WO2005000933A1 - 紫外線吸収性樹脂水エマルション及びエマルション樹脂組成物 - Google Patents
紫外線吸収性樹脂水エマルション及びエマルション樹脂組成物 Download PDFInfo
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- WO2005000933A1 WO2005000933A1 PCT/JP2003/008014 JP0308014W WO2005000933A1 WO 2005000933 A1 WO2005000933 A1 WO 2005000933A1 JP 0308014 W JP0308014 W JP 0308014W WO 2005000933 A1 WO2005000933 A1 WO 2005000933A1
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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
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0809—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups
- C08G18/0814—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups containing ammonium groups or groups forming them
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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
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines containing two hydroxy groups
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/3851—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing three nitrogen atoms in the ring
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6523—Compounds of group C08G18/3225 or C08G18/3271 or polyamines of C08G18/38
- C08G18/6535—Compounds of group C08G18/3271
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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
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
Definitions
- the present invention relates to an ultraviolet-absorbing resin water emulsion and a water-emulsion resin composition containing the same, which is excellent in light resistance and chemical resistance.
- ultraviolet absorber In order to improve the durability of the water emulsion resin to ultraviolet rays (light resistance), it is customary to add an ultraviolet absorber.
- ultraviolet absorbers include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 5-chloro-2- (2'-hydroxy-13 ', 5'-di-tert- Benzotriazoles such as benzotriazole and benzophenones such as 2,4-dihydroxybenzophenone and 2-hydroxy-14-octyloxybenzophenone are known.
- a group having a polymerizable double bond such as a vinyl group is added to the ultraviolet absorber, and this is polymerized to have a high molecular weight, thereby improving the compatibility with the resin.
- Attempts have been made to prevent volatilization, volatilization of the UV absorber, thermal decomposition, leaching, etc. (Japanese Patent Application Laid-Open Nos. 60-38411 and 62-181316) No. 0, Japanese Unexamined Patent Application Publication No. 3-281865).
- these UV-absorbing polymers have the following disadvantages, and there is room for improvement. That is, since these ultraviolet absorbing polymers are not hydrophilic, they cannot be mixed stably and uniformly when blended in a water emulsion resin. In addition, depending on the type of the water emulsion resin, the compatibility is insufficient, which also lowers the mechanical strength of the resin. This tendency is particularly remarkable in a thermoplastic resin obtained from a polyolefin water emulsion, a polyvinylidene chloride water emulsion, or the like. It is still not satisfactory in terms of long-term light resistance.
- resins obtained from polyvinylidene chloride water emulsion, polyester water emulsion, polyurethane resin water emulsion, etc. have extremely high mechanical strength, and are widely used as various coating materials or binding materials.
- Vinylidene chloride, polycarbonate, polyester and polyurethane resins have the disadvantage that they are decomposed by alkali components and their mechanical strength is reduced.All of them are expected to have improved chemical resistance such as alkali resistance and solvent resistance. .
- An object of the present invention is to provide excellent light resistance without deteriorating the preferable properties of the synthetic resin, and to improve the blending stability of the synthetic resin with a water emulsion while maintaining excellent compatibility with a wide range of synthetic resins.
- An object of the present invention is to provide a resin composition. Disclosure of the invention
- a first aspect of the present invention is that a polyol component (A) having an ultraviolet absorbing group, an optionally added polyol (B), an alkyl or arylidanolamine compound (C), and an organic polyisocyanate (D). ) In an organic solvent (E), followed by a diluting reaction with an organic solvent (F) having a boiling point of less than 100 ° C. The resin solution obtained is diluted with a neutralizing agent (G). A water emulsion of an ultraviolet-absorbing resin obtained by dispersing in water after neutralization with water.
- a second aspect of the present invention is a water emulsion of the ultraviolet absorbent resin according to the first aspect of the present invention, wherein the polyol component (A) containing an ultraviolet absorbing group is a compound represented by the following formula: provide.
- a third aspect of the present invention is the ultraviolet absorbent according to the first aspect of the present invention, which is obtained by removing the organic solvent (E) by 1 to 100% and then diluting with an organic solvent (F). Provide resin water emulsion.
