JPH08127740A - Fluorescent inorganic coating material - Google Patents

Abstract

PURPOSE: To obtain a fluorescent inorganic coating material which can give a coating film excellent in weather resistance and does not deteriorate in luminous efficiency for a long time by mixing a specified inorganic coating material having a silicone main chain with a fluorescent pigment based on an inorganic material. CONSTITUTION: This material comprises an inorganic coating material having a silicone main chain, having a chemical composition of 20-200 pts.wt. silicon compound represented by the general formula: Si(OR<1> )4 and/or a colloidal silica, 100 pts.wt. silicon compound represented by the general formula: R<2> Si(OR<1> )3 and 0-60 pts.wt. silicon compound represented by the general formula: R<2> 2 Si(0 R1 )2 ,and having a weight-average molecular weight of 900 or above (in terms of polystyrene) and a fluorescent pigment based on an inorganic maternal. In the above formulas, R<1> and R<2> are each a hydrocarbon group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorescent inorganic coating material having a fluorescent property, for example, a fluorescent inorganic coating material useful for coating an induction sign or the like.

[0002]

2. Description of the Related Art In a fluorescent organic paint having a fluorescent property using an acrylic resin as a vehicle, the organic resin deteriorates when used for a long period of time, and particularly when used outdoors,
It has a drawback that it must be frequently repainted due to deterioration due to ultraviolet rays. Further, the light emission ratio of the phosphor to the light received such as visible light and ultraviolet light is referred to as the light emission efficiency. However, since the vehicle absorbs the ultraviolet light, this light emission efficiency is inferior. As a paint used for road signs and the like, a paint having good weather resistance and fluorescence is required.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above facts, and an object of the present invention is to provide a fluorescent inorganic coating having excellent weather resistance and good luminous efficiency even when used for a long period of time. To provide.

[0004]

The fluorescent inorganic coating composition according to claim 1 of the present invention comprises an inorganic coating composition having the following composition containing silicone as a main chain and a fluorescent pigment containing an inorganic material as a main component. Characterize.

The above-mentioned inorganic coating is (a) general formula: Si (O
20 to 200 parts by weight of a silicon compound represented by R ¹ ) ₄ and / or colloidal silica, and (b) a general formula:
The silicon compound represented by R ² Si (OR ¹ ) ₃ is 100
Parts by weight, and (c) general formula: R ² ₂ Si (OR ¹ ) ₂
The weight average molecular weight of the inorganic coating material containing the silicon compound represented by the above in a proportion of 0 to 60 parts by weight and (d) containing these is 900 or more in terms of polystyrene. [The above R ¹ and R ² represent a monovalent hydrocarbon group. The fluorescent inorganic coating material according to claim 2 of the present invention is characterized in that the fluorescent coating material containing an inorganic material as a main component is contained in the inorganic coating material having the following composition containing silicone as a main chain.

The above inorganic coating composition comprises (a) 0.001 of water per 1 mol of X in colloidal silica in which a hydrolyzable organosilane represented by the following general formula [1] is dispersed in an organic solvent or water. A silica-dispersed oligomer solution of organosilane partially hydrolyzed under the condition of using 0.5 mol, and R ³ _n SiX _4-n [1] [wherein, R ³ is the same or different substituted or unsubstituted carbon The monovalent hydrocarbon groups of the numbers 1 to 8 are shown, n is an integer of 0 to 3, and X is a hydrolyzable group. (B) A polyorganosiloxane having a silanol group in the molecule represented by the following formula [2], and R ⁴ _a Si (OH) _b O _{(4-ab) / 2} [2] [In the formula, R ⁴ represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and a and b are 0.2 ≦ a ≦ 2 and 0.0001 ≦ b ≦, respectively. 3, a +
It is a number that satisfies the relationship of b <4. (C) a catalyst, and (D) the colloidal silica of the silica-dispersed oligomer solution has a silica content of 5 to 95% by weight.
At least 50 mol% of the hydrolyzable organosilane is an organosilane in which n in the formula [1] is 1, and (e) 1 to 1 of the above silica-dispersed oligomer solution.
9 parts by weight of 9 parts by weight of the above polyorganosiloxane
9 to 1 part by weight.

