JP5585753B2 - Lacquer and lacquer manufacturing method - Google Patents
Lacquer and lacquer manufacturing method Download PDFInfo
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- JP5585753B2 JP5585753B2 JP2009070392A JP2009070392A JP5585753B2 JP 5585753 B2 JP5585753 B2 JP 5585753B2 JP 2009070392 A JP2009070392 A JP 2009070392A JP 2009070392 A JP2009070392 A JP 2009070392A JP 5585753 B2 JP5585753 B2 JP 5585753B2
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- 239000004922 lacquer Substances 0.000 title claims description 105
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000011248 coating agent Substances 0.000 claims description 60
- 238000000576 coating method Methods 0.000 claims description 60
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 55
- 239000010419 fine particle Substances 0.000 claims description 28
- 239000011787 zinc oxide Substances 0.000 claims description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- 239000003973 paint Substances 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 16
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 239000010954 inorganic particle Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- -1 polysiloxane Polymers 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 238000004898 kneading Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 claims 1
- 235000014692 zinc oxide Nutrition 0.000 description 26
- 239000007788 liquid Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 238000005406 washing Methods 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- RMTXUPIIESNLPW-UHFFFAOYSA-N 1,2-dihydroxy-3-(pentadeca-8,11-dienyl)benzene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1O RMTXUPIIESNLPW-UHFFFAOYSA-N 0.000 description 5
- QARRXYBJLBIVAK-UEMSJJPVSA-N 3-[(8e,11e)-pentadeca-8,11-dienyl]benzene-1,2-diol;3-[(8e,11e)-pentadeca-8,11,14-trienyl]benzene-1,2-diol;3-[(8e,11e,13e)-pentadeca-8,11,13-trienyl]benzene-1,2-diol;3-[(e)-pentadec-8-enyl]benzene-1,2-diol;3-pentadecylbenzene-1,2-diol Chemical compound CCCCCCCCCCCCCCCC1=CC=CC(O)=C1O.CCCCCC\C=C\CCCCCCCC1=CC=CC(O)=C1O.CCC\C=C\C\C=C\CCCCCCCC1=CC=CC(O)=C1O.C\C=C\C=C\C\C=C\CCCCCCCC1=CC=CC(O)=C1O.OC1=CC=CC(CCCCCCC\C=C\C\C=C\CC=C)=C1O QARRXYBJLBIVAK-UEMSJJPVSA-N 0.000 description 5
- IYROWZYPEIMDDN-UHFFFAOYSA-N 3-n-pentadec-8,11,13-trienyl catechol Natural products CC=CC=CCC=CCCCCCCCC1=CC=CC(O)=C1O IYROWZYPEIMDDN-UHFFFAOYSA-N 0.000 description 5
- 238000002845 discoloration Methods 0.000 description 5
- DQTMTQZSOJMZSF-UHFFFAOYSA-N urushiol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1O DQTMTQZSOJMZSF-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 235000013162 Cocos nucifera Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000005562 fading Methods 0.000 description 3
- 235000014413 iron hydroxide Nutrition 0.000 description 3
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 3
- 239000007762 w/o emulsion Substances 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 241000737241 Cocos Species 0.000 description 2
- 108010029541 Laccase Proteins 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical class OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 239000002929 natural lacquer Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000012463 white pigment Substances 0.000 description 2
- XLHUBROMZOAQMV-UHFFFAOYSA-N 1,4-benzosemiquinone Chemical compound [O]C1=CC=C(O)C=C1 XLHUBROMZOAQMV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 102000003886 Glycoproteins Human genes 0.000 description 1
- 108090000288 Glycoproteins Proteins 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 244000044283 Toxicodendron succedaneum Species 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000004826 dibenzofurans Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000012812 general test Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
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- 238000007670 refining Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- 239000010902 straw Substances 0.000 description 1
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Description
本発明は、耐候性や耐洗浄性の優れた漆塗料及びその製造方法並びに当該漆塗料で塗装した物品（塗装材）に関するものである。 The present invention relates to a lacquer paint excellent in weather resistance and washing resistance, a method for producing the same, and an article (paint material) coated with the lacquer paint.
