JP6966185B2 - Manufacturing method of cured product - Google Patents

Description

The present invention relates to a novel method for producing a cured product. It also relates to a novel cured product obtained by the method.

As a method for molding a (thio) urethane resin (urethane-based resin), a mold polymerization method or the like in which a resin raw material monomer is poured into a gap between glass molds and then the monomer is cured is known. The cured product produced by mold polymerization is widely used as an optical material for optical articles and the like. In this mold polymerization method, it is essential to use a so-called mold release agent in order to release the cured product from the mold.

The release agent is roughly classified into an external release agent and an internal release agent. Since the external mold release agent needs to be applied to the inner surface of the mold (the surface in contact with the cured product) each time it is molded, there is a problem that the productivity of the cured product is lowered. Further, there is a problem that the external mold release agent migrates to the surface of the cured product, causing unevenness on the surface of the cured product.

On the other hand, the internal mold release agent is a mold release agent that is added in advance to the resin raw material monomer, and unlike the external mold release agent, it does not need to be applied to the mold each time it is molded, which is advantageous for improving productivity. be. However, the conventional internal mold release agent has problems such as a weak releasability effect, low compatibility between the resin raw material monomer and the cured product, and the resulting cured product having veins and cloudiness. there were.

As an internal mold release agent used for an optical material or the like, a phosphoric acid ester compound is known as one that can solve the problem of the internal mold release agent (see, for example, Patent Document 1). Specifically, Patent Document 1 describes that a cured product having excellent transparency can be obtained by using a phosphoric acid ester as an internal mold release agent.

However, according to the study by the present inventors, the phosphoric acid ester described in Patent Document 1 is still insufficient in releasability, and it is necessary to further improve the releasability in order to improve the manufacturing yield. It turned out to be. Further, in the case of producing a cured product made of a urethane-based resin, since the phosphoric acid ester acts as a urethanization catalyst, there is room for improvement in terms of the stability of the curable composition.

On the other hand, in recent years, many cured products (optical articles) having photochromic properties have been developed in which a photochromic compound typified by a chromene compound, a flugide compound, a spirooxazine compound and the like is mixed with a urethane resin. The photochromic characteristic is that the color changes quickly when irradiated with light containing ultraviolet rays such as sunlight or mercury lamp light, and returns to the original color when the light is stopped and placed in a dark place (photochromic). Gender). Taking advantage of this property, the cured product is used in various applications, particularly applications for optical materials.

In order to impart photochromic properties to an optical material, a photochromic compound is generally used in combination with a plastic material (resin), and specifically, the following means are known.

(A) A method of directly molding an optical material such as a lens by dissolving a photochromic compound in a monomer and polymerizing the compound. This method is called the kneading method.

(B) A method in which a resin layer in which a photochromic compound is dispersed is provided on the surface of a plastic molded product such as a lens by coating or cast polymerization. This method is called the laminating method.

(C) Two optical sheets are joined by an adhesive layer formed of an adhesive resin in which a photochromic compound is dispersed. This method is called the binder method.

The kneading method (a) and the casting polymerization method (b) are methods of curing the monomer in a mold or forming a resin layer. That is, the (a) kneading method and the (b) casting polymerization are a kind of template polymerization. Then, optical materials such as optical articles to which photochromic properties are imparted are mass-produced using a glass mold (glass mold) (see, for example, Patent Documents 2 and 3). Specifically, Patent Document 2 and Patent Document 3 describe that a photochromic compound is added to or suggested to be added to a monomer composition containing a polyisocyanate monomer and a poly (chi) all monomer. There is. A photochromic lens formed by polymerizing and curing these compositions has a (thio) urethane bond, so that the mechanical strength is very high. However, since there is a hard segment portion of the (thio) urethane bond, the degree of freedom of the photochromic compound is remarkably reduced, and there is room for improvement in terms of photochromic properties.

On the other hand, the present inventors have developed an optical article having high mechanical strength and high photochromic properties by using polyrotaxane even when a urethane-based resin is used (see, for example, Patent Document 4). ). However, in the method described in Patent Document 4, it cannot be said that the releasability is sufficiently satisfied in the kneading method, and there is room for improvement in that the yield in manufacturing can be improved.

As described above, according to the currently known techniques, when an optical article made of a urethane resin is produced, moldability such as releasability, transparency, and storage stability (production stability) of the curable composition are used. There was room for improvement. In particular, even in urethane-based resins (cured products) having photochromic properties, whose demand has been increasing in recent years, there is room for improvement in photochromic properties and the like in addition to the problem of releasability. Photochromic compounds add value to optical articles, and methods that can improve the yield of optical articles containing photochromic compounds have high industrial utility value. In addition, in an optical article containing a photochromic compound, there is also a problem of color tone, so improving transparency has been a very important issue.

International Publication No. WO2011 / 055540 Pamphlet International Publication No. WO2012 / 176439 Pamphlet International Publication No. WO2014 / 08433 Pamphlet International Publication No. WO2015 / 068798 Pamphlet

Therefore, an object of the present invention is to provide a method for producing a cured product which is excellent in mold releasability and moldability, and as a result, the yield is improved and the transparency is also excellent. In addition, when the cured product contains a photochromic compound, it is an object of the present invention to provide a method for producing a cured product having excellent mold releasability and moldability and improved photochromic characteristics.

As a result of diligent studies to solve the above problems, the present inventors have made an internal demolding agent in a cured product (optical article) formed from a polyiso (thio) cyanate compound and a poly (thio) all compound. Various phosphate ester compounds were examined. As a result, they have found that such a problem can be solved by using a specific phosphoric acid ester compound, and have completed the present invention. In particular, by using the phosphoric acid ester compound, even an optical article (cured product) containing a photochromic compound can have excellent transparency (no turbidity in the lens) and can improve the yield. We have found and completed the present invention.

The present invention comprises (A) a polyiso (thio) cyanate compound having two or more isocyanate groups and / or isothiocyanate groups in one molecule, and (B) a poly having two or more hydroxyl groups and / or thiol groups in one molecule. It contains (h) all compounds and (C) phosphate ester compounds.
The (C) phosphate ester compound is
(C1) The following formula (1)

{In the formula,
R ¹ is an alkyl group having 10 to 50 carbon atoms, an alkenyl group having 10 to 50 carbon atoms, an alkynyl group having 10 to 50 carbon atoms, or the following formula (2).

(During the ceremony,
R ³ and R ⁴ are independently hydrogen atoms, methyl groups, or ethyl groups, respectively.
R ⁵ is an alkyl group having 1 to 20 carbon atoms.
n is an integer of 1-18. ) Is the group
R ² represents a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an alkenyl group having 1 to 9 carbon atoms, an alkynyl group having 1 to 9 carbon atoms, or the following formula (3)

(During the ceremony,
R ⁶ and R ⁷ are independent hydrogen atoms, methyl groups, or ethyl groups, and R ⁸ is an alkyl group having 1 to 5 carbon atoms.
m is an integer of 1-2. ) Is the group indicated by. }
Contains the first phosphate ester compound represented by (hereinafter, may be simply referred to as "first phosphate ester compound").
When the total amount of the (C) phosphoric acid ester compound is 100 parts by mass, the curable composition having a blending ratio of the (C1) first phosphoric acid ester compound of 50 to 100 parts by mass is cured. This is a method for producing a cured product.

The method for producing the cured product in the present invention can preferably take the following forms.

(1) When the total amount of the (A) polyiso (thio) cyanate compound and the (B) poly (thio) all compound is 100 parts by mass, the (C) phosphate ester compound is 0.001 to 5 It should be contained in the range of parts by mass.

(2) (D) It is characterized by containing at least one amine compound selected from a secondary amine and a tertiary amine.

(3) When the total amount of the (C) phosphoric acid ester compound is 100 parts by mass, the (D) amine compound is contained in the range of 10 to 1000 parts by mass.

(4) (E) It is characterized by containing a polyrotaxane having a complex molecular structure composed of an axis molecule and a plurality of cyclic molecules that include the axis molecule.

(5) The polyrotaxane (E) is characterized in that a side chain having at least one polymerizable group selected from an OH group and an SH group is introduced into the cyclic molecule.

(6) When the total amount of the (A) polyiso (thio) cyanate compound and the (B) poly (thio) all compound is 100 parts by mass, the (C) phosphate ester compound is 0.001 to 5 It is characterized by containing parts by mass and the polyrotaxane (E) in the range of 0.5 to 20 parts by mass.

(7) (F) It is characterized by containing a photochromic compound.

(8) When the total amount of the (A) polyiso (thio) cyanate compound and the (B) poly (thio) all compound is 100 parts by mass, the (C) phosphate ester compound is 0.001 to 5 It contains parts by mass and the above-mentioned (E) photochromic compound in the range of 0.001 to 10 parts by mass.

(9) Contains a mono-all compound having one (G) hydroxyl group or one thiol group in one molecule.

(10) When the total amount of the (A) polyiso (thio) cyanate compound and the (B) poly (thio) all compound is 100 parts by mass, the (C) phosphate ester compound is 0.001 to 5 It shall contain parts by mass and the (G) mono (thi) all compound in the range of 2 to 40 parts by mass.

According to the present invention, there is provided a cured product obtained by curing the above curable composition. In addition, a combination composition in which the above components are combined is provided.

According to the method for producing a cured product of the present invention, as shown in Examples described later, a cured product having excellent mold releasability, moldability, transparency, and improvement in production yield can be produced. .. Furthermore, when a photochromic compound is contained, a cured product exhibiting photochromic properties can be obtained.

As described above, the excellent mold releasability, moldability, transparency, and improvement in production yield are caused by the mold release agent selected from the specific phosphoric acid ester compounds. I think like this.

It was considered that the hydrogen bond between the phosphoric acid ester and the glass mold used for polymerization is important for the expression of the releasability of the phosphoric acid ester compound. That is, it was considered that the releasability can be exhibited by the transfer of the phosphoric acid ester compound to the interface between the cured product and the mold due to the hydrogen bond between the hydroxyl group of the phosphoric acid ester compound and the mold interface.

The molecular weight of the organic group (length of the organic machine) of the ester moiety of the phosphoric acid ester compound affects the releasability, and the ester moiety having a certain molecular weight is required to develop the releasability. I thought it was necessary. Furthermore, in the case of phosphoric acid diesters, if the organic groups at the two ester sites both have a large molecular weight or are bulky, the hydrogen bond between the phosphoric acid ester compound and the mold is inhibited, and the releasability is lowered (thio). ) It was presumed that the cured product would become cloudy due to the decrease in compatibility with the urethane resin.

Based on these findings, the present inventors have developed a phosphate ester compound having a molecular design in which one ester chain has a molecular weight suitable for improving releasability and the other ester chain has a low molecular weight. It is presumed that the use can suppress the decrease in the releasability of the cured product. That is, the present inventor produces a cured product having excellent releasability and transparency by using the first phosphoric acid ester compound represented by the formula (1) as a main component as an internal release agent. I think it can be done. As a result, according to the present invention, a cured product, that is, a cured product of high quality can be obtained while significantly improving the yield of the optical article. This effect becomes remarkable in the case of producing a cured product containing a photochromic compound.

It is a figure which showed the mold used for the cast polymerization at the time of producing a photochromic laminate using the photochromic curable composition of this invention. It is the schematic which shows the molecular structure of polyrotaxane used in this invention.

In the present invention, the cured product is
(A) A polyiso (thio) cyanate compound having two or more isocyanate groups and / or isothiocyanate groups in one molecule.
(B) A poly (thio) all compound having two or more hydroxyl groups and / or thiol groups in one molecule, and
It can be produced by curing a curable composition containing (C) a phosphoric acid ester compound. A characteristic part of the present invention is that the (C) phosphate ester compound contains the first phosphate ester compound represented by the formula (1).

Further, in the method for producing the cured product, the cured product is composed of at least one amine compound selected from (D) secondary amines and tertiary amines, depending on the mode of use.
(E) A polyrotaxane having a complex molecular structure composed of an axis molecule and a plurality of cyclic molecules that include the axis molecule.
(F) Photochromic compound,
(G) A mono-all compound having one hydroxyl group or one thiol group in one molecule is appropriately blended. In addition, it contains other known formulations.

First, (A) a polyiso (thio) cyanate compound having two or more isocyanate groups and / or isothiocyanate groups in one molecule will be described.

<(A) Polyiso (thio) cyanate compound having two or more isocyanate groups and / or isothiocyanate groups in one molecule>
In the present invention, a polyiso (thio) cyanate compound having two or more isocyanate groups and / or isothiocyanate groups constituting the curable composition in one molecule (hereinafter simply (A) "polyiso (thio) cyanate compound", or (A may be a component) has two or more isocyanate groups in one molecule, two or more isothiocyanate groups in one molecule, and the total number of groups of the isocyanate group and the isothiocyanate group. It is a compound that is present in two or more in one molecule.

Among the (A) polyiso (thio) cyanate compounds, examples of the polyisocyanate compound include aliphatic isocyanates, alicyclic isocyanates, aromatic isocyanates, sulfur-containing aliphatic isocyanates, aliphatic sulfide isocyanates, and aromatic sulfide compounds. Examples thereof include isocyanates, aliphatic sulfone-based isocyanates, aromatic sulfone-based isocyanates, sulfonic acid ester-based isocyanates, aromatic sulfonic acid amide-based isocyanates, and sulfur-containing heterocyclic isocyanates. Specific examples of these polyisocyanate compounds include the following compounds. In the present invention, as the (A) polyiso (thio) cyanate compound, one kind of compound may be used, or a plurality of kinds of compounds may be used. When a plurality of types of compounds are used, the reference mass is the total amount of the plurality of types of compounds.

Aliphatic isocyanate; ethylene diisocyanis, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanis, nonamethylene diisocyanis, 2,2'-dimethylpentane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanis, decamethylene diisocyanis , Buten diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-trimethylundecamethylene diisocyanate, 1,3,6-trimethylhexamethylene diisocyanate, 1,8-Diisocyanis-4-isamethylene methyl octane, 2,5,7-trimethyl-1,8-diisocyanis-5-isocyanide methyl octane, bis (isocyanisethyl) carbonate, bis (isocyanisethyl) ether, 1, 4-butylene glyco-ldipropyl ether ω, ω'-diisocyanate, lysine diisocyanate methyl ester, lysine triisocyanate, 2-isocyanisethyl-2,6-diisocyanate hexanoate, 2-isocyanspropyl-2,6-diisocyanate hexa Noate, 2,4,4-trimethylhexamethylene diisocyanate.

Alicyclic isocyanates; isophorone diisocyanates, (bicyclo [2.2.1] heptane-2,5-diyl) bismethylene diisocyanates, (bicyclo [2.2.1] heptane-2,6-diyl) bismethylene diisocyanates, 2β, 5α-bis (isocyanate) norbornan, 2β, 5β-bis (isocyanate) norbornan, 2β, 6α-bis (isocyanate) norbornan, 2β, 6β-bis (isocyanate) norbornan, 2,6-di (isocyanate methyl) furan , Bis (isocyanate methyl) cyclohexane, dicyclohexylmethane-4,4'-diisocyanate, 4,4-isopropylidenebis (cyclohexylisocyanate), cyclohexanediisocyanate, methylcyclohexanediisocyanate, dicyclohexyldimethylmethanediisocyanate, 2,2'-dimethyldicyclohexylmethane Diisocyanate, bis (4-isocyanate-n-butylidene) pentaerythritol, diisocyanate dimerate, 2-isocyanatemethyl-3- (3-isocyanatepropyl) -5-isocyanatemethyl-bicyclo [2,2,1] -Heptane, 2-isocyanatemethyl-3- (3-isocyanatepropyl) -6-isocyanatemethyl-bicyclo [2,2,1] -heptane, 2-isocyanatemethyl-2- (3-isocyanatepropyl) -5-isocyanate Methyl-bicyclo [2,2,1] -heptane, 2-isocyanatemethyl-2- (3-isocyanatepropyl) -6-isocyanatemethyl-bicyclo [2,2,1] -heptane, 2-isocyanatemethyl-3- (3-Isocyanatepropyl) -5- (2-Isocyanateethyl) -bicyclo [2,2,1] -heptane, 2-isocyanatemethyl-3- (3-isocyanatepropyl) -6- (2-isocyanateethyl)- Bicyclo [2,1,1] -heptane, 2-isocyanatemethyl-2- (3-isocyanatepropyl) -5- (2-isocyanateethyl) -bicyclo [2,2,1] -heptane, 2-isocyanatemethyl- 2- (3-Isocyanatepropyl) -6- (2-isocyanate ethyl) -bicyclo [2,2,1] -heptane, 2,5-bis (isocyanatemethyl) -bicyclo [2,2,1] -heptane, 2,6-bis (isocyanate methyl) -bicyclo [2 , 2,1] -Heptane, 1,3,5-tris (isocyanatemethyl) cyclohexane, 3,8-bis (isocyanatemethyl) tricyclodecane, 3,9-bis (isocyanatemethyl) tricyclodecane, 4,8 -Bis (isocyanate methyl) tricyclodecane, 4,9-bis (isocyanate methyl) tricyclodecane, 1,5-diisocyanate decalin, 2,7-diisocyanate decalin, 1,4-diisocyanate decalin, 2,6-diisocyanate decalin , Bicyclo [4.3.0] nonane-3,7-diisocyanate and bicyclo [4.3.0] nonane-4,8-diisocyanate mixture, bicyclo [2.2.1] heptane-2,5-diisocyanate And bicyclo [2.2.1] heptane-2,6-diisocyanate, bicyclo [2,2,2] octane-2,5-diisocyanate and bicyclo [2,2,2] octane-2,6-diisocyanate mixtures of tricyclo [5.2.1.0 ^2.6] decane-3,8-diisocyanate and tricyclo [5.2.1.0 ^2.6] decane-4,9-mixtures of diisocyanates.

