JPH09124995A - Primer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a primer compsn. which can be cured upon heating in a short time to form a film having excellent adhesion and smoothness, thereby markedly improving the impact resistance of a plastic optical component by including a combination of particular compds. SOLUTION: This primer compsn. comprises 0.1 to 20wt.% polyvinyl acetal, represented by formula I (wherein R1 represents H or a 1-20C alkyl group; (a) is 10 to 90; (b) is 10 to 90; (c) is 0 to 10; and a+b+c=100), as an indispensable component, 0.01 to 10wt.% organosilane compd. represented by formulae II or III (wherein R<2> , R<3> , R<5> and R<6> represent a 1-8C hydrocarbon radical; R4 represents a 2-8C org. group; X<1> and X<2> represent a hydrolysis group; (d) and (e) are each 0 to 3; and (f) and (g) are each 0 to 2) or a hydrolyzate thereof as a cross-linking agent, 0.01 to 10wt.% organometal alkoxide compd. represented by formula IV (wherein R<7> represents a 1-4C alkyl or alkoxy group; R<8> and R<9> represent a 1-4C alkyl group; M represents Al or Ti; (o) is 0 to 2; (p) is 1 to 4; and o+p are 3 or 4), and 0 to 30wt.% fine particles of an inorg. material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a primer composition, and more particularly, it is coated on a plastic optical component such as a plastic lens and can be cured by heat treatment at a relatively low temperature for a short time, and has a smoothness. The present invention relates to a primer composition which can form a film excellent in impact resistance, heat resistance, scratch resistance, chemical resistance, weather resistance, and plastic optical parts excellent in appearance, and has a long usable life. .

[0002]

2. Description of the Related Art Plastic lenses are lightweight, shock-resistant,
It has advantages such as easy workability and dyeability, and has rapidly spread in recent years in the field of optical materials, particularly spectacle lenses. But,
Generally, plastic lenses have the drawback of being very vulnerable. Therefore, a silicon-based hard coat film is usually provided on the surface of the lens for the purpose of improving the surface hardness. In addition, for the purpose of suppressing the surface reflection which is a cause of image flicker (a decrease in light reflectance and an improvement in light transmittance and a decrease in contrast due to image superposition (flare) or double imaging (ghost)), By providing an antireflection film formed by depositing an inorganic substance on the surface of the hard coat film, high added value is given to the plastic lens.

However, a plastic lens provided with both a hard coat film and an antireflection film has flexibility, that is, shock absorption, as compared with a plastic lens provided with no film or a plastic lens provided with only a hard coat film. Has a drawback that the impact resistance is significantly reduced. In the United States, safety standards have been set for medical devices and pharmaceuticals including eyeglasses.
There is a safety standard called nistration (hereinafter referred to as "FDA"). According to FDA standards, a diameter of 5/8 inch (1
6.3mm), drop an iron ball weighing 0.56 ounces (15.9g),
It is required that the debris does not scatter. Still,
In the case of a plus lens, the center thickness is thick enough so
Although it passes the DA standard, the minus lens may not pass the FDA standard because the center thickness is thin.
In particular, a recent tendency is that the center thickness of the minus lens tends to be thin as a problem in appearance, and this is a big problem in terms of impact resistance.

[0004]

Some methods have already been proposed for passing the impact resistance test of the US FDA standard for plastic lenses having surface treatment such as hard coat and antireflection coat. There is. As a first method, the impact resistance is improved by increasing the center thickness of the minus lens.

However, this increases the edge thickness of the lens, which impairs the appearance and also increases the weight of the lens, which is not preferable in practice. Further, depending on the material of the plastic lens, it may not be possible to provide a lens that passes the impact resistance test of the FDA standard only by increasing the center thickness. As a second method, a plastic lens material having an impact strength sufficient to pass the impact resistance test of the US FDA standard even if the impact resistance is lowered by providing both a hard coat film and an antireflection film. Has been made quite a bit. For example, JP-A-61-170701, JP-A-1-244401, and JP-A-2-36
216, JP-A-4-159309, JP-A-4-161414, JP-A-4-126710, JP-A-5-5011, and JP-A-4-14231.
5, JP-A-4-161410, JP-A-4-161410
161411, Japanese Patent Laid-Open No. 4-202308,
Japanese Patent Application Laid-Open No. 4-202309.

However, neither of the proposals has an FD in which neither the hard coat film nor the antireflection film is applied.
It passed the A standard and the minimum center thickness of the lens was 1.
At present, a plastic lens material having a thickness as thick as 5 mm or 2 mm and exhibiting a practically sufficient impact resistance has not been proposed yet. A third method is to provide a primer layer made of a resin composition between the plastic lens substrate and the hard coat film.

Originally, the primer layer was proposed as a method for improving the adhesion between the plastic lens substrate and the hard coat film, and like the surface modification method such as saponification and plasma treatment, the primer layer has a good adhesion property. Improvement was the main objective. As a prior art of the primer layer proposed for this purpose, a method using an epoxy compound (Japanese Patent Laid-Open No. 60-214)
No. 301), a method containing an acrylic and / or methacrylic compound and an aromatic vinyl compound as main components (JP-A-60-214302), and a primer composition comprising an acrylic polyol and a polyfunctional organic isocyanate compound. Method (Japanese Patent Laid-Open No. 61-114203). In each case, the improvement of the adhesion, which is the main purpose, was achieved, and the characteristics such as chemical resistance were obtained, but the impact resistance was not improved.

