阅读说明：本技术 光致变色性聚轮烷化合物、和包含该光致变色性聚轮烷化合物而成的固化性组合物 (Photochromic polyrotaxane compound, and curable composition comprising same ) 是由 竹中润治 百田润二 川崎刚美 野口誉夫 清水康智 宫崎真行 于 2018-06-18 设计创作，主要内容包括：提供光致变色性聚轮烷化合物、以及包含该光致变色性聚轮烷化合物和聚合性化合物的固化性组合物,所述光致变色性聚轮烷化合物由轴分子和包合该轴分子的多个环状分子形成,在该环状分子的至少1者上键合有包含至少1个光致变色部位的侧链。(Disclosed is a photochromic polyrotaxane compound which is composed of an axial molecule and a plurality of cyclic molecules that enclose the axial molecule, and to at least 1 of which a side chain containing at least 1 photochromic site is bonded, and a curable composition containing the photochromic polyrotaxane compound and a polymerizable compound.)

1. A photochromic polyrotaxane compound comprising an axial molecule and a plurality of cyclic molecules including the axial molecule, wherein a side chain including a photochromic moiety is bonded to at least 1 of the cyclic molecules.

2. The photochromic polyrotaxane compound according to claim 1, which further has a side chain containing a polymerizable group bonded to at least 1 of the cyclic molecules.

3. The photochromic polyrotaxane compound according to claim 1, wherein the side chain containing a photochromic site has at least an ether bond.

4. The photochromic polyrotaxane compound according to claim 2 or 3, wherein the group containing the polymerizable group has at least an ether bond.

5. The photochromic polyrotaxane compound according to any one of claims 1 to 4, wherein the cyclic molecule is a cyclodextrin ring.

6. The photochromic polyrotaxane compound according to any one of claims 1 to 5, wherein the axial molecule is formed of a side chain main chain and bulky groups at both ends thereof, a chain main chain is formed of polyethylene glycol, and bulky groups at both ends are adamantyl groups.

7. The photochromic polyrotaxane compound according to any one of claims 1 to 6, wherein the photochromic moiety has at least 1 structure selected from the group consisting of naphthopyrans, spirooxazines, spiropyrans, fulgides, fulgimides and diarylethenes.

8. The photochromic polyrotaxane compound according to any one of claims 1 to 7, wherein the photochromic site is indeno [2,1-f ] naphtho [1,2-b ] pyran.

9. The photochromic polyrotaxane compound according to any one of claims 1 to 8, wherein the polymerizable group is selected from the group consisting of acryloyl, methacryloyl, allyl, vinyl, 4-vinylphenyl, epoxy, episulfide, thietanyl, OH, SH, NH, and the like₂At least 1 group selected from the group consisting of a NCO group and an NCS group.

10. The photochromic polyrotaxane compound according to any one of claims 1 to 9, wherein the side chain containing a photochromic site is represented by the following formula (1):

here, the number of the first and second electrodes,

PC is a photochromic group;

R¹is a linear or branched alkylene group having 2 to 8 carbon atoms;

R²a linear or branched alkylene group having 2 to 8 carbon atoms, a linear or branched alkylene group having 3 to 8 carbon atoms and having an acetyl group branch, or a linear or branched alkylene group having 3 to 8 carbon atoms and having an ether bond;

l is a 2-valent group represented by the following formula (2),

here, the number of the first and second electrodes,

R³a single bond, a straight or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an aromatic group having 6 to 12 carbon atoms,

R⁴a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or a dialkylsilyl group having a linear or branched alkyl group having 1 to 20 carbon atoms,

R⁵is a straight or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an aromatic group having 6 to 12 carbon atoms,

X¹and X²Each independently is a single bond, O, or NH,

c is an integer of 0 to 50, d is an integer of 0 to 50, e is an integer of 0 or 1,

in the case where c is 2 or more, the 2-valent groups enclosed by the parentheses of c are each optionally the same or different,

in the case where d is 2 or more, the 2-valent groups enclosed by the parentheses for d are optionally the same or different, respectively;

a is an integer of 1 to 50, b is an integer of 0 to 50;

in the case where a is 2 or more, the 2-valent groups enclosed by the parentheses of a are optionally the same or different, respectively;

in the case where b is 2 or more, the 2-valent groups enclosed by the parentheses of b are optionally the same or different, respectively.

11. The photochromic polyrotaxane compound according to any one of claims 2 to 10, wherein the side chain having a polymerizable group is represented by the following formula (3):

here, the number of the first and second electrodes,

z is a polymerizable group;

R⁶is a linear or branched alkylene group having 2 to 8 carbon atoms;

R⁷a linear or branched alkylene group having 2 to 8 carbon atoms, a linear or branched alkylene group having 3 to 8 carbon atoms and having an acetyl group branch, or a linear or branched alkylene group having 3 to 8 carbon atoms and having an ether bond;

l 'is a 2-valent group represented by the following formula (2'),

here, the number of the first and second electrodes,

R³¹a single bond, a straight or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an aromatic group having 6 to 12 carbon atoms,

R⁴¹a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or a dialkylsilyl group having a linear or branched alkyl group having 1 to 20 carbon atoms,

R⁵¹is a straight or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an aromatic group having 6 to 12 carbon atoms,

X¹¹and X²¹Each independently is a single bond, O, or NH,

c₁is an integer of 0 to 50, d₁Is an integer of 0 to 50, e₁Is an integer of 0 or 1, and,

c₁in the case of 2 or more, the 2-valent groups are optionally the same or different,

d₁in the case of being 2 or more, the 2-valent groups are optionally the same or different, respectively;

f is an integer of 1 to 50, g is an integer of 0 to 50;

when f is 2 or more, the 2-valent groups are optionally the same or different, respectively;

when g is 2 or more, the 2-valent groups are optionally the same or different, respectively.

12. The photochromic polyrotaxane compound according to any one of claims 1 to 10, wherein the cyclic molecule is a cyclodextrin ring, and 1 to 100% of side chains bonded to the cyclodextrin ring are the side chains containing the photochromic site and 0 to 99% of the side chains having the polymerizable group.

13. A curable composition comprising the photochromic polyrotaxane compound according to any one of claims 1 to 12 and a polymerizable compound other than the photochromic polyrotaxane compound.

14. The curable composition according to claim 13, wherein the other polymerizable compound than the photochromic polyrotaxane compound is a compound having at least 1 radical polymerizable group selected from the group consisting of an acryloyl group, a methacryloyl group, an allyl group, a vinyl group, and a 4-vinylphenyl group.

15. The curable composition according to claim 13, wherein the other polymerizable compound than the photochromic polyrotaxane compound is a compound having at least 1 polymerizable group selected from the group consisting of an epoxy group, an episulfide group, and a thietanyl group.

16. The curable composition according to claim 13, wherein the other polymerizable compound other than the photochromic polyrotaxane compound has a structure selected from the group consisting of OH, SH, and NH₂At least 1 polymerizable group selected from the group consisting of NCO group and NCS group.

17. A photochromic cured product obtained by curing the photochromic polyrotaxane compound according to any one of claims 2 to 12.

18. A photochromic cured product obtained by curing the curable composition according to any one of claims 13 to 16.

Technical Field

The present invention relates to a novel photochromic polyrotaxane compound and a curable composition containing the photochromic polyrotaxane compound.

Background

Photochromic compounds represented by naphthopyran compounds, fulgide compounds, spirooxazine compounds, and the like have a characteristic (photochromic property) that they rapidly change color when irradiated with light including ultraviolet rays such as sunlight or light from a mercury lamp, and return to the original color when the irradiation with light is stopped and the compounds are put in a dark place, and can be applied to various applications, particularly to optical materials, by utilizing this characteristic.

For example, photochromic spectacle lenses to which photochromic properties are imparted by using photochromic compounds are rapidly developed and function as sunglasses outdoors where they are irradiated with light including ultraviolet rays such as sunlight, and are faded and function as transparent ordinary spectacles indoors where they are not irradiated with such light, and there has been an increasing demand in recent years.

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

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

(b) A method of providing a resin layer in which a photochromic compound is dispersed on the surface of a plastic molded article such as a lens by coating or cast polymerization. This method is called a lamination method.

(c) A method for joining 2 optical sheets by using an adhesive layer formed of an adhesive resin in which a photochromic compound is dispersed. This method is called a bonding method.

However, the following characteristics are further required for optical materials such as optical articles to which photochromic properties are imparted.

(I) The color development degree (initial color development) in the visible light region before the ultraviolet irradiation is low.

(II) the color development degree (color development concentration) when irradiated with ultraviolet light is high.

(III) the rate (fading rate) from the stop of the irradiation of ultraviolet rays to the return to the original state is high.

(IV) the reversible color-fading action has good repeated durability.

(V) high storage stability.

(VI) can be easily molded into various shapes.

(VII) imparting photochromic properties without lowering mechanical strength.

Therefore, in order to satisfy the above-mentioned requirements even when an optical material having photochromic properties is produced by using the above-mentioned means (a), (b), and (c), various proposals have been made.

The kneading method described above has an advantage that a large amount of photochromic plastic lenses can be produced at low cost using a glass mold. Most photochromic plastic lenses are currently produced by this method (see patent document 1, patent document 2). In the conventional kneading method, since the strength is required for the lens base material, it is necessary to improve the mechanical strength of the matrix resin in which the photochromic compound is dispersed. Therefore, it becomes difficult to exhibit excellent photochromic properties. That is, since the degree of freedom of molecules of the photochromic compound present in the matrix resin is reduced, the photochromic reversible reaction may be impaired.

Regarding such a kneading method, patent document 1 describes a method of adding a photochromic compound to a monomer composition containing an isocyanate monomer and a thiol monomer. Patent document 2 discloses a photochromic curable composition containing a specific (meth) acryloyl polymerizable monomer and a photochromic compound.

However, photochromic lenses molded by polymerizing and curing these compositions have high mechanical strength, but have room for improvement in photochromic properties, particularly in fading speed.

On the other hand, in the lamination method or the bonding method, photochromic properties are expressed by thin layers formed on the surfaces of various substrates, as compared with the aforementioned kneading method (for example, see patent documents 3,4, and 5). Therefore, in order to achieve a color development concentration equivalent to that in the kneading method, it is necessary to dissolve the photochromic compound at a high concentration. In this case, depending on the type of the photochromic compound, there are problems such as insufficient solubility and precipitation during storage. Further, since the layer exhibiting photochromic properties is thin, the durability of the photochromic compound may be poor.

Patent document 3 discloses that a photochromic curable composition is applied to a plastic lens by spin coating or the like and photocured to form a photochromic coating layer (this lamination method is also referred to as a coating method). Further, patent document 4 discloses the following method: a gap is secured between the plastic lens and the glass mold by using a member such as an elastomer gasket, an adhesive tape, or a spacer, and a photochromic curable composition is poured into the gap and polymerized and cured to form a photochromic layer (hereinafter, also referred to as a 2-stage polymerization method). Further, patent document 5 discloses a method of manufacturing a laminated sheet by joining transparent carbonate sheets with a urethane resin adhesive layer containing a photochromic compound (bonding method).

However, in any of patent documents 3 to 5, it is necessary to express photochromic properties by a thin layer containing a photochromic compound. Therefore, when a photochromic compound having low solubility is used, the color development concentration tends to decrease, and there is room for improvement in durability of the photochromic compound.

In addition, a photochromic curable composition containing a novel compound has been studied in view of the above improvement points (see patent document 6). Patent document 6 discloses a photochromic curable composition containing a polyrotaxane compound. The polyrotaxane compound has a composite molecular structure formed of an axial molecule and a plurality of cyclic molecules including the axial molecule. Patent document 6 discloses a cured product having excellent mechanical properties, moldability, color development concentration, and fading speed, which is obtained by adding a photochromic compound to the polyrotaxane compound.

Disclosure of Invention

Problems to be solved by the invention

In patent document 6, by blending a polyrotaxane compound, an excellent photochromic curable composition and a cured product can be obtained. However, in recent years, more excellent photochromic properties have been required for the color development density, the fading speed, and the like. The color development density and the fading speed are basically in a trade-off relationship, and therefore, it is difficult to compromise them.

An object of the present invention is to provide: a cured product capable of improving the fading rate while maintaining a high color development concentration, a photochromic compound obtained therefrom, and a curable composition using the same.

Means for solving the problems

The present inventors have made extensive studies to solve the above problems, and have focused on polyrotaxane compounds and made various studies. The reason why excellent photochromic properties can be obtained in a photochromic curable composition using a polyrotaxane compound is presumed to be as follows. That is, since a cyclic molecule of polyrotaxane can slide on an axial molecule, a space is formed around the cyclic molecule. Then, a reversible structural change of the photochromic compound occurs rapidly through the space, and this result is considered to bring about an improvement in the fading speed and an improvement in the developed color density. It is further considered that the presence of the cyclic molecule having the side chain introduced therein contributes to more rapidly generating a reversible structural change of the photochromic compound present in the vicinity of the side chain having high flexibility.

However, in the conventional method in which a curable composition is obtained by mixing a polyrotaxane compound with another polymerizable compound and then adding a photochromic compound thereto, there is room for improvement in the following points.

That is, it goes without saying that the probability of the photochromic compound existing in the vicinity of the polyrotaxane compound decreases with decreasing the amount of the polyrotaxane compound to be blended. In order to prevent this, although the amount of the polyrotaxane compound to be blended can be increased, the viscosity of the polyrotaxane compound is generally extremely high, and therefore, there arises a problem that handling becomes difficult in the production of a lens. In order to overcome the above problems, the present inventors have studied and found that: the present inventors have completed the present invention by finding that photochromic compounds can be disposed in the vicinity of polyrotaxane compounds to maximize photochromic properties.

That is, according to the present invention,

(1) disclosed is a photochromic polyrotaxane compound (hereinafter, also referred to as a component (A)) which is characterized by being a polyrotaxane compound comprising an axial molecule and a plurality of cyclic molecules enclosing the axial molecule, wherein a side chain containing a photochromic site is bonded to at least 1 of the cyclic molecules.

In the present invention, the polyrotaxane is a molecular complex having the following structure: the shaft molecule penetrates through the rings of the plurality of cyclic molecules, and bulky groups are bonded to both ends of the shaft molecule, so that the cyclic molecules cannot be extracted from the shaft molecule due to steric hindrance. Molecular complexes such as polyrotaxane are generally called supramolecules (supramolecules).

The following can be suitably adopted for the photochromic curable composition of the present invention.

(2) The photochromic polyrotaxane compound according to the item (1) (component (A)) wherein a side chain containing a polymerizable group is further bonded to at least 1 of the cyclic molecules.

(3) The photochromic polyrotaxane compound according to the above (1) or (2), wherein the side chain containing the photochromic moiety has at least an ether bond portion.

(4) The photochromic polyrotaxane compound according to any one of the above (1) to (3), wherein the group containing the polymerizable group has at least an ether bond.

(5) The photochromic polyrotaxane compound according to any one of the above (1) to (4), wherein the cyclic molecule is a cyclodextrin ring.

(6) The photochromic polyrotaxane compound according to any one of the above (1) to (5), wherein the axial molecule is composed of a chain main chain and bulky groups at both ends thereof, the chain main chain is composed of polyethylene glycol, and the bulky groups at both ends are adamantyl groups.

(7) The photochromic polyrotaxane compound according to any one of the above (1) to (6), wherein the photochromic moiety has at least 1 structure selected from the group consisting of naphthopyrans, spirooxazines, spiropyrans, fulgides, fulgimides and diarylethenes.

(8) The photochromic polyrotaxane compound according to any one of the above (1) to (7), wherein the photochromic site is indeno [2,1-f ] naphtho [1,2-b ] pyran.

(9) The photochromic polyrotaxane compound according to any one of the above (1) to (8), wherein the polymerizable group is selected from the group consisting of an acryloyl group, a methacryloyl group, an allyl group, a vinyl group, a 4-vinylphenyl group, an epoxy group and an episulfide groupHydride group, thietanyl group, OH group, SH group, NH group₂At least 1 group selected from the group consisting of a NCO group and an NCS group.

(10) The photochromic polyrotaxane compound according to any one of the above (1) to (9), wherein the side chain containing a photochromic moiety is represented by the following formula (1):

here, the number of the first and second electrodes,

PC is a photochromic group;

R¹is a linear or branched alkylene group having 2 to 8 carbon atoms;

R²a linear or branched alkylene group having 2 to 8 carbon atoms, a linear or branched alkylene group having 3 to 8 carbon atoms and having an acetyl group branch, or a linear or branched alkylene group having 3 to 8 carbon atoms and having an ether bond;

l is a 2-valent group represented by the following formula (2),

here, the number of the first and second electrodes,

R³is a directly linked, straight or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or an aromatic group having 6 to 12 carbon atoms,

R⁴is a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or a dialkylsilyl group having a linear or branched alkyl group having 1 to 20 carbon atoms, R⁵Is a straight or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an aromatic group having 6 to 12 carbon atoms,

X¹and X²Each independently is a direct bond, O, or NH,

c is an integer of 0 to 50, d is an integer of 0 to 50, e is an integer of 0 or 1,

in the case where c is 2 or more, the 2-valent groups of the units of a plurality of c are optionally the same or different,

when d is 2 or more, the 2-valent groups of the units of d are optionally the same or different;

a is an integer of 1 to 50, b is an integer of 0 to 50;

when a is 2 or more, the 2-valent groups of the units of a are optionally the same or different;

when b is 2 or more, the 2-valent groups of the units of b are optionally the same or different.

