JPH09241336A - Production of optical article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce optical articles while the release from a mold is improved, and improved yields of moldings and cost down can be realized by cast- polymerizing a starting polymerization solution based on a monomer having at least two unsaturations in such a manner that a mold release is previously added to the polymerization solution. SOLUTION: Optical articles are produced by cast-polymerizing a starting polymerization solution based on a monomer having at least two unsaturations in such a manner that a mold release is previously added to the polymerization solution. The unsaturations are desirably radical-polymerizable ones. The monomer having at least two unsaturations desirably contains at least either a thio(meth)acrylate compound or a urethane (meth)acrylate compound. The mold releases are particularly desirably acid phosphoric esters and acid phosphorous esters. The mold release is desirably used in an amount of 50-10,000ppm based on the polymerization solution.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing optical articles such as spectacle lenses, sunglasses lenses and optical lenses, and more particularly to a method for producing optical articles such as plastic lenses suitable for cast polymerization.

[0002]

2. Description of the Related Art A polymerization stock solution containing a monomer having two or more radically polymerizable unsaturated groups as a main component is cast-polymerized,
For the technique of obtaining a plastic lens, see JP-A-64
-31759, JP-A-1-297242, JP-A1-1
85308 and JP-A-60-51706 are known. (In this specification, both one kind of monomer and many kinds of monomer mixture are expressed as a monomer). However, the plastic lens produced by the cast polymerization method is usually produced by a method in which the polymerization stock solution injected into the glass mold is polymerized and solidified by heat or actinic rays, and then released from the mold. When the adhesion to the mold is strong, it is not easy to release the plastic lens from the mold.

Further, as a technique of using a releasing agent in casting polymerization of a thiocarbamic acid ester type plastic lens, there are disclosed in Japanese Patent Laid-Open Nos. 64-45611 and 1-18.
8511, JP-A 1-213601, and JP-A 1-213
602 and the like are known. Thiocarbamic acid ester-based plastic lenses generally have the drawback of low heat resistance.

[0004]

As described above, in the production method using the monomer having two or more radically polymerizable unsaturated groups, cracks, cracks,
There were many problems because the mold was easily damaged. Problems at the time of releasing the mold lead to a decrease in the molding yield and an increase in operating costs, and therefore, improvement is necessary.

The present invention is intended to improve the mold release of an optical article such as a plastic lens from the mold, thereby improving the molding yield and reducing the cost.

[0006]

The inventors of the present invention have accomplished the present invention as a result of studying a manufacturing method for improving the releasability of an optical article such as a plastic lens from a mold.

That is, the present invention is characterized in that a mold release agent is added to a polymerization stock solution when the polymerization stock solution containing a monomer having two or more unsaturated groups as a main component is cast-polymerized. The present invention relates to a method for manufacturing an article.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The monomer having two or more unsaturated groups used in the present invention is preferably a radical-polymerizable one, and includes (meth) acrylic compounds, urethane (meth) acrylate compounds, and allyl compounds. Examples thereof include compounds and vinyl compounds.

The (meth) acrylic compound used in the present invention includes ethylene glycol, diethylene glycol, 2,2-bis-4-hydroxyphenylpropane, 2,2-bis-4-hydroxyethoxyphenylpropane, pentaerythritol, Bis (hydroxyethylthio) ethane, 4,4'-hydroxyphenyl sulfide, 1,4-bis (hydroxyethylenethio) benzene, 1,4-benzenedithiol, 1,4-bis (mercaptomethylene) benzene, 1,4 -Bis (2-mercaptoethylenethio) benzene, 1,4-bis (2-mercaptoethylenethiomethylene) benzene, 1,4-bis (mercaptomethyleneoxy) benzene, 4,4'-thiodithiophenol, 1,6 -Hexanedithiol, 2
-Mercaptoethyl sulfide, 1,2-bis-2-mercaptoethylthioethane, 1,2-bis-2-mercaptoethoxyethane, di-, tri (meth) acrylates such as pentaerythritol tetrathioglycolate, and the like.

The urethane (meth) acrylate compound used in the present invention has one (meth) acryloyl group and one hydroxyl group such as 2-hydroxyethyl (meth) acrylate and xylylenediol mono (meth) acrylate. Examples thereof include compounds in which diisocyanate compounds such as hexamethylene diisocyanate and xylylene diisocyanate have urethane bonds at both ends, and di (meth) acrylates having the following skeleton.

[0011]

Embedded image (In the formula, R is H or CH ₃ , M and Y are aliphatic compound residues, alicyclic compound residues, aromatic compound residues and compound residues having an aromatic ring in the molecule, n Represents an integer of 1 to 20).

