JP3811015B2 - Paint, production method thereof, coating film, production method thereof, and pressure-sensitive adhesive sheet - Google Patents
Paint, production method thereof, coating film, production method thereof, and pressure-sensitive adhesive sheet Download PDFInfo
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- JP3811015B2 JP3811015B2 JP2001054577A JP2001054577A JP3811015B2 JP 3811015 B2 JP3811015 B2 JP 3811015B2 JP 2001054577 A JP2001054577 A JP 2001054577A JP 2001054577 A JP2001054577 A JP 2001054577A JP 3811015 B2 JP3811015 B2 JP 3811015B2
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- Prior art keywords
- thermoplastic resin
- dehalogenated
- resin solution
- acid value
- pigment
- 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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- 238000000576 coating method Methods 0.000 title claims description 38
- 239000011248 coating agent Substances 0.000 title claims description 37
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims description 30
- 239000003973 paint Substances 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 229920005992 thermoplastic resin Polymers 0.000 claims description 65
- 239000002253 acid Substances 0.000 claims description 47
- 239000000049 pigment Substances 0.000 claims description 39
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- -1 acrylic polyol Chemical class 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 239000010410 layer Substances 0.000 claims description 10
- 238000004132 cross linking Methods 0.000 claims description 8
- 239000005056 polyisocyanate Substances 0.000 claims description 8
- 229920001228 polyisocyanate Polymers 0.000 claims description 8
- 229920005862 polyol Polymers 0.000 claims description 8
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 description 27
- 239000011347 resin Substances 0.000 description 27
- 239000000463 material Substances 0.000 description 20
- 239000000178 monomer Substances 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 9
- 238000005520 cutting process Methods 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 238000005695 dehalogenation reaction Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- SWZOQAGVRGQLDV-UHFFFAOYSA-N 4-[2-(4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)ethoxy]-4-oxobutanoic acid Chemical compound CC1(C)CC(O)CC(C)(C)N1CCOC(=O)CCC(O)=O SWZOQAGVRGQLDV-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 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
- 230000037303 wrinkles Effects 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は脱ハロゲン熱可塑性樹脂を使用した塗料及びその製造方法、並びにその塗料を使用して作成した塗膜（フィルム）、その塗膜（フィルム）の製造方法、及び、屋内外の広告ステッカー類や表示用ステッカー類等として好適に用いられる、前記塗膜を用いた粘着シートに関する。
尚、本発明における粘着シートには粘着フィルムも包含されるものであり、上記用途に用いられる粘着シートは一般に、マーキングフィルムと称される場合が多い。
【０００２】
【従来の技術】
この様なマーキングフィルムは一般に、塩化ビニル系樹脂フィルムを基材として、目的に応じて基材に顔料を練り込んで着色したり、基材に印刷、塗装を施した後、片面に用途に応じて適当な感圧接着剤を塗布して粘着剤層を形成し、さらに粘着剤層を保護する目的で剥離紙等の剥離材を貼り合わせて構成されており、使用時には、この剥離材を剥離して露出した粘着剤層を被着体の所定の箇所に貼り付ける。
このマーキングフィルムは、屋外で使用されることが多く、看板、広告塔、シャッター、ショーウィンドウ等に用いられる広告ステッカー類；自動車、二輪車等の車両やモーターボート等の船舶に用いられる装飾用ストライプステッカー類；交通標識、道路標識、案内板等に用いられる表示用ステッカー類等の用途に用いられる。
このため、マーキングフィルムは耐候性を有し、且つ三次曲面に貼り付けるための適度な柔軟性（形状追従性）を有することが要求される。
