JP2023011060A - Polymerizable composition for optical material, molded object obtained from that composition, and applications thereof - Google Patents

Abstract

To provide a polymerizable composition for an optical material that has excellent handleability (pot life).SOLUTION: The polymerizable composition for an optical material according to the present invention contains: (a) a polyether polyol; (b) a compound represented by the general formula (1) in the figure; and (c) a polymerization reactive compound (excluding the polyether polyol (a)).SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a polymerizable composition for optical materials, a molded article obtained from the composition, and uses thereof.

Plastic lenses are lightweight, hard to crack, and can be dyed, so they are rapidly becoming popular as optical materials for spectacle lenses, camera lenses, etc. So far, lens moldings using various plastic materials have been developed and used. ing.

Typical examples include allyl resins obtained from diethylene glycol bisallyl carbonate or diallyl isophthalate, (meth)acrylic resins obtained from (meth)acrylates, and polythiourethane resins obtained from isocyanate compounds and thiol compounds. .

Patent Document 1 discloses a polymerizable composition for optical materials, which contains a compound having one or more mercapto groups, an aliphatic linear oligomer having a number average molecular weight of 200 or more, and an isocyanate compound. . This document describes that an aliphatic linear oligomer such as polycaptolactonediol functions as a soft segment.

Patent Document 2 discloses a polymerizable composition for optical materials containing a block copolymer, a photochromic compound, a polythiol and a polyiso(thio)cyanate compound.

Patent Document 3 discloses a polymerizable composition for optical materials containing a polyether polyol, a photochromic compound, a polythiol and a polyiso(thio)cyanate compound.

Patent Document 4 describes that p-toluenesulfonic acid or the like has the effect of improving the pot life of polyurethane.

JP 2006-265402 A WO2018/070383 WO2019/117305 U.S. Patent No. 4,877,829

P. Alexandridis, T.A. Hatton/Colloids Surfaces A: Physicochem. Eng. Aspects 96 (1995) 1-46 Phys. Chem. Chem. Phys., 1999, 1, 3331-3334

In the prior arts of Patent Documents 1 to 3, there is room for improvement in handleability (pot life) due to thickening of the polymerizable composition. Patent Document 4 does not describe the use of polyether polyols.

As a result of extensive studies, the present inventors have found that the above problems can be solved by using a combination of a polyether polyol, a compound represented by a given general formula, and a polymerizable compound, and completed the present invention. rice field.

（一般式（１）中、Ｘは炭素原子またはＳ（＝Ｏ）を示す。ｎは０または１を示す。
Ｒ^１はＣ１～Ｃ５のアルキル基、Ｃ１～Ｃ５のハロアルキル基、置換または無置換のフェニル基を示す。
Ｒ^２は水素原子、Ｃ１～Ｃ５のアルキル基、Ｃ１～Ｃ５のハロアルキル基、置換または無置換のフェニル基を示す。
ただし、Ｘが炭素原子であり、かつＲ^１がＣ１～Ｃ５のハロアルキル基である場合を除く。）
［２］ ポリエーテルポリオール（ａ）はポリオキシエチレン鎖を備える化合物を含む、［１］に記載の光学材料用重合性組成物。
［３］ ポリエーテルポリオール（ａ）は下記一般式（ａ）で表される化合物を含む、［１］または［２］に記載の光学材料用重合性組成物。

