JP2007001088A - Stainproof printing base material, printed matter and printable object using this base material - Google Patents
Stainproof printing base material, printed matter and printable object using this base material Download PDFInfo
- Publication number
- JP2007001088A JP2007001088A JP2005182473A JP2005182473A JP2007001088A JP 2007001088 A JP2007001088 A JP 2007001088A JP 2005182473 A JP2005182473 A JP 2005182473A JP 2005182473 A JP2005182473 A JP 2005182473A JP 2007001088 A JP2007001088 A JP 2007001088A
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- JP
- Japan
- Prior art keywords
- group
- layer
- printing
- antifouling
- organic
- 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.)
- Pending
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- 150000001875 compounds Chemical class 0.000 claims abstract description 21
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- 238000000576 coating method Methods 0.000 claims description 23
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
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- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002704 decyl 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])* 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
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- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000007648 laser printing Methods 0.000 description 1
- 238000007644 letterpress printing Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical compound [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 description 1
- 125000006178 methyl benzyl group Chemical group 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical group [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/056—Forming hydrophilic coatings
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Catalysts (AREA)
- Printing Methods (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明は、光触媒活性作用による自己浄化性を有する防汚性印刷用基材およびそれを用いた印刷物および印刷体に関するものである。 The present invention relates to an antifouling printing substrate having a self-cleaning property by a photocatalytic activity, a printed matter and a printed body using the same.
光触媒活性材料は、超親水化による表面浄化作用があることから、看板等の表面をメイテンナンスフリーで美麗に保つ、いわゆる防汚効果が期待され、具体的に種々の方法が提案され、試みられている。 The photocatalytically active material has a surface purification action by superhydrophilicity, so it can be expected to keep the surface of signboards, etc. beautiful and free of taint, and various methods have been proposed and attempted. It has been.
例えば、外気に直接暴露又は長期間展示される印刷物において、少なくとも印刷層と、光活性を遮断する無機物からなる活性遮断層、及び光活性をもつ防汚層とから構成される保護層とを順次積層した積層体からなる耐候性印刷物が提案されている。（特許文献１参照）
この耐候性印刷物は、印刷面に粉塵や油分による汚れが付着しても、油分を分解し洗い流したり拭き取ることができ、表面の粉塵による汚染を防止し、紫外線遮断層との相乗作用で印刷物の光による変色や褪色を防止する効果を期待できる。
しかし、特許文献１の印刷物は、基材の表面に印刷を施し、その上層に活性遮断層、光活性層を塗り重ねて施すので、塗工時に使用する有機溶剤や加熱乾燥工程で印刷のにじみ、インクの蒸発気化などの発生により印刷の鮮明さを損なう可能性があった。また、経済性も考慮した連続生産を考えた場合には、定形の同一印刷物が多量にあることが望ましいが、印刷物は少量多品種の場合がほとんどで、その都度何回も塗工する工程が必要になり非常に手間がかかった。
For example, in a printed matter that is directly exposed to the outside air or displayed for a long period of time, at least a printed layer, an active blocking layer made of an inorganic material that blocks photoactivity, and a protective layer made up of a photoactive antifouling layer sequentially There has been proposed a weather-resistant printed material comprising a laminated body. (See Patent Document 1)
This weather-resistant printed matter can decompose and wash off or wipe off the oil even if dirt due to dust or oil adheres to the printed surface, prevent contamination by dust on the surface, and synergistic action with the UV blocking layer. Expected to prevent discoloration and fading due to light.
However, since the printed matter of Patent Document 1 is printed on the surface of the base material, and the active blocking layer and the photoactive layer are applied again on the upper layer, the printing blots in the organic solvent used at the time of coating or the heat drying process. In addition, there is a possibility that the clearness of printing may be impaired due to the occurrence of evaporation of ink. In addition, considering continuous production in consideration of economic efficiency, it is desirable that there are a large amount of the same fixed-size printed matter, but the printed matter is almost always in a small amount and many varieties. It was necessary and very time consuming.
また、基材の一方の面上に、光触媒機能を有する金属酸化物を含有する防汚層を少なくとも有し、かつ、昇華転写印刷法により、防汚層の表面から内部を透過して基材に画像を転写形成してなる印刷体が提案されている。（特許文献２参照）
しかし、特許文献２に記載の方法は、防汚層側から昇華転写印刷法により印刷を行うので、昇華インクが防汚層に残り、防汚性を初期的に低下させる、あるいは、昇華インクが経時的にブリードアウトして光触媒活性を低下させる危惧があった。
また、防汚層の形成において、ポーラスの層とするため、低温ゾル−ゲル法とし、印刷方法も昇華転写印刷法に限定されるなど、技術的制限があり、広く一般の印刷に適応できないという問題があった。
Further, the substrate has at least an antifouling layer containing a metal oxide having a photocatalytic function on one surface of the substrate, and passes through the inside of the antifouling layer by a sublimation transfer printing method. There has been proposed a printed material obtained by transferring and forming an image. (See Patent Document 2)
However, since the method described in
In addition, since it is a porous layer in the formation of the antifouling layer, there is a technical limitation such as a low-temperature sol-gel method and the printing method is limited to the sublimation transfer printing method, and it cannot be widely applied to general printing. There was a problem.
以上、多品種少量の印刷物において、印刷層に影響を及ぼすことなく防汚処理を施せる実用性のある印刷物は、未だ開発されていない。
さらに、多品種少量の印刷物に対応できる防汚効果のある印刷用基材であって、美粧な印刷が可能な、高い印刷適性を有する印刷用基材は、未だ得られていない。
As described above, there has not yet been developed a practical printed material capable of performing antifouling treatment without affecting the printed layer in a small variety of printed materials.
Furthermore, a printing base material having an antifouling effect that can be applied to a small amount of various kinds of printed matter and capable of performing beautiful printing and having high printability has not yet been obtained.
本発明は、上記従来技術の問題点を解決するためになされたものであって、その目的は、長期間において光触媒活性作用による自己浄化性を有する防汚性印刷用基材およびそれを用いた印刷物および印刷体を提供することにある。 The present invention has been made to solve the above-described problems of the prior art, and an object of the present invention is to use an antifouling printing substrate having self-cleaning properties due to photocatalytic activity over a long period of time and the use thereof. It is to provide a printed matter and a printed body.
本発明者らは、上記目的を達成すべく鋭意研究した結果、予め有機基材の一方の面に活性遮蔽層、光触媒活性層形成した印刷用基材を準備し、他方の面に印刷を施すことで上記課題を解決できることを見出した。 As a result of diligent research to achieve the above object, the present inventors prepared a printing substrate in which an active shielding layer and a photocatalytic active layer were previously formed on one surface of an organic substrate, and printed on the other surface. It was found that the above problems can be solved.
すなわち、本発明は、
（１）有機基材の一方の面に活性遮断層を介して光触媒活性層を有し、他方の面を印刷面とすることを特徴とする防汚性印刷用基材、
（２）前記（１）に記載の防汚性印刷用基材に印刷を施してなることを特徴とする防汚性印刷物、
（３）前記（２）記載の防汚性印刷物の表面に粘着層を施してなることを特徴とする防汚性印刷体
を提供するものである。
That is, the present invention
(1) An antifouling printing base material having a photocatalytic active layer on one surface of an organic base material via an active blocking layer, and the other surface being a printing surface,
(2) An antifouling printed matter obtained by printing on the antifouling printing substrate according to (1),
(3) Provided is an antifouling printed material characterized in that an adhesive layer is applied to the surface of the antifouling printed matter described in (2).
本発明の防汚性印刷用基材（以下「印刷用基材」という。）は、有機基材の一方の面に活性遮断層を介して光触媒活性層を有し、他方の面を印刷面とし、印刷後の印刷層を透明な有機基材よって隔離された構成としているので、印刷を施した後において、光触媒活性層が印刷層に悪影響を及ぼすことがなく、活性遮断層、光触媒活性層を構成する組成物を耐候性、耐クラック性と相俟って、長期間、印刷層を美麗かつ明瞭に保持できる。
本発明の印刷用基材によれば、透明性有機基材の一方の表面に活性遮断層を介して光触媒活性層を既に設けているので、印刷物の大きさや、量に応じて、印刷用基材を必要数準備し、この印刷用基材の他方の面に所要の印刷を施せばよいので、多種少量の印刷内容にも柔軟に対応でき、広告媒体等として、自己浄化作用による防汚性を有する多種多様の屋外展示用等の防汚性印刷物および印刷体を提供できる。加えて、防汚機能が初期的に付加されているので家庭用の印刷機（プリンター）にて、各ユーザーが容易に任意の写真や絵などを印刷し、屋外に汚れ付かずで掲示することが可能になる。
さらにこの印刷時に、白色顔料等を印刷面に付着させることで、印刷彩度を向上させることができる。
また、本発明の印刷体は、印刷層の表面に粘着層を設けてなるので、看板の基板や、建築物のガラス、壁面等への貼着が容易になる。
本発明の印刷物、印刷体は、印刷層自体が、活性遮断層や、光触媒層と直接接しないので、これらの層に使用される溶媒等を考慮することなく、種々のインクを選択使用できるので、発色性の良い、鮮やかな表示物、例えば、写真、絵やポスター等とすることができ、光触媒作用による自浄効果と相俟って、高い宣伝効果を発現できる。
さらに、ビルや建屋のガラスや壁などに施工し洗浄目的で水を掛けてやると、超親水効果により水が全面に濡れ広がり、打ち水効果でその施工対象物を冷却する効果も期待できる。
光触媒機能により、降雨または散水により自己浄化できるので、屋外シアターに類似した内部照明を利用した屋外美術展示用途、ガーデニング資材用途（印刷垣根、印刷花壇など）、あるいは季節に合わせて何度でも掲示、取り外しをする屋外掲示用資材用途（例えば印刷クリスマスツリー、印刷鯉のぼり、印刷おひな様、印刷ステンドグラス、印刷自作カレンダーなど）等に、表面が美麗な状態で長期間あるいは繰り返し使用することができる。
The antifouling printing substrate of the present invention (hereinafter referred to as “printing substrate”) has a photocatalytic active layer on one surface of an organic substrate through an active blocking layer, and the other surface is a printing surface. The printed layer after printing is isolated by a transparent organic substrate, so that after the printing, the photocatalytic active layer does not adversely affect the printed layer, and the active blocking layer, the photocatalytic active layer Combined with the weather resistance and crack resistance of the composition constituting the composition, the printed layer can be maintained beautifully and clearly for a long period of time.
According to the printing substrate of the present invention, since the photocatalytic active layer is already provided on one surface of the transparent organic substrate via the active blocking layer, depending on the size and amount of the printed matter, the printing substrate Prepare the required number of materials and apply the required printing to the other side of the substrate for printing, so it can flexibly handle a small amount of printed content, and as an advertising medium, etc. It is possible to provide a variety of antifouling prints and prints for outdoor exhibitions and the like. In addition, since an antifouling function is added initially, each user can easily print any photo or picture on a home printing machine (printer) and post it outdoors without getting dirty. Is possible.