天然の漆液は、化学的にはウルシオール（カテコール誘導体）、ゴム質（植物多糖類及び酵素ラッカーゼを含むタンパク質類）、含窒素物（糖タンパク質）から構成され、油状成分であるウルシオール中にゴム質の水溶液が乳化分散して、油中水滴（Ｗ／Ｏ）型エマルションを形成している。漆の木から掻きとった漆液から夾雑物を除去した「生漆」は、更に、ナヤシ、クロメという工程を経て塗装用の精製漆に加工される（製漆工程）。製漆工程において、ナヤシというのは攪拌操作、クロメというのは加熱攪拌操作のことである。製漆工程を経た漆液は、「透漆」と呼ばれ、鉄粉又は水酸化鉄で黒く着色した漆液は、「黒漆」と呼ばれている。 Natural lacquer fluid is chemically composed of urushiol (catechol derivative), rubbery (proteins including plant polysaccharides and enzyme laccase), and nitrogenous substances (glycoprotein). An aqueous rubber solution is emulsified and dispersed to form a water-in-oil (W / O) emulsion. “Nama-lacquer”, which is made by removing impurities from the lacquer liquid scraped from the lacquer tree, is further processed into refined lacquer for painting through the processes of coconut palm and chrome (lacquering process). In the lacquering process, coconut is a stirring operation, and chrome is a heating and stirring operation. The lacquer liquid that has undergone the lacquering process is called “translucent lacquer”, and the lacquer liquid colored black with iron powder or iron hydroxide is called “black lacquer”.
製漆工程において、生漆の水分は約１５〜４０重量％、精製漆の水分は約３〜９重量％である。生漆や精製漆は、ウルシオールが酵素ラッカーゼにより酸化されウルシオールセミキノンラジカルとなり、以下ウルシオールキノン、ジベンゾフラン類、ビフェニル類、キノン−側鎖オレフィン反応物などが生成し、順次高分子化して塗膜を形成する。生漆や精製漆の乾燥硬化には高湿度環境が必要である。漆液を塗布された漆器類は、通常漆風呂と呼ばれる高湿度空間で乾燥される。 In the lacquering process, the moisture of fresh lacquer is about 15 to 40% by weight, and the moisture of purified lacquer is about 3 to 9% by weight. In raw lacquer and refined lacquer, urushiol is oxidized by the enzyme laccase to form urushiol semiquinone radical, and urushiol quinone, dibenzofurans, biphenyls, quinone-side chain olefin reactants, etc. are generated and coated in succession. A film is formed. A high-humidity environment is required for drying and curing raw lacquer and refined lacquer. Lacquerware coated with lacquer liquid is usually dried in a high humidity space called a lacquer bath.
天然漆液は古来より塗料として利用されており、漆塗膜の耐久性は４０００年とも５０００年とも言われている。しかし、それは日光の当たらない所に保存された場合のことで、屋外での耐久性は１年程度である。漆塗膜の最大の欠点は耐候性が弱いことで、紫外線により劣化するため、塗料としての用途は、主に椀・盆・重箱などの屋内用途に限られていた。 Natural lacquer has been used as a paint since ancient times, and the durability of lacquer coating is said to be 4000 or 5000 years. However, it is a case where it is stored in a place not exposed to sunlight, and its durability outdoors is about one year. The biggest drawback of lacquer coating film is its weak weather resistance, which deteriorates due to ultraviolet rays, so its use as a paint was limited mainly to indoor use such as baskets, trays, and heavy boxes.
また、漆塗膜は、耐洗浄性にも問題があり、漆塗りの椀は、通常、食器洗浄機では洗浄しないように取扱説明書に記載してある。 In addition, lacquer coating film has a problem in washing resistance, and lacquered straw is usually described in the instruction manual so as not to be washed by a dishwasher.
