JP3301430B2 - Primer composition for plastic lens - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an improved appearance,
Also, the present invention relates to a primer composition for a plastic lens for producing a plastic lens excellent in abrasion resistance, impact resistance, dyeability, antireflection property, weather resistance, chemical resistance, and adhesion of a coating film.

[0002]

2. Description of the Related Art In recent years, plastics that are lighter than glass have attracted attention as a material for eyeglasses, and accordingly, many plastic lenses having a high refractive index and low chromatic aberration have been provided. In general, plastic lenses have the disadvantage that they are very easily damaged, so a silicon-based or other hard coat film is usually provided on the surface of the lens, and the surface, which causes flickering of the image, is placed on the hard coat film. It is provided with an antireflection film on which an inorganic substance is deposited to suppress reflection.

Generally, the refractive index of the hard coat layer is 1.40.
And the plastic lens substrate usually has a refractive index of 1.50 or more. When the difference from the refractive index is large, there is no problem if the film thickness of the hard coat layer is uniform. However, if the film thickness is not uniform, interference fringes can be seen and the lens becomes very unsightly in appearance. However, it is very difficult in production to make the thickness of the hard coat layer uniform.

To solve this problem, Japanese Patent Application Laid-Open No.
11801 and JP-A-1-217402 disclose that a primer layer satisfying the following two conditions is provided between a lens substrate and a hard coat layer. Condition 1 The refractive index n _{P of the} primer layer is

[Number 1] ^{_{(n s · n H) 1/2}} + | n s -n H | / 4 ≧ n p ≧
^{_{(N s · n H) 1/2}} - | n s -n H | / 4 (n s is the refractive index of the plastic lens substrate, n _H is the refractive index of the hard coat layer) to satisfy the equation represented by . Condition 2 The thickness d of the primer layer satisfies the expression represented by d = λ / (4n _P ) (λ is 450 to 650 nm in the wavelength of visible light).

[0005]

Problems to be Solved by the Invention
In the method disclosed in No. 1, a material selected from an aromatic homopolymer, a copolymer of an aromatic homopolymer and an acrylic compound, an epoxy compound, and a silicon compound is used as a material of a primer layer. The impact resistance of the plastic lens provided with the prevention layer is insufficient. Japanese Patent Application Laid-Open No. 1-217402 discloses that polyurethane is used for a primer layer. However, in order to satisfy the expression of Condition 1, the refractive index is set to 1.50 or more. Must contain an aromatic ring, which is a major cause of deterioration of the weather resistance (yellowing) of the plastic lens of the product. In other words, no interference fringes are seen, impact resistance after antireflection coating is excellent, and a plastic lens having good weather resistance has not yet been obtained.

An object of the present invention is to provide a composition for a primer layer for producing a plastic lens which shows no interference fringes, has excellent impact resistance after antireflection coating, and has good weather resistance (yellowing resistance). With the goal.

[0007]

The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that Al, Ti, Zr, Sn, Sb
A primer layer of polyurethane containing at least one metal compound selected from among the following, a hard coat layer, and a single-layer or multilayer anti-reflection layer formed by vapor deposition of an inorganic substance are laminated in this order from the lens surface. Condition 1
It was found that a plastic lens satisfying the conditions of (1) and (2) had no interference fringes, had excellent impact resistance after antireflection coating, and had good weather resistance (yellowing resistance).

