JP6963514B2 - A (meth) acrylate compound and a photochromic curable composition containing the (meth) acrylate compound. - Google Patents

Description

The present invention relates to a novel (meth) acrylate compound and a novel curable composition containing the (meta) acrylate compound and useful in producing an optical article having photochromic properties.

Photochromic eyeglasses are ordinary eyeglasses that are transparent and fade in the outdoors where the lens is rapidly colored and functions as sunglasses when exposed to light including ultraviolet rays such as sunlight, and indoors where there is no such light irradiation. These are glasses that function as. In recent years, the demand for photochromic eyeglasses has increased.

As for photochromic spectacle lenses, those made of plastic are particularly preferred from the viewpoint of light weight and safety. The addition of photochromic properties to such a plastic lens is generally performed by combining an organic photochromic compound with a polymerizable monomer or a lens.

As a compounding method, a method of directly obtaining a photochromic lens by dissolving a photochromic compound in a polymerizable monomer and polymerizing the compound (hereinafter referred to as a kneading method) is known (Patent Document 1). reference).

In addition to this, a method of providing a coat layer having photochromic properties (hereinafter, also referred to as a photochromic coat layer) on the surface of a plastic lens by using a coating agent containing a photochromic compound (hereinafter, also referred to as a photochromic coating agent) (hereinafter, also referred to as a photochromic coat layer). , A coating method) is also known (see Patent Document 2).

In general, in a plastic lens imparted with the above-mentioned photochromic properties, the photochromic compound is gradually decomposed by light when used for a long period of time. Therefore, there is a problem in terms of durability that the color density is lowered and the lens is colored yellow. In order to prevent this, a method of adding a light stabilizer typified by a hindered amine compound is taken.

However, the most common hindered amine compound having a 2,2,6,6-tetramethyl-4-piperidyl group represented by a sebacic acid (1,2,2,6,6-pentamethyl-4-piperidyl) diester. When (TINUVIN765 manufactured by BASF) was used, it was found that there is room for improvement in the following points when sufficient durability is provided, although it depends on the blending amount. That is, when a sufficient amount of the hindered amine compound is used, there is a problem that the hindered amine compound gradually bleeds out from the lens base material or the coating layer, and the surface of the lens base material or the coating layer becomes turbid. Further, particularly in the kneading method, although it depends on the blending amount of the hindered amine compound, the phenomenon that the obtained lens is easily peeled off from the glass mold (mold) is likely to occur in the process of polymerization curing of the lens, and the lens surface is exposed. There was also a problem that the lens was defective due to polymerization inhibition.

In order to solve the above problems, Patent Document 1 has a 2,2,6,6-tetramethyl-4-piperidyl group and a (meth) acrylic group in the molecule, both of which are directly ester-bonded. It has also been proposed to use a (meth) acrylate compound having a 2,2,6,6-tetramethyl-4-piperidyl group (for example, Adecastab LA-87 manufactured by ADEKA Co., Ltd.). Since the (meth) acrylate compound is chemically bonded to the cured product, the above-mentioned bleed-out problem does not occur.

However, according to the studies by the present inventors, it has been found that the effect of improving the durability that should be originally exhibited is not sufficiently exhibited, and that the photochromic property is lowered, particularly the fading speed is slowed down.

International Publication No. 2001/5854 Pamphlet International Publication No. 2003/11967 Pamphlet International Publication No. 2013/058218 Pamphlet

The present inventors have proposed the following compounds as compounds capable of further improving durability in order to further improve the invention described in Patent Document 1 (see Patent Document 3). Specifically, Patent Document 3 has a 2,2,6,6-tetramethyl-4-piperidyl skeleton and a (meth) acrylic group in the molecule, and both groups are designated as specific divalent groups. It has been proposed to use a (meth) acrylate compound having a bound 2,2,6,6-tetramethyl-4-piperidyl skeleton.

When the (meth) acrylate compound having a specific divalent group of Patent Document 3 is used, the durability of the obtained lens coating layer is higher than that when the compound described in Patent Document 1 is used. Can be improved.

However, in recent years, the characteristics of the lens coating layer (for example, a cured product having a high hardness) and the photochromic property have been exhibited while maintaining a higher level of durability than the compound described in Patent Document 3. It has been desired to develop a compound capable of producing a compound.

Therefore, an object of the present invention is to reduce the problem of turbidity of the lens surface due to bleed-out and peeling in the manufacturing process due to the hindered amine compound, and further, the photochromic having excellent durability and high photochromic property and surface hardness. It is an object of the present invention to provide a compound capable of producing a lens and a photochromic curable composition.

The present inventors have conducted diligent studies in order to solve the above problems. Specifically, various sites for improving the durability of the 2,2,6,6-tetramethyl-4-piperidyl skeleton and the bonding sites with the (meth) acrylic group to be polymerized and cured were examined. As a result, a site that improves the durability of the 2,2,6,6-tetramethyl-4-piperidyl skeleton and a (meth) acrylic group (in the present invention, the (meth) acrylic group is a methacryl group and / Alternatively, it refers to an acrylic group), and found that a compound bonded with an alkylene glycol chain and a bonding portion having an amide bond can solve the above-mentioned problems, and has completed the present invention.

