WO2011013497A1 - Photocurable hydrophilic coating agent, hydrophilic coating film, and hydrophilically coated article - Google Patents
Photocurable hydrophilic coating agent, hydrophilic coating film, and hydrophilically coated article Download PDFInfo
- Publication number
- WO2011013497A1 WO2011013497A1 PCT/JP2010/061633 JP2010061633W WO2011013497A1 WO 2011013497 A1 WO2011013497 A1 WO 2011013497A1 JP 2010061633 W JP2010061633 W JP 2010061633W WO 2011013497 A1 WO2011013497 A1 WO 2011013497A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mass
- group
- meth
- hydrophilic coating
- hydrophilic
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
- C08G18/6254—Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8108—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group
- C08G18/8116—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate group
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
- C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/343—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate in the form of urethane links
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
Definitions
- the acrylic resin (A) in the present invention comprises a copolymer obtained by copolymerizing 40 to 95% by mass of a radically polymerizable monomer having a hydrophilic group and 5 to 60% by mass of a (meth) acrylic acid alkyl monomer. Have as.
- radical polymerizable monomer having an amino group as a hydrophilic group examples include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate and the like.
- the (meth) acrylic acid alkyl monomer for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, And dicyclopentadienyl (meth) acrylate.
- methyl (meth) acrylate is preferably used from the point which is excellent in hardness.
- the content of the radically polymerizable monomer having a hydroxyl group is 5 to 30% by mass, preferably 10 to 20% by mass, based on the total amount of monomers constituting the acrylic resin (A).
- the content ratio of the radically polymerizable monomer having a hydroxyl group is less than 5% by mass, sufficient hydrophilicity tends not to be obtained, and when it exceeds 30% by mass, the coating properties such as water resistance are poor. There is a tendency to decrease.
- the hydroxyl value of the acrylic resin (A) is 1 to 100 mgKOH / g, preferably 5 to 90 mgKOH / g.
- the hydroxyl value of the (meth) acryloyl group-containing acrylic polyol (A1) is in the range of 1 to 90 mgKOH / g, preferably 5 to 80 mgKOH / g.
- the hydroxyl value is too low, the hydrophilicity of the resulting film tends to be insufficient.
- the hydroxyl value is too high, the coating film properties such as water resistance tend to decrease.
- the hydroxyl value is a value measured by potentiometric titration in accordance with JIS-K0070.
- ethylene oxide chain in polyoxyethylene-polyoxypropylene block copolymer (B) [(total mass of ethylene oxide chain in copolymer) / (ethylene oxide chain and propylene oxide chain in copolymer) The total mass) ⁇ 100] is preferably 5 to 99% by mass, more preferably 10 to 90% by mass, and particularly preferably 10 to 70% by mass.
- Examples of the photopolymerizable polyfunctional compound having two photopolymerizable groups in one molecule include alkylenes such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and neopentyl glycol di (meth) acrylate.
- Examples of the photopolymerizable polyfunctional compound having three photopolymerizable groups in one molecule include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, and tris.
- Examples of the photopolymerizable polyfunctional compound having four photopolymerizable groups in one molecule include ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, and their modified alkylene oxides. .
- Examples of the photopolymerizable polyfunctional compound having five photopolymerizable groups in one molecule include dipentaerythritol penta (meth) acrylate or their modified alkylene oxides.
- benzophenone photopolymerization initiator examples include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide, and 2,4,6-trimethylbenzophenone.
- acylphosphine oxide photopolymerization initiator examples include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like.
- the photocurable hydrophilic coating agent of the present invention includes an ultraviolet absorber, an antioxidant, a light stabilizer, a heat stabilizer, an antistatic agent, and an antifoaming agent as necessary within the range not impairing the effects of the present invention.
- Various additives such as these may be further blended.
- the applied photocurable hydrophilic coating is irradiated with light such as ultraviolet rays to be photocured to form a hydrophilic film. Since the photocurable hydrophilic coating of the present invention uses photocuring for film formation, it can form a film with higher productivity than the thermosetting hydrophilic coating. There is no risk of the material being thermally degraded.
- composition in Table 2 is represented by the resin content.
- the ratio of the number of moles of isocyanate groups (NCO) to the number of moles of hydroxyl groups (OH) (NCO / OH) was 0.5, and that of Synthesis Example 16 was 1.
- gelation occurred during the reaction, and the reaction was completed.
- Table 2 summarizes the composition of the reaction components in Synthesis Examples 9 to 16, and the hydroxyl value (mgKOH / g), weight average molecular weight (Mw), viscosity (Gardner / 25 ° C.) and nonvolatile content concentration of the obtained reaction product. Show.
- the coatings obtained in Comparative Examples 1 to 5 have an ⁇ E of 3.2 or more in the oil wiping evaluation, and are found to have poor fingerprint wiping properties. Further, the water contact angle and oil contact angle were high, and the hydrophilicity and lipophilicity were poor. This is because the acrylic polyol does not contain a radically polymerizable monomer unit having a hydrophilic group other than a hydroxyl group, or the content ratio is low, so that the hydrophilicity of the film becomes poor, so that the oil content becomes unemployed during wiping. This is thought to be because it becomes difficult to migrate.
- the hydrophilic coating agent of the present invention can form a hydrophilic coating or hydrophilic coating having a high fingerprint wiping property and a high surface hardness on the surface of an article, so that it is disposed in the outermost layer of an image display device such as a display.
- the hydrophilic coating agent of the present invention is effective not only for wiping off fingerprints but also for wiping off other oily soils.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
また、特許文献2に記載された耐指紋性光硬化性組成物を用いてコート層が表面に形成されたタッチパネルにおいては、コート層が水酸基を含有しないために親水性に乏しく、指紋汚れとタッチパネルの界面に水が浸透して充分に皮脂を浮き出させて拭き取ることが困難であった。 In the touch panel obtained by applying the hard coat film described in Patent Document 1, the surface has poor hydrophilicity. Therefore, when the fingerprint stain is wiped with water, water penetrates into the interface between the fingerprint stain and the touch panel. It was difficult to lift off the sebum sufficiently.
Moreover, in the touch panel in which the coating layer was formed on the surface using the fingerprint-resistant photocurable composition described in Patent Document 2, since the coating layer does not contain a hydroxyl group, the coating layer has poor hydrophilicity, and the fingerprint stain and the touch panel It was difficult for water to permeate into the interface and sufficiently raise the sebum and wipe it off.
