JP2007092070A - Thermoset type aqueous ultra-violet ray protection paint, and ultra-violet light protection cut-glass bottle and plate glass - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoset aqueous ultra-violet (UV) light protecting paint with excellent in hardness of a coated film, resistances to heat, water or a chemical substance, and friendly to a human body and the environment, and a UV light protection cut-glass bottle and plate glass. <P>SOLUTION: The thermoset aqueous UV light protecting paint is composed of water as a dispersing medium or solvent by blending (A) 100 pts.wt. of a solid mass of water based urethane resin, (B) 5-150 pts.wt. of a UV light absorbing agent, (C) 3-100 pts.wt. of an amino resin and (D) 0.01-20 pts.wt. of an adhesiveness improving agent, and 5-60 wt.% of the solid mass concentration. The UV light protection cut-glass bottle and plate glass are prepare by coating the thermoset aqueous UV light protecting paint followed by thermal curing. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention is a UV-cut paint suitable for applications that require coating hardness, heat resistance, water resistance, chemical resistance, etc., and is a thermosetting water-based ultraviolet ray based on a water-based resin emulsion that is friendly to the human body and the environment. The present invention relates to a cut paint, and an ultraviolet cut glass bottle and a plate glass that are thermally cured by applying the paint.

  In recent years, the harmful effects of ultraviolet rays on the human body have been strongly recognized and their prevention is strongly desired. Furthermore, a wide range of studies are being conducted on effective methods for preventing deterioration, deterioration, and discoloration of various parts and members made of plastic, as well as beverages, foods, and the like due to ultraviolet rays.

  As one of the prevention methods, there has been proposed a so-called kneading method, in which an ultraviolet absorber is blended into plastic parts, members and food and drink containers. Although this kneading method can prevent deterioration of parts, members and containers due to ultraviolet rays, it is necessary to knead a large amount of ultraviolet absorbers in order to prevent deterioration, deterioration and discoloration of food and drink in the containers. . When a large amount of UV absorber is kneaded in this way, the kneaded UV absorber bleeds out to the surface over time, so not only the UV-cut performance deteriorates over time, but also food and drink When used as a container, it has been pointed out that bleed-out ultraviolet absorbers enter foods and drinks, which is a major problem in health and safety. For such applications, a method of applying an ultraviolet cut paint capable of stably blending a large amount of an ultraviolet absorber on the outer surface is effective.

  In addition, instead of the plastic parts, members, and food and drink containers, an ultraviolet cut paint is applied to a base material such as a glass bottle. Further, UV cut paint is also applied to glass windows of office buildings, houses, automobiles and the like for the purpose of preventing deterioration of furniture furniture, adversely affecting indoor residents, and heat insulation. Since it is necessary to endure the environment and conditions in which the coating film applied to these glass products is actually used, the coating film performance is required to have a certain level of hardness, water resistance, chemical resistance, and the like. In order to satisfy these required performances, for example, as disclosed in JP-A-7-196959, an organic solvent-based UV-cut paint is used. However, organic solvents are harmful to the fire and the human body due to ignition, and the organic solvent evaporated during painting and drying fills the building and adversely affects the human body and the environment. .

As a countermeasure against this, the present applicant has developed a water-based UV-cut paint and has published an application of JP-A-2001-149845. In this published patent publication, a monomer component is emulsion-polymerized in the presence of inorganic fine particles having a high compatibility with glass such as colloidal silica to produce a highly transparent acrylic aqueous substrate, and the coating thickness is 20 μm and the wavelength is 370 nm or less. An aqueous and transparent acrylic UV-blocking coating liquid prepared by adding an ultraviolet absorber in an amount of 95 to 100% to absorb ultraviolet rays, and having a transmittance of 90% or more for visible light when the thickness is 10 μm. is suggesting. This acrylic UV-cut coating liquid material is excellent in transparency, UV-absorbing property, waterproofness, adhesion to glass, etc. was there. This is a serious drawback especially in the case of window glass.
JP-A-7-196959 JP 2001-149845 A

  An object of the present invention is to solve the problems of the above-described UV-cut paint, and is excellent in hardness, heat resistance, water resistance, chemical resistance of the coating film, and is thermosetting water-based UV cut paint that is friendly to human body and environment, and UV It is in providing a cut glass bottle and plate glass.

