JPH03223309A - Production of plastic lens - Google Patents

Abstract

PURPOSE:To produce a high refractive index lens in good yields while preventing it from releasing from the mold by adding a specified compound to the system in cast-polymerizing a polymerizable monomer component essentially consisting of a sulfur-containing polymerizable monomer component in the presence of a polymerization initiator. CONSTITUTION:A process for producing a plastic lens comprising cast- polymerizing a polymerizable monomer component comprising at least one sulfur-containing polymerizable monomer [e.g. a monomer of any one of formu las I-IV (wherein R1 is H, CH3 or Cl; R2 is H or CH3; X1 and X2 are each H or halogen except F; X3 is halogen except F; (n) is 0-4; (m) is 1-4, (l) is 1-4; B is 1-8C (l)-valent alkyl or aryl which may contain an ether, thioether, ester or thioester group; (p) is 0-2; (q) is 1 or 2; and (r) is 0-3)] in the presence of a polymerization initiator, wherein the polymerization is performed after a compound having a sec- or tert- alcoholic hydroxyl group is added to the mono mer component. The hydroxyl groups of the compound added are bonded with the surface of the mold through hydrogen bonding, so that the lens can be prevented from releasing from the mold to improve the yields in molding lenses.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application J] The present invention relates to a method for manufacturing a high refractive index plastic lens.

[Conventional technology]

In recent years, transparent plastics have come to be widely used as optical components such as lenses, prisms, and optical waveguides, mirror components, and decorative components or glazing in fields such as vehicles, ships, and architecture.

In general, plastic optical materials have superior characteristics such as being lightweight and easy to dye compared to Noh-like glass, and are widely used especially in eyeglass lenses that require fashionability. However, diethylene glycol bisallyl carbonate resin, which is widely used as plastic lenses for eyeglasses, has a refractive index of 1.
．． 50, which has the disadvantage that the edge and center thickness of the lens is thicker than lenses made of materials with a high refractive index.

In order to improve the above-mentioned drawbacks, plastic lenses for spectacles using high refractive index resins have been developed. To manufacture plastic lenses from high refractive index resins, vinyl monomers or prepolymers (hereinafter referred to as monomers) containing halogen atoms such as chlorine and bromine atoms, nitrogen and sulfur atoms such as urethane and thiol, or aromatic rings are required. A cast polymerization method is used in which the polymer is injected into a lens mold and polymerized.

However, how to cast-polymerize these monomers to produce high refractive index plastic lenses? The yield of lens molding is poor compared to the case of cast resin.

Generally, the polymerization of these monomers is more difficult to control than the polymerization of allyl carbonate, resulting in distortions remaining in the lens or poor adhesion to the mold, resulting in the lens peeling off from the mold.

[Problem 1 to be solved by the present invention The present invention solves the above problems.

Therefore, an object of the present invention is to provide a method for manufacturing a plastic lens made of a high refractive index resin by casting polymerization of a polymerizable monomer.

[Means and effects for solving the problem] The present inventors
As a result of extensive research in light of the current situation, we have developed a method for manufacturing plastic lenses by adding a polymerization initiator to a polymerizable monomer component, which has a sulfur-containing polymerizable monomer component as an essential component, and performing cast polymerization. The present invention was achieved by discovering that a plastic lens can be obtained at a high yield by adding a compound having a secondary or tertiary alcoholic hydroxyl group to the polymerizable monomer component and polymerizing it late.

That is, the present invention provides a method for producing a high refractive index plastic lens by adding a polymerization initiator to a polymerizable monomer component containing a sulfur-containing polymerizable monomer as an essential component and performing cast polymerization.
The present invention relates to a method for producing a high refractive index plastic lens, which comprises adding and polymerizing a compound having a primary or tertiary alcoholic hydroxyl group.

The sulfur-containing polymerizable monomer used in the present invention is not particularly limited as long as it contains a small number (at least one sulfur atom and a vinyl group polymerizable) in the monomer molecule, but sulfur-containing (meth)acrylic Using esters and their derivatives,
This is preferable because a plastic lens with a high refractive index can be obtained.

