JPH01209421A - Spectacle lens having transparent hard coated film - Google Patents

Abstract

PURPOSE:To provide a coated film which is hard and tough by forming the coated film of org. high-polymer polysiloxane network and fine inorg. silica particles dispersed therein and chemically bonding both via a specific bond. CONSTITUTION:The coated film consists of the org. high-polymer polysiloxane network and the fine inorg. silica particles dispersed therein and both are chemically bonded via the bond expressed by formula I. In formula I, Si is derived from a silanol group having silica and C is derived from an epoxy group having polysiloxane. The transparent hard coated film which is harder and tougher is thereby obtd. and, therefore, the lens surface is resistant to flawing and has the higher impact resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a plastic eyeglass lens whose surface is coated with a transparent hard coating film to prevent scratches.

[Conventional technology]

Plastic eyeglass lenses are popular because they are lighter, more unbreakable, easier to manufacture, and can be dyed than glass lenses, and the demand for them is increasing.

However, it has the disadvantage that the surface is more easily scratched than glass.

Therefore, a plastic eyeglass lens whose surface is coated with a transparent hard coating has been proposed and is already commercially available. Commercially available transparent hard coatings are polysiloxane-based coatings.

[Problem to be solved by the invention]

However, conventional paint films are either hard but brittle or tough but soft; there is no such thing as hard and strong; ■ hardness decreases when dyed;
Problems such as difficulty in removing stains such as sweat and fingerprints, ■poor water resistance, ■easy fogging when exposed to steam in cold weather, ■poor abrasion resistance, and ■susceptibility to alkali chemicals. had.

Therefore, the objects of the present invention are: 1. The transparent hard coating film is hard and tough, so the lens surface is hard to be damaged and has excellent impact resistance, 2. The hardness of the coating film does not decrease even when dyed, and . Even if there is dirt such as sweat or fingerprints on the surface, it is easy to remove.■
To provide a plastic eyeglass lens whose coating film is excellent in water resistance, (i) the lens does not fog up even when exposed to water vapor in cold weather, and (ii) the coating film is excellent in abrasion resistance.

[Means to solve the problem]

As a result of intensive research, the present inventor has discovered that the structure is composed of an organic polymer polysiloxane network and inorganic silica fine particles dispersed therein, and both of them have the following bond A: -3i -0-CH-(OH) - I ((However, Si is derived from the silanol group possessed by silica, and C is derived from the epoxy group possessed by polysiloxane.) A transparent hard coating film that is chemically bonded through They succeeded in producing this for the first time, and discovered that the above object could be achieved for the first time by coating the surface of a plastic eyeglass lens with this coating film, leading to the present invention.

Therefore, the present invention provides ``a plastic eyeglass lens whose surface is coated with a transparent hard coating film, wherein the coating film is composed of an organic polymer polysiloxane network and inorganic silica fine particles dispersed therein; Both are chemically bonded via the bond A].

[Effect]

Bond A in the present invention is generated by reacting a silanol group (Si-OH) provided on the surface of a silica fine particle with an epoxy group provided in a polysiloxane network.

Therefore, in the present invention, it is necessary to use "a silanol compound having an epoxy group" as a monomer serving as a starting material for forming a polysiloxane network, and "fine silica particles having a silanol group on the surface" as fine silica particles. becomes.

A silanol compound containing an epoxy group can be easily obtained by hydrolyzing an alkoxysilane corresponding to -m.

Such alkoxysilanes are generally the following General 2 (1)
This is shown in .

R2゜ "R', Si (OR3) -----b
(1) In the formula, R1 is an organic group having an epoxy group, R2
is hydrogen, the hydrocarbon base film having 1 to 6 carbon atoms is a vinyl group, R3
is a hydrocarbon group having 1 to 5 carbon atoms, an alkoxyalkyl group, or an acyl group having 1 to 4 carbon atoms, a is 1 to 2, b is O-1, and a+b≦2.

Specific examples of the alkoxysilane represented by the general formula (1) are as follows.

