JP3064040B2 - Eyeglass lens manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to spectacles made of an acrylic resin having a cured film having high hardness and excellent adhesion on the surface.
The present invention relates to a method for manufacturing a lens .

[0002]

2. Description of the Related Art Transparent plastics, especially acrylic resins typified by methyl methacrylate polymer, have good transparency, light weight, and are easy to process because of their characteristics. Are used in various fields as optical elements such as prisms. However, acrylic resins generally have insufficient surface hardness, so that the surface is coated as necessary to form a hardened film to solve this problem. For the surface cured film, a method using an organopolysiloxane-based, polyfunctional acrylate-based, or amino resin-based curing liquid is known. Among them, when the base material is an acrylic resin, a polyfunctional acrylate-based curing liquid is used. The method used is dominant.
However, when using a multifunctional acrylate-based curing liquid, it is common to use strong ultraviolet rays during curing, but dyes, infrared absorbers, photochromic substances, etc. are added to the base material or cured film in order to increase product value. In the case of curing, the effect is diminished by ultraviolet irradiation during curing, it is easy to disappear,
There is a problem that the base material or the cured film turns yellow and deteriorates. Therefore, it is known to use an organopolysiloxane-based curing liquid for these improvements. JP-A-61-166824 discloses a coating composition comprising a hydrolyzate of an organosilicon compound, an epoxy resin compound and an epoxy curing agent as an example of using an organopolysiloxane-based curing liquid as the acrylic resin. ing.

[0003]

However, the coating film obtained from the organopolysiloxane-based composition disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 61-166824 has insufficient surface hardness. Poor abrasion resistance to excessive cleaning and contact. Thus, when a metal colloid, which is a general wear resistance improver, is added to this organopolysiloxane composition, the film hardness is improved, but the adhesion to the base resin is significantly reduced. Was. This trend is
When the crosslinking density of the base resin is increased in order to improve the strength, heat resistance, solvent resistance, etc., it becomes more remarkable.

[0004] Further, as a method for improving the adhesion between the base resin and the cured film, general methods include a method in which the base resin is previously treated with a chemical such as an acid or an alkali, and a method in which the base resin is plasma-treated. And a method of providing a primer layer between the base resin and the cured film. However, in order to overcome such drawbacks of the acrylic resin and to sufficiently adhere the cured film, conventional treatment with an acid or alkali or plasma treatment alone is completely insufficient, and a method of providing a primer layer is the only method. It was an effective method.

However, in this method, coating, drying and heat curing must be performed for each of the primer layer and the cured film, and the process is complicated, and the greatest problem is that the chance of contamination by foreign matters increases during that time. And there were some aspects that were not practical.

The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to manufacture a spectacle lens having a polyorganosiloxane-based cured film having excellent surface hardness and excellent adhesion to a substrate. It is to provide a method.

[0007]

The method for producing a spectacle lens according to the present invention, which achieves the above object, comprises the following steps (1) and (2).
And (3). (1) A step of casting a monomer mixture containing the following components (a) and (b) as main components to obtain a plastic molded article. (A) at least one methacrylic monomer selected from a monofunctional methacrylate and a polyfunctional methacrylate; (b) at least one selected from (meth) acrylic acid and a hydroxyl group-containing (meth) acrylate (2) The plastic molded article obtained in the step (1)
A step of performing a plasma treatment under a non-polymerizable gas atmosphere ; (3) A coating composition containing the following components (c) and (d) as main components is applied to the plastic molded body subjected to the plasma treatment in the step (2), and cured to form a cured film, thereby forming an eyeglass lens . The step of obtaining. (C) an organosilicon compound having a silanol group and an epoxy group, and (d) colloidal silica. As described above, the method for manufacturing a spectacle lens of the present invention includes the steps (1), (2) and (3). These steps will be described sequentially.