（一般式（ａ）中、Ｒ_１およびＲ_２は、水素原子あるいは炭素数１～１８のアルキル基を表し、少なくともどちらか一方は水素原子である。複数存在するＲ_１同士は同一または相異なっていてもよく、複数存在するＲ_２同士は同一または相異なっていてもよい。ｍは１５以上５００以下の整数を示す。）
［４］ 化合物（ｂ）は、メタンスルホン酸、ｐ－トルエンスルホン酸、トリフルオロメタンスルホン酸無水物、酢酸、メタンスルホン酸無水物から選択される少なくとも１種を含む、［１］～［３］のいずれかに記載の光学材料用重合性組成物。
［５］ 化合物（ｂ）を１０ｐｐｍ以上含む、［１］～［４］のいずれかに記載の光学材料用重合性組成物。
［６］ 前記ポリイソ（チオ）シアネート化合物が、脂肪族ポリイソ（チオ）シアネート化合物、脂環族ポリイソ（チオ）シアネート化合物、または芳香族ポリイソ（チオ）シアネート化合物である、［１］～［５］のいずれかに記載の光学材料用重合性組成物。
［７］ さらにスズ触媒（ｄ）を含む、［１］～［６］のいずれかに記載の光学材料用重合性組成物。
［８］ さらにフォトクロミック化合物（ｅ）を含む、［１］～［７］のいずれかに記載の光学材料用重合性組成物。
［９］ ［１］～［８］のいずれかに記載の光学材料用重合性組成物を硬化した成形体。
［１０］ ［９］に記載の成形体からなる光学材料。
［１１］ ［９］に記載の成形体からなるプラスチックレンズ。 That is, the present invention can be shown below.
[1] (a) a polyether polyol;
(b) a compound represented by the following general formula (1);
(c) a polyiso(thio)cyanate compound and a polymerizable compound (excluding polyether polyol (a)) containing a difunctional or higher active hydrogen compound;
A polymerizable composition for optical materials, comprising:

(In general formula (1), X represents a carbon atom or S (=O). n represents 0 or 1.
R ¹ represents a C1-C5 alkyl group, a C1-C5 haloalkyl group, or a substituted or unsubstituted phenyl group.
R ² represents a hydrogen atom, a C1-C5 alkyl group, a C1-C5 haloalkyl group, or a substituted or unsubstituted phenyl group.
with the proviso that X is a carbon atom and R ¹ is a C1-C5 haloalkyl group. )
[2] The polymerizable composition for optical materials according to [1], wherein the polyether polyol (a) contains a compound having a polyoxyethylene chain.
[3] The polymerizable composition for optical materials according to [1] or [2], wherein the polyether polyol (a) contains a compound represented by the following general formula (a).

(In the general formula (a), R ₁ and R ₂ represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, at least one of which is a hydrogen atom. Multiple R _1s are the same or different and a plurality of R ₂ may be the same or different, and m represents an integer of 15 or more and 500 or less.)
[4] Compound (b) contains at least one selected from methanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic anhydride, acetic acid, and methanesulfonic anhydride [1] to [3] The polymerizable composition for optical materials according to any one of the above.
[5] The polymerizable composition for optical materials according to any one of [1] to [4], containing 10 ppm or more of the compound (b).
[6] The polyiso(thio)cyanate compound is an aliphatic polyiso(thio)cyanate compound, an alicyclic polyiso(thio)cyanate compound, or an aromatic polyiso(thio)cyanate compound [1] to [5] The polymerizable composition for optical materials according to any one of the above.
[7] The polymerizable composition for optical materials according to any one of [1] to [6], further comprising a tin catalyst (d).
[8] The polymerizable composition for optical materials according to any one of [1] to [7], further comprising a photochromic compound (e).
[9] A molded article obtained by curing the polymerizable composition for optical materials according to any one of [1] to [8].
[10] An optical material comprising the molded article according to [9].
[11] A plastic lens comprising the molded article according to [9].

ADVANTAGE OF THE INVENTION According to this invention, the polymerizable composition for optical materials excellent in handleability (pot life) can be provided.

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below.
The polymerizable composition for optical materials of the present invention is
(a) a polyether polyol;
(b) a compound represented by the general formula (1);
(c) a polyiso(thio)cyanate compound and a polymerizable compound (excluding polyether polyol (a)) containing a difunctional or higher active hydrogen compound;
including.
The polymerizable composition for optical materials of the present invention is excellent in handleability (pot life) due to the inclusion of these components.

[Polyether polyol (a)]
As the polyether polyol (a), known compounds can be used as long as the effects of the present invention can be obtained.

One embodiment of polyether polyol (a) comprises at least one polyether segment and is either a polyester, polycarbonate, poly(meth)acrylate, polyamide, polyethyleneimine, polysiloxane, polysulfide, polyolefin, or polystyrene. It is a block copolymer optionally combined with at least one segment.

Another embodiment of polyether polyol (a) is a linear polyether block copolymer having at least two different segments. The structure of the segment includes divalent organic groups derived from ethylene glycolate, propylene glycolate, butylene glycolate, etc., and divalent organic groups derived from thiolates such as ethanedithiolate, propanedithiolate, etc. A segmented structure can be mentioned.