As a primer layer for improving impact resistance, a method using a polyurethane resin has been proposed. JP-A-63-14001, JP-A-63-8
The method disclosed in Japanese Patent No. 7223 is a method in which a polyurethane resin solution is applied to a plastic lens and then the solvent is volatilized to obtain a polyurethane resin layer. The obtained polyurethane layer is a so-called thermoplastic resin having no crosslinked structure. Of the film. When the lens is dipped in a hard coat solution to form a hard coat film on a plastic lens having this polyurethane layer, the polyurethane of the primer layer dissolves in the solvent of the hard coat solution and is eluted into the hard coat solution to form the hard coat solution. Often pollutes. In addition, the primer layer is often opaque because it is corroded by the solvent and loses its transparency. Further, JP-A-61-114203 discloses that a primer composition comprising an acrylic polyol and a polyfunctional organic isocyanate compound is applied and cured to form a polyurethane layer having a crosslinked structure. However, since an isocyanate compound capable of reacting with active hydrogen at room temperature is used, the reaction between the hydroxyl group of the polyol and the isocyanate group proceeds even during storage of the primer solution, so that the usable time of the primer solution cannot be extended for a long time.

Japanese Unexamined Patent Publication Nos. 3-109502 and 4
JP-A-366801 and JP-A-5-25299 disclose a method of suppressing the reaction with a polyol at a low temperature by using a block-type isocyanate to improve the usable time of a primer solution. However, in order to cure the primer solution after coating it on the lens, it is necessary to first remove the blocking agent, which requires a high temperature exceeding 120 ° C. As a result, there is a restriction that this method itself cannot be applied to a plastic substrate whose softening temperature is not so high, and there is a problem that the color tone of a plastic lens dyed with an organic dye is significantly changed.

The present invention has been made in view of the above problems of the prior art. It has a long usable time and can be cured by heat treatment at a relatively low temperature and a short time.
Along with being able to form a film with excellent smoothness,
Provided is a primer composition which has an effect of remarkably improving the impact strength of a plastic optical component, which hardly changes the color tone of a dyed optical component, and has almost no elution from the primer layer during formation of a hard coat film. It was intended.

[0011]

As a result of intensive studies to solve the above problems, the essential active ingredient is (A) general formula (I).

[0012]

Embedded image

(In the formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and a is the composition of the repeating unit having an acetal group (fraction of constitutional units).
˜90, b is the composition of repeating units having OH groups (fraction of constitutional units) 10 to 90, c is the composition of repeating units having acetyl groups (fraction of constitutional units), 0-1
0 and a + b + c = 100. ) And a polyvinyl acetal represented by the formula (B) and a general formula (II)

[0014]

[Chemical 6]

(Wherein R ² and R ³ are substituted or unsubstituted hydrocarbon groups having 1 to 8 carbon atoms, X ¹ is a hydrolyzable group, and d and e are 0 to 3). It is an integer.)
A hydrolyzable organosilane compound or a hydrolyzate thereof, and a general formula (III)

[0016]

Embedded image

(Wherein, R ⁴ is an organic group having 2 to 8 carbon atoms, R ⁵ and R ⁶ are substituted or unsubstituted hydrocarbon groups having 1 to 8 carbon atoms, and X ² is Is a hydrolyzable group,
f and g are integers from 0 to 2. ) At least one cross-linking agent selected from the group consisting of hydrolyzable organosilane compounds or hydrolyzates thereof, and (C) the general formula (IV)

[0018]

Embedded image

(In the formula, R ⁷ is an alkyl group or an alkoxy group having 1 to 4 carbon atoms, and R ⁸ and R ⁹ are 1 carbon atoms.
~ 4 alkyl groups, M is Al or Ti, o
Is an integer from 0 to 2, p is an integer from 1 to 4, and o + p is 3 or 4 in the valence number of M. ) A primer composition comprising at least one compound selected from the organometallic alkoxide compounds represented by the formula (D) and (D) inorganic fine particles, wherein the content of the polyvinyl acetal as the component (A) is 0.1-20% by weight
And the content of the crosslinking agent as the component (B) is 0.01 to
10% by weight, the content of the organometallic alkoxide compound as the component (C) is 0.01 to 10% by weight,
The content of the inorganic fine particles as the component (D) is 0 to 30% by weight.
And a primer composition characterized by containing 0.002 to 1% by weight of a curing catalyst can be cured by a heat treatment at a relatively low temperature and a short time with a long usable time, A hard coat film that can form a film with excellent adhesion and smoothness, has the effect of significantly improving the impact strength of plastic optical parts, and that the color tone of dyed optical parts hardly changes. It has been found to have very useful properties with little elution from the primer layer during formation.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The polyvinyl acetal represented by the general formula (I), which is the main component of the primer composition of the present invention, is preferably an acetal having an alkyl group with a carbon number of 0 to 20. Is from 0 to 10, particularly preferably polyvinyl butyral in which the alkyl group has 3 carbon atoms. A polyvinyl acetal having an acetalization degree of 10 to 90% can be used, and a polyvinyl acetal having an acetalization degree of 20 to 80% is preferable.

