WO2016047430A1 - 防曇剤組成物及びこれを用いた防曇性物品 - Google Patents
防曇剤組成物及びこれを用いた防曇性物品 Download PDFInfo
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- WO2016047430A1 WO2016047430A1 PCT/JP2015/075382 JP2015075382W WO2016047430A1 WO 2016047430 A1 WO2016047430 A1 WO 2016047430A1 JP 2015075382 W JP2015075382 W JP 2015075382W WO 2016047430 A1 WO2016047430 A1 WO 2016047430A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
- C03C17/322—Polyurethanes or polyisocyanates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
- C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
- C08G18/8077—Oximes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8093—Compounds containing active methylene groups
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- 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
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/24—Homopolymers or copolymers of amides or imides
- C09D133/26—Homopolymers or copolymers of acrylamide or methacrylamide
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
Definitions
- the present invention relates to an antifogging agent composition having excellent antifogging performance and an antifogging article using the same.
- a lighting device such as an automobile headlamp is configured such that a transparent member made of glass or plastic is disposed in front of a light source, and light emitted from the light source is irradiated to the outside through the transparent member. .
- a transparent member made of glass or plastic is disposed in front of a light source, and light emitted from the light source is irradiated to the outside through the transparent member.
- the intensity of the irradiation light may decrease and the aesthetic appearance of the irradiation light may be impaired.
- Patent Document 1 discloses an antifogging agent composition that can be used to prevent the occurrence of fogging in the lighting device as described above.
- This anti-fogging agent composition contains the following components.
- antifogging performance is obtained based on the properties of the monomer (A), and good adhesion and water resistance are obtained based on the properties of the monomer (B). And good antifogging performance is obtained by the function of the surfactant (E).
- the surfactant (E) gradually flows out in applications such as automobile headlamps used in an environment where repeated condensation occurs. End up. Therefore, in the antifogging article in which the antifogging agent composition described in Patent Document 1 is used, the antifogging performance (water film forming ability) may decrease with use.
- an object of the present invention is to provide an antifogging agent composition excellent in sustainability of antifogging performance and an antifogging article using the same.
- an antifogging agent composition comprises a copolymer (A), a polyfunctional blocked isocyanate compound (B), and a surfactant (C).
- the copolymer (A) includes a monomer (A-1) represented by the following general formula (1) or (2) and a monomer (A-2) represented by the following general formula (3). And a monomer (A-3) represented by the following general formula (4) or (5).
- R 1 is a hydrogen atom or a methyl group
- R 2 is a linear or branched alkyl group having 1 to 4 carbon atoms, —C (CH 3 ) 2 CH 2 COCH 3 , —C 2 H 4 N (CH 3 ) 2 , or —C 3 H 6 N (CH 3 ) 2
- R 3 is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.
- R 4 is a hydrogen atom or a methyl group.
- R 5 is a hydrogen atom or a methyl group
- R 6 is a linear, branched, or cyclic alkyl group having 1 to 16 carbon atoms.
- R 7 is a hydrogen atom or a methyl group
- R 9 is a hydrogen atom or a methyl group
- R 10 is a linear or branched alkylene group having 1 to 4 carbon atoms.
- the monomer (A-1) is 35% with respect to a total of 100 parts by weight of the monomer (A-1), the monomer (A-2), and the monomer (A-3).
- the amount of the monomer (A-2) is 5 to 60 parts by weight, and the amount of the monomer (A-3) is 5 to 30 parts by weight.
- the NCO / OH ratio which is the ratio of the isocyanate group content (NCO) of the polyfunctional blocked isocyanate compound (B) and the hydroxyl group content (OH) of the copolymer (A), is 0.1 to 1.5. Is within the range.
- the surfactant (C) is used in an amount of 1.00 to 10.0 parts by weight of an anionic surfactant (C-1) and 0.01 to 3 parts per 100 parts by weight of the copolymer (A). And 0.000 part by weight of a cationic surfactant (C-2).
- the combined use of the anionic surfactant (C-1) and the cationic surfactant (C-2) makes it difficult for the surfactant to flow out due to moisture caused by condensation. For this reason, in this anti-fogging agent composition, the anti-fogging performance (water film forming ability) is not easily lowered with use, and the excellent anti-fogging performance is maintained.
- the anionic surfactant (C-1) may be a fluorosurfactant. With this configuration, the surface tension of water can be reduced more favorably.
- An antifogging article includes a base material and an antifogging film.
- the antifogging film is formed by heat-curing the antifogging composition applied to the substrate.
- One embodiment of the present invention relates to a technique for providing an antifogging film on the surface of a base material to which an antifogging performance is imparted, such as a transparent member used for an automotive headlamp.
- the antifogging film according to this embodiment is formed by heat curing an antifogging agent composition that is a mixture of a plurality of types of materials.
- the component of the antifogging agent composition is determined so that the durability of the antifogging performance can be satisfactorily obtained in the antifogging film after heat curing.
- the antifogging agent composition according to the present embodiment has a copolymer (A), a polyfunctional blocked isocyanate compound (B), and a surfactant (C).