このような光硬化型親水性被覆剤を用いた場合には、(メタ)アクリロイル基含有アクリル樹脂中(A1)の(メタ)アクリロイル基が架橋点となって、光重合性多官能化合物(C)と架橋を形成するために、より硬度の高い被膜が得られる。 The acrylic resin (A) preferably has a hydroxyl value in the range of 1 to 100 mgKOH / g. The acrylic resin (A) comprises 5 to 30% by mass of a radically polymerizable monomer having a hydroxyl group, 20 to 90% by mass of a radically polymerizable monomer having a hydrophilic group other than a hydroxyl group, and a (meth) acrylic acid alkyl ester. A (meth) acryloyl group-containing acrylic polyol (A1) obtained by adding an isocyanate group-containing (meth) acrylate to a copolymer obtained by copolymerizing 5 to 60% by mass of monomers is preferable.
When such a photocurable hydrophilic coating agent is used, the (meth) acryloyl group in (A1) in the (meth) acryloyl group-containing acrylic resin serves as a crosslinking point, and the photopolymerizable polyfunctional compound (C ) And a crosslink, a higher hardness film is obtained.
また、本発明の親水性被塗物は、基材の表面に上記の光硬化型親水性被覆剤を塗布した後、光硬化させて得られる。 The hydrophilic coating film of the present invention is obtained by photocuring the above-mentioned photocurable hydrophilic coating agent.
The hydrophilic article of the present invention is obtained by applying the above-mentioned photocurable hydrophilic coating to the surface of a substrate and then photocuring it.
本発明におけるアクリル樹脂(A)は、親水性基を有するラジカル重合性モノマー 40~95質量%および(メタ)アクリル酸アルキルモノマー 5~60質量%を共重合して得られる共重合体を主鎖として有する。 <Acrylic resin (A)>
The acrylic resin (A) in the present invention comprises a copolymer obtained by copolymerizing 40 to 95% by mass of a radically polymerizable monomer having a hydrophilic group and 5 to 60% by mass of a (meth) acrylic acid alkyl monomer. Have as.
具体的には、親水性基を有するラジカル重合性モノマーは、水酸基を有するラジカル重合性モノマーまたは水酸基以外の親水性基を有するラジカル重合性モノマーを単独で使用することができる。また、水酸基を有するラジカル重合性モノマーと水酸基以外の親水性基を有するラジカル重合性モノマーとを組み合わせて用いてもよい。
水酸基以外の親水性基を有するラジカル重合性モノマーは、ジメチルアクリルアミドであるのが好ましい。 The radically polymerizable monomer having a hydrophilic group imparts hydrophilicity to the acrylic resin. The radical polymerizable monomer having such a hydrophilic group is a monomer having a radical polymerizable unsaturated bond and further having a hydrophilic group such as a hydroxyl group, an amide group, a polyalkylene glycol group, and an amino group. Each monomer may be used alone, or two or more monomers having different hydrophilic groups may be used.
Specifically, as the radical polymerizable monomer having a hydrophilic group, a radical polymerizable monomer having a hydroxyl group or a radical polymerizable monomer having a hydrophilic group other than a hydroxyl group can be used alone. Moreover, you may use combining the radically polymerizable monomer which has a hydroxyl group, and the radically polymerizable monomer which has hydrophilic groups other than a hydroxyl group.
The radical polymerizable monomer having a hydrophilic group other than a hydroxyl group is preferably dimethylacrylamide.
誘導体としては、例えば、イソシアネート基をブロック剤でマスキングしたイソシアネート基を有する(メタ)アクリレート等が挙げられる。その具体例としては、メタクリル酸2-(0-[1’-メチルプロピリデンアミノ]カルボキシアミノ)エチル(昭和電工(株)製の商品名「カレンズMOI-BM」)等が挙げられる。これらは単独で用いても2種以上を組み合わせて用いてもよい。 As the isocyanate group-containing (meth) acrylate, for example, 2-acryloyloxyethyl isocyanate (trade name “KARENZ MOI” manufactured by Showa Denko KK), 2-methacryloyloxyethyl isocyanate, (meth) acryloyl group is carbon. Examples thereof include (meth) acryloyl isocyanate or a derivative thereof bonded to an isocyanate group via an alkylene group of 2 to 6.
Examples of the derivative include (meth) acrylate having an isocyanate group obtained by masking an isocyanate group with a blocking agent. Specific examples thereof include 2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate (trade name “Karenz MOI-BM” manufactured by Showa Denko KK). These may be used alone or in combination of two or more.
また、(メタ)アクリロイル基含有アクリルポリオール(A1)の水酸基価は、1~90mgKOH/g、好ましくは5~80mgKOH/gの範囲であるのがよい。
水酸基価が低すぎる場合には、得られる被膜の親水性が不充分になる傾向がある。また、水酸基価が高すぎる場合には、耐水性等の塗膜物性が低下する傾向がある。なお、水酸基価は、JIS-K0070に準拠して電位差滴定法により測定された値である。 The hydroxyl value of the acrylic resin (A) is 1 to 100 mgKOH / g, preferably 5 to 90 mgKOH / g.
The hydroxyl value of the (meth) acryloyl group-containing acrylic polyol (A1) is in the range of 1 to 90 mgKOH / g, preferably 5 to 80 mgKOH / g.
When the hydroxyl value is too low, the hydrophilicity of the resulting film tends to be insufficient. Moreover, when the hydroxyl value is too high, the coating film properties such as water resistance tend to decrease. The hydroxyl value is a value measured by potentiometric titration in accordance with JIS-K0070.
ポリオキシエチレン-ポリオキシプロピレンブロック共重合体(B)は、形成される被膜に親水性および親油性を付与する成分である。 <Polyoxyethylene-polyoxypropylene block copolymer (B)>
The polyoxyethylene-polyoxypropylene block copolymer (B) is a component that imparts hydrophilicity and lipophilicity to the formed film.
光重合性多官能化合物(C)は光重合することにより高い硬度を有する塗膜形成成分として作用する。 <Photopolymerizable polyfunctional compound (C)>
The photopolymerizable polyfunctional compound (C) acts as a film forming component having high hardness by photopolymerization.
