JP2520994B2 - Reflector manufacturing method - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a reflecting mirror used as a reflecting plate for lighting equipment.

[0002]

2. Description of the Related Art Conventionally, iron, aluminum, stainless steel, reinforced plastics, etc. have been used for reflectors used for outdoor lighting reflectors, etc., but since they are all used outdoors, they are corrosion resistant and scratch resistant. There was a flaw in. For this reason,
Attempts have been made to coat the surface of the reflector with an organic paint, but sufficient performance could not be obtained because the coating itself lacks heat resistance, weather resistance and corrosion resistance. Therefore, in order to improve it, for example, JP-A-60-51577 and JP-A-62-89775 attempt coating with an inorganic coating material containing an alkali metal silicate as a main component.

On the other hand, the reflector of the lighting equipment for HID light source such as outdoor sports lighting, factory lighting, road lighting, and plaza lighting can endure high specularity (reflectance) and high temperature (due to radiant heat of the lamp). In addition, it is required to have good resistance to moisture and corrosive gas. In order to satisfy these requirements and further increase the reflectance of the reflecting mirror, a heat-resistant resin is baked on the surface of the metal base material to make the surface smooth, and a bright metal such as Al and SiO ₂ A multi-layered reflective plate in which various oxide films were sequentially deposited was considered. In particular, as the output of lamps of lighting fixtures has increased in recent years, when the reflector plate is required to have higher heat resistance of 200 ° C. or higher, the resin of the underlayer is made of an organic material that does not have the conventional heat resistance. The paints have become unusable. Therefore, a heat resistant base coating for a multilayer coating reflector has been proposed in JP-A-59-98842. Also, to further improve heat resistance,
As in JP-A-2-160305, an inorganic coating material containing silicon alkoxide as a main component has been proposed.

[0004]

In a coating material containing an alkali metal silicate as a main component, the alkali metal inevitably remains in the coating film, which causes a white bloom phenomenon in a long-term practical test. In the above-mentioned publication, a post-treatment with a nitric acid solution is proposed in order to improve it, but even with this treatment, the alkali metal in the coating film is not completely removed, and the process becomes complicated. is there. In addition, the coating material containing an alkali metal silicate as a main component requires a high baking temperature of 200 ° C. or higher, which raises a problem of an increase in energy cost.

Therefore, according to the present invention, a protective film having excellent heat resistance, weather resistance and the like is applied to a reflecting mirror, and further, baking is performed.
A first object is to provide a method for manufacturing a reflecting mirror that can be performed at a low temperature of ℃ or less. When the undercoating proposed in the above publication is used for the undercoating layer, the main component is a thermosetting acrylic type, so that thermal deterioration occurs at 200 to 300 ° C., and the diffuse reflectance is high, so that the reflection characteristics are poor. . In the case of an inorganic coating material containing silicon alkoxide as a main component as described in the above publication, although it has heat resistance, it still has a slightly high diffuse reflectance and is not sufficiently satisfactory in reflection characteristics.

Therefore, the present invention improves the underlying layer of the multilayer coating reflecting mirror as described above,
A second object is to provide a method for manufacturing a reflecting mirror that has heat resistance and is excellent in reflection characteristics, particularly diffuse reflectance.

[0007]

In order to solve the above-mentioned first problem, in the method for manufacturing a reflecting mirror of the present invention, a protective film is formed on the surface of a substrate using a coating material prepared as described below. To do. In order to solve the second problem described above, a method for manufacturing a reflecting mirror of the present invention (hereinafter, this manufacturing method may be referred to as a "manufacturing method for a multilayer coating reflecting mirror").
In the method for manufacturing a reflecting mirror in which an underlayer is formed on the surface of a substrate, a glittering metal layer is formed on the underlayer, and an inorganic compound protective coating layer is formed on the glittering metal layer in this order. It is formed using the coating material prepared as described above.