Furthermore, printing saturation can be improved by attaching a white pigment or the like to the printing surface during printing.
Moreover, since the printing body of this invention provides the adhesion layer in the surface of a printing layer, the sticking to the board | substrate of a signboard, the glass of a building, a wall surface, etc. becomes easy.
In the printed matter and printed matter of the present invention, since the printing layer itself does not directly contact the active blocking layer or the photocatalyst layer, various inks can be selectively used without considering the solvent used in these layers. It can be a vivid display with good color development, for example, a photograph, a picture, a poster, etc., and a high advertising effect can be realized in combination with the self-cleaning effect by the photocatalytic action.
Furthermore, when it is applied to the glass or wall of a building or building and sprayed with water for the purpose of washing, the super-hydrophilic effect causes the water to spread over the entire surface, and the effect of cooling the construction object by the water hammer effect can be expected.
The photocatalytic function allows self-purification by rain or watering, so it can be used for outdoor art exhibitions that use internal lighting similar to outdoor theaters, gardening materials (print fences, print flower beds, etc.), or posted many times according to the season, It can be used for a long period of time or repeatedly with a beautiful surface, such as a material for outdoor signage to be removed (for example, a printing Christmas tree, a printing carp streamer, a printing doll, a printing stained glass, a printing self-made calendar, etc.).
本発明の印刷用基材に使用できる有機基材としては、印刷層の支持体をなし、印刷物、印刷体として支障のない程度の強度を有するとともに、屋外や太陽光暴露に耐え得る劣化の少ない材料であって、すくなくとも、印刷内容が光触媒活性層側から視認できる程度の透明性を有する有機材料から選ばれる。
本発明の有機基材の形体としては、フィルム、シート、板材物等であって、透明性を有し、印刷用インクとの化学吸着力、親和力、相溶性に優れるプラスチック等が好ましく用いられる。
また、自立性のある看板等とする場合は、板状等の厚みのある透明材料が好ましい。板状材の場合は、必ずしも中実で均一肉厚のものである必要がなく、上下のライナー間に平行のリブを有するプラスチックダンボール状のものや、上下のライナー間に独立した円柱状空間を有するシート状物であっても、ライナー表面が、印刷や活性遮断層を形成するのに十分な平坦性を有するものであれば使用することができる。これらを使用すれば、取付け工事等における軽量による利便性や、コストの削減を図ることができる。
さらに、本発明に使用できる有機基材には、透明性を有する合成繊維、天然繊維等の織布や不織布あるいは合成紙を含めることができる。
繊維状の有機基材は、意匠性等の必要に応じて、熱カレンダーローラー等でフィルム状にしてもよい。
The organic substrate that can be used for the printing substrate of the present invention is a support for the printing layer, has a strength that does not hinder printed matter and printed matter, and has little deterioration that can withstand exposure to the outdoors or sunlight. The material is at least selected from organic materials having such transparency that the printed content is visible from the photocatalytic active layer side.
As the form of the organic substrate of the present invention, a film, sheet, plate material or the like, which is transparent and has excellent transparency, chemical adsorption power, affinity, and compatibility with printing ink is preferably used.
Moreover, when it is set as a self-supporting signboard etc., the transparent material with thickness, such as plate shape, is preferable. In the case of a plate-like material, it is not always necessary to have a solid and uniform wall thickness, and a plastic corrugated cardboard having parallel ribs between the upper and lower liners, or an independent cylindrical space between the upper and lower liners. Even if it has a sheet-like material, it can be used as long as the liner surface has sufficient flatness to form a printing or active blocking layer. If these are used, it is possible to reduce the cost and convenience in terms of weight in installation work.
Furthermore, the organic base material that can be used in the present invention can include a synthetic fiber having transparency, a woven or non-woven fabric such as natural fiber, or synthetic paper.
The fibrous organic base material may be formed into a film shape with a heat calender roller or the like as required for design and the like.
上記有機基材としては、例えばポリメチルメタクリレートなどのアクリル樹脂、ポリスチレンやＡＢＳ樹脂などのスチレン系樹脂、ポリエチレンやポリプロピレンなどのオレフィン系樹脂、ポリエチレンテレフタレートやポリエチレンナフタレートなどのポリエステル系樹脂、６−ナイロンや６，６−ナイロンなどのポリアミド系樹脂、ポリ塩化ビニル系樹脂、ポリ塩化ビニリデン系樹脂、ポリカーボネート系樹脂、ポリフェニレンサルファイド系樹脂、ポリフェニレンエーテル系樹脂、ポリイミド系樹脂、ポリエーテルイミド系樹脂、セルロースアセテートなどのセルロース系樹脂などからなる基材を挙げることができる。なかでも、ポリメチルメタクリレートなどのアクリル樹脂、ポリエチレンテレフタレートやポリエチレンナフタレートなどのポリエステル系樹脂、ポリ塩化ビニル系樹脂、ポリ塩化ビニリデン系樹脂、ポリカーボネート系樹脂が透明性という点で好適である。 Examples of the organic base material include acrylic resins such as polymethyl methacrylate, styrene resins such as polystyrene and ABS resins, olefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, and 6-nylon. Polyamide resins such as 1,6-6-nylon, polyvinyl chloride resins, polyvinylidene chloride resins, polycarbonate resins, polyphenylene sulfide resins, polyphenylene ether resins, polyimide resins, polyetherimide resins, cellulose acetate Examples thereof include a base material made of a cellulose-based resin. Among them, acrylic resins such as polymethyl methacrylate, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyvinyl chloride resins, polyvinylidene chloride resins, and polycarbonate resins are preferable in terms of transparency.
これらの有機基材は、活性遮断層あるいは印刷インクとの密着性をさらに向上させるために、所望により、酸化法や凹凸化法などにより表面処理を施すことができる。上記酸化法としては、例えばコロナ放電処理、クロム酸処理（湿式）、火炎処理、熱風処理、オゾン・紫外線照射処理などが挙げられ、また、凹凸化法としては、例えばサンドブラスト法、溶剤処理法などが挙げられる。これらの表面処理法は基材の種類に応じて適宜選ばれる。
有機基材は、印刷層が視認できる程度の透明性が必要であるが、必ずしも無色透明である必要はなく、印刷彩度を上げるために着色された透明であってもよい。
透明性としては、概ね全光線透過率が７０％以上のものが使用できる。
These organic base materials can be subjected to a surface treatment by an oxidation method, a concavo-convex method or the like, if desired, in order to further improve the adhesion to the active blocking layer or the printing ink. Examples of the oxidation method include corona discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment and the like, and examples of the unevenness method include sand blast method and solvent treatment method. Is mentioned. These surface treatment methods are appropriately selected according to the type of substrate.
The organic substrate needs to be transparent so that the printed layer can be visually recognized. However, the organic substrate does not necessarily need to be colorless and transparent, and may be colored and transparent to increase printing saturation.
As the transparency, those having a total light transmittance of 70% or more can be used.
有機基材の一方の面に設ける活性遮断層は、光触媒作用による有機基材の劣化を防止するためおよび印刷層への影響を阻止するために設けるもので、有機基材に対する密着性を向上させる機能も有しており、通常、光触媒フィルムの保護層として用いられるものを使用できる。
一般に保護層としては、シリコーン樹脂やアクリル変性シリコーン樹脂などからなる厚さ数μｍ程度のものが用いられており、本発明においてこれらのものも使用できる。
本発明において、前記従来の中間層を活性遮断層としてもよいが、その際、要すれば、有機基材表面には、前述の表面処理や変性材料によるラミネートを施してもよい。変性材料としては、アクリル、ポリエステルや、エポキシ基、ウレタン基を含むものが好適に使用される。
The active blocking layer provided on one surface of the organic base material is provided to prevent the deterioration of the organic base material due to photocatalytic action and to prevent the influence on the printing layer, thereby improving the adhesion to the organic base material. It also has a function, and what is usually used as a protective layer of a photocatalytic film can be used.
In general, a protective layer made of a silicone resin, an acrylic-modified silicone resin or the like having a thickness of about several μm is used, and these can also be used in the present invention.
In the present invention, the conventional intermediate layer may be used as an active blocking layer. In this case, if necessary, the surface of the organic substrate may be laminated with the above-described surface treatment or modified material. As the modified material, those containing acrylic, polyester, epoxy group or urethane group are preferably used.
屋外展示用等の印刷物としてより高い耐久性、耐候性を望む場合には、活性遮断層は、有機高分子化合物と金属酸化物系化合物とが化学的に結合した複合体を含み、かつ金属成分の含有率が該膜の厚み方向に連続的に変化する成分傾斜構造を有するものであって、実質上、光触媒活性層との界面では金属酸化物系化合物成分の濃度が高く、かつ有機基材に当接している面では有機高分子化合物成分の濃度が高い有機−無機複合傾斜層とすることがより望ましい。 When higher durability and weather resistance are desired for printed materials for outdoor exhibitions, etc., the active blocking layer includes a composite in which an organic polymer compound and a metal oxide compound are chemically bonded, and a metal component. Having a component gradient structure in which the content ratio of the metal oxide continuously changes in the thickness direction of the film, and the concentration of the metal oxide compound component is substantially high at the interface with the photocatalytic active layer, and the organic base material It is more desirable to use an organic-inorganic composite gradient layer in which the concentration of the organic polymer compound component is high on the surface in contact with.
