。
【0010】
本発明にいうシクロヘキサン誘導体とは、6員環の環状パラフィンであって、メチル基、エチル基などの残基を有するものであって、メチルシクロヘキサン、エチルシクロヘキサン、1,2−ジメチルシクロヘキサン、1,3−ジメチルシクロヘキサン、1,4−ジメチルシクロヘキサン、プロピルシクロヘキサン、イソプロピルシクロヘキサン、1,2−メチルエチルシクロヘキサン、1,3−メチルエチルシクロヘキサン、1,4−メチルエチルシクロヘキサン、1,2,3−トリメチルシクロヘキサン、1,2,4−トリメチルシクロヘキサンおよび1,3,5−トリメチルシクロヘキサンなどを例示することができる。
【0011】
本発明にいう木材とは、その樹種は特に限定されるものではないが、特に家具、建材に使用されるものをいう。例えば、国産材では、ヒノキ科のヒノキ、サワラ、ネズコ、ヒバ、マツ科のモミ、トドマツ、カラマツ、エゾマツ、アカマツ、ツガ、スギ科のスギ、カバノキ科のハンノキ、ミズメ、シラカンバ、マカンバ、────
ブナ科のコジイ,シイノキ、ブナ、ミズナラ、シラカシ、クスノキ科のクスノキ、タブノキ、モクセイ科のタモ、ニレ科のハルニレ、ケヤキなどをあげることが─────
できる。また、輸入材では、ナンヨウスギ科のアガチス、フープパイン、マツ科のメルクシマツ、フタバガキ科のメルサワ、アピトン、カプール、ホワイトセラヤ、ライトレッドメランチ、ダークメランチ、トウダイグサ科のゴム、ノボタン科のジョンコン、アカテツ科のニヤトー、などをあげることができる。
【0012】
【実施例】
以下実施例をあげて本発明を更に具体的に説明するが、本発明の主旨はこれに限定されるものではない。
【0013】
(実施例1)
主剤としてジメチルシクロヘキサン15重量部を秤量し、容器に入れた。これにアルキッド樹脂ポリオールとして、脂肪酸変性アルキッドポリオール樹脂(大日本インキ化学工業株式会社製、バーノックD−145−55BA)を73重量部加え、よく撹拌した。次いで撹拌しながら研磨助剤としてステアリン酸亜鉛(正同化学工業株式会社製)を4重量部、体質顔料として含水ケイ酸マグネシウム(林化成株式会社製、タルクPK)を8重量部入れ、15分間撹拌した。一方、硬化剤として酢酸ブチル10重量部と酢酸エチル12重量部を秤量し、容器に入れた。これにTDI/TMPアダクトタイプポリイソシアネート(日本ポリウレタン工業株式会社製、コロネートL)を19重量部とTDIイソシアヌレートタイプポリイソシアネート(日本ポリウレタン工業株式会社製、コロネート2030)を59重量部加え、10分間撹拌した。希釈剤として酢酸ブチル40重量部、酢酸エチル50重量部、酢酸メトキシプロピル10重量部を加え、5分間撹拌した。塗装配合は、主剤:硬化剤:希釈剤=2:1:2として塗料を調製し、中塗り塗料として使用した。
【0014】
(実施例2)
主剤としてジメチルシクロヘキサン10重量部、酢酸エチル10重量部、酢酸ブチル17重量部を秤量し、容器に入れた。撹拌しながら硝化綿(旭化成株式会社製、硝化綿HIG1/4)を6重量部加え、溶解するまで撹拌を続けた。これに脂肪酸変性アルキッドポリオール樹脂(大日本インキ化学工業株式会社製、バーノックD−145−55BA)を54重量部加え、よく撹拌した。次いで、艶消し剤としてケイ酸微粉末(富士シリシア工業株式会社製、サイリシア350)を3重量部加え、30分間撹拌した。一方、硬化剤として酢酸エチル20重量部、酢酸ブチル25重量部を秤量し、容器に入れた。これにHDI/TMPアダクトタイプポリイソシアネート(日本ポリウレタン工業株式会社製、コロネートHL)を15重量部とTDIイソシアヌレートタイプポリイソシアネート(日本ポリウレタン工業株式会社製、コロネート2030)を40重量部加え、10分間撹拌した。希釈剤として酢酸エチル50重量部、酢酸ブチル40重量部、酢酸メトキシプロピル10重量部を加え、5分間撹拌した。塗装配合は、主剤:硬化剤:希釈剤=2:1:1.5として塗料を調製し、上塗り塗料として使用した。
【0015】
(実施例3)
主剤として酢酸エチル15重量部、酢酸ブチル22重量部を秤量し、容器に入れた。撹拌しながら硝化綿(旭化成株式会社製、硝化綿HIG1/4)を6重量部加え、溶解するまで撹拌を続けた。これに脂肪酸変性アルキッドポリオール樹脂(大日本インキ化学工業株式会社製、バーノックD−145−55BA)を54重量部加え、よく撹拌した。次いで、艶消し剤としてケイ酸微粉末(富士シリシア工業株式会社製、サイリシア350)を3重量部加え、30分間撹拌した。一方、硬化剤として酢酸エチル20重量部、酢酸ブチル25重量部を秤量し、容器に入れた。これにHDI/TMPアダクトタイプポリイソシアネート(日本ポリウレタン工業株式会社製、コロネートHL)を15重量部とTDIイソシアヌレートタイプポリイソシアネート(日本ポリウレタン工業株式会社製、コロネート2030)を40重量部加え、10分間撹拌した。希釈剤としてジメチルシクロヘキサン15重量部、酢酸エチル40重量部、酢酸ブチル35重量部、酢酸メトキシプロピル10重量部を加え、5分間撹拌した。塗装配合は、主剤:硬化剤:希釈剤=2:1:1.5として塗料を調製し、上塗り塗料として使用した。
【0016】
(実施例4)
主剤としてジメチルシクロヘキサン15重量部を秤量し、容器に入れた。これにアルキッド樹脂ポリオールとして、脂肪酸変性アルキッドポリオール樹脂(大日本インキ化学工業株式会社製、バーノックD−145−55BA)を73重量部加え、よく撹拌した。次いで撹拌しながら、沈降防止剤としてケイ酸微粉末(日本アエロジル株式会社製、アエロジル#300)を2重量部、体質顔料として含水ケイ酸マグネシウム(林化成株式会社製、タルクPK)を10重量部入れ、15分間撹拌した。一方、硬化剤として酢酸ブチル25重量部と酢酸エチル25重量部を秤量し、容器に入れた。これにTDI/TMPアダクトタイプポリイソシアネート(日本ポリウレタン工業株式会社製、コロネートL)を20重量部とTDIイソシアヌレートタイプポリイソシアネート(日本ポリウレタン工業株式会社製、コロネート2030)を30重量部加え、10分間撹拌した。希釈剤として酢酸ブチル40重量部、酢酸エチル50重量部、酢酸メトキシプロピル10重量部を加え、5分間撹拌した。塗装配合は、主剤:硬化剤:希釈剤=1:1:0.6として塗料を調製し、下塗り塗料として使用した。
【0017】
(比較例1)
主剤として酢酸ブチル8重量部を秤量し、容器に入れた。これにアルキッド樹脂ポリオールとして、脂肪酸変性アルキッドポリオール樹脂(大日本インキ化学工業株式会社製、ベッコゾール1308)を80重量部加え、よく撹拌した。次いで、撹拌しながら研磨助剤としてステアリン酸亜鉛(正同化学工業株式会社製)を4重量部、体質顔料として含水ケイ酸マグネシウム(林化成株式会社製、タルクPK)を8重量部入れ、15分間撹拌した。一方、硬化剤として酢酸ブチル10重量部と酢酸エチル12重量部を秤量し、容器に入れた。これにTDI/TMPアダクトタイプポリイソシアネート(日本ポリウレタン工業株式会社製、コロネートL)を19重量部、TDIイソシアヌレートタイプポリイソシアネート(日本ポリウレタン工業株式会社製、コロネート2030)を59重量部加え、10分間撹拌した。希釈剤としてキシレン35重量部、酢酸エチル45重量部、酢酸ブチル20重量部を加え、5分間撹拌した。塗装配合は、主剤:硬化剤:希釈剤=2:1:2として塗料を調製し、中塗り塗料として使用した。