That is, the present invention
(1) The following formula (1)

[During the ceremony,
R ¹ is a hydrogen atom or a methyl group,
R ² is a hydrogen atom or a methyl group.
R ³ is a linear or branched alkylene group having 1 to 5 carbon atoms.
a is a number from 2 to 20 on average,
X is the following formula (2)

（式中、
Ｒ^４は、炭素数１〜５の直鎖状、又は分岐状のアルキレン基であり、
ｂは、平均値で０〜２０の数である。）で示される基であり、
ただし、ａ＋ｂは、平均値で２〜２０の数である。］
で示されるヒンダードアミン（メタ）アクリレート化合物（以下、単に（Ａ）成分とする場合もある。）である。

(During the ceremony,
R ⁴ is a linear or branched alkylene group having 1 to 5 carbon atoms,
b is a number from 0 to 20 on average. ) Is the group
However, a + b is a number of 2 to 20 on average. ]
It is a hindered amine (meth) acrylate compound represented by (hereinafter, may be simply referred to as a component (A)).

The present invention can also take the following aspects.

(2) A (meth) acrylate compound (B) other than the hindered amine (meth) acrylate compound (A) of the above (1) and the hindered amine (meth) acrylate compound (A) (hereinafter, may be simply a component (B)). A photochromic curable composition containing the photochromic compound (C) (hereinafter, may be simply referred to as the component (C)).

(3) 0.01 to 20 parts by mass of the hindered amine (meth) acrylate compound (A), 100 parts by mass of the (meth) acrylate compound (B), and 0.01 to 20 parts by mass of the photochromic compound (C). The photochromic curable composition according to (2) above, which contains parts by mass.

(4) The (meth) acrylate compound (B) has the following formula (3).

(During the ceremony,
R ⁵ and R ⁶ are independently hydrogen atoms or methyl groups, respectively.
R ⁷ is a 3- to hexavalent organic group having 1 to 10 carbon atoms.
c is a number from 0 to 10 on average,
d is an integer of 3 to 6. )
A trifunctional or higher functional (meth) acrylate compound (B1) represented by (hereinafter, may be simply referred to as a (B1) component),
The following formula (4)

(During the ceremony,
R ⁸ and R ⁹ are independently hydrogen atoms or methyl groups, respectively.
e and f are each independently an integer of 0 or more, and e + f is an integer of 2 or more on average. )
Glycol-based (meth) acrylate compound (B2) represented by (hereinafter, may be simply referred to as (B2) component), and
Other (meth) acrylate compounds (B3) other than the trifunctional or higher functional (meth) acrylate compound (B1) represented by the formula (3) and the glycol-based (meth) acrylate compound (B2) represented by the formula (4). ) (Hereinafter, it may be simply used as the component (B3)). The photochromic curable composition according to (2) or (3) above.

(5) The (meth) acrylate compound (B) is 100 to 10,000 mass by mass of the glycol-based (meth) acrylate compound (B2) with respect to 100 parts by mass of the trifunctional or higher functional (meth) acrylate compound (B1). The photochromic curable composition of (4), which comprises 30 to 300 parts by mass of the portion and the other (meth) acrylate compound (B3).

(6) A coating agent containing the photochromic curable composition according to any one of (2) to (5) above.

(7) An optical material having a photochromic coat layer obtained by curing the coating agent (6) above on at least one surface of an optical base material.

(8) A photochromic cured product obtained by curing the photochromic curable composition according to any one of (2) to (5) above.

By using the hindered amine (meth) acrylate compound of the present invention, the obtained cured product exhibits excellent effects. That is, even if the hindered amine (meth) acrylate compound is used alone, by having an alkylene glycol chain and a bonding portion having an amide bond, a 2,2,6,6-tetramethyl-4-piperidyl group or the like can be obtained. The durable site is fully capable of exercising in the cured body. Therefore, it is considered that the durability can be further improved because the generated radicals and the like can be efficiently captured. Further, it is considered that by having an alkylene glycol chain and a bonding portion having an amide bond, the molecules become dense due to hydrogen bonds and the like, and the hardness of the cured product can be improved.

Since the hindered amine (meth) acrylate compound of the present invention can exert the above-mentioned effect, it can exert a particularly excellent effect when used in combination with a photochromic compound and / or other radically polymerizable monomer. can. For example, the photochromic curable composition containing the hindered amine (meth) acrylate compound and the photochromic compound has a moiety such as a 2,2,6,6-tetramethyl-4-piperidyl group in the cured product obtained from the composition. Is immobilized in the cured product by chemical bonding, so that bleed-out can be suppressed. Therefore, turbidity on the surface of the lens base material or the coating layer can be suppressed. In addition, it is possible to reduce the lens from peeling off from the glass mold during polymerization curing. Furthermore, since it has an alkylene glycol chain and a bond having an amide bond as compared with the conventional (meth) acrylate compound, the obtained cured product was efficiently generated without inhibiting the motility of the photochromic compound. It is thought that radicals and the like can be captured. Furthermore, it is considered that the characteristics of the cured product can be further improved due to the influence of hydrogen bonds and the like.

As a result, by using the (meth) acrylate compound of the present invention, it has the characteristics of the lens coating layer (for example, a cured product having high hardness) and photochromic properties while maintaining a higher degree of durability. A cured product can be obtained.