If the degree of acetalization is less than 10%, the impact strength is insufficiently improved, and polyvinyl acetal having a degree of acetalization of 90% or more is difficult to synthesize, and even if it is possible to synthesize it, it is possible to form a plastic base material. A decrease in adhesion is expected. The polymerization degree of polyvinyl acetal is preferably 5,000 or less, more preferably 10 or less.
It is from 0 to 3,000. If the degree of polymerization is too high, it will be difficult to dissolve in a solvent, and it will be difficult to synthesize a polyvinyl acetal having an optimum degree of acetalization. Conversely, if the degree of polymerization is too low, the impact strength will not be sufficiently improved.

The acetyl group in the polyvinyl acetal of the general formula (I) is not an essential component in the present invention, but since the polyvinyl alcohol, which is the raw material for the polyvinyl acetal, is synthesized by the hydrolysis of polyvinyl acetate, a small amount of it is necessary. It remains. The addition amount of polyvinyl acetal in the primer composition is 0.1 to 20% by weight, preferably 1 to 10% by weight. If the amount of polyvinyl acetal added is too large, the viscosity of the primer composition will be too high, making it difficult to apply to plastic optical parts, and the primer coating layer will be too thick and the uniformity of the coated surface will be lost. On the other hand, when the amount of polyvinyl acetal added is too small, the primer coating layer becomes too thin and the impact strength is insufficiently improved.

As the crosslinking agent, an organosilane compound represented by the general formula (II) or the general formula (III) is used. The hydrolyzable group in the organosilane compound hydrolyzes to form a silanol group, which reacts with the organometallic alkoxide compound of the general formula (IV). Then, by the action of the catalyst and heat, a dehydration condensation reaction occurs with the hydroxyl group in the polyvinyl acetal, and crosslinking is carried out intermolecularly or intramolecularly. The molecule that participates in crosslinking is a hydrolyzate of an organosilane compound or a condensate thereof. The organosilane compound may be added as it is, or may be previously hydrolyzed. Further, one kind of organosilane compound may be used alone, or two or more kinds of organosilane compound may be mixed and used.

Examples of the organosilane compound include halosilane compounds whose hydrolyzable group is a halogen atom, alkoxysilane compounds whose hydrolyzable group is an alkoxy group, carboxysilane compounds whose hydrolyzable group is a carboxy group, or hydrolyzed compounds. A ketoxime silane compound whose group is a ketoxime group can be used, but an alkoxysilane compound is preferable.

Specific examples of the hydrolyzable organosilane compound represented by the general formula (II) include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, phenylmethyldimethoxysilane and phenylmethyl. Diethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-
Chloropropylmethyldiethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane , Γ-aminopropylmethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxy Silane, methyltripropoxysilane,
Methyltributoxysilane, methyltris (2-methoxyethoxy) silane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane,
Ethyltributoxysilane, ethyltris (2-methoxyethoxy) silane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, vinyltrimethoxysilane, vinyl Triethoxysilane, vinyltris (2-methoxyethoxy) silane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxy Silane, 3,3,3-trifluoropropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-aminop Ropyltrimethoxysilane, γ
-Aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, N-β-aminoethyl) -γ-aminopropyltrimethoxysilane , N
-Β-aminoethyl) -γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane,
(3,4-epoxycyclohexylmethyl) trimethoxysilane, (3,4-epoxycyclohexylmethyl)
Triethoxysilane, β- (3,4-epoxycyclohexylethyl) trimethoxysilane, β- (3,4-epoxycyclohexylethyl) triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, And so on.

Specific examples of the hydrolyzable organosilane compound represented by the general formula (III) include 1,1
-Bis (trimethoxysilyl) ethane, 1,1-bis (triethoxysilyl) ethane, 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, 1,3-bis (Trimethoxysilyl) propane, 1,3-bis (triethoxysilyl) propane, 2,2-bis (trimethoxysilyl) propane,
2,2-bis (triethoxysilyl) propane, and the like.

The amount of the organosilane compound added to the primer composition is 0.01 to 10% by weight, preferably 0.1 to 5% by weight. As the organometallic alkoxide compound of the general formula (IV), an aluminum or titanium alkoxide or alkoxide diketonate compound is used. These may be used alone or as a mixture of two or more compounds. The organometallic alkoxide compound easily reacts with the organosilane compound or its hydrolytic condensate, and the product thereof reacts with the hydroxyl group in the polyvinyl acetal by the action of catalyst and heat. The organometallic alkoxide compound acts as a catalyst that accelerates the dehydration condensation reaction between the silanol group in the organosilane compound generated by hydrolysis and the hydroxyl group in the polyvinyl acetal, and as a crosslinking agent that hydrolytically condenses with the organosilane compound. Is considered to have the effect of.