本発明の光硬化型親水性被覆剤における樹脂成分中のアクリル樹脂(A)の含有割合は、樹脂成分の総質量に対して3~40質量%であり、好ましくは6~35質量%、さらに好ましくは、10~30質量%の範囲である。アクリル樹脂(A)の含有割合が、樹脂成分の総質量に対して3質量%未満の場合には、得られる親水性被膜に充分な親水性および親油性が低下するために親水性被膜の指紋拭き取り性が低下する。また、アクリル樹脂(A)の含有割合が40質量%を超える場合には得られる親水性被膜に充分な表面硬度が低下する。 <Photocurable hydrophilic coating agent>
The content ratio of the acrylic resin (A) in the resin component in the photocurable hydrophilic coating agent of the present invention is 3 to 40% by mass, preferably 6 to 35% by mass, further based on the total mass of the resin component. Preferably, it is in the range of 10 to 30% by mass. When the content ratio of the acrylic resin (A) is less than 3% by mass with respect to the total mass of the resin component, hydrophilicity and lipophilicity sufficient for the obtained hydrophilic coating are lowered, and thus the fingerprint of the hydrophilic coating is reduced. The wiping property decreases. Moreover, when the content rate of an acrylic resin (A) exceeds 40 mass%, surface hardness sufficient for the hydrophilic film obtained will fall.
(合成例1)
反応容器中に、溶媒としてメチルエチルケトン(MEK)233部を仕込み、70℃まで昇温した。 << Synthesis Example of Acrylic Resin (A) >>
(Synthesis Example 1)
In a reaction vessel, 233 parts of methyl ethyl ketone (MEK) was charged as a solvent, and the temperature was raised to 70 ° C.
モノマー成分として、MMA 30部、DMAA 50部、および2-HEA 20部からなるモノマー成分を用いた以外は合成例1と同様にして、アクリルポリオールを含有する樹脂溶液を得た。得られたアクリルポリオールの水酸基価は31mgKOH/gであり、重量平均分子量(Mw)は10000であった。また、得られた樹脂溶液の粘度(ガードナー/25℃)はA4であった。 (Synthesis Example 2)
A resin solution containing an acrylic polyol was obtained in the same manner as in Synthesis Example 1 except that a monomer component consisting of 30 parts of MMA, 50 parts of DMAA, and 20 parts of 2-HEA was used as the monomer component. The obtained acrylic polyol had a hydroxyl value of 31 mgKOH / g and a weight average molecular weight (Mw) of 10,000. Moreover, the viscosity (Gardner / 25 degreeC) of the obtained resin solution was A4.
モノマー成分として、MMA 10部、DMAA 80部、および2-HEA 10部からなるモノマー成分を用いた以外は合成例1と同様にして、アクリルポリオールを含有する樹脂溶液を得た。得られたアクリルポリオールの水酸基価は16mgKOH/gであり、重量平均分子量(Mw)は13000であった。また、得られた樹脂溶液の粘度(ガードナー/25℃)はA4であった。 (Synthesis Example 3)
A resin solution containing an acrylic polyol was obtained in the same manner as in Synthesis Example 1 except that a monomer component consisting of 10 parts of MMA, 80 parts of DMAA, and 10 parts of 2-HEA was used as the monomer component. The obtained acrylic polyol had a hydroxyl value of 16 mgKOH / g and a weight average molecular weight (Mw) of 13,000. Moreover, the viscosity (Gardner / 25 degreeC) of the obtained resin solution was A4.
モノマー成分として、MMA 10部、DMAA 70部、および2-HEA 20部からなるモノマー成分を用いた以外は合成例1と同様にして、アクリルポリオールを含有する樹脂溶液を得た。得られたアクリルポリオールの水酸基価は31mgKOH/gであり、重量平均分子量(Mw)は11000であった。また、得られた樹脂溶液の粘度(ガードナー/25℃)はA4であった。 (Synthesis Example 4)
A resin solution containing an acrylic polyol was obtained in the same manner as in Synthesis Example 1 except that a monomer component consisting of 10 parts of MMA, 70 parts of DMAA, and 20 parts of 2-HEA was used as the monomer component. The obtained acrylic polyol had a hydroxyl value of 31 mgKOH / g and a weight average molecular weight (Mw) of 11,000. Moreover, the viscosity (Gardner / 25 degreeC) of the obtained resin solution was A4.
モノマー成分として、MMA 40部、メトキシポリエチレングリコール400メタクリレート(新中村化学工業(株)製の「NKエステル M-90G」) 50部、および2-HEA 10部からなるモノマー成分を用いた以外は合成例1と同様にして、アクリルポリオールを含有する樹脂溶液を得た。得られたアクリルポリオールの水酸基価は20mgKOH/gであり、重量平均分子量(Mw)は11000であった。また、得られた樹脂溶液の粘度(ガードナー/25℃)はA4であった。 (Synthesis Example 5)
As the monomer component, synthesis was performed except that 40 parts of MMA, 50 parts of methoxypolyethylene glycol 400 methacrylate (“NK ester M-90G” manufactured by Shin-Nakamura Chemical Co., Ltd.), and 10 parts of 2-HEA were used. In the same manner as in Example 1, a resin solution containing an acrylic polyol was obtained. The obtained acrylic polyol had a hydroxyl value of 20 mgKOH / g and a weight average molecular weight (Mw) of 11,000. Moreover, the viscosity (Gardner / 25 degreeC) of the obtained resin solution was A4.
モノマー成分として、MMA 90部、および2-HEA 10部からなるモノマー成分を用いた以外は合成例1と同様にして、アクリルポリオールを含有する樹脂溶液を得た。得られたアクリルポリオールの水酸基価は16mgKOH/gであり、重量平均分子量(Mw)は10000であった。また、得られた樹脂溶液の粘度(ガードナー/25℃)はA4であった。 (Synthesis Example 6)
A resin solution containing an acrylic polyol was obtained in the same manner as in Synthesis Example 1 except that a monomer component consisting of 90 parts of MMA and 10 parts of 2-HEA was used as the monomer component. The obtained acrylic polyol had a hydroxyl value of 16 mgKOH / g and a weight average molecular weight (Mw) of 10,000. Moreover, the viscosity (Gardner / 25 degreeC) of the obtained resin solution was A4.
モノマー成分として、MMA 100部からなるモノマー成分を用いた以外は合成例1と同様にして、アクリル樹脂を含有する樹脂溶液を得た。得られたアクリル樹脂の水酸基価は0であり、重量平均分子量(Mw)は12000であった。また、得られた樹脂溶液の粘度(ガードナー/25℃)はA4であった。 (Synthesis Example 7)
A resin solution containing an acrylic resin was obtained in the same manner as in Synthesis Example 1 except that a monomer component consisting of 100 parts of MMA was used as the monomer component. The obtained acrylic resin had a hydroxyl value of 0 and a weight average molecular weight (Mw) of 12,000. Moreover, the viscosity (Gardner / 25 degreeC) of the obtained resin solution was A4.