  In order to solve the above-mentioned problems, the present inventors are well balanced in all aspects of coating film hardness, water resistance, chemical resistance, and heat resistance with conventional water-based UV-cut paints, particularly room temperature dry paints. Since it is difficult to form a coated film, the present invention has been achieved by paying attention to a thermosetting water-based ultraviolet cut paint having good storage stability.

  That is, the thermosetting water-based UV-cut paint of the present invention uses water as a dispersion medium or solvent, and (A) 5 to 150 parts by weight of the UV absorber with respect to 100 parts by weight of the solid content of the water-based urethane resin. (C) 3 to 100 parts by weight of amino resin and (D) 0.01 to 20 parts by weight of silane coupling agent are blended, and the solid content concentration is 5 to 60% by weight. .

  In the thermosetting water-based ultraviolet light-cut paint of the present invention, (A) the water-based urethane resin is at least one selected from the group of ester-based, ether-based, polycarbonate-based, and acrylic composite-based resins, and the water-based urethane resin Is coated on transparent glass, dried at room temperature, and then heat-treated at 100 ° C. for 1 hour, the pencil hardness is H or more.

  Moreover, in the thermosetting water-based ultraviolet cut paint of the present invention, the (B) ultraviolet absorbent is a benzotriazole-based absorbent.

  Moreover, in the thermosetting water-based ultraviolet ray-cut paint of the present invention, the (C) amino resin is a melamine resin.

  The ultraviolet cut glass bottle of the present invention is an ultraviolet cut glass bottle obtained by applying the thermosetting water-based ultraviolet cut paint to a glass bottle, drying at room temperature, and then heat-curing.

  Moreover, the ultraviolet-cut plate glass of this invention is an ultraviolet-cut plate glass obtained by apply | coating the said thermosetting type water-based ultraviolet cut coating material to plate glass, drying at normal temperature, and heat-hardening.

  Since the present invention is a water-based UV-cut paint, it does not have the problem of fire caused by ignition and the problem of adversely affecting the human body and the environment as compared with conventional solvent-based paints. Even if applied to the inside of the glass, there is no discomfort or adverse effect on indoor residents.

  The paint of the present invention uses water as a dispersion medium or solvent, (A) 100 parts by weight of an aqueous urethane resin as a base resin, (B) 5 to 150 parts by weight of an ultraviolet absorber, and (C) 3 amino resins. ~ 100 parts by weight, (D) 0.01-20 parts by weight of silane coupling agent is blended, so the coating film obtained by applying to transparent glass, drying at room temperature, and heat curing is based on glass or the like. Excellent adhesion to the material, pencil hardness of 3H or higher, high hardness despite water-based paint, and high transparency with light transmittance of 80% or more in the visible light region when the film thickness is 10 μm, 370 nm It has high UV absorption performance that cuts 85% or more of the following UV rays.

  Furthermore, the ultraviolet-cut glass bottle of the present invention has a pencil hardness of 3H or more and a visible light region having a light transmittance of 80% or more and a UV transmittance of 370 nm or less of 85% or more even after immersion for 1 hour in boiling water. The performance to cut is maintained, and what was applied to a glass bottle for beverages can be sterilized by immersing in boiling water for 1 hour.

  In the thermosetting water-based UV-cut paint of the present invention, a pencil hardness of a coating film obtained by applying an aqueous urethane resin to a transparent plate glass and drying at room temperature, followed by heat treatment at 100 ° C. for 1 hour, is H or more, preferably 2H or more ( A) Since the water-based urethane resin is used and the (C) amino resin is used in combination, the coating of the present invention is applied to a transparent glass, dried at room temperature, and then heated at 150 ° C. for 30 minutes. A high hardness with a pencil hardness of 3H or higher or 4H or higher is obtained.