- an anionic surfactant (C-1) and a cationic surfactant (C-2) are used in combination as the surfactant (C).
- the anion of the anionic surfactant (C-1) and the cation of the cationic surfactant (C-2) form an ion pair. This makes it difficult for the anionic surfactant (C-1) and the cationic surfactant (C-2) to flow out due to moisture caused by condensation.
- the antifogging accompanying use is caused by the action of the anionic surfactant (C-1) and the cationic surfactant (C-2).
- the performance water film forming ability
- excellent anti-fogging performance is maintained.
- the anionic surfactant (C-1) is a fluorosurfactant
- the surface tension of water can be reduced more favorably in the antifogging film obtained from the antifogging agent composition. Anti-fogging performance is obtained.
- the amount of the anionic surfactant (C-1) is preferably in the range of 1.00 to 10.00 parts by weight with respect to 100 parts by weight of the copolymer (A).
- the amount of the anionic surfactant (C-1) is less than 1.00 parts by weight, the antifogging performance of the antifogging film is lowered and the antifogging performance after the heat resistance test is lowered.
- the amount of the anionic surfactant (C-1) exceeds 10.00 parts by weight, water dripping marks are easily noticeable on the antifogging film.
- the amount of the cationic surfactant (C-2) is preferably in the range of 0.01 to 3.00 parts by weight with respect to 100 parts by weight of the copolymer (A).
- the amount of the cationic surfactant (C-2) is less than 0.01 parts by weight, the durability of the antifogging performance in the antifogging film is lowered.
- the amount of the anionic surfactant (C-1) exceeds 3.00 parts by weight, water dripping marks are easily noticeable on the antifogging film.
- the copolymer (A) is composed of a monomer (A-1), a monomer (A-2), and a monomer (A-3).
- the monomer (A-1) is represented by the following general formula (1) or (2).
- the monomer (A-2) is represented by the following general formula (3).
- the monomer (A-3) is represented by the following general formula (4) or (5).
- R 1 is a hydrogen atom or a methyl group
- R 2 is a linear or branched alkyl group having 1 to 4 carbon atoms, —C (CH 3 ) 2 CH 2 COCH 3 , —C 2 H 4 N (CH 3 ) 2 , or —C 3 H 6 N (CH 3 ) 2
- R 3 is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.
- R 4 is a hydrogen atom or a methyl group.
- R 5 is a hydrogen atom or a methyl group
- R 6 is a linear, branched, or cyclic alkyl group having 1 to 16 carbon atoms.
- R 7 is a hydrogen atom or a methyl group
- R 9 is a hydrogen atom or a methyl group
- R 10 is a linear or branched alkylene group having 1 to 4 carbon atoms.
- the adhesion of the antifogging film obtained from the antifogging agent composition to the substrate is particularly excellent.
- the amount of the monomer (A-1) is 35 to 50 parts per 100 parts by weight in total of the monomer (A-1), the monomer (A-2), and the monomer (A-3). It is preferably within the range of 90 parts by weight.
- the amount of the monomer (A-1) is less than 35 parts by weight, the durability of the antifogging performance of the antifogging film is lowered.
- the amount of the monomer (A-1) exceeds 90 parts by weight, water dripping traces are easily noticeable on the antifogging film.
- the antifogging performance of the antifogging film obtained from the antifogging agent composition after the heat resistance and moisture resistance test is particularly excellent.
- the number of carbon atoms is more than 16, the antifogging performance after the heat resistance and moisture resistance test of the antifogging film obtained from the antifogging agent composition is lowered.
- the amount of the monomer (A-2) is 5 to 5 parts per 100 parts by weight in total of the monomer (A-1), the monomer (A-2), and the monomer (A-3). It is preferably within the range of 60 parts by weight.
- the amount of the monomer (A-2) is less than 5 parts by weight, water dripping marks are easily noticeable on the antifogging film.
- the amount of the monomer (A-2) exceeds 60 parts by weight, the durability of the antifogging performance of the antifogging film is lowered.
- the antifogging performance of the antifogging film obtained from the antifogging agent composition is particularly excellent.
- the amount of the monomer (A-3) is 5 to 5 parts per 100 parts by weight in total of the monomer (A-1), the monomer (A-2), and the monomer (A-3). It is preferably within the range of 30 parts by weight.
- the amount of the monomer (A-3) is less than 5 parts by weight, the water resistance of the antifogging film is lowered, and water dripping marks are easily noticeable in the antifogging film.
- the amount of the monomer (A-3) exceeds 30 parts by weight, the adhesion of the antifogging film to the substrate is lowered.
- Polyfunctional blocked isocyanate compound (B) When the polyfunctional blocked isocyanate compound (B) is diethyl malonate blocked isocyanate, the antifogging composition is cured well at a low temperature (about 120 ° C.) without adding a catalyst.
- the isocyanate group content in the polyfunctional block isocyanate compound (B) is “NCO” and the hydroxyl group content of the copolymer (A) is “OH”, the isocyanate group content NCO is converted into the copolymer (A).