漆塗膜が褪色（白亜化）する主な原因として、塗膜中にあるゴム質が紫外線や洗浄で溶出されることにより、塗膜表面に光に干渉する程の凹凸が生じることが挙げられる。 The main cause of the lacquer coating film fading (chalking) is that the rubber material in the coating film is eluted by ultraviolet rays or washing, resulting in unevenness on the coating film surface that interferes with light. .
乾燥した漆塗膜の耐久性は、エマルションである漆液の粒子径を微細化することで、向上することが知られている。例えば下記特許文献１には、ナヤシ操作に分散乳化機を用いることにより、ウルシオールと含窒素物およびゴム質が超微細化され、光沢性や透明性の良好な漆塗膜が得られることが示されている。
It is known that the durability of the dried lacquer coating film is improved by refining the particle size of the lacquer liquid which is an emulsion. For example, in
更に、下記特許文献２には、油中水滴型エマルションの粒径が１０〜８０ｎｍであることを特徴とする、光沢性及び耐久性に優れた漆塗膜を与える漆系塗料が、また特許文献３には、油中水滴型エマルションに含まれる水滴の平均粒径を約１００ｎｍの大きさまで小さくする微細化工程を含む耐久性に優れた漆系塗料の製造方法が提案されている。
Furthermore,
また、特許文献４には、漆の有機溶剤溶液とチタニウムアルコキシドの有機溶剤溶液とを混合してチタニウムアルコキシドの加水分解により生じる酸化チタンを漆中に含有させることにより、漆塗膜の耐候性が向上することが示されている。 Patent Document 4 describes the weather resistance of a lacquer coating film by mixing a lacquer organic solvent solution and an organic solvent solution of titanium alkoxide and adding titanium oxide produced by hydrolysis of titanium alkoxide in the lacquer. It has been shown to improve.
酸化チタンは、白色顔料として各種塗料に用いられており、紫外線吸収作用が塗膜の耐候性を向上させることが知られている。特許文献４によれば、漆塗料中でチタニウムアルコキシドから生成する酸化チタンは一般的な塗料に配合される酸化チタン系顔料に比べると極めて微細であるため、紫外線遮蔽作用にすぐれ、塗膜の耐候性を顕著に向上させる。チタニウムアルコキシドの比率が高くなるほど耐候性は良くなるが、耐酸性や熱水に対する耐性は悪くなるとされている。 Titanium oxide is used as a white pigment in various paints, and it is known that the ultraviolet absorption action improves the weather resistance of the coating film. According to Patent Document 4, titanium oxide produced from titanium alkoxide in a lacquer coating is extremely fine compared to a titanium oxide pigment blended in a general coating, so it has an excellent ultraviolet shielding effect and weather resistance of the coating film. Remarkably improve the performance. The higher the titanium alkoxide ratio, the better the weather resistance, but the acid resistance and the resistance to hot water are said to deteriorate.
更に、同じ白色顔料として古くから用いられている酸化亜鉛（亜鉛華）について、特許文献５には、平均一次粒子径がサブミクロンサイズ以下（例えば２００ｎｍ以下）の微粒子酸化亜鉛の分散方法が提案されており、紫外線吸収性を期待する場合には超微粒子酸化亜鉛が使用されること、当該方法に従い製造された酸化亜鉛濃度２５〜３５重量％の酸化亜鉛分散ペーストを配合した塗料、粘着剤などは、沈殿や分離を起こすことがなく、貯蔵安定性に優れたものになるとされている。
Furthermore, with respect to zinc oxide (zinc white), which has been used for a long time as the same white pigment,
この発明は、漆塗膜の最大の弱点が耐候性にあること及び耐洗浄性にも問題があることに鑑み、耐候性に優れ、耐洗浄性にも優れた漆塗膜を形成することが可能な漆塗料及び当該漆塗料の製造方法を提供することを課題としている。 In view of the fact that the greatest weakness of the lacquer coating film is weather resistance and there is a problem with washing resistance, the present invention can form a lacquer coating film having excellent weather resistance and excellent washing resistance. It is an object of the present invention to provide a possible lacquer coating and a method for producing the lacquer coating.