  As described above, the thermosetting water-based UV-cut paint of the present invention has coating film hardness, water resistance, chemical resistance, etc. comparable to or surpassing that of solvent-based paints. It can be widely used as an ultraviolet cut paint for plastic containers, wooden products, etc., for glass windows for automobiles, railways, buses, etc., and for glass bottles for liquor, wine, various foods, and cosmetics.

Next, each composition of the thermosetting water-based UV-cut paint of the present invention will be described.
(A) Aqueous urethane resin Examples of the aqueous urethane resin used in the present invention include various aqueous urethane resins such as ester-based, ether-based, polycarbonate-based, and acrylic composite-based materials from the structure introduced in the main chain. However, in order to achieve the physical properties of the coating film after thermosetting, which is the object of the present invention, it is selected in consideration of the physical properties of the coating film of the urethane resin alone. Various water-based urethane resins to be selected are coated on a transparent plate glass, dried at room temperature, dried at room temperature, and then heat-treated at 100 ° C. for 1 hour to produce a coating film. A thing, Preferably the thing of 2H or more is selected. More preferably, in order to select an aqueous urethane resin having excellent water resistance and chemical resistance, the coating film is immersed in water, ethanol, toluene, 10% NaOH aqueous solution, 10% acetic acid aqueous solution for 5 days at room temperature, Select a water-based urethane resin that forms a coating that does not show significant changes in appearance such as transparency and shape changes.

The aqueous urethane resin (A) is preferably selected from ester urethane resins and ether urethane resins that form a high hardness coating film. Specific examples of commercially available products include, for example, Adekabon titer HUX-232, HUX-240, HUX-320, and HUX-350 manufactured by Asahi Denka Kogyo Co., Ltd., such as HD-8208, HD-8261 manufactured by Hawthaway, HD-8284, HD-8533, HD-8588, etc. are mentioned.
Next, the water-based urethane resin selected above is finally selected by examining the combination of various UV absorbers, that is, the combination of the water-based urethane resin and the UV absorber that can be stably incorporated into the resin.

(B) Ultraviolet absorber (B) The ultraviolet absorber absorbs incident ultraviolet light and converts light energy into a harmless form such as thermal energy, thereby suppressing ultraviolet light transmission and coating film deterioration. There is an effect. As the ultraviolet absorber (B) used in the present invention, an organic ultraviolet absorber is desirable in consideration of the transparency of the coating film. Various ultraviolet absorbers such as salicylate, benzophenone, benzotriazole, and triazine are used. The selection is made according to the compatibility with the aqueous urethane resin used.

  Specific examples of the salicylate-based absorbent include phenyl salicylate, p-octylphenyl salicylate, 4-tert-butylphenyl salicylate, and the like.

  Specific examples of the benzophenone-based absorbent include 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-octadecyloxy Benzophenone, sodium 2,2′-dihydroxy-4,4′-dimethoxy-5-sulfobenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 5-chloro-2 -Hydroxy Nzophenone, resorcinol monobenzoate, 2,4-dibenzoylresorcinol, 4,6-dibenzoylresorcinol, hydroxydodecylbenzophenone, 2,2'-dihydroxy-4 (3-methacryloxy-2-hydroxypropoxy) benzophenone Can do.

  Specific examples of the benzotriazole-based absorbent include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- ( 2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2 -(2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-t-amylphenyl) benzotriazole 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole, 2- {2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydro Such as tall imide methyl) -5'-methylphenyl} benzotriazole and the like.

  Specific examples of the triazine-based absorbent include 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-isooctyloxyphenyl) -1,3,5-triazine, 2- [4 ((2-hydroxy-3-dodecyloxypropyl) -oxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [ 4-((2-Hydroxy-3-tridecyloxypropyl) -oxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- ( 2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and the like.

  It is also important to select the function of the UV absorber, for example, the absorption wavelength range of the UV region, and use the UV absorber alone or in a mixed system with other UV absorbers. is there. The main component is preferably a benzotriazole-based or benzophenone-based UV absorber, more preferably a benzotriazole-based UV absorber, particularly 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole and Its derivatives, or 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole and its derivatives are preferably used.