【０００３】
また、軟質塩化ビニル系樹脂フィルムを基材とする従来のマーキングフィルムは、焼却処理して廃棄する際に塩化水素ガスやダイオキシンが発生するため、簡単な焼却設備では処理できず、さらには焼却設備の耐久性を低下させるという問題点があった。
そのため最近では、簡単な焼却設備で処理できる低環境負荷型のマーキングフィルムへの要望が高まってきており、種々の試みがなされている。
【０００４】
例えば特開平３−４５６７２号公報には、脱ハロゲン熱可塑性樹脂としてのウレタンフィルムを基材としたマーキングフィルムが開示されている。
即ちこの公報には、架橋した脂肪族イソシアネート系ウレタンフィルムを基材とし、この基材に粘着剤を転写して得たマーキングフィルムについて、柔軟性を有する被着体のフレキシブルな動きに追従し得るので、所謂しわやトンネルが生じない旨が開示されている。
【０００５】
一方、マーキングフィルムは、着色した装飾粘着シートとして屋外で使用されることが多く、上記公報にもカラフルな色調が要求されるとの記載があり、基材であるウレタンフィルムの製造方法としては、表面平滑性の点でキャステイング法等が好ましいと記載されている。
【０００６】
キャステイング法で着色したフィルムを得るには、先ず、樹脂溶液に顔料を分散してなる塗料を調製し、この塗料を離型紙等にキャステイングし、乾燥硬化する方法が知られている。
【０００７】
【発明が解決しようとする課題】
しかし、上記公報には、ウレタン系樹脂溶液に顔料を分散してなる塗料を調製することについては、具体的記載が見当たらず、キャステイング法で着色したフィルムを製造するための具体的知見を得ることは出来ない。
本発明者の検討によれば、顔料を、例えばウレタン系樹脂やアクリル系樹脂のような脱ハロゲン熱可塑性樹脂溶液に分散させるには、樹脂溶液の酸価が高い方が好ましいが、余り酸価が高いと、硬化剤との反応により増粘し可使時間が短いために良好な成形性を確保できないという問題点がある。
【０００８】
そこで本発明は、上記従来のマーキングフィルムの問題点、及び本発明者が把握した低環境負荷型のマーキングフィルムに関する問題点に鑑み、優れた顔料分散性と長い可使時間の両方を満たす脱ハロゲン熱可塑性樹脂系の塗料とその製造方法、並びにその塗料を使用して作成した優れた柔軟性（形状追従性）、耐候性を有する塗膜（フィルム）、その塗膜（フィルム）の製造方法、及び、前記塗膜を用いた施工性、カッテイング性、耐候性が良好であり簡単な焼却設備で焼却可能な粘着シートを提供することを目的とする。
【０００９】
【課題を解決するための手段】
上記目的を達成するために、請求項１記載の発明は、顔料を分散させた酸価の高い脱ハロゲン熱可塑性樹脂溶液と、酸価の低い脱ハロゲン熱可塑性樹脂溶液とを混合することにより得られる、顔料によって着色された脱ハロゲン熱可塑性樹脂溶液Ａと、硬化剤Ｂとからなる塗料を提供する。
【００１０】
請求項２記載の発明は、酸価の高い脱ハロゲン熱可塑性樹脂溶液に顔料を添加し分散させ、酸価の低い脱ハロゲン熱可塑性樹脂溶液と混合して、顔料によって着色された脱ハロゲン熱可塑性樹脂溶液Ａを得るとともに、硬化剤Ｂと組み合わせるか、又は硬化剤Ｂと混合する請求項１記載の塗料の製造方法を提供する。
【００１１】
請求項３記載の発明は、顔料を分散させた酸価の高い脱ハロゲン熱可塑性樹脂溶液と、酸価の低い脱ハロゲン熱可塑性樹脂溶液とを混合することにより得られる、顔料によって着色された脱ハロゲン熱可塑性樹脂溶液Ａと、硬化剤Ｂとが混合されて硬化されてなる着色された脱ハロゲン熱可塑性樹脂塗膜を提供する。
【００１２】
請求項４記載の発明は、顔料を分散させた酸価の高い脱ハロゲン熱可塑性樹脂溶液と、酸価の低い脱ハロゲン熱可塑性樹脂溶液とを混合することにより得られる、顔料によって着色された脱ハロゲン熱可塑性樹脂溶液Ａと、硬化剤Ｂとを混合した状態の塗料を離型フィルム上に塗布し、乾燥硬化させる着色された脱ハロゲン熱可塑性樹脂塗膜の製造方法を提供する。
【００１３】
請求項５記載の発明は、請求項３記載の着色された脱ハロゲン熱可塑性樹脂塗膜の一面に粘着剤層が設けられている粘着シートを提供する。
【００１４】
請求項６記載の発明は、脱ハロゲン熱可塑性樹脂がアクリル系ポリオールであり、硬化剤が、架橋点間距離２２０〜５７０のポリイソシアネート系架橋剤である請求項５記載の粘着シートを提供する。
【００１５】
以下本発明について更に詳述する。
本発明における脱ハロゲン熱可塑性樹脂、即ち、実質的にハロゲン元素を含有しない熱可塑性樹脂としては、各種官能基を有する樹脂が挙げられ、好ましくは、例えば各種水酸基を有するアクリル系ポリオールが挙げられる。
アクリル系ポリオールとしては、アクリルモノマー、メタクリルモノマー等と共重合可能なモノマーとの共重合体であり重量平均分子量が１０００〜２０００００、ガラス転移温度Ｔｇが０〜１００℃の範囲に入るものである。
【００１６】
水酸基含有モノマーとしては２ーヒドロキシエチル（メタ）アクリレート、４ーヒドロオキシブチルアクリレート、ポリオキシエチレン（メタ）アクリレート、ポリオキシプロピレン（メタ）アクリレート、カプロラクトン変成（メタ）アクリレート等がある。
これら水酸基含有モノマーと共重合可能なモノマーとしては、炭素数１〜１２のアルキル基を有するアルコールの（メタ）アクリル酸エステル、具体的には、（メタ）アクリル酸ｎーブチル、（メタ）アクリル酸２ーエチルヘキシル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸ｎーオクチル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸ラウリル等を挙げることができる。これらは、単独、又は組み合わせて用いることができる。
【００１７】
また、これらのビニルモノマー以外にこれらと共重合可能なモノマーが共重合されてもかまわない。このようなモノマーとしては、（メタ）アクリル酸、マレイン酸、フマル酸、イタコン酸等のカルボキシル基含有モノマー又はその無水物やスチレン等が挙げられる。カルボキシル基含有モノマー又はその無水物の添加量により、熱可塑性樹脂溶液の酸価を調製することができる。
【００１８】
上記各種共重合成分の内で酸成分の比率を調整して、通常、酸価が３〜４０KOHmg/gになる様に調整した熱可塑性樹脂溶液を、酸価の高い顔料分散用樹脂として使用する。顔料分散用樹脂の酸価が３KOHmg/gより低いと顔料分散性が悪化し４０KOHmg/gを越えると樹脂全体の耐水性が悪化する傾向がある。
また、通常、酸価が０．１〜２KOHmg/gになる様に調整した熱可塑性樹脂を主な樹脂として使用する。主な樹脂として使用する樹脂の酸価が０．１ KOHmg/g より低いと硬化速度が遅くなり２を越えると可使時間が低下する場合がある。
【００１９】
本発明の塗料の製造方法では、酸価の高い脱ハロゲン熱可塑性樹脂溶液に顔料を添加し分散させ、酸価の低い脱ハロゲン熱可塑性樹脂溶液と混合して、顔料によって着色された脱ハロゲン熱可塑性樹脂溶液Ａを得る際に、酸価の高い樹脂と酸価の低い樹脂の配合割合は、各々固形分換算で酸価の高い樹脂が１〜２０重量％、酸価の低い樹脂が８０〜９９重量％％の比率で混合することが望ましい。
高酸価樹脂の混合比率が２０重量％を越えると可使時間が低下し、１重量％未満であると顔料の分散性が悪くなる。