That is, the coating material used in the present invention comprises the following A component, B component and C component, in which the ratio of the A component and the B component is 1 to 99 parts by weight of the B component 9 parts.
It was prepared by mixing 9 to 1 part by weight (total of 100 parts by weight of the component A and the component B). (A) the general formula ^{_{R 1 n SiX 4-n ...}} (I) [wherein, R ¹ represents a monovalent hydrocarbon group substituted or unsubstituted C1-8 identical or different, n represents 0 An integer of 3 and X represents a hydrolyzable group. ] In the colloidal silica dispersed in an organic solvent or water, at least 50 mol% of the organosilane in which n = 1 is 0, and water is added to 1 mol of the hydrolyzable group (X). A silica-dispersed oligomer solution of organosilane, which is partially hydrolyzed under the condition of using 0.001 to 0.5 mol, and contains 5 to 95% by weight of silica as a solid content. (B) Average composition formula R ² _a Si (OH) _b O _{(4-ab) / 2} (II) [In the formula, R ² is the same or different and is a substituted or unsubstituted monovalent group having 1 to 8 carbon atoms. Represents a hydrocarbon group, and a and b are 0.2 ≦ a ≦ 2, 0.0001 ≦ b ≦ 3, and a + b, respectively.
It is a number that satisfies the relationship of <4. ] The polyorganosiloxane containing the silanol group in a molecule represented by these. (C) Catalyst.

The silica-dispersed oligomer of the component A used in the present invention is the main component of the base polymer having a hydrolyzable group (X) as a functional group which is involved in the curing reaction when forming a film. This is obtained by adding one or more kinds of the hydrolyzable group-containing organosilane represented by the general formula (I) to colloidal silica dispersed in an organic solvent or water, and then adding water in the colloidal silica or separately. It is obtained by partially hydrolyzing the hydrolyzable organosilane with water.

R ¹ in the hydrolyzable group-containing organosilane represented by the general formula (I) represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, such as a methyl group,
Alkyl groups such as ethyl, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group; cycloalkyl groups such as cyclopentyl group, cyclohexyl group; aralkyl groups such as 2-phenylethyl group, 3-phenylpropyl group An aryl group such as a phenyl group and a tolyl group; an alkenyl group such as a vinyl group and an allyl group; a chloromethyl group, a γ-chloropropyl group, 3,
Halogen-substituted hydrocarbon groups such as 3,3-trifluoropropyl group; and γ-methacryloxypropyl group, γ-glycidoxypropyl group, 3,4-epoxycyclohexylethyl group, γ-mercaptopropyl group, etc. Substituted hydrocarbons can be exemplified. Among them, the number of carbon atoms is 1 to 1 because of easy synthesis or easy availability.
Preferred are alkyl groups of 4 and phenyl groups. Examples of the hydrolyzable group X include an alkoxy group, an acetoxy group, an oxime group, an enoxy group, an amino group, an aminoxy group and an amide group. An alkoxy group is preferable because it is easily available and a silica-dispersed oligomer solution is easily prepared.

Examples of such a hydrolyzable group-containing organosilane are mono-, di-, tri-, and tetra-functional alkoxysilanes in which n in the general formula (I) is an integer of 0 to 3. , Acetoxysilanes, oxime silanes,
Examples thereof include enoxysilanes, aminosilanes, aminoxysilanes, amidosilanes and the like. Alkoxysilanes are preferred because they are easily available and easy to prepare a silica-dispersed organosilane oligomer solution.

Particularly, tetramethoxysilane, tetraethoxysilane and the like can be exemplified as the tetraalkoxysilane of n = 0, and methyltrimethoxysilane, methyltriethoxysilane and methyltriisosilane are examples of the organotrialkoxysilane of n = 1. Propoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane,
3,3,3-trifluoropropyltrimethoxysilane and the like can be exemplified. Examples of the diorganodialkoxysilane having n = 2 include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane,
Examples include diphenyldiethoxysilane and methylphenyldimethoxysilane. Examples of the triorganoalkoxysilane having n = 3 include trimethylmethoxysilane, trimethylethoxysilane, trimethylisopropoxysilane, and dimethylisobutylmethoxysilane. Furthermore, the organosilane compound generally called a silane coupling agent is also included in the alkoxysilanes.

