JPH0749569B2 - Coating protection composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a coating film-protecting composition, and more particularly to a coating film-protecting composition which has a large ultraviolet shielding effect and contributes to improving the weather resistance of the coating film.

[Problems to be Solved by Conventional Techniques and Inventions] There are many known polish agents used for protecting coating films, the main components of which are wax-like substances and silicone oils, and paste-like substances. Alternatively, it is used in a solid form. Since this polish has poor weather resistance, it has been attempted to add a UV absorber such as benzophenone or benzotriazole to prevent deterioration of the coated surface due to UV rays. However, this has a problem that it cannot sustain its efficacy for a long time.

It is an object of the present invention to provide a coating film-protecting composition which solves the above-mentioned conventional problems, has a large ultraviolet shielding effect, and can improve the weather resistance of the coating film.

[Means for Solving Problems] That is, the present invention provides (A) a wax-like substance in an amount of 2 to 15% by weight,
(B) Silicone oil 3 to 15% by weight, (C) Metal soap 0.1 to 5% by weight, (D) Inorganic powder 10 to 60% by weight,
(E) Titanium oxide and / or hydrated titanium oxide spherical particles 0.01 to 50% by weight and (F) Hydrocarbon solvent 30 to
It is intended to provide a coating film protective composition comprising 90% by weight.

In the composition of the present invention, a wax-like substance, that is, a wax or a wax-like substance is used as the component (A). There is no particular limitation on the source of the waxy material,
Various waxes such as vegetable wax, animal wax, petroleum wax, etc. can be mentioned. Further, it does not matter whether it is liquid or solid. Specifically, paraffin wax, polyethylene wax, microcrystalline wax, carnauba wax, etc. are used, and paraffin wax, polyethylene wax, microcrystalline wax are particularly preferable, and these are used alone or in combination of two or more kinds. It preferably has an average molecular weight of 20 to 2000 and a melting point of 50 to 150 ° C.
Those in the range are preferred. The component (A) should be added in an amount of 2 to 15% by weight, especially 7 to 12% by weight, based on the whole composition of the present invention. When the content is less than 2% by weight, the formed film does not show an excellent effect of protecting the coating film, and the effect of preventing rust on the metal part is reduced.

On the other hand, if it exceeds 15% by weight, the viscosity of the composition is increased and the coating properties and the wiping properties are deteriorated, which is not preferable.

Next, the silicone oil which is the component (B) of the present invention is not particularly limited, but it has a viscosity of 200 to 100 at 25 ° C.
A silicone oil of 0 cSt, preferably 400-700 cSt is desirable. Specific examples of the silicone oil include dimethylpolysiloxane, methylphenylpolysiloxane, methylphenylmethylpolysiloxane, ethylphenylmethylpolysiloxane, phenylpropylpolysiloxane, phenylbutylpolysiloxane, propylphenylhexylpolysiloxane, or amino-modified silicone oil, Polyether modified silicone oil, olefin modified silicone oil, epoxy modified silicone oil,
Fluorine-modified silicone oil, α-methylstyrene-modified silicone oil, alcohol-modified silicone oil,
Examples thereof include sulfur-modified silicone oil, methoxy-modified silicone oil, fatty acid-modified silicone oil, and hydrogen polysiloxane. These may be used alone or in combination of two or more. The component (B) as described above is
3 to 15% by weight, especially 5 to 12% by weight of the total composition of the invention
Should be blended in the proportion of. If the blending amount is less than 3% by weight, the polishing effect and the wiping property are not sufficient, while 15
If it exceeds the weight%, it is not preferable because it comes out on the surface of the protective film.

Next, the metal soap which is the component (C) of the present invention is a metal salt of fatty acid, resin acid or naphthenic acid. In the present invention, various metal soaps can be used as the component (C), but higher fatty acid salts such as aluminum, calcium and magnesium (for example, palmitate, stearate, oleate, linoleic acid) are preferred. salt,
Linolenic acid salt). In the present invention,
At least one kind of such metal soap is used as the component (C). The component (C) is incorporated in the composition of the present invention in an amount of 0.1 to 5% by weight, preferably 0.5 to 3% by weight. If the blending ratio is less than 0.1% by weight, the dispersibility of the inorganic powder wax is extremely reduced, which is not preferable.

On the other hand, if it exceeds 5% by weight, the protective property and the wiping property deteriorate, which is not preferable.

Next, the inorganic powder which is the component (D) of the present invention is added for the purpose of improving the wiping property, and is usually calcium carbonate, magnesium carbonate or a water-insoluble basic inorganic powder similar to them. A single body or a mixture of bodies is used. The average particle size of these inorganic powders is 0.1
Those having a thickness of up to 1.5 μm, particularly 0.8 to 1.2 μm are suitable. The component (D) should be added in an amount of 10 to 60% by weight, preferably 10 to 40% by weight, based on the entire composition of the present invention. If the blending ratio is less than 10% by weight, the wiping property will be insufficient, and further, the film formation of the composition will be adversely affected by the increase in the content of other film components, and if it exceeds 60% by weight, the dry film will be formed. The removal property (wiping property) is improved, but the coating film protection property and the gloss property are deteriorated, which is not suitable.

