JPH07138530A - Production of hard coat - Google Patents

Abstract

PURPOSE:To improve the hardness of a hard coat by applying a mixture of a specific silane compd. with a metal alkoxide to a substrate, copolymerizing the silane compd. with the alkoxide in the resulting coating film, and thermally curing the film. CONSTITUTION:A transparent hard coat is obtd. by mixing 10-40mol% silane compd. of the formula: R<1>nSiX<1>(4-n) (wherein R<1> is an org. group; X<1> is a 1-4C alkoxy group; and n is 1 or 2)(e.g. triethoxyphenylsilane) and 90-60mol% metal alkoxide of the formula: MX<2> (wherein M is Sb, Sn, In, Nb, etc.; X<2> is a 1-4C alkoxy group: and n is the valence of M, being 3-5)(e.g. antimony triethoxide) into a solvent (e.g. ethanol), adding water and a catalyst (e.g. hydrochloric acid) to the resulting mixture, applying the mixture to a substrate (e.g. a plastic substrate) in a coating thickness of 0.1-5.0mum within from about 5min to about 10min after the start of hydrolysis and condensation, heating the coating film to a specified temp. at a temp. increase rate of about 1-10 deg.C/min, and keeping the film at the temp. for about 24-36hr to cure it.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a hard coat obtained by using a silane compound and a metal alkoxide. In particular, the present invention is an optical lens, a spectacle lens,
It is useful as a method for producing a hard coat of a plastic optical product such as an optical prism.

[0002]

2. Description of the Related Art In recent years, optical products such as optical lenses, spectacle lenses, optical prisms, etc. have advantages in impact resistance, light weight, workability, dyeability, etc., instead of those made of inorganic glass. Those made of organic glass, that is, plastic, are increasing. However, the surface hardness of plastic is lower than that of inorganic glass, and a slight contact with a foreign substance causes scratches. Therefore, a plastic optical product is generally protected by forming a hard coat on the optical surface. The hard coat currently used is, for example,
By preparing a coating liquid containing a silane coupling agent or a coating liquid in which a sol of metal oxide fine particles and a silane coupling agent are mixed, and dipping or spin-coating the optical product as an object to be coated with heat treatment, Has been formed.

Specifically, for example, Japanese Patent Publication No. 5-45612
In the publication, trimethoxymethylsilane and glycidyloxyethyltrimethylsilane are hydrolyzed and partially condensed at room temperature for 24 hours using an aqueous solution of aluminum diphosphate in a methanol solvent to prepare a coating agent. It is disclosed that a hard coat film is formed by coating on and heat treatment. However, recently, along with the increase in the refractive index of optical products, there is an increasing demand for a hard coat having a high refractive index. On the other hand, in the examples of the above publications, only the silane compounds trimethoxymethylsilane and glycidyloxyethyltrimethylsilane are used as raw materials. for that reason,
The formed film has a low refractive index, and cannot provide a hard coat having a high refractive index. The above-mentioned coating agent has already undergone a hydrolysis reaction and a partial condensation reaction to form a fine particle sol of both silane compounds. Therefore, the film obtained by using this is a gel of fine particle sol and has many microdomains. As a result, the obtained film was found to be fogged, non-uniform and poor in film quality.

[0004]

Therefore, it has been attempted to prepare a high refractive index hard coat by using a coating liquid prepared by mixing a sol of metal oxide fine particles having a high refractive index and a silane coupling agent. . However, in order to form a high refractive index hard coat, it is necessary to prepare a coating liquid using a sol of metal oxide fine particles having a high refractive index. However, the sol of high-refractive-index metal oxide fine particles such as titanium and antimony lacks stability and causes white turbidity or precipitation due to aggregation of the fine particles. Therefore, it is difficult to prepare such a coating liquid, and there are few examples in which it is put into practical use. The hard coat obtained by using the above coating liquid is a gel of metal oxide fine particles and a silane coupling agent. Therefore, there is a defect that the film quality is poor because it has microdomains and is inhomogeneous.

"Color Material Association Magazine" Vol. 65, No. 11, 67
On pages 6 to 683, a metal alkoxide solution or sol of aluminum tripropoxide, aluminum tributoxide, titanium tetrapropoxide, zirconium propoxide, etc. should be prepared, coated on a plastic substrate, and then heat-treated. Has reported that a hard coat film is prepared. The above "Coloring Materials Magazine"
The film prepared in 1. used a metal alkoxide having a high refractive index as a raw material and had a relatively high refractive index. However, since only metal alkoxide is used, the adhesion to the plastic substrate is poor, and the film obtained from any metal alkoxide has numerous cracks due to thermal expansion and contraction during heat treatment. It had the drawback of being bad.

[Journal of Non-Crystalline Solids] Vol. 100, pp. 418-423 (198)
8 years), it is reported that a hard coat film is prepared by a sol-gel method using titanium tetraethoxide and diphenylsilanediol as raw materials. In this report, titanium tetraethoxide was added to a toluene-ethanol mixed solvent, glacial acetic acid was further added, and reflux was carried out at 50 ° C., then diphenylsilanediol was added, reflux (reflux) was added, and water was added to 150 ° C. After heating, a viscous yellow transparent solution is obtained. A hard coat film is formed by coating this solution on phosphate glass and heat-treating it. In the method for producing a film reported in the above-mentioned "Journal of Non-Crystalline Solid", a mixed solution of titanium tetraethoxide and diphenylsilanediol is heated before and after adding water.
Therefore, the finally obtained viscous yellow liquid has undergone hydrolysis and condensation reactions considerably and is a fine particle sol of both raw materials. Therefore, the film obtained by using this is a gel of fine particle sol and has many micro domains. As a result, the obtained film was found to be cloudy, inhomogeneous and poor in film quality.
Further, since the amount of titanium tetraethoxide having a high refractive index added is small, there is a problem that the refractive index of the obtained film is low.