- the NCO / OH ratio obtained by dividing by the hydroxyl group content OH is preferably in the range of 0.1 to 1.5.
- the NCO / OH ratio When the NCO / OH ratio is less than 0.1, the water resistance of the antifogging film is lowered, and water dripping marks are easily noticeable on the antifogging film. On the other hand, when the NCO / OH ratio exceeds 1.5, the durability of the antifogging performance of the antifogging film is lowered.
- an antifogging agent composition is applied to the surface of an article that is a base material to which antifogging performance is imparted, and the antifogging agent composition on the surface of the article is heated and cured. Can be manufactured.
- Articles to which the present embodiment is applicable are not particularly limited.
- the anti-fogging article according to the present embodiment has a high anti-fogging performance and sustainability
- the present embodiment can be more suitably applied to an article used in an environment where condensation is likely to occur.
- Examples of such articles include automobile headlamps.
- the solution of the copolymer (A) was obtained by stirring the solution in the reaction vessel after dropping the solution (a) and the solution (b) for 1 hour.
- the polymerization conversion rate of the charged monomer of the copolymer (A) measured by gas chromatography was 100%.
- the weight average molecular weight of the copolymer (A) measured by gel permeation chromatography was 93,000.
- the hydroxyl value of the copolymer (A) was calculated according to the following formula.
- polyfunctional blocked isocyanate compound (B) 83.5 parts by weight of a hexamethylene diisocyanate malonate block isocyanate having an NCO / OH ratio of 1.0 (trade name: Duranate MF- manufactured by Asahi Kasei Chemicals Corporation) K60B (NCO concentration 6.5 wt%)] was used.
- anionic surfactant (C-1) 5.0 parts by weight of sodium di (2-ethylhexyl) sulfosuccinate [trade name: Rapisol A80 manufactured by NOF Corporation (active ingredient 80.0% by weight) ] was used.
- C-2 As the cationic surfactant (C-2), 0.01 parts by weight of didecyldimethylammonium chloride [trade name: NISSAN cation 2DB500E (active ingredient 50.0% by weight) manufactured by NOF CORPORATION] is used. It was.
- a leveling agent 0.01 part by weight of a polyether-modified polydimethylsiloxane [trade name: BYK333 manufactured by Big Chemie Japan Co., Ltd.] was used.
- the above copolymer (A), polyfunctional blocked isocyanate compound (B), anionic surfactant (C-1), cationic surfactant (C-2), and leveling agent are mixed to prevent defogging.
- An agent composition was obtained.
- polyfunctional blocked isocyanate compound (B) 51.7 parts by weight of a dimethylpyrazole block isocyanate body of hexamethylene diisocyanate having an NCO / OH ratio of 1.0 (trade name: Sumika Bayer Urethane Co., Ltd. Module 3575/1 (NCO concentration 10.5 wt%)] was used.
- anionic surfactant (C-1) 5.0 parts by weight of sodium di (2-ethylhexyl) sulfosuccinate [trade name: Rapisol A80 manufactured by NOF Corporation (active ingredient 80.0% by weight) ] was used.
- C-2 a cationic surfactant (C-2)
- 1-methyl-1-hydroxyethyl-2-tallow alkyl-imidazolium chloride trade name: NISSAN cation AR manufactured by NOF Corporation] -4 (active ingredient 35.0% by weight)
- a leveling agent 0.01 part by weight of a polyether-modified polydimethylsiloxane [trade name: BYK333 manufactured by Big Chemie Japan Co., Ltd.] was used.
- a polycarbonate resin plate was used as a base material for forming the antifogging film.
- the antifogging agent composition was applied to a polycarbonate resin plate by a spray coating method so that the film thickness of the antifogging film after curing was 5 ⁇ m.
- the anti-fogging agent composition was heat-hardened by hold
- Anti-fogging film performance evaluation (3-1) Anti-fogging performance (a) Sustainability test
- the anti-fogging film test piece is placed below the anti-fogging film test piece at a height of 2 cm from the surface of the hot water bath maintained at 80 ° C.
- steam irradiation of the antifogging film test piece with a warm water bath was performed on the antifogging film, and then the antifogging film test piece was dried for 1 hour at room temperature in a state where the antifogging film test piece was set up vertically. After repeating this 50 times, the presence or absence of fogging 10 seconds after the steam irradiation was visually evaluated in the following four stages.
- the evaluation of the antifogging film formed on the antifogging film test piece is “C” or more, there is no practical problem, “B” is preferable, and “A” is more preferable.
- the evaluation of the antifogging film formed on the antifogging film test piece is “C” or more, there is no practical problem, “B” is preferable, and “A” is more preferable.
- the evaluation of the antifogging film formed on the antifogging film test piece is “C” or more, there is no practical problem, “B” is preferable, and “A” is more preferable.
- the evaluation of the antifogging film formed on the antifogging film test piece is “C” or more, there is no practical problem, “B” is preferable, and “A” is more preferable.