モノマー成分として、MMA 80部、DMAA 10部、および2-HEA 10部からなるモノマー成分を用いた以外は合成例1と同様にして、アクリルポリオールを含有する樹脂溶液を得た。得られたアクリルポリオールの水酸基価は16mgKOH/gであり、重量平均分子量(Mw)は10000であった。また、得られた樹脂溶液の粘度(ガードナー/25℃)はA4であった。
以上の結果を表1にまとめて示す。 (Synthesis Example 8)
A resin solution containing an acrylic polyol was obtained in the same manner as in Synthesis Example 1 except that a monomer component consisting of 80 parts of MMA, 10 parts of DMAA, and 10 parts of 2-HEA was used as the monomer component. The obtained acrylic polyol had a hydroxyl value of 16 mgKOH / g and a weight average molecular weight (Mw) of 10,000. Moreover, the viscosity (Gardner / 25 degreeC) of the obtained resin solution was A4.
The above results are summarized in Table 1.
(合成例9~16)
表2の組成に従って、反応容器中に、合成例1~6および合成例8で得られたアクリルポリオールの樹脂溶液(不揮発分30%)、2-メタクリロイルオキシエチルイソシアネート(MOI)(昭和電工(株)製の「カレンズMOI」)、ハイドロキノン(HQ)、ジブチルスズジラウレート、MEKを仕込み、酸素を吹き込みながら60℃に温度制御して6時間反応させることにより、各アクリルポリオールとイソシアネート基含有メタクリレートとの反応物を得た。なお、表2中の組成は樹脂分で表している。合成例9~15については水酸基(OH)のモル数に対するイソシアネート基(NCO)のモル数の割合(NCO/OH)は0.5であり、合成例16については1であった。合成例16では反応途中でゲル化を起こり、反応を終了した。 << Synthesis of reaction product (A1) of acrylic polyol and isocyanate group-containing methacrylate >>
(Synthesis Examples 9 to 16)
According to the composition in Table 2, in the reaction vessel, the acrylic polyol resin solutions obtained in Synthesis Examples 1 to 6 and Synthesis Example 8 (non-volatile content 30%), 2-methacryloyloxyethyl isocyanate (MOI) (Showa Denko K.K. ) "Karens MOI"), hydroquinone (HQ), dibutyltin dilaurate, MEK, and the reaction between each acrylic polyol and isocyanate group-containing methacrylate by reacting for 6 hours while controlling the temperature at 60 ° C while blowing oxygen. I got a thing. In addition, the composition in Table 2 is represented by the resin content. In Synthesis Examples 9 to 15, the ratio of the number of moles of isocyanate groups (NCO) to the number of moles of hydroxyl groups (OH) (NCO / OH) was 0.5, and that of Synthesis Example 16 was 1. In Synthesis Example 16, gelation occurred during the reaction, and the reaction was completed.
〈ポリエーテルポリオール(B)〉
・ポリエチレンオキサイド-ポリプロピレンオキサイドグリコールエーテル:U105(第一工業製薬(株)製の「エバンU105」、重量平均分子量 6400、エチレンオキシド含有率 50質量%)
〈1分子中に2以上の光重合性基を有する光重合性多官能化合物(C)〉
・ペンタエリスリトールトリアクリレートヘキサメチレンジイソシアネートウレタンプレポリマー:UA-306H(共栄社化学(株)製の「UA-306H」;1分子中に6個の光重合性基を有する。)
・フェニルグリシジルエーテルアクリレートヘキサメチレンジイソシアネートウレタンプレポリマー:AH-600(共栄社化学(株)製の「AH-600」;1分子中に2個の光重合性基を有する。)
・ジペンタエリスリトールヘキサアクリレート:DPE-6A(共栄社化学(株)製の「ライトアクリレートDPE-6A」;1分子中に6個の光重合性基を有する。)
・ペンタエリスリトールトリアクリレート:PE-3A(共栄社化学(株)製の「ライトアクリレートPE-3A」;1分子中に3個の光重合性基を有する。)
〈光重合開始剤〉
2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン:DAROCUR 1173(チバ・スペシャルティ・ケミカルズ(株)製の「DAROCUR 1173」)
〈光反応性希釈剤〉
アクリロイルモルフォリン:ACMO(興人(株)製の「ACMO」) Other raw materials used in this example will be described collectively below.
<Polyether polyol (B)>
Polyethylene oxide-polypropylene oxide glycol ether: U105 (“Evan U105” manufactured by Daiichi Kogyo Seiyaku Co., Ltd., weight average molecular weight 6400, ethylene oxide content 50 mass%)
<Photopolymerizable polyfunctional compound (C) having two or more photopolymerizable groups in one molecule>
Pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer: UA-306H (“UA-306H” manufactured by Kyoeisha Chemical Co., Ltd .; having 6 photopolymerizable groups in one molecule)
Phenyl glycidyl ether acrylate hexamethylene diisocyanate urethane prepolymer: AH-600 (“AH-600” manufactured by Kyoeisha Chemical Co., Ltd .; having two photopolymerizable groups in one molecule)
Dipentaerythritol hexaacrylate: DPE-6A (“Light acrylate DPE-6A” manufactured by Kyoeisha Chemical Co., Ltd .; having 6 photopolymerizable groups in one molecule)
Pentaerythritol triacrylate: PE-3A (“Light acrylate PE-3A” manufactured by Kyoeisha Chemical Co., Ltd .; having three photopolymerizable groups in one molecule)
<Photopolymerization initiator>
2-hydroxy-2-methyl-1-phenyl-propan-1-one: DAROCUR 1173 ("DAROCUR 1173" manufactured by Ciba Specialty Chemicals Co., Ltd.)
<Photoreactive diluent>
Acryloylmorpholine: ACMO (“ACMO” manufactured by Kojin Co., Ltd.)
合成例1で得られたアクリルポリオールを含有する、不揮発分30%の樹脂溶液10部(樹脂分3部)、ポリエチレンオキサイド-ポリプロピレンオキサイドグリコールエーテル(U105)0.5部、ペンタエリスリトールトリアクリレートヘキサメチレンジイソシアネートウレタンプレポリマー(UA-306H)27部、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン(DAROCUR 1173)0.8部、およびMEK63部を撹拌混合することにより光硬化型親水性被覆剤を調製した。 Example 1
10 parts of a resin solution containing 30% non-volatile content (3 parts of resin) containing acrylic polyol obtained in Synthesis Example 1, 0.5 parts of polyethylene oxide-polypropylene oxide glycol ether (U105), pentaerythritol triacrylate hexamethylene Light curing type by stirring and mixing 27 parts of diisocyanate urethane prepolymer (UA-306H), 0.8 part of 2-hydroxy-2-methyl-1-phenyl-propan-1-one (DAROCUR 1173) and 63 parts of MEK A hydrophilic coating was prepared.