(11) The photochromic polyrotaxane compound according to any one of the above (2) to (10), wherein the side chain containing a polymerizable group is represented by the following formula (3):

here, the number of the first and second electrodes,

z is a polymerizable group;

R⁶is a linear or branched alkylene group having 2 to 8 carbon atoms;

R⁷a linear or branched alkylene group having 2 to 8 carbon atoms, a linear or branched alkylene group having 3 to 8 carbon atoms and having an acetyl group branch, or a linear or branched alkylene group having 3 to 8 carbon atoms and having an ether bond;

l 'is a 2-valent group represented by the following formula (2'),

here, the number of the first and second electrodes,

R³¹is a directly linked, straight or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or an aromatic group having 6 to 12 carbon atoms,

R⁴¹a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or a dialkylsilyl group having a linear or branched alkyl group having 1 to 20 carbon atoms,

R⁵¹is a straight or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an aromatic group having 6 to 12 carbon atoms,

X¹¹and X²¹Each independently is a direct bond, O, or NH,

c₁is an integer of 0 to 50, d₁Is an integer of 0 to 50, e₁Is an integer of 0 or 1, and,

c₁in the case of 2 or more, a plurality of c₁The 2-valent groups of the units of (A) are optionally each the same or different,

d₁in the case of 2 or more, a plurality of d₁The 2-valent groups of the units of (a) are optionally each the same or different;

f is an integer of 1 to 50, g is an integer of 0 to 50;

when f is 2 or more, the 2-valent groups of the units of f are optionally the same or different;

when g is 2 or more, the 2-valent groups of the units of g are optionally the same or different.

(12) The photochromic polyrotaxane compound according to any one of the above (1) to (10), wherein the cyclic molecule is a cyclodextrin ring, and 1 to 100% of side chains bonded to the cyclodextrin ring are the side chains including the photochromic moiety and 0 to 99% of the side chains having the polymerizable group.

(13) A curable composition comprising the photochromic polyrotaxane compound according to any one of the above (1) to (12) and a polymerizable compound other than the photochromic polyrotaxane compound.

(14) The curable composition according to the item (13), wherein the polymerizable compound other than the photochromic polyrotaxane compound is a compound having at least 1 radical polymerizable group selected from the group consisting of an acryloyl group, a methacryloyl group, an allyl group, a vinyl group, and a 4-vinylphenyl group.

(15) The curable composition according to the item (13), wherein the polymerizable compound other than the photochromic polyrotaxane compound is a compound having at least 1 polymerizable group selected from the group consisting of an epoxy group, an episulfide group, and a thietanyl group.

(16) The curable composition according to the item (13), wherein the polymerizable compound other than the photochromic polyrotaxane compound has a radical selected from the group consisting of OH, SH, and NH₂At least 1 polymerizable group selected from the group consisting of NCO group and NCS group.

(17) A photochromic cured product obtained by curing the photochromic polyrotaxane compound according to any one of the above (2) to (12).

(18) A photochromic cured product obtained by curing the curable composition of any one of (13) to (16).

ADVANTAGEOUS EFFECTS OF INVENTION

The photochromic polyrotaxane compound of the present invention exhibits excellent photochromic properties. Further, even when a polymerizable compound other than the photochromic polyrotaxane compound is contained, a cured product exhibiting photochromic properties excellent in color development density and fading speed can be obtained.

Drawings

Fig. 1 is a schematic diagram showing the molecular structure of polyrotaxane.

Fig. 2 is a schematic view showing a molecular structure of a photochromic polyrotaxane compound of the present invention.

Detailed Description

The present invention is a photochromic polyrotaxane compound,

the polyrotaxane compound is formed by an axial molecule and a plurality of cyclic molecules including the axial molecule, and a side chain including a photochromic part is bonded to at least 1 of the cyclic molecules.

The present invention also provides a curable composition obtained by blending the photochromic polyrotaxane compound with another polymerizable compound other than the photochromic polyrotaxane compound. The details thereof will be described below.

(polyrotaxane skeleton)

Polyrotaxane is a known compound, and as shown in fig. 1, a polyrotaxane molecule represented as a whole by "1" has a composite molecular structure formed of a chain-like axial molecule "2" and a cyclic molecule "3". That is, a plurality of cyclic molecules "3" include chain-like axial molecules "2", and the axial molecules "2" penetrate the inside of the ring of the cyclic molecules "3". Therefore, the cyclic molecule "3" can freely slide on the axial molecule "2". Bulky terminal groups "4" are formed at both ends of the axial molecule "2", thereby preventing the cyclic molecule "3" from falling off from the axial molecule "2".

That is, as described above, since the cyclic molecule "3" can slide on the axial molecule "2", a space that can allow a reversible reaction of the photochromic compound is secured, and a high color developing concentration and a high fading speed can be obtained. Further, since a side chain having a photochromic site is bonded to the cyclic molecule, the probability that the photochromic site is present in the space is higher, and it is considered that excellent photochromic properties can be exhibited.

In the photochromic polyrotaxane compound used in the present invention, various known substances can be used as the axial molecule of the polyrotaxane. For example, the chain portion may be straight or branched as long as it can pass through the ring of the cyclic molecule, and is usually formed of a polymer.

Examples of the polymer forming the chain portion of the axial molecule include: polyvinyl alcohol, polyvinyl pyrrolidone, cellulose-based resins (carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc.), polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyvinyl acetal, polyvinyl methyl ether, polyamine, polyethyleneimine, casein, gelatin, starch, olefin-based resins (e.g., polyethylene, polypropylene, etc.), polyester, polyvinyl chloride, styrene-based resins (e.g., polystyrene, acrylonitrile-styrene copolymer resin, etc.), acrylic resins (e.g., poly (meth) acrylic acid, polymethyl methacrylate, polymethyl acrylate, acrylonitrile-methyl acrylate copolymer resin, etc.), polycarbonate, polyurethane, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral, polyisobutylene, polytetrahydrofuran, polyaniline, acrylonitrile-butadiene-styrene copolymer (e.g., ABS resin), and the like, Polyamides (e.g., nylon, etc.), polyimides, polydienes (e.g., polyisoprene, polybutadiene, etc.), polysiloxanes (e.g., polydimethylsiloxane, etc.), polysulfones, polyimines, polyacetic anhydride, polyureas, polythioethers, polyphosphazenes, polyketepolylenes, polyhaloolefins, etc. These polymers may be suitably copolymerized or modified.

Among the photochromic polyrotaxane compounds used in the present invention, polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, polypropylene, polyvinyl alcohol or polyvinyl methyl ether among those described above are suitable as the polymer forming the chain portion, and polyethylene glycol is most suitable.

Further, the bulky group formed at both ends of the chain portion is not particularly limited as long as it is a group that prevents detachment of the cyclic molecule from the shaft molecule, and from the viewpoint of the bulky group, an adamantyl group, a trityl group, a fluorescein group (fluorosceinyl group), a dinitrophenyl group, and a pyrenyl group can be exemplified. Among them, an adamantyl group is particularly preferable in terms of ease of introduction and the like.

The molecular weight of the axial molecule is not particularly limited, and if it is too large, the compatibility with other components, for example, other polymerizable compounds than photochromic polyrotaxane compounds which are suitably blended tends to be poor, and if it is too small, the mobility of the cyclic molecule tends to be lowered, and the photochromic property tends to be lowered. From such a viewpoint, the weight average molecular weight Mw of the axial molecule is, for example, preferably 1000 to 100000, more preferably 3000 to 80000, and particularly preferably in the range of 5000 to 30000.

Among them, the compound forming the axial molecule may be a low molecular weight substance in order to further improve the compatibility with other polymerizable compounds and suppress the increase in viscosity. Specifically, the weight average molecular weight of the axial molecule is preferably 200 to 50000, more preferably 1000 to 20000. The weight average molecular weight Mw is a value measured by the GPC measurement method described in the following examples.

The cyclic molecule may have any ring that can enclose the above-mentioned axial molecular size, and examples of such a ring include: cyclodextrin rings, crown ether rings, benzo crown ether rings, dibenzo crown ether rings, and bicyclohexane crown ether rings. Among them, cyclodextrin ring is particularly preferable.

Among the cyclodextrin rings, α -mer (ring inner diameter 0.45-0.6 nm), β -mer (ring inner diameter 0.6-0.8 nm), and γ -mer (ring inner diameter 0.8-0.95 nm) are preferable, but in the present invention, α -cyclodextrin ring and β -cyclodextrin ring are particularly preferable, and α -cyclodextrin ring is most preferable.

The cyclic molecule having the above-mentioned ring includes a plurality of cyclic molecules in 1 axial molecule, and generally, when the maximum number of inclusion of the cyclic molecule which can be included per 1 axial molecule is 1 on average, the number of inclusion of the cyclic molecule is preferably in the range of 0.001 to 0.6, more preferably 0.002 to 0.5, and further preferably 0.003 to 0.4. If the number of inclusions of the cyclic molecules is too large, the cyclic molecules are densely present with respect to one axial molecule, and thus the mobility of the cyclic molecules is reduced, and the photochromic property tends to be reduced. If the number of inclusions is too small, gaps between the axial molecules become narrow, and gaps that allow reversible reaction of photochromic compound molecules decrease, so that photochromic properties still tend to decrease.

The maximum number of clathrates of a cyclic molecule with respect to one axis molecule can be calculated from the length of the axis molecule and the thickness of the ring that the cyclic molecule has.

For example, in the case where the chain portion of the axial molecule is formed of polyethylene glycol and the ring of the cyclic molecule is α -cyclodextrin ring, the maximum number of inclusions can be calculated as follows.

I.e., the repeating unit [ -CH ] of polyethylene glycol₂-CH₂O-]The length of 2 units (b) is approximately equal to the thickness of 1 α -cyclodextrin ring, therefore, the number of repeating units can be calculated from the molecular weight of the polyethylene glycol, 1/2 of the number of repeating units can be determined as the maximum number of clathrates of the cyclic molecule, the maximum number of clathrates is set to 1.0, and the number of clathrates of the cyclic molecule is adjusted toThe foregoing ranges.

In the photochromic polyrotaxane compound used in the present invention, a side chain including a photochromic site is introduced into the cyclic molecule. In addition, a side chain containing a polymerizable group is further introduced into the cyclic molecule. This side chain is indicated by "5" in FIG. 1.

In the present invention, a photochromic site or a polymerizable group is introduced into the side chain. Fig. 2 shows an example of a photochromic polyrotaxane compound "1 a" suitable in the present invention. The axial molecule "2", the cyclic molecule "3" and the bulky terminal group "4" are the same as those illustrated in fig. 1. In addition, a photochromic site "6" and a polymerizable group (not shown) are introduced into the side chain "5" in FIG. 2.

Fig. 2 shows a case where a photochromic site "6" is introduced into a first side chain "5 a" which is one of the side chains "5". As will be described in detail below, in the photochromic polyrotaxane compound "1 a" of the present invention, it is preferable to introduce a first side chain "5 a" into the cyclic molecule "3" and further extend the chain to form a side chain "5" in consideration of productivity and the like. The photochromic moiety "6" may be introduced not only into the first side chain "5 a" but also into the side chain "5". However, if the productivity of the photochromic polyrotaxane compound of the present invention is taken into consideration, it is preferable to introduce the photochromic site "6" into the first side chain "5 a". The polymerizable group may be introduced into any of the first side chain "5 a" and the side chain "5".

That is, by introducing such a side chain "5" (and/or first side chain "5 a") into the ring, an appropriate space can be more reliably formed between adjacent axial molecules, a gap that allows a reversible reaction of photochromic compound molecules can be reliably ensured, and excellent photochromic properties can be exhibited. In addition, such a side chain "5" forms a similar crosslinked structure in the polyrotaxane, whereby the mechanical strength of a photochromic cured product formed using the photochromic polyrotaxane compound of the present invention can be improved.

The side chain is not particularly limited, and the average molecular weight of the side chain is preferably 45 to 10000, more preferably 100 to 8000, further preferably 200 to 5000, and particularly preferably 300 to 2000.

The average molecular weight of the side chain can be adjusted depending on the amount of the compound used in introducing the side chain. The average molecular weight of the side chain does not include a photochromic moiety or the molecular weight of a polymerizable group.

If the side chain is too small, the function of securing a gap that allows reversible reaction of the photochromic moiety is insufficient, and if the side chain is too large, it is difficult to dispose the photochromic moiety, which will be described later, in the vicinity of the polyrotaxane, and as a result, it tends to be difficult to sufficiently utilize the space secured by the polyrotaxane.

In addition, the side chain is introduced by modifying the functional group of the ring of the cyclic molecule, for example, α -cyclodextrin has 18 hydroxyl groups as the functional group, and the side chain is introduced via the hydroxyl groups, that is, a maximum of 18 side chains can be introduced into 1 α -cyclodextrin ring, in the present invention, in order to sufficiently exert the function of the side chain, it is preferable that 6% or more, particularly 30% or more of the total number of functional groups of such rings are modified by the side chain, and it is noted that, in the case where 9 of the 18 hydroxyl groups of the α -cyclodextrin ring are bonded with the side chain, the degree of modification is 50%, and the remaining is of course a hydroxyl group.

In the present invention, the side chain (organic chain) may be linear or branched as long as the size thereof is within the above range. Ring-opening polymerization is utilized; free radical polymerization; cationic polymerization; anionic polymerization; living radical polymerization such as atom transfer radical polymerization, RAFT polymerization, NMP polymerization, and the like, and a suitable compound is reacted with the functional group of the cyclic molecule, so that a side chain having a suitable size can be introduced. The side chain formed by the polymerization or the like may be extended at its end by various known reactions, or a photochromic moiety or a polymerizable group described in detail below may be introduced. However, the photochromic moiety and the polymerizable group may be directly bonded to the side chain. As described above, the average molecular weight of the side chain formed by polymerization or the like or the side chain extended by various reactions is preferably 300 to 2000 in the case where the side chain is other than the photochromic moiety and the polymerizable group as described above.

For example, a side chain derived from a cyclic compound such as a cyclic ether, a cyclic siloxane, a lactone compound, a cyclic acetal, a cyclic amine, a cyclic carbonate, a cyclic imino ether, or a cyclic thiocarbonate can be introduced by ring-opening polymerization. Among them, from the viewpoint of easy availability, high reactivity, and easy adjustment of the size (molecular weight), cyclic ethers, cyclic siloxanes, lactone compounds, and cyclic carbonates are preferably used. Specific examples of suitable cyclic compounds are shown below.

Cyclic ether:

ethylene oxide, 1, 2-propylene oxide, epichlorohydrin, epibromohydrin, 1, 2-butylene oxide, 2, 3-butylene oxide, isobutylene oxide, oxetane, 3-methyloxetane, 3-dimethyloxetane, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran.

Cyclic siloxane:

hexamethylcyclotrisiloxane and octamethylcyclotetrasiloxane.

Lactone compound:

four-membered ring lactones such as β -propiolactone, β -methylpropanolide, L-serine- β -lactone and the like.

Five-membered cyclic lactones, for example γ -butyrolactone, γ -caprolactone, γ -heptolactone, γ -octalactone, γ -decalactone, γ -dodecalactone, α -hexyl- γ -butyrolactone, α -heptyl- γ -butyrolactone, α -hydroxy- γ -butyrolactone, γ -methyl- γ -decalactone, α -methylene- γ -butyrolactone, α -dimethyl- γ -butyrolactone, D-erythronolide, α -methyl- γ -butyrolactone, γ -nonalactone, DL-pantolactone, γ -phenyl- γ -butyrolactone, γ -undecalactone, γ -valerolactone, 2-pentamethylene-1, 3-dioxolan-4-one, α -bromo- γ -butyrolactone, γ -crotonolactone, α -methylene- γ -butyrolactone, α -methacryloyloxy- γ -butyrolactone, α 0-methacryloyloxy- γ -butyrolactone.

