Compounds for optical materials, curable compositions, cured bodies, and optical articles

Abstract

A novel compound for optical materials, and a curable composition, a cured body, and an optical article comprising the compound for optical materials are provided. According to an embodiment, a compound for optical materials represented by the following formula (Ia) is provided. In formula (Ia), X1 and X2 are each NH, S, or O. R1 is an organic residue with a value of 1 to 30. R3 is a group comprising a polymer of repeating units selected from the group consisting of -(CH2)mO-, -(CH2CH2O)-, -(CH(CH3)CH2O)-, -(CH2CH(CH3)O)-, and -(C(=O)-CH2CH2CH2CH2CH2CH2O)-, -(C(=O)-O-CH2CH2CH2CH2CH2CH2O)-, a random copolymer of at least two repeating units selected from the group, or a block copolymer of at least two repeating units selected from the group.

Description

Technology Field

[0001] The present invention relates to a compound for optical materials, a curable composition, a cured body, and an optical article. Background Technology

[0002] The demand for photochromic glasses with photochromic properties is expanding globally. Since the transmittance of the lens changes depending on the ambient brightness (amount of ultraviolet rays), photochromic glasses can control glare.

[0003] In recent years, the development of plastic lenses having photochromic properties has been underway. Such photochromic lenses are obtained, for example, by curing a polymerizable composition containing a photochromic compound whose structure changes depending on the amount of ultraviolet light. As a technique to improve photochromic performance, a technique has been proposed to improve dispersibility by suppressing the aggregation of the photochromic compound in the cured body (Patent Documents 1 to 3). Prior art literature

[0004] International Publication No. WO2014 / 007154 Japanese Patent Publication No. 2008-506031 Japanese Patent Publication No. Hei 1-152182

[0005] Chem. Mater., 2014, 26, 724-744 The problem to be solved

[0006] The object of the present invention is to provide a novel compound for optical materials, and a curable composition, a cured body, and an optical article comprising the compound for optical materials. means of solving the problem

[0007] The present invention includes the following inventions.

[0008] 1. A compound for optical materials represented by the following formula (Ia).

[0009]

[0010] Among the above formula (Ia),

[0011] X1 and X 2 are, respectively, NH, S, or O, and

[0012] R 1 It is an organic residue with a valence of 1 to 30, and

[0013] R 2 is H, or CH3, and

[0014] R 3 silver,

[0015] -(CH2) m O-,

[0016] -(CH2CH2O)-,

[0017] -(CH(CH3)CH2O)-,

[0018] -(CH2CH(CH3)O)-,

[0019] -(C(=O)-CH2CH2CH2CH2CH2O)-,

[0020] -(C(=O)-O-CH2CH2CH2CH2CH2O)-, and

[0021] -(C(=O)-O-CH2CH2CH2CH2CH2CH2O)-

[0022] A polymer of repeating units selected from the group consisting of

[0023] A random copolymer of at least two repeating units selected from the above group, or,

[0024] A group comprising a block copolymer of at least two repeating units selected from the above group, and

[0025] R 4 Is,

[0026] H,

[0027] H2C=CH-C(=O)-,

[0028] H2C=C(CH3)-C(=O)-,

[0029] H2C=CH-C(=O)-OCH2CH2NHC(=O)-,

[0030] HS-CH2-CH2-C(=O)-, or

[0031] It is a glycidyl group, and

[0032] a is an integer from 0 to 29, b is 0 or 1, c is 0 or 1, d is an integer from 1 to 30, a+d is an integer from 1 to 30, and m is an integer from 3 to 20.

[0033] 2. The above R 1 A compound for optical materials described in claim 1, which is a monovalent, divalent, trivalent, tetravalent, or hexavalent organic residue.

[0034] 3. The above R 1 A compound for optical materials described in claim 1, which is an organic residue represented by the following formulas (IIIa), (IIIb), (IIIc), or (IIId).

[0035] C(CH2) e (CH2CH3) f (IIIa)

[0036] In the above formula (IIIa), e is 1 to 4, f is 0 to 3, e+f is 4, and

[0037] C(CH2OC(=O)CH2CH2) g (CH2CH3) h (IIIb)

[0038] In the above formula (IIIb), g is 1 to 4, h is 0 to 3, g+h is 4, and

[0039] C(CH2O-C(=O)CH2CH2) α (CH2CH3) β -CH2OCH2-C(CH2O-C(=O)CH2CH2) γ (CH2CH3) δ (IIIc)

[0040] In the above formula (IIIc), α is 0 to 3, β is 0 to 3, α+β is 3, γ is 0 to 3, δ is 0 to 3, γ+δ is 3, and α+γ is 1 to 6,

[0041] C(CH2O)ε (CH2CH3) ζ -CH2OCH2-C(CH2O) η (CH2CH3) ι (IIId)

[0042] In the above equation (IIId), ε is 0 to 3, ζ is 0 to 3, ε+ζ is 3, η is 0 to 3, ι is 0 to 3, η+ι is 3, and ε+η is 1 to 6.

[0043] 4. The above R 1 A compound for optical materials described in claim 1, which is an organic residue selected from the group consisting of formulas (4c), (4b), (5d), (5a), (6h), (6a), and (6e) described below.

[0044] 5. The above R 3 A compound for optical materials described in any one of claims 1 to 4, comprising a polymer having -(CH2CH2O)- as a repeating unit and a block copolymer of a polymer having (CH2CH(CH3)O)- as a repeating unit.

[0045] 6. The above R 3 A compound for optical materials described in any one of claims 1 to 5, comprising a block copolymer represented by the following formula (IIa).

[0046] -(CH2CH2O) x -(CH2CH(CH3)O) y -(CH2CH2O) z - (IIa)

[0047] In the above equation (IIa), x is an integer from 0 to 20, y is an integer from 5 to 40, and z is an integer from 1 to 20.

[0048] 7. A curable composition comprising a compound for optical materials (component D) described in any one of claims 1 to 6, and at least one compound (component B) selected from the group consisting of polyisocyanate compounds and polyisothiocyanate compounds.

[0049] 8. R in Equation (Ia) 4 A curable composition comprising a compound for optical materials (component D) described in claim 7, which is H2C=CH-C(=O)-, H2C=C(CH3)-C(=O)-, or H2C=CH-C(=O)-OCH2CH2NHC(=O)-.

[0050] 9. A curable composition as described in claim 7 or 8, further comprising a photochromic compound (component A).

[0051] 10. A cured body obtained by curing a curable composition described in any one of claims 7 to 9.

[0052] 11. An optical article comprising the hardened body described in the preceding paragraph 10. Effects of the invention

[0053] According to the present invention, a novel compound for optical materials, a curable composition, a cured body, and an optical article comprising the compound for optical materials are provided.

[0054] The photochromic curable body and optical article comprising the compound for optical materials of the present invention have a maximum absorption wavelength (λmax), a color intensity, and a fading half-life [τ 1 / 2 It has excellent photochromic properties such as (sec)〕 and excellent durability of color development. Specific details for implementing the invention

[0055] [Compounds for Optical Materials]

[0056] The compound for optical materials related to the embodiment is represented by the following formula (Ia).

[0057]

[0058] In equation (Ia), X 1 and X 2 are, respectively, NH, S, or O. X 1 and X 2 It is preferable that each be NH or S. X 1 and X2 When amine compounds in which g is NH and thiol compounds in which g is S are used as materials, cured bodies with high durability and photochromic properties tend to be obtained. 1 and X 2 It is more desirable that each be S.

[0059] a is an integer from 0 to 29. It is preferable that a is 0, 1, or 2, and more preferable that a is 0. b is 0 or 1. It is preferable that b is 0. That is, when a compound that does not have S or NH is used, a cured body with high durability and photochromic properties tends to be obtained.

[0060] R 1 It is an organic residue with a valence of 1 to 30. R 1 It is preferable that the organic residue be monovalent, divalent, trivalent, tetravalent, pentavalent, hexavalent, heliovalent, or decivalent, and more preferable that the organic residue be divalent, trivalent, tetravalent, or hexavalent. When a compound with a high valence of the organic residue is used, a cured body with excellent photochromic properties tends to be obtained. Details regarding the organic residue will be described later.

[0061] R 2 is H, or CH3. R 2 It is desirable that it be H.

[0062] c is 0 or 1. When using a compound for optical materials having a structure in which c is 1, that is, a subscript c attached, the durability of the cured body tends to increase. When using a compound for optical materials having a structure in which c is 0, that is, a structure in which the subscript c is attached, a cured body with both durability and photochromic properties tends to be obtained.

[0063] R 3 silver,

[0064] -(CH2) m O-,

[0065] -(CH2CH2O)-,

[0066] -(CH(CH3)CH2O)-,

[0067] -(CH2CH(CH3)O)-,

[0068] -(C(=O)-CH2CH2CH2CH2CH2O)-,

[0069] -(C(=O)-O-CH2CH2CH2CH2CH2O)-, and

[0070] -(C(=O)-O-CH2CH2CH2CH2CH2CH2O)-

[0071] A polymer of repeating units selected from the group consisting of

[0072] A random copolymer of at least two repeating units selected from the above group, or,

[0073] It is a group comprising a block copolymer of at least two repeating units selected from the above group. m is an integer from 3 to 20. It is more preferable that m is an integer of 4 or more.

[0074] R 3 It is a homopolymer of one repeating unit selected from the above group, a random copolymer of at least two repeating units selected from the above group, or a block copolymer of at least two repeating units selected from the above group.

[0075] R 3 It is a group containing a polymer, and is a flexible chain having a relatively flexible structure. In the cured body, the flexible chain R 3 The neighborhood region of tends to have higher flexibility. Therefore, flexible chain R 3 Compounds that undergo structural changes, such as photochromic compounds located in the vicinity, are difficult to have their structural changes hindered. Therefore, flexible chain R 3 When using a compound for optical materials related to an embodiment having, the photochromic performance of the cured body is enhanced. In the compound for optical materials related to an embodiment, this flexible chain R 3 This, organic residue R 1Because it is connected through a structure with arbitrarily attached subscripts c and b, this flexible chain R 3 It is easier to increase the flexibility of the nearby area, and durability is increased over a long period of time.

[0076] R 3 -(CH2CH2O)-, -(CH2CH(CH3)O)-, and -(CH2) m It is preferable that the composition comprises a polymer of repeating units selected from the group consisting of O-, a random copolymer of at least two repeating units selected from said group, or a block copolymer of at least two repeating units selected from said group. When using an optical material compound comprising a polymer having -(CH2CH2O)- as a repeating unit, a cured body with excellent durability tends to be obtained. When using an optical material compound comprising a polymer having -(CH2CH(CH3)O)- as a repeating unit, a cured body with excellent photochromic properties tends to be obtained. -(CH2) m When using optical material compounds containing polymers with O- as repeating units, a cured body with excellent durability tends to be obtained.

[0077] R 3 It is preferable that the polymer comprises a polymer having -(CH2CH2O)- as a repeating unit and a block copolymer of a polymer having -(CH2CH(CH3)O)- as a repeating unit. In this block copolymer, the polymer having -(CH2CH2O)- as a repeating unit comprises organic residue R through the polymer having -(CH2CH(CH3)O)- as a repeating unit. 1 It is preferable for it to be positioned facing the surface, that is, to be located on the outer side in the structural formula of the compound for optical materials. When using a compound for optical materials having such a structure, the durability of the cured body tends to be higher.

[0078] The number of repetitions of each repeating unit is, for example, 2 to 30, preferably 5 to 20, more preferably 7 to 16, and even more preferably 7, 9, 10, 11, 12, 15, or 16. When a compound for optical materials with a large number of repetitions is used, a cured body with high photochromic properties tends to be obtained. On the other hand, if the number of repeating units is excessive, there is a risk that the durability and photochromic properties of the cured body will be reduced.

[0079] R 3 It is more preferable that the compound comprises a block copolymer represented by the following formula (IIa). When a compound for optical materials containing such a structure is used, the durability and photochromic properties of the cured body tend to increase.

[0080] -(CH2CH2O) x -(CH2CH(CH3)O) y -(CH2CH2O) z - (IIa)

[0081] In equation (IIa), x is an integer from 0 to 20, y is an integer from 5 to 40, and z is an integer from 1 to 20.

[0082] R 4 Is,

[0083] H,

[0084] H2C=CH-C(=O)-,

[0085] H2C=C(CH3)-C(=O)-,

[0086] H2C=CH-C(=O)-OCH2CH2NHC(=O)-,

[0087] HS-CH2-CH2-C(=O)-, or

[0088] It is a glycidyl group.

[0089] R 4 A compound for optical materials in which is H is suitable as a material for polyurethane resins.

[0090] R 4H2C=CH-C(=O)-, H2C=C(CH3)-C(=O)-, or,

[0091] A compound for optical materials having H2C=CH-C(=O)-OCH2CH2NHC(=O)- is suitable as a material for (meth)acrylic resins.

[0092] R 4 A compound for optical materials that is HS-CH2-CH2-C(=O)- is suitable as a material for polyurethane resins.

[0093] R 4 A compound for optical materials having a glycidyl group is suitable as a material for epoxy resin or acrylic resin.

[0094] d is an integer from 1 to 30. a+d is an integer from 1 to 30. d is, for example, 1, 2, 3, 4, 5, 6, or 7. d and organic residue R 1 The ratio of the valence (d / valence) is preferably 0.5 or higher, more preferably 0.8 or higher, and even more preferably 1. That is, organic residue R 1 It is desirable that the bonding ratio between the bonding loss of and the structure with the subscript d attached is high. Flexible chain R in a compound for optical materials 3 By increasing the proportion of this, there is a tendency to obtain a cured body with high durability and photochromic properties.

[0095] In the compound for optical materials related to the embodiment, an organic residue R having one or more valencies 1 To use, one or more flexible chains R 3 It is possible to introduce [it]. Therefore, when using this optical material compound, a hardened body with excellent durability is obtained.

[0096] <Organic residue R 1 >

[0097] Organic residue R 1The structure of is explained with specific examples. In the exemplified structural formulas, parts with dashed lines indicate bonding hands that combine with other structures. Organic residue R 1 Specific examples of this include the following type of display.

[0098] Specific examples of monovalent organic residues include alkyl groups having 1 to 20 carbon atoms, polyoxyethylene monomethyl ether groups, propionic acid derivative groups represented by the following formula (2a).

[0099]

[0100] In Equation (2a), R 6 It is an alkyl group having 1 to 20 carbon atoms, or a polyoxyethylene monomethyl ether group.

[0101] Specific examples of divalent organic residues include an alkylene group having 1 to 20 carbon atoms, a polyoxyethylene glycol group, a divalent propionic acid derivative group represented by the following formula (3a), and a polyoxyethylene-block-polyoxypropylene-block-polyoxyethylene glycol group represented by the following formula (3b).

[0102]

[0103] In Equation (3a), R 5 is an alkylene group having 1 to 20 carbon atoms, or a polyoxyethylene group.

[0104]

[0105] In equation (3b), q is 1 to 20 and r is 5 to 40.

[0106] Specific examples of the trivalent organic residue include a trimethylolpropane tripropionate derivative group represented by the following formula (4c), a glycerol derivative group represented by the following formula (4a), and a trimethylolpropane derivative group represented by the following formula (4b).

[0107]

[0108]

[0109]

[0110] Examples of tetravalent organic residues include a ditrimethylolpropane tetrapropionate derivative group, a pentaerythritol tetrapropionate derivative group represented by the following formula (5d), a pentaerythritol group represented by the following formula (5a), a diglycerol derivative group represented by the following formula (5b), and an erythritol derivative group represented by the following formula (5c).

[0111]

[0112]

[0113]

[0114]

[0115] Examples of organic residues of 5 include the D-glucopyranose group represented by the following formula (6d).

[0116]

[0117] Examples of hexavalent organic residues include a dipentaerythritol hexapropionate derivative group represented by the following formula (6h), a dipentaerythritol group represented by the following formula (6a), a sorbitol group represented by the following formula (6b), and a mannitol group represented by the following formula (6c). Additionally, mannitol is a stereoisomer of sorbitol.

