JPH0690322B2 - Method for forming primer layer - Google Patents

Description

The present invention relates to a plastic lens or an optical panel plate or film having improved wear resistance.

[Outline of Invention]

The present invention, in a plastic lens or an optical panel plate or film having improved wear resistance, a primer layer made of an acrylic-styrene emulsion resin is applied on a substrate, and before the layer is completely dried or cured. , The silicone component is impregnated by applying a silicon-based coating liquid and then completely cured to improve the adhesion between the primer and the cured film, and at the same time, to improve the chemical resistance by including the silicon component in the primer component. It has improved durability and durability.

[Conventional technology]

Conventionally, for imparting wear resistance, for example, Japanese Patent Publication No. 52-39
691, JP-B-55-8548, JP-B-57-2735, etc., or a method of applying a silicon-based cured film, or JP-B-57-15608
JP-A-48-43018 and JP-B-57-43578 disclose methods for applying an acrylic cured film.

Further, as an example of a method of obtaining the adhesion between a synthetic resin as a base material and a cured film, an example of using a primer is disclosed in Japanese Patent Laid-Open No.
No. 57-140162 and the like.

In addition, we first applied a primer made of acrylic-styrene emulsion to a high refractive index plastic substrate, provided a silicone cured layer on the surface layer, and further laminated an antireflection film made of an inorganic material on the surface layer of the plastic. In the method of manufacturing a lens, the fact that the primer exhibits strong adhesion between the synthetic resin substrate and the silicone-based cured layer was found, and a patent application was filed. (Japanese Patent Application Sho 59-72092
(Problems and Objectives to be Solved by the Invention) However, in the above-mentioned conventional technique, first, Japanese Patent Publication No. 52-39691.
No. 55-8548, No. 57-2735, the silicon-based cured film disclosed in the present invention has insufficient adhesion to the substrate described in the present invention, and peeling occurs due to thermal or mechanical shock. To do.

In addition, Japanese Examined Patent Publication Nos. 57-15608, 48-43018, and 57-4357.
Even the acrylic cured film disclosed in No. 8 has insufficient adhesion and hardness.

Further, the method of primer treatment disclosed in JP-A-57-140162 does not have sufficient adhesion to the upper silicon-based cured layer, and for example, a tape can be easily prepared by immersing it in warm water at 60 ° C. for 1 hour. The adhesiveness of the cured coating film is reduced to such an extent that it peels off.

In addition, in the method described in Japanese Patent Application No. 59-72092, which was previously filed by us, although sufficient adhesion can be obtained, immersion in warm water,
It was discovered that immersion in acetone caused whitening of the coating film.

Therefore, the present invention solves such a problem, and an object of the present invention is to provide a silicon-based hardened layer which is rich in workability and is capable of forming an antireflection film made of an inorganic material and the like. In obtaining an optical substrate, a primer composition for improving the adhesion between the substrate and the cured layer to obtain excellent durability and water resistance and a method for forming the primer composition are provided.

[Means for solving problems]

The method for forming the primer layer of the present invention is to provide a primer layer on the surface layer of a transparent synthetic resin optical substrate, and further to provide a silicone-based cured film layer on the surface layer, wherein the primer resin is in a semi-dry state, or Characterized by applying a silicon-based coating solution in a state of being swollen with a solvent, impregnating a part of the composition for forming a cured film, and then sufficiently heating to remove the solvent to complete the curing reaction. To do.

This will be described in more detail.

Here, the method for forming the primer layer is as follows: a) The primer has a theoretical glass transition point of 0 ° C. to 60 ° C.
Using a copolymer emulsion resin solution consisting mainly of acrylic and styrene at ℃, b) coating on a transparent substrate, and during the process of drying and heat curing, interrupt the heating before forming a completely homogeneous coating layer. ,
Cooled c) Colloidal silica with a particle size of 1 to 100 millimicrons, and general formula (However, in the formula, R ¹ is an organic group containing an epoxy group, R ² is hydrogen, methyl, ethyl, propyl, vinyl group, R ³ is a hydrocarbon group having 1 to 4 carbon atoms, an alkoxyalkyl group, or One or more compounds of the organosilicon compound represented by an acyl group having 1 to 4 carbon atoms, and a is 0 to 2) and / or a hydrolyzate and a partial condensate thereof.