That is, the present invention provides a hard coat layer made of a silicon-based resin and a monolayer or multilayer antireflection film made of an inorganic substance provided on the surface of the hard coat layer.
A plastic lens primer composition used to provide a thermosetting urethane impact-resistant primer layer on a plastic lens substrate surface, comprising a block type polyisocyanate, a polyol, Al, Ti, Zr,
It contains at least one kind of metal oxide fine particles selected from Sn and Sb and a solvent, wherein the fine particles have an average diameter of 1 to 300 mμ, and the fine particles have a weight of 20 to 60 wt % in the primer layer. % And a predetermined amount such that the refractive index of the primer layer is 1.45 to 1.60.
The ratio of cyanate to the polyol is isocyanate
Ratio of 0.8 to 1.25, expressed as a molar ratio of a hydroxyl group to a hydroxyl group
In it is contained, and wherein the block-type polyisocyanate is a cyclic trimer of hexamethylene diisocyanate β-
100 ° C or less , blocked by diketone
It is a primer composition for plastic lenses that cures even at the following temperatures .

Hereinafter, the present invention will be described in more detail. In the present invention, the type of the plastic lens substrate is not particularly limited, and is a transparent 1.50 to 1.50 resin such as polycarbonate, acrylic resin, styrene resin, urethane resin, and allyl resin.
Although a resin having a refractive index of 1.70 can be used, a lens made of a polymer obtained by radical polymerization of a monomer having diethylene glycol bisallyl carbonate as a main component represented by the following formula (1):

Embedded image A plastic lens made of a polymer obtained by radical polymerization of a monomer mixture containing an N-substituted phenylmaleimide derivative is particularly preferably used.
The polymerization method of these lenses is almost the same as that of ordinary plastic lenses, and the monomer mixture is poured into a mold assembled by a glass mold and a gasket made of ethylene-vinyl acetate copolymer, and heated at a predetermined temperature for a predetermined time. Then, after taking out from the glass mold, the lens is obtained by post-curing at a predetermined temperature for a predetermined time.

In the present invention, first, a layer comprising a metal compound and polyurethane is provided as a primer layer on the lens. Polyurethane is obtained by reacting a polyol which is an active hydrogen compound with a polyisocyanate.Examples of the polyol include polyester, polyether, polycaprolactone, polycarbonate and polyacrylate having a plurality of hydroxyl groups in one molecule. .

The polyisocyanate includes a block type and a non-block type, and the polyisocyanate used in the present invention is preferably a block type. The block type polyisocyanate is one in which an isocyanate group is protected by a so-called blocking agent. The reason why the block type polyisocyanate is preferable in the present invention is that when the non-block type polyisocyanate is used, the reaction between the active hydrogen of the polyol and the isocyanate group proceeds at room temperature, so that the pot life of the paint becomes extremely short. is there. On the other hand, a blocked polyisocyanate can react with active hydrogen only when the blocking agent is dissociated by heating, so that the pot life at room temperature is very long.

Examples of the polyisocyanate include hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, and modified products thereof. Examples of the modified polyisocyanate include biuret, isocyanurate, allophanate, carbodiimide and the like. Further, a block type polyisocyanate in which these isocyanate groups are protected by a blocking agent is also a preferred example.
Blocking agents include β-diketones, oximes, phenols, caprolactam, and the like. Among them, a particularly preferred example is a product obtained by blocking hexamethylene diisocyanate isocyanurate (cyclic trimer) with β-diketone. The reason for this is that the blocking agent has a low dissociation temperature, can be cured at a temperature of 100 ° C. or less, and has a lens with poor heat resistance, such as a glass transition temperature of 1
This is because it can be used for a plastic lens of 10 ° C. or less. Examples of β-diketones include acetylacetone,
2,4-hexanedione, 2,4-heptanedione,
3,5-heptanedione and the like are preferred.

Examples of the polyol include polyesters, polyethers and the like having a plurality of hydroxyl groups in one molecule.
Examples include polycaprolactone, polycarbonate, and polyacrylate. The ratio of the block type polyisocyanate to the polyol is preferably from 0.5 to 1.5, particularly preferably from 0.85 to 1.2, in terms of the molar ratio of isocyanate groups to hydroxyl groups. If the molar ratio is less than 0.5 or greater than 1.5, the crosslinked density of the cured film is too small, and the impact resistance tends to be hardly improved.

