Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/50—Multilayers
  • B05D7/52—Two layers
  • B05D7/54—No clear coat specified
  • B05D7/546—No clear coat specified each layer being cured, at least partially, separately
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31652—Of asbestos
  • Y10T428/31663—As siloxane, silicone or silane
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31652—Of asbestos
  • Y10T428/31667—Next to addition polymer from unsaturated monomers, or aldehyde or ketone condensation product

Definitions

• the present invention relates to a functional coated product having photocatalytic activity and a process for producing the same and the use thereof.
• the resulting coating is irradiated by ultraviolet light to exhibits a decomposing effect of organic substances, deodorizing effect, antifungal effect, etc.
• a coating material having such photocatalytic function for example, a photocatalytic organic paint in which photocatalytic particles are dispersed in organic resin is known.
• the photocatalytic organicpaint has a drawback that the coating is deteriorated due to ultraviolet rays and photocatalytic function.
• An inorganic paint in which photocatalytic particles are dispersed in an inorganic composition such as a silicate, a phosphate or a zirconate, is known as a coating material having photocatalytic function.
• an inorganic composition such as a silicate, a phosphate or a zirconate
• These inorganic paints have much better durability than that of photocatalytic organic paints, however, it is necessary to conduct baking at a high temperature of 200° C. or more. Therefore, the range of usage is limited, and it was not suitable for applying them directly to a construction material or plastic which has inferior heat resistance.
• the silicate inorganic paint has also a drawback that an alkali was eluted to cause a whitening phenomenon easily.
• an inorganic paint in which a metal alkoxide is contained is disclosed.
• This inorganic paint is cured at a temperature of not more than 200° C., however, the coating does not have flexibility and there was a problem that crack easily occurred.
• An object of the present invention is to provide a functional coated product which has excellent adhesion properties to various substrates, hardly causes the deterioration of the substrate and a coating due to the action of a photocatalyst and also has high photocatalytic function, and a process for producing the same and the use thereof.
• the functional coated product of the present invention has the first coating layer comprising a cured coating made of an acryl-modified silicone resin coating material, and the second coating layer comprising a cured coating made of a functional coating material (1) or (2) below.
• the present invention also provides a production method of the functional coated product and use thereof.
• the functional coated product of the present invention has a first coating layer comprising a cured coating made of an acryl-modified silicone resin coating material, and a second coating layer comprising a cured coating made of a functional coating material (1) or (2).
• a process for producing a functional coated product of the present invention which comprises the following steps:
• the acryl-modified silicone resin coating material contains the following components (A), (B), (C) and (D).
• the functional coating material (1) contains the following components (E) and (F).
• the functional coating material (2) contains the following components (A), (B), (C), and (F).
• (meth)acrylate indicates either acrylate or methacrylate or both of them.
• acryl-modified silicone resin coating material it is preferred that 1 to 94 parts by weight of Component (B) and 5 to 35 parts by weight of Component (D) are formulated in 1 to 94 parts by weight of Component (A), based on the solid content of the whole condensate (provided that the total amount of Components (A), (B) and (D) comes to 100 parts by weight).
• the above-mentioned acryl-modified silicone resin coating material may contain a pigment.
• the above-mentioned substrate is selected from the group consisting of a metallic substrate, an organic substrate and a substrate coated with an organic substance in which either one of the above substrates has a coating formed from an organic substance on the surface thereof.
• the coated product of the present invention can be used for, for example, a member related to building construction, particularly, an outdoor member related to building construction, a gate for a building, and a member to be used for that purpose (e.g., a gate pier, etc.), a wall for a building and a member to be used for that purpose, a window (e.g., a lighting window, etc.), and a member to be used for that purpose (e.g., a window frame, etc.), an automobile, mechanical equipment, particularly, outdoor mechanical equipment, a member for highway-related construction, (particularly, a traffic-control sign), a post for public notice, particularly, an outdoor post for public notice, an indoor or outdoor lighting fixture and a member to be used for that purpose (e.g., a resin material, a metal material, etc.), by equipping it with at least a part of the above-mentioned materials.
• a member related to building construction particularly, an outdoor member related to building construction, a gate for a building,
• Silica compounds (E1) to (E3) which are used as a raw material of Component (E) of the functional coating material (1), can be represented by the general formula R 6 nSi(OR 5 ) 4-n (IV)
• R 5 and R 6 indicate a monovalent hydrocarbon group, and n indicates an integer of 0 to 2.
• R 6 is not specifically limited, but may be, for example, a substituted or nonsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms.
• alkyl groups such as methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, heptyl groups or octyl groups; cycloalkyl groups such as cyclopentyl groups or cyclohexyl groups; aralkyl groups such as 2-phenylethyl groups, 2-phenylpropyl groups, 3-phenylpropyl groups; aryl groups such as phenyl groups or tolyl groups; alkenyl groups such as vinyl groups or allyl groups; halogen-substituted hydrocarbon groups such as chloromethyl groups or ⁇ -chloropropyl groups or 3,3,3-trifluoropropyl groups; substituted hydrocarbon groups such as ⁇ -methacryloxypropyl groups, ⁇ -
• R 5 is not specifically limited, but alkyl groups having 1 to 4 carbon atoms are used as a main material.
• examples of the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane and the like.
• examples of the organotrialkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, etc.
• examples of the diorganodialkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane and the like.
• R 5 and R 6 may be the same or different among silica compounds (E1) to (E3).
• the above-mentioned organosiloxane (E) can be prepared, for example, by diluting the raw materials (E1) to (E3) with a suitable solvent, adding the necessary amount of water and a catalyst as a curing agent thereto, and conducting hydrolysis and polycondensation to prepare a prepolymer.
• the weight-average molecular weight of the resulting prepolymer is adjusted to 800 or more, preferably 850 or more, more favorably 900 or more, in terms of polystyrene.
• it is adjusted so that the upper limit of the molecular weight is not more than 50,000, preferably 45,000, more favorably 40,000.
• the distribution of molecular weight of the prepolymer (the weight-average molecular weight (Mw)) is less than 800, the cure shrinkage at the time of the polycondensation of the functional coating material is large, and therefore, crack is liable to occur on the coating after curing. Further, if the molecular weight is more than 50,000, the time for the curing reaction is required, which may result in an insufficient hardness of the coating.
• the amount of raw materials (E1) to (E3) to be used at the time of preparing organosiloxane (E) is 5 to 30,000 parts by weight (preferably 10 to 25,000 parts by weight, more favorably 20 to 20,000 parts by weight) of (E1), 0 to 60 parts by weight (preferably 0 to 40 parts by weight, more favorably 0 to 30 parts by weight) of (E3), based on 100 parts by weight of (E2). If the amount of (E1) used is less than the above range, there is a problem that the desired hardness of the cured coating is not obtained (the hardness is lowered).
• Colloidal silica which can be used as a material (E1) is not specifically limited.
• water-dispersed or non-aqueous organic solvent (e.g., alcohol)-dispersed colloidal silica can be used.
• colloidal silica contains 20 to 50% by weight of silica as a solid content. From this value, the amount of silica to be formulated can be determined.
• water-dispersed colloidal silica water existing as a component other than the solid content can be used as a curing agent as described bellow. Water-dispersed colloidal silica is usually made from water-glass, but it can be easily obtained as a commercially available product.
• organic solvent-dispersed colloidal silica can be easily prepared by replacing the water in the above-mentioned water-dispersed colloidal silica with an organic solvent.
• organic solvent-dispersed colloidal silica can be easily obtained as a commercially available product.
• the kind of the organic solvent, in which colloidal silica is dispersed is not specifically limited.
• Examples thereof include lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol or isobutanol; ethylene glycol derivatives such as ethylene glycol, ethylene glycol monobutyl ether or ethylene acetate glycol monoethyl ether; diethylene glycol derivatives such as diethylene glycol or diethylene glycol monobutyl ether; and diacetone alcohols, etc.
• One or two or more solvents selected from the above groups can be used.
• toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime and the like can also be used.
• water is used as a curing agent at the time of the hydrolytic polycondensation reaction.
• the amount of water is preferably 0.01 to 3.0 mol, more favorably 0.3 to 1.5 mol, based on 1 mol equivalent of OR 5 groups of silica compounds (E1) to (E3).
• a diluting solvent to be used at the time of the hydrolytic polycondensation reaction of raw materials (E1) to (E3) is not specifically limited.
• those which were described as a dispersing solvent of colloidal silica can be used.
• a pH value of the above-mentioned organosiloxane (E) is not specifically limited. It is preferred to adjust it in the range between 3.8 and 6. If the pH value is within this range, it is possible to use organosiloxane (E) stably within the above-mentioned molecular weight. When the pH value is out of the above range, the stability of organosiloxane (E) is deteriorated, therefore, the available term after a paint is prepared is limited.
• a method of adjusting a pH value is not specifically limited.