Six-membered ring lactones, for example delta-valerolactone, delta-caprolactone, delta-octalactone, delta-nonalactone, delta-decalactone, delta-undecalactone, delta-dodecalactone, delta-tridecanolide, delta-tetradecanolide, DL-mevalonolactone, 4-hydroxy-1-cyclohexanecarboxylic acid delta-lactone, monomethyl-delta-valerolactone, monoethyl-delta-valerolactone, monohexyl-delta-valerolactone, 1, 4-dioxan-2-one, 1, 5-dioxepan-2-one.

Seven-membered ring lactones, for example epsilon-caprolactone, monomethyl-epsilon-caprolactone, monoethyl-epsilon-caprolactone, monohexyl-epsilon-caprolactone, dimethyl-epsilon-caprolactone, di-n-propyl-epsilon-caprolactone, di-n-hexyl-epsilon-caprolactone, trimethyl-epsilon-caprolactone, triethyl-epsilon-caprolactone, tri-n-epsilon-caprolactone, 5-nonyl-oxepan-2-one, 4, 6-trimethyl-oxepan-2-one, 4,6, 6-trimethyl-oxepan-2-one, 5-hydroxymethyl-oxepan-2-one.

Eight-membered ring lactones, for example delta-heptalactone (Enanthanolactone).

Other lactones are for example: lactone, lactide, dilactide, tetramethyl glucoside, 1, 5-dioxepan-2-one and tert-butyl caprolactone.

A cyclic carbonate;

ethylene carbonate, propylene carbonate, 1, 2-butylidene glycerol 1, 2-carbonate, 4- (methoxymethyl) -1, 3-dioxolan-2-one, (chloromethyl) ethylene carbonate, vinylene carbonate, 4, 5-dimethyl-1, 3-dioxolan-2-one, 4-chloromethyl-5-methyl-1, 3-dioxolan-2-one, 4-vinyl-1, 3-dioxolan-2-one, 4, 5-diphenyl-1, 3-dioxolan-2-one, 4-dimethyl-5-methylene-1, 3-dioxolan-2-one, propylene carbonate, 1, 2-butylidene glycerol 1, 2-carbonate, 4- (methoxymethyl) -1, 3-dioxolan-2-one, 4-chloromethyl-5-dioxolan-2-one, 4-vinyl-1, 3-dioxolan-2, 1, 3-dioxan-2-one, 5-methyl-5-propyl-1, 3-dioxolan-2-one, 5-diethyl-1, 3-dioxolan-2-one.

The cyclic compounds can be used alone, or in combination of 2 or more.

In the present invention, lactone compounds and cyclic carbonates are preferably used, and lactone compounds such as e-caprolactone, α -acetyl-y-butyrolactone, α -methyl-y-butyrolactone, y-valerolactone and y-butyrolactone are particularly preferable, and e-caprolactone is most preferable.

In addition, when a side chain is introduced by reacting a cyclic compound by ring-opening polymerization, a functional group (for example, a hydroxyl group) bonded to the cyclic compound may be poor in reactivity, and it may be difficult to directly react a large molecule due to steric hindrance or the like. In such a case, for example, the following means can be adopted: in order to react caprolactone and the like, first, a low-molecular-weight compound such as propylene oxide is reacted with a functional group to hydroxypropylate the compound, and then a functional group (hydroxyl group) having high reactivity is introduced, followed by ring-opening polymerization using the above-described cyclic compound to introduce a side chain. Hereinafter, a side chain formed by ring-opening polymerization of a low-molecular compound such as propylene oxide and a cyclic compound may be referred to as a first side chain (as described above, "5 a" in fig. 2 corresponds to the first side chain).

In the present invention, the polyrotaxane compound most suitably used is a cyclic molecule having α -cyclodextrin ring, with polyethylene glycol having adamantyl groups bonded to both ends as an axial molecule.

(A) Photochromic polyrotaxane compound: photochromic polyrotaxane compound having photochromic moiety and cyclic molecule bonded to side chain thereof

The polyrotaxane compound used in the present invention has a side chain containing a photochromic site bonded to a cyclic molecule. Thus, since the photochromic portion can be always arranged in the vicinity of the polyrotaxane compound, the fading speed can be increased while maintaining a high color development concentration even when the photochromic portion is combined with a polymerizable compound other than the photochromic polyrotaxane compound.

The photochromic moiety can be bonded to the cyclic molecule by using the side chain and further combining a linking group L as necessary. That is, a chain including a photochromic site can be introduced into the cyclic molecule by reacting the first side chain with the photochromic site having the linking group L and bonding the first side chain to the linking group L. In the above case, the "chain" includes a portion formed by reacting the first side chain with the linking group L "and is a portion including the first side chain and the linking group L. As described above, the "chain" corresponds to the side chain. However, as described above, the photochromic moiety may be directly bonded to the first side chain, and in the above case, the first side chain may be regarded as the "chain" and the "chain" may be a side chain (the first side chain is a side chain).

The average molecular weight of the "chain" excluding the photochromic moiety is preferably 45 to 10000, more preferably 100 to 8000, further preferably 200 to 5000, and particularly preferably 300 to 2000.

As the photochromic portion, known one can be used, and these may be used alone or in combination of 2 or more.

Typical examples of such photochromic sites include naphthopyrans, spirooxazines, spiropyrans, fulgides, fulgimides, and diarylethenes.

Among them, indenonaphthopyrans are preferable, and among them, indeno [2,1-f ] naphtho [1,2-b ] pyrans are particularly preferable, from the viewpoint of exhibiting excellent photochromic properties particularly in color development concentration and color fading speed.

The indeno [2,1-f ] naphtho [1,2-b ] pyran exemplified as a particularly preferable example of the photochromic site is represented by the following formula (4):

here, the number of the first and second electrodes,

R⁸and R⁹Each independently represents a group directly bonded to L described later, a hydroxyl group, an alkyl group, a haloalkyl group, an optionally substituted cycloalkyl group, an alkoxy group, an amino group (a group containing a primary amine or a secondary amine), a heterocyclic group having a nitrogen atom constituting a ring and bonded to a carbon atom to which the substituent is bonded through the nitrogen atom (wherein the substituent may be substituted), a cyano group, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a halogen atom, an optionally substituted aralkyl group, an optionally substituted aralkyloxy group, an optionally substituted aryloxy group, an optionally substituted aryl group, an alkylthio group, a cycloalkylthio group, an optionally substituted arylsulfur groupThe base group is a group of a compound,

in addition, R⁸And R⁹Each independently optionally being integrated with each other adjacent to each other to form an aliphatic ring optionally containing an oxygen atom, a nitrogen atom, a sulfur atom (wherein, optionally, a substituent is present),

R¹⁰and R¹¹Each independently a group directly bonded to L described later, a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a halogen atom, an aralkyl group optionally having a substituent, an aralkyloxy group optionally having a substituent, an aryloxy group optionally having a substituent or an aryl group optionally having a substituent,

in addition, R¹⁰And R¹¹These two may be integrated together with the carbon atom at position 13 to which they are bonded to form an aliphatic ring having 3 to 20 carbon atoms constituting a ring, a condensed polycyclic ring having an aromatic ring or an aromatic heterocyclic ring added to the aliphatic ring, a heterocyclic ring having 3 to 20 carbon atoms constituting a ring, or a condensed polycyclic ring having an aromatic ring or an aromatic heterocyclic ring added to the heterocyclic ring, wherein these rings may have a substituent,

R¹²and R¹³Each independently an aryl group optionally having a substituent, or a heteroaryl group optionally having a substituent,

h is an integer of 0 to 4,

i is an integer of 0 to 4,

a plurality of R under the condition that h is 2-4⁸Optionally the same or different from each other,

when i is 2 to 4, a plurality of R⁹Optionally the same or different from each other,

wherein R is⁸、R⁹、R¹⁰、R¹¹、R¹²Or a substituent on the aryl or heteroaryl group of (A), or R¹³At least 1 of the substituents on the aryl or heteroaryl group in (b) is a substituent L described later.

In addition, R is as defined above⁸、R⁹、R¹⁰、R¹¹、R¹²And R¹³These groups, or these groupsThe substituents optionally contained in the ring group formed by the group are introduced mainly for controlling the color tone of the developed color, etc., and the effects of the present invention are not impaired by these substituents. Therefore, R is not particularly limited, and R is preferably mentioned⁸And R⁹The groups exemplified.

In the above, the carbon number of the alkyl group is preferably 1 to 6, the carbon number of the haloalkyl group is preferably 1 to 6, the carbon number of the cycloalkyl group is preferably 3 to 8, the carbon number of the alkoxy group is preferably 1 to 6, the carbon number of the alkylcarbonyl group is preferably 2 to 7, the carbon number of the alkoxycarbonyl group is preferably 2 to 7, the carbon number of the aralkyl group is preferably 7 to 11, the carbon number of the aralkyloxy group is preferably 7 to 11, the carbon number of the aryloxy group is preferably 6 to 12, the carbon number of the aryl group is preferably 6 to 12, the carbon number of the alkylthio group is preferably 1 to 6, the carbon number of the cycloalkylthio group is preferably 3 to 8, and the carbon number of.

Examples of the indeno [2,1-f ] naphtho [1,2-b ] pyran in which the photochromic site is formed may include, without limitation, International publication No. 1996/014596 pamphlet, International publication No. 2001/019813 pamphlet, International publication No. 2001/060811, International publication No. 2005/028465 pamphlet, WO2006/110221, International publication No. 2007/073462 pamphlet, International publication No. 2007/140071 pamphlet, International publication No. 2008/054942 pamphlet, International publication No. 2010/065393 pamphlet, International publication No. 2011/10744 pamphlet, International publication No. 2011/016582, International publication No. 2011/025056, International publication No. 2011/034202 pamphlet, International publication No. 2011/078030 pamphlet, International publication No. 2012/102409 pamphlet, International publication No. 2011/034202 pamphlet, International publication No. 2011/078030 pamphlet, International publication No. 2012/102409, Examples of the compound include those described in International publication No. 2012/102410 pamphlet and International publication No. 2012/121414 pamphlet.

Next, the side chain including the photochromic moiety is represented by the following formula (1):

here, the number of the first and second electrodes,

PC is a photochromic group;

R¹is a linear or branched chain having 2 to 8 carbon atomsAn alkyl group;

R²a linear or branched alkylene group having 2 to 8 carbon atoms, a linear or branched alkylene group having 3 to 8 carbon atoms and having an acetyl group branch, or a linear or branched alkylene group having 3 to 8 carbon atoms and having an ether bond;

l is a 2-valent group represented by the following formula (2),

here, the number of the first and second electrodes,

R³is a directly linked, straight or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or an aromatic group having 6 to 12 carbon atoms,

R⁴a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or a dialkylsilyl group having a linear or branched alkyl group having 1 to 20 carbon atoms,

R⁵is a straight or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an aromatic group having 6 to 12 carbon atoms,

X¹and X²Each independently is a direct bond, O, or NH,

c is an integer of 0 to 50, d is an integer of 0 to 50, e is an integer of 0 or 1,

in the case where c is 2 or more, the 2-valent groups of the units of a plurality of c are optionally the same or different,

when d is 2 or more, the 2-valent groups of the units of d are optionally the same or different.

a is an integer of 1 to 50, b is an integer of 0 to 50;

when a is 2 or more, the 2-valent groups of the units of a are optionally the same or different;

when b is 2 or more, the 2-valent groups of the units of b are optionally the same or different.

Wherein, if particularly preferred groups are exemplified, then

R¹Ethyl, propyl, isopropyl, or butyl is preferred, and isopropyl is particularly preferred. a is preferably 1 to 10, and particularly preferably 1.

R²Particularly preferred is butylene, pentylene, or hexylene. b is preferably 1 to 10, particularly preferably 2 to 8.

In addition, in L represented by the above formula (2),

R³preferably a single bond (in this case, X)¹Directly bonded to the oxygen atoms of the units of b), or ethylene, propylene, cyclohexylene. More particularly, a single bond or an ethylene group is preferable.

X¹And X²Each is more preferably a single bond (in this case, the carbonyl group is directly bonded to R)³And R⁴Bonded), or O.

R⁴Ethylene, propylene, butylene, or dimethylsilyl groups are preferable, and ethylene and dimethylsilyl groups are particularly preferable.

c is preferably 2, d is preferably 1 to 10, particularly preferably 1 to 5, and e is preferably 0.

Among these, L has the following structure as a particularly preferable example.

It is to be understood that in the formula (1), the portion other than PC corresponds to a "chain", and the average molecular weight of the "chain" other than PC is preferably 45 to 10000, more preferably 100 to 8000, further preferably 200 to 5000, and particularly preferably 300 to 2000.

(photochromic polyrotaxane Compound in which a chain having a polymerizable group is bonded to a cyclic molecule)

In the photochromic polyrotaxane compound of the present invention, a chain containing a polymeric group may be further bonded to the cyclic molecule. This enables to obtain a cured product having excellent photochromic properties by polymerizing and curing the photochromic polyrotaxane compound alone or further in combination with a polymerizable compound other than the photochromic polyrotaxane compound described later.

Such a chain containing a polymerizable group can be bonded to a cyclic molecule by using the side chain (first side chain) and further combining a linking group L as necessary, similarly to the chain containing a photochromic site. The terminal of the first side chain may be a polymerizable group, and in this case, the first side chain corresponds to a chain containing a polymerizable group. In addition, when the polymerizable group is introduced into the cyclic molecule by reacting the first side chain with a polymerizable group-containing compound having a linking group L and bonding the first side chain to the linking group L, the "chain" includes a portion formed by reacting the first side chain with the linking group L "and a portion including the first side chain and the linking group L. As described above, the "chain" corresponds to the side chain. The average molecular weight of the "chain" excluding the polymerizable group is preferably 45 to 10000, more preferably 100 to 8000, further preferably 200 to 5000, and particularly preferably 300 to 2000.

That is, a chain containing a polymerizable group is introduced into a cyclic molecule by the following formula (3),

here, the number of the first and second electrodes,

z is a polymerizable group;

R⁶is a linear or branched alkylene group having 2 to 8 carbon atoms;

R⁷a linear or branched alkylene group having 2 to 8 carbon atoms, a linear or branched alkylene group having 3 to 8 carbon atoms and having an acetyl group branch, or a linear or branched alkylene group having 3 to 8 carbon atoms and having an ether bond;

l 'is a 2-valent group represented by the following formula (2'),

here, the number of the first and second electrodes,

R³¹is a single bond, has a carbon number of1 to 20 linear or branched alkylene groups, 3 to 12 cycloalkyl groups, or 6 to 12 aromatic groups,

R⁴¹a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or a dialkylsilyl group having a linear or branched alkyl group having 1 to 20 carbon atoms,

R⁵¹is a straight or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an aromatic group having 6 to 12 carbon atoms,

X¹¹and X²¹Each independently is a direct bond, O, or NH,

c₁is an integer of 0 to 50, d₁Is an integer of 0 to 50, e₁Is an integer of 0 or 1, and,

c₁in the case of 2 or more, a plurality of c₁The 2-valent groups of the units of (A) are optionally each the same or different,

d₁in the case of 2 or more, a plurality of d₁The 2-valent groups of the units of (a) are optionally each the same or different.

f is an integer of 1 to 50, g is an integer of 0 to 50;

when f is 2 or more, the 2-valent groups of the units of f are optionally the same or different;

when g is 2 or more, the 2-valent groups of the units of g are optionally the same or different.

It is to be understood that in the formula (3), the portion other than Z corresponds to a "chain", and the average molecular weight of the "chain" other than Z is preferably 45 to 10000, more preferably 100 to 8000, further preferably 200 to 5000, and particularly preferably 300 to 2000.

The polymerizable group is typically a radical polymerizable group such as an acryloyl group, a methacryloyl group, an allyl group, a vinyl group, or a 4-vinylphenyl group, but depending on the kind of polymerizable compound other than the photochromic polyrotaxane compound, an epoxy group, an episulfide group, a thietanyl group, an OH group, an SH group, or an NH group₂A base,An NCO group or NCS group can also be used as a polymerizable group.

Wherein, if particularly preferred groups are exemplified, then

R⁶Ethyl, propyl, isopropyl, or butyl is preferred, and isopropyl is particularly preferred. f is preferably 1 to 10, and particularly preferably 1.

R⁷Particularly preferred is butylene, pentylene, or hexylene. g is preferably 1 to 10, particularly preferably 2 to 8.

In L 'represented by the above formula (2'),

R³¹a single bond is preferred, or an ethylene group, a propylene group, or a cyclohexylene group is preferred, and a single bond or an ethylene group is particularly preferred.

X¹¹Preferably a single bond, or O.

X²¹Preferably a single bond, or O or NH.

R⁴¹Ethylene, propylene, butylene, and dimethylsilyl groups are preferable, and ethylene and dimethylsilyl groups are particularly preferable.

R⁵¹Preferred are methylene, ethylene and propylene.

c₁Preferably 2, d₁Preferably 1 to 10, particularly preferably 1 to 5, e₁Preferably 0.