"Macromolecules" Vol. 24, No. 3
On pages 449 to 3450 (1991), it is reported that a hard coat film is formed by a sol-gel method using titanium tetrapropoxide and an organic oligomer-substituted triethoxysilane as raw materials. In this report, after adding titanium tetrapropoxide to a tetrahydrofuran solvent containing hydrochloric acid (10N) to form a titania sol,
An organic oligomer-substituted triethoxysilane was added to prepare a mixed sol of both raw materials, which was coated on a poly (4-methyl-1-pentene) substrate and heat-treated at 60 ° C. to form a film. There is. Further, the obtained film is peeled from the base material and heat-treated at 200 ° C. to obtain a hard coat film. The film made in the above-mentioned report of "Macromolecules" has a high refractive index of 1.6 to 1.75. However, in the production method, titanium tetrapropoxide is added to a tetrahydrofuran solvent containing hydrochloric acid (10N) which is a hydrolysis catalyst to form a sol by hydrolysis reaction and condensation reaction, and then an organic oligomer-substituted triethoxysilane is added to form a sol Therefore, the fine particle sol of each raw material is mixed. Therefore, the film obtained using this was a gel of fine particle sol, had many microdomains, generation of fogging was observed, and the film was inhomogeneous and the film quality was poor. Further, in order to obtain sufficient hardness, it is necessary to perform heat treatment at about 200 ° C, but plastic substrates generally cannot withstand heating at 200 ° C. Therefore, the film must be peeled off from the plastic substrate, which is unsuitable for application to a hard coat for optical products.

As described above, the conventional methods have the above-mentioned problems and drawbacks, and a hard coat useful for an optical product made of a high refractive index plastic has not been obtained. Therefore, an object of the present invention is to have a high hardness, which is the basic performance as a hard coat film, has a high refractive index that can correspond to a high refractive index of an optical product, and has excellent adhesion to a plastic substrate, It is an object of the present invention to provide a method for producing a hard coat, which does not have heterogeneity due to microdomains, has high transparency, and can cure a film by heat treatment in a temperature range in which a plastic substrate has heat resistance.

[0009]

Therefore, the present invention provides a mixture of a silane compound and a metal alkoxide, which mixture is applied to the surface of an object to be coated, and then the silane compound and the metal in the applied mixture are mixed. It relates to a method for producing a hard coat, which comprises copolymerizing with an alkoxide and heating the resulting copolymer film to cure.
A feature of the present invention is that a hydrolysis reaction and a condensation reaction of a silane compound and a metal alkoxide are simultaneously started, and the hydrolysis reaction and the condensation reaction are mainly applied to the surface of an object to be coated and then allowed to proceed. .

In a preferred embodiment of the production method of the present invention, (A) general formula (I) R ¹ _m Si X ¹ _(4-m) (I) (wherein R ¹ represents an organic group, X ¹ Represents -OR ² ,
R ² represents an alkyl group having 1 to 4 carbon atoms, m is 1 or 2
Is an integer. ) One or more kinds of silane compounds (component A), and (B) general formula (II) MX ² _n (II) (wherein M is Sb, Sn, In, Nb, Ta). , Ti, Z
r, X ² represents —OR ³ , and R ³ has 1 to 4 carbon atoms.
Represents an alkyl group, and n is a valence of a metal atom represented by M and is an integer of 3 to 5. ), One or two
At least one metal alkoxide (component B) is used. Furthermore, the mixing ratio of the component A and the component B is 10 to 40 mol% for the component A and 90 for the component B with respect to the total amount of the component A and the component B.
It is preferably in the range of -60 mol%.

The present invention will be described in detail below. In the silane compound represented by the general formula (I) (component A), the silane atom is substituted with one or two organic groups, and the remaining bonds are all substituted with alkoxy groups. R ¹ has the effect of increasing the adhesion to the plastic substrate.
This adhesiveness means that covalent bond, ionic bond,
This is due to bond formation such as coordination bond and hydrogen bond, van der Waals force, and affinity such as electrostatic attraction. Examples of the organic group R ¹ include, for example, methyl group, ethyl group, n-
Propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, octadecyl group, n-octyl group, chloromethyl group, methoxyethyl group, hydroxyethyl group, aminoethyl group, mercaptopropyl group. Group, phenyl group, benzyl group, hydroxyphenyl group, chlorophenyl group, aminophenyl group,
Examples thereof include vinyl group, allyl group, acryloxyethyl group, methacryloxyethyl group, glycidoxypropyl group and acetoxy group. The alkoxy group of X ¹ is Si-O-
It is a functional group for forming Si bond and Si-OM bond, and is hydrolyzed by water and released as alcohol. Examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group. The number of carbon atoms of R ² is 1 to 4 from the viewpoint that the molecular weight of the alcohol to be eliminated is relatively small, the removal is easy, and the deterioration of the denseness of the formed film can be suppressed.
It is preferably in the range of.