• the pH value is adjusted to within the above-mentioned range using a basic reagent such as ammonia. If the pH value exceeds 6, it may be adjusted using an acidic reagent such as hydrochloric acid. Further, depending on the pH value, the molecular weight remains small and the reaction does not proceed, therefore, it takes a long time to reach the above-mentioned range of the molecular weight. In that case, organosiloxane (E) may be heated to accelerate the reaction. Further, after making the reaction proceed using an acidic reagent to reduce the pH value, the pH value may be increased to the predetermined value using a basic reagent.
• a functional coating material (1) contains a curing catalyst when it is cured by heating; however, the functional coating material (1) may optionally contain such a catalyst in order to accelerate the heat-curing of an applied coating or to cure the applied coating at a normal temperature by accelerating the polycondensation reaction of organosiloxane (E).
• the curing catalyst is not specifically limited.
• alkyl titanates metal salts of carboxylic acid such as tin octylate, dibutyltin dilaurate or dioctyltin dimaleate; amine salts such as dibutylamine-2-hexoate, dimethylamine acetate or ethanolamine acetate; quaternary ammonium salts of carboxylic acid such as tetramethylammonium acetate; amine salts such as tetraethylpentamine; amine-type silane coupling agents such as N- ⁇ -aminoethyl- ⁇ -aminopropyltrimethoxysilane or N- ⁇ -aminoethyl- ⁇ -aminopropylmethyldimethoxysilane; acids such as p-toluenesulfonic acid, phthalic acid or hydrochloric acid; aluminum compounds such as aluminum chelate; alkali metal salts such as lithium acetate, potassium acetate, lithium
• the functional coating material (1) also contains a curing catalyst (C)
• a curing catalyst (C) it is preferable to use not more than 25% by weight, more favorably not more than 20% by weight of the curing catalyst, based on the solid content of the whole condensate of organosiloxane (E). If it is more than 45% by weight, storage stability of the coating solution may be deteriorated.
• the photocatalyst to be used as Component (F) for functional coating materials (1) and (2) (a photocatalyst (F)) is not specifically limited.
• examples thereof include oxides such as titanium oxide, zinc oxide, tin oxide, zirconium oxide, tungsten oxide, chromium oxide, molybudenum oxide, iron oxide, nickel oxide, ruthenium oxide, cobalt oxide, copper oxide, manganese oxide, germanium oxide, lead oxide, cadmium oxide, vanadium oxide, niobium oxide, tantalum oxide, rhodium oxide or rhenium oxide.
• titanium oxide, zinc oxide, tin oxide, zirconium oxide, tungsten oxide, iron oxide, niobium oxide are preferred because they show activity even if the bake-curing is conducted at a low temperature of not more than 100° C.
• the particularly preferred is titanium oxide.
• the average diameter of the primary particle is not more than 50 ⁇ m, more favorably not more than 5 ⁇ m, most favorably not more than 0.5 ⁇ m.
• One photocatalyst may be used for the photocatalyst (F). Also, two or more catalyst may be used in combination thereof.
• a photocatalyst generates active oxygen (photocatalytic properties) when ultraviolet is irradiated in the atmosphere.
• the active oxygen can oxidize and decompose organic substances. Therefore, utilizing the properties of such a catalyst, a self-cleaning effect of the decomposition of dirt originating in carbon, which is adhered to a coated product, (e.g., a carbon component contained in the exhaust gas of an automobile, nicotine of tobacco); a deodorizing effect of the decomposition of a malodorous component represented by an amine compound and an aldehyde compound; and an antifungal effect of the prevention of the generation of bacteria represented by Escherichia coli and Staphylococcus aureus and the like can be obtained.
• a coated product e.g., a carbon component contained in the exhaust gas of an automobile, nicotine of tobacco
• a deodorizing effect of the decomposition of a malodorous component represented by an amine compound and an aldehyde compound e.g.,
• the photocatalyst (F) may be the one in which a metal is incorporated.
• the metal to be incorporated is not specifically limited. Examples thereof include gold, silver, copper, iron, zinc, nickel, cobalt, platinum, ruthenium, palladium, rhodium, cadmium and the like. Among them, one or two or more can be suitably used.
• the photocatalytic function is exhibited more effectively.
• the photocatalyst (F) in which a metal is incorporated has an oxidizing ability in the presence of light. By this oxidizing performance, the deodorizing effector anti-fungal effect is exhibited.
• a clay crosslinking material in which the photocatalyst (F) is incorporated between layers.
• fine particles are incorporated in the photocatalyst (F) to improve the photocatalytic performance.
• the method for dispersing the photocatalyst (F) in the functional coating material (1) or (2) is not specifically limited.
• a silica-dispersed organosilane oligomer solution (A) to be used as Component (A) in the acryl-modified silicone resin coating material or the functional coating material (2) is a main component of a base polymer having a hydrolytic group (X) as a functional group which is involved with the curing reaction at the time of forming a cured coating.
• R 1 represented by the above-mentioned general formula (I) in the hydrolytic organosilane is not specifically limited as long as it is substituted or nonsubstituted hydrocarbon group having 1 to 8 carbon atoms.
• R 1 may be the same or different.
• alkyl groups such as methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, heptyl groups or octyl groups; cycloalkyl groups such as cyclopentyl groups or cyclohexyl groups; aralkyl groups such as 2-phenylethyl groups, 2-phenylpropyl groups, 3-phenylpropyl groups; aryl groups such as phenyl groups or tolyl groups; alkenyl groups such as vinyl groups or allyl groups; halogen-substituted hydrocarbon groups such as chloromethyl groups or ⁇ -chloropropyl groups or 3,3,3-trifluoropropyl groups; substituted hydrocarbon groups such as ⁇ -methacryloxypropyl groups, ⁇ -glycidyloxypropyl groups, 3,4-epoxycyclohexylethyl groups or ⁇ -mercaptopropyl groups.
• the hydrolytic group X is not specifically limited.
• an alkoxy group, an acetoxy group, an oxime group, an enoxy group, an amino group, an aminoxy group, an amide group and the like are included.
• an alkoxy group is preferred because it is easily available and a silica-dispersed organosilane oligomer solution (A) is easily prepared.
• hydrolytic organosilane examples include those which are represented by the above general formula (I) wherein m is an integer of 0 to 3, i.e., such as those having a mono-, di-, tri- or tetra-functionality.
• m is an integer of 0 to 3, i.e., such as those having a mono-, di-, tri- or tetra-functionality.
• Concrete examples thereof include alkoxysilanes, acetoxysilanes, oximesilanes, enoxysilanes, aminosilanes, aminoxysilanes, amidesilanes and the like.
• the preferred are alkoxysilanes because they are easily available and a silica-dispersed organosilane oligomer solution (A) is easily prepared.
• silane coupling agents are included in alkoxysilanes.
• Colloidal silica contained in Component (A) has an effect of enhancing hardness of cured coating of the coating material and improving smoothness and crack-arresting ability.
• the colloidal silica is not specifically limited.
• those mentioned as a raw material (E1) of organosiloxane (E) can be used.
• water-dispersed colloidal silica water, which is present as a component other than the solid content, can be used for the hydrolysis of the above-mentioned hydrolytic organosilane. Also, it can be used as a curing agent of the coating material.
• colloidal silica is contained, as a silica content, preferably in an amount of 5 to 95% by weight, more favorably 10 to 90% by weight, most favorably 20 to 80% by weight, based on the solid content of the whole condensate of organosilane (I).
• the content is less than 5% by weight, the desired coating hardness is not likely to be obtained.
• it exceeds 95% by weight uniform dispersion of silica is difficult, which may cause various problems such as the gelation of Component (A), or the frequent occurrence of crack in the cured coating because it is too hard.
• the formulation ratio of Component (A) in the coating material is a value including a dispersion medium of colloidal silica.
• the amount of water to be used at the time of preparing a silica-dispersed organosilane oligomer solution (A) is 0.001 to 0.5 mol, preferably 0.01 to 0.4 mol, based on 1 mol equivalent of the hydrolytic group (X) that the above-mentioned hydrolytic organosilane has. If the amount of water to be used is less than 0.001 mol, a sufficiently partially hydrolyzed compound is not obtained. If it exceeds 0.5 mol, the stability of the partially hydrolyzed compound is deteriorated.
• the above-mentioned amount of water used in the partial hydrolytic reaction of the hydrolytic organosilane is the amount of water which is separately added when using the colloidal silica containing no water (e.g., the colloidal silica in which an organic solvent alone is used as a dispersion medium).
• the above-mentioned amount of water is the amount of water which is contained in the colloidal silica beforehand plus at least the amount of water which is contained in the colloidal silica along with the separately added water.
• the amount of water contained in the colloidal silica beforehand alone satisfies the above-mentioned amount to be used, it is not necessary to add water separately.
• the amount of water contained in the colloidal silica beforehand alone does not satisfy the above-mentioned amount to be used, it is necessary to add water separately until the amount of water satisfies the above-mentioned amount to be used.
• the amount of the above-mentioned water to be used is the total amount of the water contained in the colloidal silica beforehand and the water which is added separately. Further, even if the water contained in the colloidal silica alone satisfies the above-mentioned amount to be used, water may be added separately.
