JPH0314880A - Coating composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention provides an anti-reflective material made of an inorganic material that has excellent transparency, dyeability, and is coated on the surface of a base material such as a transparent plastic material and cured. The present invention relates to a coating composition that is characterized by imparting adhesion to a coat thin film (hereinafter referred to as an inorganic vapor deposited film). [Prior Art] Among the plastic materials currently used, acrylic, methacrylic, vinyl, polycarbonate, and allyl transparent plastic materials have better impact resistance, lighter weight, and processability than glass. Because of its excellent properties such as colorability, it is used in large quantities in place of inorganic glass as an optical material, such as in lenses and transparent glass. However, these have the disadvantage of being inferior in scratch resistance and chemical resistance compared to inorganic glasses. Diethylene glycol bisallyl carbonate resin (hereinafter referred to as CR-39) is a resin that has relatively excellent scratch resistance, but this resin is also not sufficient for practical use. As a means to improve these drawbacks of plastic materials, for example, Japanese Patent Publication No. 57-2735
In the issue, a thermosetting paint consisting of colloidal silica and an epoxy group-containing alkoxysilane was also introduced.
43168, 56-34033, 55-29102
No., JP-A-57-67666, etc. disclose thermosetting paints containing epoxy group-containing alkoxysilanes and tetraalkoxysilanes as main components. 57-43578, 57-20968, JP-A-57-
No. 128755 discloses photopolymerizable paints, each of which is designed to improve chemical resistance and scratch resistance. On the other hand, as a paint that has the performance of a partner of these thermosetting paints and photocurable paints, it has been proposed in Japanese Patent Publication No. 57-500984 that it consumes less thermal energy and has excellent adhesion to plastic substrates. ing. Also, JP-A No. 59-204669, No. 60-13793
No. 9 etc. disclose a method of increasing the affinity with polyfunctional acrylates using hydrophobic colloidal silica. [Problem to be Solved by the Invention 1] However, although the above-mentioned thermosetting paint has sufficient adhesion to CR-39, it has poor adhesion to certain plastics such as polycarbonate, bonomethyl methacrylate, and polystyrene. It is insufficient. Moreover, no material has been obtained that fully satisfies both dyeability and adhesion to the inorganic vapor-deposited film. In addition, the photocurable paint has no staining properties! Poor adhesion to vapor film,
The aforementioned Japanese Patent Publication No. 57-500984, Japanese Patent Publication No. 60-13
Although the method according to No. 7939 improves the hardness and durability of the coating film, it does not improve the dyeability and adhesion to the inorganic vapor deposited film, which are the objectives of the present invention. [Means for Solving the Problems 1] The present inventors conducted intensive studies to solve these problems, and found that silica fine particles, polyfunctional monomers, or prepolymers [(meth)acrylate is the same as methacrylate. acrylate], a polymerizable silane compound, and a multitubular (meth)acnol compound by combining photocuring and heat curing to obtain a coating film that has excellent transparency and dyeability. It has been found that excellent performance can be obtained in terms of adhesion to inorganic vapor-deposited films. That is, the present invention uses at least the following component fAl(Bl
, (C) and (D) as main components. fAl A polyfunctional monomer or brevolimer having two or more (mek)acrylic groups in one molecule, 5 to 30% by weight FB+A polyfunctional monomer or preform having one or more (mek)acrylic groups in one molecule Polymer, 5-30% by weight FC) Silica fine particles with particle size l-100 millimicrons, 1