Among them, as a particularly preferable example, the following structure can be exemplified for L'.

Here, the epoxy group, episulfide group, thietanyl group and NH group are the same as those of the polymerizable compound other than the photochromic polyrotaxane compound of the present invention₂Reacting the base and NCO.

The OH group and SH group react with NCO group and NCS group of the polymerizable compound other than the photochromic polyrotaxane compound of the present invention to form a urethane bond and a thiocarbamate bond.

NCO groupThe NCS group is bonded to an OH group, an SH group or an NH group of a polymerizable compound other than the photochromic polyrotaxane compound of the present invention₂And (4) reacting.

(number of side chains having photochromic moiety and side chains having polymerizable group is suitable)

The number of side chains containing photochromic sites that can be introduced into one molecule of the polyrotaxane compound is not particularly limited, and is preferably 3 to 1000, since the number of side chains is 1 to 5000 per molecule on average, and if the number is too small, the color development concentration becomes insufficient, and if the number is too large, the color development concentration becomes saturated, and the photochromic sites cannot function effectively. The number of side chains is an average.

The number of side chains containing a polymerizable group is not particularly limited, and may be 0 to 5000, but if it is too small, it is difficult to polymerize alone, and even when a polymerizable compound other than the photochromic polyrotaxane compound is blended, it may bleed out in the cured product without bonding, and it is preferably 10 to 5000. The number of chains is the average.

In addition, in the case where the cyclic molecule is a cyclodextrin ring, from the viewpoint of imparting excellent photochromic properties, a photochromic polyrotaxane compound in which 1 to 100%, preferably 5 to 80%, more preferably 10 to 60% of the side chains bonded to the cyclodextrin ring are the side chains having the photochromic moiety and 0 to 99%, preferably 20 to 95%, more preferably 40 to 90% of the side chains having the polymerizable group is particularly preferable. However, as described above, side chains (including the first side chain) are not introduced into all the functional groups of the cyclic molecule.

In addition, photochromic sites and polymerizable groups may not be introduced into all the side chains (including the first side chain). For example, when the polymerizable group of the polymerizable compound is a radical polymerizable group, in the case of a photochromic polyrotaxane compound combined with the polymerizable compound, considering productivity, photochromic properties, and polymerizability with another polymerizable compound, it is more preferable that the side chain having a photochromic site is 5 to 50%, the side chain having a radical polymerizable group is 10 to 90%, and the side chain having no photochromic site and no polymerizable group (side chain having a hydroxyl group or another group at the end) is 5 to 50%, and it is further preferable that the side chain having a photochromic site is 10 to 40%, the side chain having a polymerizable group is 20 to 80%, and the side chain having no photochromic site and no polymerizable group is 10 to 40%, among the side chains bonded to the cyclodextrin ring.

The photochromic polyrotaxane compound of the present invention is not particularly limited, but the weight average molecular weight Mw is preferably 6000 to 200000, more preferably 8000 to 150000. In particular, the weight average molecular weight Mw of the photochromic polyrotaxane compound is more preferably 10000 to 120000, and particularly preferably 7000 to 100000, in order to improve compatibility with other polymerizable compounds and to introduce a large number of photochromic sites without excessively increasing the viscosity of the monomer before curing and to obtain an excellent effect.

(method for producing photochromic polyrotaxane Compound)

The photochromic polyrotaxane compound of the present invention can be produced by the following method without limiting the production method.

First, a polyrotaxane skeleton is produced by a known method. Next, a first side chain is introduced into the cyclic molecule of the polyrotaxane skeleton by a known method. In this case, the terminal of the first side chain is preferably formed with a reactive group (for example, an OH group or the like) in advance.

In addition, a group having a photochromic moiety capable of reacting with at least the first side chain is separately introduced. Preferably, the group is preferably a group forming the aforementioned L.

Then, the photochromic polyrotaxane compound of the present invention can be produced by reacting the polyrotaxane having the first side chain with a group capable of forming the aforementioned L. The photochromic moiety may be directly reacted with the first side chain (in the above case, L is a single bond).

The reaction of the group capable of forming the aforementioned L with the terminal of the first side chain is not particularly limited.

For example, when the terminal of the first side chain is an OH group, the above-mentioned L can be formed by an esterification reaction with a compound having a carboxylic acid as a terminal. Specifically, the reaction can be carried out by stirring the mixture in a solvent such as toluene in the presence of an inorganic acid such as sulfuric acid or hydrochloric acid, an organic acid such as an aromatic sulfonic acid, or a lewis acid such as boron fluoride ether, if necessary, while heating, and removing the produced water by azeotropy. In the esterification reaction, as a method for removing water, there may be mentioned: a method for removing water by using drying agents such as anhydrous magnesium sulfate or molecular sieves; or a method of removing water in the presence of a dehydrating agent typified by dicyclohexylcarbodiimide.

The above-mentioned L may be formed by an esterification reaction with a compound having a carboxylic acid halide at the terminal. Specifically, the following method may be employed: removing the generated hydrogen halide by stirring in an ether solvent such as tetrahydrofuran in the presence of an alkali such as pyridine or dimethylaniline, if necessary; and the like.

Further, L may be formed by an esterification reaction with a compound having an acid anhydride terminal. Specifically, the following method may be employed: stirring in a solvent such as toluene in the presence of a catalyst such as sodium acetate or pyridine, if necessary, while heating; and the like.

In addition, the L may be formed by a urethanization reaction with a compound having an NCO group at the end as another method. Specifically, the following method may be employed: in the presence of an amine catalyst such as triethylenediamine or a tin catalyst such as dibutyltin dilaurate, stirring the mixture while heating the mixture as necessary in a solvent such as toluene or the like without a solvent; and the like.

The method of introducing the chain having a polymerizable group may be the same as the above-described method. The compound having a photochromic moiety substituted with a polymerizable group may be reacted with a group capable of forming the above-mentioned L'. In addition, when the reactive group at the end of the first side chain is a polymerizable group in the present invention, it may be used as it is as a polymerizable group.

(polymerizable Compound other than photochromic polyrotaxane Compound)

The photochromic composition of the present invention may contain a polymerizable compound other than the photochromic polyrotaxane compound, if necessary. Examples of such polymerizable compounds (which may be referred to as component (B)) include a radically polymerizable compound (B1), an epoxy polymerizable compound (B2), a urethane or urea polymerizable compound (B3) capable of forming a urethane bond, a urea bond, or the like, and a polymerizable compound (B4) other than (B1 to B3). In particular, when a polymerizable group is introduced into a photochromic polyrotaxane compound, a polymerizable compound capable of reacting with such a polymerizable group is suitably used.

(B1) Radical polymerizable compound:

in particular, when a radically polymerizable functional group is introduced into a side chain of a photochromic polyrotaxane compound, a radically polymerizable compound (B1) is suitably used, and the radical polymerizable compound is roughly classified into: a (meth) acrylic polymerizable compound (B1-1) having a (meth) acryloyl group; a vinyl polymerizable compound having a vinyl group (B1-2); an allyl polymerizable compound having an allyl group (B1-3); a silsesquioxane-based polymerizable compound (B1-4).

Specific examples thereof are shown below.

(B1) Examples of the (meth) acrylic polymerizable compound:

(B1-1-1) 2-functional (meth) acrylic polymerizable Compound

The photochromic curable composition of the present invention preferably contains (B1-1-1) 2-functional (meth) acrylic polymerizable compound. Specific examples thereof are shown below. Specifically, the compounds are represented by the following formulae (5), (6) and (7). Hereinafter, the compound represented by the following formula (5) may be abbreviated as the component (B1-1-1-1), the compound represented by the following formula (6) may be abbreviated as the component (B1-1-1-2), and the compound represented by the following formula (7) may be abbreviated as the component (B1-1-1-3). Further, a 2-functional (meth) acrylic polymerizable compound having a urethane bond (hereinafter, also referred to as (B1-1-1-4) component), a 2-functional (meth) acrylic polymerizable compound not corresponding to the (B1-1-1-1) component, the (B1-1-1-2) component, the (B1-1-1-3) component, and the (B1-1-1-4) component (hereinafter, also referred to as (B1-1-1-5) component) will be described.

(B1-1-1-1) Compound represented by the following formula (5)

In the formula, R¹⁴And R¹⁵Each is a hydrogen atom or a methyl group, j and k are each independently an integer of 0 or more, and j + k is 2 or more and 50 or less in average.

The polymerizable compound represented by the above formula (5) is usually obtained as a mixture of molecules having different molecular weights. Therefore, j and k are represented as an average value.

The compounds represented by the above formula (5) are specifically exemplified as follows.

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 (having 2 repeating units of polyethylene and 2 repeating units of polypropylene) formed from a mixture of polypropylene glycol and polyethylene glycol, polyethylene glycol dimethacrylate (particularly having an average molecular weight of 330), polyethylene glycol dimethacrylate (particularly having an average molecular weight of 536), polyethylene glycol dimethacrylate (particularly having an average molecular weight of 736), tripropylene glycol dimethacrylate, polypropylene, Tetrapropylene glycol dimethacrylate, polypropylene glycol dimethacrylate (especially 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).

(B1-1-1-2) Compound represented by the following formula (6)

In the formula, R¹⁶And R¹⁷Are each a hydrogen atom or a methyl group,

R¹⁸and R¹⁹Are each a hydrogen atom or a methyl group,

R²⁰is a hydrogen atom or a halogen atom,

b is-O-, -S-, - (SO)₂)-、-CO-、-CH₂-、-CH＝CH-、-C(CH₃)₂-、-C(CH₃)(C₆H₅) -any of the above-mentioned (I) or (II),

l and m are each an integer of 1 or more, and l + m is 2 or more and 30 or less in average value.

The polymerizable compound represented by the above formula (6) is usually obtained as a mixture of molecules having different molecular weights. Therefore, l and m are expressed as average values.

Specific examples of the compound represented by the above formula (6) include, for example, the following bisphenol a di (meth) acrylate.

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

(B1-1-1-3) Compound represented by the following formula (7)

In the formula, R²¹And R²²Are each a hydrogen atom or a methyl group,

n is a number of 1 to 20 in terms of average value,

a and A ' are each a linear or branched alkylene group having 2 to 15 carbon atoms, and when a plurality of A's are present, the plurality of A's may be the same group or different groups.

The compound represented by the above formula (7) can be produced by reacting a polycarbonate diol with (meth) acrylic acid.

The polycarbonate diol used herein includes the following ones. Specifically, the method comprises the following steps: polycarbonate diols (having a number average molecular weight of 500 to 2000) obtained by the phosgene treatment of polyalkylene glycols such as trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol and nonamethylene glycol;

polycarbonate diols (number average molecular weight 500 to 2000) obtained by the phosgene treatment of a mixture of 2 or more polyalkylene glycols, for example, a mixture of trimethylene glycol and tetramethylene glycol, a mixture of tetramethylene glycol and hexamethylene glycol, 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.);

a polycarbonate diol (number average molecular weight 500-2000) obtained by phosgene-oxidation of 1-methyltrimethylene glycol.

(B1-1-1-4) 2-functional (meth) acryloyl-polymerizable Compound having urethane bond

As the (B1-1-1-4) component, a reaction product of a polyol and a polyisocyanate is representative. Examples of the polyisocyanate include: hexamethylene diisocyanate, isophorone diisocyanate, lysine isocyanate, 2, 4-hexamethylene diisocyanate, dimer acid diisocyanate, isopropylidene bis-4-cyclohexyl isocyanate, dicyclohexylmethane diisocyanate, norbornene methane diisocyanate or methylcyclohexane diisocyanate.

On the other hand, as the polyol, there can be mentioned: a polyalkylene glycol having a repeating unit of ethylene oxide, propylene oxide or hexane oxide having 2 to 4 carbon atoms, or a polyester glycol such as polycaprolactone glycol. In addition, the following can be exemplified: 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, and the like.

Further, urethane (meth) acrylate which is a reaction mixture obtained by further reacting a urethane prepolymer produced by the reaction of these polyisocyanate and polyol with 2-hydroxy (meth) acrylate or a reaction mixture obtained by directly reacting the diisocyanate with 2-hydroxy (meth) acrylate may be used.

Examples of the 2-functional (meth) acryloyl polymerizable compound having a urethane bond include SHIN-NAKAMURA CHEMICAL CO., U-2PPA (molecular weight 482) manufactured by LTD., UA-122P (molecular weight 1100), 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, and EB4858 (molecular weight 454) manufactured by Dail-UCB Company, and UX-2201, UX3204, UX4101, 6101, 7101, and 8101 manufactured by Nippon Kasei corporation.

(B1-1-1-5) other 2-functional (meth) acrylic polymerizable Compound

The component (B1-1-1-5) includes compounds having (meth) acryloyl groups at both ends of an optionally substituted alkylene group. The component (B1-1-1-5) is preferably a component having an alkylene group having 6 to 20 carbon atoms. Specific examples thereof include 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, 1, 9-nonanediol diacrylate, 1, 9-nonanediol dimethacrylate, 1, 10-decanediol diacrylate and 1, 10-decanediol dimethacrylate.

Further, as the component (B1-1-1-5), a 2-functional (meth) acrylate monomer containing a sulfur atom is exemplified. The sulfur atoms preferably form part of the molecular chain in the form of sulfur radicals. Specific examples thereof 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.

Among the above components (B1-1-1-1), (B1-1-1-2), (B1-1-1-3), (B1-1-1-4) and (B1-1-1-5), individual components among the respective components may be used, or plural components described above may be used. When a plurality of components are used, the mass to be the reference of the component (B1-1-1) is the total amount of the plurality of components.

Next, (B1-1-2) a polyfunctional (meth) acrylic polymerizable compound will be described.

(B1-1-2) polyfunctional (meth) acrylic polymerizable compound

Examples of the component (B1-1-2) include: a compound represented by the following formula (8) (hereinafter, also referred to as a component (B1-1-2-1) in some cases), a polyfunctional (meth) acrylic polymerizable compound having a urethane bond (hereinafter, also referred to as a component (B1-1-2-2) in some cases), and a polyfunctional (meth) acrylic polymerizable compound which does not correspond to the component (B1-1-2-1) and the component (B1-1-2-2) in some cases (hereinafter, also referred to as a component (B1-1-2-3) in some cases).

(B1-1-2-1) Compound represented by the following formula (8)

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

In the formula, R²³Is a hydrogen atom or a methyl group,

R²⁴is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms,

R²⁵is a C1-10 organic group having a valence of 3-6,

o is a number of 0 to 3 in average value, and p is a number of 3 to 6.

As R²⁴The alkyl group having 1 to 2 carbon atoms is preferably a methyl group. As R²⁵Examples of the organic group include groups derived from a polyol, a hydrocarbon group having a valence of 3 to 6, and an organic group having a urethane bond having a valence of 3 to 6.

Specifically, the compounds represented by the above formula (8) are shown below. Trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetramethacrylate, tetramethylolmethane tetraacrylate, trimethylolpropane triethylene glycol trimethacrylate, trimethylolpropane triethylene glycol triacrylate, ditrimethylolpropane tetramethacrylate, ditrimethylolpropane tetraacrylate.

(B1-1-2-2) polyfunctional (meth) acrylic polymerizable compound having urethane bond

The component (B1-1-2-2) is obtained by reacting the polyisocyanate compound described in the component (B1-1-1-4) with a polyol compound such as glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol and the like, and has 3 or more (meth) acrylate groups in the molecule. Commercially available products include SHIN-NAKAMURA CHEMICAL CO., U-4HA (molecular weight 596, functional group number 4), U-6HA (molecular weight 1019, functional group number 6), U-6LPA (molecular weight 818, functional group number 6) and U-15HA (molecular weight 2300, functional group number 15) manufactured by LTD.

(B1-1-2-3) other polyfunctional (meth) acrylic polymerizable compound

The component (B1-1-2-3) is a compound obtained by modifying the end of a polyester compound with a (meth) acryloyl group. Commercially available products of various polyester (meth) acrylate compounds based on the molecular weight of the polyester compound as a raw material and the modification amount of the (meth) acryloyl group can be used. Specifically, there may be mentioned 4-functional polyester oligomers (molecular weight: 2500 to 3500, Daicel Ucb Kk, EB80, etc.), 6-functional polyester oligomers (molecular weight: 6000 to 8000, Daicel Ucb Kk, EB450, etc.), 6-functional polyester oligomers (molecular weight: 45000 to 55000, Daicel Ucb Kk, EB1830, etc.), 4-functional polyester oligomers (particularly, first Industrial pharmaceutical Co., Ltd. having a molecular weight of 10000, GX8488B, etc.), and the like.

By using the (B1-1-2) component ((B1-1-2-1), (B1-1-2-2) and (B1-1-2-3)) as exemplified above, the crosslinking density is improved by polymerization, and the surface hardness of the resulting cured product can be improved. Therefore, in particular, when a photochromic cured product (laminate) obtained by a coating method is formed, it is preferable that the component (B1-1-2) is contained. Among the (B1-1-2) components, the (B1-1-2-1) component is particularly preferably used.