Next, in the present invention, spherical particles of titanium oxide and / or hydrated titanium oxide are used as the component (E). The spherical particles are amorphous, and their average particle size is 1000
It is desirable that the particle size is less than or equal to Å, preferably 300 to 600 Å, and the range of particle size distribution is 50 to 1200 Å, preferably 100 to 500 Å.

Here, use one with an average particle size of more than 1000Å,
Alternatively, use of spherical particles having a particle size distribution range of more than 1200 Å is not suitable because a composition having a sufficient ultraviolet ray preventing effect cannot be obtained. The component (E) as described above can be produced by various methods. For example, a method in which a liquid aerosol of a hydrolyzable titanium compound is hydrolyzed by contacting it with water vapor in a dynamic flow (US Pat. No. 916883); fog droplets of a liquid metal oxide precursor in an inert atmosphere. By heating to the atmosphere, evaporative pyrolysis and gasification, and then catalytically reacting with an oxygen-containing gas in the gas phase (JP-A-59-
107904); evaporative gasification of a hydrolyzable titanium compound in an inert atmosphere and thermally decomposing it, or a method in which thermal decomposition and hydrolysis are used in combination (JP-A-60-186418) be able to.

In the present invention, the titanium oxide, hydrated titanium oxide or a mixture thereof obtained in this way is used as the component (E). Further, the titanium oxide, hydrated titanium oxide or a mixture thereof obtained as described above, which has been surface-treated with oleyl alcohol or the like, can be used as the component (E). By this surface treatment, dispersibility in oils and fats is improved, which is more preferable. In the present invention, the above component (E) is added to the composition as a whole.
The amount is 01 to 50% by weight, preferably 0.01 to 25% by weight. If the blending ratio is less than 0.01% by weight, the composition obtained cannot be expected to have a sufficient ultraviolet shielding effect. On the other hand, 50
If it exceeds the weight%, the paintability, wiping-off property and glossiness are not sufficient.

Next, the hydrocarbon solvent which is the component (F) of the present invention is not particularly limited, but its boiling point range is usually 150 ° C to 200 ° C.
A temperature of ℃, preferably 150-180 ℃ is suitable. In particular, those containing an aliphatic hydrocarbon or alicyclic hydrocarbon having the above boiling point range as a main component are preferable. Specific examples include industrial gasoline, kerosene, normal paraffin solvent, isoparaffin solvent, and the like. The component (F) is 30 to 30% of the total composition.
90% by weight, preferably 50 to 70% by weight.
By using the component (F) within this range, it can be uniformly suspended and dispersed.

The coating film-protecting composition of the present invention comprises the above (A), (B),
Although the components (C), (D), (E) and (F) are essential components, various additives usually used in conventional polishes and the like are added as necessary. be able to. Such additives include di-t-butyl-
Antioxidants such as p-cresol, polishes such as petrolatum, water repellents such as fluorine oil, lubricating oils such as spindle oil, plasticizers such as polybutene, antistatic agents, dispersants,
Examples include abrasives and gelling agents.

The composition of the present invention is produced by blending these raw materials and dissolving and mixing. For example, first, raw materials other than the component (B) and the component (D) are mixed and heated and melted at a temperature of 85 to 100 ° C. until it becomes transparent. Then, after being rapidly cooled to 30 to 50 ° C., the components (B) and (D) are added, and the mixture is stirred for 30 to 60 minutes with a homogenizer or the like to obtain a solid or paste composition.

[Effects of the Invention] The coating film-protecting composition of the present invention obtained as described above comprises:
Since it is excellent in uniform dispersibility, it has a great effect of shielding ultraviolet rays. By applying the composition onto a coating film such as a paint, the weather resistance of the coating film, plastic, decorative sheet, etc. is remarkably improved. Further, the coating film formed from the coating film-protecting composition of the present invention is excellent in both gloss and transparency, and improves the appearance of the coating film by a paint or the like. Further, its wiping property is also good.

Therefore, the coating film-protecting composition of the present invention is used as a protective agent and a polish for coating films, plastics, decorative boards, etc. formed from various coating materials (alkyd-based coating materials, urethane-based coating materials, plastic coating materials, etc.). It is useful.

[Examples] Next, the present invention will be described in detail with reference to Examples.

Example 1 (1) As a raw material for producing spherical particles composed of titanium oxide and hydrated titanium oxide, titanium tetraisopropoxide [Ti
(OC ₃ H ₈ ) ₄ ] was evaporated by a vaporizer, and helium gas containing 0.05 mol% of water was used as a carrier gas, and these were put into a reactor having an inner diameter of 30 mm in which titanium oxide fine particles were previously attached to the inner wall. After the introduction, the reaction of thermal decomposition and hydrolysis was carried out at 350 ° C. After the reaction was completed, the reaction product was immediately cooled and the fine particles adhering to the surface of the cooling pipe were collected.