形成された硬化膜を以下の評価方法に従って評価した。 The obtained photocurable hydrophilic coating was coated with a bar coater No. 1 so that the dry film thickness was about 5 μm. 10 was applied onto a polyethylene terephthalate (PET) film. Then, after removing the solvent by heating at 80 ° C. for 2 minutes, the photocurable hydrophilic coating applied by exposing to ultraviolet light at 400 mJ / cm 2 using a high pressure mercury lamp (120 W / cm) is cured. I let you.
The formed cured film was evaluated according to the following evaluation methods.
JIS K 5600-1-1の4.4「塗膜の概観」の試験法に準拠して、下記の基準により透明性およびクラックの有無を判定した。
優:無色透明であり、クラックなし。
劣:白濁し、またはクラックが発生した。 <Appearance of coating>
Based on the test method of 4.4 “Overview of coating film” of JIS K 5600-1-1, the transparency and the presence or absence of cracks were determined according to the following criteria.
Excellent: colorless and transparent, no cracks.
Inferior: White turbidity or crack occurred.
JIS K 5600-5-4「引っ掻き硬度(鉛筆法)」の試験法に準拠して、鉛筆硬度試験を実施した。鉛筆硬度試験においては、硬度が低い方から高いほうにB、HB、F、Hの順に並べられる。また、「H」の前に付く数字が大きいほど硬度が高く、「B」の前に付く数字が大きいほど硬度が低い。 <Pencil hardness>
A pencil hardness test was carried out according to the test method of JIS K 5600-5-4 “Scratch hardness (pencil method)”. In the pencil hardness test, B, HB, F, and H are arranged in order from the lower hardness to the higher hardness. Also, the greater the number that precedes “H”, the higher the hardness, and the greater the number that precedes “B”, the lower the hardness.
JIS K 5600-5-6の「クロスカット法」の試験法に準拠して、密着性試験を実施した。
具体的には、試験板に塗布した被膜をカッターナイフで縦横方向に切断して基材に達するような100個のクロスカット(切断片)を形成した。そして、クロスカット上に粘着テープ(ニチバン(株)製の「ニチバンテープ1号」)を貼り付けた。そして、貼り付けられたセロハン粘着テープを剥離した後に、剥離せずに残ったクロスカットの数を数えた。 <Adhesion>
An adhesion test was performed in accordance with the “cross-cut method” test method of JIS K 5600-5-6.
Specifically, 100 crosscuts (cut pieces) were formed by cutting the coating applied to the test plate in the vertical and horizontal directions with a cutter knife and reaching the substrate. Then, an adhesive tape (“Nichiban Tape No. 1” manufactured by Nichiban Co., Ltd.) was pasted on the crosscut. And after peeling the cellophane adhesive tape affixed, the number of crosscuts which remained without peeling was counted.
試験板の表面にノルマルヘキサデカンを0.1g垂らした。そして、試験板表面に付着したノルマルヘキサデカンをセルロース製不織布(旭化成(株)製の「ベンコットM-3」)により、300gの荷重を掛けて10回拭き取った。ヘーズメーターNDH5000(日本電色工業社製)を用いて試験前および試験後の試験板表面のヘーズ(濁度)を測定した。そして、試験前および試験後のヘーズの差ΔEを算出した。このΔEの値が小さいほど、皮脂に起因する指紋跡の拭き取り性が良好であり、すなわち、防汚性が良好であることを示す。 <Oil wiping off>
0.1 g of normal hexadecane was dropped on the surface of the test plate. Then, normal hexadecane adhering to the test plate surface was wiped 10 times with a cellulose nonwoven fabric (“Bencot M-3” manufactured by Asahi Kasei Co., Ltd.) under a load of 300 g. Using a haze meter NDH5000 (manufactured by Nippon Denshoku Industries Co., Ltd.), haze (turbidity) on the surface of the test plate before and after the test was measured. Then, a haze difference ΔE before and after the test was calculated. It shows that the smaller the value of ΔE, the better the wiping property of fingerprint marks caused by sebum, that is, the better the antifouling property.
試験板表面に0.4μLの水滴を垂らし、接触角計(協和界面科学社製の「Drop Master500」)により接触角を測定した。 <Water contact angle>
A 0.4 μL water droplet was dropped on the surface of the test plate, and the contact angle was measured with a contact angle meter (“Drop Master 500” manufactured by Kyowa Interface Science Co., Ltd.).
試験板表面に0.4μLのオレイン酸を垂らし、接触角計(協和界面科学社製の「Drop Master500」)により接触角を測定した。
これらの試験結果を表3に示す。 <Oil contact angle>
0.4 μL of oleic acid was dropped on the test plate surface, and the contact angle was measured with a contact angle meter (“Drop Master 500” manufactured by Kyowa Interface Science Co., Ltd.).
These test results are shown in Table 3.
表3および表4の組成に従って光硬化型親水性被覆剤を調製した以外は、実施例1と同様にして光硬化型親水性被覆剤を得た。結果を表3および表4に示す。 (Examples 2 to 20 and Comparative Examples 1 to 14)
A photocurable hydrophilic coating agent was obtained in the same manner as in Example 1 except that a photocurable hydrophilic coating agent was prepared according to the compositions in Tables 3 and 4. The results are shown in Table 3 and Table 4.
なお、本発明の親水性被覆剤は、指紋の拭き取りだけでなく、他の油分汚れの拭き取りにも有効である。 The hydrophilic coating agent of the present invention can form a hydrophilic coating or hydrophilic coating having a high fingerprint wiping property and a high surface hardness on the surface of an article, so that it is disposed in the outermost layer of an image display device such as a display. The surface of the image display panel to be installed, the surface of the surface protective film to be bonded to the surface to protect the image display panel, the surface of the lens such as glasses and goggles, the window material for construction, vehicle use, and instrumentation In addition to the surface, etc., it can be suitably used for the surface of the touch panel.
The hydrophilic coating agent of the present invention is effective not only for wiping off fingerprints but also for wiping off other oily soils.