A high refractive index plastic lens using the sulfur-containing polymerizable monomer according to the present invention has a higher Atsube number than a high refractive index plastic lens using only an aromatic monomer, and Even when aromatic monomers are used together as the high refractive index imparting monomer component, since the sulfur-containing polymerizable monomer is used, the amount of aromatic monomers used can be reduced. Birefringence is less likely to occur.

Examples of the sulfur-containing polymerizable monomer used in the present invention include vinyl monomers represented by the following general formulas (1) to (4).

General formula (1) % formula % or CHs, n represents an integer of 0 to 4, and m represents an integer of 1 to 4. ) General formula (2) (or CH, X, and X2 are each independently a halogen atom excluding H or F, n is an integer of O to 4, m is 1 to 4
) General formula (3) % Formula % An integer of 4, B represents an alkyl group or aryl group which may contain an 01 to C6 ether, thioether, ester, and thioester with a valence of 2. ) General formula (4) % formula % (halogen atom, p is an integer of O to 2, q is 1 or 2, r is an integer of 0 to 3) General formulas (1) and (2
Since the sulfur-containing polymerizable monomer represented by ) has an alicyclic condensed ring, it has a high refractive index and a very high Abbé number, so it can reduce chromatic aberration.

The sulfur-containing polymerizable monomer represented by the general formula (3) contains sulfur through a thioester group and a sulfide bond, so it has a high sulfur content, and therefore a high refractive index can be easily achieved.

Since the sulfur-containing polymerizable monomer represented by general formula (4) has a thiophene ring, it has a high refractive index by itself, and can easily be used to form plastic lenses with an even higher refractive index by nuclear halogenation. In the present invention, the sulfur-containing polymerizable monomers include general formulas (1) to (
Although one type of 4) may be used, two or more types may be used in combination.

In the present invention, the amount of the sulfur-containing polymerizable monomer in the polymerizable monomer component can be varied over a wide range depending on the desired effect, but is preferably 30% by weight or more in order to obtain a significant effect. An amount of less than 30% by weight, which is desirable, may have a small contribution to the refractive index of the resulting resin.

The present invention relates to a method for manufacturing plastic lenses with a high yield by adding a polymerization initiator to a polymerizable monomer component containing a sulfur-containing polymerizable monomer as an essential component and performing cast polymerization. In general, it is difficult to control the polymerization of vinyl monomers compared to the polymerization of allyl compounds.This is because polymerization generates a large amount of heat, so polymerization may proceed too quickly and the optical properties of the lens may no longer be satisfied. be. Among these, many cases are caused by incomplete transfer of the lens surface due to internal distortion during polymerization and peeling from the lens mold. In the production of high refractive index plastic lenses obtained from a polymerizable monomer component containing a sulfur polymerizable monomer, peeling from the lens mold is prevented and the yield is improved. The compound having a secondary or tertiary alcoholic hydroxyl group according to the present invention forms a hydrogen bond with the surface of the mold, improves the adhesion between the mold and the plastic lens, and improves the molding yield of lenses. .

In the production of a high refractive index plastic lens obtained from a polymerizable monomer component containing a sulfur-containing polymerizable monomer according to the present invention, when using a compound having a primary alcoholic hydroxyl group, it is necessary to The effect of improving the adhesion between the lenses is small, and the molding yield of lenses cannot be improved unless it is added in large amounts.If added in large amounts, the refractive index tends to decrease, and water absorption increases, resulting in clouding under high humidity. , transparency may decrease.