【0018】
(比較例2)
主剤として酢酸エチル5重量部と酢酸ブチル10重量部を秤量し、容器に入れた。これにアルキッド樹脂ポリオールとして、脂肪酸変性アルキッドポリオール樹脂(大日本インキ化学工業株式会社製、バーノックD−145−55BA)を73重量部加え、よく撹拌した。次いで、撹拌しながら研磨助剤としてステアリン酸亜鉛(正同化学工業株式会社製)を4重量部、体質顔料として含水ケイ酸マグネシウム(林化成株式会社製、タルクPK)を8重量部入れ、15分間撹拌した。一方、硬化剤として酢酸ブチル10重量部と酢酸エチル12重量部を秤量し、容器に入れた。これにTDI/TMPアダクトタイプポリイソシアネート(日本ポリウレタン工業株式会社製、コロネートL)を19重量部とTDIイソシアヌレートタイプポリイソシアネート(日本ポリウレタン工業株式会社製、コロネート2030)を59重量部加え、10分間撹拌した。希釈剤として酢酸ブチル40重量部、酢酸エチル50重量部、酢酸メトキシプロピル10重量部を加え、5分間撹拌した。塗装配合は、主剤:硬化剤:希釈剤=2:1:2として塗料を調製し、中塗り塗料として使用した。
【0019】
(比較例3)
主剤として酢酸エチル15重量部と酢酸ブチル22重量部を秤量し、容器に入れた。撹拌しながら硝化綿(旭化成株式会社製、硝化綿HIG1/4)を6重量部加え、溶解するまで撹拌を続けた。これに脂肪酸変性アルキッドポリオール樹脂(大日本インキ化学工業株式会社製、バーノックD−145−55BA)を54重量部加え、よく撹拌した。次いで、艶消し剤としてケイ酸微粉末(富士シリシア工業株式会社製、サイリシア350)を3重量部加え、30分間撹拌した。一方、硬化剤として酢酸エチル20重量部、酢酸ブチル25重量部を秤量し、容器に入れた。これにHDI/TMPアダクトタイプポリイソシアネート(日本ポリウレタン工業株式会社製、コロネートHL)を15重量部とTDIイソシアヌレートタイプポリイソシアネート(日本ポリウレタン工業株式会社製、コロネート2030)を40重量部加え、10分間撹拌した。希釈剤として酢酸エチル50重量部、酢酸ブチル40重量部、酢酸メトキシプロピル10重量部を加え、5分間撹拌した。塗装配合は、主剤:硬化剤:希釈剤=2:1:1.5として塗料を調製し、上塗り塗料として使用した。
【0020】
(比較例4)
主剤として酢酸エチル5重量部、酢酸ブチル17重量部、キシレン10重量部を秤量し、容器に入れた。撹拌しながら硝化綿(旭化成株式会社製、硝化綿HIG1/4)を6重量部加え、溶解するまで撹拌を続けた。これに脂肪酸変性アルキッドポリオール樹脂(大日本インキ化学工業株式会社製、ベッコゾール1308)を59重量部加え、よく撹拌した。次いで、艶消し剤としてケイ酸微粉末(富士シリシア工業株式会社製、サイリシア350)を3重量部加え、30分間撹拌した。一方、硬化剤として酢酸エチル20重量部、酢酸ブチル25重量部を秤量し、容器に入れた。これにHDI/TMPアダクトタイプポリイソシアネート(日本ポリウレタン工業株式会社製、コロネートHL)を15重量部とTDIイソシアヌレートタイプポリイソシアネート(日本ポリウレタン工業株式会社製、コロネート2030)を40重量部加え、10分間撹拌した。希釈剤として酢酸エチル30重量部、酢酸ブチル25重量部、酢酸メトキシプロピル10重量部、トルエン15重量部、キシレン20重量部を加え、5分間撹拌した。塗装配合は、主剤:硬化剤:希釈剤=2:1:1.5として塗料を調製し、上塗り塗料として使用した。
【0021】
(比較例5)
主剤として酢酸ブチル8重量部を秤量し、容器に入れた。これにアルキッド樹脂ポリオールとして、脂肪酸変性アルキッドポリオール樹脂(大日本インキ化学工業株式会社製、ベッコゾール1308)を80重量部加え、よく撹拌した。次いで撹拌しながら、沈降防止剤としてケイ酸微粉末(日本アエロジル株式会社製、アエロジル#300)を2重量部、体質顔料として含水ケイ酸マグネシウム(林化成株式会社製、タルクPK)を10重量部入れ、15分間撹拌した。一方、硬化剤として酢酸ブチル25重量部と酢酸エチル25重量部を秤量し、容器に入れた。これにTDI/TMPアダクトタイプポリイソシアネート(日本ポリウレタン工業株式会社製、コロネートL)を20重量部、TDIイソシアヌレートタイプポリイソシアネート(日本ポリウレタン工業株式会社製、コロネート2030)を30重量部加え、10分間撹拌した。希釈剤としてキシレン35重量部、酢酸エチル45重量部、酢酸ブチル20重量部を加え、5分間撹拌した。塗装配合は主剤:硬化剤:希釈剤=1:1:0.6として塗料を調製し、下塗り塗料として使用した。
【0022】
(比較例6)
主剤として酢酸エチル5重量部と酢酸ブチル10重量部を秤量し、容器に入れた。これにアルキッド樹脂ポリオールとして、脂肪酸変性アルキッドポリオール樹脂(大日本インキ化学工業株式会社製、バーノックD−145−55BA)を73重量部加え、よく撹拌した。次いで、撹拌しながら沈降防止剤としてケイ酸微粉末(日本アエロジル株式会社製、アエロジル#300)を2重量部、体質顔料として含水ケイ酸マグネシウム(林化成株式会社製、タルクPK)を10重量部入れ、15分間撹拌した。一方、硬化剤として酢酸ブチル25重量部と酢酸エチル25重量部を秤量し、容器に入れた。これにTDI/TMPアダクトタイプポリイソシアネート(日本ポリウレタン工業株式会社製、コロネートL)を20重量部、TDIイソシアヌレートタイプポリイソシアネート(日本ポリウレタン工業株式会社製、コロネート2030)を30重量部加え、10分間撹拌した。希釈剤として酢酸ブチル40重量部、酢酸エチル50重量部、酢酸メトキシプロピル10重量部を加え、5分間撹拌した。塗装配合は主剤:硬化剤:希釈剤=1:1:0.6として塗料を調製し、下塗り塗料として使用した。
【0023】
(試験例1)
配合された実施例1、比較例1および比較例2の中塗り塗料を、ゴム集成材に1.5mmスプレーガンにより、80g/m2 の塗装を行った。塗装面の評価は表1に示した方法により行い、その結果を表2に示した。表2から明らかなように塗料組成中にジメチルシクロヘキサンを使用することにより、発泡、肉持ち、吸い込み、沈殿などの特性が改善された。特に、吸い込みに大きな効果が得られることが確認できた。また、実施例1の塗料、比較例1および比較例2の塗料に含まれるトルエンおよびキシレンの含有量並びに塗装面から放散するトルエンおよびキシレンの放散量を表3に示した。このように比較例1を除いて、トルエンおよびキシレンの含有量は認められず、トルエンおよびキシレンの放散量は測定定量下限値以下であった。
【0024】
【表1】
【0025】
【表2】
【0026】