【００２０】
本発明の塗料は、顔料を分散させた酸価の高い脱ハロゲン熱可塑性樹脂溶液と、酸価の低い脱ハロゲン熱可塑性樹脂溶液とを混合することにより得られる、顔料によって着色された脱ハロゲン熱可塑性樹脂溶液Ａと、硬化剤Ｂとからなるものであり、本発明の塗料の製造方法は、上述の如くして熱可塑性樹脂溶液Ａを得るとともに、硬化剤Ｂと組み合わせるか、又は硬化剤Ｂと混合するものである。即ち、本発明の塗料は、熱可塑性樹脂溶液Ａと硬化剤Ｂとを混合する前の状態のもの、及び混合した後の状態のもの、何れの形態の塗料をも包含するものである。
【００２１】
硬化剤Ｂとしては、イソシアネート硬化剤が好適に使用できる。マーキングフィルムの用途であるので、耐候性の良好な脂肪族イソシアネートであるヘキサメチレンジイソシアネートのトリメチロールプロパン付加物、ビウレット体、イソシアヌレート体又はその混合物若しくはその縮合物が特に良好に使用できる。
また、より好ましくは、架橋点間距離（重量平均分子量／イソシアネート基数）が２２０〜５７０のポリイソシアネートが、適度の柔軟性を有しカッティング性のよい基材が得られる点で好ましい。
また、硬化剤Ｂとして、複数の異なる架橋点間距離を有するポリイソシアネートを混合して使用し、平均の架橋点間距離が２２０〜５７０となる様にしたものであっても良い。
【００２２】
上述の塗料には必要に応じて、紫外線吸収剤、特にベンゾトリアゾール系紫外線吸収剤（ＵＶＡ）や、安定剤、特にヒンダードアミン系光安定剤（ＨＡＬＳ）、等の安定剤の他、消泡剤、表面調整剤等を、適宜添加して使用してもよい。
【００２３】
本発明の着色された脱ハロゲン熱可塑性樹脂塗膜の製造方法では、上記着色された脱ハロゲン熱可塑性樹脂溶液Ａと、硬化剤Ｂとを混合した状態の塗料を、例えば、コンマコーター、リバースコーター、ナイフコーター、スプレーガン、スクリーン印刷等によって、離型フィルム上にキャステイングし、乾燥硬化させることにより塗膜（フィルム）を得るのである。
【００２４】
本発明の着色された脱ハロゲン熱可塑性樹脂塗膜は、顔料を分散させた酸価の高い脱ハロゲン熱可塑性樹脂溶液と、酸価の低い脱ハロゲン熱可塑性樹脂溶液とを混合することにより得られる、顔料によって着色された脱ハロゲン熱可塑性樹脂溶液Ａと、硬化剤Ｂとが混合されて硬化されてなるものであり、塗膜（フィルム）の厚みは、通常２０〜２００ミクロンとされ、好ましくは４０〜１００ミクロンとされる。
【００２５】
本発明の粘着シートは、上記着色された脱ハロゲン熱可塑性樹脂塗膜の一面に粘着剤層が設けられ、一般に剥離材が積層されているもので、通常、基材としての熱可塑性樹脂塗膜と粘着剤層との合計厚みは５０〜２５０ミクロンとされる。合計厚みが５０ミクロンより薄いとシートの腰が弱いために作業性が低下し、２５０ミクロンより厚くなると３次曲面への追従性が劣ることとなる。
【００２６】
上記粘着剤層を構成する粘着剤としては、アクリル樹脂系、ゴム系粘着剤等が挙げられ、マーキングフィルムが屋外での使用が前提となっていることから、耐候性の高いアクリル系粘着剤が好ましく用いられる。
本発明の粘着剤は溶媒中で重合した溶剤型アクリル粘着剤であっても良いし、水中で重合したエマルジョン系粘着剤であっても良い。また、モノマー混合物に紫外線照射した塊状重合型粘着剤であっても良い。
粘着剤層の厚さは２０〜５０μｍが好ましい。
【００２７】
マーキングフィルムは一般に粘着剤をコンマコーター、リバースコーター等を用いた定量的な塗工法により剥離材に塗布し、加熱乾燥させた後、基材層と積層することにより製造される。
さらに本発明のマーキングフィルムの剥離材としては、特に限定されることはなく、例えばシリコン塗布型剥離紙などが使用できる。
脱ハロゲン熱可塑性樹脂がアクリル系ポリオールであり、硬化剤が、架橋点間距離２２０〜５７０のポリイソシアネート系架橋剤である場合は、基材としての熱可塑性樹脂塗膜の架橋の程度が適度の範囲のものとなり、結局、適度の柔軟性を有しカッティング性のよい粘着シートが得られる点で好ましい。
【００２８】
【実施例】
以下、本発明を実施例に基づいてより詳細に説明するが、本発明は以下の例によって限定されるものではない。尚、以下に単に「部」とあるのは「重量部」を意味する。
【００２９】
＜実施例１＞
上記着色化した高酸価樹脂１０部と低酸価樹脂９０部をディスパーで攪拌混合し、顔料によって着色された脱ハロゲン熱可塑性樹脂溶液Ａを得た。
このとき、同時に高酸価アクリルポリオール及び低酸価アクリルポリオールの合計樹脂分１００重量部に対し、ヒンダードアミン系光安定剤（ＨＡＬＳ）「チヌビン６２２」（チバ・スペシャリティ・ケミカルス株式会社製）０．２部、ベンゾトリアゾール系紫外線吸収剤（ＵＶＡ）「チヌビン３２７」（チバ・スペシャリティ・ケミカルス株式会社製）０．２部を添加した。
（塗料の調製）
上記熱可塑性樹脂溶液Ａ100部に対し、硬化剤Ｂとして脂肪族ポリイソシアネート「スミジュールHT」（架橋点間距離244,重量平均分子量1100、住友バイエルウレタン社製）を24部添加し、混合撹拌して、塗料を調製した。
【００３０】
〔粘着シートの作成〕
上記塗料をリバースコーターでＰＥＴフィルム上に塗布し、乾燥硬化させて４０ミクロンの塗膜（フイルム）を得た。
一方、２液硬化型アクリル系粘着剤を、コンマコーターによってドライ厚み３０μｍとなるようにシリコン塗布型剥離紙に塗工し製膜した。これを粘着シートの基材となる塗膜（フイルム）にラミネート積層し、粘着剤層を有する目的とするマーキングシ−トを得た。
【００３１】
＜実施例２＞
前記実施例１において、低酸価樹脂をブチルメタクリレート59部、ヒドロキシエチルメタクリレート10部、メチルメタクリレート30部、メタクリル酸１部を、酢酸エチル等の溶剤の存在下にセハラブルフラスコ中で重合を行い、重量平均分子量Ｍｗ8000のポリマー（酸価１．０、固形分５０％）を得た。
これら以外は実施例１と同様にして目的とするマーキングフィルムを得た。
【００３２】
＜実施例３＞
前記実施例１において、使用する硬化剤を脂肪族ポリイソシアネート「コロネートＨＬ」（架橋点間距離250,Ｍｗ850,日本ポリウレタン工業社製）を27部添加したこと以外は、実施例１と同様にして目的マーキングフィルムを得た。
＜実施例４＞
前記実施例１において、高酸価樹脂と低酸価樹脂の混合比率を10:90 から15:85に変更すること以外は、実施例１と同様にして目的とするマーキングフィルムを得た。
【００３３】
＜比較例１＞
実施例１において,混合する低酸価樹脂の代わりに全量を高酸価樹脂に置き換えること以外は、実施例１と同様にしてマーキングフィルムを得た。
＜比較例２＞
実施例１において,顔料分散用高酸価樹脂の代わりに,低酸価樹脂を使用する事以外は同様にしてマーキングフィルムを得た。
＜比較例３＞
比較例１において使用する硬化剤をヘキサメチレンジイソシアネート「デスモジュールＨ」（架橋点間距離84, Ｍｗ168 ,住友バイエルウレタン社製)18部に変更すること以外は、同様にして目的とするマーキングフィルムを得た。
【００３４】
以上の実施例、比較例で得られた、塗料、塗膜、粘着シートを以下の方法で評価し、その結果を表１に記載した。
【００３５】
【表１】
〔評価方法〕
＜可使時間＞