As the above-mentioned polyisocyanate and / or polyol, those containing an aromatic ring which increases the refractive index, for example, polyesters of terephthalic acid and propylene glycol, and isocyanurates of tolylene diisocyanate blocked with β-diketone are used. However, it is preferable that the plastic lens is not used as much as possible, since it greatly causes deterioration of the weather resistance (yellowing) of the plastic lens of the product.

When a blocked polyisocyanate blocked with β-diketone is reacted with a polyol, a curing catalyst is not particularly required.

In the present invention, the primer coating is diluted with a solvent. Examples of the solvent used for dilution include alcohols, ketones, esters, and ethers, and other known solvents can also be used. Particularly preferred are diacetone alcohol, ethyl acetate, methyl ethyl ketone and propylene glycol monomethyl ether, but these may be used alone or as a mixed solvent of two or more. Further, a leveling agent for improving coatability, an ultraviolet absorber and an antioxidant for improving weather resistance can be added to the primer coating. The method for applying the primer coating is not particularly limited as long as it is a known method such as a spin coating method or a dipping method. Further, it is preferable that the lens is subjected to a pretreatment such as an alkali treatment, a plasma treatment, and an ultraviolet treatment as necessary.

In the present invention, a specific metal compound is used for polyurethane to increase the refractive index of the primer layer.

The metal compound used in the present invention includes aluminum (Al), titanium (Ti), zirconium (Z
r), at least one metal compound selected from tin (Sn) and antimony (Sb), (1) fine particles of an oxide of the metal, (2) alcoholate, acylate, chelate of the metal and An organic metal compound such as an oligomer or a polymer obtained by decomposition polycondensation. As used herein, the term “acylate” refers to a compound in which at least one of the substituents bonded to a metal atom is a carboxyl group obtained by acylation.

Examples of the metal oxide fine particles include aluminum oxide, titanium oxide, zirconium oxide, tin oxide, and antimony oxide. These may be used alone or in combination of two or more. The average particle diameter of the fine particles is preferably 1 to 300 μm,
~ 200mμ is particularly preferred. Those having an average particle size of less than 1 μm are difficult to produce, are expensive, and are not practical. On the other hand, if it exceeds 300 μm, the primer layer becomes cloudy. The refractive index of these metal oxide fine particles is Zr
O ₂ 2.0, SnO ₂ 2.0, TiO ₂ 2.1, S
b ₂ O ₅ 1.7 and Al ₂ O ₃ 1.66, and when these are contained in the primer layer in an equal weight, the increase in the refractive index of the primer layer is caused by the large refractive index of the metal oxide fine particles. It becomes bigger.

As the organometallic compound, tetra-n
-Butoxytitanium, tetrastearyloxytitanium, di-n-butoxybis (triethanolaminato) titanium, titanium-i-propoxyoctylene glycolate, tri-i-propoxyaluminum, tetra-n-
Alcoholates such as butoxyzirconium, tri-n-butoxyantimony, and tetra-n-butoxides; acylates such as titanium stearate and tri-n-butoxytitanium monostearate; propanedioxytitanium bis (ethylacetoacetate) and propanedioxytitanium (Acetylacetonate) (ethylacetoacetate)
Oligomers such as tetra-n-butoxytitanium dimer and tetramer; and polymers such as tri-n-butoxytitanium monostearate polymer, and these may be used alone. Or, a plurality of them may be used in combination.

The content of the metal compound is preferably 1 to 80% by weight, particularly preferably 5 to 70% by weight, and further preferably 20 to 60% by weight. If it is less than 1%, there is almost no effect on the improvement of the refractive index of the primer layer, and the refractive index of the primer layer is less than 1.45. And conversely 80
%, The primer layer becomes cloudy.

The type and content of the metal compound are selected so that the refractive index of the primer layer is in the range of 1.45 to 1.60 and the condition 1 is satisfied.