Examples of the silane compound represented by the general formula (I) include dimethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldi-n-propoxysilane, diisopropyldiisopropoxysilane and di-n-butyldi-n. -Butyloxysilane, di-sec-butyldi-s
ec-butyroxysilane, di-t-butyldi-t-butyloxysilane, methyloctadecyldimethoxysilane,
Methyldodecyldiethoxysilane, methyloctadecyldimethoxysilane, methyloctadecyldiethoxysilane, n-octylmethyldimethoxysilane, n-octylmethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyl Isopropoxysilane, methyl-
n-butyroxysilane, methyltri-sec-butyroxysilane, methyltri-t-butyroxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethylisopropoxysilane, ethyl-n-butyroxysilane, ethyltri-
sec-butyroxysilane, ethyltri-t-butyroxysilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane, n-hexyltrimethoxysilane, hexadecyltrimethoxysilane, n-octyltrimethoxysilane, n-dodecyltrimethoxysilane,
n-octadecyltrimethoxysilane, n-propyltriethoxysilane, isobutyltriethoxysilane, n
Hexyltriethoxysilane, hexadecyltriethoxysilane, n-octyltriethoxysilane, n-dodecyltrimethoxysilane, n-octadecyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, dibenzyldimethoxysilane, dibenzyldi Ethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dibenzyltrimethoxysilane, dibenzyltriethoxysilane, 3-acetoxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxy Silane, 4-aminobutyltriethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N- (2-aminoethyl)-
3-aminopropylmethyldimethoxysilane, N- (2
-Aminoethyl) -3-aminopropyltrimethoxysilane, 6- (aminohexylaminopropyl) trimethoxysilane, p-aminophenyltrimethoxysilane,
p-aminophenylethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, ω-aminoundecyltrimethoxysilane, amyltriethoxysilane, benzoxailepine dimethyl ester, 5- (bicyclohep (Tenyl) triethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, 8-bromooctyltrimethoxysilane, bromophenyltrimethoxysilane, 3-bromopropyltrimethoxysilane, n-butyltrimethoxysilane , 2-chloromethyltriethoxysilane, chloromethylmethyldiethoxysilane, chloromethylmethyldiisopropoxylan, p- (chloromethyl) phenyltrimethoxysilane, chloromethyltriethoxysilane, chloro Phenyltriethoxysilane, 3
-Chloropropylmethyldimethoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 2- (4-chlorosulfonylphenyl) ethyltrimethoxysilane, 2-cyanoethyltriethoxysilane, 2-cyanoethyltrimethoxysilane , Cyanomethylphenethyltriethoxysilane, 3-
Cyanopropyltriethoxysilane, 2- (3-cyclohexenyl) ethyltrimethoxysilane, (cyclohexylaminomethyl) methyldiethoxysilane, (3-cyclopentadienylpropyl) triethoxysilane,
N, N-diethyl-3-aminopropyl) trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, (3-glycidoxypropyl)
Methyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 1,2,3,4,7,7, -hexachloro-6-methyldiethoxysilyl-2-norbornene, 1,2,3,4,7 , 7, -Hexachloro-6-triethoxysilyl-2-norbornene, 3-iodopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, (mercaptomethyl) methyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3 -Mercaptopropyldimethoxysilane, 3
-Mercaptopropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, methyl {2-
(3-Trimethoxysilylpropylamino) ethylamino} -3-propionate, 7-octenyltrimethoxysilane, R-N-α-phenethyl-N'-triethoxysilylpropylurea, S-N-α-phenethyl-
N'-triethoxysilylpropylurea, phenethyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, phenylvinyldiethoxysilane, 3
-Thiocyanatopropyltriethoxysilane, (tridecafluoro-1,1,2,2, -tetrahydrooctyl) triethoxysilane, N- {3- (triethoxysilyl) propyl} phthalamic acid, (3,3,3- Trifluoropropyl) methyldimethoxysisilane, (3,
3,3-trifluoropropyl) trimethoxysisilane, 1-trimethoxysilyl-2- (chloromethyl) phenylethane, 2- (trimethoxysilyl) ethylphenylsulfonyl azide, β-trimethoxysilylethyl-2-pyridine , Trimethoxysilylpropyldiethylenetriamine, N-{(3-trimethoxysilyl) propyl} ethylenediaminetriacetic acid sodium salt, N- (3-trimethoxysilylpropyl) pyrrole, vinylmethyldiethoxylane, vinylethoxysilane, vinyltrimethoxy Examples thereof include silane, vinyltriphenoxysilane, vinyltris-t-butoxysilane and the like.

The metal alkoxide (component B) represented by the general formula (II) is one in which all bonds of metal atoms are substituted with alkoxy groups. The alkoxy group of X ² is M-
It is a functional group for forming an O-M bond or a Si-O-M bond, and is hydrolyzed by water and released as an alcohol. The same alkoxy group as the alkoxy group described for X ¹ can be used. The alkoxy group represented by X ² suitably has a carbon number in the range of 1 to 4. Within this range, the molecular weight of the alcohol to be eliminated is relatively small, the alcohol can be easily removed, and the denseness of the formed film can be suppressed. The metal atom represented by M is preferably Sb, Sn, In, Nb, Ta, Ti, Zr or the like. Since these metal atoms have a high atomic refractive index, the refractive index of the copolymer film obtained can be increased by copolymerizing the metal alkoxide containing these metal atoms. In addition, there are other metal atoms having a relatively high atomic refractive index such as alkali metals and alkaline earth metals. However, those metal atoms may have low stability of bonds such as Si—O—M bond or M—O—M bond to be formed, or may not be formed, so that caution is required during use.