Hereinafter, the present invention will be described in detail. The fluorescent inorganic paint of the present invention is an inorganic paint having a silicone main chain,
Contains a fluorescent pigment.

The above-mentioned fluorescent pigment is a phosphor powder containing an inorganic material as a main component, and a fluorescent material that emits a fluorescent color immediately when exposed to ultraviolet rays and an internal energy that is stored when exposed to ultraviolet rays and gradually stores energy. Examples thereof include a light-storing material that emits light while emitting light. As a commercially available product,
Specifically, the fluorescent material is NP-202-01, NP-
103-03, NP-2310-55 (trade name of Nichia Chemical Industry Co., Ltd.) and the like, and the phosphorescent material is NP-2.
800 (trade name of Nichia Chemical Co., Ltd.), GSS-Green (trade name of Nemoto Special Chemical Co., Ltd.) and the like. The content of the fluorescent pigment is not limited, but is preferably 5 to 50% by weight based on the solid content of the inorganic coating material described below.

Next, the inorganic coating material will be described. The general formula of the inorganic coating material according to claim 1 of the present invention is represented by the following formula [3].
20 to 200 parts by weight of a silicon compound represented by the formula: and / or colloidal silica: 100 parts by weight of a silicon compound represented by the following formula [4], the general formula: Si (OR ¹ ) ₄ [3]. And a general formula: R ² Si (OR ¹ ) ₃ [4] a silicon compound represented by the following formula [5]
It is contained in a proportion of parts by weight. General formula: R ² ₂ Si (OR ¹ ) ₂ [5] In addition, the above R ¹ and R ² represent a monovalent hydrocarbon group.

The above-mentioned silicon compound has the following general formula [6]:
It is what is represented. R² _nSi (OR¹)_4-n [6] [n = 0 to 3, indicating R¹, R²Is a monovalent hydrocarbon group
Show. ] R of the previous formula [6]¹, R²Is a monovalent hydrocarbon group
Without limitation, R ²As C1-8 substitution or
Represents an unsubstituted hydrocarbon group, such as a methyl group or ethyl group.
Group, propyl group, butyl group, pentyl group, hexyl group
Group, alkyl group such as heptyl group, octyl group, cyclopentyl group
Cycloalkyl groups such as ethyl and cyclohexyl groups, 2
-Ara such as phenylethyl group and 3-phenylpropyl group
Aryl group such as alkyl group, phenyl group and tolyl group, vinyl group
Group, alkenyl group such as allyl group, chloromethyl group, γ
-Chloropropyl group, 3,3,3-trifluoropropyl group, etc.
Halogen-substituted hydrocarbon group and γ-methacryloxy
Propyl group, γ-glycidoxypropyl group, 3,4-E
Poxycyclohexylethyl group, γ-mercaptopropy
And a substituted hydrocarbon group such as a rutile group. Above all synthetic
Because of its ease or availability, it has 1 to 4 carbon atoms.
A kill group and a phenyl group are preferred.

As R ¹ in the above formula [6], ^one having an alkyl group having 1 to 4 carbon atoms as a main raw material is used. In particular, n = 0
Examples of the tetraalkoxysilane include tetramethoxysilane and tetraethoxysilane. Examples of the organotrialkoxysilane with n = 1 include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane and phenyltrimethoxysilane. , Phenyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane and the like. Furthermore, n = 2
Examples of the diorganodialkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane. Examples of the triorganoalkoxysilane with n = 3 include trimethylmethoxysilane. , Trimethylethoxysilane, trimethylisopropoxysilane, dimethylisobutylmethoxysilane and the like.

The above R ¹ and R ² are represented by the above formulas [3], [4],
In [5], the same hydrocarbon group may be present or may be different.

The above-mentioned inorganic coating is prepared by, for example, diluting a silicon compound represented by the above formulas [3], [4] and [5] with a solvent, adding water or a catalyst as a curing agent, and hydrolyzing the compound. Also, it is prepared by performing a polycondensation reaction. The weight average molecular weight (Mw) of these silicon compounds is calculated in terms of polystyrene. At the time of this preparation, the weight average molecular weight (Mw) of the inorganic coating material is adjusted to 900 or more in terms of polystyrene. When the weight average molecular weight (Mw) is less than 900 in terms of polystyrene, curing shrinkage becomes large during the polycondensation reaction, and cracks are likely to occur in the coating film of the baked inorganic coating material.