In another embodiment of polyether polyol (a), the polyether block copolymer is a branched block copolymer such as dendrimers, star block copolymers, graft block copolymers. A branched block copolymer may have at least three branches made by combining at least two different segments.
Examples of the structure of the branched portion include trivalent organic groups derived from glycerol, trioxyethylamine, trioxyethyl(alkyl)ammonium salts, etc., and tetravalent organic groups derived from ethylenediamine, alkylammonium salts, etc. , Tetraoxyethylenediamine, a tetravalent organic group derived from the oxy type of pentaerythritol, etc., a structure having a trivalent or higher organic group such as a hexavalent organic group derived from the oxy type of dipentaerythritol, etc. can be mentioned.

Examples of the polyether include, but are not particularly limited to, polyethylene glycol, polypropylene glycol, polybutylene glycol, and the like.
Said polyesters include, but are not limited to, compositions resulting from the condensation of dicarboxylic acids and diols.
Examples of the dicarboxylic acid include adipic acid, succinic acid, etc., or a combination thereof.

Examples of the diol include ethylene-1,2-diol, butane-1,4-diol, hexane-1,6-diol, propane-1,2-diol, 3-methylpentane-1,5-diol, 2- Methylpropane-1,3-diol, 2,2-dimethylpropane-1,3-diol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, pentane-1,5-diol, heptane-1,7- diols, etc., or combinations thereof.

The polyester may also include polycaprolactone, polybutyrolactone, polyvalerolactone, polylactic acid, polyglycolic acid, or combinations thereof.
Examples of the polycarbonate include, but are not limited to, a composition obtained by condensation of a carbonate and a diol.

Examples of the diol include ethylene-1,2-diol, butane-1,4-diol, hexane-1,6-diol, propane-1,2-diol, 3-methylpentane-1,5-diol, 2- Methylpropane-1,3-diol, 2,2-dimethylpropane-1,3-diol, pentane-1,5-diol, heptane-1,7-diol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene Glycol and the like, or a combination thereof.

Examples of the poly(meth)acrylate include, but are not limited to, methyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, benzyl (Meth)acrylates, phenyl (meth)acrylates, etc., or combinations thereof may be mentioned.

Examples of the polyamide include, but are not limited to, a composition obtained by condensation of a dicarboxylic acid and a diamine.
Examples of the dicarboxylic acid include adipic acid, succinic acid, etc., or a combination thereof. Hexamethylene diamine etc. can be mentioned as said diamine.

The polyamides may also include lactams such as polycaprolactam.
Polyethyleneimine chains, which are polymer chains, include polyethyleneimine chains, polypropionylaziridine chains, polyacetylaziridine chains, polyformylaziridine chains, and the like.

Examples of polysiloxane chains, which are polymer chains, include polydimethylsiloxane chains and polymethylphenylsiloxane chains.
The polysulfides can include polyethylene sulfide chains and the like.
The polyolefins may include polyethylene, polypropylene, etc., or combinations thereof.
The polystyrene can include polystyrene, polystyrene sulfonate, etc., or combinations thereof.

The polyether block copolymers of the present embodiments can preferably form micelles by microphase separation to provide uniformly dispersed nano-sized structures. A micellar structure may be included in the cured polyurethane thermoset or may be formed during the curing process. The morphology of the micelles depends on the nature, concentration, and temperature of the block copolymer and can include, for example, spherical, worm-like, and vesicular.
The micellar structure contributes to useful properties such as improved resin toughness, and also effectively binds functional molecules such as photochromic dyes while maintaining the glass transition temperature, mechanical and optical properties of poly(thio)urethane resins. can be distributed in

In this embodiment, the polyether polyol (a) can contain a compound represented by the following general formula (a).

In general formula (a), R ₁ and R ₂ each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, at least one of which is a hydrogen atom. A plurality of R ₁ 's may be the same or different, and a plurality of R ₂ 's may be the same or different. m represents an integer of 15 or more and 500 or less.