Of these hydrolyzable group-containing organosilanes represented by the general formula (I), 50 mol% or more is n = 1.
It is necessary that the compound is a trifunctional compound represented by. They are more preferably 60 mol% or more, and most 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 the component A is essential for increasing the hardness of the cured coating film of the coating material. As such colloidal silica, water-dispersible or non-aqueous organic solvent-dispersed colloidal silica such as alcohol can be used. Generally, such colloidal silica contains 20 to 50% by weight of silica as a solid content. When water-dispersible colloidal silica is used, water present as a component other than the solid content can be used as a curing agent, as will be shown later. These are usually made from water glass, but such colloidal silica is readily available commercially. The organic solvent-dispersed colloidal silica can be easily prepared by substituting the water of the water-dispersible colloidal silica with an organic solvent. Such an organic solvent-dispersed colloidal silica can be easily obtained as a commercial product like the water-dispersed colloidal silica. The type of organic solvent in which colloidal silica is dispersed is, for example, methanol, ethanol,
Lower aliphatic alcohols such as isopropanol, n-butanol and isobutanol; ethylene glycol derivatives such as ethylene glycol, ethylene glycol monobutyl ether and acetic acid ethylene glycol monoethyl ether; diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether and diacetone alcohol And the like, and one or more selected from the group consisting of these can be used. Toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime, etc. can be used together as these hydrophilic organic solvents.

When colloidal silica is used as the component (A), the mixing ratio is by weight including the dispersion medium. In the component A, colloidal silica is contained in the range of 5 to 95% by weight as a silica content, more preferably 10 to 90% by weight, and most preferably 20 to 85% by weight. If the content is less than 5% by weight, the desired coating hardness cannot be obtained, and if it exceeds 95% by weight, it is difficult to uniformly disperse silica, and the component A may cause inconvenience such as gelation.

The silica-dispersed oligomer of component A can be usually obtained by partially hydrolyzing a hydrolyzable group-containing organosilane in water-dispersed colloidal silica or organic solvent-dispersed colloidal silica. The amount of water used with respect to the hydrolyzable organosilane is preferably 0.001 to 0.5 mol of water with respect to 1 mol of the hydrolyzable group (X). If it is less than 0.001 mol, a sufficient partial hydrolyzate 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 the hydrolyzable organoalkoxysilane and colloidal silica may be mixed and a necessary amount of water may be added and blended. At this time, the partial hydrolysis reaction proceeds at room temperature. You may heat to 60-100 degreeC in order to accelerate a partial hydrolysis reaction. Further, for the purpose of accelerating the partial hydrolysis reaction, hydrochloric acid, acetic acid, silane halide, chloroacetic acid, citric acid, benzoic acid, dimethylmalonic acid, formic acid, propionic acid, glutaric acid, glycolic acid, maleic acid, malonic acid, toluene. Organic and inorganic acids such as sulfonic acid and oxalic acid may be used as catalysts.

In order to obtain stable performance over a long period of time, the component A has a pH of 2.0 to 7.0, preferably 2.5 to 7.0.
It is better to set it to 6.5, and more preferably to 3.0 to 6.0.
When the pH is out of this range, especially when the amount of water used is 0.3 mol or more per 1 mol of X, the long-term performance deterioration of the component A is remarkable. When the pH of the component A is outside this range, it may be adjusted by adding a basic reagent such as ammonia or ethylenediamine if it is on the acidic side of this range. It may be adjusted using an acidic reagent such as. However, the adjusting method is not particularly limited.

The silanol group-containing polyorganosiloxane as the component B is an important component which characterizes the present invention.
Such component B can be represented by the average composition formula (II). In the formula (II), R ² is R in the formula (I).
^The same as ¹ is illustrated, but preferably has 1 to 1 carbon atoms.
4 alkyl group, phenyl group, vinyl group, γ-glycidoxypropyl group, γ-methacryloxypropyl group, γ-
Substituted hydrocarbon groups such as aminopropyl group and 3,3,3-trifluoropropyl group, more preferably methyl group and phenyl group. Further, in the formula, a and b are numbers that satisfy the above relationship, and if a is less than 0.2 or b is more than 3, there is an inconvenience such as cracking in the cured film, and a is 2 If more than 4 or less or b
Is less than 0.0001, curing does not proceed well.

