JP2016194026A - Method for producing photochromic composition - Google Patents

Abstract

PURPOSE: To provide a method for producing a photochromic composition capable of producing a lens base material with high yield by suppressing the occurrence of poor appearance such as foaming when formed into a lens base material.SOLUTION: There is provided a method for producing a photochromic composition comprising (A) an iso(thio)cyanate reactive group-containing compound containing a polyrotaxane in which a side chain having an iso(thio)cyanate reactive group is introduced into at least a part of a ring contained in a cyclic molecule, (B) a polyiso(thio)cyanate compound and (C) a photochromic compound, which comprises: a defoaming step of removing bubbles in (A) the iso(thio)cyanate reactive group-containing compound by keeping (A) the iso(thio)cyanate reactive group-containing compound at 80 to 150°C; and subsequently a step of mixing (B) the polyiso(thio)cyanate compound and (C) the photochromic compound at 50°C or less.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a novel photochromic composition.

  Photochromic compounds represented by chromene compounds, fulgide compounds, spirooxazine compounds, etc., change color quickly when irradiated with light containing ultraviolet rays such as sunlight or light from mercury lamps. It has the property of returning to its original color (photochromic property), and is used for various uses, particularly for optical materials, taking advantage of this property.

  For example, photochromic eyeglass lenses that have been provided with photochromic properties through the use of photochromic compounds can quickly color and function as sunglasses outdoors exposed to light containing ultraviolet rays such as sunlight. Indoors where there is no color, it functions as normal glasses that fade and become transparent, and in recent years, its demand has increased.

In order to impart photochromic properties to optical materials, photochromic compounds are generally used in combination with plastic materials, and kneading methods are known as one of the means.
The kneading method is a method of directly molding an optical material such as a lens by dissolving a photochromic compound in a compound and polymerizing it.

By the way, the following characteristics are required for optical materials such as optical articles to which photochromic properties are imparted.
(I) The coloring degree (initial coloring) in the visible light region before irradiation with ultraviolet rays is low.
(II) The coloring degree (color density) when irradiated with ultraviolet rays is high.
(III) The speed (fading speed) from when the irradiation of ultraviolet rays is stopped until it returns to the original state is high.
(IV) Good durability against reversible action of color development to fading.
(V) High storage stability.
(VI) It must be easy to mold into various shapes.
(VII) Photochromic properties are imparted without lowering the mechanical strength.

  Accordingly, various proposals have been made to satisfy the above requirements when manufacturing optical materials having photochromic properties, etc., but more excellent photochromic properties with respect to color density and fading speed are proposed. Currently, it is required to be expressed.

  For example, the above-mentioned kneading method has an advantage that a photochromic plastic lens can be produced in a large amount at a low cost using a glass mold. Currently, many photochromic plastic lenses are produced by this method. Yes.

  However, since the kneading method requires strength for the lens substrate, it is necessary to increase the mechanical strength of the matrix resin in which the photochromic compound is dispersed. For this reason, it is difficult to develop excellent photochromic properties. That is, since the degree of molecular freedom of the photochromic compound present in the matrix resin is reduced, the photochromic reversible reaction is impaired.

  For example, regarding such a kneading method, Patent Documents 1 and 2 disclose that a photochromic compound is added to a monomer composition containing a polyisocyanate monomer and a poly (thiol) monomer as having a high lens base material strength. Is described. However, the photochromic lens formed by polymerizing and curing these compositions has a (thio) urethane bond and thus has a very high mechanical strength, but has a (thio) urethane bond hard segment site. The degree of freedom of the photochromic compound was remarkably lowered, and the photochromic property was unsatisfactory.

  Therefore, the present inventors, as a photochromic composition that achieves both the mechanical strength of the cured lens base material and the excellent photochromic property in the lens base material, from an axial molecule and a plurality of cyclic molecules that include the axial molecule. A composition comprising a polyrotaxane, a polyisocyanate monomer, and a photochromic compound having a side chain containing a polymerizable functional group in a part of a cyclic molecule as a part of a cyclic molecule. The present inventors have succeeded in achieving both excellent mechanical strength and excellent photochromic properties due to the presence of free space formed by bonding polyrotaxane to a part of polyurethane, and have already filed applications for the photochromic composition (Patent Document 3). reference).

International Publication WO2012 / 176439 International Publication WO2014 / 084339 International Application PCT / JP2014 / 79560

  However, when the photochromic composition described in Patent Document 3 is cured by a usual method to form a lens base material, an appearance defect that seems to be a bubble often occurs in the lens base material. The present inventors have found that there is a problem that the yield of manufacturing materials is low. When producing a lens substrate, the photochromic composition is defoamed in advance and then the composition is polymerized, but the appearance frequency does not decrease even if the defoaming process is performed for a long time. Also turned out.

  Accordingly, an object of the present invention is to provide a method for producing a photochromic composition capable of suppressing the occurrence of appearance defects such as foaming when used as a lens substrate and producing a lens substrate with a high yield. is there.

  The present inventors have made extensive studies to solve the above problems. Since the bubbles in the photochromic composition are not sufficiently removed by the defoaming treatment before the polymerization of the photochromic composition, various studies have been made on the defoaming treatment of the photochromic composition. As a result, the viscosity of the photochromic composition is high and the defoaming treatment is sufficient. We obtained the knowledge that it was not completed. Therefore, since the polyrotaxane is solid at room temperature, it is presumed that the photochromic composition containing the polyrotaxane has a high viscosity and the defoaming treatment is not completely completed, and the polyrotaxane is heated in advance to a liquid state. After the defoaming treatment, the production of a photochromic composition by mixing other components can suppress the occurrence of poor appearance such as foaming when the photochromic composition is cured to form a lens substrate. As a result, the present invention has been completed.

That is, according to the present invention,
(A) A side having a complex molecular structure composed of an axial molecule and a plurality of cyclic molecules that include the axial molecule, and having an iso (thio) cyanate-reactive group in at least a part of the ring contained in the cyclic molecule (B) a polyiso (thio) cyanate compound having two or more isocyanate groups and / or isothiocyanate groups in one molecule, and (C) ) A photochromic composition comprising a photochromic compound, comprising:
50 degree | times after the defoaming process which hold | maintains the said (A) iso (thio) cyanate reactive group containing compound at 80-150 degreeC, and removes the bubble in (A) iso (thio) cyanate reactive group containing compound. Below, the manufacturing method of the photochromic composition characterized by mixing the said (B) polyiso (thio) cyanate compound and (C) photochromic compound is provided.

  In the method for producing a photochromic composition of the present invention, the defoaming step is preferably performed under a reduced pressure of 10 KPa to 0.1 KPa.

By using the method for producing a photochromic composition of the present invention, it is possible to produce a photochromic lens having excellent photochromic properties and good moldability, as shown in Examples described later.
The improvement in moldability as described above is due to maintaining an iso (thio) cyanate-reactive group-containing compound containing a polyrotaxane having an iso (thio) cyanate-reactive group at 80 to 150 degrees, The present inventors consider the reason as follows.

  That is, when the composition of the present invention is used as an optical article, it is necessary to distill off bubbles and moisture in the composition. If bubbles or moisture remain in the composition, defects such as bubbles remain when the cured product is formed, or moisture and iso (thio) cyanate react to cause decarboxylation. The composition in the present invention has a complex molecular structure composed of an axial molecule and a plurality of cyclic molecules that include the axial molecule, and an iso (thio) cyanate reaction occurs in at least part of the ring contained in the cyclic molecule. It contains a polyrotaxane into which a side chain having a functional group is introduced, and has a molecular weight and a hydrogen bond, so that it is solid at room temperature. Here, the iso (thio) cyanate-reactive group is a group that can react with an isocyanate group and / or an isothiocyanate group. When such a polyrotaxane is used in the composition, the viscosity of the composition is drastically increased, and there are cases where air and moisture inside the composition cannot be completely distilled off at room temperature. Moreover, when heating and defoaming the composition, the iso (thio) cyanate and the iso (thio) cyanate-reactive group-containing compound contained in the composition may react during the defoaming. there were. Therefore, in the present invention, when the iso (thio) cyanate-reactive group-containing compound containing the polyrotaxane is kept at 80 to 150 ° C., the iso (thio) cyanate-reactive group-containing compound becomes liquid, The bubbles in the iso (thio) cyanate-reactive group-containing compound can be efficiently removed by degassing the contained iso (thio) cyanate-reactive group-containing compound in advance at 80 to 150 ° C., and the cured product after polymerization. It was found that bubbles could not be formed and an excellent photochromic cured product could be obtained. It can be inferred that this makes it possible to remove internal air and moisture by loosening hydrogen bonds and reducing the viscosity in the iso (thio) cyanate-reactive group-containing compound. In addition, by degassing the activated hydrogen compound as described above, a good photochromic cured product can be molded with a short time of defoaming when defoaming again in the photochromic composition.

  As understood from this, in the photochromic composition manufacturing method of the present invention, in the case of molding a photochromic lens, the moldability of the photochromic cured product can be improved, and photochromic properties (color density and color fading) can be improved. (Speed) is not impaired.

Schematic showing the molecular structure of the polyrotaxane used in the present invention

The method for producing a photochromic composition of the present invention comprises (A) a complex molecular structure composed of an axial molecule and a plurality of cyclic molecules that enclose the axial molecule. An iso (thio) cyanate-reactive group-containing compound containing at least a polyrotaxane in which a side chain having an iso (thio) cyanate-reactive group is introduced,
(B) When producing a photochromic composition containing a polyiso (thio) cyanate compound having two or more isocyanate groups and / or isothiocyanate groups in one molecule and (C) a photochromic compound, It is characterized in that the (thio) cyanate-reactive group-containing compound is defoamed at a specific temperature. First, each component which comprises a photochromic composition is demonstrated.

<(A) It has a complex molecular structure composed of an axial molecule and a plurality of cyclic molecules that include the axial molecule, and has an iso (thio) cyanate-reactive group in at least a part of the ring contained in the cyclic molecule Iso (thio) cyanate-reactive group-containing compound containing polyrotaxane having a side chain introduced>
(A) which is a constituent component of the photochromic composition of the present invention, has a complex molecular structure composed of an axial molecule and a plurality of cyclic molecules that enclose the axial molecule, and at least a part of the ring included in the cyclic molecule To an iso (thio) cyanate-reactive group-containing compound containing a polyrotaxane in which a side chain having an iso (thio) cyanate-reactive group is introduced (hereinafter also simply referred to as “iso (thio) cyanate-reactive group-containing compound”) Is a side chain having a complex molecular structure composed of an axial molecule and a plurality of cyclic molecules that enclose the axial molecule, and having an iso (thio) cyanate-reactive group in at least a part of the ring contained in the cyclic molecule Is introduced into the polyrotaxane (hereinafter also referred to simply as “iso (thio) cyanate-reactive group-containing polyrotaxane”).

<A side chain having a complex molecular structure composed of an axial molecule and a plurality of cyclic molecules that include the axial molecule, and having an iso (thio) cyanate-reactive group in at least a part of the ring contained in the cyclic molecule Introduced polyrotaxane>
The above-mentioned iso (thio) cyanate-reactive group-containing polyrotaxane is a known compound, and as shown in FIG. 1, the polyrotaxane molecule indicated as “1” as a whole is a chain axis molecule “2”. And a complex molecular structure formed of cyclic molecule “3”. In other words, the chain molecule “2” is surrounded by a plurality of cyclic molecules “3”, and the axial molecule “2” penetrates the inside of the ring of the cyclic molecule “3”. Therefore, the cyclic molecule “3” can freely slide on the axial molecule “2”, but the end molecules “4” are formed at both ends of the axial molecule “2”. Dropping from the “3” axial molecule “2” is prevented. Furthermore, the polyrotaxane used in the present invention has a side chain “5” from the cyclic molecule, and the side chain of the polyrotaxane of the present invention has an iso (thio) cyanate reactive group. As described above, the iso (thio) cyanate-reactive group is a group that can react with an isocyanate group and / or an isothiocyanate group. When the photochromic composition obtained by the production method of the present invention is cured, A (thio) cyanate-reactive group and a polyiso (thio) cyanate compound react to form a cured product. Thus, the iso (thio) cyanate reactive group is present at the end of the side chain.

  Since the cyclic molecule “3” of the polyrotaxane containing iso (thio) cyanate-reactive group as described above can slide on the axial molecule “2”, a space is formed around the cyclic molecule. Thus, it is believed that a reversible structural change of the photochromic compound occurs rapidly, and as a result, the fading speed and the color density are improved. Furthermore, since the polyrotaxane of the present invention has the side chain “5”, it is possible to more surely form an appropriate space between adjacent axial molecules, and to provide a gap that allows a reversible reaction of photochromic compound molecules. It can be ensured reliably and can exhibit excellent photochromic properties. Further, such a side chain “5” forms a pseudo-crosslinked structure in the polyrotaxane, thereby improving the mechanical strength of the photochromic cured product formed using the photochromic composition of the present invention.

  In the above-mentioned iso (thio) cyanate-reactive group-containing polyrotaxane, various types of axial molecules are known. For example, the chain portion may be linear or linear as long as it can penetrate the ring of the cyclic molecule. It may be branched and is generally formed by a polymer.

  Examples of the polymer that forms the chain portion of the axial molecule include polyvinyl alcohol, polyvinyl pyrrolidone, cellulose resins (carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc.), polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, Polyvinyl acetal, polyvinyl methyl ether, polyamine, polyethyleneimine, casein, gelatin, starch, olefin resin (polyethylene, polypropylene, etc.), polyester, polyvinyl chloride, styrene resin (polystyrene, acrylonitrile-styrene copolymer resin, etc.), acrylic Resin (poly (meth) acrylic acid, polymethyl methacrylate, polymethyl acrylate, acrylic resin) Nitrile-methyl acrylate copolymer resin), polycarbonate, polyurethane, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral, polyisobutylene, polytetrahydrofuran, polyaniline, acrylonitrile-butadiene-styrene copolymer (ABS resin), polyamide (nylon) Etc.), polyimide, polydiene (polyisoprene, polybutadiene, etc.), polysiloxane (polydimethylsiloxane, etc.), polysulfone, polyimine, polyacetic anhydride, polyurea, polysulfide, polyphosphazene, polyketone polyphenylene, polyhaloolefin, etc. Can do. These polymers may be appropriately copolymerized or may be modified.