Specific examples of the organometallic alkoxide compound represented by the general formula (IV) include aluminum trimethoxide, aluminum triethoxide, aluminum tripropoxide, aluminum tributoxide, titanium tetramethoxide and titanium tetraethoxy. , Titanium tetrapropoxide, titanium tetrabutoxide, aluminum dipropoxide acetylacetonate, aluminum dipropoxide ethyl acetoacetate, aluminum dibutoxide acetylacetonate, aluminum dibutoxide ethyl acetoacetate, titanium dimethoxide bis (acetylacetonate) , Titanium diethoxide bis (acetylacetonate), titanium dipropoxide bis (acetylacetonate), titani Arm dibutoxide bis (acetyl acetonate), titanium dipropoxide Sid bis (ethylacetoacetate), etc. titanium dibutoxide bis (ethylacetoacetate) and the like. Among these, titanium alkoxide is particularly preferable.

The amount of the organic metal alkoxide compound added to the primer composition is 0.01 to 10% by weight, preferably 0.1 to 3% by weight, but 50 mol% or less of the organosilane compound is preferable. The amount of the organometallic alkoxide compound added is 50 times the amount of the organosilane compound added.
If it exceeds mol%, the impact resistance decreases.

The inorganic fine particles include BaTiO ₃ , Sr.
TiO ₃ , BaZrO ₃ , CoFe ₂ O ₄ , NiFe ₂ O ₄ ,
Fine particles of compound oxide such as MnFe ₂ O ₄ or (Ba,
Sr) TiO ₃ , Sr (Ti, Zr) O ₃ , (Mn, Z
n) fine particles of a compound oxide solid solution such as Fe ₂ O ₄ ,
They may be used alone, or two or more kinds of compound oxide fine particles or compound oxide solid solution fine particles may be mixed and used. These compound oxide fine particles or compound oxide solid solution fine particles can be easily prepared from the corresponding metal alkoxide compound by the sol-gel method. The average particle diameter of the compound oxide fine particles or the compound oxide solid solution fine particles is 1 to 300 nm, preferably 1 to 50 n.
m. If the average particle size exceeds 300 nm, the lens becomes cloudy due to light scattering.

The amount of the inorganic fine particles added to the primer composition is 0.1 to 30% by weight in terms of solid content, but the refractive index of the primer cured film should be the same as or extremely close to that of the plastic lens. The type and amount of the inorganic fine particles are adjusted. In the case of a high refractive index plastic lens substrate having a refractive index of 1.60 or more, it is preferable to add 1 to 5 parts by weight of inorganic fine particles to 1 part by weight of polyvinyl acetal.

The curing catalyst is not particularly limited as long as it accelerates the dehydration condensation reaction with the hydrolysis condensation product of the organosilane compound, the organometallic alkoxide compound and the polyvinyl acetal, and the dehydration condensation reaction between the silanol groups. Absent. Specifically, organic tin compounds such as dibutyltin dilaurate, dibutyltin dioctate and dibutyltin diacetate, organic amines such as propylamine, butylamine, dipropylamine, dibutylamine, triethanolamine, tetramethylguanidine, methylimidazole and dicyandiamide. Organometallic complexes such as aluminum compounds, aluminum acetylacetonate, and iron acetylacetonate can be used. Of these, organotin compounds are particularly preferable. These may be used alone or in combination of two or more kinds of catalysts.

The amount of the curing catalyst added to the primer composition is 0.002 to 10% by weight, preferably 0.00
It is 5 to 1% by weight. As the organic solvent in the primer composition, hydrocarbons, halogenated hydrocarbons, alcohols, ketones, esters, ethers, and other known solvents can be used to dissolve polyvinyl acetal well and to disperse inorganic fine particles well. You can use what you do. Particularly preferred are methanol, ethanol, propanol, butanol, hexanol, methyl cellosolve and ethyl cellosolve, but these may be used alone or as a mixture of two or more organic solvents.

Water in the primer composition is added in an amount of 0.1 to 20% by weight as a component necessary for hydrolysis of the organosilane compound. If the amount of water added is too large, the smoothness of the primer-coated surface is lost, and if the amount of water added is too small, the usable time of the primer solution becomes shorter. The primer composition in the present invention is further various leveling agents for the purpose of improving coating properties or ultraviolet absorbers and antioxidants for the purpose of improving weather resistance, further dyes and pigments, photochromic dyes and photochromic pigments, and other films. Known additives for enhancing performance or adding functions can be used in combination.

The method for applying the primer composition of the present invention onto a plastic optical component is not particularly limited as long as it is a known method such as a spin coating method or a dipping method.
Moreover, it is preferable that the surface of the plastic optical component is subjected to a pretreatment such as an alkali treatment, a plasma treatment, or an ultraviolet treatment, if necessary. There are no particular restrictions on the material or molding method of the plastic optical component.

