JPS6363726A - Composition for surface treatment - Google Patents

Abstract

PURPOSE:To obtain the titled composition which is excellent in long-term stability and can give a film excellent in adhesion, transparency and antistatic property, by mixing a specified metal oxide sol with an organic polymer dissolved or dispersed in water and/or a water-soluble organic solvent. CONSTITUTION:Particles (a) of a condensate of a (hydro)oxide of a metal selected from among Ti, Zr, Ce, V, Nb, Ta, Al, Ga, In, Sn, Mn, Ni, Co and Fe are dispersed in the presence of 0.05-2.0mol, per mol of the metal (b) of component (a), of a chelating agent which is preferably a beta-dicarbonyl compound in a medium (c) which is water and/or a water-soluble organic solvent to obtain a metal oxide sol (A) of a mean particle diameter <=0.01mum. Separately, an organic polymer (d) is dissolved or dispersed in component (c) to obtain a solu tion or dispersion (B) of component (d). Component A is mixed with component B in a mixing ratio of 5-95/95-5 (in terms of the solid matter0 and a pigment, an ultraviolet absorber, an anticorrosive agent etc., are optionally added to component (B).

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel surface treatment composition. More specifically, it can be used to improve antistatic properties, drip-proofing, chemical resistance, weather resistance, etc. by treating the surface of various base materials, such as plastics, and to modify the surface of inorganic materials such as ceramics and metals. The present invention relates to a surface treatment composition that can be used.

(Prior art) Plastics, which have been used in large quantities in recent years, are sometimes used as is, but in many cases they have been subjected to some kind of surface modification depending on the purpose of use. Various methods have been proposed so far.

For example, JP-A-60-219266 and JP-A-60-243166 propose an antistatic coating for transparent plastics in which conductive oxide powder is dispersed in an organic polymer solution or dispersion. ing. However, since the conductive oxide powder used in these proposed antistatic paints has a particle size of approximately 0.1 μm, although some degree of antistatic property can be expected, the dispersion stability of the powder in the liquid is poor. Moreover, the adhesion and transparency of the film obtained from the paint are insufficient. Also, JP-A-60-2
In Publication No. 21702, 1 selected from Atl Tit Zr+ Sn+ Sb with an average particle diameter of 1-300 mμ
A molded article having a transparent coating layer containing one or more metal oxides has been proposed. However, within the above particle size range of conventionally known metal acid f arsenide fine particles, 0.01, .
, a) If the particle size is below, the particles may gel or agglomerate when formed into a composite with an organic polymer.
There is a problem that the dispersion stability in the composite is poor, and that it cannot be put to practical use. In addition, special public service 1986-105
No. 07 discloses Z as a component of the coating composition.
Acetylacetone metal salt compounds containing metals such as nu C0rFe and Cr are also disclosed in Japanese Patent Application Laid-open No. 60-2021.
In Publication No. 57, an aluminum chelate compound is also proposed as a component of a coating composition, but these use a metal chelate as a curing agent for membrane rupture, which is different from the spirit of the present invention. be.

(Problems to be Solved by the Invention) Therefore, the present invention provides a coating that does not impair transparency and has excellent adhesion and antistatic properties by coating a transparent plastic substrate or glass substrate on the substrate surface. The object of the present invention is to provide a surface treatment composition that is suitable for preparation and has excellent stability over time.

(Means for Solving the Problems) As a result of intensive research by the present inventors in order to solve the current situation, we have found that in a composite consisting of a metal oxide and an organic polymer, it is possible to improve the surface of plastics. Adhesion,
It has been found that properties such as transparency and antistatic properties of the film are significantly improved in the region where the particle size of metal oxide and/or hydroxide particles is extremely small, ie, 0.01 μm or less.

Furthermore, metal oxides and/or
It has also been found that the dispersion stability of hydroxide particles in a medium consisting of water and/or a water-soluble organic solvent can be dramatically improved by interposing a chelating agent.

The present invention takes advantage of the characteristics of various metal oxide-based sols as inorganic materials, such as nonflammability, solvent resistance, abrasion resistance, antistatic properties, and abundant resources, and eliminates the disadvantages of inorganic coating films. This was discovered while conducting research on organic-inorganic composite paints that complement brittleness by combining them with organic polymers.

That is, the present invention provides a surface treatment composition containing the following components (A) and (B) and having excellent liquid stability over time, membrane rupture adhesion, transparency, and antistatic property. It is related to.

uQ: 'ri +Zr +Ce +V+Nb, Ta
1AtIG&, In.