【表3】
【0027】
(試験例2)
試験例1で塗装されたそれぞれの塗板を乾燥硬化させた後、研磨し、塗り重ねができる状態にした。その後、各塗板に比較例3の塗料を1.5mmスプレーガンにより、50g/m2の上塗り塗装を行った。塗装1週間後に表1の評価方法により塗装面の評価を行った。その結果は、表4に示したとおりであって、塗膜間の密着においては、比較例2のトルエンおよびキシレンの代替品を使用した場合、塗膜性能が落ちたが、ジメチルシクロヘキサンを使用することにより、従来のトルエン、キシレンを使用した塗料と同等の塗膜性能が確認できた。
【0028】
【表4】
【0029】
(試験例3)
配合された実施例2および実施例3並びに比較例3および比較例4の上塗り塗料を、ゴム集成材に中塗り塗装を施し、乾燥、硬化後、サンドペーパー#400で研磨した板に1.5mmスプレーガンにより、50g/m2の塗装を行った。なお、実施例2と実施例3との相違は、ジメチルシクロヘキサンを塗料主成分に対し予め添加しているか、塗装直前に混合するかの差であり、比較例3はトルエンおよびキシレンを添加しない配合であり、比較例4は従来のトルエンおよびキシレンを含有している塗料である。塗装面の評価は表5に示した方法で行い、その結果は表6に示した。表6からわかるように、乾燥性では実施例3が実施例2より早く、実施例3は樹脂とジメチルシクロヘキサンとのなじみが十分でないため溶媒の飛散が早くなったものと考えられる。その他の項目では、実施例2の方が実施例3よりも評価が高かった。また、実施例2および実施例3共に、比較例3に比べ、すべての点で改善が見られ、比較例4との比較でも、総合評価では実施例2の方が高かった。
【0030】
【表5】
【0031】
【表6】
【0032】
(試験例4)
配合された実施例4、比較例5および比較例6の下塗り塗料を、ゴム集成材に1.5mmスプレーガンにより、80g/m2の塗装を行った。塗装面の評価は、表7に示した方法により行い、その結果を表8に示した。表8から明らかなように塗料組成中にジメチルシクロヘキサンを使用することにより、発泡、肉持ち、吸い込み、目詰まり、などの特性が改善された。特に、発泡、吸い込み、目詰まりに大きな効果が得られることが確認できた。
【0033】
【表7】
【0034】
【表8】
【0035】
【発明の効果】
本発明の環境対応型2液型ポリウレタン塗料は、溶媒の一部にシクロヘキサン誘導体を使用することで、トルエンおよびキシレンを排除し、且つ樹脂と溶媒の親和度が過度に増さない設計を行うことができた。一般にエステル類、ケトン類と比べ、分子極性の低い溶媒を併用すると、溶媒全体としての親和度を下げることになる。しかし、従来より塗料に使用されてきた低極性溶媒である直鎖または枝分かれ型の脂肪族炭化水素では、トルエンおよびキシレンの代替溶媒としては、樹脂との親和度が極端に低く、樹脂の溶解性を著しく低下させるため、事実上使用することは不可能であった。そこで、その他の低極性溶媒について検討した結果、メチルシクロヘキサンやジメチルシクロヘキサンに代表されるシクロヘキサン誘導体が最も適していることを見出し、従来の非トルエンおよび非キシレン溶媒による2液型ポリウレタン塗料の、性能面での欠点を改良することができ、且つ、トルエンおよびキシレンを溶媒として含有する非環境対応型2液型ポリウレタン塗料に比べても実用作業性および性能面でも問題のない環境に配慮した木材用塗料を開発することができた。[0001]
BACKGROUND OF THE INVENTION
The present invention is a 2-component polyurethane paint, to a timber paint using cyclo-hexane derivatives as a solvent.
[0002]
[Prior art]
Conventionally, two-component polyurethane paints have been widely used as wood paints. The main composition is a resin, an extender pigment for enhancing the function, and the solvent has been composed of esters, ketones, aromatic toluene, xylene, and the like (see, for example, Patent Document 1).
[0003]
In recent years, the effects of volatile organic compounds generated in living spaces on the human body have become a problem, and the Ministry of Health, Labor and Welfare has formulated the indoor concentration guideline values, taking into account the detection amount and harmfulness. Since this target substance contains toluene and xylene (June 2000), the paint used for the coating of wood products used indoors contains these substances that cause the generation of volatile organic compounds from its composition. It has become necessary to make a design that does not. Although the initial design focused on eliminating toluene and xylene, a paint that did not contain toluene and xylene was obtained, but as a result, the affinity between the resin and the solvent was excessively increased, and the inherent function of the paint was improved. It has been found that the balance is likely to shift.
[0004]