Of these, when M is an aliphatic compound residue, typical examples are an alkylene diol having 2 to 10 carbon atoms, a dithiol residue and 2 to 3 carbon atoms, and the number of repeating units. And an alkylene (thio) glycol residue having about 1 to 10 is mentioned. When M is an alicyclic compound residue, typical examples thereof include a cycloalkylene diol having 5 to 10 carbon atoms, a dithiol residue, and both a cycloalkyl compound and a direct chain alkyl compound within its structure. Examples thereof include diols and dithiol residues. Further, when M is an aromatic compound residue or an aromatic compound-containing compound residue, typical examples include those shown below.

[0013]

Embedded image (Wherein L ₁ , L ₂ , L ₃ , L ₄ , L ₅ , L ₆ , L ₇ , L ₈ .L ₉
Represents O or S) Y is a diisocyanate compound residue, and is hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, bis (isocyanatomethyl) cyclohexane, tolylene diisocyanate, di-
Examples thereof include diisocyanate compound residues such as t-butylbenzene diisocyanate.

As the allyl compound used in the present invention, diethylene glycol di (meth) allyl carbonate, 1,4-benzenebis (meth) allyl carbonate, 4,4'-diphenylpropane bis (meth) allyl carbonate, 4, 4′-diphenylsulfone bis (meth) allyl carbonate, 4,4′-bis (hydroxyethoxy) diphenylpropane bis (meth) allyl carbonate, phthalic acid bis (meth) allyl ester, terephthalic acid bis [(meth) allyloxyethyl ester ]ester,
Examples thereof include fumaric acid bis (meth) allyl ester and trimellitic acid tri (meth) allyl ester.

Examples of the vinyl compound used in the present invention include metadivinylbenzene and paradivinylbenzene, which may be used alone or in combination.

Examples of the monomer having two or more unsaturated groups which are particularly preferably used in the present invention include thio (meth) acrylate compounds and urethane (meth) acrylate compounds. Among them, di (meth) acrylate of 1,4-bis (2-mercaptoethylenethiomethylene) benzene and di (meth) acrylate compound having the following structure are preferable.

[0017]

Embedded image (In the formula, R is H or CH ₃ , M and Y are aliphatic compounds, alicyclic compounds, aromatic compounds and compounds having an aromatic ring in the molecule, and n is an integer of 1 to 20. ).
More preferably, M has the following structure.

[0018]

Embedded image (In the formula, L ₈ and L ₉ represent O or S) In the present invention, as a component of the monomer having two or more unsaturated groups, a thio (meth) acrylate compound and / or a urethane (meth) acrylate compound are used. It is preferable that at least one compound is contained. These compounds are effective in obtaining a plastic lens having a higher refractive index.

According to the present invention, the above-mentioned monomer having two or more unsaturated groups is 40% by weight of all monomers used in the cast polymerization.
The above is preferable when it accounts for 50% by weight or more. When the amount of the monomer having two or more unsaturated groups is less than 40% by weight, the heat resistance of the plastic lens tends to be low, and the suitability as a lens tends to be lost.

The monomers having two or more unsaturated groups used in the present invention may be used alone or as a mixture, but other monomers such as styrene, ethylvinylbenzene,
Bromostyrene, α-methylstyrene, phenyl (meth) acrylate, chlorophenyl (meth) acrylate, bromophenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) Acrylate, butyl (meth) acrylate, propyl (meth) acrylate, (meth) acryloylthiobenzene, (meth) acryloylthiomethylbenzene,
It is also possible to use one kind or a mixture of two or more kinds of monofunctional monomers such as (meth) acryloylthioethyloxybenzene and (meth) acryloylthioethylthiobenzene.

Examples of the release agent used for achieving the present invention include a surfactant, an ammonium salt and a phosphorus compound, preferably a fluorine-based nonionic surfactant, a silicone-based nonionic surfactant and an alkyl group. Examples thereof include quaternary ammonium salt, acidic phosphoric acid ester, and acidic phosphorous acid ester. Among them, diisopropyl phosphate, diisopropyl phosphite, dibutyl phosphate, dibutyl phosphite, dioctyl phosphate, dioctyl phosphite, di (meth) acryloyloxyethyl phosphate, di (meth) acryloyloxyethyl phosphite, Monoisopropyl phosphate, monoisopropyl phosphite, monobutyl phosphate, monobutyl phosphite, monooctyl phosphate, monooctyl phosphite, mono (meth) acryloyloxyethyl phosphate, mono (meth) acryloyloxy phosphite Phosphates such as ethyl, phosphites, especially acid phosphite, acid phosphite have high release effect, do not color plastic lens substrate, and reduce the adhesion of hard coat film It is preferably used because it is not allowed.