この発明では、天然産漆液またはその生漆を原料とする精製漆に、酸化亜鉛の無機微粒子を添加し、３本ロールミルやミキサー等の混練装置を用いて当該無機微粒子をサブミクロン台の粒径にして均一に分散すると共に、ゴム質の粒径を微細化することで、漆系塗料の塗膜の耐候性を顕著に向上させることを可能にしている。 In the present invention, the purification lacquer to the naturally occurring lacquer solution or a raw lacquer raw material, adding an oxidizing zinc inorganic fine particles, the particle the inorganic fine particles of submicron table using a kneading apparatus such as a three-roll mill or mixer It is possible to remarkably improve the weather resistance of the coating film of the lacquer-based paint by uniformly dispersing the diameter and reducing the rubber particle size.
無機微粒子としては酸化亜鉛（ＺｎＯ）、特にシリカ・アルミナコーティング又はポリシロキサンコーティングをした酸化亜鉛が優れており、色差及び光沢残存率の両評価基準で顕著な耐候性が認められた。また、シリカ・アルミナコーティングをした酸化亜鉛の微粒子を添加した漆は、耐洗浄性にも顕著な改善が認められた。更に、酸化亜鉛微粒子を添加した漆塗膜は、水酸化鉄を用いた黒漆と同等な色味の黒色を有する。一方、シリカの添加により、光沢残存率が著しく改善される。無機微粒子の添加量は、１〜２０重量％であり、耐洗浄性を付与するには多めに添加するのが好ましい。複数種の無機微粒子を添加する好ましい例としては、酸化亜鉛の微粒子とシリカの微粒子を添加する例を挙げることができる。 As the inorganic fine particles, zinc oxide (ZnO), particularly zinc oxide coated with silica / alumina or polysiloxane was excellent, and remarkable weather resistance was recognized in both evaluation criteria of color difference and gloss residual ratio. In addition, lacquer added with silica / alumina-coated zinc oxide fine particles showed a marked improvement in washing resistance. Furthermore, the lacquer coating film to which the zinc oxide fine particles are added has a black color similar to that of black lacquer using iron hydroxide. On the other hand, the addition of silica significantly improves the gloss residual ratio. The addition amount of the inorganic fine particles is 1 to 20% by weight, and it is preferable to add a large amount in order to impart washing resistance. Preferable examples of adding a plurality of types of inorganic fine particles include an example of adding fine particles of zinc oxide and fine particles of silica.
本発明の黒色漆塗料は、従来品よりも耐候性及び耐洗浄性に優れた塗膜を有する。添加する無機微粒子として酸化亜鉛を用いることにより、褪色及び光沢残存率の両方において優れた耐候性を示し、耐洗浄性にも優れた漆塗膜を形成する漆塗料が得られる。また、酸化亜鉛の添加量を多くすることで、塗膜に黒漆と同等な色味を付与することができる。一方、無機微粒子として酸化チタン又はシリカを用いた場合は、褪色に関しては効果が認められなかった。 The black lacquer paint of the present invention has a coating film that is superior in weather resistance and washing resistance than conventional products. The Rukoto using zinc oxide as the inorganic fine particles to be added, shows excellent weather resistance in both fading and gloss remaining ratio, lacquer coating is obtained which forms a lacquer coating film excellent in washing resistance. Moreover, the color equivalent to black lacquer can be provided to a coating film by increasing the addition amount of a zinc oxide. On the other hand, when titanium oxide or silica was used as the inorganic fine particles, no effect was observed with respect to discoloration .
なお、本願発明に係る漆塗料は、漆塗膜の褪色原因となるゴム質の溶出を防ぐ効果がある。これは、添加したサブミクロン台の無機微粒子が混練により漆液中を均一に混練・分散するとき、ゴム質の分散粒子に衝突し、塗膜から溶出されにくい状態まで微細化・分散させる作用を果たすことで、ゴム質が塗膜中で固定化しているためと考えられる。 In addition, the lacquer coating material which concerns on this invention has an effect which prevents the elution of the rubber | gum which becomes a fading cause of a lacquer coating film. This is because when the added submicron-level inorganic fine particles are kneaded and dispersed uniformly in the lacquer liquid by kneading, they collide with the rubber-like dispersed particles and make them finer and dispersed so that they are not easily eluted from the coating film. This is probably because the rubber is fixed in the coating film.