This imbalance causes various problems in the fundamental performance of the paint. In particular, clogging and foaming, which are regarded as important in primer coatings for two-component polyurethane paints for wood, are toluene and By eliminating xylene, the resin component of the paint is likely to penetrate into the wood, and the drying of the bottom of the paint film is greatly delayed compared to the surface part, and foaming of the conduit part that did not occur conventionally is likely to occur, Furthermore, the important clogging property also worsened. Further, it has been found that the metal soaps generally used for the undercoat are not uniform in the coating film, which greatly impairs the adhesion between the coated films. Further, it has been found that, due to the improvement of the affinity of the solvent, in the overcoating of the two-component polyurethane coating, gloss unevenness due to foaming from the conduit portion and partial drying delay which did not occur conventionally occurs.
[0005]
In the case of an undercoat paint, in order to obtain the surface smoothness of the final coated product, it is often polished with sandpaper, etc., and at this time, the coating powder generated by polishing is less likely to adhere to the sandpaper surface. For this purpose, a metal soap such as zinc stearate is often blended. As mentioned above, when the affinity between the resin and the solvent is excessively increased by the design that only eliminates toluene and xylene from the coating material, the metal soap and the resin will not be wet (chemical inquiry). In addition, by analyzing the components of the paint film surface that has been polished stepwise, the resin component of the paint is more likely to penetrate into the wood interior. It was found that the amount of soap increased extremely. When the paint film in such a state is polished and the same paint or another paint is applied repeatedly, the adhesion between the paint films is greatly reduced due to the nature of the metal soap on the polished paint film surface. Performance may not be obtained. In addition, when the affinity between the resin and the solvent is excessively increased, the evaporation of the solvent from the coated film is delayed. By significantly delaying compared to the surface portion, foaming from the conduit portion and gloss unevenness due to partial drying delay, which did not occur conventionally, occur. Since the drying of the bottom of the coating film is significantly delayed compared to the drying of the surface, the coating film is pushed up and foamed by the evaporation of the solvent at the bottom of the coating film. In addition, in the matte-type top coat, the solvent contained in the paint evaporates and leaves the resin, so that the gloss on the surface disappears according to the amount of the matting agent blended. In the portion where the evaporation is delayed, the gloss is cured in a state where the gloss does not disappear, and uneven gloss occurs. On the other hand, it was also found that these phenomena do not occur in conventional paints containing an aromatic solvent such as toluene and xylene, as in the case of the above-mentioned decrease in adhesion.
