JP2023011059A - 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) and can provide a molded object excellent in shock resistance and dyeability.SOLUTION: The polymerizable composition for an optical material according to the present invention contains: at least one polyol compound (a) selected from (a1) polyether polyols and (a2) polyester polyols; an acid (b) having a pKa less than 0; and a polymerization reactive compound (c) (excluding the polyol compound (a)) including a polyiso(thio)cyanate compound and an at least difunctional active hydrogen compound.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.

JP 2006-265402 A WO2018/070383 WO2019/117305

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

In general, plastic lenses are required to have excellent impact resistance in order to prevent cracking due to impact such as dropping. However, the improvement in impact resistance sometimes lowers the dyeability, and there is a trade-off relationship between the improvement in impact resistance and the improvement in dyeability.
In Patent Documents 1 to 3, there is room for improvement in both impact resistance and dyeability. Furthermore, the polymerizable composition obtained by mixing each component may have a fast thickening speed after mixing, and there is room for improvement in handleability (pot life).

As a result of intensive studies, the present inventors have found that the above problems can be solved by using a combination of a polyol compound, a polymerization-reactive compound other than the polyol compound, and an acid having a predetermined pKa value. perfected the invention.

（一般式（ａ１）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。）
［５］ ポリエステルポリオール（ａ２）は下記一般式（ａ２）で表される化合物を含む、［１］～［４］のいずれかに記載の光学材料用重合性組成物。

（一般式（ａ２）中、Ｑは、ジオールから誘導される２価の基、または少なくとも３つの第１級アルコール基を有するポリオールから誘導される３～３０価の基を表し、ｍは３～１０の整数を示し、ｎは２～２００の整数を示し、複数存在するｎの数は同一でも異なっていてもよい。ｑは２～３０の整数を示す。）
［６］ 酸（ｂ）を２００ｐｐｍ以上含む、［１］～［５］のいずれかに記載の光学材料用重合性組成物。
［７］ 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］～［６］のいずれかに記載の光学材料用重合性組成物。
［８］ さらに内部離型剤（ｄ）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］ さらにスズ触媒（ｅ）を含む、［１］～［８］のいずれかに記載の光学材料用重合性組成物。
［１０］ さらにフォトクロミック化合物（ｆ）を含む、［１］～［９］のいずれかに記載の光学材料用重合性組成物。
［１１］ ［１］～［１０］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。
［１２］ ポリオール化合物（ａ）のミクロ相分離構造体を含む、［１１］に記載の成形体。
［１３］ 前記ミクロ相分離構造体の平均粒径は１～５０ｎｍである、［１２］に記載の成形体。
［１４］ ［１０］～［１３］のいずれかに記載の成形体からなるレンズ基材と、
ハードコート層と、
反射防止層と、
をこの順で備える、積層体。
［１５］ 前記レンズ基材と前記ハードコート層との間に、プライマーコート層を備える、［１４に記載の積層体。
［１６］ ［１１］～［１３］のいずれかに記載の成形体または［１４］または［１５］に記載の積層体からなる光学材料。
［１７］ ［１１］～［１３］のいずれかに記載の成形体または［１４］または［１５］に記載の積層体からなるプラスチックレンズ。
［１８］ （ａ）ポリエーテルポリオール（ａ１）およびポリエステルポリオール（ａ２）から選択される少なくとも１種のポリオール化合物と、（ｂ）ｐＫａが０未満の酸と、（ｃ）ポリイソ（チオ）シアネート化合物および二官能以上の活性水素化合物を含む重合反応性化合物（ポリオール（ａ）を除く）と、を含む、光学材料用重合性組成物の製造方法であって、
前記ポリイソ（チオ）シアネート化合物と、ポリオール化合物（ａ）と、ｐＫａが０未満の酸（ｂ）と、を混合する工程と、
前記工程で得られた混合液に、二官能以上の前記活性水素化合物を混合する工程と、
を含む、光学材料用重合性組成物の製造方法。
［１９］ （ａ）ポリエーテルポリオール（ａ１）およびポリエステルポリオール（ａ２）から選択される少なくとも１種のポリオール化合物と、（ｂ）ｐＫａが０未満の酸と、（ｃ）ポリイソ（チオ）シアネート化合物および二官能以上の活性水素化合物を含む重合反応性化合物（ポリオール（ａ）を除く）と、（ｅ）内部離型剤とを含む、光学材料用重合性組成物の製造方法であって、
二官能以上の前記活性水素化合物としてポリチオール化合物を含み、
内部離型剤（ｄ）と前記ポリイソ（チオ）シアネート化合物とを混合し、次いでポリオール化合物（ａ）を混合する工程と、
前記工程で得られた混合液に、ｐＫａが０未満の酸（ｂ）を混合し、次いでポリチオール化合物を混合する工程と、
を含む、光学材料用重合性組成物の製造方法。 That is, the present invention can be shown below.
[1] (a) at least one polyol compound selected from polyether polyol (a1) and polyester polyol (a2);
(b) an acid with a pKa of less than 0;
(c) a polyiso(thio)cyanate compound and a polymerizable compound containing a difunctional or higher active hydrogen compound (excluding the polyol compound (a));
A polymerizable composition for optical materials, comprising:
[2] The polymerizable composition for optical materials according to [1], wherein the acid (b) contains at least one selected from hydrochloric acid, methanesulfonic acid, p-toluenesulfonic acid, and vinylsulfonic acid.
[3] The polymerizable composition for optical materials according to [1] or [2], wherein the polyol compound (a) has a weight average molecular weight of 2000 or more.
[4] The polymerizable composition for optical materials according to any one of [1] to [3], wherein the polyether polyol (a1) contains a compound represented by the following general formula (a1).

(In general formula (a1), R ₁ and R ₂ represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and at least one of them is a hydrogen atom. Multiple R _1s present 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.)
[5] The polymerizable composition for optical materials according to any one of [1] to [4], wherein the polyester polyol (a2) contains a compound represented by the following general formula (a2).

