KR100905261B1 - Primer composition for high refractive lense, method for preparation thereof, high refractive coating lense comprising the same, and method for preparing high refractive coating lense comprising the same - Google Patents

Abstract

The present invention relates to a primer composition for a high refractive lens, a manufacturing method thereof, a high refractive coating lens including the same, and a manufacturing method of a high refractive coating lens, and more specifically, a polyurethane resin, a high refractive metal oxide particle, a surfactant, a pH adjusting agent, It relates to a primer composition for a high refractive lens comprising a leveling agent, and a solvent, pH 7.0 to 10.0, a preparation method thereof, a high refractive coating lens comprising the same, and a method for producing a high refractive coating lens.

Primer composition for a high refractive lens of the present invention is excellent in storage stability, and the primer coating layer prepared therefrom is excellent in impact resistance, colorability, and adhesion, high refractive coating lens comprising this is less milky discoloration and no interference phenomenon There is an advantage.

Primer, pH, surfactant, lens, coating, high refractive index

Description

Primer composition for a high refractive lens, a manufacturing method thereof, a high refractive coating lens comprising the same, and a manufacturing method of a high refractive coating lens REFRACTIVE COATING LENSE COMPRISING THE SAME}

[Industrial use]

The present invention relates to a primer composition for a high refractive lens, a manufacturing method thereof, a high refractive coating lens comprising the same, and a manufacturing method of a high refractive coating lens, and more particularly, excellent storage stability, impact resistance, colorability, and adhesion. The present invention relates to a primer composition for a high refractive lens for forming an excellent primer coating layer, and a high refractive coating lens having little milky discoloration and no interference phenomenon.

[Private Technology]

Clean and transparent plastic materials are widely used as a substitute for glass in many applications due to their unique properties such as light weight, ease of handling and ease of forming products.

However, most plastic materials have the drawback of being weak and easily scratched. Therefore, before using it in any application field, it has become common practice to cover plastic materials with scratch-resistant hard coating compositions to compensate for friction resistance and the like. Such hard coating composition is preferably a clean, uncolored coating composition.

Examples of the organic coating composition include thermosetting epoxy and polyurethane resins and ultraviolet curable acrylic resins. Although organic coating compositions tend to be cheaper than siloxane coating compositions, their friction resistance is generally not very good.

Clark, US Pat. No. 3,986,997, describes an example of a siloxane coating composition that, when applied to a substrate and cured, provides good friction resistance on the surface of the plastic substrate. The hard coating composition described in the patent has the advantage of providing friction resistance and scratch resistance to applications such as glasses glass, safety glasses, building and vehicle windows, plastic panels, etc., but in some applications It is also known to reduce impact.

Recently, high refractive index plastic materials have been used to make spectacle lenses. As their refractive index increases, the thickness of the lens required to achieve the same level of correction becomes thinner. The lenses manufactured in this way are thinner and lighter, which makes users more preferred. However, these high refractive plastic materials still tend to be relatively weaker and easier to scratch than glass.

Known organic or siloxane coating compositions can be applied to these plastic materials to form protective friction resistant coating layers. However, when the hard coating composition is applied to a high refractive index plastic material, their impact resistance tends to be inferior to that of the uncoated plastic material. In particular, this problem is recognized very seriously because such a decrease in impact resistance may be lower than the government standard. In addition, the application of additional coating layers, such as antireflective coating compositions, to these plastic materials may further exacerbate the impact strength.

One way to solve this problem is to apply an elastomeric primer layer, such as polyurethane, between the plastic material and the friction resistant coating composition. This primer layer acts as an energy absorbing layer that prevents cracks formed in the hard coating layer from advancing to the plastic substrate by impact.

However, since a general polyurethane resin has a low crosslinking structure, it may be dissolved in a solvent or a monomer of a friction resistant coating layer applied on the primer layer, which also has a detrimental effect on the transparency of the friction resistant coating layer, and the primer layer itself also has transparency. Can be lost.

Although Japanese Patent Laid-Open No. 1996-231807, Japanese Patent Laid-Open No. 2003-055601, and US Patent No. 6890644 describe high refractive primers containing metal oxides, there is a problem of poor storage stability and transparency.

The present invention is to solve the above problems, an object of the present invention is to reduce the haze caused by the pH difference between the high refractive metal oxide particles and the polyurethane, which is the raw material of the coating composition, excellent storage stability, discoloration phenomenon It is to provide a primer composition for a high refractive lens without.