  In the present invention, a polymer that forms a chain portion is preferably polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, polypropylene, polyvinyl alcohol, or polyvinyl methyl ether. Polyethylene glycol is most preferred.

  Furthermore, 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, an adamantyl group, a trityl group, A fluoresceinyl group, a dinitrophenyl group, and a pyrenyl base can be exemplified, and an adamantyl group can be exemplified particularly in terms of ease of introduction.

  The molecular weight of the above-described axial 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 is lowered and the photochromic property is reduced. There is a tendency to decrease. From such a viewpoint, it is preferable that the weight average molecular weight Mw of the axial molecule is in the range of 1000 to 100,000, particularly 5,000 to 80,000, particularly preferably 10,000 to 50,000.

  In addition, the cyclic molecule has a ring of a size that can include the axial molecule as described above. Examples of such a ring include a cyclodextrin ring, a crown ether ring, a benzocrown ring, a dibenzocrown ring, and a dibenzocrown ring. A cyclohexanocrown ring can be mentioned, and a cyclodextrin ring is particularly preferable.

  The cyclodextrin ring includes an α-form (ring inner diameter 0.45-0.6 nm), a β-form (ring inner diameter 0.6-0.8 nm), and a γ-form (ring inner diameter 0.8-0.95 nm). However, in the present invention, α-cyclodextrin ring and γ-cyclodextrin ring are particularly preferable, and α-cyclodextrin ring is most preferable.

  A plurality of cyclic molecules having a ring as described above are included in one axial molecule. In general, when the maximum inclusion number of cyclic molecules that can be included per axial molecule is 1, the cyclic molecule is cyclic. The number of molecular inclusions is preferably in the range of 0.001 to 0.6, more preferably 0.002 to 0.5, and still more preferably 0.003 to 0.4. If the number of inclusions of the cyclic molecule is too large, the cyclic molecules are densely present with respect to one axial molecule, so that the mobility is lowered and the photochromic property tends to be lowered. On the other hand, when the number of inclusions is too small, the gap between the axial molecules becomes narrow, the gap that allows the reversible reaction of the photochromic compound molecule decreases, and the photochromic property also tends to be lowered.

  In addition, the maximum inclusion number 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 shaft molecule is formed of polyethylene glycol and the ring of the cyclic molecule is an α-cyclodextrin ring, the maximum inclusion number 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 the polyethylene glycol, and 1/2 of the number of repeating units is obtained as the maximum inclusion number of the cyclic molecule. This maximum inclusion number is 1.0, and the inclusion number of the cyclic molecule is adjusted to the above-mentioned range.

  In addition, by introducing the side chain “5” into the ring, it is possible to more reliably form an appropriate space between adjacent axial molecules, and to ensure a gap that allows a reversible reaction of the photochromic compound molecules. And can exhibit excellent photochromic properties. Further, such a side chain “5” forms a pseudo-crosslinked structure in the polyrotaxane and can improve the mechanical strength of the photochromic cured product formed thereby.

  The side chain is preferably formed by repeating organic chains having 3 to 20 carbon atoms, and the average weight molecular weight of such a side chain is 300 to 10,000, preferably 350 to It may be in the range of 8000, more preferably in the range of 350 to 5,000, and most preferably in the range of 400 to 1500. That is, if the side chain is too small, the function of ensuring a gap that allows the reversible reaction of the photochromic compound molecule is insufficient, and if the side chain is too large, the photochromic compound described later can be intimately mixed with the polyrotaxane. In the end, it tends to be difficult to fully utilize the space secured by the polyrotaxane.

  The side chain contains an iso (thio) cyanate reactive group. As described above, the iso (thio) cyanate-reactive group is a group that can react with an isocyanate group and / or an isothiocyanate group. When the photochromic composition obtained by the production method of the present invention is cured, it reacts with an iso (thio) cyanate reactive group and a polyiso (thio) cyanate compound to form a cured product. Thus, the iso (thio) cyanate reactive group is present at the end of the side chain. Specific examples of the iso (thio) cyanate reactive group include a hydroxyl group, a thiol group, an epoxy group, a carboxylic acid group, and an amino group. From the viewpoint of easy introduction of the iso (thio) cyanate reactive group and the stability of the reactive group, a hydroxyl group or a thiol group is preferable.

  Further, the side chain as described above is introduced by modifying a functional group of the ring included in the cyclic molecule. For example, the α-cyclodextrin ring has 18 hydroxyl groups as functional groups, and side chains are introduced through 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 sufficiently 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 the size is in the above-described range, and ring-opening polymerization. Radical polymerization; cation polymerization; anion polymerization; living radical polymerization such as atom transfer radical polymerization, RAFT polymerization, NMP polymerization, etc., and the like, by reacting an appropriate compound with the functional group of the ring. Side chains can be introduced.

  For example, when a side chain derived from a cyclic compound such as cyclic lactone, cyclic ether, cyclic acetal, cyclic amine, cyclic carbonate, cyclic imino ether, cyclic thiocarbonate, etc. is introduced by ring-opening polymerization, Iso (thio) cyanate reactive groups can be introduced. Among these, it is preferable to use a cyclic ether, a cyclic siloxane, a cyclic lactone, or a cyclic carbonate from the viewpoint of easy availability, high reactivity, and easy adjustment of the size (molecular weight). . Specific examples of suitable cyclic compounds are as follows.

Cyclic ether; ethylene oxide, 1,2-propylene oxide, epichlorohydrin, epibromohydrin, 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide, oxetane, 3-methyloxetane, 3,3- Dimethyloxetane, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran cyclic siloxane; hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane cyclic lactone;
4-membered ring lactone; β-propiolactone, β-methylpropiolactone, L-serine-β-lactone and the like.
5-membered ring lactone; γ-butyrolactone, γ-hexanolactone, γ-heptanolactone, γ-octanolactone, γ-decanolactone, γ-dodecanolactone, α-hexyl-γ-butyrolactone, α-heptyl-γ -Butyrolactone, α-hydroxy-γ-butyrolactone, γ-methyl-γ-decanolactone, α-methylene-γ-butyrolactone, α, α-dimethyl-γ-butyrolactone, D-erythronolactone, α-methyl-γ-butyrolactone , Γ-nonanolactone, DL-pantolactone, γ-phenyl-γ-butyrolactone, γ-undecanolactone, γ-valerolactone, 2,2-pentamethylene-1,3-dioxolan-4-one, α-bromo- γ-butyrolactone, γ-crotonolactone, α-methylene-γ-butyrolactone, α-methacryloyl Luoxy-γ-butyrolactone, β-methacryloyloxy-γ-butyrolactone, and the like.
6-membered ring lactone; δ-valerolactone, δ-hexanolactone, δ-octanolactone, δ-nonanolactone, δ-decanolactone, δ-undecanolactone, δ-dodecanolactone, δ-tridecanolactone, δ- Tetradecanolactone, DL-mevalonolactone, 4-hydroxy-1-cyclohexanecarboxylic acid δ-lactone, monomethyl-δ-valerolactone, monoethyl-δ-valerolactone, monohexyl-δ-valerolactone, 1,4-dioxane-2 -On, 1,5-dioxepane-2-one and the like.

7-membered ring lactone; nonalkyl-ε-caprolactone, dialkyl-ε-caprolactone, monomethyl-ε-caprolactone, monoethyl-ε-caprolactone, monohexyl-ε-caprolactone, dimethyl-ε-caprolactone, di-n-propyl-ε- Caprolactone, di-n-hexyl-ε-caprolactone, trimethyl-ε-caprolactone, triethyl-ε-caprolactone, tri-n-ε-caprolactone, ε-caprolactone, 5-nonyl-oxepan-2-one, 4,4 6-trimethyl-oxepan-2-one, 4,6,6-trimethyl-oxepan-2-one, 5-hydroxymethyl-oxepan-2-one and the like.
8-membered ring lactone; ζ-enanthlactone and the like.
Other cyclic lactones; lactone, lactide, dilactide, tetramethylglycoside, 1,5-dioxepan-2-one, t-butylcaprolactone and the like.
Cyclic carbonate; ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, glycerol 1,2-carbonate, 4- (methoxymethyl) -1,3-dioxolan-2-one, (chloromethyl ) Ethylene carbonate, vinylene carbonate, 4,5-dimethyl-1,3-dioxo-2-one, 4-chloromethyl-5-methyl-1,3-dioxo-2-one, 4-vinyl -1,3-dioxolan-2-one, 4,5-diphenyl-1,3-dioxolan-2-one, 4,4-dimethyl-5-methylene-1,3-dioxolan-2-one, 1,3 -Dioxane-2-one, 5-methyl-5-propyl-1,3-dioxolan-2-one, 5,5-diethyl-1,3-dioxolan-2-one The above cyclic compounds are used alone moron Or, multiple types can be used in combination.

  In the present invention, cyclic lactone and cyclic carbonate are preferably used, and ε-caprolactone, α-acetyl-γ-butyrolactone, α-methyl-γ-butyrolactone, γ-valerolactone, γ-butyrolactone, etc. Are particularly preferred, with ε-caprolactone being most preferred.

  In addition, when a side chain is introduced by reacting a cyclic compound by ring-opening polymerization, a functional group (for example, a hydroxyl group) bonded to the ring is poor in reactivity, and a large molecule can be directly reacted particularly due to steric hindrance. It can be difficult. In such cases, for example, in order to react caprolactone, etc., a low molecular weight compound such as propylene oxide is reacted with a functional group to perform hydroxypropylation to introduce a functional group (hydroxyl group) rich in reactivity. After that, a means of introducing a side chain by ring-opening polymerization using the above-described cyclic compound can be employed.

  In addition, the compound used for introducing the side chain using radical polymerization is a radical polymerizable compound, but the ring possessed by the polyrotaxane cyclic molecule has an active site serving as a radical starting point. Not. For this reason, prior to reacting the radical polymerizable compound, the compound for forming a radical initiation point is reacted with the functional group (hydroxyl group) possessed by the ring to form an active site serving as a radical initiation point. It is necessary to keep.

  As the compound for forming the radical initiation point as described above, an organic halogen compound is representative, for example, 2-bromoisobutyryl bromide, 2-bromobutyric acid, 2-bromopropionic acid, 2-chloropropion. An acid, 2-bromoisobutyric acid, epichlorohydrin, epibromohydrin, 2-chloroethyl isocyanate, etc. can be mentioned.

  That is, the organic halogen compound is bonded to the ring by a condensation reaction with the functional group of the ring of the cyclic molecule, and a group containing a halogen atom (organic halogen compound residue) is introduced. In this organic halogen compound residue, radicals are generated by the movement of halogen atoms or the like during radical polymerization, and this serves as a radical polymerization starting point and radical polymerization proceeds.

  In addition, the group having an active site that serves as a radical polymerization initiation point (organic halogen compound residue) as described above is, for example, an amine, a carboxylic acid, an isocyanate, an imidazole, an acid anhydride, etc. It can also be introduced by reacting a compound having a functional group, introducing a functional group other than a hydroxyl group, and reacting the above-described organic halogen compound with the other functional group.

  Moreover, as a radically polymerizable compound used for introducing a side chain by radical polymerization, at least one functional group such as a (meth) acryl group, a vinyl group, or a styryl group having an ethylenically unsaturated bond is used. The compound having (hereinafter referred to as an ethylenically unsaturated monomer) is preferably used.

Examples of such ethylenically unsaturated monomers include the following compounds.
Alkyl (meth) acrylate; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) Acrylate, stearyl (meth) acrylate, hydroxy (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate cyano (meth) Acrylate; cyanoethyl (meth) acrylate amino (meth) acrylate; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-dimethylaminoethyl (Meth) acrylate, maleimide (meth) acrylate fluoroalkyl (meta Acrylate; trifluoroethyl (meth) acrylate, pentafluorobutyl (meth) acrylate siloxanyl (meth) acrylate; tris (trimethylsiloxanyl) silylpropyl (meth) acrylate alkylene glycol Polyol (meth) acrylate; ethylene glycol (meth) acrylate, triethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, propylene glycol (meth) acrylate -Polypropylene glycol (meth) acrylate aromatic vinyl compound; styrene, p-methylstyrene, m-methoxystyrene, p-hydroxystyrene vinyl salt compound; 4-vinyl sodium benzoate, p-styrene sulfonic acid Sodium zwitterionic (meth) acrylate 2-methoxyacryloyloxyethyl phosphorylcholine, [2- (methacryloyloxy) ethyl] dimethyl (3-sulfopropyl) ammonium hydroxide unsaturated monocarboxylic acid or ester thereof; cinnamic acid, crotonic acid oxirane compound; glycidyl (meth) Acrylate oxetane compound; 2-oxetanemethyl (meth) acrylate unsaturated polycarboxylic acid (anhydride); (anhydrous) maleic acid, (anhydrous) fumaric acid

In addition to ethylenically unsaturated monomers, oligomers or polymers having terminal ethylenically unsaturated bonds (hereinafter referred to as macromonomers) can also be used.
The following can be illustrated as a component which forms the principal chain of such a macromonomer.
Polyether; polyethylene oxide, polypropylene oxide, polytetramethylene oxide polyester; polyethylene terephthalate, polycaprolactone Polymer having hydrocarbon main chain; polyethylene, polypropylene, polystyrene, polyvinyl methyl ether, poly (meth) acrylate polyamide Polyhexamethylene adipamide Other polymers; Polyimide acid, polyimineamine, polyurethane, polyurea, polydimethylsiloxane, polycarbonate polymer Copolymers of various polymers listed above;
Each of the above-mentioned monomers or macromonomers can be used alone or in combination of two or more.