Aromatic isocyanate; xylylene diisocyanate (o-, m-, p-), tetrachloro-m-xylylene diisocyanate, methylenediphenyl-4,4'-diisocyanate, 4-chloro-m-xylylene diisocyanate, 4,5 -Dichloro-m-xylylene diisocyanate, 2,3,5,6-tetrabrom-p-xylylene diisocyanate, 4-methyl-m-xylylene diisocyanate, 4-ethyl-m-xylylene diisocyanate, bis (isocyanate ethyl) Benzene, bis (isocyanate propyl) benzene, 1,3-bis (α, α-dimethylisocyanate methyl) benzene, 1,4-bis (α, α-dimethylisocyanate methyl) benzene, α, α, α', α' -Tetramethylxylylene diisocyanate, bis (isocyanate butyl) benzene, bis (isocyanate methyl) naphthalin, bis (isocyanate methyl) diphenyl ether, bis (isocyanate ethyl) phthalate, mesityrylene triisocyanate, 2,6-di (isocyanate) Methyl) furan, phenylenediocyanate, tolylene diisocyanate, ethyl phenylenediocyanate, isopropyl phenylenedi isocyanate, dimethyl phenylenedi isocyanate, diethyl phenylenedi isocyanate, diisopropyl phenylenedi isocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, 1,3,5-triisocyanate methyl benzene , Naphthalene diisocyanate, methyl naphthalenediocyanate, biphenyl diisocyanate, trizine diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, bibenzyl-4,4'-diisocyanate, bis (isocyanatephenyl) ) Ethylene, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, triphenylmethane triisocyanate, polypeptide MDI, naphthalin triisocyanate, diphenylmethane-2,4,4'-triisocyanate, 3-methyldiphenylmethane-4, 4', 6-triisocyanate, 4-methyl-diphenylmethane-2,3,4', 5,6-pentaisocyanate, phenylisocyanate methylisocyanate, phenylisocyanate ethyl isocyanate, tetrahi Dronaftylene diisocyanate, hexahydrobenzene diisocyanate, hexahydrodiphenylmethane-4,4'-diisocyanate, diphenyl ether diisocyanate, ethylene glycol diphenyl ether diisocyanate, 1,3-propylene glycoldiphenyl ether diisocyanate, benzophenone diisocyanate, diethylene glycol diphenyl ether diisocyanate , Dibenzofuran isocyanate, carbazole diisocyanate, ethylcarbazole diisocyanate, dichlorocarbazole diisocyanate.

Sulfur-containing aliphatic isocyanate; thiodiethyldiisocyanate, thiodipropyldiisocyanate, thiodihexyldiisocyanate, dimethylsulfondiisocyanate, dithiodimethyldiisocyanate, dithiodiethyldiisocyanate, 1-isocyanatemethylthio-2,3-bis (2-isocyanatoethylthio) propane , 1,2-Bis (2-isocyanate ethylthio) ethane, 1,1,2,2-tetrakis (isocyanatemethylthio) ethane, 2,2,5,5-tetrakis (isocyanatemethylthio) -1,4-ditian, 2,4-Dithiapentane-1,3-diisocyanate, 2,4,6-trithiaheptan-3,5-diisocyanate, 2,4,7,9-tetrathiapentane-5,6-diisocyanate, bis (isocyanate methylthio) ) Phenylmethane, bis (isocyanate methylthio) methane, bis (isocyanate ethyl thio) methane, bis (isocyanate ethyl thio) ethane, bis (isocyanate methyl thio) ethane, 1,5-isocyanate 2-isocyanate methyl-3-thiapentane aliphatic sulfide Isocyanates; bis [2- (isocyanate methylthio) ethyl] sulfide, dicyclohexyl sulfide-4,4'-diisocyanate, bis (isocyanate methyl) sulfide, bis (isocyanate ethyl) sulfide, bis (isocyanate propyl) sulfide, bis (isocyanate hexyl) ) Sulfate, bis (isocyanate methyl) disulfide, bis (isocyanate ethyl) disulfide, bis (isocyanate propyl) disulfide.

Aromatic sulfide-based isocyanates; diphenylsulfide-2,4'-diisocyanate, diphenylsulfide-4,4'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanate dibenzylthioether, bis (4-isocyanate methylbenzene) ) Sulfide, 4,4'-methoxybenzenethioethylene glycol-3,3'-diisulfate, diphenyldisulfide-4,4'-disulfide, 2,2'-dimethyldiphenyldisulfide-5,5'-diisulfate, 3 , 3'-dimethyldiphenyl disulfide-5,5'-diisulfate, 3,3'-dimethyldiphenyldisulfide-6,6'-diisulfide, 4,4'-dimethyldiphenyldisulfide-5,5'-diisulfate, 3,3 '-Dimethoxydiphenyl disulfide-4,4'-diisulfate, 4,4'-dimethoxydiphenyldisulfide-3,3'-diisulfate.

Aliphatic sulfone-based isocyanate; bis (isocyanate methyl) sulfone.

Aromatic sulfone-based isocyanates; diphenyl sulfone-4,4'-diisocyanate, diphenylsulfone-3,3'-diisocyanate, benzylidene sulfone-4,4'-diisocyanate, diphenylmethanesulfone-4,4'-diisocyanate, 4-methyldiphenylmethane Sulfone-2,4'-diisulfone, 4,4'-dimethoxydiphenylsulfone-3,3'-diisulfone, 3,3'-dimethoxy-4,4'-diisocyanate dibenzylsulfone, 4,4'-dimethyldiphenylsulfone -3,3'-diisulfone, 4,4'-di-tert-butyldiphenylsulfone-3,3'-diisulfone, 4,4'-dimethoxybenzeneethylenedisulfone-3,3'-diisulfone, 4,4'- Dichlorodiphenyl sulfone-3,3'-diisocyanate sulfonic acid ester-based isocyanate; 4-methyl-3-isocyanatebenzenesulfonyl-4'-isocyanatephenol ester, 4-methoxy-3-isocyanidebenzenesulfonyl-4'-isocyanatorpheno- Ruester.

Aromatic sulfonic acid amide-based isocyanate; 4-methyl-3-isocyanate benzenesulfonylanilide-3'-methyl-4'-isocyanate, dibenzenesulfonyl-ethylenediamine-4,4'-diisocyanate, 4,4'-dimethoxybenzenesulfonyl -Isocyanate-3,3'-diisocyanate, 4-methyl-3-isocyanate benzenesulfonylanilide-4-methyl-3'-isocyanate.

Sulfur-containing heterocyclic isocyanate; thiophene-2,5-diisocyanate, thiophene-2,5-diisocyanate methyl, 1,4-dithian-2,5-diisocyanate, 1,4-dithian-2,5-diisocyanate methyl, 1, 3-Dithiolane-4,5-diisocyanate, 1,3-dithiolane-4,5-diisocyanatemethyl, 1,3-dithiolane-2-methyl-4,5-diisocyanatemethyl, 1,3-dithiolane-2,2- Diisocyanate ethyl, tetrahydrothiophene-2,5-diisocyanate, tetrahydrothiophene-2,5-diisocyanate methyl, tetrahydrothiophene-2,5-diisocyanate ethyl, tetrahydrothiophene-3,4-diisocyanatemethyl, tricyclothiaoctane diisocyanate, 2- (1,1-Diisocyanate methyl) thiophene, 3- (1,1-diisocyanate methyl) thiophene, 2- (2-thienylthio) -1,2-diisocyanate propane, 2- (3-thienylthio) -1,2-diisocyanate Propane, 3- (2-thienyl) -1,5-diisocyanate-2,4-dithiapentane, 3- (3-thienyl) -1,5-diisocyanate-2,4-dithiapentane, 3- (2-thienylthio)- 1,5-Diisocyanate-2,4-dithiapentane, 3- (3-thienylthio) -1,5-diisocyanate-2,4-dithiapentane, 3- (2-thienylthiomethyl) -1,5-diisocyanate-2, 4-Dithiapentane, 3- (3-thienylthiomethyl) -1,5-diisocyanate-2,4-dithiapentane, 2,5- (diisocyanatemethyl) thiophene, 2,3- (diisocyanatemethyl) thiophene, 2,4- (Diisocyanatemethyl) thiophene, 3,4- (diisocyanatemethyl) thiophene, 2,5- (diisocyanatemethylthio) thiophene, 2,3- (diisocyanatemethylthio) thiophene, 2,4- (diisocyanatemethylthio) thiophene, 3,4- (Diisocyanatemethylthio) Thiophene, 2,4-bisisocyanatemethyl-1,3,5-tritian.

Further, the halogen-substituted product, the alkyl-substituted product, the alkoxy-substituted product, the nitro-substituted product of the polyisocyanate, the prepolymer-type modified product with the polyvalent alcohol, the carbodiimide modified product, the urea-modified product, the biuret-modified product, and the dimer-. Chemical or trimmerized reaction products and the like can also be used.

Next, among the (A) polyiso (thio) cyanate compounds, examples of the polyisothiocyanate compound include aliphatic isothiocyanate, alicyclic isothiocyanate, aromatic isothiocyanate, heterocyclic isothiocyanate, and sulfur-containing fatty group. Examples thereof include isothiocyanate, sulfur-containing aromatic isothiocyanate, and sulfur-containing heterocyclic isothiocyanate. Specific examples of these polyiso (thio) cyanate compounds include the following compounds.

Alibo isothiocyanate; 1,2-diisothiocyanate ethane, 1,3-diisothiocyanate propane, 1,4-diisothiocyanate butane, 1,6-diisothiocyanate hexane, p-phenylenediisopropylidene diisothiocyanate ..

Alicyclic isothiocyanates; cyclohexaneisothiocyanate, cyclohexanediisothiocyanate, 2,4-bis (isothiocyanatomethyl) norbornane, 2,5-bis (isothiocyanatomethyl) norbornane, 3,4-bis (isothiocyanate) Methyl) norbornane, 3,5-bis (isothiocyanatomethyl) norbornane.

Aromatic isothiocyanate; phenylisothiocyanate, 1,2-diisothiocyanate benzene, 1,3-diisothiocyanate benzene, 1,4-diisothiocyanate benzene, 2,4-diisothiocyanate toluene, 2,5-di Isothiocyanate-m-xylenedisocyanate, 4,4'-diisothiocyanate-1,1'-biphenyl, 1,1'-methylenebis (4-isothiocyanatebenzene), 1,1'-methylenebis (4-isothiocyanate 2) -Methylbenzene), 1,1'-methylenebis (4-isothiocyanate3-methylbenzene), 1,1'-(1,2-ethandyl) bis (4-isothiocyanatebenzene), 4,4'-diiso Thiothiocyanate benzophenone, 4,4'-diisothiocyanate-3,3'-dimethylbenzophenone, benzanilide-3,4'-diisothiocyanate, diphenylether-4,4'-diisothiocyanate, diphenylamine-4,4'-di Isothiocyanate.

Heterocyclic isothiocyanate; 2,4,6-triisothiocyanate-1,3,5-triazine.

Carbonyl isothiocyanate; hexanedioil diisothiocyanate, nonandioil diisothiocyanate, carbonic diisothiocyanate, 1,3-benzenedicarbonyldiisothiocyanate, 1,4-benzenedicarbonyldiisothiocyanate, (2,2'- Bipyridine) -4,4'-dicarbonyldiisothiocyanate.

Further, a polyfunctional isothiocyanate having at least one sulfur atom in addition to the sulfur atom of the isothiocyanate group can also be used. The following compounds can be exemplified as such polyfunctional isothiocyanates.

Sulfur-containing aliphatic isothiocyanate; thiobis (3-isothiocyanate propane), thiobis (2-isothiocyanate ethane), dithiobis (2-isothiocyanate ethane).

Sulfur-containing aromatic isothiocyanate; 1-isothiocyanate 4-{(2-isothiocyanate) sulfonyl} benzene, thiobis (4-isothiocyanate benzene), sulfonylbis (4-isothiocyanate benzene), sulfinylbis (4-isothiocyanate) Benzene), dithiobis (4-isothiocyanatebenzene), 4-isothiocyanate-1-{(4-isothiocyanatephenyl) sulfonyl} -2-methoxy-benzene, 4-methyl-3-isothiocyanatebenzenesulfonyl-4'- Isothiocyanate phenyl ester, 4-methyl-3-isothiocyanate benzenesulfonylanilide-3'-methyl-4'-isothiocyanate.

Sulfur-containing heterocyclic isothiocyanate; thiophene-2,5-diisothiocyanate, 1,4-dithian-2,5-diisothiocyanate.

The (A) polyiso (thio) cyanate compound exemplified as described above can be used alone or two or more kinds of compounds can be used.

<Preferable (A) polyiso (thio) cyanate compound>
Among the above-mentioned (A) polyiso (thio) cyanate compounds, a compound suitable for forming an optical article having excellent transparency and mechanical strength, particularly suitable for producing an optical article containing a photochromic compound. Examples of the compound are as follows.

A preferred example of the (A) polyiso (thio) cyanate compound is a compound represented by the following formulas (4) to (9).

(Compound with alkylene chain)
The following formula (4)

(During the ceremony,
A is an alkylene group having 1 to 10 carbon atoms, and may be a group in which a carbon atom in the chain of the alkylene group is replaced with a sulfur atom. ) Is preferably used.

A is an alkylene group having 1 to 10 carbon atoms, and may be a linear group or a branched chain group. Among them, some of the hydrogen atoms of the pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, linear group, pentamethylene group, hexamethylene group, heptamethylene group, and octamethylene group are methyl. A branched chain-like group substituted with a group is preferable. Further, as the alkylene group in which the carbon atom is replaced with the sulfur atom, the −CH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ − group is preferable.

Specific examples of the compound represented by the formula (4) include pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, 2,4,4-trimethylhexanemethylene diisocyanate, and 1,2-bis (). 2-Isocyanatoethylthio) ethane and the like can be mentioned. These compounds may be used alone, or two or more kinds of compounds may be used.

(Compound having a phenyl group or a cyclohexane group (ring))
The following formula (5), the following formula (6)

(During the ceremony,
R ⁹ is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, respectively, and may be the same group or different groups.
R ¹⁰ is an alkyl group having 1 to 4 carbon atoms, and when a plurality of groups are present, it may be the same group or a different group.
a is an integer of 2 or 3, b is an integer of 0 to 4, and c is an integer of 0 to 4. ) Is preferably used. The difference between the compound represented by the formula (5) and the compound represented by the formula (6) is that the compound has a phenyl group (the compound represented by the formula (5)) and the compound has a cyclohexane group (ring) (the above). This is a difference from the compound represented by the formula (5).

In R ⁹ , the alkyl group having 1 to 4 carbon atoms may be a linear group or a branched chain group. Of these, R ⁹ is particularly preferably a hydrogen atom, a methyl group, or an ethyl group.

In R ¹⁰ , the alkyl group having 1 to 4 carbon atoms may be a linear group or a branched chain group. Of these, R ¹⁰ is particularly preferably a hydrogen atom, a methyl group, or an ethyl group.