[0118]

[0119]

[0120]

[0121]

[0122] As organic residues of 1 to 21 valence, a β-cyclodextrin group represented by the following formula (6e) may be used. In the β-cyclodextrin group, when the valence is less than 21, the sites that become bonding hands are selected randomly. Sites that are not bonding hands are modified, for example, by OH or CH3.

[0123]

[0124] Examples of organic residues with a valence of 1 to 18 include an α-cyclodextrin group represented by the following formula (6f). In the α-cyclodextrin group, when the valence is less than 18, the sites that become bonding hands are selected randomly. Sites that are not bonding hands are modified, for example, by OH or CH3.

[0125]

[0126] Examples of organic residues with a valence of 1 to 24 include a γ-cyclodextrin group represented by the following formula (6g). In the γ-cyclodextrin group, when the valence is less than 24, the sites that become bonding hands are selected randomly. Sites that are not bonding hands are modified, for example, by OH or CH3.

[0127]

[0128] Organic residue R 1It is preferable that the organic residue be an organic residue of a compound represented by the following formulas (IIIa), (IIIb), (IIIc), or (IIId). The organic residue represented by formula (IIIa) is a 1 to 4-valent pentaerythritol derivative group. The organic residue represented by formula (IIIb) is a 1 to 4-valent pentaerythritol propionate derivative group. The organic residue represented by formula (IIIc) is a 1 to 6-valent dipentaerythritol propionate derivative group. The organic residue represented by formula (IIId) is a 1 to 6-valent dipentaerythritol derivative group. When using a compound for optical materials having these organic residues, the durability and photochromic properties of the cured body tend to be high. In terms of excellent handling properties, it is preferable to use the organic residue represented by formula (IIIa) or (IIIb).

[0129] C(CH2) e (CH2CH3) f (IIIa)

[0130] In equation (IIIa), e is 1 to 4, f is 0 to 3, and e+f is 4.

[0131] C(CH2OC(=O)CH2CH2) g (CH2CH3) h (IIIb)

[0132] In equation (IIIb), g is 1 to 4, h is 0 to 3, and g+h is 4.

[0133] C(CH2O-C(=O)CH2CH2) α (CH2CH3) β -CH2OCH2-C(CH2O-C(=O)CH2CH2) γ (CH2CH3) δ (IIIc)

[0134] In the above formula (IIIc), α is 0 to 3, β is 0 to 3, α+β is 3, γ is 0 to 3, δ is 0 to 3, γ+δ is 3, and α+γ is 1 to 6.

[0135] C(CH2O) ε (CH2CH3) ζ -CH2OCH2-C(CH2O) η (CH2CH3) ι (IIId)

[0136] In equation (IIId), ε is 0 to 3, ζ is 0 to 3, and ε+ζ is 3. η is 0 to 3, ι is 0 to 3, η+ι is 3, and ε+η is 1 to 6.

[0137] Examples of compounds for optical materials

[0138] Below, compounds (7a) to (25a) are described as specific examples of compounds for optical materials related to the embodiments.

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153] Among the formulas (22a), 10 of the randomly selected Rs are molecular chains shown below.

[0154]

[0155]

[0156] Below, compounds (24a) and (25a) are described as other specific examples of compounds for optical materials related to the embodiments.

[0157]

[0158]

[0159] [Method for manufacturing compounds for optical materials]

[0160] Michael's Reaction

[0161] The synthesis method for compounds for optical materials is not particularly limited. For example, compounds for optical materials related to the embodiment can be obtained by a Michael addition reaction. The Michael addition reaction is, for example, the reaction shown in Reaction Scheme 1 below, and known reaction conditions may be used (Non-Patent Document 1).

[0162]

[0163] Specifically, organic residue R acting as a nucleophile 1 A compound having the structure and a polymer group R activated against nucleophilic attack 3 A compound for optical materials related to the embodiment can be synthesized by mixing a compound having a structure and then stirring it for a certain period of time under a nitrogen atmosphere.

[0164] Organic residue R acting as a nucleophile 1 As a compound having the structure, for example, the aforementioned organic residue R 1 Use compounds in which the bonding hands are modified by OH, SH, or NH2.

[0165] Organic residue R acting as a nucleophile 1Specific examples of compounds having the structure include, for example, tridecyl (3-mercaptopropionate), trimethylolpropanetris (3-mercaptopropionate), pentaerythritoltetrakis (3-mercaptopropionate), and dipentaerythritolhexakis (3-mercaptopropionate).

[0166] Polymer group R 3 Specific examples of compounds having the structure include, for instance, polyethylene glycol monoacrylate, polyethylene glycol polypropylene glycol polyethylene glycol, etc.

[0167] Polymer group R activated against nucleophilic attack 3 Compounds having the structure, for example, polymer group R 3 A compound having a structure is obtained by acrylate treatment.

[0168] Nucleophilic Substitution Reaction

[0169] The compound for optical materials related to the embodiment can also be synthesized, for example, by a nucleophilic substitution reaction. The nucleophilic substitution reaction is, for example, the reaction shown in Reaction Scheme 2 below, and known reaction conditions may be used.

[0170]

[0171] Specifically, the polymer group R acting as a nucleophile 3 An organic residue R that anionizes a compound having the structure with a base and has a detaching group L activated against nucleophilic attack. 1 After mixing, a compound for optical materials related to the embodiment can be synthesized by stirring for a certain period of time under a nitrogen atmosphere.

[0172] Polymer group R acting as a nucleophile 3 Specific examples of compounds having the structure include polyethylene glycol, polypropylene glycol, polyethylene glycol, polyethylene glycol, polyethylene glycol, polytetramethylene glycol, and the like.

[0173] Examples of bases used in the above nucleophilic substitution reaction include metal hydroxides, sodium hydride, potassium tert-butoxide, etc.

[0174] In the above reaction scheme 2, L is a degreasing group, and as long as it forms an ether bond as a result of the above nucleophilic substitution reaction, it is not particularly limited and examples include a chlorine atom, a bromine atom, an iodine atom, a p-toluenesulfonyloxy group, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, etc.

[0175] Organic residue R having a release agent L activated against nucleophilic attack 1 Specific examples of this include pentaerythrityltetrabromide.

[0176] The above nucleophilic substitution reaction can be carried out in a solvent. As for the solvent, it is not particularly limited as long as it does not interfere with the nucleophilic substitution reaction, and examples include non-protonic polar solvents such as tetrahydrofuran, acetonitrile, and dimethylformamide.

[0177] [Curable composition]

[0178] The compound for optical materials (component D) represented by formula (Ia) can be used as a component of a curable composition.

[0179] A cured body is obtained by curing a curable composition. In addition to the compound for optical materials represented by formula (Ia) (component D), the curable composition may contain a polyisocyanate compound and a polyisothiocyanate compound (component B). Additionally, it may include at least one selected from the group consisting of an active hydrogen-containing compound (component C), a photochromic compound (component A), a curing accelerator (component E), and other additives.

[0180] Urethane-based curable composition

[0181] The compound for optical materials (Component D) can be used as a component of a urethane-based curable composition. In addition to the compound for optical materials (Component D), the urethane-based curable composition comprises at least one of a polyisocyanate compound and a polyisothiocyanate compound, namely, a polyiso(thio)cyanate compound (Component B). It is preferable to add an active hydrogen-containing compound (Component C) immediately before curing the urethane-based curable composition.

[0182] The content of the optical material compound (component D) in the urethane-based curable composition is preferably 1 mass% or more, more preferably 3 mass% or more, and even more preferably 8 mass% or more. If the content of the optical material compound (component D) is high, the photochromic properties of the cured body tend to increase. On the other hand, from the perspective of increasing the durability of the cured body, the content of the optical material compound (component D) is preferably 50 mass% or less, more preferably 30 mass% or less, and even more preferably 20 mass% or less.

[0183] The amount of compound for optical materials (component D) to a total of 100 parts by mass of polyiso(thio)cyanate compound (component B) and active hydrogen-containing compound (component C) is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 5 parts by mass or more and 35 parts by mass or less, and even more preferably 10 parts by mass or more and 25 parts by mass or less.

[0184] Polyiso(thio)cyanate compound (Component B)

[0185] "Polyiso(thio)cyanate compound (component B)" is a compound having two or more isocyanate groups, a compound having two or more isothiocyanate groups, or a compound having one or more isocyanate groups and one or more isothiocyanate groups.

[0186] Polyisocyanate compounds (component B) include aliphatic isocyanate compounds, alicyclic isocyanate compounds, aromatic isocyanate compounds, sulfur-containing heterocyclic isocyanate compounds, sulfur-containing aliphatic isocyanate compounds, aliphatic sulfide-based isocyanate compounds, aromatic sulfide-based isocyanate compounds, aliphatic sulfonate-based isocyanate compounds, aromatic sulfonate-based isocyanate compounds, sulfonic acid ester-based isocyanate compounds, aromatic sulfonamide-based isocyanate compounds, etc.

[0187] In addition, the polyisocyanate compound (component B) includes a blocked isocyanate compound, etc., in which the isocyanate group of the isocyanate compound is blocked by at least one blocking agent selected from the group consisting of alcohols, lactams, phenols, oximes, pyrazols, thiols, active methylene compounds, malonic acid diester compounds, and acetoacetic acid ester compounds.

[0188] In a urethane-based curable composition, the amount of polyiso(thio)cyanate compound (component B) is preferably 10 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of active hydrogen-containing compound (component C), and more preferably 50 parts by mass or more and 150 parts by mass or less.

[0189] Among polyisocyanate compounds (component B), compounds suitable for forming optical articles with excellent transparency and mechanical strength, particularly compounds suitable for manufacturing optical articles including photochromic compounds (component A), may be compounds represented by the following formulas (I) to (VIII).

[0190] As a preferred aliphatic isocyanate compound, the following formula

[0191]

[0192] (during food, R 100It is an alkylene group having 1 to 10 carbon atoms, and a portion of the methylene group in the chain of the alkylene group is substituted with a sulfur atom.)

[0193] Examples of compounds represented by can be found.

[0194] The above R 100 The group is an alkylene group having 1 to 10 carbon atoms, and may be in a straight chain or a branched chain. Among these, a straight chain group of a pentamethylene group, a hexamethylene group, or a heptamethylene group or an octamethylene group, or a branched chain group in which some of the hydrogen atoms of a pentamethylene group, a hexamethylene group, a heptamethylene group, or an octamethylene group are substituted with methyl groups is preferred. Additionally, among alkylene groups in which some of the methylene groups are substituted with sulfur atoms, a -CH2CH2SCH2CH2SCH2CH2- group is preferred.

[0195] Specific examples of compounds represented by formula (I) include pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, 2,4,4-trimethylhexanethylene diisocyanate, 1,2-bis(2-isocyanatoethylthio)ethane, etc. These compounds may be used alone or as a combination of two or more compounds.

[0196] Preferred cycloaliphatic isocyanate compounds and aromatic isocyanate compounds include the following formula (II) and the following formula (III).

[0197]

[0198]

[0199] (during the meal,

[0200] R 101 Each is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and both have the same contribution and the other contribution,

[0201] R 102is an alkyl group having 1 to 4 carbon atoms, and if multiple groups are present, they may have the same contribution and different contributions, and

[0202] a 100 is an integer 2 or 3, and b 100 is an integer from 0 to 4, and c 100 Examples of compounds represented by (where is an integer from 0 to 4) can be given. The difference between the compound represented by formula (II) and the compound represented by formula (III) is that the compound having a phenyl group (compound represented by formula (II)) and the compound having a cyclohexane group (compound represented by formula (III)).

[0203] R 101 In this case, the alkyl group having 1 to 4 carbon atoms contributes in a straight chain or a branched chain form. Among these, R 101 It is particularly preferable that it be silver, a hydrogen atom, a methyl group, or an ethyl group. In addition, R 102 In this case, the alkyl group having 1 to 4 carbon atoms contributes in a straight chain or a branched chain form. Among these, R 102 It is particularly preferable that it be a methyl group or an ethyl group.

[0204] Specific examples of compounds represented by formula (II) or formula (III) include isophorone diisocyanate, xylene diisocyanate (o-, m-, p-), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, etc. These compounds may be used alone or as a combination of two or more compounds.

[0205] In addition, as a preferred cycloaliphatic isocyanate compound and an aromatic isocyanate compound, the following formula (IV) and the following formula (V)

[0206]

[0207]

[0208] (during food, R 103 Each is an alkyl group having 1 to 4 carbon atoms, or a hydrogen atom, and is of the same contribution and of different contribution, d 100 Examples of compounds represented by (where is an integer from 0 to 4) can be given. The difference between the compound represented by formula (IV) and the compound represented by formula (V) is the difference between a compound having two phenyl groups (compound represented by formula (IV)) and a compound having two cyclohexane groups (compound represented by formula (V)).

[0209] R 103 In this case, the alkyl group having 1 to 4 carbon atoms contributes in a straight chain or a branched chain form. Among these, R 103 It is particularly desirable that it be silver, hydrogen atoms, methyl groups, or ethyl groups.

[0210] Specific examples of compounds represented by formula (IV) or formula (V) include 4,4'-diphenylmethane diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, etc. These compounds may be used alone or in combination of two or more types of compounds.

[0211] In addition, as a preferred cycloaliphatic isocyanate compound, the following formula (VI)

[0212]

[0213] (during food, R 104 are, respectively, an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and are equal contributions and different contributions, and e 100 Examples of compounds represented as (which is an integer from 0 to 4) can be used.

[0214] R 104 In this case, the alkyl group having 1 to 4 carbon atoms contributes in a straight chain or a branched chain form. Among these, R 104 It is particularly desirable that it be a hydrogen atom, a methyl group, or an ethyl group.

[0215] Specific examples of compounds represented by formula (VI) include norbornandiisocyanate, 2,5-bis(isocyanatomethyl)-bicyclo[2,2,1]-heptane, and 2,6-bis(isocyanatomethyl)-bicyclo[2,2,1]-heptane.

[0216] These compounds may be used alone or in combination of two or more types of compounds.

[0217] (Sulfur-containing heterocyclic isocyanate compounds)

[0218] Preferred sulfur-containing heterocyclic isocyanate compounds include the following formulas (VII) and (VIII).

[0219]

[0220]

[0221] (during the meal,

[0222] R 105 Each is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and both have the same contribution and different contribution,

[0223] R 106 It is a silver, methylene group, or sulfur atom, and R 107 is an alkylene group having 1 to 6 carbon atoms, or a group in which a portion of the methylene group in the chain of the alkylene group having 1 to 6 carbon atoms is substituted with a sulfur atom, and f 100 Examples of compounds represented as (which is an integer from 0 to 2) can be included.

[0224] Specific examples of compounds represented by formula (VII) or formula (VIII) include 2,5-bis(isocyanatomethyl)thiophene, 2,5-bis(isocyanatomethyl)-1,4-dithione, 3,4-bis(isocyanatomethyl)tetrahydrothiophene, 4,5-bis(isocyanatomethyl)-1,3-dithiolane, etc. These compounds may be used alone or in combination of two or more types of compounds.

[0225] In addition, halogen substituents, alkyl substituents, alkoxy substituents, nitro substituents of the above polyisocyanate, or prepolymer-type modified products with polyhydric alcohols, carbodiimide modified products, urea modified products, biuret modified products, dimerization or trimerization reaction products, etc., may also be used.

[0226] As polyisothiocyanate compounds, compounds in which the isocyanate group is changed to an isothiocyanate group can be used among polyisocyanate compounds represented by formulas (I) to (VIII). More specifically, examples include aliphatic isothiocyanate compounds, alicyclic isothiocyanate compounds, aromatic isothiocyanate compounds, sulfur-containing heterocyclic isothiocyanate compounds, heterocyclic isothiocyanate compounds, sulfur-containing aliphatic isothiocyanate compounds, sulfur-containing aromatic isothiocyanate compounds, etc.

