JP2916654B2 - Coating composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

This invention relates to coating compositions.

[0002]

2. Description of the Related Art Plastics molded products are:
In recent years, they have been widely used in automobiles, aircraft, buildings, and the like because they are lighter than metals, glass, and the like. However, plastics have a drawback that they are weak to ultraviolet rays and cause surface degradation and cracks due to degradation and decomposition. In order to prevent this, there is a method of mixing an ultraviolet absorber into plastics. However, if only the ultraviolet absorber is mixed, the ultraviolet absorption effect decreases with time, and finally, the plastic substrate is damaged. is there.

On the other hand, there is a method in which a protective film is formed by applying an organic resin coating composition containing an ultraviolet absorbent to the surface of a plastic substrate, and the protective film absorbs ultraviolet light and converts it into heat energy. However, this method also has the drawback that the effect of absorbing ultraviolet light decreases over time, as described above, and properties such as abrasion resistance are not satisfactory with a protective film made of an organic resin paint.

As an inorganic coating film formed on plastics, an abrasion-resistant film composed of colloidal silica and polysiloxane, and an ultraviolet absorbing film composed of colloidal titania and polysiloxane are generally well known. However, the former cannot block ultraviolet rays, and when used outdoors, there is a drawback that the plastics of the base material is deteriorated by the ultraviolet rays of the sun. The effect of blocking is not satisfactory.

[0005]

SUMMARY OF THE INVENTION In view of the above problems, the present inventor has formed a protective film which can prevent deterioration of plastics and the like due to ultraviolet rays and can impart excellent abrasion resistance. I've been studying hard to do this. As a result, using a specific silanol compound as a film-forming component, according to the coating composition containing particulate parsley A thereto, it has an excellent UV blocking effect, and abrasion resistance, stain resistance, etc. An excellent protective film can be formed, and by blending the resin-modified silicone resin with it, the flexibility of the formed film becomes good, thick coating becomes possible, and the adhesion to plastics material is good. The present invention has been completed here.

Thus, the present invention provides, (a) i) Formula R ² _n Si (OR ¹⁾ in _4-n (wherein, R ¹ represents hydrogen or a lower alkyl group, R ² is a lower alkyl group, vinyl group, Fluoropropyl group, γ
A glycidoxypropyl group or a γ- (meth) acryloxypropyl group, and n is 0 or 1. At least one 100 parts by weight of the silanol compound and a partial condensate thereof represented by), and ii) 5% by weight or more in the composition particulate parsley A 2-3000 parts by the total amount, and (b) resin-modified silicone 5-50 resin in the composition
It is intended to provide a coating composition characterized by containing by weight.

The coating composition of the present invention has the formula R ² _n Si
(OR ¹ ) _4-n (wherein R ¹ , R ² and n are the same as above) and a ceramic film-forming substance comprising at least one of a silanol compound and a partial condensate thereof as a film-forming component. It is necessary to.

In the above general formula, the lower alkyl group represented by R ¹ or R ² includes methyl, ethyl, n-
Examples thereof include an alkyl group having 1 to 3 carbon atoms such as propyl and isopropyl. Further, as a fluoropropyl group,
Preferably, a 3,3,3-trifluoropropyl group can be exemplified.

[0009] Specific examples of the formula R ² _n Si (OR ¹⁾ silanol compounds represented by _4-n may be exemplified the following compounds.

[0010]

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The partial condensate of the silanol compound is not particularly limited, and condensates of the same or different types of compounds among the silanol compounds represented by the above general formula can be used. Combinations, ratios and the like can be freely changed. The degree of condensation is not particularly limited, but is preferably about 2 to 10 mer. Specific examples of the condensate include the following:

[0012]