[0006]
[Patent Document 1]
JP-A-7-305026 (page 4, right column, pages 25-31)
[0007]
[Problems to be solved by the invention]
In view of such a situation, development of a coating material that does not cause the above-described problem in a two-component polyurethane coating material that does not use toluene and xylene as solvents has been an issue in the industry.
[0008]
[Means for Solving the Problems]
As a result of intensive studies to solve these problems, the present inventor has come to provide a two-component polyurethane paint that does not use toluene and xylene as solvents. That is, in the 2-component polyurethane paint, a wood paint, which comprises using cyclohexane derivative as a solvent, the content occupied in painting formulation total amount of the above carboxy-cyclohexane derivatives 1-50 it is good Masui is%. The cyclohexane derivative is methylcyclohexane, ethylcyclohexane, 1,2-dimethylcyclohexane, 1,3-dimethylcyclohexane, 1,4-dimethylcyclohexane, propylcyclohexane, isopropylcyclohexane, 1,2-methylethylcyclohexane, 1, Any one or more of 3-methylethylcyclohexane, 1,4-methylethylcyclohexane, 1,2,3-trimethylcyclohexane, 1,2,4-trimethylcyclohexane and 1,3,5-trimethylcyclohexane Preferably there is.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The polyurethane-based paint used in the present invention is a polyol such as polyester polyol, fatty acid or oil-modified alkyd, acrylic polyol, epoxy ester, polyether polyol (preferred hydroxyl value is 20 to 400 KOHmg / g in terms of resin solids) or. In addition to these polyol resins, a so-called two-component type in which a main component in which fiber elements such as nitrified cotton and cellulose acetate butyrate are mixed, and a polyisocyanate compound are mixed. Specific examples of the polyisocyanate compound include tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 4,4-methylenebiscyclohexyl diisocyanate, 2,4-methylenebiscyclohexyl diisocyanate, Examples thereof include polyfunctional aromatic polyisocyanates such as isophorone diisocyanate, polyfunctional aliphatic polyisocyanates, and adducts and derivatives thereof.
[0010]
The cyclohexane derivative referred to in the present invention is a 6-membered cyclic paraffin having a residue such as a methyl group or an ethyl group, and includes methylcyclohexane, ethylcyclohexane, 1,2-dimethylcyclohexane, 1, 3-dimethylcyclohexane, 1,4-dimethylcyclohexane, propylcyclohexane, isopropylcyclohexane, 1,2-methylethylcyclohexane, 1,3-methylethylcyclohexane, 1,4-methylethylcyclohexane, 1,2,3-trimethylcyclohexane 1,2,4-trimethylcyclohexane, 1,3,5-trimethylcyclohexane and the like.
[0011]
The wood referred to in the present invention is not particularly limited, but is particularly used for furniture and building materials. For example, in domestic timber, cypress of the cypress family, Sawara, Nezuko, hiba, pine fir, todomatsu, larch, spruce, red pine, tsuji, cedar, cypress, birch, birch, birch, ── ──
Beech, Koinoi, Beech, Mizunara, Shirashi, Anemone camphor, Tabinus, Oxaceae tamo, Elmaceae haruni, Quercus, etc.
it can. In addition, among imported materials, Agariaceae agathis, hoop pine, pine family Merck pine, Dipterocarp melsawa, Apiton, Kapoor, white Celaya, light red merante, dark merante, euphorbiaceae johnson, acatez Nyato of the department, etc.
[0012]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples, but the gist of the present invention is not limited thereto.
[0013]
Example 1
As a main agent, 15 parts by weight of dimethylcyclohexane was weighed and placed in a container. As the alkyd resin polyol, 73 parts by weight of a fatty acid-modified alkyd polyol resin (Dainippon Ink Chemical Co., Ltd., Barnock D-145-55BA) was added and stirred well. Next, while stirring, 4 parts by weight of zinc stearate (manufactured by Shodo Chemical Co., Ltd.) as a grinding aid and 8 parts by weight of hydrous magnesium silicate (manufactured by Hayashi Kasei Co., Ltd., talc PK) as an extender are added for 15 minutes. Stir. On the other hand, 10 parts by weight of butyl acetate and 12 parts by weight of ethyl acetate were weighed as curing agents and put in a container. 19 parts by weight of TDI / TMP adduct type polyisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate L) and 59 parts by weight of TDI isocyanurate type polyisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate 2030) were added for 10 minutes. Stir. As diluents, 40 parts by weight of butyl acetate, 50 parts by weight of ethyl acetate and 10 parts by weight of methoxypropyl acetate were added and stirred for 5 minutes. For coating formulation, a paint was prepared as a main agent: curing agent: diluent = 2: 1: 2, and used as an intermediate coating.
[0014]
(Example 2)
As main agents, 10 parts by weight of dimethylcyclohexane, 10 parts by weight of ethyl acetate and 17 parts by weight of butyl acetate were weighed and put into a container. While stirring, 6 parts by weight of nitrified cotton (manufactured by Asahi Kasei Co., Ltd., nitrified cotton HIG1 / 4) was added, and stirring was continued until dissolved. To this was added 54 parts by weight of a fatty acid-modified alkyd polyol resin (Dainippon Ink Chemical Co., Ltd., Barnock D-145-55BA) and stirred well. Next, 3 parts by weight of fine silicate powder (manufactured by Fuji Silysia Kogyo Co., Ltd., Silicia 350) was added as a matting agent and stirred for 30 minutes. On the other hand, 20 parts by weight of ethyl acetate and 25 parts by weight of butyl acetate as a curing agent were weighed and placed in a container. To this, 15 parts by weight of HDI / TMP adduct type polyisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate HL) and 40 parts by weight of TDI isocyanurate type polyisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate 2030) are added for 10 minutes. Stir. As diluents, 50 parts by weight of ethyl acetate, 40 parts by weight of butyl acetate and 10 parts by weight of methoxypropyl acetate were added and stirred for 5 minutes. For coating formulation, a paint was prepared with a main agent: curing agent: diluent = 2: 1: 1.5 and used as a top coat.