Sn + Sin, Ni, Co and Fe p7
an oxide of at least one metal selected from the group consisting of:
Alternatively, a metal oxide sol (B) having an average particle diameter of 0.01 μm or less is obtained by dispersing hydroxide condensate particles in a liquid medium made of water and/or a water-soluble organic solvent using a chelating agent. : An organic polymer dissolved or dispersed in water and/or a water-soluble organic solvent (function) Chelating agents for the metal oxide sol used in the present invention include oxyphenols such as catechol and pyrogallol, and jetanol. Amino alcohols such as amines and triethanolamine, oxyacids such as glycol, lactic acid, and hydroxyacrylic acid, and their methyl,
Esters such as ethyl and hydroxyethyl, oxidialdehydes such as glycolaldehyde, amino acids such as glycine and alanine, β-diketones such as acetylacetone, benzoylacetone, stearoyl acetone', stearoyl benzoylmethane, and dibenzoylmethane. , the like, β-keto-acids such as acetoacetic acid, propionylacetic acid, benzoylacetic acid and their methyl, ethyl, n-propyl, is.

- Esters such as propyl, n-butyl, and tert-butyl are mentioned, but β-nocarbonyl compounds such as β-dinoketones or β-keto acids and their esters are preferably used. The metal components in the particles that make up the physical sol include titanium, zirconium, cerium, panazome, niobium, mental,
aluminum, gallicum, indium, tin, manganese,
The main component is at least one metal selected from the group of nickel, cobalt, and iron. The amount of the chelating agent molecules added is preferably in the range of 0.05 to 2.0 times the number of moles relative to the metal atoms in the particles. If the amount is less than 0.005 times, the effect is small, and even if it is added more than 2.0 times, the total effect is small and it is not economical.The method for producing metal oxide-based sol that can be applied to the present invention is particularly limited. Instead, any known method can be used. For example, inorganic salts such as metal chlorides, nitrates, and sulfates, and organic acid salts such as oxalic acid and acetic acid are converted into metal oxides or metal hydroxide condensates by alkaline hydrolysis, thermal hydrolysis, ion exchange, etc. in water. Alternatively, an organometallic compound such as a metal alkoxide or an alcoholic solution thereof may be added to water to completely hydrolyze the alkoxide to form a hydroxide condensate, or fine metal particles may be hydrolyzed to form a hydroxide condensate. It is also possible to use a method of making it into a hydrasol. Further, as another specific example, one or more oxygen-containing organic compounds are used as a dispersion medium during alkaline hydrolysis, thermal hydrolysis or ion exchange of metal fences, or a mixed solution of these with water is used. A stable metal oxide-based sol can also be produced by using the above.

Examples of the oxygen-containing organic compounds include alcohols such as methanol, ethanol, pronol, butanol, ketones such as acetone and methyl ethyl ketone, ethers such as methyl ethyl ether and dimoxane, and esters such as methyl formate and methyl acetate. etc. can be suitably used.

In the method for producing the metal oxide sol described above, there are no restrictions on the timing and method of adding the chelating agent, and as described above, it may be added before, during, after the formation of fine particles, or during fractional addition. Finally, by coexisting the fine particles and the chelating agent, the effect of preventing the aggregation of the fine particles is exerted.

Although the stabilization mechanism of the metal oxide sol of the β-Tukanoabonyl compound, which is a particularly preferred chelating agent of the present invention, is not fully elucidated, it is localized on the surface of the oxide or hydroxide fine particles. It is thought that the coordinative bonding of the β-dicargonylated compound to the portion with a positive surface charge makes the particle surface non-hydrophilic and prevents agglomeration caused by collisions between particles. The agglomeration here refers to particles [in the present invention, linear 411 (metal element-oxygen) bonds connected in a three-dimensional shape; C-bonded irregular-shaped objects and their A jelly-forming phenomenon is caused by particle growth due to dehydration condensation between particles (the mixture is called particles) and hydrogen bonding between particles.

By using a metal oxide sol stabilized using the specific method described above, we were able to obtain a surface treatment composition with excellent stability over time, even when it was first composited with an organic polymer. be.