[0227] Specific examples of suitable isothiocyanate compounds include aliphatic isothiocyanate compounds such as hexamethylene diisothiocyanate, 1,2-diisothiocyanate ethane, 1,3-diisothiocyanate propane, 1,4-diisothiocyanate butane, 1,6-diisothiocyanate hexane, 2,4,4-trimethylhexane methylene diisothiocyanate, thiobis(3-isothiocyanate propane), thiobis(2-isothiocyanate ethane), and dithiobis(2-isothiocyanate ethane).

[0228] Examples of cycloaliphatic isothiocyanate compounds and aromatic isothiocyanate compounds include p-phenylenediisopropylidene diisothiocyanate, 1,2-diisothiocyanatebenzene, 1,3-diisothiocyanatebenzene, 1,4-diisothiocyanatebenzene, 2,4-diisothiocyanatetoluene, isophorone diisothiocyanate, xylene diisothiocyanate (o-, m-, p-), 2,4-tolylene diisothiocyanate, 2,6-tolylene diisothiocyanate, cyclohexane diisothiocyanate, etc., and also 1,1'-methylenebis(4-isothiocyanatebenzene), 1,1'-methylenebis(4-isothiocyanate2-methylbenzene), Examples include 1,1'-methylenebis(4-isothiocyanate 3-methylbenzene).

[0229] In addition, preferred cycloaliphatic isothiocyanate compounds include 2,4-bis(isothiocyanatomethyl)norbornan, 2,5-bis(isothiocyanatomethyl)norbornan, 2,6-bis(isothiocyanatomethyl)norbornan, 3,5-bis(isothiocyanatomethyl)norbornan, norbornandiisocyanate, etc.

[0230] Preferred sulfur-containing heterocyclic isothiocyanate compounds include thiophene-2,5-diisothiocyanate, 1,4-dithian-2,5-diisothiocyanate, 2,5-bis(isothiocyanatomethyl)-1,4-dithian, 4,5-bis(isothiocyanatomethyl)-1,3-dithiolane, etc.

[0231] Examples of compounds having both isocyanate and isothiocyanate groups include the following compounds. For instance, in the polyisocyanate compounds specifically exemplified above, at least one isocyanate group is an isothiocyanate group. Additionally, in the polyisothiocyanate compounds specifically exemplified above, at least one isothiocyanate group is an isocyanate group.

[0232] A compound having an iso(thio)cyanate group blocked by a blocking agent (hereinafter also referred to as a blocked iso(thio)cyanate compound) can be obtained by reacting at least one blocking agent selected from the group consisting of alcohols, lactams, phenols, oximes, pyrazoles, thiols, active methylene compounds, malonic acid diester compounds, and acetoacetic acid ester compounds with the iso(thio)cyanate group of the above-mentioned polyiso(thio)cyanate compound. Since the conditions for reacting the blocking agent with the iso(thio)cyanate group vary depending on the type of blocking agent, they can be appropriately determined according to the selected blocking agent. In addition, the protection of the iso(thio)cyanate group by the blocking agent can be confirmed by Fourier transform infrared spectroscopy (FT-IR).

[0233] By using a blocked iso(thio)cyanate compound, the pot life of the urethane-based curable composition can be further extended.

[0234] Preferred examples of isocyanate compounds include pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, isophorone diisocyanate, norbornane diisocyanate, 2,5-bis(isocyanatomethyl)-bicyclo[2,2,1]-heptane, 2,6-bis(isocyanatomethyl)-bicyclo[2,2,1]-heptane, 1,2-bis(2-isocyanateethylthio)ethane, xylene diisocyanate (o-, m-, p-), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and Examples include 4,4'-diphenylmethane diisocyanate, which can be used alone or as a mixture thereof.

[0235] Active hydrogen-containing compound (Component C)

[0236] Examples of active hydrogen-containing compounds (component C) include aliphatic poly(thi)ol compounds and aromatic poly(thi)ol compounds. Aliphatic poly(thi)ol compounds include aliphatic polyol compounds and aliphatic polythiol compounds. Aromatic poly(thi)ol compounds include aromatic polyol compounds and aromatic polythiol compounds.

[0237] In a urethane-based curable composition, the amount of an active hydrogen-containing compound (component C) is preferably 10 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of a polyiso(thio)cyanate compound (component B), and more preferably 80 parts by mass or more and 150 parts by mass or less.

[0238] Among poly(thi)ol compounds, compounds suitable for forming optical articles with excellent transparency and heat resistance, particularly compounds suitable for manufacturing optical articles including a photochromic compound (component A), may be compounds represented by the following formulas (IX) to (XVII).

[0239] (Aliphatic poly(thi)ol compounds)

[0240] A preferred aliphatic poly(thi)ol compound is the following formula (IX)

[0241]

[0242] {during the meal,

[0243] R 108 Silver, hydrogen atoms, or the following formula (X)

[0244]

[0245] (during food, R 111 It is an alkylene group having 1 to 6 carbon atoms.)

[0246] It is a term of agreement with, and may be identical or different,

[0247] R 109 are, respectively, a hydrogen atom, a methyl group, or an ethyl group, and may be the same or different, and

[0248] R 110 It is silver, a hydrogen atom, or an alkyl group having 1 to 6 carbon atoms, and if multiple are present, they may be the same or different, and

[0249] o 100 is 0 to 2, and p 100 is 1 to 6, and q 100 is 0 to 10, and r 100 It is 2 to 4, and o 100 +r 100 It is 4.

[0250] Examples of compounds represented as can be found.

[0251] R 111 It is an alkylene group having 1 to 6 carbon atoms, and can also be a straight-chain or branched-chain component. Among these, R 111 It is particularly desirable that it be a methylene group, an ethylene group, a trimethylene group, or a propylene group.

[0252] Specific examples of compounds represented by formula (IX) include trimethylolpropane, pentaerythritol, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), etc.

[0253] Among preferred aliphatic poly(thi)ol compounds, as polyfunctional poly(thi)ol compounds having ether bonds, the following formula (XI)

[0254]

[0255] {during the meal,

[0256] F 100 Each, an alkyl group having 1 to 6 carbon atoms, or the following formula (XII)

[0257]

[0258] (during the meal,

[0259] R 112 is a hydrogen atom, or a group synonymous with the above formula (X), and has the same contribution and the other contribution,

[0260] R 113 Each is a hydrogen atom, a methyl group, or an ethyl group, and both contribute equally and contribute differently,

[0261] s 100 is 1 to 6, and t 100 It is 0 to 10.)

[0262] Examples of compounds represented by can be found.

[0263] F 100 Silver is a group in which at least two are represented by formula (XII). Other groups may include alkyl groups having 1 to 6 carbon atoms, and may also be chain-like or branched-chain types. Among these, F 100 It is particularly preferable that it be silver, a methyl group, an ethyl group, a trimethyl group, or a propyl group. In addition, F 100 If two or more groups are represented by formula (XII), each has the same contribution and the other. Specific examples of compounds represented by formula (XI) include ditrimethylolpropane, dipentaerythritol, ditrimethylolpropanetetrakis(3-mercaptopropionate), dipentaerythritolhexakis(3-mercaptopropionate), etc.

[0264] Among the preferred aliphatic poly(thi)ol compounds, as polyfunctional polythiol compounds, the following formula (XIII)

[0265]

[0266] (during the meal,

[0267] R 114 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a group in which a portion of the methylene group of the alkyl group having 1 to 6 carbon atoms is substituted with a sulfur atom, and R 114 If there are multiple instances, they can be the same contribution or different contributions,

[0268] R 115is an alkylene group having 1 to 10 carbon atoms, wherein a portion of the methylene group in the chain of the alkylene group having 1 to 10 carbon atoms is substituted with a sulfur atom, or a portion of the hydrogen atoms of the alkylene group having 1 to 10 carbon atoms are substituted with a thiol group, and R 115 If there are multiple instances, they can be the same contribution or different contributions,

[0269] u 100 is an integer from 2 to 4, and v 100 is an integer from 0 to 2, and u 100 +v 100 It is 4.)

[0270] It is preferable to use a compound represented by .

[0271] R 114 In this case, the alkyl group having 1 to 6 carbon atoms contributes to a straight chain or a branched chain, and among them, R 114 It is preferable that the group be a hydrogen atom, a methyl group, or an ethyl group. In addition, specific groups in which a portion of the methylene group in the chain of an alkyl group having 1 to 6 carbon atoms is substituted with a sulfur atom include -CH2SCH3, etc.

[0272] R 115 In this case, the alkylene group having 1 to 10 carbon atoms contributes to a straight chain or a branched chain. Among these, R 115 Methylene groups, ethylene groups, trimethylene groups, and propylene groups are particularly preferred. In addition, specific groups in which a portion of the methylene group in the chain of an alkyl group having 1 to 10 carbon atoms is substituted with a sulfur atom include -CH2S-, -CH2CH2S-, -CH2CH2CH2S-, etc. In addition, groups in which a portion of the hydrogen atoms of an alkyl group having 1 to 6 carbon atoms are substituted with a thiol group include -CH2SCH(SCH2SH)-.

[0273] Specific examples of compounds represented by formula (XIII) include 4-mercaptomethyl-1,8-dimercapto-3,6-dithioctane, 1,1,1,1-tetrakis(mercaptomethyl)methane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 4,7-bismercaptomethyl-3,6,9-trithio-1,11-undecanediol, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithioundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithioundecane, etc.

[0274] Among the preferred aromatic poly(thi)ol compounds, as phenyl group-containing polythiol compounds, the following formula (XIV)

[0275]

[0276] (during the meal,

[0277] R 116 It is an alkylene group having 1 to 6 carbon atoms, or a group in which a portion of the methylene group in the chain of the alkylene group having 1 to 6 carbon atoms is substituted with a sulfur atom, and w 100 It is 3.)

[0278] Examples of compounds represented by can be found.

[0279] R 116 In this case, the alkylene group having 1 to 6 carbon atoms contributes to a straight chain or a branched chain. Among these, R 116 It is preferable that the group be a methylene group, an ethylene group, a trimethylene group, or a propylene group. In addition, the group in which a portion of the methylene group in the chain of an alkylene group having 1 to 6 carbon atoms is substituted with a sulfur atom can be specifically -CH2CH2CH2SCH2-, -CH2CH2SCH2-, -CH2SCH2-, etc. A specific example of a compound represented by formula (XIV) is 1,3,5-tris(mercaptopropylthiomethyl)benzene.

[0280] Among the preferred poly(thi)ol compounds other than those mentioned above, poly(thi)ol compounds having a triazine ring include the following formula (XV)

[0281]

[0282] {during the meal,

[0283] R 117 Each, an alkyl group having 1 to 6 carbon atoms, or the following formula (XVI)

[0284]

[0285] (during the meal,

[0286] R 118 , and R 119 is an alkylene group having 1 to 6 carbon atoms, and

[0287] R 120 It is silver, an oxygen atom, or a sulfur atom)

[0288] It is a device indicated as, provided that the above R 117 At least two of are elements represented by the above equation (XVI), and R 117 It can be the same contribution and a different contribution.

[0289] Examples of compounds represented by can be found.

[0290] R 118 , and R 119 In this case, the alkylene group having 1 to 6 carbon atoms contributes to a straight chain or a branched chain. Among these, R 118 , and R 119 It is preferable that the group be a methylene group, an ethylene group, a trimethylene group, or a propylene group. Specific examples of compounds represented by formula (XV) include 2-mercaptomethanol and tris-{(3-mercaptopropionyloxy)-ethyl}-isocyanurate.

[0291] Among the preferred poly(thi)ol compounds other than those mentioned above, it is possible to use a compound having a silsesquioxane structure. A compound having a silsesquioxane structure takes on various molecular structures such as cage, ladder, and random phases, and is a compound represented by the following formula (XVII).

[0292]

[0293] (among the food, multiple Rs 500 The group may be identical or different from one another and is an organic group comprising a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a phenyl group, and at least two hydroxyl groups and / or a thiol group in at least one molecule, and n 100 is an integer from 3 to 100.)

[0294] The above poly(thi)ol compounds can be used without particular limitation and may be used in multiple combinations, taking into account the photochromic properties and mechanical properties of the resulting cured body. Among these, in order to manufacture a photochromic optical article having excellent properties and for the curable composition to have excellent moldability and good handling, it is preferable to use a poly(thi)ol compound having 3 to 6 active hydrogen-containing groups per molecule.

[0295] As a preferred poly(thi)ol compound, it is preferable to use at least one of trimethylolpropanetris(3-mercaptopropionate), pentaerythritoltetrakis(3-mercaptopropionate), dipentaerythritolhexakis(3-mercaptopropionate), 4-mercaptomethyl-1,8-dimercapto-3,6-dithioctane, and tris-{(3-mercaptopropionyloxy)-ethyl}-isocyanurate, and among these, it is more preferable to use at least one of trimethylolpropanetris(3-mercaptopropionate), pentaerythritoltetrakis(3-mercaptopropionate), and dipentaerythritolhexakis(3-mercaptopropionate).

[0296] Among these, dipentaerythritol hexakis(3-mercaptopropionate) is particularly preferred because it can improve the photochromic and mechanical properties of the resulting cured body. From the perspective of photochromic properties, it is preferable to use dipentaerythritol hexakis(3-mercaptopropionate) alone as a poly(thi)ol compound; however, since dipentaerythritol hexakis(3-mercaptopropionate) has high viscosity, other poly(thi)ol compounds may be mixed in to control viscosity when obtaining a cured body by template polymerization. Other poly(thi)ol compounds include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), 1,6-hexanediol bis(3-mercaptopropionate), 1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane, 2,2-bis(mercaptomethyl)-1,4-butanedithiol, 2,5-bis(mercaptomethyl)-1,4-dithian, 4-mercaptomethyl-1,8-dimercapto-3,6-dithioctane, 1,1,1,1-tetrakis(mercaptomethyl)methane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, and 1,1,2,2-tetrakis(mercaptomethylthio)ethane. It is preferable that 4,6-bis(mercaptomethylthio)-1,3-dithian, tris-{(3-mercaptopropionyloxy)-ethyl}-isocyanurate be used, and particularly preferred when trimethylolpropane tris(3-mercaptopropionate) is used in combination, as this can improve handling properties while maintaining excellent photochromic properties.

[0297] <Photochromic Compound (Component A)>

[0298] The photochromic compound (component A) may be used without special restrictions as long as it is a compound exhibiting photochromic properties, and may be used as a single type or in combination of two or more types.

[0299] Representative examples of such photochromic compounds (component A) include known photochromic compounds such as chromene compounds, fulgimide compounds, spirooxazine compounds, and spiropyran compounds, which can be used without any limitation.

[0300] Examples of the above-mentioned fulgimide compounds, spirooxazine compounds, spiropyran compounds, and chromene compounds include compounds described in Japanese Patent Publication No. Hei 2-28154, Japanese Patent Publication No. Sho 62-288830, pamphlet WO94 / 22850, pamphlet WO96 / 14596, etc.