The compound represented by formula (a) may have a weight average molecular weight of 2,000 or more, preferably 5,000 or more, and more preferably 10,000 or more, from the viewpoint of the effects of the present invention. In addition, from the viewpoint of maintaining good transparency of the resin, it can be 20,000 or less, preferably 15,000 or less.

In this embodiment, one or a combination of two or more selected from compounds represented by the general formula (a) can be used as the polyether polyol (a).
As the compound represented by the general formula (a), a compound represented by the following general formula (a-1) can be specifically used.

In general formula (a-1), R ₃ and R ₄ each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, at least one of which is a hydrogen atom. a+c is an integer of 2 or more and 499 or less, preferably 2 or more and 400 or less, and b is an integer of 1 or more and 300 or less, preferably 1 or more and 100 or less. Multiple R ₃ and R ₄ may be the same or different.

Examples of such compounds include the Pluronic series manufactured by BASF. The structures of compounds contained in Pluronics are shown in Non-Patent Document 1.
In addition, the terminal hydroxyl group of the compound represented by the general formula (a) may react with the polymerizable compound (c) such as isocyanate.

In this embodiment, the compound represented by the following general formula (a-2) or the following general formula (a-3) can be used as the compound represented by the general formula (a).

In general formula (a-2), a, b, and c each represent the number of units and are each independently an integer of 3 or more and 300 or less.
Examples of such compounds include the Pluronic series (manufactured by BASF).

In general formula (a-3), a, b, and c each represent the number of units, each independently being an integer of 3 or more and 300 or less.
Examples of such compounds include the Pluronic R series (manufactured by BASF).

The weight average molecular weight of the polyether polyol (a) can be 2,000 or more, preferably 5,000 or more, more preferably 10,000 or more, from the viewpoint of the effects of the present invention. In addition, from the viewpoint of maintaining good transparency of the resin, it can be 20,000 or less, preferably 15,000 or less.

[Compound (b)]
Compound (b) is represented by the following general formula (1).

In general formula (1), X represents a carbon atom or S (=O). When X represents S (=O), two =O bonds to the sulfur atom. n represents 0 or 1;
R ¹ represents a C1-C5 alkyl group, a C1-C5 haloalkyl group, or a substituted or unsubstituted phenyl group. R ² represents a hydrogen atom, a C1-C5 alkyl group, a C1-C5 haloalkyl group, or a substituted or unsubstituted phenyl group.

Substituents for the substituted phenyl group include halogen atoms, hydroxyl groups, carboxyl groups, amino groups, C1-C3 alkyl groups, C1-C3 haloalkyl groups, and the like.

Compound (b) includes at least one selected from methanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic anhydride, acetic acid, and methanesulfonic anhydride.
By including these compounds as the compound (b), it is possible to obtain a polymerizable composition for an optical material which is more excellent in handleability (pot life).

From the viewpoint of the effects of the present invention, the polymerizable composition for optical materials of the present embodiment contains the compound (b) in an amount of 10 ppm or more, preferably 50 ppm or more, more preferably 100 ppm or more.

In the present embodiment, the compound (b) does not include compounds in which X is a carbon atom and R ¹ is a C1-C5 haloalkyl group in general formula (1). Such compounds excluded from compound (b) include trifluoroacetic acid and the like.

[Polymerization-reactive compound (c)]
The polymerization-reactive compound (c) has a polymerizable functional group capable of self-polymerization, copolymerization, or addition polymerization in the presence or absence of additives such as initiators and catalysts added as necessary. A polymerizable compound having at least one is included. Incidentally, the polymerizable compound (c) does not contain the polyether polyol (a).

As the polymerization-reactive compound, known compounds can be used as long as the effect of the present invention can be obtained. (thio)epoxy compounds having one or more, oxetane compounds having one or more oxetanyl groups, thietane compounds having one or more thietanyl groups or having an oxetanyl group and a thietanyl group, a methacryloyloxy group, an acryloyloxy group, a methacryloylthio group , an acryloylthio group, a methacrylamide group, or a (meth)acrylic compound having one or more acrylamide groups, a (meth)allyl compound having one or more methallyl groups or allyl groups, a methacryloyloxy group, an acryloyloxy group, a methacryloylthio group , an alkene compound having at least one polymerizable carbon-carbon double bond group other than an acryloylthio group, a methacrylamide group, or an acrylamide group, an alkyne compound having at least one polymerizable carbon-carbon triple bond group, and a difunctional or higher activity Hydrogen compounds, acid anhydrides having one or more acid anhydride groups, and the like can be mentioned, and one or more compounds selected from these can be used.