To cure the primer coat film applied to the surface of the plastic optical component, heating at 50 to 120 ° C., preferably 70 to 110 ° C. for 1 to 60 minutes may be performed.
With the hydrolyzed organosilane compound in the primer composition applied by heat treatment, and the hydrolyzed condensate of the organotitanate compound and the hydroxyl group contained in the polyvinyl acetal are dehydrated and condensed to crosslink the polyvinyl acetal molecule. The water generated by the condensation reaction and the organic solvent and water previously contained in the primer composition evaporate. In this way, a three-dimensionally crosslinked polyvinyl acetal primer layer is formed on the surface of the plastic optical component.

For a plastic optical component provided with a cured primer layer, a hard coat film can be formed by a known method for the purpose of improving the surface hardness. Further, a vapor deposition film of an inorganic compound having an antireflection function can be formed on the surface provided with the hard coat film by a known method.
The reason why the impact resistance of the plastic optical component provided with the cured coating of the primer composition in the present invention is remarkably improved is not necessarily clear, but it is considered as follows. That is, since the cured film of the primer composition in the present invention has a high degree of elasticity and a high degree of flexibility,
It is considered to play a role in absorbing the energy of plastic optical components when they are impacted.

Further, since the cured coating of the primer composition in the present invention is three-dimensionally cross-linked, polyvinyl acetal and other substances are dissolved in the hard coat liquid even when performing a hard coat by a wet method, and the hard coat liquid is It does not pollute. Furthermore, since the polyvinyl acetal, which is the main component of the primer composition in the present invention, has an appropriate hydroxyl group, it is possible to three-dimensionally crosslink, and at the same time, the primer layer and the plastic optical component, and the primer layer and the hard coat film are sufficient. It is considered that the adhesiveness is achieved.

[0039]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited thereto. [A] Preparation of compound oxide fine particles / polyvinyl butyral solution (1) BaTiO ₃ / polyvinyl butyral solution (A-
Preparation of 1) Isopropanol 28 was placed in a reaction vessel equipped with a rotor.
7.4 parts by weight, 43.9 parts by weight of barium diisopropoxide and 48.9 parts by weight of titanium tetraisopropoxide are sequentially charged and heated under reflux for 2 hours. After the solution was cooled to room temperature, 18.6 parts by weight of pure water was slowly added dropwise over 10 minutes, and BaTiO ₃ having an average particle size of 20 to ₃₀ nm was added.
The compound oxide fine particles of were prepared. 1.2 parts by weight of diisobutylamine as a stabilizer in this solution, and polyvinyl butyral resin S-REC-2 manufactured by Sekisui Chemical Co., Ltd.
A solution prepared by dissolving 20 parts by weight of 180 parts by weight of isopropanol was added and sufficiently stirred for 1 hour to obtain 600 parts by weight of an isopropanol solution of BaTiO ₃ / polyvinyl butyral. (2) Preparation of compound oxide fine particles / polyvinyl butyral solution (A-2) to (A-10) Compound oxide fine particles / polyvinyl butyral solution (A-)
Compound oxide fine particles / polyvinyl butyral solution (A-2) to the compound shown in Table 1 and Table 2 in the same manner as 1).
(A-10) was prepared. The polyvinyl butyral resin used is shown below.

Polyvinyl butyral resin S-REC BM-1 manufactured by Sekisui Chemical Co., Ltd., average polymerization degree 600, butyralization degree 65% S-REC BM-2 manufactured by Sekisui Chemical Co., Ltd., average polymerization degree 800, butyralization degree 68% S-REC BM -5 Sekisui Chemical Co., Ltd., average degree of polymerization 850, butyralization degree 65% S-REC BH-S Sekisui Chemical Co., Ltd., average degree of polymerization 1,000, butyralization degree 70% [B] Primer composition Preparation (1) Preparation of primer composition (B-1) 4.3 parts by weight of methyltrimethoxysilane and 20 parts by weight of isopropanol were charged in a reaction vessel equipped with a rotor,
1.7 parts by weight of 0.01N hydrochloric acid was added and stirred for 1 hour for hydrolysis.

Titanium tetra n- was added to the above hydrolyzate.
A solution prepared by dissolving 2.7 parts by weight of butoxide in 20 parts by weight of isopropanol was added and stirred for 30 minutes to obtain an organoalkoxysilane / titanium alkoxide hydrolyzed condensate. The resulting hydrolyzed condensate solution was mixed with BaTiO ₃ /
600 parts by weight of a polyvinyl butyral solution (A-1), 2 parts by weight of dibutyltin dilaurate as a curing catalyst, and 1 part by weight of Fluorosurfactant FC430 manufactured by Sumitomo 3M Limited as a leveling agent are sequentially added. Furthermore, 200 parts by weight of methanol and 10 parts of isopropanol
8.3 parts by weight and 40 parts by weight of pure water are sequentially added, and the mixture is stirred for 1 hour. Then, it filtered with a 3 micrometer membrane filter and prepared the primer composition (B-1). (2) Preparation of Primer Compositions (B-2) to (B-10) In the same manner as in the primer composition (B-1), the composition shown in Tables 3 and 4 was used to prepare the primer composition (B-2). (B-1
0) was prepared. The surfactants used are shown below.