As the metal alkoxide represented by the general formula (II), antimony trimethoxide, antimony triethoxide, antimony tri-n-propoxide, antimony tri-i-propoxide, antimony tri-n-butoxide, Antimony tri-sec-butoxide, antimony tri-t-butoxide, antimony pentamethoxide, antimony pentaethoxide, antimony penta-n-propoxide, antimony penta-i-propoxide, antimony penta-n-butoxide, antimony penta- sec-Butoxide, antimony penta-t-
Butoxide, tin tetramethoxide, tin tetraethoxide, tin tetra-n-propoxide, tin tetra-i.
-Propoxide, tin tetra-n-butoxide, tin tetra-sec-butoxide, tin tetra-t-butoxide, tin tetramethoxide, tin tetraethoxide, tin tetra-n-propoxide, tin tetra-i-propoxide, tin tetra-n- Butoxide, tin tetra-s
ec-butoxide, tin tetra-t-butoxide, indium trimethoxide, indium triethoxide, indium tri-n-propoxide, indium tri-i.
-Propoxide, indium tri-n-butoxide, indium tri-sec-butoxide, indium tri-
t-Butoxide, niobium pentamethoxide, niobium pentaethoxide, niobium penta-n-propoxide, niobium penta-i-propoxide, niobium penta-n-butoxide, niobium penta-sec-butoxide, niobium penta-t-butoxide, tantalum pentamethoxide. , Tantalum pentaethoxide, tantalum penta-n-propoxide, tantalum penta-i-propoxide, tantalum penta-n-butoxide, tantalum penta-sec-butoxide, tantalum penta-t-butoxide, titanium tetramethoxide, titanium tetra. Ethoxide, titanium tetra-n-propoxide, titanium tetra-i-propoxide, titanium tetra-n-butoxide, titanium tetra-s
ec-butoxide, titanium tetra-t-butoxide, zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetra-n-propoxide, zirconium tetra-i-propoxide, zirconium tetra-n-butoxide, zirconium tetra-sec-butoxide. , Zirconium tetra-t-butoxide, and the like.

As described above, the silane compound (component A) represented by the general formula (I) having an organic group which enhances the adhesive force to the plastic substrate and the general formula (II) having a metal atom having a high atomic refractive index. By copolymerizing with a metal alkoxide represented by () (component B), a hard coat film having good adhesion to a plastic substrate and a high refractive index can be obtained.
The above-mentioned copolymerization of component A and component B is a hydrolysis reaction initiated by adding component A and component B to an organic solvent to prepare a mixture, and further adding water and a hydrolysis catalyst to the mixture. And the condensation reaction that follows the hydrolysis reaction. The concentrations of component A and component B in the organic solvent can be appropriately selected depending on the types and mixing ratios of component A and component B, the film thickness of the hard coat, the coating method, and the like.
Generally, for example, the total of the components A and B is 10 to 60.
It is suitable to set it in the range of% by weight. The above mixture can be obtained by adding a predetermined amount of component A and component B to an organic solvent at room temperature or higher and 50 ° C. or lower with stirring, and then continuing stirring until the solution becomes homogeneous. In addition, various additives such as a colorant and an ultraviolet absorber may be added to the above mixture, if necessary. The mixing ratio of the component A and the component B is preferably 10 to 40 mol% of the component A and 90 to 60 mol% of the component B with respect to the total amount of the component A and the component B. The reason is that when the content of the component A is less than 10 mol% (that is, when the content of the component B is more than 90 mol%), the adhesive force to the plastic substrate becomes insufficient and peeling or cracking from the plastic substrate easily occurs. Because it will be. On the other hand, when the component B is less than 60 mol% (that is, when the component A is more than 40 mol%), the refractive index tends to decrease. More preferably, Component A is in the range of 20 to 30 mol% and Component B is in the range of 80 to 70 mol%. Examples of the organic solvent used here include aromatic hydrocarbons such as benzene, toluene and xylene, alcohol solvents such as methanol, ethanol and i-propanol, ether solvents such as diethyl ether and tetrahydrofuran, and known hydrolysis reaction and condensation. The solvent used for the reaction, a mixed solvent of two or more kinds of these solvents and the like can be mentioned. Further, as the hydrolysis catalyst, a known hydrolysis catalyst can be used as it is. Examples of such a hydrolysis catalyst include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid, citric acid, tartaric acid, ammonia, sodium hydroxide, potassium hydroxide, ethanolamine and the like. Further, the catalyst amount can be appropriately adjusted depending on the types of the components A and B, the type of the catalyst, and the like,
For example, 0.01 mol per 1 mol of the total of component A and component B
It is suitable to be in the range of 0.5 mol.