The above-mentioned inorganic coating material may be used in combination with the silicon compound represented by the above formula [3], or alternatively, colloidal silica may be used as a component. The colloidal silica is
It is a water-dispersible colloidal silica dispersed in water or an organic solvent-dispersible colloidal silica dispersed in a non-aqueous organic solvent such as alcohol. The colloidal silica contains 20 to 50% by weight of silica as a solid content.
In the preparation of the inorganic coating material, the water-dispersible colloidal silica can use water existing as a component other than the solid content as a curing agent. Further, the organic solvent-dispersible colloidal silica can be easily prepared by substituting water for the organic solvent. Examples of the organic solvent in which the colloidal silica is dispersed include lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol, and isobutanol, ethylene glycol, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether acetate. Ethylene glycol derivatives, diethylene glycol, diethylene glycol derivatives such as diethylene glycol monobutyl ether, and diacetone alcohol, and the like, and one or more of these may be used. Furthermore, in combination with a hydrophilic organic solvent, toluene, xylene, ethyl acetate, butyl acetate,
Methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime and the like can also be used. The amount of the colloidal silica blended is the weight including the dispersion medium.

Water is generally used as a curing agent when producing an inorganic coating, and the amount of this water is preferably 45% or less, more preferably 25% or less in the inorganic coating.

The organic solvent used for preparing the inorganic coating is, for example, lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol and isobutanol, ethylene glycol, ethylene glycol monobutyl ether and ethylene glycol monoacetate. Examples thereof include ethylene glycol derivatives such as ethyl ether, diethylene glycol, diethylene glycol derivatives such as diethylene glycol monobutyl ether, and diacetone alcohol. One or two of these may be mentioned.
More than one seed is used. Further, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime, etc. can be used in combination with the hydrophilic organic solvent.

When preparing the above-mentioned inorganic paint, p of the inorganic paint is used.
It is desirable that H be 3.8 to 6. When the pH is in this range, the inorganic coating composition has good storage stability, and when it is out of this pH range, the period from the preparation period to the coating period is limited. The method of adjusting the pH is not limited, but for example, when the pH becomes less than 3.8 when the materials are mixed, it may be adjusted by adding a basic reagent such as ammonia, and the pH exceeds 6 In this case, it may be adjusted by adding an acidic reagent such as hydrochloric acid.
Further, depending on the pH, when the progress of the reaction is slow in the state where the molecular weight is small, it may be heated to accelerate the reaction,
The pH may be lowered with an acidic reagent to proceed the reaction, and then a basic reagent may be added to adjust the pH to a predetermined value.

Since the inorganic coating material having the above composition has good weather resistance, the fluorescent inorganic coating material of the present invention can maintain good luminous efficiency even when used for a long time.

Next, the inorganic coating material according to claim 2 will be described. This inorganic coating is prepared by subjecting a hydrolyzable organosilane represented by the following general formula [1] to an organic solvent or water-dispersed colloidal silica in an amount of 0.001 of water to 0.001 mol of water.
A silica-dispersed oligomer solution of organosilane partially hydrolyzed under the condition of using 1 to 0.5 mol and a general formula: R ³ _n SiX _4-n [1] [wherein R ³ is the same or different substitution Alternatively, it represents an unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, n is an integer of 0 to 3, and X is a hydrolyzable group. ] A polyorganosiloxane having a silanol group in a molecule whose average composition formula is represented by the following formula [2], and an average composition formula: R ⁴ _a Si (OH) _b O _{(4-ab) / 2} [2 [Wherein, R ⁴ represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and a and b are 0.2 ≦ a ≦ 2 and 0.0001 ≦ b, respectively. ≦ 3, a +
It is a number that satisfies the relationship of b <4. ] It consists of a catalyst. Furthermore, in the above-mentioned inorganic coating material, the silica-dispersed oligomer solution contains silica in an amount of 5 to 95% by weight as a solid content, and at least 5
0 mol% is an organosilane in which n in the formula [1] is 1, and the silica-dispersed oligomer solution is used in an amount of 1 to 99%.
99 to 100 parts by weight of the above polyorganosiloxane based on parts by weight.
Contains 1 part by weight.