Another object of the present invention to provide a method for producing a primer composition for a high refractive lens.

Still another object of the present invention is to provide a high refractive index coated lens prepared using the high refractive index primer composition and a method of manufacturing the same.

In order to achieve the above object, the present invention provides a primer composition for a high refractive lens including a polyurethane resin, high refractive metal oxide particles, a surfactant, a pH adjusting agent, a leveling agent, and a solvent having a pH of 7.0 to 10.0.

The present invention also comprises the steps of mixing the high refractive metal oxide particles, and a surfactant, and adjusting the pH to 7.0 to 10.0 by adding a pH adjusting agent to prepare a filler composition; And it provides a method for producing a primer composition for a high refractive lens comprising the step of adjusting the filler composition prepared in a pH 6.5 to 10.0 polyurethane aqueous emulsion, a solvent, and a leveling agent to pH 7.0 to 10.0.

The invention also provides a high refractive lens substrate; A high refractive primer coating layer coated on the surface of the high refractive lens substrate; And a hard coating layer coated on the high refractive primer coating layer, wherein the high refractive primer coating layer is prepared from the primer composition for the high refractive lens.

The present invention also comprises coating the primer composition for the high refractive lens on the surface of the high refractive lens substrate, followed by drying to form a high refractive primer layer; And coating a hard coating solution on the surface of the high refractive primer layer, followed by curing to form a hard coating layer.

Hereinafter, the present invention will be described in more detail.

Primer composition for a high refractive lens of the present invention comprises a polyurethane resin, high refractive metal oxide particles, surfactants, pH adjusting agent, leveling agent, and a solvent, characterized in that the pH of the final composition is 7.0 to 10.0, more specifically Is based on 100 parts by weight of the polyurethane resin, 10 to 90 parts by weight of high refractive metal oxide particles, 0.1 to 1.0 parts by weight of surfactant, 0.1 to 1.0 parts by weight of leveling agent, and 500 to 1000 parts by weight of solvent. Since the pH adjusting agent is added in an amount satisfying the pH range, a specific content is not described.

In the conventional high refractive lens primer composition for storage stability is not good, milky discoloration phenomenon is a phenomenon that occurs in the refractive index difference between the high refractive metal oxide particles and polyurethane emulsion used in the composition. However, the present invention solves this problem by stabilizing the surface of the high refractive metal oxide particles using a surfactant, and then by adjusting the pH to minimize the pH difference between the high refractive metal oxide particles and the polyurethane emulsion.

The polyurethane resin to be added to the primer composition of the present invention is added to improve the impact resistance at the time of forming the primer layer, it is preferably an aqueous emulsion of polyurethane having an elongation of 200 to 500%.

Preferably, the high refractive metal oxide particles are in a fine particle state that is indistinguishable to the naked eye, and an average particle diameter of at least 1 nm or more is sufficient to obtain a sufficient refractive index improvement effect, and 300 nm is appropriate to prevent diffuse reflection. The average particle diameter is most preferably 1 to 50 nm.

The metal oxide particles are at least one metal selected from the group consisting of titanium oxide, tin oxide, zirconium oxide, molybdenum oxide, aluminum oxide, iron oxide, silicon dioxide, cerium oxide, tungsten oxide, antimony oxide, zinc oxide, and beryllium oxide. It is preferable to include an oxide, and at least one metal oxide selected from the group consisting of titanium oxide, tin oxide, and zirconium oxide is most preferred in view of high refractive index.

The surfactant serves to stabilize and surround the metal oxide particles, and is preferably a nonionic surfactant. The nonionic surfactant is a surfactant that does not have a group separated from ions in an aqueous solution, and mainly has a hydroxyl group. Non-limiting examples of the surfactant include an ether, an ester ether, an ester, and a nitrogen-containing group. It is preferable that it is 1 or more types.

The pH adjusting agent is added to adjust the pH of the primer composition to the above range, but may be any basic compound, but consisting of ammonia water, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide (TMAH) and choline It is preferable that it is 1 or more types chosen from the group.

The leveling agent is added for the purpose of improving the surface condition at the time of application of the primer composition, and since the conventional leveling agent can be used, the present invention is not particularly limited, but it is preferable to use a silicone-based leveling agent, It is more preferable to use the Silwet L series.