Step (1) Step (1) is a step of casting a monomer mixture containing the components (a) and (b) as main components to obtain a plastic molded product. The reason for using the methacrylic monomer as the component (a) as the monomer is to realize the excellent optical properties of the acrylic resin, such as high transparency and high Abbe number, of the obtained spectacle lens . In addition, as the methacrylic monomer of the component (a), at least one selected from monofunctional methacrylates and polyfunctional methacrylates is used. Examples of the monofunctional methacrylate include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, ethylhexyl methacrylate, benzyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, adamantyl methacrylate, and the like. Examples of the polyfunctional methacrylate include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate,
Examples include 1,6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, glycerin dimethacrylate, and the like. The preferred content of the methacrylic monomer of the component (a) is 30 to 95% by weight, more preferably 40 to 95% by weight, based on the total monomer mixture. If the amount of these monomers is less than 30% by weight of the total monomer mixture, problems such as the inability to obtain excellent transparency and light resistance inherent in the acrylic resin and insufficient strength arise.
If it exceeds 5% by weight, the content of the component (b), which is a monomer having a hydrophilic group, is relatively reduced, so that the improvement of the adhesion to the cured film becomes insufficient.

As the hydrophilic monomer as the component (b), at least one selected from (meth) acrylic acid and a hydroxyl group-containing (meth) acrylate ester is used. In this specification, “(meth) acrylic acid” means both “acrylic acid” and “methacrylic acid”.
Examples of these include acrylic acid, methacrylic acid, hydroxyethyl ester of acrylic acid or methacrylic acid,
Chlorohydroxypropyl ester of acrylic acid or methacrylic acid; The preferred content of these monomers is from 5 to 50% by weight, more preferably from 5 to 30% by weight, based on the total monomer mixture. When the amount of these monomers is less than 5% by weight of the total monomer mixture, the improvement in adhesion to the cured film becomes insufficient, and when the amount exceeds 50% by weight, the water absorption becomes large and the physical properties of the resin surface become poor. Become unstable, rough,
Pocking and the like are likely to occur. In addition, the mold releasability at the time of shaping is deteriorated, and problems such as difficulty in obtaining good transferability and difficulty in shaping occur, which is not preferable as an optical element.

In the present invention, other monomers copolymerizable with these monomers can be added as long as the effects of the present invention are not impaired. Examples of such monomers include methyl acrylate, ethyl acrylate, n-butyl acrylate, ethylhexyl acrylate, sirohexyl acrylate, benzyl acrylate, phenyl acrylate, isobornyl acrylate, ethylene glycol diacrylate, triglycol Ethylene glycol diacrylate, 1,6-
Acrylates such as hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, styrene, methylstyrene, dimethylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, p-chloromethylstyrene, divinylbenzene, etc. Examples include nuclear-substituted styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, maleic anhydride, and N-substituted maleimide.

In the step (1), a cast molding method is used for producing a plastic molded article . In terms of polymerization energy, ultraviolet curing polymerization and radiation curing polymerization are also used,
Usually, thermosetting polymerization is employed. That is, this is a method in which an appropriate amount of a polymerization initiator is added to the monomer mixture, the mixture is injected into a mold, and heat polymerization is performed. As the polymerization initiator at this time,
Azo initiators such as 2'-azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile) can be suitably used. Benzoyl peroxide, lauroyl peroxide, t-butylperoxy-2-
A peroxide-based initiator such as ethylhexanoate can be used, but a dye, an infrared absorber, or the like, whose effect is reduced or easily eliminated by a peroxide-based initiator, is added to the base material. In such a case, it is better to use an azo initiator.
These initiators are usually used in an amount of 0.001 to 5.0 based on the total amount of the monomers.
It is preferable to use it in the range of weight%. The heating polymerization temperature varies depending on the initiator used, but is usually 20 to 80.
It is in the range of ° C.

Further, in addition to the above, a small amount of a heat stabilizer, an antioxidant, an ultraviolet absorber, a release agent, an antistatic agent and the like can be contained in the plastic molded article, if necessary. Step (2) The plastic molded body obtained in step (1) is subjected to a plasma treatment in a non-polymerizable gas atmosphere in step (2). This plasma treatment improves the adhesion between the plastic molded body obtained in step (1) and the cured film provided in step (3). The plasma treatment is carried out under an atmosphere of 0.01 to 10 Torr of a non-polymerizable gas such as air, helium, argon, hydrogen, oxygen, or nitrogen, although the conditions slightly vary depending on the size, type, and shape of the apparatus used. 60
Done within seconds.

Step (3) The plastic molded body that has been subjected to the plasma treatment in step (2) is desirably applied with a coating composition and cured in step (3) within 24 hours to form a cured film.