Such silanol group-containing polyorganosiloxane is prepared by a known method using one or a mixture of two or more of methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, or the corresponding alkoxysilane. Can be obtained by hydrolysis with a large amount of water. When a silanol group-containing polyorganosiloxane is hydrolyzed by a known method using alkoxysilane, a small amount of an unhydrolyzed alkoxy group 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 curing catalyst which is the component C of the present invention accelerates the condensation reaction between the components A and B as described above to cure the coating film. Examples of such catalysts include metal salts of carboxylic acids such as alkyl titanates, tin octylate and dibutyltin dilaurate, dioctyltin dimaleate; amines such as dibutylamine-2-hexoate, dimethylamine acetate, ethanolamine acetate. Salts; carboxylic acid quaternary ammonium salts such as tetramethylammonium acetate; amines such as tetraethylpentamine; N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-
Amine-based silane coupling agents such as γ-aminopropylmethyldimethoxysilane; acids such as p-toluenesulfonic acid, phthalic acid and hydrochloric acid; aluminum compounds such as aluminum alkoxides and aluminum chelates; alkali catalysts such as potassium hydroxide; tetraisopropyl Titanium compounds such as titanate, tetrabutyl titanate and titanium tetraacetylacetonate, halogenated silanes such as methyltrichlorocine, dimethyldichlorosilane, trimethylmonochlorosilane, etc., but condensation with A component and B component in addition to the above catalyst There is no particular limitation as long as it is effective for the reaction.

The mixing ratio of the A component and the B component is 99 to 1 parts by weight of the B component to 1 to 99 parts by weight of the A component,
More preferably, component B is 5 to 95 parts by weight with respect to component B 9
5 to 5 parts by weight, most preferably 90 to 10 parts by weight of component B to 10 to 90 parts by weight of component A. When the amount of the component A is less than 1 part by weight, the room temperature curability is poor and sufficient coating hardness cannot be obtained. On the other hand, if the amount of the component A exceeds 99 parts by weight, the curability may be unstable and a good coating film may not be obtained.

The amount of the component C added is preferably 0.0001 to 10 parts by weight, more preferably 0.0005, relative to 100 parts by weight of the total of the components A and B.
To 8 parts by weight, and most preferably 0.0007 to 5 parts by weight. If the amount of the component C added is less than 0.0001 parts by weight, it will not cure at room temperature, and if it exceeds 10 parts by weight, the heat resistance and weather resistance will be poor.

The hydrolyzable group contained in the silica-dispersed oligomer of the component A and the silanol group of the component B are subjected to a condensation reaction by heating at room temperature or low temperature in the presence of the curing catalyst of the component C to form a cured coating film. To do. Therefore, like the moisture-curing type coating composition, the coating material (coating composition) used in the present invention is hardly affected by humidity even when cured at room temperature. Further, the heat treatment can accelerate the condensation reaction to form a cured film. When manufacturing the reflector, considering productivity,
It is preferable to bake at 60 ° C. or higher for 10 minutes or longer.

This coating material can be diluted with various organic solvents for easy handling. The type of the organic solvent can be selected according to the type or the molecular weight of the monovalent hydrocarbon group of the component A or the component B. As such an organic solvent, lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol, and isobutanol, which are shown as a dispersion solvent for colloidal silica, ethylene glycol, ethylene glycol monobutyl ether, and ethylene glycol monoethyl acetate. Examples thereof include ethylene glycol derivatives such as ethers; diethylene glycol, diethylene glycol derivatives such as diethylene glycol monobutyl ether, and diacetone alcohol. One or more kinds selected from the group consisting of these can be used. . In combination with these hydrophilic organic solvents, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime, etc. can be exemplified.

A pigment can be added to this coating material. The pigment type to be added is carbon black,
Organic pigments such as quinacridone, naphthol red, cyanine blue, cyanine green, and Hansa yellow; inorganic pigments such as titanium oxide, barium sulfate, rouge, complex metal oxides are good, and one or more selected from these groups Can be used in combination.