上記方法により作成した硬化剤混合後の塗料を常温で放置し、経時による粘度変化を測定しゲル化するまでの時間を測定し、その時間で評価した。
＜顔料分散性評価＞
上記方法により作成した塗料をコーティングして出来上がったフィルムのムラの状態を目視評価した。
３：顔料分散が良好でありムラの無いシートが作成された。
２：一部顔料分散不良が発生しスジ状のムラが発生した。
１：顔料の分散不良が発生し全面的なムラが発生した。
【００３７】
＜カッテイング性＞
上記の方法により作成したシートをＭＩＭＡＫＩ社カッテイングマシーン「ＣＧ４５」でカッテイングを実施し、状況を３段階で評価した。
３：良好にカッテイングできる。
２：一部にカッテイング面の毛羽立ちが発生した。
１：カッテイング面の顕著な毛羽立ちが発生した。
【００３８】
＜焼却可能判定＞
上記の方法により作成したシートを５ｃｍ四方サンプリングし、これを密閉容器にて燃焼させ、燃焼ガスをシリンジに採取し、ガスクロマトグラフにて塩化水素、塩素ガスの存在を定性分析した。
○・・・塩化水素、水素ガスが検出されず
×・・・塩化水素、水素ガスが検出された
【００３９】
＜施工性＞
上記の方法で作成した各シートを図１に示す二次曲面を有するコルゲート板の山部に接着させ、次に谷部へ専用の施工工具にて押し込みを実施した。これを２３℃で３日間放置後、シートの浮き状態を下記基準で評価
５：谷部での浮きは全く発生しなかった。
４：押し込み時にシートの裂けが一部に発生した。
３：谷部での若干の浮きが発生した。
２：押し込み時にシートの裂けが顕著に発生した。
１：谷部に著しい浮きが発生した。
＜乾燥硬化性＞
上記の方法で作成した塗料を硬化剤と混合した後、アプリケーターで乾燥厚み４０ミクロンで成形し、１１０℃で１０分乾燥させた後にフィルム表面のタック感を３段階で評価した。
３：表面タック感無し
２：表面タック感若干有り
１：表面タック感顕著に有り
【００４０】
【発明の効果】
本発明の塗料は、顔料分散性が良好であり、硬化剤との混合時の可使時間が長く、脱ハロゲン熱可塑性樹脂からなる塗膜を提供し得る。
本発明の塗料の製造方法によれば、可使時間が長く、顔料分散性が良好な塗料が得られる。
本発明の着色された脱ハロゲン熱可塑性樹脂塗膜は、顔料が良好に分散されており、また、ハロゲン元素を実質的に含まないので、環境に及ぼす負荷が低いものである。
本発明の着色された脱ハロゲン熱可塑性樹脂塗膜の製造方法によれば、顔料が良好に分散され、かつ、環境に及ぼす負荷が低い塗膜を提供することが出来る。
本発明の粘着シートは、基材として脱ハロゲン熱可塑性樹脂塗膜を用いているので、埋め立て廃棄の必要が無く、簡単な焼却設備に於いて焼却廃棄できるマーキングフィルムであるので、環境低負荷型の製品としてこの分野においては極めて有用なものである。
特に、脱ハロゲン熱可塑性樹脂がアクリル系ポリオールであり、硬化剤が、架橋点間距離２２０〜５７０のポリイソシアネート系架橋剤である粘着シートは、環境低負荷型であることに加え、耐候性に優れ、また基材が適度の柔軟性を有しているため、施工性・カッティング性に優れている。
【図面の簡単な説明】
【図１】 折曲面を有するコルゲート板の断面図。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a coating material using a dehalogenated thermoplastic resin, a method for producing the same, a coating film (film) prepared using the coating material, a method for producing the coating film (film), and indoor and outdoor advertising stickers. It is related with the adhesive sheet using the said coating film used suitably as a sticker for display, etc.
In addition, the adhesive sheet in this invention includes an adhesive film, and the adhesive sheet used for the said use is generally called a marking film in many cases.
[0002]
[Prior art]
Such a marking film is generally based on a vinyl chloride resin film, kneaded with a pigment according to the purpose and colored, or after printing or painting on the substrate, depending on the application on one side In order to protect the pressure-sensitive adhesive layer, a suitable pressure-sensitive adhesive is applied to form a pressure-sensitive adhesive layer. Then, the exposed pressure-sensitive adhesive layer is attached to a predetermined portion of the adherend.
This marking film is often used outdoors. Advertising stickers used for signs, advertising towers, shutters, show windows, etc .; decorative stripe stickers used for vehicles such as automobiles, motorcycles, and motor boats Used for applications such as display stickers used for traffic signs, road signs, information boards, etc.
For this reason, the marking film is required to have weather resistance and to have appropriate flexibility (shape followability) for attaching to a cubic curved surface.
[0003]
In addition, conventional marking film based on soft vinyl chloride resin film generates hydrogen chloride gas and dioxin when incinerated and discarded, so it cannot be processed with simple incineration equipment. There was a problem of lowering the durability.