4 to 60% by weight (DJ Silane compound having at least one polymerizable reactive group, 25 to 70% by weight) The fAl component used in the present invention has a (meth)acrylic group in the molecule as a photopolymerizable group. It is a monomer or polymer having two or more of these compounds, and is the main component of the curing component. Specific examples of these compounds include (poly)ethylene glycol, brobylene glycol, hexanediol, glycerin, and trimethylolpropane. di- or tri(meth)acrylate, pentaerythri 1
- Tri-, tetra-, or hexa(meth)acrylates of sorbitol, dipentaerythritol, sorbitol, and sorbicun. In addition, subirane (mek) acrylate, which is obtained by introducing a polymerizable unsaturated group such as 2-hydroxyethyl (meth)acrylate into an unsulfated cycloacecool compound such as diarylidenebentaerythritol, also has good adhesion to substrates. It is effective for improving In order to increase the hardness of the cured film, increase the number of reactive functional groups mentioned above, or use di(meth)acrylate, a polyhydric alcohol with ethylene oxide added to bisphenol A or hydroquinone skeleton. This is effective. In addition, in order to improve adhesiveness, polyvalent acrylates such as bonobutadiene, which are made by acrylating the reactive groups in the resin, are used, silicone acrylates with acrylic groups at the terminals of silicone oligomers, and methylolmelamine and 2- Melamine acrylate derived from hydroxyethyl (meth)acrylate or the like can be used to improve the heat resistance and chemical resistance of the coating film. In addition, polyester di(meth)acrylates and polyurethane acrylates derived from polyhydric alcohols such as ethylene glycol and polybasic acids such as phthalic acid can be used. Two or more of these polyvalent (meth)acrylates may be used in combination, and the amount used should be 5 to 30% by weight of the total composition. That is, if it is less than 5% by weight, the adhesion to certain plastics tends to be insufficient, and if it exceeds 30% by weight, the adhesion to inorganic vapor deposition becomes insufficient. Subsequently, the (meth)acrylic group-containing polyfunctional monomer or prepolymer of the fBl component can be produced by an addition reaction between a (poly)isocyanate compound and a hydroxyl group-containing (meth)acrylate.
Examples of the (poly)isocyanate compound include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, isocyanoethyl methacrylate, and probyl isocyanate. , trimers to pentamers of these incyanate compounds, incyanate groups obtained by reaction of incyanate compounds with compounds having at least <J2 active hydrogen atoms such as amino groups, hydroxyl groups, carboxyl groups, water, etc. Compounds that have the following properties can also be used.
Examples of the hydroxyl group-containing (meth)acrylates to be reacted with the (poly)isocyanate include 2-hydroxyethyl (meth)acrylate, 2-hydroxybrobyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. meth)acrylate, monoepoxy compounds such as butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, addition reaction products of glycidyl methacrylate, etc. and (meth)acrylic acid, polyethylene glycol, polybrobylene glycol, etc. Examples include (meth)acrylic acid monoester. The addition reaction between a (poly)isocyanate and a (meth)acrylate containing a hydroxyl group can be carried out using a known method, for example, in the presence of an incyanate compound.
It can be produced by dropping a mixture of acrylate and a catalyst such as dibutyltin dilaurate at 50°C and 90°C. By including these polyfunctional monomers or prepolymers, it has become possible to improve not only the dyeability but also the adhesion to the inorganic vapor deposited film. In particular, when hydrophilic groups such as polyethylene glycol groups, polybrobylene glycol groups, polyester groups, etc. are introduced into the polyfunctional monomer or prepolymer molecule for the purpose of improving dyeability, a coating film with even better dyeability can be obtained. These polyfunctional monomers or prepolymers are prepared by reacting the above-mentioned (poly)isocyanate with the above-mentioned (poly)hydroxy compound having a hydrophilic group so that the ratio is in the range of 1=0.05 to l:0.9. After that, it can be produced by reacting a hydroxyl group-containing (meth)acrylate. Specific examples of (poly)hydroxy compounds include polyethylene glycol (average molecular weight 200-5000). Polybrobylene glycol (average molecular weight 200-5000)