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(R ₁ and R ₂ are the same as above, and n is 1 to 5
It is about. ) The present invention is a particulate Seri A <br/> incorporated into the compositions, particle size from 5 to 150 millimicrons about cerium oxide (CeO ₂ ) And can be formulated as a fine powder or a colloidal solution. The colloid solution has a particle size of 5
A dispersion of cerium oxide of about 150 millimicrons in water or an organic solvent alone or in a mixed solvent can be used, and one having a solid content of about 1 to 50% by weight is preferable. As the organic solvent of the colloid solution, usually, lower alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and propylene glycol monoalkyl Hydrocarbon ether alcohols having methyl, ethyl, propyl, butyl, etc. as alkyl groups such as ethers, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, dipropylene glycol monoalkyl ether acetate Acetates of the above-mentioned hydrocarbon ether alcohols such as Alcohols acetic esters such as ethyl acetate, methyl acetate, ethyl acetate, propyl acetate, acetic acid esters of butyl acetate, acetone, xylene, benzene, n-hexane or the like is used.

The compositions of the present invention, a ceramic coating-forming material comprising at least one silanol compound and a partial condensate thereof described above is intended for use in combination with a particulate Seri A, silanol compound or a partial condensate thereof polymerization, the film formed by the gelation, heat resistance, abrasion resistance, water resistance, becomes a ceramic coating with excellent non-staining, etc., also particulate Seri a formulated 190
Since the ultraviolet ray in a wide range of about 380 nm is sufficiently absorbed, the ultraviolet ray does not reach the base material and the base material does not deteriorate. Although absorbed ultraviolet light is thermally converted, mainly, because of the ceramic coating consisting of silica and glyceryl A, it does not receive little deterioration due to heat film.

The coating composition of the present invention shows the above-mentioned ceramic coating forming substance and particulate parsley A water, an organic solvent, or can be obtained by dissolving or dispersing these mixed solvents, ceramic coating forming substance without the use of solvents which is liquid at itself, may this particulate <br/> Seri a dissolved or dispersed in. Examples of the organic solvent include lower alcohols such as methanol, ethanol, propanol, isopropanol, butanol and isobutanol, and alkyl groups such as ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and propylene glycol monoalkyl ether. Above, such as hydrocarbon ether alcohols having methyl, ethyl, propyl, butyl, etc., ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, dipropylene glycol monoalkyl ether acetate, etc. Acetates of ether alcohols, ethoxyethyl acetate, etc. Acetic acid esters of alcohols, methyl acetate, ethyl acetate, propyl acetate, acetic acid esters of butyl acetate, acetone, xylene, benzene, n-hexane or the like.

[0016] In the compositions of the present invention, the mixing ratio of the ceramic film-forming material and particulate parsley A is 2-3 the ceramic film-forming substance 100 parts by weight, the particulate parsley A
It may be about 000 parts by weight, preferably about 20 to 500 parts by weight.

Further, in the present invention compositions, the total amount of the ceramic film-forming material and particulate parsley A is preferably more than about 5% by weight in the composition, more preferably about 10 to 50 wt%. Further, the composition of the present invention contains about 5 to 50% by weight of a resin-modified silicone resin described below in the composition.

In the present invention, a pigment, a filler, a coating reinforcing agent, a metal powder, a colloidal substance and the like can be added to the coating composition as required.

As the pigment or filler, both inorganic and organic pigments can be used. For example, magnesium oxide, silicon nitride, titanium nitride, nickel oxide, quartz,
Silica, zirconium silicate, alumina, titanium oxide, titanium yellow, magnesium carbonate, dolomite, silicon carbide, tungsten carbide, iron oxide (red, black), barium yellow, antimony yellow, cobalt blue, cobalt violet, cobalt green, manganese black , Manganese blue, manganese pink, manganese violet, strontium chromate, talc, chromium oxide hydrate green, chromium oxide green, zinc green, barium carbonate, chalk, precipitated calcium carbonate, aluminum hydrate, zinc oxide,
Fluorite, molybdenum red, molybdenum orange, chrome yellow, lead chromate, ultramarine, vermilion, basic lead carbonate, azo pigments and the like can be used. By incorporating a pigment and / or a filler, the film thickness can be increased, and by adding a pigment, the appearance can be improved. The film containing the pigment and / or the filler can be used in an outdoor condition of 20 to 30.
It does not discolor for a year, has a high surface hardness and is hardly damaged, and is non-staining, so it is hard to be stained. Even if it becomes dirty, it can be immediately returned to its original state. Further, by blending a pigment having far-infrared radiation performance, far infrared radiation can be further imparted to the formed film. In addition, a lubricating film can be formed by mixing molybdenum disulfide, carbon graphite, fluororesin, boron nitride, etc. as a filler, and a wear-resistant film is formed by using a wear-resistant ceramic. it can. The pigment and the filler can be compounded together with a dispersant, a thickener and the like based on a conventional method. Known dispersants, thickeners and the like may be used.