The pigment may be dispersed by a usual method.
At that time, a dispersant, a dispersing aid, a thickener, a coupling agent and the like can be used. Furthermore, a leveling agent,
Dyes, metal powders, glass powders, antioxidants, ultraviolet absorbers and the like can be added. In the manufacturing method of a multilayer coating reflecting mirror, an underlayer is formed by adhesion on a substrate, a glittering metal film is formed by adhesion on this underlayer, and further an inorganic compound protective film is formed by adhesion on this glittering metal film. In such a reflecting mirror, by using the above-mentioned coating material used in the present invention as the underlayer, a reflecting mirror having excellent reflection characteristics can be manufactured.

Here, the brilliant metal used for the brilliant metal film
Examples thereof include Al, Ag, Cr and Ni. I
However, from the viewpoints of scarcity, reflectance, cost, and ease of vapor deposition, Al
Is most practical. Inorganic compound protective film
As the inorganic compound used for, for example, SiO, Si
O ₂, TiO₂, Al₂O₃, MgF₂Etc.
You. However, in terms of transparency, stability, and economy, S
iO₂Is most practical. Also, protect
As the film, apply the above-mentioned coating material used in the present invention.
You may wear and bake at low temperature.

The manufacturing method of the multilayer coating reflecting mirror of the present invention is carried out, for example, as follows using the above-mentioned raw materials. That is, a substrate such as a metal substrate (the surface serving as a reflecting surface may be a flat surface or a curved surface) is degreased and dried in advance, and the coating material used in the present invention is sprayed, electrostatically coated, or dipped. And the like. In this case, the coating film thickness is preferably 5 μm or more in order to eliminate the influence of the unevenness of the base material. Next, this coating film is dried and baked to form a base layer. In the case of this coating material, the baking temperature is sufficiently hardened even at a low temperature of about 80 ° C., but it is preferable to bake at a temperature of 150 ° C. or higher in order to avoid clouding of the glittering metal film due to residual solvent in the coating film. . Then, a glittering metal is vapor-deposited on the underlayer. The vapor deposition may be performed by a usual method. That is, the glittering metal is evaporated by resistance heating or electron beam heating under a vacuum of 10 ⁻⁴ to 10 ⁻⁵ Torr to form a metal film on the underlayer. This film thickness is preferably set in the range of 300 to 1000Å. When the film thickness is less than 300Å, the underlying layer becomes transparent and the reflectance becomes poor. On the other hand, even if it exceeds 1000Å, the effect cannot be expected to increase any more, and it becomes uneconomical in terms of cost. If necessary, a bombarding process may be performed immediately before vapor deposition in order to improve the adhesion between the underlayer and the metal film. Next, an inorganic compound is vapor-deposited on the metal film. That is, an inorganic compound is evaporated by electron beam heating under a vacuum of 10 ⁻⁴ to 10 ⁻⁵ Torr to form a predetermined film. This film thickness is preferably set in the range of 0.3 to 2 μm. If the film thickness is less than 0.3 μm, the inorganic compound protective film will have many pinholes and the corrosion resistance will be poor. On the contrary, if the thickness exceeds 2 μm, further increase in the effect cannot be expected, and vapor deposition takes time, which is uneconomical. When forming the inorganic compound protective film, if necessary, a bombarding treatment may be performed immediately before the inorganic compound vapor deposition to improve the adhesion between the inorganic compound protective film and the metal film. Further, as a method for forming the inorganic compound protective film, an ion plating method is used to further improve the adhesion between the inorganic compound protective film and the metal film, and cracks are generated in the inorganic compound protective film due to radiant heat when the lamp is lit. The temperature may be increased. After forming the protective film, the reflecting mirror may be subjected to aging treatment at 150 ° C to 300 ° C for 1 to 12 hours.

The substrate used in the present invention is not limited to the plate-shaped one.

[0030]

By using an inorganic coating material that cures at a low temperature, the heat resistance can be improved even when baked at a low temperature of 120 ° C or less.
It is possible to obtain a reflecting mirror having excellent coating performance such as weather resistance. When the underlayer is formed using such an excellent coating material, heat resistance, moisture resistance, corrosion resistance, etc. can be ensured to be equivalent to those of conventional inorganic coating materials, and a multi-layer coating reflecting mirror with excellent spectral reflectance characteristics. Can be manufactured.