以下、この発明の幾つかの実施例を挙げて、この発明の好ましい実施形態を具体的に説明する。漆塗膜の促進耐候性試験における３００時間は、屋外での２年間に相当する。また、漆器の食器洗浄機試験の１０００回は、１日３回洗浄した場合の１年間の使用に相当する。紫外線による漆塗膜の褪色に関し、色差の評価基準（日本工業規格JISK 5600-4 塗料一般試験方法−第４部：塗膜の視覚特性に準拠）は、表１のように定めている。漆塗膜の耐候性については、屋外で２年間使用した場合の光沢残存率７０％以上、色差５以下が目標値と考えられる。 Hereinafter, preferred embodiments of the present invention will be specifically described with reference to some examples of the present invention. 300 hours in the accelerated weathering test of the lacquer coating film corresponds to two years outdoors. Moreover, 1000 times of the lacquerware dishwasher test is equivalent to 1 year of use when washed 3 times a day. Regarding the discoloration of the lacquer coating film by ultraviolet rays, the evaluation criteria for color difference (Japanese Industrial Standard JISK 5600-4 Paint General Test Method-Part 4: Based on the visual characteristics of the coating film) are defined as shown in Table 1. Regarding the weather resistance of the lacquer coating film, it is considered that a gloss remaining ratio of 70% or more and a color difference of 5 or less when used outdoors for 2 years is a target value.
（無機粒子を添加した漆液の調整）
水分、粘度調整をした中国産精製漆液に粒径１００ｎｍ以下の無機微粒子（シリカ・アルミナコーティングをした酸化亜鉛、ポリシロキサンコーティングをした酸化亜鉛、コーティングなしの酸化亜鉛、酸化チタン及びシリカ）を漆液に混ぜ、分散混練用の３本ロールミル（ローラー材質 硬質セラミック［ハイアルミナ］、ローラー硬度 ８．８〜９．０［モース硬度］、ローラー直径 ４２ｍｍ、ローラー長さ１８０ｍｍ、ローラー回転比１：２：４、ロール回転数６０ｒｐｍで各漆液５０ｇを３回混練した。
(Adjustment of lacquer liquid with inorganic particles added)
Lacquered inorganic fine particles (zinc oxide with silica / alumina coating, zinc oxide with polysiloxane coating, zinc oxide without coating, titanium oxide and silica) with a particle size of 100 nm or less in purified lacquer solution made in China with moisture and viscosity adjusted 3 roll mill for mixing and dispersing (roller material hard ceramic [high alumina], roller hardness 8.8 to 9.0 [Mohs hardness], roller diameter 42 mm, roller length 180 mm, roller rotation ratio 1: 2 : 4, 50 g of each lacquer solution was kneaded 3 times at a roll rotation number of 60 rpm.
上記の配合率の漆液を自転・公転ミキサーを使用し、公転２０００ｒｐｍ、１６分間の条件で混合した結果、漆液状態で無機粒子が均一に分散されていることが確認された。また、無機粒子の添加量（重量率）が高いほど、粘度が高く、添加量が低いほど、塗料として塗布しやすいことが分かった。精製した漆液の粘度を図１に示す。 As a result of mixing the lacquer liquid with the above blending ratio using a rotation / revolution mixer under conditions of revolution 2000 rpm and 16 minutes, it was confirmed that the inorganic particles were uniformly dispersed in the lacquer liquid state. Moreover, it turned out that it is easy to apply | coat as a coating material, so that the viscosity is so high that the addition amount (weight ratio) of an inorganic particle is high, and the addition amount is low. The viscosity of the purified lacquer liquid is shown in FIG.