Is used as a main component, and after being diluted with a solvent, it is hydrolyzed, and a silicone-based coating liquid containing a partially dehydrated condensate is applied, dried and heated to be completely cured.

Here, the primer layer is dried and cured by heating at an ambient temperature of 5
It is necessary to perform pre-curing within the range of 40 ° C to 40 ° C in an atmosphere having a relative humidity of 35% or more and a curing temperature not exceeding 50 ° C from the glass transition temperature of the primer component. If the humidity is 35% or less, the solvent and water will be vaporized significantly during the drying after applying the primer, and an appropriate swelling state cannot be maintained. Further, if the ambient temperature is 5 ° C. or lower, sagging or scratched skin is generated on the primer-coated surface, which is not preferable. Further, at an ambient temperature of 40 ° C. or higher, the evaporation of the solvent from the coating liquid is severe, which is inconvenient for handling the coating liquid.

Also, the curing temperature of the primer is the most important factor. It is preferable that this temperature is selected from the range after the glass transition of the primer composition resin (Tg ° C.) and Tg + 50 (° C.), and the composition is dried and cured with a curing time of 5 minutes to 120 minutes.
When the curing temperature is Tg or lower, the formed primer layer becomes brittle, and when it exceeds Tg + 50 (° C), the silicone resin to be applied next is not soaked and the effect is halved.

Here, the acrylic-styrene-based primer composition used in the present invention includes acrylic acid and methacrylic acid, and lower alcohols such as methanol, ethanol, i-propanol, and n-butanol as examples of acrylic and methacrylic monomers. Or an ester of an aromatic compound having an alcoholic hydroxyl group such as benzyl alcohol. Examples of the remaining aromatic vinyl compound include styrene, chlorostyrene and bromostyrene. It is preferable that these monomers are radical emulsion-polymerized in a dispersion using a nonionic or anionic surfactant to prepare an aqueous emulsion. Further, the number average molecular weight at this time is 10,000 or more, and the particle diameter is required to be 10 to 500 mμ. That is, in the solution polymerization, a copolymer having a molecular weight of 10,000 or less can be obtained, but these do not have sufficient adhesion and the final product has poor water resistance and weather resistance. Further, emulsion is diluted with cellosolve, alcohol or the like, and if necessary, a silicone-based or fluorine-based surfactant is added to prepare a primer coating liquid.

In addition, the application is dipping, spinner, spray,
It is performed by a method such as flow coating, and the dry weight is 0.1 to 2
Apply to a thickness of μ.

Next, particles 1-10 of the components of the silicone-based coating liquid are
0 millimicron colloidal silica is obtained by uniformly dispersing fine particles of silicon dioxide having a particle size of 1 to 100 millimicrons in water or an organic solvent.

Also, the general formula (R ¹ , R ² , R ³ and a are as described above), the silane compound having an epoxy group as an organic chain, the organic group residue is (However, P and q are 1 to 6 and r is 0 to 2). Specific examples of such compounds include r-glycidoxypropyltrimethoxysilane, r-glycidoxypropyltriethoxysilane, r-glycidoxypropyl (methyl) trimethoxysilane, β3,4-epoxyxylohexyl) ethyl. Examples include triethoxysilane. In addition, this alkoxyl group is partially or wholly hydrolyzed at the time of use, and a part thereof is dehydrated and condensed. Therefore, instead of the alkoxyl group, a hydrolyzable group such as alkoxyalkyl, acyl or hydrogen chloro , An acetoxy group or the like may be used. This component is used as it is or after being hydrolyzed with a mineral acid or an organic acid as a catalyst in a solvent such as water, alcohol, cellosolve, or ketone.

It is also useful to add the above-mentioned surfactant to this width to improve the coatability.

After curing with these two components as the main components, further on the surface layer,
SiO, Si by vacuum deposition method and ion sputtering method
O _2, by _{Si 3 N 4, TiO 2,} TiO 3, ZrO 2, Al 2 O 3, MgF 2, laminating Ta ₂ O ₅ monolayer or multilayer thin film made of dielectric material such as, air and the lens It is also useful to form a layer that suppresses the reflection at the interface to a low level.