[0031]

EXAMPLES Specific examples and comparative examples of the present invention will be shown below, but the present invention is not limited to the following examples.
In the following, "part" means "part by weight". First, A
An example of preparation of the components will be shown. -Preparation example of component A 1-Methanol-dispersed colloidal silica sol MA-ST (particle diameter 10 to 20 mμ, solid content 30) in a flask equipped with a stirrer, heating jacket, condenser and thermometer.
%, H ₂ O 0.5%, manufactured by Nissan Chemical Industries, Ltd.) 100 parts, methyltrimethoxysilane 68 parts, and water 10.8 parts are added and partially hydrolyzed at a temperature of 65 ° C. for about 5 hours with stirring. The reaction was performed and cooled to obtain the component A. This product had a solid content of 36% when left to stand at room temperature for 48 hours.
The component A obtained here is referred to as A-1. Preparation conditions for A-1 Molar number of water per mol of hydrolyzable group: 0.4-Silica content of component A: 47.3% Molar% of hydrolyzable group-containing organosilane with n = 1 ... 100 mol% -Preparation example of component A 2-Isolated isopropyl alcohol in colloidal silica sol IPA-ST (particle diameter 10 to 20 m) in a flask equipped with a stirrer, heating jacket, condenser and thermometer.
μ, solid content 30%, H ₂ O 0.5%, manufactured by Nissan Chemical Industries, Ltd.) 100 parts, methyltrimethoxysilane 68 parts, dimethyldimethoxysilane 18 parts, water 2.7 parts, acetic anhydride 0.1 part. Then, while stirring, the partial hydrolysis reaction was carried out at a temperature of 80 ° C. for about 3 hours, followed by cooling to obtain the component A. This product had a solid content of 36% when left to stand at room temperature for 48 hours. The component A obtained here is referred to as A-2. Preparation conditions for A-2 Molar number of water per mol of hydrolyzable group 0.1 0.1 Silica content of A component 40.2% Molar% of hydrolyzable group-containing organosilane of n = 1 77 mol% Next, a preparation example of the component B will be shown.

Preparation Example of Component B 1-Measure a mixed solution of 220 parts (1 mol) of methyltriisopropoxysilane and 150 parts of toluene in a flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel and a thermometer. Then, 108 parts of a 1% hydrochloric acid aqueous solution was added dropwise to the above mixed solution in 20 minutes to hydrolyze methyltriisopropoxysilane. After 40 minutes from the dropping, stirring was stopped, the lower layer mixed solution containing a small amount of hydrochloric acid separated into two layers and isopropyl alcohol were separated, and then the remaining hydrochloric acid of the resin solution of toluene was removed by washing with water. After toluene was removed under reduced pressure, it was diluted with isopropyl alcohol to obtain a 40% isopropyl alcohol solution of silanol group-containing organopolysiloxane having an average molecular weight of about 2000. B-
It is called 1.

Preparation Example 2-Component B 2-1000 parts of water and 50 parts of acetone were weighed into a flask equipped with a stirrer, heating jacket, condenser, dropping funnel and thermometer, and methyltrichlorosilane 44 was added to the mixed solution. 2.8 parts (0.3 mol), dimethyldichlorosilane 38.7 parts (0.3 mol), phenyltrichlorosilane 84.6 parts (0.4 mol) and toluene 200
What was melt | dissolved in the part was hydrolyzed, dropping under stirring. After 40 minutes from the dropping, stirring was stopped, the reaction solution was transferred to a separating funnel and allowed to stand still, the lower layer hydrochloric acid water separated into two layers was separated and removed, and then the toluene solution of the upper organopolysiloxane was depressurized. Water and hydrochloric acid remaining by stripping were distilled off together with excess toluene to obtain a 60% toluene solution of a silanol group-containing organopolysiloxane having an average molecular weight of about 3000. This is called B-2.

-Mixing Examples 1 to 5 of Components A, B and C As shown in Table 1, components A, B and C were mixed and stirred in predetermined amounts to obtain coating materials. As the C component, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane was used.