In the present invention, as the primer layer,
Polyurethane obtained from the above-mentioned polyol and polyisocyanate, and the above-mentioned metal compound, and have a refractive index n _P (for light having a wavelength of 550 nm).
There is in the range of 1.45 to 1.60, yet chosen for an index of refraction n _P calculated based on formulas of the above formula 3 is applied. n _P is calculated by the following equation (2) in condition 1.

[Number 2] ^{_{(n s · n H) 1/2}} + | n s -n H | / 4 ≧ n p ≧
^{_{(N s · n H) 1/2}} - | n s -n H | / 4 (n s is the refractive index of the plastic lens substrate a wavelength for 550nm light, n _H is the refractive hard coat layer for light of 550nm Rate) is more preferably satisfied.

When the thickness d of the primer layer is equal to the following condition 2, d = λ / (4n _P ) (where λ is the wavelength of visible light,
The thickness d is controlled so as to satisfy any value in the range of 50 nm.

By satisfying both the conditions 1 and 2, the light reflected at the interface between the plastic lens substrate and the primer layer and the light reflected at the interface between the primer layer and the hard coat layer are obtained. The interference fringes generated by the interference with the light are almost invisible.

Formation of thermosetting polyurethane primer layer
It is Po polyol, polyisocyanate, a metal compound, a solvent (dispersion medium) and a coating material comprising a curing catalyst is coated on the lens base material used as necessary, a polyol and a polyisocyanate while thereafter volatilizing the solvent (dispersion medium) React
It is obtained by doing. This method is preferred because it to form a polyurethane consideration of insoluble type crosslinking solvent providing a hard coat layer on the primer layer can be <br/>.

In the present invention, a hard coat layer is provided on the polyurethane primer layer. The hard coat agent used for forming the hard coat layer is preferably a silicon-based resin, particularly preferably (1) -a colloidal silica,
Inorganic oxide particles having an average particle diameter of 50 to 200 angstroms, such as colloidal antimony oxide;
Or (1) a silane compound having no -b functional group;
(2) A composition containing a co-hydrolyzate with a silane compound having a functional group such as an epoxy group or a methacryl group as a main component. (1) is 5 for the sum of (1) and (2)
Preferably, it is contained in an amount of up to 50%. Examples of the silane compound having a functional group include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyl-methyl-diethoxysilane, and γ-methacryloyloxypropyltrimethoxysilane.

The silicone resin as the hard coat layer is preferably used because it gives a hard coat layer harder than melamine or acrylic resins. If the hardness is not so important, a melamine or acrylic resin may be used as the hard coat layer. The method for applying the hard coat agent may be any method generally used, such as a dipping method, a spray method, and a spin coating method. The dipping method is most suitable in consideration of workability. After applying the hard coat agent, a hardening treatment is performed by a method according to the hardening means of the hard coat agent such as heat curing, ultraviolet curing, and electron beam curing. Thus, a hard coat layer is formed on the polyurethane primer layer on the surface of the plastic lens. The preferred thickness of this hard coat layer (after curing) is 2
-5 μm and usually has a refractive index of 1.40-1.50.

Further, in the present invention, a single-layer or multilayer antireflection film is further provided on the hard coat layer. Examples of the substance used for forming the antireflection film include inorganic substances such as metal, metal or metalloid oxides, and fluorides. Specifically, metal oxides such as SiO ₂ and ZrO ₂ and fluorides such as MgF ₂ are preferable representative examples. As a method of forming a single-layer or multilayer anti-reflection film, for example, a vacuum evaporation method, a sputtering method, an ion plating method,
An ion beam assist method is exemplified.

Examples of the multilayer antireflection film include ZrO ₂ , SiO ₂ , ZrO ₂ , and SiO ₂ from the hard coat layer side.
Λo / 12, λo / 12, λo /
2, and those formed with an optical film thickness of λo / 4. Here, λo is the light wavelength of 520 nm.