．． Polycabrolactone (average molecular weight 200-5
000). Bisphenol A ethylene oxide or
Diol of propylene oxide adduct (molecular weight 500~
5000), diol of ethylene oxide or propylene oxide adduct of bisphenol S (500~
5000) etc. In the present invention, the polyfunctional monomer or prepolymer having 1 or more (mek)acrylic groups in one molecule is
One type can be used alone or two or more types can be used in combination, and the amount used should be 5 to 30% by weight of the total composition. That is, if it is less than 5% by weight, the dyeability will be insufficient, and if it exceeds 30% by weight, the water resistance and weather resistance of the coating film will tend to be insufficient. continue,(
Effective examples of silica fine particles having a particle size of 1 to 100 millimicrons for the Cl component include silica sol and powdered silica fine particles. Silica sol is a colloidal dispersion of high molecular weight silicic acid anhydride in a dispersion medium such as water, alcohol, or other organic solvent. Powdered silica particles are colloidal silica particles whose surface has been hydrophobized, and are commercially available. For the purposes of this invention, particles with an average particle size of 1 to 100 millimeters are used, preferably 5 to 30 millimeters. If the particle size is less than 1 millimicron, fine particulate silica will not exist stably,
Consistent quality cannot be obtained. Moreover, if it is 100 millimicrons or more, a problem arises in that the coating film becomes cloudy. Further, the amount used should be 14 to 60% by weight of the total composition. In other words, if it is less than 14% by weight, it is inorganic vapor! The adhesion to the pus will be insufficient, or the abrasion resistance of the coating will be insufficient. Moreover, if it exceeds 60% by weight,
Cracks occur in the paint film. In addition, the stainability is also insufficient. Subsequently, (Dl component is a silane compound having a polymerizable reactive group such as a vinyl group, an allyl group, an acrylic group, a methacrylic group, an epoxy group, a mercabuto group, a cyano group, an isocyano group, an amine group, etc.) Examples include vinyltrialkoxysilane, vinyltrichlorosilane,
Vinyltri(β-methoxyethoxy)silane, allyltrialkoxysilane, acryloxybrobyltrialkoxysilane, methacryloxybrobyltrialkoxysilane, methacryloxybrobyl dialkoxymethylsilane, j-glycidoxybrobyltrialkoxysilane , β-(3,4-epoxycyclohexyl)-12tyldrylkoxysilane, mercabutprobyltrialkoxysilane, j-aminoprobyltrialkoxysilane, N-β(aminoethyl)1j-aminobrobylmethyldi There are alkoxysilanes, etc. Is this fD) component used after hydrolysis?
It is more effective to perform acid treatment on the film after it has hardened, or to use one of these methods. Further, the amount of component (D) used must be 25 to 70% by weight of the total composition. That is, if it is less than 25% by weight, the adhesion to the Ti-free vapor deposited film tends to be insufficient. Moreover, if it exceeds 70% by weight, it causes cracks in the cured film, which is undesirable. fAl, FB+. ((:) and fDl
In addition to the components, it is possible to add a photopolymerization initiator and a reaction diluting monomer or brevolimer consisting of 1 liter or more of a compound 1 having 1 or more photopolymerizable groups per molecule. Examples of photopolymerization initiators include benzoin, benzoin methyl ether, benzoin ethyl ether, penzoin isobrobyl ether, acetoin, petitin, toluoin, benzyl, penzophenone, p-chlorobenzophenone, p-methoxybenzophenone, etc. carbonyl compounds, and sulfur compounds such as tetramethylthiuram monosulfide. Examples of the thermal polymerization initiator include azo compounds such as azobisisobutyronitrile and azobis-2,4-dimethylpaleronitrile, and peroxide compounds such as penzoyl peroxide and ditertiary butyl peroxide. These photopolymerization initiators and thermal polymerization initiators can be used alone.