The silica-dispersed oligomer of the silica-dispersed oligomer solution is the main component of the base polymer having a hydrolyzable group as a functional group that is involved in the curing reaction when forming a coating film. This silica-dispersed oligomer is an organic solvent,
Alternatively, the colloidal silica dispersed in water may be added to the above formula [1]
It is obtained by partially hydrolyzing the hydrolyzable organosilane with water in colloidal silica or water added separately, by adding one or more hydrolyzable organosilanes represented by

R ³ of the hydrolyzable organosilane represented by the above formula [1] is a substituted or unsubstituted 1 having 1 to 8 carbon atoms.
A valent hydrocarbon group is shown, and specifically, a hydrocarbon group similar to the above R ² is exemplified.

Examples of X representing the hydrolyzable group include an alkoxy group, an acetoxy group, an oxime group, an enoxy group, an amino group, an aminoxy group and an amide group. Among these, the alkoxy group is preferable because it is easily available and the silica dispersion oligomer solution is easily prepared.

Such a hydrolyzable organosilane is
Monofunctional, di-, tri-, and tetra-functional alkoxysilanes, acetoxysilanes, oximesilanes, and enoxysilanes in which n in the chemical formula represented by the above formula [1] is an integer of 0 to 3 And aminosilanes, aminoxysilanes, amidosilanes and the like. Among these, alkoxysilanes are preferable because they are easily available and a silica dispersion oligomer solution is easily prepared. Examples of the tetraalkoxysilane with n = 0 include tetramethoxysilane and tetraethoxysilane,
Examples of the organotrialkoxysilane having n = 1 include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and 3,3,3-trifluoropropyltrimethoxysilane. Is exemplified. Further, as a diorganodialkoxysilane of n = 2,
Examples of dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, and the like are given. As triorganoalkoxysilane of n = 3,
Examples include trimethylmethoxysilane, trimethylethoxysilane, trimethylisopropoxysilane, and dimethylisobutylmethoxysilane. Furthermore, an organosilane compound generally called a silane coupling agent is also included in the above alkoxysilanes.

It is necessary that at least 50 mol% of the above hydrolyzable organosilane is a trifunctional organosilane represented by the formula [1] where n is 1. The proportion of the trifunctional organosilane is preferably 60 mol% or more, more preferably 70 mol% or more. If this content is less than 50 mol%, sufficient coating film hardness cannot be obtained, and the dry curability tends to be poor.

The colloidal silica in which the above hydrolyzable organosilane is dispersed in an organic solvent or water enhances the hardness of the cured coating film of the inorganic coating material. Examples of the colloidal silica include the water-dispersible colloidal silica and the organic solvent-dispersible colloidal silica described above in the first exemplary inorganic coating material.

The colloidal silica contains silica in a solid content of 5 to 95% by weight. This content is 1
0 to 90% by weight is preferable, more preferably 20 to 85
% By weight. When the content is less than 5% by weight, the hardness of the coating film of the inorganic coating cannot be obtained, and when the content exceeds 95% by weight, it becomes difficult to uniformly disperse silica, and problems such as easy gelation occur. Cheap.

The hydrolyzable organosilane represented by the above formula [1] is partially hydrolyzed in an organic solvent or colloidal silica dispersed in water to obtain a silica-dispersed oligomer solution of organosilane. The amount of water relative to the hydrolyzable organosilane was 0.
001 to 0.5 mol is preferable. If the amount of water is less than 0.001 mol, sufficient partial hydrolysis cannot be obtained, and if it exceeds 0.5 mol, the stability of the partial hydrolyzate becomes poor. The method of partial hydrolysis is not particularly limited, and it is sufficient to mix the hydrolyzable organosilane and colloidal silica and add predetermined water, at which time the partial hydrolysis reaction proceeds at room temperature. In addition, you may heat at 60-100 degreeC in order to accelerate | stimulate the said partial hydrolysis reaction. Further, for the purpose of promoting partial hydrolysis reaction, 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, Organic and inorganic acids such as toluene sulfonic acid and oxalic acid may be used as catalysts.