Is it organic in the present invention? Lie can be used without any particular restriction as long as it is in the form of a solution or dispersion in a medium consisting of water and/or a water-soluble organic solvent, but it tends to be complexed with the metal oxide sol, and therefore the durability of the coating may be reduced. It is preferable to have a functional group in the molecule that can interact with the metal oxide sol to improve the performance. Such functional groups include
For example, hydroxyl group, epoxy group, carboxyl group, carbonyl group, ester group, aldehyde group, methylol group, silanol group, halogen group, phletane group, mercapto group, polymerizable unsaturated group, aguno group, amide group, aryl group, etc. Examples of birimers having one or more of these functional groups in the molecule include polyvinyl alcohol, resin, silicone resin, acrylic resin, and vinyl acetate. Examples include resins, hol, ester resins, amine resins, phenol resins, latent vinyl chloride resins, vinylidene chloride resins, polyurethane resins, polybutadiene resins, and polyamide resins. There are no restrictions on the composition or manufacturing method of these organic polymers, and they can be manufactured according to conventional methods. For example, acrylic resins, vinyl acetate resins, etc. can be produced by methods such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization, and polyester resins and silicone resins can be produced by polycondensation reactions.

When using an organic polymer, it is necessary to form a solution or dispersion in a medium consisting of water and/or a water-soluble organic solvent. , alcohols such as 7' lovanol and butanol, ketones such as acetone and methyl ethyl ketone, ethers such as methyl ethyl ether and dioxane, esters such as methyl formate and methyl acetate, amines such as ethanolamine and pyridine,
Examples include mercaptans, and 11 or more of these can be used, but in the present invention, it is particularly preferable to use alcohols and ketones.

The surface treatment composition of the present invention comprises all of the metal oxide sol and organic polymer described above, and can be obtained by simply mechanically mixing them. From the viewpoint of workability during mixing, it is preferable to use a solution or dispersion in a medium consisting of /' or a water-soluble organic solvent. Therefore, when using acrylic resins, vinyl acetate resins, etc. as organic polymers, the polymerization reaction product can be used as it is as a solution or dispersion of the organic polymer, so it is possible to use whole solution polymerization or emulsion polymerization of these polymers. It is a preferred embodiment of the present invention to obtain The surface treatment composition of the present invention thus obtained may be further heat-treated at a temperature below the boiling point of the medium in order to improve the stability of the liquid over time and the physical properties of the resulting film.

In the surface treatment composition of the present invention, the blending ratio of the metal oxide sol and the organic polymer is not particularly limited, but the adhesion, antistatic properties, and flexibility of the film can be optimized. In order to retain, preferably 5/9 in terms of solid content
5 to 9515, more preferably 10/90
It can be in the range of ~90/10.

The surface treatment composition of the present invention may also contain known additives such as pigments, ultraviolet absorbers, heat stabilizers, rust preventives, crosslinking agents, dispersants, antifoaming agents, etc., without departing from the purpose of the present invention. may be included as appropriate.

Plastics to which the surface treatment composition of the present invention can be applied include polyethylene, polynolopyrene, polystyrene, polyvinyl chloride, polycarbonate, polymethyl methacrylate, nylon, Bakelite, epoxy resin unsaturated and saturated polyester resins, ABS resins, polyamide resins, It is a conventionally known resin such as Boliimi P sugar beet. Among these, resins containing oxygen or nitrogen atoms in their polymer chains have particularly good affinity with the hydroxyl groups possessed by the metal oxide sol, and thus give favorable results. The shape of the glass may be any shape such as plate, film, fiber, granule, or molded body.

When using the surface treatment composition of the present invention, any conventionally known coating method such as spraying, dipping, roll coater, knife coater, brush coating, etc. can be employed. Drying may be carried out by room temperature drying, heat drying, active energy ray drying, or the like.

The reason why when the surface treatment composition of the present invention is applied to all plastics etc., a film with good adhesion and excellent transparency and antistatic properties is formed is not clear, but it is thought to be roughly as follows. That is, as a result of the particle surface of the metal oxide sol becoming partially lipophilic due to the effect of the chelating agent, the metal oxide sol acts like a surfactant and lowers the surface tension of the sol. Therefore, the compatibility with organic polymers and the wettability with plastic substrates are improved, and the particles of the sol are stabilized in a fine state of 0.01 μm or less, thereby reducing the active hydroxyl groups on the surface of the particles of the sol. Adhesion is developed due to the combined effect of the bonding force based on hydrogen bonding between the organic polymer, the plastic substrate, and the like. Further, the antistatic property is developed when the particles of the sol are localized on the surface of the coating film. This antistatic property is expressed by proton conductivity based on surface hydroxyl groups, but unlike surfactants, the sol's (; particles are strongly bonded with the organic polymer matrix. Moreover, the antistatic property lasts semi-permanently. However, the present invention is not limited by these reasons in any way.