- the anti-fogging film test was carried out by placing the anti-fogging film test piece with the anti-fogging film facing down at a position 2 cm above the surface of the hot water bath maintained at 80 ° C. After irradiating the piece of anti-fogging film with steam in a warm water bath, the anti-fogging film test piece was dried vertically at room temperature for 1 hour. The presence or absence of water dripping marks on the antifogging film test piece after drying was visually evaluated in the following four stages.
- the evaluation of the antifogging film formed on the antifogging film test piece is “C” or more, there is no practical problem, “B” is preferable, and “A” is more preferable.
- the evaluation of the antifogging film formed on the antifogging film test piece is “B” or more, there is no practical problem, and “A” is more preferable.
- the antifogging membrane test piece was allowed to stand in warm water at 40 ° C. for 240 hours, and further allowed to stand at room temperature for 1 hour. Thereafter, the appearance of the antifogging film of the antifogging film test piece was visually evaluated in the following four stages.
- A There is no change in the appearance before the test.
- B The coating film surface is slightly rough.
- C The coating film surface is rough or slightly whitened or stained.
- D Part or all of the coating film is dissolved, or whitening or spots are clearly observed.
- the evaluation of the antifogging film formed on the antifogging film test piece is “C” or more, there is no practical problem, “B” is preferable, and “A” is more preferable.
- Example 1-4 From the results of Example 1-4, when both the anionic surfactant (C-1) and the cationic surfactant (C-2) are small, the antifogging performance of the antifogging film tends to be slightly lowered. It was observed.
- Examples 1-10 to 1-21 In Examples 1-10 to 1-21, the types of monomer (A-1), monomer (A-2), and monomer (A-3) were mainly examined. All of the antifogging film test pieces according to Examples 1-10 to 1-21 were produced by the same method as described above. Table 2 shows the composition (parts by weight) of the antifogging agent composition according to Examples 1-10 to 1-21, and the performance of the antifogging film test piece in which the antifogging film was formed by the antifogging agent composition. The evaluation results are shown.
- the monomer (A-1) is a dialkylacrylamide
- the monomer (A-2) is an acrylic having 6 carbon atoms. Particularly good performance was obtained when it was an acid ester and when the monomer (A-3) was hydroxyethyl methacrylate or hydroxyethyl acrylamide.
- Example 1-17 From the results of Example 1-17, when the monomer (A-2) is an acrylic acid ester having 16 carbon atoms, there is a tendency that the anti-fogging performance of the anti-fogging film and the anti-fogging performance after the heat test are slightly lowered. It was.
- Example 1-15 when the monomer (A-2) is an acrylate ester having 1 carbon atom, the water dripping trace tends to be slightly noticeable in the antifogging film.
- the monomer (A-1) was monoalkylacrylamide, diacetoneacrylamide, dimethylaminopropylacrylamide, or acryloylmorpholine. And when the monomer (A-3) is a long-chain hydroxyacrylate, the adhesion of the antifogging film in the antifogging film specimen tends to be slightly lowered.
- Examples 1-22 to 1-26 the monomer (A-1), the monomer (A-2), the monomer (A-3), and the polyfunctional blocked isocyanate compound (B) are mainly used. The amount of was examined. All of the antifogging film test pieces according to Examples 1-22 to 1-26 were produced by the same method as described above. Table 3 shows the composition (parts by weight) of the antifogging agent composition according to Examples 1-22 to 1-26 and the performance of the antifogging film test piece in which the antifogging film was formed by the antifogging agent composition. The evaluation results are shown.
- Examples 2-1 to 2-9 In Examples 2-1 to 2-9, the anionic surfactant (C-1) and the cationic interface mainly in the case of using a fluorine-based surfactant as the anionic surfactant (C-1) The type and amount of the active agent (C-2) were examined. All of the antifogging film test pieces according to Examples 2-1 to 2-9 were produced by the same method as described above. Table 4 shows the composition (parts by weight) of the antifogging agent composition according to Examples 2-1 to 2-9 and the performance of the antifogging film test piece having the antifogging film formed by the antifogging agent composition. The evaluation results are shown.
- Example 2-4 From the results of Example 2-4, when both the anionic surfactant (C-1) and the cationic surfactant (C-2) are small, the antifogging performance of the antifogging film tends to be slightly lowered. It was observed.
- Examples 2-10 to 2-21 In Examples 2-10 to 2-21, the monomer (A-1) and the monomer (A) in the case where a fluorosurfactant was mainly used as the anionic surfactant (C-1). -2) and the type of monomer (A-3). All of the antifogging film test pieces according to Examples 2-10 to 2-21 were produced by the same method as described above.
- Table 5 shows the composition (parts by weight) of the antifogging agent composition according to Examples 2-10 to 2-21 and the performance of the antifogging film test piece formed with the antifogging film by the antifogging agent composition. The evaluation results are shown.
- monomer (A-1) is dialkylacrylamide
- monomer (A-2) is an acrylic having 6 carbon atoms.
- the acid ester was used, and when the monomer (A-3) was hydroxyethyl methacrylate or hydroxyethyl acrylamide, particularly good performance of the antifogging film was obtained.