In order to obtain long-term stable performance of the silica-dispersed oligomer solution, the pH of the solution is 2.0 to 7.0.
The pH is preferably 2.5 to 6.5, more preferably the pH.
Is preferably 3.0 to 6.0. When the pH is out of this range, particularly when the amount of water is 0.3 mol or more relative to 1 mol of the hydrolyzable group (X), the long-term performance deterioration of the silica-dispersed oligomer solution is remarkable. The method of adjusting the pH is not limited, but when the pH of the liquid deviates from the above range to the acidic side, it may be adjusted by adding a basic reagent such as ammonia or ethylenediamine. When the pH deviates to the basic side, hydrochloric acid is added. ,
It may be adjusted by adding an acidic reagent such as nitric acid or acetic acid.

The silanol group-containing polyorganosiloxane of the above-mentioned inorganic paint has an average compositional formula represented by the above formula [2].

R ⁴ in the above formula [2] represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and specific examples thereof include the same hydrocarbon group as R ² described above. However, preferably, an alkyl group having 1 to 4 carbon atoms, phenyl group, vinyl group, γ-glycidoxypropyl group, γ-methacryloxypropyl group, γ-aminopropyl group, 3,3,3-trifluoro group It is a substituted hydrocarbon group such as a propyl group, more preferably a methyl group and a phenyl group. Further, a and b in the formula [2] are 0.2 ≦ a ≦ 2 and 0.0001, respectively.
It is a number that satisfies the relationship of ≦ b ≦ 3 and a + b <4. If a is less than 0.2 or b is more than 3, there is an inconvenience such as cracking in the cured coating film, and if a is more than 2.0 and less than 4 or b is less than 0.0001, curing proceeds well. do not do.

As the polyorganosiloxane having a silanol group, methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, or one or a mixture of two or more alkoxysilanes corresponding thereto is known. It can be obtained by hydrolysis with a large amount of water according to the method.
In order to obtain the polyorganosiloxane containing the silanol group, when hydrolyzed with an alkoxysilane,
A small amount of unhydrolyzed alkoxy groups may remain. That is, a polyorganosiloxane in which a silanol group and an extremely small amount of an alkoxy group coexist may be obtained, but such a polyorganosiloxane may be used.

The above catalyst promotes the condensation reaction between the above-mentioned silica-dispersed oligomer solution and polyorganosiloxane,
It cures the coating film. Examples of the catalyst include alkyl titanates, tin octylate and diptyltin dilaurate, metal salts of carboxylic acids such as dioctyltin dimaleate, dibutylamine-2-hexoate, dimethylamine acetate, amine salts such as ethanolamine acetate, Carboxylic acid quaternary ammonium salts such as tetramethylammonium acetate, amines such as tetraethylpentamine, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxy Amine-based silane coupling agents such as silanes, acids such as p-toluenesulfonic acid, phthalic acid and hydrochloric acid, aluminum compounds such as aluminum alkoxides and aluminum chelates, alkali catalysts such as sodium hydroxide, tetraisopropyl titanate , Tetrabutyl titanate, titanium compounds such as titanium tetraacetyl acetonate, methyltrichlorosilane, dimethyldichlorosilane, halogenated silane such as trimethyl monochloro silane, and the like.

The blending ratio of the silica-dispersed oligomer solution and the polyorganosiloxane is 1 to 99 parts by weight of the silica-dispersed oligomer solution and 99 to 1 parts by weight of the polyorganosiloxane, preferably the silica. The dispersion oligomer solution is 5 to 95 parts by weight, and the polyorganosiloxane is 95 to 5 parts by weight, and more preferably, the silica dispersion oligomer solution is 10 to 9 parts by weight.
90 to 90 parts by weight of the above polyorganosiloxane
10 parts by weight. If the proportion of the silica-dispersed oligomer solution is less than the above range, it is difficult to cure at room temperature, and sufficient hardness of the coating film cannot be obtained. If the ratio of the silica-dispersed oligomer solution is more than the above range, the curability becomes unstable.

The content of the catalyst is preferably 0.0001 to 10 parts by weight based on 100 parts by weight of the total amount of the silica-dispersed oligomer solution and the polyorganosiloxane. It is more preferably 0.0005 to 8 parts by weight, and most preferably 0.0007 to 5 parts by weight. 0.00 catalyst
If it is less than 01 parts by weight, it will not cure at room temperature, and if it exceeds 10 parts by weight, heat resistance and weather resistance will be poor.