(In the general formula (a2), Q represents a divalent group derived from a diol or a 3- to 30-valent group derived from a polyol having at least three primary alcohol groups, and m represents 3 to represents an integer of 10, n represents an integer of 2 to 200, the number of multiple n may be the same or different, and q represents an integer of 2 to 30.)
[6] The polymerizable composition for optical materials according to any one of [1] to [5], containing 200 ppm or more of acid (b).
[7] 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 [6] The polymerizable composition for optical materials according to any one of the above.
[8] The polymerizable composition for optical materials according to any one of [1] to [7], further comprising an internal release agent (d).
[9] The polymerizable composition for optical materials according to any one of [1] to [8], further comprising a tin catalyst (e).
[10] The polymerizable composition for optical materials according to any one of [1] to [9], further comprising a photochromic compound (f).
[11] A molded article obtained by curing the polymerizable composition for optical materials according to any one of [1] to [10].
[12] The molded article according to [11], which contains a microphase-separated structure of the polyol compound (a).
[13] The compact according to [12], wherein the microphase-separated structure has an average particle size of 1 to 50 nm.
[14] a lens substrate comprising the molded article according to any one of [10] to [13];
a hard coat layer;
an antireflection layer;
in that order.
[15] The laminate of [14], comprising a primer coat layer between the lens substrate and the hard coat layer.
[16] An optical material comprising the molded article according to any one of [11] to [13] or the laminate according to [14] or [15].
[17] A plastic lens comprising the molded article according to any one of [11] to [13] or the laminate according to [14] or [15].
[18] (a) at least one polyol compound selected from polyether polyol (a1) and polyester polyol (a2), (b) an acid having a pKa of less than 0, and (c) a polyiso(thio)cyanate compound and a polymerizable compound (excluding polyol (a)) containing a difunctional or higher active hydrogen compound, and a method for producing a polymerizable composition for an optical material,
A step of mixing the polyiso(thio)cyanate compound, the polyol compound (a), and an acid (b) having a pKa of less than 0;
a step of mixing the mixed solution obtained in the above step with the active hydrogen compound having a functionality of two or more;
A method for producing a polymerizable composition for optical materials, comprising:
[19] (a) at least one polyol compound selected from polyether polyol (a1) and polyester polyol (a2), (b) an acid having a pKa of less than 0, and (c) a polyiso(thio)cyanate compound and a polymerizable compound (excluding polyol (a)) containing a difunctional or higher active hydrogen compound; and (e) an internal release agent.
including a polythiol compound as the active hydrogen compound having a functionality of two or more,
mixing the internal mold release agent (d) and the polyiso(thio)cyanate compound, and then mixing the polyol compound (a);
A step of mixing an acid (b) having a pKa of less than 0 with the mixed solution obtained in the above step, and then mixing a polythiol compound;
A method for producing a polymerizable composition for optical materials, comprising:

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a polymerizable composition for an optical material that gives a molded article that is excellent in handleability (pot life), impact resistance, and dyeability.

1 is a TEM photograph of a molded article produced in Example 1. FIG. 4 is a TEM photograph of a molded article produced in Example 2. FIG. 4 is a TEM photograph of a molded article produced in Example 3. FIG. 4 is a TEM photograph of a molded article produced in Example 4. FIG. 10 is a TEM photograph of a molded article produced in Example 5. FIG. 11 is a TEM photograph of a molded article produced in Example 6. FIG. 4 is a TEM photograph of a molded article produced in Comparative Example 1. FIG.

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 comprises at least one polyol compound (a) selected from polyether polyols (a1) and polyester polyols (a2), an acid (b) having a pKa of less than 0, and a polymerizable compound (c) (excluding the polyol compound (a)).
ADVANTAGE OF THE INVENTION According to this invention, the molded object excellent in handleability (pot life), impact resistance, and dyeability can be obtained. Furthermore, the polymerizable composition for an optical material of the present invention is excellent in handleability (pot life), is excellent in transparency, heat resistance, impact resistance and dyeability, and does not generate optical distortion (striae). It is possible to obtain a molded article that is suppressed, has excellent light resistance, and has an excellent balance of these properties.

[Polyol compound (a)]
The polyol compound (a) of the present embodiment consists of at least one selected from polyether polyol (a1) and polyester polyol (a2).

The weight average molecular weight of the polyol compound (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.

(Polyether polyol (a1))
As the polyether polyol (a1), known compounds can be used as long as the effects of the present invention can be obtained.
In this embodiment, the polyether polyol (a1) can contain a compound represented by the following general formula (a1).

In general formula (a1), 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.
From the viewpoint of the effect of the present invention, the compound represented by formula (a1) may have a weight average molecular weight of 2000 or more, preferably 5000 or more, more preferably 10000 or more. 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 the present embodiment, one or a combination of two or more selected from compounds represented by the general formula (a1) can be used as the polyether polyol (a1).
As the compound represented by general formula (a1), a compound represented by general formula (a1-1) below can be specifically used.

In general formula (a1-1), 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 (a1) may react with the polymerizable compound (c) such as isocyanate.

In the present embodiment, a compound represented by general formula (a1-2) or general formula (a1-3) below can be used as the compound represented by general formula (a1-1).

In general formula (a1-2), 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 (a1-3), 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 R series (manufactured by BASF).

(Polyester polyol (a2))
A known compound can be used as the polyester polyol (a2) as long as the effects of the present invention can be obtained.
In this embodiment, the polyester polyol (a2) can contain a compound represented by the following general formula (a2).

In general formula (a2), Q represents a divalent group derived from a diol or a 3- to 30-valent group derived from a polyol having at least three primary alcohol groups, and m is 3 to 10. , n is an integer of 2 to 200, and the number of n's present in plurality may be the same or different. q represents an integer of 2-30.

In the formula, the oxygen atom directly linked to Q is an oxygen atom derived from a diol or an oxygen atom derived from a polyol.

Diols include ethylene glycol, propylene glycol, neopentyl glycol, 1,2-propanediol, 1,4-butanediol, 1,6-hexanediol and the like.

Polyols having at least three primary alcohol groups include trimethylolpropane, pentaerythritol, dipentaerythritol, and the like.

As the compound represented by the general formula (a2), those having a weight average molecular weight of 1000 or more, preferably 2000 or more, more preferably 3000 or more can be used 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 10,000 or less, preferably 5,000 or less.

As the alcohol compound represented by the general formula (3b), the CAPA polycaprolactone polyol series manufactured by PERSTORP, the PLACCEL series manufactured by DEICEL, and the like can be used. These alcohol compounds may be used alone or as a mixture of two or more.

In the present embodiment, the polyether polyol (a1) represented by the general formula (a1) and the polyester polyol (a2) represented by the general formula (a2) can be used together.

[acid (b) with pKa less than 0]
As the acid (b) of the present embodiment, a known acid having a pKa of less than 0 can be used as long as the effects of the present invention can be obtained.

The polymerizable composition for an optical material of the present embodiment uses an acid (b) having a pKa of less than 0 together with the components (a) and (c), whereby thickening is suppressed and handling (pot life ), and a molded article having excellent impact resistance and dyeability can be obtained.

In the present embodiment, the acids (b) having a pKa of less than 0 include hydrochloric acid (pKa: -3.7), methanesulfonic acid (pKa: -2.6), p-toluenesulfonic acid (pKa: -2. 8), vinylsulfonic acid (pKa: -2.7) and the like, preferably hydrochloric acid, methanesulfonic acid, p-toluenesulfonic acid and vinylsulfonic acid, more preferably hydrochloric acid, methanesulfonic acid and vinylsulfonic acid. preferable. The acid (b) with a pKa of less than 0 can contain at least one selected from these.
By using these acids, thickening is suppressed, so it is possible to obtain a polymerizable composition for optical materials with excellent handling properties (pot life), and the composition has better impact resistance and dyeability. An excellent molded article can be obtained.

The polymerizable composition for optical materials of the present embodiment can contain an acid (b) having a pKa of less than 0 in an amount of 200 ppm or more, preferably 300 ppm or more, more preferably 500 ppm or more, from the viewpoint of the effects of the present invention. Although the upper limit is not particularly limited, it may be 5000 ppm or less, preferably 3000 ppm or less, more preferably 2000 ppm or less from the viewpoint of handling properties of the polymerizable composition for optical materials.