Specific examples of the compound represented by the formula (5) or the formula (6) include isophorone diisocyanate, xylene diisocyanate (o-, m-, p-), 2,4-tolylene diisocyanate, 2, 6-Toluene diisocyanate and the like can be mentioned. These compounds may be used alone, or two or more kinds of compounds may be used.

(Compound having two phenyl groups or two cyclohexane groups (rings))
The following formula (7), the following formula (8)

(During the ceremony,
R ¹¹ is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, respectively, and may be the same group or different groups.
d is an integer and is 0 to 4. ) Is preferably used. The difference between the compound represented by the formula (7) and the compound represented by the formula (8) is that the compound has two phenyl groups (the compound represented by the formula (7)) and two cyclohexane groups (rings). This is a difference from the compound having (the compound represented by the above formula (8)).

In R ^11, an alkyl group having 1 to 4 carbon atoms may be linear, or branched chain groups. Of these, R ¹¹ is particularly preferably a hydrogen atom, a methyl group, or an ethyl group.

Specific examples of the compound represented by the formula (7) or the formula (8) include 4,4'-diphenylmethane diisocyanate, dicyclohexylmethane-4,4'-diisocyanate and the like. These compounds may be used alone, or two or more kinds of compounds may be used.

(Compound with norbornane ring)
The following formula (9)

(During the ceremony,
R ¹² is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, respectively, and may be the same group or different groups, and e is an integer of 0 to 4. ) Is a compound.

In R ¹² , the alkyl group having 1 to 4 carbon atoms may be a linear group or a branched chain group. Of these, R ¹² is particularly preferably a hydrogen atom, a methyl group, or an ethyl group.

Specific examples of the compound represented by the formula (9) include norbornane diisocyanate, 2,5-bis (isocyanate methyl) -bicyclo [2,2,1] -heptane, 2,6-bis (isocyanate methyl). -Bicyclo [2,2,1] -heptane can be mentioned. These compounds may be used alone, or two or more kinds of compounds may be used.

Next, (B) a poly (thio) all compound having two or more hydroxyl groups and / or thiol groups in one molecule will be described.

<(B) Poly (thio) all compound having two or more hydroxyl groups and / or thiol groups in one molecule>
In the present invention, a poly (thio) all compound having two or more hydroxyl groups and / or thiol groups in one molecule constituting the curable composition (hereinafter, simply "(B) poly (thio) all compound", or The "component (B)") has two or more hydroxyl groups (-OH groups) in one molecule, two or more thiol groups (-SH groups) in one molecule, and hydroxyl groups (-OH groups) and thiols. It is a compound in which the total number of groups including the group (-SH group) is two or more in one molecule. In the present invention, as the (B) poly (thio) all compound, one kind of compound may be used, or a plurality of kinds of compounds may be used. When a plurality of types of compounds are used, the reference mass is the total amount of the plurality of types of compounds.

Among the poly (thio) all compounds, examples of the polyol compound include di-, tri-, tetra-, penta-, and hexa-hydroxy compounds, and polyesters containing two or more OH groups in one molecule. Polyol), a polyether containing two or more OH groups in one molecule (hereinafter referred to as a polyether polyol), a polymer containing two or more OH groups in one molecule (polycarbonate polyol), in one molecule A typical example is a polycaprolactone (polycaprolactone polyol) containing two or more OH groups, and an acrylic polymer (polyacrylic polyol) containing two or more OH groups in one molecule. Specific examples of these compounds are as follows.

Alibo alcohols; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, 1,5-dihydroxypentane, 1,6-dihydroxyhexane, 1,7-dihydroxyheptan, 1,8-dihydroxyoctane, 1,9 -Dihydroxynonane, 1,10-dihydroxydecane, 1,11-dihydroxyundecane, 1,12-dihydroxydodecane, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, dimethylolpropane, glyceryl monooleate, monoeridine , Trimethylolpropane tripolyoxyethylene ether (for example, TMP-30, TMP-60, TMP-90, etc. of Nippon Emulsifier Co., Ltd.), trimethylolpropane polyoxyethylene ether, butanetriol, 1,2-methylglucoside, penta Erythritol, dipentaerytitol, tripentaerytitol, sorbitol, erythritol, slateol, livitol, arabinitol, xylitol, aritol, mannitol, dolsitol, imidazole, glycol, inositol, hexanetriol, triglycerol, diglycerol, triethylene glycol, polyethylene glycol, tris (2-hydroxyethyl) isocyanurate, cyclobutanediol, cyclopentane diol, cyclohexane diol, cycloheptane diol, cyclooctane diol, cyclohexane dimethanol, hydroxypropyl cyclohexanol, tricyclo [5,2,1,0 ^2,6] Decane-dimethanol, bicyclo [4,3,0] -nonanediol, dicyclohexanediol, tricyclo [5,3,1,1 ^3,9 ] dodecanediol, bicyclo [4,3,0] nonane dimethanol, tricyclo [5,3,1,1 ^3,9 ] dodecane-diethanol, hydroxypropyltricyclo [5,3,1,1 ^3,9 ] dodecanol, spiro [3,4] octanediol, butylcyclohexanediol, 1,1 '-Bicyclohexylidenediol, cyclohexanetriol, sucrose, maltitol, lactitol, 3-methyl-1,5-dihydroxypentane, dihydroxyneopentyl, 2-ethyl-1,2-dihydroxyhexane, 2-methyl-1, 3-Dihydroxypropane, 1,4 -Cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, o-dihydroxyxylylene, m-dihydroxyxylylene, p-dihydroxyxylylene, 1,4-bis (2-hydroxyethyl) Benzene, 1,4-bis (3-hydroxypropyl) benzene, 1,4-bis (4-hydroxybutyl) benzene, 1,4-bis (5-hydroxypentyl) benzene, 1,4-bis (6-hydroxy) Hexyl) benzene, 2,2-bis [4- (2 "-hydroxyethyloxy) phenyl] propane, glyceryl monooleate, monoeridine, dimethylolpropane.

Aromatic alcohols; dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxybenzene, benzenetriol, biphenyltetraol, pyrogallol, (hydroxynaphthyl) pyrogallol, trihydroxyphenanthrene, bisphenol A, bisphenol F, xylylene glycol, tetrabrom bisphenol A, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,2-bis (4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) phenylmethane, bis (4) -Hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) -1-naphthylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2- (4-hydroxyphenyl) -2- (3-) Hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2 -Bis (4-hydroxyphenyl) pentane, 3,3-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl) octane, 2 , 2-bis (4-hydroxyphenyl) -4-methylpentane, 2,2-bis (4-hydroxyphenyl) heptane, 4,4-bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxyphenyl) Hydroxyphenyl) tridecane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-ethyl-4-hydroxyphenyl) Propane, 2,2-bis (3-n-propyl-4-hydroxyphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis (3-sec-butyl-) 4-Hydroxyphenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 2,2-bis (3) -Allyl-4'-hydroxyphenyl) propane, 2,2-bis (3-methoxy-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2 -Bis (2, 3,5,6-Tetramethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) cyanomethane, 1-cyano-3,3-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) Hydroxyphenyl) Hexafluoropropane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cycloheptane, 1, 1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dichloro-4-hydroxyphenyl) ) Cyclohexane, 1,1-bis (3-methyl-4-hydroxyphenyl) -4-methylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-Hydroxyphenyl) Norbornan, 2,2-bis (4-hydroxyphenyl) adamantan, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, ethylene glycol bis (4-hydroxyphenyl) Hydroxyphenyl) ether, 4,4'-dihydroxydiphenylsulfide, 3,3′-dimethyl-4,4′-dihydroxydiphenylsulfide, 3,3′-dicyclohexyl-4,4′-dihydroxydiphenylsulfide, 3,3′ -Diphenyl-4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenylsulfoxide, 3,3'-dimethyl-4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfone, 4,4' -Dihydroxy-3,3'-dimethyldiphenyl sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3-methylphenyl) ketone, 7,7'-dihydroxy-3,3', 4,4' -Tetrahydro-4,4,4', 4'-Tetramethyl-2,2'-spirobi (2H-1-benzopyran), trans-2,3-bis (4-hydroxyphenyl) -2-butene, 9, 9-bis (4-hydroxyphenyl) fluorene, 3,3-bis (4-hydroxyphenyl) -2-butanone, 1,6-bis (4-hydroxyphenyl) -1,6-hexanedione, 4,4' -Dihydroxybiphenyl, hydroquinone reso Rushin.

Sulfur-containing polyol; bis- [4- (hydroxyethoxy) phenyl] sulfide, bis- [4- (2-hydroxypropoxy) phenyl] sulfide, bis- [4- (2,3-dihydroxypropoxy) phenyl] sulfide, bis -[4- (4-Hydroxycyclohexyloxy) phenyl] sulfide, bis- [2-methyl-4- (hydroxyethoxy) -6-butylphenyl] sulfide, the above sulfur-containing polyol, with an average of 3 molecules per hydroxyl group. Compounds with the following ethylene oxide and / or propylene oxide added, di- (2-hydroxyethyl) sulfide, bis (2-hydroxyethyl) disulfide, 1,4-dithian-2,5-diol, bis (2,3) -Dihydroxypropyl) sulfide, tetrakis (4-hydroxy-2-thiabutyl) methane, bis (4-hydroxyphenyl) sulfone, tetrabromobisphenol S, tetramethylbisphenol S, 4,4'-thiobis (6-tert-butyl- 3-Methylphenol), 1,3-bis (2-hydroxyethylthioethyl) -cyclohexane.

Sulfur-containing heterocyclic polyol; 2,5-bis (hydroxymethyl) -1,4-dithiane, 3-hydroxy-6-hydroxymethyl-1,5-dithiacycloheptane, 3,7-dihydroxy-1,5- Dithiane cyclooctane.

Polyester polyol; a compound obtained by a condensation reaction between a polyol and a polybasic acid.

Polyether polyol; a compound obtained by reacting a compound having two or more active hydrogen-containing groups in the molecule with an alkylene oxide and a modified product thereof.

Polycaprolactone polyol; a compound obtained by ring-opening polymerization of ε-caprolactone.

Polycarbonate polyol; a compound obtained by phosgenation of one or more kinds of low molecular weight polyols, a compound obtained by a transesterification method using ethylene carbonate, diethyl carbonate, diphenyl carbonate and the like.

Polyacrylic polyol; a compound obtained by a copolymer of a hydroxyl group-containing acrylic acid ester or methacrylic acid ester and a monomer copolymerizable with these esters.

Examples of the polythiol compound include aliphatic polythiols, aromatic polythiols, halogen-substituted aromatic polythiols, heterocyclic polythiols, and aromatic polythiols and mercapto groups containing sulfur atoms in addition to the mercapto groups. Examples thereof include aliphatic polythiols containing a sulfur atom and heterocyclic polythiols containing a sulfur atom in addition to the mercapto group. Specific examples of these compounds are as follows.

Aliper polythiol; methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6-hexanedithiol, 1 , 2,3-Propanetrithiol, tetrakis (mercaptomethyl) methane, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane- 1,2-dithiol, 2-methylcyclohexane-2,3-dithiol, bicyclo [2,2,1] hepta-exo-cis-2,3-dithiol, 1,1-bis (mercaptomethyl) cyclohexane, thioapple Acid bis (2-mercaptoethyl ester), 2,3-dimercaptosuccinic acid (2-mercaptoethyl ester), 2,3-dimercapto-1-propanol (2-mercaptoacetate), 2,3-dimercapto-1- Propanol (3-mercaptoacetate), diethylene glycolbis (2-mercaptoacetate), diethyleneglycolbis (3-mercaptopropionate), 1,2-dimercaptopropylmethyl ether, 2,3-dimercaptopropylmethyl ether, 2, 2-Bis (mercaptomethyl) -1,3-propanedithiol, bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), 1,4- Bis (3-mercaptobutyryloxy) butane, 1,4-butanediol bis (3-mercaptopropionate), 1,4-butanediol bis (thioglycolate), 1,6-hexanediol bis (thioglycolate) Rate), tetraethylene glycol bis (3-mercaptopropionate), trimetylolpropanthris (2-mercaptoacetate), trimethylolpropanthris (3-mercaptopropionate), trimethylol ethanetris (3-mercaptobutyrate) ), Trimethylolpropanthris (3-mercaptobutyrate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 1,2-bis (2-mercaptoethylthio) -3 -Mercaptopropane, Dipentaerythritol Hexakis (3-Mercaptopro) Pionate), pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutylyloxy) butane, trimethylolethanepropanthris (3-mercaptobutyrate), trimethylolethane ethanetris (3-mercaptobutyrate) Rate), 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane, 2-mercaptomethyl-1,3-propanedithiol, 2-mercaptomethyl-1,4-butandithiol, 2,4 , 5-Tris (mercaptomethyl) -1,3-dithiolane, 2,2-bis (mercaptomethyl) -1,4-butanedithiol, 4,4-bis (mercaptomethyl) -3,5-dithiaheptan-1, 7-Dithiol, 2,3-bis (mercaptomethyl) -1,4-butanedithiol, 2,6-bis (mercaptomethyl) -3,5-dithiaheptan-1,7-dithiol, 4-mercaptomethyl-1, 8-Dimercapto-3,6-dithiaoctane, 2,5-bismercaptomethyl-1,4-dithiolane, 1,1,3,3-tetrakis (mercaptomethylthio) propane, 5,7-dimercaptomethyl-1,11 -Dimercapto-3,6,9-Trithearcapto, 4,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiandecane, 4,8-Dimercaptomethyl-1,11-Dimercapto -3,6,9-trithiaundecane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane.

Aromatic polythiol; 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, 1,2-bis ( Mercaptomethoxy) Benzene, 1,3-bis (mercaptomethoxy) benzene, 1,4-bis (mercaptomethoxy) benzene, 1,2-bis (mercaptoethoxy) benzene, 1,3-bis (mercaptoethoxy) benzene, 1 , 4-bis (mercaptoethoxy) benzene, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) ) Benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris ( Mercaptoethyl) benzene, 1,3,5-tris (mercaptoethyl) benzene, 1,2,3-tris (mercaptomethoxy) benzene, 1,2,4-tris (mercaptomethoxy) benzene, 1,3,5- Tris (mercaptomethoxy) benzene, 1,2,3-tris (mercaptoethoxy) benzene, 1,2,4-tris (mercaptoethoxy) benzene, 1,3,5-tris (mercaptoethoxy) benzene, 1,2, 3,4-Tetramercaptobenzene, 1,2,3,5-tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene, 1,2,3,4-tetrakis (mercaptomethyl) benzene, 1,2 , 3,5-tetrakis (mercaptomethyl) benzene, 1,2,4,5-tetrakis (mercaptomethyl) benzene, 1,2,3,4-tetrakis (mercaptoethyl) benzene, 1,2,3,5- Tetrax (mercaptoethyl) benzene, 1,2,4,5-tetrakis (mercaptoethyl) benzene, 1,2,3,4-tetrakis (mercaptoethyl) benzene, 1,2,3,5-tetrakis (mercaptomethoxy) Benzene, 1,2,4,5-tetrakis (mercaptomethoxy) Benzene, 1,2,3,4-tetrakis (mercaptoetoki) B) Benzene, 1,2,3,5-tetrakis (mercaptoethoxy) benzene, 1,2,4,5-tetrakis (mercaptoethoxy) benzene, 2,2'-dimercaptobiphenyl, 4,4'-dimercapto Biphenyl, 4,4'-dimercaptobibenzyl, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7 -Naphthalenedithiol, 2,4-dimethylbenzene-1,3-dithiol, 4,5-dimethylbenzene-1,3-dithiol, 9,10-anthracene dimethanethiol, 1,3-di (p-methoxyphenyl) Propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, 2,4-di (p-mercaptophenyl) pentane, 1,4-bis (mercapto) Propylthiomethyl) benzene.

Halogen-substituted aromatic polythiol; 2,5-dichlorobenzene-1,3-dithiol, 1,3-di (p-chlorophenyl) propane-2,2-dithiol, 3,4,5-tribrom-1,2-di Mercaptobenzene, 2,3,4,6-tetrachloro-1,5-bis (mercaptomethyl) benzene.