Therefore, recently, there has been an increasing demand for a low environmental load type marking film that can be processed with a simple incineration facility, and various attempts have been made.
[0004]
For example, JP-A-3-45672 discloses a marking film based on a urethane film as a dehalogenated thermoplastic resin.
That is, in this publication, a marking film obtained by using a crosslinked aliphatic isocyanate-based urethane film as a base material and transferring an adhesive to the base material can follow the flexible movement of the adherend having flexibility. Therefore, it is disclosed that so-called wrinkles and tunnels do not occur.
[0005]
On the other hand, the marking film is often used outdoors as a colored decorative adhesive sheet, and there is a description that a colorful color tone is also required in the above publication, and as a method for producing a urethane film as a substrate, It is described that a casting method or the like is preferable in terms of surface smoothness.
[0006]
In order to obtain a colored film by the casting method, first, a method is known in which a paint is prepared by dispersing a pigment in a resin solution, and this paint is cast on a release paper and dried and cured.
[0007]
[Problems to be solved by the invention]
However, in the above publication, there is no specific description about preparing a paint in which a pigment is dispersed in a urethane resin solution, and specific knowledge for producing a film colored by a casting method is obtained. I can't.
According to the study of the present inventor, in order to disperse the pigment in a dehalogenated thermoplastic resin solution such as a urethane resin or an acrylic resin, it is preferable that the acid value of the resin solution is high, but the acid value is too high. If it is high, there is a problem in that good moldability cannot be ensured because the viscosity increases due to reaction with the curing agent and the pot life is short.
[0008]
Therefore, in view of the problems of the conventional marking film and the problems of the low environmental load type marking film ascertained by the present inventor, the present invention is a dehalogenation that satisfies both excellent pigment dispersibility and a long pot life. Thermoplastic resin-based paint and production method thereof, and excellent flexibility (shape followability) created using the paint, weather-resistant coating film (film), production method of the coating film (film), Another object of the present invention is to provide a pressure-sensitive adhesive sheet that has good workability, cutting properties, and weather resistance using the coating film and can be incinerated with simple incineration equipment.
[0009]
[Means for Solving the Problems]
In order to achieve the above object, the invention according to claim 1 is obtained by mixing a dehalogenated thermoplastic resin solution having a high acid value in which a pigment is dispersed and a dehalogenated thermoplastic resin solution having a low acid value. A paint comprising a dehalogenated thermoplastic resin solution A colored with a pigment and a curing agent B is provided.