- the fourth aspect of the present invention is that after removing the organic solvent (E) by 1 to 100%, the organic solvent (F) is removed. 2.
- a fifth aspect of the present invention provides a water emulsion of the ultraviolet absorbent resin according to the first aspect of the present invention, which is obtained by removing the organic solvent (F).
- a sixth aspect of the present invention provides a water emulsion of the ultraviolet absorbing resin according to the second aspect of the present invention, which is obtained by removing the organic solvent (F).
- a seventh aspect of the present invention provides a water emulsion of the ultraviolet absorbing resin according to the third aspect of the present invention, which is obtained by removing the organic solvent (F).
- An eighth aspect of the present invention provides a water emulsion of the ultraviolet absorbent resin according to the fourth aspect of the present invention, which is obtained by removing the organic solvent (F).
- a ninth aspect of the present invention is any of the first to eighth aspects of the present invention, wherein the polyol component (A) having an ultraviolet absorbing group is contained in the ultraviolet absorbing resin in an amount of 10% by weight or more.
- a tenth aspect of the present invention is a water emulsion resin composition
- a water emulsion resin composition comprising the water-absorbing resin water emulsion (I) according to any one of the first to eighth aspects of the present invention and a water emulsion (II) of another resin. Offer things.
- the eleventh aspect of the present invention is directed to a water emulsion of the ultraviolet absorbent resin according to the ninth aspect of the present invention.
- the water emulsion (I) of the ultraviolet absorbing resin of the present invention comprises a polyol component (A) having an ultraviolet absorbing group, an optionally added polyol (B), an alkyl or aryl dialkanolamine compound (C), and an organic compound.
- Polyisocyanate (D) is urethanized in organic solvent (E), and its boiling point is less than 100 ° C
- the resin solution obtained by diluting the organic solvent (F) is neutralized with a neutralizing agent (G) and then dispersed in water.
- the polyol component (A) having an ultraviolet absorbing group is preferably a triazole ring-containing polyol, for example, 1,1-bis [3- (2H-benzotriazo-1-yl-2-yl) represented by the formula (1). [4-Hydroxy-benzeneethanol] methane.
- an ultraviolet absorber containing the compound represented by the formula (1) it is preferable to use an ultraviolet absorber containing the compound represented by the formula (1) as an effective component, and a synthetic product or a commercially available product can be used.
- the polyol component (A) is contained in the ultraviolet absorbing resin in an amount of 10% by weight or more, preferably 40 to 70% by weight.
- the polyol (B) is a component that is optionally added.
- examples of the polyol (B) include polyester polyol, polyether polyol, polyacrylonitrile, poly (meth) acryl polyol, polyalkyl polyol, and polyalkylene polyol. And the like. These polyols are used alone or in combination of two or more.
- the polyol (B) is added in an amount of 0 to 200 parts by weight, preferably 0 to 100 parts by weight, based on 100 parts by weight of the component (A).
- alkyl or aryldialkanolamine compound (C) examples include lactone addition using N-methyljetanolamine, N-ethyljetanolamine, N-phenyljetanolamine, N-ethylethanolamine or the like as an initiator.
- lactone examples include ⁇ -force prolactone, trimethyl- ⁇ -force prolactone, monomethyl-1- ⁇ -force prolactone, aptyloractone, ⁇ -valerolactone and the like.
- the number of moles of lactone added is 1 to 10 moles, preferably 1 to 6 moles, per mole of the initiator.
- the component (C) is added in an amount of 4 to 25 parts by weight, preferably 8 to 15 parts by weight, based on 100 parts by weight of the component (A).
- organic polyisocyanate (D) examples include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,2'-diphenyl methane diisocyanate, 4'-Diphenylmethane diisocyanate, 4,4'-Diphenylmethane diisocyanate, diphenyldimethylmethane diisocyanate, dibenzyl diisocyanate, naphthylene diisocyanate, phenylene diisocyanate Aromatic diisocyanates such as neat, xylene diisocyanate, tetramethyl xylylene diisocyanate; tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,1, 5-di-socyanate, 3-methylpentane-1,5-diisocyanate, 2,2,4-trimethylhexane-1
- organic polyisocyanates are used alone or in combination of two or more.