このような、前記活性遮断層が、（Ａ）一般式（Ｉ）で表される金属アルコキシドの加水分解縮合物を少なくとも1種類以上含むコーティング組成物から形成されていることが望ましい。
ＭＲ1 x（ＯＲ2）m-x ‥（Ｉ）
（式中、ＭはＳｉ，Ｔｉ，Ａｌ，Ｚｒの金属、Ｒ1はアルキル基、アルケニル基、アルキニル基、アリール基、アラルキル基又はアシル基、Ｒ2は炭素数１〜６のアルキル基、mは金属Mの価数、ｘは０〜２の整数を示す。）
前記一般式（Ｉ）において、Ｒ1は非加水分解性基であって、そのうちのアルキル基は
、炭素数１〜２０のアルキル基が好ましく、また、アルケニル基およびアルキニル基は、
炭素数２〜２０のものが好ましい。アリール基は、炭素数６〜２０、アラルキル基は、炭
素数７〜２０のものが好ましい。さらに、アシル基としては、炭素数２〜２０の脂肪族ア
シル基や、炭素数７〜２０の芳香族アシル基（アロイル基）を好ましく挙げることができ
る。
一方、ＯＲ2は加水分解性基であって、Ｒ2で示される炭素数１〜６のアルキル基は、直
鎖状、分岐状、環状のいずれであってもよく、その例としては、メチル基、エチル基、ｎ
−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅ
ｒｔ−ブチル基、ペンチル基、ヘキシル基、シクロペンチル基、シクロヘキシル基などが
挙げられる。ｘは０〜２の整数であり、Ｒ1が複数ある場合、各Ｒ1はたがいに同一であっ
てもよいし、異なっていてもよく、またＯＲ2が複数ある場合、各ＯＲ2はたがいに同一で
もよいし、異なっていてもよい。
このような、有機−無機複合傾斜層による前記活性遮断層を、（Ｂ）非晶質酸化チタン形成用化合物および（Ｃ）無機塩類、有機塩類およびアルコキシド類の中から選ばれる少なくとも１種のチタン以外の金属の化合物とを含むコーティング組成物から形成することが、耐久性、耐クラック性、耐候性の点でより望ましい。
前記（Ｂ）非晶質酸化チタン形成用化合物すなわち（Ｂ）成分としては、例えば一般式（II）
ＴｉＲ1 x（ＯＲ2）4-x …（II）
（式中、Ｒ1はアルキル基、アルケニル基、アルキニル基、アリール基、アラルキル基又
はアシル基、Ｒ2は炭素数１〜６のアルキル基、ｘは０〜２の整数を示す。）
で表されるチタンアルコキシドをそのまま含むものであってもよいし、その加水分解・縮合物を含むものであってもよく、あるいはその両方を含むものであってもよいが、加水分解・縮合物がより好ましい。
The active blocking layer is preferably formed from a coating composition containing at least one hydrolyzed condensate of metal alkoxide represented by (A) general formula (I).
MR 1 x (OR 2 ) mx (I)
(Wherein M is a metal of Si, Ti, Al, Zr, R 1 is an alkyl group, alkenyl group, alkynyl group, aryl group, aralkyl group or acyl group, R 2 is an alkyl group having 1 to 6 carbon atoms, m Represents the valence of metal M, and x represents an integer of 0 to 2.)
In the general formula (I), R 1 is a non-hydrolyzable group, in which the alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, and the alkenyl group and alkynyl group are
Those having 2 to 20 carbon atoms are preferred. The aryl group preferably has 6 to 20 carbon atoms, and the aralkyl group preferably has 7 to 20 carbon atoms. Furthermore, as an acyl group, a C2-C20 aliphatic acyl group and a C7-C20 aromatic acyl group (aroyl group) can be mentioned preferably.
On the other hand, OR 2 is a hydrolyzable group, and the alkyl group having 1 to 6 carbon atoms represented by R 2 may be linear, branched, or cyclic. Group, ethyl group, n
-Propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, te
Examples thereof include an rt-butyl group, a pentyl group, a hexyl group, a cyclopentyl group, and a cyclohexyl group. x is an integer of 0 to 2, when R 1 are a plurality, each R 1 may be mutually identical or different and, where OR 2 there are a plurality, each OR 2 is another May be the same or different.
The active blocking layer formed of such an organic-inorganic composite gradient layer is made of (B) an amorphous titanium oxide forming compound and (C) at least one kind of titanium selected from inorganic salts, organic salts, and alkoxides. It is more desirable in terms of durability, crack resistance, and weather resistance to form a coating composition containing a metal compound other than the above.
Examples of the (B) amorphous titanium oxide forming compound, that is, the component (B) include, for example, the general formula (II)
TiR 1 x (OR 2 ) 4-x (II)
(Wherein R 1 represents an alkyl group, alkenyl group, alkynyl group, aryl group, aralkyl group or acyl group, R 2 represents an alkyl group having 1 to 6 carbon atoms, and x represents an integer of 0 to 2)
It may contain the titanium alkoxide represented by the above as it is, it may contain its hydrolysis / condensation product, or it may contain both, but it may contain the hydrolysis / condensation product. Is more preferable.
前記一般式（II）において、Ｒ1は非加水分解性基であって、そのうちのアルキル基は
、炭素数１〜２０のアルキル基が好ましく、また、アルケニル基およびアルキニル基は、
炭素数２〜２０のものが好ましい。アリール基は、炭素数６〜２０、アラルキル基は、炭
素数７〜２０のものが好ましい。さらに、アシル基としては、炭素数２〜２０の脂肪族ア
シル基や、炭素数７〜２０の芳香族アシル基（アロイル基）を好ましく挙げることができ
る。
In the general formula (II), R 1 is a non-hydrolyzable group, and the alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, and the alkenyl group and alkynyl group are
Those having 2 to 20 carbon atoms are preferred. The aryl group preferably has 6 to 20 carbon atoms, and the aralkyl group preferably has 7 to 20 carbon atoms. Furthermore, as an acyl group, a C2-C20 aliphatic acyl group and a C7-C20 aromatic acyl group (aroyl group) can be mentioned preferably.
一方、ＯＲ2は加水分解性基であって、Ｒ2で示される炭素数１〜６のアルキル基は、直
鎖状、分岐状、環状のいずれであってもよく、その例としては、メチル基、エチル基、ｎ
−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅ
ｒｔ−ブチル基、ペンチル基、ヘキシル基、シクロペンチル基、シクロヘキシル基などが
挙げられる。ｘは０〜２の整数であり、Ｒ1が複数ある場合、各Ｒ1はたがいに同一であっ
てもよいし、異なっていてもよく、またＯＲ2が複数ある場合、各ＯＲ2はたがいに同一で
もよいし、異なっていてもよい。
On the other hand, OR 2 is a hydrolyzable group, and the alkyl group having 1 to 6 carbon atoms represented by R 2 may be linear, branched, or cyclic. Group, ethyl group, n
-Propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, te
Examples thereof include an rt-butyl group, a pentyl group, a hexyl group, a cyclopentyl group, and a cyclohexyl group. x is an integer of 0 to 2, when R 1 are a plurality, each R 1 may be mutually identical or different and, where OR 2 there are a plurality, each OR 2 is another May be the same or different.
この一般式（II）で表されるチタンアルコキシドの中ではチタンテトラアルコキシドが
好ましく、該チタンテトラアルコキシドの例としては、チタンテトラメトキシド、チタン
テトラエトキシド、チタンテトラ−ｎ−プロポキシド、チタンテトライソプロポキシド、
チタンテトラ−ｎ−ブトキシド、チタンテトライソブトキシド、チタンテトラ−ｓｅｃ−
ブトキシドおよびチタンテトラ−ｔｅｒｔ−ブトキシドなどが好ましく挙げられる。これ
らは１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
Among the titanium alkoxides represented by the general formula (II), titanium tetraalkoxide is preferable. Examples of the titanium tetraalkoxide include titanium tetramethoxide, titanium tetraethoxide, titanium tetra-n-propoxide, titanium tetraalkoxide. Isopropoxide,
Titanium tetra-n-butoxide, titanium tetraisobutoxide, titanium tetra-sec-
Preferred are butoxide and titanium tetra-tert-butoxide. These may be used individually by 1 type and may be used in combination of 2 or more type.
本発明の活性遮断層を形成する組成物において、加水分解・縮合に用いる溶媒としては、アルコール類が好ましく、炭素数３以上のエーテル系酸素を有するアルコール類が、加水分解−縮合反応の制御および縮合物の安定化の点からさらに好ましい。
この炭素数３以上のエーテル系酸素を有するアルコール類としては、チタンアルコキシドに対して相互作用を有する溶剤、例えばエチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテルなどのセロソルブ系溶剤、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノプロピルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテルなどを挙げることができる。これらの中で、特にセロソルブ系溶剤が好ましい。これらの溶剤は１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
In the composition forming the active blocking layer of the present invention, as a solvent used for hydrolysis / condensation, alcohols are preferable, and alcohols having ether oxygen having 3 or more carbon atoms are used for controlling hydrolysis-condensation reaction and More preferable from the viewpoint of stabilization of the condensate.
Examples of alcohols having ether oxygen having 3 or more carbon atoms include solvents having an interaction with titanium alkoxide, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and the like. Cellosolve solvents such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether . Among these, cellosolve solvents are particularly preferable. These solvents may be used singly or in combination of two or more.
チタンテトラアルコキシドの加水分解・縮合物を用いる場合、チタンテトラアルコキシ
ドの加水分解−縮合反応は、チタンテトラアルコキシドに対し、好ましくは４〜２０倍モ
ル、より好ましくは５〜１２倍モルの前記アルコール類と、好ましくは０．５以上４倍モ
ル未満、より好ましくは１〜３．０倍モルの水を用い、塩酸、硫酸、硝酸などの酸性触媒
の存在下、通常０〜７０℃、好ましくは２０〜５０℃の範囲の温度において行われる。酸
性触媒は、チタンテトラアルコキシドに対し、通常０．１〜１．０倍モル、好ましくは０
．２〜０．７倍モルの範囲で用いられる。
When using the hydrolysis / condensation product of titanium tetraalkoxide, the hydrolysis-condensation reaction of titanium tetraalkoxide is preferably 4 to 20 times mol, more preferably 5 to 12 times mol of the alcohol, relative to titanium tetraalkoxide. And preferably 0.5 to less than 4 times mol, more preferably 1 to 3.0 times mol of water, and usually 0 to 70 ° C., preferably 20 in the presence of an acidic catalyst such as hydrochloric acid, sulfuric acid or nitric acid. It is carried out at a temperature in the range of ~ 50 ° C. The acidic catalyst is usually 0.1 to 1.0 times mol, preferably 0, with respect to titanium tetraalkoxide.
. It is used in the range of 2 to 0.7 times mole.
一方、（Ｄ）成分であるチタン以外の金属化合物は、非晶質酸化チタンの結晶化阻
害化合物として機能するものであり、効果の点から、無機塩類、有機塩類およびアルコキ
シド類の中から選ばれる化合物、具体的には、硝酸、酢酸、硫酸、塩化アルミニウムなら
びにジルコニウムの各塩類、ならびに、これら無機塩類の水和物、アルミニウムトリアセ
チルアセトナートなどのアルミニウムキレート類、テトラ−ｎ−プロポキシジルコニウム
、テトラエトキシシラン、フェニルトリメトキシシランなどの金属アルコキシド類、なら
びにこれら化合物の加水分解物、あるいは、その縮合物を挙げることができる。これらの
中で、異種金属がアルミニウムおよび／またはジルコニウムであるものが好ましく、特に硝酸アルミニウムならびにその水和物がより好ましい。前記金属化合物は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
On the other hand, the metal compound other than titanium, which is component (D), functions as a crystallization inhibiting compound for amorphous titanium oxide, and is selected from inorganic salts, organic salts, and alkoxides from the viewpoint of effects. Compounds such as nitric acid, acetic acid, sulfuric acid, aluminum chloride and zirconium salts, and hydrates of these inorganic salts, aluminum chelates such as aluminum triacetylacetonate, tetra-n-propoxyzirconium, tetra Examples thereof include metal alkoxides such as ethoxysilane and phenyltrimethoxysilane, hydrolysates of these compounds, and condensates thereof. Among these, those in which the different metal is aluminum and / or zirconium are preferred, and aluminum nitrate and hydrates thereof are particularly preferred. The said metal compound may be used individually by 1 type, and may be used in combination of 2 or more type.