[0015]
Example 3
As main agents, 15 parts by weight of ethyl acetate and 22 parts by weight of butyl acetate were weighed and placed in a container. While stirring, 6 parts by weight of nitrified cotton (manufactured by Asahi Kasei Co., Ltd., nitrified cotton HIG1 / 4) was added, and stirring was continued until dissolved. To this was added 54 parts by weight of a fatty acid-modified alkyd polyol resin (Dainippon Ink Chemical Co., Ltd., Barnock D-145-55BA) and stirred well. Next, 3 parts by weight of fine silicate powder (manufactured by Fuji Silysia Kogyo Co., Ltd., Silicia 350) was added as a matting agent and stirred for 30 minutes. On the other hand, 20 parts by weight of ethyl acetate and 25 parts by weight of butyl acetate as a curing agent were weighed and placed in a container. To this, 15 parts by weight of HDI / TMP adduct type polyisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate HL) and 40 parts by weight of TDI isocyanurate type polyisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate 2030) are added for 10 minutes. Stir. As diluents, 15 parts by weight of dimethylcyclohexane, 40 parts by weight of ethyl acetate, 35 parts by weight of butyl acetate and 10 parts by weight of methoxypropyl acetate were added and stirred for 5 minutes. For coating formulation, a paint was prepared with a main agent: curing agent: diluent = 2: 1: 1.5 and used as a top coat.
[0016]
Example 4
As a main agent, 15 parts by weight of dimethylcyclohexane was weighed and placed in a container. As the alkyd resin polyol, 73 parts by weight of a fatty acid-modified alkyd polyol resin (Dainippon Ink Chemical Co., Ltd., Barnock D-145-55BA) was added and stirred well. Next, while stirring, 2 parts by weight of fine silicate powder (Aerosil # 300, manufactured by Nippon Aerosil Co., Ltd.) as an anti-settling agent, and 10 parts by weight of magnesium silicate hydrate (manufactured by Hayashi Kasei Co., Ltd., talc PK) as an extender pigment And stirred for 15 minutes. On the other hand, 25 parts by weight of butyl acetate and 25 parts by weight of ethyl acetate were weighed as curing agents and put in a container. 20 parts by weight of TDI / TMP adduct type polyisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate L) and 30 parts by weight of TDI isocyanurate type polyisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate 2030) were added for 10 minutes. Stir. As diluents, 40 parts by weight of butyl acetate, 50 parts by weight of ethyl acetate and 10 parts by weight of methoxypropyl acetate were added and stirred for 5 minutes. For coating formulation, a paint was prepared as a base agent: a curing agent: a diluent = 1: 1: 0.6, and used as an undercoat paint.
[0017]
(Comparative Example 1)
As a main agent, 8 parts by weight of butyl acetate was weighed and placed in a container. To this, 80 parts by weight of fatty acid-modified alkyd polyol resin (Dainippon Ink Chemical Co., Ltd., Beccosol 1308) was added as an alkyd resin polyol and stirred well. Next, while stirring, 4 parts by weight of zinc stearate (manufactured by Shodo Chemical Co., Ltd.) as a grinding aid and 8 parts by weight of hydrous magnesium silicate (manufactured by Hayashi Kasei Co., Ltd., talc PK) as an extender pigment were added. Stir for minutes. On the other hand, 10 parts by weight of butyl acetate and 12 parts by weight of ethyl acetate were weighed as curing agents and put in a container. 19 parts by weight of TDI / TMP adduct type polyisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate L) and 59 parts by weight of TDI isocyanurate type polyisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate 2030) were added for 10 minutes. Stir. As diluents, 35 parts by weight of xylene, 45 parts by weight of ethyl acetate and 20 parts by weight of butyl acetate were added and stirred for 5 minutes. For coating formulation, a paint was prepared as a main agent: curing agent: diluent = 2: 1: 2, and used as an intermediate coating.
[0018]
(Comparative Example 2)
As main agents, 5 parts by weight of ethyl acetate and 10 parts by weight of butyl acetate were weighed and placed in a container. As the alkyd resin polyol, 73 parts by weight of a fatty acid-modified alkyd polyol resin (Dainippon Ink Chemical Co., Ltd., Barnock D-145-55BA) was added and stirred well. Next, while stirring, 4 parts by weight of zinc stearate (manufactured by Shodo Chemical Co., Ltd.) as a grinding aid and 8 parts by weight of hydrous magnesium silicate (manufactured by Hayashi Kasei Co., Ltd., talc PK) as an extender pigment were added. Stir for minutes. On the other hand, 10 parts by weight of butyl acetate and 12 parts by weight of ethyl acetate were weighed as curing agents and put in a container. 19 parts by weight of TDI / TMP adduct type polyisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate L) and 59 parts by weight of TDI isocyanurate type polyisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate 2030) were added for 10 minutes. Stir. As diluents, 40 parts by weight of butyl acetate, 50 parts by weight of ethyl acetate and 10 parts by weight of methoxypropyl acetate were added and stirred for 5 minutes. For coating formulation, a paint was prepared as a main agent: curing agent: diluent = 2: 1: 2, and used as an intermediate coating.