- Example 2-17 From the results of Example 2-17, when the monomer (A-2) is an acrylic ester having 16 carbon atoms, the moisture resistance of the antifogging film and the antifogging performance after the heat test tend to be slightly lowered. It was.
- Example 2-15 From the results of Example 2-15, when the monomer (A-2) was an acrylate ester having 1 carbon atom, it was observed that the water dripping traces were slightly noticeable on the antifogging film.
- the monomer (A-1) is monoalkylacrylamide, diacetoneacrylamide, dimethylaminopropylacrylamide, or acryloylmorpholine.
- the monomer (A-3) is a further long-chain hydroxyacrylate, the adhesion of the antifogging film in the antifogging film specimen tends to be slightly lowered.
- Examples 2-22 to 2-26 In Examples 2-22 to 2-26, the monomer (A-1) and the monomer (A) in the case where a fluorosurfactant was mainly used as the anionic surfactant (C-1). -2), the amount of the monomer (A-3), and the polyfunctional blocked isocyanate compound (B) were examined. All of the antifogging film test pieces according to Examples 2-22 to 2-26 were produced by the same method as described above. Table 6 shows the composition (parts by weight) of the antifogging agent composition according to Examples 2-22 to 2-26 and the performance of the antifogging film test piece in which the antifogging film was formed by the antifogging agent composition. The evaluation results are shown.
- Comparative Example Table 7 shows the composition (parts by weight) of the antifogging agent composition according to Comparative Examples 1 to 6 and the evaluation results of the performance of the antifogging film test piece in which the antifogging film was formed by the antifogging agent composition. It shows. All of the antifogging film test pieces according to Comparative Examples 1 to 6 are produced by the same method as described above.
- the antifogging agent composition according to Comparative Examples 1 and 2 does not contain a cationic surfactant (C-2).
- C-2 cationic surfactant
- the antifogging films according to Comparative Examples 1 and 2 were not able to obtain sufficient sustainability of the antifogging performance.
- the water dripping trace was slightly noticeable.
- the antifogging agent composition according to Comparative Example 3 does not contain an anionic surfactant (C-1).
- C-1 anionic surfactant
- the antifogging film according to Comparative Example 3 could not obtain sufficient antifogging performance.
- membrane which concerns on the comparative example 3 the anti-fogging property after a heat test was a little low, and the water dripping trace was a little conspicuous.