この（Ｃ）成分である異種金属化合物は、前記（Ｂ）成分を含む液にそのまま添加すれ
ばよく、その添加順序については特に制限はない。
本発明の活性遮断層の形成においては、（Ｃ）成分であるチタン以外の金属化合物の使用量は、チタン原子に対して、通常５〜５０モル％の範囲で選定される。使用量が５モル％以上であれば、良好な結晶化阻害効果が得られ、また５０モル％以下では非晶質酸化チタンが本来有する物理的性質が良好に発揮される。異種金属化合物として硝酸アルミニウムを用いる場合の特に好ましい使用量は１０〜３０モル％の範囲である。
The dissimilar metal compound as the component (C) may be added as it is to the liquid containing the component (B), and the order of addition is not particularly limited.
In the formation of the active blocking layer of the present invention, the amount of the metal compound other than titanium as the component (C) is usually selected in the range of 5 to 50 mol% with respect to the titanium atom. When the amount used is 5 mol% or more, a good crystallization inhibitory effect can be obtained, and when it is 50 mol% or less, the physical properties inherent to amorphous titanium oxide are satisfactorily exhibited. When aluminum nitrate is used as the dissimilar metal compound, a particularly preferable amount of use is in the range of 10 to 30 mol%.
このようにして得られた本発明の活性遮断層形成用コーティング組成物は、前述した性状を有するものであり、その固形分濃度は、通常０．１〜３０質量％程度、好ましくは０．５〜２０質量％程度である。このコーティング組成物を、所望の基材上に、乾燥厚さが０．０１〜２μｍ程度、好ましくは０．０２〜０．７μｍになるように塗布し、例えば常温乾燥することにより、あるいは所望により、さらに加熱処理することにより、無色で透明性に優れ、５０ｎｍ〜５μｍ程度の長さの微小なクラックなどが新たに発生しにくい非晶質酸化チタン複合塗膜を形成することができる。 The coating composition for forming an active blocking layer of the present invention thus obtained has the properties described above, and the solid content concentration is usually about 0.1 to 30% by mass, preferably 0.5. About 20% by mass. The coating composition is applied onto a desired substrate so that the dry thickness is about 0.01 to 2 μm, preferably 0.02 to 0.7 μm, and is dried at room temperature, for example, or as desired. Further, by further heat treatment, it is possible to form an amorphous titanium oxide composite coating film that is colorless and excellent in transparency, and is unlikely to newly generate micro cracks having a length of about 50 nm to 5 μm.
本発明の活性遮断層形成用コーティング組成物は、さらに、（Ｄ）非晶質酸化チタンと化学結合し得る有機成分を含ませることにより、有機基材上に塗膜を設けた場合に、非晶質酸化チタン成分の含有率が、該塗膜の表面から基材に向かって傾斜する、自己傾斜性を有する組成物からなる塗膜とすることができる。 The coating composition for forming an active barrier layer of the present invention further comprises (D) an organic component that can be chemically bonded to amorphous titanium oxide, thereby providing a non-coated coating on an organic substrate. It can be set as the coating film which consists of a composition which has the self-gradient property in which the content rate of a crystalline titanium oxide component inclines toward the base material from the surface of this coating film.
この（Ｄ）非晶質酸化チタンと化学結合し得る有機成分としては、例えば（ａ）金属を含まないエチレン性不飽和単量体と、（ｂ）カップリング性ケイ素含有基を有するエチレン性不飽和単量体とを共重合させることにより得られる有機高分子化合物を好ましく挙げることができる。 Examples of the organic component capable of chemically bonding with (D) amorphous titanium oxide include (a) an ethylenically unsaturated monomer containing no metal and (b) an ethylenically unsaturated group having a coupling silicon-containing group. An organic polymer compound obtained by copolymerizing with a saturated monomer can be preferably exemplified.
上記（ａ）金属を含まないエチレン性不飽和単量体としては、例えば一般式（III） Examples of the (a) metal-free ethylenically unsaturated monomer include, for example, the general formula (III)
で表されるエチレン性不飽和単量体、好ましくは一般式（III−ａ）
An ethylenically unsaturated monomer represented by the formula (III-a)
ゲン原子若しくはエーテル結合を有する炭化水素基を示す。）
で表されるエチレン性不飽和単量体を一種または二種以上混合して使用してもよい。
One or a mixture of two or more ethylenically unsaturated monomers represented by
上記一般式（III−ａ）で表されるエチレン性不飽和単量体において、Ｒ4で示される炭
化水素基としては、炭素数１〜１０の直鎖状若しくは分岐状のアルキル基、炭素数３〜１
０のシクロアルキル基、炭素数６〜１０のアリール基、炭素数７〜１０のアラルキル基を
好ましく挙げることができる。炭素数１〜１０のアルキル基の例としては、メチル基、エ
チル基、ｎ−プロピル基、イソプロピル基、および各種のブチル基、ペンチル基、ヘキシ
ル基、オクチル基、デシル基などが挙げられる。炭素数３〜１０のシクロアルキル基の例
としては、シクロペンチル基、シクロヘキシル基、メチルシクロヘキシル基、シクロオク
チル基などが、炭素数６〜１０のアリール基の例としては、フェニル基、トリル基、キシ
リル基、ナフチル基、メチルナフチル基などが、炭素数７〜１０のアラルキル基の例とし
ては、ベンジル基、メチルベンジル基、フェネチル基、ナフチルメチル基などが挙げら
れる。エポキシ基、ハロゲン原子若しくはエーテル結合を有する炭化水素基としては、こ
れらの基、原子若しくは結合を有する炭素数１〜１０の直鎖状若しくは分岐状のアルキル
基、炭素数３〜１０のシクロアルキル基、炭素数６〜１０のアリール基、炭素数７〜１０
のアラルキル基を好ましく挙げることができる。上記置換基のハロゲン原子としては、塩
素原子等が挙げられる。
In the ethylenically unsaturated monomer represented by the general formula (III-a), as the hydrocarbon group represented by R 4 , a linear or branched alkyl group having 1 to 10 carbon atoms, carbon number 3 to 1
Preferred examples include a cycloalkyl group having 0, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and various butyl groups, pentyl groups, hexyl groups, octyl groups, and decyl groups. Examples of the cycloalkyl group having 3 to 10 carbon atoms include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, and a cyclooctyl group. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a tolyl group, and a xylyl group. Examples of the aralkyl group having 7 to 10 carbon atoms such as a group, a naphthyl group, and a methylnaphthyl group include a benzyl group, a methylbenzyl group, a phenethyl group, and a naphthylmethyl group. Examples of the hydrocarbon group having an epoxy group, a halogen atom or an ether bond include a linear or branched alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms having an atom or a bond. , An aryl group having 6 to 10 carbon atoms, 7 to 10 carbon atoms
The aralkyl group can be preferably exemplified. A chlorine atom etc. are mentioned as a halogen atom of the said substituent.
この一般式（III−ａ）で表されるエチレン性不飽和単量体の例としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート、グリシジル（メタ）アクリレート、３−グリシドキシプロピル（メタ）アクリレート、２−（３，４−エポキシシクロヘキシル）エチル（メタ）アクリレート、２−クロロエチル（メタ）アクリレート、２−ブロモエチル（メタ）アクリレートなどが挙げられる。これらは単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Examples of the ethylenically unsaturated monomer represented by the general formula (III-a) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl ( (Meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, 3-glycidoxypropyl (meth) acrylate, 2- ( 3,4-epoxycyclohexyl) ethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 2-bromoethyl (meth) acrylate, and the like. These may be used alone or in combination of two or more.
また、前記一般式（III）で表されるエチレン性不飽和単量体としては、これら以外にもスチレン、α−メチルスチレン、α−アセトキシスチレン、ｍ−、ｏ−またはｐ−ブロモスチレン、ｍ−、ｏ−またはｐ−クロロスチレン、ｍ−、ｏ−またはｐ−ビニルフェノール、１−または２−ビニルナフタレンなど、さらにはエチレン性不飽和基を有する重合性高分子用安定剤、例えばエチレン性不飽和基を有する、酸化防止剤、紫外線吸収剤および光安定剤なども用いることができる。これらは単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 In addition to these, the ethylenically unsaturated monomer represented by the general formula (III) includes styrene, α-methylstyrene, α-acetoxystyrene, m-, o- or p-bromostyrene, m -, O- or p-chlorostyrene, m-, o- or p-vinylphenol, 1- or 2-vinylnaphthalene and the like, and stabilizers for polymerizable polymers having an ethylenically unsaturated group, for example, ethylenic Antioxidants, ultraviolet absorbers and light stabilizers having an unsaturated group can also be used. These may be used alone or in combination of two or more.
一方、前記（ｂ）カップリング性ケイ素含有基を有するエチレン性不飽和単量体としては、例えば一般式（IＶ） On the other hand, as the (b) ethylenically unsaturated monomer having a coupling silicon-containing group, for example, the general formula (IV)
基又はエチル基を示す。）
で表される化合物を好ましく挙げることができる。前記一般式（III）において、３つの
Ｒ6はたがいに同一でも異なっていてもよい。
この一般式（IＶ）で表されるエチレン性不飽和単量体の例としては、２−（メタ）ア
クリロキシエチルトリメトキシシラン、２−（メタ）アクリロキシエチルトリエトキシシ
ラン、γ−（メタ）アクリロキシプロピルトリメトキシシラン、γ−（メタ）アクリロキ
シプロピルトリエトキシシランなどが挙げられる。
この（Ｄ）成分のカップリング性ケイ素含有基を有するエチレン性不飽和単量体は、１
種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
Preferred examples include compounds represented by: In the general formula (III), the three R 6 may be the same or different.
Examples of the ethylenically unsaturated monomer represented by the general formula (IV) include 2- (meth) acryloxyethyltrimethoxysilane, 2- (meth) acryloxyethyltriethoxysilane, γ- (meta ) Acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, and the like.
The ethylenically unsaturated monomer having a coupling silicon-containing group as the component (D) is 1
A seed may be used independently and may be used combining two or more sorts.
前記（ａ）成分の金属を含まないエチレン性不飽和単量体と、（ｂ）成分のカップリン
グ性ケイ素含有基を有するエチレン性不飽和単量体とを、ラジカル重合開始剤の存在下、
ラジカル重合させることにより、（Ｄ）成分の成分として用いられるカップリング性ケイ
素含有基を有する有機高分子化合物からなる自己傾斜性を有する化合物が得られる。
In the presence of a radical polymerization initiator, the ethylenically unsaturated monomer containing no metal of the component (a) and the ethylenically unsaturated monomer having a coupling silicon-containing group of the component (b),
By radical polymerization, a compound having a self-gradient composed of an organic polymer compound having a coupling silicon-containing group used as a component of the component (D) is obtained.