[0301] In particular, regarding chromene compounds, in addition to those described in the above patent document, chromene compounds having excellent photochromic properties are known, and such chromene compounds can be suitably used as component A. As such chromene compounds, Japanese Patent Publication No. 2001-031670, Japanese Patent Publication No. 2001-011067, Japanese Patent Publication No. 2001-011066, Japanese Patent Publication No. 2000-344761, Japanese Patent Publication No. 2000-327675, Japanese Patent Publication No. 2000-256347, Japanese Patent Publication No. 2000-229976, Japanese Patent Publication No. 2000-229975, Japanese Patent Publication No. 2000-229974, Japanese Patent Publication No. 2000-229973, Japanese Patent Publication No. 2000-229972, Japanese Patent Publication No. 2000-219678, Japanese Patent Publication No. 2000-219686, Japanese Patent Publication No. Hei 11-322739, Japanese Patent Publication Hei 11-286484, Japanese Patent Publication Hei 11-279171, Japanese Patent Publication Hei 09-218301, Japanese Patent Publication Hei 09-124645, Japanese Patent Publication Hei 08-295690, Japanese Patent Publication Hei 08-176139, Japanese Patent Publication Hei 08-157467, U.S. Patent Publication No. 5645767, U.S. Patent Publication No. 5658501, U.S. Patent Publication No. 5961892, U.S. Patent Publication No. 6296785, Japanese Patent Publication No. 4424981, Japanese Patent Publication No. 4424962, WO2009 / 136668 Pamphlet, WO2008 / 023828 Pamphlet, Japanese Patent Publication No. 4369754, Japanese Patent No. 4301621 Publication, Japanese Patent Publication No. 4256985, WO2007 / 086532 Pamphlet, Japanese Patent Publication Hei 2009-120536, Japanese Patent Publication No. 2009-67754, Japanese Patent Publication No. 2009-67680, Japanese Patent Publication No. 2009-57300, Japanese Patent Publication No. 4195615, Japanese Patent Publication No. 4158881, Japanese Patent Publication No. 4157245,Japanese Patent Publication No. 4157239, Japanese Patent Publication No. 4157227, Japanese Patent Publication No. 4118458, Japanese Patent Publication No. 2008-74832, Japanese Patent Publication No. 3982770, Japanese Patent Publication No. 3801386, Pamphlet No. WO2005 / 028465, Pamphlet No. WO2003 / 042203, Japanese Patent Publication No. 2005-289812, Japanese Patent Publication No. 2005-289807, Japanese Patent Publication No. 2005-112772, Japanese Patent Publication No. 3522189, Pamphlet No. WO2002 / 090342, Japanese Patent Publication No. 3471073, Japanese Patent Publication No. 2003-277381, WO2001 / 060811 They are disclosed in pamphlets, such as WO00 / 71544. As for fulgide compounds, chromene compounds, and spirooxazine compounds, they are disclosed in many documents, for example, Japanese Patent Publication No. Hei 2-28154, Japanese Patent Publication No. Sho 62-288830, pamphlet WO94 / 22850, pamphlet WO96 / 14596, etc.

[0302] Among the known photochromic compounds, it is more preferable to use a chromene compound having an indeno[2,1-f]naphtho[1,2-b]pyran skeleton in terms of photochromic properties such as color intensity, initial colorability, durability, and fading speed.

[0303] In addition to the above, photochromic compounds having oligomeric chains within the molecule can also be suitably used. Photochromic compounds having such oligomeric chains are disclosed in many literatures, such as WO2000 / 015630, WO2004 / 041961, WO2009 / 146509, WO2012 / 149599, WO2012 / 162725, WO2013 / 078086, WO2019 / 013249, and WO2019 / 203205. Among photochromic compounds having oligomeric chains within these molecules, in order to exhibit superior photochromic properties and durability, it is preferable to use photochromic compounds having oligomeric chains as described in pamphlets WO2019 / 013249 and WO2019 / 203205.

[0304] A compound represented by the following formula is preferred as a photochromic compound (component A).

[0305]

[0306] Each of the above-mentioned various photochromic compounds (component A) may be used alone or in combination of two or more types, and the amount used may be small, for example, in the range of 0.001 to 10 parts by mass, particularly 0.01 to 5 parts by mass, with respect to 100 parts by mass of the total of the polyiso(thio)cyanate compound (component B) and the active hydrogen-containing compound (component C).

[0307] In the urethane-based curable composition related to the embodiment, the mixing ratio of the mass of the polyiso(thio)cyanate compound (component B), the active hydrogen-containing compound (component C), and the optical material compound (component D) is not particularly limited, but it is preferable that the polyiso(thio)cyanate compound (component B) is in the range of 20 to 75 parts by mass, the active hydrogen-containing compound (component C) is in the range of 20 to 75 parts by mass, and the optical material compound (component D) is in the range of 5 to 40 parts by mass, based on 100 parts by mass of the total of the polyiso(thio)cyanate compound (component B), the active hydrogen-containing compound (component C), and the optical material compound (component D). If within this range, the photochromic properties and durability of the cured body tend to increase. This ratio is more preferably in the range of 25 to 70 parts by mass of the polyiso(thio)cyanate compound (component B), 25 to 70 parts by mass of the active hydrogen-containing compound (component C), and 5 to 35 parts by mass of the optical material compound (component D), and even more preferably in the range of 30 to 60 parts by mass of the polyiso(thio)cyanate compound (component B), 30 to 60 parts by mass of the active hydrogen-containing compound (component C), and 10 to 25 parts by mass of the optical material compound (component D).

[0308] <Curing Accelerator (Component E)>

[0309] The urethane-based curable composition may further include various curing accelerators (component E) to rapidly promote the polymerization curing, depending on the type of component described above. Reaction catalysts or condensation agents for urethane or urea used in the reaction between hydroxyl groups and thiol groups and isocyanate groups and isothiocyanate groups are used as curing accelerators (component E).

[0310] (Reaction catalyst for urethane or urea)

[0311] This reaction catalyst for urethane or urea is used in the formation of poly(thio)urethane bonds by the reaction of polyiso(thio)cyanate with a polyol or polythiol. Examples of these reaction catalysts for urethane or urea include tertiary amines and their corresponding inorganic or organic salts, phosphines, quaternary ammonium salts, quaternary phosphonium salts, Lewis acids, or organic sulfonic acids. Specific examples thereof may be exemplified as follows. Furthermore, depending on the type of compound described above selected, if the catalytic activity is too high, it is possible to suppress the catalytic activity by using a mixture of tertiary amines and Lewis acids.

[0312] 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.

[0313] Phosphines; trimethylphosphine, triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tribenzylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,2-bis(dimethylphosphino)ethane.

[0314] Quaternary ammonium salts; tetramethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide.

[0315] Quaternary phosphonium salts; tetramethylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide.

[0316] Lewis acid; triphenylaluminum, dimethyltin dichloride, dimethyltin bis(isooctylthioglycolate), dibutyltin dichloride, dibutyltin dilaurate, dibutyltin maleate, dibutyltin maleate polymer, dibutyltin diricinoleate, dibutyltin bis(dodecylmercaptide), dibutyltin bis(isooctylthioglycolate), dioctyltin dichloride, dioctyltin maleate, dioctyltin maleate polymer, dioctyltin bis(butylmaleate), dioctyltin dilaurate, dioctyltin diricinoleate, dioctyltin dioleate, dioctyltin di(6-hydroxy)caproate, dioctyltin bis(isooctylthioglycolate), Didodecyl tin diricinoleate.

[0317] Organic sulfonic acids; methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid.

[0318] (Condensation agent)

[0319] Specific examples of condensation agents include the following.

[0320] Inorganic acids; hydrogen chloride, hydrogen bromide, sulfuric acid or phosphoric acid, etc.

[0321] Organic acids; p-toluenesulfonic acid, camphosulfonic acid, etc.

[0322] Acidic ion exchange resins; Amberlite, Amberlist, etc.

[0323] Carbodiimide; dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopyrrolyl)-carbodiimide.

[0324] Each of the above-mentioned various curing accelerators (component E) may be used alone or in combination of two or more types, and the amount used may be a so-called catalyst amount, for example, a small amount in the range of 0.001 to 10 parts by mass, particularly 0.01 to 5 parts by mass, per 100 parts by mass of the total of the polyiso(thio)cyanate compound (component B) and the active hydrogen-containing compound (component C).

[0325] Other Additives

[0326] In the curable composition, various additives known in themselves, such as ultraviolet absorbers, antistatic agents, infrared absorbers, ultraviolet stabilizers, antioxidants, anti-coloring agents, antistatic agents, fluorescent dyes, dyes, pigments, fragrances, etc., solvents, leveling agents, internal release agents, and furthermore, polymerization modifiers such as thiols such as t-dodecyl mercaptan, may be incorporated as needed, within a range that does not impair the effect.

[0327] (stabilizator)

[0328] Among these, considering the improvement of the durability of the photochromic compound (component A), it is suitable to use a UV stabilizer. Examples of such UV stabilizers include hindered amine light stabilizers, hindered phenol antioxidants, and sulfur-based antioxidants.

[0329] Particularly suitable UV stabilizers include bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, 2,6-di-t-butyl-4-methyl-phenol, ethylenebis(oxyethylene)bis[3-(5-t-butyl-4-hydroxy-m-tolyl)propionate], and commercially available products include Adekastab LA-52, LA-57, LA-62, LA-63, LA-67, LA-77, LA-82, LA-87 manufactured by Asahi Denka Kogyo Co., Ltd., and IRGANOX 1010, 1035, 1075, 1098, 1135, 1141, 1222, 1330, 1425, 1520, 259, 3114 manufactured by Ciba Specialty Chemicals. Examples include 3790, 5057, 565, etc.

[0330] (UV absorber)

[0331] In addition, considering the improvement of durability or photochromic properties of the photochromic compound (component A), it is suitable to use a UV absorber. Examples of such UV absorbers include benzotriazole-based UV absorbers, triazine-based UV absorbers, benzophenone-based UV absorbers, cyanoacrylate-based UV absorbers, diphenylacrylate-based UV absorbers, phenol-based UV absorbers, oxanilide-based UV absorbers, and malonic acid ester-based UV absorbers and cinnamic acid ester-based UV absorbers.

[0332] Among them, it is suitable to use cyanoacrylate-based UV absorbers, diphenylacrylate-based UV absorbers, phenol-based UV absorbers, oxanilide-based UV absorbers, malonic acid ester-based UV absorbers, and cinnamic acid ester-based UV absorbers. In particular, it is especially desirable to use cinnamic acid ester-based UV absorbers, as they can improve durability without damaging photochromic properties (especially color intensity) compared to when UV absorbers are not used.

[0333] (Lee Hyung-je)

[0334] In addition, if the release properties of the optical article are poor, an internal release agent may be used. As such an internal release agent, any agent that has a release effect and does not impair physical properties such as the transparency of the resin may be used; preferably, a surfactant is used. Among these, phosphate ester-based surfactants are preferred. The internal release agents referred to herein include those among the various catalysts mentioned above that exhibit a release effect, and may also include, for example, quaternary ammonium salts and quaternary phosphonium salts. These internal release agents are appropriately selected based on the combination with the monomer, polymerization conditions, economic feasibility, and ease of handling. Specific examples of phosphate ester internal release agents are as follows.

[0335] Alkyl acid phosphates; mono-n-butyl phosphate, mono-2-ethylhexyl phosphate, mono-n-octyl phosphate, mono-n-butyl phosphate, bis(2-ethylhexyl)phosphate, di(2-ethylhexyl)phosphate, 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), isotridene acid phosphate (mono-, di- mixture), tetracosyl acid phosphate (mono-, di- mixture), stearyl acid phosphate (mono-, di- mixture),

[0336] Other phosphate esters; examples include oleyl acid phosphate (mono-, di-mixture), dibutyl pyrophosphate, ethylene glycol acid phosphate (mono-, di-mixture), butoxyethyl acid phosphate (mono-, di-mixture), etc.

[0337] In addition, to impart desired characteristics to the photochromic optical article, such as blue light cutting ability, anti-glare properties, or high contrast, a specific wavelength absorber that absorbs light in a specific wavelength range may also be incorporated as needed. For example, if a blue light absorber having an absorption peak in the range of 400 nm to 450 nm is incorporated, blue light harmful to the eyes can be cut. In addition, if an organic pigment having an absorption peak in the range of 550 nm to 600 nm is incorporated, the contrast is strengthened, and visibility can be improved.

[0338] (Blue light absorber)

[0339] Considering the need to cut blue light harmful to the eyes, it is appropriate to use a blue light absorber. Such blue light absorbers can be used without particular restrictions as long as they are compounds having an absorption peak in the range of 400 nm to 450 nm, and commercially available compounds may also be used. Examples of such blue light absorbers include perylene-based compounds, porphyrin compounds, carotenoids, and cyanine-based compounds.

[0340] Among these, it is preferable to use porphyrin compounds. In addition, porphyrin metal complexes having a metal atom at the center may also be used. Commercially available products may be used for such porphyrin metal complexes. For example, FDB-001, FDB-002, etc. manufactured by Yamada Kagaku High School, or products from Tokyo Kasei High School may be used.

[0341] Among these, it is particularly desirable to use a porphyrin compound represented by the following formula (XVIII).

[0342]

[0343] Among the above formula (XVIII),

[0344] Y 11 to Y 81 Silver, respectively, hydrogen atom, halogen atom,

[0345] Straight-chain, branched, or cyclic alkyl group, straight-chain, branched, or cyclic alkoxy group,

[0346] Substituted or unsubstituted ethenyl group, substituted or unsubstituted ethinyl group,

[0347] Substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted aryloxycarbonyl group,

[0348] Substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group,

[0349] Substituted or unsubstituted aralkyl group, substituted or unsubstituted aralkyloxy group,

[0350] Substituted or unsubstituted acile,

[0351] Straight-chain, branched, or cyclic halogenoalkyl group, straight-chain, branched, or cyclic halogenoalkoxy group,

[0352] Straight-chain, branched, or cyclic alkoxyalkyl group, straight-chain, branched, or cyclic alkoxyalkoxyalkyl group,

[0353] Substituted or unsubstituted aryloxyalkyl group, substituted or unsubstituted aralkyloxyalkyl group, straight-chain, branched or cyclic halogenoalkoxyalkyl group,

[0354] It is a substituent selected from, and

[0355] Also, Y 11 to Y 81 Adjacent groups selected from may bond with each other to form a substituted or unsubstituted aromatic ring together with the substituted carbon atom.

[0356] Z 1 To Z 4 are respectively substituted or unsubstituted aryl groups, and

[0357] M is two hydrogen atoms, a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, or a metal oxide.

[0358] Among them, in order to achieve a higher effect,

[0359] Y 11 to Y 81 Preferably, each is a hydrogen atom, a halogen atom, a straight-chain alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, and

[0360] Z 1 To Z 4 It is preferable that each is a substituted or unsubstituted aryl group, and

[0361] M is preferably copper, magnesium, zinc, cobalt, titanium, iron, vanadium, or vanadium oxide.

[0362] In addition, suitable porphyrin compounds can be more specifically exemplified by copper porphyrin complexes, vanadium porphyrin complexes, magnesium porphyrin complexes, and zinc porphyrin complexes.

[0363] (Organic pigment having an absorption peak in the range of 550 nm to 600 nm)

[0364] Considering the improvement of visibility, it is suitable to use organic pigments having an absorption peak in the range of 550 nm to 600 nm. Examples of such organic pigments include nitro compounds, azo compounds, anthraquinone compounds, trene compounds, porphyrin compounds, and rare earth metal compounds. Among these, porphyrin compounds and rare earth compounds are preferred. Furthermore, porphyrin compounds are most preferred from the perspective of compatibility with the curable composition.

[0365] As for the above-mentioned porphyrin-based compounds, they may have various substituents on the porphyrin backbone. For example, compounds described in Japanese Patent Publication No. Hei 5-194616, Japanese Patent Publication No. Hei 5-195446, Japanese Patent Publication No. 2003-105218, Japanese Patent Publication No. 2008-134618, Japanese Patent Publication No. 2013-61653, Japanese Patent Publication No. 2015-180942, WO2012 / 020570 Pamphlet, Japanese Patent No. 5626081, Japanese Patent No. 5619472, Japanese Patent No. 5778109, etc. may be suitably used. In addition, commercially available products may be used. For example, FDG-005, FDG-006, FDG-007, FDR-001, and PD-320 manufactured by Yamamoto Kasei Co., Ltd. can be used. Among these, a particularly suitable porphyrin compound is a tetraazaporphyrin compound represented by the following formula (XIX).

[0366]

[0367] Among the above equation (XIX),

[0368] Y 12 , Y 32 , Y 52 , and Y 72 is a hydrogen atom,

[0369] Y 22 , Y 42 , Y 62 , and Y 82 Each is a straight-chain or branched alkyl group having 1 to 6 carbon atoms, and

[0370] M is a divalent metal atom or a metal oxide atom.

[0371] Examples of straight-chain or branched alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 1,2-dimethylpropyl, 1-methylbutyl, 2-methylbutyl, n-hexyl, 2-methylpentyl, 4-methylpentyl, 4-methyl-2-pentyl, 1,2-dimethylbutyl, 2,3-dimethylbutyl, and 2-ethylbutyl groups.