From the electron micrographs, it was found that the fine particles thus obtained had an average particle size of 300Å and a particle size distribution range of 50 to 400Å. The electron micrograph is shown in FIG. As a result of thermal analysis, the weight loss rate (up to 500 ° C) was 13.9% by weight. Further, as a result of examining the X-ray diffraction pattern of these fine particles, it was confirmed to be amorphous. The X-ray diffraction pattern (Cu-K _d line used) measured here is shown in FIG.

(2) Production of Composition Three kinds of polyethylene wax, microcrystalline wax and paraffin wax are used as a wax-like substance, and aluminum stearate is used as a metal soap.
Fine particles of di-t-butyl-p-cresol as an antioxidant and the titanium oxide and the hydrated titanium oxide obtained in (1) above were added to the hydrocarbon solvent in the proportions shown in Table 1. Next, this mixed solution is heated to 90 ° C to dissolve with stirring, and when it becomes transparent, it is rapidly cooled with stirring to 40 ° C.
At the time of cooling to 0, calcium carbonate with an average particle size of 1 μm as inorganic powder and viscosity at 25 ° C as silicone oil
500 cSt of dimethylpolysiloxane was added at a ratio shown in Table 1 and stirred for 30 minutes with a homogenizer to obtain a composition.

(3) Evaluation of Composition 1 g of the composition obtained in (2) above was spread on a test piece coated with a red melamine alkyd-based paint using a urethane sponge until the coated surface became transparent. Next, this coated surface was dried at room temperature for 30 minutes, and the gloss and transparency of the glossy film were visually evaluated. Further, an outdoor exposure test was carried out for 2 months and 6 months in a state where the coated surface was inclined 45 degrees to the south. The results of these evaluations are shown in Table 2.

Example 2 Example 2 was repeated except that the mixing ratio of the fine particles of titanium oxide and hydrated titanium oxide produced in Example 1- (1) and the mixing ratio of the solvent were changed as shown in Table 1. A composition was prepared in the same manner as in Example 1- (2), and Example 1-
Evaluation was performed in the same manner as (3). The results are shown in Table 2.

Comparative Example 1 Example 1- (2) except that amorphous spherical crystalline titanium oxide particles (P-25 manufactured by Degussa) were used in place of the spherical particles composed of titanium oxide and hydrated titanium oxide in Example 1. A composition was prepared in the same manner as in Example 1 and evaluated in the same manner as in Example 1- (3). The results are shown in Table 2.

Comparative Example 2 The same as Example 1- (2) except that 0.05% by weight of 2,4-dihydroxybenzophenone was used as an ultraviolet absorber instead of the spherical particles composed of titanium oxide and hydrated titanium oxide in Example 1. A composition was prepared in this manner, and this composition was evaluated in the same manner as in Example 1- (3). The results are shown in Table 2.

Reference Example 1 Spherical particles composed of titanium oxide and hydrated titanium oxide prepared in Example 1- (1) were added to a solvent (olive oil 97% by weight, benzene 3% by weight) so that the content was 1% by weight. The mixture was stirred for 12 hours, a thickness of 5 μm was formed on quartz glass, and the absorbance of ultraviolet rays having a wavelength of 300 nm was measured by a spectrophotometer to find that it was 0.45.

Reference Example 2 Spherical particles composed of titanium oxide and hydrated titanium oxide produced in Example 1- (1) were placed in oleyl alcohol at 80 ° C.
With respect to the surface-treated particles having the oleyl group on the surface of the particles that had been immersed for 48 hours, the absorbance of ultraviolet rays was measured in the same manner as in Reference Example 1, and it was 0.53.

Reference Example 3 With respect to the amorphous amorphous titanium oxide particles used in Comparative Example 1, the absorbance of ultraviolet rays was measured in the same manner as in Reference Example 1, and it was 0.22.

[Brief description of drawings]

FIG. 1 is an electron micrograph (20,000 times) showing the particle structure of the fine particles obtained in Example 1- (1). FIG. 2 is an X-ray diffraction pattern of the fine particles obtained in Example 1- (1). In addition, θ in FIG. 2 represents a Bragg angle.

Claims (2)

[Claims] 1. A waxy substance 2 to 15% by weight, (B)
Silicone oil 3 to 15% by weight, (C) Metal soap 0.
1 to 5% by weight, (D) inorganic powder 10 to 60% by weight, (E)
Spherical particles of titanium oxide and / or hydrated titanium oxide 0.
A coating film protective composition comprising 01 to 50% by weight and (F) a hydrocarbon solvent of 30 to 90% by weight. 2. The average particle size of spherical particles of titanium oxide and / or hydrated titanium oxide is 1000 Å or less, and the particle size distribution is in the range of 50 to 1200 Å.
The coating film-protecting composition according to item.