Further, an epoxy compound, perchloric acid, perchlorate, an ultraviolet absorber, an antioxidant, a titanium compound or the like is added to the silicone coating liquid to improve the flexibility of the cured film or to improve the refractive index. It is possible to increase the rate, or to achieve multi-functionality such as imparting dyeability with a disperse dye.

The material of the transparent synthetic resin optical substrate used is preferably a transparent resin containing an aromatic or a transparent material currently used for optical applications such as polymethylmethacrylate and polydiethylene glycol bisallyl carbonate.

Further, as a product, it is useful for optical applications such as a plastic lens, a plastic panel, and a plastic film. In particular, the plastic lens is particularly useful for the plastic base material described below.

That is, the following are the main ingredients, and
80 to 20 parts by weight of comonomer is applied to plastic lenses made of a copolymer obtained by radical polymerization. (In the formula, R ₁ represents hydrogen or a methyl group, X ¹ and X ² are halogens excluding fluorine, and m + n is an integer of 0 to 8). The lens is obtained.

[Action]

According to the above configuration, the present invention, the primer layer, since the silicon-based composition having excellent chemical resistance enters, by the anchor effect of the silicon-based cured layer, and the action of affinity,
It is considered that the adhesion between the primer and the silicone-based cured layer was increased, and the chemical resistance and water resistance were improved.

〔Example〕

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited thereto.

In addition, the part in an Example represents a weight part.

Example 1 (1) Production of high refractive index plastic lens 50 parts of styrene, 48.5 parts of 2,2-bis (3,5-dibromo-4-methacryloyloxyethoxyphenyl) propane, diethylene glycol bisallyl carbonate 2.8 parts, t
-Butyl baroxyneodecanate 1.5 parts, 2- (2 '
12 parts of -hydroxy-3'-methylphenyl) benzotriazole are mixed and stirred. Next, the insoluble matter of this mixed solution was removed with a filter, and the solution was poured into a space defined by a gasket formed of soft polyvinyl chloride and two glass molds. Next, 30 ℃ for 4 hours, 30 ℃ to 50 ℃ linearly for 10 hours, 50 ℃ to 70 ℃ linearly for 2 hours, 70
After heating for 1 hour at 80 ° C. for 2 hours at 80 ° C., the gasket and the glass mold were separated. Further obtained lens
Annealing was performed at 110 ° C. for 2 hours to eliminate distortion inside the lens. The lens thus obtained has a refractive index of 1,59
5. The Abbe's number was 33, which was good as a high refractive index plastic optical lens.

(2) Preparation and coating curing of primer coating liquid 800 parts of distilled water, sodium dodecylbenzene sulfonate (Nippon Yushi Co., Ltd., trade name "Nurex R") was added to 3 SUS autoclaves equipped with a stirrer. Add 4 parts,
The mixture was kept at 30-35 ° C and stirred at 40-60 rpm to dissolve the contents. Then, 5 parts of n-dodecyl mercaptan was dissolved in 300 parts of methyl methacrylate, 20 parts of -n-butyl acrylate, and 200 parts of styrene, which had been distilled to remove the polymerization inhibitor, and added to the above autoclave. After replacing the atmosphere in the container with a sufficient amount of nitrogen,
Stirring was started at 500 rpm.

Then, dissolve 4 parts of potassium persulfate in 36 parts of distilled water,
It dripped over 1 hour.

Then, set the speed to 50 rpm and heat the internal temperature to 80 ° C for about 3 minutes.
Reacted for hours.

After completion of the reaction, a solution prepared by dissolving 3 parts of sodium dimethyldithiocarbamate in 100 parts of distilled water was injected as a stop solution to stop the reaction.

The emulsion solution thus obtained had a solid content concentration of 37% and a particle size of 500 mμ or less.
Further, Tg was 45 ° C, and the molecular weight of this polymer approximated by the viscosity method was about 100,000.

Next, 30 parts of this emulsion solution was slowly stirred,
Add 60 parts methanol, followed by methyl cellosolve 50
Part, dimethylformamide 10 parts, silicon-based surfactant (manufactured by Nippon Unicar Co., Ltd., trade name "Y-7002") 0.05
Was added to prepare a primer solution.