You may use a combination of more than one species. The appropriate amount to be used is 0:1 to 5% by weight of the curing component. If it is less than 0.1% by weight, polymerization will not proceed sufficiently, and if it exceeds 5% by weight, the effect will not improve. In addition, it is effective to use a photosensitizer in combination with a photopolymerization initiator. Examples of such compounds include n-butylamine, di-n-butylamine, tri101butylphosphine allylthiourea, diethylaminoethyl methacrylate, triethylenetetramine, and the like. Next, as a reaction diluting monomer or prepolymer consisting of one or more compounds having one or more photopolymerizable groups in one molecule, methyl (meth)acrylate, ethyl (meth)acrylate, 2-ethylhexyl Acrylate, butyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylonitrile, hydroxyethyl (meth)acrylate, hydroxybutyl (meth)acrylate,
meth)acrylate, vinyl acetate, styrene, alpha-methylstyrene, alpha-chlorostyrene, (meth)acrylamide, vinylnaphthalene, vinylrubazole, γ-methoxysilane, beta-
Acryloyloxyethyltrimethoxysilane and the like are used. The purpose of this use is to lower the viscosity of the fAl component and improve coating workability, which then polymerizes and gives the coating film appropriate elasticity and adhesion. O. 1 to 60% by weight, more preferably
It is desirable to use 2 to 40% by weight. That is, fAl
When combining a composition that produces appropriate elasticity and stiffness with only the ingredients, the diluent heptanomer for reaction may be omitted, but it is better to use 2% by weight or more of -119 to obtain a homogeneous cured film. It will be done. Moreover, if this component is used in an amount exceeding 60% by weight, the adhesion to the inorganic vapor deposited film becomes insufficient, which is not preferable.
The coating composition thus obtained can be diluted with a solvent and used if necessary. As the solvent, alcohols, esters, ketones, ethers, aromatic solvents, etc. are used. It is also useful to add silicone surfactants, nonionic surfactants, thixotropic agents, slip agents such as silicone oil, ultraviolet absorbers, and antistatic agents to improve defects on the coated surface. It is also useful to add a curing catalyst such as silanol or epoxy compound. The most preferable catalyst is magnesium perchlorate, but there are also 6
, metal acetylacetonates such as aluminum acetylacetonate, amines, amino acids such as glycine, Lewis acids, organic acid metal salts, and ammonium perchlorate. The amount added is preferably within the range of 0.01 to 5.0% of the solid content concentration. The thickness of the cured film in the present invention is O○5~30
Preferably μ. That is, if it is less than 0.05μ, basic performance cannot be achieved, and if it exceeds 30μ, surface smoothness may be impaired or optical distortion may occur, which is not preferable. Application methods include dipping, spraying, roll coating, spin coating, and flow coating. The coating composition thus obtained is applied to a substrate, photocured, and then thermally cured. In other words, the most preferable curing method is to use a combination of light and heat. For photocuring, active light with a wavelength of 200 to 800 nm is preferred. As for the atmosphere for irradiation, an atmosphere of an inert gas such as nitrogen gas or an atmosphere with a reduced oxygen concentration may of course be used, but the coating composition according to the present invention is sufficient even under a normal air atmosphere. As a light source, well-known chemical lamps, xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, etc. can be used. In addition, for thermosetting, a method of carrying out a condensation reaction in hot air at 80°C to 200°C is preferred. In particular, in the case of substrates with poor heat resistance, a temperature between 80°C and 130°C is more desirable. It is possible to provide the antireflection coating described below on the plastic substrate having the cured coating thus obtained. That is, SiO, Sift. Six N4
．． TiOx. Reflection at the interface with the atmosphere can be suppressed by laminating single or multilayer thin films made of inorganic derivatives such as ZrOt, AI20x, and MgFx. In addition to these materials, for example: S
b*Os. CaFz. Cent
．． CeFs. Nag AI Fa
．． Law Os. LaFs.