In order to achieve the present invention, the above-mentioned releasing agent is preferably 50 to 10,000 relative to the polymerization stock solution.
ppm, more preferably in the range of 200 to 6,000 ppm, and used. If the addition amount is less than 50 ppm, the releasing effect becomes weak, and if it exceeds 10,000 ppm, the lens and the mold spontaneously release during polymerization,
A so-called sink-like optical defect tends to be formed on the lens surface.

The releasing agent of the present invention is particularly preferably used in the entire dioptric power range for plus lenses and in the range of 0D to -4.00D for minus lenses. This is because the adhesion between the plastic lens and the mold generally tends to be too strong in the plus lens full power range and the minus lens weakness range.

The polymerization stock solution used in the present invention generally contains a polymerization inhibitor, an antioxidant, an ultraviolet absorber, a bluing dye and the like in addition to the releasing agent, and other additives as required. May be included. Furthermore, the polymerization stock solution used in the present invention, after adding a polymerization initiator against heat and light,
It is poured into a mold and cast-polymerized.

[0025]

The present invention will now be described more specifically with reference to examples.

Example 1 1,4-bis (2-mercaptoethylenethiomethylene)
85% by weight dimethacrylate of benzene, 15 styrene
To the wt% mixture was added 200 ppm di-n-butyl phosphite as a release agent. As a polymerization initiator, 0.2% by weight of benzoyl peroxide was added and stirred well to obtain a polymerization stock solution. This polymerization stock solution was poured into a mold composed of a glass mold and a gasket. Subsequently, the mold containing the polymerization stock solution was heated in a hot air oven at 50 ° C to 120 ° C.
The temperature was raised to 15 ° C over 15 hours, the temperature was maintained at 120 ° C for 3 hours, and then the temperature was lowered to 90 ° C over 2 hours, and a plastic lens having a lens power of -2.00D was cast-polymerized. Table 1 shows the mold release state of the lens after polymerization.
Shown in

Example 2 1,000 pp of di-n-butyl phosphite was used as a release agent.
m, and a plastic lens having a lens power of +4.00 D was cast-polymerized in the same manner as in Example 1. Table 1 shows the mold release state of the lens after polymerization.

Example 3 5,000 pp of di-n-butyl phosphite was used as a release agent.
m, and a plastic lens having a lens power of +8.00 D was cast-polymerized in the same manner as in Example 1. Table 1 shows the mold release state of the lens after polymerization.

Example 4 To a mixture of 70% by weight of 4,4'-thiodithiophenol, 20% by weight of styrene and 10% by weight of α-methylstyrene, 2,000 ppm of trimethylcetyl ammonium chloride was added as a releasing agent. 0.2% by weight of benzoyl peroxide was added as a polymerization initiator to obtain a polymerization stock solution. The obtained polymerization stock solution was cast-polymerized in the same manner as in Example 2. The mold release state from the mold after polymerization is shown in Table 1.

Example 5 1,4-bis (2-mercaptoethylenethiomethylene)
65% by weight of benzene dimethacrylate, styrene 2
0% by weight, 2-hydroxyethyl methacrylate 15
200 ppm of dimethacryloyloxyethyl phosphite was added as a release agent to the mixture of wt%. 0.2% by weight of benzoyl peroxide was added as a polymerization initiator to obtain a polymerization stock solution. The resulting polymerization stock solution was cast-polymerized in the same manner as in Example 1, and the mold release state after polymerization is shown in Table 1.

Example 6 A plastic lens was cast-polymerized in the same manner as in Example 5 except that dimethacryloyloxyethyl phosphite was used as a releasing agent at 3,000 ppm and the lens power was +8.00 D. Table 1 shows the releasing state from the mold after the polymerization.

Example 7 1,4-bis (2-mercaptoethylenethiomethylene)
Mold release to a mixture of 20% by weight of dimethacrylate of benzene, 30% by weight of commercially available divinylbenzene (a mixture of about 55% by weight of divinylbenzene and about 45% by weight of ethylvinylbenzene), 30% by weight of diethylene glycol dimethacrylate and 20% by weight of styrene. As an agent, 2,000 ppm of di-n-butyl phosphate was added. As a polymerization initiator, 0.2% by weight of benzoyl peroxide was added to obtain a polymerization stock solution. The obtained polymerization stock solution was cast-polymerized in the same manner as in Example 1. The releasing state from the mold after the polymerization was good.