Glycidoxymethyltrimethoxysilane Glycidoxymethyltriethoxysilane β-glycidoxyethyltrimethoxysilane β-glycidoxyethyltriethoxysilane T-glycidoxypropyltriethoxysilane γ-glycidoxypropyltriethoxysilane γ-glycidoxypropyltri(methoxyethoxy)silane γ-glycidoxypropyltriacetoxysilane δ-glycidoxybutyltrimethoxysilane δ-glycidoxybutyltriethoxysilane glycidoxymethyldimethoxysilane glycidoxymethyl( methyl) dimethoxysilane glycidoxymethyl (ethyl) dimethoxysilane glycidoxymethyl (phenyl) dimethoxysilane glycidoxymethyl (vinyl) dimethoxysilane β-glycidoxyethyl (methyl) dimethoxysilane β-glycidoxyethyl (ethyl) ) dimethoxysilane T-glycidoxypropyl (methyl) dimethoxysilane T-glycidoxypropyl (ethyl) dimethoxysilane δ-glycidoxybutyl (methyl) dimethoxysilane δ-glycidoxybutyl (ethyl) dimethoxysilane bis( Glycidoxymethyl) dimethoxysilane bis(glycidoxymethyl) dimethoxysilane bis(glycidoxyethyl) dimethoxysilane bis(glycidoxyethyl) dimethoxysilane bis(glycidoxypropyl) dimethoxysilane bis(glycidoxy) propyl)jetoxysilane glycidylmethyltrimethoxysilane glycidylmethyltriethoxysilane β-glycidylethyltrimethoxysilane β-glycidylethyltriethoxysilane T-glycidylpropyltrimethoxysilane γ-glycidylpropyltriethoxysilane γ-glycidylpropyltriethoxysilane ethoxy)silane γ-glycidylpropyltriacetoxysilane 3.4-
Epoxycyclohexylmethyltrimethoxysilane 3.4-Epoxycyclohexylmethyltriethoxysilane 3.4-Epoxycyclohexylethyltrimethoxysilane 3.4-Epoxycyclohexylprobyltrimethoxysilane 3.4-Epoxycyclohexylbutyltrimethoxysilane These may be used alone or in combination of two or more.

The silanol group produced by hydrolyzing the alkoxysilane is unstable, and two silanol groups immediately undergo dehydration condensation to form a siloxane bond (-3i -0-
3i −). This condensation, also called precondensation or partial condensation, proceeds in a chain to some extent by simply hydrolyzing the alkoxysilane, producing mainly linear, low molecular weight polysiloxane oligomers.

Hydrolysis is carried out by adding and stirring pure water or an acidic aqueous solution such as hydrochloric acid or sulfuric acid. During hydrolysis, alcohol, alkoxy alcohol, organic carboxylic acids such as acetic acid, etc. are produced, so hydrolysis can be carried out without a solvent. It is also possible to replace the solvent by removing an appropriate amount of the solvent generated by hydrolysis by heating, reducing pressure, etc., and then adding an appropriate solvent. As the solvent, alcohols, esters, ethers, ketones, halogenated hydrocarbons, aromatic hydrocarbons, etc. can be used depending on the purpose.

After hydrolysis, it may be left to mature overnight or for several days.

By replacing a part of the alkoxysilane with [an alkoxysilane that does not have an epoxy group] during the hydrolysis before synthesizing the oligomer, and performing cohydrolysis,
Modified oligomers may be synthesized and are within the scope of this invention. Specific examples of such alkoxysilanes are as follows.

Methyltrimethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, tetraethoxysilane,
Phenyltrimethoxysilane, phenylmethyldimethoxysilane, vinyltriethoxysilane, vinyl-tris(β-methoxyethoxy)silane, vinyltriacetoxysilane, T-methacryloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- β
-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-bis(β-hydroxyethyl)-di-aminopropyltriethoxysilane, N-β-(aminoethyl)-T-aminopropyl(methyl)dimethoxysilane , γ-chloropropyltrimethoxysilane, T-mercaptopropyltrimethoxysilane. These may be used alone or in combination of two or more.

The above-mentioned "alkoxysilane without epoxy group" is
In some cases, an oligomer without an epoxy group may be synthesized by hydrolysis alone without being subjected to co-hydrolysis, and then a portion of the oligomer having an epoxy group may be replaced.

In any case, the oligomer must have on average more than two silanol groups per molecule and on average more than one epoxy group per molecule.

In order to have more than two silanol groups per molecule on average, (1) either use a mixture of difunctional and trifunctional alkoxysilanes, or use a trifunctional one alone;
Alternatively, as an oligomer, one having two silanol groups per molecule and one having three silanol groups may be used as a mixture, or one having three silanol groups may be used alone. .

Such oligomers contain water due to the synthesis process and are in the form of a solution. Then, this oligomer is added with [silica fine particles having a silanol group on the surface], and if necessary, a curing catalyst surfactant, a thickener, a leveling agent, a dye, a pigment, an ultraviolet absorber, an antioxidant, a fragrance, and a filler. ,
A crosslinking agent that reacts with epoxy groups, epoxy resin, amino resin, etc. are added and mixed uniformly to form a paint. If necessary, the paint is filtered to remove dust and undesirable gelled substances.

The above-mentioned silica fine particles have a particle size of 1 to 200 nm, and are available as a commercial product (called silica sol). For the purpose of the present invention, particles with a particle size of 5 to 30 nm are particularly preferred.

The silica fine particles used in the present invention have silanol groups on the surface, and for the purpose of the present invention, particles having 2 to 10 silanol groups per square nanometer ((ns+)2) of surface area are preferred. .

The amount of silica fine particles is generally 10 to 200 parts by weight, preferably 30 to 15 parts by weight per 100 parts by weight of oligomer (solid content equivalent).
Use 0 parts by weight. A paint containing oligomers and silica particles is applied to plastic eyeglass lenses. Application methods include brush painting, spray painting, dipping, spin code, bar code, etc.

After coating, (1) dry at room temperature or under slight heat to form a soft coating film, and then heat cure or (2) directly heat cure to obtain the desired transparent hard coating.

