JP5732273B2 - 耐プレッシャーマーク性及び耐擦り疵性に優れたクリヤ塗装ステンレス鋼板 - Google Patents
耐プレッシャーマーク性及び耐擦り疵性に優れたクリヤ塗装ステンレス鋼板 Download PDFInfo
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- JP5732273B2 JP5732273B2 JP2011029016A JP2011029016A JP5732273B2 JP 5732273 B2 JP5732273 B2 JP 5732273B2 JP 2011029016 A JP2011029016 A JP 2011029016A JP 2011029016 A JP2011029016 A JP 2011029016A JP 5732273 B2 JP5732273 B2 JP 5732273B2
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- steel sheet
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- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- AFCAKJKUYFLYFK-UHFFFAOYSA-N tetrabutyltin Chemical compound CCCC[Sn](CCCC)(CCCC)CCCC AFCAKJKUYFLYFK-UHFFFAOYSA-N 0.000 description 1
- 239000012974 tin catalyst 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
- 150000003852 triazoles Chemical class 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 150000003672 ureas Chemical class 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
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
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- C—CHEMISTRY; METALLURGY
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- 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
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- 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
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
- Y10T428/24372—Particulate matter
- Y10T428/24405—Polymer or resin [e.g., natural or synthetic rubber, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/254—Polymeric or resinous material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Description
前記クリヤ塗装膜は、
水酸基、カルボキシル基またはアルコキシシラン基のうち1種以上の架橋性官能基を含み、ガラス転移点が30〜90℃であり、数平均分子量が3000〜50000であるアクリル樹脂(A1)、前記アクリル樹脂(A1)を架橋硬化させるブロックイソシアネート樹脂及びアミノ樹脂よりなる架橋硬化樹脂(A2)、を含む熱硬化性樹脂組成物(A)と、
前記熱硬化性樹脂組成物の固形分100質量部あたり0.5〜4.0質量部の樹脂ビーズ(B)と、を含有し、前記樹脂ビーズ(B)の平均粒径が、2.4〜5.0μmであり、かつ前記クリヤ塗装膜の膜厚の0.8〜1.0倍であることを特徴とする耐プレッシャーマーク性及び耐擦り疵性に優れたクリヤ塗装ステンレス鋼板。
(2) 前記クリヤ塗装膜の膜厚が、3〜5μmであることを特徴とする(1)に記載の耐プレッシャーマーク性及び耐擦り疵性に優れたクリヤ塗装ステンレス鋼板。
(3) 前記樹脂ビーズが、架橋型アクリル樹脂ビーズ、架橋型ウレタン樹脂ビーズ、フッ素樹脂ビーズのうちの1種または2種以上であることを特徴とする(1)または(2)に記載の耐プレッシャーマーク性及び耐擦り疵性に優れたクリヤ塗装ステンレス鋼板。
更に、本発明のクリヤ塗装ステンレス鋼板によれば、樹脂ビーズの平均粒径をクリヤ塗装膜の膜厚との関係で規定することで、クリヤ塗装ステンレス鋼板の耐プレッシャーマーク性及び耐擦り疵性をより高めることができる。
熱硬化性樹脂組成物(A)は、水酸基、カルボキシル基またはアルコキシシラン基のうち1種以上の架橋性官能基を含み、ガラス転移点が30〜90℃であり、数平均分子量が3000〜50000であるアクリル樹脂(A1)と、前記アクリル樹脂を架橋硬化させるブロックイソシアネート樹脂及びアミノ樹脂よりなる架橋硬化樹脂(A2)と、を少なくとも含有する。
本発明における水酸基、カルボキシル基、アルコキシシラン基などから選ばれる1種、2種の架橋性官能基を有するアクリル樹脂(A1)は、塗料用樹脂として既知の方法により得られるものである。
次に、熱硬化性樹脂組成物(A)のもう一つの構成成分である架橋硬化樹脂(A2)は、ブロックイソシアネート樹脂とアミノ樹脂の混合物である。
また、n-ブチル化メラミン樹脂としては、マイコート506、508(以上、三井サイテック(株)製)、ユーバン20SB、20SE、21R、22R、122、125、128、220、225、228、28-60、20HS、2020、2021、2028、120(以上、三井化学(株)製)、PLASTOPAL EBS 100A、100B、400B、600B、CB(以上、BASF(株)製)スーパーベッカミンJ-820、L-109、L-117、L-127、L-164(以上、DIC(株)製)、メラン21A、22、220、1303、2000、2030、8000(以上、日立化成工業(株)製)、テスアジン3020、3021、3036(以上、日立化成ポリマー(株)製)を例示できる。
更に、イソブチル化メラミン樹脂としては、ユーバン60R、62、62E、360、361、165、166-60、169、2061(以上、三井化学(株)製)、スーパーベッカミンG-821、L-145、L-110、L-125(以上、DIC(株)製)、PLASTOPAL EBS 4001、FIB、H731B、LR8824(以上、BASF(株)製)メラン27、28、28D、245、265、269、289(以上、日立化成工業(株)製)を例示できる。
更にまた、混合アルキル化メラミン樹脂としては、サイメル267、285、232、235、236、238、211、254、204、212、202、207(以上、三井サイテック(株)製)などを例示できる.