[0031]

According to the present invention, a primer layer having a controlled refractive index is provided between the plastic lens and the hard coat layer by applying, drying and curing the above-mentioned specific primer composition. Therefore, interference fringes cannot be seen. In addition, since the primer layer is a thermosetting polyurethane whose refractive index is controlled by a metal compound, the primer layer has excellent impact resistance after antireflection coating and good weathering yellowing.

Furthermore, by using a primer layer according to the present invention, further excellent impact resistance, to pass the US FDA standards. Further, even when a lens provided with a thermosetting polyurethane primer layer in the present invention is immersed in a hard coat liquid, the polyurethane which is a primer component has a cross-linked structure and does not elute into the hard coat liquid, and the hard coat liquid does not elute. No need to worry about contaminating the coating solution. Further, the primer of the present invention
-Can the composition cure at temperatures below 100 ° C
Lenses with poor heat resistance, such as glass rolls
Whitening of plastic lenses with a transfer temperature of 110 ° C or less
It can be applied without causing it.

[0033]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described, but the present invention is not limited by these embodiments. In addition, the performance evaluation of the plastic lens having a plurality of films was performed by the following method.

1) Adhesion of film In order to evaluate the adhesion of the film, a cross-cut tape test was performed by the following method. That is, the surface of the lens having the film is cut with a cutter on a 1 mm square goban eye (100 pieces), a cellophane tape is stuck thereon, and then the cellophane tape is vigorously peeled off without being peeled off from the lens. The number m of gobangs of the remaining membrane was counted. And the result was represented like "m / 100". "100
"/ 100" indicates that no film was peeled off as a result of the cross-cut tape test.

2) Abrasion resistance A plastic substrate having a primer layer and a hard coat layer was rubbed with # 0000 steel wool to determine the degree of scratch resistance. A: Does not hurt even when rubbed strongly B: Slightly scratches when rubbed strongly C: Scratched even with weak friction

3) Dyeing properties: Plax brown D (a common disperse dye)
2 parts of Hattori Seiko) and 3 parts of plaque dyeing assistant
000 parts in a dye bath at 90 ° C. for 10 minutes by immersion dyeing, and the visible light transmittance was TOPCON.
Sunglass Tester (Tokyo Optical Machinery)
, And those having a value of 80% or less were judged as having good dyeability.

4) Adhesion of anti-reflection coat A four-layer SiO ₂ / ZrO ₂ anti-reflection film is formed on a plastic substrate having a primer layer and a hard coat layer by a vacuum deposition method. Was rubbed with # 0000 steel wool, and the change in reflected color was determined as follows. A: Reflection color does not change even if strongly rubbed B: Scratches are caused by strong rubbing, and the scratched part becomes white,
The reflection color of the part other than the scratch does not change. C: The film is scraped off even with weak friction, and the rubbed part becomes completely white.

5) Impact resistance Evaluated by a steel ball drop test. The steel balls shown in Table 1 were naturally dropped in order from the lightest one from a height of 127 cm toward the center of the lens, and the weight of the steel ball immediately before cracking was taken as the impact resistance of the lens. Table 2 shows the center thickness of the lens used in this test.

[0039]

[Table 1] 球 Steel ball weight comparison table-------------------No ) Weight (g)----------1 6.35 1.04 2 7.96 2.04 3 8.73 2.72 24 9.53 3. 53 5 10.00 4.08 6 10.32 4.48 7 11.11 5.59 8 11.96 6.88 9 12.30 7.60 10 12.70 8.36 11 13.49 10.02 12 14.29 11.90 13 15.08 13.99 14 15.88 16.32 15 16.66 18.89 16 17.46 21.72 17 18.26 24.52 18 19.05 28.20 19 19.84 31.87 20 20.64 35.85 21 21.43 40.15 2 22.23 44.78 23 23.02 49.75 24 23.81 55.07 25 24.00 56.88 26 25.00 63.73 27 25.40 66.84 28 26.99 80.17 29 28 .58 95.17 30 30.16 111.9 31 31.75 130.5 32 33.34 151.1 33 34.93 173.8 34 36.51 198.5 35 38.10 225.6 36 41. 28 286.8 37 44.45 858.2 38 17.63 440.6 3950.80 534.7}