- modified products such as these modified products of adduct, carbodiimide, modified arophanet, modified biuret, modified uretdione, modified uretimine, modified isocyanurate and the like can also be used.
- hexamethylene diisocyanate isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylamine are preferred.
- Diisocyanate is preferred.
- the amount of the organic polyisocyanate (D) used is such that the isocyanate group of the component (D) is 0.7 to 100% of the total of the active hydrogens of the components (A), (B) and (C). It is 1.4 equivalent times, preferably 0.8 to 1.2 equivalent times.
- organic solvent (E) used in the above reaction examples include formamide, N, N-dimethylformamide, dimethylsulfoxide, dimethylsulfone, sulfolane, 2,4-dimethylsulfolane, N_methylpyrrolidone, and the like. These organic solvents (E) are used alone or in combination of two or more.
- the amount of the organic solvent (E) to be used is 0.4 to 2 times, preferably 0.7 to 1 time, per 100 parts by weight of the obtained ultraviolet absorbing resin (nonvolatile content).
- organic solvent (F) for dilution examples include acetone, methyl ethyl ketone, and tetrahydrofuran. These organic solvents (F) may be used alone or in combination of two or more.
- the amount of the organic solvent (F) used is 0.7 to 2.3 times, and preferably 0.9 to 1.5 times, based on 100 parts by weight of the obtained ultraviolet absorbing resin (nonvolatile content).
- Examples of the neutralizing agent (G) include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid; organic acids such as formic acid, acetic acid, propionic acid, and butyric acid; methyl chloride, methyl bromide, dimethyl sulfate, getyl sulfate, and benzyl chloride.
- Examples include quaternizing agents such as p-nitrobenzyl chloride, benzyl bromide, ethylene chlorohydrin, ethylene bromhydrin, epichlorohydrin, and brombutane. These neutralizing agents may be used alone or in combination of two or more.
- Component (A), Component (B), Component (C) and Organic Polyisocyanate (D) Is performed in an organic solvent (E), for example, at a reaction temperature of 65 ° C. for 12 hours.
- the urethane resin solution containing the obtained reaction product After removing the organic solvent (E) by 1 to 100%, if necessary, for example, by evaporator or vacuum distillation, the urethane resin solution containing the obtained reaction product has a boiling point of 10%.
- the resin solution obtained by diluting in an organic solvent (F) at a temperature of less than 0 ° C is neutralized with the above-mentioned neutralizing agent (G), and if necessary, an emulsifier such as dodecylbenzenesulfonic acid or polyoxyethylene nonylphenyl ether.
- G neutralizing agent
- an emulsifier such as dodecylbenzenesulfonic acid or polyoxyethylene nonylphenyl ether.
- Water emulsion (I) as an ultraviolet absorbing resin can be used at a nonvolatile content of 5 to 60% by weight.
- the organic solvent (F) can be removed as necessary to obtain a water emulsion containing no organic solvent, or the resin can be dried to obtain an ultraviolet absorbing resin. Accordingly, the present invention also discloses an ultraviolet absorbing resin obtained by a urethanization reaction of the component (A), the component (C), and the optional component (B) with the organic polyisocyanate (D).
- the urethanized resin as described above has a quaternary ammonium salt introduced as a hydrophilic group into the molecule in order to have a water dispersing ability.
- Anionic polar groups such as salts, sulfonates, phosphates, and phosphonates, cationic polar groups other than quaternary ammonium salts, and nonionic polar groups such as ether groups may be introduced.
- the water emulsion resin composition of the present invention comprises a water emulsion (I) of the ultraviolet absorbing resin, and a water emulsion ( ⁇ ) of another resin described below.
- the mixing ratio of (I) and (II) is not particularly limited and may be appropriately selected from a wide range.
- (I): ( ⁇ ) is expressed as a weight ratio (non-volatile content conversion) of 20 to 0.005: 80 to 99.995, preferably 10 to 0.1: 90 to 99.9 (the sum of both).