The present invention relates to a novel hindered amine (meth) acrylate compound (component (A)). The present invention also relates to a radically polymerizable composition (I) containing the component (A), a photochromic curable composition containing the photochromic compound (II), and the like. Hereinafter, the description will be given step by step.

<Ingredient (A)>
In the present invention, a hindered amine moiety such as a 2,2,6,6-tetramethyl-4-piperidyl group and a (meth) acrylic group are bonded to each other in the molecule by a bond having an amide bond with an alkylene glycol chain (). Meta) It is an acrylate compound.

Specifically, the following equation (1)

[During the ceremony,
R ¹ is a hydrogen atom or a methyl group,
R ² is a hydrogen atom or a methyl group.
R ³ is a linear or branched alkylene group having 1 to 5 carbon atoms.
a is a number of 1 to 20 on average,
X is the following formula (2)

（式中、
Ｒ^４は、炭素数１〜５の直鎖状、又は分岐状のアルキレン基であり、
ｂは、平均値で０〜２０の数である。）で示される基であり、
ただし、ａ＋ｂは、平均値で１〜２０の数である。］
で示されるヒンダードアミン（メタ）アクリレート化合物である。

(During the ceremony,
R ⁴ is a linear or branched alkylene group having 1 to 5 carbon atoms,
b is a number from 0 to 20 on average. ) Is the group
However, a + b is a number of 1 to 20 on average. ]
It is a hindered amine (meth) acrylate compound represented by.

It is considered that the component (A) exerts an excellent effect by having an alkylene glycol chain and an amide bond.

In the above formula (1), R ¹ is a hydrogen atom or a methyl group, and a methyl group is particularly preferable because it has excellent compatibility with the component (B) described later and further high durability can be obtained.

In the above formula (1), R ² is a hydrogen atom or a methyl group, and a methyl group is preferable from the viewpoint of hardness of the photochromic cured product.

In the formula (1), R ³ is a linear or branched alkylene group having 1 to 5 carbon atoms, and is a methylene group, an ethylene group, an n-propylene group, an i-propylene group, or an n-butylene group. , N-pentylene group and the like. Among them, a methylene group, an ethylene group, an n-propylene group, and an i-propylene group are preferable in that particularly excellent durability can be obtained.

b indicates a repeating unit of (−OR ³⁻ ), and has an average value of 1 to 20. That is, the component (A) may ^{be a mixture of (-OR 3-} ) having different repeating units, and a is an average value. As the number of a increases, the number of moles of the 2,2,6,6-tetramethylpiperidine skeleton contained in the unit mass of the (meth) acrylate compound decreases. Therefore, in consideration of obtaining a sufficient durability effect, a is preferably an average value of 1 to 15, more preferably an average value of 1 to 10, and most preferably a is 1 to 1. This is the case of 5.

When a plurality of mixtures having different numbers of a are used as the component (A), the average value of a in the mixture may be a positive number of 1 to 20. Therefore, when a mixture is used, the average value of a is preferably a positive number of 1 to 10, and more preferably a positive number of 1 to 5. However, when a mixture is used, it is preferable that a in each of the (meth) acrylate compounds satisfies the range of 1 to 20.

Further, in the present invention, the average value of a + b is 1 to 20. When the average value satisfies 1 to 20, the lens coating layer has characteristics (for example, a cured product having a high hardness) and photochromic properties while maintaining durability, and the component (B) described later is obtained. Since it has excellent compatibility with, it exerts an excellent effect. Among them, the average value of a + b is preferably 1 to 18, more preferably 1 to 15, and further preferably 1 to 10. In particular, it is preferable that b = 0 and the average value of a is 1 to 5 because a sufficient durability effect can be obtained.

<Suitable combination of groups and suitable component (A)>
In the present invention, the component (A) is
R ¹ is a methyl group, R ² is a hydrogen atom or a methyl group, R ³ is a methylene group, an ethylene group, an n-propylene group or an i-propylene group, X is an oxygen atom, or R ⁴ is a methylene group or an ethylene group. , N-propylene group or i-propylene group is preferably used according to the above formula (2).

Specific examples of the suitable component (A) include the following compounds.