Heterocyclic polythiol; 2-methylamino-4,6-dithiol sym-triazine, 2-ethylamino-4,6-dithiol sym-triazine, 2-amino-4,6-dithiol sym-triazine, 2-morpholino- 4,6-Dithiol sym-triazine, 2-cyclohexylamino-4,6-dithiol sym-triazine, 2-methoxy-4,6-dithiol sim-triazine, 2-phenoxy-4,6-dithiol sym-triazine, 2 -Thiobenzeneoxy-4,6-dithiol sym-triazine, 2-thiobutyloxy-4,6-dithiol sym-triazine, 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3 5-Triazine-2,4,6 (1H, 3H, 5H) -trione.

Aromatic polythiol containing sulfur atoms in addition to the mercapto group; 1,2-bis (mercaptomethylthio) benzene, 1,3-bis (mercaptomethylthio) benzene, 1,4-bis (mercaptomethylthio) benzene, 1 , 2-bis (mercaptoethylthio) benzene, 1,3-bis (mercaptoethylthio) benzene, 1,4-bis (mercaptoethylthio) benzene, 1,2,3-tris (mercaptomethylthio) benzene, 1, 2,4-Tris (mercaptomethylthio) benzene, 1,3,5-tris (mercaptomethylthio) benzene, 1,2,3-tris (mercaptoethylthio) benzene, 1,2,4-tris (mercaptoethylthio) Benzene, 1,3,5-tris (mercaptoethylthio) benzene, 1,2,3,4-tetrakis (mercaptomethylthio) benzene, 1,2,3,5-tetrakis (mercaptomethylthio) benzene, 1,2, 4,5-tetrakis (mercaptomethylthio) benzene, 1,2,3,4-tetrakis (mercaptoethylthio) benzene, 1,2,3,5-tetrakis (mercaptoethylthio) benzene, 1,2,4,5 -Tetrakiss (mercaptoethylthio) benzene.

An aliphatic polythiol containing a sulfur atom in addition to the mercapto group; bis (mercaptomethyl) sulfide, bis (mercaptoethyl) sulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethylthio) methane, bis (2-mercaptoethyl) Thio) methane, bis (3-mercaptopropyl) methane, 1,2-bis (mercaptomethylthio) ethane, 1,2- (2-mercaptoethylthio) ethane, 1,2- (3-mercaptopropyl) ethane, 1, , 3-bis (mercaptomethylthio) propane, 1,3-bis (2-mercaptoethylthio) propane, 1,3-bis (3-mercaptopropylthio) propane, 1,2-bis (2-mercaptoethylthio) -3-Mercaptopropane, 2-mercaptoethylthio-1,3-propanedithiol, 1,2,3-tris (mercaptomethylthio) propane, 1,2,3-tris (2-mercaptoethylthio) propane, 1, 2,3-Tris (3-mercaptopropylthiomethyl) propane, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (3-mercaptopropylthiomethyl) methane, bis (2,3-) Dimercaptopropyl) sulfide, 2,5-dimercapto-1,4-dithian, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) disulfide, thioglycolic acid or mercaptopropionic acid of the above compounds Estel, hydroxymethyl sulfide bis (2-mercaptoacetate), hydroxymethyl sulfide bis (3-mercaptopropionate), hydroxyethyl sulfide bis (2-mercaptoacetate), hydroxyethyl sulfide bis (3-mercaptopropionate) ), Hydroxypropyl sulfide bis (2-mercaptoacetate), hydroxypropyl sulfide bis (3-mercaptopropionate), hydroxymethyl disulfide bis (2-mercaptoacetate), hydroxymethyl disulfide bis (3-mercaptopropionate), Hydroxyethyl disulfide bis (2-mercaptoacetate), hydroxyethyl disulfide bis (3-mercaptopropionate), hydroxypropyl disulfide bis (2-mercaptoacetate), hydroxypropyl disulfide Dobis (3-mercaptopropionate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-mercaptoethyl ether bis (3-mercaptopropionate), 1,4-dithiane-2,5- Didiolbis (2-mercaptoacetate), 1,4-dithiane-2,5-diolbis (3-mercaptopropionate), 2,5-bis (mercaptomethyl) -1,4-dithiane, 2,5-bis ( 2-Mercaptoethyl) -1,4-dithiane, 2,5-bis (3-mercaptopropyl) -1,4-dithiane, 2- (2-mercaptoethyl) -5-mercaptomethyl-1,4-dithiane, 2- (2-Mercaptoethyl) -5- (3-Mercaptopropyl) -1,4-dithiane, 2-Mercaptomethyl-5- (3-Mercaptopropyl) -1,4-dithiane, bis thioglycolate ( 2-Mercaptoethyl ester), thiodipropionic acid bis (2-mercaptoethyl ester), 4,4'-thiodibutylate bis (2-mercaptoethyl ester), dithiodiglycolic acid bis (2-mercaptoethyl ester), dithio Dipropionic acid bis (2-mercaptoethyl ester), 4,4'-dithiodibutylate bis (2-mercaptoethyl ester), thiodiglycolic acid bis (2,3-dimercaptopropyl ester), thiodipropionic acid bis (2,3-dimercaptopropyl ester), dithiodiglycolic acid bis (2,3-dimercaptopropyl ester), dithiodipropionic acid (2,3-dimercaptopropyl ester), 2-mercaptomethyl-6-mercapto -1,4-dithiacycloheptane, 4,5-bis (mercaptomethylthio) -1,3-dithiolane, 4,6-bis (mercaptomethylthio) -1,3-dithiane, 2-bis (mercaptomethylthio) methyl -1,3-dithiane, 2- (2,2-bis (mercaptomethylthio) ethyl) -1,3-dithiane, 1,2,7-trimercapto-4,6-dithiaheptan, 1,2,9-tri Mercapto-4,6,8-trithianonan, 1,2,11,-trimercapto-4,6,8,10-tetrathiandecan, 1,2,13-trimercapto-4,6,8,10,12 -Pentathia tridecane, 1,2,8,9-tetramercapto-4,6-dithiane, 1,2,10,11-tetramercapto-4,6,8-trithianecan, 1,2,12,13-tetramercapto-4,6,8,10-tetrathiatridecane, bis (2,5-dimercapto-4-thiapentyl) disulfide, bis (2,7-dimercapto-4,6- Dithiane heptyl) disulfide, 1,2,5-trimercapto-4-thiapentane, 3,3-dimercaptomethyl-1,5-dimercapto-2,4-dithiopentane, 3-mercaptomethyl-1,5-dimercapto- 2,4-Dithianepentane, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptan, 3,6-dimercaptomethyl-1,9-dimercapto-2,5,8-trithianonane, 3,7-di Mercaptomethyl-1,9-dimercapto-2,5,8-trithianonan, 4,6-dimercaptomethyl-1,9-dimercapto-2,5,8-trithianonan, 3-mercaptomethyl-1,6-dimercapto- 2,5-Dithiane hexane, 3-mercaptomethylthio-1,5-dimercapto-2-thiapentane, 1,1,2,2-tetrakis (mercaptomethylthio) ethane, 1,1,3,3-tetrakis (mercaptomethylthio) propane , 1,4,8,11-Tetramercapto-2,6,10-Trithiandecan, 1,4,9,12-Tetramercapto-2,6,7,11-Tetrathioaddecane, 2,3-Dithiolane -1,4-Butandithiol, 2,3,5,6-Tetrathian-1,7-Heptanedithiol, 2,3,5,6,8,9-Hexatia-1,10-decandithiol, 2- (1) -Mercapto-2-mercaptomethyl-3-thiabutyl) -1,3-dithiolane, 1,5-dimercapto-3-mercaptomethylthio-2,4-dithianepentane, 2-mercaptomethyl-4-mercapto-1,3-dithiolane , 2,5-Dimercapto-1,4-dithiane, 2,6-dimercapto-1,4-dithiane, 2,4-dimercaptomethyl-1,3-dithiolane, 1,2,6,10,11-penta Mercapto-4,8-dithiolanedecane, 1,2,9,10-tetramercapto-6-mercaptomethyl-4,7-dithianecan, 1,2,9,13,14-pentamercapto-6-mercaptomethyl- 4,7,11-Trithiatetradecane, 1,2,6,10,14,15-Hexamercapto-4,8,12-Trithiapentadecane, 1,4-dithiolane-2,5-bis (4,5) − Dimercapto-2-thiapentane) , 1,4-Dithiane-2,5-bis (5,6-dimercapto-2,3-dithiane hexane).

Heterocyclic polythiol containing a sulfur atom in addition to the mercapto group; 3,4-thiophenedithiol, tetrahydrothiophene-2,5-dimercaptomethyl, 2,5-dimercapto-1,3,4-thiadiazole.

Isocyanurate group-containing polythiol; 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane, tris-{(3-mercaptopropionyloxy) -ethyl} -isocyanurate, 1,3,5-tris (3-Mercaptobutylyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate.

Further, as the above-mentioned (B) poly (thio) all compound in the present invention, a compound having one or more hydroxyl groups and one or more thiol groups in one molecule can also be used. As specific examples thereof, the following compounds can be exemplified.

2-Mercaptoethanol, 3-mercapto-1,2-propanediol, glycerindi (mercaptoacetate), 1-hydroxy-4-mercaptocyclohexane, 2,4-dimercaptophenol, 2-mercaptohydroquinone, 4-mercaptophenol, 1,3-Dimercapto-2-propanol, 2,3-dimercapto-1-propanol, 1,2-dimercapto-1,3-butanediol, pentaerythritol tris (3-mercaptopropionate), pentaerythritol mono (3) -Mercaptopropionate), pentaerythritol bis (3-mercaptopropionate), pentaerythritol tris (thioglycolate), pentaerythritol pentakis (3-mercaptopropionate), hydroxymethyl-tris (mercaptoethyl) Thiomethyl) methane, 1-hydroxyethylthio-3-mercaptoethylthiobenzene, 4-hydroxy-4'-mercaptodiphenylsulfone, 2- (2-mercaptoethylthio) ethanol, dihydroxyethylsulfide mono (3-mercaptopropio) Nate), dimercaptoethanemono (salicylate), hydroxyethylthiomethyl-tris (mercaptoethylthio) methane.

Further, as the (B) poly (thio) all compound, a compound having a silsesquioxane structure can also be used. The formula (10) below is used for silsesquioxane.

(During the ceremony,
The plurality of R ^13s may be the same or different from each other, and are organic groups containing two or more hydroxyl groups and / or thiol groups in at least one molecule, other than organic groups having hydroxyl groups or thiol groups. R ¹³ is a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, or a phenyl group, and the degree of polymerization f is an integer of 6 to 100. ) Is a compound.

Further, ^{as the alkyl group in R 13} , an alkyl group having 1 to 10 carbon atoms is preferable. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group and an n-hexyl group. , N-octyl group, isooctyl group and the like.

As the cycloalkyl group, a cycloalkyl group having 3 to 8 carbon atoms is preferable. Examples of the cycloalkyl group having 3 to 8 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclooctyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like.

As the alkoxy group, an alkoxy group having 1 to 6 carbon atoms is preferable. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group and the like.

In general, silsesquioxane compounds can have various structures such as cage-like, ladder-like, and random. In the present invention, it is preferable to use a mixture having a plurality of structures.

<Preferable compound of (B) poly (chi) all compound>
Among the (B) poly (thio) all compounds as described above, a compound suitable for forming an optical article having excellent transparency and mechanical strength, particularly suitable for producing an optical article containing a photochromic compound. Examples of the compound are as follows. Specific examples thereof include compounds represented by the following formulas (11) to (13), (15) to (17), and (19) to (23).

(Poly-all compound having an alkylene chain or the like)
The following formula (11)

(During the ceremony,
B is an alkylene group or an alkenyl group having 2 to 30 carbon atoms.
R ¹⁴ is a hydroxyl group or an SH group, respectively, and may be the same group or different groups. ) Is preferably used.

B is an alkylene group or an alkenyl group having 2 to 30 carbon atoms, and may be either a linear group or a branched chain group. It is preferably a linear alkylene group having 2 to 15 carbon atoms.

Specific examples of the compound represented by the following formula (11) include polyethylene polyol (2 to 15 carbon atoms), 1,10-decandithiol, and 1,8-octanedithiol.

(Preferable (B) poly (thi) all compound having two or more ether bonds or ester bonds)
The following formula (12) or the following formula (13)

{In the formula,
D is an alkylene group or an alkenyl group having 2 to 15 carbon atoms.
R ¹⁵ is a hydrogen atom or the following formula (14), respectively.

(During the ceremony,
R ¹⁶ is an alkylene group having 1 to 6 carbon atoms. )
It is a group indicated by, and may be the same group or a different group.
l is an average value of 1 to 100. } Is preferably used.

D is an alkylene group or an alkenyl group having 2 to 15 carbon atoms, and may be a linear group or a branched chain group. It is preferably a linear alkylene group having 2 to 6 carbon atoms.

R ¹⁶ is an alkylene group having 1 to 6 carbon atoms, and may be a linear group or a branched chain group. Of these, R ¹⁶ is particularly preferably a methylene group, an ethylene group, a trimethylene group, or a propylene group.

Specific examples of the compound represented by the formula (11) or the compound represented by the formula (12) include polyethylene glycol (l = 1 to 100), polycaprolactone polyol (l = 1 to 100), and tetraethylene. Glycol bis (3-mercaptopropionate), 1,4-butanediol bis (3-mercaptopropionate), 1,6-hexanediolbis (3-mercaptopropionate) and the like can be mentioned.

(Suitable carbonate polyol compound)
The following formula (15)

(During the ceremony,
E and E'are alkylene groups having 2 to 15 carbon atoms, respectively, and may be the same group or different groups.
g is a number of 1 to 20 on average. ) Is preferably used.

E and E'are alkylene groups having 2 to 15 carbon atoms, and may be linear or branched chain groups. Among them, E and E'are trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, nonamethylene group, dodecamethylene group, pentadecamethylene group, 1-methyltriethylene group, 1-ethyl. It is particularly preferably a triethylene group or a 1-isopropyltriethylene group. Specific examples of the compound represented by the formula (15) include polycarbonate polyols (E and E'are pentamethylene groups and hexamethylene groups, g = 4 to 10).

(Polyfunctional polyol compound)
The following formula (16)

(During the ceremony,
R ¹⁷ is an alkyl group having 1 to 6 carbon atoms, and when a plurality of them are present, they may be the same or different.
R ¹⁸ is a hydrogen atom or the same as the above formula (14) and may be the same or different. R ¹⁹ is a hydrogen atom, a methyl group, an ethyl group or a hydrogen atom, respectively, and is the same or different. May,
o is 0-2, q is 2-4, o + q is 4, p is 0-10, and r is 1-6. ) Is preferably used.

R ¹⁷ is an alkyl group having 2 to 15 carbon atoms, and may be a linear group or a branched chain group. Of these, R ¹⁷ is particularly preferably a methylene group, an ethylene group, a trimethylene group, or a propylene group.

Specific examples of the compound represented by the formula (16) include trimethylolpropane, trimethylolpropane tripolyoxyethylene ether (TMP-30 manufactured by Nippon Emulsifier Co., Ltd.), trimethylolpropane, pentaerythritol, and trimethylolpropane tris. (3-Mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate) and the like can be mentioned.

(Polyol compound having an ether bond)
The following formula (17)

{In the formula,
F is an alkyl group of 1 to 6, respectively, or the following formula (18).

(During the ceremony,
R ²⁰ is a hydrogen atom or the above formula (1).
It is a group synonymous with 4), and may be the same group or a different group.
R ²¹ is a methyl group, an ethyl group, or a hydrogen atom, respectively, and may be the same group or different groups.
s is 0 to 10 and t is 1 to 6. )
However, at least two or more of the groups F are the groups represented by the above formula (18). } Is preferably used.

F is a group whose at least two are represented by the above formula (18). Examples of the other groups include alkyl groups 1 to 6, which may be chain-like or branched-chain-like groups. Of these, F is particularly preferably a methyl, ethyl group, trimethylene group, or propylene group. Further, F may be the same group or different groups as long as two or more are groups represented by the above formula (18).

Specific examples of the compound represented by the formula (17) include ditrimethylolpropane, dipentaerythritol hexakis (3-mercaptopropionate) and the like.

(Polyol compound having two hydroxyl groups)
The following formula (19)

(During the ceremony,
R ²² is an alkyl group or an alkenyl group having 1 to 30 carbon atoms. ) Is preferably used.