PbFx. NdFs. PrsO
++. Thaw. ThF+. Zn
S. Ge. PbTe. Tit Ox
．． HfOz. TatOs. Yz O
s. There are materials such as Ybi Ox. What is the thickness of the anti-reflection film used here? /4 (circle.・
= 450 to 650 nm), or a single layer structure. /
4-L. /2 Ichimaru. /4 or hmm. /4-Eh. /4 Ichiyu. A multilayer film with a three-layer structure with different refractive indexes of /4, or
It is useful to use a multilayer antireflection thin film partially replaced with an equivalent film, and its refractive index is, for example, in the case of a single layer, air, antireflection film, base material (or hardened coating layer). The refractive index of no. rl+. If we say ni. n
The least reflection occurs when +=M. In the case of a multilayer film, it is possible to achieve better effects than a single layer film by combining films with different refractive indexes, as shown in some examples. When forming an antireflection thin film by vacuum evaporation, it is sometimes possible to improve adhesion by pre-treating the surface of the lens with gas plasma such as oxygen or argon. This will be explained in more detail below using examples. [Examples] The present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. Example 1 (1) Preparation of coating liquid 15 g of diventaerythritol hexaacrylate, 15 g of trimethylolpropane triacrylate, and 1 g of diethylene glycol diacrylate were mixed, and then 5 g of tetrahydrofurfuryl acrylate and 5 g of glycidyl acrylate were mixed. ．． 25 g of urethane dimethacrylate obtained by reacting xylylene diisocyanate and 2-hydroxybrobyl methacrylate was added to this liquid mixture, and this liquid was designated as liquid (A). In addition, methanol dispersion Coroiglucilikyriki (manufactured by Catalysts Kasei Kogyo Co., Ltd., trade name "Saiskull 1132J solid content concentration 30%)" 14
To 7 g, 78 g of j-methacrylic trimethoxysilane and 205 g of a 0.05N hydrochloric acid aqueous solution were added, stirred for 6 hours, and then aged overnight. This liquid (B)
It was made into a liquid. This (AJ solution and (B) solution were mixed, and a silicone surfactant (product name: rY, manufactured by Nippon Unicar Co., Ltd.) was added.
7002J), 0.07 g of a penzotriazole ultraviolet absorber (manufactured by Nippon Ciba Geigy Co., Ltd., trade name "Tinuvin PJ", and 2 g of benzophenone were added to prepare a coating liquid. (2) Application and curing. The coating solution obtained was applied to a CR-39 eyeglass lens using the Svinner method.The coating conditions were as follows: Number of revolutions: 20O
After applying the coating for 10 seconds at 1,700 rpm and 10 seconds at 200 rpm, air drying at 80°C for 15 minutes, using a 4KW high-pressure mercury lamp, place both sides 15cm directly below the light source.
It was irradiated for 1 second, and then baked at 130°C for 90 minutes. Can you get it like this? The thickness of the cured film was approximately 2 microns, and the appearance and dyeability were excellent. Example 2 An antireflection coating thin film made of an inorganic material was formed on each of the lenses obtained in Example 1 using the following method. (1) Formation of anti-reflection thin film The obtained lens is subjected to plasma treatment (argon plasma 4
0 0 W x 6 0 seconds), SiO*. ZrOa, siO2. ZrO
i. An antireflection multilayer film consisting of five layers of SiOz was deposited using a vacuum evaporation method (manufactured by Shinku Kikai Kogyo Co., Ltd.: BMC-1000).
). The Ili thickness is the first Sin.