1,2,2,6,6-pentamethyl-4-piperidyl-urethane ethoxyacrylate,
1,2,2,6,6-pentamethyl-4-piperidyl-urethaneethoxymethacrylate,
1,2,2,6,6-pentamethyl-4-piperidyl-urethane diethoxyacrylate,
1,2,2,6,6-pentamethyl-4-piperidyl-urethanediethoxymethacrylate,
1,2,2,6,6-pentamethyl-4-piperidyl-urethaneethoxy (average value of a 4) acrylate,
1,2,2,6,6-pentamethyl-4-piperidyl-urethaneethoxy (average value 4 of a) methacrylate 1,2,2,6,6-pentamethyl-4-piperidyl-ethoxyurethaneethoxyacrylate,
1,2,2,6,6-pentamethyl-4-piperidyl-ethoxyurethaneethoxymethacrylate,
1,2,2,6,6-pentamethyl-4-piperidyl-i-propoxyurethane ethoxyacrylate,
1,2,2,6,6-pentamethyl-4-piperidyl-i-propoxyurethaneethoxymethacrylate,
1,2,2,6,6-pentamethyl-4-piperidyl-diethoxyurethaneethoxyacrylate,
1,2,2,6,6-pentamethyl-4-piperidyl-diethoxyurethaneethoxymethacrylate,
1,2,2,6,6-pentamethyl-4-piperidyl-dii-propoxyurethane ethoxyacrylate,
1,2,2,6,6-pentamethyl-4-piperidyl-dii-propoxyurethaneethoxymethacrylate,
1,2,2,6,6-pentamethyl-4-piperidyl-ethoxy (average value of b 4) urethane ethoxyacrylate,
1,2,2,6,6-pentamethyl-4-piperidyl-ethoxy (average value of b 4) urethane ethoxymethacrylate,
1,2,2,6,6-pentamethyl-4-piperidyl-i-propoxy (average value of b 4) urethane ethoxyacrylate,
1,2,2,6,6-pentamethyl-4-piperidyl-i-propoxy (average value of b 4) urethane ethoxymethacrylate,
1,2,2,6,6-pentamethyl-4-piperidyl-ethoxy (average value of b 8) urethane ethoxyacrylate,
1,2,2,6,6-pentamethyl-4-piperidyl-ethoxy (average value of b 8) urethane ethoxymethacrylate,
1,2,2,6,6-pentamethyl-4-piperidyl-i-propoxy (average value of b 88) urethane ethoxyacrylate,
1,2,2,6,6-pentamethyl-4-piperidyl-i-propoxy (average value of b 8) urethane ethoxymethacrylate.

<Manufacturing method of component (A)>
The method for producing the component (A) is not particularly limited, and examples thereof include the following methods.

The following formula (5);

(During the ceremony,
^{R 2,} R 3, a has the same meaning as the groups described in the formula (1). )
By urethanizing the isocyanate compound represented by the formula (6) and the hindered amine compound represented by the following formula (6), the hindered amine (meth) acrylate compound (component (A)) represented by the formula (1) can be obtained. can.

(In the formula, R ¹ and X have the same meaning as the group described in the formula (1).)

The isocyanate compound represented by the formula (5) can be used without particular limitation, and a commercially available compound can also be used. In particular,
2-Isocyanatoethyl methacrylate (trade name: Calends MOI; manufactured by Showa Denko KK),
2- (2-Methylloyloxyethyloxy) ethyl isocyanate (trade name: Calends MOI-EG; manufactured by Showa Denko KK)
2-Isocyanatoethylacryllate (trade name: Calends AOI; manufactured by Showa Denko KK) can be mentioned.

Further, the hindered amine compound represented by the above formula (6) can also be used without particular limitation, and a commercially available compound or a known compound can be used.

The urethanization reaction is carried out, for example, in the presence of a tin catalyst such as dibutyl tin dilaurate, in a solvent-free or inert solvent, in a temperature range of about 23 to 150 ° C. The isocyanate compound represented by the formula (5) may be added dropwise to the hindered amine compound represented by the formula (6) to cause a reaction. Normally, it is preferable to stir for 1 to 48 hours for the reaction.

Examples of the inert solvent include dichloromethane, chloroform, acetone, methyl ethyl ketone, tetrahydrofuran, toluene, xylene and the like. Additives such as dibutylhydroxytoluene can also be used for the purpose of promoting the reaction and suppressing side reactions.

<Photochromic curable composition>
The component (A) of the present invention can also be used alone. Among them, the component (A) is a (meth) acrylate compound (B) (component (B)) other than the hindered amine (meth) acrylate compound (A) (component (A)), and a photochromic compound (C) ( An excellent effect is exhibited when the photochromic curable composition is combined with the component (C).

In the present invention, the photochromic curable composition contains the component (A), the component (B), and the component (C). The component (B) will be described.

<(Meta) acrylate compound (B) other than (component (B); component (A))>
In the present invention, a (meth) acrylate compound (B) other than the component (A) can also be used. The (meth) acrylate compound (B) (component (B)) other than the component (A) refers to a compound other than the component (A) and having a (meth) acrylic group in the molecule. The component (B) used in the photochromic curable composition of the present invention is not particularly limited as long as it is a compound other than the component (A) and has a (meth) acrylic group. Above all, in order for the cured product obtained from the photochromic curable composition to exert a more excellent effect, the component (B) contains the following components (B1), (B2), and (B3). Is preferable.

<(B1) component; trifunctional or higher functional (meth) acrylate compound (B1)>
The photochromic curable composition of the present invention has the following formula (3).

(During the ceremony,
R ⁵ and R ⁶ are independently hydrogen atoms or methyl groups, respectively.
R ⁷ is a 3- to hexavalent organic group having 1 to 10 carbon atoms.
c is a number from 0 to 10 on average,
d is an integer of 3 to 6. )
It is preferable to contain a trifunctional or higher functional (meth) acrylate compound (B1) (component (B1)) represented by (1).

In the above formula (3), R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group, and R ⁵ is preferably methyl in that it has excellent compatibility with other components (B). R ⁶ is preferably a methyl group.