[0010]
According to the second aspect of the present invention, a dehalogenated thermoplastic resin colored by a pigment is added to and dispersed in a dehalogenated thermoplastic resin solution having a high acid value, mixed with the dehalogenated thermoplastic resin solution having a low acid value. The method for producing a coating material according to claim 1, wherein the resin solution A is obtained and combined with the curing agent B or mixed with the curing agent B.
[0011]
According to the third aspect of the present invention, a deacidified thermoplastic resin solution having a high acid value in which a pigment is dispersed and a dehalogenated thermoplastic resin solution having a low acid value are mixed with each other to remove the pigment. Provided is a colored dehalogenated thermoplastic resin coating film obtained by mixing and curing a halogen thermoplastic resin solution A and a curing agent B.
[0012]
The invention according to claim 4 is a desalting process colored by a pigment obtained by mixing a dehalogenated thermoplastic resin solution having a high acid value in which a pigment is dispersed and a dehalogenating thermoplastic resin solution having a low acid value. Provided is a method for producing a colored dehalogenated thermoplastic resin coating film in which a coating material in a state in which a halogen thermoplastic resin solution A and a curing agent B are mixed is applied onto a release film and dried and cured.
[0013]
The invention according to claim 5 provides a pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive layer is provided on one side of the colored dehalogenated thermoplastic resin coating film according to claim 3.
[0014]
The invention according to claim 6 provides the pressure-sensitive adhesive sheet according to claim 5, wherein the dehalogenated thermoplastic resin is an acrylic polyol, and the curing agent is a polyisocyanate-based crosslinking agent having a distance between crosslinking points of 220 to 570.
[0015]
The present invention is described in detail below.
Examples of the dehalogenated thermoplastic resin in the present invention, that is, a thermoplastic resin substantially not containing a halogen element, include resins having various functional groups, and preferably, for example, acrylic polyols having various hydroxyl groups.
The acrylic polyol is a copolymer of a monomer copolymerizable with an acrylic monomer, a methacrylic monomer or the like, and has a weight average molecular weight of 1,000 to 200,000 and a glass transition temperature Tg of 0 to 100 ° C.
[0016]
Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl acrylate, polyoxyethylene (meth) acrylate, polyoxypropylene (meth) acrylate, and caprolactone modified (meth) acrylate.
Monomers that can be copolymerized with these hydroxyl group-containing monomers include (meth) acrylic acid esters of alcohols having 1 to 12 carbon atoms, specifically, n-butyl (meth) acrylate, (meth) acrylic acid. Examples thereof include 2-ethylhexyl, isooctyl (meth) acrylate, n-octyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, and the like. These can be used alone or in combination.
[0017]
In addition to these vinyl monomers, monomers copolymerizable with these may be copolymerized. Examples of such a monomer include carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, fumaric acid, and itaconic acid, anhydrides thereof, and styrene. The acid value of the thermoplastic resin solution can be adjusted by the addition amount of the carboxyl group-containing monomer or its anhydride.
[0018]
The ratio of the acid component among the above various copolymerization components is adjusted, and usually a thermoplastic resin solution adjusted to have an acid value of 3 to 40 KOHmg / g is used as a pigment dispersion resin having a high acid value. . When the acid value of the pigment dispersing resin is lower than 3 KOHmg / g, the pigment dispersibility is deteriorated, and when it exceeds 40 KOHmg / g, the water resistance of the whole resin tends to be deteriorated.
Usually, a thermoplastic resin adjusted to have an acid value of 0.1 to 2 KOHmg / g is used as the main resin. If the acid value of the resin used as the main resin is lower than 0.1 KOHmg / g, the curing rate will be slow, and if it exceeds 2, the pot life may be reduced.
[0019]
In the method for producing a paint according to the present invention, a pigment is added to and dispersed in a dehalogenated thermoplastic resin solution having a high acid value, mixed with a dehalogenated thermoplastic resin solution having a low acid value, and dehalogenated heat colored by the pigment. When the plastic resin solution A is obtained, the blending ratio of the resin having a high acid value and the resin having a low acid value is 1 to 20% by weight for a resin having a high acid value in terms of solid content, and 80 to 80% for a resin having a low acid value It is desirable to mix in a ratio of 99% by weight.
When the mixing ratio of the high acid value resin exceeds 20% by weight, the pot life decreases, and when it is less than 1% by weight, the dispersibility of the pigment is deteriorated.
[0020]
The coating material of the present invention has a dehalogenation heat colored by a pigment obtained by mixing a dehalogenation thermoplastic resin solution having a high acid value in which the pigment is dispersed and a dehalogenation thermoplastic resin solution having a low acid value. The method for producing a coating material according to the present invention comprises the thermoplastic resin solution A and the curing agent B, and the thermoplastic resin solution A is obtained as described above, and is combined with the curing agent B or the curing agent B. It is something to be mixed with. That is, the coating material of the present invention includes any type of coating material in a state before mixing the thermoplastic resin solution A and the curing agent B and in a state after mixing.
[0021]
As the curing agent B, an isocyanate curing agent can be preferably used. Since it is an application of a marking film, a trimethylolpropane adduct, biuret, isocyanurate, or a mixture thereof or a condensate thereof of hexamethylene diisocyanate, which is an aliphatic isocyanate having good weather resistance, can be used particularly well.