The coating reinforcing agent is inorganic and fibrous, and typical examples thereof include potassium titanate, silicon carbide,
There are fibers such as quartz, silicate glass, alumina, beryllia, and boron carbide. By adding a coating reinforcement,
The film becomes more tough. In addition, silver, copper, platinum, vanadium, palladium, aluminum, nickel, brass and the like can be used as the metal powder. By blending the metal powder, conductivity can be imparted to the film, and depending on the type of metal, it can also function as a catalyst for deodorizing and the like. The metal powder may be used as a metal-carrying ceramic powder in which a metal is supported on a ceramic. Examples of the colloidal substance include colloidal silica, colloidal alumina, colloidal titanium, colloidal zirconium silicate, colloidal zirconium oxide, and colloidal aluminum hydroxide.By adding the colloidal substance, The formed ceramic layer is densified.

The compounding amount of the pigment and / or filler can be up to about 70% by weight, preferably about 3 to 40% by weight in the composition. The amount of the coating reinforcing agent can be up to about 70% by weight, preferably about 1 to 20% by weight in the composition. The compounding amount of the metal powder and / or the metal-carrying ceramic powder can be up to about 50% by weight, preferably about 3 to 30% by weight, as the metal powder in the composition. The compounding amount of the colloidal substance is 7 in the composition.
It can be up to about 0% by weight, preferably about 3 to 40% by weight.

Further, according to the present invention, the composition comprises a resin
By blending the modified silicone resin , flexibility can be imparted to the formed ceramic film, and thick coating can be performed. Silicone resin can improve the flexibility of the ceramic film, and by using resin-modified resin, good adhesion to plastic materials can be maintained. Examples of the type of resin modification include, for example, epoxy modification, polyester modification, alkyd modification, phenol modification, and acrylic modification, and the resin-modified silicone resin is not limited as long as it is soluble in the coating composition of the present invention. Can be used. The compounding amount of the resin-modified silicone resin may be about 5 to 50% by weight in the composition.

The composition of the present invention contains powdered resins such as fluororesin, silicone resin, polyester resin, nylon resin, acrylic resin, polyethylene resin, polyphenylene sulfide resin, polyphenyl ether resin, vinyl chloride resin and polyimide resin. it can. The addition of the powdery resin can impart properties such as flexibility and shock absorption. The powdery resin may be any resin as long as it can be mixed in the form of powder like the filler, and the particle size is preferably about 0.1 μm to 50 μm. The compounding amount may be 50% by weight or less, preferably about 5 to 40% by weight in the coating composition.

The above composition further comprises a carboxylic acid as a buffering latent catalyst capable of accelerating the polymerization of the composition by dissociating by heating without accelerating the polymerization of the composition at room temperature. Metal salts, amine carboxylate, quaternary ammonium carboxylate, nitrate and the like can be added to the composition up to about 1.5 weight percent. Such buffered latent catalysts include dimethylamine acetate, ethanolamine acetate, dimethylaniline formate, sodium acetate, sodium propionate, potassium formate, sodium formate, benzyltrimethylammonium acetate, sodium nitrate, ammonium nitrate, ammonium acetate and the like. Is exemplified.

The composition of the present invention is preferably adjusted to a pH of about 2.5 to 6.0 in order to prevent rapid gelation. For pH adjustment, for example, hydrochloric acid, acetic acid, chloroacetic acid, citric acid, maleic acid, oxalic acid, toluenesulfonic acid,
Organic acids and inorganic acids such as glutaric acid, dimethylmalonic acid, benzoic acid and hydrogen peroxide can be used.