[0019]
(Comparative Example 3)
As main ingredients, 15 parts by weight of ethyl acetate and 22 parts by weight of butyl acetate were weighed and placed in a container. While stirring, 6 parts by weight of nitrified cotton (manufactured by Asahi Kasei Co., Ltd., nitrified cotton HIG1 / 4) was added, and stirring was continued until dissolved. To this was added 54 parts by weight of a fatty acid-modified alkyd polyol resin (Dainippon Ink Chemical Co., Ltd., Barnock D-145-55BA) and stirred well. Next, 3 parts by weight of fine silicate powder (manufactured by Fuji Silysia Kogyo Co., Ltd., Silicia 350) was added as a matting agent and stirred for 30 minutes. On the other hand, 20 parts by weight of ethyl acetate and 25 parts by weight of butyl acetate as a curing agent were weighed and placed in a container. To this, 15 parts by weight of HDI / TMP adduct type polyisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate HL) and 40 parts by weight of TDI isocyanurate type polyisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate 2030) are added for 10 minutes. Stir. As diluents, 50 parts by weight of ethyl acetate, 40 parts by weight of butyl acetate and 10 parts by weight of methoxypropyl acetate were added and stirred for 5 minutes. For coating formulation, a paint was prepared with a main agent: curing agent: diluent = 2: 1: 1.5 and used as a top coat.
[0020]
(Comparative Example 4)
As main agents, 5 parts by weight of ethyl acetate, 17 parts by weight of butyl acetate and 10 parts by weight of xylene were weighed and put in a container. While stirring, 6 parts by weight of nitrified cotton (manufactured by Asahi Kasei Co., Ltd., nitrified cotton HIG1 / 4) was added, and stirring was continued until dissolved. To this was added 59 parts by weight of a fatty acid-modified alkyd polyol resin (Dainippon Ink Chemical Co., Ltd., Beccosol 1308) and stirred well. Next, 3 parts by weight of fine silicate powder (manufactured by Fuji Silysia Kogyo Co., Ltd., Silicia 350) was added as a matting agent and stirred for 30 minutes. On the other hand, 20 parts by weight of ethyl acetate and 25 parts by weight of butyl acetate as a curing agent were weighed and placed in a container. To this, 15 parts by weight of HDI / TMP adduct type polyisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate HL) and 40 parts by weight of TDI isocyanurate type polyisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate 2030) are added for 10 minutes. Stir. As diluents, 30 parts by weight of ethyl acetate, 25 parts by weight of butyl acetate, 10 parts by weight of methoxypropyl acetate, 15 parts by weight of toluene and 20 parts by weight of xylene were added and stirred for 5 minutes. For coating formulation, a paint was prepared with a main agent: curing agent: diluent = 2: 1: 1.5 and used as a top coat.
[0021]
(Comparative Example 5)
As a main agent, 8 parts by weight of butyl acetate was weighed and placed in a container. To this, 80 parts by weight of fatty acid-modified alkyd polyol resin (Dainippon Ink Chemical Co., Ltd., Beccosol 1308) was added as an alkyd resin polyol and stirred well. Next, while stirring, 2 parts by weight of fine silicate powder (Aerosil # 300, manufactured by Nippon Aerosil Co., Ltd.) as an anti-settling agent, and 10 parts by weight of magnesium silicate hydrate (manufactured by Hayashi Kasei Co., Ltd., talc PK) as an extender pigment And stirred for 15 minutes. On the other hand, 25 parts by weight of butyl acetate and 25 parts by weight of ethyl acetate were weighed as curing agents and put in a container. 20 parts by weight of TDI / TMP adduct type polyisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate L) and 30 parts by weight of TDI isocyanurate type polyisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate 2030) were added for 10 minutes. Stir. As diluents, 35 parts by weight of xylene, 45 parts by weight of ethyl acetate and 20 parts by weight of butyl acetate were added and stirred for 5 minutes. The coating composition was prepared as a base agent: a curing agent: a diluent = 1: 1: 0.6, and used as an undercoat paint.
[0022]
(Comparative Example 6)
As main agents, 5 parts by weight of ethyl acetate and 10 parts by weight of butyl acetate were weighed and placed in a container. As the alkyd resin polyol, 73 parts by weight of a fatty acid-modified alkyd polyol resin (Dainippon Ink Chemical Co., Ltd., Barnock D-145-55BA) was added and stirred well. Next, 2 parts by weight of silicic acid fine powder (Nippon Aerosil Co., Ltd., Aerosil # 300) is used as an anti-settling agent while stirring, and 10 parts by weight of hydrous magnesium silicate (Hayashi Kasei Co., Ltd., talc PK) is used as an extender pigment. And stirred for 15 minutes. On the other hand, 25 parts by weight of butyl acetate and 25 parts by weight of ethyl acetate were weighed as curing agents and put in a container. 20 parts by weight of TDI / TMP adduct type polyisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate L) and 30 parts by weight of TDI isocyanurate type polyisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate 2030) were added for 10 minutes. Stir. As diluents, 40 parts by weight of butyl acetate, 50 parts by weight of ethyl acetate and 10 parts by weight of methoxypropyl acetate were added and stirred for 5 minutes. The coating composition was prepared as a base agent: a curing agent: a diluent = 1: 1: 0.6, and used as an undercoat paint.
[0023]
(Test Example 1)
The blended Example 1, Comparative Example 1 and Comparative Example 2 intermediate coatings were applied to a rubber assembly by 80 g / m 2 using a 1.5 mm spray gun. The painted surface was evaluated by the method shown in Table 1, and the results are shown in Table 2. As can be seen from Table 2, the use of dimethylcyclohexane in the coating composition improved properties such as foaming, meat retention, inhalation and precipitation. In particular, it was confirmed that a great effect was obtained on the suction. Table 3 shows the contents of toluene and xylene contained in the paint of Example 1 and the paints of Comparative Examples 1 and 2 and the amounts of toluene and xylene diffused from the coated surface. Thus, except for Comparative Example 1, the contents of toluene and xylene were not recognized, and the emission amounts of toluene and xylene were below the lower limit of measurement quantification.