These compounds can be selected from conventionally known compounds and used as long as the effects of the present invention can be obtained. For example, the compounds described in International Publication No. 2018/070383 can be used.
In the present embodiment, the polymerizable compound (c) preferably contains the polyiso(thio)cyanate compound and the active hydrogen compound having a functionality of two or more.

Examples of polyiso(thio)cyanate compounds include xylylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6 -bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, hexamethylene diisocyanate, pentamethylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, and dicyclohexylmethane diisocyanate. xylylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, and 2,6-bis(isocyanatomethyl)bicyclo-[ 2.2.1]-heptane.

Examples of bifunctional or higher active hydrogen compounds include poly(thiol) compounds having two or more hydroxy groups or mercapto groups, polyamine compounds having two or more amino groups or secondary amino groups, and poly( Carboxylic acid compounds and the like can be mentioned. Also included are compounds having two or more active hydrogen groups selected from hydroxyl groups, mercapto groups, amino groups, secondary amino groups, carboxyl groups, etc. in one molecule. Two or more active hydrogen groups may be the same or different.

These compounds can be selected from conventionally known compounds and used as long as the effects of the present invention can be obtained. For example, the compounds described in International Publication No. 2018/070383 can be used.

Examples of polyol compounds include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butylene glycol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, ditrimethylolpropane, butanetriol, pentaerythritol, Aliphatic polyols such as sorbitol, triethylene glycol, polyethylene glycol, cyclohexanediol, cyclohexanedimethanol, tricyclo[5.2.1.02,6]decane-dimethanol, and the like;
Dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxybenzene, benzenetriol, biphenyltetraol, pyrogallol, (hydroxynaphthyl)pyrogallol, trihydroxyphenanthrene, bisphenol A, bisphenol F, xylylene glycol, di(2-hydroxyethoxy) Aromatic polyols such as benzene, bisphenol A-bis-(2-hydroxyethyl ether), tetrabromobisphenol A, and tetrabromobisphenol A-bis-(2-hydroxyethyl ether) can be mentioned. In this embodiment, at least one selected from these can be used in combination.

Polythiol compounds include, for example, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9 - trithiundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol tetrakis ( 2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 2,5-bis(mercaptomethyl)-1,4-dithiane, bis(mercaptoethyl) sulfide, 1,1,3,3-tetrakis (Mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane, 1,1,2,2 -tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, tris(mercaptomethylthio)methane, and ethylene glycol bis(3-mercaptopropionate).
Preferably, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane , 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and pentaerythritol tetrakis (3-mercaptopro pionate) is at least one selected from the group consisting of

[Tin catalyst (d)]
The polymerizable composition for optical materials of the present embodiment can further contain a tin catalyst (d) when the polymerizable compound (c) contains a polyiso(thio)cyanate compound and a difunctional or higher active hydrogen compound. .

When the tin catalyst (d) is contained, the polymerizable composition for optical materials tends to increase in viscosity and the pot life tends to be shortened. , It is excellent in the effect of suppressing thickening, and it is possible to improve the pot life while taking advantage of the catalytic performance of the tin catalyst.

Examples of the tin catalyst (d) include dibutyltin dilaurate, dibutyltin dichloride, dimethyltin dichloride, and the like, and they can be used singly or in combination of two or more.
The amount of the tin catalyst (d) used is not particularly limited, but is in the range of 0 to 10 parts by weight per 100 parts by weight of the polymerizable compound (c).

[Photochromic compound (e)]
The polymerizable composition for optical materials of the present embodiment can further contain a photochromic compound (e).

Examples of the photochromic compound (e) include compounds whose absorption characteristics (absorption spectrum) change with respect to light of a specific wavelength. Known photochromic compounds can be used, for example, naphthopyran, chromene, spiropyran, spirooxazine and thiospiropyran, benzopyran, stilbene, azobenzene, thioindigo, bisimidazole, spirodihydroindolizine, quinine, perimidine spiro. Compounds derived from compounds such as cyclohexadienone, viologen, fulgide, fulgimide, diarylethene, hydrazine, aniline, aryldisulfide, arylthiosulfonate, spiroperimidine, triarylmethane, and the like.
In this embodiment, it is preferable to use a naphthopyran derivative as the photochromic compound (e).