  The blending amount of the UV absorber varies depending on the type of the UV absorber used, that is, the absorption characteristics of the UV absorber, the absorption wavelength range, etc., but usually (A) a solid contained in the aqueous urethane resin The ultraviolet absorber is blended in an amount of 5 to 150 parts by weight per 100 parts by weight. If the amount is less than 5 parts by weight, the UV-cutting performance of the paint becomes insufficient. On the other hand, if the amount is more than 150 parts by weight, the UV absorber may easily bleed out from the coating film, or the coating film hardness may decrease. So undesirable. And considering coating film hardness etc., the compounding quantity is usually desirably 10 to 100 parts by weight, and more desirably 20 to 80 parts by weight.

(C) Amino resin Examples of the (C) amino resin that is a thermosetting agent employed in the present invention include various aqueous amino resins such as melamine resin, urea resin, urea glyoxal resin, and benzoguanamine resin. It blends well with the (A) water-based urethane resin blended with the UV absorber to form a colorless and transparent coating film. Even if it is heat-treated at 150 ° C. for 30 minutes, the pencil hardness is maintained while maintaining transparency. Is selected to form a coating film of 3H or more, preferably 4H or more. In the selection of the amino resin (C), the storage stability is not deteriorated by blending the amino resin. That is, when the paint is stored in a sealed state at 40 ± 1 ° C., it is more preferably 10 days or more. The standard is that it is stable even after being left for more than one month and no abnormality is observed. Further, a film that forms a coating film having a pencil hardness of 3H or more, preferably 4H or more is selected without impairing the transparency of the finally heat-cured coating film. (C) Among amino resins, melamine resins that satisfy the above selection criteria are preferred. Moreover, various compounds which accelerate | stimulate thermosetting reaction with an amino resin, ie, various catalysts, can also be mix | blended.

  Next, regarding the compounding amount of (C) amino resin, although it changes with kinds of amino resin to be used, the compounding amount of amino resin is 3-100 weight with respect to 100 weight part of solid content of (A) water-based urethane resin. Parts, preferably 5 to 80 parts by weight. If it is less than 3 parts by weight, the film hardness, water resistance, chemical resistance and other properties after heat curing tend to be insufficient, and conversely if it is added in excess of 100 parts by weight, the storage stability at 40 ± 1 ° C. Since it may worsen, it is not preferable.

(D) Silane coupling agent The (A) water-based urethane resin / (C) amino resin / (B) UV absorber system has particularly insufficient adhesion to plate glass and glass bottles. ) Add an adhesion improver. In this case, depending on the type of the adhesion improver, the coating film may be devitrified or the storage stability is not good, but the adhesion improver employed in the present invention may be used in the molecule. A so-called silane coupling agent having an alkoxysilyl group and an organic functional group is useful. Examples of the silane coupling agent include amino, ureido, epoxy, isocyanate, vinyl, methacryl, and mercapto silane coupling agents. In selecting the silane coupling agent, it is necessary to select the silane coupling agent in consideration of the transparency, the storage stability of the paint, and the physical properties of the coating film as in the case of selecting the (C) amino resin. About the compounding quantity of this silane coupling agent, although it changes with kinds of silane coupling agent to be used, the amount of active ingredients of a silane coupling agent is 0.01-0.1 normally with respect to 100 weight part of solid content of aqueous | water-based urethane resin. It is blended so as to be 20 parts by weight, more desirably 0.05 to 10 parts by weight. At this time, if the blending amount is less than 0.01 parts by weight, the adhesion to a substrate such as glass becomes insufficient, and if it is blended more than 20 parts by weight, the storage stability of the paint is deteriorated, which is not desirable.

  Among the above silane coupling agents, amino-based silane coupling agents include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane. , Γ-phenylaminopropyltrimethoxysilane, and the like. As the ureido silane coupling agent, ureidopropyltriethoxysilane, ureidopropyltrimethoxysilane, and epoxy silane coupling agent are β- (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, iso Examples of anate-based silane coupling agents include γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, and vinyl-based silane coupling agents include vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltris (β-methoxyethoxy). ) Silane, vinylmethyldimethoxysilane, methacrylic silane coupling agents include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, mercapto silane coupling agents Examples thereof include γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. Of these, γ-aminopropyltriethoxysilane and γ-aminopropyltrimethoxysilane are preferable.