R ²² is an alkyl group having 1 to 30 carbon atoms or an alkenyl group having 1 to 30 carbon atoms, and may be a linear group or a branched chain group. Since the above formula (19) can be obtained from the condensation reaction of fatty acid and glycerin, R ²² specifically includes an alkyl fatty acid and an alkenyl group moiety. Examples of fatty acids include capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, oleic acid, linoleic acid, arachidic acid, behenic acid, lignoceric acid and the like.

Specific examples of the compound represented by the formula (19) include glyceryl monooleate (monoolein manufactured by Tokyo Chemical Industry Co., Ltd.), monoellaidine, glyceryl monolinoleate, glyceryl monobehenate and the like.

(Polyfunctional polythiol compound)
The following formula (20)

(During the ceremony,
R ²³ is a hydrogen atom, group part is -S- bond of carbon atoms in the chain in the alkyl group, or said alkyl group having 1 to 6 carbon atoms having 1 to 6 carbon ^{atoms, R 23} is plurality of If so, they may be the same group or different groups.
R ²⁴ is an alkylene group having 1 to 10 carbon atoms, and is a group in which a part of carbon atoms in the chain of the alkylene group having 1 to 10 carbon atoms forms an −S— bond, or the group having 1 to 10 carbon atoms. A group in which a part of the hydrogen atom of the alkylene group of the above is substituted with an SH group, and ^{when a plurality of R 24s} are present, the group may be the same group or a different group.
u is an integer of 2 to 4, and v is an integer of 0 to 2. ) Is preferably used.

In R ²³ , the alkyl group having 1 to 6 carbon atoms may be a linear group or a branched chain group, and among them, R ²³ is preferably a hydrogen atom, a methyl group or an ethyl group. Further, as a specific group in which a part of carbon atoms in the chain of an alkyl group having 1 to 6 carbon atoms forms an −S— bond, −CH ₂ SCH ^{3 and the} like can be mentioned.

In R ²⁴ , the alkylene group having 1 to 10 carbon atoms may be a linear group or a branched chain group. Of these, R ²⁴ is particularly preferably a methyl, ethyl group, trimethylene group, or propylene group. Specific groups in which some of the carbon atoms in the chain of the alkylene group having 1 to 10 carbon atoms form an -S- bond include -CH ₂ S- _{, -CH 2} CH ₂ S-, and -CH _2. CH ₂ CH ₂ S- and the like can be mentioned. Further, examples of the group in which a part of the hydrogen atom of the alkyl group having 1 to 6 carbon atoms is substituted with an SH group include a group such as _{−CH 2} SCH (SCH _{2 SH) −.}

Specific examples of the compound represented by the formula (20) include 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane and 2,2-bis (mercaptomethyl) -1,4. -Butanedithiol, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 1,1,1,1-tetrakis (mercaptomethyl) methane, 1,1,3,3-tetrakis (mercaptomethylthio) propane , 1,1,2,2-tetrakis (mercaptomethylthio) ethane and the like.

(Cyclic polythiol compound)
The following formula (21)

(During the ceremony,
R ²⁵ is a carbon atom or a sulfur atom, and at least two of the three ^{R 25s are sulfur atoms.}
R ²⁶ is an alkylene group having 1 to 6 carbon atoms or a group in which a part of carbon atoms in the chain of the alkylene group having 1 to 6 carbon atoms forms an —S— bond. ) Is preferably used.

In R ^26, an alkylene group having 1 to 6 carbon atoms may be linear, or branched chain groups. Among them, R ²⁶ is methyl, ethyl, trimethylene group, or a propylene group. Further, the groups in which some of the carbon atoms in the chain of the alkylene group having 1 to 6 carbon atoms form an -S- bond are specifically -CH ₂ S- _{, -CH 2} CH ₂ S-, and the like. Can be mentioned.

Specific examples of the compound represented by the formula (21) include 2,5-bis (mercaptomethyl) -1,4-dithiane, 4,6-bis (mercaptomethylthio) -1,3-dithiane and the like. Can be mentioned.

(Phenyl group-containing polythiol compound)
The following formula (22)

(During the ceremony,
R ²⁷ is an alkylene group having 1 to 6 carbon atoms, or a part of carbon atoms in the chain of the alkylene group having 1 to 6 carbon atoms forms an —S— bond, and w is 2 to 3 Is. ) Can be used.

In R ²⁷ , the alkylene group having 1 to 6 carbon atoms may be a linear group or a branched chain group. Of these, R ²⁷ is preferably a methyl, ethyl group, trimethylene group, or propylene group. Further, the group in which a part of the carbon atom in the chain of the alkylene group having 1 to 6 carbon atoms forms an −S− bond is specifically −CH ₂ CH ₂ CH ₂ SCH ₂ −, −. CH ₂ CH ₂ SCH _2- , −CH ₂ SCH _2-, and the like can be mentioned.

Specific examples of the compound represented by the formula (22) include 1,4-bis (mercaptopropylthiomethyl) benzene.

(Poly (ti) all compound having a triazine ring)
The following formula (23)

{In the formula,
R ²⁸ is an alkyl group having 1 to 6 carbon atoms, respectively, or the following formula (24).

(During the ceremony,
R ²⁹ and R ³⁰ are alkylene groups having 1 to 6 carbon atoms.
R ³¹ is an oxygen atom or a sulfur atom)
In a group represented, provided that at least two of said R ²⁸ is a group represented by the formula (24), wherein R ²⁸ can be the same group or may be different groups. } Is preferably used.

In R ²⁹ and R ³⁰ , the alkylene group having 1 to 6 carbon atoms may be a linear group or a branched chain group. Of these, R ²⁹ and R ³⁰ are preferably methyl, ethyl, trimethylene, and propylene groups.

Specific examples of the compound represented by the formula (24) include 2-mercaptomethanol and tris-{(3-mercaptopropionyloxy) -ethyl} -isocyanurate.

Next, the (C) phosphoric acid ester compound will be described.

<(C) Phosphate ester compound>
In the present invention, the (C) phosphoric acid ester compound (hereinafter, may be simply referred to as “component (C)”) containing the (C1) first phosphoric acid ester compound represented by the following formula (1) is used. Is a feature. When producing a poly (thio) urethane cured product (hereinafter, also referred to as a cured product) obtained by curing the (A) polyiso (thio) cyanate compound and the (B) poly (thio) all compound, casting is performed. In the case of polymerization, the phosphoric acid ester compound (C) moves to the mold interface, and the cured product can be released from the mold. In particular, by using the (C1) first phosphoric acid ester compound represented by the above formula (1), an excellent effect is exhibited.

First, this (C1) first phosphoric acid ester compound will be described.

(C1) First Phosphate Ester Compound (C1) The first phosphate ester compound is a compound represented by the following formula (1).
The following formula (1)

{In the formula,
R ¹ is an alkyl group having 10 to 50 carbon atoms, an alkenyl group having 10 to 50 carbon atoms, an alkynyl group having 10 to 50 carbon atoms, or the following formula (2).

(During the ceremony,
R ³ and R ⁴ are independently hydrogen atoms, methyl groups, or ethyl groups, respectively.
R ⁵ is an alkyl group having 1 to 20 carbon atoms.
n is an integer of 1-18. ) Is the group
R ² represents a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an alkenyl group having 1 to 9 carbon atoms, an alkynyl group having 1 to 9 carbon atoms, or the following formula (3)

(During the ceremony,
R ⁶ and R ⁷ are independent hydrogen atoms, methyl groups, or ethyl groups, and R ⁸ is an alkyl group having 1 to 5 carbon atoms.
m is an integer of 1-2. ) Is the group indicated by. }
It is the first phosphoric acid ester compound represented by.

Wherein, in ^{R 1,} an alkyl group having 10 to 50 carbon atoms, an alkenyl group having 10 to 50 carbon atoms, and an alkynyl group having 10 to 50 carbon atoms, be linear or branched radicals good. Above all, in order to exhibit good releasability, a linear group having at least 10 to 50 carbon atoms is preferable. Considering the (A) polyiso (thio) cyanate compound, the (B) poly (thio) all compound, and compatibility in the cured product (transparency of the cured product), an alkyl having 10 to 40 carbon atoms. The group is preferably an alkenyl group having 10 to 40 carbon atoms, and further preferably an alkyl group having 10 to 30 carbon atoms or an alkenyl group having 10 to 30 carbon atoms. Specifically, a linear alkyl group having 10 to 30 carbon atoms, a branched isostearyl group, a palmitrail group which is an alkenyl group, an ellaidyl group, an oleyl group, a linoleyl group, and an elelide linoleyl group. , Linolenyl group, elelide linolenyl group, elsyl group and the like.

Further, R ¹ may be a group represented by the above formula (2). In the formula (2), R ⁵ is an alkyl group having 1 to 20 carbon atoms, may be linear or branched groups. Among them, in consideration of good releasability and compatibility, an alkyl group having 1 to 8 carbon atoms is preferable, and specifically, a methyl group, an ethyl group, a trimethylene group, a propylene group, a tetramethylene group, It is preferably a heptamethylene group, a hexamethylene group, an octamethylene group, a nonamethylene group, or a dodecamethylene group.

Further, n is preferably be determined by the length and adjustment of the chain of the R ^5, considering the better releasability, and compatibility, n is preferably 1 to 10.

Among the above descriptions, R ¹ is most preferably a linear alkyl group having 10 to 30 carbon atoms, a branched isostearyl group, a palmitrail group which is an alkenyl group, an ellaidyl group, or an oleyl group.

In R ^2, an alkyl group having 1 to 9 carbon atoms, an alkenyl group having 1 to 9 carbon atoms, an alkynyl group having 1 to 9 carbon atoms may be linear, or branched chain groups. Of these, a hydrogen atom, a methyl group, and an ethyl group are preferable in order to exhibit good releasability.

Further, R ² may be a group represented by the above formula (3). In the formula (3), R ⁸ is alkyl of 1 to 5 carbon atoms may be linear, or branched chain groups. Of these, a methyl group and an ethyl group are preferable. Further, it is most preferable that ^{R 2 becomes a hydrogen atom.}

Since the (C1) first phosphate ester compound has different R ¹ and R ² , it is considered that the first phosphoric acid ester compound exhibits an excellent effect. That is, since it has R ¹ and R ² having different molecular chain lengths, it is considered that both compatibility and releasability are satisfied.

As the (C1) first phosphoric acid ester compound, a single compound may be used, or a plurality of types of compounds may be used. When a plurality of types of compounds are used, the reference mass is the total amount of the plurality of types.

((C2) Other phosphate ester compounds)
The (C) phosphoric acid ester compound used in the present invention may be only the (C1) first phosphoric acid ester, or other phosphoric acid ester compound (hereinafter, (C2) other phosphoric acid ester compound). In some cases) may be included.

(C2) Other phosphoric acid ester compounds are not particularly limited. Examples of specific compounds include the following compounds. For example, mono-n-butyl phosphate, mono-2-ethylhexyl phosphate, mono-n-octyl phosphate, mono-n-butyl phosphate, di (2-ethylhexyl) phosphate, di-n-octyl phosphate. , Di-n-butyl phosphate, O, O-dimethyl dithiophosphate, O, O-diethyl dithiophosphate, O, O-bis (2-ethylhexyl) dithiophosphate, O, O-dimethyl thiophosphate, O thiophosphate, Examples thereof include O-diethyl, O-diethyl thiophosphate, O-bis (2-ethylhexyl), O dithiophosphate, O-diethyl S-methyl and the like. These may use a single compound, or may use a plurality of kinds of compounds. When a plurality of types of compounds are used, the reference mass is the total amount of the plurality of types.

<Composition ratio of (C) phosphate ester compound>
In the present invention, when the total amount of the (C) phosphoric acid ester compound is 100 parts by mass, in order to improve the excellent mold releasability, the transparency of the cured product and the like, and the production yield, the above (C1) The blending ratio of the first phosphoric acid ester compound is preferably 50 to 100 parts by mass ((C2) other phosphoric acid ester compound 0 to 50 parts by mass), and 70 to 100 parts by mass ((C2) other phosphoric acid). It is more preferably 0 to 30 parts by mass of the ester compound), and further preferably 85 to 100 parts by mass ((C2) other phosphoric acid ester compound 0 to 15 parts by mass). That is, it is preferable that the (C1) first phosphoric acid ester compound is the main component, and the above (C1) is excluded except for the inevitably contained phosphoric acid ester compound other than the (C1) first phosphoric acid ester compound. Most preferably, it contains only the first phosphate ester compound (100 parts by mass). The phosphoric acid ester compounds that are inevitably contained include those that cannot be separated, decomposition products, and the like.

<Mixing ratio of (C) phosphoric acid ester compound>
In the curable composition used in the present invention, the blending amount of the (C) phosphoric acid ester compound is appropriately determined according to the types of the (A) component, the (B) component, the (C) component and the like used. Just do it. However, if the blending ratio of the component (C) is too small, the contribution of releasability is small, and if it is too large, the hardness of the cured product tends to decrease, and defects such as pulsation tend to occur. Therefore, the blending amount of (C) is preferably 0.001 to 5 parts by mass, preferably 0.01 to 5 parts by mass, when the total amount of the components (A) and (B) is 100 parts by mass. It is more preferably 3 parts by mass, and most preferably 0.1 to 2 parts by mass.

Next, other components contained in the curable composition used in the present invention will be described. First, at least one amine compound selected from (D) secondary amines and tertiary amines will be described.

<(D) Amine compound selected from secondary amines and tertiary amines>
In the present invention, an amine compound selected from (D) secondary amine and tertiary amine (hereinafter, may be simply referred to as (D) amine compound or (D) component) is blended into the curable composition. be able to. It is considered that the compound (D) forms a salt with the phosphoric acid ester compound of the component (C), but the solubility and compatibility of the component (C) in the curable composition can be improved. Further, the component (C) has the catalytic activity of the urethanization catalyst and can be used as a catalyst. However, if the catalytic activity of the component (C) is too high, the component (D) can be added to the (C) component. It is considered that a salt of the component (C) and the component (D) is formed, but the catalytic activity of the component (C) can be suppressed. As a result, the transparency of the obtained cured product and the thermal stability (storage stability) of the curable composition can be improved. In addition, it is possible to suppress an increase in the viscosity of the curable composition and improve the yield of the cured product.

In the present invention, known secondary amines and tertiary amines can be used as the component (D) without any limitation. A secondary amine or a tertiary amine may be contained in one molecule. Specific examples of the secondary amine and the tertiary amine include the following amine compounds.

Secondary amines: dimethylamine, diethylamine, din-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-t-butylamine, dihexylamine, di (2-ethylhexyl) amine, N-isopropyl-N- Isobutylamine, di-sec-butylamine, N-methylhexylamine, 2-methylpiperidine, 3-methylpiperidine, 4-methylpiperidine, piperidine, 2,4-dimethylpiperidine, 2,6-dimethylpiperidine, 3,5 -Dimethylpiperidine, morpholin, piperazine, pyrrol, N-methylbenzylamine and the like can be mentioned.

Secondary and tertiary amines: N, N, N-trimethylethylenediamine, N, N, N-triethylethylenediamine, imidazole, 1-methylpiperazine.

Tertiary amines: triethylamine, tripropylamine, dipropylethylamine, tributylamine, trihexylamine, dimethylcyclohexylamine, triethylenediamine, tetramethylethylenediamine, tetraethylethylenediamine, tetrapropylethylenediamine, tetrabutylethylenediamine, N, N-diisopropylethylamine, N-Isopropyl-N-Methylbutylamine, N, N, N, N, N-Pentamethyldiethylenetriamine, N, N, N, N, N-Pentaethyldiethylenetriamine, N, N, N, N, N-Pentapropyldiethylenetriamine , N, N, N, N, N-pentabutyldiethylenetriamine, N-methylpiperidine, N-ethylpiperidine, N-propylpiperidine, N-butylpiperidine, N, N-dimethylpiperazine, N, N-diethylpiperazine, N , N-Dipropylpiperazin, N, N-dibutylpiperazine, Hexamethylenetetramine, N-Methylmorpholin, N-ethylmorpholin, N-propylmorpholin, N-butylmorpholin, N-methylpiperidone, N-methylpyrrolidin, N-ethyl Pyrrolidine, N-propylpyrrolidin, N-butylpyrrolidin, N-methylpyrrolidone, N, N-dimethylbenzylamine, N, N-dimethylaniline, N-methyldibenzylamine, pyridine, N-methylpyrazole, 1-methylimidazole , 1,2-dimethylimidazole, benzylmethylimidazole, N-methylpyrrole, diphenylmethylamine and the like.