[0372] Examples of divalent metal atoms include Cu, Zn, Fe, Co, Ni, Ru, Pd, Pt, Mn, Mg, Ti, Ba, Cd, Hg, Sn, etc. Examples of metal oxide atoms include VO, MnO, TiO, etc.

[0373] The above other compounding agents may each be used as a single type or in combination of two or more types, and the amount used may be small. For example, they may be used in an amount of 0.0001 to 10 parts by mass per 100 parts by mass of the total of the polyiso(thio)cyanate compound (component B) and the polyol compound, and preferably, in an amount of 0.001 to 10 parts by mass.

[0374] Acrylic Curable Composition

[0375] The acrylic curable composition contains a polymerizable monomer component. The acrylic curable composition may contain a photochromic compound (Component A), a curing accelerator (Component E), and additives. Examples of additives include stabilizers.

[0376] The compound for optical materials (component D) can be used as a polymerizable monomer component of an acrylic curable composition. In addition to the compound for optical materials (component D) related to the embodiment, the acrylic curable composition may include at least one of an acrylate compound and a methacrylate compound, i.e., a (meth)acrylate compound.

[0377] The content of the optical material compound (component D) in the acrylic curable composition is preferably 1 mass% or more, more preferably 3 mass% or more, and even more preferably 5 mass% or more. If the content of the optical material compound (component D) is high, the photochromic properties of the cured body tend to increase. On the other hand, from the perspective of increasing the durability of the cured body, the content of the optical material compound is preferably 50 mass% or less, more preferably 30 mass% or less, and even more preferably 20 mass% or less.

[0378] The amount of compound for optical materials (component D) per 100 parts by mass of (meth)acrylate compound is preferably 1 part by mass or more and 50 parts by mass or less, and more preferably 5 parts by mass or more and 35 parts by mass or less.

[0379] R in Equation (Ia) 4 A compound for optical materials (component D) that is H2C=CH-C(=O)-, H2C=C(CH3)-C(=O)-, or H2C=CH-C(=O)-OCH2CH2NHC(=O)- is particularly suitable as a material for an acrylic curable composition because it can itself function as a (meth)acrylate compound.

[0380] These R 4The content of this (meth)acrylic group compound for optical materials (component D) is, for example, 90 mass% or more and 100 mass% or less, and may constitute most of the acrylic curable composition.

[0381] <(Met)Acrylate Compounds>

[0382] As for the (meth)acrylate compound, for example, a difunctional (meth)acrylic polymerizable compound, a polyfunctional (meth)acrylic polymerizable compound, a monofunctional (meth)acrylic polymerizable compound, etc. can be used, and it is preferable to include a difunctional (meth)acrylic polymerizable compound.

[0383] (Difunctional (meth)acrylic polymerizable compound)

[0384] Examples of difunctional (meth)acrylic polymerizable compounds include compounds shown in the following formulas (5), (6) and (7).

[0385]

[0386] During the meal, R 14 and R 15 Each is a hydrogen atom or a methyl group, and j and k are each independently integers greater than or equal to 0, and also j+k is an average value between 2 and 50.

[0387] In addition, the polymerizable compound represented by the above formula (5) is typically obtained in the form of a mixture of molecules with different molecular weights. For this reason, j and k are expressed as average values.

[0388] A specific example of a compound represented by the above formula (5) is as follows.

[0389] Diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, pentaethylene glycol dimethacrylate, pentapropylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, pentaethylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, pentapropylene glycol diacrylate, dimethacrylate comprising a mixture of polypropylene glycol and polyethylene glycol (having two repeating units of polyethylene and two repeating units of polypropylene), polyethylene glycol dimethacrylate (particularly average molecular weight 330), polyethylene glycol dimethacrylate (particularly average molecular weight 536), polyethylene glycol dimethacrylate (particularly average molecular weight 736), tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, polypropylene glycol dimethacrylate (particularly average molecular weight 536), polyethylene glycol diacrylate (especially average molecular weight 258), polyethylene glycol diacrylate (especially average molecular weight 308), polyethylene glycol diacrylate (especially average molecular weight 508), polyethylene glycol diacrylate (especially average molecular weight 708), polyethylene glycol methacrylate acrylate (especially average molecular weight 536).

[0390]

[0391] During the meal, R 16 and R 17 Each is a hydrogen atom or a methyl group, and

[0392] R 18 and R 19 are, respectively, a hydrogen atom or a methyl group, and

[0393] R 20 It is a silver, hydrogen atom, or halogen atom, and

[0394] B is any of -O-, -S-, -(SO2)-, -CO-, -CH2-, -CH=CH-, -C(CH3)2-, -C(CH3)(C6H5)-, and

[0395] l and m are each integers greater than or equal to 1, and l+m is the mean value between 2 and 30.

[0396] In addition, the polymerizable compound represented by the above formula (6) is typically obtained in the form of a mixture of molecules with different molecular weights. For this reason, l and m are expressed as average values.

[0397] Specific examples of the compound represented by the above formula (6) include, for instance, the following bisphenol A di(meth)acrylate.

[0398] 2,2-Bis[4-methacryloyloxy·ethoxy)phenyl]propane(l+m=2), 2,2-Bis[4-methacryloyloxy·diethoxy)phenyl]propane(l+m=4), 2,2-Bis[4-methacryloyloxy·polyethoxy)phenyl]propane(l+m=7), 2,2-Bis(3,5-dibromo-4-methacryloyloxyethoxyphenyl)propane(l+m=2), 2,2-Bis(4-methacryloyloxydipropoxyphenyl)propane(l+m=4), 2,2-Bis[4-acryloyloxy·diethoxy)phenyl]propane(l+m=4), 2,2-Bis[4-acryloyloxy·polyethoxy)phenyl]propane(l+m=3), 2,2-bis[4-acryloyloxy·polyethoxy)phenyl]propane(l+m=7), 2,2-bis[4-methacryloyloxy(polyethoxy)phenyl]propane(l+m=10), 2,2-bis[4-methacryloyloxy(polyethoxy)phenyl]propane(l+m=17), 2,2-bis[4-methacryloyloxy(polyethoxy)phenyl]propane(l+m=30), 2,2-bis[4-acryloyloxy(polyethoxy)phenyl]propane(l+m=10), 2,2-bis[4-acryloyloxy(polyethoxy)phenyl]propane(l+m=20).

[0399]

[0400] During the meal, R 21 and R 22 are, respectively, a hydrogen atom or a methyl group, and

[0401] n is a number between 1 and 20 as the average value, and

[0402] A and A' may be the same or different from each other and are each straight-chain or branched alkylene groups having 2 to 15 carbon atoms, and if there are multiple A's, the multiple A's may be the same contribution or different contributions.

[0403] The compound represented by the above formula (7) can be prepared by reacting polycarbonate diol with (meth)acrylic acid.

[0404] Herein, the following are exemplified as polycarbonate diols used: polycarbonate diols obtained by phosgenation of polyalkylene glycols such as trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, nonamethylene glycol, etc. (having a number average molecular weight of 500 to 2,000);

[0405] Polycarbonate diol (number average molecular weight 500 to 2,000) obtained by phosgenation of a mixture of two or more polyalkylene glycols (e.g., a mixture of trimethylene glycol and tetramethylene glycol, a mixture of tetramethylene glycol and hexamethylene diglycol, a mixture of pentamethylene glycol and hexamethylene glycol, a mixture of tetramethylene glycol and octamethylene glycol, a mixture of hexamethylene glycol and octamethylene glycol, etc.);

[0406] Polycarbonate diol obtained by phosgenation of 1-methyltrimethylene glycol (number average molecular weight 500 to 2,000);

[0407] As a (meth)acrylate compound, a difunctional (meth)acrylic polymerizable compound having urethane bonds may be used.

[0408] A difunctional (meth)acrylic polymerizable compound having a urethane bond is, for example, a reaction product of a polyol and a polyisocyanate. Here, examples of polyisocyanates include, for example, hexamethylene diisocyanate, isophorone diisocyanate, lysine isocyanate, 2,2,4-hexamethylene diisocyanate, dimer acid diisocyanate, isopropylidene bis-4-cyclohexyl isocyanate, dicyclohexyl methane diisocyanate, norbornene diisocyanate, norbornene methane diisocyanate, or methylcyclohexane diisocyanate.

[0409] Meanwhile, examples of polyols include polyalkylene glycols having repeating units of ethylene oxide, propylene oxide, or hexamethylene oxide having 2 to 4 carbon atoms, or polyester diols such as polycaprolactone diol. In addition, examples include polycarbonate diol, polybutadiene diol, or ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, etc.

[0410] In addition, a reaction mixture in which a urethane prepolymer made by reacting these polyisocyanates and polyols is further reacted with 2-hydroxy(meth)acrylate, or a urethane(meth)acrylate in which the diisocyanate is directly reacted with 2-hydroxy(meth)acrylate, can also be used.

[0411] As difunctional (meth)acrylic polymerizable compounds having urethane bonds, U-2PPA (molecular weight 482), UA-122P (molecular weight 1,100), U-122P (molecular weight 1,100), U-108A, U-200PA, UA-511, U-412A, UA-4100, UA-4200, UA-4400, UA-2235PE, UA-160TM, UA-6100, UA-6200, U-108, UA-4000, UA-512 manufactured by Shin-Nakamura Chemical Co., Ltd., and EB4858 (molecular weight 454) manufactured by Daicel UCB, and UX-2201, UX3204, UX4101 manufactured by Nippon Kayaku Co., Ltd. Examples include 6101, 7101, 8101, etc.

[0412] As the (meth)acrylate compound, other difunctional (meth)acrylic polymerizable compounds may be used. Examples of such (meth)acrylate compounds include compounds having (meth)acrylic groups at both ends of an alkylene group that may have a substituent. As such (meth)acrylate compounds, it is preferable to have an alkylene group having 6 to 20 carbon atoms. Specifically, examples include 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol diacrylate, 1,10-decanediol dimethacrylate, etc.

[0413] Other (meth)acrylate compounds include difunctional (meth)acrylate monomers containing a sulfur atom. It is preferable that the sulfur atom forms part of the molecular chain as a sulfide group. Specifically, examples include bis(2-methacryloyloxyethylthioethyl)sulfide, bis(methacryloyloxyethyl)sulfide, bis(acryloyloxyethyl)sulfide, 1,2-bis(methacryloyloxyethylthio)ethane, 1,2-bis(acryloyloxyethyl)ethane, bis(2-methacryloyloxyethylthioethyl)sulfide, bis(2-acryloyloxyethylthioethyl)sulfide, 1,2-bis(methacryloyloxyethylthioethylthio)ethane, 1,2-bis(acryloyloxyethylthioethylthio)ethane, 1,2-bis(methacryloyloxyisopropylthioisopropyl)sulfide, and 1,2-bis(acryloyloxyisopropylthioisopropyl)sulfide.

[0414] In the above (meth)acrylate compounds, a single component of each component may be used, or multiple types as described above may be used.

[0415] (Polyfunctional (meth)acrylic polymerizable compound)

[0416] Next, polyfunctional (meth)acrylic polymerizable compounds will be described.

[0417] Examples of polyfunctional (meth)acrylic polymerizable compounds include compounds represented by the following formula (8).

[0418]

[0419] During the meal, R 23 It is silver, a hydrogen atom, or a methyl group, and

[0420] R 24 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and

[0421] R 25 is a 3 to 6-valent organic group having 1 to 10 carbon atoms, and

[0422] o is a number from 0 to 3 as the average value, and p is a number from 3 to 6.

[0423] R 24 As the alkyl group having 1 to 2 carbon atoms represented by R, a methyl group is preferred. 25 Examples of organic groups represented by saturates include groups derived from polyols, hydrocarbon groups of 3 to 6 valence, and organic groups comprising urethane bonds of 3 to 6 valence.

[0424] The compound represented by the above formula (8) is specifically described as follows: trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetramethacrylate, tetramethylolmethane tetraacrylate, trimethylolpropane triethylene glycol trimethacrylate, trimethylolpropane triethylene glycol triacrylate, ditrimethylolpropane tetramethacrylate, ditrimethylolpropane tetraacrylate.

[0425] In addition, as a polyfunctional (meth)acrylic polymerizable compound, a polyfunctional (meth)acrylic polymerizable compound having urethane bonds can be cited.

[0426] Polyfunctional (meth)acrylic polymerizable compounds having urethane bonds are obtained by reacting a polyisocyanate compound, described as a difunctional (meth)acrylic polymerizable compound having urethane bonds, with a polyol compound such as glycerin, trimethylolpropane, pentaerythritol, or dipentaerythritol, and are compounds having three or more (meth)acrylate groups in their molecule. Examples of commercially available products include U-4HA (molecular weight 596, number of functional groups 4), U-6HA (molecular weight 1,019, number of functional groups 6), U-6LPA (molecular weight 818, number of functional groups 6), and U-15HA (molecular weight 2,300, number of functional groups 15) manufactured by Shin-Nakamura Chemical Co., Ltd.

[0427] In addition, compounds other than those described above may be used as polyfunctional (meth)acrylic polymerizable compounds. Examples of such polyfunctional (meth)acrylic polymerizable compounds include compounds in which the terminals of a polyester compound are modified with (meth)acrylic groups. Various commercially available polyester (meth)acrylate compounds may be used, depending on the molecular weight of the raw polyester compound or the amount of modification of the (meth)acrylic groups. Specifically, examples include tetrafunctional polyester oligomers (molecular weight 2,500 to 3,500, Daicel UCB, EB80, etc.), hexafunctional polyester oligomers (molecular weight 6,000 to 8,000, Daicel UCB, EB450, etc.), hexafunctional polyester oligomers (molecular weight 45,000 to 55,000, Daicel UCB, EB1830, etc.), tetrafunctional polyester oligomers (particularly Daiichi Kogyo Seyaku Co., GX8488B, molecular weight 10,000, etc.).

[0428] By using the polyfunctional (meth)acrylic polymerizable compounds exemplified above, the crosslinking density can be improved through polymerization, and the surface hardness of the resulting cured body can be increased. Therefore, it is particularly desirable to use polyfunctional (meth)acrylic polymerizable compounds when forming a photochromic cured body (laminated body) obtained by a coating method.

[0429] The above polyfunctional (meth)acrylic polymerizable compounds may be used as a single component for each component, or multiple types as described above may be used.

[0430] (Monofunctional (meth)acrylic polymerizable compound)

[0431] Next, monofunctional (meth)acrylic polymerizable compounds will be described.

[0432] Examples of monofunctional (meth)acrylic polymerizable compounds include compounds represented by the following formula (9).

[0433]

[0434] During the meal, R 26 It is silver, a hydrogen atom, or a methyl group, and

[0435] R 27 It is silver, a hydrogen atom, a methyldimethoxysilyl group, a trimethoxysilyl group, or a glycidyl group, and

[0436] q is an integer from 0 to 10, and

[0437] r is an integer from 0 to 20.

[0438] The compound represented by the above formula (9) is specifically described as follows.

[0439] Methoxypolyethylene glycol methacrylate (especially average molecular weight 293), methoxypolyethylene glycol methacrylate (especially average molecular weight 468), methoxypolyethylene glycol acrylate (especially average molecular weight 218), methoxypolyethylene glycol acrylate (especially average molecular weight 454), stearyl methacrylate, lauryl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, lauryl acrylate, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, glycidyl methacrylate.

[0440] <Curing Accelerator (Component E)>

[0441] As a curing accelerator (component E), at least one of a thermal polymerization initiator and a photopolymerization initiator may be used.

[0442] Examples of thermal polymerization initiators include benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide, and acetyl peroxide as diacyl peroxides.

[0443] Examples of peroxyesters include t-butylperoxy-2-ethylhexanate, t-butylperoxyneodecanate, cumylperoxyneodecanate, and t-butylperoxybenzoate.

[0444] Examples of percarbonates include diisopropylperoxydicarbonate and di-sec-butylperoxydicarbonate.