- the antifogging agent composition according to Comparative Example 4 is a nonionic surfactant instead of the anionic surfactant (C-1) and the cationic surfactant (C-2). Agent (C-3) is used.
- the antifogging film according to Comparative Example 4 could not obtain sufficient antifogging performance.
- membrane which concerns on the comparative example 4 the antifogging property after a heat test was a little low, and the water dripping trace was a little conspicuous.
- the antifogging agent composition according to Comparative Example 5 uses a nonionic surfactant (C-3) instead of the cationic surfactant (C-2). .
- C-3 nonionic surfactant
- C-2 cationic surfactant
- the antifogging agent composition according to Comparative Example 6 uses a nonionic surfactant (C-3) instead of the anionic surfactant (C-1). .
- C-3 nonionic surfactant
- the antifogging film according to Comparative Example 6 could not obtain sufficient antifogging performance.
- membrane which concerns on the comparative example 6 the antifogging property after a heat test was a little low, and the water dripping trace was a little conspicuous.
- Nonionic surfactant (6-7)
- Neugen EA-140 Polyoxyethylene alkylphenyl ether
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Abstract
Description
・単量体(A):非架橋性の水溶性ビニル系単量体
・単量体(B):非架橋性の非水溶性ビニル系単量体
・単量体(C):水酸基を有するビニル系単量体
・イソシアネート基を有する架橋剤(D)
・界面活性剤(E)
上記共重合体(A)は、下記一般式(1)又は(2)により表される単量体(A-1)と、下記一般式(3)により表される単量体(A-2)と、下記一般式(4)又は(5)により表される単量体(A-3)とから構成される。
上記単量体(A-1)、上記単量体(A-2)、及び上記単量体(A-3)の合計100重量部に対して、上記単量体(A-1)が35~90重量部で、上記単量体(A-2)が5~60重量部で、上記単量体(A-3)が5~30重量部である。
上記多官能ブロックイソシアネート化合物(B)のイソシアネート基含有量(NCO)と、上記共重合体(A)の水酸基含有量(OH)との比であるNCO/OH比が0.1~1.5の範囲内である。
上記界面活性剤(C)は、上記共重合体(A)100重量部に対して、1.00~10.0重量部のアニオン系界面活性剤(C-1)と、0.01~3.00重量部のカチオン系界面活性剤(C-2)とを含む。
この構成により、水の表面張力をより良好に低下させることができる。
上記防曇膜は、上記基材に塗布された上記防曇剤組成物が加熱硬化されてなる。
この構成により、使用に伴って防曇性能(水膜形成能)が低下しにくく、優れた防曇性能が持続する防曇膜が形成された防曇性物品が得られる。
本発明の一実施形態は、例えば、自動車の前照灯などに用いられる透明部材などの、防曇性能を付与する対象である基材の表面に防曇膜を設けるための技術に関する。本実施形態に係る防曇膜は、複数種類の材料の混合物である防曇剤組成物を加熱硬化させることにより形成される。防曇剤組成物の含有成分は、加熱硬化後の防曇膜において防曇性能の持続性が良好に得られるように決定される。
本実施形態に係る防曇剤組成物は、共重合体(A)と多官能ブロックイソシアネート化合物(B)と界面活性剤(C)とを有する。
本実施形態に係る防曇剤組成物では、界面活性剤(C)として、アニオン系界面活性剤(C-1)と、カチオン系界面活性剤(C-2)とが併用される。この構成では、アニオン系界面活性剤(C-1)のアニオンと、カチオン系界面活性剤(C-2)のカチオンとがイオンペアを形成する。これにより、アニオン系界面活性剤(C-1)及びカチオン系界面活性剤(C-2)は結露などによって生じる水分による流出が生じにくくなる。
共重合体(A)は、単量体(A-1)と、単量体(A-2)と、単量体(A-3)とから構成される。単量体(A-1)は、下記一般式(1)又は(2)により表される。単量体(A-2)は、下記一般式(3)により表される。単量体(A-3)は、下記一般式(4)又は(5)により表される。
多官能ブロックイソシアネート化合物(B)がジエチルマロネートブロックイソシアネートである場合に、防曇剤組成物は触媒を添加することなく低温(120℃程度)で良好に硬化する。
本実施形態に係る防曇性物品は、防曇性能を付与する対象である基材となる物品の表面に防曇剤組成物を塗布し、物品の表面の防曇剤組成物を加熱硬化させることにより製造可能である。本実施形態を適用可能な物品は特に限定されない。
(1-1)共重合体(A)の合成
温度計、攪拌装置、窒素導入管及び冷却管を備えた反応容器を用い、有機溶媒である213重量部のt-アミルアルコールを、窒素ガスを吹き込みながら80℃に加熱した。この反応容器中に、以下の溶液(a)及び溶液(b)を2時間かけて滴下した。