(other ingredients)
In the present embodiment, in addition to the components (a), (b) and (c), and the component (d) or component (e) added as necessary, an ultraviolet absorber and an internal release agent , a light stabilizer, a polymerization catalyst, a resin modifier, and the like.

<Method for producing polymerizable composition for optical material>
The polymerizable composition for optical materials of the present embodiment can be obtained by mixing the above components by a conventionally known method.

<Molded article and its use>
In this embodiment, a molded article can be obtained by curing the polymerizable composition for optical materials.

Molded articles having various shapes and optical materials comprising such molded articles can be obtained by changing the shape of the mold when polymerizing the polymerizable composition for optical materials. The molded article of this embodiment can be used as various optical materials by forming a desired shape and including a coat layer and other members formed as necessary.

Examples of optical materials include plastic lenses, light emitting diodes (LEDs), prisms, optical fibers, information recording substrates, and filters. In particular, it is suitable as a plastic lens.
A plastic lens made of the molded article of this embodiment will be described below. A plastic lens can be manufactured as follows.

<Manufacturing method of plastic lens>
The plastic lens of the present embodiment is usually manufactured by a cast polymerization method using the above-described polymerizable composition for optical materials. The method for producing a plastic lens of the present embodiment specifically includes a step of forming a lens substrate by cast-polymerizing a polymerizable composition for optical materials.

In this step, the obtained composition of the present embodiment is injected into a cavity consisting of a glass mold and a gasket or tape, and is polymerized and cured by heating or irradiation with radiation such as ultraviolet rays other than infrared rays. A shaped resin and a plastic lens substrate made of the resin are manufactured. Through this step, the polymerizable reactive compound (c) is polymerized to form a resin, the polymer (a) forms a microphase-separated structure, and the resin, the microphase-separated structure, and the acid (b) A plastic lens substrate consisting of can be obtained.

The polymerization conditions are not limited because the conditions vary greatly depending on the polymerizable composition for optical materials, the type and amount of catalyst used, the shape of the mold, etc. It takes 50 hours.

The lens substrate obtained by releasing from the mold may be subjected to reheating treatment (annealing) as necessary for the purpose of completing polymerization or removing strain due to residual stress.
In the present embodiment, a laminate can be obtained in which a hard coat layer and an antireflection layer are provided in this order on a lens substrate made of a molded body.
From the viewpoint of impact resistance, it is also preferable to provide a primer coat layer between the lens substrate and the hard coat layer.

Examples of coating agents used for the primer layer include polyester-based resins, polyamide-based resins, polyurethane-based resins, epoxy-based resins, phenol-based resins, (meth)acrylic-based resins, polyvinyl acetate-based resins, polyethylene and polypropylene. A coating agent containing a resin such as a polyolefin resin, a copolymer thereof, a modified resin, or a cellulose resin as a main component of a vehicle can be used.

The laminate can be provided with functional coating layers such as a dimming coating layer and an antistatic coating as other layers. In addition, various functions such as dyeing to add fashionability, polishing of the surface and edges, etc., and addition of polarizing film inside or pasting on the surface for the purpose of imparting polarization. Processing or the like for imparting properties may be performed.

Furthermore, for the purpose of improving the adhesion between these functional coating layers and the base material, the surface of the obtained lens base material (molded body) was subjected to corona treatment, ozone treatment, oxygen gas, nitrogen gas, or the like. Physical or chemical treatments such as low-temperature plasma treatment, glow discharge treatment, oxidation treatment with chemicals or the like, and flame treatment can also be applied.

The plastic lens of the present embodiment, which is composed of the molded article or laminate thus obtained, can be used for various lens applications such as spectacle lenses, camera lenses, pickup lenses, Fresnel lenses, prism lenses, and lenticular lenses. Particularly preferred applications among them include spectacle lenses with smooth surfaces, camera lenses, and pickup lenses.

Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than those described above can be employed within the scope that does not impair the effects of the present invention.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these.

In addition, in the following examples, physical properties were measured by the following measuring methods.
・Viscosity: Measured according to JIS K 7117.
・Photochromic properties Measurement method:
・ ΔT% @ 550 nm: Transmittance at 550 nm after irradiating a molded body processed to a thickness of 2 mm at a temperature of 23 ° C for 15 minutes using a USHIO MS-35AAF/FB xenon lamp light source device (illuminance of 50000 lux) was measured, and the amount of change in light transmittance at 550 nm before and after color development was calculated. The larger the amount of change, the higher the light-shielding property during color development.
・Fading speed t1/2 (half-life of color fading): After irradiating the molded body with light for 15 minutes in the same manner as above, the absorbance at 550 nm of the molded body sample after stopping the light irradiation recovers to the intermediate value of the absorbance before and after color development. was measured. This time was defined as the fading half-life. Molded articles with a fast fading half-life are judged to have good dimming performance.

[Example 1]
2.0 parts by weight of polyol L64 (manufactured by Kaneka Corporation) as polyether polyol (a), 0.2 parts by weight of acidic phosphate ester JP-506H (manufactured by Johoku Chemical Industry Co., Ltd.), and methanesulfonic acid as compound (b) (manufactured by Tokyo Kasei Co., Ltd.) and 40.22 parts by weight of meta-xylylene diisocyanate were mixed at room temperature. To this mixture was subsequently added 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9- Trithiundecane and 47.82 parts by weight of a polythiol composition containing 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane are added, and a tin catalyst (d) is added. A polymerizable composition was prepared by adding 10 parts by weight of meta-xylylene diisocyanate in which 0.005 part by weight of dimethyltin dichloride (manufactured by Tokyo Kasei Co., Ltd.) was dissolved. The polymerizable composition was stirred at 20° C., and the viscosity of the polymerizable composition after 1 hour, 3 hours, and 5 hours from immediately after preparation of the polymerizable composition was measured using a Brookfield viscometer (manufactured by Brookfield). and measured. The measurement results are shown in Table-1.

[Reference Example 1, Examples 2 to 15, Comparative Examples 1 to 10]
The polyether polyol (a), the type and amount of compound (b) added, and the amount of tin catalyst (d) added were changed to the values shown in Tables 1 and 2, as described in Example 1. A polymerizable composition was prepared by the method and the viscosity was measured. The measurement results are shown in Table-1 and Table-2.

[Example 16]
0.078 parts by weight of Reversacol Wembley Gray (manufactured by Vivimed) and 0.064 parts by weight of Reversacol Heath green (manufactured by Vivimed) as the photochromic compound (e), and polyol L64 (manufactured by Kaneka) 2 as the polyether polyol (a). .0 parts by weight, 0.2 parts by weight of acidic phosphate ester JP-506H (manufactured by Johoku Kagaku Kogyo Co., Ltd.), 0.05 parts by weight of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) as compound (b), and meta-xylylene 40.22 parts by weight of isocyanate were mixed at room temperature. To this mixture was subsequently added 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9- Trithiundecane and 47.82 parts by weight of a polythiol composition containing 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane are added, and a tin catalyst (d) is added. After preparing a polymerizable composition by adding 10 parts by weight of meta-xylylene diisocyanate in which 0.004 parts by weight of dimethyltin dichloride (manufactured by Tokyo Kasei Co., Ltd.) is dissolved, the polymerizable composition is stirred at 20 ° C. for 1 hour. bottom. The polymerizable composition was filtered through a 1 μm PTFE membrane filter while decompressing at a degree of decompression of 133 to 400 Pa using a vacuum pump, and degassing was performed under reduced pressure with a vacuum pump for 40 minutes while stirring until bubbles disappeared. . The polymerizable composition was injected into a glass mold having a thickness of 2 mm, and the temperature was raised from room temperature to 120° C. in an oven to cure the polymerizable composition to prepare a molded article. The viscosity of the polymerizable composition did not increase rapidly during the preparation of the polymerizable composition, and the polymerizable composition could be injected into the glass mold. Table 3 shows the measurement results of the photochromic properties.