[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 optional additives such as initiators and catalysts. includes a polymerizable compound having at least one or more of The polymerizable compound (c) does not contain the polymer (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 of, oxetanin compounds having one or more oxetanyl groups, thietane compounds having one or more thietanyl groups or having an oxetanyl group and a thietanyl group, methacryloyloxy groups, acryloyloxy groups, methacryloylthio groups , 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.

Polyiso(thio)cyanate compounds include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate. , lysine diisocyanatomethyl ester, lysine triisocyanate, xylylene diisocyanate and other aliphatic polyisocyanate compounds;
isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, dicyclohexyldimethylmethane isocyanate, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6- bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 3,8-bis(isocyanatomethyl)tricyclodecane, 3,9-bis(isocyanatomethyl)tricyclodecane, 4,8- Alicyclic polyisocyanate compounds such as bis(isocyanatomethyl)tricyclodecane and 4,9-bis(isocyanatomethyl)tricyclodecane;
aromatic polyisocyanate compounds such as tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, diphenyl sulfide-4,4-diisocyanate, and phenylene diisocyanate;
2,5-diisocyanatothiophene, 2,5-bis(isocyanatomethyl)thiophene, 2,5-diisocyanatotetrahydrothiophene, 2,5-bis(isocyanatomethyl)tetrahydrothiophene, 3,4-bis( isocyanatomethyl)tetrahydrothiophene, 2,5-diisocyanato-1,4-dithiane, 2,5-bis(isocyanatomethyl)-1,4-dithiane, 4,5-diisocyanato-1,3-dithiolane, 4, Heterocyclic polyisocyanate compounds such as 5-bis(isocyanatomethyl)-1,3-dithiolane;
Hexamethylene diisothiocyanate, lysine diisothiocyanate methyl ester, lysine triisothiocyanate, m-xylylene diisothiocyanate, bis(isothiocyanatomethyl) sulfide, bis(isothiocyanatoethyl) sulfide, bis(isothiocyanatoethyl) Aliphatic polyisothiocyanate compounds such as disulfides;
isophorone diisothiocyanate, bis(isothiocyanatomethyl)cyclohexane, bis(isothiocyanatocyclohexyl)methane, cyclohexanediisothiocyanate, methylcyclohexanediisothiocyanate, 2,5-bis(isothiocyanatomethyl)bicyclo-[2. 2.1]-heptane, 2,6-bis(isothiocyanatomethyl)bicyclo-[2.2.1]-heptane, 3,8-bis(isothiocyanatomethyl)tricyclodecane, 3,9-bis Alicyclic polyisothiocyanate compounds such as (isothiocyanatomethyl)tricyclodecane, 4,8-bis(isothiocyanatomethyl)tricyclodecane, 4,9-bis(isothiocyanatomethyl)tricyclodecane;
aromatic polyisothiocyanate compounds such as tolylene diisothiocyanate, 4,4-diphenylmethane diisothiocyanate, diphenyl disulfide-4,4-diisothiocyanate; be able to.

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, 1,2- Methyl glucoside, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, erythritol, threitol, ribitol, arabinitol, xylitol, allitol, mannitol, dulcitol, iditol, glycol, inositol, hexanetriol, triglycerose, diglyperol, triethylene Glycol, polyethylene glycol, tris(2-hydroxyethyl) isocyanurate, cyclobutanediol, cyclopentanediol, cyclohexanediol, cycloheptanediol, cyclooctanediol, cyclohexanedimethanol, hydroxypropylcyclohexanol, tricyclo[5.2.1. 0 ^2,6 ]decane-dimethanol, bicyclo[4.3.0]-nonanediol, dicyclohexanediol, tricyclo[5.3.1.1]dodecanediol, bicyclo[4.3.0]nonanedimethanol , tricyclo[5.3.1.1]dodecanediethanol, hydroxypropyltricyclo[5.3.1.1]dodecanol, spiro[3.4]octanediol, butylcyclohexanediol, 1,1′-bicyclohexyl Aliphatic polyols such as dendiol, cyclohexanetriol, maltitol, lactose;
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, tetrabromobisphenol A-bis-(2-hydroxyethyl ether);
Halogenated polyols such as dibromoneopentyl glycol;
Polymeric polyols such as epoxy resins can be mentioned. In this embodiment, at least one selected from these can be used in combination.

Polythiol compounds include methanedithiol, 1,2-ethanedithiol, 1,2,3-propanetrithiol, 1,2-cyclohexanedithiol, bis(2-mercaptoethyl) ether, tetrakis(mercaptomethyl)methane, diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), trimethylolpropane tris(2-mercaptoacetate) , trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (2-mercaptoacetate), trimethylolethane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol Tetrakis(3-mercaptopropionate), bis(mercaptomethyl)sulfide, bis(mercaptomethyl)disulfide, bis(mercaptoethyl)sulfide, bis(mercaptoethyl)disulfide, bis(mercaptopropyl)sulfide, bis(mercaptomethylthio) Methane, bis(2-mercaptoethylthio)methane, bis(3-mercaptopropylthio)methane, 1,2-bis(mercaptomethylthio)ethane, 1,2-bis(2-mercaptoethylthio)ethane, 1,2 -bis(3-mercaptopropylthio)ethane, 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3- mercaptopropylthio)propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 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, tetrakis(mercaptomethylthiomethyl ) methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, bis(2,3-dimercaptopropyl) sulfide, 2,5-dimercaptomethyl-1,4-dithiane , 2,5-dimercapto-1 ,4-dithiane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane and their esters of thioglycolic acid and mercaptopropionic acid, hydroxymethylsulfide bis(2-mercaptoacetate), hydroxy methyl sulfide bis (3-mercaptopropionate), hydroxyethyl sulfide bis (2-mercaptoacetate), hydroxyethyl sulfide bis (3-mercaptopropionate), hydroxymethyl disulfide bis (2-mercaptoacetate), hydroxymethyl disulfide bis(3-mercaptopropionate), hydroxyethyl disulfide bis(2-mercaptoacetate), hydroxyethyl disulfide bis(3-mercaptopropinate), 2-mercaptoethyl ether bis(2-mercaptoacetate), 2-mercaptoethyl ether bis(3-mercaptopropionate), thiodiglycolic acid bis(2-mercaptoethyl ester), thiodipropionic acid bis(2-mercaptoethyl ester), dithiodiglycolic acid bis(2-mercaptoethyl ester), Bis(2-mercaptoethyl ester) dithiodipropionate, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 4,6-bis(mercapto aliphatic polythiol compounds such as methylthio)-1,3-dithiane, tris(mercaptomethylthio)methane, tris(mercaptoethylthio)methane;
1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis(mercaptomethyl)benzene, 1,3-bis(mercaptomethyl)benzene, 1,4- bis(mercaptomethyl)benzene, 1,2-bis(mercaptoethyl)benzene, 1,3-bis(mercaptoethyl)benzene, 1,4-bis(mercaptoethyl)benzene, 1,3,5-trimercaptobenzene, 1,3,5-tris(mercaptomethyl)benzene, 1,3,5-tris(mercaptomethylenoxy)benzene, 1,3,5-tris(mercaptoethyleneoxy)benzene, 2,5-toluenedithiol, 3, aromatic polythiol compounds such as 4-toluenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol;
2-methylamino-4,6-dithiol-sym-triazine, 3,4-thiophenedithiol, bismuthiol, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercapto heterocyclic polythiol compounds such as methylthio)ethyl)-1,3-dithiethane;

[Internal release agent (d)]
The polymerizable composition for optical materials of the present invention may further contain an internal mold release agent (d) for the purpose of improving releasability from the mold after molding.
The internal mold release agent (d) is not particularly limited, and conventionally known agents can be used, and examples thereof include acidic phosphate esters. Acidic phosphates include phosphate monoesters and phosphate diesters, each of which can be used alone or in combination of two or more.