Surfactant Fluorard FC430 Fluorosurfactant manufactured by Sumitomo 3M Ltd. SH30PA Silicone surfactant manufactured by Toray Dow Corning L7001 Silicone surfactant manufactured by Nippon Unicar Co., Ltd. [C] Hard coat liquid Preparation of (1) Silicon-based high refractive index hard coat liquid (C-1)
Preparation of γ-glycidoxypropyltrimethoxysilane (180 parts by weight) was charged into a reaction vessel equipped with a rotor, and the mixture was vigorously stirred with a magnetic stirrer at 0.01%.
40 parts by weight of a normal hydrochloric acid aqueous solution was added at once and hydrolysis was continued for 1 hour to obtain a partially condensed hydrolyzate.

The above hydrolyzate was added to S manufactured by Nissan Chemical Co., Ltd.
nO ₂ / WO ₃ composite fine particle dispersed methanol sol (HIS-
30 MN), 630 parts by weight, ethylenediaminetetraacetic acid aluminum 4 parts by weight as a curing catalyst, and Toray Dow Corning Co., Ltd. silicon-based surfactant SH30PA as a leveling agent 0.45 parts by weight, and sufficiently stirred and mixed. Then, it was filtered through a 3 μm membrane filter to prepare a hard coat solution (C-1). (2) Preparation of Silicon-based High Refractive Index Hard Coat Liquid (C-2) 210 parts by weight of γ-glycidoxypropyltrimethoxysilane was charged into a reaction vessel equipped with a rotor and vigorously stirred using a magnetic stirrer. 0.01 with stirring
40 parts by weight of a normal hydrochloric acid aqueous solution was added at once and hydrolysis was continued for 1 hour to obtain a partially condensed hydrolyzate.

Nissan Chemical Co., Ltd. S
b ₂ 0 ₅ fine particle dispersion methanol sol (AMT-130S)
600 parts by weight, aluminum acetylacetonate 4 parts by weight as a curing catalyst, and silicon surfactant L7001 manufactured by Nippon Unicar Co., Ltd. as a leveling agent.
5 parts by weight was added, and the mixture was sufficiently stirred and mixed, and then filtered through a 3 μm membrane filter to prepare a hard coat solution (C-2). [D] Preparation and Performance Evaluation of Plastic Lens Having Composite Film [Example 1] (1-1) Application and Curing of Primer Composition -4.00 Diopter, Center Thickness 1.0 mm, Refractive Index Thermosetting urethane resin plastic lens NLIV made of 1.66 of 10% N at 60 ° C as pretreatment
It was immersed in an aOH aqueous solution for 5 minutes, washed with warm water and dried. The primer composition (B-1) was applied to both surfaces of this plastic lens by the dipping method (withdrawing speed 5 mm / sec), and heat-treated at 90 ° C. for 30 minutes to cure the primer. (1-2) Application and Curing of Silicon-based High Refractive Index Hard Coat Liquid A silicone-based high refractive index hard coat liquid (C-1) is applied to both surfaces of the plastic lens having the primer layer obtained in (1-1). Dipping method (Pulling speed 5mm /
Second). The coated lens was heated at 100 ° C. for 4 hours to cure the hard coat layer. (1-3) Formation of Antireflection Film SiO ₂ / Z is formed on both surfaces of the plastic lens having the primer layer and the hard coat layer obtained in (1-2).
A 5-layer antireflection film of rO ₂ system was formed by a vacuum evaporation method. (1-4) Performance Evaluation of Plastic Lens Having Composite Film The plastic lens having the composite film obtained in (1-3) was subjected to the following tests to evaluate the performance.
The evaluation results are shown in Table 5. 1) Adhesion of film The crosshatch tape test was carried out by the following method in order to evaluate the adhesion of the film. Make a 1 mm square grid (100 squares) on the surface of the coating layer with a cutter knife, and then strongly adhere a cellophane adhesive tape (trade name "Cellotape" manufactured by Nichiban Co., Ltd.). Was repeated ten times.

After that, it was examined how many grids of the grid remained on the surface of the coating layer without being peeled off from the lens, and the number of grids that were not peeled off was expressed as X / 100. In this case, the larger the value of X, the better the adhesion. That is, the result of the cross hatch tape test is “1”.
"00/100" indicates that the film was not peeled at all. 2) Scratch resistance The surface of the antireflection film of the plastic lens having the composite film is rubbed with steel wool (# 0000) under a load of 600 g for 30 times, and the degree of scratching is evaluated as follows. It was evaluated by.

A: A scratched area is within 10%. B: The scratched area is more than 10% and less than 30%. C: The scratched area exceeds 30%. 3) Impact resistance The impact resistance of the plastic lens having the composite film was evaluated by a hard ball falling ball test. 20.0g of hard sphere 127c
It was dropped naturally from the height of m toward the center of the plastic lens, and the number of times before the plastic lens was cracked or cracked was taken as the impact resistance of the lens, and the plastic lens was dropped up to 5 times. 4) Heat resistance After leaving the plastic lens having the composite film in a constant temperature oven at 100 ° C for 10 minutes, it was taken out in a normal temperature environment, and the presence or absence of cracks at that time, the thickness of the cracks and the change with time were as follows. It evaluated by various standards. Fine cracks can be confirmed to have cracks, but have disappeared after being left for 15 minutes. Medium-sized cracks are 15 after cracks have been confirmed.
It was assumed that it would not disappear even if left for a minute.