漆塗膜試料を走査型電子顕微鏡（ＳＥＭ）で観察し、無機粒子が塗膜中均一に分散されていた。また、無機粒子を添加しない漆塗膜と比べて、漆塗膜中のゴム質の粒子全てがサブミクロンオーダーで微細化されていることが確認された。 The lacquer coating film sample was observed with a scanning electron microscope (SEM), and the inorganic particles were uniformly dispersed in the coating film. Moreover, it was confirmed that all the rubber-like particles in the lacquer coating film were refined on a submicron order as compared with the lacquer coating film to which inorganic particles were not added.
（漆塗膜試料の作成）
上記で作成した各漆液を、幅８０×長さ１２０×厚さ３ｍｍのＡＢＳ板に間隙１００μｍのフラットブレードアプリケータを用いて塗布した。塗布した試料板を温度２０±２℃湿度７０±２０％ＲＨの恒温恒湿器に入れ、塗膜を乾燥した。漆液に添加した粒子の種類と粒径および漆への添加率を表２に示す。
(Creation of lacquer coating sample)
Each lacquer solution created above was applied to an ABS plate having a width of 80 × length of 120 × thickness of 3 mm using a flat blade applicator having a gap of 100 μm. The coated sample plate was placed in a constant temperature and humidity chamber with a temperature of 20 ± 2 ° C. and a humidity of 70 ± 20% RH, and the coating film was dried. Table 2 shows the types and particle sizes of the particles added to the lacquer liquid and the rate of addition to the lacquer.
（耐候性試験）
作成した漆塗膜にサンシャインウェザーメータ（スガ試験機(株)製、WEL-SUN-HC）を用いてサンシャインカーボンアーク光源を照射することにより促進耐候性試験を実施した。照射時間１０２分、降雨時間１８分、計１２０分を１サイクルとし、１４４サイクル（２８８時間）実施した。漆塗膜試料の色味および光沢を、スペクトロカラーメータ（日本電色工業製、SZ-Σ80型）およびデジタル光沢計（BYK-Gardner製、micro-TRI-gloss μ）を用いて、それぞれ測定した。さらに、試験前後の色差および光沢残存率を算出することにより、無機粒子添加による漆塗膜の耐候性を評価した。結果を以下の表３−１及び表３−２に示す。
(Weather resistance test)
The accelerated weather resistance test was performed by irradiating the created lacquer coating film with a sunshine carbon arc light source using a sunshine weather meter (WEL-SUN-HC, manufactured by Suga Test Instruments Co., Ltd.). The irradiation time was 102 minutes, the rainfall time was 18 minutes, and the total time was 120 minutes, which was 144 cycles (288 hours). The color and gloss of lacquer coating samples were measured using a spectrocolor meter (Nippon Denshoku Industries, SZ-Σ80 type) and a digital gloss meter (BYK-Gardner, micro-TRI-gloss μ), respectively. . Furthermore, the weather resistance of the lacquer coating film by addition of inorganic particles was evaluated by calculating the color difference before and after the test and the residual gloss rate. The results are shown in Tables 3-1 and 3-2 below.
（耐洗浄性試験）
前記と同様に作成した漆塗膜試料（試料名：ＺｎＯＡ−５）を漆器洗浄試験機（ホシザキ電機(株)製、JWE-400TUA3）を用いて耐洗浄性試験を実施した。洗浄時間は１サイクル１８０秒（洗浄時間９０秒、洗浄温度４０〜８５℃、休止時間９０秒）で１０００サイクル実施した。漆塗膜試料の色味および光沢を、スペクトロカラーメータ（日本電色工業製、SZ-Σ80型）およびデジタル光沢計（BYK-Gardner製、micro-TRI-gloss μ）を用いて、それぞれ測定した。さらに、試験前後の色差および光沢残存率を算出することにより、無機粒子添加の有無による漆塗膜の耐洗浄性を評価した。結果を以下の表４−１及び表４−２に示す。
(Cleaning resistance test)
A lacquer coating film sample (sample name: ZnOA-5) prepared in the same manner as described above was subjected to a cleaning resistance test using a lacquer ware cleaning tester (manufactured by Hoshizaki Electric Co., Ltd., JWE-400TUA3). The cleaning time was 1000 cycles with a cycle of 180 seconds (cleaning time 90 seconds, cleaning
（酸化亜鉛添加による黒味の比較）
酸化亜鉛添加により、水酸化鉄を利用した黒漆と同等以上の黒味が得られた。
表５に示した各試料名の漆塗膜試料３枚の平均Ｌ値（色の明るさを示し、数値が低い程黒い）をスペクトロカラーメータ（日本電色工業製、SZ-Σ80型）で測定したデータを表５に示す。
(Comparison of blackness by adding zinc oxide)
By adding zinc oxide, a blackness equivalent to or better than black lacquer using iron hydroxide was obtained.