Acidic phosphates include ZelecUN (manufactured by STEPAN), MR internal mold release agent (manufactured by Mitsui Chemicals), JP series manufactured by Johoku Chemical Industry Co., Ltd., Phosphanol series manufactured by Toho Chemical Industry Co., Ltd., Daihachi Chemical Kogyosha's AP and DP series can be used, and ZelecUN (manufactured by STEPAN), MR internal mold release agent (manufactured by Mitsui Chemicals, Inc.), and Johoku Chemical's JP series are more preferable.

The amount of the internal release agent (d) used is not particularly limited, but is in the range of 0.0001 to 10 parts by weight per 100 parts by weight of the polymerizable composition for optical materials.

[Tin catalyst (e)]
The polymerizable composition for optical materials of the present embodiment can further contain a tin catalyst (e) when the polymerizable compound (c) contains a polyiso(thio)cyanate compound and a difunctional or higher active hydrogen compound. .
When the tin catalyst (e) is contained, the polymerizable composition for optical materials tends to increase in viscosity and the pot life tends to be shortened, but the polymerizable composition for optical materials of the present embodiment has a pKa of less than 0 (b ), 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 (e) 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 (e) 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 (f)]
The polymerizable composition for optical materials of the present embodiment can further contain a photochromic compound (f).

Examples of the photochromic compound (f) 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 (f).

(other ingredients)
In the present embodiment, in addition to the components (a), (b) and (c), the component (d) added as necessary, the component (e) or the component (f), an ultraviolet absorbing agents, light stabilizers, polymerization catalysts, resin modifiers, 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.

In the present embodiment, when the polymerization-reactive compound (c) contains a polyiso(thio)cyanate compound and a difunctional or higher active hydrogen compound, from the viewpoint of handling properties and obtaining a desired composition, the following method can be obtained.

First, a polyiso (thio) cyanate compound, a polyol compound (a), and an acid (b) having a pKa of less than 0 are mixed to prepare a mixed solution, and then the mixed solution is added with a difunctional or higher active hydrogen Mix the compounds.
The bifunctional or higher active hydrogen compound may be added to the mixture all at once, or may be added gradually.

Further, the polymerizable composition for an optical material of the present embodiment contains an internal release agent (d), and the polymerization-reactive compound (c) is a polyiso(thio)cyanate compound and a difunctional or higher active hydrogen compound. When a polythiol compound is included, it can be obtained by the following method from the viewpoint of obtaining handleability and a desired composition.

The internal release agent (d) and the polyiso(thio)cyanate compound are mixed, and then the polyol compound (a) is mixed. Then, the resulting mixture is mixed with an acid (b) having a pKa of less than 0, and then mixed with a polythiol compound.
The polyol compound (a) and the acid (b) may be added to the mixed solution all at once, or added gradually.

<Molded article and its use>
In this embodiment, a molded article can be obtained by curing the polymerizable composition for optical materials. The molded article of this embodiment contains a microphase-separated structure of the polyol compound (a). By including the microphase-separated structure in the molded article, it is more excellent in impact resistance and dyeability.

Although the relationship between the microphase-separated structure and the effect is not clear, the presence of the microphase-separated structure in the molded body, especially near the surface of the molded body, improves impact absorption and hydrophilicity. As a result, it is considered that the impact resistance and dyeability are more excellent.
The microphase-separated structure tends to be unevenly distributed in the vicinity of the surface of the molded body, which is thought to further improve impact absorption and hydrophilicity.
The average particle size of the microphase-separated structure is 1 to 50 nm, preferably 2 to 30 nm, more preferably 5 to 20 nm, from the viewpoint of the effects of the present invention. Average particle size can be measured by cross-sectional TEM analysis.

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.
First, evaluation methods in the examples of the present invention are shown below.

<Evaluation method>
- Viscosity: After preparing the polymerizable composition for optical materials of the present embodiment, stirring was continued for 5 hours at 15°C in a nitrogen atmosphere, and then BROOKFIELD ENGINEERING LABS. INC. The viscosity of the composition was measured using a B-type viscometer (model: LVT) manufactured by the company.

- Transparency: The obtained resin was irradiated with a projector in a dark place, and the presence or absence of cloudiness (including elution from the tape) and opaque substances was visually judged. When no cloudiness (including elution from the tape) or opaque substance was observed, it was evaluated as "O" (transparency), and when it was confirmed, it was evaluated as "X" (no transparency).

- Haze value: A haze meter (model number: NDH 2000) manufactured by Nippon Denshoku Industries Co., Ltd. was used to measure the HAZE value of a resin plate having a thickness of 2.5 mm. If the HAZE value is less than 0.70, the lens can be used without any problem.

・Distortion (striae): The obtained lens is projected onto a high-pressure UV lamp, and "◎" (no striae) indicates that there is no distortion in the lens. When there was no distortion, it was evaluated as "○", and when distortion was observed in the lens by visual observation, it was evaluated as "X" (with striae).

• Refractive index (ne) and Abbe number (νe): measured at 20°C using a Pulfrich refractometer.
· Heat resistance: The glass transition temperature Tg was measured by the TMA penetration method (50 g load, pin tip 0.5 mmφ, heating rate 10°C/min).
- Specific gravity: Measured by the Archimedes method.

· Impact resistance (drop ball test): After laminating a hard coat layer (C-415 manufactured by SDC Technologies Inc.) and an antireflection layer (Duracote 1.60 manufactured by Optotech) on a lens with a center thickness of 1 mm, the US FDA , the steel ball was dropped from a height of 127 cm to a height of 127 cm in order from lighter to heavier until it broke, and the impact resistance was evaluated based on the weight of the broken steel ball. Steel balls were measured in the order of 8g→16g→28g→33g→45g→67g→95g→112g→174g→225g→530g.

・Impact resistance (High Mass Impact Test): According to American ANSI Z87.1, a lens with a center thickness of 2 mm was dropped from a height of 127 cm with a weight of 500 g, and the percentage of resin that did not break was passed. evaluated as a rate.