Water It should be noted that the paint of the present invention, in addition to the above-mentioned (A) ~ (D) component, as a dispersion medium or a solvent thereof (A) ~ (D) components include water. Tap water, ion exchange water, distilled water, etc. can be used for water.

  Furthermore, additives such as surfactants, leveling agents, antifoaming agents, viscosity modifiers, and antioxidants can be blended with the coating composition having the above basic composition as necessary. The components and blending amounts of these additives are applied to a plate glass with a solution in which the blending amount of each component blended in the aqueous UV-cutting paint is changed, dried at room temperature, and then heat-treated at 150 ° C. for 30 minutes. The essential conditions are that the pencil hardness of the film is 3H or more, preferably 4H or more, the light transmittance in the visible light region when the film thickness is 10 μm is 80% or more, and the ultraviolet rays of 370 nm or less are cut by 85% or more. Select. Furthermore, in applications where it is applied to glass bottles for beverages, etc., the applied glass bottle may be immersed in boiling water for 1 hour for sterilization treatment. Even if immersed for 1 hour, the coating film does not peel off from the glass substrate, and the same hardness, transparency, and UV-cutting performance before and after boiling water treatment are selected.

  Surfactants include anionic surfactants such as sulfonate type, sulfonate type, and phosphate ester type, cationic surfactants such as quaternary cation type, imidazole type, and amine oxide type, and alkylphenol ethylene oxide. Type, alcohol ethylene oxide type, propylene oxide-ethylene oxide copolymer type, fatty acid ester type, amide type, polyethylene glycol and other nonionic surfactants, betaine type amphoteric surfactants, etc. Soluble organically modified polysiloxane compounds, fluorocarbon-modified acrylic compounds, etc., as antifoaming agents, antifoaming agents consisting of organic polymers and organometallic compounds compatible with water, antifoaming agents consisting of modified silicone compounds, etc. As viscosity modifiers, polycarboxylic acid amides Compounds, such as special-modified urea compounds, hindered phenol compounds as an antioxidant, such as hindered amine compounds each is preferably used.

  The preparation method of the paint of the present invention requires (A) an aqueous urethane resin, (B) an ultraviolet absorber dissolved in a specific solvent is added and mixed, and the ultraviolet absorber is dissolved in the urethane resin and then necessary. In accordance with the above, an additive such as a leveling agent is blended to prepare an ultraviolet cut paint. In that case, water etc. are added and it adjusts suitably so that it may become predetermined | prescribed solid content concentration. Thereafter, (C) the amino resin is added and mixed and stirred uniformly, and then (D) the silane coupling agent is mixed and stirred to prepare the coating liquid of the present invention. At this time, it is possible to reverse the addition order of (C) amino resin and (D) silane coupling agent or to add them simultaneously. And this liquid is refine | purified by filtering with a 1 micrometer opening filter, for example. Further, the solid content concentration of the coating material of the present invention is appropriately adjusted according to the application to be used and the coating method, but is usually 5 to 60% by weight, preferably 15 to 40% by weight, as a dispersion medium or solvent. Adjust by adding water.

  Examples of the base material to which the paint of the present invention is applied include various base materials having a relatively high hardness that require an ultraviolet cut function such as glass products such as window glass and glass bottles.

  Next, applications that make use of the effects of the paint of the present invention will be specifically described in comparison with the prior art.

  In recent years, awareness of the harmful effects of ultraviolet rays has increased, and it has been widely practiced to apply films containing UV absorbers and paints on window glass of vehicles such as ordinary households, buildings, automobiles, railways, and buses. It is like that. In the case of film, in addition to the disadvantage that seams appear when pasted on large window glass, the kneaded UV absorber bleeds out and the UV blocking performance of the film deteriorates, making it impossible to use for a long time. There is a problem that the film surface is easily damaged. On the other hand, the conventional method of applying UV paint to window glass can obtain a seamless and durable coating, but the surface hardness of the coating is low and easy with nails. As a result, the range of use is extremely limited. On the other hand, the coating material of the present invention has a high hardness of the coating film, hardly scratches by nails, is excellent in water resistance, chemical resistance, UV cut rate, and its effect lasts for a long time. Suitable for painting various window glass.