[0035]

[Table 1]

First, examples in which the coating materials obtained in Mixing Examples 1 to 5 are used as a top coat (low temperature curing protective film) will be shown. -Examples 1-5-A 1 mm thick aluminum plate 5 cm x is used as the base of the reflector.
A piece cut into a size of 8 cm was used. In order to form the coating layer, the aluminum plate is degreased and dried, and then the mixing example 1
~ 5 coating materials were applied by spraying. The coating amount was set so as to have a thickness of 3 μm after curing. After setting for 10 minutes after coating, baking was performed at 100 ° C. for 20 minutes.

The performance of the obtained reflecting mirror (reflecting plate) was evaluated as follows. The results are shown in Table 2. Heating was carried out for 10 days in a thermostat having a heat resistance of 160 ° C., and the occurrence of cracks and white sinter was evaluated. O indicates that neither cracks nor white sinters occurred, and X indicates that either or both of the cracks and white sinters occurred. The mercury lamp irradiation was carried out for 10 days in a thermostatic chamber with a weather resistance of 120 ° C. to evaluate the occurrence of cracks and white sinter. O indicates that neither cracks nor white sinters occurred, and X indicates that either or both of the cracks and white sinters occurred.

-Comparative Example 1-Using the same aluminum plate as in Example, after the same degreasing and drying,
A commercial alkali silicate inorganic coating was applied by spraying.
The coating amount was set so as to have a thickness of 3 μm after curing. After setting for 10 minutes after application, apply 2 at 200 ℃.
It was baked for 0 minutes. The evaluation was performed in the same manner as in the examples. The results are shown in Table 2.

[0039]

[Table 2]

As shown in Table 2, the reflecting mirrors obtained in Examples 1 to 5 were excellent in both heat resistance and weather resistance, whereas Comparative Example 1 had a high baking temperature. All of it's performance was inferior. Next, an example in which a multilayer coating reflecting mirror is obtained by using the coating materials obtained in the mixing examples 1 to 5 as the underlayer is shown.

-Examples 6 to 10-A coating material was applied in the same manner as in Examples 1 to 5 except that the coating amount was set to be 5 μm after curing. The baking conditions were 200 ° C. × 40 minutes to completely remove the solvent in the coating film to form a base layer. Next, the substrate on which the underlayer is formed is attached to a vapor deposition apparatus and 5 × 1
High-purity aluminum (99.99%) was vapor-deposited by resistance heating in a vacuum of 0 ^-5 Torr to form a glittering metal layer composed of an aluminum film of 1000 Å on the underlayer. Next, with the degree of vacuum kept at 5 × 10 ⁻⁵ Torr, SiO ₂ was vapor-deposited by electron beam heating to form a protective film layer made of a SiO ₂ film of 5000 Å. The spectral reflectance characteristic of the multilayer coating reflection plate thus obtained was measured by a spectrophotometer (UV-350: manufactured by Shimadzu Corporation) in a wavelength range of 38.
It was measured at 0 to 780 nm. Table 3 shows the average values of the total reflectance and diffuse reflectance of each sample.

-Comparative Example 2- 100 parts of methyltrimethoxysilane, 15 parts of tetraethoxysilane and IPA organosilica sol (trade name "O")
SCAL1432 "manufactured by Catalysts & Chemicals Industry Co., Ltd.) 70 parts, dimethyldimethoxysilane 35 parts, and isopropyl alcohol (IPA) 100 parts were mixed, and further, H ₂ O 95 parts was added and stirred. The molecular weight of this was measured in a constant temperature bath at 60 ° C.
It was adjusted to w = 1000 (Mw / Mn = 1.49). This coating material was used for forming a base layer and Examples 6 to 1 were used.
A multilayer coated reflector was obtained in the same manner as in 0. The results of this spectroscopic measurement are shown in Table 3.