[0445] Examples of azo compounds include azobis(isobutyronitrile) and 2,2'-azobis(2,4-dimethylvaleronitrile).

[0446] Examples of photopolymerization initiators include acetophenone-based compounds such as 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, and 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one.

[0447] Examples of α-dicarbonyl compounds include 1,2-diphenylethanedione and methylphenylglycoxylate.

[0448] Examples of acylphosphine oxide compounds include 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine methyl ester, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide.

[0449] In addition, when using a photopolymerization initiator, known polymerization curing accelerators such as tertiary amines may also be used in combination.

[0450] The acrylic polymerizable composition may further include the photochromic compound (component A), curing accelerator (component E), and other additives described in the urethane polymerizable composition in the proportions described above.

[0451] [Method for manufacturing a curable composition]

[0452] The curable composition is obtained by mixing a compound for optical materials (Component D) and a polyiso(thio)cyanate compound (Component B) by a known method. The curable composition may also include a photochromic compound (Component A), an active hydrogen-containing compound (Component C), a curing accelerator (Component E), and other additives.

[0453] For example, a urethane-based curable composition can be obtained by mixing a polyiso(thio)cyanate compound (component B) and a compound for optical materials (component D), and then adding an active hydrogen-containing compound (component C) and stirring. The stirring temperature can be appropriately adjusted within the range of 0 to 100°C, and the stirring time within the range of 0.1 to 48 hours. To suppress the incorporation of moisture, it is preferable to manufacture under an inert gas atmosphere such as argon or nitrogen.

[0454] Here, in the case of a urethane-based curable composition, when a polyiso(thio)cyanate compound (component B) and an active hydrogen-containing compound (component C) are mixed, a polymerization reaction can be initiated immediately to produce a cured body. Therefore, it is preferable that the preparation of the urethane-based curable composition be carried out immediately before obtaining the cured body. For example, the preparation of the urethane-based curable composition may be performed using a preparation kit comprising a first container holding a polyiso(thio)cyanate compound (component B) and a second container holding a mixture of an active hydrogen-containing compound (component C), a compound for optical materials (component D), and other optional components. By using such a preparation kit, the contents of the first container and the contents of the second container can be mixed and stirred at a desired timing to prepare the urethane-based curable composition.

[0455] An acrylic curable composition is obtained by mixing a polymerizable monomer component containing a compound for optical materials (Component D) by a known method. A photochromic compound (Component A), a curing accelerator (Component E), additives, etc. may be added to the acrylic curable composition.

[0456] [Curing Body]

[0457] A cured body is obtained by curing a curable composition. As a curing method, for example, radical polymerization, ring-opening polymerization, anionic polymerization, or condensation polymerization can be performed by irradiation with active energy rays such as ultraviolet rays, alpha rays, beta rays, and gamma rays, heat, or a combination of both.

[0458] A cured body is obtained, for example, by thermal polymerization of a curable composition. When thermally polymerizing a curable composition, the temperature, in particular, can affect the properties of the resulting cured body. Since these temperature conditions are influenced by the type and amount of the thermal polymerization initiator or the type of compound, they cannot be uniformly limited; however, generally, it is suitable to start the polymerization at a relatively low temperature and gradually increase the temperature. As polymerization time and temperature vary depending on various factors, it is appropriate to determine the optimal time according to these conditions in advance; generally, it is desirable to select conditions such that the polymerization is completed within 2 to 48 hours.

[0459] [Method of manufacturing optical articles]

[0460] Optical articles, such as lenses, comprise a cured body of a curable composition. The cured body related to the embodiment is particularly suitable for use in photochromic optical articles. A photochromic optical article comprises a cured body of a curable composition containing a photochromic compound (component A). Examples of photochromic optical articles include photochromic lenses. Photochromic lenses can be manufactured by known methods such as the pouring method, mold polymerization method, glass bonding method, and binder method.

[0461] A photochromic optical article produced by the injection method can be manufactured by injecting a curable composition containing a photochromic compound between glass molds supported by, for example, an elastomer gasket or spacer, and after sufficient degassing, by mold polymerization by heating in air or water to form a photochromic cured body (photochromic optical article) that is molded into the shape of an optical material such as a lens.

[0462] An optical article produced by a mold polymerization method can be manufactured by mold polymerization using an inner mold in which, for example, an optical substrate such as a lens substrate is arranged to form a predetermined void, a curable composition containing a photochromic compound is injected into the void, and polymerization is performed by heating in this state, thereby producing a photochromic lens (a laminate in which a photochromic optical article is laminated) in which a photochromic layer is formed on the surface of the optical substrate.

[0463] As for the optical substrate, there are no particular limitations, and an optical substrate including known plastics may be used. Specifically, examples include plastic materials such as (meth)acrylic resin, polycarbonate-based resin, allyl-based resin, thiourethane-based resin, urethane-based resin, and thioepoxy-based resin.

[0464] When forming a photochromic layer on the surface of an optical substrate by the mold polymerization method as described above, the adhesion between the photochromic layer and the optical substrate may be improved by first performing chemical treatment with an alkaline solution, an acidic solution, etc., or physical treatment by corona discharge, plasma discharge, polishing, etc., on the surface of the optical substrate. Of course, it is also possible to provide a transparent adhesive resin layer on the surface of the optical substrate.

[0465] A photochromic optical article by a glass bonding method is obtained by, for example, applying a required amount of a curable composition containing a photochromic compound onto an optical substrate such as glass on one side having a spacer placed thereon, placing another optical substrate such as glass on the coating film, and then curing the coating film to bond a pair of optical substrates such as glass.

[0466] When manufacturing a photochromic lens by a bonding method, first, a photochromic curable composition is applied onto a substrate, and the coating film is dried to form an adhesive layer sheet. The obtained photochromic sheet is placed between two optical sheets, and they are bonded by applying pressure. In this way, a photochromic laminate is obtained in which two optical sheets are bonded through an adhesive layer containing a photochromic compound.

[0467] In addition, for the production of the adhesive layer sheet, a coating solution in which a photochromic curable composition is dissolved in an organic solvent may be used.

[0468] A photochromic laminate produced in this manner is, for example, mounted in a mold, and then injection-molded with a thermoplastic resin (e.g., polycarbonate) for optical substrates such as lenses, thereby obtaining a photochromic lens of a predetermined shape in which the photochromic laminate is laminated onto a lens. Additionally, this photochromic laminate may be adhered to the surface of an optical substrate such as a lens using an adhesive, and thereby a photochromic lens may be obtained.

[0469] In addition, when manufacturing a photochromic lens as described above, it is preferable to use a polyurethane-based adhesive. The adhesive preferably contains a urethane or urea-based polymerizable compound, and more preferably contains a urethane-based polymerizable compound. Using a polyurethane-based adhesive can improve adhesion to the optical substrate.

[0470] The resulting photochromic cured body / laminated body can exhibit excellent photochromic properties such as color intensity and fading speed, and is effectively used in the production of photochromic optical substrates, such as photochromic lenses (photochromic optical articles).

[0471] In addition, depending on the application, the above-described photochromic cured body may be laminated with other functional layers or dyed using dyes such as disperse dyes, within a range that does not impair the effects of the present invention. Furthermore, a hard coating film may be fabricated thereon using a hard coating agent whose main component is a silane coupling agent or a sol of silicon, zirconium, antimony, aluminum, tin, tungsten, etc. Additionally, a thin film may be fabricated by depositing metal oxides such as SiO2, TiO2, ZrO2, etc. Anti-reflective treatment may be performed using a thin film coated with an organic polymer. Antistatic treatment may also be performed.

[0472] In addition, as a lamination with the other functional layer mentioned above, a polarizing film may be laminated for the purpose of imparting polarizing properties to the resulting photochromic cured body. The position of the polarizing film is not particularly limited and may be laminated anywhere—outside the photochromic cured body, between the photochromic cured body and another layer, or within the adhesive layer when an adhesive layer is used—but from the perspective of adhesion, it is preferable to embed it within the adhesive layer when an adhesive layer is used.

[0473] The method of laminating polarizing films is not particularly limited, and any known method may be adopted. For example, in the case of the above-described mold polymerization method, when injecting a photochromic curable composition into a glass mold, a polarizing film may be placed between the front or rear mold and the photochromic curable composition or within the photochromic composition, and then laminated by polymerizing the photochromic curable composition.

[0474] In addition, in the case of the glass bonding method, it is preferable to laminate a polarizing film on one side of an optical substrate containing inorganic glass in advance. When laminating the polarizing film, the optical substrate containing inorganic glass and the polarizing film may be bonded using a known thermosetting adhesive or a UV-curing adhesive.

[0475] As for the polarizing film, commercially available polarizing films can be used without any particular restrictions.

[0476] The thickness of the polarizing film can suitably be 20 to 100 μm. The polarizing film is formed by stretching polyvinyl alcohol dyed with a dichromatic material, such as iodine or a dichromatic dye.

[0477] As for the dichromatic dye included in the polarizing film, commercially available dichromatic dyes can be used without limitation. Examples include azo-based and anthraquinone-based dyes. Specifically, examples include Chloranthine Fast Red (CI28160), Congo Red (CI22120), Brilliant Blue B (CI24410), Benzofurpurine (CI23500), Chlorazole Black BH (CI22590), Direct Blue 2B (CI22610), Diamine Green (CI30295), Chrysophenin (CI24895), Sirius Yellow (CI29000), Direct Fast Red (CI23630), Acid Black (CI20470), Direct Sky Blue (CI24400), Solophenyl Blue 4GL (CI34200), Direct Copper Blue 2B (CI24185), Nippon Brilliant Violet BKconc (CI27885), etc. Among these dichromatic dyes, two or more pigments may be selected and used depending on the purpose. In addition, the Colour Index No. listed in the Organic Synthesis Association’s “New Edition of the Dye Handbook” (Maruzen Co., Ltd., 1970) is indicated in parentheses.

[0478] By using the photochromic curable composition described above, even polarizing films with a visual transmittance of 10 to 60% and a polarization degree of 70.0 to 99.9, which are typically difficult to bond, can be bonded firmly.

[0479] To enhance its function and adhesion, the polarizing film may have cellulose authicate films laminated on both sides. The thickness of the cellulose authicate film is preferably 20 to 200 μm, and more preferably 20 to 100 μm.

[0480] In addition, to adjust the amount of moisture contained in the polarizing film or to ensure dimensional stability of the polarizing film, a heat treatment may be performed on the polarizing film at 40 to 100°C for 5 seconds to 30 minutes before manufacturing the photochromic cured body of the present invention.

[0481] Examples

[0482] The present invention will be described in detail below by way of examples, but the present invention is not limited by these examples.

[0483] [Synthesis of compounds (7a) to (23a) for optical materials]

[0484] The raw materials used in the synthesis are as follows.

[0485] TDMP: Tridecyl(3-mercaptopropionate) represented by the following formula (10) (prepared by Yodo Kagaku Co., Ltd.)

[0486] PEMP: Pentaerythritol tetrakis(3-mercaptopropionate) represented by the following formula (11) (S. Yuki Kagaku Co., Ltd.)

[0487] Blemmer AE-400: Polyethylene glycol monoacrylate represented by the following formula (12) (manufactured by Nichiyu Co., Ltd.)

[0488] TMMP: Trimethylolpropane tris(3-mercaptopropionate)

[0489] Neutral Alumina: MP Alumina N-Super I (Sold by Fujifilm Wako Junyaku Co., Ltd.)

[0490] Pluronic (registered trademark) L31: Polyethylene glycol, polypropylene glycol, polyethylene glycol (Aldrich, weight average molecular weight 1100)

[0491] Pluronic (registered trademark) L34: Polyethylene glycol, polypropylene glycol, polyethylene glycol (Aldrich, weight average molecular weight 1600)

[0492] Pluronic (registered trademark) L35: Polyethylene glycol, polypropylene glycol, polyethylene glycol (Aldrich, weight average molecular weight 1900)

[0493] Pluronic (registered trademark) L44: Polyethylene glycol, polypropylene glycol, polyethylene glycol (Aldrich, weight average molecular weight 2000)

[0494] Pluronic (registered trademark) L64: Polyethylene glycol, polypropylene glycol, polyethylene glycol (Aldrich, weight average molecular weight 2900)

[0495] Me-β-CD: Degree of methylation 1.5 / glucose unit, molecular weight 1282 (Sold by Junse Kagaku)

[0496] In addition, the obtained compound is dissolved in deuterium chloroform, and then 1 It was identified using an H-nuclear magnetic resonance spectrum measuring device (Nihon Denshi JNM-ECA400II, 400 MHz, reference material: TMS).

[0497]

[0498] (Example 1) Synthesis of compound (7a)

[0499] After homogeneously mixing TDMP (6.9 g, 23.9 mmol) and AE-400 (12.2 g, 23.9 mmol), 15 g of neutral alumina was added and stirred at room temperature for 5 hours under a nitrogen atmosphere. After the reaction was finished, 150 mL of toluene was added and stirred for 5 minutes. Then, the neutral alumina was separated by filtration (PTFE, 0.5 μm), and the solvent was removed by vacuum distillation to obtain compound (7a) (yield: 99%).

[0500] In addition, the proton nuclear magnetic resonance spectrum of compound (7a) was measured and showed the following peaks.

[0501] δ0.85(m, 9H), 1.26(br-m,14H), 1.61(m, 2H), 1.63(t, 1H), 2.65-2.78(m, 8H), 3.60-3.679(m, 38H), 4.11(m, 2H), 4.31(m, 2H).

[0502] (Example 2) Synthesis of compound (8a)

[0503] PEMP (5.8 g, 12.0 mmol) and AE-400 (12.2 g, 23.9 mmol) were uniformly mixed, then 15 g of neutral alumina was added and stirred at room temperature for 5 hours under a nitrogen atmosphere. After the reaction was finished, 150 mL of toluene was added and stirred for 5 minutes. Then, the neutral alumina was separated by filtration (PTFE, 0.5 μm), and the solvent was removed by vacuum distillation to obtain compound (8a) (yield: 99%).

[0504] In addition, the proton nuclear magnetic resonance spectrum of compound (8a) was measured and showed the following peaks.

[0505] δ1.63(t, 4H), 2.68-2.78(m, 24H), 3.60-3.79(m, 76H), 4.19(s, 8H), 4.31(m, 4H).

[0506] (Example 3) Synthesis of compound (9a)

[0507] PEMP (2.9 g, 6.0 mmol) and AE-400 (12.2 g, 23.9 mmol) were uniformly mixed, then 15 g of neutral alumina was added and stirred at room temperature for 5 hours under a nitrogen atmosphere. After the reaction was finished, 150 mL of toluene was added and stirred for 5 minutes. Then, the neutral alumina was separated by filtration (PTFE, 0.5 μm), and the solvent was removed by vacuum distillation to obtain compound (9a) (yield: 99%).

[0508] In addition, the proton nuclear magnetic resonance spectrum of compound (9a) was measured and showed the following peaks.

[0509] δ1.63(t, 4H), 2.68-2.78(m, 32H), 3.60-3.79(m, 152H), 4.19(s, 8H), 4.31(m, 8H).

[0510] (Example 4) Synthesis of compound (10a)

[0511] Pluronic (registered trademark) L-31 (14.3 g, 13.0 mmol) and toluenesulfonic acid monohydrate (0.74 g, 3.9 mmol) were dissolved in 120 mL of toluene, 3-mercaptopropionic acid (4.1 g, 39.0 mmol) was added, and dehydration condensation was performed by heating under reflux at 130°C for 10 hours. After the reaction, the solvent was removed by vacuum distillation, dissolved in dichloromethane, and the organic layer was washed with 1% ammonia water. Subsequently, the organic layer was washed three times with ion-exchanged water, dried with magnesium sulfate, and the solvent was removed by vacuum distillation to obtain the 3-mercaptopropionic acid ester of Pluronic (registered trademark) L-31 (yield: 95%).