R ⁷ is a 3- to 6-valent organic group having 1 to 10 carbon atoms, specifically, a 3- to 6-valent hydrocarbon group having 1 to 10 carbon atoms and a chain having 1 to 10 carbon atoms. Examples thereof include a 3- to 6-valent group containing an oxygen atom (for example, an organic group containing a 3- to 6-valent ester bond) and an organic group containing a 3- to 6-valent urethane bond.

c is a number of 0 to 10 on average, and is preferably 0 to 5 on average, more preferably 0 to 3 in terms of the hardness of the composition and compatibility with the other component (B). The component (B1) is usually obtained in the form of a mixture of molecules having different molecular weights. Therefore, c is shown as an average value.

d is an integer of 3 to 6, and is preferably 3 to 4 in terms of the hardness of the composition and compatibility with other components.

Examples of the (B1) component that can be preferably used include the following compounds.

Trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethanetrimethacrylate, trimethylolmethanetriacrylate, tetramethylolmethanetetramethacrylate, tetramethylolmethanetetraacrylate, trimethylolpropanetriethylene glycol trimethacrylate, trimethylolpropanetriethylene Glycoltriacrylate, ditrimethylolpropane tetramethacrylate, ditrimethylolpropane tetraacrylate, polyester oligomer having 4 (meth) acrylic groups, polyester oligomer having 6 (meth) acrylic groups, polyurethane having 4 (meth) acrylic groups A polyurethane oligomer having 6 oligomers and (meth) acrylic groups.

<(B2) component; trifunctional or higher functional (meth) acrylate compound (B2)>
The photochromic curable composition of the present invention has the following formula (4).

(During the ceremony,
R ⁸ and R ⁹ are independently hydrogen atoms or methyl groups, respectively.
e and f are each independently an integer of 0 or more, and e + f is an integer of 2 or more on average. ), It is preferable to contain the glycol-based (meth) acrylate compound (B2) (component (B2)).

In the above formula (4), R ⁸ and R ^{9 are independently hydrogen atoms or methyl groups, respectively, and R 8} is methyl in terms of compatibility with other components (B) and hardness of the cured product. A group is preferable, and R ⁹ is preferably a methyl group.

Further, e and f are independently integers of 0 or more, and e + f is an integer of 2 or more on average. The upper limit of the average value of e + f is not particularly limited, but is preferably an integer of 2 to 25. The component (B2) is usually obtained in the form of a mixture of molecules having different molecular weights. Therefore, e and f are shown as average values.

Examples of the (B2) component that can be preferably used include the following compounds.
Ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate (average chain length of ethylene glycol chain 9, average molecular weight 536), polyethylene glycol dimethacrylate (average of ethylene glycol chain) Chain length 14, average molecular weight 736), polyethylene glycol dimethacrylate (average chain length 23 of ethylene glycol chain, average molecular weight 1136), tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, polypropylene glycol dimethacrylate (average propylene glycol chain) Chain length 9, average molecular weight 662), ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate (average chain length of ethylene glycol chain 9, average molecular weight 508), polyethylene Glycol diacrylate (average chain length of ethylene glycol chain 14, average molecular weight 708), dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, polypropylene glycol diacrylate (average chain length of propylene glycol chain 7, Average molecular weight 536)), polypropylene glycol diacrylate (average chain length of propylene glycol chain 12, average molecular weight 808).

<(B3) component; (B) component, (B1) component, and (meta) acrylate compound other than (B2) component>
The photochromic curable composition of the present invention corresponds to the (meth) acrylate compound (B) (component (B)) other than the component (A), and is other than the component (B1) and the component (B2). , It is preferable to contain a (meth) acrylate compound (B3) (component (B3)) having a (meth) acrylic group in the molecule. As a matter of course, the component (B3) does not contain the component (A).

The component (B3) is not particularly limited, but is preferably the following component. (B3) A specific example of the component is shown.

<(B3-a) Compound represented by the following formula (7)>

During the ceremony
R ¹⁰ and R ¹¹ are hydrogen atoms or methyl groups, respectively, and
g is an average number of 1 to 20
A and A'may be the same or different from each other, and are linear or branched alkylene groups having 2 to 15 carbon atoms, respectively. When a plurality of A's are present, the plurality of A's are the same group. It may be a different group.

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

Examples of the compound represented by the above formula (7) that can be preferably used include the following polycarbonate diols.

Polycarbonate diol obtained by phosgenation of polyalkylene glycols such as trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, and nonamethylene glycol (those having a number average molecular weight of 500 to 2,000). ,
Mixtures of two or more polyalkylene glycols, such as trimethylene glycol and tetramethylene glycol, tetramethylene glycol and hexamethylene diglycol, pentamethylene glycol and hexamethylene glycol, tetramethylene glycol and octamethylene glycol. Mixture,
Polycarbonate diol (number average molecular weight 500-2,000) obtained by phosgenation of hexamethylene glycol and octamethylene glycol, etc.
Polycarbonate diol (number average molecular weight 500-2,000) obtained by phosgenation of 1-methyltrimethylene glycol.