Furthermore, since the surface treatment composition of the present invention contains a metal oxide sol and an organic polymer, it can be used not only for surface treatment of organic materials such as plastics, but also for metals, glass, ceramics, concrete, It can also be suitably used for surface treatment of inorganic materials such as asbestos, and materials such as paper and wood.

(Example) All embodiments of the present invention are shown below in Examples, but these examples are for specifically explaining the present invention, and are not intended to limit the scope of the present invention.Example 1 Production of metal oxide sol (A-1): Titanium tetrachloride aqueous solution (Ti content 16 to 1689, pure water 447 m/, 7"z yv7 setone 12.3 g
All were added to form a homogeneous solution. To this solution, 600 g of an anion exchange resin (Amberlite TRA-68 manufactured by Mund.) whose ion exchange groups had been previously converted to OH type was added, and 600 g of fully wet resin was added, and the mixture was allowed to come into contact at 25°C for 35 minutes. A metal compound sol (A-1) containing Ti as a metal was produced by distributing all the ion exchange resins from one house to another. This sol (A-
The composition of 1) is that titania is converted to T + 0 2 and is 7
．． 5% by weight, 0.65% by weight of chloride ions (cf'')
Acetylacetone (number of moles)/TI (number of atoms) −
0. It was 2. The average particle size of the sol (A-1) was 40X when observed with a dynamic light scattering photometer (DLS-700 manufactured by Union Giken).

Production of metal oxide sol (A-2): Titanium tetrachloride aqueous solution (Ti content 168% by weight) 168
y, water, methanol (1:1 weight ratio) mixed solvent 447y
and 35.4g of acetylacetone? It was added to make a homogeneous solution.

To this solution, an anion exchange resin (TRA-68') whose ion exchange groups had been converted into OH type in advance was added with a wet resin of 900.9%, and after contacting at 25°C for 45 minutes, the above ion exchange fat was removed from each house. A metal hydride sol (A-2) was produced using Tif as the metal. This sol (
The composition of A-2) is 7.3% by weight of titania calculated as T+02, 0.04% by weight of chlorine ion (C4-), and the ratio of A-2) is tylacetone (number of moles)/Ti (number of atoms).
= 0. It was 6. The average particle size of the sol (A-2) was 30 when observed using a dynamic light scattering photometer.
It was X.

The metal oxide sol (A-1) produced according to the above procedure and the organic polymer dispersions (B-1) and (B-2) shown in Table 1 were mixed in a weight ratio of 4:1. They were mixed to obtain surface treatment compositions (1-1) and (1-2). This is biaxially stretched polyethylene terephthalate film (hereinafter referred to as PET), acrylic board (hereinafter referred to as PMM),
It's called A. ), I recarbonate board (hereinafter referred to as pc).

) and transparent hard vinyl chloride board (hereinafter referred to as PVC) using a percoater so that the film thickness after heat drying was approximately 1 μm. 120
Surface specific resistance value and transparency of the eardrum after heat treatment at ℃ for 3 minutes,
Properties such as adhesion to the substrate were measured by the method shown below.

The results are shown in Table 2. Note that the surface treatment composition (1-
In the case of 1) and (1-2), no change was observed in the state of the liquid even after 4 months had passed, and the characteristics of the film obtained from the composition after 4 months had also not changed.

・Surface specific resistance-YHP-4329A high re
sistance meter 16008A resi
Measurement was performed using sNvity cell (Horizontal Hewlett-Packard company standard) at 25° C. and 55% relative humidity.

- Transparency - The transparency of the coating film was visually evaluated in four stages.

◎・・・Almost the same transparency as the substrate O: Transparent but slightly cloudy.

Δ...Slightly less transparent.

×...When the film is completely white, a cross-cut is made according to the method specified by JIS 5400, 645, and an adhesive cellophane 7" is pasted on the surface, and it is sharply tightened. Evaluation was made based on the residual rate of the coating film when it was removed.

Example 2 Metal oxide sol (A-2) produced in Example 1 and Table -
The organic polymer dispersion (B-2) shown in 1 was mixed at a weight ratio of 4:1 to obtain a surface treatment composition (2). This was applied onto a PET film substrate in the same manner as in Example 1, and the properties of the film were measured. The results are shown in Table-3. It should be noted that this surface treatment composition (2) showed no change in the liquid state at all even after 6 months had passed, and the properties of the film obtained from this composition (2) also remained unchanged.