本発明の活性遮断層においては、このようにして得られた（Ｄ）成分であるカップリング性ケイ素含有基を有する有機高分子化合物をアルコール、ケトン、エーテルなどの適当な溶剤中に溶解させた溶液と、前述の（Ｂ）成分であるチタンアルコキシドの加水分解・縮合物と、（Ｃ）成分のチタン以外の金属化合物単体および／またはそれを含む反応液を必要により希釈した溶液とを混合することにより、前記有機高分子化合物中のカップリング性ケイ素含有基が加水分解し、（Ｂ）成分の反応液におけるチタンアルコキシドの加水分解縮合物と選択的に反応し、有機−無機複合傾斜膜形成用のコーティング組成物、すなわち本発明における印刷用基材の活性遮断層用組成物が得られる。
なお、この際、用いるチタンアルコキシドの加水分解縮合物を含む反応液の希釈溶媒としては、前述した理由により炭素数３以上のエーテル系酸素を有するアルコール類を含む溶媒を使用することが望ましい。
In the active barrier layer of the present invention, the organic polymer compound having a coupling silicon-containing group as component (D) thus obtained was dissolved in a suitable solvent such as alcohol, ketone, ether or the like. The solution, the hydrolysis / condensation product of titanium alkoxide as component (B) described above, and a solution obtained by diluting the metal compound other than titanium as component (C) and / or a reaction solution containing the same as necessary are mixed. As a result, the coupling silicon-containing group in the organic polymer compound is hydrolyzed and selectively reacted with the hydrolysis condensate of titanium alkoxide in the reaction solution of component (B) to form an organic-inorganic composite gradient film. Coating composition, that is, a composition for an active barrier layer of a printing substrate in the present invention is obtained.
In this case, as a diluting solvent for the reaction solution containing the hydrolysis condensate of titanium alkoxide used, it is desirable to use a solvent containing an alcohol having an ether oxygen having 3 or more carbon atoms for the reason described above.
このようなコーティング組成物を用いることにより、有機基材に塗布、乾燥した際に、
実質上有機基材側が有機高分子化合物成分で、その反対側が非晶質酸化チタン成分であっ
て、両者の含有割合が膜厚方向に連続的に変化する良好な成分傾斜構造を有する有機−無
機複合傾斜膜を、安定して形成することができる。そして、この有機−無機複合傾斜膜を活性遮断層とすることができる。
By using such a coating composition, when applied to an organic substrate and dried,
Organic-inorganic having a good component gradient structure in which the organic base material side is substantially an organic polymer compound component and the opposite side is an amorphous titanium oxide component, and the content ratio of both is continuously changed in the film thickness direction A composite gradient film can be formed stably. The organic-inorganic composite gradient film can be used as an active blocking layer.
この複合傾斜性の活性遮断層は、無機成分として非晶質酸化チタン成分を含むことにより、促進耐候試験下に曝露されても、無機成分の結晶化が抑えられるため、機械的特性の低下、クラックの発生、透明性の低下などが抑制される。 This composite gradient active barrier layer contains an amorphous titanium oxide component as an inorganic component, so that crystallization of the inorganic component can be suppressed even when exposed under an accelerated weathering test. Generation of cracks, decrease in transparency, and the like are suppressed.
有機基材上に、活性遮断層としての複合傾斜膜を形成させるには、このようにして得られた本発明のコーティング組成物を、乾燥塗膜の厚さが、通常５μｍ以下、好ましくは０．０１〜１．０μｍ、より好ましくは０．０２〜０．７μｍの範囲になるように、ディップコート法、スピンコート法、スプレーコート法、バーコート法、ナイフコート法、ロールコート法、ブレードコート法、ダイコート法、グラビアコート法などの公知の手段により塗布し、溶媒を揮散させて塗膜を形成させる。
なお、本発明における有機基材は、前に例示した有機系材料以外の材料、例えばガラスや透明性セラミックス系材料からなる基材の表面に、有機系塗膜を有するものも包含する。
In order to form a composite gradient film as an active blocking layer on an organic base material, the coating composition of the present invention thus obtained has a dry coating thickness of usually 5 μm or less, preferably 0. .01 to 1.0 μm, more preferably 0.02 to 0.7 μm, dip coating method, spin coating method, spray coating method, bar coating method, knife coating method, roll coating method, blade coating It is applied by a known means such as a method, a die coating method or a gravure coating method, and a coating film is formed by evaporating the solvent.
In addition, the organic base material in this invention includes what has an organic type coating film on the surface of materials other than the organic type material illustrated previously, for example, the base material which consists of glass and a transparent ceramics type material.
また、活性遮断層の傾斜構造の確認は、例えば塗膜表面にスパッタリングを施して膜を削っていき、経時的に膜表面の炭素原子とチタン原子の含有率を、Ｘ線光電子分光法などにより測定することによって、行うことができる。
この活性遮断層としての複合傾斜膜における金属成分の含有量は、特に制限はないが、金属酸化物換算で、通常５〜９８質量％、好ましくは２０〜９８質量％、特に好ましくは５０〜９５質量％の範囲である。有機高分子化合物の重合度や分子量としては、製膜化しうるものであればよく特に制限されず、高分子化合物の種類や所望の傾斜膜材料の物性などに応じて適宜選定すればよい。
In addition, the inclination structure of the active blocking layer can be confirmed by, for example, sputtering the surface of the coating to scrape the film, and the carbon and titanium atom content on the surface of the film over time can be determined by X-ray photoelectron spectroscopy. This can be done by measuring.
The content of the metal component in the composite gradient film as the active blocking layer is not particularly limited, but is usually 5 to 98% by mass, preferably 20 to 98% by mass, and particularly preferably 50 to 95% in terms of metal oxide. It is the range of mass%. The degree of polymerization and the molecular weight of the organic polymer compound are not particularly limited as long as they can be formed into a film, and may be appropriately selected according to the type of polymer compound and the desired physical properties of the gradient film material.
本発明の光触媒活性層としては、一般的に光触媒層として用いられているアナターゼ型の酸化チタンをバインダーで固めた層でもよいが、耐久性、耐候性を考慮して、次の組成物により構成することが望ましい。
すなわち、本発明の改良された光触媒活性層のコーティング組成物としては、前記（Ａ）、（Ｃ）にさらに、（Ｅ）光触媒機能を有する微粒子および／またはシリカ微粒子を含めることができる。
前記光触媒機能を有する微粒子としては、アナターゼ型結晶を主成分とする酸化チタン
粒子を用いることができる。
前記アナターゼ型結晶を主成分とする酸化チタン微粒子（以下、アナターゼ結晶酸化チ
タン粒子と称すことがある。）は、光触媒粒子であり、少量のルチル型結晶が混在してい
てもよく、また、窒化チタンや低次酸化チタン等を一部含む可視光応答型の光触媒粒子も
使用することができる。このアナターゼ結晶酸化チタン粒子の平均粒子径は、１〜５００
ｎｍの範囲が好ましく、１〜１００ｎｍの範囲がより好ましく、１〜５０ｎｍの範囲が優
れた光触媒機能を有するために最も好ましい。上記平均粒子径は、レーザー光を利用した
散乱法によって測定することができる。
The photocatalytic active layer of the present invention may be a layer in which anatase-type titanium oxide generally used as a photocatalytic layer is hardened with a binder, but is composed of the following composition in consideration of durability and weather resistance. It is desirable to do.
That is, the improved photocatalytically active layer coating composition of the present invention may further include (E) fine particles having a photocatalytic function and / or silica fine particles in the (A) and (C).
As the fine particles having a photocatalytic function, titanium oxide particles mainly composed of anatase type crystals can be used.
The titanium oxide fine particles containing the anatase crystal as a main component (hereinafter sometimes referred to as anatase crystal titanium oxide particles) are photocatalyst particles, and may contain a small amount of rutile crystal, and nitriding. Visible light responsive photocatalyst particles partially containing titanium, low-order titanium oxide, or the like can also be used. The average particle size of the anatase crystalline titanium oxide particles is 1 to 500.
The range of nm is preferable, the range of 1 to 100 nm is more preferable, and the range of 1 to 50 nm is most preferable because it has an excellent photocatalytic function. The average particle diameter can be measured by a scattering method using laser light.
また、当該酸化チタン粒子の内部および／またはその表面に、第二成分として、Ｖ、Ｆ
ｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｒｕ、Ｒｈ、Ｐｄ、Ａｇ、ＰｔおよびＡｕの中から選ばれ
る少なくとも１種の金属および／または金属化合物を含有させると、一層高い光触媒機能
を有するため好ましい。前記の金属化合物としては、例えば、金属の酸化物、水酸化物、
オキシ水酸化物、硫酸塩、ハロゲン化物、硝酸塩、さらには金属イオンなどが挙げられる。
第二成分の含有量はその物質の種類に応じて適宜選定される。
Further, as a second component, V, F may be present inside and / or on the surface of the titanium oxide particles.
It is preferable to contain at least one metal and / or metal compound selected from e, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Pt, and Au, since this has a higher photocatalytic function. Examples of the metal compound include metal oxides, hydroxides,
Examples thereof include oxyhydroxides, sulfates, halides, nitrates, and metal ions.
The content of the second component is appropriately selected according to the type of the substance.
このアナターゼ結晶酸化チタン粒子は、従来公知の方法によって製造することができる
が、塗工液中に均質に分散させるために酸化チタンゾルの形態で用いるのが有利である。
該酸化チタンゾルを製造するには、例えば粉末状のアナターゼ結晶酸化チタンを酸やアルカリの存在下で解こうさせてもよいし、粉砕によって粒子径を制御してもよい。また、硫酸チタンや塩化チタンを熱分解あるいは中和分解して得られる含水酸化チタンを物理的、化学的な方法で結晶子径、粒子径の制御を行ってもよい。さらにゾル液中での分散安定性を付与するために、分散安定剤を使用することができる。
The anatase crystalline titanium oxide particles can be produced by a conventionally known method, but it is advantageous to use the titanium oxide sol in the form of a titanium oxide sol so as to be homogeneously dispersed in the coating liquid.
In order to produce the titanium oxide sol, for example, powdered anatase crystalline titanium oxide may be dissolved in the presence of an acid or alkali, or the particle diameter may be controlled by pulverization. In addition, the hydrous or neutralized decomposition of titanium sulfate or titanium chloride may be used to control the crystallite size and particle size by physical and chemical methods. Furthermore, a dispersion stabilizer can be used to impart dispersion stability in the sol solution.