• the amount of the above-mentioned water to be used is also the total amount of the water contained in the colloidal silica beforehand and the water which is added separately. However, water is added separately so that the total amount does not exceed the above-mentioned upper limit (0.5 mol based on 1 mol equivalent of the hydrolytic group (X)).
• the method for conducting partial hydrolysis of hydrolytic organosilane is not specifically limited.
• hydrolytic organosilane and colloidal silica may be mixed (when no water is contained or the necessary amount of water is not contained in the colloidal silica, water is added to that).
• partial hydrolytic reaction proceeds at room temperature.
• the mixture may be optionally heated (e.g., at 60 to 100° C.) or a catalyst may be used. This catalyst is not specifically limited.
• One or two or more organic acids and inorganic acids such as hydrochloric acid, acetic acid, halogenated silane, chloroacetic acid, citric acid, benzoic acid, dimethylmalonic acid, formic acid, propionic acid, glutaric acid, glycolic acid, maleic acid, malonic acid, toluenesulfonic acid or oxalic acid, can be used.
• organic acids and inorganic acids such as hydrochloric acid, acetic acid, halogenated silane, chloroacetic acid, citric acid, benzoic acid, dimethylmalonic acid, formic acid, propionic acid, glutaric acid, glycolic acid, maleic acid, malonic acid, toluenesulfonic acid or oxalic acid.
• a pH value of Component (A) is from 2.0 to 7.0, more favorably 2.5 to 6.5, most favorably 3.0 to 6.0, in order to obtain its performance stably for a long period of time. If the pH value is out of this range, particularly, when the amount of water to be used is 0.3 mol or more, based on 1 mol equivalent of the hydrolytic group (X), the performance of Component (A) is not maintained and it is remarkably deteriorated. If the pH value of Component (A) is out of the above-mentioned range, e.g., if it is in the acidic side from this; range, a basic reagent such as ammonia or ethylenediamine may be added to adjust the pH value. If it is in the basic side from this range, an acidic reagent such as hydrochloric acid, nitric acid or acetic acid may be added to adjust the pH value. However, the adjusting method is not specifically limited.
• a silanol group-containing polyorganosiloxane (B) to be used as the Component (B) in an acryl-modified silicone resin coating material and a functional coating material (2) is a crosslinking agent for forming a three-dimensional crosslinking structure in a cured coating by the condensation reaction with Component (A), which is a base polymer having a hydrolytic group serving as a functional group in the curing reaction.
• Component (B) has an effect of absorbing the distortion due to the cure shrinkage of Component (A) and preventing the occurrence of crack.
• R 2 in the above-mentioned average compositional formula (II) representing (B) is not specifically limited, and the same groups as R 1 in the above-mentioned formula (I) are exemplified.
• Preferred examples thereof include substituted hydrocarbon groups such as alkyl groups having 1 to 4 carbon atoms, phenyl groups, vinyl groups, ⁇ -glycidyloxypropyl groups, ⁇ -methacryloxypropyl groups, ⁇ -aminopropyl groups or 3,3,3-trifluoropropyl groups. More favorably, methyl groups and phenyl groups are included.
• a and b are numbers which separately satisfy the above-mentioned condition. If a is less than 0.2 or b is more than 3, there is trouble such as the occurrence of crack in the cured coating. Further, if a is more than 2 and less than 4, or b is less than 0.0001, the curing does not proceed favorably.
• the silanol group-containing polyorganosiloxane (B) is not specifically limited.
• it can be obtained by hydrolyzing, for example, methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, or a mixture of one or 2 or more alkoxysilanes corresponding to the above-mentioned compounds, using a large amount of water according to a known method.
• the polyorganosiloxane thus obtained is adjusted so that it has an average-molecular weight (Mw) in terms of polystyrene of 700 to 20,000, preferably 750 to 18,000, more favorably 800 to 16,000.
• silanol group-containing polyorganosiloxane (B) when an alkoxysilane is hydrolyzed according to a known method, the small amount of alkoxy groups which are not hydrolyzed may remain. Namely, polyorganosiloxane containing both silanol groups and the very small amount of alkoxy groups is sometimes obtained. In the present invention, such polyorganosiloxane may be used.
• the curing catalyst (C) include all of those which may be optionally contained in the functional coating material (1) mentioned above.
• the curing catalyst (C) is not specifically limited as long as it is useful for the acceleration of the condensation reaction of Component (A) with Component (B), in addition to the above-mentioned catalysts.
• Acrylic resin (D) contained in the acryl-modified silicone resin coating material, which is to be used as Component (D), has an effect of improving the toughness of the cured coating made of the acryl-modified silicone resin coating material. Thereby, the occurrence of crack is prevented and it makes it possible to thicken the coating. Further, the acrylic resin (D) is incorporated into a crosslinking condensate of Component (A) and Component (B), which is to be a three-dimensional bone structure of the cured coating made of the acryl-modified silicone resin coating material, to make the crosslinking condensate acryl-modified.
• the adhesion properties between the cured coating made of the acryl-modified silicone resin coating material and the substrate are improved.
• Both the cured coating made of the acryl-modified silicone resin coating material and that made of the functional coating material (1) or 2) are silicone resin cured products having a polysiloxane structure, therefore, the adhesion properties between both of the coatings are high.
• a cured coating made of the acryl-modified silicone resin coating material having high adhesion properties to them is to be interposed, which eventually improves the adhesion properties between the cured coating of the functional coating material (1) cr (2) and the substrate.
• the acryl-modified silicone resin shows high weathering resistance and durability, therefore, it is not influenced by a photocatalyst contained in the functional coating materials (1) and (2), which are on the upper layer.
• Examples of the first (meth)acrylate in the above-mentioned formula (III), which is one of the compositional monomers of the acrylic resin (D), include the ones in which R 4 is represented by at least one substituted or nonsubstituted monovalent hydrocarbon group having 1 to 9 carbon atoms, for example, alkyl groups such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group or octyl group; cycloalkyl groups such as cyclopentyl group or cyclohexyl group; aralkyl groups such as 2-phenylethyl group, 2-phenylpropyl group or 3-phenylpropyl group; aryl groups such as phenyl group or tolyl group; halogenated hydrocarbon
• Examples of the second (meth)acrylate in the above-mentioned general formula (III), which is another compositional monomers of the acrylic resin (D), include the ones in which R 4 is represented by a group selected from the group consisting of epoxy groups, glycidyl groups and hydrocarbon groups (e.g., ⁇ -glycidyloxypropyl groups, etc.) containing at least either of the above.
• R 4 is represented by a group selected from the group consisting of epoxy groups, glycidyl groups and hydrocarbon groups (e.g., ⁇ -glycidyloxypropyl groups, etc.) containing at least either of the above.
• the preferred are epoxy groups and glycidyl groups.
• the second (meth) acrylate in the above-mentioned formula (III) may be a mixture thereof.
• Examples of the third (meth)acrylate in the above-mentioned general formula (III), which is one more another compositional monomers of the acrylic resin (D), include the ones in which R 4 is represented by a hydrocarbon group containing an alkoxysilyl group and/or a halogenated silyl group, the hydrocarbon group being exemplified by trimethoxysilylpropyl group, dimethoxymethylsilylpropyl group, monomethoxydimethylsilylpropyl group, triethoxysilylpropyl group, diethoxymethylsilylpropyl group, ethoxydimethylsilylpropyl group, trichlorosilylpropyl group, dichloromethylsilylpropyl group, chlorodimethylsilylpropyl group, chlorodimethoxysilylpropyl groupsb and dichloromethoxysilylpropyl groups.
• R 4 is represented by a hydrocarbon group containing an alkoxysily
• trimethoxysilylpropyl groups dimethoxysilylpropyl group and triethoxysilylpropyl group.
• the third (meth)acrylate in the above-mentioned formula (III) may be a mixture thereof.
• the acrylic resin (D) is a (meth)acrylate copolymer of at least three kinds of monomers comprising at least one of the first (meth)acrylates, at least one of the second (meth) acrylates and the at leastr one of third (meth)acrylates.
• the acrylic resin (D) may be a copolymer further containing one or two or more methacrylates selected from the above-mentioned first, second and third methacrylates, or it may also be a copolymer further containing one or two or more methacrylates selected from those other than the above-mentioned methacrylates.
• the above-mentioned first (meth)acrylate is an essential component for improving the toughness of the cured coating of the acryl-modified silicone resin coating material. Further, it also has an effect of improving the compatibility between Component (A) and Component (B). In order to obtain a greater effect of them, it is preferred that the substituted or nonsubstituted hydrocarbon group of R 4 has a volume at least to some degree. Therefore, the number of carbon atoms is preferably 2 or more.
• the second (meth)acrylate is an essential component for improving the adhesion properties between the cured coating made of the acryl-modified silicone resin coating material and the substrate.
• the third (meth)acrylate forms a chemical bond between the acrylic resin (D) and Components (A) and (B) at the time of curing the coating made of the acryl-modified silicone resin coating material. Thereby, the acrylic resin (D) is set in the cured coating. Further, the third (meth)acrylate also has an effect of improving the compatibility between the acrylic resin (D) and Components (A) and (B).