[0024]
[Table 1]
[0025]
[Table 2]
[0026]
[Table 3]
[0027]
(Test Example 2)
Each of the coated plates coated in Test Example 1 was dried and cured, and then polished to make it possible to repeat coating. Thereafter, the top coat of 50 g / m 2 of the paint of Comparative Example 3 was applied to each coated plate using a 1.5 mm spray gun. One week after coating, the painted surface was evaluated by the evaluation method shown in Table 1. The result is as shown in Table 4, and in the adhesion between the coating films, when the substitutes of toluene and xylene of Comparative Example 2 were used, the coating film performance was lowered, but dimethylcyclohexane was used. As a result, the same coating film performance as that of the conventional paint using toluene or xylene was confirmed.
[0028]
[Table 4]
[0029]
(Test Example 3)
The top coat paints of Example 2 and Example 3 and Comparative Example 3 and Comparative Example 4 which were blended were subjected to intermediate coating on a rubber laminated material, dried and cured, and then 1.5 mm on a plate polished with sandpaper # 400. 50 g / m 2 was applied with a spray gun. The difference between Example 2 and Example 3 is the difference in whether dimethylcyclohexane is added in advance to the main component of the paint or is mixed immediately before coating, and Comparative Example 3 is a formulation in which toluene and xylene are not added. Comparative Example 4 is a conventional paint containing toluene and xylene. The painted surface was evaluated by the method shown in Table 5, and the results are shown in Table 6. As can be seen from Table 6, in terms of dryness, Example 3 is faster than Example 2, and Example 3 is thought to be due to the earlier diffusion of the solvent due to insufficient familiarity between the resin and dimethylcyclohexane. In other items, Example 2 was higher in evaluation than Example 3. Moreover, both Example 2 and Example 3 were improved in all points as compared with Comparative Example 3, and in comparison with Comparative Example 4, Example 2 was higher in comprehensive evaluation.
[0030]
[Table 5]
[0031]
[Table 6]
[0032]
(Test Example 4)
The blended undercoat paints of Example 4, Comparative Example 5 and Comparative Example 6 were applied to a rubber laminated material at 80 g / m 2 with a 1.5 mm spray gun. The painted surface was evaluated by the method shown in Table 7, and the results are shown in Table 8. As is clear from Table 8, the use of dimethylcyclohexane in the coating composition improved the properties such as foaming, meat retention, suction, and clogging. In particular, it was confirmed that a great effect was obtained on foaming, suction, and clogging.
[0033]
[Table 7]
[0034]
[Table 8]
[0035]
【The invention's effect】
The environmentally friendly two-component polyurethane paint of the present invention should be designed so as to eliminate toluene and xylene by using a cyclohexane derivative as a part of the solvent and not excessively increase the affinity between the resin and the solvent. I was able to. In general, when a solvent having a low molecular polarity is used in combination with esters and ketones, the affinity of the solvent as a whole is lowered. However, linear or branched aliphatic hydrocarbons, which are low-polar solvents conventionally used in paints, have extremely low affinity with resins as alternative solvents for toluene and xylene, and the solubility of the resins In practice, it was impossible to use. Therefore, as a result of examining other low-polarity solvents, it was found that cyclohexane derivatives represented by methylcyclohexane and dimethylcyclohexane were most suitable, and performance aspects of conventional two-component polyurethane paints using non-toluene and non-xylene solvents Wood-based paint that can improve the disadvantages of the above and is environmentally friendly compared to non-environmentally compatible two-component polyurethane paints containing toluene and xylene as solvents. Could be developed.
Claims (3)
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| JP2002335460A JP3812833B2 (en) | 2002-03-18 | 2002-11-19 | Environmental coating agent |
| KR10-2003-0003197A KR20030076249A (en) | 2002-03-18 | 2003-01-17 | Environmental non-contamination coating agent |
| CN031045278A CN1218003C (en) | 2002-03-18 | 2003-02-13 | Environment-friendly type coating material |
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| JP2002335460A JP3812833B2 (en) | 2002-03-18 | 2002-11-19 | Environmental coating agent |
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| JP4836542B2 (en) * | 2004-10-29 | 2011-12-14 | 関西ペイント株式会社 | Paint composition |
| CN101913837B (en) * | 2010-07-27 | 2014-03-05 | 肖子双 | Multifunctional solvent coating |
| FR2974368B1 (en) * | 2011-04-22 | 2014-08-29 | Rhodia Poliamida E Especialidades Ltda | SOLVENT SYSTEM FOR PAINTS, VARNISHES, INKS OR ADHESIVES COMPRISING A MIXTURE OF A CYCLOHEXANE COMPOUND AND OXYGEN SOLVENTS |
| KR102050921B1 (en) | 2018-08-02 | 2019-12-03 | 에스케이이노베이션 주식회사 | Organic solvent composition and paint composition comprising the same |
-
2002
- 2002-11-19 JP JP2002335460A patent/JP3812833B2/en not_active Expired - Fee Related
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2003
- 2003-01-17 KR KR10-2003-0003197A patent/KR20030076249A/en not_active Ceased
- 2003-02-13 CN CN031045278A patent/CN1218003C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2003342524A (en) | 2003-12-03 |
| CN1218003C (en) | 2005-09-07 |
| CN1448451A (en) | 2003-10-15 |
| KR20030076249A (en) | 2003-09-26 |
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