[0512] Next, the obtained 3-mercaptopropionic acid ester of Pluronic (registered trademark) L-31 (15.3 g, 12.0 mmol) and AE-400 (12.2 g, 23.9 mmol) were uniformly mixed, then 15 g of neutral alumina was added and stirred at room temperature for 5 hours under a nitrogen atmosphere. After the reaction was finished, 150 mL of toluene was added and stirred for 5 minutes. Afterward, the neutral alumina was separated by filtration (PTFE, 0.5 μm), and the solvent was removed by vacuum distillation to obtain compound (10a) (yield: 99%).

[0513] In addition, the proton nuclear magnetic resonance spectrum of compound (10a) was measured and showed the following peaks.

[0514] δ1.14(m, 48H), 2.68-2.81(m, 16H), 3.40-3.70(m, 128H), 4.10-4.30(m, 8H).

[0515] (Example 5) Synthesis of compound (11a)

[0516] Pluronic (registered trademark) L-34 (64.0 g, 40.0 mmol) and sodium hydroxide (0.8 g, 20.0 mmol) were dissolved in 150 mL of a mixed solvent of tetrahydrofuran / water (2:1), then acrylate chloride (1.8 g, 20.0 mmol) was added and stirred at room temperature for 15 hours. After the reaction, the mixture was extracted with chloroform, and the organic layer was washed three times with water. The organic layer was dried with magnesium sulfate, and the solvent was removed by vacuum distillation to obtain Pluronic (registered trademark) L-34 monoacrylate (yield: 85%).

[0517] After homogeneously mixing TMMP (3.19 g, 8.0 mmol) and Pluronic (registered trademark) L-34 monoacrylate (39.5 g, 23.9 mmol), 15 g of neutral alumina was added and stirred at room temperature for 5 hours under a nitrogen atmosphere. After the reaction was finished, 150 mL of toluene was added and stirred for 5 minutes. Then, the neutral alumina was separated by filtration (PTFE, 0.5 μm), and the solvent was removed by vacuum distillation to obtain compound (11a) (yield: 99%).

[0518] In addition, the proton nuclear magnetic resonance spectrum of compound (11a) was measured and showed the following peaks.

[0519] δ0.91(t, J=8Hz, 3H), 1.14(m, 144H), 1.50(q,J=8Hz, 2H), 2.68-2.81(m, 24H), 3.40-3.70(m, 306H), 4.08(s, 6H), 4.31(m, 6H).

[0520] (Example 6) Synthesis of compound (12a)

[0521] Pluronic (registered trademark) L-34 monoacrylate was prepared in the same manner as described in Example 5. PEMP (2.9 g, 6.0 mmol) and Pluronic (registered trademark) L-34 monoacrylate (39.5 g, 23.9 mmol) were uniformly mixed, then 15 g of neutral alumina was added and stirred at room temperature for 5 hours under a nitrogen atmosphere. After the reaction was finished, 150 mL of toluene was added and stirred for 5 minutes. Subsequently, the neutral alumina was separated by filtration (PTFE, 0.5 μm), and the solvent was removed by vacuum distillation to obtain compound (12a) (yield: 99%).

[0522] In addition, the proton nuclear magnetic resonance spectrum of compound (12a) was measured and showed the following peaks.

[0523] δ1.14(m, 192H), 2.68-2.78(m, 32H), 3.40-3.70(m, 408H), 4.19(s, 8H), 4.31(m, 8H).

[0524] (Example 7) Synthesis of compound (13a)

[0525] Pluronic (registered trademark) L-34 monoacrylate was prepared in the same manner as described in Example 5. DPMP (3.15 g, 4.0 mmol) and Pluronic (registered trademark) L-34 monoacrylate (39.5 g, 23.9 mmol) were uniformly mixed, then 15 g of neutral alumina was added and stirred at room temperature for 5 hours under a nitrogen atmosphere. After the reaction was finished, 150 mL of toluene was added and stirred for 5 minutes. Subsequently, the neutral alumina was separated by filtration (PTFE, 0.5 μm), and the solvent was removed by vacuum distillation to obtain compound (13a) (yield: 99%).

[0526] In addition, the proton nuclear magnetic resonance spectrum of compound (13a) was measured and showed the following peaks.

[0527] δ1.14(m, 288H), 2.68-2.78(m, 48H), 3.40-3.70(m, 636H), 4.16(s, 12H), 4.31(m, 12H).

[0528] (Example 8) Synthesis of compound (14a)

[0529] Sodium hydride (0.57 g, 23.9 mmol) was dispersed in dry THF (150 mL), then Pluronic (registered trademark) L-34 (38.2 g, 23.9 mmol) was added and stirred at room temperature for 30 minutes. After that, pentaerythrityltetrabromide (2.33 g, 6.0 mmol) was added and stirred at room temperature for 2 hours under a nitrogen atmosphere. After the reaction was finished, ion-exchanged water was added to stop the reaction, and then the mixture was extracted with dichloromethane. After washing the organic layer three times, the solvent was removed by vacuum distillation to obtain compound (14a) (yield: 85%).

[0530] In addition, the proton nuclear magnetic resonance spectrum of compound (14a) was measured and showed the following peaks.

[0531] δ1.14(m, 192H), 3.40-3.70(m, 424H).

[0532] (Example 9) Synthesis of compound (15a)

[0533] Compound (15a) was obtained by synthesizing in the same manner as in Example 8, except that Pluronic (registered trademark) L-35 (45.4 g, 23.9 mmol) was used instead of Pluronic (registered trademark) L-34 (yield: 82%).

[0534] In addition, the proton nuclear magnetic resonance spectrum of compound (15a) was measured and showed the following peaks.

[0535] δ1.14(m, 192H), 3.40-3.70(m, 520H).

[0536] (Example 10) Synthesis of compound (16a)

[0537] Compound (16a) was obtained by synthesizing in the same manner as in Example 8, except that Pluronic (registered trademark) L-44 (47.8 g, 23.9 mmol) was used instead of Pluronic (registered trademark) L-34 (yield: 82%).

[0538] In addition, the proton nuclear magnetic resonance spectrum of compound (16a) was measured and showed the following peaks.

[0539] δ1.14(m, 252H), 3.40-3.70(m, 548H).

[0540] (Example 11) Synthesis of compound (17a)

[0541] Compound (17a) was obtained by synthesizing in the same manner as in Example 8, except that Pluronic (registered trademark) L-64 (69.3 g, 23.9 mmol) was used instead of Pluronic (registered trademark) L-34 (yield: 80%).

[0542] In addition, the proton nuclear magnetic resonance spectrum of compound (17a) was measured and showed the following peaks.

[0543] δ1.14(m, 360H), 3.40-3.70(m, 784H).

[0544] (Example 12) Synthesis of compound (18a)

[0545] Sodium hydride (0.57 g, 23.9 mmol) was dispersed in dry THF (150 mL), then pentaerythritol (0.82 g, 6.0 mmol) was added and stirred at room temperature for 30 minutes. After that, propylene oxide (11.1 g, 192 mmol) was added and stirred at room temperature for 2 hours under a nitrogen atmosphere. After the reaction was finished, polyethylene glycol monotosylate (average value of oxyethylene units 7, 11.3 g, 23.9 mmol) was added and stirred at room temperature for 18 hours. Then, ion-exchanged water was added to stop the reaction, and the mixture was extracted with dichloromethane. After washing the organic layer three times, the solvent was removed by vacuum distillation to obtain compound (18a) (yield: 85%).

[0546] In addition, the proton nuclear magnetic resonance spectrum of compound (18a) was measured and showed the following peaks.

[0547] δ1.14(m, 96H), 3.40-3.70(m, 216H).

[0548] (Example 13) Synthesis of compound (19a)

[0549] Sodium hydride (0.57 g, 23.9 mmol) was dispersed in dry THF (150 mL), then pentaerythritol (0.82 g, 6.0 mmol) was added and stirred at room temperature for 30 minutes. After that, propylene oxide (22.2 g, 384 mmol) was added and stirred at room temperature for 2 hours under a nitrogen atmosphere. After the reaction was finished, polyethylene glycol monotosylate (average value of oxyethylene units 10, 14.2 g, 23.9 mmol) was added and stirred at room temperature for 18 hours. Then, ion-exchanged water was added to stop the reaction, and the mixture was extracted with dichloromethane. After washing the organic layer three times, the solvent was removed by vacuum distillation to obtain compound (19a) (yield: 82%).

[0550] In addition, the proton nuclear magnetic resonance spectrum of compound (19a) was measured and showed the following peaks.

[0551] δ1.14(m, 192H), 3.40-3.70(m, 360H).

[0552] (Example 14) Synthesis of compound (20a)

[0553] PE-4A (2.9 g, 6.0 mmol) and 11-mercapto-1-undecanol (4.9 g, 23.9 mmol) were homogeneously mixed, then 15 g of neutral alumina was added and stirred at room temperature for 5 hours under a nitrogen atmosphere. After the reaction was finished, 150 mL of toluene was added and stirred for 5 minutes. Then, the neutral alumina was separated by filtration (PTFE, 0.5 μm), and the solvent was removed by vacuum distillation to obtain compound (20a) (yield: 99%).

[0554] In addition, the proton nuclear magnetic resonance spectrum of compound (20a) was measured and showed the following peaks.

[0555] δ1.20-1.58(m, 72H), 2.68-2.78(m, 24H), 3.60(t, 8H), 4.19(s, 8H).

[0556] (Example 15) Synthesis of compound (21a)

[0557] PE-4A (2.9 g, 6.0 mmol) and 12-amino-1-dodecanol (4.8 g, 23.9 mmol) were uniformly mixed, then 15 g of neutral alumina was added and stirred at room temperature for 5 hours under a nitrogen atmosphere. After the reaction was finished, 150 mL of toluene was added and stirred for 5 minutes. Then, the neutral alumina was separated by filtration (PTFE, 0.5 μm), and the solvent was removed by vacuum distillation to obtain compound (21a) (yield: 99%).

[0558] In addition, the proton nuclear magnetic resonance spectrum of compound (21a) was measured and showed the following peaks.

[0559] δ1.20-1.58(m, 80H), 2.05(br-s,4H), 2.68-2.78(m, 24H), 3.60(t, 8H), 4.19(s, 8H).

[0560] (Example 16) Synthesis of compound (22a)

[0561] Me-β-CD (16.7 g, 13.0 mmol) and toluenesulfonic acid monohydrate (0.74 g, 3.9 mmol) were dissolved in 120 mL of toluene, 3-mercaptopropionic acid (4.1 g, 39.0 mmol) was added, and dehydration condensation was performed by heating at 130°C for 10 hours under reflux. After the reaction, the solvent was removed by vacuum distillation, dissolved in dichloromethane, and the organic layer was washed with 1% ammonia water. Subsequently, the organic layer was washed three times with ion-exchanged water, dried with magnesium sulfate, and the solvent was removed by vacuum distillation to obtain Me-β-CD in which 95% of the total hydroxyl groups were esterified with 3-mercaptopropionic acid. In addition, Pluronic (registered trademark) L-34 monoacrylate was prepared in the same manner as described in Example 5.

[0562] Next, the obtained 3-mercaptopropionic acid ester of Me-β-CD (25.4 g, 12.0 mmol) and Pluronic (registered trademark) L-34 monoacrylate (39.5 g, 23.9 mmol) were uniformly mixed, then 15 g of neutral alumina was added and stirred at room temperature for 5 hours under a nitrogen atmosphere. After the reaction was finished, 150 mL of toluene was added and stirred for 5 minutes. Then, the neutral alumina was separated by filtration (PTFE, 0.5 μm), and the solvent was removed by vacuum distillation to obtain compound (22a) (yield: 99%).

[0563] In addition, the proton nuclear magnetic resonance spectrum of compound (22a) was measured and showed the following peaks.

[0564] 1.14(m, 480H), 2.68-2.78(m, 80H), 3.10-3.71(m, 1100H), 4.31(m, 20H).

[0565] (Example 17) Synthesis of compound (23a)

[0566] Compound (14a) (6.5 g, 1.0 mmol) synthesized in Synthesis Example 8 was dissolved in 50 mL of dry toluene, and 5 mg of dibutylhydroxytoluene (polymerization inhibitor) was added, followed by the addition of 0.73 g (5.1 mmol) of 2-acryloyloxyethyl isocyanate. 10 mg of dibutyltin dilaurate was added as a catalyst, and the mixture was heated and stirred at 70°C for 4 hours. This solution was added dropwise into hexane and vigorously stirred, after which the phase-separated hexane layer was decanted to obtain compound (23a) (yield 95%).

[0567] In addition, the proton nuclear magnetic resonance spectrum of compound (23a) was measured and showed the following peaks.

[0568] δ1.14(m, 192H), 3.40-3.70(m, 424H), 4.15(m, 8H), 4.31(m, 8H), 5.84(d, J=10Hz, 4H), 6.16(dd, J=10Hz, 17Hz, 4H), 6.43(d, J=17Hz, 4H).

[0569] [Curable composition and cured body]

[0570] Preparation of Urethane-based Curable Composition and Cured Body

[0571] Next, photochromic optical articles were manufactured using compounds (7a) to (23a) obtained by the methods of Examples 1 to 17. The materials used and the evaluation methods are as follows.

[0572] <Photochromic Compound (Component A)>

[0573] PC1: A compound represented by the following formula

[0574]

[0575] Polyisocyanate Compound (Component B)

[0576] H6XDI: 1,3-Bis(isocyanatomethyl)cyclohexane (isomer mixture)

[0577] NBDI: Norbornandiisocyanate

[0578] IPDI: Isophorone diisocyanate

[0579] XDI: m-xylylene diisocyanate

[0580] <Active hydrogen-containing compounds (Component C): Polythiol compounds>

[0581] TMMP: Trimethylolpropane tris(3-mercaptopropionate)

[0582] PEMP: Pentaerythritol tetrakis(3-mercaptopropionate)

[0583] DPMP: Dipentaerythritol hexakis(3-mercaptopropionate)

[0584] <Compounds for Optical Materials (Component D)>

[0585] Compounds (7a) to (22a)

[0586] <Curing Accelerator (Component E)>

[0587] E1: Dimethyldichlortin

[0588] Other ingredients

[0589] HP: Stabilizer ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate]

[0590] Dye1: Tetraazaporphyrin compound FDG-006 (absorption wavelength: 585 nm, Yamada Kagaku High School).

[0591] Dye2: Blue light absorber FDB-002 (Absorption wavelength: 431 nm, Yamada Kagaku High School)

[0592] [Evaluation Method]

[0593] <Photochromic properties>

[0594] The photochromic cured bodies obtained in the examples and comparative examples were evaluated by the method described below.

[0595] The following values ​​were measured using a spectrophotometer (instantaneous multi-channel photodetector MCPD3000) manufactured by Otsuka Denshi High School Co., Ltd.

[0596] Maximum absorption wavelength (λmax): This is the maximum absorption wavelength after color development.

[0597] Color intensity: Absorbance (A) after light irradiation for 300 seconds at 23℃ at the above maximum absorption wavelength 300 It is the difference in absorbance (A0) between ) and light irradiation.

[0598] Fading half-life [τ 1 / 2 (sec)〕: At 23℃, after irradiating with light for 300 seconds, when the irradiation is stopped, the absorbance of the sample at the above maximum absorption wavelength is {A 300 This is the time required to decrease to 1 / 2 of -A0}.

[0599] Durability

[0600] Residual rate (%) = [(A 96) / (A0)×100〕: Using a Suga Shikenki Xenon Weather Meter X25, the photochromic cured body was accelerated for 96 hours. The color intensity was evaluated before and after the accelerated degradation test, and the color intensity of the photochromic cured body before the test (A0) and the color intensity of the photochromic cured body after the test (A 96 The ratio of )(A 96 / A0) was used as the retention rate and as an indicator of color durability. A higher retention rate indicates higher color durability.

[0601] (Example 18)

[0602] As shown in Table 1, a photochromic curable composition was prepared by mixing each component.