This primer solution was thoroughly passed through a membrane filter having 1 μm pores, and then applied to the base lens obtained in (1) by a dipping method. By setting the pulling rate at this time to 10 cm / min, a primer film having a cured film thickness of 0.5 μm was obtained. At this time, the environmental humidity was kept at 55% and the room temperature was kept at 20 ° C.

This lens is dried and cured at 60 ° C for 30 minutes,
Cooled to room temperature.

(3) Preparation of Silicone Coating Coating Liquid and Coating Hardening In a flask equipped with a stirrer, under a nitrogen atmosphere, isopropanol-dispersed colloidal silica (Catalyst Kasei Kogyo Co., Ltd.)
"OSCAL-1432" solid content concentration 30%) 330 parts, isopropanol 220 parts, and r-glycidoxypropyltrimethoxysilane 108 parts were sequentially added with stirring, and 0.05 N hydrochloric acid 5
Two parts were added dropwise over 30 minutes. Subsequently, 0.1 part of the above-mentioned silicon-based surfactant was added to obtain a coating liquid.
This solution was left standing at 0 ° C. for 24 hours for thermal formation to obtain a silicon-based coating liquid.

Then, the coating liquid was applied to the lens obtained in (2) by a taping method. The pulling speed at this time is
I went at 20 cm per minute. This lens is heated in a hot air drying oven to 100
It was kept at 2 ° C. for 2 hours and cured by heating. The cured layer thus obtained was hard, transparent, and had good adhesion. In addition, the thickness of this cured layer should be the same as that of the primer layer.
It was 2.6μ.

(4) Formation of Antireflection Layer The lens obtained in (3) was exposed to Ar gas plasma at a power of 200 W for 30 seconds in a vacuum, and then the first vacuum deposition method was used.
An antireflection layer having a film structure as shown in the figure was provided. That is,
Once from the lens side to the atmosphere side, ZrO ₂ , Al ₂ O ₃ , ZrO ₂ , SiO ₂
Of four layers, the optical thickness of which is, in order, ZrO ₂
The total thickness of the Al ₂ O ₃ and is, λ _0/4, the next ZrO ₂ are λ _0/4, SiO ₂ of the top layer is λ _0/4. Note that λ ₀ is 510 nm.

The lens thus obtained had low surface reflection and excellent impact resistance.

(5) Test and evaluation results In the enlarged photograph of the cross section of the coating film of the obtained lens by an electron microscope, the infiltration of the silicon component into the primer was confirmed. The characteristics were evaluated by the method described below. The results are shown in Table 1.

a) Abrasion resistance: Using commercially available steel wool (# 0000), a rectangular test surface of 1 cm x 3 cm is rubbed for 10 reciprocations with a load of 1 kg, and the scratched state of the surface is ranked next. Evaluated separately.

A: No scratches in the area of 1 cm x 3 cm.

B: 1 to 10 scratches are made within the above range.

C: 10 to 100 scratches are made within the above range.

D: There are countless scratches, but there is still a smooth surface.

E: No smooth surface remains due to scratches on the surface.

b) Chemical resistance: After being immersed in alcohol, acetone, and kerosene for 48 hours, the surface condition was examined, and the one with no abnormality was evaluated as good.

c) Warm water resistance: After dipping in hot water at 60 ° C. for 1 hour, it was dried and evaluated for the check for the presence or absence of abnormal appearance and the adhesion described in d).

d) Adhesion: The adhesion was evaluated according to the JIS D-0202 coating film adhesion evaluation method. That is, a knife was used to form scratches on the surface of the test piece at intervals of 1 mm to form 100 squares of 1 mm ² . next,
After strongly sticking cellophane adhesive tape (trade name "Cellotape" manufactured by Nichiban Co., Ltd.) to the upper surface, from the surface
Pull it all at once in the direction of 90 °, peel off the tape,
Those with 95 or more squares in which the coating film was completely left were regarded as good.

Example 2 In Example 1, a polyethylene terephthalate film (biaxially stretched film, thickness 188 μ) was used instead of the high refractive index plastic lens.

The primer and hard coat used were as described below.