• the molecular weight of the acrylic resin (D) greatly relies on the compatibility between the acrylic resin (D) and Components (A) and (B).
• the weight-average molecular weight of the acrylic resin (D) exceeds 50,000 in terms of polystyrene, phase separation occurs, and the whitening of the coating may occur.
• the weight-average molecular weight of the acrylic resin (D) is not more than 50,000 in terms of polystyrene.
• the lower limit of the weight-average molecular weight of the acrylic resin (D) is 1,000 in terms of polystyrene. If the molecular weight is less than 1,000, the toughness of the coating is deteriorated, and crack is liable to occur, which is not preferred.
• the second (meth)acrylate is contained in the copolymer of the acrylic resin (D) in a monomer molar ratio of 2% or more. If it is less than 2%, the adhesion properties of the coating tends to be insufficient.
• the third (meth)acrylate is contained in the copolymer in a monomer molar ratio of 2 to 50%. If it is less than 2%, the compatibility between the acrylic resin (D) and Components (A) and (B) is poor and the whitening of the coating may occur. On the other hand, if it is more than 50%, the bonding density is too high, and therefore there tends to be no apparent improvement in the toughness, an improvement of which is an original object of the acrylic resin.
• the synthesis of the acrylic resin (D) can be conducted, for example, by a solution polymerization method in an organic solvent, an emulsion polymerization method, a radical polymerization method, a suspension polymerization method, an anion polymerization method, a cation polymerization method or the like. However it is not limited to the above.
• the radical polymerization method using solution polymerization it is conducted according to a known method.
• the above-mentioned first, second third (meth)acrylate monomers are dissolved in an organic solvent in a reaction container. Further, a radical polymerizing agent is added to that. Then, the mixture is heated under a nitrogen atmosphere and reacted.
• the organic solvent to be used is not specifically limited. Examples thereof include toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, ethylene acetate glycol monoethyl ether and the like.
• the radical polymerizing agent is not specifically limited.
• a chain transfer agent can be added.
• the chain transfer agent is not specifically limited.
• Examples thereof include quinones such as monoethyl hydroquinone or p-benzoquinone; thiols such as mercaptoacetic acid-ethyl ester, mercaptoacetic acid-n-butyl ester, mercaptoacetic acid-2-ethyl hexyl ester, mercaptocyclohexane, mercaptocyclopentane or 2-mercaptoethanol; thiophenols such as di-3-chlorobenzene thiol, p-toluene thiol or benzene thiol; thiol derivatives such as ⁇ -mercaptopropyltrimethoxysilane; phenylpycrylhydrazine; diphenylamine; tert-butyl catechol, etc.
• quinones such as monoethyl hydroquinone or p-benzoquinone
• thiols such as mercaptoacetic acid-
• the formulation ratio of the photocatalyst (F) in the functional coating material (1) is not specifically limited because the photocatalytic performance is exhibited regardless of the amount of the photocatalyst.
• the formulation ratio of the photocatalyst (F) in the functional coating material (2) is not specifically limited because the photocatalytic performance is exhibited regardless of the amount of the photocatalyst.
• the amount of the photocatalyst (F) is less than 10 parts by weight, there tends to be obtained no sufficient photocatalytic performance. If it is more than 90 parts by weight, the coating which is fragile and has no smoothness tends to be obtained.
• the formulation ratio of Components (A) and (B) in the functional coating material (2) is not specifically limited.
• 99 to 1 parts by weight of component (B) is used with 1 to 99 parts by weight of Component (A)
• 95 to 5 parts by weight of Component (B) is used with 5 to 95 parts by weight of Component (A)
• 90 to 10 parts by weight of Component (B) is used with 10 to 90 parts by weight of Component (A) (provided that the total of Components (A) and (B) comes to 100 parts by weight).
• Component (A) is less than 1 part by weight, the cold-curing properties are poor, or a coating having insufficient hardness is likely to be obtained.
• Component (A) is more than 99 parts by weight, the curability of the coating is unstable, or there tends to occur crack on the coating.
• the formulation ratio of Component (C) in the functional coating material (2) is not specifically limited. For example, it is preferable to use 0.0001 to 10 parts by weight, more favorably 0.005 to 8 parts by weight, most favorably 0.007 to 5 parts by weight, based on 100 parts by weight of the total of the solid content of the whole condensate of Components (A) and (B). If Component (C) is less than 0.0001 parts by weight, the coating is not likely to be cured at a normal temperature. On the other hand, if it is more than 10 parts by weight, the heat resistance or weathering resistance of the cured coating tends to be deteriorated.
• the formulation ratio of Component (C) in the acryl-modified silicone resin coating material is not specifically limited. For example, it is preferable to use 0.001 to 10 parts by weight, more favorably, 0.005 to 8 parts by weight, most favorably 0.007 to 5 parts by weight, based on 100 parts by weight of the total of the solid content of the whole condensate of Components (A), (B) and (C). If Component (C) is less than 0.001 parts by weight, the coating is not likely to be cured at a normal temperature. On the other hand, if it is more than 10 parts by weight, the heat resistance or weathering resistance of the cured coating tends to be deteriorated.
• the formulation ratio of Components (A), (B) and (D) in the acryl-modified silicone resin coating material is not specifically limited.
• 94 to 1 parts by weight of Component (B) and 5 to 35 parts by weight of Component (D) are used with 1 to 94 parts by weight of Component (A)
• 95 to 5 parts by weight of Component (B) and 5 to 35 parts by weight of Component (D) are used with 5 to 95 parts by weight of Component (A)
• 94 to 10 parts of Component (B) and 5 to 35 parts by weight of Component (D) are used with 10 to 94 parts by weight of Component (A) (provided that the total of Components (A), (B) and (D) comes to 100 parts by weight).
• Component (A) is less than 1 part by weight, the cold-curing properties are poor, or there tends to obtain no coating having sufficient hardness. On the other hand, if it is more than 94 parts by weight, the curing properties are unstable or crack is liable to occur on the coating. Further, if Component (D) is less than 5 parts by weight, there tends to be obtained no sufficient toughness or adhesion properties. If Component (D) is more than 35 parts by weight, there is high possibility that the deterioration of the coating may be accelerated due to the photocatalyst in the upper layer.
• a cured coating is formed by the condensation reaction of hydrolytic groups contained in Component (E), by heating at a low temperature or by adding a curing catalyst and leaving them to stand at a normal temperature. Accordingly, the functional coating material (1) is hardly influenced by humidity even if it is cured at a normal temperature. Further, if heat treatment is conducted, condensation reaction can be accelerated without using a curing catalyst and a cured coating can be formed.
• a cured coating is formed by the condensation reaction of a hydrolytic group in the organosilane oligomer, which is contained in Component (A), with a silanol group contained in Component (B), in the presence of a curing catalyst (C), by leaving them to stand at a normal temperature or by heating at a low temperature. Accordingly, the functional coating material (2) is hardly influenced by humidity even if it is cured at a normal temperature. Further, the condensation reaction is accelerated by heat treatment, thus, a cured coating can also be formed.
• a cured coating is formed by the condensation reaction of a hydrolytic group in the organosilane oligomer, which is contained in Component (A) and a hydrolytic group contained in acrylic resin (D) with a silanol group contained in Component (B), in the presence of a curing catalyst (C), by leaving them to stand at a normal temperature or by heating at a low temperature. Accordingly, the acryl-modified silicone resin coating material is hardly influenced by humidity even if it is cured at a normal temperature. Further, the condensation reaction is accelerated by heat treatment, thus, a cured coating can also be formed.
• the acryl-modified silicone resin coating material may optionally contain a pigment.
• the pigment to be used is not specifically limited. Examples thereof include organic pigments such as carbon black, quinacridone, naphthol red, Cyanine blue, Cyanine green or Ransa yellow; and inorganic pigments such as titanium oxide, barium sulfate, red oxide or composite metal oxide. One or two or more selected from the above may also be used in combination.
• the method for the dispersion of the pigment is not specifically limited, and it may be conducted by a conventional method, for example, by dispersing pigment powder directly using a Dyno mill, a paint shaker, etc.
• the amount of the pigment to be added is not specifically limited because the opacifying properties differ depending on the kind of the pigment. For example, it is preferable to use 5 to 80 parts by weight, more favorably 10 to 60 parts by weight, based on 100 parts by weight of the total of the solid content of the whole condensate of Components (A), (B) and (D). If the amount of the pigment to be added is less than 5 parts by weight, the opacifying properties tend to be deteriorated. If it is more than 80 parts by weight, the smoothness of the coating may be deteriorated.
• a levelling agent, a dye, metal powder, glass powder, an anti-fungus agent, an anti-oxidizing agent, an antistatic agent, an ultraviolet absorber and the like may be contained in an inorganic coating material composition as long as they do not adversely affect the effect of the prevent invention.
• the respective functional coating materials (1), (2) and the acryl-modified silicone resin coating material may be optionally diluted with various organic solvents because of easy handling. Further, the dilute solution diluted with the above solvents may be used.