一方、コロイダルシリカは光触媒膜に、暗所保持時においても超親水性維持性能を発現させる作用を有している。
光触媒は、紫外線などの光の照射によって、その表面に存在する有機物質を分解する性
質や、超親水化を発現するが、暗所では、一般にこのような光触媒機能が発現されない。
しかし、光触媒膜中にコロイダルシリカを含有させることにより、該光触媒膜は、暗所でも超親水性維持性能を発現する。
このコロイダルシリカは、高純度の二酸化ケイ素（ＳｉＯ2）を水またはアルコール系
溶剤に分散させてコロイド状にした製品であって、平均粒子径は、通常１〜２００ｎｍ、
好ましくは５〜５０ｎｍの範囲である。シリコンアルコキシドの加水分解・縮合物では、
反応が終結していないので、水で溶出されやすく、それを含む光触媒膜は耐水性に劣る。
一方、コロイダルシリカは、反応終結微粒子であるため、水で溶出されにくく、それを含む光触媒膜は、耐水性が良好なものとなる。
このコロイダルシリカは、塗膜の強度や硬度を向上させる作用の他に、表面を凹凸化させる作用も発現させる場合がある。
On the other hand, colloidal silica has a function of causing the photocatalytic film to exhibit superhydrophilicity maintenance performance even in a dark place.
A photocatalyst exhibits the property of decomposing an organic substance existing on the surface thereof by irradiation with light such as ultraviolet rays and superhydrophilicity, but generally does not exhibit such a photocatalytic function in a dark place.
However, by including colloidal silica in the photocatalyst film, the photocatalyst film exhibits super-hydrophilicity maintaining performance even in a dark place.
This colloidal silica is a product in which high-purity silicon dioxide (SiO 2 ) is dispersed in water or an alcohol solvent to form a colloid, and the average particle size is usually 1 to 200 nm,
Preferably it is the range of 5-50 nm. In the hydrolyzed / condensed product of silicon alkoxide,
Since the reaction is not terminated, it is easily eluted with water, and the photocatalyst film containing it is inferior in water resistance.
On the other hand, colloidal silica is a reaction-terminated fine particle, so it is difficult to elute with water, and a photocatalyst film containing it has good water resistance.
This colloidal silica sometimes exhibits an effect of making the surface uneven, in addition to an effect of improving the strength and hardness of the coating film.
本発明の光触媒活性層に用いる、光触媒機能を有するコーティング組成物は、その一例として、前記（Ｂ）成分であるチタンアルコキシドの加水分解・縮合物と（Ｃ）成分であるチタン以外の金属化合物単体および／またはその反応液を含む液に、所定量のアナターゼ結晶酸化チタンゾルと場合によりコロイダルシリカを加え、均質に分散させることにより、調製することができる。 The coating composition having a photocatalytic function used for the photocatalytic active layer of the present invention includes, as an example, a hydrolysis / condensation product of titanium alkoxide as the component (B) and a metal compound other than titanium as the component (C). In addition, a predetermined amount of anatase crystalline titanium oxide sol and optionally colloidal silica may be added to a liquid containing the reaction liquid and dispersed uniformly.
このようにして調製された光触媒機能を有するコーティング組成物を活性遮断層が形成された有機基材上に、公知の方法、例えばディップコート法、スピンコート法、スプレーコート法、バーコート法、ナイフコート法、ロールコート法、ブレードコート法、ダイコート法、グラビアコート法などにより塗布し、成膜したのち、自然乾燥または加熱乾燥することにより、所望の光触媒膜すなわち光触媒活性層が得られる。加熱乾燥する場合は、２００℃以下の温度を採用することができる。
このように、成膜したのち、低温での保持処理により、形成された光触媒膜は、十分な
光触媒機能を発現し得るので、本発明の防汚性印刷用基材として、好適に用いることができる。
The coating composition having the photocatalytic function thus prepared is applied to a known method such as a dip coating method, a spin coating method, a spray coating method, a bar coating method, a knife on an organic substrate on which an active blocking layer is formed. A desired photocatalyst film, that is, a photocatalytic active layer, is obtained by coating by a coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, and the like, followed by natural drying or heat drying. In the case of heat drying, a temperature of 200 ° C. or lower can be adopted.
Thus, after the film formation, the formed photocatalyst film can exhibit a sufficient photocatalytic function by holding treatment at a low temperature. Therefore, it can be suitably used as the antifouling printing substrate of the present invention. it can.
本発明の有機基材は、厚み５０μｍ以上の透明なプラスチックフィルムまたはプラスチックシートとすることができる。
厚みが５０μｍ未満では、印刷工程や、光触媒の塗工工程での取扱いが難しく、また、薄いために、外力により、変形、伸び、破損等が生じやすい。
本発明の有機基材の厚みは、印刷後の取扱い性、被貼付体への追従性、看板等としての自立性など、使用目的、用途に応じて適宜決定される。
また、本発明の有機基材の形態は、フィルム、シート等で巻取り可能なものであれば、長尺のロール状のものが、活性遮断層、光触媒活性層、印刷層等の連続形成に便利である。
厚みのある板状物であれば、定尺にカットされたものを使用する。
また、印刷用基材は、印刷方法等によって、連続ロール状としたり、枚葉のシート状とすればよい。
一方、本発明の有機基材の幅は、印刷適性の点から２０００ｍｍ以下、好ましくは３００ｍｍ〜１６００ｍｍのものを使用できる。２０００ｍｍを超えると、印刷時の取扱いがし難くなる。
The organic substrate of the present invention can be a transparent plastic film or plastic sheet having a thickness of 50 μm or more.
If the thickness is less than 50 μm, it is difficult to handle in the printing process and the photocatalyst coating process, and because it is thin, deformation, elongation, breakage, etc. are likely to occur due to external force.
The thickness of the organic base material of the present invention is appropriately determined according to the purpose of use and use, such as handleability after printing, followability to the adherend, and self-supporting property as a signboard.
Moreover, if the form of the organic base material of this invention can be wound up with a film, a sheet | seat, etc., a long roll-shaped thing is for continuous formation of an active interruption | blocking layer, a photocatalytic active layer, a printing layer, etc. Convenient.
If it is a plate-shaped object with thickness, what was cut to a fixed scale is used.
Further, the printing substrate may be formed into a continuous roll shape or a sheet-like sheet shape by a printing method or the like.
On the other hand, the width of the organic base material of the present invention is 2000 mm or less, preferably 300 mm to 1600 mm from the viewpoint of printability. If it exceeds 2000 mm, handling during printing becomes difficult.
本発明においては、有機基材の一方の面の表層に耐候性向上剤を含有させて紫外線遮断層を設け、紫外線による劣化や表面のひび割れ、脆性等による破壊を防止することができる。本発明に使用できる耐候性向上剤としては、例えばベンゾフェノール系、ベンゾトリアゾール系、シュウ酸アニリド系、シアノアクリレート系、トリアジン系等の有機系紫外線吸収剤や、ヒンダードアミン系光安定剤、励起エネルギー吸収剤、ラジカル捕捉剤等が例示されるが、これらに限定されるものではない。耐候性向上剤は、有機基材中に含有させる代わりに、有機基材上に耐候性向上層として一層を設けてもよく、この場合は、使用する耐候性向上剤の使用量を削減でき、コスト低減を図ることができる。 In the present invention, a weather resistance improver is included in the surface layer on one surface of the organic base material to provide an ultraviolet blocking layer, and deterioration due to ultraviolet rays, surface cracks, and brittleness can be prevented. Examples of the weather resistance improver that can be used in the present invention include organic ultraviolet absorbers such as benzophenol, benzotriazole, oxalic anilide, cyanoacrylate, triazine, hindered amine light stabilizer, excitation energy absorption, and the like. Examples thereof include, but are not limited to, agents and radical scavengers. A weather resistance improver may be provided as a weather resistance improvement layer on the organic base material instead of being contained in the organic base material.In this case, the amount of the weather resistance improvement agent to be used can be reduced, Cost reduction can be achieved.
本発明の印刷用基材の表面には、インク受容層を設けることができる。単に表面を改質しただけのインク受容層は、印刷インクとの密着性を向上させるためのもので、酸化法や凹凸化法などにより表面処理を施すことにより設けることができる。上記酸化法としては、例えばコロナ放電処理、クロム酸処理（湿式）、火炎処理、熱風処理、オゾン・紫外線照射処理などが挙げられ、また、凹凸化法としては、例えばサンドブラスト法、溶剤処理法などが挙げられる。これらの表面処理法は有機基材の種類、印刷インクの種類に応じて適宜選ばれる。インクジェット用のインク受容層としては、シリカやアルミナを含有した多孔質のハイブリッド膜や、三菱樹脂株式会社のホットメルト式のインクジェットメディア“プリメイクＨＬ”と同様の特殊親水性樹脂などを必要に応じて適宜選択できる。 An ink receiving layer can be provided on the surface of the printing substrate of the present invention. The ink receiving layer whose surface has simply been modified is for improving the adhesion to the printing ink, and can be provided by subjecting it to a surface treatment by an oxidation method or a concavo-convex method. Examples of the oxidation method include corona discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment and the like, and examples of the unevenness method include sand blast method and solvent treatment method. Is mentioned. These surface treatment methods are appropriately selected according to the type of organic substrate and the type of printing ink. As the ink receiving layer for inkjet, a porous hybrid film containing silica or alumina, a special hydrophilic resin similar to the hot-melt type inkjet media “Pre-Make HL” manufactured by Mitsubishi Plastics Co., Ltd., or the like is required. It can be selected as appropriate.
本発明の防汚性印刷物を製造する際の印刷方法は、特に限定されないが、被印刷体に適応した印刷方法を採用できる。例えば、平版方式のオフセット印刷、凹版式のグラビア印刷、凸版印刷、シルクスクリーン印刷などの版式や、インクジェットプリンター、静電プリンター、昇華性インク転写、レーザー印刷等任意の印刷手段により行うことができる。
印刷は、印刷面側から見て、印像が正規の視覚時と鏡像関係にある、いわゆる反転印刷を行えば、光触媒活性層側から見て、正規の状態で視認できる。
一方、窓ガラスの外側に本発明の印刷物を貼付し、主として室内から視覚する目的の場合は、反転させることなく通常の印刷を行えばよい。
また、目的の印刷物の上に背景となる白色等の着色地を印刷すれば、印刷内容を際立たせることができる。
印刷用インクとしては、溶剤系顔料等によるインクのほか各種のものを使用できる。
Although the printing method at the time of manufacturing the antifouling printed matter of the present invention is not particularly limited, a printing method suitable for a substrate to be printed can be employed. For example, the printing can be performed by any printing means such as lithographic offset printing, intaglio gravure printing, letterpress printing, silk screen printing, etc., ink jet printers, electrostatic printers, sublimation ink transfer, laser printing and the like.
