JPS63301267A - Coating composition - Google Patents

Abstract

PURPOSE:To obtain a coating composition which has a controllable refractive index and, when applied to the surface of a transparent plastic material and heat-set, can give a film excellent in scratch resistance, chemical resistance, weathering resistance, etc., essentially consisting of a colloidal dispersion of fine zirconium oxide particles and a hydrolyzate of a specified silxane compound. CONSTITUTION:This coating composition essentially consists of a colloidal dispersion (A) of fine zirconium oxide particles in water or another medium and a hydrolyzate (B) of at least one silane compound of formula I (wherein R<1> is an alkyl, alkenyl, phenyl, halogen or the like, R<2> is an organic group including an epoxy, amino, amido, mercapto, cyano, vinyl or nucleus-substituted haloaromatic ring-containing group, a and b are each 0, 1 or 2 and a+b=1-3). Components A and B are preferably present in such an amount that A is 10-90wt.% and B is 90-10wt.% in the cured film constitution.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides excellent scratch resistance, chemical resistance, dyeability, transparency, and This is an inspiration for coating compositions that impart heat-resistant bracken and weather resistance.

[Conventional technology]

Among the plastic materials currently in use, acrylic, methacrylic, vinyl, polycarbonate, and allyl transparent plastic materials have better impact resistance, light weight, processability, and color resistance compared to glass. Because of its excellent properties, it is used in large quantities in place of inorganic glass as an optical material, such as in lenses and transmitting glass. However, these have the disadvantage of being inferior in scratch resistance and chemical resistance compared to inorganic glass.Diethylene glycol bisallyl carbonate resin (hereinafter referred to as CR-30) is a resin that has relatively excellent scratch resistance. However, this is not sufficient for practical use.As a means to improve these drawbacks of plastic materials, it is effective to laminate layers containing polysiloxane.In other words, methyltrimethoxysilane/ A combination of condensate and colloidal silica (Special Publication No. 52-30001, No. 5B-18625)
JP-A-50-41200, JP-A No. 5G-42640, and JP-A No. 57-100108) are known, and some of them have been commercialized. Furthermore, Japanese Patent Publication No. 57-2735 discloses a coating agent containing a combination of an epoxy-containing organic silane and colloidal silica.

[Problem that the invention seeks to solve]

A coating composition that combines a partially integrated methyltrimethoxysilane and j l-j idal silica has a high curing temperature. Alternatively, it requires a long time and cannot be dyed, so it is not versatile.

Furthermore, coating compositions containing a combination of epoxy-containing 1″R Uchitsuki silane and colloidal silica have problems in chemical resistance, especially water resistance.

Again top a! -The silane-based coating composition has a refractive index of around 1.5, so it is suitable for applications where you want to increase the refractive index of a thin film, such as when applying it to the surface of a plastic material with a refractive index higher than 1.5. was not possible.

Therefore, we solved these problems and lost the advantages of plastic rope materials, such as lightness, impact resistance, dyeability, flexibility, and the ability to not break into pieces and scatter even when broken. A coating that provides a cured film with excellent scratch resistance, chemical resistance, water resistance, hot water resistance, heat resistance, weather resistance, and stainability without staining, and allows adjustment of the refractive index. The object of the present invention is to provide a composition for

[Means for solving problems]

The present invention relates to a coating composition containing the following essential components A and B. -A, colloidal dispersion of zirconium oxide fine particles dispersed in water or other solvent.

(However, in the formula, R' is an alkyl group, an alkenyl group, a phenyl group, a halogen group, etc., and R'' is an epoxy group, an amino group, an amide group, a mercapto group, a methacryloxy group, a cyano group, a vinyl group, a nuclear substituted group, etc.) Indicates an a group including a group having a halogenated aromatic ring, and X indicates a hydrolyzable group such as a halogen group, an alkoxyl group, an alkoxyalkoxyl group, an acyloxy group, etc. In addition, avb is 0, 1, or 2, respectively. and a+b is 1 to 3.) A hydrolyzate of 1!11 or two or more of the silane compounds represented by the following.

The zirconium oxide fine particles which are a component constituting the coating composition of the present invention are preferably colloidal dispersions of zirconium oxide fine particles having a particle size of 1 to 100 mμ dispersed in water or other solvent. The particle size of the zirconium oxide fine particles used is 1 to 1° Omμ, more preferably 5 to 50 mμ.