6) Appearance Transparency was visually observed by irradiating a lens with light from a fluorescent lamp in a dark room. 7) Interference fringes Monochromatic light having a wavelength of 550 nm was applied to the lens in a dark room, and the degree of interference fringes due to reflection was visually evaluated. The evaluation was performed according to the following criteria. A: Interference fringes are almost invisible B: Interference fringes are slightly conspicuous C: Interference fringes are clearly conspicuous 8) Weathering yellowing 240-hour weathering test using an ultraviolet long life fade meter (manufactured by Suga Test Instruments Co., Ltd.) , And the subsequent yellowness was measured.

The appearance, abrasion resistance, anti-reflection coating adhesion and impact resistance tests were performed on all of the primer layer, hard coating layer and anti-reflection coating layer. The interference fringe and weathering yellowing test is a performance test before applying the antireflection coat layer, that is, when only the primer layer and the hard coat layer are applied.

Example 1 (1) Production of Plastic Lens Substrate 20 parts by weight of 2-chlorophenylmaleimide, 2,2-
Bis (3,5-dibromo-4-methacryloyloxyethoxyphenyl) propane 20 parts by weight, tribromophenyl methacrylate 30 parts by weight, diallyl isophthalate 25 parts by weight, n = 4 polyethylene glycol dimethacrylate 5 parts by weight, ultraviolet absorber As 2-
1 part by weight of (2'-hydroxy-3 ', 5'-ditert-butylphenyl) -5-chlorobenzotriazole and 2 parts by weight of t-butylperoxy (2-ethylhexanoate) as a radical polymerization initiator Was poured into a mold assembled by a glass mold and a gasket made of an ethylene-vinyl acetate copolymer, and heated from 40 ° C. to 120 ° C. over 20 hours. The lens was taken out of the glass mold and post-cured at 120 ° C. for 1 hour. The obtained lens was good as an optical plastic lens having a refractive index n _s of 1.595 and no internal distortion. In the following, this was used as a plastic lens substrate.

(2) Preparation of primer composition and coating curing 2.40, a commercially available polyester type polyol "Desmophen 1700" (manufactured by Sumitomo Bayer Urethane Co., Ltd.)
Parts by weight, commercially available block-type polyisocyanate "Desmodur LS-2759" (block obtained by blocking the isocyanate group of a cyclic trimer of hexamethylene diisocyanate with β-diketone, manufactured by Sumitomo Bayer Urethane Co., Ltd.)
0.80 parts by weight, commercially available antimony pentoxide sol “Sun Colloid AME-130” (manufactured by Nissan Chemical Industries, Ltd.)
00 parts by weight, 0.01 part by weight of a commercially available fluorinated leveling agent "Fluorard FC-430" (manufactured by Sumitomo 3M Limited) as a leveling agent, 46.90 parts by weight of propylene glycol monomethyl ether as a solvent, 46.89 parts by weight of toluene The mixture consisting of parts was sufficiently stirred until it became a uniform state, and this was used as a primer composition.

The primer composition was applied on the plastic lens substrate obtained in (1), which had been subjected to alkali treatment as a pretreatment, by a dipping method (pulling speed: 10 cm / min), and the lens was allowed to stand at room temperature. After air drying for 15 minutes 9
The primer is cured by heating at 0 ° C. for 30 minutes, and the thickness is 0.090 μm. The refractive index n _P is 1.53 on the lens.
A second primer layer was formed.