The above amine compounds can be used alone or a plurality of types of amine compounds can be used. When a plurality of types of amine compounds are used, the reference mass is the total amount of the plurality of types of amine compounds.

In the present invention, the component (D) is preferably a tertiary amine from the viewpoint of stability when mixed with the component (A), the component (B), and the component (C), and further has a basic strength. Aliphatic amines and alicyclic amines are preferred.

(Mixing ratio of component (D))
In the present invention, the blending ratio of the component (D) is not particularly limited. Above all, improvement of solubility / compatibility of component (C) in the curable composition, thermal stability / storage stability of the curable composition, and reduction of molding defects such as pulsation of the obtained cured product. Considering the effect and the like, it is preferable to use the following blending ratio. That is, when the total amount of the component (C) is 100 parts by mass, the amount of the component (D) used is preferably 10 to 1000 parts by mass, preferably 10 to 100 parts by mass. It is more preferably a part.

Next, a polyrotaxane having a composite molecular structure composed of (E) an axis molecule and a plurality of cyclic molecules enclosing the axis molecule will be described.

<(E) Polyrotaxane having a complex molecular structure composed of an axis molecule and a plurality of cyclic molecules that encapsulate the axis molecule>
In the present invention, in order to further improve the mechanical properties of the obtained cured product, the curable composition has a composite molecular structure composed of an (E) axis molecule and a plurality of cyclic molecules enclosing the axis molecule. Polyrotaxane (hereinafter, may be simply referred to as “(E) polyrotaxane” or “(E) component”) may also be blended. The polyrotaxane is a known compound, and as shown in FIG. 2, the polyrotaxane molecule represented by “10” as a whole is formed from a chain shaft molecule “20” and a cyclic molecule “30”. Has a complex molecular structure. That is, a plurality of cyclic molecules "30" are included in the chain-shaped shaft molecule "20", and the shaft molecule "20" penetrates the inside of the ring of the cyclic molecule "30". Therefore, the cyclic molecule "30" can freely slide on the axial molecule "20", but bulky terminal groups "40" are formed at both ends of the axial molecule "20", and the cyclic molecule is formed. The "30" shaft molecule "20" is prevented from falling off.

In this way, the cyclic molecule "30" possessed by the polyrotaxane can slide on the axial molecule "20", so that when it is made into a cured product, it becomes easy to relieve local pressure from the outside and the cured product is cured. It is possible to improve the mechanical strength of the body, especially the tensile strength. The (E) polyrotaxane can be synthesized by the method described in International Publication No. WO2015 / 0668798 pamphlet and the like. The composition of the component (E) will be described.

In the polyrotaxane (E), various shaft molecules are known. For example, the chain portion may be a linear or branched chain as long as it can penetrate the ring of the cyclic molecule. , Generally formed by a polymer. Specifically, it is described in the pamphlet of International Publication No. WO2015 / 068798.

Suitable polymers for forming the chain portion of such shaft molecules include, for example, polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, polypropylene, polyvinyl alcohol or polyvinylmethyl. It is an ether and includes polyethylene glycol.

Further, the bulky group formed at both ends of the chain portion is not particularly limited as long as it is a group that prevents the elimination of the cyclic molecule from the axial molecule, but from the viewpoint of bulkiness, for example, an adamantyl group or a trityl group. , A fluoresenyl group, a dinitrophenyl group, and a pyrenyl substrate, and an adamantyl group can be mentioned particularly in terms of ease of introduction.

The molecular weight of the shaft molecule is not particularly limited, but if it is too large, the compatibility with other components tends to be poor, and if it is too small, the mobility of the cyclic molecule tends to be lowered. From this point of view, the weight average molecular weight Mw of the shaft molecule is preferably in the range of 1,000 to 100,000, particularly 5,000 to 80,000, particularly preferably 10,000 to 50,000. be.

Further, the cyclic molecule has a ring having a size capable of including the axial molecule as described above, and examples of such a ring include a cyclodextrin ring, a crown ether ring, a benzocrown ring, a dibenzocrown ring and the like. A dicyclohexanocrown ring can be mentioned, and a cyclodextrin ring is particularly preferable.

Cyclodextrin rings include α-form (ring inner diameter 0.45 to 0.6 nm), β-form (ring inner diameter 0.6 to 0.8 nm), and γ-form (ring inner diameter 0.8 to 0.95 nm). In particular, the α-cyclodextrin ring is most preferable.

A plurality of cyclic molecules having a ring as described above are included in one axial molecule. Generally, when the maximum number of cyclic molecules that can be included per shaft molecule is 1, the number of cyclic molecules involved is 0.001 to 0.6, more preferably 0.002 to 0. 5, more preferably in the range of 0.003 to 0.4.

The maximum number of inclusions of a cyclic molecule with respect to one axial molecule can be calculated from the length of the axial molecule and the thickness of the ring of the cyclic molecule.

For example, taking the case where the chain portion of the axis molecule is formed of polyethylene glycol and the ring of the cyclic molecule is an α-cyclodextrin ring, the maximum number of inclusions is calculated as follows. ..

That is, two repeating units [-CH _2- CH ₂ O-] of polyethylene glycol approximate the thickness of one α-cyclodextrin ring. Therefore, the number of repeating units is calculated from the molecular weight of this polyethylene glycol, and 1/2 of the number of repeating units is obtained as the maximum number of inclusions of cyclic molecules. The maximum number of inclusions is set to 1.0, and the number of inclusions of the cyclic molecule is adjusted within the above-mentioned range.

Further, a side chain may be introduced into the ring of the above-mentioned cyclic molecule, and this side chain is indicated by "50" in FIG.

Further, such a side chain "50" forms a pseudo-crosslinked structure on the polyrotaxane, whereby the mechanical strength of the cured product formed by using the curable composition can be improved.

The side chain is preferably formed of repeating units of an organic chain having a carbon number in the range of 3 to 20, and the average weight molecular weight of such a side chain is preferably 200 to 10000. It is preferably in the range of 250 to 8000, more preferably 300 to 5,000, and most preferably in the range of 300 to 1500. That is, if the side chain is too small, it becomes difficult to form a crosslinked structure, and if the side chain is too large, the viscosity of the curable composition increases, which tends to make casting into a mold difficult. be.

Further, the side chain as described above is introduced by utilizing the functional group of the ring of the cyclic molecule and modifying this functional group. For example, the α-cyclodextrin ring has 18 hydroxyl groups as functional groups, and a side chain is introduced via these hydroxyl groups. That is, a maximum of 18 side chains can be introduced into one α-cyclodextrin ring. In the present invention, in order to fully exert the function of the side chain described above, it is preferable that 6% or more, particularly 30% or more, of the total number of functional groups of such a ring is modified with the side chain. .. Incidentally, when the side chain is bonded to 9 of the 18 hydroxyl groups of the α-cyclodextrin ring, the degree of modification is 50%.

In the present invention, the side chain (organic chain) as described above may be linear or branched as long as its size is within the above-mentioned range, and may be ring-opened polymerization. Radical polymerization; Cationic polymerization; Anion polymerization; Living radical polymerization such as atom transfer radical polymerization, RAFT polymerization, NMP polymerization, etc. is used, and an appropriate compound is reacted with the functional group of the ring to obtain an appropriate size. Side chains can be introduced.

For example, ring-opening polymerization can introduce side chains derived from cyclic compounds such as cyclic lactones, cyclic ethers, cyclic acetals, cyclic amines, cyclic carbonates, cyclic imino ethers, and cyclic thiocarbonates. Among these, cyclic ether, cyclic siloxane, cyclic lactone, and cyclic carbonate can be used from the viewpoint of easy availability, high reactivity, and easy adjustment of size (molecular weight). preferable. As specific examples of suitable cyclic compounds, those described in International Publication No. WO2015 / 068798 pamphlet can be used. Among them, cyclic lactones and cyclic carbonates are preferably used, and lactones such as ε-caprolactone, α-acetyl-γ-butyrolactone, α-methyl-γ-butyrolactone, γ-valerolactone, and γ-butyrolactone. Is particularly preferred, the most preferred being ε-caprolactone.

Further, when a cyclic compound is reacted by ring-opening polymerization to introduce a side chain, the functional group (for example, a hydroxyl group) bonded to the ring has poor reactivity, and a large molecule may be directly reacted particularly due to steric hindrance or the like. It can be difficult. In such a case, for example, in order to react caprolactone or the like, a low molecular weight compound such as propylene oxide is reacted with a functional group to carry out hydroxypropylation, and a highly reactive functional group (hydroxyl group) is introduced. After that, a means of introducing a side chain by ring-opening polymerization using the above-mentioned cyclic compound can be adopted.

As described above, the side chain can be introduced into (E) polyrotaxane by ring-opening polymerization, but of course, the side chain can also be introduced by other known methods and compounds.

It is presumed that the (E) polyrotaxane used in the present invention is polymerized with at least one compound of the component (A) and the component (B) to have voids formed by the polyrotaxane in the cured product. NS. As a result, it is considered that the component (C) is easily transferred to the mold interface and the releasability can be improved. In addition, due to the presence of the voids, when the (F) photochromic compound described in detail below is used, the photochromic compound is uniformly maintained in a dispersed state, and excellent photochromic properties are continuously expressed. It is thought that it can be made to.

As described above, by blending the component (E), the mechanical properties of the obtained cured product can be improved, and further, the releasability and the photochromic properties can be further improved. Therefore, from the viewpoint of improving the releasability, it is preferable that the side chain of the (E) polyrotaxane has a group selected from the group consisting of a hydroxyl group and a thiol group.

Further, depending on the type of functional group possessed by the compound used for introducing the side chain, a part of this side chain may be bonded to the functional group of the ring of the cyclic molecule possessed by another axis molecule. It may also form a crosslinked structure. Such a polymerizable functional group is introduced by utilizing the above-mentioned side chain, and is introduced by using an appropriate compound for forming the side chain.

In the present invention, the most preferably used (E) polyrotaxane is a cyclic molecule having an α-cyclodextrin ring, with polyethylene glycol bonded at both ends as an adamantyl group as a shaft molecule, and further by polycaprolactone. A side chain (OH group at the end) is introduced into the ring.

<Mixing ratio of component (E)>
In the present invention, when (E) polyrotaxane is used, the blending amount of (E) polyrotaxane is taken into consideration in consideration of physical properties such as mechanical strength of the obtained cured product, releasability, and viscosity of the curable composition. Is preferably in the following range. Specifically, when the total of the component (A) and the component (B) is 100 parts by mass, the component (E) is preferably 0.5 to 25 parts by mass. At this time, the component (C) is preferably 0.001 to 5 parts by mass. In order to exert the above effect more, when the total amount of the component (A) and the component (B) is 100 parts by mass, the component (C) is 0.01 to 2 parts by mass and the component (E). Is more preferably contained in the range of 1 to 20 parts by mass, and the component (C) is more preferably contained in the range of 0.1 to 1 part by mass and the component (E) in the range of 1 to 15 parts by mass.

Next, the (F) photochromic compound to be added to the obtained cured product to increase the added value will be described.

<(F) Photochromic compound>
In the present invention, the curable composition may contain an (F) photochromic compound exhibiting photochromic properties (hereinafter, may be simply a component (F)). By containing the (F) photochromic compound, the obtained cured product can be imparted with photochromic properties. As the (F) photochromic compound, a compound known per se can be used. The (F) photochromic compound may be used alone or in combination of two or more. When two types of photochromic compounds are used, the reference mass is the total amount of the plurality of types of photochromic compounds.

Typical examples of such photochromic compounds are flugide compounds, chromene compounds and spirooxazine compounds. For example, JP-A-2-28154, JP-A-62-288830, WO94 / 22850 pamphlet, WO96. It is disclosed in many documents such as the / 14596 pamphlet.

In the present invention, among known photochromic compounds, an indeno [2,1-f] naphtho [1,2-b] pyran skeleton is used from the viewpoint of photochromic properties such as color density, initial colorability, durability, and fading rate. It is more preferable to use a chromene compound having a molecular weight of 540 or more, and a chromene compound having a molecular weight of 540 or more is particularly preferably used because it is particularly excellent in color development density and fading rate.

The chromene compounds shown below are examples of chromene compounds that are particularly preferably used in the present invention.

<Mixing ratio of component (F)>
By using the photochromic compound (F) described above, a cured product having photochromic properties can be obtained. The blending ratio of the (F) photochromic compound is not particularly limited, but the blending ratio is preferably as follows in order for the obtained cured product to exhibit excellent photochromic properties. Specifically, when the total amount of the component (A) and the component (B) is 100 parts by mass, the component (C) is 0.001 to 5 parts by mass and the component (F) is 0.001 to 10 parts by mass. It is preferably contained in the range of parts by mass, more preferably the component (C) in the range of 0.01 to 2 parts by mass and the component (F) in the range of 0.005 to 8 parts by mass, and the component (C). Is more preferably contained in the range of 0.1 to 1 part by mass and the component (F) in the range of 0.01 to 6 parts by mass.

Next, a mono (thio) all compound having one (G) hydroxyl group or one thiol group in one molecule will be described.

<A mono (thio) all compound having one (G) hydroxyl group or one thiol group in one molecule>
In the present invention, the curable composition further contains a (G) hydroxyl group or a thiol group in one molecule (hereinafter, simply "mono (ti) all compound" or "mono (ti) all compound" or ". It may be referred to as "component (G)").

A mono (thio) all compound having one hydroxyl group or thiol group in one molecule has only one hydroxyl group or thiol group, and therefore has fewer hydrogen bonds than a poly (thio) all compound, resulting in less hydrogen bonds. , The viscosity of the curable composition can be reduced. In addition, during casting polymerization, handling performance can be improved and moldability can be improved. Further, in the curable composition which becomes solid at room temperature, there is also an effect of facilitating the dissolution of the curable composition by blending the component (G).

In the present invention, the following compounds can be exemplified as specific examples of the above-mentioned (G) mono (thi) all compound used in the curable composition.

One hydroxyl group compound in one molecule; polyethylene glycol monooleyl ether, polyoxyethylene oleate, polyethylene glycol monolaurate, polyethylene glycol monosteelant, polyethylene glycol mono-4-octylphenyl ether, linear Polyoxyethylene alkyl ether (polyethylene glycol monomethyl ether, polyoxyethylene lauryl ether, polyoxyethylene-2-ethylhexyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether), polypropylene glycol monomethyl Ether, glyceryl dioleate, saturated alkyl alcohol having 5 to 30 carbon atoms in a linear or branched form.

One thiol compound in one molecule; 3-methoxybutyl thioglycolate, 2-ethylhexyl thioglycolate, 2-mercaptoethyl octanoic acid ester, 3-mercaptopropionic acid-3-methoxybutyl, 3- Ethyl mercaptopropionate, -2-octyl 3-mercaptopropionate, n-octyl-3-mercaptopropionate, methyl-3-mercaptopropionate, tridecyl-3-mercaptopropionate, stearyl-3-mercaptopropionate Pionate, a saturated alkyl thiol having a linear or branched structure having 5 to 30 carbon atoms.

(Amount of component (G) blended)
In the present invention, the blending amount of the component (G) contained in the curable composition is not particularly limited. Above all, in consideration of lowering the viscosity of the curable composition and the mechanical strength of the obtained cured product, when the total amount of the component (A) and the component (B) is 100 parts by mass, the above (G) ) The component is preferably blended in an amount of 2 to 40 parts by mass, more preferably 3 to 30 parts by mass, and even more preferably 4 to 25 parts by mass.

<(H) Polymerization curing accelerator>
In the present invention, in addition to the components (A), (B), and (C), (H) polymerization curing is promoted for the purpose of improving the refractive index, improving the moldability, adjusting the hardness of the cured product, and the like. Additional agents may be included. These will be described.

In the present invention, various polymerization curing accelerators (hereinafter, may be simply referred to as “component (H)”) are used in order to rapidly accelerate the polymerization curing thereof, depending on the type of the compound described above. Can be done.

For example, when used for the reaction of a hydroxyl group and a thiol group with an NCO group and an NCS group, a urethane or urea reaction catalyst or a condensing agent is used as a polymerization curing accelerator.

When an episulfide compound, a thietanyl compound, or an epoxy compound is used, an epoxy curing agent or a cationic polymerization catalyst or an anionic polymerization catalyst for ring-opening polymerization of an epoxy group is used as a polymerization curing accelerator.