film thickness, next total film thickness of ZrOx and SiO■, next Zr
The Oz film thickness and the top layer Sing film thickness were all formed to be a circle/4. Note that the design wavelength λ was 520 nm. (2) Test and evaluation results The lens obtained in Example 1l (hereinafter referred to as hard coat lens) and the lens obtained in Example 2 (hereinafter referred to as hard multi-coat lens) were tested by the methods described below. A test was conducted and the results are shown in Table 1. Adhesion in the test content refers to hard coat lenses, lenses and hard coat films, hard multi-coat lenses,
We evaluate the adhesion between the lens and the hard coat film, and between the hard coat film and the multi-coat film. a) Abrasion resistance (hard multi-coated lenses only): #O
A load of Ikg was applied with O00 steel wool, and the surface was rubbed 10 times back and forth, and the degree of damage was visually evaluated in the following stages. A: There is no scratch at all in an area of 1 cm x 3 cm. B: 1 to 10 scratches are formed within the above range. C: 10 to 100 scratches are made within the above range. D = Countless scratches, but a smooth surface remains. E: No smooth surface remains due to scratches on the surface. b) Water resistance/chemical resistance It was immersed in dihydrate, alcohol, and kerosene for 48 hours, and the surface condition was examined. C) Acid resistance and detergent resistance: o. Immersed in iN hydrochloric acid and 1% Mama Lemon (manufactured by Lion Yushi Co., Ltd.) aqueous solution for 12 hours,
The surface condition was investigated. d) Weather resistance: The surface condition was examined after being exposed to a sunshine weather meter using a xenon lamp for 400 hours. e) Adhesion: The adhesion between the cured film and the substrate and between the inorganic vapor deposited film and the cured film was determined by a crocut tape test in accordance with JI SD-0202. That is, using a knife, incisions are made on the lens surface at one interval to form 100 12 squares. Next, firmly press cellophane adhesive tape (Cellotape manufactured by Nitto Kagaku Co., Ltd.) on top of it, then suddenly pull it off in the 90" direction from the surface, and then use the remaining squares of the coating film to measure the adhesion. f) Durability: Considering that durability is essentially an adhesive connection, the cross force table test described above was conducted for those tested in a) to d) to evaluate them. g) Heat resistance Temperature (cooling cycle): The lens was stored in warm air at 70°C for 1 hour and its appearance was examined.
The cycle of 15 minutes at 0°C was repeated 5 times, and the appearance and cross-cut table test were conducted, and those with no peeling of the coating film were evaluated as good. h) Stainability (hard coat lenses only) = 9
A dyeing solution was prepared by dispersing 2 g of Seiko Blacks Diamond Coat dye Amber D in pure water at 2°C. The material was immersed in this solution for 5 minutes for dyeing, and was evaluated as good if there was no uneven dyeing and the difference in total light transmittance between before and after dyeing was 30% or more. Example 3 (1) Preparation of coating liquid 25 g of pentaerythritol tetraacrylate, 25 g of diventaerythritol penquaacrylate, 30 g of acrylate ester of tetrahydrofurfuryl acrylate log and diarylidene pentaerythritol,
Hexanediol dimethacrylate 10g and 2.2
- Add 2 g of diethoxyacetophenone, mix and stir, add 50 g of urethane diacrylate obtained by reacting dicyclohexylmethane diisocyanate and 2-hydroxybutyl acrylate, mix and stir, and add this to liquid (C). It was. Additionally, 100 g of j-glycidoxybutyltrimethoxysilane was added to 50 g of ethyl acetate. 0
．． 28 g of 05N hydrochloric acid aqueous solution, 80 g of silica fine particles (manufactured by Nippon Airosil Co., Ltd., trade name ``Airosil J'') and 0.3 g of magnesium perchlorate were added, stirred for 3 hours, and aged overnight. This solution was used as solution (D). This (C)
Mix liquid and (D) liquid, add 0.3 gg of Tinuvin P mentioned above.