  Using such a radical polymerizable compound, radical polymerization (preferably atom transfer radical polymerization, RAFT polymerization (reversible addition-cleavage transfer chain polymerization), in the presence of the ring in which the radical polymerization initiation point is introduced, Living radical polymerization such as NMP polymerization (radical polymerization via nitroxide) is performed, and the degree of polymerization is adjusted to an appropriate range. In the radical reaction described above, since the reaction terminal is not an iso (thio) cyanate reactive group, when an iso (thio) cyanate reactive group is introduced into such a side chain, an isoton having an unsaturated bond is introduced. The (thio) cyanate-reactive group-containing compound may be reacted last so that the iso (thio) cyanate-reactive group is at the end. Examples of such compounds include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, and 1-methyl-4. -(1-methylvinyl) cyclohexanethiol, propionic acid-2-mercapto-2-butenyl ester and the like.

  In the present invention, the (A) component iso (thio) cyanate-reactive group-containing polyrotaxane most preferably used is an α-cyclodextrin ring having a polyethylene glycol bonded at both ends with an adamantyl group as an axis molecule. Further, a side chain (terminal is an OH group) is introduced into the ring by polycaprolactone.

<Other iso (thio) cyanate-reactive group-containing compounds>
Moreover, the photochromic composition in the present invention includes an iso (thio) cyanate reactive group-containing compound other than the iso (thio) cyanate reactive group-containing polyrotaxane in the (A) iso (thio) cyanate reactive group-containing compound. The viscosity of the photochromic composition can be adjusted, and the hardness of the photochromic cured product can be adjusted by adding them.

  The other iso (thio) cyanate-reactive group-containing compound is a poly (thi) ol compound having two or more hydroxyl groups and / or thiol groups in one molecule (hereinafter also simply referred to as “poly (thi) ol compound”). ) And mono (thi) ol compounds having one hydroxyl group or thiol group in one molecule (hereinafter also simply referred to as “mono (thi) ol compounds”), polyamine compounds, epoxy compounds, carboxylic acid compounds, and the like. It is done.

<Poly (thio) ol compound having two or more hydroxyl groups and / or thiol groups in one molecule>
When a poly (thi) ol compound is used as another iso (thio) cyanate-reactive group-containing compound, a (thio) urethane bond is obtained by reacting the polyiso (thio) cyanate compound with the poly (thi) ol compound. It is preferable because a rigid cured body having a network structure having a high molecular strength can be formed, and a photochromic cured body having excellent mechanical strength can be obtained. Among the poly (thi) ol compounds, as the polyol compound, for example, di-, tri-, tetra-, penta-, hexa-hydroxy compounds, polyester containing two or more OH groups in one molecule (polyester) Polyol) polyether containing two or more OH groups in one molecule (hereinafter referred to as polyether polyol), polycarbonate containing two or more OH groups in one molecule (polycarbonate polyol), 1 A typical example is polycaprolactone (polycaprolactone polyol) containing two or more OH groups in the molecule, and an acrylic polymer (polyacryl polyol) containing two or more OH groups in the molecule.

  Polythiol compounds include aliphatic polythiols, aromatic polythiols, halogen-substituted aromatic polythiols, heterocyclic polythiols, and aromatic polythiols containing sulfur atoms in addition to thiol groups, sulfur other than thiol groups. Examples include aliphatic polythiols containing atoms and heterocyclic polythiols containing sulfur atoms in addition to thiol groups. Specific examples of these compounds are as follows.

Aliphatic alcohol: ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, 1,5-dihydroxypentane, 1,6-dihydroxyhexane, 1,7-dihydroxy Heptane, 1,8-dihydroxyoctane, 1,9-dihydroxynonane, 1,10-dihydroxydecane, 1,11-dihydroxyundecane, 1,12-dihydroxydodecane, neopentyl glycol, glycerin, trimethylolethane, trimethylo -Rupropane, butanetriol, 1,2-methylglucoside, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, erythritol, slate tol, libitol, Arabinite, xylitol, antitol Mannitol, Dolitol, Iditol, Glycol, Inositol, Hexanetriol, Triglycerol, Diglycerol, Triethylene glycol, Polyethylene glycol, Tris (2-hydroxyethyl) isocyanurate -Cyclobutanediol, cyclopentanediol, cyclohexanediol, cycloheptanediol, cyclooctanediol, cyclohexanedimethanol, hydroxypropylcyclohexanol, tricyclo [5,2,1,02,6] decane-dimethanol , Bicyclo [4,3,0] -nonanediol, dicyclohexanediol, tricyclo [5,3,1,13,9] dodecanediol, bicyclo [4,3,0] nonanedimethanol, tricyclo [5,3, 1,13,9] dodecane Tanol, hydroxypropyltricyclo [5,3,1,13,9] dodecanol, spiro [3,4] octanediol, butylcyclohexanediol, 1,1'-bicyclohexylidenediol, cyclohexanetriol, 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) ben 1,4-bis (4-hydroxybutyl) benzene, 1,4-bis (5-hydroxypentyl) benzene, 1,4-bis (6-hydroxyhexyl) benzene, 2,2-bis [4- ( 2 "-hydroxyethyloxy) phenyl] propane aromatic alcohol; dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxybenzene, benzenetriol, biphenyltetraol, pyrogallol, (hydroxynaphthyl) pyrogallol, trihydroxyphenanthrene, bisphenol A, bisphenol F, xylylene glycol, tetrabromobisphenol A, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,2-bis (4-hydroxypheny) ) Ethane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) -1-naphthylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenyl Ethane, 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) 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) Lopan, 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) 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) norbornane, 2,2-bis (4 -Hydroxyphenyl) adamantane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, ethylene glycol bis (4-hydroxyphenyl) ether, 4,4'-dihydroxydiphenyl sulfide, 3,3′-dimethyl-4,4′-dihydroxydiphenyl sulfide 3,3′-dicyclohexyl-4,4′-dihydroxydiphenyl sulfide, 3,3′-diphenyl-4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl sulfoxide, 3,3′-dimethyl-4, 4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3-methyl) Phenyl) 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) fluore 3,3-bis (4-hydroxyphenyl) -2-butanone, 1,6-bis (4-hydroxyphenyl) -1,6-hexanedione, 4,4′-dihydroxybiphenyl, hydroquinone resorcinol 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, and an average of 3 or less ethylene oxide per hydroxyl group And / or a compound to which propylene oxide is 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-dithiacyclooctane polyester polyol; polyol Compound obtained by condensation reaction with polybasic acid Polyether polyol; Compound obtained by reaction of compound having two or more iso (thio) cyanate reactive groups in the molecule and alkylene oxide and its modified product Polycaprolactone polyol; Compound obtained by ring-opening polymerization of ε-caprolactone Polycarbonate polyol; Compound obtained from one or more types of phosgenation of low molecular weight polyols, ester using ethylene carbonate, diethyl carbonate, diphenyl carbonate, etc. Compound obtained by exchange method Polyacryl polyol; Compound obtained by copolymer of acrylic acid ester or methacrylic acid ester containing hydroxyl group and monomer copolymerizable with these ester, etc.

Aliphatic 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-dimercapto Succinic acid (2-mercaptoethyl ester), 2,3-dimercapto-1-propanol (2-mercaptoacetate), 2,3-dimercapto-1-propanol (3-mercaptoacetate), Diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl 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 ( -Mercaptopropionate), 1,4-butanediol bis (thioglycolate), 1,6-hexanediol bis (thioglycolate), tetraethylene glycol bis (3-mercaptopropionate), trimethylol Propane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate) ), Pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane, di Pentaerythritol hexakis (3-mercaptopro Pionate), pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, trimethylolpropane tris (3-mercaptobutyrate), trimethylol Ruethanetris (3-mercaptobutyrate), 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane, 2-mercaptomethyl-1,3-propanedithiol, 2-mercaptomethyl-1, 4-butanedithiol, 2,4,5-tris (mercaptomethyl) -1,3-dithiolane, 2,2-bis (mercaptomethyl) -1,4-butanedithiol, 4,4-bis (mercaptomethyl)- 3,5-dithiaheptane-1,7-dithiol, 2,3-bis (mercaptomethyl) -1,4-butanedithiol, , 6-bis (mercaptomethyl) -3,5-dithiaheptane-1,7-dithiol, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,5-bismercaptomethyl-1,4- Dithiane, 1,1,3,3-tetrakis (mercaptomethylthio) propane, 5,7-dimercaptomethyl-1,11-dimercapto-, 3,6,9-trithiaundecane, 4,7-dimercaptomethyl- 1,11-dimercapto-3,6,9-trithiaundecane, 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-dimer Ptobenzene, 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 (merca Tomethyl) 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-tetra Mercaptobenzene, 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-tetrakis (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 (mercaptoethoxy) ) Benzene, 1,2,3,5-tetrakis (mercaptoethoxy) benzene, 1,2,4,5-tetra Sus (mercaptoethoxy) benzene, 2,2′-dimercaptobiphenyl, 4,4′-dimercaptobiphenyl, 4,4′-dimercaptobibenzyl, 2,5-toluenedithiol, 3,4-toluenedithiol, , 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 (mercaptopropi Thiomethyl) benzene halogen-substituted aromatic polythiol; 2,5-dichlorobenzene-1,3-dithiol, 1,3-di (p-chlorophenyl) propane-2,2-dithiol, 3,4,5-tribromo-1, 2-dimercaptobenzene, 2,3,4,6-tetrachloro-1,5-bis (mercaptomethyl) benzene-containing 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 sym-triazine, 2-phenoxy-4,6-di All-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 polythiols containing sulfur atoms in addition to thiol groups; 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-tetrakis (Mercaptoethylthio) benzene Aliphatic polythio containing sulfur atoms in addition to thiol groups Bis (mercaptomethyl) sulfide, bis (mercaptoethyl) sulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropyl) methane, , 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-mercaptopropylthio) propane, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthio) Methyl) methane, tetrakis (3-mercaptopropylthiomethyl) methane, bis (2,3-dimercaptopropyl) sulfide, 2,5-dimercapto-1,4-dithiane, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) ), Disulfide, bis (mercaptopropyl) disulfide, thioglycolic acid or mercaptopropionic acid ester of the above compound, hydroxymethyl sulfide bis (2-mercaptoacetate), hydroxymethyl sulfide bis (3-mercaptopropiate) Onate), hydroxyethyl sulfide bis (2-mercaptoacetate), hydroxyethyl sulfide bis (3-mercaptopropionate), hydroxypropyl sulfide bis (2-mercaptoacetate), hydroxypropyl sulfide bis (3-mercapto) Propionate), 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 bis (3-mercaptopropionate), 2-mercapto Tyl ether bis (2-mercaptoacetate), 2-mercaptoethyl ether bis (3-mercaptopropionate), 1,4-dithian-2,5-diol bis (2-mercaptoacetate), 1,4 Dithian-2,5-diol bis (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, thioglycolate bis (2 Mercaptoethyl ester), thiodipropionic acid bis (2-mercaptoethyl ester), 4,4′-thiodibutyric acid bis (2-mercaptoethyl ester), dithiodiglycolic acid bis (2-mercaptoethyl ester), dithiodipropion Acid bis (2-mercaptoethyl ester), 4,4′-dithiodibutyric acid bis (2-mercaptoethyl ester), thiodiglycolic acid bis (2,3-dimercaptopropyl ester), thiodipropionic acid bis (2 , 3-dimercaptopropyl ester), bis (2,3-dimercaptopropyl ester) dithiodiglycolate, dithiodipropionic acid (2,3-dimercaptopropyl ester), 2-mercaptomethyl-6-mercapto-1 , 4-dithiacycloheptane, 4,5-bis (mel Ptomethylthio) -1,3-dithiolane, 4,6-bis (mercaptomethylthio) -1,3-dithiane, 2-bis (mercaptomethylthio) methyl-1,3-dithietane, 2- (2,2-bis ( Mercaptomethylthio) ethyl) -1,3-dithietane, 1,2,7-trimercapto-4,6-dithiaheptane, 1,2,9-trimercapto-4,6,8-trithianonane, 1,2,11, -Trimercapto-4,6,8,10-tetrathiaundecane, 1,2,13-trimercapto-4,6,8,10,12-pentathiatridecane, 1,2,8,9-tetramercapto -4,6-dithianonane, 1,2,10,11-tetramercapto-4,6,8-trithiaundecane, 1,2,12,13-tetramercapto-4,6,8,10- Trathiatridecane, bis (2,5-dimercapto-4-thiapentyl) disulfide, bis (2,7-dimercapto-4,6-dithiaheptyl) disulfide, 1,2,5-trimercapto-4-thiapentane, 3 , 3-Dimercaptomethyl-1,5-dimercapto-2,4-dithiapentane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, 3-mercaptomethylthio-1,7-dimercapto-2,6 -Dithiaheptane, 3,6-dimercaptomethyl-1,9-dimercapto-2,5,8-trithianonane, 3,7-dimercaptomethyl-1,9-dimercapto-2,5,8-trithianonane, 4,6 -Dimercaptomethyl-1,9-dimercapto-2,5,8-trithianonane, 3-mercaptomethyl-1, 6-dimercapto-2,5-dithiahexane, 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-trithiaundecane, 1,4,9,12-tetramercapto-2,6,7,11-tetrathiadecane, 2, , 3-dithia-1,4-butanedithiol, 2,3,5,6-tetrathia-1,7-heptanedithiol, 2,3,5,6,8,9-hexathia-1,10-decanedithiol, 2- (1-mercapto-2-mercaptomethyl-3-thiabutyl) -1,3-dithiolane, 1,5-dimercapto-3-mercaptomethylthio-2, -Dithiapentane, 2-mercaptomethyl-4-mercapto-1,3-dithiolane, 2,5-dimercapto-1,4-dithiane, 2,6-dimercapto-1,4-dithiane, 2,4-dimercaptomethyl- 1,3-dithietane, 1,2,6,10,11-pentamercapto-4,8-dithiaundecane, 1,2,9,10-tetramercapto-6-mercaptomethyl-4,7-dithiadecane, , 2,9,13,14-pentamercapto-6-mercaptomethyl-4,7,11-trithiatetradecane, 1,2,6,10,14,15-hexamercapto-4,8,12-tri Thiapentadecane, 1,4-dithian-2,5-bis (4,5-dimercapto-2-thiapentane), 1,4-dithian-2,5-bis (5,6-dimercapto- , 3-Jichiahekisan)
Heterocyclic polythiols containing sulfur atoms in addition to thiol groups; 3,4-thiophenedithiol, tetrahydrothiophene-2,5-dimercaptomethyl, 2,5-dimercapto-1,3,4-thiadiazole isocyanurate groups Polythiol; 1,2-bis [(2-mercaptoethyl) thio] -3-mercapto, propane, tris-{(3-mercaptopropionyloxy) -ethyl} -isocyanurate, 1,3,5-tris (3 -Mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate

In addition, as another iso (thio) cyanate-reactive group-containing compound in the present invention, a compound having at least one hydroxyl group and one thiol group in one molecule can be used. Specific examples thereof include the following compounds.
2-mercaptoethanol, 3-mercapto-1,2-propanediol, glycerol di (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-tolutris (3-mercaptopropionate), pentaerythritol mono (3-mercaptopropionate), pentaerythritol bis (3-mercaptopropionate), pentaerythritol-tolutris (thioglycolate), pentaerythris Litholpentakis (3-mercaptopropionate), hydroxyme Ru-tris (mercaptoethylthiomethyl) methane, 1-hydroxyethylthio-3-mercaptoethylthiobenzene, 4-hydroxy-4'-mercaptodiphenylsulfone, 2- (2-mercaptoethylthio) ethanol, dihydroxyethyl Sulfide mono (3-mercaptopropionate), dimercaptoethane mono (salicylate), hydroxyethylthiomethyl-tris (mercaptoethylthio) methane

  In addition, as the poly (thi) ol compound, a compound having a silsesquioxane structure can be used. Silsesquioxane is a compound represented by the following formula (1).