If the beaten particle size is 100 mμ or more, the Fll film after curing will become cloudy or have no color, depending on the wavelength of light in the visible region. If the particle size is less than 1 mμ, the hardness of the thin film after curing will be insufficient and the durability of the film will be poor. In addition to water, examples of dispersion media for zirconium oxide particles include alcoholic dispersion media such as methanol, ethanol, isopropyl alcohol, and methyl cellosolve, acetic acid, propionic acid,
Carboxylic acids such as acetic acid are used. In addition, when water is used as a dispersion medium, the whole oxide fine particles are stabilized with acetic acid, &l'l acid, sulfuric acid, organic 1m (oxalic acid, tartaric acid, malic acid, citric acid, aminorf!i, etc.), etc. You can also use a different one.

If the content of the zirconium oxide fine particles is less than 10% by weight, the water resistance of the coating film will decrease and the dyeability will also deteriorate. On the other hand, if the amount is more than 0.00% by weight, cracks will occur in the coating film and the adhesion properties will decrease, resulting in a thin film that does not have sufficient hardness.

Next, the general formula 12 a′ S IX a −+
In the silane compound represented by l-h1-b', %R2 is an alkyl group, alkenyl group, phenyl group, halogen group, etc., and R is an epoxy group, an amino group, an amide group, a mercapto group, a methacryloxy group, a cyano group. , a vinyl group, a group that forms a nuclear-substituted halogenated aromatic ring, etc., and X represents a hydrolyzable group such as a halogen group, an alkoxyl group, an alkoxyalkoxyl group, or an acyloxy group. Further, a and b are each 0.1 or 2, and a+b is 1 to 3. Examples of these compounds include tetrafunctional silanes such as tetramethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, γ-chloropropyltrimethoxysilane, vinyltrimethoxysilane, and γ-methacryloyloxypropyltrimethoxy. Silane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-
Glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, N-1β-(aminoethyl)-7
Trifunctional silanes such as -aminopropyltrimethoxysilane/, γ-ureidopropyltrimethoxysilane, γ-cyanopropyltrimethoxysilane, γ-morpholinopropyltrimethoxysilane, and N-phenylaminopropyltrimethoxysilane; Examples include trifunctional silanes in which part of the functional silane is converted to methyl, ethyl, or vinyl groups. In addition, hydrolysates, partially fused products, etc. of these materials also exhibit similar properties.

It is necessary that the content of the silane compound is from DO!1IIfft% to 10rrllt%, but this means that if the content of the silane compound is OOBiQ% or more, the water resistance of the coating film will decrease. The properties of the dye decrease, and the dyeability also deteriorates.
On the other hand, if it is less than tom%, cracks will occur in the coating film, and the vB nailing properties will decrease, making it impossible to obtain a thin film with sufficient hardness. This silane compound is F! It is an essential ingredient for giving JI22 its hardness and toughness. Also, 2! I! Hydrolysates of the above sila/compounds can also be used.

In addition, the following are generally used as curing catalysts for silanol.

Amines such as n-pudylamine, triethylamine, guanidi/, biguanide, amino acids such as glycine, fully bent acetylacetonates such as aluminum acetylacetonate, chromium acetylacetonate, titania acetylacetonate, cobalt acetylacetonate, Sodium acetate A, zinc leafthenate, cobalt naphthenate, jkujiru I''I! , jnjlead, tin octylate, and other acid salts, S n Cla , AlC
l5, FeCl5, TicI4, ZnCItlSbCl
There are Lewis acids such as s, but magnesium perchlorate is superior in all properties.

In addition to the above-mentioned thin film forming material, an appropriate solvent is added to the liquid coating composition in the present invention in consideration of problems in coating workability. As a solvent, alcohols, ketones, cellosolves, formamides, water, freon, etc. are used.
Solutions containing 1 to 20% solids are preferred, but are not necessarily limited.

Further, surfactants, ultraviolet absorbers, antioxidants, anti-oxidizing agents, pigments, dyes, antistatic agents, JO conductive particles, etc. can also be added.

The composition thus obtained is applied by a known method,
A coating film is formed by curing. Stamping, flow coating, dip coating, spin cording, V-ru coating, spray coating and various improved application methods can be used.

Further, drying and curing are determined depending on the components used, but preferably curing by heating at 40° C. to 130° C. for 10 minutes to 10 hours is practical.