· Impact resistance (High Velocity Impact Test): After laminating the following primer layer, hard coat layer, and antireflection layer on the lens with a center thickness of 2 mm obtained in Examples and Comparative Examples, US ANSI Z87.1 , an iron ball with a diameter of 6.35 mm was shot at the lens at a speed of 45 meters per second, and the rate at which the resin did not break was evaluated as a pass rate.
Primer layer: (PR-1135 manufactured by SDC Technologies Inc., film thickness 1.3 μm)
Hard coat layer: (C-415 manufactured by SDC Technologies Inc., film thickness 2.5 μm)
Antireflection layer: (Duracote 1.60 manufactured by Optotech, film thickness 2.6 nm)

・ Dyeability: A dyeing solution in which 40 g of dye (manufactured by BPI gray / Brain Power Inc.) is dissolved in 1960 g of water is heated to 90 ° C., and a test piece of 9.0 mm × 50.0 mm × 1.4 mm is immersed for 60 minutes. After that, the transmittance at each wavelength was measured with an ultraviolet-visible spectrophotometer.

・Light resistance: QUV test with a Q-Lab accelerated weather resistance tester using a 2.5 mm thick plate (light source: UVA-340, intensity: 0.50 W / m ² , test conditions: 50 ° C. × 150 hours) was carried out, and the hue change before and after irradiation was measured.

・Solvent resistance: A non-woven fabric impregnated with acetone is pressed against the surface of the obtained lens for 10 seconds. Those that were confirmed were marked with "x" (no solvent resistance).

Observation of nanodomains: Observation of the shape of the nanodomains in the obtained resin was performed by staining the sample with ruthenium tetroxide and then using a transmission electron microscope (TEM/Hitachi High-Technologies Corporation H-7650) at 100 kV. went.

[Example 1]
49.56 parts by weight of meta-xylylene diisocyanate, 1.50 parts by weight of an ultraviolet absorber (manufactured by Kyodo Yakuhin Co., Ltd.; trade name: Biosorb 583), and 0.30 parts by weight of an internal release agent (manufactured by Johoku Kagaku Co., Ltd.; trade name: JP506H). After mixing and dissolving to make a uniform solution, poly (ethylene glycol) poly (propylene glycol) poly (ethylene glycol) block copolymer with a weight average molecular weight of 13300 (manufactured by Sigma Aldrich; trade name Pluronic F-127) 1.98 weight were charged and reacted at 20° C. for 1 hour. 0.10 parts by weight of methanesulfonic acid was mixed and dissolved in the solution to obtain a uniform solution, and then 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7 - dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, composition containing 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane 48. 45 parts by weight were mixed and dissolved to form a uniform solution. After defoaming at 400 Pa, it was injected into a molding mold. This was put into a polymerization oven, and the temperature was gradually raised from 20° C. to 120° C. over 24 hours for polymerization. After completion of the polymerization, the product was removed from the oven and removed from the mold. The releasability was good, and no peeling of the mold was observed. The obtained compact was further annealed at 120° C. for 2 hours. As a result of observation of nanodomains in the resulting molded product, it was observed from the TEM photograph that particles with a diameter of 5 to 8 nm were uniformly dispersed in the resin. The composition and evaluation results of the obtained molded body are shown in Table 1, and a TEM photograph is shown in FIG.

[Example 2]
49.58 parts by weight of meta-xylylene diisocyanate, 1.50 parts by weight of an ultraviolet absorber (manufactured by Kyodo Yakuhin Co., Ltd.; trade name: Biosorb 583), and 0.30 parts by weight of an internal release agent (manufactured by Johoku Kagaku Co., Ltd.; trade name: JP506H). After mixing and dissolving to make a uniform solution, poly (ethylene glycol) poly (propylene glycol) poly (ethylene glycol) block copolymer with a weight average molecular weight of 6800 (manufactured by Sigma Aldrich; trade name Pluronic F-77) 1.98 weight were charged and reacted at 20° C. for 1 hour. 0.10 parts by weight of methanesulfonic acid was mixed and dissolved in the solution to obtain a uniform solution, and then 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7 - dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, composition containing 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane 48. 44 parts by weight were mixed and dissolved to form a uniform solution. After defoaming at 400 Pa, it was injected into a molding mold. This was put into a polymerization oven, and the temperature was gradually raised from 20° C. to 120° C. over 24 hours for polymerization. After completion of the polymerization, the product was removed from the oven and removed from the mold. The releasability was good, and no peeling of the mold was observed. The obtained compact was further annealed at 120° C. for 2 hours. As a result of observation of nanodomains in the resulting compact, it was difficult to observe the domains and measure the particle size in the TEM photograph. The composition and evaluation results of the obtained molded body are shown in Table 1, and a TEM photograph is shown in FIG.

[Example 3]
49.61 parts by weight of meta-xylylene diisocyanate, 1.50 parts by weight of an ultraviolet absorber (manufactured by Kyodo Yakuhin Co., Ltd.; trade name: Biosorb 583), and 0.30 parts by weight of an internal release agent (manufactured by Johoku Kagaku Co., Ltd.; trade name: JP506H). After mixing and dissolving to make a uniform solution, poly (ethylene glycol) poly (propylene glycol) poly (ethylene glycol) block copolymer with a weight average molecular weight of 2900 (manufactured by Sigma Aldrich; trade name Pluronic L-64) 1.98 weight were charged and reacted at 20° C. for 1 hour. 0.10 parts by weight of methanesulfonic acid was mixed and dissolved in the solution to obtain a uniform solution, and then 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7 - dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, composition containing 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane 48. 40 parts by weight were mixed and dissolved to form a uniform solution. After defoaming at 400 Pa, it was injected into a molding mold. This was put into a polymerization oven, and the temperature was gradually raised from 20° C. to 120° C. over 24 hours for polymerization. After completion of the polymerization, the product was removed from the oven and removed from the mold. The releasability was good, and no peeling of the mold was observed. The obtained compact was further annealed at 120° C. for 2 hours. As a result of the observation of the nanodomains in the obtained compact, the TEM photograph showed that the domains were slightly uniformly dispersed, but it was difficult to measure the particle size. The composition and evaluation results of the obtained molded body are shown in Table 1, and the TEM photograph is shown in FIG.

[Example 4]
49.61 parts by weight of meta-xylylene diisocyanate, 1.50 parts by weight of an ultraviolet absorber (manufactured by Kyodo Yakuhin Co., Ltd.; trade name: Biosorb 583), and 0.30 parts by weight of an internal release agent (manufactured by Johoku Kagaku Co., Ltd.; trade name: JP506H). were mixed and dissolved to form a homogeneous solution, 1.98 parts by weight of polycaprolactone diol (manufactured by Perstorp; trade name: CAPA 2302A) having a weight average molecular weight of 3000 was charged and reacted at 20°C for 1 hour. 0.10 parts by weight of methanesulfonic acid was mixed and dissolved in the solution to obtain a uniform solution, and then 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7 - dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, composition containing 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane 48. 41 parts by weight were mixed and dissolved to form a homogeneous solution. After defoaming at 400 Pa, it was injected into a molding mold. This was put into a polymerization oven, and the temperature was gradually raised from 20° C. to 120° C. over 24 hours for polymerization. After completion of the polymerization, the product was removed from the oven and removed from the mold. The releasability was good, and no peeling of the mold was observed. The obtained compact was further annealed at 120° C. for 2 hours. As a result of observation of nanodomains in the resulting molded product, it was observed from the TEM photograph that particles with a diameter of 5 to 10 nm were uniformly dispersed in the resin. The composition and evaluation results of the obtained molded body are shown in Table 1, and a TEM photograph is shown in FIG.