{Where
A plurality of R1 may be the same or different from each other,
At least one molecule is an organic group containing two or more hydroxyl groups and / or thiol groups,
R1 other than an organic group having a hydroxyl group or a thiol group is a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, or a phenyl group,
The degree of polymerization n is an integer of 6-100. }
Moreover, as an alkyl group in R1, a C1-C10 alkyl group is preferable. Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, An n-octyl group, an isooctyl group, etc. are mentioned.

  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, and a cyclooctyl group.

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

  In general, the silsesquioxane compound can have various structures such as cage shape, ladder shape, and random shape. In the present invention, a mixture composed of a plurality of structures is preferable.

  Preferred examples of the poly (thi) ol compound include polyethylene polyol, polycaprolactone polyol, polycarbonate polyol, trimethylolpropane, pentaerythritol, trimethylolpropane tris (3-mercaptopropionate), penta Erythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycolbis (3-mercaptopropionate), 1,4-butanediolbis ( 3-mercaptopropionate), 1,6-hexanediol bis (3-mercaptopropionate), 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane, 2,2-bis ( Mercaptomethyl) -1,4-but Dithiol, 1,4-bis (mercaptopropylthiomethyl) benzene, 2,5-bis (mercaptomethyl) -1,4-dithiane, 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, 4,6-bis (mercapto) Methylthio) -1,3-dithiane, 2-mercaptomethanol, tris-{(3-mercaptopropionyloxy) -ethyl} -isocyanurate is preferred.

<Mono (thi) ol compound having one hydroxyl group or one thiol group in one molecule>
In addition to the poly (thi) ol compound as the other iso (thio) cyanate-reactive group-containing compound having no polyrotaxane structure, the monochromium compound is further used to cure the photochromic composition. When a rigid cured product having a network structure having a (thio) urethane bond is obtained by the reaction of a polyiso (thio) cyanate compound and a poly (thi) ol compound, a mono-terminated structure having a free structure at one end is obtained. Since the (thio) all compound is taken into the network structure, a flexible space is formed around the mono (thio) ol compound. Accordingly, since a reversible structural change of the photochromic compound existing in the vicinity of the space is generated more rapidly, it is possible to produce a photochromic cured product having excellent photochromic properties (color density, fading speed).

  Furthermore, since the mono (thi) ol compound has only one hydroxyl group or thiol group, it has fewer hydrogen bonds than the poly (thi) ol compound, and as a result, the viscosity of the photochromic composition can be reduced. It is possible and the handling performance at the time of casting can be improved. Specific examples of the mono (thi) ol compound used in the photochromic composition of the present invention include the following compounds.

One hydroxyl compound in one molecule; polyethylene glycol monooleyl ether, polyoxyethylene oleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol mono-4-octylphenyl ether, linear polyoxy Ethylene alkyl ether (polyethylene glycol monomethyl ether, polyoxyethylene lauryl ether, polyoxyethylene-2-ethylhexyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether), 5 to 5 carbon atoms 30 saturated alkyl alcohols having a linear or branched structure, one thiol compound per molecule; 3-methoxybutyl thioglycolate, 2-ester Tylhexyl thioglycolate, 2-mercaptoethyl octanoate, 3-mercaptopropionate-3-methoxybutyl, ethyl 3-mercaptopropionate, 2-octyl 3-mercaptopropionate, n-octyl-3-mercaptopropio , Methyl-3-mercaptopropionate, tridecyl-3-mercaptopropionate, stearyl-3-mercaptopropionate, saturated alkyl thiol having a linear or branched structure having 5 to 30 carbon atoms Preferred examples of the (thi) ol compound include polyethylene glycol monooleyl ether, polyethylene glycol monolaurate, polyethylene glycol monostearate, 1-dodecanethiol, stearyl-3-mercaptopropionate, n-Octyl-3-mercaptopropionate is preferred.

<Polyamine compound>
A polyamine compound is a compound having two or more amino groups (—NH ₂ ) in one molecule, which forms a urea bond by reaction with polyisocyanate, and forms a thiourea bond by reaction with polyisothiocyanate. To do. These monomers may be added for adjusting the hardness. Specific examples thereof include the following compounds.
Ethylenediamine, hexamethylenediamine, isophoronediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, metaxylenediamine, 1,3-propanediamine, putrescine, 2- (2-aminoethylamino) ethanol, diethylenetriamine, p-phenylenediamine, m-phenylenediamine, melamine, 1,3,5-benzenetriamine

<Epoxy compound>
The epoxy compound has an epoxy group in the molecule as a polymerizable group, and is cured by ring-opening polymerization. These compounds may be added for adjusting the refractive index and adjusting the lens hardness. Such an epoxy compound is roughly classified into an aliphatic epoxy compound, an alicyclic epoxy compound, and an aromatic epoxy compound, and specific examples thereof include the following.
Aliphatic epoxy compounds; ethylene oxide, 2-ethyloxirane, butylglycidyl ether, phenylglycidyl ether, 2,2′-methylenebisoxirane, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, Triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, tetrapropylene glycol diglycidyl ether, nonapropylene Glycol diglycidyl ether, neopentyl glycol diglycy Diether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, diglycerol tetraglycidyl ether, pentaerythritol tetraglycidyl ether, diglycidyl ether of tris (2-hydroxyethyl) isocyanurate, tris (2-hydroxyethyl) isocyanurate Triglycidyl ether of alicyclic epoxy compound; isophoronediol diglycidyl ether, bis-2,2-hydroxycyclohexylpropane diglycidyl ether aromatic epoxy compound; resorcin diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl Ether, bisphenol S diglycidyl ether, orthophthalic acid diglycidyl ester, pheno Le novolak polyglycidyl ether, cresol novolak polyglycidyl ether

In addition to the above, an epoxy compound having a sulfur atom in the molecule can be used together with the epoxy group. Such a sulfur-containing atom epoxy compound particularly contributes to the improvement of the refractive index, and includes a chain aliphatic type and a cycloaliphatic type. Specific examples thereof are as follows.
Chain aliphatic sulfur-containing atom epoxy compounds; bis (2,3-epoxypropyl) sulfide, bis (2,3-epoxypropyl) disulfide, bis (2,3-epoxypropylthio) methane, 1,2- Bis (2,3-epoxypropylthio) ethane, 1,2-bis (2,3-epoxypropylthio) propane, 1,3-bis (2,3-epoxypropylthio) propane, 1,3-bis ( 2,3-epoxypropylthio) -2-methylpropane, 1,4-bis (2,3-epoxypropylthio) butane, 1,4-bis (2,3-epoxypropylthio) -2-methylbutane, , 3-bis (2,3-epoxypropylthio) butane, 1,5-bis (2,3-epoxypropylthio) pentane, 1,5-bis (2,3-epoxypropylthio) 2-methylpentane, 1,5-bis (2,3-epoxypropylthio) -3-thiapentane, 1,6-bis (2,3-epoxypropylthio) hexane, 1,6-bis (2,3- Epoxypropylthio) -2-methylhexane, 3,8-bis (2,3-epoxypropylthio) -3,6-dithiaoctane, 1,2,3-tris (2,3-epoxypropylthio) propane, 2 , 2-bis (2,3-epoxypropylthio) -1,3-bis (2,3-epoxypropylthiomethyl) propane, 2,2-bis (2,3-epoxypropylthiomethyl) -1- ( 2,3-epoxypropylthio) butane cycloaliphatic sulfur-containing atom epoxy compound; 1,3-bis (2,3-epoxypropylthio) cyclohexane, 1,4-bis (2,3-epoxy (Lopylthio) cyclohexane, 1,3-bis (2,3-epoxypropylthiomethyl) cyclohexane, 1,4-bis (2,3-epoxypropylthiomethyl) cyclohexane, 2,5-bis (2,3-epoxypropyl) Thiomethyl) -1,4-dithiane, 2,5-bis [<2- (2,3-epoxypropylthio) ethyl> thiomethyl] -1,4-dithiane, 2,5-bis (2,3-epoxy Propylthiomethyl) -2,5-dimethyl-1,4-dithiane

<Carboxylic acid compound>
A carboxylic acid compound is a compound having a COOH group in one molecule, and forms a thiourethane bond by reaction with a polyisothiocyanate, which forms a urethane bond by reaction with a polyisocyanate. These monomers may be added for adjusting the hardness. Specific examples thereof include the following compounds and acid anhydrides thereof.
Aliphatic polycarboxylic acid; succinic acid, adipic acid, maleic anhydride, sebacic acid, dimer acid Aromatic polycarboxylic acid; orthophthalic acid, naphthalenedicarboxylic acid, phthalic acid, isophthalic acid and terephthalic acid

<(A) preferred blending ratio of iso (thio) cyanate-reactive group-containing compound>
The suitable blending ratio of the iso (thio) cyanate-reactive group-containing polyrotaxane compound and the other iso (thio) cyanate-reactive group-containing compound for the photochromic composition in the present invention to exhibit excellent photochromic properties is When the total is 100 parts by mass, the iso (thio) cyanate-reactive group-containing polyrotaxane compound is 10 to 100 parts by mass, and the other iso (thio) cyanate-reactive group-containing compound is 0 to 90 parts by mass, more preferably Is 12-70 parts by mass of an iso (thio) cyanate-reactive group-containing polyrotaxane compound and 30-88 parts by mass of another iso (thio) cyanate-reactive group-containing compound, most preferably iso (thio) cyanate-reactive. 14-40 parts by mass of a group-containing polyrotaxane compound, other iso (thio) cyanate reaction Preferably contains a group containing compound in the range of 60 to 86 parts by weight.

<(B) Polyiso (thio) cyanate compound having two or more isocyanate groups and / or isothiocyanate groups in one molecule>
A polyiso (thio) cyanate compound (hereinafter also simply referred to as “polyiso (thio) cyanate compound”) having two or more isocyanate groups and / or isothiocyanate groups in one molecule which is a constituent component of the photochromic composition in the present invention, It is a compound having two or more isocyanate groups and / or isothiocyanate groups in a polyiso (thio) cyanate compound. Among the polyiso (thio) cyanate compounds, polyisocyanate compounds include aliphatic isocyanates, alicyclic isocyanates, aromatic isocyanates, sulfur-containing aliphatic isocyanates, aliphatic sulfide isocyanates, aromatic sulfide isocyanates, and aliphatic sulfones. Examples include isocyanates, aromatic sulfone isocyanates, sulfonate ester isocyanates, aromatic sulfonic acid amide isocyanates, and sulfur-containing heterocyclic isocyanates.

  Polyisothiocyanate compounds include aliphatic isothiocyanate, alicyclic isothiocyanate, aromatic isothiocyanate, heterocycle-containing isothiocyanate, sulfur-containing aliphatic isothiocyanate, sulfur-containing aromatic isothiocyanate, and sulfur-containing heterocycle isothiocyanate. Etc. Specific examples of these polyiso (thio) cyanate compounds include the following compounds.