A coating liquid was prepared by adding 0.3 g of a nonionic surfactant (manufactured by Nippon Oil & Fats Co., Ltd., trade name: "Nissan Nonion LT-220J"). (2) Application and curing The coating liquid thus obtained So, Seiko Highroad M
The coating was applied to a fabric lens for X (manufactured by Seiko Epson Corporation) using the same spinner method as in Example 1l. After coating, it was air-dried at 80°C for 10 minutes, then both sides were irradiated for 15 seconds using a 4KW high-pressure mercury lamp placed 15cm directly below the light source, and then baked at 100°C for 120 minutes. The thickness of the cured film thus obtained was approximately 3 microns, and the appearance and dyeability were excellent. Example 4 (1) Formation of anti-reflection thin film An anti-reflection coating consisting of an inorganic substance; iiiIIM was formed on the lens obtained in Example-3 in the same manner as in Example-2. (2) Test and evaluation results The lenses obtained in Examples 3 and 4 were tested in the same manner as in Examples 1 and 2, and the results are shown in Table 1. Example 5 (1) Preparation of coating liquid 15 g of diventaerythritol hexaacrylate, 15 g of dipentaerythritol pentaacrylate, 7.0 g of diventaerythritol tetraacrylate, 80 g of trimethylolpropane triacrylate, 5 g of tetrahydrofurfuryl acrylate, Og, 2 g of penzophenone, and 130 g of toluene were mixed and stirred. Add tetramethylxylene m-diisocyanate and 2
-Add 50g of urethane diacrylate obtained by reacting hydroxybacterium acrylate, and mix this liquid with (
E) It was made into a liquid. In addition, Improvil alcohol-dispersed colloidal silica (
Manufactured by Catalysts Kasei Kogyo Co., Ltd., product name: "Oscar 1432J solid content concentration 30%) 747g. 68g of oO5N hydrochloric acid aqueous solution and 0.4g of magnesium perchlorate were added to 250g of j-glycidoxybutyltrimethoxysilane and 540g of butyl cellosolve. After stirring for 6 hours, the mixture was aged all day and night, and this liquid was used as liquid (F).This liquid (E) and (F)
The liquids were mixed, and 0.3 g of a silicone surfactant (manufactured by Nippon Unicar Co., Ltd., trade name: rY7002J) and 0.4 g of an anti-aging agent (manufactured by Kawaguchi Chemical Co., Ltd., trade name "Antage BHTJ") were added. (2) Coating and curing The coating solution thus obtained was coated on an acrylic plate (manufactured by Mitsubishi Rayon Co., Ltd., trade name: "Acrylite LJ: 100").
(mm x 30 mm x 2 mm) was applied using the dipping method. What is the lifting speed? The speed was set to 20cm/min. This is 5
After air-drying for 10 minutes at 0°C, using an 80W high-pressure mercury lamp,
Both sides were placed 10 cm directly below the light source and exposed to light for 20 seconds. This was further baked at 80° C. for 4 hours.6 The thickness of the cured film thus obtained was approximately 2.5 microns, and the appearance was excellent in dyeability. Example 6 (1) Formation of antireflection thin film The acrylic plate obtained in Example 5 was subjected to the formation of an antireflection coating thin film made of an inorganic substance in the same manner as in Example 2. (2) Test and evaluation results The acrylic plates obtained in Examples 5 and 6 were
Tests were conducted in the same manner as in 2, and the results are shown in Table 1. Example 7 (1) Preparation of coating liquid 40 g of dipentaerythritol benquaacrylate. 30 g of pentaerythritol triacrylate, 20 g of triethylene glycol dimethylate, 3 g of 2-hydroxy-2-methyl-1-phenylpropane-1-one
, toluene l○Og, ethyl acetate 30g, and ethylene glycol monoethyl ether loog were mixed and stirred, and to this was added 2.5 mol of inphorone diisocyanate.
Voribrobylene glycol (manufactured by ADEKA Co., Ltd., trade name rP)
-100J average molecular weight 1000) 1.5 mol and 2-
60g of urethane diacrylate reacted with 2mol1 of hydroxyethyl acrylate was added, and this liquid was converted into (G)
It was. Additionally, 780 g of (isobrobyl alcohol) dispersed colloidal silicate (trade name: rI PA-ST, manufactured by Nissan Chemical Co., Ltd., solid content concentration 30%), 165 g of γ-glycidoxybutyltrimethoxysilane, 4 ml of a 0.05 N hydrochloric acid aqueous solution.
5g was added, stirred for 4 hours, and then aged for a day and night.
H). The (G) and (H) solutions were mixed, and a silicone surfactant (trade name: BYK-300 manufactured by Big Chemie Co., Ltd.) was added.