Printing can be visually recognized in a normal state when viewed from the photocatalytic active layer side by performing so-called reversal printing in which the printed image has a mirror image relationship with that at normal visual time when viewed from the printing surface side.
On the other hand, when the printed matter of the present invention is attached to the outside of the window glass and the object is to visually observe mainly from the room, normal printing may be performed without inversion.
Moreover, if a colored background such as white as a background is printed on a target printed matter, the printed content can be made to stand out.
As the printing ink, various inks other than solvent pigments can be used.
また、本発明において、印刷表面に直接粘着層を形成した印刷体としてもよい。
なお、この粘着層は、粘着後の再剥離を予測される場合であるが、再剥離を予定しない場合は接着層であってもよい。
粘着層の、粘着剤は、有機基材との粘着性、印刷層への影響度、被粘着対象物との粘着力等を勘案して、選択される。使用できる粘着剤としては、例えば従来から一般的に使用されているアクリル系、ウレタン系、シリコーンゴム系、ゴム系などの粘着剤を適宜使用でき、特に限定されるものでないが、粘着力と再剥離性を設計しやすいアクリル系粘着剤がより好ましい。
粘着層の表面には、セパレータ(剥離紙)を積層しておくことが望ましく、また、保護層を設けた場合においても、セパレータを介在させておくことが望ましい。
Moreover, in this invention, it is good also as a printing body which formed the adhesion layer directly on the printing surface.
In addition, although this adhesion layer is a case where the re-peeling after adhesion is estimated, an adhesive layer may be sufficient when re-peeling is not planned.
The pressure-sensitive adhesive of the pressure-sensitive adhesive layer is selected in consideration of the pressure-sensitive adhesiveness with the organic substrate, the degree of influence on the printed layer, the pressure-sensitive adhesive force with the adherend. Examples of adhesives that can be used include acrylic, urethane, silicone rubber, and rubber adhesives that are commonly used in the past, and are not particularly limited. An acrylic pressure-sensitive adhesive that allows easy design of peelability is more preferable.
It is desirable to laminate a separator (release paper) on the surface of the adhesive layer, and it is desirable to interpose a separator even when a protective layer is provided.
以下、本発明を実施例及び比較例により説明するが、本発明は、以下の例によってなんら限定されるものではない。
なお、各例に示す全光線透過率、ヘイズは、以下に示す要領に従って求めた。
（塗膜の全光線透過率）
ＪＩＳ Ｋ７３６１−１に準拠し、下記の装置、測定サンプルを用いて、全光線透過率とヘイズを測定した。
装置名； 日本電色（株）製 Ｈａｚｅ Ｍａｔｅｒ ＮＤＨ２０００
（Ｘ線光電子分光測定法）
ＸＰＳ装置「ＰＨＩ−５６００」［アルバックファイ（株）製］を用い、アルゴンスパッタリング（４ｋＶ）を３分間隔で施して膜を削り、膜表面の炭素原子と各金属原子の含有率を測定し、傾斜性を調べた。
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention, this invention is not limited at all by the following examples.
The total light transmittance and haze shown in each example were determined according to the following procedure.
(Total light transmittance of coating film)
Based on JIS K7361-1, the total light transmittance and haze were measured using the following apparatus and a measurement sample.
Device name: Haze Mater NDH2000 manufactured by Nippon Denshoku Co., Ltd.
(X-ray photoelectron spectroscopy)
Using an XPS apparatus “PHI-5600” [manufactured by ULVAC-PHI Co., Ltd.], argon sputtering (4 kV) was applied at intervals of 3 minutes to scrape the film, and the content of carbon atoms and each metal atom on the film surface was measured. The inclination was examined.
実施例１
（光触媒層つきフィルムの作成）
（１）活性遮断層の成膜
１Ｌセパラブルフラスコに窒素雰囲気下でメチルイソブチルケトン４２４．０ｇ、メタクリル酸メチル２００．０ｇ、メタクリロキシプロピルトリメトキシシラン２３．５ｇを添加し、６０℃まで昇温した。この混合溶液にアゾビスイソブチロニトリル１．９ｇを溶かしたメチルイソブチルケトン溶液を滴下し重合反応を開始し、３０時間攪拌し有機成分溶液（ａ）を得た。
チタンテトライソプロポキシド３５．５５ｇをエチルセルソルブ７０．０２ｇに溶解した溶液に、６０質量％硝酸５．９４ｇ、水２．１４ｇとエチルセロソルブ２７．３９ｇの混合溶液を攪拌しながらゆっくりと滴下し、その後３０℃で４時間攪拌し混合溶液（ｂ）を得た。
次いで、上記混合溶液（ｂ）とエチルセルソルブおよびチタン以外の金属化合物として硝酸アルミニウムを用いて、硝酸アルミニウムの添加量がＴｉ原子に対して１５モル％、溶液全体の固形分濃度が５質量％になるように調製し、複合金属化合物の溶液（ｃ）を得た。
次いで、上記溶液（ａ）１．４６ｇ、メチルイソブチルケトン４７．１５ｇ、エチルセルソルブ１９.０１ｇ、溶液（ｃ）２９.６０ｇおよびコロイダルシリカ分散液２．７８ｇを混合し、１５分間攪拌した。その後５〜１０℃で一晩保管し、有機―無機成分傾斜溶液（ｅ）を得た。
次に、図１に示す有機基材２として、ポリエチレンテレフタレート（ＰＥＴ）フィルム基材（東レ製、Ｔ−６０ 厚み１００μｍ、幅１６００ｍｍ）２ａの上面にＨＡＬＳ（アデカアーガス社製、アデカスタブLA-68、MW=1900）による紫外線遮蔽層２ｂを設けた全厚み１０５μｍＰＥＴフィルムにグラビアコートにて膜厚が１００ｎｍになるように成膜して、活性遮断層３を形成した。
前記のＸＰＳ測定法により、この活性遮断層３の成分傾斜性を調べたところ、有機成分と無機成分の成分傾斜が確認された。ＸＰＳ測定結果を図２に示す。
Example 1
(Creation of a film with a photocatalyst layer)
(1) Film formation of active blocking layer In a 1 L separable flask, 424.0 g of methyl isobutyl ketone, 200.0 g of methyl methacrylate, and 23.5 g of methacryloxypropyltrimethoxysilane were added in a nitrogen atmosphere, and the temperature was raised to 60 ° C. did. To this mixed solution, a methyl isobutyl ketone solution in which 1.9 g of azobisisobutyronitrile was dissolved was added dropwise to initiate the polymerization reaction, followed by stirring for 30 hours to obtain an organic component solution (a).
To a solution obtained by dissolving 35.55 g of titanium tetraisopropoxide in 70.02 g of ethyl cellosolve, a mixed solution of 5.94 g of 60% by mass nitric acid, 2.14 g of water and 27.39 g of ethyl cellosolve was slowly added dropwise with stirring. Then, the mixture was stirred at 30 ° C. for 4 hours to obtain a mixed solution (b).
Next, using the above mixed solution (b), ethyl cellosolve, and aluminum nitrate as a metal compound other than titanium, the amount of aluminum nitrate added is 15 mol% with respect to Ti atoms, and the solid content concentration of the entire solution is 5 mass%. The composite metal compound solution (c) was obtained.
Next, 1.46 g of the above solution (a), 47.15 g of methyl isobutyl ketone, 19.01 g of ethyl cellosolve, 29.60 g of the solution (c) and 2.78 g of colloidal silica dispersion were mixed and stirred for 15 minutes. Thereafter, it was stored overnight at 5 to 10 ° C. to obtain an organic-inorganic component gradient solution (e).
Next, as the
When the component gradient of the active blocking layer 3 was examined by the above XPS measurement method, the component gradient of the organic component and the inorganic component was confirmed. The XPS measurement results are shown in FIG.
（２）光触媒活性層の成膜ならびに粘着処理による印刷用基材の作製
エチルセルソルブ４０.６３ｇ、１−プロパノール４４.５０ｇの混合溶媒に、６０質量％硝酸０.３４ｇ、水６.８４ｇ、光触媒分散液（チタン工業社製「ＰＣ−２０１、固形分濃度２０.７重量％」）０.４８３ｇおよびコロイダルシリカ分散液（日産化学社製「スノーテックス ＩＰＡ−ＳＴ、固形分濃度３０重量％」）２.１６７ｇを添加し、さらに上記溶液（ｂ）５.００ｇを加え、全体の固形分濃度が１質量％になるように調製し、光触媒液（ｆ）を作製した。
この光触媒溶液を、上記活性遮断層３を備えたＰＥＴフィルムにグラビアコートにて膜厚が４０ｎｍになるように成膜して、光触媒活性層４を形成した。さらに、この光触媒活性層の上に厚さ３０μｍのＰＥＴ製剥離フィルム（図示省略）をコールドラミネートし印刷用基材１としての光触媒フィルムを得た。
(2) Preparation of substrate for printing by film formation and adhesion treatment of photocatalytic active layer In a mixed solvent of ethyl cellosolve 40.63 g and 1-propanol 44.50 g, 60 mass% nitric acid 0.34 g, water 6.84 g, 0.483 g of photocatalyst dispersion (Titanium Kogyo “PC-201, solid concentration 20.7 wt%”) and colloidal silica dispersion (Nissan Chemical “Snowtex IPA-ST,
This photocatalyst solution was formed into a film having a thickness of 40 nm by gravure coating on a PET film provided with the active blocking layer 3 to form a photocatalytic
（３）印刷用基材の評価
この印刷用基材１としての光触媒フィルムを前記の測定要領で全光線透過率ならびにヘイズを測定したところ、全光線透過率９１％、ヘイズ１．０％であった。
この印刷用基材をカーボンアーク式サンシャインウェザーメータ(ＳＷＭ)（スガ試験機社製、Ｓ３００）にて２０００時間の加速耐候試験を実施したところ、全光線透過率は９０％、ヘイズ１．５％であり、全光線透過率の低下および、ヘイズの上昇の少ない印刷用基材であることが確認できた。
(3) Evaluation of substrate for printing When the photocatalyst film as the substrate for printing 1 was measured for total light transmittance and haze in the above-described measurement procedure, the total light transmittance was 91% and haze was 1.0%. It was.
When this printing substrate was subjected to an accelerated weathering test for 2000 hours using a carbon arc sunshine weather meter (SWM) (S300, S300), the total light transmittance was 90% and the haze was 1.5%. Thus, it was confirmed that the substrate was a printing substrate with a reduced total light transmittance and a small increase in haze.