Claims (9)
- (A)アクリル樹脂 3~40質量%、(B)ポリオキシエチレン-ポリオキシプロピレンブロック共重合体 0.1~5質量%、および(C)1分子中に2以上の光重合性基を有する光重合性多官能化合物 55~95質量%を含む樹脂成分を含有し、
前記アクリル樹脂(A)は、親水性基を有するラジカル重合性モノマー40~95質量%および(メタ)アクリル酸アルキルエステルモノマー5~60質量%を共重合して得られる共重合体を主鎖として有することを特徴とする光硬化型親水性被覆剤。 (A) Acrylic resin 3 to 40% by mass, (B) Polyoxyethylene-polyoxypropylene block copolymer 0.1 to 5% by mass, and (C) Two or more photopolymerizable groups in one molecule A resin component containing 55 to 95% by mass of a photopolymerizable polyfunctional compound;
The acrylic resin (A) has, as a main chain, a copolymer obtained by copolymerizing 40 to 95% by mass of a radically polymerizable monomer having a hydrophilic group and 5 to 60% by mass of a (meth) acrylic acid alkyl ester monomer. A photocurable hydrophilic coating, characterized by comprising: - 前記アクリル樹脂(A)は、水酸基価が1~100mgKOH/gの範囲である請求項1に記載の光硬化型親水性被覆剤。 The photocurable hydrophilic coating according to claim 1, wherein the acrylic resin (A) has a hydroxyl value in the range of 1 to 100 mgKOH / g.
- 前記アクリル樹脂(A)が、水酸基を有するラジカル重合性モノマー5~30質量%、水酸基以外の親水性基を有するラジカル重合性モノマー20~90質量%、および(メタ)アクリル酸アルキルエステルモノマー5~60質量%を共重合して得られる共重合体に、イソシアネート基含有(メタ)アクリレートを付加して得られる(メタ)アクリロイル基含有アクリルポリオール(A1)である請求項1に記載の光硬化型親水性被覆剤。 The acrylic resin (A) is a radical polymerizable monomer having a hydroxyl group of 5 to 30% by mass, a radical polymerizable monomer having a hydrophilic group other than a hydroxyl group of 20 to 90% by mass, and a (meth) acrylic acid alkyl ester monomer 5 to 5% by mass. The photocurable type according to claim 1, which is a (meth) acryloyl group-containing acrylic polyol (A1) obtained by adding an isocyanate group-containing (meth) acrylate to a copolymer obtained by copolymerizing 60% by mass. Hydrophilic coating agent.
- 前記アクリル樹脂(A)の重量平均分子量が5000~30000の範囲である請求項1に記載の光硬化型親水性被覆剤。 The photocurable hydrophilic coating according to claim 1, wherein the acrylic resin (A) has a weight average molecular weight in the range of 5,000 to 30,000.
- 1個の光重合性基を有する光重合性単官能化合物を樹脂成分中50質量%以下の割合でさらに含有する請求項1に記載の光硬化型親水性被覆剤。 The photocurable hydrophilic coating according to claim 1, further comprising a photopolymerizable monofunctional compound having one photopolymerizable group in a proportion of 50% by mass or less in the resin component.
- 前記親水性基が水酸基、アミド基,ポリアルキレングリコール基またはアミノ基である請求項1に記載の光硬化型親水性被覆剤。 The photocurable hydrophilic coating according to claim 1, wherein the hydrophilic group is a hydroxyl group, an amide group, a polyalkylene glycol group or an amino group.
- 前記親水性基を有するラジカル重合性モノマーのうち、水酸基以外の親水性基を有するラジカル重合性モノマーがジメチルアクリルアミドである請求項1に記載の光硬化型親水性被覆剤。 The photocurable hydrophilic coating agent according to claim 1, wherein, among the radical polymerizable monomers having a hydrophilic group, the radical polymerizable monomer having a hydrophilic group other than a hydroxyl group is dimethylacrylamide.
- 請求項1に記載の光硬化型親水性被覆剤を光硬化させて得られることを特徴とする親水性被膜。 A hydrophilic film obtained by photocuring the photocurable hydrophilic coating agent according to claim 1.
- 請求項1に記載の光硬化型親水性被覆剤を基材の表面に塗布した後、光硬化させて得られることを特徴とする親水性被塗物。 A hydrophilic article to be obtained, which is obtained by applying the photocurable hydrophilic coating agent according to claim 1 to the surface of a substrate and then photocuring it.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201080001424.XA CN102405264B (en) | 2009-07-30 | 2010-07-08 | Photocurable hydrophilic coating agent, hydrophilic coating film, and hydrophilically coated article |
KR1020107023554A KR101315153B1 (en) | 2009-07-30 | 2010-07-08 | Photocuring-type hydrophilic coating agent, hydrophilic film and hydrophilic coated material |
JP2010542419A JP5341105B2 (en) | 2009-07-30 | 2010-07-08 | Photocurable hydrophilic coating, hydrophilic coating, and hydrophilic article |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009-177717 | 2009-07-30 | ||
JP2009177717 | 2009-07-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011013497A1 true WO2011013497A1 (en) | 2011-02-03 |
Family
ID=43529159
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2010/061633 WO2011013497A1 (en) | 2009-07-30 | 2010-07-08 | Photocurable hydrophilic coating agent, hydrophilic coating film, and hydrophilically coated article |
Country Status (4)
Country | Link |
---|---|
JP (1) | JP5341105B2 (en) |
KR (1) | KR101315153B1 (en) |
CN (1) | CN102405264B (en) |
WO (1) | WO2011013497A1 (en) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013161323A (en) * | 2012-02-07 | 2013-08-19 | Riken Technos Corp | Capacitance type touch panel |
WO2013129339A1 (en) * | 2012-03-01 | 2013-09-06 | 株式会社きもと | Surface protective sheet, electronic device, and method for manufacturing electronic device component |
WO2014024686A1 (en) * | 2012-08-10 | 2014-02-13 | ハリマ化成株式会社 | Two-pack type curable coating agent |
WO2014045195A1 (en) | 2012-09-18 | 2014-03-27 | Arjowiggins Security | Method for producing an electronic chip structure and structure produced in this way |
WO2015011804A1 (en) * | 2013-07-24 | 2015-01-29 | ハリマ化成株式会社 | Coating material and coating composition |
JP2016040343A (en) * | 2014-08-12 | 2016-03-24 | 株式会社きもと | Surface protective film, and hard coat film with surface protective film |
JP2016511779A (en) * | 2013-02-26 | 2016-04-21 | エルジー・ケム・リミテッド | Coating composition and plastic film produced therefrom |
JPWO2015022905A1 (en) * | 2013-08-12 | 2017-03-02 | 東邦化学工業株式会社 | Antifogging coating composition |
JP2019123798A (en) * | 2018-01-16 | 2019-07-25 | 共栄社化学株式会社 | Reactive polymer having antifogging property and manufacturing method therefor, resin composition for antifogging |
JP2020063453A (en) * | 2014-03-30 | 2020-04-23 | オムノバ ソリューソンズ インコーポレーティッド | Aqueous dispersion liquid |