In the present invention, the above-mentioned coating composition is applied onto a substrate by a spray method, a roll coating method, a dipping method, a curtain flow method, a printing method, or the like, and polymerized and gelled to form a ceramic coating layer. Can be formed. There is no particular limitation on the type of the substrate, and in addition to organic substrates such as plastics, organic coatings, glass, paper, fiber, and wood, metals and ceramics can be used as the substrate.

The polymerization gelation of the composition of the present invention proceeds even at room temperature, but heating reduces the gelation time, increases the polymerization density, and makes the ceramic film more dense. The higher the heating temperature is, the more dense the ceramic layer can be.
It is appropriate to heat at about 200 ° C. for about 10 to 30 minutes. In order to completely prevent the occurrence of pinholes in the ceramic film, after coating and drying or heat curing of the coating composition of the present invention, one or more coating compositions of the same or different types are further applied. It is preferable that two or more ceramic films are formed by coating and curing two or more layers.

The thickness of the film formed by the composition of the present invention may be appropriately changed depending on the type of the base material, the use of the film, etc. Usually, the total thickness is about 3 to 150 μm. Good.

[0029]

Coating formed from the coating composition of the present invention according to the present invention is basically a transparent ceramic coating, for auction A <br/> absorbs ultraviolet wide wavelength of about 190μm~380μm In addition, ultraviolet rays do not reach the surface of the substrate, so that deterioration of the substrate can be prevented. Especially plastics, organic paints, paper,
When applied to the surface of an organic material such as wood or fiber, deterioration of the organic material due to ultraviolet rays can be prevented, and browning, cracks, peeling, whitening, and the like can be prevented. Further, the film is excellent in heat resistance, water resistance and non-staining property, and can improve scratch resistance, abrasion resistance and the like.
When the film is formed on plastics, the surface hardness, abrasion resistance and the like can be improved, and it can be used as a substitute for glass.

The composition of the present invention hardly undergoes polymerization gelation during storage and has good storage stability.

Further, since the film formed from the composition has non-staining properties, it can be formed on an organic coating film or plastics to prevent adhesion of dirt when used outdoors. It is effective as a pollution control coating.

Further, by coating the surface of the metal, the corrosion resistance, abrasion resistance, scratch resistance and the like can be improved. By coating the glass, the transmission of ultraviolet light is prevented, and the glass can be used as a window glass that does not transmit ultraviolet light.

Furthermore, by adding various compounding agents such as pigments and fillers to the composition of the present invention, properties according to the type of compounding agent, for example, far-infrared radiation, aesthetics, deodorant, conductive properties, etc. Properties, gas decomposability, antibacterial properties, etc. can be further provided.

As described above, the coating composition of the present invention comprises:
It has excellent properties such as corrosion resistance, heat resistance, weather resistance, UV resistance, abrasion resistance, heat insulation, insulation, optical properties, stain resistance, scratch resistance, solvent resistance, chemical resistance, etc. , Vehicles (automobiles, bicycles, motorcycles, airplanes, trains), ships, appliances, civil engineering, space, gas, oil, power, glass, glasses, tanks, plants, communications, etc. New products with unprecedented performance can be provided.

Hereinafter, the present invention will be described in more detail with reference to Reference Examples .

[0036] Koroidoseri the Seri A of Reference Example 1 grain size of about 20mμ was dispersed in water
A ) (35% by weight), 0.3 g of acetic acid and 28 g of isopropyl alcohol were added and dissolved, and 12.5 g of methyltrimethoxysilane was added thereto and mixed by stirring.
5.8 g of a transparent aqueous liquid composition was obtained.

The above composition was applied to the surface of a substrate shown in Table 1 below, and heated at 80 ° C. to 200 ° C. for 5 minutes to 20 minutes to form a clear film having a thickness of 0.5 to 7 μm.

[0038]

[Table 1]

The results of the physical properties tests on the obtained samples are shown in Table 2 below.