The compound having an alcoholic hydroxyl group used in the present invention is not particularly limited as long as it contains one or more secondary or tertiary alcoholic hydroxyl group in the molecule, but it has a polymerizable functional group in the molecule, for example, It is more preferable to have a carbon-carbon double bond such as a (meth)acryloyl group, allyl group, vinyl group, etc. Specific examples include S-butyl alcohol, t-butyl alcohol, cyclohexyl alcohol, 4-t -Butylcyclohexyl alcohol, 2,2-bis(4-(2-hydroxypropoxy)phenyl]propane, 2,2-bis(4-(2,3-dihydroxypropoxy)phenyl)propane, 2-hydroxypropyl (meth) Acrylate, 2-hydroxybutyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate 2-hydroxy-3-
Phenoxyprobyl (meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, 1,2-bis(2-hydroxy-3-
(meth)acryloyloxypropoxy)ethane, 1.
2-bis(2-hydroxy-3-(meth)acryloyloxypropoxy)propane, 1,3-bis(2-hydroxy-3-(meth)acryloyloxypropoxy)
Propane, 2,2-bis[4-(2-hydroxy-3-
(meth)acryloyloxypropoxy) -3,5-
dibromophenyl]propane, 1,3-bis[(meth)
The compound is a compound having a secondary or tertiary alcoholic hydroxyl group such as acryloyloxy]-2-hydroxyisobutane, and a polymerizable compound containing a secondary or tertiary alcoholic hydroxyl group is more preferable.

The amount of the compound having an alcoholic hydroxyl group used in the present invention can be varied over a wide range depending on the desired effect. The amount is preferably 0.1 to 20 parts by weight. If it is less than 0.1 part by weight, the effect of the addition may not be sufficiently expressed, and if it is more than 20 parts by weight, the adhesion to the lens mold may become too strong and it may not be possible to release it from the mold.

The polymerizable monomer component used in the present invention is a sulfur-containing polymerizable monomer, a compound having an alcoholic hydroxyl group according to the present invention, and if necessary, copolymerized with other sulfur-containing polymerizable monomers. It may also contain possible polymerizable monomers. If necessary, an incyanate compound, a silane coupling agent, a carboxyl compound, an epoxy compound, etc. may be used in combination as an adhesion improving agent, or known additives such as ultraviolet absorbers, anti-hyperoxidants, etc. , a drip-proofing agent, a coloring agent, etc. may be included as appropriate.

[Effects of the present invention] The present invention involves adding a compound having a secondary or tertiary alcoholic hydroxyl group in the production of a plastic lens obtained from a polymerizable monomer component containing a sulfur-containing polymerizable monomer as an essential component. As a result, the hydroxyl group forms a hydrogen bond with the mold surface to prevent peeling from the mold, thereby increasing the molding yield (productivity) of the lens.

[Example] Hereinafter, the present invention will be specifically explained with reference to Examples. In addition, the method of physical property evaluation in Examples is as follows.

[Lens Appearance] The hue, transparency, and optical surface condition were visually observed, and those that were colorless and transparent and had a good surface condition were designated as "good." For other items, their status is described.

"Poor surface condition" indicates that the transfer of the lens surface is incomplete due to early flaking in the furnace.

[Yield] Among the 20 lenses, a good proportion of the optical surfaces were exhibited.

[Refractive index] Measured using an Abbe refractometer according to JIS K7105.

[Heat Resistance] The lenses were placed in a hot air dryer at a predetermined temperature for 2 hours, and deformations such as warp were observed during that time. Those in which no deformation was observed are marked with an O mark.

[Cutting workability] The edges of the lens were polished using a beading machine, and the condition was observed. Those with no cracks, cracks, fusion, etc. are marked with a circle.

Example 1 Bis(2-methacryloylthioethyl) sulfide 50
parts by weight, 40 parts by weight of styrene, 10 parts by weight of acrylonitrile, 5 parts by weight of 3-chloro-2-hydroxypropyl methacrylate, 2,2°-
Azobis(2,4-dimethylisovaleronitrile) 0.
A mixture of 2 parts by weight and 0.1 part by weight of lauroyl peroxide was injected into a cavity formed by two glass molds and a gasket made of soft polyvinyl chloride. After keeping this at 50°C for 5 hours, the temperature was gradually raised to 120°C over 15 hours, and the temperature was further held at 120°C for 30 minutes to carry out polymerization. After cooling, it was released from the mold to obtain a -3.0D lens. The optical surface condition of the obtained lens was good. Furthermore, the evaluation results of the obtained lenses are shown in Table 1.