(3) Coating and Hardening of Silicon Hard Coating Agent A commercially available dyeable silicon hard coating agent “C-3”
39 "(manufactured by NRC) on the primer layer of the plastic lens substrate having the primer layer obtained in (2) (pulling speed: 40 cm /
Min). After the coated lens was air-dried at room temperature for 15 minutes, it was heated at 120 ° C. for 60 minutes, and the thickness of the thinnest portion was 2 μm, and the thickness of the thickest portion was 4 μm.
A hard coat layer having a refractive index n _H of 1.470 was formed.

The refractive index n of the plastic lens substrate
_s = 1.595, refractive index n _H of the hard coat layer = 1.4
When the values on the left and right sides of the expression of Condition 1 are calculated from 70, they are 1.562 and 1.500, respectively, and the refractive index n _P = 1.532 of the primer layer satisfies the expression of Condition 1. Further, the refractive index n _P of the primer layer is 1.53.
The value of the right-hand side of the expression of the condition 2 was calculated to be 0.090 μm from the wavelength of λ = 552 nm and the wavelength of visible light λ = 552 nm.

(4) Formation of anti-reflection film SiO ₂ was formed on the plastic lens substrate having the primer layer and the silicon-based hard coat layer obtained in the above (3).
A / ZrO ₂ -based four-layer antireflection film was formed by a vacuum evaporation method. That is, from the hard coat layer side, ZrO ₂ ,
The films of SiO ₂ , ZrO ₂ , and SiO ₂ are sequentially formed by λo /
12, λo / 12, λo / 2, and λo / 4. Here, λo is the wavelength of light 520
nm. Table 2 shows the test results of the plastic lens having the composite film thus manufactured.

[0048]

[Table 2] 膜 Dyeing resistance of film I Anti-outside resistance Abrasion protection, weathering, wear resistance, observation stripes, yellowness, sticking property, changeability (g) property --- --- --- --- ---------------------- −−−−−−−−−−− Example 1 100/100 A good A 31.87 good A 2.2 Example 2 Same as above A good A 28.20 good A 2.2 Comparative example 1 ＡA bad A 4.48 Good C 2.0 Comparative Example 2 {A Poor A 4.08 Good A 2.1 Comparative Example 3} A Good A 28.20 Good A 5.2 ──────────────────────

[0049]

[0050]

[0051]

[0052]

[0053]

Example 2 50 parts of styrene, 2,2-bis (3,5-dibromo, 4
-Methacryloyloxyethoxyphenyl) propane 4
8.5 parts, 2.8 parts of diethylene glycol bisallyl carbonate, t-butyl peroxyneodecanate
5 parts and 0.2 parts of 2- (2'-hydroxy-3'-methylphenyl) benzotriazole are mixed and stirred. Next, the insoluble matter of the mixed solution was removed with a filter, and the solution was injected into a space formed by a gasket formed of soft polyvinyl chloride and two glass molds. Then at 30 ° C 4
Time, linearly from 30 ° C to 50 ° C for 10 hours, 50 ° C
To 70 ° C for 2 hours, 70 ° C for 1 hour, 80 hours
After heating at 2 ° C. for 2 hours, the gasket and the glass mold were separated. Further, the obtained lens was annealed at 110 ° C. for 2 hours to remove distortion inside the lens. The lens thus obtained was good as an optical plastic lens having a refractive index of 1.595. The glass transition temperature of this lens was 108 ° C.

The same procedure as in Example 1 was carried out except that this was used as a plastic lens substrate and the hard coat was cured by heating at 90 ° C. for 6 hours. The test results are shown in Table 2.

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

Comparative Example 1 A plastic lens having a composite film was produced in the same manner as in Example 1 except that no primer layer was provided. The test results are shown in Table 2.