[Example 5]
49.60 parts by weight of meta-xylylene diisocyanate, 1.50 parts by weight of an ultraviolet absorber (manufactured by Kyodo Pharmaceutical Co., Ltd.; trade name: Biosorb 583), and 0.30 parts by weight of an internal release agent (manufactured by Johoku Kagaku Co., Ltd.; trade name: JP506H). were mixed and dissolved to form a uniform solution, 1.98 parts by weight of polycaprolactone diol (manufactured by Perstorp; trade name: CAPA 2403D) having a weight average molecular weight of 4000 was charged and reacted at 20°C for 1 hour. 0.10 parts by weight of methanesulfonic acid was mixed and dissolved in the solution to obtain a uniform solution, and then 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7 - dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, composition containing 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane 48. 42 parts by weight were mixed and dissolved to form a uniform solution. Furthermore, a uniform solution obtained by mixing and dissolving 0.0060 parts by weight of dimethyltin dichloride (manufactured by Honjo Chemical Co., Ltd.; trade name Nestin P) as a tin catalyst with 10.0 parts by weight of meta-xylylene diisocyanate is added to the prepared solution and mixed. dissolved to obtain a homogeneous solution. After defoaming at 400 Pa, it was injected into a molding mold. This was put into a polymerization oven, and the temperature was gradually raised from 20° C. to 120° C. over 24 hours for polymerization. After completion of the polymerization, the product was removed from the oven and removed from the mold. The releasability was good, and no peeling of the mold was observed. The obtained compact was further annealed at 120° C. for 2 hours. As a result of observation of nanodomains in the resulting molded product, it was observed from the TEM photograph that particles with a diameter of 5 to 20 nm were uniformly dispersed in the resin. The composition and evaluation results of the obtained molded body are shown in Table 1, and a TEM photograph is shown in FIG.

[Example 6]
49.61 parts by weight of meta-xylylene diisocyanate, 1.50 parts by weight of an ultraviolet absorber (manufactured by Kyodo Yakuhin Co., Ltd.; trade name: Biosorb 583), and 0.30 parts by weight of an internal release agent (manufactured by Johoku Kagaku Co., Ltd.; trade name: JP506H). were mixed and dissolved to form a homogeneous solution, 1.98 parts by weight of polycaprolactone diol (manufactured by Perstorp; trade name: CAPA 2302A) having a weight average molecular weight of 3000 was charged and reacted at 20°C for 1 hour. 0.10 parts by weight of methanesulfonic acid was mixed and dissolved in the solution to obtain a uniform solution, and then 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7 - dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, composition containing 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane 48. 41 parts by weight were mixed and dissolved to form a uniform solution. Furthermore, a uniform solution obtained by mixing and dissolving 0.0060 parts by weight of dimethyltin dichloride (manufactured by Honjo Chemical Co., Ltd.; trade name Nestin P) as a tin catalyst with 10.0 parts by weight of meta-xylylene diisocyanate is added to the prepared solution and mixed. dissolved to obtain a homogeneous solution. After defoaming at 400 Pa, it was injected into a molding mold. This was put into a polymerization oven, and the temperature was gradually raised from 20° C. to 120° C. over 24 hours for polymerization. After completion of the polymerization, the product was removed from the oven and removed from the mold. The releasability was good, and no peeling of the mold was observed. The obtained compact was further annealed at 120° C. for 2 hours. As a result of observation of nanodomains in the resulting molded product, it was observed from the TEM photograph that particles with a diameter of 5 to 8 nm were uniformly dispersed in the resin. The composition and evaluation results of the obtained molded body are shown in Table 1, and a TEM photograph is shown in FIG.

[Example 7]
Hydrogen chloride gas was blown into meta-xylylene diisocyanate and dissolved to prepare a solution having a hydrogen chloride concentration of 3000 ppm. 16.3 parts by weight of meta-xylylene diisocyanate was added to 33.3 parts by weight of this solution, 1.50 parts by weight of an ultraviolet absorber (manufactured by Kyodo Yakuhin Co., Ltd.; trade name Biosorb 583), and an internal release agent (manufactured by Johoku Kagaku Co., Ltd.; After mixing and dissolving 0.30 parts by weight of JP506H (trade name) to form a uniform solution, 1.98 parts by weight of polyoxyethylene polyoxypropylene glycol (manufactured by Sigma Aldrich; trade name: Pluronic F-127) having a weight average molecular weight of 13300. was charged and reacted at 20° C. for 1 hour. 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 were mixed and dissolved to form a homogeneous solution. After defoaming at 400 Pa, it was injected into a molding mold. This was put into a polymerization oven, and the temperature was gradually raised from 20° C. to 120° C. over 24 hours for polymerization. After completion of the polymerization, the product was removed from the oven and removed from the mold. The releasability was good, and no peeling of the mold was observed. The obtained compact was further annealed at 120° C. for 2 hours. Table 1 shows the composition and the evaluation results of the obtained molding.

[Example 8]
49.56 parts by weight of meta-xylylene diisocyanate, 1.50 parts by weight of an ultraviolet absorber (manufactured by Kyodo Yakuhin Co., Ltd.; trade name: Biosorb 583), and 0.30 parts by weight of an internal release agent (manufactured by Johoku Kagaku Co., Ltd.; trade name: JP506H). After mixing and dissolving to make a homogeneous solution, 1.98 parts by weight of polyoxyethylene polyoxypropylene glycol having a weight average molecular weight of 13300 (manufactured by Sigma Aldrich; trade name: Pluronic F-127) was charged and heated to 20 ° C. for 1 reacted over time. 0.10 parts by weight of vinylsulfonic acid was mixed and dissolved in the solution to form a homogeneous solution, and then 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7 - dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, composition containing 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane 48. 45 parts by weight were mixed and dissolved to form a homogeneous solution. After defoaming at 400 Pa, it was injected into a molding mold. This was put into a polymerization oven, and the temperature was gradually raised from 20° C. to 120° C. over 24 hours for polymerization. After completion of the polymerization, the product was removed from the oven and removed from the mold. The releasability was good, and no peeling of the mold was observed. The obtained compact was further annealed at 120° C. for 2 hours. Table 1 shows the composition and the evaluation results of the obtained molding.

[Example 9]
49.56 parts by weight of meta-xylylene diisocyanate, 1.50 parts by weight of an ultraviolet absorber (manufactured by Kyodo Yakuhin Co., Ltd.; trade name: Biosorb 583), and 0.30 parts by weight of an internal release agent (manufactured by Johoku Kagaku Co., Ltd.; trade name: JP506H). After mixing and dissolving to make a homogeneous solution, 1.98 parts by weight of polyoxyethylene polyoxypropylene glycol having a weight average molecular weight of 13300 (manufactured by Sigma Aldrich; trade name: Pluronic F-127) was charged and heated to 20 ° C. for 1 reacted over time. 0.10 parts by weight of p-toluenesulfonic acid was mixed and dissolved in the solution to obtain a uniform solution, and then 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4, Compositions containing 7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane 48 .45 parts by weight were mixed and dissolved to form a uniform solution. After defoaming at 400 Pa, it was injected into a molding mold. This was put into a polymerization oven, and the temperature was gradually raised from 20° C. to 120° C. over 24 hours for polymerization. After completion of the polymerization, the product was removed from the oven and removed from the mold. The releasability was good, and no peeling of the mold was observed. The obtained compact was further annealed at 120° C. for 2 hours. Table 1 shows the composition and the evaluation results of the obtained molding.