  In addition, it is known that beverages such as liquor and wine are discolored and deteriorated in taste due to ultraviolet rays, and that foods and cosmetics are similarly altered and deteriorated. Opacity is made opaque, or containers such as glass bottles themselves are colored in a color that makes it difficult for ultraviolet rays to pass through. In addition, UV cut paint is also applied to the surface of the container, but in this case, considering the hardness, water resistance, chemical resistance, etc. of the coating film, it may cause fire problems, damage to the human body and the environment. Solvent-based UV-cut paint is used with the knowledge of adverse effects. On the other hand, the thermosetting water-based UV cut paint of the present invention can improve the problem of fire caused by solvents and adverse effects on the human body and the environment. And is excellent in hot water resistance, it is suitable for coating various glass containers, particularly glass bottles.

  Examples of the method for applying the paint of the present invention include a flow coating method, a bar coating method, a dipping method, a spray method, and the like, which can be appropriately selected according to the application and shape. The applied coating can be heated with a hot air drier, far infrared heater, etc., and heat cured to obtain a coating with excellent hardness, water resistance, and chemical resistance. The heating temperature varies depending on the use of urethane resin, amino resin, and addition of a curing catalyst, but it is usually desirable to be able to cure in the range of 60 to 200 ° C, preferably in the range of 80 to 160 ° C.

The coating amount of the paint obtained by the paint of the present invention is usually 3 to 50 g / m ² , preferably 10 to 30 g / m ² in terms of solid content. And since the specific gravity of this coating material is about 1, as a dry film thickness of a coating film, it will be 3-50 micrometers, Preferably it will be 10-30 micrometers. Moreover, although the coating of the coating film by the above method can usually be finished once, it can be applied twice or more.

  As described above, the present invention has been described with respect to the colorless and transparent type thermosetting water-based ultraviolet ray-cutting paint, but it is also possible to add various pigments and dyes to the paint and color it. In this case, it goes without saying that the light transmittance in the visible light region may be 80% or less depending on the pigments and dyes to be blended.

Hereinafter, the present invention will be described in more detail with reference to examples.
[Example 1]
(Selection of water-based urethane resin)
Various aqueous urethane resins were applied to a transparent plate glass, dried at room temperature, then heated at 100 ° C. for 1 hour to prepare a coating film, and a coating film having a pencil hardness of H or higher was selected from these coating films. Next, the selected coating film is immersed in water, ethanol, toluene, 10% NaOH aqueous solution, 10% acetic acid aqueous solution for 5 days at room temperature, and a coating film in which no significant change in appearance such as transparency and shape change is observed. Aqueous urethane resin I to be formed (Adekabon titer HUX-240 manufactured by Asahi Denka Kogyo Co., Ltd.) was selected.

(Preparation of paint A)
Water based urethane resin so that the amount of active ingredient is 30 parts by weight of TINUVIN 1130 manufactured by Ciba Specialty Chemicals Co., Ltd., which is a benzotriazole-based ultraviolet absorber, with respect to 100 parts by weight of the solid content of water based urethane resin I. Formulated in I. To this was added water in which a silicone leveling agent was mixed and dissolved to adjust the total solids concentration to 30%, and then the mesh was filtered through a 1 μm filter to prepare Paint A.

  The paint A was applied to a transparent plate glass so that the film thickness after drying was 10 μm, and the coating film dried at room temperature cuts 95% or more of ultraviolet rays of 370 nm or less, and the light transmittance in the visible light region was 90%. That was all. The pencil hardness of the coating film was H.