The solvent is preferably one or more selected from the group consisting of water, alcohols, hydrocarbons, halides, esters, ethers and ketones, and more preferably a mixed solvent of water and alcohols.

The primer composition for a high refractive lens of the present invention may further comprise at least one additive selected from the group consisting of UV absorbers, antioxidants, dyes, pigments, and adhesion promoters, in addition to the above components, depending on the use of the high refractive lens. It may include.

Primer composition for a high refractive lens of the present invention may be prepared by mixing a filler composition comprising a high refractive metal oxide particles with a polyurethane aqueous emulsion, more specifically, a high refractive metal oxide particles, and a surfactant is mixed, Adding to adjust the pH to 7.0 to 10.0 to prepare a filler composition; And it may be prepared by a method comprising the step of adjusting the filler composition prepared in a pH 6.5 to 10.0 polyurethane aqueous emulsion, a solvent, and a leveling agent to a pH 7.0 to 10.0.

In this case, examples of the high refractive metal oxide particles of the present invention to be used are as described above, it is preferable to use in a dispersion state dispersed in a solid content of 10 to 50% by weight, the pH of the metal oxide particle dispersion is 7.0 It is preferable to use those which are from 10.0.

At this time, it is preferable that the pH difference between the filler composition and the polyurethane aqueous emulsion is ± 1, the filler and the urethane resin are more preferable in terms of stability, and the solvent used in the dispersion is alcohol It is preferable that it is a kind.

Specific examples of the metal oxide particle dispersion include DH-40 (catalytic chemical company, titanium oxide, tin oxide, and zirconium oxide containing, 30 wt% solids, dispersion solvent methyl alcohol, spherical form, crystal phase, Particle diameters of 5 to 20 nm), and DH-10 (catalytic chemical company, titanium oxide, iron oxide, and silica, solid content 20% by weight, dispersion solvent methyl alcohol, particle size 10 nm), but are not limited thereto. .

The polyurethane aqueous emulsion preferably comprises a polyurethane resin in a particle state such that the primer coating layer is small so as to be transparent, more preferably a polyurethane resin in a particle state having an average particle diameter of 10 to 100 nm. In addition, the polyurethane aqueous emulsion preferably has a solid content of 5% to 40% by weight, and a pH value of 6.5 to 10 is preferred.

Examples of commercially available polyurethane aqueous emulsions include Witcobond W-240 (registered trademark, Witcobond W-240) (manufactured by Witco), Neorez R-9637 (registered trademark, NeoRez R-9637) (manufactured by ICI Resin). , Superflex 107M (registered trademark, Superflex 107M) (manufactured by Daiichi Pharmaceutical Co., Ltd.), and Superflex 105 (registered trademark, Superflex 105) (manufactured by Daiichi Pharmaceutical Co., Ltd.). The above examples are only examples of preferred polyurethane aqueous emulsions, and the present invention is not limited to the above examples.

By using the primer composition for a high refractive lens, it is possible to manufacture a high refractive coating lens having excellent impact resistance and storage stability and less discoloration. The high refractive coating lens of the present invention is a high refractive lens substrate; A high refractive primer coating layer coated on the surface of the high refractive lens substrate; And a hard coating layer coated on the high refractive primer coating layer, wherein the high refractive primer coating layer is prepared from the primer composition for the high refractive lens.

The high refractive coating lens is coated with the high refractive lens primer composition on the surface of the high refractive lens substrate, and then dried to form a high refractive primer layer; And coating a hard coating solution on the surface of the high refractive primer layer, followed by curing to form a hard coating layer.

In this case, the process of coating the primer composition for high refractive lens may be performed according to a conventional method, and may be applied by spray coating or by dipping the lens substrate into the primer composition. In this invention, it is more preferable to use the method of immersion.

The step of drying in the process of forming the high refractive primer layer may proceed to the extent that the primer composition is appropriately dried, preferably at 60 to 130 ℃ for 10 to 120 minutes.

Since the high refractive lens base material and the hard coating liquid used for the manufacture of the high refractive coating lens can be used as they are used for conventional high refractive hard coating lens, it is not particularly limited in the present invention. However, the hard coating solution is preferably used a siloxane-based hard coating solution prepared from an organosiloxane compound.

Forming the hard coating solution is preferably cured for 60 to 240 minutes at 90 to 130 ℃. The drying and curing temperatures and times described in the method of manufacturing the high-refractive coating lens are only intended to represent preferred examples, and the content of the present invention is not limited to the above range.