By heating and curing, the silanol groups of the oligomer undergo dehydration condensation with each other to form a polymer. At this time, since the oligomer has an average of more than two silanol groups per molecule, polymerization proceeds three-dimensionally, and an organic polymer polysiloxane network with a network structure is completed.

At this time, there are silanol groups on the surface of the silica particles,
Since the oligomer has an epoxy group, if the conditions (paint composition and heat curing conditions) are selected, the two will react and form the bond A.
generate. Depending on the conditions, even if silica fine particles having silanol groups on the surface are dispersed in an organic polymer polysiloxane network, a coating film may be obtained in which the bond A is not formed. not achieved.

The thickness of the transparent hard coating film is generally 0.1 to 10 μm, preferably 1 to 5 μm.

The base material of the eyeglass lens is plastic, such as polymethyl methacrylate and copolymers thereof, acrylonitrile-styrene copolymer, ABS resin,
Thermoplastic resins such as polygapo-green, carroto acetate, cellulose acetate butyrate, polyvinyl chloride, polyethylene terephthalate, or epoxy resins,
Urethane resin, unsaturated polyester resin, diethylene glycol bisallyl carbonate polymer (CR-39)
It is molded from thermosetting resin such as

The spectacle lens of the present invention can be dyed (front surface dyeing,
(gradation dyeing, multiple dyeing) may be applied, or an inorganic antireflection film or a colored film may be provided on the coating film.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

(Example) (1) Hydrolysis (synthesis of oligomer) 236 g of T-glycidoxypropyltrimethoxysilane was charged into a reactor equipped with a rotor, kept at 106 C, and heated to 0 while stirring with a magnetic stirrer. 54 g of .01N aqueous hydrochloric acid solution was gradually added dropwise. After dropping, stop cooling and
A T-glycidoxypropyltrimethoxysilane hydrolyzed/partial condensate (oligomer) was prepared. The solids content of this oligomer was 66%.

(2) Adjustment of paint Add 100g (solid content equivalent) of the oligomer from (1) above to
100 g of Nlica fine particles (methanol-dispersed colloidal form TL) with an average particle size of 13 ± lnm and having 3 to 4 silanol groups per 1 (nm) surface area (solid content equivalent)
In addition, acetylacetone/aluminum rust body 0.2
5g (acetylacetone Ig) and bisphenol A1
3 g of a curing catalyst silicone surfactant consisting of 3 g and 50 g of tetraethylene glycol were added and uniformly mixed to prepare the paint once.

(3) Painting A diethylene glycol bisallyl caponate polymer lens (
Apply to lens (75nm diameter, 2.1nm thickness) using the dipping method with a pull-up rate of 10cm+/min, heat harden in a hot air dryer at 90°C for 30 minutes, and then heat harden at 130°C for 2 hours. In this way, the spectacle lens of this example was obtained.

(4) Test The obtained lenses were subjected to the following tests. The results are shown in Table 1.

(a) Steel wool Rub the coated surface strongly with steel wool with a hardness of #0000 to judge the extent of scratches.

(b) Place an impact-resistant lens on the floor with its convex side facing up, drop a steel ball into the center of the lens, and check the degree of cracking.

(c) Hardness after dyeing By immersing the lens in a dyeing bath at 80° for 30 minutes,
After dyeing the Hard X coating, the steel wool hardness was examined in the same way as in (a).

(iv) Stain resistance: Apply artificial sweat to the surface of the lens, leave it for a day and night, then wipe off the dirt with gauze and judge by looking at the degree of dirt.

(e) Water-resistant lenses in 0.001% sodium hydroxide aqueous solution at 50°C.
After immersion for 0 hours, changes in the appearance of the coating film were examined.

(F) After the anti-fog lens was cooled to 5°C, it was exposed to water vapor and the degree of fogging was evaluated.

(G) The surface of the abrasion-resistant coating was rubbed 1 million times to examine changes in the appearance of the coating.

The above results were evaluated in four grades: ◎Excellent, ○Good, ΔSlightly Poor, and ×Poor.

Table 1 [Effects of the Invention] As described above, according to the present invention, (1) the transparent cured coating film is hard and tough, so the lens surface is hard to be scratched (and has excellent impact resistance), and (2) it can be dyed. However, the hardness of the coating film does not decrease,
■ Even if there is dirt such as sweat or fingerprints on the lens surface, it is easy to remove. ■ The coating film has excellent water resistance. ■ The lens does not fog up even when exposed to water in cold weather. ■ The coating film has excellent abrasion resistance. Plastic eye lenses are offered for the first time.

Applicant: Nippon Kogaku Kogyo Co., Ltd.

Claims (1)

[Scope of Claim] A plastic eyeglass lens whose surface is coated with a transparent hard coating film, wherein the coating film consists of an organic polymer polysiloxane network and inorganic silica fine particles dispersed therein, and is the following bond A: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, Si is derived from the silanol group of silica, and C is derived from the epoxy group of polysiloxane.) An eyeglass lens characterized by being chemically bonded through a lens.