JP2021533225A (en) * | 2019-04-01 | 2021-12-02 | エルジー・ケム・リミテッド | Antibacterial Polymer Coating Compositions and Antibacterial Polymer Films |
JPWO2022191147A1 (en) * | 2021-03-11 | 2022-09-15 |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5686228B1 (en) * | 2013-03-27 | 2015-03-18 | Dic株式会社 | Active energy ray-curable composition, cured film thereof, and article having the cured film |
KR101980215B1 (en) * | 2015-09-18 | 2019-05-20 | 주식회사 일진저스템 | Nozzle manufacturing method for cleaning substrate using vibrating body |
CA3029434A1 (en) * | 2016-06-30 | 2018-01-04 | The University Of Akron | Uv-curable contact stabilization coating material for electrical contact surfaces |
JP7082327B2 (en) | 2018-09-12 | 2022-06-08 | 株式会社Ihi | Sideways butt welding method |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01281932A (en) * | 1988-05-09 | 1989-11-13 | Nisshin Steel Co Ltd | Stainless steel sheet excellent in detergency against finger print |
JPH03215589A (en) * | 1989-05-26 | 1991-09-20 | Panelgraphic Corp | Anti-fogging covering |
JPH03247672A (en) * | 1990-02-26 | 1991-11-05 | Nippon Oil & Fats Co Ltd | Ultraviolet ray curing type coating composition and preparation of ultraviolet ray cured film |
JPH047388A (en) * | 1990-04-25 | 1992-01-10 | Kyoto Karitasu:Kk | Non-fogging composition, non-fogging molding and method for preventing fogging |
JPH06172676A (en) * | 1992-12-03 | 1994-06-21 | Nippon Oil & Fats Co Ltd | Uv-curable antifogging agent composition |
JPH0987576A (en) * | 1995-09-22 | 1997-03-31 | Kansai Paint Co Ltd | Composition for hydrophilization treatment and method for hydrophilization treatment |
JP2001131445A (en) * | 1999-10-29 | 2001-05-15 | Mitsubishi Rayon Co Ltd | Coating film resin composition and resin molded article with coating film |
JP2002173633A (en) * | 2000-12-06 | 2002-06-21 | Hitachi Chem Co Ltd | Anti-fogging coating, method for producing the same, method for forming anti-fogging coating film and formed product having anti-fogging coating film |
JP2004359834A (en) * | 2003-06-05 | 2004-12-24 | Mitsubishi Chemicals Corp | Agent for imparting resistance to contamination and contamination-resistant article using the same |
JP2008231163A (en) * | 2007-03-16 | 2008-10-02 | Toppan Printing Co Ltd | Composition for forming hardcoat layer, and hardcoat film obtained using the same and its manufacturing method |
WO2009090803A1 (en) * | 2008-01-15 | 2009-07-23 | Kimoto Co., Ltd. | Curable composition, cured product and laminate |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3247672B2 (en) * | 1999-10-28 | 2002-01-21 | 昇 大森 | Aid for walking on slopes |
CN101481437B (en) * | 2009-01-23 | 2011-04-27 | 华南理工大学 | Preparation of high closeness polyacrylacid ester dispersion |
-
2010
- 2010-07-08 KR KR1020107023554A patent/KR101315153B1/en active IP Right Grant
- 2010-07-08 JP JP2010542419A patent/JP5341105B2/en active Active
- 2010-07-08 CN CN201080001424.XA patent/CN102405264B/en active Active
- 2010-07-08 WO PCT/JP2010/061633 patent/WO2011013497A1/en active Application Filing
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01281932A (en) * | 1988-05-09 | 1989-11-13 | Nisshin Steel Co Ltd | Stainless steel sheet excellent in detergency against finger print |
JPH03215589A (en) * | 1989-05-26 | 1991-09-20 | Panelgraphic Corp | Anti-fogging covering |
JPH03247672A (en) * | 1990-02-26 | 1991-11-05 | Nippon Oil & Fats Co Ltd | Ultraviolet ray curing type coating composition and preparation of ultraviolet ray cured film |
JPH047388A (en) * | 1990-04-25 | 1992-01-10 | Kyoto Karitasu:Kk | Non-fogging composition, non-fogging molding and method for preventing fogging |
JPH06172676A (en) * | 1992-12-03 | 1994-06-21 | Nippon Oil & Fats Co Ltd | Uv-curable antifogging agent composition |
JPH0987576A (en) * | 1995-09-22 | 1997-03-31 | Kansai Paint Co Ltd | Composition for hydrophilization treatment and method for hydrophilization treatment |
JP2001131445A (en) * | 1999-10-29 | 2001-05-15 | Mitsubishi Rayon Co Ltd | Coating film resin composition and resin molded article with coating film |
JP2002173633A (en) * | 2000-12-06 | 2002-06-21 | Hitachi Chem Co Ltd | Anti-fogging coating, method for producing the same, method for forming anti-fogging coating film and formed product having anti-fogging coating film |
JP2004359834A (en) * | 2003-06-05 | 2004-12-24 | Mitsubishi Chemicals Corp | Agent for imparting resistance to contamination and contamination-resistant article using the same |
JP2008231163A (en) * | 2007-03-16 | 2008-10-02 | Toppan Printing Co Ltd | Composition for forming hardcoat layer, and hardcoat film obtained using the same and its manufacturing method |
WO2009090803A1 (en) * | 2008-01-15 | 2009-07-23 | Kimoto Co., Ltd. | Curable composition, cured product and laminate |
Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013161323A (en) * | 2012-02-07 | 2013-08-19 | Riken Technos Corp | Capacitance type touch panel |
WO2013129339A1 (en) * | 2012-03-01 | 2013-09-06 | 株式会社きもと | Surface protective sheet, electronic device, and method for manufacturing electronic device component |
CN104144786A (en) * | 2012-03-01 | 2014-11-12 | 木本股份有限公司 | Surface protective sheet, electronic device, and method for manufacturing electronic device component |
US9692412B2 (en) | 2012-03-01 | 2017-06-27 | Kimoto Co., Ltd. | Surface protective sheet, electronic device, and method for manufacturing electronic device component |
JPWO2013129339A1 (en) * | 2012-03-01 | 2015-07-30 | 株式会社きもと | Surface protection sheet, electronic device and method for manufacturing electronic device component |