Hereinafter, preferred embodiments of the present invention are described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited to the following examples.

[Preparation of Primer Composition]

Example 1

(Production of Filler Composition)

In a jacket reactor, 350 g of DH-40 (catalytically oxidized industrial dispersion, pH 3-4, solid content 30 wt%, spherical shape, crystal phase, particle size 5-20 nm) and a ethylene glycol 1 surfactant The filler composition was prepared by adding g and stirring for about 30 minutes and dropwise addition of ammonia water until the pH reached 7.5.

(Preparation of Primer Composition)

In a jacket reactor capable of maintaining a reaction temperature of 25 ° C., Superflex 107M1 (manufactured by Daiichi Pharmaceutical Co., Ltd.) as a polyurethane aqueous emulsion (solid content 25 wt%, pH = 6.5 to 8.5) 101.7 g, methanol 406.7 g, water 406.7 g, and 84.4 g of the filler composition prepared above were added and stirred for about 1 hour, and 0.5 g of a leveling additive Silwet L 7001 (manufactured by Witco) was added to prepare a primer composition having a final pH of 7.5.

Example 2

A primer composition was prepared at the final pH 9.2 in the same manner as in Example 1 except that the filler composition was prepared by adding ammonia water until the pH was 8.5.

Example 3

A primer composition having a pH of 9.2 was prepared in the same manner as in Example 2, except that Superflex 107M, which was a polyurethane aqueous emulsion, was replaced with Superflex 150 (manufactured by Daiichi Pharmaceutical Co., Ltd.) (solid weight 30%, pH = 8.0 to 10). .

Comparative Example 1

A primer composition was prepared in the same manner as in Example 1 except that only DH-40 was used instead of the filler composition.

The storage stability was evaluated by the viscosity change when the primer composition prepared according to Examples 1 to 3, and Comparative Example 1 for 3 months at 25 ℃, the results are summarized in Table 1 below.

The storage stability was visually observed because it was difficult to quantify the degree, and was classified as ○ when the degree of change was slight, △ when there was a small change, and × when there was a significant change.

TABLE 1

Example 1 Example 2 Example 3 Comparative Example 1 pH 7.5 9.2 9.2 6.0 Storage stability ○ ○ ○ ×

As shown in Table 1, the primer composition of the present invention can be seen that the storage stability is superior to the primer composition of Comparative Example 1.

[Manufacture of Coating Lens]

Example 4

The high refractive lens for spectacles (MR-8 manufactured by German, refractive index 1.60) was immersed and coated in the primer composition prepared according to Example 1 without pretreatment, and dried at 60 ° C. for 30 minutes to prepare a primer coating layer.

The coated lens was immersed in a hard coating solution TN-161 (manufactured by LG Chemical), and then coated, and then cured at 120 ° C. for 2 hours to prepare a high refractive coating lens.

Example 5

A high refractive coating lens was prepared in the same manner as in Example 4, except that the primer composition prepared according to Example 2 was used.

Example 6

A high refractive coating lens was prepared in the same manner as in Example 4, except that the primer composition prepared according to Example 3 was used.

Comparative Example 2

A high refractive coating lens was prepared in the same manner as in Example 4, except that the primer composition prepared according to Comparative Example 1 was used.

Comparative Example 3

The high refractive lens for spectacle lenses (MR-8, German Refractive Index 1.60) was coated with a hard coating solution TN-161 (manufactured by LG Chemical) without coating the primer coating layer, and then cured at 120 ° C. for 2 hours. Prepared.

In Examples 4 to 6, Comparative Example 2, and Comparative Example 3 for the high refractive coating lens prepared by the following method was measured the appearance, friction resistance, adhesion, and impact resistance, the results are shown in Table 2 In summary.

-Appearance: The film formed on the high refractive coating lens was visually observed to confirm the occurrence of pinhole or crack.

-Friction resistance: Steel wool (# 0000 steel wool) is horizontally mounted on the tip of a cylinder with a diameter of 25 mm, rotates 5 times with a load of 100 g in contact with the surface of the prepared coating lens, and visually observes the surface. It was. (Circle) when there was no surface damage, (triangle | delta) when there was some surface damage, and (x) when there were many surface damages.