The above-mentioned component (B1-1-2-1), component (B1-1-2-2) and component (B1-1-2-3) may be used alone or in combination of two or more of the above-mentioned components. When a plurality of components are used, the mass to be the reference of the component (B1-1-2) is the total amount of the plurality of components.

Next, (B1-1-3) a monofunctional (meth) acrylic polymerizable compound will be described.

(B1-1-3) monofunctional (meth) acrylic polymerizable Compound

Examples of the component (B1-1-3) include compounds represented by the following formula (9).

In the formula, R²⁶Is a hydrogen atom or a methyl group,

R²⁷is a hydrogen atom, a methyldimethoxysilyl group, a trimethoxysilyl group, or a glycidyl group,

q is an integer of 0 to 10,

r is an integer of 0 to 20.

Specifically, the compounds represented by the above formula (9) are shown below.

Methoxypolyethylene glycol methacrylate (in particular average molecular weight 293), methoxypolyethylene glycol methacrylate (in particular average molecular weight 468), methoxypolyethylene glycol acrylate (in particular average molecular weight 218), methoxypolyethylene glycol acrylate (in particular average molecular weight 454), stearyl methacrylate, lauryl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, lauryl acrylate, gamma-methacryloxypropyltrimethoxysilane, gamma-methacryloxypropylmethyldimethoxysilane, glycidyl methacrylate.

(B1-2) vinyl polymerizable compound:

examples of the vinyl-based polymerizable compound having a vinyl group include methyl vinyl ketone, ethyl vinyl ether, styrene, vinylcyclohexane, butadiene, 1, 4-pentadiene, divinyl sulfide, divinyl sulfone, 1, 2-divinylbenzene, 1, 3-divinyl-1, 1,3, 3-tetramethylpropanedisiloxane, diethylene glycol divinyl ether, adipic acid divinyl ester, sebacic acid divinyl ester, ethylene glycol divinyl ether, divinyl sulfoxide, divinyl sulfide, dimethyldivinyl silane, 1,2, 4-trivinylcyclohexane, methyltrivinylsilane, α -methylstyrene and α -methylstyrene dimer.

Among the vinyl polymerizable compounds exemplified above, α -methylstyrene and α -methylstyrene dimers function as polymerization regulators, and the moldability of the photochromic composition is improved.

(B1-3) allyl polymerizable Compound

Examples of the allyl polymerizable compound having an allyl group include the following compounds. Diethylene glycol bisallyl carbonate, methoxypolyethylene glycol allyl ether (in particular average molecular weight 550), methoxypolyethylene glycol allyl ether (in particular average molecular weight 350), methoxypolyethylene glycol allyl ether (in particular average molecular weight 1500), polyethylene glycol allyl ether (in particular average molecular weight 450), methoxypolyethylene glycol polypropylene glycol allyl ether (in particular average molecular weight 750), butoxypolyethylene glycol polypropylene glycol allyl ether (in particular average molecular weight 1600), methacryloxypolyethylene glycol allyl ether (in particular average molecular weight 560), phenoxypolyethylene glycol allyl ether (in particular average molecular weight 600), methacryloxypolyethylene glycol allyl ether (in particular average molecular weight 430), acryloxypolyethylene glycol allyl ether (in particular average molecular weight 420), Vinyloxypolyethyleneglycol allyl ether (especially average molecular weight 560), vinyloxypolyethyleneglycol allyl ether (especially average molecular weight 650), methoxypolyhydroxyethylthiol allyl sulfide (especially average molecular weight 730).

The allyl polymerizable compound functions as a chain transfer agent, and the photochromic properties (color development concentration and fading speed) of the curable composition can be improved.

(B1-4) silsesquioxane polymerizable compound:

the silsesquioxane-polymerizable compound has various molecular structures such as a cage-like, stepwise, and random structure, and has a radical polymerizable group such as a (meth) acryloyl group.

Examples of such silsesquioxane polymerizable compounds include compounds represented by the following formula (10).

Wherein s is a polymerization degree and is an integer of 3 to 100,

plural R²⁸Optionally the same or different from each other, is a radical polymerizable group, an organic group containing a radical polymerizable group, a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or a phenyl group, and at least 1R²⁸Is a radical polymerizable group or an organic group containing a radical polymerizable group.

Here, as R²⁸Examples of the radical polymerizable group or the organic group containing a radical polymerizable group include: a (meth) acryloyl group; organic groups having a (meth) acryloyl group such as a (meth) acryloyloxypropyl group and a (3- (meth) acryloyloxypropyl) dimethylsiloxy group; an allyl group; organic groups having allyl groups such as allyl propyl group and allyl propyl dimethylsiloxy group; a vinyl group; and vinyl-containing organic groups such as vinyl propyl and vinyl dimethylsiloxy.

(B2) Epoxy-based polymerizable compound:

the polymerizable compound has an epoxy group in the molecule as a polymerizable group, and particularly a hydroxyl group or NH is introduced into the side chain of the polyrotaxane (A)₂The radical and NCO group are particularly suitable as the polymerizable functional group.

Such epoxy polymerizable compounds are roughly classified into: specific examples of the aliphatic epoxy compound, alicyclic epoxy compound and aromatic epoxy compound include the following.

Examples of the aliphatic epoxy compound include ethylene oxide, 2-ethyloxysilane, butyl glycidyl ether, phenyl glycidyl ether, 2' -methylenedioxysilane, 1, 6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, tetrapropylene glycol diglycidyl ether, nonapropyleneglycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, diglycerol tetraglycidyl ether, pentaerythritol tetraglycidyl ether, triglycidyl ether of tris (2-hydroxyethyl) isocyanurate, and mixtures thereof, Triglycidyl ethers of tris (2-hydroxyethyl) isocyanurate.

Examples of the alicyclic epoxy compound include isophorone glycol diglycidyl ether and bis-2, 2-hydroxycyclohexyl propane diglycidyl ether.

Examples of the aromatic epoxy compound include resorcinol diglycidyl ether, bisphenol a diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, diglycidyl phthalate, phenol novolac polyglycidyl ether, and cresol novolac polyglycidyl ether.

In addition to the above, an epoxy polymerizable compound having a sulfur atom in the molecule together with an epoxy group may be used. The sulfur atom-containing epoxy polymerizable compound is particularly advantageous for improving the refractive index, and there are chain aliphatic compounds and cyclic aliphatic compounds, and specific examples thereof are as follows.

Examples of the chain aliphatic sulfur atom-containing epoxy polymerizable compound include bis (2, 3-epoxypropyl) sulfide, bis (2, 3-epoxypropyl) disulfide, bis (2, 3-epoxypropylthio) methane, 1, 2-bis (2, 3-epoxypropylthio) ethane, 1, 2-bis (2, 3-epoxypropylthio) propane, 1, 3-bis (2, 3-epoxypropylthio) -2-methylpropane, 1, 4-bis (2, 3-epoxypropylthio) butane, 1, 4-bis (2, 3-epoxypropylthio) -2-methylbutane, 1, 3-bis (2, 3-epoxypropylthio) butane, 1, 5-bis (2, 3-epoxypropylthio) pentane, 1, 5-bis (2, 3-epoxypropylthio) -2-methylpentane, 1, 5-bis (2, 3-epoxypropylthio) -3-thiapentane, 1, 6-bis (2, 3-epoxypropylthio) hexane, 1, 6-bis (2, 3-epoxypropylthio) -2-methylhexane, 3, 8-bis (2, 3-epoxypropylthio) -3, 6-dithiaoctane, 1,2, 3-tris (2, 3-epoxypropylthio) propane, 2-bis (2, 3-epoxypropylthio) -1, 3-bis (2, 3-epoxypropylthiomethyl) propane, 2, 2-bis (2, 3-epoxypropylthiomethyl) -1- (2, 3-epoxypropylthio) butane.

Examples of the cyclic aliphatic sulfur atom-containing epoxy polymerizable compound include 1, 3-bis (2, 3-epoxypropylthio) cyclohexane, 1, 4-bis (2, 3-epoxypropylthio) cyclohexane, 1, 3-bis (2, 3-epoxypropylthiomethyl) cyclohexane, 1, 4-bis (2, 3-epoxypropylthiomethyl) cyclohexane, 2, 5-bis (2, 3-epoxypropylthiomethyl) -1, 4-dithiane, 2, 5-bis [ < 2- (2, 3-epoxypropylthio) ethyl > thiomethyl ] -1, 4-dithiane, 2, 5-bis (2, 3-epoxypropylthiomethyl) -2, 5-dimethyl-1, 4-dithiane.

(B3) Urethane polymerizable compound (including urea polymerizable compound):

the polymerizable compound is obtained by linking a repeating unit of polymerization by a urethane bond or a urea bond, and particularly, an epoxy group, an episulfide group, a thietanyl group, an OH group, an SH group, or NH group is introduced into a side chain of the photochromic polyrotaxane compound (A)₂The group, NCO group or NCS group is effective as the polymerizable functional group.

For example, urethane bonds are formed by the reaction of a polyol with a polyisocyanate, and include thiourethane bonds formed by the reaction of a polyol with a thiopolyisocyanate, or by the reaction of a polythiol with a thiopolyisocyanate.

In addition, the urea bond is formed by the reaction of polyamine and polyisocyanate, and the urea bond also includes a thiourea bond formed by the reaction of polyamine and thiopolyisocyanate.

As understood from the above description, in the present invention, as the urethane or urea-based polymerizable compound, a plurality of compounds selected from polyols (B3-1), polythiols (B3-2), polyamines (B3-3), polyisocyanates (B3-4), and polyisothiocyanates (B3-5) are used so as to form the urethane bond (thiourethane bond) or the urea bond (thiourea bond).

In addition, hydroxyl group, mercapto group (SH group), NH are introduced into the side chain of the polyrotaxane₂When the polymerizable group is an NCO group, the urethane or urea polymerizable compound (hereinafter, both may be collectively referred to as "urethane polymerizable compound") is preferable because a side chain is incorporated into the formed polymer chain.

As 1 type of compound used as such a urethane polymerizable compound, specifically, the following compounds are used.

(B3-1) polyol:

the polyol is a compound having 2 or more OH groups in one molecule, and is typically, for example, a di-, tri-, tetra-, penta-, hexa-hydroxy compound, a polyester (polyester polyol) having 2 or more OH groups in 1 molecule, a polyether (hereinafter referred to as polyether polyol) having 2 or more OH groups in 1 molecule, a polycarbonate (polycarbonate polyol) having 2 or more OH groups in 1 molecule, a polycaprolactone (polycaprolactone polyol) having 2 or more OH groups in 1 molecule, and an acrylic polymer (polyacrylic polyol) having 2 or more OH groups in 1 molecule.

These compounds are specifically exemplified as follows.

Examples of the aliphatic alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, butanetriol, 1, 2-methylglucoside, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, erythritol, threitol, ribitol, arabitol, xylitol, allitol, mannitol, dulcitol, iditol, ethylene glycol, inositol, hexanetriol, triglycerol, diglycerol, triethylene glycol, polyethylene glycol, tris (2-hydroxyethyl) isocyanurate, cyclobutanediol, cyclopentanediol, cyclohexanediol, cycloheptanediol, cyclooctanediol, cyclohexanedimethanol, hydroxypropylcyclohexanol, tricyclo [ 5,2,1,0,2,6 ] decane-dimethanol, bicyclo [4, 3,0 ] -nonanediol, and the like, Dicyclohexyl glycol, tricyclo [ 5,3,1, 1] dodecanediol, bicyclo [4, 3,0 ] nonanedimethanol, tricyclo [ 5,3,1, 1] dodecane-diethanol, hydroxypropyl tricyclo [ 5,3,1, 1] dodecanol, spiro [3, 4] octanediol, butylcyclohexanediol, 1, 1' -dicyclohexylidene glycol, cyclohexanetriol, maltitol, lactitol.

Examples of the aromatic alcohol include dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxybenzene, benzenetriol, biphenyltetraol, pyrogallol, (hydroxynaphthyl) pyrogallol, trihydroxyphenanthrene, bisphenol a, bisphenol F, benzenedimethanol, and tetrabromobisphenol a.

Examples of the sulfur-containing polyol include bis- [4- (hydroxyethoxy) phenyl ] sulfide, bis- [4- (2-hydroxypropoxy) phenyl ] sulfide, bis- [4- (2, 3-dihydroxypropoxy) phenyl ] sulfide, bis- [4- (4-hydroxycyclohexyloxy) phenyl ] sulfide, and bis- [ 2-methyl-4- (hydroxyethoxy) -6-butylphenyl ] sulfide.

Examples of the compound obtained by adding ethylene oxide and/or propylene oxide of 3 molecules or less on average per 1 hydroxyl group in the sulfur-containing polyol include bis- (2-hydroxyethyl) sulfide, bis (2-hydroxyethyl) disulfide, 1, 4-dithiane-2, 5-diol, bis (2, 3-dihydroxypropyl) sulfide, tetrakis (4-hydroxy-2-thietanyl) methane, bis (4-hydroxyphenyl) sulfone, tetrabromobisphenol S, tetramethylbisphenol S, 4' -thiobis (6-tert-butyl-3-methylphenol), and 1, 3-bis (2-hydroxyethylthioethyl) -cyclohexane.

Examples of the polyester polyol include compounds obtained by a condensation reaction of a polyhydric alcohol and a polybasic acid.

Examples of the polyether polyol include compounds obtained by the reaction of a compound having 2 or more active hydrogen-containing groups in the molecule and an alkylene oxide, and modified products thereof.

Examples of the polycaprolactone polyol include compounds obtained by ring-opening polymerization of epsilon-caprolactone.

Examples of the polycarbonate polyol include: a compound obtained by the carboacylchlorination of 1 or more species of low-molecular-weight polyhydric alcohols; a compound obtained by a transesterification method using ethylene carbonate, diethyl carbonate, diphenyl carbonate, or the like.

Examples of the polyacrylic polyol include compounds obtained from a copolymer of a hydroxyl group-containing acrylate or methacrylate and a monomer copolymerizable with these esters.

(B3-2) polythiol:

the polythiol is a compound having 2 or more SH groups in one molecule, and specifically, the following compounds can be exemplified.

Examples of the aliphatic polythiol include methanedithiol, 1, 2-ethanedithiol, 1-propanedithiol, 1, 2-propanedithiol, 1, 3-propanedithiol, 2-propanedithiol, 1, 6-hexanedithiol, 1,2, 3-propanetrithiol, tetrakis (mercaptomethyl) methane, 1-cyclohexanedithiol, 1, 2-cyclohexanedithiol, 2-dimethylpropane-1, 3-dithiol, 3, 4-dimethoxybutane-1, 2-dithiol, 2-methylcyclohexane-2, 3-dithiol, bicyclo [2, 2, 1] hepta-exo-cis-2, 3-dithiol, 1-bis (mercaptomethyl) cyclohexane, bis (2-mercaptoethyl) thiomalate, 2, 3-dimercaptosuccinic acid (2-mercaptoethyl ester), 2, 3-dimercapto-1-propanol (2-mercaptoacetate), 2, 3-dimercapto-1-propanol (3-mercaptoacetate), diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), 1, 2-dimercaptopropylmethyl ether, 2, 3-dimercaptopropylmethyl ether, 2-bis (mercaptomethyl) -1, 3-propanedithiol, bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), 1, 4-bis (3-mercaptobutyryloxy) butane, 1, 4-butanediol bis (3-mercaptopropionate), 1, 4-butanediol-bis (mercaptoacetate), 1, 6-hexanediol-bis (mercaptoacetate), tetraethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 1, 2-bis (2-mercaptoethylthio) -3-mercaptopropane, dipentaerythritol hexa (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), 1, 4-bis (3-mercaptobutyryloxy) butane, ethylene glycol bis (3-mercaptopropionate), ethylene glycol bis (2-mercaptoacetate), ethylene glycol tris (2-mercaptopropionate), ethylene glycol tris (3-mercaptobutyrate), ethylene glycol tris (2-mercaptoacetate), ethylene glycol tris (3-mercaptopropionate, Trimethylolpropane tris (3-mercaptobutyrate), trimethylolethane tris (3-mercaptobutyrate), 1, 2-bis [ (2-mercaptoethyl) thio ] -3-mercaptopropane, 2-mercaptomethyl-1, 3-propanedithiol, 2-mercaptomethyl-1, 4-butanedithiol, 2,4, 5-tris (mercaptomethyl) -1, 3-dithiolane, 2-bis (mercaptomethyl) -1, 4-butanedithiol, 4-bis (mercaptomethyl) -3, 5-dithiaheptane-1, 7-dithiol, 2, 3-bis (mercaptomethyl) -1, 4-butanedithiol, 2, 6-bis (mercaptomethyl) -3, 5-dithiaheptane-1, 7-dithiol, 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane, 2, 5-dimercaptomethyl-1, 4-dithiane, 1,3, 3-tetrakis (mercaptomethylthio) propane, 5, 7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane, 4, 8-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane, 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane.