The coating composition used in the present invention comprises an organosilicon compound having a silanol group and an epoxy group in the molecule [component (c)], colloidal silica [component (d)].
It is necessary to include As the component (c), an organosilicon compound having at least two silanol groups and at least one epoxy group in the molecule is preferable.

[0015]

Embedded image

(Wherein R ¹ is an alkyl group having 1 to 4 carbon atoms and R ² is an alkylene group having 1 to 4 carbon atoms) obtained by hydrolyzing a trifunctional organosilicon compound represented by the formula: Hydrolyzate. R ¹ in the formula is a methyl group,
More preferably, they are an ethyl group, a propyl group or a butyl group, and R ² is a methylene group, an ethylene group, a propylene group or a butylene group.

On the other hand, as the colloidal silica as the component (d), a high-concentration water-dispersed colloidal silica (for example, a SiO ₂ solid content of 40% Above) are preferably used. The average particle diameter is preferably in the range of 5 to 100 mμ, and more preferably 5 to 30 mμ. By using an organopolysiloxane-based coating composition containing a high concentration of colloidal silica, a cured film having higher hardness can be obtained. Therefore, the coating composition used in the present invention exhibits its usefulness when it contains a high concentration of colloidal silica. In that sense, in the present invention, the amount of colloidal silica in the coating composition is preferably set to 55 to 90 mol% (in terms of SiO ₂ solid content) based on the total amount of colloidal silica and the organosilicon compound. The preferred range is 75-9
0 mol%.

A curing agent is usually used, and examples thereof include an imidazole derivative, and an acetylacetone metal complex compound, particularly an acetylacetone aluminum complex compound, is particularly effective. The amount of addition is sufficient to cure the colloidal silica and the hydrolyzate of the organosilicon compound, that is, 1 to 10 g per 1 mol of the total of the hydrolyzate of the colloidal silica (in terms of SiO ₂ ) and the organosilicon compound. It is preferred that

An organic acid is used for the hydrolysis of the organosilicon compound of the formula (I). These include formic acid, acetic acid, propionic acid and the like, but it is preferable to use acetic acid in view of the stability of the coating composition. The addition amount of the organic acid is preferably 5 to 30 g based on 1 mol of the total amount of the colloidal silica and the organosilicon compound. If the amount is less than this, gelling of the coating composition is apt to occur, and if it is more than this, odor becomes strong, which is not preferable in work.

Further, in order to make the hydrolysis uniform and to adjust the degree thereof appropriately, it is preferable to add an appropriate solvent to the coating composition. As such a solvent, cellosolves such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve are preferable, and a combination with isopropyl alcohol, butanol and the like is more preferable. The proportion of cellosolve is preferably at least 3% by weight of the total solvent amount, particularly preferably at least 10% by weight. When the proportion of colloidal silica is large, gelation tends to occur during preparation of the coating composition when the proportion of cellosolve in the solvent is less than 3% by weight of the total solvent.

[0021] To the coating composition used in the present invention, a silicone surfactant may be added for the purpose of improving the smoothness of the coating film. Further, an ultraviolet absorber, an antioxidant and the like can be added for the purpose of improving light resistance or preventing deterioration of the coating film.

The coating composition can be applied to a plastic molded product by a dipping method, a spin coating method, a roll coating method, a spraying method or the like. Curing of the applied coating composition is performed by heat treatment, and the heating temperature is preferably from 40 to 150 ° C, particularly preferably from 80 to 130 ° C. The heating time is preferably 1 to 4 hours. The cured film obtained after application and curing of the coating composition has excellent adhesion to the plastic molded body because the plastic molded body is subjected to the plasma treatment in the step (2). After forming the cured film, the cured film may be coated by vapor deposition.

[0023]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. In addition, the method of the physical property evaluation in an Example and a comparative example is as follows.

(A) Surface Hardness The surface was rubbed 50 times (reciprocating) with steel wool # 0000 and an additional load of 1000 g, and the degree of scratch resistance was determined according to the following criteria. A: Almost no damage. B: Very slightly scratched. C: Slightly scratched. D: Many scratches are made.

(B) Adhesiveness The surface of the cured film was cut into squares (1 × 10) at 1 mm intervals, and a cellophane adhesive tape (No.
405) was strongly adhered, and the number of goban eyes remaining after being peeled off sharply in the direction of 90 degrees was examined.