Evaluation criteria of physical properties (1) Weather resistance: 3000 hours of QUV test (2) Weather resistance: Sunshine weatherometer 300
0 hours (3) Salt spray resistance: JIS-Z-2371 salt spray test 3000 hours (4) Water resistance: 25 ° C tap water immersion 240 hours (5) Gasoline resistance: 25 ° C gasoline immersion 240 hours (6) Adhesion Properties: Adhesion test of JIS-K-5400 coating film (7) Hardness: Pencil hardness (8) Stain resistance: Washing and removing test for mud stains (9) Stain resistance: Thinner washing test for magic ink (10) Chemical resistance: 5% H ₂ SO ₄ spot dripping 24
Time (11) Chemical resistance: 3% NaOH spot dripping for 24 hours (12) Heat resistance: Temperature measurement at which the substrate changes.

(13) Scratch resistance: steel wool (# 0
Rubbing 10 times with a load of 100 g / cm ² at 000) (14) Boiling water resistance: 24 hours immersion in boiling water Evaluation result criteria (1) No change in base material and coating film. 〇 (2) Slight abnormality in coating film without change in substrate △ (3) Slight abnormality in substrate without change in coating film △ (4) Large abnormality in substrate or coating film × Evaluation result

[0042]

[Table 2]

As can be seen from the above results, the transparent film formed by the above-mentioned coating composition has excellent weather resistance, chemical resistance, etc., excellent water repellency, abrasion resistance, etc. Of rust, improvement of water resistance of resin, and improvement of water repellency of paper, wood, cement board, tile, ceramics and the like.

[0044] with the covering composition as defined above, was performed actual vehicle test by forming a film on the top coating film and an automobile window glass of an automobile (Plastics and glass). As a result, since there is almost no discoloration or scratching of the film, there is no need for any wax or the like, and there is little adhesion of dirt.
It was easily removed just by washing with water. Further, the coating on the window glass prevented the discoloration of the interior parts due to the ultraviolet rays, and there was little irritation to the eyes and the like due to the strong ultraviolet rays, so that long-time operation was easy.

Reference Example 2 A mixed solvent of 40 g of isopropyl alcohol and 40 g of propylene glycol monoethyl ether was added with a particle size of 20 μm.
The Seri A 20g Koroidoseri A containing dispersed, mixed with 50% condensate 40g of tetramethoxysilane run, by adding water 5g and acetic acid 0.5g, and heated for 1 hour at 60 ° C., cell <br/> promoting re a sol and partially reacted, made clear liquid composition stable one-pack (composition a).

[0046] Koroidoseri dispersed isopropyl alcohol 40g and glyceryl A 20g of the particle size 20mμ in a mixed solvent of propylene glycol monoethyl ether 40g
A ) 20% of the partial condensate of methyltrimethoxysilane
The isopropyl alcohol solution was mixed, 5 g of water and 0.5 g of acetic acid were added, and the mixture was heated at 60 ° C. for 1 hour to form a stable one-liquid transparent non-aqueous liquid composition (composition B).

[0047] Koroidoseri dispersed isopropyl alcohol 40g and glyceryl A 20g of the particle size 20mμ in a mixed solvent of propylene glycol monoethyl ether 40g
A , a 20% isopropyl alcohol solution of a partial condensate of methyltrimethoxysilane and tetramethoxysilane is mixed, and 5 g of water and 0.5 g of acetic acid are added thereto. A non-aqueous liquid composition (Composition C) was prepared.

The above composition A, ginseng respectively B and C
It applied to a substrate surface as shown in considered Example 1 0.5~7μm thick, and heated at 80 ° C. to 200 DEG ° C. 5 to 20 minutes to form a transparent film. When a hard vinyl chloride plate, styrene plate, acrylic plate, paper or wood is used as the substrate, it is necessary to heat it at a low temperature. Therefore, 1 g of ethanolamine acetate was added to the composition as a buffering latent catalyst. A physical property evaluation test was performed on each of the obtained samples in the same manner as in Reference Example 1. All were good results, and were found to be excellent in UV deterioration prevention, abrasion resistance improvement, scratch prevention, non-staining, heat resistance, solvent resistance, chemical resistance, and the like.