- Is 100.) Water emulsion of other resins ( ⁇ )]
- the water emulsion ( ⁇ ) of the above other resin is not particularly limited, and conventionally known ones can be widely used. Considering the ease of adding the water emulsion (I) of the ultraviolet absorbing resin, etc. Then, a water emulsion of a thermoplastic resin can be more preferably used.
- thermoplastic resin examples include vinyl chloride, polyvinylidene chloride, polyolefin, polyacrylonitrile, polystyrene, (meth) acrylic resin, polyamide, polyester, acrylonitrile-butadiene-styrene (ABS) resin, and (I).
- polyvinyl chloride, polyvinylidene chloride, polyolefin, polystyrene, polystyrene, (meth) acrylic resin, polyamide, polyester, ABS resin, polyurethane resin and the like can be preferably used.
- thermoplastic resins having poor alkali resistance such as polyvinyl chloride, polyvinylidene chloride, polypropionate, polyester, and polyurethane resin, and thermoplastic resins having poor solvent resistance such as polyamide can be particularly preferably used.
- these water emulsions of other resins may be used alone or in combination of two or more.
- the water emulsion resin composition of the present invention, or the water emulsion (I) of the ultraviolet absorbing resin may contain an antioxidant, a light stabilizer, a processing stabilizer, an antioxidant, a compatibilizer, etc., if necessary. At least one known additive.
- antioxidants examples include 1,6-hexanediol-bis [3- (3,5 Hindered phenolic antioxidants such as DG-tert-butyl-4-hydroxyphenyl) propionate], 3,5-DG-tert-butyl-1-hydroxybenzylphosphonate-Jethylester; dilauryl 3,3'-dithiodipropionate;
- organic antioxidant examples include phosphorus-based antioxidants such as trialkyl phenyl phosphate.
- Light stabilizers include, for example, hindered amine light stabilizers such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and nickel salt such as nickel dibutyldithiocarbamate. Light stabilizers and the like can be mentioned.
- processing stabilizer examples include, for example, phosphorus-based processing stabilizers such as Tris, (2,4-di-tert-butylphenyl) phosphate and the like.
- anti-aging agent examples include 1,1-bis (4-hydroxyphenyl) cyclohexene, N, N'-diphenyl-p-phenylenediamine and the like.
- the amount of these additives is not particularly limited, but is usually about 0.01 to 20% by weight based on the water emulsion resin composition or the nonvolatile resin of the water-absorbing resin (I). Preferably, it is used.
- the water emulsion resin composition of the present invention can be used for all applications in which a water emulsion of a resin is used, but can be particularly preferably used particularly for applications that may be exposed to light including sunlight or ultraviolet rays.
- Specific examples include glass substitutes and their surface coating materials, windows for housing, facilities, and transportation equipment, coating materials for daylighting glass and light source protection glass, interior and exterior materials for housing, facilities, and transportation equipment, and interior and exterior materials.
- Exterior paints, members for light sources that emit ultraviolet light such as fluorescent lamps and mercury lamps, members for precision instruments, electronic and electrical equipment, materials for blocking electromagnetic waves generated from various displays, containers or packaging materials for food, chemicals, chemicals, etc.
- Agricultural and industrial sheets or films printed materials, dyed goods, anti-fading agents such as dyes and pigments, sunscreen creams, shampoos, rinses, hairdressing products, and other cosmetics, sportswear, stockings, hats, and other clothing textile products and fibers , Curtains, carpets, wallpaper and other home interior goods, plastic lenses, contact lenses,
- medical instruments such as artificial eyes, optical filters, prisms, mirrors, optical articles such as photographic materials, stationery such as tapes and inks, sign boards, sign boards, and their surface coating materials.
- % and parts indicate% by weight and parts by weight.
- the mixture is heated to 95 ° C under a reduced pressure of 40 to 5 OmmHg to remove 190 parts by weight of DMF and dissolve and dilute with 240 parts by weight of methyl ethyl ketone (MEK).
- MEK methyl ethyl ketone
- 14.1 parts by weight of acetic acid was added to quaternize the amine component, and 560 parts by weight of water was added dropwise to form an emulsion. Thereafter, the solvent MEK was removed under reduced pressure to obtain the desired UV-absorbing resin water emulsion (1-1).