(C) Appearance Transparency, colored state, surface state, etc. were examined with the naked eye.

[Preparation of Coating Composition] Colloidal silica having a SiO ₂ concentration of 40% (Snowtex-40,
Water-dispersed silica, average particle size of 10 to 20 mμ, manufactured by Nissan Chemical Co., Ltd.
95 parts by weight of γ-glycidoxypropyltrimethoxysilane (trifunctional organosilicon compound) was added dropwise while stirring the solution containing 20 parts by weight of acetic acid at 35 ° C., and the mixture was stirred at room temperature for 8 hours, and then allowed to stand for 16 hours. . This hydrolysis solution 32
To 0 parts by weight, 80 parts by weight of methyl cellosolve, 120 parts by weight of isopropyl alcohol, 40 parts by weight of butyl alcohol, 16 parts by weight of aluminum acetylacetone, 0.2 part by weight of a silicone surfactant, and 0.1 part by weight of an ultraviolet absorber are added. After stirring for 8 hours, the mixture was aged at room temperature for 24 hours to obtain a coating composition. This is designated as coating composition (A). At this time, the amount of colloidal silica in the coating composition was 80% based on the total amount of colloidal silica and γ-glycidoxypropyltrimethoxysilane.
mol% (in terms of SiO ₂ solid content).

A coating composition (B) was obtained in the same manner as in the preparation of the coating composition (A) except that the amount of γ-glycidoxypropyltrimethoxysilane was changed to 67 parts by weight. At this time, the amount of colloidal silica in the coating composition was 85 mol% based on the total amount of colloidal silica and γ-glycidoxypropyltrimethoxysilane.
(In terms of SiO ₂ solid content).

The coating composition (C) was prepared in the same manner as in the preparation of the coating composition (A) except that the amount of γ-glycidoxypropyltrimethoxysilane was changed to 253 parts by weight.
I got At this time, the amount of the colloidal silica in the coating composition was 60 mol based on the total amount of the colloidal silica and γ-glycidoxypropyltrimethoxysilane.
% (In terms of SiO ₂ solid content).

Ion-exchanged water 1 instead of colloidal silica
A coating composition (D) was obtained in the same manner as in the preparation of the coating composition (A) except that 20 parts by weight was used.

Example 1 20 parts by weight of methacrylic acid, 20 parts by weight of ethylene glycol dimethacrylate, 0.30 part by weight of an azobis radical polymerization initiator (azobisisobutyronitrile), 60 parts by weight of methyl methacrylate, ultraviolet rays Absorbent (Tinuvin P manufactured by Ciba Geigy) 0.0
5 parts by weight, release agent (Shin-Etsu Silicone K, manufactured by Shin-Etsu Chemical Co., Ltd.)
F353A) 0.01 part by weight was added and mixed and dissolved. This mixture was poured into a mold composed of two glass molds and a plastic gasket, placed in a hot-air circulation heating furnace, heated at 50 ° C. for 12 hours, and then heated to 85 ° C. over 4 hours. The mixture was heated for 2 hours to carry out polymerization. The polymer obtained by removing the mold was a highly transparent plastic molded article forming a meniscus lens having a diameter of 75 mm, a thickness of 2.0 mm, and a power of 0.00 diopter. This was further heated at 120 ° C. for 2 hours for annealing.

The plastic molded body was subjected to a plasma treatment for 1 second under an atmosphere of 0.6 Torr nitrogen using PR-501A manufactured by Yamato Scientific Co., Ltd.

Subsequently, the coating composition (A) was applied by a dipping method (pulling speed: 20 cm / min), and this was heated and cured at 120 ° C. for 90 minutes to form a cured film.

The evaluation results of the thus-obtained spectacle lens with a cured film were excellent in surface hardness, adhesion and appearance as shown in Table 1.