Comparative Example 2 6.8 parts by weight of γ-glycidoxypropyltrimethoxysilane and 84.0 parts by weight of methyl isobutyl ketone were added to a beaker and stirred, followed by 48 parts by weight of isopropyl alcohol and 6 parts by weight of acetylacetone.
By weight, a uniform solution was obtained. Next, 15.5 parts by weight of a tetramer of tetra-n-butoxytitanium was added, and the mixture was stirred for 30 minutes. After aging for 24 hours, a small amount of ammonium perchlorate and a surfactant were added to obtain a primer composition.

Using this primer composition, the procedure was the same as in Example 1 except that the curing temperature of the primer was 100 ° C. The thickness of the obtained primer layer is 0.081 μm.
m and the refractive index were 1.545. The test results are shown in Table 2.

[Comparative Example 3] A commercially available polyester type polyol "desmophen 670- containing an aromatic ring"
80B "(manufactured by Sumitomo Bayer Urethane Co., Ltd.), 6.60 parts by weight, commercially available block-type polyisocyanate" Desmodur LS-2759 "(having the isocyanate group of the cyclic trimer of hexamethylene diisocyanate blocked with β-diketone) , Manufactured by Sumitomo Bayer Urethane Co., Ltd.)
A mixture consisting of 6.30 parts by weight, 0.05 part by weight of a commercially available fluorine-based leveling agent "Fluorard FC-430" (manufactured by Sumitomo 3M Limited) as a leveling agent, and 87.05 parts by weight of propylene glycol monomethyl ether as a solvent. The mixture was sufficiently stirred until a uniform state was obtained, and this was used as a primer composition.

Except that this primer composition was used, all procedures were the same as in Example 1. The refractive index of the obtained primer layer was 1.533. The test results are shown in Table 2.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08K 5/56 C08K 5/56 C08L 75/04 C08L 75/04 75/06 75/06 C09D 5/00 C09D 5/00 D G02B 1/10 G02B 1/10 Z 1/11 A (72) Inventor Satoshi Ishizuka 3-5-11 Doshomachi, Chuo-ku, Osaka City Inside Nihonita Glass Co., Ltd. (72) Inventor Hisayoshi Kayaki Doshu, Chuo-ku, Osaka City 3-5-11, Machi-cho, Nihon-Sheet Glass Co., Ltd. (72) Inventor Naoto Hirayama 3-5-11, Doshu-cho, Chuo-ku, Osaka-shi, Nippon Sheet Glass Co., Ltd. (56) Reference European Patent 518687 (EP, B1) U.S. Pat. No. 5,946,641 (US, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 175/04

Claims (4)

(57) [Claims] An impact resistance of a thermosetting urethane on a surface of a plastic lens substrate before a hard coat layer made of a silicon resin and a single-layer or multi-layer anti-reflection film made of an inorganic substance are provided on the surface of the hard coat layer. A primer composition for a plastic lens used to provide a functional primer layer, and a block-type polyisocyanate,
A polyol, at least one metal oxide fine particle selected from Al, Ti, Zr, Sn, and Sb, and a solvent, wherein the fine particles are 1 to 300 m
having a mean diameter of μ, a predetermined amount of the fine particles is contained in the primer layer within a range of 20 to 60% by weight and a refractive index of the primer layer is 1.45 to 1.60, and The block type polyisocyanate and the poly
The molar ratio of isocyanate groups to hydroxyl groups is
Expressed in, is contained in a proportion of 0.8 to 1.25, and the block-type polyisocyanate is cured in the cyclic trimer is obtained by blocked by β- diketone 100 ° C. below the temperature of hexamethylene diisocyanate <br/> A primer composition for plastic lenses. Wherein said plastic lens primer composition further contains a curing catalyst according to claim 1 plastic lens primer composition. 3. The polyol according to claim 1, wherein the polyol is a polyester polyol and / or an acrylic polyol.
Or a primer composition for a plastic lens according to item 2. 4. The polyester polyol and / or
Or acrylic polyols do not contain aromatic rings
4. The primer for a plastic lens according to claim 3, wherein
Composition.