[0603] After thoroughly degassing the prepared photochromic curable composition, it was injected into a glass mold with a 2 mm gap, and the photochromic curable composition was polymerized by mold polymerization. Polymerization was carried out over 18 hours using an air furnace while gradually increasing the temperature from 27°C to 120°C. After polymerization, the cured body was separated from the glass mold to obtain a photochromic cured body (photochromic optical article) with a thickness of 2 mm. The evaluation results of the photochromic cured body are shown in Tables 1 to 4.

[0604] (Examples 19 to 48, Comparative Example 1)

[0605] Except for changing the formulations shown in Tables 1 to 4, photochromic cured bodies were prepared in the same manner as in Example 18 and evaluated. The evaluation results are shown in Tables 1 to 4, just as in Example 18.

[0606] (Example 49)

[0607] As shown in Table 4, a photochromic curable composition was prepared by mixing each component.

[0608] Subsequently, after sufficiently degassing the prepared photochromic curable composition, it was injected into a mold containing a glass plate with a 1 mm gap and a thiourethane-based plastic lens with a refractive index of 1.60, and the photochromic composition was polymerized by mold polymerization. The polymerization was carried out using an air furnace, and curing was performed over 18 hours while gradually increasing the temperature from 27°C to 120°C. After polymerization, the glass plate was separated to obtain a bonded photochromic optical article in which a 1 mm thick photochromic cured body was laminated on the surface of a thiourethane-based plastic lens with a refractive index of 1.60.

[0609] For the obtained photochromic optical article, photochromic properties and durability were evaluated in the same manner as in Example 18, and the evaluation results are shown in Table 4.

[0610] (Example 50)

[0611] As shown in Table 4, a photochromic curable composition was prepared by mixing each component.

[0612] Next, a photochromic optical article was manufactured by bonding a pair of glass plates for optical articles using a prepared photochromic curable composition as an adhesive. First, the photochromic curable composition was applied to one glass plate for an optical article having a 0.1 mm thick spacer placed thereon, and after placing the other glass plate for an optical article thereon, the photochromic curable composition was polymerized. The polymerization was cured over 18 hours using an air furnace while gradually increasing the temperature from 27°C to 120°C, thereby bonding the pair of plates for optical articles to obtain a glass-bonded photochromic optical article having a 0.1 mm thick photochromic layer.

[0613] For the obtained photochromic optical article, photochromic properties and durability were evaluated in the same manner as in Example 18, and the evaluation results are shown in Table 4.

[0614]

[0615]

[0616]

[0617]

[0618] <Preparation of Acrylic Curable Composition and Cured Body>

[0619] <Photochromic Compound (Component A)>

[0620] PC1

[0621] Polymerizable monomer components

[0622] Compound (23a)

[0623] Polyethylene glycol dimethacrylate (average molecular weight 736)

[0624] Polyethylene glycol dimethacrylate (average molecular weight 536)

[0625] Trimethylolpropane trimethacrylate

[0626] γ-Methacryloyloxypropyltrimethoxysilane

[0627] Glycidyl methacrylate

[0628] pr2: It is a polyrotaxane synthesized by the method described in International Publication No. 2018 / 235771. The axial molecule is formed of polyethylene glycol with a molecular weight of 11,000, the bulky groups at both ends are adamantyl groups, the cyclic molecule is α-cyclodextrin, and ε-caprolactone is polymerized to an average of 3.5 molecules through oxypropylene groups.

[0629] The characteristics of pr2 are shown below.

[0630] Inclusion amount of α-cyclodextrin: 0.25.

[0631] Side chain formula: 0.5.

[0632] Molecular weight of side chains: Approximately 100 on average.

[0633] Molecular weight of the chain containing the polymerizable group (acrylic group): approximately 650 on average (excluding the polymerizable group).

[0634] Weight-average molecular weight: 200,000.

[0635] From these results, it can be seen that pr2 has a structure in which an acrylic group is introduced as a polymerizable group to 50% of the side chain, and 50% of the side chain has an OH group at the terminal. In addition, 1 From H-NMR measurements, it was found that a chain having an average of about 140 polymerizable groups (acrylic groups) per molecule was introduced.

[0636] <Curing Accelerator (Component E)>

[0637] Irgacure819: Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (polymerization initiator manufactured by BASF)

[0638] <Other ingredients> Stabilizer

[0639] HP: Ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate]

[0640] (Examples 51 to 52, Comparative Example 2)

[0641] A photochromic curable composition was prepared by mixing each component according to the formulation shown in Table 5. Subsequently, a thiourethane-based plastic lens with a center thickness of 2 mm and a refractive index of 1.60 was prepared as an optical substrate. In addition, this thiourethane-based plastic lens was previously subjected to alkaline etching at 50°C for 5 minutes using a 10% aqueous sodium hydroxide solution, and then thoroughly washed with distilled water.

[0642] On the surface of the above plastic lens, a moisture-curing primer (product name: TR-SC-P, manufactured by Tokuyama Co., Ltd.) was coated using a spin coater (1H-DX2, manufactured by MIKASA) at a rotation speed of 70 rpm for 15 seconds, followed by 1000 rpm for 10 seconds. Then, about 2 g of the photochromic composition obtained above was spin-coated at a rotation speed of 60 rpm for 40 seconds, followed by 600 rpm for 10 to 20 seconds, so that the film thickness of the photochromic coating layer became 40 μm.

[0643] The lens having the coating agent applied to its surface in this manner was irradiated with light for 90 seconds using a metal halide lamp with an output of 200 mW / ㎠ in a nitrogen gas atmosphere to cure the coating film. Subsequently, by heating at 110°C for 1 hour, a photochromic optical article having a photochromic cured body coated on the surface of the plastic lens was obtained.

[0644] For the obtained photochromic optical article, photochromic properties and durability were evaluated in the same manner as in Example 18, and the evaluation results are shown in Table 5.

[0645]

[0646] (Example 53) Synthesis of compound (24a)

[0647] Compound (14a) (6.5 g, 1.0 mmol) synthesized in Example 8 and toluenesulfonic acid monohydrate (0.076 g, 0.4 mmol) were dissolved in 50 mL of dry toluene, then 3-mercaptopropionic acid (0.47 g, 4.4 mmol) was added, and dehydration condensation was performed by heating under reflux at 130°C for 10 hours. After the reaction, the solvent was removed by vacuum distillation and dissolved in dichloromethane, and the organic layer was washed with 1% ammonia water. Subsequently, the organic layer was washed three times with ion-exchanged water, dried with magnesium sulfate, and the solvent was removed by vacuum distillation to obtain compound (24a) (yield: 92%).

[0648] In addition, the proton nuclear magnetic resonance spectrum of compound (24a) was measured and showed the following peaks.

[0649] δ1.14(m, 192H), 2.68-2.81(m, 16H), 3.40-3.70(m, 416H), 4.10(m, 8H).

[0650] (Example 54) Synthesis of compound (25a)

[0651] Compound (14a) (6.5 g, 1.0 mmol) synthesized in Example 8 was dissolved in 50 mL of dry tetrahydrofuran, and then 60% sodium hydride (0.24 g, 6.0 mmol) was added to the solution and stirred at room temperature for 1 hour. Epichlorohydrin (0.56 g, 6.0 mmol) was added to the solution after stirring and stirred at room temperature for 15 hours. After the reaction, the solvent was removed by vacuum distillation and dissolved in dichloromethane, and the organic layer was washed three times with ion-exchanged water. Compound (25a) was obtained by drying the organic layer with magnesium sulfate and removing the solvent by vacuum distillation. As a result of proton nuclear magnetic resonance spectrum analysis, the introduction rate of glycidyl groups was 70%.

[0652] (Example 55)

[0653] A photochromic curable composition was prepared by mixing each component according to the formulation shown in Table 6.

[0654] Next, after sufficiently degassing the prepared photochromic curable composition, the composition was used as an adhesive to manufacture a photochromic optical article by a glass bonding method having a polarizing film layer and a photochromic layer.

[0655] Specifically, first, a pair of glass plates for optical articles were prepared. An acrylic adhesive was applied to one side of one glass plate for optical articles by spin coating to form a coating film. A polarizing film (thickness 27 μm, luminous transmittance 42.5%, polarization degree 99.2%, gray color, polyvinyl alcohol base) was laminated onto this coating film. Subsequently, the coating film was cured by UV irradiating it through the glass plate. In this way, a first laminate was obtained in which one glass plate and the polarizing film were bonded through an acrylic adhesive layer.

[0656] Next, a photochromic curable composition was applied to a glass plate for an optical article on the other side, having a 0.1 mm thick spacer placed at the end, to form a coating film. The first laminate obtained by the above method was laminated onto this coating film such that a polarizing film was in contact with the coating film.

[0657] Subsequently, the coating was cured to obtain a photochromic optical article in which a glass plate on the other side and a polarizing film were bonded through a photochromic resin layer. The polymerization of the photochromic curable composition was carried out by gradually increasing the temperature from 27°C to 120°C over 18 hours using an air furnace. The film thickness of the photochromic resin layer was 0.1 mm.

[0658] For the obtained photochromic optical article, photochromic properties and durability were evaluated in the same manner as in Example 18, and the evaluation results are shown in Table 6.

[0659] (Example 56)

[0660] A photochromic cured body was prepared and evaluated in the same manner as in Example 18, except that the formulation was changed to the one shown in Table 6. The results of this evaluation are shown in Table 6.

[0661] (Example 57)

[0662] A photochromic cured body was prepared and evaluated in the same manner as in Example 49, except that the formulation was changed to the one shown in Table 6. The results of this evaluation are shown in Table 6.

[0663] (Example 58)

[0664] A photochromic cured body was prepared and evaluated in the same manner as in Example 50, except that the formulation was changed to the one shown in Table 6. The results of this evaluation are shown in Table 6.

[0665] (Example 59)

[0666] A photochromic cured body was prepared and evaluated in the same manner as in Example 55, except that the formulation was changed to the one shown in Table 6. The results of this evaluation are shown in Table 6.

[0667] (Example 60) Synthesis of compound (26a)

[0668]

[0669] Polyethylene glycol 400 (Fujifilm Wako Junyaku, 16.0 g, 40.0 mmol) and imidazole (2.72 g, 40.0 mmol) were dissolved in 150 mL of dichloromethane, then t-butyldimethylsilyl chloride (Aldrich, 6.03 g, 40.0 mmol) was added, and the mixture was stirred at room temperature for 15 hours. After the reaction, the organic layer was washed three times with water. The organic layer was dried with magnesium sulfate, and the solvent was removed by vacuum distillation.

[0670] Next, the obtained compound and triethylamine (4.05 g, 40.0 mmol) were dissolved in 150 mL of dichloromethane, followed by the addition of p-toluenesulfonic acid chloride (Tokyo Kasei, 7.63 g, 40.0 mmol), and the mixture was stirred at room temperature for 15 hours. After the reaction, the organic layer was washed three times with water. The organic layer was dried with magnesium sulfate, and the solvent was removed by vacuum distillation (yield: 70%).

[0671] Next, sodium hydride (0.60 g, 25.0 mmol) was dispersed in dry THF (150 mL), polytetramethylene oxide 1000 (Fujifilm Wako Junyaku, 12.5 g, 12.5 mmol) was added, and the mixture was stirred at room temperature for 30 minutes. Then, the compound obtained above (17.1 g, 25.0 mmol) was added, and the mixture was stirred at room temperature for 5 hours under a nitrogen atmosphere. After the reaction was finished, ion-exchanged water was added to stop the reaction, and the mixture was extracted with dichloromethane. The organic layer was washed with water three times, and the solvent was removed by vacuum distillation. Subsequently, the obtained compound was dissolved in THF, a tetrabutylammonium fluoride 1 mol / LTHF solution (Tokyo Kasei, 25.0 mL, 25.0 mmol) was added, and the mixture was stirred at room temperature for 15 hours. After the reaction, the organic layer was washed with water three times. Compound (26a) was obtained by drying the organic layer with magnesium sulfate and then removing the solvent by vacuum distillation (yield: 85%).

[0672] In addition, the proton nuclear magnetic resonance spectrum of compound (26a) was measured and showed the following peaks.

[0673] δ1.55-1.70(m, 56H), 3.40-3.70(m, 128H).

[0674] (Example 61) Synthesis of compound (27a)

[0675]

[0676] Sodium hydride (0.60 g, 25.0 mmol) was dispersed in dry THF (150 mL), then compound (26a) (45.0 g, 25.0 mmol) synthesized by the method described in Example 60 was added and stirred at room temperature for 30 minutes. After that, pentaerythrityltetrabromide (2.33 g, 6.0 mmol) was added and stirred at room temperature for 4 hours under a nitrogen atmosphere. After the reaction was finished, ion-exchanged water was added to stop the reaction, and then the mixture was extracted with dichloromethane. After washing the organic layer three times, the solvent was removed by vacuum distillation to obtain compound (27a) (yield: 75%).

[0677] In addition, the proton nuclear magnetic resonance spectrum of compound (27a) was measured and showed the following peaks.

[0678] δ1.55-1.70(m, 224H), 3.40-3.70(m, 520H).

[0679] (Examples 62 to 63)

[0680] A photochromic cured body was prepared and evaluated in the same manner as in Example 18, except that the formulation was changed to the one shown in Table 6. The results of this evaluation are shown in Table 6.

[0681] (Example 64)

[0682] A photochromic cured body was prepared and evaluated in the same manner as in Example 49, except that the formulation was changed to the one shown in Table 6. The results of this evaluation are shown in Table 6.

[0683] (Example 65)

[0684] A photochromic cured body was prepared and evaluated in the same manner as in Example 50, except that the formulation was changed to the one shown in Table 6. The results of this evaluation are shown in Table 6.

[0685] (Example 66)

[0686] A photochromic cured body was prepared and evaluated in the same manner as in Example 55, except that the formulation was changed to the one shown in Table 6. The results of this evaluation are shown in Table 6.

[0687] (Comparative Example 3)

[0688] As shown in Table 6, photochromic cured bodies were prepared and evaluated in the same manner as Comparative Example 1, except that the amount of TDMP was increased and the amounts of H6XDI and TMMP were reduced. The results of this evaluation are shown in Table 6.

[0689] (Comparative Example 4)

[0690] As shown in Table 6, a photochromic cured body was prepared and evaluated in the same manner as in Example 18, except that compound 7a was omitted and the amounts of H6XDI and TMMP were increased. The results of this evaluation are shown in Table 6.

[0691] Industrial applicability

[0692] The compound for optical materials, the curable composition, and the cured body of the present invention can be used in optical articles having photochromic properties, such as plastic lenses.

Claims

Claim 1 A compound for optical materials represented by the following formula (Ia). Among the above equation (Ia), X 1 and X 2 are, respectively, NH, S, or O, and R 1 is the following formulas (4c), (4a), (4b), (5d), (5a), (5b), (6h), or (6a), R 2 is H, or CH3, and R 3 is a group comprising a block copolymer represented by the following formula (IIa), -(CH2CH2O) x -(CH2CH(CH3)O) y -(CH2CH2O) z - (IIa) In the above formula (IIa), x is an integer from 5 to 20, y is an integer from 5 to 40, z is an integer from 1 to 20, and R 4 is,H,H2C=CH-C(=O)-, or,H2C=C(CH3)-C(=O)-, and,a is 0, b is 1, c is 0 or 1, and d is 3, 4, or 6. Claim 2 In paragraph 1, the above R 1 A compound for optical materials, which is an organic residue selected from the group consisting of the following formulas (4c), (4b), (5d), (5a), (6h), and (6a). Claim 3 A curable composition comprising a compound for optical materials described in claim 1 or 2 (component D) and at least one compound selected from the group consisting of polyisocyanate compounds and polyisothiocyanate compounds (component B). Claim 4 In paragraph 3, R in formula (Ia) 4 A curable composition comprising a compound for optical materials (component D) that is H2C=CH-C(=O)- or H2C=C(CH3)-C(=O)-. Claim 5 A curable composition according to paragraph 3, further comprising a photochromic compound (component A). Claim 6 A cured body obtained by curing the curable composition described in paragraph 3. Claim 7 An optical article comprising a hardened body as described in paragraph 6. Claim 8 delete Claim 9 delete Claim 10 delete Claim 11 delete

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