Adhesion: A cross cut cellotape peel test was performed on the surface of the hard coat layer. That is, eleven graduations each cut to the substrate at 1 mm intervals were engraved on the film to make 100 eyes of 1 mm ² area, and then a cello tape was attached and sharply removed. After repeating such an operation three times at one place, it evaluated as (circle) when there was no peeling, (triangle | delta) when the number of peeling eyes was 1-50, and x when the number of peeling eyes was 51-100.

Impact resistance: A steel ball weighing 16.32 g and 24.82 g was set at a height of 131 cm and 154 cm, dropped downward to impinge on the convex surface of the lens, and the impact energy was gradually increased to perform a fracture test. When the lens was broken or cracked, the collision energy amount one step before was expressed as impact collision energy (J). FDA standards require a shock resistance of at least 0.2 J.

TABLE 2

division Example 4 Example 5 Example 6 Comparative Example 2 Comparative Example 3 Exterior ○ ○ ○ Milky severity ○ Friction resistance ○ ○ ○ ○ ○ Adhesion ○ ○ ○ ○ ○ Impact resistance (J) > 0.35 > 0.35 > 0.35 > 0.35 <0.2

As shown in Table 2, it can be seen that the high refractive coating lens prepared from the high refractive lens primer composition of the present invention has excellent friction resistance, adhesion, and impact resistance, and no milky discoloration.

 Primer composition for a high refractive lens of the present invention is excellent in storage stability, and the primer coating layer prepared therefrom is excellent in impact resistance, colorability, and adhesion, high refractive coating lens comprising this is less milky discoloration and no interference phenomenon There is an advantage.

Claims (12)

A filler composition having a pH of 7.0 to 10.0 comprising high refractive metal oxide particles, a surfactant, and a pH adjusting agent; polyurethane aqueous emulsions having a pH of 6.5 to 10.0; Leveling agents; And a solvent, The pH adjusting agent is one or more selected from the group consisting of ammonia water, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, and choline, PH difference between the filler composition and the polyurethane aqueous emulsion is ± 1, Primer composition for a high refractive lens of pH 7.0 to 10.0. delete The method of claim 1, The high refractive metal oxide particles are at least one selected from the group consisting of titanium oxide, tin oxide, zirconium oxide, molybdenum oxide, aluminum oxide, iron oxide, silicon dioxide, cerium oxide, tungsten oxide, antimony oxide, zinc oxide, and beryllium oxide. Primer composition for a high refractive lens comprising a metal oxide. The method of claim 1, The surfactant is a non-ionic surfactant primer composition for a high refractive lens. delete The method of claim 1, The solvent is a primer composition for a high refractive lens of at least one selected from the group consisting of water, alcohols, hydrocarbons, halides, esters, ethers and ketones. The method of claim 1, The primer composition comprises 10 to 90 parts by weight of high refractive metal oxide particles, 0.1 to 1.0 parts by weight of surfactant, 0.1 to 1.0 part by weight of leveling agent, and 500 to 1000 parts by weight of solvent based on 100 parts by weight of polyurethane aqueous emulsion. A primer composition for phosphorus high refractive lens. Mixing the high refractive metal oxide particles, and the surfactant, and adjusting the pH to 7.0 to 10.0 by adding a pH adjusting agent to prepare a filler composition; And Mixing the prepared filler composition with a polyurethane aqueous emulsion, a solvent, and a leveling agent having a pH difference of ± 1 and a pH of 6.5 to 10.0, and adjusting the filler composition to pH 7.0 to 10.0. Method for producing a primer composition for a high refractive lens comprising a. The method of claim 8, wherein the polyurethane aqueous emulsion has a solid content of 5 to 40% by weight. High refractive lens substrates; A high refractive primer coating layer coated on the surface of the high refractive lens substrate; And Hard coating layer coated on the high refractive primer coating layer Including; The high refractive index coating layer is a high refractive coating lens is prepared from the primer composition for a high refractive lens according to any one of claims 1, 3 to 4, or 6 to 7. After coating the primer composition for a high refractive lens according to any one of claims 1, 3 to 4, or 6 to 7 on the surface of the high refractive lens substrate, and dried to form a high refractive primer layer ; And Coating a hard coating solution on the surface of the high refractive primer layer and curing to form a hard coating layer Method for producing a high refractive coating lens comprising a. The method of claim 11, Forming the high refractive primer layer includes the step of drying for 10 to 120 minutes at 60 to 130 ℃, Forming the hard coating solution is a method for producing a high refractive coating lens comprising the step of curing for 60 to 240 minutes at 90 to 130 ℃.