A coating liquid was prepared by adding 0.5 g and 0.2 g of an anti-aging agent (trade name: Irganox 1 222, manufactured by Ciba Gaiki Co., Ltd.). (2) Application and curing Using the above coating liquid, injection molded acrylic plate (Bellet: Acryvet VH manufactured by Mitsubishi Rayon Co., Ltd.)
100mm x 100mm x 3mm) was painted using the spray method. For spraying, use Iwakwider 61 (manufactured by Iwata Painting Machine Co., Ltd.) with a nozzle diameter of 1 mm.
Spray pressure 3Kg/crtI'', paint discharge amount 100m
It was carried out at l/min. After air drying this at 50℃ for 10 minutes, 80W/c
m Using 3 high pressure mercury lamps, 2m/mi at 10cm below the light source
It was cured by passing it at a speed of n. This was further post-cured at 80°C for 2 hours. The thickness of the cured film thus obtained was approximately 6 microns, and it had excellent appearance and dyeability. Example 8 (1) Formation of antireflection thin film The acrylic plate obtained in Example 7 was subjected to the formation of an antireflection coating thin film made of an inorganic substance in the same manner as in Example 2. (2) Test and evaluation results The acrylic plates obtained in Examples 7 and 8 were
Tests were conducted in the same manner as in 2, and the results are shown in Table 1. Comparative Example-1 In Example-1, xylylene diisocyanate and 2
The same procedure was followed except that 25 g of urethane dimethacrylate obtained by reacting with -hydroxybuvir methacrylate was not added. Comparative Example 2 An antireflection film was formed on the lens obtained in Comparative Example 1 in the same manner as in Example 2. Comparative Example 3 The same method as in Example 3 was repeated except that the coating liquid was the same as the liquid (D). Comparative Example 4 An antireflection film was formed on the lens obtained in Comparative Example 3 in the same manner as in Example 2. Comparative Example-5 In Example-7, inphorone diisocyanate and 2
The same method was used except that the urethane diacrylate obtained by reacting -hydroxyethyl acrylate was not added, and the coating liquid was prepared without the (H) solution. Comparative Example 6 An antireflection film was formed on the acrylic plate obtained in Comparative Example 5 in the same manner as in Example 2. Comparative Examples 1 to 6 were all tested in the same manner as Examples 1 and 2, and the results are shown in Table 1. [Effects of the Invention] As detailed above, the present invention makes it possible to simultaneously obtain good dyeability and adhesion to an inorganic antireflection film, which were impossible with conventional thermosetting paints. It has become possible to increase the hardness of its surface, and it has also made it possible to apply anti-reflection processing using inorganic materials, which has not been put into practical use with conventional optical plastic materials such as acrylic resin due to insufficient adhesion. ．． In other words, plastic lens materials include (meth)acrylic resin, styrene resin,
Carbonate resin, allyl resin, allyl carbonate {
Degreasing, vinyl resin, polyester resin, polyether resin, polymers of new monomers and comonomers, etc. f!
Plastic materials with excellent scratch resistance, good dyeability, and good adhesion to inorganic anti-reflection films, which can be obtained by applying highly functional resins, can be used for eyeglass lenses, camera lenses, and light beam condensing lenses. It can be widely used for consumer and industrial purposes as optical lenses such as light diffusion lenses and light diffusion lenses. Further, the effects of the present invention can be applied to transparent glasses such as watch glasses and cover glasses for displays, and transparent plastics for optical purposes such as cover glasses in general, and the effects obtained are great. that's all

Claims (1)

[Claims] At least the following components (A), (B), (C) and (
A coating composition characterized by containing D) as a main component. (A) Polyfunctional monomer or prepolymer having two or more (meth)acrylic groups in one molecule, 5 to 30% by weight (B) Urethane having one or more (meth)acrylic groups in one molecule (Meth)acrylate, 5 to 30% by weight (C) Silica fine particles with a particle size of 1 to 100 millimicrons, 1
4-60% by weight (D) Silane compound having at least one polymerizable reactive group, 25-70%