• the kind of the organic solvent can be suitably selected according to mono-valent hydrocarbon groups contained in Components (A), (B), (D) or (E), or to the size of the molecular weight of Components (A), (B), (D) or (E). Such an organic solvent is not specifically limited.
• Examples thereof include lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol or isobutanol; ehtylene glycol derivatives such as ethylene glycol, ethylene glycol monobutyl ether or ethylene acetate glycol monoethyl ether; diethylene glycol derivatives such as diethylene glycol or diethylene glycol mono butyl ether; and toluene, xylene, hexane, heptane, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime, diacetone alcohol, etc.
• One or two or more selected from the above can be used in combination.
• the dilution ratio of the organic solvent is not specifically limited, and it may be suitably decided at need.
• the method for applying the respective coating materials to the substrate is not specifically limited.
• various conventional coating methods such as brushing, spraying, dipping, flow-coating, roll coating, curtain coating, knife coating or spin coating can be selected.
• the method for curing the respective coating materials, which are applied to the substrate is not specifically limited and it may be conducted by known methods. Further, the temperature when curing is not specifically limited, and the temperature in the wide range between a normal temperature and a heated temperature can be taken, according to the desired cured coating performance, whether the curing catalyst is used or not, and the heat resistance of the photocatalyst, etc.
• the thickness of the cured coating formed from the functional coating materials (1) or (2) is not specifically limited, because the photocatalytic performance is exhibited regardless of its thickness.
• the thickness of about 0.01 to 10 ⁇ m may be acceptable, but it is preferred that the thickness thereof is 0.05 to 5 ⁇ m, more favorably 0.05 to 2 ⁇ m, in order to adhere and maintain the cured coating stably for a long period of time and also to prevent crack or peeling.
• the thickness of the cured coating formed from the acryl-modified silicone resin coating material is not specifically limited.
• the thickness of about 0.1 to 100 ⁇ m may be acceptable, but it is preferred that the thickness thereof is 0.5 to 50 ⁇ m, in order to restrain deterioration of the substrate caused by the photocatalyst, to adhere and maintain the cured coating stably for a long period of time and also to prevent crack or peeling.
• the process for producing the functional coated product of the present invention is not specifically limited.
• the process of the present invention is preferred.
• the acryl-modified silicone coating material is applied to the surface of the substrate as the first, coating layer, and then the first coating layer is semi-cured.
• the functional coating material (1) or (2) is applied to the surface of this semi-cured coating layer. That is, while the first coating layer is semi-cured, the functional coating material (1) or (2) is applied to that.
• the first coating layer is completely cured before applying the functional coating material (1) or (2), the functional coating material (1) or (2) is peeled off due to the completely cured first coating layer, and therefore a coating cannot be formed.
• the functional coating material (1) or (2) is applied while the first coating layer is still wet, the first coating layer causes lifting (the adhesion properties between the first coating layer and the substrate cannot be obtained).
• “semi-curing” indicates “tack free drying” prescribed in JIS-K5400-1990. It means the condition such that no scratch is marked on the surface of the coating when the center of the coating is gently rubbed with a fingertip. Further, “complete curing” indicates “hard drying” prescribed in JIS-K5400-1990. It means the condition such that no depression due to a fingerprint is marked on the surface of the coating and the movement of the coating is not felt, and also no scratch is marked even when the center of the coating is rubbed fast with the fingertip repeatedly. Furthermore, “the coating layer is still wet” means the condition such that the fingertip is stained when the center of the coating is gently touched with the fingertip.
• the second coating layer is formed by applying the functional coating material (1) or (2) to the surface of the semi-cured layer made of the acryl-modified silicone resin coating material, these semi-cured coating layer and second coating layer are cured.
• the process for obtaining the functional coated product of the present invention is not limited to the production process of the present invention.
• the substrate to be used in the present invention is not specifically limited.
• a substrate selected from the group consisting of a metallic substrate, an organic substrate and a substrate coated with an organic substance in which either one of the above substrates has a coating formed from an organic compound on the surface thereof.
• the substrate is limited to them.
• an inorganic substrate other than the metallic substrate and a substrate coated with an organic substance having a coating formed with an organic substance on the surface of the inorganic substrate other than the metallic substrate may also be used.
• the inorganic substrate other than the metallic substrate is not specifically limited. Examples thereof include a glass substrate, enamel, a water-glass ornamental plate, an inorganic construction material such as an inorganic cured material, ceramic and the like.
• the metallic material is not specifically limited. Examples thereof include non-ferrous metal [e.g., aluminum (JIS-H4000, etc.), aluminum alloy (duralumin, etc.), copper, zinc, etc.], iron, steel [e.g., rolled steel (JIS-G3101, etc.), hot-dip zinc-coated steel (JIS-G3302), (rolled) stainless steel (JIS-G4304, G4305, etc.), etc.], tinplate (JIS-G3303, etc.), and the whole range of other metal (including alloy).
• non-ferrous metal e.g., aluminum (JIS-H4000, etc.), aluminum alloy (duralumin, etc.), copper, zinc, etc.
• iron, steel e.g., rolled steel (JIS-G3101, etc.), hot-dip zinc-coated steel (JIS-G3302), (rolled) stainless steel (JIS-G4304, G4305, etc.), etc.]
• tinplate JIS-G3303, etc.
• the glass material is not specifically limited. Examples thereof include sodium soda glass, Pyrex glass, quartz glass, no-alkali glass and the like.
• the above-mentioned enamel is formed by coating the surface of the metal with an enamel glass agent by means of baking.
• the substrate include, a mild steel plate, a steel plate, cast iron, aluminum and the like. However, it is not limited to them.
• Concerning the enamel agent conventional ones may be used and it is not specifically limited.
• the above-mentioned water-glass ornamental plate indicates an ornamental plate obtained, for example, by applying sodium silicate to a cement substrate such as slate, followed by baking.
• the inorganic cured material is not specifically limited. Examples thereof include the whole range of substrates obtained by cure-molding inorganic materials such as a fiber reinforced cement plate (JIS-A5430, etc.), a ceramic siding (JIS-A5422, etc.), a cemented excelsior board (JIS-A5404, etc.), pulp cement flat sheet (JIS-A5414, etc.), slate/excelsior cemented laminated plate (JIS-A5426, etc.) a gypsum board product (JIS-A6901, etc.), a clay roof tile (JIS-A5208, etc.), a thick slate (JIS-A5402), a ceramic tile (JIS-A5209, etc.), a concrete block for construction (JIS-A5406, etc.), terrazzo (JIS-A5411, etc.), prestressed concrete double T slab (JIS-A5412, etc.), an ALC panel (JIS-A5416, etc.), a hollow prestre
• the ceramic material is not specifically limited. Examples thereof include alumina, zirconia, silicon carbide, silicon nitride and the like.
• the organic substrate is not specifically limited. Examples thereof include plastic, wood, timber, paper and the like.
• the plastic is not specifically limited.
• thermosetting or thermoplastic plastics such as polycarbonate resin, acrylic resin, ABS resin, vinyl chloride resin, epoxy resin or phenol resin, and fiber reinforced plastic (FRP) obtained by reinforcing the above plastics with glass fiber, nylon fiber, carbon fiber, etc.
• the organic coating forming a substrate coated with an organic substance is not specifically limited. Examples thereof include a cured coating made of a coating material containing organic resin such as acrylic resin, alkyd resin, polyester resin, epoxy resin, urethane resin, acrylsilicone resin, chlorinated rubber resin, phenolic resin or melamine resin.
• organic resin such as acrylic resin, alkyd resin, polyester resin, epoxy resin, urethane resin, acrylsilicone resin, chlorinated rubber resin, phenolic resin or melamine resin.
• the form of the substrate is not specifically limited. Examples thereof include a film-shaped, sheet-shaped, plate-shaped, fiber-shaped substrate and the like. Further, the substrate may be a molded material made of the materials of these shapes or a compositional material a part of which has at least one of the molded materials of the above shapes or the compositional materials.
• the substrate may be formed from the above-mentioned various materials alone, or it may be a composite material comprising at least two of the above-mentioned various materials or a laminated material comprising the lamination of at least two of the above-mentioned various materials.
• the functional coated product of the present invention can be suitably used for the following use, by means of providing at least a part of various materials or products, using various effects originating in the excellent photocatalytic action.
• a material or article related to building construction such as a sheathing material (e.g., a material for outside wall, a roof tile such as a flat roof tile, a clay roof tile or a metal roof tile), a rainwater guttering such as a resin rainwater guttering (e.g., a PVC rainwater guttering) or a metal rainwater guttering (e.g., a stainless steel rainwater guttering, etc.), a gate and a material to be used for that (e.g., a gate door leaf, a gate pier, a gate fence, etc.), a fence and a material to be used for that, a garage door leaf, a home terrace, a door, a stanchion, a carport, a cycle port, a sign post, a delivery post, a wiring apparatus such as a switchboard/switch, a gas meter, an interphone, a main body and a camera lens portion of a video intercom, an electric lock, an entrance pole, a
• the first coating layer and the second coating layer may be directly formed on at least a part of the above-mentioned materials or articles.