Examples 8-10 [2,2-bis (4-hydroxyethoxy-3,5-dibromophenyl) propane mono-terminated monomethacrylate] / [2,2-bis (4-hydroxyethoxy-3,2)
5-dibromophenyl) propane] = 2/1 (molar ratio)
About 90% by weight of compound A having the following structure by reacting a mixture of
A mixture A containing (the rest being a ring having no double bond) was obtained. According to HPLC analysis and GPC analysis of the mixture A, n
Was less than 20.

[0034]

[Chemical 6] Mixture A, 2,2-bis (4-hydroxyethoxy-
3,5-Dibromophenyl) propane dimethacrylate (hereinafter referred to as compound B), commercially available divinylbenzene and styrene were mixed as shown in Table 2, and mono-n-butyl phosphate was added as a release agent. As a polymerization initiator,
0.1% by weight of t-butyl peroxyisobutyrate was added to prepare a polymerization stock solution.

This polymerization stock solution was poured into a mold composed of a glass mold and a gasket. Then, the mold containing the polymerization stock solution is heated in a hot air oven from room temperature to 75 ° C. for 2 minutes.
Cast polymerization was carried out at 75 ° C. for 8 hours, 75 ° C. to 110 ° C. for 4 hours, 110 ° C. for 2 hours, and 110 ° C. to 70 ° C. for 2 hours. Table 2 shows the mold release state of the lens after the polymerization.

Example 11 A mixture of 85% by weight of urethane dimethacrylate and 15% by weight of methyl methacrylate obtained by reacting urethane with 2-hydroxymethacrylate and xylylenediisocyanate in a molar ratio of 2/1 and phosphoric acid as a releasing agent. Diisopropyl 2,000 ppm and 0.1% by weight of t-butylperoxyisobutyrate as a polymerization initiator were added to prepare a polymerization stock solution. In the same manner as in Example 9, a + 4.00D plastic lens was cast-polymerized. The releasing state from the mold after the polymerization was good.

Comparative Example 1 A plastic lens was cast-polymerized in the same manner as in Example 2 except that the releasing agent was not added. Table 1 shows the releasing state from the mold after the polymerization.

Comparative Example 2 A plastic lens was cast-polymerized in the same manner as in Example 4 except that the releasing agent was not added. Table 1 shows the releasing state from the mold after the polymerization.

[0039]

[Table 1]

[Table 2]

[0040]

EFFECTS OF THE INVENTION By adding a mold release agent to the stock solution of polymerization, the mold releasability of an optical article such as a plastic lens from the mold can be improved and the molding yield can be improved.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location B29L 11:00

Claims (12)

[Claims] 1. A method for producing an optical article, wherein a mold releasing agent is added to a polymerization stock solution when the polymerization stock solution containing a monomer having two or more unsaturated groups as a main component is cast-polymerized. Method. 2. The method for producing an optical article according to claim 1, wherein the unsaturated group is a radical-polymerizable unsaturated group. 3. The method for producing an optical article according to claim 1, wherein the monomer having two or more unsaturated groups contains a thio (meth) acrylate compound. 4. The method for producing an optical article according to claim 1, wherein the monomer having two or more unsaturated groups contains a urethane (meth) acrylate compound. 5. The thio (meth) acrylate compound is 1,4-bis (2-mercaptoethylenethiomethylene).
The method for producing an optical article according to claim 3, which is a di (meth) acrylate of benzene. 6. The method for producing an optical article according to claim 4, wherein the urethane (meth) acrylate compound has the following structure. Embedded image (In the formula, R is H or CH ₃ , M and Y are aliphatic compound residues, alicyclic compound residues, aromatic compound residues and compound residues having an aromatic ring in the molecule, n Represents an integer of 1 to 20) 7. The method for producing an optical article according to claim 1, wherein the release agent is a phosphorus compound. 8. The method for producing an optical article according to claim 7, wherein the phosphorus compound is an acidic phosphoric acid ester. 9. The method for producing an optical article according to claim 7, wherein the phosphorus compound is an acid phosphorous acid ester. 10. The method for producing an optical article according to claim 1, wherein the release agent is an ammonium salt. 11. A release agent is added in an amount of 50 to 50 with respect to the polymerization stock solution.
10. Addition of 10,000 ppm
A method for manufacturing an optical article according to item 1. 12. The method for producing an optical article according to claim 1, wherein the optical article is a plastic lens.