Aliphatic isocyanate; ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 2,2'-dimethylpentane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, decamethylene diisocyanate , Butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-trimethylundecamethylene diisocyanate, 1,3,6-trimethylhexamethylene diisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 2,5,7-trimethyl-1,8-diisocyanate Anate-5-isocyanate methyl octane, bis (isocyanate ethyl) carbonate, bis (isocyanate ethyl) ether, 1,4-butylene glycol dipropyl ether ω, ω′-diisocyanate, lysine diisocyanate methyl ester, lysine triisocyanate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, 2-isocyanatepropyl-2,6-diisocyanatohexanoate alicyclic isocyanate; isophorone diisocyanate, (bicyclo [2.2.1] heptane-2, 5-diyl) bismethylene diisocyanate, (bicyclo [2.2.1] heptane-2,6-diyl) bismethylene diisocyanate, 2β, 5α-bis (isocyanate) norbornane, 2β, 5β-bis (I Cyanate) norbornane, 2β, 6α-bis (isocyanate) norbornane, 2β, 6β-bis (isocyanate) norbornane, 2,6-di (isocyanatemethyl) furan, bis (isocyanatemethyl) cyclohexane, dicyclohexylmethane diisocyanate, 4,4- Isopropylidenebis (cyclohexyl isocyanate), cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2′-dimethyldicyclohexylmethane diisocyanate, bis (4-isocyanate-n-butylidene) pentaerythritol, dimer acid diisocyanate, 2-Isocyanatomethyl-3- (3-isocyanatopropyl) -5-isocyanatomethyl-bishi Chro [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6-isocyanatomethyl-bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-2- (3 -Isocyanatopropyl) -5-isocyanatomethyl-bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6-isocyanatomethyl-bicyclo [2,2,1] -heptane 2-isocyanatomethyl-3- (3-isocyanatopropyl) -5- (2-isocyanatoethyl) -bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6 -(2-isocyanatoethyl) -bicyclo [2,1,1] -heptane, 2-isocyanate Nate methyl-2- (3-isocyanatepropyl) -5- (2-isocyanatoethyl) -bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6- (2- Isocyanatoethyl) -bicyclo [2,2,1] -heptane, 2,5-bis (isocyanatomethyl) -bicyclo [2,2,1] -heptane, 2,6-bis (isocyanatomethyl) -bicyclo [2, 2,1] -heptane, 1,3,5-tris (isocyanatemethyl) cyclohexane, 3,8-bis (isocyanatemethyl) tricyclodecane, 3,9-bis (isocyanatemethyl) tricyclodecane, 4,8- Bis (isocyanatomethyl) tricyclodecane, 4,9-bis (isocyanatomethyl) 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 mixture, bicyclo [2, A mixture of 2,2] octane-2,5-diisocyanate and bicyclo [2,2,2] octane-2,6-diisocyanate, tricyclo [5.2.12.02.6] decane-3,8-diisocyanate A mixture of tricyclo [5.2.1.02.6] decane-4,9-diisocyanate, an aromatic isocyanate; Xylylene diisocyanate (o-, m-, p-), tetrachloro-m-xylylene diisocyanate, 4-chloro-m-xylylene diisocyanate, 4,5-dichloro-m-xylylene diisocyanate, 2, 3, 5 , 6-Tetrabromo-p-xylylene diisocyanate, 4-methyl-m-xylylene diisocyanate, 4-ethyl-m-xylylene diisocyanate, bis (isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene, 1,3-bis (Α, α-dimethylisocyanatomethyl) benzene, 1,4-bis (α, α-dimethylisocyanatomethyl) benzene, α, α, α ′, α′-tetramethylxylylene diisocyanate, bis (isocyanatobutyl) benzene, Bis (isocyanatomethyl) naphthalene Bis (isocyanate methyl) diphenyl ether, bis (isocyanate ethyl) phthalate, mesitylylene triisocyanate, 2,6-di (isocyanate methyl) furan, phenylene diisocyanate, tolylene diisocyanate, ethylphenylene diisocyanate, isopropylphenylene diisocyanate, dimethyl Phenylene diisocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, 1,3,5-triisocyanate methylbenzene, naphthalene diisocyanate, methyl naphthalene diisocyanate, biphenyl diisocyanate, tolidine diisocyanate, 4,4'-diphenylmethane Diiso Anate, 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate, bibenzyl-4,4′-diisocyanate, bis (isocyanatephenyl) ethylene, 3,3′-dimethoxybiphenyl-4,4′-diisocyanate, triphenyl Methane triisocyanate, polymeric MDI, naphthalene triisocyanate, diphenylmethane-2,4,4′-triisocyanate, 3-methyldiphenylmethane-4,4 ′, 6-triisocyanate, 4-methyl-diphenylmethane-2,3,4 ′ , 5,6-pentaisocyanate, phenyl isocyanate methyl isocyanate, phenyl isocyanate ethyl isocyanate, tetrahydronaphthylene diisocyanate, hexahydrobenzene diisocyanate, hexahydrodipheny Rumethane-4,4′-diisocyanate, diphenyl ether diisocyanate, ethylene glycol diphenyl ether diisocyanate, 1,3-propylene glycol diphenyl ether diisocyanate, benzophenone diisocyanate, diethylene glycol diphenyl ether diisocyanate, dibenzofuran isocyanate, carbazole diisocyanate, ethyl carbazole diisocyanate, dichloro Carbazole diisocyanate Sulfur-containing aliphatic isocyanate; thiodiethyl diisocyanate, thiodipropyl diisocyanate, thiodihexyl diisocyanate, dimethyl sulfone diisocyanate, dithiodimethyl diisocyanate, dithiodiethyl diisocyanate, 1-isocyanatomethylthio 2,3-bis (2-isocyanatoethylthio) propane, 1,2-bis (2-isocyanatoethylthio) ethane, 1,1,2,2-tetrakis (isocyanatomethylthio) ethane, 2,2,5, 5-tetrakis (isocyanatomethylthio) -1,4-dithiane, 2,4-dithiapentane-1,3-diisocyanate, 2,4,6-trithiaheptane-3,5-diisocyanate, 2,4,7,9- Tetrathiapentane-5,6-diisocyanate, bis (isocyanatemethylthio) phenylmethane, bis (isocyanatemethylthio) methane, bis (isocyanateethylthio) methane, bis (isocyanateethylthio) ethane, bis (isocyanatemethylthio) ethane, 1, 5-isocyanate 2-isocyanate methyl- 3-thiapentane aliphatic sulfide-based isocyanate; bis [2- (isocyanatomethylthio) ethyl] sulfide, dicyclohexylsulfide-4,4′-diisocyanate, bis (isocyanatemethyl) sulfide, bis (isocyanateethyl) sulfide, bis (isocyanatepropyl) Sulfide, bis (isocyanate hexyl) sulfide, bis (isocyanate methyl) disulfide, bis (isocyanate ethyl) disulfide, bis (isocyanatepropyl) disulfide aromatic sulfide type isocyanate; diphenyl sulfide-2,4′-diisocyanate, diphenyl sulfide-4, 4′-diisocyanate, 3,3′-dimethoxy-4,4′-diisocyanate dibenzylthioether, bis (4-i Socyanate methylbenzene) sulfide, 4,4′-methoxybenzenethioethylene glycol-3,3′-diisocyanate, diphenyl disulfide-4,4′-diisocyanate, 2,2′-dimethyldiphenyl disulfide-5,5 ′ Diisocyanate, 3,3′-dimethyldiphenyl disulfide-5,5′-diisocyanate, 3,3′-dimethyldiphenyl disulfide-6,6′-diisocyanate, 4,4′-dimethyldiphenyl disulfide-5,5′-diisocyanate 3,3′-dimethoxydiphenyl disulfide-4,4′-diisocyanate, 4,4′-dimethoxydiphenyl disulfide-3,3′-diisocyanate aliphatic sulfone isocyanate; bis (isocyanatomethyl) sulfone aromatic sulfone isocyanate Diphenylsulfone-4,4′-diisocyanate, diphenylsulfone-3,3′-diisocyanate, benzylidenesulfone-4,4′-diisocyanate, diphenylmethanesulfone-4,4′-diisocyanate, 4-methyldiphenylmethanesulfone-2 , 4′-diisocyanate, 4,4′-dimethoxydiphenylsulfone-3,3′-diisocyanate, 3,3′-dimethoxy-4,4′-diisocyanate dibenzylsulfone, 4,4′-dimethyldiphenylsulfone-3, 3'-diisocyanate, 4,4'-di-tert-butyldiphenylsulfone-3,3'-diisocyanate, 4,4'-dimethoxybenzeneethylene disulfone-3,3'-diisocyanate, 4,4'-dichlorodiphenylsulfone -3,3'-diisocyanate 4-methyl-3-isocyanatebenzenesulfonyl-4'-isocyanate phenol ester, 4-methoxy-3-isocyanatobenzenesulfonyl-4'-isocyanate phenol ester aromatic sulfonic acid amide isocyanate; 4 -Methyl-3-isocyanatobenzenesulfonylanilide-3'-methyl-4'-isocyanate, dibenzenesulfonyl-ethylenediamine-4,4'-diisocyanate, 4,4'-dimethoxybenzenesulfonyl-ethylenediamine-3,3'-diisocyanate 4-methyl-3-isocyanatobenzenesulfonylanilide-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-diisocyanate methyl, 1,3-dithiolane-2-methyl-4,5-diisocyanate methyl, 1,3-dithiolane-2,2-diisocyanate ethyl, tetrahydrothiophene-2,5-diisocyanate, tetrahydrothiophene-2 , 5-diisocyanate methyl, tetrahydrothiophene-2,5-diisocyanate ethyl, tetrahydrothiophene-3,4-diisocyanate methyl, tricyclothiaoctane diisocyanate, 2- (1,1-diisocyanate methyl) thiophene, 3- (1,1 - Cyanate methyl) thiophene, 2- (2-thienylthio) -1,2-diisocyanatepropane, 2- (3-thienylthio) -1,2-diisocyanatepropane, 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- ( Diisocyanate methylthio) thiophene, 3,4- (diisocyanatemethylthio) thiophene, 2,4-bisisocyanatomethyl-1,3,5-trithiane Further, halogen substitution, alkyl substitution, alkoxy substitution, nitro substitution of the above polyisocyanate Or a prepolymer type modified product with a polyhydric alcohol, a carbodiimide modified product, a urea modified product, a biuret modified product, a dimerization or trimerization reaction product, and the like.

Aliphatic isothiocyanate; 1,2-diisothiocyanate ethane, 1,3-diisothiocyanate propane, 1,4-diisothiocyanate butane, 1,6-diisothiocyanate hexane, p-phenylene diisopropylidene diisothiocyanate Cycloaliphatic isothiocyanate; cyclohexyl isothiocyanate, cyclohexane diisothiocyanate, 2,4-bis (isothiocyanatomethyl) norbornane, 2,5-bis (isothiocyanatomethyl) norbornane, 3,4-bis (isothiocyanato) Methyl) norbornane, 3,5-bis (isothiocyanatomethyl) norbornane aromatic isothiocyanate; phenyl isothiocyanate, 1,2-diisothiocyanate benzene, 1,3-diisothiocyanate benzene, 1,4 Diisothiocyanate benzene, 2,4-diisothiocyanate toluene, 2,5-diisothiocyanate-m-xylene diisocyanate, 4,4′-diisothiocyanate-1,1′-biphenyl, 1,1′-methylenebis ( 4-isothiocyanate benzene), 1,1′-methylene bis (4-isothiocyanate 2-methylbenzene), 1,1′-methylene bis (4-isothiocyanate 3-methylbenzene), 1,1 ′-(1,2 -Ethanediyl) bis (4-isothiocyanate benzene), 4,4'-diisothiocyanate benzophenone, 4,4'-diisothiocyanate-3,3'-dimethylbenzophenone, benzanilide-3,4'-diisothiocyanate, Diphenyl ether-4,4'-diisothiocyanate, diphenylamine- , 4'-diisothiocyanate containing heterocyclic isothiocyanate; 2,4,6-triisothiocyanate-1,3,5-triazine carbonyl isothiocyanate; hexane dioil diisothiocyanate, nonanedioyl diisothiocyanate, carbonic diiso Thiocyanate, 1,3-benzenedicarbonyldiisothiocyanate, 1,4-benzenedicarbonyldiisothiocyanate, (2,2′-bipyridine) -4,4′-dicarbonyldiisothiocyanate and sulfur of the isothiocyanate group Polyfunctional isothiocyanates having at least one sulfur atom in addition to the atoms can also be used. Examples of such a polyfunctional isothiocyanate include the following compounds.
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), sulfonyl bis (4-isothiocyanate benzene), sulfinyl bis (4-isothiocyanate) Benzene), dithiobis (4-isothiocyanate benzene), 4-isothiocyanate-1-{(4-isothiocyanate phenyl) sulfonyl} -2-methoxy-benzene, 4-methyl-3-isothiocyanate benzenesulfonyl-4′- Isothiocyanate phenyl ester, 4-methyl-3-isothiocyanate benzenesulfonylanilide-3'-methyl-4'-isothiocyanate sulfur containing heterocyclic isothiocyanate; thiophene-2,5-diisothiocyanate Door, 1,4-dithiane-2,5-diisothiocyanate

<Preferred examples of component (B)>
Preferred examples of the polyiso (thio) cyanate compound as the component (B) include pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, 2,5-bis (isocyanate methyl)- Bicyclo [2,2,1] -heptane, 2,6-bis (isocyanatemethyl) -bicyclo [2,2,1] -heptane, 1,2-bis (2-isocyanato-ethylthio) ethane, xylene diisocyanate (o -, M-, p-), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and mixtures thereof of 4,4'-diphenylmethane diisocyanate are preferred.

<Preferred blending ratio of component (A) and component (B)>
In the composition of the present invention, a suitable blending ratio of (A) and (B) for expressing excellent photochromic properties is as follows when the total of (A) and (B) is 100 parts by mass: A) is 30 to 80 parts by mass, (B) is 20 to 70 parts by mass, more preferably (A) is 35 to 75 parts by mass, (B) is 25 to 65 parts by mass, and most preferably (A). 40 to 67 parts by mass and (B) in the range of 33 to 60 parts by mass are preferable.

<(C) Photochromic compound>
As the photochromic compound exhibiting photochromic properties, those known per se can be used, and these can be used alone or in combination of two or more.
Typical examples of such photochromic compounds are fulgide compounds, chromene compounds and spirooxazine compounds. For example, JP-A-2-28154, JP-A-62-228830, WO94 / 22850 pamphlet, WO96. / 14596 pamphlet and other documents.

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

<(D) Resin modifier, (E) Polymerization curing accelerator, (F) Internal mold release agent>
In the present invention, in addition to the components (A), (B), and (C), a resin modifier (D ), A polymerization curing accelerator (D), and an internal mold release agent (F). These will be described.

<(D) Resin modifier>
In the present invention, a resin modifier can be added for the purpose of improving the refractive index of the obtained cured product and adjusting the hardness. For example, an olefin compound including an episulfide compound, a thietanyl compound, a (meth) acrylate compound, and the like can be given. A specific example will be described below.

<Episulfide compounds>
An episulfide compound is a compound having two or more episulfide groups in one molecule, and is cured by ring-opening polymerization. These compounds may be added to increase the refractive index. Specific examples of such episulfide compounds include the following.