A: No cracks were generated in the environment of 100 ° C. for 10 minutes. B: Fine cracks were generated in an environment of 100 ° C. for 10 minutes. C: Medium-sized cracks were generated at 100 ° C. for 10 minutes. 5) Weather resistance The weather resistance of a plastic lens having a composite film is determined by an ultraviolet long life fade meter (manufactured by Suga Test Instruments Co., Ltd.).
Was used for a 300-hour weather resistance test, and the degree of yellowing of the lens was measured thereafter. The evaluation was performed according to the following criteria.

A: Yellowing degree after 300 hours is less than 2.0. B: Yellowing degree after 300 hours is 2.0 or more and less than 2.5. C: Yellowing degree after 300 hours is 2.5 or more. 6) Appearance Regarding the appearance of the plastic lens having the composite film, the transparency was visually observed by shining light of a fluorescent lamp in a dark room. The evaluation was performed according to the following criteria.

A: No cloudiness. B: Kumori stands out a little. C: Kumori is clearly visible. 7) Interference fringes The presence or absence of interference fringes in a plastic lens having a composite film depends on whether the light of the fluorescent lamp is reflected on the lens surface in a dark room.
The generation of a striped pattern due to light interference was visually observed. The evaluation was performed according to the following criteria.

A: No striped pattern is observed. B: A slight striped pattern is recognized. C: A striped pattern is noticeable. [Example 2] to [Example 20] [Example 1] using the primer solutions and hard coat solutions shown in Tables 5 and 6
A plastic lens having a composite film was obtained by the same procedure as in. The plastic lens substrate used was NLIV with a power of -4.00 diopter and a center thickness of 1.0 mm,
Or the frequency is -4.00 diopter and the central thickness is 1.0m
m, NLEF and shown in Table 5 and Table 6. Each performance evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Tables 5 and 6.

Comparative Example 1 (1) Preparation of Primer Composition (D-1) 100 parts by weight of hexamethylene diisocyanate type unblocked polyisocyanate (trade name "Coronate HX" manufactured by Nippon Polyurethane Industry Co., Ltd.) , 167 parts by weight of a polyester type polyol (trade name “Nipporan 125” manufactured by Nippon Polyurethane Industry Co., Ltd.), 2 parts by weight of zinc octylate as a curing catalyst, 0.1 parts by weight of Florard FC430 as a leveling agent, and a solvent. 500 parts by weight of ethyl acetate and 250 of methyl ethyl ketone
The parts by weight were mixed uniformly. (2) Preparation of Plastic Lens Having Composite Film and Performance Evaluation The same procedure as in [Example 1] except that the primer composition (D-1) was used and the curing condition of the primer was 60 ° C. for 30 minutes. A plastic lens having a composite film was prepared. The plastic lens substrate used was NLIV having a power of -4.00 diopter and a center thickness of 1.0 mm. Each performance evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 6.

Comparative Example 2 (1) Preparation of Primer Composition (D-2) Block type polyisocyanate (trade name "Coronate 2")
529 "manufactured by Nippon Polyurethane Industry Co., Ltd., 250 parts by weight, and polyester type polyol (trade name" Nipporan 1100 "manufactured by Nippon Polyurethane Industry Co., Ltd.) 180
Parts by weight, and 2 parts by weight of zinc octylate as a curing catalyst,
1.5 parts by weight of a silicon-based surfactant as a leveling agent, 1000 parts by weight of ethyl cellosolve as a solvent, and 1500 parts by weight of methanol were uniformly mixed. (2) Preparation of plastic lens having composite film and performance evaluation The same procedure as in [Example 1] except that the primer composition (D-2) was used and the curing condition of the primer was 130 ° C. for 60 minutes. Then, a plastic lens having a composite film was prepared. The plastic lens substrate used was NLEF having a power of -4.00 diopter and a center thickness of 1.0 mm. Each performance evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 6.

[Comparative Example 3] A plastic lens having a hard coat layer and an antireflection coat layer was prepared without forming a primer layer using an NL plastic lens having a diopter of -4.00 diopter and a center thickness of 1.0 mm. Then
The same performance evaluation as in [Example 1] was performed. Table 6 shows the evaluation results.