（４）印刷
前記（２）で得られた印刷用基材１の光触媒活性層４と反対側の面５にセイコーインスツルメント社（ＳＩＩ）製インクジェット式プリンター（商品名６４Ｓ）にて、溶剤系顔料（ＩＰ６シリーズ）を用いて任意の絵柄の画像を印刷した印刷層９を形成し、この上から３８μｍのＰＥＴ製剥離フィルム６に粘着剤層７を有する粘着剤付き剥離フィルム８をラミネートし、光触媒活性層上の厚さ３０μｍのＰＥＴ製剥離フィルム（図示省略）を剥離して、図３に示す印刷物１０を得た。この印刷物１０を、国道沿いの電柱看板に貼り合わせて置き、汚れの付き具合ならびに意匠性の変化を1年後に確認した。汚れが殆どついておらず印刷層９は鮮明であり意匠性が維持されていた。
(4) Printing On the
比較例１
ポリエチレンテレフタレート（ＰＥＴ）フィルム基材２ａの上面に実施例１と同一のＨＡＬＳによる紫外線遮蔽層２ｂを設けた全厚み１００μｍのＰＥＴフィルム（東レ製、ＴＰ−６０）に予め厚さ３８μｍのＰＥＴ製剥離フィルム８をラミネートし、比較サンプルを作製した。
（印刷用基材としての評価）
このフィルムについて実施例１と同一要領で、全光線透過率ならびにヘイズを測定したところ、全光線透過率９１％、ヘイズ１．０％であった。
この比較サンプル品について、カーボンアーク式サンシャインウェザーメータ(ＳＷＭ)（スガ試験機社製、Ｓ３００）にて２０００時間の加速耐候試験を実施したところ、全光線透過率は９０％、ヘイズ３．０％であった。
（印刷）
このＰＥＴフィルム上に実施例１と同様にＳＩＩ製インクジェット式プリンター（商品名：６４Ｓ）にて、溶剤系顔料（ＩＰ６シリーズ）を用いて実施例１と同一の任意の絵柄の画像を印刷した後、この上から前記剥離フィルムを貼り付けた。これを、国道沿いの電柱看板に貼り合わせて、汚れの付き具合ならびに意匠性の変化を1年後に確認した。汚れが付着し、意匠性が低下していた。
Comparative Example 1
A PET film having a thickness of 38 μm is previously peeled off from a PET film (Toray, TP-60) having a total thickness of 100 μm in which the same ultraviolet
(Evaluation as a substrate for printing)
When the total light transmittance and haze of this film were measured in the same manner as in Example 1, the total light transmittance was 91% and the haze was 1.0%.
This comparative sample product was subjected to an accelerated weathering test for 2000 hours using a carbon arc type sunshine weathermeter (SWM) (S300, manufactured by Suga Test Instruments Co., Ltd.). The total light transmittance was 90%, and the haze was 3.0%. Met.
(printing)
After printing an image of the same arbitrary pattern as in Example 1 on this PET film using a solvent-based pigment (IP6 series) with an SII inkjet printer (trade name: 64S) as in Example 1. The release film was attached from above. This was pasted on a power pole signboard along the national highway, and the change in the appearance of the dirt and the design was confirmed one year later. Dirt adhered and the designability was reduced.
本発明の防汚性印刷用基材は、有機基材の一方の面に耐候性および耐クラック性を改良した活性遮断層および光触媒活性層を形成し、有機基材の他方の面を印刷面とし、これに印刷を施すので、光触媒層からの印刷層対する悪影響がなく、光触媒活性層の自浄作用による防汚効果を有する印刷用基材として利用できる。
また、本発明の防汚性印刷物および防汚性印刷体は、印刷層の意匠性を長期にわたって維持できるので、屋外美術展示や屋外展示物の案内表示、広告宣伝用の看板、ガーデニング用資材（印刷垣根、印刷花壇など）、屋外シアターに類似した内部照明を利用した屋外美術展示用途、屋外掲示用（例えば印刷クリスマスツリー、印刷鯉のぼり、印刷おひな様、印刷ステンドグラス、印刷自作カレンダーなど）や家庭の窓貼り用装飾性印刷物等として有効に利用できる。
The antifouling printing substrate of the present invention has an active blocking layer and a photocatalytic active layer with improved weather resistance and crack resistance formed on one surface of an organic substrate, and the other surface of the organic substrate is a printed surface. Since this is printed, there is no adverse effect on the printing layer from the photocatalyst layer, and it can be used as a printing substrate having an antifouling effect due to the self-cleaning action of the photocatalytic active layer.
In addition, the antifouling printed matter and the antifouling printed material of the present invention can maintain the design properties of the printed layer for a long period of time, so that it is possible to display outdoor art exhibitions, outdoor display information displays, advertising signs, gardening materials ( Printing fences, printing flowerbeds, etc., outdoor art exhibitions using internal lighting similar to outdoor theaters, outdoor postings (such as printing Christmas trees, printing streamers, printing dolls, printing stained glass, printing self-made calendars, etc.) It can be effectively used as a decorative printed material for pasting windows at home.
１． 印刷用基材
２． 有機基材
２ａ． フィルム基材
２ｂ． 紫外線遮蔽層
３． 活性遮断層（傾斜膜層）
４． 光触媒活性層
５． 基材表面
６． 剥離フィルム
７． 粘着剤層
８． 粘着剤付き剥離フィルム
９． 印刷層
１０． 印刷物
1. 1. Substrate for printing
4). 4. Photocatalytic
Claims (14)
ＭＲ1 x（ＯＲ2）m-x ‥（Ｉ）
（式中、ＭはＳｉ，Ｔｉ，Ａｌ，Ｚｒの金属、Ｒ1はアルキル基、アルケニル基、アルキニル基、アリール基、アラルキル基又はアシル基、Ｒ2は炭素数１〜６のアルキル基、mは金属Mの価数、ｘは０〜２の整数を示す。） The active blocking layer is formed of a coating composition containing at least one or more types of hydrolysis condensates of metal alkoxides represented by (A) the general formula (I). The substrate for antifouling printing as described.
MR 1 x (OR 2 ) mx (I)
(Wherein M is a metal of Si, Ti, Al, Zr, R 1 is an alkyl group, alkenyl group, alkynyl group, aryl group, aralkyl group or acyl group, R 2 is an alkyl group having 1 to 6 carbon atoms, m Represents the valence of metal M, and x represents an integer of 0 to 2.)
ＴｉＲ1 x（ＯＲ2）4-x …（II）
（式中、Ｒ1はアルキル基、アルケニル基、アルキニル基、アリール基、アラルキル基又
はアシル基、Ｒ2は炭素数１〜６のアルキル基、ｘは０〜２の整数を示す。）
で表されるチタンアルコキシドおよび／またはその加水分解・縮合物からなる非晶質酸化チタン塗膜形成用コーティング組成物から形成されてなる請求項６記載の防汚性印刷用基材。 The compound for forming amorphous titanium oxide as the component (B) has the general formula (II)
TiR 1 x (OR 2 ) 4-x (II)
(Wherein R 1 represents an alkyl group, alkenyl group, alkynyl group, aryl group, aralkyl group or acyl group, R 2 represents an alkyl group having 1 to 6 carbon atoms, and x represents an integer of 0 to 2)
The antifouling printing substrate according to claim 6, which is formed from a coating composition for forming an amorphous titanium oxide coating film comprising a titanium alkoxide represented by the formula (1) and / or a hydrolysis / condensation product thereof.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005182473A JP2007001088A (en) | 2005-06-22 | 2005-06-22 | Stainproof printing base material, printed matter and printable object using this base material |
| PCT/JP2005/012870 WO2006137173A1 (en) | 2005-06-22 | 2005-07-12 | Antifouling base for printing, printed matter using same and printed body |
| TW094123875A TW200700477A (en) | 2005-06-22 | 2005-07-14 | Antifouling substrate for printing and printing product and printing body of using them |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005182473A JP2007001088A (en) | 2005-06-22 | 2005-06-22 | Stainproof printing base material, printed matter and printable object using this base material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2007001088A true JP2007001088A (en) | 2007-01-11 |
Family
ID=37570211
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005182473A Pending JP2007001088A (en) | 2005-06-22 | 2005-06-22 | Stainproof printing base material, printed matter and printable object using this base material |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2007001088A (en) |
| TW (1) | TW200700477A (en) |
| WO (1) | WO2006137173A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009051271A1 (en) * | 2007-10-16 | 2009-04-23 | Ube Nitto Kasei Co., Ltd. | Photocatalytic film, method for production of photocatalytic film, article, and hydrophilization method |
| WO2009122750A1 (en) | 2008-04-03 | 2009-10-08 | 味の素株式会社 | Feed additive composition for ruminants and method of producing the same |
| CN104269106A (en) * | 2014-10-15 | 2015-01-07 | 张建新 | Fabrication method of hydrolytic printed signboard |
| CN106739610A (en) * | 2016-12-27 | 2017-05-31 | 安徽星光标识***有限公司 | A kind of manufacture craft for printing label |
| CN108671903A (en) * | 2018-05-18 | 2018-10-19 | 福州大学 | A kind of optic catalytic composite material of graphene package titanium dioxide diauxic growth |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009027155A (en) * | 2007-06-19 | 2009-02-05 | Ube Nitto Kasei Co Ltd | Coating liquid for forming ink-accepting film, manufacturing method therefor, the ink-accepting film, laminated substrate and wiring material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000208796A (en) * | 1999-01-13 | 2000-07-28 | Dainippon Printing Co Ltd | Surface protective sheet for solar cell module and solar cell using the same |
| JP4048912B2 (en) * | 2002-10-22 | 2008-02-20 | 松下電工株式会社 | Surface antifouling composite resin film, surface antifouling article, decorative board |
-
2005
- 2005-06-22 JP JP2005182473A patent/JP2007001088A/en active Pending
- 2005-07-12 WO PCT/JP2005/012870 patent/WO2006137173A1/en active Application Filing
- 2005-07-14 TW TW094123875A patent/TW200700477A/en unknown
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009051271A1 (en) * | 2007-10-16 | 2009-04-23 | Ube Nitto Kasei Co., Ltd. | Photocatalytic film, method for production of photocatalytic film, article, and hydrophilization method |
| JP2009208062A (en) * | 2007-10-16 | 2009-09-17 | Ube Nitto Kasei Co Ltd | Photocatalytic film, its manufacturing method, article, and hydrophilization method |
| WO2009122750A1 (en) | 2008-04-03 | 2009-10-08 | 味の素株式会社 | Feed additive composition for ruminants and method of producing the same |
| CN104269106A (en) * | 2014-10-15 | 2015-01-07 | 张建新 | Fabrication method of hydrolytic printed signboard |
| CN106739610A (en) * | 2016-12-27 | 2017-05-31 | 安徽星光标识***有限公司 | A kind of manufacture craft for printing label |
| CN108671903A (en) * | 2018-05-18 | 2018-10-19 | 福州大学 | A kind of optic catalytic composite material of graphene package titanium dioxide diauxic growth |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200700477A (en) | 2007-01-01 |
| WO2006137173A1 (en) | 2006-12-28 |
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