Further, in order to promote crosslinking and polymerization reactions of reactive groups in the components used, curing can also be carried out by illumination with infrared rays, ultraviolet rays, γ rays, or electron beams.

The coating composition prepared in the above manner can be used for polycarbonate, polycarbonate, polycarbonate, etc.
, polymethacrylate, polyvinyl chloride, polyethylene terephthalate, C! 7-39, other copolymers of styrene and nuclear-substituted halogenated bisphenol monomers, or allyl resins, the effect can be enhanced by applying it to transparent plastic materials.

〔Example〕

The present invention will be explained in more detail with reference to examples, but the present invention is not limited thereto. In addition, the part in the examples indicates inmr6.

Example 1 (1) RA preparation of β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane hydrolyzate In a reactor, 7238 parts of β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and 0.05N Hydrochloric acid aqueous solution E32
．． After stirring for 8 hours, the mixture was aged day and night.

(2)! 2! Liquid Preparation Place a stirring bar in a 1β Erlenmeyer flask, add 482.23 parts of isopropyl alcohol, 73.11 parts of the hydrolyzate of (1), and add the northernmost zirconium sol (water-dispersed sol, average particle Diameter 15mmμ, solid content 0 degrees 20%) 31
2.48 parts and 0.18 parts of a silicone surfactant were added and thoroughly stirred and mixed to obtain a dawn liquid.

(3)! 2! The cloth and the cured coating solution thus obtained were applied to a polycarbonate eyeglass lens that had been subjected to argon gas plasma treatment (400 W, 20 seconds) by a diffusing method.

The pulling speed at this time is 15 cm/min
I went there. This lens was heated in a heating drying oven at 80°C for 1 hour.
Further, the mixture was cured at 100° C. for 1 hour. The obtained lens had no abnormality in appearance and had excellent transparency. Also, this! According to analysis of the surface reflection spectrum, the No. 21 film had a film thickness of 1.5 μm (refractive index: 1.58).

(4) Evaluation test and results The lenses obtained were tested and evaluated using the method described below. The results are shown in table m1.

a) Scratch resistance: aoooo sudir wool (product name “
Using Bonstar (Nippon Bonstar ■ product), the surface of a 1cs x 3cm square test piece was
It was rubbed back and forth, and the degree of damage was visually evaluated in the following stages.

Rank A: No scratches in the above range.

Rank Ro: 1 to IO scratches within the above range Rank C: 10 to about 50 scratches within the above range Rank D: Innumerable scratches, but a smooth surface remains.

Rank E: Surface smoothness is impaired due to scratches on the surface b) ii # Water and chemical resistance: 4 in water, alcohol, and kerosene
It was immersed for 8 hours and its surface texture was examined.

C) Weather resistance: The surface of the plate was examined after being exposed to a fade meter using a Cannon lamp (manufactured by Suga Test Instruments) for 400 hours.

d) Adhesion: The adhesion of vlg is based on JISD-0202.
A crosscapto tape test was conducted according to the method.

That is, using a knife, incisions are made on the surface of the test piece at intervals of one fin to form 100 1-year squares. Next, after strongly pressing cellophane adhesive tape (product name "Cello Tape" Nichiban 4 products) on top of it, it suddenly pulled in a 90° direction from the surface. After the film was removed, the remaining squares of the paint film were used as an index of bamboo quality.

e) Warm water resistance: It was immersed in near 0°C warm water for 3 hours, the appearance was examined, and those with no abnormalities were judged as good. In addition, the adhesion of the membrane after the hot water test a was evaluated by the crosscaptape test described above.

r) Hot water resistance: The appearance of the molded product after immersion in boiling water for 2 hours was examined for abnormalities in the top and center membranes. Furthermore, the adhesion of the coating film after the hot water resistance test was evaluated by the crosscaptape test described above.

Example 2 (1) Preparation, application and curing of coating liquid A stirring bar was placed in an Erlenmeyer flask of 1ρ, and 79.30 parts of γ-glycidoxypropyltrinthoxysilane, 0.08
N1! After adding 21.80 parts of I acid aqueous solution and stirring for 8 hours, the mixture was aged day and night. After that, Medil Cellosolve 507
．． 49 parts, 1.50 parts of magnesium perchlorate, 330.63 parts of the above-mentioned zirconium oxide sol, and 0.19 parts of a silicone-based surfactant activator, stirred and aged, filtered with a filter, and prepared for dipping. It was made into a coating liquid.