[Example 10]
49.56 parts by weight of meta-xylylene diisocyanate, 1.50 parts by weight of an ultraviolet absorber (manufactured by Kyodo Yakuhin Co., Ltd.; trade name: Biosorb 583), and 0.30 parts by weight of an internal release agent (manufactured by Johoku Kagaku Co., Ltd.; trade name: JP506H). After mixing and dissolving to make a homogeneous solution, 1.98 parts by weight of polyoxyethylene polyoxypropylene glycol having a weight average molecular weight of 13300 (manufactured by Sigma Aldrich; trade name: Pluronic F-127) was charged and heated to 20 ° C. for 1 reacted over time. 0.10 parts by weight of methanesulfonic acid was mixed and dissolved in the solution to obtain a uniform solution, and then 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7 - dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, composition containing 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane 48. 45 parts by weight were mixed and dissolved to form a uniform solution. Furthermore, a uniform solution obtained by mixing and dissolving 0.0020 parts by weight of dimethyltin dichloride (manufactured by Honjo Chemical Co., Ltd.; trade name Nestin P) as a tin catalyst in 10.0 parts by weight of meta-xylylene diisocyanate is added to the prepared solution and mixed. dissolved to obtain a homogeneous solution. After defoaming at 400 Pa, it was injected into a molding mold. This was put into a polymerization oven, and the temperature was gradually raised from 20° C. to 120° C. over 24 hours for polymerization. After completion of the polymerization, the product was removed from the oven and removed from the mold. The releasability was good, and no peeling of the mold was observed. The obtained compact was further annealed at 120° C. for 2 hours. Table 1 shows the composition and the evaluation results of the obtained molding.

[Comparative Example 1]
50.70 parts by weight of meta-xylylene diisocyanate, 1.50 parts by weight of an ultraviolet absorber (manufactured by Kyodo Pharmaceutical Co., Ltd.; trade name: Biosorb 583), an internal mold release agent (manufactured by Mitsui Chemicals; trade name: internal mold release agent for MR) After mixing and dissolving 0.10 parts by weight to form a uniform solution, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7-dimercaptomethyl-1,11 - Mix and dissolve 49.30 parts by weight of a composition containing dimercapto-3,6,9-trithiundecane and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, A homogeneous solution was obtained. Furthermore, a uniform solution obtained by mixing and dissolving 0.0080 parts by weight of dimethyltin dichloride (manufactured by Honjo Chemical Co., Ltd.; trade name Nestin P) as a tin catalyst with 10.0 parts by weight of meta-xylylene diisocyanate is added to the prepared solution and mixed. dissolved to obtain a homogeneous solution. After defoaming at 400 Pa, it was injected into a molding mold. This was put into a polymerization oven, and the temperature was gradually raised from 20° C. to 120° C. over 24 hours for polymerization. After completion of the polymerization, the product was removed from the oven and removed from the mold. The releasability was good, and no peeling of the mold was observed. The obtained compact was further annealed at 120° C. for 2 hours. As a result of observation of nanodomains in the resulting molded product, no particles were confirmed in the resin from the TEM photograph. The composition and evaluation results of the obtained molded body are shown in Table-1, and the TEM photograph is shown in FIG.

[Comparative Example 2]
49.56 parts by weight of meta-xylylene diisocyanate, 1.50 parts by weight of an ultraviolet absorber (manufactured by Kyodo Yakuhin Co., Ltd.; trade name: Biosorb 583), and 0.30 parts by weight of an internal release agent (manufactured by Johoku Kagaku Co., Ltd.; trade name: JP506H). After mixing and dissolving to make a homogeneous solution, 1.98 parts by weight of polyoxyethylene polyoxypropylene glycol having a weight average molecular weight of 13300 (manufactured by Sigma Aldrich; trade name: Pluronic F-127) was charged and heated to 20 ° C. for 1 reacted over time. After mixing and dissolving 0.10 parts by weight of formic acid in the solution to obtain a uniform solution, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, Mercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 48.45 wt. The parts were mixed and dissolved to form a uniform solution. After defoaming at 400 Pa, it was injected into a molding mold. This was put into a polymerization oven, and the temperature was gradually raised from 20° C. to 120° C. over 24 hours for polymerization. After completion of the polymerization, the product was removed from the oven and removed from the mold. The releasability was good, and no peeling of the mold was observed. The obtained compact was further annealed at 120° C. for 2 hours. The molded article obtained had a heat resistance of 95° C. and was transparent, but had many cracks, so physical properties could not be evaluated.

[Comparative Example 3]
49.56 parts by weight of meta-xylylene diisocyanate, 1.50 parts by weight of an ultraviolet absorber (manufactured by Kyodo Yakuhin Co., Ltd.; trade name: Biosorb 583), and 0.30 parts by weight of an internal release agent (manufactured by Johoku Kagaku Co., Ltd.; trade name: JP506H). After mixing and dissolving to make a homogeneous solution, 1.98 parts by weight of polyoxyethylene polyoxypropylene glycol having a weight average molecular weight of 13300 (manufactured by Sigma Aldrich; trade name: Pluronic F-127) was charged and heated to 20 ° C. for 1 reacted over time. 0.10 parts by weight of oxalic acid was mixed and dissolved in the solution to obtain a uniform solution, and then 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7- Compositions containing dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane 48.45 Parts by weight were mixed and dissolved to form a uniform solution. After defoaming at 400 Pa, it was injected into a molding mold. This was put into a polymerization oven, and the temperature was gradually raised from 20° C. to 120° C. over 24 hours for polymerization. After completion of the polymerization, the product was removed from the oven and removed from the mold. The releasability was good, and no peeling of the mold was observed. The obtained compact was further annealed at 120° C. for 2 hours. Table 1 shows the composition and the evaluation results of the obtained molding.

[Comparative Example 4]
49.56 parts by weight of meta-xylylene diisocyanate, 1.50 parts by weight of an ultraviolet absorber (manufactured by Kyodo Yakuhin Co., Ltd.; trade name: Biosorb 583), and 0.30 parts by weight of an internal release agent (manufactured by Johoku Kagaku Co., Ltd.; trade name: JP506H). After mixing and dissolving to make a homogeneous solution, 1.98 parts by weight of polyoxyethylene polyoxypropylene glycol having a weight average molecular weight of 13300 (manufactured by Sigma Aldrich; trade name: Pluronic F-127) was charged and heated to 20 ° C. for 1 reacted over time. 0.10 parts by weight of trifluoroacetic acid was mixed and dissolved in the solution to obtain a homogeneous solution, and then 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7 - dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, composition containing 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane 48. 45 parts by weight were mixed and dissolved to form a uniform solution. After defoaming at 400 Pa, it was injected into a molding mold. This was put into a polymerization oven, and the temperature was gradually raised from 20° C. to 120° C. over 24 hours for polymerization. After completion of the polymerization, the product was removed from the oven and removed from the mold. The releasability was good, and no peeling of the mold was observed. The obtained compact was further annealed at 120° C. for 2 hours. Table 1 shows the composition and the evaluation results of the obtained molding.