Examples 2 to 10 In the same manner as in Example 1 except that the plasma treatment conditions shown in Table 1 and the coating compositions (A), (B) and (C) containing SiO ₂ were used. Thus, a spectacle lens with a cured film was produced and evaluated in the same manner. The results were excellent as shown in Table 1. [Comparative Examples 1 to 3] A spectacle lens with a cured film was produced in the same manner as in Example 1 except that the plasma treatment conditions shown in Table 1 and the coating composition (D) containing no SiO ₂ were used (Comparative Examples 1 to 3). Example 1). The obtained without plasma treatment, coating composition comprising SiO ₂ (A) and SiO ₂ and contained no coating composition (D) a cured film with a spectacle lens in the same manner as in Example 1, except that the catalyst, respectively (Comparative Example 2
And Comparative Example 3). These evaluation results were inferior in film hardness and adhesion as shown in Table 1. [Comparative Examples 4 to 6] A spectacle lens with a cured film in the same manner as in Example 1 except that the chemical treatment shown in Table 1 was performed instead of the plasma treatment.
And a similar evaluation was performed. The results were inferior in film hardness and adhesion as shown in Table 1.

[0036]

[Table 1]

[Examples 11 to 16] The hydrophilic monomers as the component (b) in the monomer mixture were listed in the following Table.
A spectacle lens with a hardened film was produced in the same manner as in Example 1 except that it was changed as in Example 2, and the evaluation was performed in the same manner. The results were excellent in surface hardness, adhesion and appearance as shown in Table-2.

[0038]

[Table 2]

[Examples 17 to 24] Except that the composition of the monomer mixture was changed as shown in Table 3, a spectacle lens with a cured film was produced in the same manner as in Example 1 and evaluated in the same manner. . The results are as shown in Table-3, surface hardness,
Both the adhesion and the appearance were excellent.

Comparative Example 7 A spectacle lens was prepared and evaluated in the same manner as in Example 1, except that the composition of the monomer mixture was changed as shown in Table 3. As a result, when the composition of the monomer mixture did not satisfy the requirements of the present invention, the film hardness and adhesion were poor as shown in Table-3.

[0041]

[Table 3]

Example 25 0.06 parts by weight of a near-infrared absorbing agent (SIR-114, manufactured by Mitsui Toatsu Dye Co., Ltd.) was added to the monomer mixture of Example 1,
Thereafter, a spectacle lens was manufactured in the same manner as in Example 1. this
The spectacle lens has a surface hardness of A and a cured film adhesion of 100/10
It was excellent as 0 and selectively absorbed light having a wavelength of 650 to 780 nm, so that it could be suitably used as a lens for laser protective glasses.

As can be seen from these examples, according to the present invention, it is possible to give a good cured film having an extremely high hardness and excellent adhesion to the acrylic resin. On the other hand, as can be seen from the comparative example, the spectacle lens , a requirement constituting the present invention, that is, the base resin composition, the plasma treatment, if any of the coating composition is inappropriate or missing, good
Eyeglass lenses are not available. In addition, the present invention can exert its effects by using it for a functional lens as in the twenty-fifth embodiment.

[0044]

According to the present invention, a cured film having extremely high hardness and high durability, which has been mainly used for diethylene glycol bisallyl carbonate resin, can be sufficiently adhered to the acrylic resin. In addition, according to the present invention, contamination due to foreign matter in the process via a primer layer, which is a problem of the conventional method, can be reduced to half, which is extremely practical.

Continuation of the front page (51) Int.Cl. ⁷ identification code FI G02B 1/10 G02B 1/10 Z (58) Field surveyed (Int.Cl. ⁷ , DB name) G02B 1/00-3/14 G02C 1 / 00-13/00 C08F 6/00-264/00

Claims (1)

(57) [Claims] 1. The following steps (1), (2) and (3)
A method for manufacturing a spectacle lens , comprising: (1) A step of casting a monomer mixture containing the following components (a) and (b) as main components to obtain a plastic molded article. (A) at least one methacrylic monomer selected from a monofunctional methacrylate and a polyfunctional methacrylate; (b) at least one selected from (meth) acrylic acid and a hydroxyl group-containing (meth) acrylate (2) The plastic molded article obtained in the step (1)
A step of performing a plasma treatment under a non-polymerizable gas atmosphere ; (3) A coating composition containing the following components (c) and (d) as main components is applied to the plastic molded body subjected to the plasma treatment in the step (2), and cured to form a cured film, thereby forming an eyeglass lens . The step of obtaining. (C) an organosilicon compound having a silanol group and an epoxy group, and (d) colloidal silica.