これらは、単独もしくは併用で使用しても良い。
続いて、クリヤ塗装ステンレス鋼板の品質を確保するために重要な耐プレッシャーマーク性と耐疵付き性を発現させる樹脂ビーズ(B)について述べる。
含有する樹脂ビーズ量が0.5質量部未満では、耐疵付き性の効果が得られない。また、4.0質量部超では、クリヤ塗装膜の透明性が劣化すると共に、塗装作業性も低下する。この樹脂ビーズ量は、特には1.0〜3.0質量部が好ましく、さらには1.0〜2.0質量部が好ましい。
樹脂ビーズ(B)の平均粒径は、クリヤ塗装膜の塗装必要膜厚の0.3〜2.0倍が特に好ましく、さらには0.5〜1.3倍が好ましい。さらに望ましいのは0.8〜1.0倍である。樹脂ビーズ(B)の平均粒径は一般にレーザー回折法による粒度分布から求められる。
また架橋型ウレタン樹脂ビーズには、アートパールC-100、C-200、C-300、C-400、C-800、CZ-400、P-400T、P-800T、HT-400BK、U-600T、CF-600T、MT-400BR、MT-400YO(以上、根上工業(株)製)等が例示される。
更に、フッ素樹脂ビーズにはDYNEON PTFE マイクロパウダー TF-9201、TF-9205、TF-9207(以上、住友3M(株)製)、Fluon PTFE ルブリカント L-150J、L-169J、L-170J、L-172J、L-173J(以上、旭硝子(株)製)等が例示される。
これらはそれぞれ必要に応じて添加すればよく、単独もしくは、混合して使用しても良い。
また、エポキシ系シランカップリング剤としては、2-(3,4エポキシシクロヘキシル)エチルトリメトキシシラン、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン等のシランカップリング剤が挙げられる。
これらは、単独もしくは混合して使用しても良い。
温度計、還流冷却器、攪拌器、滴下ロート、窒素ガス導入管を備えた4つ口フラスコに表1の通りトルエン、酢酸ブチルを規定量入れ、110℃まで昇温し窒素ガスを吹き込みながら攪拌し、メタアクリル酸メチル、スチレン、メタアクリル酸n−ブチル、メタアクリル酸2−ヒドロキシエチル、アクリル酸2−ヒドロキシエチル、アクリル酸メチル、アゾビスイソブチロニトリル(AIBN)から選ばれる原料の混合物を3時間かけて滴下し、滴下終了後さらにAIBNを追加して同温度でさらに3時間反応させることにより、不揮発分50重量%のアクリル系共重合体(アクリル樹脂)を得た。
なお、表1に、アクリル樹脂の数平均分子量及びガラス転移点を表1に示す。
また、表4に示すように、塗膜厚さと樹脂ビーズ平均粒径の影響を確認するために、塗膜厚さを3、10、18μmとなるように実施例8、参考例9〜11のクリヤ塗装ステンレス鋼板を得た。
更に、表4に示すように、樹脂ビーズの種類の影響を確認するために、実施例12〜14のクリヤ塗装ステンレス鋼板を得た。
また、樹脂ビーズDは、根上工業製の架橋型ウレタン樹脂ビーズであり、平均粒径は3μmである。更に、樹脂ビーズEは、旭硝子製のフッ素系樹脂ビーズであり、平均粒径は3μmで有る。
さらに、実施例14に用いた樹脂ビーズFは、BYK−Chemie製のPE樹脂ビーズであり、平均粒径は3.5μmである。
また、ポリエチレンワックスは、CERAFLOUR 961(BYK−Chemie(ビックケミー)社製)の平均粒径3.5μmのものを用いた。
評価方法は以下の通りである。結果を表2〜4に示す。
供試材を2枚重ね、40℃の雰囲気で10kg/cm2の圧力でプレスし、24時間後にその耐プレッシャーマーク性を評価した。評価はランク1〜5の5段階で評価した。
ランク5:プレッシャーマークがない(合格)
ランク4:ほとんどプレッシャーマークが目立たない(合格)
ランク3:見る角度によっては、はっきりとプレッシャーマークが確認できる(不合格)
ランク2:プレッシャーマークによって色調・光沢の劣化が見られる。(不合格)
ランク1:著しく光沢が低下し、どの方向からもプレッシャーマークが確認できる(不合格)