In the present invention, water and a hydrolysis catalyst are added to the above mixture at a temperature of room temperature or more and 50 ° C. under stirring, whereby the hydrolysis reaction of the components A and B is started almost at the same time. It After the hydrolysis reaction is started by adding water or a hydrolysis catalyst, stirring is stopped and the solution is applied to the surface of the object to be coated. However, from the viewpoint of obtaining a hard coat film with high homogeneity, after starting the hydrolysis reaction,
It is preferable to apply it promptly. However, the time period during which the homogeneity can be maintained depends on the types and mixing ratios of the components A and B contained in the mixture, the types of organic solvents, the amount of water added, the types and amounts of catalysts, and the like. In general, it is suitable to apply it to the surface of the plastic substrate as the article to be coated within 10 minutes, preferably within 5 minutes after the initiation of the hydrolysis reaction. When hydrolysis occurs, the condensation reaction subsequently proceeds. Ingredient A
There is a difference in the reaction rate of the hydrolysis and the condensation reaction between the component B and the component B, and the difference in the reaction rate may cause the hard coat to be inhomogeneous. Therefore, in the present invention, after the hydrolysis reaction is started, before the fine particle sol is substantially formed by the progress of the condensation reaction, the mixture is applied to a plastic substrate, and the hydrolysis reaction is further condensed on the plastic substrate. The reaction is allowed to proceed and copolymerize. Therefore, the hard coat (copolymerization) film obtained by the present invention is a homogenous random copolymerization film having a three-dimensional crosslinked structure of a silane compound and a metal alkoxide without forming microdomains due to the formation of fine particle sol. Becomes

The above-mentioned mixture can be applied to the surface of the plastic substrate which is the object to be coated by a method such as a spin coating method, a dip coating method or a spraying method. Further, the coating amount of the mixture can be appropriately determined in consideration of the physical properties and the film thickness required for the obtained hard coat film. The film thickness is, for example, 0.1 to 5.0
It is suitable to set it in the range of μm.

In the present invention, heat treatment is applied to increase the degree of crosslinking of the copolymer film formed on the article to be coated. This heat treatment is carried out at a temperature not higher than the glass transition temperature when the plastic substrate to be coated exhibits a glass transition temperature, and at a temperature not higher than the softening temperature when it does not exhibit the glass transition temperature, for example, for 24 to 36 hours. Can be done by. The coating film thus obtained has sufficient hardness and denseness as a hard coat. The degree of cross-linking increases as the heat treatment temperature increases, and both the hardness and the denseness of the film increase. However, when heat treatment is performed at a temperature higher than the above temperature, the film quality is deteriorated because cracks are generated in the film. Generally, in order to increase the degree of cross-linking of the copolymer film, the heat treatment is performed at a rate of 1 to 10 ° C./minute to a predetermined temperature and holding at this temperature for 24 to 36 hours. After heating, 5
Return to room temperature by cooling at a rate of 15 ° C / min,
An article having a hard coat can be obtained.

The article to be coated in the present invention includes all articles requiring a hard coat. For example,
Examples thereof include plastic substrates for plastic optical products such as optical lenses, spectacle lenses, and optical prisms. However, the glass transition temperature of the plastic substrate is 90
It is preferably at least ° C. As such plastics, polyester, polyamide, polyimide, polyurethane, polycarbonate, polyether, polysulfide, polysulfone, polyacetal, phenol resin, a polymer synthesized by polycondensation and polyaddition of urea resin, polyethylene, polypropylene, polyvinyl, etc. Known polymers such as alcohols, poly (meth) acrylates, polystyrene, and other polymers synthesized by vinyl polymerization, copolymers of two or more types of monomers constituting these polymers, and polymer alloys of two or more types thereof You can

The present invention will be described in detail below with reference to examples.

EXAMPLES The physical properties of the hard coats obtained in the following examples were evaluated by the following methods. Film thickness: Measured with a stylus roughness meter (Taylor Hobson Co., Ltd.). Refractive index: The hard coat peeled from the substrate was measured by an Abbe refractometer (manufactured by Atago Co., Ltd.) according to a conventional method for film measurement. Hardness: It was performed based on a pencil hardness test (JIS KS 400). Adhesiveness: Parallel lines of 2 mm at equal intervals and 2 mm of parallel lines orthogonal to them on the hard coat surface are drawn so as to reach the base material and cut the hard coat, and then the cellophane adhesive tape (trade name "Cellotape") (Nichiban Co., Ltd.) was strongly adhered to the entire surface of the coat, and then rapidly peeled in a direction perpendicular to the adhered surface, and the peeled area of the hard coat was 10 mm.
² following ones 3, peeling area representing those 10 to 40 mm ² 2, as 1 shall peeling area of 40 mm ² or more. Film quality: The hard coat peeled from the base material was observed visually and by an electron microscope (manufactured by Akashi Co., Ltd.). 3 without cloudiness, cracks and domains, 2 with cloudiness,
Those with cloudiness, domains, and cracks were designated as 1. The physical property evaluation results of the hard coats obtained in each of the examples and comparative examples are summarized in Tables 1 to 3.