Examples of the aromatic polythiol include 1, 2-dimercaptobenzene, 1, 3-dimercaptobenzene, 1, 4-dimercaptobenzene, 1, 2-bis (mercaptomethyl) benzene, 1, 3-bis (mercaptomethyl) benzene, 1, 4-bis (mercaptomethyl) benzene, 1, 2-bis (mercaptoethyl) benzene, 1, 3-bis (mercaptoethyl) benzene, 1, 4-bis (mercaptoethyl) benzene, 1, 2-bis (mercaptomethoxy) benzene, 1, 3-bis (mercaptomethoxy) benzene, 1, 4-bis (mercaptomethoxy) benzene, 1, 2-bis (mercaptoethoxy) benzene, 1, 3-bis (mercaptoethoxy) benzene, 1, 4-bis (mercaptoethoxy) benzene, 1,2, 3-trimercaptobenzene, 1,2, 4-trimercaptobenzene, 1,2, 3-trimercaptobenzene, and the like, 1,3, 5-trimercaptobenzene, 1,2, 3-tris (mercaptomethyl) benzene, 1,2, 4-tris (mercaptomethyl) benzene, 1,3, 5-tris (mercaptomethyl) benzene, 1,2, 3-tris (mercaptoethyl) benzene, 1,2, 4-tris (mercaptoethyl) benzene, 1,3, 5-tris (mercaptoethyl) benzene, 1,2, 3-tris (mercaptomethoxy) benzene, 1,2, 4-tris (mercaptomethoxy) benzene, 1,3, 5-tris (mercaptomethoxy) benzene, 1,2, 3-tris (mercaptoethoxy) benzene, 1,2, 4-tris (mercaptoethoxy) benzene, 1,3, 5-tris (mercaptoethoxy) benzene, 1,2,3, 4-tetramercaptobenzene, 1,2,3, 5-tetramercaptobenzene, 1,2,4, 5-tetramethylbenzene, 1,2,3, 4-tetrakis (mercaptomethyl) benzene, 1,2,3, 5-tetrakis (mercaptomethyl) benzene, 1,2,4, 5-tetrakis (mercaptomethyl) benzene, 1,2,3, 4-tetrakis (mercaptoethyl) benzene, 1,2,3, 5-tetrakis (mercaptoethyl) benzene, 1,2,4, 5-tetrakis (mercaptoethyl) benzene, 1,2,3, 4-tetrakis (mercaptoethyl) benzene, 1,2,3, 5-tetrakis (mercaptomethoxy) benzene, 1,2,4, 5-tetrakis (mercaptomethoxy) benzene, 1,2,3, 4-tetrakis (mercaptoethoxy) benzene, 1,2,3, 5-tetrakis (mercaptoethoxy) benzene, 1,2,4, 5-tetrakis (mercaptoethoxy) benzene, 2 '-dimercaptobiphenyl, 2, 4' -dimercaptobiphenyl, 4,4 '-dimercaptobiphenyl, 4' -dimercaptobibenzyl, 2, 5-methanebenzenedithiol, 3, 4-methanebenzenedithiol, 1, 4-naphthalenedithiol, 1, 5-naphthalenedithiol, 2, 6-naphthalenedithiol, 2, 7-naphthalenedithiol, 2, 4-dimethylbenzene-1, 3-dithiol, 4, 5-dimethylbenzene-1, 3-dithiol, 9, 10-anthracenedimethanethiol, 1, 3-di (p-methoxyphenyl) propane-2, 2-dithiol, 1, 3-diphenylpropane-2, 2-dithiol, phenylmethane-1, 1-dithiol, 2, 4-di (p-mercaptophenyl) pentane, 1, 4-bis (mercaptopropylthiomethyl) benzene.

Examples of the halogen-substituted aromatic polythiol include 2, 5-dichlorobenzene-1, 3-dithiol, 1, 3-bis (p-chlorophenyl) propane-2, 2-dithiol, 3,4, 5-tribromo-1, 2-dimercaptobenzene, and 2,3,4, 6-tetrachloro-1, 5-bis (mercaptomethyl) benzene.

Examples of the heterocycle-containing polythiol include: 2-methylamino-4, 6-dithiol-s-triazine, 2-ethylamino-4, 6-dithiol-s-triazine, 2-amino-4, 6-dithiol-s-triazine, 2-morpholinyl-4, 6-dithiol-s-triazine, 2-cyclohexylamino-4, 6-dithiol-s-triazine, 2-methoxy-4, 6-dithiol-s-triazine, 2-phenoxy-4, 6-dithiol-s-triazine, 2-thiophenoxy-4, 6-dithiol-s-triazine, 2-thiobutyloxy-4, 6-dithiol-s-triazine, 1,3, 5-tris (3-mercaptobutyryloxyethyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione,

examples of the aromatic polythiol containing a sulfur atom in addition to a mercapto group include: 1, 2-bis (mercaptomethylthio) benzene, 1, 3-bis (mercaptomethylthio) benzene, 1, 4-bis (mercaptomethylthio) benzene, 1, 2-bis (mercaptoethylthio) benzene, 1, 3-bis (mercaptoethylthio) benzene, 1, 4-bis (mercaptoethylthio) benzene, 1,2, 3-tris (mercaptomethylthio) benzene, 1,2, 4-tris (mercaptomethylthio) benzene, 1,3, 5-tris (mercaptomethylthio) benzene, 1,2, 3-tris (mercaptoethylthio) benzene, 1,2, 4-tris (mercaptoethylthio) benzene, 1,3, 5-tris (mercaptoethylthio) benzene, 1,2,3, 4-tetrakis (mercaptomethylthio) benzene, 1,2,3, 5-tetrakis (mercaptomethylthio) benzene, 1,2,4, 5-tetrakis (mercaptomethylthio) benzene, 1,2,3, 4-tetrakis (mercaptoethylthio) benzene, 1,2,3, 5-tetrakis (mercaptoethylthio) benzene, 1,2,4, 5-tetrakis (mercaptoethylthio) benzene, and nuclear alkylates of the above polythiols.

Examples of the aliphatic polythiol containing a sulfur atom in addition to a mercapto group include bis (mercaptomethyl) sulfide, bis (mercaptoethyl) sulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropyl) methane, 1, 2-bis (mercaptomethylthio) ethane, 1,2- (2-mercaptoethylthio) ethane, 1,2- (3-mercaptopropyl) ethane, 1, 3-bis (mercaptomethylthio) propane, 1, 3-bis (2-mercaptoethylthio) propane, 1, 3-bis (3-mercaptopropylthio) propane, 1, 2-bis (2-mercaptoethylthio) -3-mercaptopropane, 2-mercaptoethylthio-1, 3-propanedithiol, 1,2, 3-tris (mercaptomethylthio) propane, 1,2, 3-tris (2-mercaptoethylthio) propane, 1,2, 3-tris (3-mercaptopropylthio) propane, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (3-mercaptopropylthiomethyl) methane, bis (2, 3-dimercaptopropyl) sulfide, 2, 5-dimercapto-1, 4-dithiane, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) disulfide.

Examples of the ester of thioglycolic acid or mercaptopropionic acid as the above-mentioned compound include hydroxymethyl sulfide bis (2-mercaptoacetate), hydroxymethyl sulfide bis (3-mercaptopropionate), hydroxyethyl sulfide bis (2-mercaptoacetate), hydroxyethyl sulfide bis (3-mercaptopropionate), hydroxypropyl sulfide bis (2-mercaptoacetate), hydroxypropyl sulfide bis (3-mercaptopropionate), hydroxymethyl disulfide bis (2-mercaptoacetate), hydroxymethyl disulfide bis (3-mercaptopropionate), hydroxyethyl disulfide bis (2-mercaptoacetate), hydroxyethyl disulfide bis (3-mercaptopropionate), hydroxypropyl disulfide bis (2-mercaptoacetate), hydroxypropyl disulfide bis (3-mercaptopropionate), and mixtures thereof, 2-mercaptoethylether bis (2-mercaptoacetate), 2-mercaptoethylether bis (3-mercaptopropionate), 1, 4-dithiane-2, 5-diol bis (2-mercaptoacetate), 1, 4-dithiane-2, 5-diol bis (3-mercaptopropionate), 2, 5-bis (mercaptomethyl) -1, 4-dithiane, 2, 5-bis (2-mercaptoethyl) -1, 4-dithiane, 2, 5-bis (3-mercaptopropyl) -1, 4-dithiane, 2- (2-mercaptoethyl) -5-mercaptomethyl-1, 4-dithiane, 2- (2-mercaptoethyl) -5- (3-mercaptopropyl) -1, 4-dithiane, 2-mercaptomethyl-5- (3-mercaptopropyl) -1, 4-dithiane, bis (2-mercaptoethyl) thioglycolate, bis (2-mercaptoethyl) thiodipropionate, bis (2-mercaptoethyl) 4, 4' -thiodibutyrate, bis (2-mercaptoethyl) dithiodiacetate, bis (2-mercaptoethyl) dithiodipropionate, bis (2-mercaptoethyl) 4, 4' -dithiodibutyrate, bis (2, 3-dimercaptopropyl) thiodiacetate, bis (2, 3-dimercaptopropyl) thiodipropionate, bis (2, 3-dimercaptopropyl) dithiodiacetate, and (2, 3-dimercaptopropyl) dithiodipropionate.

Examples of the heterocycle-containing polythiol containing a sulfur atom in addition to a mercapto group include 3, 4-thiophenedithiol, 2, 5-dimercaptomethyl-tetrahydrothiophene, and 2, 5-dimercapto-1, 3, 4-thiadiazole.

Examples of the isocyanurate group-containing polythiol include 1, 2-bis [ (2-mercaptoethyl) thio ] -3-mercaptopropane, tris- { (3-mercaptopropionyloxy) -ethyl } -isocyanurate, 1,3, 5-tris (3-mercaptobutyryloxyethyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, and tris- [ (3-mercaptopropionyloxy) -ethyl ] -isocyanurate.

(B3-3) polyamine:

the polyamine has more than 2 NH groups in one molecule₂Specific examples of the compound of the group include the following compounds. Specific examples thereof include ethylenediamine, hexamethylenediamine, isophoronediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, metaxylylenediamine, 1, 3-propanediamine, putrescine, 2- (2-aminoethylamino) ethanol, diethylenetriamine, p-phenylenediamine, m-phenylenediamine, melamine and 1,3, 5-benzenetriamine.

(B3-4) polyisocyanate:

the polyisocyanate is a compound having 2 or more NCO groups in one molecule, and specific examples thereof include the following compounds.

Examples of the aliphatic isocyanate include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 2' -dimethylpentane diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, decamethylene diisocyanate, butene diisocyanate, 1, 3-butadiene-1, 4-diisocyanate, 2,4, 4-trimethylhexamethylene diisocyanate, 1,6, 11-undecane triisocyanate, 1,3, 6-hexamethylene triisocyanate, 1, 8-diisocyanate, 4-isocyanatomethyloctane, 2,5, 7-trimethyl-1, 8-diisocyanate-5-isocyanatomethyloctane, and, Bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, 1, 4-butanediol dipropyl ether-omega, omega' -diisocyanate, lysine diisocyanatomethyl ester, lysine triisocyanate, 2-isocyanatoethyl-2, 6-diisocyanate hexanoate, 2-isocyanatopropyl-2, 6-diisocyanate hexanoate.

As the alicyclic isocyanate, there may be mentioned isophorone diisocyanate, norbornane diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2' -dimethyldicyclohexylmethane diisocyanate, bis (4-isocyanaton-butylidene) pentaerythritol, dimer acid diisocyanate, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -5-isocyanatomethyl-bicyclo [2, 2, 1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6-isocyanatomethyl-bicyclo [2, 2, 1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5-isocyanatomethyl-bicyclo [2, 2, 1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6-isocyanatomethyl-bicyclo [2, 2, 1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2,1, 1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5- (2-isocyanatoethyl) -bicyclo [2, 2, 1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2, 2, 1] -heptane, 1,3, 5-tris (isocyanatomethyl) cyclohexane.

As the aromatic isocyanate, xylene diisocyanate, bis (isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene, α ', α' -tetramethylxylene diisocyanate, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatomethyl) diphenyl ether, bis (isocyanatoethyl) phthalate, mesitylene triisocyanate, 2, 6-bis (isocyanatomethyl) furan, benzene diisocyanate, toluene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, dimethylbenzene diisocyanate, diethylbenzene diisocyanate, diisopropylbenzene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, naphthalene diisocyanate, methylnaphthalene diisocyanate, biphenyl diisocyanate, tolidine diisocyanate, 4,4 '-diphenylmethane diisocyanate, 3' -dimethyldiphenylmethane-4, 4 '-diisocyanate, bibenzyl-4, 4' -diisocyanate, bis (isocyanatophenyl) ethylene, 3 '-dimethoxybiphenyl-4, 4' -diisocyanate, triphenylmethane triisocyanate, MDI, triisocyanate, polymeric diphenylmethane-4, 2 '-diphenylene-2, 4' -diphenylmethane-diisocyanate, 3 '-diphenylene-2' -diphenylene-diisocyanate, 3 '-diphenylene-4' -diphenylene-2, 4 '-diphenylene-diisocyanate, 3' -diphenylene-4 '-diphenylmethane diisocyanate, 3, 4' -diphenylene-diisocyanate, 3 '-diphenylene-2, 3' -diphenylene-2 '-diphenylmethane diisocyanate, 3' -diphenylene-2, 6 '-diphenylene-2, 3' -diphenylene-2 '-diphenylmethane-diisocyanate, 6-diphenylene-2, 6-diphenylene-diisocyanate, 3' -diphenylene-2 '-diisocyanate, 3' -diphenylene-2 '-diphenylmethane-2' -diisocyanate, 3 '-diphenylmethane-diphenylene-2' -diisocyanate, 4 '-diisocyanate, 3' -diphenylene-phenylene-.

Examples of the sulfur-containing aliphatic isocyanate include thiodiethyl diisocyanate, thiodipropyl diisocyanate, thiodihexyl diisocyanate, dimethylsulfone diisocyanate, dithiodimethyl diisocyanate, dithiodiethyl diisocyanate, dithiodipropyl diisocyanate, dicyclohexylsulfide-4, 4' -diisocyanate, 1-isocyanatomethylthio-2, 3-bis (2-isocyanatoethylthio) propane, 1, 2-bis (2-isocyanatoethylthio) ethane, 1,2, 2-tetrakis (isocyanatomethylthio) ethane, 2,2,5, 5-tetrakis (isocyanatomethylthio) -1, 4-dithiane, 2, 4-dithian-1, 3-diisocyanate, 2,4, 6-trithioheptane-3, 5-diisocyanate, 2,4,7, 9-tetrathiapentane-5, 6-diisocyanate, bis (isocyanatomethylthio) phenylmethane.

Examples of the aliphatic thioether-based isocyanate include bis [2- (isocyanatomethylthio) ethyl ] sulfide.

Examples of the aromatic thioether-based isocyanate include diphenylsulfide-2, 4 '-diisocyanate, diphenylsulfide-4, 4' -diisocyanate, 3 '-dimethoxy-4, 4' -diisocyanate dibenzyl sulfide, bis (4-isocyanatomethylbenzene) sulfide, and 4,4 '-methoxybenzenethioglycol-3, 3' -diisocyanate.

Examples of the aromatic disulfide isocyanate include diphenyl disulfide-4, 4 ' -diisocyanate, 2 ' -dimethyldiphenyl disulfide-5, 5 ' -diisocyanate, 3 ' -dimethyldiphenyl disulfide-6, 6 ' -diisocyanate, 4 ' -dimethyldiphenyl disulfide-5, 5 ' -diisocyanate, 3 ' -dimethoxydiphenyl disulfide-4, 4 ' -diisocyanate, and 4,4 ' -dimethoxydiphenyl disulfide-3, 3 ' -diisocyanate.

Examples of the aromatic sulfone-based isocyanate include diphenylsulfone-4, 4 '-diisocyanate, diphenylsulfone-3, 3' -diisocyanate, benzylidene sulfone-4, 4 '-diisocyanate, diphenylmethanesulfone-4, 4' -diisocyanate, 4-methyldiphenylmethanesulfone-2, 4 '-diisocyanate, 4' -dimethoxydiphenylsulfone-3, 3 '-diisocyanate, 3' -dimethoxy-4, 4 '-diisocyanate dibenzylsulfone, 4' -dimethyldiphenylsulfone-3, 3 '-diisocyanate, 4' -di-tert-butyldiphenylsulfone-3, 3 '-diisocyanate, 4' -dimethoxyphenylenedisulfone-3, 3 ' -diisocyanate, 4 ' -dichlorodiphenyl sulfone-3, 3 ' -diisocyanate.