When an olerine type containing a (meth) acrylic group is contained, a radical polymerization initiator is used as a polymerization curing accelerator.

<(H) Polymerization curing accelerator; reaction catalyst for urethane or urea>
This reaction catalyst is used in the formation of the (A) polyiso (thia) cyanate compound and the (B) poly (thi) all compound poly (thio) urethane bond. Examples of these reaction catalysts include tertiary amines and their corresponding inorganic or organic salts, phosphines, quaternary ammonium salts, quaternary phosphonium salts, Lewis acids, or organic sulfonic acids. note that. When a tertiary amine is used as the (D) amine compound, it is considered that the tertiary amine also acts as a reaction catalyst.

Examples of specific reaction catalysts include the following.

Examples of the tertiary amine include those exemplified by the (D) amine compound.

Phosphines; trimethylphosphine, triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tribenzylphosphine, 1,2-bis (diphenylphosphine) ethane, 1, 2-Bis (dimethylphosphine) ethane.

Quaternary ammonium salts; tetramethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide.

Tertiary phosphonium salts; tetramethylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide.

Luis acid; triphenylaluminum, dimethyltin dichloride, dimethyltinbis (isooctylthioglycolate), dibutyltin dichloride, dibutyltin dilaurate, dibutyltin maleate, dibutyltinmalate polymer, dibutyltin diricinolate, dibutyltinbis (dodecyl mercaptide) , Dibutyltin bis (isooctylthioglycolate), dioctyl tin dichloride, dioctyl tin maleate, dioctyl tin maleate polymer, dioctyl tin bis (butyl maleate), dioctyl tin dilaurate, dioctyl tin diricinolate, dioctyl tin dioleate , Dioctyl tin di (6-hydroxy) caproate, dioctyl tin bis (isooctyl thioglycolate), didodecyl tin diricinolate.

Lewis acid; various metal salts such as copper oleate, copper acetylacetoneate, iron acetylacetoneate, iron naphthenate, iron lactate, iron citrate, iron gluconate, potassium octanoate, 2-ethylhexyl titanate.

Organic sulfonic acid; methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid.

The reaction catalyst for urethane urethane or urea has been described above as the component (H), but if necessary, a known condensing agent, epoxy curing agent, cationic polymerization catalyst, or radical polymerization catalyst may be added as a polymerization accelerator. You can also.

<(H) Compounding ratio of polymerization accelerator>
Each of the various (I) polymerization curing accelerators described above may be used alone or in combination of two or more, but the amount used may be a so-called catalyst amount. Specifically, it is preferably 0.001 to 10 parts by mass, and 0.01 to 5 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the (B). preferable. When the curable composition contains the component (E) and the component (G), the total of the components (A), (B), (E), and (G) is 100 parts by mass. On the other hand, the amount of the (H) polymerization accelerator is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass.

When the tertiary amine is used for both the (D) amine compound and the (H) polymerization accelerator, the preferable blending ratio (usage amount) of the component (D) and the preferred amount of the component (H) are preferable. It is preferable to adjust so as to satisfy the total range of the compounding ratio (used amount).

<Other ingredients contained in the curable composition>
In the present invention, various compounding agents known per se, for example, ultraviolet absorbers, antioxidants, infrared absorbers, ultraviolet stabilizers, antioxidants, anticoloring agents, antioxidants, and fluorescent compounds, as long as the effects are not impaired. Includes various stabilizers such as dyes, dyes, pigments, fragrances, additives, solvents, leveling agents, internal mold release agents other than phosphoric acid ester compounds, episulfide compounds, thietanyl compounds, epoxy compounds, and (meth) acrylate compounds. A resin modifier such as an olefin compound and thiols such as t-dodecyl mercaptan can be added to the curable composition as a polymerization modifier, if necessary.

Above all, it is preferable to use an ultraviolet stabilizer because the durability of the photochromic compound can be improved. As such an ultraviolet stabilizer, a hindered amine light stabilizer, a hindered phenol antioxidant, a sulfur-based antioxidant and the like are known. Particularly suitable UV stabilizers are as follows.

Bis (1,2,2,6,6-pentamethyl-4-piperidyl) Sevacate, Adecaster LA-52, LA-57, LA-62, LA-63, LA-67, manufactured by Asahi Denka Kogyo Co., Ltd. LA-77, LA-82, LA-87, 2,6-di-t-butyl-4-methyl-phenol, ethylenebis (oxyethylene) bis [3- (5-t-butyl-4-hydroxy) -M-Trill) Propionate], IRGANOX 1010, 1035, 1075, 1098, 1135, 1141, 1222, 1330, 1425, 1520, 259, 3114, 3790, 5057, 565, 245, manufactured by Ciba Specialty Chemicals.

The amount of such an ultraviolet stabilizer to be used is not particularly limited as long as the effect of the present invention is not impaired, but usually, the amount of the ultraviolet stabilizer is generally 100 parts by mass based on the total of the component (A) and the component (B). It is preferable to use 0.001 part by mass to 10 parts by mass of the ultraviolet stabilizer, and preferably 0.01 part by mass to 1 part by mass. When the curable composition contains the component (E) and the component (G), the total mass of the component (A), the component (B), the component (E), and the component (G) is 100 mass. It is preferable to use 0.001 part by mass to 10 parts by mass, and more preferably 0.01 part by mass to 1 part by mass of the ultraviolet stabilizer.

When the curable composition contains the (F) photochromic compound, and particularly when a hindered amine light stabilizer is used, the effect of improving durability differs depending on the type of the photochromic compound. It is preferable to prevent color deviation of the developed color tone from occurring. In this case, the amount of the product domin light stabilizer is preferably 0.5 to 30 mol, more preferably 1 to 20 mol, still more preferably 2 to 15 mol, per 1 mol of the component (F).

<Preparation of curable composition>
In the present invention, the curable composition contains (A) component, (B) component, (C) component, and, if necessary, other components including (D) component, (E) component, and (F) component. It can be mixed and prepared together. It is also possible to prepare by mixing a plurality of components of these components in advance to form a premixture, and then mixing the premixture with a residual component or another premixture.

As a method for adjusting the curable composition of the present invention, the components (A), (B), and (C) can be prepared in advance, and then the premixtures thereof can be mixed.

Above all, a method in which the first premix with the component (B) and the component (C) is premixed and adjusted, and then mixed with the component (A) is preferable. That is, a combination composition composed of a combination of the component (A) and the first premixture can be obtained.

Further, in the present invention, when the curable composition contains the component (D),
(I) A method of preparing a second premix of the components (B), (C) and (D) in advance, and then mixing the second premix with the component (A), or
(Ii) A method in which the first premixture of the component (B) and the component (C) is prepared in advance and the component (A) and the component (D) are mixed is preferable. That is, (i) a combination composition composed of a combination of the component (A) and the second premixture, or the first premixture, the component (A), and the component (C). (Ii) It can be a combination composition.

Further, when the component (E) and the component (G) are used, the component (E) and the component (G) are predicted to contain the component (B) in the above methods (i) and (ii). A method of premixing in the mixture is preferable. When the component (F) is used, it is preferable that the component (F) is premixed with the component (A) in the methods (i) and (ii) above. By separating the component (A), the component (C), and the component (D) as described above, it is possible to prevent the component (A) from undergoing a curing reaction with water or the like, and to preserve the component (A). It is possible to improve the stability and stably reproduce the physical properties of the cured product.

Further, even when (I) a polymerization curing accelerator is used, the component (I) is added and adjusted at the end in the above method, or is premixed in a premix containing the component (B). The method of leaving is preferable.

When the premix contains other components such as the above-mentioned (H) component and (J) component in addition to the above-mentioned (A) to (G) and (I) components, other components are used. It may be appropriately contained in a suitable premix in consideration of reactivity with the components. Further, in that case, other components can be made independent and used without being contained in the premixture.

Further, in the present invention, the blending ratio of each component in the curable composition is as described above, but in particular, it is adjusted so as to satisfy the blending ratio and the following conditions. Is preferable. That is, when the molar ratio of the functional group of the hydroxyl group and the thiol group to the isocyanate group and the thioisocyanate group is 1 mol and the total number of moles of the isocyanate group and the thioisocyanate group is 1, the total number of moles of the hydroxyl group and the thiol group is 0. It is preferably .8 to 1.2 mol, more preferably 0.85 to 1.15 mol, and even more preferably 0.9 to 1.1 mol.

<Preferable composition of photochromic composition>
In the present invention, by mixing the photochromic compound (F) with the curable composition, a cured product exhibiting photochromic properties can be obtained by a kneading method (cast polymerization). When exhibiting excellent photochromic properties, it is preferable to use the component (E) or the component (G), and it is more preferable to use the two components of the component (E) and the component (G). This is because the components (E) and (G) are cured to facilitate the formation of the free space required for exhibiting the photochromic properties of the photochromic compound.

<Manufacturing method of cured product>
In the present invention, the curable composition is polymerized and cured to prepare a cured product by heat, or, if necessary, irradiation with active energy rays such as ultraviolet rays, α rays, β rays, and γ rays, or both. It is carried out by performing radical polymerization, ring-opening polymerization, anionic polymerization or polycondensation polymerization by combined use or the like. That is, an appropriate polymerization means may be adopted according to the form of the cured product to be formed.

When the curable composition of the present invention is thermally polymerized, the temperature particularly affects the properties of the cured product. This temperature condition is affected by the type and amount of thermal polymerization initiator and the type of compound, so it cannot be unconditionally limited, but in general, a method of starting polymerization at a relatively low temperature and slowly raising the temperature is used. Suitable. Since the polymerization time also differs depending on various factors as well as the temperature, it is preferable to determine the optimum time according to these conditions in advance, but in general, the conditions are set so that the polymerization is completed in 2 to 48 hours. It is preferable to choose.

As a method for producing the cured product, the curable composition mixed by the above-mentioned method for adjusting the curable composition is injected between the glass molds held by the elastomer gasket or the spacer or tape. After sufficient defoaming, depending on the type of polymerization curing accelerator, curing is formed into the form of an optical material such as a lens by casting polymerization by heating in an air furnace or irradiation with active energy rays such as ultraviolet rays. You can get the body.

According to such a method, the spectacle lens can be directly manufactured. When the curable composition contains the component (F), a spectacle lens or the like with photochromic properties can be obtained.

Further, in the present invention, a cured product can be formed on the surface of the lens base material (plastic lens) by two-stage polymerization.

In the method of forming a cured product by two-stage polymerization, for example, as shown in FIG. 1, the lens base material 1 is faced with a mold 2 for casting polymerization (for example, a glass mold) and fixed. Here, in the mold 2, a jig such as an elastomer gasket or a spacer is formed so that a molding space (cavity) 3 corresponding to the photochromic layer is formed between the plastic lens base material 1 and the mold 2. 4 is attached.

The curable composition is injected into the molding space 3 thus formed in the same manner as described above, and polymerized and cured by heating, whereby the curable composition is formed on the surface of the lens base material 1. A thick film made of the cured product of No. 1 can be laminated. When the curable composition contains the component (F), the photochromic layer can be laminated on the lens base 1. The plastic lens base material used for forming the photochromic laminate thus formed includes (meth) acrylic resin, polycarbonate resin, allyl resin, thiourethane resin, urethane resin and thioepoxy. A typical one is formed of a based resin or the like, and the present invention can be applied to any plastic lens base material. As described above, prior to fixing the lens base material 1 to the mold 2, the surface of the lens base material 1 on which the photochromic layer is formed is subjected to alkali treatment, acid treatment, surfactant treatment, UV ozone treatment, and inorganic treatment. Alternatively, polishing treatment with fine particles of organic matter, primer treatment, plasma or corona discharge treatment is effective in further improving the adhesion.

As a matter of course, as the glass mold used for the casting polymerization, it is also possible to use a glass mold coated with an external mold release agent.

Further, in the present invention, it is also possible to form a cured product on the surface of the lens base material (plastic lens) by the coating method. In the method of forming a cured product by the coating method, first, the curable composition is appropriately dissolved in an organic solvent to prepare a coating liquid, and a plastic lens is prepared by spin coating, dipping, spray coating or the like. The coating liquid is applied to the surface of an optical base material such as a base material. Next, when an organic solvent is used, the organic solvent is dried and removed, and polymerization curing is performed by heating or the like, whereby a layer made of a curable composition can be laminated on the surface of the optical substrate. When the curable composition contains the component (F), a photochromic layer is formed (coating method).

Further, the cured product obtained by the method of the present invention is mainly composed of dyes using dyes such as disperse dyes, silane coupling agents and sol such as silicon, zirconium, antimony, aluminum, tin and tungsten, depending on its use. Preparation of a hard coat film using a hard coat agent, _{thin film formation by vapor deposition of metal oxides such as SiO 2} , TiO ₂ , ZrO ₂ , antireflection treatment with a thin film coated with an organic polymer, antistatic It is also possible to perform post-processing such as processing.

Next, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to the present examples. In the following Examples and Comparative Examples, the methods for evaluating each of the above components and photochromic characteristics are as follows.

(A) A polyiso (thio) cyanate compound having two or more isocyanate groups and / or isothiocyanate groups in one molecule;
XDI: m-xylene diisocyanate.
IPDI: Isophorone diisocyanate.
NBDI: (bicyclo [2.2.1] heptane-2,5 (2,6) -diyl) bismethylene diisocyanate.
HDI: Hexamethylene diisocyanate.

(B) A poly (thio) all compound having two or more hydroxyl groups and / or thiol groups in one molecule;
Polyol;
PL1: Duranoal manufactured by Asahi Kasei Chemicals Co., Ltd. (polycarbonate diol, number average molecular weight 500).
TMP: Trimethylol propane.
DTMP: Ditrimethylolpropane.
TMP-30: Trimethylolpropane tripolyoxyethylene ether manufactured by Nippon Emulsifier Co., Ltd.
monool: Monoolein manufactured by Tokyo Chemical Industry Co., Ltd. (glyceryl monooleate).
Polythiol;
PEMP: Pentaerythritol tetrakis (3-mercaptopropionate).
TMMP: Trimethylolpropanetris (3-mercaptopropionate).
DPMP: Dipentaerythritol hexakis (3-mercaptopropionate).
EGFP-4: Tetraethylene glycol rubis (3-mercaptopropionate).
SH-1: 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane.

(C) Phosphate ester compound (C1) First phosphoric acid ester compound P-1: The ester chain is a linear alkyl group.

P-2: The ester chain is a linear alkyl group <Method for adjusting P-2>
In a nitrogen atmosphere, 50 mL of dehydrated pyridine was dissolved in 2 g of P-12, 2.35 g of DCC (N, N-dicyclohexylcarbodiimide) was added thereto, 0.24 g of methanol was added, and the mixture was stirred at room temperature for 48 hours. Then, after distilling off pyridine, it was washed with hexane. 50 mL of distilled water and 1.5 g of triethylamine were added to the washed solid, and the mixture was stirred for 30 minutes, the insoluble matter was filtered by filtration, and then the distilled water and triethylamine were distilled off to obtain P-2 as the target product. The target product was _{measured with CDCl 3 by a} ¹ H-NMR measuring device (JNM-ECA400II manufactured by JEOL RESONANCE) and confirmed.

(C2) Other Phosphate Ester Compound P-3:

P-4: Commercially available phosphoric acid ester, which is a mixture of monoesters and diesters having the same ester chain and having a monoester content of less than 50% by mass.
A-8: 2-Ethylhexyl acid phosphate manufactured by SC Organic Chemistry Co., Ltd. (ester chain is 2-ethylhexyl group).

(D) Secondary amines and tertiary amines Secondary amines
s-A: Di (2-ethylhexyl) amine.
Tertiary amine t-A: N, N-diisopropylethylamine.

(E) A polyrotaxane having a complex molecular structure composed of an axis molecule and a plurality of cyclic molecules that encapsulate the axis molecule;
RX-1: A polyrotaxane having a side chain having a hydroxyl group in the side chain and having an average molecular weight of about 600 and a weight average molecular weight of 700,000.
RX-2: A polyrotaxane having a side chain having a hydroxyl group in the side chain and having an average molecular weight of about 300 and a weight average molecular weight of 170,000.
RX-3: A polyrotaxane having a thiol group in the side chain and having an average molecular weight of about 400 in the side chain and a weight average molecular weight of 200,000.

<RX-1 adjustment method>
The method for adjusting RX-1 of the component (E) described above is described below.