[0021]

[Table 1]

[0022]

[Table 2]

[0023]

[Table 3]

Example 1 In a room at a temperature of 24 ± 1 ° C. and a relative humidity of 50 to 55%, 20
To 100 ml of dehydrated 40 ° C. ethanol in a 0 ml beaker, 7.2 g of triethoxyphenylsilane (0.03 mol, while stirring with a magnetic stirrer)
15 mol% (ratio to the total amount of raw materials) and 43.6 g (0.17 mol, 85 mol%) of antimony triethoxide
(Ratio to the total amount of raw materials) was added to obtain a homogeneous mixture. While stirring, 1 ml of hydrochloric acid (10N) was added to the mixture kept at 40 ° C. as a hydrolysis catalyst, stirring was stopped after 30 seconds, and the mixture was allowed to stand for 1 minute, then 20 mm × 20 mm.
A × 2 mm polymethylmethacrylate (PMMA) plate is dipped in the mixture in a direction perpendicular to the thickness direction,
After 1 minute, 20 mm / min in the direction perpendicular to the thickness direction
Pulled up at the speed of. The coated PMMA plate was placed in a constant temperature bath maintained at 40 ° C., and after 10 minutes, the temperature was raised to 100 ° C. at a heating rate of 2 ° C./min, and heat treatment was continued for 24 hours. Thereafter, the temperature was returned to room temperature at a cooling rate of 5 ° C./min, and vacuum drying was performed for 24 hours to obtain a colorless and transparent hard coat having a film thickness of 0.18 μm.

Example 2 As a silane compound (component A), 9.6 g of triethoxyphenylsilane (0.04 mol, 20 mol% (ratio to the total amount of raw materials)) and antimony triethoxide 41 as a metal alkoxide (component B) were used. .1g (0.16mo
Using 1 and 80 mol% (ratio to the total amount of raw materials), the same procedure as in Example 1 was carried out to obtain a colorless and transparent hard coat having a film thickness of 0.21 μm.

Example 3 As a silane compound (component A), 16.8 g of triethoxyphenylsilane (0.07 mol, 35 mol% (ratio to the total amount of raw materials)), and as a metal alkoxide (component B), antimony triethoxide 33. .4g (0.13mo
1, 65 mol% (ratio to the total amount of raw materials)) and by the same operation as in Example 1, a colorless and transparent hard coat having a film thickness of 0.22 μm was obtained.

Example 4 As a silane compound (component A), 9.6 g of triethoxyphenylsilane (0.04 mol, 20 mol% (ratio to the total amount of raw materials)) and tin tetraethoxide 47 as a metal alkoxide (component B) were used. 0.7 g (0.16 mol, 8
The same procedure as in Example 1 was carried out using 0 mol% (ratio to the total amount of raw materials) to obtain a colorless and transparent hard coat having a film thickness of 0.23 μm.

Example 5 As a silane compound (component A), 9.6 g of triethoxyphenylsilane (0.04 mol, 20 mol% (ratio to the total amount of raw materials)) and indium triethoxide 40 as a metal alkoxide (component B) were used. 0.0 g (0.16 mo
Using 1 and 80 mol% (ratio to the total amount of raw materials), the same procedure as in Example 1 was carried out to obtain a colorless and transparent hard coat having a film thickness of 0.21 μm.

Example 6 As a silane compound (component A), 9.6 g of triethoxyphenylsilane (0.04 mol, 20 mol% (ratio to the total amount of raw materials)) and tantalum pentaethoxide 65 as a metal alkoxide (component B) were used. 0.0 g (0.16 mo
Using 1 and 80 mol% (ratio to the total amount of raw materials), the same procedure as in Example 1 was carried out to obtain a colorless and transparent hard coat having a film thickness of 0.23 μm.

Example 7 As a silane compound (component A), 9.6 g of triethoxyphenylsilane (0.04 mol, 20 mol% (ratio to the total amount of raw materials)), and niobium pentaethoxide 50 as a metal alkoxide (component B) were used. 0.9 g (0.16 mol,
Example 1 using 80 mol% (ratio to the total amount of raw materials)
By the same operation as above, a colorless and transparent hard coat having a film thickness of 0.23 μm was obtained.

Example 8 As a silane compound (component A), 9.6 g of triethoxyphenylsilane (0.04 mol, 20 mol% (ratio to the total amount of raw materials)) and titanium tetraethoxide 36 as a metal alkoxide (component B). 0.5 g (0.16 mol,
Example 1 using 80 mol% (ratio to the total amount of raw materials)
By the same operation as above, a colorless and transparent hard coat having a film thickness of 0.24 μm was obtained.

Example 9-1 As a silane compound (component A), 9.6 g of triethoxyphenylsilane (0.04 mol, 20 mol% (ratio to the total amount of raw materials)) and zirconium tetraethoxy as a metal alkoxide (component B). 43.4g (0.16m
ol, 80 mol% (ratio to the total amount of raw materials)) and by the same operation as in Example 1, a colorless film having a thickness of 0.23 μm,
A transparent hard coat was obtained.

Example 9-2 As a silane compound (component A), 9.6 g of triethoxyphenylsilane (0.04 mol, 20 mol% (ratio to the total amount of raw materials)) and titanium tetraethoxy as a metal alkoxide (component B). 36.5 g (0.16 mol,
Example 1 using 80 mol% (ratio to the total amount of raw materials)
By the same operation as above, a colorless and transparent hard coat having a film thickness of 0.18 μm was obtained.

Comparative Example 1 48.0 g (0.2 mol) of triethoxyphenylsilane was used as the silane compound (component A), and the same procedure as in Example 1 was performed without adding the metal alkoxide (component B). A colorless and transparent hard coat of 0.26 μm was obtained.