More preferably, a polyisocyanate having a distance between crosslinking points (weight average molecular weight / isocyanate group number) of 220 to 570 is preferable in that a base material having appropriate flexibility and good cutting properties can be obtained.
Further, as the curing agent B, polyisocyanates having a plurality of different distances between crosslinking points may be mixed and used so that the average distance between crosslinking points is 220 to 570.
[0022]
In addition to stabilizers such as ultraviolet absorbers, particularly benzotriazole ultraviolet absorbers (UVA) and stabilizers, particularly hindered amine light stabilizers (HALS), anti-foaming agents, A surface conditioner or the like may be appropriately added and used.
[0023]
In the method for producing a colored dehalogenated thermoplastic resin coating film of the present invention, a paint in a state where the colored dehalogenated thermoplastic resin solution A and the curing agent B are mixed is used, for example, a comma coater or a reverse coater. The coating film (film) is obtained by casting on a release film by knife coater, spray gun, screen printing or the like and drying and curing.
[0024]
The colored dehalogenated thermoplastic resin coating film of the present invention can be obtained by mixing a high acid value dehalogenated thermoplastic resin solution in which a pigment is dispersed and a low acid value dehalogenated thermoplastic resin solution. The dehalogenated thermoplastic resin solution A colored with the pigment and the curing agent B are mixed and cured, and the thickness of the coating film (film) is usually 20 to 200 microns, preferably 40 to 100 microns.
[0025]
The pressure-sensitive adhesive sheet of the present invention is one in which a pressure-sensitive adhesive layer is provided on one side of the above-mentioned colored dehalogenated thermoplastic resin coating, and generally a release material is laminated. Usually, a thermoplastic resin coating as a base material And the pressure-sensitive adhesive layer have a total thickness of 50 to 250 microns. If the total thickness is less than 50 microns, the workability is lowered because the sheet is weak, and if the thickness is more than 250 microns, the followability to a cubic surface is inferior.
[0026]
Examples of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer include acrylic resin-based and rubber-based pressure-sensitive adhesives. Since the marking film is assumed to be used outdoors, an acrylic pressure-sensitive adhesive with high weather resistance is used. Preferably used.
The pressure-sensitive adhesive of the present invention may be a solvent-type acrylic pressure-sensitive adhesive polymerized in a solvent or an emulsion pressure-sensitive adhesive polymerized in water. Moreover, the block polymerization type adhesive which irradiated the ultraviolet-ray to the monomer mixture may be sufficient.
As for the thickness of an adhesive layer, 20-50 micrometers is preferable.
[0027]
The marking film is generally produced by applying a pressure-sensitive adhesive to a release material by a quantitative coating method using a comma coater, a reverse coater or the like, heating and drying, and then laminating with a base material layer.
Furthermore, the release material for the marking film of the present invention is not particularly limited, and for example, a silicon-coated release paper can be used.
When the dehalogenated thermoplastic resin is an acrylic polyol and the curing agent is a polyisocyanate crosslinker having a distance between crosslink points of 220 to 570, the degree of crosslinking of the thermoplastic resin coating film as a base material is moderate. This is preferable in that a pressure-sensitive adhesive sheet having moderate flexibility and good cutting properties can be obtained.
[0028]
【Example】
EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited by the following examples. Hereinafter, “part” simply means “part by weight”.
[0029]
<Example 1>
10 parts of the colored high acid value resin and 90 parts of the low acid value resin were stirred and mixed with a disper to obtain a dehalogenated thermoplastic resin solution A colored with a pigment.
At this time, the hindered amine light stabilizer (HALS) “Tinuvin 622” (manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.2 with respect to 100 parts by weight of the total resin content of the high acid value acrylic polyol and the low acid value acrylic polyol. Part, 0.2 part of a benzotriazole ultraviolet absorber (UVA) “Tinuvin 327” (manufactured by Ciba Specialty Chemicals Co., Ltd.) was added.
(Preparation of paint)
24 parts of aliphatic polyisocyanate “Sumijour HT” (crosslink point distance 244, weight average molecular weight 1100, manufactured by Sumitomo Bayer Urethane Co., Ltd.) is added as curing agent B to 100 parts of the above thermoplastic resin solution A, and mixed and stirred. A paint was prepared.
[0030]
[Creation of adhesive sheet]
The paint was applied onto a PET film with a reverse coater and dried and cured to obtain a 40 micron coating film.
On the other hand, a two-component curable acrylic pressure-sensitive adhesive was coated on a silicon-coated release paper so as to have a dry thickness of 30 μm using a comma coater to form a film. This was laminated and laminated on a coating film (film) serving as a base material of the pressure-sensitive adhesive sheet to obtain a target marking sheet having a pressure-sensitive adhesive layer.
[0031]
<Example 2>
In Example 1, 59 parts of butyl methacrylate, 10 parts of hydroxyethyl methacrylate, 30 parts of methyl methacrylate and 1 part of methacrylic acid were polymerized in a securable flask in the presence of a solvent such as ethyl acetate. , A polymer (acid value 1.0, solid content 50%) having a weight average molecular weight Mw of 8000 was obtained.
Except for these, the target marking film was obtained in the same manner as in Example 1.
[0032]
<Example 3>
In Example 1, the same curing agent as used in Example 1 except that 27 parts of aliphatic polyisocyanate “Coronate HL” (distance between crosslinks 250, Mw850, manufactured by Nippon Polyurethane Industry Co., Ltd.) was added. A target marking film was obtained.