(1) Preparation of primer coating liquid and coating curing F430 (Showa High Polymer Co., Ltd. product, Tg = 32 ° C. solid content concentration 45%) was used as a commercially available acrylic-styrene-based aqueous emulsion. That is, to 20 parts of the aqueous emulsion,
While stirring vigorously, add 20 parts of pure water and 20 parts of methanol while adding gently.
Subsequently, 80 parts of ethyl cellosolve and 10 parts of propylene glycol monomethyl ether were added. Then, para-t-
2.5 parts of butylphenyl salicylate and 0.5 parts of a stabilizer for polymer (manufactured by Sankyo Co., Ltd., trade name "Sanol LS-770") were added, and further an ultraviolet absorber 2- (2'-hydroxy-).
After 0.2 part of 3'-methylphenyl) benzotriazole was added and sufficiently dissolved, insoluble matter was removed by filtration to obtain a primer coating solution.

This coating liquid was applied in the same manner as in Example 1 and dried at 60 ° C. for 30 minutes to obtain a primer coating film. The film thickness at this time is 0.
It was 5μ.

(2) Preparation and Coating Hardening of Silicone Coating Coating Liquid 100 parts of the coating solution obtained in (3) of Example 1 was mixed with 20 parts of acetylacetone and tetraoctylene glycol titanate (Nippon Soda Co., Ltd., trade name “TNi”). −33 ”) 10
Part, tetrabutoxytitanium polymer (same trade name as "TBT-1
0 ") 20 parts was added to make a uniform solution. This was prepared in the same manner as in Example 1 and the above-mentioned film (10 cm square) was used.
Was applied and cured. The thickness of the cured film thus obtained, including the primer, was 3.5 μm. In addition, a good film was obtained without interference between the lens substrate and the hard coat.

(3) Test and Evaluation Results The lens thus obtained was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Examples 3 to 7 (1) Preparation and coating / curing of primer coating liquid As a commercially available acrylic-styrene-based aqueous emulsion,
Sebian A4719 (manufactured by Daicel Chemical Industries, Ltd., Tg = 30 ° C,
Solid content 50%) 20 parts, water 30 parts, methyl cellosolve 10
0 part, 20 parts of dimethylformamide and a small amount of a silicon-based surfactant were added to prepare a primer coating solution (P-3).

Immerse the base material described below in this primer coating solution,
After pulling up at / min for 1 minute and air-drying, it was heated at 50 ° C. for 30 minutes and semi-cured. At this time, the film thickness was set to about 0.6μ, and the environmental humidity was set to 55% (20 ° C), and the operation was performed.

(2) Hard Coat Processing and Antireflection Processing The substrate thus obtained was formed with a hard coat and an antireflection film in the same manner as in Example 1.

(3) Test and evaluation results Test evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

The panel plate used had a thickness of 1 mm and a square of 10 cm.

Example 8 A high-refractive-index plastic lens having an antireflection film was obtained in the same manner as in Example 3 using the high-refractive-index plastic lens obtained in Example 1. The evaluation results are shown in Table 1.

Example 9 The procedure of Example 8 was repeated except that the silicon-based coating liquid described below was used as the silicon-based coating liquid and no antireflection film was applied.

That is, the silicon-based coating liquid was prepared as follows.

First, γ-glycidoxypropyltrimethoxysilane 11
Hydrolysis was performed by adding 53 parts of 0.05N hydrochloric acid to a solution consisting of 8 parts, 271 parts of isopropanol-dispersed colloidal silica (solid content concentration 30%) and 395 parts of isopropanol. After this solution was aged at 0 ° C. for 24 hours, 164 parts of glycerin diglycidyl ether and 5 parts of magnesium perchlorate were added and stirred to obtain a coating liquid.

The silicon-based coating liquid thus obtained was applied and cured by the method described above to obtain a high refractive index plastic lens having a hard coat. Also, this lens was easy to dye with a disperse dye. The evaluation results are shown in Table 1.

Comparative Example 1 A plastic lens having a good appearance was obtained in the same manner as in Example 1 except that the heating temperature of the primer was 100 ° C. In an enlarged photograph of the cross section of the coating film of this lens by an electron microscope, it was observed that there was almost no penetration of the silicon component into the primer layer.

The evaluation results are shown in Table 1.

Comparative Example 2 A plastic lens having a good appearance was obtained in the same manner as in Example 1 except that the environmental humidity was 20% (20 ° C.).