Comparative Example 2 45.6 g of titanium tetraethoxide as a metal alkoxide (component B) without adding a silane compound (component A).
(0.2 mol) and by the same operation as in Example 1,
A colorless and transparent hard coat having a film thickness of 0.17 μm was obtained.

Comparative Example 3 In a room at a temperature of 24 ± 1 ° C. and a relative humidity of 50 to 55%, 20
After adding 1 ml of hydrochloric acid (10N) to 100 ml of dehydrated 40 ° C. ethanol in a 0 ml beaker while stirring with a magnetic stirrer, 9.6 g of triethoxyphenylsilane (0.04 mol, 20 mol% (total The ratio to the amount of raw material)) was added and refluxed for 10 minutes.
Further, 36.5 g of titanium tetraethoxide (0.16 mol, 80 mol% (ratio to the total amount of raw materials)) was added and 10
Reflux for minutes to obtain a viscous mixture. A 20 mm x 20 mm x 2 mm PMMA plate is immersed in the mixture kept at 40 ° C in the direction perpendicular to the thickness direction, and after 1 minute, pulled up at a speed of 20 mm / min in the direction perpendicular to the thickness direction. It was The coated PMMA plate was placed in a constant temperature bath maintained at 40 ° C, and after 10 minutes, at a temperature rising rate of 2 ° C / min, 10
The temperature was raised to 0 ° C., and heat treatment was continued for 24 hours. After that, the temperature is returned to room temperature at a cooling rate of 5 ° C / min, and vacuum drying is performed for 2 hours.
This was carried out for 4 hours to obtain a colorless and transparent hard coat having a film thickness of 0.17 μm.

Example 10 As a silane compound (component A), 9.6 g of triethoxyphenylsilane (0.04 mol, 20 mol% (ratio to the total amount of raw materials)) and antimony triethoxide 41 as a metal alkoxide (component B) were used. .1g (0.16mo
1, 80 mol% (ratio to the total amount of raw materials)) was used, the plastic substrate was polycarbonate (PC), and the heat treatment was performed at 130 ° C. for 24 hours. A colorless and transparent hard coat of 0.19 μm was obtained.

Example 11 As a silane compound (component A), 9.6 g of triethoxyphenylsilane (0.04 mol, 20 mol% (ratio to the total amount of raw materials)) and tin tetraethoxide 47 as a metal alkoxide (component B) were used. 0.7 g (0.16 mol, 8
0 mol% (ratio to the total amount of raw materials)), the plastic base material is polycarbonate (PC), and the heat treatment is 130
By the same operation as in Example 1 except that the temperature was set at 24 ° C. for 24 hours, a colorless and transparent hard coat having a film thickness of 0.21 μm was obtained.

Example 12 As a silane compound (component A), 9.6 g of triethoxyphenylsilane (0.04 mol, 20 mol% (ratio to the total amount of raw materials)) and indium triethoxide 40 as a metal alkoxide (component B) were used. 0.0 g (0.16 mo
1, 80 mol% (ratio to the total amount of raw materials)), and by the same operation as in Example 11, colorless film having a thickness of 0.21 μm,
A transparent hard coat was obtained.

Example 13 As a silane compound (component A), 9.6 g of triethoxyphenylsilane (0.04 mol, 20 mol% (ratio to the total amount of raw materials)) and tantalum pentaethoxide 65 as a metal alkoxide (component B) were used. 0.0 g (0.16 mo
1, 80 mol% (ratio to the total amount of raw materials)), and by the same operation as in Example 11, colorless film having a thickness of 0.23 μm,
A transparent hard coat was obtained.

Example 14 As a silane compound (component A), 9.6 g of triethoxyphenylsilane (0.04 mol, 20 mol% (ratio to the total amount of raw materials)), and niobium pentaethoxide 50 as a metal alkoxide (component B) were used. 0.9 g (0.16 mol,
Example 1 using 80 mol% (ratio to the total amount of raw materials)
By the same operation as in 1, a colorless and transparent hard coat having a film thickness of 0.24 μm was obtained.

Example 15 As a silane compound (component A), 9.6 g of triethoxyphenylsilane (0.04 mol, 20 mol% (ratio to the total amount of raw materials)), and titanium tetraethoxide 36 as a metal alkoxide (component B). 0.5 g (0.16 mol,
Example 1 using 80 mol% (ratio to the total amount of raw materials)
By the same operation as in 1, a colorless and transparent hard coat having a film thickness of 0.25 μm was obtained.

Example 16 As a silane compound (component A), 9.6 g of triethoxyphenylsilane (0.04 mol, 20 mol% (ratio to the total amount of raw materials)), and zirconium ethoxide as a metal alkoxide (component B) 43. 4 g (0.16 mol,
Example 1 using 80 mol% (ratio to the total amount of raw materials)
By the same operation as in 1, a colorless and transparent hard coat having a film thickness of 0.24 μm was obtained.

Example 17 As a silane compound (component A), 11.6 g (0.04 mol, methacryloxypropyltriethoxysilane) of
20 mol% (ratio to the total amount of raw materials), zirconium tetraethoxide 4 as a metal alkoxide (component B)
Using 3.4 g (0.16 mol, 80 mol% (ratio to the total amount of raw materials)), a colorless and transparent hard coat having a film thickness of 0.24 μm was obtained by the same operation as in Example 1.