WO2014024686A1 (en) * | 2012-08-10 | 2014-02-13 | ハリマ化成株式会社 | Two-pack type curable coating agent |
JP2014037454A (en) * | 2012-08-10 | 2014-02-27 | Harima Chemicals Inc | Two-liquid hardenable coating agent |
KR20150023683A (en) | 2012-08-10 | 2015-03-05 | 하리마 카세이 가부시키가이샤 | Two-pack type curable coating agent |
WO2014045195A1 (en) | 2012-09-18 | 2014-03-27 | Arjowiggins Security | Method for producing an electronic chip structure and structure produced in this way |
JP2016511779A (en) * | 2013-02-26 | 2016-04-21 | エルジー・ケム・リミテッド | Coating composition and plastic film produced therefrom |
WO2015011804A1 (en) * | 2013-07-24 | 2015-01-29 | ハリマ化成株式会社 | Coating material and coating composition |
JPWO2015022905A1 (en) * | 2013-08-12 | 2017-03-02 | 東邦化学工業株式会社 | Antifogging coating composition |
JP7030101B2 (en) | 2014-03-30 | 2022-03-04 | オムノバ ソリューソンズ インコーポレーティッド | Aqueous dispersion |
JP2020063453A (en) * | 2014-03-30 | 2020-04-23 | オムノバ ソリューソンズ インコーポレーティッド | Aqueous dispersion liquid |
JP2016040343A (en) * | 2014-08-12 | 2016-03-24 | 株式会社きもと | Surface protective film, and hard coat film with surface protective film |
JP2019123798A (en) * | 2018-01-16 | 2019-07-25 | 共栄社化学株式会社 | Reactive polymer having antifogging property and manufacturing method therefor, resin composition for antifogging |
JP7051456B2 (en) | 2018-01-16 | 2022-04-11 | 共栄社化学株式会社 | Reactive polymer with anti-fog property, method for producing the same, anti-fog resin composition |
JP2021533225A (en) * | 2019-04-01 | 2021-12-02 | エルジー・ケム・リミテッド | Antibacterial Polymer Coating Compositions and Antibacterial Polymer Films |
JP7066962B2 (en) | 2019-04-01 | 2022-05-16 | エルジー・ケム・リミテッド | Antibacterial polymer coating composition and antibacterial polymer film |
US11958986B2 (en) | 2019-04-01 | 2024-04-16 | Lg Chem, Ltd. | Antibacterial polymer coating composition and antibacterial polymer film |
JPWO2022191147A1 (en) * | 2021-03-11 | 2022-09-15 | ||
WO2022191147A1 (en) * | 2021-03-11 | 2022-09-15 | Kjケミカルズ株式会社 | Coating composition, adhesive or non-adhesive coating layers formed of said coating composition, and a layered body having said coating layers |
JP7429483B2 (en) | 2021-03-11 | 2024-02-08 | Kjケミカルズ株式会社 | Coating composition, adhesive or non-adhesive coating layer comprising the coating composition, and laminate comprising these coating layers |
Also Published As
Publication number | Publication date |
---|---|
JPWO2011013497A1 (en) | 2013-01-07 |
CN102405264B (en) | 2014-03-19 |
JP5341105B2 (en) | 2013-11-13 |
KR20110025894A (en) | 2011-03-14 |
KR101315153B1 (en) | 2013-10-07 |
CN102405264A (en) | 2012-04-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5341105B2 (en) | Photocurable hydrophilic coating, hydrophilic coating, and hydrophilic article | |
KR101553079B1 (en) | Active energy ray-curable resin composition cured film laminate optical recording medium and method for producing cured film | |
KR101726201B1 (en) | Two-pack type curable coating agent | |
KR101322212B1 (en) | Vehicle member and manufacturing method thereof | |
JP6822792B2 (en) | A method for producing a photocurable resin composition, a cured coating and a coated base material formed from the composition, and a cured coating and a coated base material. | |
JP4638954B2 (en) | Fingerprint-resistant photocurable composition and painted product provided with fingerprint-resistant coating layer | |
JP4670745B2 (en) | Antistatic composition, antistatic layer and antistatic film | |
KR102406434B1 (en) | Active energy ray-curable resin composition, coating material, coating film, and film | |
JP2008255301A (en) | Fingerprint-proof photocurable composition, fingerprint-proof film, and optical display device | |
JP2008056789A (en) | Composition for antifouling hard coat | |
TWI753955B (en) | Light-resistant hard coating material | |
KR20160079641A (en) | Photocurable resin composition, cured coating film formed from the composition, and base material with coating film, and method of manufacturing the cured coating film and the base material with coating film | |
JP2013204001A (en) | Active energy ray-curable resin composition and laminate using the same | |
JP6031195B2 (en) | Photocurable resin composition and cured film thereof | |
JP2004244426A (en) | Active energy ray curing composition and use thereof | |
TW201936710A (en) | Fluorine-containing active energy ray-curable composition and article | |
JP2010260905A (en) | Photocurable composition | |
JP6493699B2 (en) | Resin sheet and manufacturing method thereof | |
JP2007070578A (en) | Active energy ray-curable coating composition | |
JP4397023B2 (en) | Curable composition and article | |
JP6147130B2 (en) | Photocurable composition capable of forming a cured coating having anti-fingerprint property, coating and coating substrate thereof | |
WO2018056370A1 (en) | Scratch-resistant hard coating material | |
KR20170011696A (en) | Photo-curable silicone-fluorine modified urethane (metha)acrylate resin having excellent anti-fouling and anti-fingerprinting and resin composition for coating including the same | |
JP4806965B2 (en) | Method for forming antistatic coating | |
JP5221159B2 (en) | Active energy ray-curable coating composition and cured product thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201080001424.X Country of ref document: CN |
|
ENP | Entry into the national phase |
Ref document number: 2010542419 Country of ref document: JP Kind code of ref document: A Ref document number: 20107023554 Country of ref document: KR Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10804244 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 10804244 Country of ref document: EP Kind code of ref document: A1 |