Examples of the sulfonate-based isocyanate include 4-methyl-3-isocyanatobenzenesulfonyl-4 '-isocyanatophenol ester and 4-methoxy-3-isocyanatobenzenesulfonyl-4' -isocyanatophenol ester.

Examples of the aromatic sulfonic acid amide isocyanate include 4-methyl-3-isocyanate benzenesulfonylaniline-3 '-methyl-4' -isocyanate, diphenylsulfonyl-ethylenediamine-4, 4 '-diisocyanate, 4' -dimethoxybenzenesulfonyl-ethylenediamine-3, 3 '-diisocyanate, and 4-methyl-3-isocyanate benzenesulfonylaniline-4-methyl-3' -isocyanate.

Examples of sulfur-containing heterocyclic isocyanates include thiophene-2, 5-diisocyanate, thiophene-2, 5-diisocyanatomethyl ester, 1, 4-dithiane-2, 5-diisocyanate, 1, 4-dithiane-2, 5-diisocyanatomethyl ester, 1, 3-dithiolane-4, 5-diisocyanate, 1, 3-dithiolane-4, 5-diisocyanatomethyl ester, 1, 3-dithiolane-2-methyl-4, 5-diisocyanatomethyl ester, 1, 3-dithiolane-2, 2-diisocyanatoethyl ester, tetrahydrothiophene-2, 5-diisocyanatotetrahydrothiophene-2, 5-diisocyanatomethyl ester, thiofuran-2, 5-diisocyanatomethyl, Tetrahydrothiophene-2, 5-diisocyanatoethyl ester and tetrahydrothiophene-3, 4-diisocyanatomethyl ester.

Further, halogen-substituted, alkyl-substituted, alkoxy-substituted, nitro-substituted polyisocyanates of the above-mentioned polyisocyanates, prepolymer-type modified products with polyols, carbodiimide-modified products, urea-modified products, biuret-modified products, dimerization or trimerization reaction products, and the like can also be used.

(B3-5) polyisothiocyanate:

polyisothiocyanates are compounds having 2 or more NCS groups in one molecule, and specific examples thereof include the following compounds.

Examples of the aliphatic isothiocyanate include 1, 2-diisothiocyanatoethane, 1, 3-diisothiocyanatopropane, 1, 4-diisothiocyanatobutane, 1, 6-diisothiocyanatohexane and p-xylylene diisothiocyanate.

Examples of the alicyclic isothiocyanate include cyclohexyl isothiocyanate and cyclohexane diisothiocyanate.

Examples of the aromatic isothiocyanate include phenyl isothiocyanate, 1, 2-benzenediisothiocyanate, 1, 3-benzenediisothiocyanate, 1, 4-benzenediisothiocyanate, 2, 4-toluylenediisothiocyanate, 2, 5-diisothiocyanatemetaxylylenediisocyanate, 4 '-diisothiocyanate1, 1' -biphenyl, 1 '-methylenebis (4-isothiocyanatobenzene), 1' -methylenebis (4-isothiocyanatobenzene, 3-methylbenzene), 1 '- (1, 2-ethanediyl) bis (4-isothiocyanatobenzene), 4' -diisothiocyanatebenzophenone, and, 4,4 ' -diisothiocyanate 3,3 ' -dimethylbenzophenone, benzanilide-3, 4 ' -diisothiocyanate, diphenyl ether-4, 4 ' -diisothiocyanate, diphenylamine-4, 4 ' -diisothiocyanate.

Examples of the heterocycle-containing isothiocyanate include 2,4, 6- triisothiocyanate 1,3, 5-triazine.

Examples of carbonyl isothiocyanates include hexanediol diisothiocyanate, nonanediol diisothiocyanate, carbonyl diisothiocyanate, 1, 3-benzenedicarbonyl diisothiocyanate, 1, 4-benzenedicarbonyl diisothiocyanate, (2,2 '-bipyridine) -4, 4' -dicarbonyl diisothiocyanate.

Further, a polyfunctional isothiocyanate having at least 1 sulfur atom in addition to the sulfur atom of the isothiocyanate group may also be used. Examples of such a polyfunctional isothiocyanate include the following compounds.

Examples of the sulfur-containing aliphatic isothiocyanate include thiobis (3-isothiocyanate propane), thiobis (2-isothiocyanate ethane) and dithiobis (2-isothiocyanate ethane).

Examples of the sulfur-containing aromatic isothiocyanate include 1-isothiocyanate-4- { (2-isothiocyanate) sulfonyl } benzene, thiobis (4-isothiocyanate benzene), sulfonylbis (4-isothiocyanate benzene), sulfinylbis (4-isothiocyanate benzene), dithiobis (4-isothiocyanate benzene), 4-isothiocyanate-1- { (4-isothiocyanate phenyl) sulfonyl } -2-methoxy-benzene, 4-methyl-3-isothiocyanate benzenesulfonyl-4 ' -isothiocyanate phenyl ester, and 4-methyl-3-isothiocyanate benzenesulfonanilide-3 ' -methyl-4 ' -isothiocyanate.

Examples of the sulfur-containing heterocyclic isothiocyanate include thiophene-2, 5-diisothiocyanate and 1, 4-dithiane-2, 5-diisothiocyanate.

The urethane polymerizable compound (B3) may be used in combination so that a urethane bond or a urea bond is formed by polymerization.

(B4) Other polymerizable compounds:

in the present invention, in addition to the polymerizable compounds (B1) to (B3), a cyclic sulfide-based polymerizable compound (B4-1) and a thietane-based polymerizable compound (B4-2) may be used for the purpose of improving the refractive index, and a monofunctional polymerizable compound (B4-3) (except for the polymerizable compounds having 1 polymerizable group exemplified above) may be used for the purpose of improving the photochromic properties. Further, a composite type polymerizable compound (B4-4) having a plurality of polymerizable groups of different types in the molecule can also be used.

(B4-1) episulfide-based polymerizable compound:

the polymerizable monomer is a compound having 2 or more episulfide groups in the molecule, and is particularly suitable for the case where an SH group is introduced as a polymerizable functional group into the side chain of the photochromic polyrotaxane compound (a). Specifically, the following compounds can be exemplified. Examples thereof include bis (1, 2-thiolethyl) sulfide, bis (1, 2-thiolethyl) disulfide, bis (2, 3-thiolpropyl) sulfide, bis (2, 3-thiolpropylthio) methane, bis (2, 3-thiolpropyl) disulfide, bis (2, 3-thiolpropyldithio) methane, bis (2, 3-thiolpropyldithio) ethane, bis (6, 7-thiolproenyl-3, 4-dithioheptyl) sulfide, bis (6, 7-thiolproenyl-3, 4-dithioheptyl) disulfide, 1, 4-dithiane-2, 5-bis (2, 3-thiolpropyldithiomethyl), 1, 3-bis (2, 3-thiolpropyldithiomethyl) benzene, 1, 6-bis (2, 3-Thiopropyldithiomethyl) -2- (2, 3-Thiopropyldithioethylthio) -4-thiahexane, 1,2, 3-tris (2, 3-Thiopropyldithio) propane, 1, 1-tetrakis (2, 3-Thiopropyldithiomethyl) methane, 1, 3-bis (2, 3-Thiopropyldithio) -2-thiapropane, 1, 4-bis (2, 3-Thiopropyldithio) -2, 3-dithiabutane, 1,1, 1-tris (2, 3-Thiopropyldithio) methane, 1,1, 1-tris (2, 3-Thiopropyldithiomethylthio) methane, 1,1,2, 2-tetrakis (2, 3-Thiopropyldithio) ethane, 1,1,2, 2-tetrakis (2, 3-epithiopropyldithiomethylthio) ethane, 1,3, 3-tetrakis (2, 3-epithiopropyldithio) propane, 1,3, 3-tetrakis (2, 3-epithiopropyldithiomethylthio) propane, 2- [1, 1-bis (2, 3-epithiopropyldithio) methyl ] -1, 3-dithiane, 2- [1, 1-bis (2, 3-epithiopropyldithiomethylthio) methyl ] -1, 3-dithiane.

(B4-2) a thietane-based polymerizable compound;

the polymerizable compound is effective when an SH group is introduced as a polymerizable functional group into a side chain of the photochromic polyrotaxane compound (A), and is a thietane compound having 2 or more thietane groups in a molecule. Such a thietane-based polymerizable compound partially has both a thietane group and an episulfide group, and is exemplified in the item of the episulfide-based polymerizable compound. Other thietane-based polymerizable compounds include: a metal-containing thietane compound having a metal atom in the molecule; and a nonmetallic thietane compound containing no metal in the molecule.

Examples of the nonmetallic thietane compound include bis (3-thietanyl) disulfide, bis (3-thietanyl) sulfide, bis (3-thietanyl) trisulfide, bis (3-thietanyl) tetrasulfide, 1, 4-bis (3-thietanyl) -1,3, 4-trithiabutane, 1, 5-bis (3-thietanyl) -1,2,4, 5-tetrathiapentane, 1, 6-bis (3-thietanyl) -1,3,4, 6-tetrathiahexane, 1, 6-bis (3-thietanyl) -1,3,5, 6-tetrathiahexane, 1, 7-bis (3-thietanyl) -1,2,4,5, 7-pentathiaheptane, 1, 7-bis (3-thietanylthio) -1,2,4,6, 7-pentathiaheptane, 1-bis (3-thietanylthio) methane, 1, 2-bis (3-thietanylthio) ethane, 1,2, 3-tris (3-thietanylthio) propane, 1, 8-bis (3-thietanylthio) -4- (3-thietanylthiomethyl) -3, 6-dithiaoctane, 1, 11-bis (3-thietanylthio) -4, 8-bis (3-thietanylthiomethyl) -3,6, 9-trithiaundecane, 1, 11-bis (3-thietanylthio) -4, 7-bis (3-thietanylthiomethyl) -3,6, 9-trithiaundecane, 1, 11-bis (3-thietanylthio) -5, 7-bis (3-thietanylthiomethyl) -3,6, 9-trithiaundecane, 2, 5-bis (3-thietanylthiomethyl) -1, 4-dithiane, 2, 5-bis [ [2- (3-thietanylthio) ethyl ] thiomethyl ] -1, 4-dithiane, 2, 5-bis (3-thietanylthiomethyl) -2, 5-dimethyl-1, 4-dithiane, Disulfiranyl sulfide, bis (thietanylthio) methane 3- [ < (thietanylthio) methylthio > methylthio ] thietane, disulfiranyl disulfide, disulfiranyl trisulfide, disulfiranyl tetrasulfide, disulfiranyl pentasulfide, 1, 4-bis (3-thietanyldithio) -2, 3-dithiobutane, 1,1, 1-tris (3-thietanyldithio) methane, 1,1, 1-tris (3-thietanyldithiomethylthio) methane, 1,1,2, 2-tetrakis (3-thietanyldithio) ethane, 1,1,2, 2-tetrakis (3-thietanyldithiomethylthio) ethane.

As the metal-containing thietane compound, a thietane compound containing an element of group 14 such as Sn atom, Si atom, Ge atom, Pb atom, etc. in the molecule; group 4 elements such as Zr atom and Ti atom; an element of group 13 such as an Al atom; or an element of group 12 such as Zn atom; the metal atom is particularly preferably used, for example, the following compounds.

Examples of alkylthio (thietanylthio) tin include methylthiotris (thietanylthio) tin, ethylthiotris (thietanylthio) tin, propylthiotris (thietanylthio) tin, and isopropylthiotris (thietanylthio) tin.

Examples of bis (alkylthio) bis (thietanylthio) tin include bis (methylthio) bis (thietanylthio) tin, bis (ethylthio) bis (thietanylthio) tin, bis (propylthio) bis (thietanylthio) tin, and bis (isopropylthio) bis (thietanylthio) tin.

Examples of alkylthio (alkylthio) bis (thietanylthio) tin include ethylthio (methylthio) bis (thietanylthio) tin, methylthio (propylthio) bis (thietanylthio) tin, isopropylthio (methylthio) bis (thietanylthio) tin, ethylthio (propylthio) bis (thietanylthio) tin, ethylthio (isopropylthio) bis (thietanylthio) tin, and isopropylthio (propylthio) bis (thietanylthio) tin.

Examples of the bis (thietanylthio) cyclic dithiotin compound include bis (thietanylthio) dithiotin (stanntane), bis (thietanylthio) dithiotin (stannane), bis (thietanylthio) dithiotin (stannnanane) and bis (thietanylthio) trithiotin (stannane).

Examples of the alkyl (thietanylthio) tin compound include methyltris (thietanylthio) tin, dimethylbis (thietanylthio) tin, butyltris (thietanylthio) tin, and tetrakis (thietanylthio) tin.

Examples of the substance containing a metal other than tin include tetrakis (thietanylthio) germanium and tris (thietanylthio) bismuth.

(B4-3) a monofunctional polymerizable compound;

the polymerizable compound is a compound having one OH group or SH group in the molecule, and can be used for improving photochromic properties by adjusting the molecular weight and the degree of crosslinking by using the polymerizable compound in combination with the polyol. Examples of such a monofunctional polymerizable compound include the following compounds. Examples thereof include polyethylene glycol monooleate ether, polyethylene glycol monomethyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, polyoxyethylene 2-ethylhexyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether and polyethylene glycol mono-4-octylphenyl ether.

(B4-4) composite polymerizable compound;

the polymerizable compound is a compound having a plurality of polymerizable groups of different types in a molecule, and by using such a polymerizable compound, various properties can be adjusted.

Examples of such a composite polymerizable compound include the following compounds.

Examples of the radical polymerization/OH type polymerizable compound include 2-hydroxymethylacrylic acid, 2-hydroxyacrylic acid, 2-hydroxypropyl acrylate, hydroxypropyl methacrylate, and the like.

Examples of the radical polymerization/isocyanate type polymerizable compound include 2-isocyanatoethyl methacrylate and 2-isocyanatoethyl acrylate.

Examples of the OH/SH type polymerizable compound include 2-mercaptoethanol, 3-mercapto-1, 2-propanediol, glycerol bis (mercaptoacetate), 1-hydroxy-4-mercaptocyclohexane, 2, 4-dimercaptophenol, 2-mercaptohydroquinone, 4-mercaptophenol, 1, 3-dimercapto-2-propanol, 2, 3-dimercapto-1-propanol, 1, 2-dimercapto-1, 3-butanediol, pentaerythritol tris (3-mercaptopropionate), pentaerythritol mono (3-mercaptopropionate), pentaerythritol bis (3-mercaptopropionate), pentaerythritol tris (mercaptoacetate), pentaerythritol penta (3-mercaptopropionate), hydroxymethyl-tris (mercaptoethylthiomethyl) methane, and mixtures thereof, 1-hydroxyethylthio-3-mercaptoethylthiobenzene, 4-hydroxy-4' -mercaptodiphenylsulfone, 2- (2-mercaptoethylthio) ethanol, dihydroxyethyl sulfide mono (3-mercaptopropionate), dimercaptoethane mono (salicylate), hydroxyethylthiomethyl-tris (mercaptoethylthio) methane.

Among the polymerizable compounds (B1) to (B4), those which are suitably used include a radical polymerizable compound (B1) and a urethane polymerizable compound (B3) in the kneading method, a radical polymerizable compound (B1) in the laminating method, and a urethane polymerizable compound (B3) in the bonding method.

(C) A polymerization curing accelerator;

in the photochromic composition of the present invention, various polymerization/curing accelerators can be used to rapidly accelerate the polymerization/curing of the polymerizable compound (B) and the photochromic polyrotaxane compound (a) depending on the types of the polymerizable functional groups introduced into the side chains thereof.

For example, in the case of using the radical polymerizable compound (B1) and in the case of introducing a radical polymerizable functional group into the side chain of the photochromic polyrotaxane compound (a), a polymerization initiator (C1) is used as the polymerization curing accelerator.

In addition, when a curable composition containing an epoxy polymerizable compound (B2), an episulfide polymerizable compound (B4-1) and a thietane based polymerizable compound (B4-2) is used, or when an epoxy group, an episulfide group or a thietane group is introduced as a polymerizable functional group into a side chain of the photochromic polyrotaxane compound (A), an epoxy curing agent (C2-1) and a cationic polymerization catalyst (C2-2) for ring-opening polymerization of the epoxy group are used as a polymerization curing accelerator.

Further, when the urethane polymerizable compound (B3) and the other polymerizable compound (B4) are used, an OH group, an SH group, or an NH group is introduced into the side chain of the photochromic polyrotaxane compound (A)₂When an NCO group or an NCS group is used as the polymerizable functional group, a urethane reaction catalyst (C3-1) or a condensing agent (C3-2) is used as the polymerization/curing accelerator.