[Example 17]
A molded body was prepared by the method described in Example 16 except that the type and amount of compound (b) added were changed to the values shown in Table 3, and the photochromic properties were measured. The measurement results are shown in Table-3.

The compounds listed in Table-1 to Table-3 are as follows.
PEG2000: polyethylene glycol (weight average molecular weight 2000, manufactured by Sigma Aldrich)
PPG2000: polypropylene glycol (weight average molecular weight 2000, manufactured by Sigma Aldrich)
Polyol L64: block PEG/PPG (manufactured by Kaneka)
DMC: dimethyltin dichloride (manufactured by Tokyo Chemical Industry Co., Ltd.)
MSA: methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
MSANa: sodium methanesulfonate (manufactured by Wako Chemical Co., Ltd.)
MSAA: methanesulfonic anhydride (manufactured by Wako Chemical Co., Ltd.)
Phosphoric acid: Phosphoric acid (manufactured by Wako Chemical Co., Ltd.)
PTSA: p-toluenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
PTSAA: p-toluenesulfonic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.)
Triflic anhydride: trifluoromethanesulfonic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.)
Acetic acid: Acetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
TFA: trifluoroacetic acid (manufactured by Wako Chemical Co., Ltd.)
Reversacol Wembley Gray: Photochromic compound (manufactured by Vivimed)
Reversacol Heath Green: Photochromic compound (manufactured by Vivimed)

From the results of Comparative Examples in Tables 1 and 2, the addition of polyether polyol or both polyether polyol and tin catalyst to the polymerizable composition increases the viscosity of the polymerizable composition. By adding the compound represented by the general formula (1) to the polymerizable composition, it is possible to suppress the viscosity increase of the polymerizable composition, and the optical material has excellent handling properties (pot life). It has become clear that a polymerizable composition for use can be provided.
Further, from the results in Table 3, even when a photochromic compound is added to the polymerizable composition containing the compound represented by the general formula (1) of the present invention, the resulting molded article (photochromic material) has good photochromic properties. It became clear that it showed the characteristic.

Claims (11)

(a) a polyether polyol;
(b) a compound represented by the following general formula (1);
(c) a polyiso(thio)cyanate compound and a polymerizable compound (excluding polyether polyol (a)) containing a difunctional or higher active hydrogen compound;
A polymerizable composition for optical materials, comprising:

(In general formula (1), X represents a carbon atom or S (=O). n represents 0 or 1.
R ¹ represents a C1-C5 alkyl group, a C1-C5 haloalkyl group, or a substituted or unsubstituted phenyl group.
R ² represents a hydrogen atom, a C1-C5 alkyl group, a C1-C5 haloalkyl group, or a substituted or unsubstituted phenyl group.
with the proviso that X is a carbon atom and R ¹ is a C1-C5 haloalkyl group. ) 2. The polymerizable composition for optical materials according to claim 1, wherein the polyether polyol (a) contains a compound having a polyoxyethylene chain. 3. The polymerizable composition for optical materials according to claim 1, wherein the polyether polyol (a) contains a compound represented by the following general formula (a).

(In the general formula (a), R ₁ and R ₂ represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, at least one of which is a hydrogen atom. Multiple R _1s are the same or different and a plurality of R ₂ may be the same or different, and m represents an integer of 15 or more and 500 or less.) The compound (b) according to any one of claims 1 to 3, comprising at least one selected from methanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic anhydride, acetic acid, and methanesulfonic anhydride. Polymerizable composition for optical materials. 5. The polymerizable composition for optical materials according to any one of claims 1 to 4, containing 10 ppm or more of the compound (b). The polyiso(thio)cyanate compound is an aliphatic polyiso(thio)cyanate compound, an alicyclic polyiso(thio)cyanate compound, or an aromatic polyiso(thio)cyanate compound, according to any one of claims 1 to 5. Polymerizable composition for optical materials. 7. The polymerizable composition for optical materials according to any one of claims 1 to 6, further comprising a tin catalyst (d). 8. The polymerizable composition for optical materials according to any one of claims 1 to 7, further comprising a photochromic compound (e). A molded article obtained by curing the polymerizable composition for optical materials according to any one of claims 1 to 8. An optical material comprising the molded article according to claim 9 . A plastic lens comprising the molded article according to claim 9 .