  Bis (1,2-epithioethyl) sulfide, bis (1,2-epithioethyl) disulfide, bis (2,3-epithiopropyl) sulfide, bis (2,3-epithiopropylthio) methane, bis (2,3 -Epithiopropyl) disulfide, bis (2,3-epithiopropyldithio) methane, bis (2,3-epithiopropyldithio) ethane, bis (6,7-epithio-3,4-dithiaheptyl) sulfide, bis (6,7-epithio-3,4-dithiaheptyl) disulfide, 1,4-dithian-2,5-bis (2,3-epithiopropyldithiomethyl), 1,3-bis (2,3-epithio) Propyldithiomethyl) benzene, 1,6-bis (2,3-epithiopropyldithiomethyl) -2- (2,3-epithiopropyldithioethylthio) ) -4-thiahexane, 1,2,3-tris (2,3-epithiopropyldithio) propane, 1,1,1,1-tetrakis (2,3-epithiopropyldithiomethyl) methane, 1,3 -Bis (2,3-epithiopropyldithio) -2-thiapropane, 1,4-bis (2,3-epithiopropyldithio) -2,3-dithiabutane, 1,1,1-tris (2,3 -Epithiopropyldithio) methane, 1,1,1-tris (2,3-epithiopropyldithiomethylthio) methane, 1,1,2,2-tetrakis (2,3-epithiopropyldithio) ethane, , 1,2,2-tetrakis (2,3-epithiopropyldithiomethylthio) ethane, 1,1,3,3-tetrakis (2,3-epithiopropyldithio) propane, 1,1,3,3- Tetrachi (2,3-epithiopropyldithiomethylthio) propane, 2- [1,1-bis (2,3-epithiopropyldithio) methyl] -1,3-dithietane, 2- [1,1-bis (2 , 3-Epithiopropyldithiomethylthio) methyl] -1,3-dithietane

<Thietanyl compound>
A thietanyl compound is a thietane compound having two or more thietanyl groups in one molecule, and is cured by ring-opening polymerization. These compounds may be added to increase the refractive index. Some of these thietanyl compounds have an episulfide group together with a plurality of thietanyl groups, which are listed in the above section on episulfide compounds. Other thietanyl compounds include a metal-containing thietane compound having a metal atom in the molecule and a non-metal thietane compound not containing a metal. As specific examples of such thietanyl compounds, the following can be exemplified.

  Non-metallic thietane compounds; bis (3-thietanyl) disulfide, bis (3-thietanyl) sulfide, bis (3-thietanyl) trisulfide, bis (3-thietanyl) tetrasulfide, 1,4-bis (3-thietanyl) -1,3,4-trithiabutane, 1,5-bis (3-thietanyl) -1,2,4,5-tetrathiapentane, 1,6-bis (3-thietanyl) -1,3,4,6 -Tetrathiahexane, 1,6-bis (3-thietanyl) -1,3,5,6-tetrathiahexane, 1,7-bis (3-thietanyl) -1,2,4,5,7-penta Thiaheptane, 1,7-bis (3-thietanylthio) -1,2,4,6,7-pentathiaheptane, 1,1-bis (3-thietanylthio) methane, 1,2-bis (3-thietanylthio) Ethane 1,2,3-tris (3-thietanylthio) propane, 1,8-bis (3-thietanylthio) -4- (3-thietanylthiomethyl) -3,6-dithiaoctane, 1,11-bis (3- Thietanylthio) -4,8-bis (3-thietanylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (3-thietanylthio) -4,7-bis (3-thietanylthiomethyl) ) -3,6,9-trithiaundecane, 1,11-bis (3-thietanylthio) -5,7-bis (3-thietanylthiomethyl) -3,6,9-trithiaundecane, 2,5 -Bis (3-thietanylthiomethyl) -1,4-dithiane, 2,5-bis [[2- (3-thietanylthio) ethyl] thiomethyl] -1,4-dithiane, 2,5-bis (3- Thietanylthiomethyl)- , 5-dimethyl-1,4-dithiane, bisthietanyl sulfide, bis (thietanylthio) methane, 3-[<(thietanylthio) methylthio> methylthio] thietane, bisthietanyl disulfide, bisthietanyl trisulfide, bisthietanyl tetra Sulfide, bisthietanyl pentasulfide, 1,4-bis (3-thietanyldithio) -2,3-dithiabutane, 1,1,1-tris (3-thietanyldithio) methane, 1,1,1-tris (3-thie Tanyldithiomethylthio) methane, 1,1,2,2-tetrakis (3-thietanyldithio) ethane, 1,1,2,2-tetrakis (3-thietanyldithiomethylthio) ethane

<Metal-containing thietane compound>
This thietane compound contains, as metal atoms, group 14 elements such as Sn atom, Si atom, Ge atom and Pb atom; group 4 elements such as Zr atom and Ti atom; group 13 elements such as Al atom. The following compounds are particularly preferably used. For example, the following compounds are used.

Alkylthio (thietanylthio) tin; methylthiotris (thietanylthio) tin, ethylthiotris (thietanylthio) tin, propylthiotris (thietanylthio) tin, isopropylthiotris (thietanylthio) tin bis (alkylthio) bis (thietanylthio) tin; bis (methylthio) Bis (thietanylthio) tin, bis (ethylthio) bis (thietanylthio) tin, bis (propylthio) bis (thietanylthio) tin, bis (isopropylthio) bis (thietanylthio) tin alkylthio (alkylthio) bis (thietanylthio) tin; ethylthio (methylthio) Bis (thietanylthio) tin, methylthio (propylthio) bis (thietanylthio) tin, isopropylthio (methylthio) bis (thietanylthio) tin, ethyl Thio (propylthio) bis (thietanylthio) tin, ethylthio (isopropylthio) bis (thietanylthio) tin, isopropylthio (propylthio) bis (thietanylthio) tin bis (thietanylthio) cyclic dithiotin compound; bis (thietanylthio) dithiastannetane, bis (Thietanylthio) dithiastannolane, bis (thietanylthio) dithiastanninane, bis (thietanylthio) trithiastannocan alkyl (thietanylthio) tin compound; methyltris (thietanylthio) tin, dimethylbis (thietanylthio) tin, butyltris (thietanylthio) tin , Tetrakis (thietanylthio) tin, tetrakis (thietanylthio) germanium, tris (thietanylthio) bismuth

<Olefin compound including (meth) acrylate compound>
An olefin compound containing a (meth) acrylate compound has a radical polymerizable group in the molecule as a polymerizable group, and is cured by radical polymerization. These compounds can be used for adjusting the lens hardness. The following can be illustrated as the specific example.

(Meth) acrylate compounds; ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol Dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, dipropylene glycol diacrylate, dipropylene glycol dimethacrylate, tripropylene glycol diacrylate, tripropylene glycol dimethacrylate, polypropylene glycol Dimethacrylate, polypropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethylene glycol bisglycidyl acrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, 2,2-bis (4- Acoxyethoxyphenyl) propane, 2,2-bis (4-methacryloxyethoxyphenyl) propane, 2,2-bis (4-acryloxydiethoxyphenyl) propane, 2,2-bis (4-methacryloxydiethoxy) Phenyl) propane, 2,2-bis (4-methacryloyloxyethoxyphenyl) propane, 2,2-bis (3,5-dibromo-4-methacryloyloxyethoxypheny) ) Propane, 2,2-bis (4-methacryloyloxydipropoxyphenyl) propane, bisphenol F diacrylate, bisphenol F dimethacrylate, 1,1-bis (4-acryloxyethoxyphenyl) methane, 1,1-bis ( 4-methacryloxyethoxyphenyl) methane, 1,1-bis (4-acryloxydiethoxyphenyl) methane, 1,1-bis (4-methacryloxyethoxy) methane, dimethylol tricyclodecane diacrylate , Trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ditrimethylolpropane tetraacrylate, ditrimethylolpropane tetramethacrylate, glycerol diacrylate, glycerol dimethacrylate, pentaerythritol Triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, methylthioacrylate methylthiomethacrylate, phenylthioacrylate, benzylthiomethacrylate, xylylenedithiol diacrylate, xylylenedithiol dimethacrylate, mercaptoethylsulfide diacrylate, mercaptoethylsulfide dimethacrylate, Bifunctional urethane acrylate, bifunctional urethane methacrylate allyl compound; allyl glycidyl ether, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate, diethylene glycol bisallyl carbonate, methoxypolyethylene glycol allyl ether vinyl compound; α Methyl Stille , Alpha-methyl styrene dimer, styrene, chlorostyrene, methyl styrene, bromostyrene, dibromostyrene, divinylbenzene, 3,9 Jibinirusupirobi (m-dioxane)

<(E) Polymerization curing accelerator>
In the photochromic composition of the present invention, various polymerization / curing accelerators can be used in order to quickly accelerate the polymerization / curing according to the kind of the compound described above.
For example, when used for the reaction of a hydroxyl group, a thiol group, an NCO group, and an NCS group, a reaction catalyst or condensing agent for urethane or urea 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 for ring-opening polymerization of an epoxy group is used as a polymerization curing accelerator.
When an oleline system containing a (meth) acryl group is included, a radical polymerization initiator is used as a polymerization curing accelerator.

<Reaction catalyst for urethane or urea>
This reaction catalyst is used in poly (thio) urethane bond formation by reaction of polyiso (thia) cyanate with a polyol or polythiol. These polymerization catalysts can include tertiary amines and the corresponding inorganic or organic salts, phosphines, quaternary ammonium salts, quaternary phosphonium salts, Lewis acids, or organic sulfonic acids. As specific examples, the following can be exemplified. Further, when the catalytic activity is too high depending on the kind of the above-mentioned compound to be selected, it is possible to suppress the catalytic activity by using a mixture of a tertiary amine and a Lewis acid.

Tertiary amines; triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, triethylamine, hexamethylenetetramine, N, N-dimethyloctylamine, N, N, N ′, N '-Tetramethyl-1,6-diaminohexane, 4,4'-trimethylenebis (1-methylpiperidine), 1,8-diazabicyclo- (5,4,0) -7-undecene phosphines; trimethylphosphine, Triethylphosphine, tri-n-propylphosphie, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tribenzylphosphine, 1,2-bis (diphenylphosphino) ethane, 1,2-bis (dimethylphosphine) Fino) ethane Quaternary ammonium salts Tetramethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide quaternary phosphonium salts; tetramethylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide Lewis acid; triphenylaluminum, dimethyltin dichloride, dimethyltin bis (isooctyl) Thioglycolate), dibutyltin dichloride, dibutyltin dilaurate, dibutyltin maleate, dibutyltin maleate polymer, dibutyltin diricinolate, dibutyltin bis (dodecyl mercaptide), dibutyltin bis (isooctylthioglycolate), dioctyltin dichloride, Dioctyltin maleate, Dioctyltin maleate polymer, Diocti Tin bis (butyl maleate), dioctyltin dilaurate, dioctyltin diricinolate, dioctyltin dioleate, dioctyltin di (6-hydroxy) caproate, dioctyltin bis (isooctylthioglycolate), didodecyltin diricinolate Various metal salts such as copper oleate, copper acetylacetonate, iron acetylacetonate, iron naphthenate, iron lactate, iron citrate, iron gluconate, potassium octoate, 2-ethylhexyl titanate organic sulfonic acid; methanesulfonic acid , Benzenesulfonic acid, p-toluenesulfonic acid

<Condensation agent>
Specific examples of the condensing agent include the following.
Inorganic acids; hydrogen chloride, hydrogen bromide, sulfuric acid, phosphoric acid, etc. Organic acids; p-toluenesulfonic acid, camphor-sulfonic acid, etc. Acidic ion exchange resins; Amberlite, Amberlyst, etc. Carbodiimides; Dicyclohexylcarbodiimides, 1-ethyl -3- (3-Dimethylaminopyrrolyl) -carbodiimide

<Epoxy curing agent>
Specific examples of the epoxy curing agent include the following.
Amine compounds and salts thereof; 2-methylimidazole, 2-ethyl-4-methylimidazole, 1,8-diaza-bicyclo (5,4,0) undecene-7-trimethylamine, benzyldimethylamine, triethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, 2- (dimethylaminomethyl) phenol quaternary ammonium salt; tetramethylammonium chloride, benzyltrimethylammonium bromide, tetrabutylammonium bromide organic phosphine compound; tetra-n-butyl Phosphonium benzotriazolate, tetra-n-butylphosphonium-o, o-diethyl phosphorodithioate metal carboxylate; chromium (III) tricarboxylate, tin octylate acetylacetone chelate compound; Muacetylacetonate

<Cationic polymerization catalyst>
Specific examples of the cationic polymerization catalyst include the following.
Lewis acid catalyst; BF ₃ / amine complex, PF ₅ , BF ₃ , AsF ₅ , SbF _5, etc. Thermosetting cationic polymerization catalyst; Phosphonium salt, quaternary ammonium salt, sulfonium salt, benzylammonium salt, benzylpyridinium salt, benzyl Sulfonium salt, hydrazinium salt, carboxylic acid ester, sulfonic acid ester, amine imide UV curable cationic polymerization catalyst; diaryliodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate

<Radical polymerization initiator>
The polymerization initiator includes a thermal polymerization initiator, and specific examples thereof are as follows.
Diacyl peroxide; benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide acetyl peroxide peroxy ester; t-butyl peroxy-2-ethyl hexanate, t-butyl peroxy neodecanate , Cumyl peroxyneodecanate, t-butyl peroxybenzoate percarbonate; diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate azo compound; azobisisobutyronitrile E) can be used alone or in combination of two or more, but the amount used can be a so-called catalytic amount, for example, a total of 100 parts by mass of the above (A) and (B) On the other hand, 0.001-10 A small amount of mass parts, particularly in the range of 0.01 to 5 mass parts may be sufficient.

<(F) Internal mold release agent>
As an example of the internal mold release agent used in the present invention, any can be used as long as it has a release effect and does not impair the physical properties such as transparency of the resin, but preferably a surfactant is used. Is done. Of these, phosphate ester surfactants are preferred. The internal mold release agent herein includes those exhibiting a mold release effect among the above-mentioned various catalysts, and may include, for example, quaternary ammonium salts and quaternary phosphonium salts. These internal mold release agents are appropriately selected from the combination with monomers, polymerization conditions, economy, and ease of handling. Specific examples of the internal release agent of the phosphate ester are as follows.