- This UV-absorbent resin water emulsion had a nonvolatile content of 37% and an average particle size of 160 nm (hereinafter, using a light scattering particle size measuring device (ELS-800, manufactured by Otsuka Electronics Co., Ltd.)).
- Example 2 In the same apparatus as in Example 1, 240 parts by weight of N-methylpyrrolidone (NMP) 136.4 parts by weight of the UV absorber MBEP used in Example 1 is charged and dissolved with 80. Next, 80.7 parts by weight of isophorone diisocyanate (IPDI) is added dropwise with stirring under a nitrogen atmosphere, and the reaction is carried out for 2 hours. Further, 22.9 parts by weight of N-methylethanolamine was added dropwise, and the reaction was continued for 4 hours. Next, the mixture is heated to 95 ° C under a reduced pressure of 40 to 5 OmmHg to remove 190 parts by weight of DMF, and diluted and dissolved with 240 parts by weight of methylethyl ketone (MEK).
- NMP N-methylpyrrolidone
- MEK methylethyl ketone
- UV-absorbing resin water emulsion had a nonvolatile content of 32% and an average particle size of 256 nm.
- Cationic water-based polyurethane emulsion F-8559D (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was added to 100 parts by weight of the ultraviolet absorbent resin water emulsion (1-1) obtained in Examples 1 and 2 above, (1-1), ( 1-2) Or the UV absorber MB EP itself is mixed in the parts by weight shown in Table 1 below and cast on a Teflon-coated glass plate so that the film thickness after drying becomes 100 m. After curing for a day, a film was obtained.
- the film is subjected to the following (1) exposure test, and the tensile strength test after exposure for 1000 hours is performed as shown in (2) below, the tensile elongation at break is measured, and the film is subjected to an exposure test up to 2000 hours. Was examined for coloring.
- the resin composition was cast and dried on a quartz glass disk having a diameter of 30 mm and a thickness of l mm using a spin coater to form a uniform thin film having a thickness of 0.9 to 1.0 m.
- the disc was placed in 70 ° C. warm water, and the absorbance at 340 nm of the thin film was measured every 2 hours.
- the initial absorbance (AO), the absorbance after 10 hours (A10) and the absorbance retention (% , A 10 / A0) are shown in Table 2.
- Example 5 Comparative Example 3
- the absorbance and absorbance retention were determined and are shown in Table 2.
- ADVANTAGE OF THE INVENTION According to this invention, it is excellent in compatibility with a wide range of synthetic resins, imparts excellent light resistance without impairing preferable characteristics of the synthetic resins, and improves the compounding stability of the synthetic resins with a water emulsion. Less bleed-out of UV-absorbing resin on the surface of the coating film obtained from the emulsion.
- a water emulsion resin composition containing a water emulsion of an ultraviolet absorbing resin and a water emulsion of another resin that can impart excellent alkali resistance to solvent resistance to a poor synthetic resin can be obtained.
- the water emulsion and the water emulsion composition of the present invention do not place a burden on the environment and form a coating film having durability (especially light resistance), the water emulsion and the water emulsion composition can be used in a wide range of industries such as automobiles, electric / electronics, and construction. It is expected to be used in the field.