<Component (B3-b); compound represented by the following formula (8)>

During the ceremony
R ¹² and R ¹³ are hydrogen atoms or methyl groups, respectively, and
R ¹⁴ and R ¹⁵ are hydrogen atoms or methyl groups, respectively, and
R ¹⁶ is a hydrogen atom or a halogen atom,
B is -O-, -S-,-(SO ₂ )-, -CO-, -CH _2- , -CH = CH-, -C (CH ₃ ) 2-, -C (CH ₃ ) (C) ₆ H ₅ )-
Is one of
h and i are integers of 1 or more, respectively, and h + i is an average value of 2 or more and 30 or less.

The polymerizable monomer represented by the above formula (8) is usually obtained in the form of a mixture of molecules having different molecular weights. Therefore, h and i are shown as average values.

Examples of the compound represented by the above formula (8) that can be preferably used include the following bisphenol A di (meth) acrylate.

2,2-Bis [4-methacryloyloxy-ethoxy) phenyl] propane (h + i = 2),
2,2-Bis [4-methacryloyloxy diethoxy) phenyl] propane (h + i = 4),
2,2-Bis [4-methacryloyloxy-polyethoxy) phenyl] propane (h + i = 7),
2,2-Bis (3,5-dibromo-4-methacryloyloxyethoxyphenyl) propane (h + i = 2),
2,2-Bis (4-methacryloyloxydipropoxyphenyl) propane (h + i = 4),
2,2-bis [4-acryloyloxy-diethoxy) phenyl] propane (h + i = 4),
2,2-bis [4-acryloyloxy-polyethoxy) phenyl] propane (h + i = 3),
2,2-bis [4-acryloyloxy-polyethoxy) phenyl] propane (h + i = 7),
2,2-Bis [4-methacryloylxi (polyethoxy) phenyl] propane (h + i = 10),
2,2-Bis [4-methacryloylxi (polyethoxy) phenyl] propane (h + i = 17),
2,2-Bis [4-methacryloylxi (polyethoxy) phenyl] propane (h + i = 30),
2,2-Bis [4-acryloylxy (polyethoxy) phenyl] propane (h + i = 10),
2,2-Bis [4-acryloylxy (polyethoxy) phenyl] propane (h + i = 20).

<Bifunctional (meth) acrylate with (B3-c) urethane bond>
Further, as the bifunctional (meth) acrylate compound, a bifunctional (meth) acrylate compound having a urethane bond in the molecule can also be preferably used. For example, known urethane (meth) acrylates can be used. The urethane (meth) acrylate can be roughly classified into those having an aromatic ring such as a benzene ring in its molecular structure and those having no aromatic ring. In the present invention, any of them can be used, but from the viewpoint of light resistance of the cured product, a non-yellowing type having no aromatic ring is preferable.

The urethane (meth) acrylate is a reaction in which a diisocyanate and a polyol are reacted to form a urethane prepolymer, which is further reacted with 2-hydroxyethyl (meth) acrylate or the like which may have an alkylene oxide chain. A urethane (meth) having a molecular weight of 400 or more and less than 20,000, which is a reaction mixture obtained by directly reacting the mixture or the diisocyanate with 2-hydroxyethyl (meth) acrylate which may have an alkylene oxide chain. ) Acrylate can be mentioned.

Examples of the diisocyanate used for producing the urethane prepolymer include hexamethylene diisocyanate, isophorone diisocyanate, lysine isocyanate, 2,2,4-trimethylhexamethylene diisocyanate, diisocyanate dimerate, isopropyridenebis-4-cyclohexylisocyanate, and dicyclohexylmethane. Examples thereof include diisocyanate, norbornene diisocyanate and methylcyclohexane diisocyanate.

Further, the polyol to be reacted with diisocyanate is roughly classified into a high molecular weight type and a low molecular weight type.

Among these, the high molecular weight polyols include ethylene oxide, propylene oxide, hexamethylene oxide and the like, polyalkylene glycol having a repeating unit of 2 to 4 carbon atoms, polyester diol such as polycaprolactone diol, polycarbonate diol, polybutadiene diol and the like. Can be mentioned.

Known low molecular weight polyols include, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, Examples thereof include 9-nonanediol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol.

<Polyfunctional (meth) acrylate monomer having (B3-d) urethane bond>
The component (B3-d) is obtained by reacting the polyisocyanate compound described in the component (B3-c) with a polyol compound, and is a compound having three or more (meth) acrylate groups in the molecule. .. As commercial products, U-4HA (molecular weight 596, functional group number 4), U-6HA (molecular weight 1,019, functional group number 6), U-6LPA (molecular weight 818, functional group number 6) manufactured by Shin-Nakamura Chemical Industry Co., Ltd. , U-15HA (molecular weight 2,300, number of functional groups 15)
Can be mentioned.

<Polyfunctional (meth) acrylate monomer having (B3-e) ester bond>
The component (B3-e) is a compound in which the end of the polyester compound is modified with a (meth) acrylate group. Various commercially available polyester (meth) acrylate compounds can be used depending on the molecular weight of the polyester compound as a raw material and the modification amount of the (meth) acrylate group. In particular,
Tetrafunctional polyester oligomer (molecular weight 2,500 to 3,500, Daicel UCB, EB80, etc.),
Bifunctional polyester oligomer (molecular weight 6,000 to 8,000, Daicel UCB, EB450, etc.),
Bifunctional polyester oligomer (molecular weight 45,000-55,000, Daicel UCB, EB1830, etc.),
Tetrafunctional polyester oligomer (especially Dai-ichi Kogyo Seiyaku Co., Ltd. with a molecular weight of 10,000, GX8488B, etc.)
And so on.