・溶液(b):0.5重量部相当のt-ヘキシルペルオキシピバレート(ラジカル重合開始剤)[日油(株)製の商品名:パーヘキシルPV(有効成分70重量%)]を20重量部のt-アミルアルコールに溶解させた溶液
[水酸基価](mgKOH/g)
=[共重合体(A)100.0重量部中の単量体(A-3)の重量部](g)/[単量体(A-3)のモル重量](g/mol)×KOH(mg)
=0.15(g)/116.12(g/mol)×56100(mgKOH)
=72.5(mgKOH/g)
100重量部相当の共重合体(A)である333重量部の固形分30.0%重合溶液に、100重量部のポリプロピレングリコールモノメチルエーテルと、200重量部のダイアセトンアルコールと、100重量部のメチルイソブチルケトンと、267重量部のn-ブタノールとを加え、固形分を10.0重量%に調整した。
100重量部相当の共重合体(A)である333重量部の固形分30.0%重合溶液に、100重量部のポリプロピレングリコールモノメチルエーテルと、200重量部のダイアセトンアルコールと、100重量部のメチルイソブチルケトンと、267重量部のn-ブタノールとを加え、固形分を10.0重量%に調整した。
防曇膜を形成する基材としてポリカーボネート樹脂板を用いた。硬化後の防曇膜の膜厚が5μmとなるように、スプレーコート法によって防曇剤組成物をポリカーボネート樹脂板に塗布した。そして、防曇剤組成物が塗布されたポリカーボネート樹脂板を130℃で30分間保持することにより防曇剤組成物を加熱硬化させた。これにより、防曇膜を有する防曇膜試験片が得られた。
(3-1)防曇性能
(a)持続性試験
80℃に保った温水浴の水面から2cmの高さの位置に、防曇膜試験片を防曇膜が下を向くように設置することにより、防曇膜試験片の防曇膜に対する温水浴によるスチーム照射を行った後、防曇膜試験片を垂直に立てた状態で室温にて1時間乾燥させた。これを50回繰り返した後、スチーム照射から10秒後の曇りの有無を目視によって次の4段階で評価した。
B:スチーム照射直後に一瞬の曇りが認められるが、すぐに水膜が形成されて曇りが解消される。
C:スチーム照射直後に曇りが認められるが、やがて水膜が形成されて曇りが解消される。
D:スチーム照射後にきれいな水膜が形成されない、もしくは水膜が形成されず曇りが認められる。
80℃に保った温水浴の水面から2cmの高さの位置に、防曇膜試験片を防曇膜が下を向くように設置することにより、防曇膜試験片の防曇膜に対する温水浴によるスチーム照射を行い、スチーム照射から10秒後の曇りの有無を目視によって次の4段階で評価した。
B:スチーム照射直後に一瞬の曇りが認められるが、すぐに水膜が形成されて曇りが解消される。
C:スチーム照射直後に曇りが認められるが、やがて水膜が形成されて曇りが解消される。
D:スチーム照射直後に曇りが認められ、水膜が形成されない。
防曇膜試験片を50℃、95%RHの条件で240時間静置し、更に室温にて1時間静置した。その後、80℃に保った温水浴の水面から2cmの高さの位置に、防曇膜試験片を防曇膜が下を向くように設置することにより、防曇膜試験片の防曇膜に対する温水浴によるスチーム照射を行い、スチーム照射から10秒後の曇りの有無を目視によって次の4段階で評価した。
B:スチーム照射直後に一瞬の曇りが認められるが、すぐに水膜が形成されて曇りが解消される。
C:スチーム照射直後に曇りが認められるが、やがて水膜が形成されて曇りが解消される。
D:スチーム照射後にきれいな水膜が形成されない、もしくは水膜が形成されず曇りが認められる。
防曇膜試験片を120℃の条件で240時間静置し、更に室温にて1時間静置した。その後、80℃に保った温水浴の水面から2cmの高さの位置に、防曇膜試験片を防曇膜が下になるように設置することにより、防曇膜試験片の防曇膜に対する温水浴によるスチーム照射を行い、スチーム照射から10秒後の曇りの有無を目視によって次の4段階で評価した。
B:スチーム照射直後に一瞬の曇りが認められるが、すぐに水膜が形成されて曇りが解消される。
C:スチーム照射直後に曇りが認められるが、やがて水膜が形成されて曇りが解消される。
D:スチーム照射後にきれいな水膜が形成されない、もしくは水膜が形成されず曇りが認められる。
80℃に保った温水浴の水面から2cmの高さの位置に、防曇膜試験片を防曇膜が下を向くように設置することにより、防曇膜試験片の防曇膜に対する温水浴によるスチーム照射を行った後、防曇膜試験片を垂直に立てた状態で室温にて1時間乾燥させた。乾燥後の防曇膜試験片に水垂れ跡の有無を目視によって次の4段階で評価した。
B:水垂れ跡がほとんど目立たない。
C:水垂れ跡がやや目立つ。
D:水垂れ跡が目立つ。
JIS K 5600-5-6に準拠して防曇膜試験片における防曇膜の剥離の有無を目視によって次の3段階で評価した。
B:一部に剥離が認められる。
D:全て剥離している。
防曇膜試験片を40℃温水に240時間静置し、更に室温にて1時間静置した。その後、防曇膜試験片の防曇膜の外観を目視によって次の4段階で評価した。
B:わずかに塗膜表面が荒れている。
C:塗膜表面が荒れているか、又はわずか白化やシミが認められる。
D:塗膜の一部または全部が溶解している、又ははっきりと白化やシミが認められる。
(4-1)実施例1-1~1-9
実施例1-1~1-9では、主に、アニオン系界面活性剤(C-1)及びカチオン系界面活性剤(C-2)の種類及び量について検討した。実施例1-1~1-9に係る防曇膜試験片はいずれも上記と同様の方法により作製されている。表1は、実施例1-1~1-9に係る防曇剤組成物の組成(重量部)と、当該防曇剤組成物によって防曇膜が形成された防曇膜試験片の性能の評価結果とを示している。
実施例1-10~1-21では、主に、単量体(A-1)、単量体(A-2)、及び単量体(A-3)の種類について検討した。実施例1-10~1-21に係る防曇膜試験片はいずれも上記と同様の方法により作製されている。表2は、実施例1-10~1-21に係る防曇剤組成物の組成(重量部)と、当該防曇剤組成物によって防曇膜が形成された防曇膜試験片の性能の評価結果とを示している。