The thus obtained solution was applied by dipping to a CR-30 flat plate that had been washed with alkaline water. The pulling speed at this time was 20 c/min. This lens was cured in a heating drying oven at 80° C. for 1 hour, and then at 110° C. for 1 hour in Japan. The obtained flat plate had no abnormalities in appearance (reflection q) was increased and had excellent transparency.The mlU of the obtained flat plate was 1.5μ (refractive index 1 .00)
The thickness of the film was adjusted accordingly.

(2) Evaluation test and results The flat plate thus obtained was subjected to an evaluation test in the same manner as in Example 1. The results are shown in table m1.

Comparative Example 1 (Otori) Preparation and Coating/Curing of Coating Liquid A stirring bar was placed in a 1ρ Erlenmeyer flask, and 05.82flS of methyltrimethoxysilane and 45°50 parts of a 0.05N aqueous hydrochloric acid solution were added and stirred for 8 hours. After adding 308.63 parts of methyl cellosolve and stirring, the mixture was aged day and night. Thereafter, methanol-dispersed silica sol (average particle diameter 13±1 mμ, solid content 20%) and 0.18 part of silicone surfactant were added and stirred. Coating and curing were carried out in the same manner as in Example 2. The obtained lens had an excellent appearance of transparency, but interference fringes appeared on the lens.

(2) Evaluation tests and results The lenses thus obtained were subjected to evaluation tests in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2 All the same procedures as in Example 1 except that methanol-dispersed silica sol was used instead of siliconium oxide.
I did the same thing. The obtained lens was similar to Comparative Example 1.
The appearance was excellent in transparency, but interference fringes appeared on the lens. The results are shown in Table 1.

Table 1 0) Each symbol in the table indicates the next plate.

O: Indicates good Δ: Slight defects are visually observed.

〔Effect of the invention〕

As described in detail above, the present invention uses a colloidal dispersion of zirconium oxide fine particles and a silane compound as components of a coating composition, thereby making it possible to dye a coating composition suitable for optical applications by curing at a relatively low temperature. It has now become possible to obtain a composition that provides a colorless and transparent scratch-resistant coating that can also have a refractive index of a'ii. Because it can be cured at low temperatures, this coating composition can be used on various plastic materials to harden the surface, allowing it to be used in applications that were previously limited due to being easily scratched and having poor chemical resistance. It goes without saying that opportunities to use plastic materials will be expanded, and in particular, the composition of the present invention can be expected to have expanded applications in optical applications due to its transparency. In addition, it can be used in ways that were difficult to use with inorganic glass and gold oat materials, such as dyeing to make it thicker and higher grade, processing into complex shapes, and strong durability against loads and heat. It is possible to expand new applications by taking advantage of the characteristics of plastic materials, such as increasing the size due to its light weight, and its utility value is great. In other words, transparent glass, structural materials, eyeglass lenses, sunglasses, goggles, camera lenses, optical disk materials,
Applicable to camera lenses, large condensing lenses, condensing lenses and diffusing lenses for analytical instruments, protective plates for light reflecting plates, watch glasses and cover glasses, display panel boards, etc., for larger size, anti-glare, and color Effects can be expected from improved functionality such as improved wear resistance and wear resistance.

that's all

Claims (2)

[Claims] (1) A coating composition A characterized by containing the following components A and B as essential components, a colloidal dispersion of fine zirconium oxide particles dispersed in water or other solvent. B. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, in the formula, R^1_■ is an alkyl group, an alkenyl group,
A phenyl group, a halogen group, etc., and R^2_■ is an organic group including an epoxy group, an amino group, an amide group, a mercapto group, a methacloxy group, a cyano group, a vinyl group, a group having a nuclear-substituted halogenated aromatic ring, etc. and X represents a hydrolyzable group such as a halogen group, an alkoxyl group, an alkoxyalkoxyl group, or an acyloxy group. Further, a and b are each 0, 1 or 2, and a+b is 1 to 3. ) A hydrolyzate of one or more silane compounds represented by: (2) The components A and B are in the composition of the cured film, and A is
The coating composition according to claim 1, wherein B is 10% to 90% by weight, and B is 90% to 10% by weight.