• the functional coated product of the present invention wherein a base film material is used namely, the functional coating comprising the first coating layer and the second coating layer formed on the surface of the base film material, may be pasted on at least a part of various materials or articles.
• a film substrate include polyethylene terephthalate (PET) resin poly butylene-terephthalate (PBT) resin, PVC resin, acrylic resin, fluorine plastics, polypropylene (PP) resin, composite resin thereof and the like, but it is not specifically limited.
• a flask equipped with a stirrer, a warming jacket, a condenser, a dropping funnel and a thermometer were charged 100 parts of methyltrimethoxysilane, 20 parts of tetraethoxysilane, 105 parts of IPA-ST (colloidal silica sol dispersed in isopropanol: a particle diameter of 10 to 20 nm, a solid content of 30%, a water content of 0.5% manufactured by Nissan Kagaku Kogyo Co.), 30 parts of dimethyldimethoxysilane, 100 parts of isopropanol.
• IPA-ST colloidal silica sol dispersed in isopropanol: a particle diameter of 10 to 20 nm, a solid content of 30%, a water content of 0.5% manufactured by Nissan Kagaku Kogyo Co.
• Functional coating materials (1-2) to (1-5) were obtained in the same manner as in Example 1, except that the amount of the photocatalyst which was added was changed such that the resin solid content/photocatalyst weight ratio was 60/40, 50/50, 40/60 and 20/80, respectively. Further, the average molecular weight of the organosiloxane was about 1,700 ((1-2) to (1-5)).
• the comparative functional coating material (1) was obtained in the same manner as in Preparation Example 1, except that no photocatalyst was used.
• the average molecular weight of the organosiloxane was about 1,700.
• Component (A) and Component (B), which are to be used in the preparation were prepared by the following method.
• IPA-ST colloidal silica sol dispsesed in isoprppanol: a particle diameter of 10 to 20 nm, a solid content of 30%, a water content of 0.5% manufactured by Nissan Kagaku Kogyo Co.
• 68 parts of methyltrimethoxysilane and 2.2 parts of water were charged.
• the hydrolysis was conducted at 65° C. for 5 hours while stirring the mixture.
• Companent (A-1) was obtained.
• the solid content of the whole condensate of this component was 37% when it was left to stand at room temperature for 48 hours.
• Component (A-1) and Component (B-1) obtained above were mixed with the following curing catalysts (C-1) and (C-2) in the following ratio.
• Component (A-1) 50 parts (solid content: 18.5 parts)
• Component (B-1) 50 parts (solid content: 20 parts)
• Component (C-1) N- ⁇ -aminoethyl- ⁇ -aminopropylmethyl Dimethoxysilane: 2 parts
• Component (C-2) dibutiltin dilaurate 0.4 parts
• the functional coating materials (2-2) to (2-5) were obtained in the same manner as in Preparation Example 2-1, except that the amount of the photocatalyst which was added was changed such that the resin solid content/photocatalyst weight ratio was 60/40, 50/50, 40/60 and 20/80, respectively.
• the comparative coating material (2) was obtained in the same manner as in Preparation Example 2-1, except that no photocatalyst was used.
• Component (A), Component (B) and Component (D), which were to be used in the preparation were prepared by the following method.
• the molar ratio of monomers BMA/SMA/GMA 1.0/0.5/8.5
• Component (A-2), Component (B-2) and Component (D-1) obtained above were mixed with the following curing catalysts (C-1) and (C-2) in the following ratio. Thereafter, the mixture was diluted with isopropyl alcohol so that the solid content was 25% to obtain the functional coating material (1).
• Component (A-2) 50 parts (solid content: 20.5 parts)
• Component (B-2) 50 parts (solid content: 30 parts)
• Component (C-1) N- ⁇ -aminoethyl- ⁇ -aminopropylmethyldimethoxy- silane 2 parts
• Component (C-2) dibutyltin dilaurate 0.4 parts
• Component (D-1) 20.25 parts (solid content: 8.1 parts)
• the acryl-modified silicone resin coating material (2) was obtained in the same manner as in Preparation Example 3, except that the formulation ratio of Components (A-2), (B-2), (C-1), (C-2) and (D-1) was changed as follows.
• the acryl-modified silicone resin coating material (3) was obtained in the same manner as in Preparation Example 3, except that the formulation ratio of Components (A-2), (B-2), (C-1), (C-2) and (D-1) was changed as follows.
• the comparative coating material (3) was obtained in the same manner as in Preparation Example 3, except that no Component (D-1) was used.
• the acryl-modified silicone resin coating material (4) was obtained in the same manner as in Preparation Example 3, except that Components (A-2) and (B-2) were changed to Components (A-1) and (B-1), respectively, and that the formulation ratio of the respective components was as follows.
• the acryl-modified silicone resin coating material (5) was obtained in the same manner as in Preparation Example 3, except that Components (A-2) and (B-2) were changed to Components (A-1) and (B-1), respectively, and that the formulation ratio of the respective components was as follows.
• the acryl-modified silicone resin coating material (6) was obtained in the same manner as in Preparation Example 3, except that Components (A-2), (B-2) and (D-1) were changed to Components (A-1), (B-1) and (D-2), respectively, and that the formulation ratio of the respective components was as follows.
• the acryl-modified silicone resin coating material (7) was obtained in the same manner as in Preparation Example 3, except that Components (A-2), (B-2) and (D-1) were changed into Components (A-1), (B-1) and (D-2), respectively, and that the formulation ratio of the respective components was as follows.
• the acryl-modified silicone resin coating material (8) was obtained in the same manner as in Preparation Example 3, except that Components (A-2), (B-2) and (D-1) were changed to Components (A-1), (B-1) and (D-3), respectively, and that the formulation ratio of the respective components was as follows.
• the acryl-modified silicone resin coating material (9) was obtained in the same manner as in Preparation Example 3, except that Components (A-2), (B-2) and (D-1) were changed to Components (A-1), (B-1) and (D-4), respectively, and that the formulation ratio of the respective components was as follows.
• the first applied layer was formed by means of spray coating with the acryl-modified silicone resin coating material (1) prepared in Preparation Example 3 so that the cured coating thickness was 1 ⁇ m. Then, the coating was cured at 60° C. for 15 minutes. After that, the setting time was provided for 10 minutes. After the completion of the setting time, the center of the coated surface was strongly pinched with a thumb and an index finger to form depressions on the coated surface due to a fingerprint. Also, the movement of the coating was felt. However, even if the center of the coating was gently rubbed with a fingertip, no scratch was formed on the coated surface. From this results, it was confirmed that the first coating layer-was a semi-cured condition.
• the second coating layer was formed by means of spray coating with the functional coating materials (1-1) to (1-5), (2-1) to (2-5) or comparative coating materials (1) and (2) so that the cured coating thickness was 0.5 ⁇ m. After that, the second coating layer was allowed to stand at room temperature for one week to obtain functional coated products (1) to (10) and a comparative coated products (1) and (2).
• Adhesion properties to the substrate were evaluated by the peeling test using adhesive tape having a pattern of squares (cellophane tape was used).
• acetaldehyde Into a 300 ml container containing a sample, 50 ppm of acetaldehyde was injected. Black light (10 W) was irradiated to the container for 60 minutes to measure the ratio of the removed aldehyde (%) by means of gas chromatography (GC14A manufactured by Shimazu Seisakusho K.K.).
• the contact angle formed by water and the coating was evaluated by measuring the contact angle formed by water and the coating.
• the contact angle was measured when the coating was in the initial stage after preparation, and after the coating was irradiated by UV light for 24 hours using an UV-irradiation device (HANDY UV300 manufactured by OAK FACTORY).
• a comparative coated product (3) was obtained in the same manner as in Example 1, except that the second coating layer was formed only with titanium oxide instead of forming a cured coating of the functional coating material.
• a comparative coated product (4) was obtained in the same manner as in Example 3, except that the first coating layer was formed with a cured coating made of a comparative coating material (3) containing no Component (D), instead of forming a cured coating made of the acryl-modified silicone resin coating material (1).
• a comparative coated product (5) was obtained in the same manner as in Example 3, except that the functional coating material (1-3) was directly applied to the surface of the substrate without using the acryl-modified silicone resin coating material and that the curing was conducted.
• a comparative coated product (6) was obtained in the same manner as in Comparative Example 1, except that the comparative functional coating material (1) was directly applied to the surface of the substrate without using the acryl-modified silicone resin coating material and that the curing was conducted.
• Functional coated products (11) to (1.3) were obtained in the same manner as in Example 3, except that the first coating layer was formed with enamel obtained by adding the following pigments (1) to (3) to the acryl-modified silicone resin coating material (1), instead of the acryl-modified silicone resin coating material (1) which was used for forming the first coating layer.
• Functional coated products (14) to (16) were obtained in the same manner as in Example 8, except that the first coating layer was formed with enamel obtained by adding the above-mentioned pigments (1) to (3) to the acryl-modified silicone resin coating material (1), instead of the acryl-modified silicone resin coating material (1) which was used for forming the first coating layer.