The hydrolyzable group contained in the silica-dispersed oligomer and the silanol group in the polyorganosiloxane undergo a condensation reaction in the presence of a catalyst at room temperature or at a low temperature of 200 ° C. or lower to form a coating film. To do. Therefore, the inorganic coating material is cured at room temperature with little influence of humidity. Further, the condensation reaction can be promoted by the above-mentioned low temperature heating.

The above-mentioned inorganic coating material can be diluted with various organic solvents for easy handling. The type of the organic solvent is appropriately selected depending on the types and molecular weights of the monovalent hydrocarbon groups in the silica-dispersed oligomer solution and the polyorganosiloxane. Examples of the organic solvent include the same organic solvents as described in the inorganic coating composition according to claim 1.

Since the inorganic coating material having the above composition has good weather resistance, the fluorescent inorganic coating material according to claim 2 of the present invention contains the above-mentioned fluorescent pigment in the inorganic coating material, so that it can be used for a long time. Good luminous efficiency can be maintained.

As the method for coating the fluorescent inorganic coating material of the present invention, various coating methods such as brush coating, spray coating, dipping, curtain and knife coating can be adopted. At the time of coating, it may be appropriately diluted with an organic solvent, if necessary. The fluorescent inorganic paint is applied to a desired material and then baked to form a coating film of the fluorescent inorganic paint. The baking conditions are appropriately selected depending on the components of the inorganic paint. The thickness of the coating film is not limited, and may be, for example, about 20 to 100 μm, but is preferably 20 to 50 μm from the viewpoint of good adhesion and being less likely to cause cracks and peeling.

[0039]

EXAMPLES Next, examples of the present invention and comparative examples will be described. The molecular weight is a value determined by gel permeation chromatography (GPC) using a measurement model HLC8020 (manufactured by Tosoh Corporation) and obtained from a calibration curve of standard polystyrene.

Example 1 An inorganic coating material (A-1) was prepared under the following conditions. IPA organosilica sol (manufactured by Catalysts & Chemicals Corporation: trade name OSCAL1432) was used as the colloidal silica, and methyltrimethoxysilane was used as the silicon compound represented by the above formula [4]. 100 parts of methyltrimethoxysilane, IP
After mixing 60 parts of A organosilica sol and 100 parts of isopropyl alcohol (IPA), 60 parts of water was added and stirred. The molecular weight of this was measured in a constant temperature bath at 60 ° C.
It was adjusted to w = 950.

The prepared inorganic coating material (A-1) was added to the phosphorescent material (NP manufactured by Nichia Corporation) as a fluorescent pigment.
-2800) in an amount of 30% by weight based on the solid content of the inorganic coating.
And added with a paint shaker to obtain a fluorescent inorganic paint.

The obtained fluorescent inorganic paint was chemically polished to 0.6 m
m aluminum plate was sprayed and dried at a temperature of 180 ° C. for 30 minutes. The film thickness of the coating film after curing was 40 μm, and this aluminum plate exhibited a green luminous property upon irradiation with sunlight.

Example 2 An inorganic coating material (A-1) prepared in the same manner as in Example 1 was added to a fluorescent material (NP- manufactured by Nichia Corporation) as a fluorescent pigment.
202-01) was added at a ratio of 35% by weight to the solid content of the inorganic coating material, and stirred with a paint shaker to obtain a fluorescent inorganic coating material. The obtained fluorescent inorganic paint was chemically polished.
Spray coating on a 6 mm aluminum plate, and heat at 180 ° C for 3
Dry for 0 minutes. The film thickness of the coating film after curing is 40 μm,
This aluminum plate emitted green fluorescence upon irradiation with an ultraviolet lamp.

Example 3 An inorganic coating material (A-2) was prepared under the following conditions. IPA organosilica sol (Catalyst Kasei Co., Ltd .: trade name OSCAL1432) as colloidal silica, methyltrimethoxysilane as the silicon compound represented by the formula [4], and dimethyldimethoxy as the silicon compound represented by the formula [5]. Silane was used.

To 100 parts of methyltrimethoxysilane, I
After mixing 80 parts of PA organosilica sol, 15 parts of dimethyldimethoxysilane and 100 parts of isopropyl alcohol (IPA), 70 parts of water was added and stirred.
The molecular weight of this was adjusted to Mw = 1050 in a 60 ° C. thermostat.