Examples 3 to 15 In the same manner as the metal oxide sol (A-2) of Example 1, each metal oxide sol/
Surface treatment compositions (3) to (a) were obtained according to the same method as in Example 2. This was coated on a PET film substrate in the same manner as in Example 1, and the characteristics of the wave film obtained were measured. The results are shown in Table-3. It should be noted that for all of these surface treatment compositions (3) to (lIQ), no change was observed in the liquid state even after 3 months had passed, and in addition, these surface treatment compositions (3) to (lIQ) obtained from the mouth The characteristics of the nuclear envelope were also different.

Table-3 Examples 16-17 Organic polymer (B-2) used in Examples 2-3
Instead, a water-dispersed polymer called Poquin modified acrylic grease-resistant (ARL-5, manufactured by Nippon Shokubai Chemical Industry Co., Ltd.)? It was used as an organic polymer (B-3) to obtain a surface treatment composition C1→~αη. The properties of the film obtained by coating it on a PET film substrate in the same manner as in Example 1 were measured. The results are shown in Table 4. In addition,
In all of these surface treatment compositions a→~dry, no change was observed in the liquid state after 3 months, and the properties of the films obtained from these compositions (10~a) also remained unchanged. won.

Table-4 Comparative Examples 11 to 3 Organic polymers (B-1), (B-2) and (B-3
), respectively, are gold tetraoxide based sol? Comparative compositions (1) to (
3) I got it. These were applied onto a PET film substrate using a percoater so that the film thickness after heat drying was approximately 1 μm, and the properties of the resulting film were measured by heat treatment at 120°C. The results are shown in Table-5.

Table 5 Comparative Example 4 Silica sol with an average particle size of 0.01 to 0.02 μm (Snow Terra 2 F8; manufactured by Nissan Chemical Company) was used instead of the metal oxide sol in the present invention, and in Table 1. The organic polymer dispersion (B-1) shown above was mixed at a weight ratio of 4:3, and then diluted with water to a total solids concentration of 14% by weight to obtain a comparative composition (A).

This was applied onto a PET film substrate in the same manner as in Example 1, and the properties of the obtained film were measured. The results are shown in Table-6. Note that this comparative composition (A) thickened in one week,
After 3 weeks, it was completely turned into jelly.

Comparative Example 5 Feather-like alumina sol (Alumina sol) with an average particle size of 0.01 ≠ 0.1 μm (Alumina sol) v 200, Nichiryoku Kagaku ■ Back) All used in the rinsing of the metal oxide-based sol in the present invention, and this and the front- A comparative composition (5) was obtained by mixing the dispersion (B-1) of the organic polymer shown in No. 1 at a ratio of 8:3 by weight, and diluting the mixture with water to a total solids concentration of 14% by weight.

This was obtained by coating it on a PET film substrate in the same manner as in Example 1.
6. Note that this comparative composition (5) was completely turned into a jelly after two days.

Table 6 (Effects of the Invention) As is clear from the above examples, the coating obtained from the surface treatment composition of the present invention containing a specific metal oxide sol and an organic polymer is Compared to a film formed only from an organic polymer that does not contain metal oxide and/or hydroxide condensate particles of a specific particle size, the metal oxide sol that adheres to plastics has a specific particle size. Since it is stabilized with a curing agent, the stability of the liquid over time is very good, and the resulting film also has excellent transparency.

Therefore, the surface treatment composition of the present invention can be applied to various plastic fibers, plates, molded products, etc. to protect the surfaces of these materials and improve antistatic properties, weather resistance, etc. This contributes to

Furthermore, the coating obtained from the surface treatment composition of the present invention is
Compared to nine films formed only from organic polymers,
Since it has excellent adhesion to inorganic materials such as metals, ceramics, and asbestos, it can also be suitably used for surface modification of these materials.

Claims (1)

[Claims] 1. A composition for surface treatment that is characterized by containing the following components (A) and (B) and has excellent liquid stability over time and film adhesion, transparency, and antistatic properties. thing. (A): Ti, Zr, Ce, V, Nb, Ta, Al, G
a, an oxide of at least one metal selected from the group consisting of In, Sn, Mn, Ni, Co, and Fe;
Or a metal oxide sol (B) with an average particle diameter of 0.01 μm or less, which is obtained by dispersing hydroxide condensate particles in a medium consisting of water and/or a water-soluble organic solvent using a chelating agent: 2. The surface treatment composition according to claim 1, wherein the organic polymer 2 dissolved or dispersed in a medium consisting of water and/or a water-soluble organic solvent and the chelating agent are a β-dicarbonyl compound. 3. The surface treatment composition according to claim 1 or 2, wherein the number of moles of the chelating agent is in the range of 0.05 to 2.0 times the number of moles of metal atoms constituting the particles.