<Example 4>
A target marking film was obtained in the same manner as in Example 1, except that the mixing ratio of the high acid value resin and the low acid value resin was changed from 10:90 to 15:85.
[0033]
<Comparative Example 1>
In Example 1, a marking film was obtained in the same manner as in Example 1 except that the entire amount was replaced with a high acid value resin instead of the low acid value resin to be mixed.
<Comparative example 2>
In Example 1, a marking film was obtained in the same manner except that a low acid value resin was used instead of the pigment-dispersing high acid value resin.
<Comparative Example 3>
The target marking film was similarly prepared except that the curing agent used in Comparative Example 1 was changed to 18 parts of hexamethylene diisocyanate “Desmodur H” (distance between cross-linking points 84, Mw168, manufactured by Sumitomo Bayer Urethane Co., Ltd.). Obtained.
[0034]
The paints, coating films, and pressure-sensitive adhesive sheets obtained in the above Examples and Comparative Examples were evaluated by the following methods, and the results are shown in Table 1.
[0035]
[Table 1]
〔Evaluation methods〕
<Pot life>
The paint after mixing the curing agent prepared by the above method was allowed to stand at room temperature, the change in viscosity over time was measured, the time until gelation was measured, and the time was evaluated.
<Evaluation of pigment dispersibility>
The state of unevenness of the film produced by coating the paint prepared by the above method was visually evaluated.
3: A sheet with good pigment dispersion and no unevenness was prepared.
2: Partial pigment dispersion occurred and streaky unevenness occurred.
1: Dispersion failure of the pigment occurred, resulting in overall unevenness.
[0037]
<Cutting properties>
The sheet prepared by the above method was cut with a cutting machine “CG45” manufactured by MIMAKI, and the situation was evaluated in three stages.
3: It can cut well.
2: Fluffing of the cutting surface occurred in part.
1: Remarkable fluffing of the cutting surface occurred.
[0038]
<Incineration judgment>
The sheet prepared by the above method was sampled 5 cm square, burned in a sealed container, the combustion gas was collected in a syringe, and the presence of hydrogen chloride and chlorine gas was qualitatively analyzed with a gas chromatograph.
○ ・ ・ ・ hydrogen chloride and hydrogen gas not detected × ・ ・ ・ hydrogen chloride and hydrogen gas detected [0039]
<Workability>
Each sheet prepared by the above method was bonded to a peak portion of a corrugated plate having a secondary curved surface shown in FIG. 1, and then pressed into a valley portion with a dedicated construction tool. After leaving this at 23 ° C. for 3 days, the floating state of the sheet was evaluated according to the following criteria. 5: No floating occurred at the valleys.
4: Sheet tearing occurred in part during pressing.
3: A slight float occurred in the valley.
2: Remarkable tearing occurred during pressing.
1: Remarkable floating occurred in the valley.
<Dry curability>
The paint prepared by the above method was mixed with a curing agent, molded with an applicator at a dry thickness of 40 microns, and dried at 110 ° C. for 10 minutes, and then the tackiness on the film surface was evaluated in three stages.
3: No surface tack feeling 2: Some surface tack feeling is present 1: There is noticeable surface tack feeling [0040]
【The invention's effect】
The paint of the present invention has a good pigment dispersibility, has a long pot life when mixed with a curing agent, and can provide a coating film made of a dehalogenated thermoplastic resin.
According to the method for producing a paint of the present invention, a paint having a long pot life and good pigment dispersibility can be obtained.
The colored dehalogenated thermoplastic resin coating film of the present invention has a low environmental load because the pigment is well dispersed and the halogen element is not substantially contained.
According to the method for producing a colored dehalogenated thermoplastic resin coating film of the present invention, it is possible to provide a coating film in which the pigment is well dispersed and the load on the environment is low.
Since the pressure-sensitive adhesive sheet of the present invention uses a dehalogenated thermoplastic resin coating as a base material, it is a marking film that does not require landfill disposal and can be incinerated and discarded in a simple incineration facility. This product is extremely useful in this field.
In particular, the pressure-sensitive adhesive sheet in which the dehalogenated thermoplastic resin is an acrylic polyol and the curing agent is a polyisocyanate-based crosslinking agent having a distance between cross-linking points of 220 to 570 is not only an environmentally low load type, but also has weather resistance Excellent, and since the base material has moderate flexibility, it has excellent workability and cutting properties.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view of a corrugated plate having a folded surface.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001054577A JP3811015B2 (en) | 2001-02-28 | 2001-02-28 | Paint, production method thereof, coating film, production method thereof, and pressure-sensitive adhesive sheet |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001054577A JP3811015B2 (en) | 2001-02-28 | 2001-02-28 | Paint, production method thereof, coating film, production method thereof, and pressure-sensitive adhesive sheet |
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| JP2002256219A JP2002256219A (en) | 2002-09-11 |
| JP3811015B2 true JP3811015B2 (en) | 2006-08-16 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008109208A1 (en) | 2007-03-02 | 2008-09-12 | 3M Innovative Properties Company | (meth)acrylic pigmented film, marking film, receptor sheet and method for preparing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2681260B2 (en) * | 2011-03-02 | 2023-05-31 | Dow Global Technologies LLC | Method for producing an aqueous dispersion |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008109208A1 (en) | 2007-03-02 | 2008-09-12 | 3M Innovative Properties Company | (meth)acrylic pigmented film, marking film, receptor sheet and method for preparing the same |
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| JP2002256219A (en) | 2002-09-11 |
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