[0049] Koroidoseri the Seri A of Reference Example 3 grain size of about 20mμ was dispersed in water
To 35 g of a (20% by weight), 0.3 g of acetic acid and 28 g of isopropyl alcohol were added and dissolved, and 15 g of zirconium silicate as a filler, 5 g of cobalt green as a pigment, and 3 g of potassium titanate as a coating reinforcing agent were added thereto. After mixing and stirring, 30 g of methyltrimethoxysilane was further added to prepare a light green liquid composition (composition D).

[0050] acetate 0.3g to Koroidoseri A 35g of a dispersion medium of water as described above and isopropyl alcohol 28g
Was added and dissolved, and 10 g of manganese oxide, 15 g of iron oxide and 3 g of potassium titanate were added thereto, and mixed and stirred.
Further, 30 g of methyltrimethoxysilane was added to prepare a black liquid composition (composition E).

To 70 g of the composition A obtained in Reference Example 2, 10 g of titanium oxide, 5 g of titanium yellow, 10 g of silica and 3 g of potassium titanate were added and mixed well to prepare a liquid composition (composition F).

To 70 g of the composition B obtained in Reference Example 2, 5 g of boron nitrite, 10 g of silica, 10 g of talc, 3 g of potassium titanate and 1 g of triethanolamine acetate were added and mixed well to obtain a liquid composition (composition G). )
Was prepared.

To 70 g of the composition C obtained in Reference Example 2, 10 g of manganese pink, 10 g of zircon silicate and 5 g of silica
, And sufficiently mixed by stirring to obtain a liquid composition (composition H).
Was prepared.

Each of the above compositions D to H was used in Reference Example 1.
Is applied on the surface of the base material shown in the above to a thickness of 0.5 μm to 100 μm, and heated at 80 ° C. to 200 ° C. for 5 to 20 minutes to form an opaque ceramic layer containing a pigment, a filler, and the like. did. The resulting film is excellent in aesthetics and absorbs ultraviolet rays, so it is less likely to deteriorate even when an organic pigment is blended, and discoloration for a long period of time is the same as when an inorganic pigment is blended. Did not. In addition, since a pigment, a filler and the like are contained, a relatively thick film coating was possible. When a base material having high heat resistance (300 ° C. to 1000 ° C.) was used, the base material could be protected by preventing the base material from being oxidized and degraded at a high temperature. The use of the far-infrared radiating pigment could show excellent far-infrared radiation as a far-infrared radiation coating. The film formed from the composition G containing boron nitrite as a filler had excellent wear resistance and lubricity from low to high temperatures, and had a friction coefficient of 0.164. The surface hardness is 9H in terms of Empitz hardness, which is very hard as compared with resin or the like, and furthermore, the film is characterized by being hard to be stained. Was.

REFERENCE EXAMPLE 4 The coating film of Reference Example 2 was overcoated with the coating film of Reference Example 3. This film is colored and glossy, and the film performance is shown in Reference Example 2.
And both of the features of Reference Example 3.

Continuation of front page (72) Inventor Akira Kitagawa 2-16-8 Nihonbashi, Chuo-ku, Tokyo Inside Parker Processing Co., Ltd. (56) References JP-A-4-126784 (JP, A) JP-A-4-220468 (JP, A) JP-A-1-245062 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C09D 183/00

Claims (1)

(57) [Claims] 1. A (a) i) Formula R ² _n Si (OR ¹⁾ in _4-n (wherein, R ¹ represents hydrogen or a lower alkyl group, R ² is a lower alkyl group, vinyl group, trifluoropropyl group , Γ
A glycidoxypropyl group or a γ- (meth) acryloxypropyl group, and n is 0 or 1. At least one 100 parts by weight of the silanol compound and a partial condensate thereof represented by), and ii) 5% by weight or more in the composition particulate parsley A 2-3000 parts by the total amount, and (b) resin-modified silicone 5-50 resin in the composition
A coating composition, characterized in that the coating composition contains 0.1% by weight.