Alkyl acid phosphate; mono-n-butyl phosphate, mono-2-ethylhexyl phosphate, mono-n-octyl phosphate, mono-n-butyl phosphate, bis (2-ethylhexyl) phosphate, di ( 2-ethylhexyl), di-n-octyl phosphate, di-n-butyl phosphate, butyl acid phosphate (mono-, di-mixture), ethyl acid phosphate (mono-, di-mixture), butoxyethyl acid phosphate ( Mono-, di-mixture), 2-ethylhexyl acid phosphate (mono-, di-mixture), isotridenic acid phosphate (mono-, di-mixture), tetracosyl acid phosphate (mono-, di-mixture), stearyl Acid phosphate (mono-, di-mixture)
Other phosphate esters; oleyl acid phosphate (mono-, di-mixture), dibutyl pyrophosphate, ethylene glycol acid phosphate (mono-, di-mixture), butoxyethyl acid phosphate (mono-, di-mixture) it can.

  Each of the various internal mold release agents (F) described above can be used alone or in combination of two or more, but the amount used can be small, for example, the sum of (A) and (B). It can use in the quantity of 0.001 mass part-10 mass parts with respect to 100 mass parts.

<Other ingredients>
The photochromic composition of the present invention has various compounding agents known per se within a range not impairing the effects of the present invention, such as an ultraviolet absorber, an antistatic agent, an infrared absorber, an ultraviolet stabilizer, an antioxidant, and an anti-coloring agent. Various stabilizers such as additives, antistatic agents, fluorescent dyes, dyes, pigments, and fragrances, additives, solvents, leveling agents, and thiols such as t-dodecyl mercaptan are added as polymerization regulators as needed. can do.

  Among these, use of an ultraviolet stabilizer is preferable because 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) sebacate, Adeka Stub 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 -Tolyl) propionate], IRGANOX 1010, 1035, 1075, 1098, 1135, 1141, 1222, 1330, 1425, 1520, 259, 3114, 3790, 5057, 565, manufactured by Ciba Specialty Chemicals.
The amount of the ultraviolet stabilizer used is not particularly limited as long as the effect of the present invention is not impaired, but is usually 0.001 with respect to a total of 100 parts by mass of (A) and (B). The range is from 10 to 10 parts by mass, particularly from 0.01 to 1 part by mass. In particular, when a hindered amine light stabilizer is used, there is a difference in the durability improving effect depending on the type of photochromic compound, and as a result, 1 mol of the photochromic compound (C) is used so as not to cause color shift of the adjusted color tone. The amount per unit is 0.5 to 30 mol, more preferably 1 to 20 mol, still more preferably 2 to 15 mol.

  Antistatic agents include alkali metal or alkaline earth metal salts, quaternary ammonium salts, surfactants (nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants). ), And ionic liquids (salts that exist as liquids at room temperature and exist as pairs of cations and anions). Specific examples are as follows.

Alkali metal or alkaline earth metal salt; alkali metal (such as lithium, sodium and potassium) or alkaline earth metal (such as magnesium and calcium) and organic acid [mono- or dicarboxylic acid having 1 to 7 carbon atoms (formic acid, acetic acid, Salt of propionic acid, oxalic acid, succinic acid, etc.), sulfonic acid having 1 to 7 carbon atoms (methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, etc.) and thiocyanic acid], and said organic acid and inorganic Salts of acids [hydrohalic acids (hydrochloric acid and hydrobromic acid, etc.), perchloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.], etc. Quaternary ammonium salts; Amidinium (1-ethyl-3-methylimidazolium, etc.) Or a salt of guanidinium (2-dimethylamino-1,3,4-trimethylimidazolinium, etc.) and the organic acid or inorganic acid, etc. Sexifier: Sucrose fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, fatty acid alkanolamide, polyoxyethylene alkyl ether, alkyl glycoside, polyoxyethylene alkyl phenyl ether, higher fatty acid salt (soap) , Α-sulfo fatty acid methyl ester salt, linear alkylbenzene sulfonate, alkyl sulfate ester salt, alkyl ether sulfate ester salt, (mono) alkyl phosphate ester salt, α-olefin sulfonate, alkane sulfonate, alkyl trimethyl Ammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, N-methylbishydroxyethylamine fat, fatty acid ester / hydrochloride, alkylammonium Fatty acid salts, alkylbetaines, alkylamine oxides, etc. Ionic liquids; 1,3-ethylmethylimidazolium bistrifluoromethanesulfonimide, 1,3-ethylmethylimidazolium tetrafluoroborate, 1-ethylpyridinium bistrifluoromethanesulfonimide 1-ethylpyridinium tetrafluoroborate, 1-ethylpyridinium hexafluorophosphate, 1-methylpyrazolium bistrifluoromethanesulfonimide, etc.

<Preferred composition of photochromic composition>
In the photochromic composition of this invention mentioned above, it superposes | polymerizes to a photochromic hardening body by a kneading method. When the photochromic property of this photochromic cured product is expressed, the photochromic compound (C) is used in an amount of 0.0001 to 10 parts by mass with respect to 100 parts by mass in total of the component (A) and (B). Preferably, it is used in an amount of 0.001 to 2 parts by mass, most preferably 0.001 to 1 part by mass.

  Furthermore, in the present invention, in order to maximize the effect of improving the photochromic properties, the molar ratio of the hydroxyl group and thiol group to the isocyanate group and thioisocyanate functional group is 1 mol of isocyanate group and thioisocyanate group. The amount of hydroxyl group and OH group is 0.8 to 1.2 mol, particularly 0.85 to 1.15 mol, and most preferably 0.9 to 1.1 mol.

  Next, the manufacturing method of the photochromic composition of this invention is demonstrated.

<Method for producing photochromic composition>
The method for producing a photochromic composition of the present invention is characterized in that (A) the defoaming step for removing bubbles of the iso (thio) cyanate-reactive group-containing compound is performed at 80 to 150 ° C. (A) By raising the iso (thio) cyanate-reactive group-containing compound to a high temperature, the viscosity of the iso (thio) cyanate-reactive group-containing compound can be lowered, and further, by dissociating hydrogen bonds in the active compound , Can help remove air bubbles and moisture. In that state, by defoaming, after mixing other components, it is possible to prevent air bubbles from being taken in when polymerizing the photochromic composition, and furthermore, by suppressing the reaction between moisture and isocyanate, carbon dioxide It is possible to prevent defoaming due to and improve the moldability. When the temperature of the defoaming step is lower than 80 ° C., the viscosity of the (A) iso (thio) cyanate reactive group-containing compound is high, and the defoaming of the iso (thio) cyanate reactive group-containing compound becomes insufficient, On the other hand, when it exceeds 150 degreeC of a defoaming process, there exists a possibility that an iso (thio) cyanate reactive group containing compound may decompose | disassemble. From the viewpoint of the defoaming effect and stability of the iso (thio) cyanate-reactive group-containing compound, the temperature of the defoaming step is preferably in the range of 90 to 140 ° C, and most preferably in the range of 100 to 130 ° C. .

  In the above defoaming step, it is preferable to perform the defoaming step under reduced pressure in order to efficiently defoam. In the vacuum degassing step, the preferable range of the degree of vacuum is 10 KPa to 0.1 KPa, and the time is preferably 10 minutes to 60 minutes. As the most preferable degree of pressure reduction, it is preferable to carry out under a reduced pressure of 5 KPa to 0.2 KPa for 15 minutes to 30 minutes. When the degree of decompression is lower than the degree of decompression described above, the time may be extended to degas.

  The (A) iso (thio) cyanate-reactive group-containing compound that has undergone the defoaming step can be made into a photochromic composition by mixing with other components, but (A) iso (thio) cyanate In order to prevent the reaction between the reactive group-containing compound and the (B) polyiso (thio) cyanate compound, the temperature of the (A) iso (thio) cyanate reactive group-containing compound when mixed with other components is 50 ° C. or less. Is necessary. About the mixing method of each component, there is no restriction | limiting in particular about the mixing order and the mixing method, What is necessary is just to perform using a well-known mixing apparatus, but from a viewpoint of performing mixing efficiently, (C) component, (D The component (E), the component (E), the component (F), and the other compounding components are preferably mixed with the component (B) in advance and made uniform.

<Use of photochromic composition>
In the above photochromic composition, the polymerization and curing for producing a photochromic cured product is performed by heat, or irradiation of active energy rays such as ultraviolet rays, α rays, β rays, γ rays, etc., if necessary, or a combination of both. Etc., by performing radical polymerization, ring-opening polymerization, anionic polymerization or condensation polymerization. That is, an appropriate polymerization means may be employed according to the form of the photochromic cured product to be formed. When the photochromic composition of the present invention is thermally polymerized, the properties of the photochromic cured product that can obtain temperature are particularly affected. This temperature condition is affected by the type and amount of the thermal polymerization initiator and the type of compound, so it cannot be limited in general. Generally, however, there is a method of starting polymerization at a relatively low temperature and slowly raising the temperature. Is preferred. Since the polymerization time varies depending on various factors as well as the temperature, it is preferable to determine the optimal time according to these conditions in advance. Generally, the conditions are set so that the polymerization is completed in 2 to 48 hours. It is preferable to choose. When obtaining a photochromic laminated sheet, it is preferable to polymerize at a temperature at which the reaction between the polymerizable functional groups proceeds, and at that time, it is preferable to determine the optimum temperature and time so as to achieve the target molecular weight. By polymerizing the photochromic composition by the above-described method, a photochromic cured product can be obtained.

When the photochromic property is expressed by the kneading method using the above-described polymerization curing, the above-described photochromic composition is injected between the glass molds held by the elastomer gasket or the spacer, After sufficiently defoaming, depending on the type of polymerization curing accelerator, it was molded into an optical material such as a lens by heating polymerization in an air furnace or by irradiation with active energy rays such as ultraviolet rays. A photochromic cured product can be obtained.
According to such a method, a spectacle lens or the like to which photochromic properties are directly imparted can be obtained.

  The photochromic composition of the present invention described above can exhibit photochromic properties with excellent color density, fading speed, etc., and is optically imparted with photochromic properties without reducing properties such as mechanical strength. It is effectively used for the production of a substrate such as a photochromic lens.

  Further, the photochromic cured product formed by the photochromic composition of the present invention may be dyed using a dye such as a disperse dye, silane coupling agent, silicon, zirconium, antimony, aluminum, tin, tungsten, etc., depending on the application. Preparation of hard coat film using hard coating agent mainly composed of sol, formation of thin film by vapor deposition of metal oxides such as SiO2, TiO2, ZrO2, antireflection treatment by thin film by applying organic polymer, charging Post-processing such as prevention treatment can also be performed.

  Next, the present invention will be described in detail using examples and comparative examples, but the present invention is not limited to the examples. In the following Examples and Comparative Examples, the above-described components, photochromic evaluation methods, and the like are as follows.

An iso (thio) cyanate-reactive group-containing polyrotaxane;
RX-1: An iso (thio) having a polyethylene glycol chain in a straight chain, an α-cyclodextrin in a cyclic molecule, an adamantane group in a blocking group, a polycaprolactone chain having a terminal hydroxyl group in a side chain, and a weight average molecular weight of 700,000. ) Cyanate-reactive group-containing polyrotaxane. Side chain modification degree: 0.5, side chain molecular weight: about 600 on average
RX-2: A polyethylene glycol chain in the straight chain, an α-cyclodextrin in the cyclic molecule, an adamantane group in the blocking group, a polyγ-butyrolactone chain having a terminal hydroxyl group in the side chain, and a weight average molecular weight of 400,000 (Thio) cyanate-reactive group-containing polyrotaxane. Inclusion amount of α-CD: 0.25, degree of modification of side chain: 0.5, molecular weight of side chain: about 500 on average
RX-3: A polyethylene glycol chain in the straight chain, an α-cyclodextrin in the cyclic molecule, an adamantane group in the blocking group, a polyγ-butyrolactone chain having a terminal hydroxyl group in the side chain, and a weight average molecular weight of 750,000 (Thio) cyanate-reactive group-containing polyrotaxane. Inclusion amount of α-CD: 0.25, degree of modification of side chain: 0.5, molecular weight of side chain: about 500 on average
RX-4: Polydimethylcyclohexane chain in the straight chain, γ-cyclodextrin as the cyclic molecule, 4,4 ′, 4 ′ ′-trimethoxytrityl chloride group as the blocking group, and polycaprolactone with a terminal hydroxyl group in the side chain An iso (thio) cyanate-reactive group-containing polyrotaxane having a chain and a weight average molecular weight of 650000. Side chain modification degree: 0.5, side chain molecular weight: about 600 on average

Other iso (thio) cyanate-reactive group-containing compounds;
PL1: Duranor manufactured by Asahi Kasei Chemicals Corporation (polycarbonate diol, number average molecular weight 500)
TMP: Trimethylolpropane Capa4101: manufactured by Perstorp Polycaprolactone polyol (polycaprolactone polyol having an average of 4 OH groups in the molecule, molecular weight 1,000)
PGME2: Polyethylene glycol monooleyl ether (n≈2)
PGME10: Polyethylene glycol monooleyl ether (n≈10)
PEMP: pentaerythritol tetrakis (3-mercaptopropionate)
DPMP: Dipentaerythritol hexakis (3-mercaptopropionate)
1-DT: 1-dodecanethiol (Mw = 204)

(B) 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 NCO-1: 1,2-bis (2-isocyanate) Ethylthio) ethane

(C) a photochromic compound;
PC1:

(E) a polymerization curing accelerator;
Reaction catalyst for urethane or urea;
DBTD: Dibutyltin dilaurate

(F) Internal mold release agent;
DBP: Di-n-butyltin JP-513: Isotriden acid phosphate (mono-, di-mixture) manufactured by Johoku Chemical Industry Co., Ltd.

Other ingredients Stabilizer;
HALS: bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (molecular weight 508)
The iso (thio) cyanate-reactive group-containing polyrotaxane was prepared by the following method.