Into the thus prepared inorganic coating material (A-2), a fluorescent material (NP-
2310-55) was added at a ratio of 40% by weight to the solid content of the inorganic coating material, and the mixture was stirred with a paint shaker to obtain a fluorescent inorganic coating material. Spray the resulting fluorescent inorganic paint onto a chemically-polished 0.6 mm aluminum plate at a temperature of 180 ° C.
And dried for 30 minutes. The film thickness of the coating film after curing was 30 μm, and this aluminum plate emitted red fluorescence upon irradiation with an ultraviolet lamp.

Example 4 An inorganic coating material (B) was prepared under the following conditions. First, (B-1 solution) was prepared as a silica-dispersed oligomer solution, and (B-2 solution) was prepared as a polyorganosiloxane.

(B-1 solution) In a flask equipped with a stirrer, a heating jacket, a condenser, and a thermometer, isopropyl alcohol-dispersed colloidal silica sol IPA-
ST (particle size 10 to 20 mμ, solid content 30%, water 0.5
%, Manufactured by Nissan Chemical Industries, Ltd.), 68 parts of methyltrimethoxysilane, 18 parts of dimethyldimethoxysilane, 2.7 parts of water, 0.1 parts of acetic anhydride, and 80 ° C. with stirring. Partially hydrolyzed for 3 hours and cooled. Then, the solid content was 36% when left at room temperature for 48 hours. Hereinafter, this silica-dispersed oligomer solution is referred to as (B-1 liquid).

The number of moles of water relative to 1 mole of the hydrolyzable group was 0.1 mole, the content of silica in the (B-1 solution) was 40.2%, and n = 1. The mol% of the decomposable group-containing organosilane was 77 mol%.

(B-2 solution) A mixed solution of 220 parts (1 mol) of methyltriisopropoxysilane and 150 parts of toluene was prepared. Next, the above mixed solution was put into a flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel and a thermometer, and 108 parts of a 1% hydrochloric acid aqueous solution was added dropwise thereto over 20 minutes to obtain methyltriisopropoxysilane. It was hydrolyzed. After 40 minutes from the dropping, stirring was stopped and the mixture was allowed to stand to separate into two layers. Of this layer, the lower layer mixed solution of water and isopropyl alcohol containing a small amount of hydrochloric acid was separated and removed, and then the remaining toluene resin solution was washed with water to remove hydrochloric acid, and toluene was further removed under reduced pressure. By diluting the component with isopropyl alcohol, a 40% isopropyl alcohol solution of a silanol group-containing organopolysiloxane having an average molecular weight of about 2000 was obtained. Less than,
This solution is referred to as (B-2 solution).

Fluorescent material (NP-103-03) manufactured by Nichia Chemical Co., Ltd. was used as a fluorescent pigment in the prepared liquid B-1.
Was added at a rate of 40% by weight and stirred with a paint shaker. 70 parts of B-1 solution containing this fluorescent pigment,
30 parts of B-2 solution, N-β-aminoethyl- as a catalyst
One part of γ-aminopropylmethyldimethoxysilane was mixed and stirred to obtain a fluorescent inorganic coating material.

The obtained fluorescent inorganic paint was chemically polished to 0.6 m
m aluminum plate was sprayed and dried at a temperature of 80 ° C. for 10 minutes. The film thickness of the coating film after curing was 30 μm, and this aluminum plate emitted blue fluorescence upon irradiation with an ultraviolet lamp.

Example 5 Example 4 was repeated except that a phosphorescent material (GSS-Green) manufactured by Nemoto Special Chemical Co., Ltd. was added as a fluorescent pigment to the solution B-1 of Example 4 at a ratio of 40% by weight. A fluorescent inorganic paint was obtained in the same manner as in. The obtained fluorescent inorganic paint was spray-coated on a chemically-polished 0.6 mm aluminum plate and dried at a temperature of 80 ° C. for 10 minutes. The film thickness of the coating film after curing was 50 μm, and this aluminum plate exhibited a green luminous property upon irradiation with sunlight.