Use a spectrocolor meter (Nippon Denshoku Industries Co., Ltd., SZ-Σ80 type) to calculate the average L value (indicating the brightness of the color, the blacker the lower the value) of the three lacquer coating film samples of each sample name shown in Table 5. Table 5 shows the measured data.
（評価）
図２〜図５は、シリカ・アルミナコーティングした酸化亜鉛微粒子を添加した場合の上記試験結果をグラフ表示した図である。
(Evaluation)
FIGS. 2 to 5 are graphs showing the test results in the case where zinc oxide fine particles coated with silica / alumina are added.
図から明らかなように、シリカ・アルミナコーティングした酸化亜鉛微粒子を添加した本願発明の漆塗料は、色差に関する耐候性について目標値を若干オーバーしているが、他の漆塗料に比べて顕著な改善が認められ、他の項目については、前記した目標値を達成している。コーティングなしの酸化亜鉛微粒子を添加したものは、試験データにばらつきが認められるが、優れた耐候性を有することが示されている。 As is clear from the figure, the lacquer paint of the present invention with the addition of silica / alumina-coated zinc oxide fine particles slightly exceeded the target value for weather resistance related to color difference, but it is a marked improvement compared to other lacquer paints. The other target items have achieved the target values described above. A sample to which fine zinc oxide fine particles without coating is added shows variation in test data, but has been shown to have excellent weather resistance.
一方、透漆は、耐候性が劣り、アルカリ洗剤による変色も著しい。黒漆は、変色は少ないけれども、紫外線により光沢度が劣化し、特にアルカリ洗剤による光沢度の劣化が著しい。 On the other hand, translucent lacquer is inferior in weather resistance, and discoloration by an alkaline detergent is also remarkable. Although black lacquer has little discoloration, the glossiness is deteriorated by ultraviolet rays, and the glossiness is particularly deteriorated by an alkaline detergent.
以上のことから、本願発明の酸化亜鉛微粒子を添加した漆塗料により形成した漆塗膜は、変色及び光沢度の両方において、従来の漆塗料に比べて優れた耐候性及び耐洗浄性を備えていることが分かる。 From the above, Urushinurimaku formed by lacquer coating an acid zinc particles were added to the present invention, in both discoloration and gloss, with excellent weather resistance and washability, compared to conventional lacquer paint I understand that
ZnOA-3 シリカ・アルミナコーティングをした酸化亜鉛微粒子を３重量％添加した漆
ZnOA-5 シリカ・アルミナコーティングをした酸化亜鉛微粒子を５重量％添加した漆
ZnOSD-3 ポリシロキサンコーティングをした酸化亜鉛微粒子を３重量％添加した漆液
ZnOP-3 コーティングなしの酸化亜鉛微粒子を３重量％添加した漆
TiO2-3 酸化チタン微粒子を３重量％添加した漆
SiO2-3 シリカ微粒子を３重量％添加した漆
ZnOA-3 Lacquer with 3% by weight of zinc oxide fine particles coated with silica / alumina
ZnOA-5 Lacquer with 5% by weight of zinc oxide fine particles coated with silica / alumina
ZnOSD-3 Lacquer solution containing 3% by weight of zinc oxide fine particles coated with polysiloxane
ZnOP-3 Lacquer with 3% by weight of zinc oxide fine particles without coating
Lacquer containing 3% by weight of TiO2-3 titanium oxide fine particles
Lacquer with 3% by weight of SiO2-3 silica fine particles
Claims (4)
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