<(B3-f) polyrotaxane polyfunctional (meth) acrylate monomer>
In a polyrotaxane compound having a composite molecular structure consisting of an axial molecule and a plurality of cyclic molecules that encapsulate the axial molecule and having a side chain having an OH group introduced into the cyclic molecule, the OH of the side chain is introduced. The group is modified with a monomer having a (meth) acrylic group in an amount of 1 mol% or more and less than 100 mol%, and more than 0 mol% and 99 mol% or less of the OH group in the side chain is modified with a compound having no polymerizable group. A polyrotaxane monomer having a residual ratio of OH groups in the side chain of 0 mol% or more and 60 mol% or less can be used.

<(B3-g) monofunctional (meth) acrylate monomer>
Examples of the component (B3-g) include compounds represented by the following formula (9).

During the ceremony
R ¹⁷ is a hydrogen atom or a methyl group and
R ¹⁸ is a hydrogen atom, a methyldimethoxysilyl group, a trimethoxysilyl group, or a glycidyl group.
j is an integer from 0 to 10 and
k is an integer from 0 to 20.

Specific examples of the compound represented by the above formula (9) are as follows.
Methoxypolyethylene glycol methacrylate (especially average molecular weight 293),
Methoxypolyethylene glycol methacrylate (especially average molecular weight 468),
Methoxypolyethylene glycol acrylate (especially average molecular weight 218),
Methoxypolyethylene glycol acrylate, (especially average molecular weight 454),
Examples thereof include stearyl methacrylate, lauryl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, lauryl acrylate, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and glycidyl methacrylate.

As the above component (B3), a single component in each component can be used, or a plurality of types described above can be used. When a plurality of types are used, the reference mass of the component (B3) is the total amount of the components <(C) component; photochromic compound>.
Next, the photochromic compounds (C) (component (C)) preferably used in the present invention will be described.

In the photochromic curable composition of the present invention, known photochromic compounds such as chromene compounds, flugimid compounds, spirooxazine compounds, and spiropyran compounds can be used without any limitation. These may be used alone or in combination of two or more.

Examples of the chromium compound, flugimid compound, spirooxazine compound and spiropyran compound are described in JP-A-2-28154, JP-A-62-288830, WO94 / 22850 pamphlet, WO96 / 14596 pamphlet and the like. Examples include compounds that have been used.

In particular, as the chromene compound, other than those described in the above patent documents, chromene compounds having excellent photochromic properties are known, and such chromene compounds can be preferably used. Such chromene compounds are disclosed, for example, in the following literature. Japanese Patent Application Laid-Open No. 2001-031670, Japanese Patent Application Laid-Open No. 2001-011067, Japanese Patent Application Laid-Open No. 2001-011066, Japanese Patent Application Laid-Open No. 2000-347761, Japanese Patent Application Laid-Open No. 2000-327675, Japanese Patent Application Laid-Open No. 2000-256347, Japanese Patent Application Laid-Open No. 2000-229996, Kai 2000-229975, Japanese Patent Application Laid-Open No. 2000-229974, Japanese Patent Application Laid-Open No. 2000-229973, Japanese Patent Application Laid-Open No. 2000-229972, Japanese Patent Application Laid-Open No. 2000-219678, Japanese Patent Application Laid-Open No. 2000-219686, Japanese Patent Application Laid-Open No. 11-322739, Japanese Patent Application Laid-Open No. 11-286484, Japanese Patent Application Laid-Open No. 11-279171, Japanese Patent Application Laid-Open No. 09-218301, Japanese Patent Application Laid-Open No. 09-124645, Japanese Patent Application Laid-Open No. 08-295690, Japanese Patent Application Laid-Open No. 08-176139, Japanese Patent Application Laid-Open No. 08-157467, US Patent No. 5645767 No., US Pat. No. 5,658,501, US Pat. No. 5,961,892, U.S. Pat. Japanese Patent No. 4369754, Japanese Patent No. 4301621, Japanese Patent No. 4256985, WO2007 / 086532 Pamphlet, Japanese Patent Application Laid-Open No. 2009-120536, Japanese Patent Application Laid-Open No. 2009-67754, Japanese Patent Application Laid-Open No. 2009-67680, Japanese Patent Application Laid-Open No. 2009-57300, Japanese Patent No. 4195615, Japanese Patent No. 4158881, Japanese Patent No. 4157245, Japanese Patent No. 4157239, Japanese Patent No. 4157227, Japanese Patent No. 4118458, Kai 2008-74832, Japanese Patent 3982770, Japanese Patent 3801386, WO2005 / 028465 pamphlet, WO2003 / 042203 pamphlet, Japanese Patent Application Laid-Open No. 2005-289812, Japanese Patent Application Laid-Open No. 2005-289807, Japanese Patent Application Laid-Open No. 2005-2895- 112772, Japanese Patent No. 3522189, WO2002 / 090342, WO2002 / 090342, Japanese Patent No. 3471073, Japanese Patent Application Laid-Open No. 2003-277381, WO2001 / 060811, WO2000 / 071544, WO2005 / 028465, WO2011 / 16582 pamphlet, WO2011 / 034202 pamphlet.