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Polyurethanes Or Polyureas (AREA)
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Abstract
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2003/008014 WO2005000933A1 (ja) | 2003-06-25 | 2003-06-25 | 紫外線吸収性樹脂水エマルション及びエマルション樹脂組成物 |
CNA038266792A CN1788029A (zh) | 2003-06-25 | 2003-06-25 | 紫外线吸收性树脂的水乳液以及树脂乳液组合物 |
US10/562,037 US20060155015A1 (en) | 2003-06-25 | 2003-06-25 | Aqueous emulsion of ultraviolet-absorbing resin and emulsion resin composition |
EP03741121A EP1637552A4 (en) | 2003-06-25 | 2003-06-25 | AQUEOUS RESIN EMULSION ABSORBING ULTRAVIOLET AND RESIN EMULSION COMPOSITION |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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PCT/JP2003/008014 WO2005000933A1 (ja) | 2003-06-25 | 2003-06-25 | 紫外線吸収性樹脂水エマルション及びエマルション樹脂組成物 |
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PCT/JP2003/008014 WO2005000933A1 (ja) | 2003-06-25 | 2003-06-25 | 紫外線吸収性樹脂水エマルション及びエマルション樹脂組成物 |
Country Status (4)
Country | Link |
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US (1) | US20060155015A1 (ja) |
EP (1) | EP1637552A4 (ja) |
CN (1) | CN1788029A (ja) |
WO (1) | WO2005000933A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016047392A1 (ja) * | 2014-09-26 | 2016-03-31 | 富士フイルム株式会社 | 感光性樹脂組成物、平版印刷版原版、平版印刷版の作製方法、及び、高分子化合物 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104073149B (zh) * | 2014-07-21 | 2016-03-02 | 朱蕾 | 一种耐光性水性聚氨酯涂料的制备方法 |
TWI656199B (zh) * | 2016-06-29 | 2019-04-11 | 臺灣永光化學工業股份有限公司 | 聚氨酯型高分子紫外線吸收劑 |
Citations (4)
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JPH09316060A (ja) * | 1996-03-28 | 1997-12-09 | Otsuka Chem Co Ltd | ビスベンゾトリアゾリルフェノール化合物 |
JP2002012823A (ja) * | 2000-04-27 | 2002-01-15 | Kansai Paint Co Ltd | 水性塗料組成物 |
JP2002187344A (ja) * | 2000-12-19 | 2002-07-02 | Daicel Chem Ind Ltd | インクジェット記録用樹脂組成物及びこれを用いた被記録材料 |
JP2003128986A (ja) * | 2001-10-24 | 2003-05-08 | Daicel Chem Ind Ltd | 木質材料コーティング用樹脂組成物 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI250171B (en) * | 2000-10-17 | 2006-03-01 | Daicel Chem | Ultraviolet absorbable resin, aqueous resin emulsion, resin composition, aqueous resin composition, the use thereof, and aqueous polyurethane emulsion |
JP2003012748A (ja) * | 2001-06-28 | 2003-01-15 | Daicel Chem Ind Ltd | 水系紫外線吸収性樹脂エマルション及びその製造方法並びにエマルション樹脂組成物 |
JP2003212951A (ja) * | 2002-01-23 | 2003-07-30 | Daicel Chem Ind Ltd | 酸化防止機能性樹脂およびそのエマルション |
-
2003
- 2003-06-25 EP EP03741121A patent/EP1637552A4/en not_active Withdrawn
- 2003-06-25 WO PCT/JP2003/008014 patent/WO2005000933A1/ja active Application Filing
- 2003-06-25 US US10/562,037 patent/US20060155015A1/en not_active Abandoned
- 2003-06-25 CN CNA038266792A patent/CN1788029A/zh active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09316060A (ja) * | 1996-03-28 | 1997-12-09 | Otsuka Chem Co Ltd | ビスベンゾトリアゾリルフェノール化合物 |
JP2002012823A (ja) * | 2000-04-27 | 2002-01-15 | Kansai Paint Co Ltd | 水性塗料組成物 |
JP2002187344A (ja) * | 2000-12-19 | 2002-07-02 | Daicel Chem Ind Ltd | インクジェット記録用樹脂組成物及びこれを用いた被記録材料 |
JP2003128986A (ja) * | 2001-10-24 | 2003-05-08 | Daicel Chem Ind Ltd | 木質材料コーティング用樹脂組成物 |
Non-Patent Citations (1)
Title |
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See also references of EP1637552A4 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016047392A1 (ja) * | 2014-09-26 | 2016-03-31 | 富士フイルム株式会社 | 感光性樹脂組成物、平版印刷版原版、平版印刷版の作製方法、及び、高分子化合物 |
JPWO2016047392A1 (ja) * | 2014-09-26 | 2017-04-27 | 富士フイルム株式会社 | 感光性樹脂組成物、平版印刷版原版、平版印刷版の作製方法、及び、高分子化合物 |
Also Published As
Publication number | Publication date |
---|---|
CN1788029A (zh) | 2006-06-14 |
EP1637552A4 (en) | 2008-07-30 |
EP1637552A1 (en) | 2006-03-22 |
US20060155015A1 (en) | 2006-07-13 |
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