Examples 2 to 10 and Comparative Examples 1 to 3 Lenses were obtained by repeating the same operations as in Example 1 using polymerizable monomer components having the compositions shown in Table 1. The evaluation results are also shown in Table 1.

Claims (1)

[Claims] 1. A polymerization initiator is added to a polymerizable monomer component containing one or more selected from sulfur-containing polymerizable monomers, followed by cast polymerization to produce a plastic lens. A method for producing a plastic lens, characterized in that a compound having a secondary or tertiary alcoholic hydroxyl group is added to the polymerizable monomer component and polymerized. 2. The sulfur-containing polymerizable monomer has the following general formulas (1) to (4)
The manufacturing method according to claim 1, wherein one or more types selected from the group consisting of: (Note) General formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R_1 is H, CH_3 or Cl, R_2 is H
or CH_3, n is an integer of 0 to 4, and m is an integer of 1 to 4. ) General formula (2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R_1 is H, CH_3 or Cl, R_2 is H
Or CH_3, X_1 and X_2 are each independently H
or a halogen atom excluding F, n is an integer of 0 to 4, and m is an integer of 1 to 4. ) General formula (3) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R_1 is H, CH_3 or Cl, l is 1 to 4
, B represents an alkyl group or an aryl group which may contain a C_1 to C_6 ether, thioether, ester, or thioester with a valence of 1. ) General formula (4) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R_1 is H, CH_3 or Cl, X_3 is F
p is an integer of 0 to 2, q is 1 or 2, and r is an integer of 0 to 3. 3. The manufacturing method according to claim 1 or 3, wherein the amount of the sulfur-containing polymerizable monomer in the polymerizable monomer component is 30% by weight or more. 4. The production method according to any one of claims 1 to 3, wherein the polymerizable monomer component comprises a sulfur-containing polymerizable monomer and another radically copolymerizable monomer [II]. 5. The polymerizable monomer [II] is styrene, styrene derivative, unsaturated nitrile, (meth)acrylic acid ester, (meth)allyl ester, allyl carbonate, allyl ether, epoxy (meth)acrylate, polyester (
5. The manufacturing method according to claim 4, wherein the monomer is one or more polymerizable monomers selected from the group consisting of meth)acrylate and urethane(meth)acrylate. 6. Claim 5 in which styrene and/or styrene derivatives are used as the polymerizable monomer [II] in an amount of 1 to 70% by weight.
Manufacturing method described. 7. The manufacturing method according to claim 5, wherein unsaturated nitrile is used as the polymerizable monomer [II] in an amount of 0.5 to 40% by weight in the polymerizable monomer component. 8. The manufacturing method according to claim 5, wherein (meth)acrylic acid ester is used as the polymerizable monomer [II] in an amount of 1 to 50% by weight based on the polymerizable monomer component. 9. As the polymerizable monomer [II], one or more selected from the group consisting of (meth)allyl ester, allyl carbonate, and allyl ether are added in an amount of 0.1 to 30% by weight in the polymerizable monomer component. 6. The method according to claim 5, wherein the method is used in an amount of %. 10. As the polymerizable monomer [II], one or more selected from the group consisting of epoxy (meth)acrylate, polyester (meth)acrylate, and urethane (meth)acrylate are included in the polymerizable monomer component. 6. The method according to claim 5, wherein the method is used in an amount of 1 to 50% by weight. 11. The amount of the compound having a secondary or tertiary alcoholic hydroxyl group added is 0.1 to 20 parts by weight per 100 parts by weight of the polymerizable monomer component.
The manufacturing method according to any one of claims 1 to 10, wherein the amount is parts by weight. 12. The manufacturing method according to claims 1 to 11, wherein at least one of the alcoholic hydroxyl groups is a secondary alcohol hydroxyl group.