[0043]

[Table 3]

As shown in Table 3, the reflecting mirrors obtained in Examples 6 to 10 have a low diffuse reflectance, whereas the reflecting mirrors obtained in Comparative Example 2 have a high diffuse reflectance. Examples 6-10
Also, the heat resistance of Comparative Example 2 was examined as follows, and all were 100/100 and OK. After heating for 10 days in a thermostatic chamber with a heat resistance of 200 ° C., evaluation was carried out by a cross-cut adhesion test (100 squares). It was examined how many 100 squares were in close contact without peeling.

[0045]

According to the method of manufacturing the reflecting mirror of the present invention,
Since the coating material containing the above specific A, B and C components is used for forming the protective film, it is possible to obtain a reflecting mirror having excellent coating performance such as heat resistance and weather resistance even when baked at a low temperature of 120 ° C. or lower. it can. According to the method for manufacturing a multilayer coating reflecting mirror of the present invention, the above-mentioned specific A
Since a coating material containing B and C components is used, it is possible to obtain a multi-layer coating reflecting mirror having excellent spectral reflectance characteristics, and the heat resistance, moisture resistance and corrosion resistance are the same as those of conventional inorganic coating materials. Can be secured.

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Claims (2)

(57) [Claims] 1. A method of manufacturing a reflection plate for forming a protective film on a surface of a substrate, wherein the protective film comprises the following A component, B component and C component, and the ratio of A component and B component is A component 1 to 1.
99 to 1 parts by weight of B component 99 to 1 parts by weight (A component and B
A total of 100 parts by weight of the components) is mixed to prepare a coating material, and the coating material is formed. (A) the general formula ^{_{R 1 n SiX 4-n ...}} (I) [wherein, R ¹ represents a monovalent hydrocarbon group substituted or unsubstituted C1-8 identical or different, n represents 0 An integer of 3 and X represents a hydrolyzable group. ] In the colloidal silica dispersed in an organic solvent or water, at least 50 mol% of the organosilane in which n = 1 is 0, and water is added to 1 mol of the hydrolyzable group (X). A silica-dispersed oligomer solution of organosilane, which is partially hydrolyzed under the condition of using 0.001 to 0.5 mol, and contains 5 to 95% by weight of silica as a solid content. (B) Average composition formula R ² _a Si (OH) _b O _{(4-ab) / 2} (II) [In the formula, R ² is the same or different and is a substituted or unsubstituted monovalent group having 1 to 8 carbon atoms. Represents a hydrocarbon group, and a and b are 0.2 ≦ a ≦ 2, 0.0001 ≦ b ≦ 3, and a + b, respectively.
It is a number that satisfies the relationship of <4. ] The polyorganosiloxane containing the silanol group in a molecule represented by these. (C) Catalyst. 2. A method for producing a reflecting mirror, comprising: a base layer on the surface of a substrate; a glittering metal layer on the underlayer; and an inorganic compound protective coating layer on the glittering metal layer. The stratum, the following A component, B component and C component, A
The ratio of component B to component B is 1 to 99 parts by weight of component B
A method for producing a reflecting mirror, characterized in that the coating material is formed by using a coating material prepared by mixing components in an amount of 99 to 1 parts by weight (total 100 parts by weight of the components A and B). (A) the general formula ^{_{R 1 n SiX 4-n ...}} (I) [wherein, R ¹ represents a monovalent hydrocarbon group substituted or unsubstituted C1-8 identical or different, n represents 0 An integer of 3 and X represents a hydrolyzable group. ] In the colloidal silica dispersed in an organic solvent or water, at least 50 mol% of the organosilane in which n = 1 is 0, and water is added to 1 mol of the hydrolyzable group (X). A silica-dispersed oligomer solution of organosilane, which is partially hydrolyzed under the condition of using 0.001 to 0.5 mol, and contains 5 to 95% by weight of silica as a solid content. (B) Average composition formula R ² _a Si (OH) _b O _{(4-ab) / 2} (II) [In the formula, R ² is the same or different and is a substituted or unsubstituted monovalent group having 1 to 8 carbon atoms. Represents a hydrocarbon group, and a and b are 0.2 ≦ a ≦ 2, 0.0001 ≦ b ≦ 3, and a + b, respectively.
It is a number that satisfies the relationship of <4. ] The polyorganosiloxane containing the silanol group in a molecule represented by these. (C) Catalyst.