(Selection of amino resin and preparation of paint B)
Various amino resins are blended in the paint A, and the storage stability of the liquid is stable at 40 ± 1 ° C. for 10 days or more, and further, it is a melamine-based amino resin from the transparency of the heat-cured coating film. Cymel 303 manufactured by Nippon Cytec Industry Co., Ltd. was selected. Next, the active ingredient amount of the selected melamine-based amino resin is blended so as to be 20 parts by weight with respect to 100 parts by weight of the solid content of the aqueous urethane resin I, and after mixing and stirring, the opening is 1 μm. The paint B was prepared by filtering with a filter.

  This paint B was applied to a transparent plate glass so that the film thickness after drying was 10 μm, and heat-treated at 150 ° C. for 30 minutes to produce a colorless and transparent coating film. The pencil hardness of this coating film was 3 to 4H, and the ultraviolet ray cutting performance and the light transmittance in the visible light region were almost the same as the coating film of the coating material A. As an adhesion of the coating film to the plate glass, a cello tape peeling test (the coating film on the plate glass is cross-cut at 100 mm with a width of 1 mm, and after the cello tape is pasted thereon, the cello tape is peeled off to examine the degree of peeling) Then, most were peeled off. Moreover, when the coating film applied to this plate glass and thermally cured was immersed in boiling water for 1 hour, it was found that the coating film was peeled off from the plate glass.

(Selection of silane coupling agent and preparation of coating material I of the present invention)
As in the case of selecting an amino resin, various silane coupling agents as an adhesion improver are blended into the paint B. Japan is an amino silane coupling agent due to the storage stability of the liquid and the transparency of the coating film. A-1106 manufactured by Unicar Co., Ltd. was selected.

  Next, the active ingredient amount of the selected amino-based silane coupling agent is blended so as to be 3 parts by weight with respect to 100 parts by weight of the solid content of the aqueous urethane resin I. Was filtered through a 1 μm filter to prepare paint I of the present invention. Although this paint I was left standing in a 40 ± 1 ° C. thermostatic chamber in a sealed state, no abnormality such as gelation, sedimentation, or separation was observed even after one month.

  The paint I was applied to a transparent plate glass so that the film thickness after drying was 10 μm, and heat-treated at 150 ° C. for 30 minutes to produce a colorless and transparent coating film. The pencil hardness of this coating film was 3-4H. This coating cuts 90% or more of ultraviolet rays of 370 nm or less, and the light transmittance in the visible light region was 80 to 85%.

  Further, the adhesion of the coating film to glass was good, and no peeling was observed in the cello tape peeling test. Furthermore, the coating film coated and heat-cured on this plate glass is immersed in boiling water for 1 hour, and after being dried at room temperature, the performances such as pencil hardness, peelability, UV cut ability, and light transmittance in the visible light region are the same as before processing. It was almost the same as the coating film.

[Example 2]
(Selection of water-based urethane resin)
According to the selection criteria of Example 1, HD-8261 manufactured by Hawthaway was selected as the aqueous urethane resin II. The aqueous urethane resin HD-8261 was applied to a transparent plate glass, dried at room temperature, and then heat-treated at 100 ° C. for 1 hour, and the pencil hardness was 2H.

(Preparation of paint C)
50 parts by weight of TINUVIN 1130 of Ciba Specialty Chemicals Co., Ltd., which is a benzotriazole-based UV absorber, was blended in 100 parts by weight of the solid content of the aqueous urethane resin II in the aqueous urethane resin II. To this was added water in which a silicone leveling agent was mixed and dissolved to adjust the total solids concentration to 25%, followed by filtration with a 1 μm mesh filter to prepare paint C.

  The paint C was applied to a transparent plate glass so that the film thickness after drying was 10 μm, and the coating film dried at room temperature cuts 90% or more of ultraviolet rays of 380 nm or less, and the light transmittance in the visible light region was 80 to 80%. It was 85%. The pencil hardness was 2H.

(Selection of amino resin and preparation of paint D)
Based on the above selection method, Amino Resin Watersol S-695 manufactured by Dainippon Ink & Chemicals, Inc. was selected. Next, the active ingredient amount of the selected amino resin is blended so as to be 25 parts with respect to 100 parts by weight of the solid content of the water-based urethane resin II, mixed and stirred, and then filtered through a 1 μm mesh filter to obtain paint D. Prepared.