<Preparation method of RX-1>
(1-1) Preparation of PEG-COOH;
A linear polyethylene glycol (PEG) having a molecular weight of 20000 was prepared as a polymer for forming an axial molecule.

The following prescription:
PEG 10g
TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy radical) 100 mg
Sodium bromide 1g
Thus, 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 stirred at room temperature for 10 minutes. Thereafter, ethanol was added in a range up to 5 mL to terminate the reaction. Then, after extraction with 50 mL of methylene chloride, the methylene chloride was distilled off and dissolved in 250 mL of ethanol, and then reprecipitated at a temperature of −4 ° C. for 12 hours, and PEG-COOH Was recovered and dried.

(1-2) Preparation of polyrotaxane;
3 g of PEG-COOH prepared above and 12 g of α-cyclodextrin (α-CD) were each dissolved in 50 mL of warm water at 70 ° C., and the resulting solutions were mixed and shaken well. Subsequently, this mixed solution was reprecipitated for 12 hours at a temperature of 4 ° C., and the deposited inclusion complex was recovered by lyophilization. Thereafter, 0.13 g of adamantaneamine was dissolved in 50 ml of dimethylformamide (DMF) at room temperature, and then the above inclusion complex was added and rapidly shaken and mixed. Subsequently, a solution prepared by dissolving 0.38 g of BOP reagent (benzotriazol 1-yl-oxy-tris (dimethylamino) phosphonium hexafluorophosphate) in DMF was further added and shaken well. Further, a solution in which 0.14 ml of diisopropylethylamine was dissolved 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. Thereafter, 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 DMF / methanol mixed solution, washing with methanol and centrifugation were performed to obtain a precipitate. The obtained precipitate was dried by vacuum drying and then dissolved in 50 mL of DMSO, and the obtained transparent solution was dropped into 700 mL of water to precipitate polyrotaxane. The precipitated polyrotaxane was collected by centrifugation and vacuum dried. Further, it was dissolved in DMSO, precipitated in water, collected and dried to obtain a purified polyrotaxane. The inclusion amount of α-CD at this time is 0.25.

Here, the amount of inclusion was measured by ¹ H-NMR measurement apparatus (JNM-LA500 manufactured by JEOL Ltd.) by dissolving polyrotaxane in DMSO-d ₆ and calculated by the following method.
Here, X, Y and X / (Y-X) have the following meanings.
X: integral value of proton derived from hydroxyl group of cyclodextrin of 4-6 ppm Y: integral value of proton derived from methylene chain of 3-4 ppm cyclodextrin and PEG X / (Y-X): proton ratio of cyclodextrin to PEG Theoretically, X / (Y-X) when the maximum inclusion amount is 1 is calculated in advance, and this value is compared with X / (Y-X) calculated from the analysis value of the actual compound. The amount was calculated.

(1-3) introduction of a side chain into a polyrotaxane;
500 mg of the polyrotaxane purified as described above was dissolved in 50 mL of 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 in an argon atmosphere. Next, using a 1 mol / L HCl aqueous solution, the above polyrotaxane solution is neutralized so that the pH is 7 to 8, dialyzed in a dialysis tube, and then freeze-dried to obtain a hydroxypropylated polyrotaxane. It was.

  The modification degree 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. The mixture was stirred at 110 ° C. for 1 hour while blowing dry nitrogen, 0.16 g of a 50 wt% xylene solution of tin (II) 2-ethylhexanoate was added, and the mixture was stirred at 130 ° C. for 6 hours. Thereafter, xylene was added to obtain a polycaprolactone-modified polyrotaxane xylene solution into which a side chain having a nonvolatile concentration of about 35% by mass was introduced.

The polycaprolactone-modified polyrotaxane xylene solution prepared above was dropped into hexane, collected, and dried to obtain a side chain-modified polyrotaxane (RX-1) having an OH group as a polymerizable functional group. The obtained hydroxypropylated polyrotaxane was identified by ¹ H-NMR and GPC, and confirmed to be a hydroxypropylated polyrotaxane having a desired structure.

The physical properties of this polyrotaxane were as follows.
Side chain modification degree: 0.5
Side chain molecular weight: about 600 on average
Polyrotaxane weight average molecular weight Mw (GPC): 700,000

<Preparation method of RX-2>
An iso (thio) cyanate-reactive group-containing polyrotaxane (RX-2) was prepared in the same manner as the preparation method of (RX-1) except that 22.5 g of ε-caprolactone was used, using PEG having a molecular weight of 35,000. )

Inclusion amount of α-CD: 0.25
Side chain modification degree: 0.5
Side chain molecular weight: about 500 on average
Polyrotaxane weight average molecular weight Mw (GPC): 700,000

<Preparation method of RX-3>
Iso (thio) cyanate was prepared in the same manner as in (RX-1) except that PEG having a molecular weight of 35,000 was used and 25.3 g of α-acetyl-γ-butyrolactone was used instead of ε-caprolactone. A reactive group-containing polyrotaxane (RX-3) was obtained.

Inclusion amount of α-CD: 0.25
Side chain modification degree: 0.5
Side chain molecular weight: about 500 on average
Polyrotaxane weight average molecular weight Mw (GPC): 750000

<Preparation method of RX-4>
(1-4) Preparation of pseudopolyrotaxane having polydimethylcyclohexane as an axis molecule;
In a 200 ml eggplant flask, 6 g of γ-cyclodextrin (γ-CD) was taken, and 20 mL of ion exchange water was added and dissolved.

  Separately, 420 mg of bis (3-aminopropyl) -terminated poly (dimethylsiloxane) (PDM, average molecular weight: 26,000) was weighed into a 200 ml flask. The above-mentioned γ-CD aqueous solution was added to the flask at a stretch while applying ultrasonic waves, and stirred for 30 minutes while applying ultrasonic waves.

  Then, it left still at room temperature (25 degreeC) for 3 days, and white suspension was obtained. The obtained suspension was stirred well again, and the suspension was evenly frozen with liquid nitrogen, and then freeze-dried for 2 days to obtain a pseudopolyrotaxane having polydimethylcyclohexane as an axis molecule.

(1-5) Preparation of polyrotaxane having polydimethylcyclohexane as an axis molecule Under argon atmosphere, 250 mg of 4,4 ′, 4 ′ ′-trimethoxytrityl chloride (TMTC) was put into a 50 ml eggplant flask, and further dehydrated 1 , 4-Dioxane (2 mL) was added to dissolve TMTC. Separately, 250 mg of the pseudopolyrotaxane obtained in (1-14) above was placed in a glass container under an argon atmosphere, and the TMTC solution was added all at once to this container. Immediately thereafter, 0.07 mL of triethylamine (TEA) was added dropwise, and the mixture was allowed to stand without stirring at room temperature (25 ° C.) for 24 hours. The pseudopolyrotaxane having polydimethylcyclohexane as an axis molecule was not dissolved in 1,4-dioxane, and the reaction was performed in a heterogeneous system. After the reaction, the heterogeneous reaction solution was again stirred well to obtain a suspension.

  This suspension was dropped into 50 mL of water rotated at high speed to obtain a white precipitate. The liquid containing the precipitate was made into a suspension by ultrasonic waves and then filtered, and the resulting solid was washed with a large amount of water to obtain a powder. The obtained powder was dried, 30 mL of acetone was added and suspended by ultrasonic waves to obtain a suspension. This suspension was filtered, and the solid was collected and washed with a large amount of acetone. The operation of washing with a large amount of water-drying-acetone suspension-filtration-acetone washing was repeated again to obtain a polyrotaxane having polydimethylcyclohexane as an axis molecule.

  When the obtained polyrotaxane was dissolved in pyridine-d5 and 1H-NMR was measured, a polyrotaxane was found by comparing the integral values of a peak derived from polydimethylsiloxane near 0.5 ppm and a peak derived from γ-CD at 4-5 ppm. It was found that the inclusion amount of γ-CD constituting 0.25 was 0.25.

(1-6) Preparation of OH group-introduced side chain modified polyrotaxane (RX-4);
500 mg of the polyrotaxane purified in the above (1-5) was dissolved in 50 mL of 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.

  The solution was neutralized with a 1 mol / L HCl aqueous solution so that the pH was 7 to 8, dialyzed with a dialysis tube, and lyophilized to obtain a hydroxypropylated polyrotaxane.

  The obtained hydroxypropylated polyrotaxane was identified by 1H-NMR and GPC, and confirmed to be a hydroxypropylated polyrotaxane having a desired structure. In addition, the modification degree to the OH group of the cyclic molecule by the hydroxypropyl group was 0.5, and the average weight molecular weight Mw was 170,000 by GPC measurement. A mixed solution in which 5 g of the hydroxypropylated polyrotaxane obtained above was dissolved in 22.5 g of ε-caprolactone at a temperature of 80 ° C. was obtained. The mixture was stirred at 110 ° C. for 1 hour while blowing dry nitrogen, 0.16 g of a 50 wt% xylene solution of tin (II) 2-ethylhexanoate was added, and the mixture was stirred at 130 ° C. for 6 hours. Thereafter, xylene was added to obtain a xylene solution. Then, it was dripped in hexane, collect | recovered, and the iso (thio) cyanate reactive group containing polyrotaxane (RX-4) was obtained by drying.

Side chain modification degree: 0.5
Side chain molecular weight: about 600 on average
Polyrotaxane weight average molecular weight Mw (GPC): 650000

<Example 1>
According to the following formulation, each component was mixed to prepare a uniform liquid (photochromic composition).
Prescription;
(A) RX-1 8 parts by mass, PL1 19 parts by mass, TMP 16 parts by mass, PGME2 1 part by mass, PGME10 9 parts by mass (B) NBDI 47 parts by mass (C) Photochromic compound: PC1 0.04 parts by mass (H ) Internal mold release agent: DBP: 0.3% by weight (based on the total amount of the mixture)

<Production of photochromic composition>
Components (A) and (A ′) were mixed and stirred uniformly, and then the defoaming step was performed at 100 ° C. and 1 KPa for 15 minutes. At the end of the defoaming step, no bubbles were observed from the component (A). After the component (A) subjected to the above treatment was cooled to 30 ° C., the components (B), (C), and (H) were added and stirred uniformly at 30 degrees to obtain a photochromic composition.

<Polymerization of photochromic composition>
After sufficiently defoaming the composition, the composition was poured into a mold comprising a mold composed of a glass mold subjected to a release treatment and a gasket made of an ethylene-vinyl acetate copolymer.
Then, it was cured over 15 hours while gradually raising the temperature from 30 ° C to 95 ° C. After completion of the polymerization, the photochromic cured product was removed from the glass mold. The obtained photochromic cured product had no appearance of bubbles and had a good appearance. The photochromic properties were a maximum absorption wavelength of 577 nm, a color density of 0.90, and a fading speed of 47 seconds. The handling property of the photochromic composition and the moldability of the obtained photochromic cured product were also good. Furthermore, L scale Rockwell hardness (HL) of the obtained photochromic cured product was 72. The appearance evaluation, maximum absorption wavelength, color density, fading speed, L scale Rockwell hardness, and moldability were evaluated as follows.

〔Evaluation item〕
(1) Appearance: The presence or absence of bubbles in the photochromic cured product was evaluated by visual observation. As evaluation criteria, 20 photochromic cured bodies were prepared, and evaluation was made based on the number of lenses in which bubbles were formed in the cured body, resulting in a defective product.
(2) Maximum absorption wavelength (λmax): The maximum absorption wavelength after color development determined by a spectrophotometer manufactured by Otsuka Electronics Co., Ltd. (instant multichannel photodetector: MCPD1000). The maximum absorption wavelength is related to the color tone at the time of color development.
(3) Color density {ε (120) −ε (0)}: difference between absorbance {ε (120)} after light irradiation for 120 seconds and absorbance ε (0) before light irradiation at the maximum absorption wavelength . It can be said that the higher this value, the better the photochromic properties. Further, when the color was developed outdoors, the color tone was visually evaluated.
(4) Fading speed [t1 / 2 (sec.)]: When light irradiation is stopped after 120 seconds of light irradiation, the absorbance at the maximum absorption wavelength of the sample is {ε (120) −ε (0)}. Time required to drop to 1/2 of It can be said that the shorter this time is, the better the photochromic property is.
(5) L scale Rockwell hardness (HL): After holding the cured body in a room at 25 ° C. for one day, the L scale Rockwell hardness of the photochromic cured body is measured using an Akashi Rockwell hardness meter (type: AR-10). It was measured.

<Examples 2 to 10, Comparative Examples 1 and 2>
A photochromic composition having the composition shown in Table 1 was produced in the same manner as in Example 1 except that the preparation method of the component (A) was used, and the obtained photochromic composition was used as in Example 1. The photochromic hardened | cured material was produced by the method and evaluated. In addition, (C), (E), (F), and other components have shown the mass part added with respect to 100 mass parts of whole quantity of (A) and (B). The results are shown in Table 2. From the results of the table, it can be seen that the yield of the example in which the component (A) was defoamed was greatly improved.

Claims (3)

(A) A side having a complex molecular structure composed of an axial molecule and a plurality of cyclic molecules that include the axial molecule, and having an iso (thio) cyanate-reactive group in at least a part of the ring contained in the cyclic molecule An iso (thio) cyanate-reactive group-containing compound containing a polyrotaxane in which a chain is introduced,
(B) A method for producing a photochromic composition comprising a polyiso (thio) cyanate compound having two or more isocyanate groups and / or isothiocyanate groups in one molecule, and (C) a photochromic compound,
After the defoaming step of holding the (A) iso (thio) cyanate reactive group-containing compound at 80 to 150 ° C. and removing bubbles in the (A) iso (thio) cyanate reactive group-containing compound, 50 ° C. Below, the said (B) polyiso (thio) cyanate compound and (C) photochromic compound are mixed, The manufacturing method of the photochromic composition characterized by the above-mentioned.   The method for producing a photochromic composition according to claim 1, wherein the defoaming step is performed under a reduced pressure of 10 KPa to 0.1 KPa.   The photochromic hardening body obtained by hardening | curing the photochromic composition obtained by the manufacturing method of the said Claim 1 or 2.

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