• a functional coated product (17) was obtained in the same manner as in Example 3, except that the thickness of the cured coating of the second coating layer was changed to 0.1 ⁇ m.
• a functional coated product (18) was obtained in the same manner as in Example 8, except that the thickness of the cured coating of the second coating layer was changed to 0.1 ⁇ m.
• a comparative coated product (7) was obtained in the same manner as in Comparative Example 1, except that the thickness of the second coating layer was changed to 0.1 ⁇ m.
• a functional coated product (19) was obtained in the same manner as in Example 3, except that the acryl-modified silicone resin coating material (2), which was obtained in Preparation Example 4, was used instead of the acryl-modified silicone coating resin material (1).
• a functional coated product (20) was obtained in the same manner as in Example 3, except that the acryl-modified silicone resin coating material (3), which was obtained in Preparation Example 5, was used instead of the acryl-modified silicone coating resin material (1).
• a functional coated product (21) was obtained in the same manner as in Example 3, except that a PVC plate having the same size as that of the PC plate was used as a substrate.
• a functional coated product (22) was obtained in the same manner as in Example 8, except that a PVC plate having the same size as that of the PC plate was used as a substrate.
• a comparative coated product (8) was obtained in the same manner as in Example 3, except that a PVC plate having the same size as that of the PC plate was used as a substrate and that the functional coating material (1-3) was directly applied to the surface of this PVC plate without using the acryl-modified silicone resin coating material.
• a functional coated product (23) was obtained in the same manner as in Example 3, except that a plate coated with an organic substance having the same size as that of the PC plate (in which an acrylic coating PERMALOCK (manufactured by Rock Paint Co.) was applied in a thickness of 10 ⁇ m to an inorganic substrate made of a stainless steel plate) was used as a substrate.
• a plate coated with an organic substance having the same size as that of the PC plate in which an acrylic coating PERMALOCK (manufactured by Rock Paint Co.) was applied in a thickness of 10 ⁇ m to an inorganic substrate made of a stainless steel plate
• a functional coated product (24) was obtained in the same manner as in Example 8, except that a plate coated with an organic substance having the same size as that of the PC plate (in which an acryl coating PERMALOCK (manufactured by Rock Paint Co.) was applied in a thickness of 10 ⁇ m to an inorganic substrate made of a stainless steel plate) was used as a substrate.
• a plate coated with an organic substance having the same size as that of the PC plate in which an acryl coating PERMALOCK (manufactured by Rock Paint Co.) was applied in a thickness of 10 ⁇ m to an inorganic substrate made of a stainless steel plate
• a comparative coated product (9) was obtained in the same manner as in Example 3, except that a plate coated with an organic substance having the same size as that of the PC plate (in which an acrylic coating PERMALOCK (manufactured by Rock Paint Co.) was applied in a thickness of 10 ⁇ m to an inorganic substrate made of a stainless steel plate) was used as a substrate and that the functional coating material (1-3) was directly applied to the surface of this plate coated with the organic substance and curing was conducted.
• PERMALOCK manufactured by Rock Paint Co.
• a functional coated product (25) was obtained in the same manner as in Example 3, except that a stainless steel plate having the same size as that of the PC plate was used as a substrate.
• a functional coated product (26) was obtained in the same manner as in Example 8, except that a stainless steel plate having the same size as that of the PC plate was used as a substrate.
• a comparative coated product (10) was obtained in the same manner as in Example 3, except that a stainless steel plate having the same size as that of the PC plate was used as a substrate and that the functional coating material (1-3) was directly applied to the surface of this stainless steel plate without applying the acryl-modified silicone resin coating material and the curing was conducted.
• a functional coated product (27) was obtained in the same manner as in Example 3, except that a glass plate having the same size as that of the PC plate was used as a substrate.
• a functional coated product (28) was obtained in the same manner as in Example 8, except that a glass plate having the same size as that of the PC plate was used as a substrate.
• a functional coated product (29) was obtained in the same manner as in Example 3, except that a tile having the same size as that of the PC plate was used as a substrate.
• a functional coated product (30) was obtained in the same manner as in Example 8, except that a tile having the same size as that of the PC plate was used as a substrate.
• a functional coated product (31) was obtained in the same manner as in Example 3, except that an enamel plate having the same size as that of the PC plate was used as a substrate.
• a functional coated product (32) was obtained in the same manner as in Example 8, except that an enamel plate having the same size as that of the PC plate was used as a substrate.
• a comparative coated product (11) was obtained in the same manner as in Example 3, except that the acryl-modified silicone resin coating material (1), which was applied to the surface of the PC plate, was baked at 150° C. for 30 minutes to conduct complete curing (the ratio of the cured acryl-modified silicone resin coating material was 100% by weight, which was obtained in the same manner as in Example 3), and then the functional coating material (1-3) was applied to the surface thereof.
• the coating of the functional coating material (1-3) could not be formed because the functional coating material (1-3) on the completely cured layer was repelled.
• a comparative coated product (12) was obtained in the same manner as in Example 3, except that the acryl-modified silicone resin coating material (1), which was applied to the surface of the PC plate, was left to stand for 10 minutes at room temperature and then the functional coating material (1-3) was applied to the surface thereof, while the applied acryl-modified silicone resin coating material (1) was in a wet condition.
• Functional coated products (33) to (37) were obtained in the same manner as in Example 3, except that a tile having the same size as that of the PC plate was used as a substrate and that the first coating layer was formed with acryl-modified silicone resin coating materials (4) to (8) instead of the acryl-modified silicone resin coating material (1).
• a functional coated product (38) was obtained in the same manner as in Example 8, except that a tile having the same size as that of the PC plate was used as a substrate and that the first coating layer was formed with an acryl-modified silicone resin coating material (9) instead of the acryl-modified silicone resin coating material (1).
• a comparative coated product (13) was obtained in the same manner as in Example 8, except that a tile having the same size as that of the PC plate was used as a substrate, that the first coating layer was formed with a commercially available epoxy-type primer (EPORO Z PRIMER, manufactured by ISAMU PAINT CO.) instead of the acryl-modified silicone resin coating material (1), and that the thickness of the cured coating of the first coating layer was changed to 8 ⁇ m.
• EPORO Z PRIMER manufactured by ISAMU PAINT CO.
• a comparative coated product (14) was obtained in the same manner as in Example 8, except that a tile having the same size as that of the PC plate was used as a substrate, that the first coating layer was formed with an acryl-modified silicone resin coating material (7) instead of the acryl-modified silicone resin coating material (1), and that the second coating layer was formed with the comparative coating material (1) instead of the functional coating material (2-3).
• the test time was 4,000 hours, and the adhesion properties and degree of discoloration of the coating was examined. Further, the adhesion properties and degree of discoloration of the coating was also examined halfway, 2,500 hours after the test.
• the degree of discoloration was conducted according to the color difference ( ⁇ E) prescribed in JIS-Z8730. In general, it is said that a person's eye can confirm the discoloration when ⁇ E is 3 or more. Further, it is said that the irradiation for 4,000 hours by the Sunshine Weatherometer corresponds to exposure outdoors for 10 years.
• the comparative coated product (13), in which the commercially available epoxy-type primer was used showed remarkable deterioration in the coating performance.
• the degree of discoloration of the coating was reduced though the first coating layer was formed from the same material as that of the functional coated product (36) in Example 36, because the photocatalyst was not contained in the second coating layer.
• EPORO E PRIMER manufactured by ISAMU PAINT, CO.
• ISAMU PAINT Matsushita Electric Works, Ltd.
• a prime coat a prime coat
• colored coating was conducted with the pigment-containing acryl-modified silicone resin coating material prepared in Example 11, so that the thickness of the cured coating was about 30 ⁇ m.
• the cured coating was a semi-cured condition.
• the functional coating material (2-3) prepared in Preparation Example 2-3 was applied thereto so that the thickness of the cured coating was about 0.5 ⁇ m. All the coating was conducted using a hand roller.
• An acryl-modified coating material (1) prepared in Preparation Example 3 was applied to a road traffic sign ((width) 600 mm ⁇ (length) 350 mm, an one-way sign) and a pole in the premise of the head office of Matsushita Electric Works, Ltd. (Kadoma, Osaka), after wiping off the dirt with ethanol, so that the thickness of the cured coating was about 5 ⁇ m. After it was left to stand for 5 hours at room temperature, it was confirmed that the cured coating was a semi-cured condition. Then, the functional coating material (1-3) prepared in Preparation Example 1-3 was applied thereto so that the thickness of the cured coating was about 0.5 ⁇ m. All the coating was conducted by means of brushing.
• the first coating layer and the second coating layer were formed on a reflective tape for a road traffic sign (manufactured by Sumitomo 3M Co.) and on a post cone for a road (manufactured by Nippon Mectron Co.) in the same manner as in Example 3.