摩擦子を、クレンザーを染み込ませたガーゼとして、供試材に対して荷重200gで50往復研磨した後、その耐擦り疵性を評価した。評価はランク1〜5の5段階で評価した。
ランク5:擦り疵がない(合格)
ランク4:ほとんど擦り疵が目立たない(合格)
ランク3:はっきりと擦り疵が確認できる(不合格)
ランク2:擦り疵で塗膜の光沢がなくなっている(不合格)
ランク1:塗膜が削れ、素地に達している(不合格)
JIS K5600 5−2(耐カッピング性)に従って評価した。評価は、クラックが生じた深さによって、ランク1〜5の5段階で評価した。
ランク5:7mm以上(合格)
ランク4:5〜7mm(合格)
ランク3:3〜5mm(不合格)
ランク2:1〜3mm(不合格)
ランク1:1mm以下(不合格)
JIS K5600 5−4 引っかき硬度(鉛筆法)に従って評価した。評価は、下記のランク1〜5の5段階で評価した。
ランク5:4H以上(合格)
ランク4:3H(合格)
ランク3:2H(不合格)
ランク2:H(不合格)
ランク1:H未満(不合格)
JIS K5600 4−7 鏡面光沢度に従って評価した。評価は、下記のランク1〜5の5段階で評価した。
ランク5:100以上(合格)
ランク4:80〜100(合格)
ランク3:60〜80(不合格)
ランク2:40〜60(不合格)
ランク1:40未満(不合格)
5%硫酸と5%水酸化ナトリウムを供試材に2mL滴下し、蓋をしたのち、16時間後の塗膜の状態を観察、評価した。評価は、下記のランク1〜5の5段階で評価した。
ランク5:跡が全く無い(合格)
ランク4:跡が僅かに認められる(合格)
ランク3:跡がやや目立つ(不合格)
ランク2:跡が濃く残る(不合格)
ランク1:剥離する(不合格)
つまり、実施例1〜8、参考例9、実施例12、13は、A−1〜A−4の熱硬化性樹脂組成物と、所定の量の樹脂ビーズとを含み、樹脂ビーズ平均粒径/塗装厚が0.20〜3.0倍であることから、耐プレッシャーマーク性と耐すり疵性のいずれか一方または両方の評価が5と大変良好であった。また、参考例10、11は樹脂ビーズの平均粒径に対して塗膜厚が薄い場合と厚い場合の例であるが、所定の量の樹脂ビーズを含有しているため耐プレッシャーマーク性及び耐すり疵性は合格レベルであった。さらに、実施例14は樹脂ビーズの種類がPEのものであるが、所定の量の樹脂ビーズを含有しているため耐プレッシャーマーク性及び耐すり疵性は合格レベルであった。
樹脂ビーズ含有量が少ないもの(比較例3)は、耐プレッシャーマーク性及び塗膜の加工性に劣る。
また、樹脂ビーズ含有量が多いもの(比較例4,5)では耐プレッシャマーク性や耐擦り疵性には優れるが、塗膜の加工性およびクリヤ塗装ステンレス鋼板の意匠性として重要な光沢度で劣っていた。
Claims (3)
- ステンレス鋼板と、前記ステンレス鋼板の片面または両面に塗布されたクリヤ塗装膜と、を具備してなり、
前記クリヤ塗装膜は、
水酸基、カルボキシル基またはアルコキシシラン基のうち1種以上の架橋性官能基を含み、ガラス転移点が30〜90℃であり、数平均分子量が3000〜50000であるアクリル樹脂(A1)、前記アクリル樹脂(A1)を架橋硬化させるブロックイソシアネート樹脂及びアミノ樹脂よりなる架橋硬化樹脂(A2)、を含む熱硬化性樹脂組成物(A)と、
前記熱硬化性樹脂組成物の固形分100質量部あたり0.5〜4.0質量部の樹脂ビーズ(B)と、を含有し、前記樹脂ビーズ(B)の平均粒径が、2.4〜5.0μmであり、かつ前記クリヤ塗装膜の膜厚の0.8〜1.0倍であることを特徴とする耐プレッシャーマーク性及び耐擦り疵性に優れたクリヤ塗装ステンレス鋼板。 - 前記クリヤ塗装膜の膜厚が、3〜5μmであることを特徴とする請求項1に記載の耐プレッシャーマーク性及び耐擦り疵性に優れたクリヤ塗装ステンレス鋼板。
- 前記樹脂ビーズが、架橋型アクリル樹脂ビーズ、架橋型ウレタン樹脂ビーズ、フッ素樹脂ビーズのうちの1種または2種以上であることを特徴とする請求項1または2に記載の耐プレッシャーマーク性及び耐擦り疵性に優れたクリヤ塗装ステンレス鋼板。
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