(Polyol compound)
P1: Poly (ethylene glycol) poly (propylene glycol) poly (ethylene glycol) block copolymer with a weight average molecular weight of 13333 (Sigma Aldrich Pluronic F-127)
P2: Poly (ethylene glycol) poly (propylene glycol) poly (ethylene glycol) block copolymer with a weight average molecular weight of 6800 (Sigma Aldrich Pluronic F-77)
P3: Poly(ethylene glycol) poly(propylene glycol) poly(ethylene glycol) block copolymer with a weight average molecular weight of 2900 (Sigma Aldrich Pluronic L-64)
P4: poly(caprolactone) diol with a weight average molecular weight of 3000 (CAPA2302A manufactured by Perstorp)
P5: poly(caprolactone) diol with a weight average molecular weight of 4000 (CAPA2403D manufactured by Perstorp)

(acid)
A1: methanesulfonic acid A2: hydrochloric acid A3: vinylsulfonic acid A4: p-toluenesulfonic acid A5: formic acid A6: oxalic acid A7: trifluoroacetic acid

(Iso(thio)cyanate compound)
I1: meta-xylylene diisocyanate

(Polythiol compound)
T1: 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane and 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane Mixture with 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane

(tin catalyst)
S1: dimethyltin dichloride

The thiourethane molded articles of Examples 1 to 10 are excellent in impact resistance and dyeability as compared with Comparative Example 1, which is a thiourethane molded article containing no polyol compound (a) and acid (b). , and other physical properties as an optical material.

Furthermore, the thiourethane molded bodies of Examples 1 to 10 showed a moderate increase in the viscosity of the prepared liquid compared to the thiourethane molded bodies (Comparative Examples 2 to 4) using an acid having a pKa of 0 or more as an additive. Therefore, it was excellent in handleability, could be smoothly handled in the process of manufacturing an optical material, and was excellent in appearance with little occurrence of optical distortion.
In addition, in the thiourethane molding (Comparative Example 2) to which formic acid was added, a large number of cracks occurred in the resin during the curing process, and physical properties could not be evaluated.

The laminate obtained by laminating the hard coat layer and the antireflection layer on the thiourethane molded article of Example 1 was compared with the laminate obtained by laminating the hard coat layer and the antireflection layer on the thiourethane molded articles of Examples 2 to 10. Furthermore, the molding itself had no striae and was excellent in appearance.

Laminates obtained by laminating a primer layer, a hard coat layer and an antireflection layer on the thiourethane molded articles of Examples 1 and 10 are obtained by laminating the thiourethane molded article of Comparative Example 1 with a primer layer, a hard coat layer and an antireflection layer. was superior in impact resistance compared to a laminate obtained by laminating

As described above, the thiourethane molded article obtained from the polymerizable composition for optical materials of the present invention has excellent transparency, heat resistance, impact resistance and dyeability, and suppresses the occurrence of optical distortion (striae). and had excellent light resistance and an excellent balance of these properties.

The thiourethane molded article obtained from the polymerizable composition for optical materials of the present invention can be suitably used in various optical materials requiring high transparency, especially spectacle lenses.

Claims (19)

(a) at least one polyol compound selected from polyether polyols (a1) and polyester polyols (a2);
(b) an acid with a pKa of less than 0;
(c) a polyiso(thio)cyanate compound and a polymerizable compound containing a difunctional or higher active hydrogen compound (excluding the polyol compound (a));
A polymerizable composition for optical materials, comprising: 2. The polymerizable composition for optical materials according to claim 1, wherein the acid (b) contains at least one selected from hydrochloric acid, methanesulfonic acid, p-toluenesulfonic acid, and vinylsulfonic acid. 3. The polymerizable composition for optical materials according to claim 1, wherein the polyol compound (a) has a weight average molecular weight of 2000 or more. 4. The polymerizable composition for optical materials according to any one of claims 1 to 3, wherein the polyether polyol (a1) contains a compound represented by the following general formula (a1).

(In general formula (a1), R ₁ and R ₂ represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and at least one of them is a hydrogen atom. Multiple R _1s present 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.) 5. The polymerizable composition for optical materials according to any one of claims 1 to 4, wherein the polyester polyol (a2) contains a compound represented by the following general formula (a2).

(In the general formula (a2), Q represents a divalent group derived from a diol or a 3- to 30-valent group derived from a polyol having at least three primary alcohol groups, and m represents 3 to represents an integer of 10, n represents an integer of 2 to 200, the number of multiple n may be the same or different, and q represents an integer of 2 to 30.) 6. The polymerizable composition for optical materials according to any one of claims 1 to 5, comprising 200 ppm or more of the acid (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 6. Polymerizable composition for optical materials. 8. The polymerizable composition for optical materials according to any one of claims 1 to 7, further comprising an internal release agent (d). 9. The polymerizable composition for optical materials according to any one of claims 1 to 8, further comprising a tin catalyst (e). 10. The polymerizable composition for optical materials according to any one of claims 1 to 9, further comprising a photochromic compound (f). A molded article obtained by curing the polymerizable composition for optical materials according to any one of claims 1 to 10. 12. The shaped article according to claim 11, comprising a microphase-separated structure of the polyol compound (a). The compact according to claim 12, wherein the microphase-separated structure has an average particle size of 1 to 50 nm. a lens substrate comprising the molded article according to any one of claims 10 to 13;
a hard coat layer;
an antireflection layer;
in that order. 15. The laminate according to claim 14, comprising a primer coat layer between the lens substrate and the hard coat layer. An optical material comprising the molded article according to any one of claims 11 to 13 or the laminated body according to claim 14 or 15. A plastic lens comprising the molded article according to any one of claims 11 to 13 or the laminated body according to claim 14 or 15. (a) at least one polyol compound selected from polyether polyol (a1) and polyester polyol (a2), (b) an acid having a pKa of less than 0, and (c) a polyiso(thio)cyanate compound and a difunctional A method for producing a polymerizable composition for optical materials, comprising:
mixing the polyiso(thio)cyanate compound, the polyol compound (a), and an acid (b) having a pKa of less than 0;
a step of mixing the mixed solution obtained in the above step with the active hydrogen compound having a functionality of two or more;
A method for producing a polymerizable composition for optical materials, comprising: (a) at least one polyol compound selected from polyether polyol (a1) and polyester polyol (a2), (b) an acid having a pKa of less than 0, and (c) a polyiso(thio)cyanate compound and a difunctional A method for producing a polymerizable composition for an optical material, comprising the above-mentioned polymerizable compound containing an active hydrogen compound (excluding the polyol (a)) and (e) an internal release agent,
including a polythiol compound as the active hydrogen compound having a functionality of two or more,
mixing the internal mold release agent (d) and the polyiso(thio)cyanate compound, and then mixing the polyol compound (a);
A step of mixing an acid (b) having a pKa of less than 0 with the mixed solution obtained in the above step, and then mixing a polythiol compound;
A method for producing a polymerizable composition for optical materials, comprising:

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