• the reflective tape was pasted on the post cone, followed by exposure for about 3 months at the side of the road in the premise of the head office of Matsushita Electric Works, Ltd. (Kadoma, Osaka). There was no dirt on the post cone and it maintained the condition in the beginning of the coating.
• the acryl-modified silicone resin coating material (1) prepared in Example 3 was applied to an outer wall (about 10 m 2 ) of the main building in the premise of the head office of Matsushita Electric Works, Ltd. (Kadoma, Osaka), so that the thickness of the cured coating was about 8 ⁇ m. After it was left to stand for 4 hours at room temperature, it was confirmed that the cured coating was a semi-cured condition. Then, the functional coating material (1-3) prepared in Preparation Example 1-3 was applied thereto so that the thickness of the cured coating was about 0.5 ⁇ m. All the coating was conducted using a hand roller. After exposure for about 3 months, there was no dirt on the coated building and it maintained the condition in the beginning of the coating.
• the acryl-modified coating material (1) prepared in Preparation Example 3 was applied to a glass having a size of 1 m 2 (a thickness of 6 mm) of the research laboratory (east side, the second floor) in the premise of the head office of Matsushita Electric Works, Ltd., after wiping off the dirt with ethanol, so that the thickness of the cured coating was about 1 ⁇ m. After it was left to stand for 2 hours at room temperature, it was confirmed that the cured coating was a semi-cured condition. Then, the functional coating material (2-3) prepared in Preparation Example 2-3 was applied thereto so that the thickness of the cured coating was about 0.5 ⁇ m. All the coating was conducted by means of flow coating.
• the acryl-modified coating material (1) prepared in Preparation Example 3 was applied to the whole apparatus of the road light (YA32020 for sidewalk, manufactured by Matsushita Electric Works, Ltd.) including front glass, a pole, an outer surface of a reflective plate, etc., in the premise of the head office of Matsushita Electric Works, Ltd., after wiping off the dirt with ethanol, so that the thickness of the cured coating was about 1 ⁇ m. After it was left to stand for 2 hours at room temperature, it was confirmed that the cured coating was a semi-cured condition. Then, the functional coating material (1-3) prepared in Preparation Example 1-3 was applied thereto so that the thickness of the cured coating was about 0.5 ⁇ m. All the coating was conducted with a sponge roller.
• the acryl-modified coating material (1) prepared in Preparation Example 3 was applied to an auto body (TOFOTA SPRINTER, the 1990 model), after wiping off the dirt with ethanol, so that the thickness of the cured coating was about 1 ⁇ m. After it was left to stand for 2 hours at room temperature, it was confirmed that the cured coating was a semi-cured condition. Then, the functional coating material (1-3) prepared in Preparation Example 1-3 was applied thereto so that the thickness of the cured coating was about 0.5 ⁇ m. All the coating was conducted with a sponge roller.
• EPORO E PRIMER manufactured by ISAMU PAINT, CO.
• a cement-type facing material manufactured by Matsushita Electric Works, Ltd., a multi-sizing brick tile pattern
• a prime coat in order to prevent the elution of an alkaline component, under predetermined conditions.
• colored coating was conducted with the pigment-containing acryl-modified silicone resin coating material prepared in Example 11, so that the thickness of the cured coating was about 30 ⁇ m. After it was left to stand for 5 hours at room temperature, it was confirmed that the cured coating was a semi-cured condition.
• the functional coating material (2-3) prepared in Preparation Example 2-3 was applied thereto so that the thickness of the cured coating was about 0.5 ⁇ m. All the coating was conducted by means of airless spray.
• a reflective plate (a steel plate coated with white melamine) for a Fuji-type fluorescent lighting apparatus (20W), (FA22063 manufactured by Matsushita Electric Works, Ltd.), was applied in the same manner as in Example 3, except that the second coating layer was dried at 90° C. for 15 minutes. All the coating was conducted by means of airless spray.
• the fluorescent lighting apparatus including the reflective plate coated in that way, was equipped in the cookery of the internal cafeteria in the premise of the head office of Matsushita Electric Works, Ltd. (Kadoma, Osaka), and it was observed. About three months later, the coated portion had less dirt compared with the other portion.
• EPORO E PRIMER manufactured by ISAMU PAINT, CO.
• a concrete electric-light pole no coated
• Matsushita Electric Works, Ltd. Kerdoma, Osaka
• a prime coat a prime coat
• colored coating was conducted with the pigment-containing acryl-modified silicone resin coating material prepared in Example 11, so that the thickness of the cured coating was about 30 ⁇ m.
• the functional coating material (1-3) prepared in Preparation Example (1-3) was applied thereto, so that the thickness of the cured coating was about 0.5 ⁇ m. All the coating was conducted using a hand roller.
• the acryl-modified silicone resin coating material (1) prepared in preparation Example 3 was applied to a protection fence (a galvanized steel plate) in the premise of the head office of Matsushita Electric Works, Ltd. (Kadoma, Osaka), after wiping off the dirt with ethanol, so that the thickness of the cured coating was about 1 ⁇ m. After it was left to stand for one hour at room temperature, it was confirmed that the cured coating was a semi-cured condition. Then, the functional coating material (1-3) prepared in Preparation Example (1-3) was applied thereto, so that the thickness of the cured coating was about 0.5 ⁇ m. All the coating was conducted using a hand roller.
• the functional coated product of the present invention is excellent in adhesion properties of the coating to various substrates for prime coat, and the deterioration of the substrate and the coating due to photocatalytic action hardly occurs. Further, the smoothness on the surface of the coating is high and therefore, it hardly has dirt and also has high photocatalytic action.
• the cured coating made of the acryl-modified silicone resin coating material is interposed, as the first coating layer, between the substrate and the cured coating made of the functional coating material containing a photocatalyst, the substrate is not directly influenced by the photocatalytic action, even if the substrate is an organic substrate or a substrate coated with an organic substance. Therefore, the deterioration of the substrate due to the photocatalytic action hardly occurs. Further, by the interposition of the first coating layer comprising the cured coating of the above-mentioned acryl-modified silicone resin coating material, the adhesion properties of the above-mentioned functional coating material to the substrate is improved.
• the functional coating material and an acryl-modified silicone resin coating material to be used in the present invention are both inorganic coating materials, therefore, the coating thereof is hardly deteriorated even if it receives the photocatalytic action.
• the functional coated product of the present invention When the functional coated product of the present invention is irradiated by ultraviolet light, dirt such as water-repellant organic substances is decomposed by the action of the photocatalyst contained in the second coating layer, so that wettability of the coating to water is improved, in addition to the effect of decomposition and deodorization of organic substances, the antifungal effect, the antimycotic effect, etc. This performance is exhibited regardless of the thickness of the coating and the amount of the photocatalyst contained therein. If the wettability of the coating to water is high, a defrosting effect, an stainproof effect due to washing action by rain-water in the outdoor use, etc. are exhibited. Accordingly, the functional coated product of the present invention also has other performance such as the prevention of moisture condensation on the window glass, etc. in winter, or the stainproof effect of architectural structure, road structure, automobiles, vehicles, etc.
• the functional coated product of the present invention shows desirable performance, even if a pigment is dispersed into the acryl-modified silicone resin coating material which forms the first coating layer. Therefore, it is possible to color the coating with an optional color.
• the functional coating material of the present invention it is possible to control coating properties such as photocatalytic performance, hardness or surface conditions of the coating, depending on the use, by changing the ratio of the amount of the resin to that of the photocatalyst.
• the coating material to be used for the functional coated product of the present invention can be used under dry-curing conditions or the temperature in the wide range, because it is possible to conduct not only heat-curing but also cold curing. Therefore, it is possible to apply a coating not only to a substrate having a configuration which is not easily uniformly heated, a substrate having a large size or a substrate having poor heat resistance, etc., but also to a place where heating is not easily conducted, for example, when coating operations are conducted outdoors. Accordingly, its industrial value is high.
• the application for forming the second coating layer is conducted while the first coating layer is in a semi-cured condition. Therefore, it is possible to conduct the coating process for a short period of time, by selecting temperature conditions, etc.
• a functional coated product having the above-mentioned excellent performance can be obtained easily and effectively.

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• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Wood Science & Technology (AREA)
• Catalysts (AREA)
• Paints Or Removers (AREA)
• Application Of Or Painting With Fluid Materials (AREA)
• Laminated Bodies (AREA)

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• 1997
  • 1997-02-28 JP JP4608797A patent/JP3182107B2/ja not_active Expired - Fee Related
  • 1997-12-11 US US10/336,919 patent/USRE38850E1/en not_active Expired - Fee Related
  • 1997-12-11 CA CA 2244752 patent/CA2244752C/en not_active Expired - Fee Related
  • 1997-12-11 EP EP97947894A patent/EP0916411A4/en not_active Withdrawn
  • 1997-12-11 KR KR1019980706271A patent/KR100325530B1/ko not_active IP Right Cessation
  • 1997-12-11 US US09/117,738 patent/US6165619A/en not_active Ceased
  • 1997-12-11 WO PCT/JP1997/004559 patent/WO1998025711A1/ja not_active Application Discontinuation

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