(C1) Polymerization initiator

The polymerization initiator includes thermal polymerization initiators and photopolymerization initiators, and specific examples thereof are as follows.

Examples of the thermal polymerization initiator include benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide, and acetyl peroxide, which are diacyl peroxides.

Examples of the peroxy ester include t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyneodecanoate, cumyl peroxyneodecanoate and t-butyl peroxybenzoate.

Examples of the percarbonate include diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate.

Examples of the azo compound include azobisisobutyronitrile and 2, 2' -azobis (2, 4-dimethylvaleronitrile).

Examples of the photopolymerization initiator include acetophenone compounds such as 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, and 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one.

Examples of the α -dicarbonyl compound include 1, 2-diphenylethanedione and methylphenylglyoxylic acid ester.

Examples of the acylphosphine oxide-based compound include 2, 6-dimethylbenzoyldiphenylphosphine oxide, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, methyl 2,4, 6-trimethylbenzoyldiphenylphosphinate, 2, 6-dichlorobenzoyldiphenylphosphine oxide, 2, 6-dimethoxybenzoyldiphenylphosphine oxide, and phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide.

When a photopolymerization initiator is used, a known polymerization curing accelerator such as a tertiary amine may be used in combination.

(C2-1) epoxy curing agent

Examples of the amine compound and its salt include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1, 8-diaza-bicyclo (5,4,0) -7-undecene, trimethylamine, benzyldimethylamine, triethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, and 2- (dimethylaminomethyl) phenol.

Examples of the quaternary ammonium salt include tetramethylammonium chloride, benzyltrimethylammonium bromide, and tetrabutylammonium bromide.

Examples of the organophosphinic compound include tetra-n-butylphosphonium benzotriazole salt and tetra-n-butylphosphonium O, O-diethyldithiophosphate.

Examples of the metal carboxylate include chromium (III) tricarboxylate and tin octylate.

Examples of the acetylacetone chelate compound include chromium acetylacetonate.

(C2-2) cationic polymerization catalyst

Examples of the Lewis acid catalyst include BF₃Amine Complex, PF₅、BF₃、AsF₅、SbF₅And the like.

Examples of the thermosetting cationic polymerization catalyst include phosphonium salts, quaternary ammonium salts, sulfonium salts, benzylammonium salts, benzylpyridinium salts, benzylsulfonium salts, hydrazonium salts, carboxylic acid esters, sulfonic acid esters, and amineimides.

Examples of the ultraviolet-curable cationic polymerization catalyst include diaryliodonium hexafluorophosphate and bis (dodecylphenyl) iodonium hexafluoroantimonate.

(C3-1) reaction catalyst for Carbamates

The reaction catalyst is used for the formation of poly (thio) urethane linkages based on the reaction of polyiso (thio) cyanates with polyols or polythiols.

As an example thereof, the following may be exemplified. There may be mentioned triethylenediamine, hexamethylenetetramine, N, N-dimethyloctylamine, N, N, N ', N ' -tetramethyl-1, 6-diaminohexane, 4 ' -trimethylenebis (1-methylpiperidine), 1, 8-diazabicyclo- (5,4,0) -7-undecene, dimethyltin dichloride, dimethyltin bis (isooctylmercaptoacetate), dibutyltin dichloride, dibutyltin dilaurate, tin dibutylmaleate, dibutyltin maleate polymer, dibutyltin ditricolate, dibutyltin bis (dodecylmercaptide), dibutyltin bis (isooctylmercaptoacetate), dioctyltin dichloride, tin dioctylmaleate polymer, dioctyltin bis (butylmaleate), dioctyltin (butylmaleate), dimethyloctyltin (dimethyloctylmercaptide), dimethyltin (dimethyltin oxide), dimethyltin, Dioctyltin dilaurate, dioctyltin ditricinoleate, dioctyltin dioleate, dioctyltin di (6-hydroxy) hexanoate, dioctyltin bis (isooctylmercaptoacetate), didodecyltin ditricinoleate. Examples of the metal salt include copper oleate, copper acetylacetonate, iron naphthenate, iron lactate, iron citrate, iron gluconate, potassium octylate, and 2-ethylhexyl titanate.

(C3-2) condensing agent

Examples of the inorganic acid include hydrogen chloride, hydrogen bromide, sulfuric acid, and phosphoric acid.

Examples of the organic acid include p-toluenesulfonic acid and camphorsulfonic acid.

Examples of the acidic ion exchange resin include resins obtained by introducing a sulfonic acid group into a styrene-divinylbenzene copolymer.

Examples of the carbodiimide include dicyclohexylcarbodiimide and 1-ethyl-3- (3-dimethylaminopyrrolyl) -carbodiimide.

(compounding ratio of polymerization curing accelerator (C))

The polymerization curing accelerator (C) may be used alone in 1 kind or in combination of 2 or more kinds, and the amount thereof may be a catalytic amount, and may be, 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 polymerizable compound (B).

Other compounding ingredients in the curable composition;

the curable composition of the present invention may contain, as necessary, various blending agents known per se, for example: a release agent, an ultraviolet absorber, an infrared absorber, an ultraviolet stabilizer, an antioxidant, an anti-coloring agent, an antistatic agent, various stabilizers such as a fluorescent dye, a pigment and a perfume, additives, a solvent, a leveling agent, and furthermore, mercaptans such as t-dodecyl mercaptan are used as the polymerization regulator.

Among them, the use of an ultraviolet stabilizer is preferable because the durability of the photochromic portion can be improved. As such an ultraviolet stabilizer, a hindered amine light stabilizer, a hindered phenol antioxidant, a sulfur antioxidant, and the like are known. Particularly suitable uv stabilizers are as follows. Bis (1,2,2,6, 6-pentamethyl-4-piperidinyl) sebacate, ADK STAB LA-52, LA-57, LA-62, LA-63, LA-67, LA-77, LA-82, LA-87, 2, 6-di-tert-butyl-4-methyl-phenol, ethylene bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate ], IRGANOX 1010, 1035, 1075, 1098, 1135, 1141, 1222, 1330, 1425, 1520, 259, 3114, 3790, 5057, 565, manufactured by adaka corporation.

The amount of such an ultraviolet stabilizer is not particularly limited as long as the effect of the present invention is not impaired, and is usually in the range of 0.001 to 10 parts by mass, particularly 0.01 to 1 part by mass, based on 100 parts by mass of the photochromic polyrotaxane compound. Particularly, when a hindered amine light stabilizer is used, the effect of improving durability varies depending on the type of photochromic site, and as a result, the amount of the hindered amine light stabilizer can be adjusted to 0.5 to 30 moles, more preferably 1 to 20 moles, and still more preferably 2 to 15 moles per 1 mole of the photochromic site so as not to cause color variation in the developed color tone after adjustment.

In addition, photochromic compounds other than the photochromic polyrotaxane compound (a) may be added within a range not to impair the effects of the present invention.

< composition suitable for curable composition >

The photochromic polyrotaxane compound of the present invention can be obtained as a photochromic cured product by homopolymerization particularly when it has a polymerizable group.

In addition, the photochromic polyrotaxane compound (a) and the polymerizable compound (B) may be used in combination.

In any case, in order to obtain a sufficient color development concentration, the mass of the photochromic moiety is preferably 0.001 to 10% by mass when the total amount of the curable composition is 100% by mass.

The mass of the photochromic portion varies depending on the mode of expression of the photochromic property, and for example, when the photochromic property is expressed by a kneading method, it is preferably 0.001 to 2 mass%, particularly 0.001 to 1 mass%, and when the photochromic property is expressed by a laminating method or a bonding method, it is preferably 0.1 to 10 mass%, particularly 1 to 7 mass%.

Further, the blending ratio of the photochromic polyrotaxane compound (a) and the polymerizable compound (B) differs depending on the number of side chains having a photochromic site included in one molecule of the photochromic polyrotaxane.

When the number of side chains of photochromic portion contained in one molecule is 1 to 30, it is preferable to blend the photochromic polyrotaxane compound (a) at a ratio of 0.5 to 80% by mass, blend the polymerizable compound (B) at a ratio of 20 to 99.5% by mass, when the number of side chains of photochromic portion contained in one molecule is 30 to 300, it is preferable to blend the photochromic polyrotaxane compound (a) at a ratio of 0.1 to 50% by mass, blend the polymerizable compound (B) at a ratio of 50 to 99.9% by mass, and blend the photochromic polyrotaxane compound (a) at a ratio of 0.01 to 20% by mass, and blend the polymerizable compound (B) at a ratio of 80 to 99.99% by mass when the number of side chains of photochromic portion contained in one molecule is 300 or more.

In the present invention, the photochromic property-improving effect of the photochromic polyrotaxane compound (a) can be exhibited to the maximum extent, and can be determined appropriately according to the type of the photochromic polyrotaxane compound (a) and the type of the polymerizable compound (B) to be used.

When the polymerizable functional group introduced into the side chain of the photochromic polyrotaxane compound (a) is an acryloyl group and/or a methacryloyl group, it is preferable to use a radical polymerizable compound (B1) in combination as the polymerizable compound (B).

In this case, the compounding ratio of the component (B1) is preferably 80 to 100 mass% in total of the components (B1-1), (B1-2), (B1-3) and (B1-4), taking into consideration the hardness, mechanical properties and photochromic properties such as color development concentration and fading speed of the resulting photochromic cured product, and the components (B1-1), (B1-2), (B1-3) and (B1-4) are preferably 0 to 20 mass% in total, when the total amount of the components (B1-1), (B1-2) and (B1-3) is 100 mass%. Further, when the total amount of the component (B1-1) is 100% by mass, it is preferable that the component (B1-1-1) is 30 to 80% by mass, the component (B1-1-2) is 10 to 50% by mass, and the component (B1-1-3) is 0 to 20% by mass.

When the polymerizable functional group introduced into the side chain of the photochromic polyrotaxane compound (A) is an OH group and/or an SH group, it is preferable to use a combination of the polyol (B3-1), the polythiol (B3-2), the polyamine (B3-3), the polyisocyanate (B3-4) and the polyisothiocyanate (B3-5) so as to form a urethane bond, a thiourethane bond, a urea bond or a thiourea bond (particularly, a urethane bond or a thiourethane bond).

In the above case, the amount of SH groups and OH groups may be in the range of 0.8 to 1.2 mol, particularly 0.85 to 1.15 mol, and most preferably 0.9 to 1.1 mol, based on 1 mol of NCO groups or NCS groups.

< use of curable composition >

In the case where a chain having a polymerizable group is introduced into the photochromic polyrotaxane compound (a), the curable composition of the present invention may be used only for the photochromic polyrotaxane compound (a). For example, a photochromic sheet (photochromic cured product) can be produced by sheet molding using the photochromic polyrotaxane compound (a).

Further, photochromic properties can be exhibited by preparing a coating solution by dispersing or dissolving the curable composition in an organic solvent, applying the coating solution to a transparent optical sheet or optical film, and drying the coating solution to form a photochromic coating layer (photochromic cured product).

However, it is generally preferable that the curable composition of the present invention contains the polymerizable compound (B) and the polymerization curing accelerator (C) in addition to the photochromic polyrotaxane compound (a), and for example, it is preferable that each component is melt-kneaded to prepare a photochromic composition, and the photochromic composition is polymerized and cured to prepare a photochromic cured product, and photochromic properties are expressed by the cured product. Although an example of the case where a curable composition containing a polymerizable compound (B) is used as a photochromic cured product will be described below, the same method as that for curing the curable composition may be employed in the case where only the photochromic polyrotaxane compound (a) having a chain having a polymerizable group introduced thereinto is used. The photochromic polyrotaxane compound (a) contained in the curable composition may or may not have a polymerizable group.

The polymerization curing for producing the photochromic cured product can be carried out by radical polymerization, ring-opening polymerization, anion polymerization or polycondensation by irradiation with active energy rays such as ultraviolet rays, α rays, β rays or γ rays, heat or a combination of both, that is, by using an appropriate polymerization means depending on the kinds of the polymerizable compound (B) and the polymerization curing accelerator (C) and the form of the photochromic cured product to be formed.

When the curable composition of the present invention containing the polymerizable compound (B) and the like is thermally polymerized, the properties of the obtained photochromic cured product are affected particularly by the temperature. The temperature conditions are not limited to a specific one because they are affected by the type and amount of the thermal polymerization initiator and the type of the polymerizable compound, but it is generally preferable to initiate polymerization at a relatively low temperature and gradually increase the temperature. The polymerization time may vary depending on various factors, as with the temperature, and it is preferable to determine the optimum time for these conditions in advance, but it is generally preferable to select the conditions so that the polymerization is completed within 2 to 48 hours. In order to obtain a photochromic laminate sheet, polymerization is carried out at a temperature at which the reaction of the polymerizable functional groups proceeds, and in this case, it is preferable to determine a temperature and a time optimal for obtaining a target molecular weight.

When the curable composition of the present invention is photopolymerized, the UV intensity particularly affects the properties of the photochromic cured product to be obtained under the polymerization conditions. The illumination condition is not limited to a general one because it is affected by the kind and amount of the photopolymerization initiator and the kind of the polymerizable monomer, but it is generally preferable to select conditions such that 50 to 500mW/cm is irradiated at a wavelength of 365nm for a period of 0.5 to 5 minutes²UV light of (1).

When photochromic properties are expressed by the kneading method using polymerization curing, the curable composition is injected between glass molds held by an elastic spacer or a spacer, and depending on the types of the polymerizable compound (B) and the polymerization curing accelerator, a photochromic cured product molded into the form of an optical material such as a lens can be obtained by casting polymerization by heating in an air oven or irradiation with an active energy ray such as ultraviolet rays.

According to the above method, a spectacle lens or the like having photochromic properties can be obtained as it is.

When photochromic properties are expressed by a lamination method, a curable composition is suitably dissolved in an organic solvent to prepare a coating liquid, the coating liquid is applied to the surface of an optical substrate such as a lens substrate by spin coating, dipping or the like, dried, the organic solvent is removed, and then polymerization curing is performed by UV irradiation in an inert gas such as nitrogen gas, heating or the like, thereby forming a photochromic layer composed of a photochromic cured product on the surface of the optical substrate (coating method).

Further, a photochromic layer formed of a photochromic cured product may be formed on the surface of an optical base material by cast polymerization in a mold (cast polymerization method) in which an optical substrate such as a lens base material is arranged to face a glass mold so as to form a predetermined void, and a curable composition is injected into the void, and in this state, polymerization curing is performed by UV irradiation, heating, or the like.

When the photochromic layer is formed on the surface of the optical substrate by the above-described lamination method (coating method and cast polymerization method), the adhesion between the photochromic layer and the optical substrate can be improved by previously subjecting the surface of the optical substrate to chemical treatment with an alkali solution, an acid solution, or the like, physical treatment with corona discharge, plasma discharge, polishing, or the like. Of course, a transparent adhesive resin layer may be provided on the surface of the optical base material in advance.

When photochromic properties are expressed by the bonding method, a photochromic sheet is produced by sheet molding using a curable composition, and the sheet is sandwiched between 2 transparent sheets (optical sheets) and subjected to polymerization and curing, whereby a photochromic laminate having a photochromic layer as a bonding layer can be obtained.

In the above case, means such as coating using a coating solution in which a curable composition is dissolved in an organic solvent may be employed for producing the photochromic sheet.

The photochromic laminate thus produced is mounted in a mold, for example, and then injection-molded with a thermoplastic resin (for example, polycarbonate) for an optical substrate such as a lens, thereby obtaining an optical substrate such as a lens having a predetermined shape to which photochromic properties are imparted. The photochromic laminate may be bonded to the surface of the optical substrate with an adhesive or the like, whereby a photochromic lens can be obtained.

In the case of producing the photochromic laminate as described above, it is preferable to use a urethane or urea-based polymerizable compound (B3), particularly a urethane-based polymerizable compound, as the polymerizable compound (B) and adjust the composition so as to form polyurethane, particularly in view of high adhesion to the optical base material.

The curable composition of the present invention can exhibit excellent photochromic properties such as color development density and fading speed, and can be effectively used for producing an optical substrate, for example, a photochromic lens, to which photochromic properties are imparted without lowering the characteristics such as mechanical strength.

Further, the photochromic layer and the photochromic cured product formed from the curable composition of the present invention may be applied, depending on the use thereof, to: dyeing with a dye such as a disperse dye; a hard coating film is produced by using a silane coupling agent and a hard coating agent containing a sol of silicon, zirconium, antimony, aluminum, tin, tungsten, or the like as a main component; based on SiO₂、TiO₂、ZrO₂Forming a thin film of metal oxide by vapor deposition; and post-processing such as antireflection treatment and antistatic treatment by coating an organic polymer on a film.