  The paint D was applied to a transparent plate glass so that the film thickness after drying was 10 μm, and heat-treated at 150 ° C. for 30 minutes to produce a colorless and transparent coating film. The pencil hardness of this coating film was 4 to 5H, and the ultraviolet ray blocking performance and the visible light transmittance were almost the same as those of the paint C. The cellophane peeling test of this coating film was poor. Moreover, when it immersed in boiling water for 1 hour, it was recognized that a coating film peels from plate glass.

(Selection of silane coupling agent and preparation of coating material II of the present invention)
Various silane coupling agents were blended in the coating material D as an adhesion improver, and AY43-031H manufactured by Toray Dow Corning Silicone Co., Ltd. was selected from the storage stability of the liquid and the transparency of the coating film.

  Next, the effective amount of the silane coupling agent is 2 parts by weight with respect to 100 parts by weight of the solid content of the aqueous urethane resin II, mixed and stirred, and then filtered through a 1 μm aperture filter. Inventive paint II was prepared. Although this paint II was left in a sealed state in a constant temperature bath of 40 ± 1 ° C., abnormal phenomena such as gelation, sedimentation and separation were not observed even after one month.

  The paint II of the present invention was applied to a transparent glass bottle so that the film thickness after drying was 10 μm, and heat-treated at 150 ° C. for 30 minutes to produce a colorless and transparent coating film. The pencil hardness of this coating film was 4-5H, and it was confirmed that there were almost no scratches even on the nails. This coating film cuts ultraviolet rays of 380 nm or less by 90% or more, and the light transmittance in the visible light region was 80 to 85%.

  Moreover, the adhesiveness of this coating film with respect to the glass bottle was good, and peeling was not recognized in the said cellophane peeling test. Furthermore, even if this glass bottle is treated in boiling water for 1 hour, it does not peel off, and performances such as pencil hardness after normal temperature drying, UV-cutting properties, and light transmittance in the visible light region are almost the same as the coating performance before treatment. Met.

  Various plastic products and concrete products are deteriorated and become brittle by ultraviolet rays when exposed to sunlight for a long time, and wooden products such as white wood are also sunburned and discolored and deteriorate in appearance when exposed to sunlight for a long time. Hardness and UV cut rate are high, prevent deterioration and discoloration due to UV rays, and the effect lasts for a long time. In addition to the above glass bottles and plate glass, it can be used for various UV prevention applications such as hard plastics, wood products and concrete products. It can be used.

  The present invention is not limited to the above-described embodiment, and can be appropriately modified and implemented without departing from the gist of the present invention.

Claims (6)

  Using water as a dispersion medium or solvent, (A) 5 to 150 parts by weight of the ultraviolet absorber, (C) 3 to 100 parts by weight of the amino resin, and 100 parts by weight of the solid content of the aqueous urethane resin, and (D) A thermosetting water-based ultraviolet ray-cutting paint comprising 0.01 to 20 parts by weight of a silane coupling agent and having a solid content concentration of 5 to 60% by weight.   (A) The aqueous urethane resin is at least one selected from the group of ester-based, ether-based, polycarbonate-based, and acrylic composite-based resins, and the aqueous urethane resin is applied to a transparent glass and dried at room temperature. The thermosetting water-based UV-cut paint according to claim 1, wherein the pencil hardness of the coating film heat-treated at 100 ° C for 1 hour is H or more.   (B) The thermosetting water-based UV-cut paint according to claim 1, wherein the UV absorber is a benzotriazole-based absorber.   (C) The thermosetting water-based UV-cut paint according to claim 1, wherein the amino resin is a melamine resin.   An ultraviolet cut glass bottle obtained by applying the thermosetting water-based ultraviolet cut paint according to any one of claims 1 to 4 to a glass bottle, drying at room temperature, and then heat curing.   The ultraviolet cut plate glass obtained by apply | coating the thermosetting water-based ultraviolet cut paint in any one of Claims 1-4 to plate glass, drying at normal temperature, and heat-hardening.