The evaluation results are shown in Table 1.

[Effects of the Invention] As described above, according to the constitution of the present invention, a layer of a primer composition for firmly adhering a silicon-based cured film having excellent abrasion resistance to a plastic substrate is used as a base material and a cured layer. In order to obtain a strong adhesive force by stacking between them, the effect of increasing the long-term durability of the adhesiveness and further chemical resistance by completing the curing with the silicone-based cured layer component impregnated in part of the primer layer It has two important effects of improving the chemical resistance and water resistance of the primer layer due to the inclusion of the excellent silicone resin component.

Therefore, by using these techniques, it is possible to commercialize abrasion-resistant plastic lenses, plastic panels, plastic films and the like, and the technical effect thereof is great.

[Brief description of drawings]

FIG. 1 shows a laminated state in which a coating film cross section of the lens of Example 1 was observed by an electron microscope, and shows a state in which a silicone component is impregnated in a primer layer in which emulsion particles are in a semi-cured state. It is a figure. FIG. 2 shows a laminated state in which the coating film cross section of the lens of Comparative Example 1 was observed by an electron microscope, and is a schematic diagram showing a state in which emulsion particles are melted and completely cured to form a uniform primer layer. is there. 11 …… High refractive index plastic lens 12 …… Primer layer 13 …… Curing layer 14 …… Anti-reflection layer 20 …… Silicon component 21 …… Emulsion particles 23 …… Silicon component 24 …… Completely cured emulsion particles

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location G02B 1/04 8807-2K

Claims (8)

[Claims] 1. A method of providing a primer layer on a surface layer of a transparent synthetic resin optical substrate and further providing a silicon-based cured film layer on the surface layer, wherein the primer resin is in a semi-dried state or in a state swollen with a solvent. Apply the silicon-based coating liquid as it is, part of the composition for forming a cured film,
A method for forming a primer layer, which comprises impregnating and then sufficiently heating to remove the solvent and complete the curing reaction. 2. The method for forming the primer layer comprises: a) using as a primer a copolymer emulsion resin solution having a glass transition point of 0 ° C. to 60 ° C. mainly consisting of acrylic and styrene; In the process of drying and heating and curing, the heating is interrupted and cooled before forming a completely homogeneous coating film. C) Colloidal silica having a particle size of 1 to 100 mm, and a general formula: (However, in the formula, R ¹ is an organic group containing an epoxy group, R ² is hydrogen, methyl, ethyl, propyl, vinyl group, R ³ is a hydrocarbon group having 1 to 4 carbon atoms, an alkoxyalkyl group, or One or more compounds of the organosilicon compound represented by an acyl group having 1 to 4 carbon atoms, and a is 0 to 2) and / or a hydrolyzate and a partial condensate thereof. The main component is, which is hydrolyzed after being diluted with a solvent, is coated with a silicon-based coating solution containing a partial dehydration condensate, is dried and heated, and is completely cured. The method for forming a primer layer according to item 1. 3. The primer layer is dried and heat-cured at an ambient temperature of 5 ° C. to 40 ° C. in an atmosphere having a relative humidity of 35% or more. The curing temperature is 50 ° C. from the glass transition temperature of the primer component. The method for forming a primer layer according to claim 2, characterized in that pre-curing is carried out within a range not exceeding ° C. 4. The silicone-based coating liquid contains only the main component or, in addition thereto, perchloric acid or perchlorates, an ultraviolet absorber, an antioxidant, a titanium-based compound,
The method for forming a primer layer according to claim 2, further comprising one or more components selected from epoxy compounds as an additive. 5. A cured film formed by using the silicon-based coating liquid, as it is, or further has an antireflection film formed by laminating thin films made of an inorganic substance. A method for forming a primer layer according to the second aspect. 6. The material of the transparent synthetic resin optical substrate is
The method for forming a primer layer according to claim 1, wherein the aromatic resin-containing transparent resin, polymethyl methacrylate, or polydiethylene glycol bisallyl carbonate is used. 7. The method for forming a primer layer according to claim 1, wherein the transparent synthetic resin optical substrate is a plastic lens. 8. The transparent synthetic resin optical base material is an optical panel cover.
A method for forming a primer layer according to the item.