(1-1) Preparation of PEG-COOH;
As a polymer for forming a shaft molecule, linear polyethylene glycol (PEG) having a molecular weight of 20000 was prepared.
The following prescription;
PEG 10g
TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy radical) 100 mg
Sodium bromide 1g
Each component was dissolved in 100 mL of water.

To this solution, 5 mL of a commercially available sodium hypochlorite aqueous solution (effective chlorine concentration 5%) was added, and the mixture was stirred at room temperature for 10 minutes. Then, etanol was added in a range of up to 5 mL to terminate the reaction. Then, after extraction with 50 mL of methylene chloride, methylene chloride was distilled off, dissolved in 250 mL of ethanol, and then reprecipitated at a temperature of -4 ° C. for 12 hours to PEG-COOH. Was recovered and dried.

(1-2) Preparation of polyrotaxane;
3 g of PEG-COOH and 12 g of α-cyclodextrin (α-CD) prepared above were each dissolved in 50 mL of warm water at 70 ° C., and the obtained solutions were mixed and shaken well. The mixed solution was then reprecipitated at a temperature of 4 ° C. for 12 hours and the precipitated inclusion complex was lyophilized and recovered. Then, 0.13 g of adamantaneamine was dissolved in 50 ml of dimethylformamide (DMF) at room temperature, the above inclusion complex was added, and the mixture was swiftly shaken well. Subsequently, a solution prepared by dissolving 0.38 g of a BOP reagent (benzotriazole-1-yl-oxy-tris (dimethylamino) phosphonium hexafluorophosphate) in DMF was further added and shaken well. Further, a solution prepared by dissolving 0.14 ml of diisopropylethylamine in DMF was added and shaken well to obtain a slurry-like reagent. The slurry-like reagent obtained above was allowed to stand at 4 ° C. for 12 hours. Then, 50 ml of a DMF / methanol mixed solvent (volume ratio 1/1) was added, mixed, and centrifuged, and the supernatant was discarded. Further, after washing with the above-mentioned DMF / metalol mixed solution, washing and centrifugation were performed using metall to obtain a precipitate. The obtained precipitate was dried by vacuum drying, then dissolved in 50 mL of DMSO, and the obtained transparent solution was added dropwise to 700 mL of water to precipitate polyrotaxane. The precipitated polyrotaxane was recovered by centrifugation and dried in vacuum. Further, it was dissolved in DMSO, precipitated in water, recovered, and dried to obtain purified polyrotaxane. The inclusion amount of α-CD at this time is 0.25.

Here, the inclusion amount was calculated by dissolving polyrotaxane in _{DMSO-d 6} ^{, measuring with a 1} H-NMR measuring device (JNM-LA500 manufactured by JEOL Ltd.), and calculating by the following method.
X, Y and X / (YX) have the following meanings.
X: Integral value of cyclodextrin derived from hydroxyl group of 4 to 6 ppm Y: Integral value of proton derived from methylene chain of cyclodextrin and PEG of 3 to 4 ppm X / (YX): Proton ratio of cyclodextrin to PEG First, Theoretically, X / (YX) when the maximum inclusion amount is 1 is calculated in advance, and inclusion is performed by comparing this value with X / (YX) calculated from the analysis value of the actual compound. The amount was calculated.

(1-3) Introduction of side chains into polyrotaxane;
500 mg of the polyrotaxane purified above was dissolved in 50 mL of a 1 mol / L NaOH aqueous solution, 3.83 g (66 mmol) of propylene oxide was added, and the mixture was stirred at room temperature for 12 hours under an argon atmosphere. Next, the above polyrotaxane solution was neutralized to a pH of 7 to 8 using a 1 mol / L HCl aqueous solution, dialyzed in a dialysis tube, and then lyophilized to obtain hydroxypropylated polyrotaxane. rice field.

The degree of modification of the cyclic molecule to the OH group by the hydroxypropyl group was 0.5. A mixed solution was prepared by dissolving 5 g of the obtained hydroxypropylated polyrotaxane in 30 g of ε-caprolactone at 80 ° C. This mixed solution was stirred at 110 ° C. for 1 hour while blowing dry nitrogen, 0.16 g of a 50 wt% xylene solution of tin 2-ethylhexanoate (II) was added, and the mixture was stirred at 130 ° C. for 6 hours. Then, xylene was added to obtain a polycaprolactone-modified polyrotaxane xylene solution into which a side chain having a non-volatile concentration of about 35% by mass was introduced.

The polycaprolactone-modified polyrotaxane xylene solution prepared above was added dropwise to hexane, recovered, and dried to obtain a side chain-modified polyrotaxane (E) having an OH group as a polymerizable functional group. The obtained hydroxypropylated polyrotaxane was ^{identified by 1} H-NMR and GPC, and it was confirmed that it was a hydroxypropylated polyrotaxane having a desired structure. The physical characteristics of this polyrotaxane (RX-1) were as follows.
Side chain modification: 0.5.
Molecular weight of side chains: about 600 on average.
Polyrotaxane Weight Average Molecular Weight Mw (GPC): 700,000.

<RX-2 adjustment method>
The polymer for shaft molecule formation was adjusted in the same manner as RX-1 except that linear polyethylene glycol (PEG) having a molecular weight of 10000 was used and ε-caprolactone was 15 g to obtain RX-2. rice field. The physical characteristics of this polyrotaxane (RX-2) were as follows.
Side chain modification: 0.5.
Molecular weight of side chains: about 300 on average.
Polyrotaxane Weight Average Molecular Weight Mw (GPC): 170000.

<Preparation method of RX-3>
To 10 g of RX-2 obtained above, 2.02 g (0.019 mol) of 3-mercaptopropionic acid, 50 g of toluene and 0.34 g (0.002 mol) of P-toluenesulfonic acid were added under a nitrogen atmosphere, and the mixture was refluxed for 6 hours. It was reacted underneath. The water produced by the reaction was azeotropically boiled with a solvent, only water was removed from the system with a separator, and the solvent was returned to the reaction vessel. Then, it was added dropwise to hexane in a nitrogen-nitrogen atmosphere to precipitate, and then the solid was recovered and dried to obtain RX-3.
The physical characteristics of this polyrotaxane (A) were as follows.
Included amount of α-CD: 0.25.
Side chain modification: 0.5.
Molecular weight of side chains: about 400 on average.
Polyrotaxane Weight Average Molecular Weight Mw (GPC): 200,000.

(F) Photochromic compound;
PC1:

(G) A mono-all compound having one hydroxyl group or thiol group in one molecule;
PGME10: Polyethylene glycol monooleyl ether (n≈10, Mw = 668).
PGMS25: Polyethylene glycol monosteert alert (n≈25, Mw = 1386).
MP-70: Polypropylene glycol monomethyl ether manufactured by Kao Corporation (Mw = 439).

(H) Polymerization curing accelerator;
Reaction catalyst for urethane or urea; DBTD: dibutyltin dilaurate.

Other compounding stabilizers;
HALS: Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (molecular weight 508).
IRG245: IRGNOX245 (bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] [ethylenebis (oxyethylene)]) manufactured by Ciba Specialty Chemicals.

Example 1
Each component was mixed according to the following formulation to prepare a uniform solution. The respective compounding amounts are shown in Tables 1 and 2.
Prescription;
(A) Polyisocyanate compound: IPDI 55 parts by mass (B) Poly (chi) all compound: monol 20 parts by mass, TMP 13 parts by mass, TMP-30 12 parts by mass (C) Phosphate ester compound: P-2 1 part by mass Part (D) DiPEA: 2 parts by mass Other compounding: 0.1 part by mass of HALS was prepared. Using a curable composition containing each of these components, the curable composition was cast into a glass mold and polymerized to obtain a cured product. The polymerization method is as shown below.

That is, the first premix obtained by preheating the component (B), the component (C), and other formulations at 80 ° C. to make them uniform and cooling to room temperature, the component (D), and the component (A) at room temperature. The mixture was sufficiently stirred and mixed while defoaming with, and after making a uniform solution, the mixed solution was poured into a mold made of a glass mold. Then, it was cured over 20 hours while gradually raising the temperature from 27 ° C. to 120 ° C. After completion of the polymerization, the cured product was removed from the glass mold of the mold. At that time, when the releasability was evaluated, the yield was good at 90% or more. Moreover, when the transparency and moldability of the obtained cured product were evaluated, both the transparency and moldability of the obtained cured product were good. The mold releasability, transparency, and moldability were evaluated as follows.

〔Evaluation item〕
(1) Releasability: The releasability of the molded cured product was confirmed, and the yield of the cured product when 30 lenses were polymerized was confirmed. It was evaluated according to the following criteria.
1: Yield is 90% or more.
2: Yield is 80% or more and less than 90%.
3: Yield is 60% or more and less than 80%.
4: Yield is less than 60%.
In the above evaluation, the yield is defined as the fact that the cured product is peeled off from the mold, and that the cured product and the mold are not scratched, so that the mold can be released.

(2) Transparency: The transparency of the molded cured product was observed. It was evaluated according to the following criteria.
1: When the white turbidity of the obtained cured product (2 mm thick) is visually evaluated, there is no white turbidity or almost no white turbidity can be seen at a level that does not cause any problem as a product. Further, when the side surface of the cured product (2 mm thick) is irradiated with the light of a high-pressure mercury lamp and the cured product is visually observed from the surface, the product has no or almost no white turbidity at a level that does not cause any problem. ..
2: When the white turbidity evaluation of the cured product (2 mm thick) is visually performed, there is no white turbidity or almost no white turbidity can be seen at a level that does not cause any problem as a product. However, when the side surface of the cured product (2 mm thick) is irradiated with the light of a high-pressure mercury lamp and the cured product is visually observed from the surface, the product is at a level that does not cause any problem but is slightly cloudy.
3: When the white turbidity evaluation of the cured product (2 mm thick) is visually performed, it is at a level where there is no problem as a product, but there is slight white turbidity. However, when the side surface of the cured product (2 mm thick) is irradiated with the light of a high-pressure mercury lamp and the cured product is visually observed from the surface, the cured product is cloudy.
4: When the white turbidity evaluation of the cured product (2 mm thick) is visually performed, there is white turbidity and it cannot be used as a product.

(3) Moldability: The optical strain of the molded cured product was visually observed. It was evaluated according to the following criteria.
1: No optical distortion.
2: Optical distortion is seen in a part of the lens that is less than half.
3: Optical distortion is seen in half of the lens.
4: Optical distortion is seen throughout the lens.
The results of the cured product evaluated as described above are shown in Table 3.

Examples 2-12, Comparative Examples 1-3
A cured product was prepared and evaluated in the same manner as in Example 1 except that the curable compositions having the compositions shown in Tables 1 and 2 were used. In addition, the composition containing the component (F) was also evaluated for its photochromic characteristics (maximum absorption wavelength, color development density, fading rate). The results are shown in Table 3. The evaluation of the maximum absorption wavelength, the color development density, and the fading rate was performed as follows.

For each component, in Examples 2 and 9, a second premixture of (i), (B) component, (C) component, and (D) component was prepared in advance, and then this second premixture was prepared (A). ) It was mixed by the method of mixing with the component. Further, in Examples 11 and 13, the first premixture of the components (ii) and (B) and the component (C) was prepared in advance, and the components (A) and (D) were mixed. When the component (E) and the component (G) are used, the component (E) and the component (G) are premixed in the premix containing the component (B). When the component (F) is used, the component (F) is premixed with the component (A).

Evaluation of photochromic characteristics of cured product (4) Maximum absorption wavelength (λmax): The maximum absorption wavelength after color development determined by a spectrophotometer (instantaneous multi-channel photodetector-MCPD1000) manufactured by Otsuka Electronics Co., Ltd. The maximum absorption wavelength is related to the color tone at the time of color development.
(5) Color development density {ε (120) -ε (0)}: Difference between the absorbance {ε (120)} after light irradiation for 120 seconds and the absorbance ε (0) before light irradiation at the maximum absorption wavelength. .. It can be said that the higher this value is, the better the photochromic property is. In addition, the color tone was visually evaluated when the color was developed outdoors.
(6) Fading rate [t1 / 2 (sec.)]: After 120 seconds of light irradiation, when the light irradiation is stopped, the absorbance of the sample at the maximum absorption wavelength is {ε (120) −ε (0)}. Time required to reduce to 1/2 of. It can be said that the shorter this time is, the better the photochromic property is.
(7) L Scale Rockwell Hardness (HL): The cured product (2 mm thick) was held in a room at 25 ° C. for 1 day, and then a photochromic cured product was used using an Akashi Rockwell hardness tester (type: AR-10). The hardness of the L scale rockwell (thickness of 2 mm) was measured.

As is clear from the above Examples and Comparative Examples, it can be seen that the cured product obtained by polymerizing the curable composition used in the Examples is extremely excellent in releasability and transparency.

Claims (12)

(A) A polyiso (thio) cyanate compound having two or more isocyanate groups and / or isothiocyanate groups in one molecule.
(B) viewed contains a hydroxyl group and / or poly (thi) ol compounds having two or more thiol groups in one molecule, and (C) phosphoric acid ester compound, further
(E) A polyrotaxane having a complex molecular structure composed of an axis molecule and a plurality of cyclic molecules that include the axis molecule.
(F) Photochromic compound, or
(G) A mono (thio) all compound having one hydroxyl group or one thiol group in one molecule,
Contains at least one selected from
The (C) phosphate ester compound is
(C1) The following formula (1)

{In the formula,
R ¹ is an alkyl group having 10 to 50 carbon atoms, an alkenyl group having 10 to 50 carbon atoms, and an alkynyl group having 10 to 50 carbon atoms.
R ² is a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an alkenyl group having 1 to 9 carbon atoms, and an alkynyl group having 1 to 9 carbon atoms. }
Contains the first phosphate ester compound indicated by
When the total amount of the (C) phosphoric acid ester compound is 100 parts by mass,
(C1) A method for producing a cured product, which comprises curing a curable composition having a blending ratio of the first phosphoric acid ester compound of 50 to 100 parts by mass. The curable composition
When the total amount of the (A) polyiso (thio) cyanate compound and the (B) poly (thio) all compound is 100 parts by mass,
The method for producing a cured product according to claim 1, wherein the (C) phosphoric acid ester compound is contained in the range of 0.001 to 5 parts by mass. The curable composition further
(D) The method for producing a cured product according to claim 1, wherein the cured product contains at least one amine compound selected from a secondary amine and a tertiary amine. The curable composition
When the total amount of the (C) phosphoric acid ester compound is 100 parts by mass,
The method for producing a cured product according to claim 3, wherein the amine compound (D) is contained in the range of 10 to 1000 parts by mass. In the curable composition , the components further contained are
(E) and the shaft molecules, method for producing a cured product according to claim 1, characterized in that a polyrotaxane having a plurality of cyclic molecules clathrate shaft molecule, a composite molecular structure consisting. The (E) polyrotaxane
The method for producing a cured product according to claim 5, wherein a side chain having at least one reactive group selected from an OH group and an SH group is introduced into the cyclic molecule. The curable composition
When the total amount of the (A) polyiso (thio) cyanate compound and the (B) poly (thio) all compound is 100 parts by mass,
The curing according to claim 5 or 6, wherein the (C) phosphoric acid ester compound is contained in the range of 0.001 to 5 parts by mass, and the (E) polyrotaxane is contained in the range of 0.5 to 25 parts by mass. How to make a body. In the curable composition , the components further contained are
(F) The method for producing a cured product according to claim 1, wherein the cured product is a photochromic compound. The curable composition
When the total amount of the (A) polyiso (thio) cyanate compound and the (B) poly (thio) all compound is 100 parts by mass,
The method for producing a cured product according to claim 8, wherein the (C) phosphoric acid ester compound is contained in the range of 0.001 to 5 parts by mass, and the (F ) photochromic compound is contained in the range of 0.001 to 10 parts by mass. In the curable composition , the components further contained are
(G) The method for producing a cured product according to claim 1, wherein the compound is a mono-all compound having one hydroxyl group or one thiol group in one molecule. The curable composition
When the total amount of the (A) polyiso (thio) cyanate compound and the (B) poly (thio) all compound is 100 parts by mass,
The method for producing a cured product according to claim 10, which contains 0.001 to 5 parts by mass of the (C) phosphoric acid ester compound and 2 to 40 parts by mass of the (G) mono (thi) all compound. .. A cured product produced by the method according to any one of claims 1 to 11.

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