実施例1-22~1-26では、主に、単量体(A-1)、単量体(A-2)、単量体(A-3)、及び多官能ブロックイソシアネート化合物(B)の量について検討した。実施例1-22~1-26に係る防曇膜試験片はいずれも上記と同様の方法により作製されている。表3は、実施例1-22~1-26に係る防曇剤組成物の組成(重量部)と、当該防曇剤組成物によって防曇膜が形成された防曇膜試験片の性能の評価結果とを示している。
実施例2-1~2-9では、主に、アニオン系界面活性剤(C-1)としてフッ素系界面活性剤を用いた場合における、アニオン系界面活性剤(C-1)及びカチオン系界面活性剤(C-2)の種類及び量について検討した。実施例2-1~2-9に係る防曇膜試験片はいずれも上記と同様の方法により作製されている。表4は、実施例2-1~2-9に係る防曇剤組成物の組成(重量部)と、当該防曇剤組成物によって防曇膜が形成された防曇膜試験片の性能の評価結果とを示している。
実施例2-10~2-21では、主に、アニオン系界面活性剤(C-1)としてフッ素系界面活性剤を用いた場合における、単量体(A-1)、単量体(A-2)、及び単量体(A-3)の種類について検討した。実施例2-10~2-21に係る防曇膜試験片はいずれも上記と同様の方法により作製されている。表5は、実施例2-10~2-21に係る防曇剤組成物の組成(重量部)と、当該防曇剤組成物によって防曇膜が形成された防曇膜試験片の性能の評価結果とを示している。
実施例2-22~2-26では、主に、アニオン系界面活性剤(C-1)としてフッ素系界面活性剤を用いた場合における、単量体(A-1)、単量体(A-2)、単量体(A-3)、及び多官能ブロックイソシアネート化合物(B)の量について検討した。実施例2-22~2-26に係る防曇膜試験片はいずれも上記と同様の方法により作製されている。表6は、実施例2-22~2-26に係る防曇剤組成物の組成(重量部)と、当該防曇剤組成物によって防曇膜が形成された防曇膜試験片の性能の評価結果とを示している。
表7は、比較例1~6に係る防曇剤組成物の組成(重量部)と、当該防曇剤組成物によって防曇膜が形成された防曇膜試験片の性能の評価結果とを示している。比較例1~6に係る防曇膜試験片はいずれも上記と同様の方法により作製されている。
表1~7で用いた物質の省略表記に対応する名称を以下にまとめる。
DMAA:N,N-ジメチルアクリルアミド
DEMA:N,N-ジエチルメタクリルアミド
IPAA:N-イソプロピルアクリルアミド、
DAAA:ジアセトンアクリルアミド
DMAPAA:ジメチルアミノプロピルアクリルアミド
ACMO:N-アクリロイルモルホリン
MMA:メチルメタクリレート
BA:n-ブチルアクリレート
CHA:シクロヘキシルアクリレート
CA:セチルアクリレート
HEA:2-ヒドロキシエチルアクリレート
HEMA:2-ヒドロキシエチルメタクリレート
HEAA:ヒドロキシエチルアクリルアミド
プラクセルFA2D:2-ヒドロキシエチルアクリレートのカプロラクトン2mol付加物
プラクセルFA5:2-ヒドロキシエチルアクリレートのカプロラクトン5mol付加物
Duranate MF-K60B:マロネートブロックイソシアネート[旭化成ケミカルズ(株)製の商品名:デュラネートMF-K60B]
Desmodur BL3575/1:ジメチルピラゾールブロックイソシアネート[住友バイエルウレタン(株)製の商品名:デスモジュ-ルBL3575/1]
Sumidur BL3175:メチルエチルケトオキシムブロックイソシアネート[住友バイエルウレタン(株)製の商品名:スミジュ-ルBL3175]
フタージェント100:フッ素含有スルホン酸塩
サーフロンS211:フッ素含有カルボン酸塩
ラピゾールA80:スルホコハク酸ジエステル塩
パーソフトSK:アルキルスルホン酸塩
ニッサンカチオン2DB500E:ジアルキル4級アンモニウム塩
ニッサンカチオンBB:モノアルキル4級アンモニウム塩
ニッサンカチオンAR-4:イミダゾリン塩
フタージェント300:フッ素含有カチオン系界面活性剤
ノイゲンEA-140:ポリオキシエチレンアルキルフェニルエーテル
以上、本発明の実施形態について説明したが、本発明は上述の実施形態にのみ限定されるものではなく、本発明の要旨を逸脱しない範囲内において種々変更を加え得ることは勿論である。
Claims (3)
- 共重合体(A)と多官能ブロックイソシアネート化合物(B)と界面活性剤(C)とからなり、
前記共重合体(A)は、
下記一般式(1)又は(2)により表される単量体(A-1)と、下記一般式(3)により表される単量体(A-2)と、下記一般式(4)又は(5)により表される単量体(A-3)とから構成され、
前記単量体(A-1)、前記単量体(A-2)、及び前記単量体(A-3)の合計100重量部に対して、前記単量体(A-1)が35~90重量部で、前記単量体(A-2)が5~60重量部で、前記単量体(A-3)が5~30重量部であり、
前記多官能ブロックイソシアネート化合物(B)のイソシアネート基含有量(NCO)と、前記共重合体(A)の水酸基含有量(OH)との比であるNCO/OH比が0.1~1.5の範囲内であり、
前記界面活性剤(C)は、前記共重合体(A)100重量部に対して、1.00~10.0重量部のアニオン系界面活性剤(C-1)と、0.01~3.00重量部のカチオン系界面活性剤(C-2)とを含む
防曇剤組成物。 - 請求項1に記載の防曇剤組成物であって、
前記アニオン系界面活性剤(C-1)がフッ素系界面活性剤である
防曇剤組成物。 - 基材と、
前記基材に塗布された請求項1又は2に記載の防曇剤組成物が加熱硬化されてなる防曇膜と
を具備する防曇性物品。
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JPWO2016047430A1 (ja) | 2017-08-10 |
CN106574167B (zh) | 2018-10-26 |
EP3199607A1 (en) | 2017-08-02 |
JP6565920B2 (ja) | 2019-08-28 |
EP3628718B1 (en) | 2020-07-15 |
CN106574167A (zh) | 2017-04-19 |
US10022945B2 (en) | 2018-07-17 |
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