[Comparative Example 4] A plastic lens having a hard coat layer and an antireflection coat layer was prepared by using an NLEF plastic lens having a diopter of -4.00 diopters and a center thickness of 1.0 mm, without forming a primer layer. Then
The same performance evaluation as in [Example 1] was performed. Table 6 shows the evaluation results. [E] Evaluation of usable time of primer composition Primer compositions (B-1) to (B- prepared in [A]
10) and the primer compositions (D-1) and (D-2) prepared in [Comparative Example 1] and [Comparative Example 2] were stored at 5 ° C, and the change in viscosity was traced. The period during which the amount of increase in viscosity was within 5% of the viscosity at the time of preparation was evaluated as the usable time of the primer composition. Table 7 shows the evaluation results. [F] Evaluation of color tone change of dyed lens Thermosetting urethane resin eyeglass plastic lens NLIV (Nikon Co., Ltd. product name) with a refractive index of 1.66, and thermosetting urethane resin with a refractive index of 1.60 90 ° C. for 10 minutes in a dye bath containing 7 parts by weight of Nikon Light Brown, which is a general disperse dye, in plastic lens for eyeglasses NLEF (product name of Nikon Corporation) in 1,000 parts by weight of water. It was dyed by immersion treatment. For the dyed plastic lens, the stimulus value Y in the LUV three-dimensional coordinate system was measured by a high speed integrating sphere type spectral transmittance measuring device DOT-3 (manufactured by Murakami Color Research Laboratory Co., Ltd.). Further, the dyed plastic lens was subjected to the same procedure as in (1-2) of [Example 1] to prepare primer compositions (B-1) to (B-10) and (D-).
After 1) and (D-2) were applied and cured, the stimulus value Y was measured again to obtain the color difference DE before and after the primer application. The color tone change of the dyed lens was evaluated according to the following criteria. Table 7 shows the evaluation results.

A: Color difference DE is less than 1.5 B: Color difference DE is 1.5 or more and less than 2.5 C: Color difference DE is 2.5 or more

[0056]

[Table 1]

[0057]

[Table 2]

[0058]

[Table 3]

[0059]

[Table 4]

[0060]

[Table 5]

[0061]

[Table 6]

[0062]

[Table 7]

[0063]

EFFECT OF THE INVENTION The primer composition of the present invention has a long usable time and can be cured by heat treatment at a relatively low temperature for a short time to form a film having excellent adhesion and smoothness. At the same time, the impact strength of the plastic optical component can be significantly improved.

Further, it has very useful characteristics that the color tone of the dyed optical component is hardly changed and there is almost no elution from the primer layer when the hard coat layer is formed. Therefore, the plastic optical component provided with all of the primer layer, the hard coat film and the antireflection layer in which the primer composition of the present invention is cured is excellent in impact resistance and passes the impact resistance test of US FDA standard. .

Claims (5)

[Claims] 1. An essential active ingredient is (A) general formula (I): (However, in the formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, a is the composition of the repeating unit having an acetal group (fraction of the constitutional unit), and 10 to 90, b is an OH group. Composition of repeating units having
10 to 90, c is the composition of the repeating unit having an acetyl group (fraction of the structural unit), 0 to 10, and a +
b + c = 100. ) And a polyvinyl acetal represented by the formula (B) and the general formula (II): (However, in the formula, R ² and R ³ are substituted or unsubstituted C 1
~ 8 are hydrocarbon groups, X ¹ is a hydrolyzable group,
d and e are integers from 0 to 3. ), A hydrolyzable organosilane compound or a hydrolyzate thereof, and a general formula (III): (However, in the formula, R ⁴ is an organic group having 2 to 8 carbon atoms, R ⁵ and R ⁶ are substituted or unsubstituted hydrocarbon groups having 1 to 8 carbon atoms, and X ² is a hydrolyzable group. And f and g are integers from 0 to 2.) and at least one cross-linking agent selected from the hydrolyzable organosilane compound represented by the formula (1) or its hydrolyzate; Formula (IV) embedded image (In the formula, R ⁷ is an alkyl group or an alkoxy group having 1 to 4 carbon atoms, R ⁸ and R ⁹ are alkyl groups having 1 to 4 carbon atoms, M is Al or Ti, and o is Is an integer from 0 to 2, p is an integer from 1 to 4, and o +
p is the valence number of M and is 3 or 4. ) A primer composition comprising at least one compound selected from the organometallic alkoxide compounds represented by the formula (D) and inorganic fine particles (D), wherein the content of the polyvinyl acetal as the component (A) is 0.1 to 20% by weight, the content of the cross-linking agent which is the component (B) is 0.01 to 10% by weight, and the content of the organometallic alkoxide compound which is the component (C) is 0.01 to 1
0% by weight, and the content of the inorganic fine particles as the component (D) is 0 to 30% by weight, the primer composition. 2. The primer composition according to claim 1, which contains 0.002 to 1% by weight of a curing catalyst. 3. The primer composition according to claim 1, wherein the polyvinyl acetal is polyvinyl butyral. 4. The hydrolyzable organosilane is an alkoxysilane compound in which a hydrolyzable group is an alkoxy group having 1 to 4 carbon atoms, and the hydrolyzable organosilane according to claim 1, Primer composition. 5. The inorganic fine particles are BaTiO ₃ , Sr.
TiO ₃ , BaZrO ₃ , CoFe ₂ O ₄ , NiFe ₂ O _4,
Compound oxide fine particles selected from MnFe ₂ O ₄
Alternatively, (Ba, Sr) TiO ₃ , Sr (Ti, Zr) O ₃ ,
(Mn, Zn) Fe ₂ O ₄ compound oxide solid solution fine particles having an average particle diameter of 1 to 300 n
m is the primer composition according to any one of claims 1 to 4.