Comparative Example 1 Commercially available fluorescent organic paint using acrylic resin as a vehicle (manufactured by Shin Loihi Co., Ltd .: Color Luminous Paint Lemon)
Was used. Chemically polished this fluorescent organic paint 0.6mm
The aluminum plate was spray-coated and dried at room temperature for 1 day. The film thickness of the coating film after curing was 40 μm, and this aluminum plate emitted yellow fluorescence upon irradiation with an ultraviolet lamp.

The weather resistance and luminous retention of the coating films applied to the aluminum plates of Examples 1 to 5 and Comparative Example 1 were evaluated. The weather resistance is 1000 based on JIS-A-1415 WS type (using a sunshine carbon arc lamp).
After irradiation for a period of time, the appearance of the coating film was visually observed. Those with no abnormalities such as wrinkles, blisters, and peeling were judged as acceptable, and those with abnormalities were judged as failed.

As for the above-mentioned luminescence retention rate, the luminescence amount was measured before and after the weather resistance test to determine the degree of retention of the luminescence amount. The amount of emitted light was measured using a color brightness type BM-5 manufactured by Tokyo Optical Machine Co., Ltd., and a commercially available fluorescent lamp of 200 lux was used as a light source. Luminous emission retention rate (%) = (emission amount after test / emission amount before test) × 100 The results are shown in Table 1, and all the examples have passed weather resistance, and the luminescence retention rate is higher than that of the comparative example. It was good.

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[Table 1]

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The fluorescent inorganic coating material according to claim 1 or 2 of the present invention contains a fluorescent pigment in the inorganic coating material having the above composition. Therefore, the coating film coated with the fluorescent inorganic coating material of the present invention has weather resistance. It is excellent and can maintain a good light emission amount even when used for a long time. In particular, it is effective as a paint applied to guide signs such as road signs used outdoors.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Meiji Goto 1048, Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Works Co., Ltd. (72) Kenyuki Yamaki, 1048, Kadoma, Kadoma City, Osaka Matsushita Electric Works Co., Ltd.

Claims (2)

[Claims] 1. A fluorescent inorganic coating material, which comprises a fluorescent pigment containing an inorganic material as a main component in an inorganic coating material containing silicone as a main chain and having the following composition. The above inorganic paint is
(A) A silicon compound represented by the general formula: Si (OR ¹ ) ₄ and / or colloidal silica of 20 to 200
Parts by weight, (b) 100 parts by weight of a silicon compound represented by the general formula: R ² Si (OR ¹ ) ₃ , and (c) silicon represented by the general formula: R ² ₂ Si (OR ¹ ) _2. Compound 0
The weight average molecular weight of the inorganic coating material containing the above components in an amount of -60 parts by weight and (d) 900 or more in terms of polystyrene. [The above R ¹ and R ² represent a monovalent hydrocarbon group. ] 2. A fluorescent inorganic paint comprising an inorganic paint comprising silicone as a main chain and having the following composition, and a fluorescent pigment containing an inorganic material as a main component. The above inorganic paint is
(A) Conditions in which 0.001 to 0.5 mol of water is used per 1 mol of X in colloidal silica in which a hydrolyzable organosilane represented by the following general formula [1] is dispersed in an organic solvent or water. A partially hydrolyzed organosilane silica-dispersed oligomer solution below, and R ³ _n SiX _4-n [1] [wherein R ³ is the same or different and is a substituted or unsubstituted monovalent C 1-8 monovalent Represents a hydrocarbon group, n represents an integer of 0 to 3, and X represents a hydrolyzable group. (B) A polyorganosiloxane having a silanol group in the molecule represented by the following formula [2], and R ⁴ _a Si (OH) _b O _{(4-ab) / 2} [2] [In the formula, R ⁴ represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and a and b are 0.2 ≦ a ≦ 2 and 0.0001 ≦ b ≦, respectively. 3, a +
It is a number that satisfies the relationship of b <4. (C) a catalyst, and (D) the colloidal silica of the silica-dispersed oligomer solution has a silica content of 5 to 95% by weight.
At least 50 mol% of the hydrolyzable organosilane is an organosilane in which n in the formula [1] is 1, and (e) 1 to 1 of the above silica-dispersed oligomer solution.
9 parts by weight of 9 parts by weight of the above polyorganosiloxane
9 to 1 part by weight.