Example 18 As a silane compound (component A), 11.6 g (0.04 mol, methacryloxypropyltriethoxysilane) of
20 mol% (ratio to the total amount of raw materials), antimony triethoxide 41.1 as metal alkoxide (component B)
g (0.16 mol, 80 mol% (ratio to the total amount of raw materials)), and by the same operation as in Example 1, the film thickness of 0.
A 23 μm colorless, transparent hard coat was obtained.

Example 19 As a silane compound (component A), 11.6 g (0.04 mol, methacryloxypropyltriethoxysilane) of
20 mol% (ratio to the total amount of raw materials), 50.9 g of niobium pentaethoxide as a metal alkoxide (component B)
(0.16 mol, 80 mol% (ratio to the total amount of raw materials)) and using the same operation as in Example 1, the film thickness of 0.
A 22 μm colorless, transparent hard coat was obtained.

Example 20 As a silane compound (component A), 11.6 g (0.04 mol, methacryloxypropyltriethoxysilane) of
20 mol% (ratio to the total amount of raw materials), 36.5 g of titanium tetraethoxide as a metal alkoxide (component B)
(0.16 mol, 80 mol% (ratio to the total amount of raw materials)) and using the same operation as in Example 1, the film thickness of 0.
A colorless and transparent hard coat of 25 μm was obtained.

Example 21 As a silane compound (component A), 10.6 g (0.04 mol, glycidyloxypropyltriethoxysilane)
20 mol% (ratio to the total amount of raw materials), zirconium tetraethoxide 4 as a metal alkoxide (component B)
Using 3.4 g (0.16 mol, 80 mol% (ratio to the total amount of raw materials)), a colorless and transparent hard coat having a film thickness of 0.23 μm was obtained by the same operation as in Example 1.

Example 22 10.6 g (0.04 mol, glycidyloxypropyltriethoxysilane) of a silane compound (component A)
20 mol% (ratio to the total amount of raw materials), antimony triethoxide 41.1 as metal alkoxide (component B)
g (0.16 mol, 80 mol% (ratio to the total amount of raw materials)), and by the same operation as in Example 1, the film thickness of 0.
A colorless and transparent hard coat having a thickness of 24 μm was obtained.

Example 23 As a silane compound (component A), 10.6 g (0.04 mol, glycidyloxypropyltriethoxysilane) of
20 mol% (ratio to the total amount of raw materials), 50.9 g of niobium pentaethoxide as a metal alkoxide (component B)
(0.16 mol, 80 mol% (ratio to the total amount of raw materials)) and using the same operation as in Example 1, the film thickness of 0.
A 21 μm colorless, transparent hard coat was obtained.

Example 24 As a silane compound (component A), 10.6 g (0.04 mol, glycidyloxypropyltriethoxysilane) of
20 mol% (ratio to the total amount of raw materials), 36.5 g of titanium tetraethoxide as a metal alkoxide (component B)
(0.16 mol, 80 mol% (ratio to the total amount of raw materials)) and using the same operation as in Example 1, the film thickness of 0.
A colorless and transparent hard coat having a thickness of 24 μm was obtained.

As shown in Tables 1 to 3, the present Examples 1 to 24
The copolymer (hard coat) obtained in (1) had a high refractive index of 1.61 to 1.73 and a hardness of 6H to 9H, and was excellent in adhesion and film quality. On the other hand, in Comparative Example 1, the hardness was high and the adhesion and the film quality were excellent, but the refractive index was as low as 1.52. Further, in Comparative Examples 2 and 3, the refractive index and hardness were high, but the adhesion and the film quality were poor.

[0053]

According to the manufacturing method of the present invention, it has a high hardness, which is a basic performance as a hard coat film, and a high refractive index that can correspond to a high refractive index of an optical product. Provided is a method for producing a hard coat, which has excellent adhesiveness, has high transparency without having heterogeneity due to microdomains, and can cure a film by heat treatment in a temperature range in which a plastic substrate has heat resistance. can do.

Claims (4)

[Claims] 1. A mixture of a silane compound and a metal alkoxide is prepared, the mixture thus obtained is applied to the surface of an object to be coated, and then the silane compound and the metal alkoxide in the applied mixture are copolymerized to obtain a mixture. A method for producing a hard coat, which comprises heating and curing the copolymer film. 2. A silane compound represented by the general formula (1): R ¹ _m S
a compound represented by iX ¹ _(4-m) (wherein R ¹ represents an organic group, X ¹ is an alkoxy group having an alkyl group having 1 to 4 carbon atoms, and m is 1 or 2) One or two or more metal alkoxides represented by the general formula (2): MX ² _n.
(Where M is Sb, Sn, In, N
b is a metal atom selected from the group consisting of Ta, Ti and Zr, X ² is an alkoxy group having an alkyl group having 1 to 4 carbon atoms, and n is a valence of the metal atom represented by M. 3 is an integer of 3 to 5). 3. The mixing ratio of the silane compound represented by the general formula (1) and the metal alkoxide represented by the general formula (2) is represented by the general formula (1) with respect to the total amount of both compounds. The silane compound is in the range of 10 to 40 mol%, and the metal alkoxide represented by the general formula (2) is 90 to 60 mol%.
The manufacturing method according to claim 1 or 2, which is in the range. 4. The manufacturing method according to claim 1, wherein the article to be coated is a plastic optical product.