Among these photochromic compounds (C), chromene having an indenonaphtho [2,1-f] naphtho [1,2-b] pyran skeleton from the viewpoint of photochromic characteristics such as color density, initial coloring, durability, and fading speed. It is more preferable to use one or more compounds. Further, among these chromium compounds, a compound having a molecular weight of 540 or more is suitable because it is particularly excellent in color development density and fading rate. Further, when a chromene compound having an indenonaphtho [2,1-f] naphtho [1,2-b] pyran skeleton is used, the effect of using the component (A) is remarkably exhibited. Specific examples of the chromene compound having an indenonaphtho [2,1-f] naphtho [1,2-b] pyran skeleton include the following.

<Mixing ratio of photochromic curable composition>
In the present invention, the blending amount of each component may be appropriately determined according to the intended use of the obtained cured product, but the following blending amounts are satisfied in order for the obtained cured product to exhibit excellent photochromic characteristics and durability. It is preferable to do so.

0.01 to 20 parts by mass of the hindered amine (meth) acrylate compound (A) (component (A)), 100 parts by mass of the (meth) acrylate compound (B) (component (B)), and the photochromic compound. It is preferable that (C) (component (C)) is contained in an amount of 0.01 to 20 parts by mass. The blending amount of the component (B) is the total amount of the component (B1), the component (B2), and the component (B3).

When the component (A) satisfies the above range (0.01 to 20 parts by mass), the obtained cured product has improved durability, appropriate hardness, and sufficient strength. Further, when the component (C) satisfies the above range (0.01 to 20 parts by mass), the obtained cured product has excellent photochromic properties.

In addition, the component (B) is
With respect to 100 parts by mass of the trifunctional or higher (meth) acrylate compound (B1)
It is preferable that the glycol-based (meth) acrylate compound (B2) is contained in an amount of 100 to 10000 parts by mass, and the other (meth) acrylate compound (B3) is contained in an amount of 30 to 300 parts by mass.

When the photochromic curable composition of the present invention is used for a photochromic spectacle lens application, it is particularly preferable to use the following blending amounts in the above-mentioned kneading method and coating method, respectively.

<Kneading method; blending ratio of suitable photochromic curable composition>
That is, in the kneading method, when the component (B) is 100 parts by mass, the component (A) is preferably 0.01 to 5 parts by mass, and further 0.02 to 3 parts by mass. It is preferably 0.05 to 1 part by mass.

Further, in the kneading method, when the component (B) is 100 parts by mass, the component (C) is preferably 0.01 to 5 parts by mass, and further 0.02 to 3 parts by mass. It is preferably 0.05 to 1 part by mass.

<Coating method; blending ratio of suitable photochromic curable composition>
In the coating method, when the component (B) is 100 parts by mass, the component (A) is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 10 parts by mass. In particular, it is preferably 1 to 5 parts by mass.

Further, in the coating method, when the component (B) is 100 parts by mass, the component (C) is preferably 0.05 to 10 parts by mass, and further 0.1 to 10 parts by mass. Is preferable, and particularly preferably 1 to 5 parts by mass.

Further, in the coating method, in order for the obtained cured product to exhibit excellent properties, the glycol-based (meth) acrylate compound is based on 100 parts by mass of the trifunctional or higher functional (meth) acrylate compound (B1). It is preferable that (B2) is contained in an amount of 100 to 2000 parts by mass and the other (meth) acrylate compound (B3) is contained in an amount of 25 to 250 parts by mass. In order to exert a more excellent effect, it is preferable that the component (B1) is contained in an amount of 100 to 1000 parts by mass and the component (B3) is contained in an amount of 25 to 200 parts by mass with respect to 100 parts by mass of the component (B1). It is more preferable that the (B2) is contained in an amount of 100 to 750 parts by mass and the component (B3) is contained in an amount of 25 to 150 parts by mass.

Further, in the coating method, the component (B3) may contain (B3-a), (B3-b), (B3-f), and (B3-a), (B3-b), (B3-f), in order for the obtained photochromic curable composition to exert an excellent effect. It is preferably composed of a combination with (B3-g). Above all, in order to exert a particularly excellent effect, when the total of the components (B3) to be blended is 100% by mass, the above (B3-a) is 0 to 95% by mass, and the above (B3-b) is It is preferable that 0 to 50% by mass, (B3-f) is 0 to 70% by mass, and (B3-g) is 0 to 30% by mass.
The (B3-a) is 30 to 95% by mass, the (B3-b) is 0 to 45% by mass, (B3-f) is 0 to 60% by mass, and (B3-g) is 1 to 25% by mass. Is more preferable
(B3-a) is 49 to 95% by mass, (B3-b) is 0 to 40% by mass, (B3-f) is 0 to 50% by mass, and (B3-g) is 1 to 10% by mass. It is more preferable to do so.

<Other ingredients>
Next, other components that can be blended in the photochromic curable composition of the present invention will be described.

In the photochromic curable composition of the present invention, in order to improve the repeatability of the photochromic compound (C), improve the color development rate, improve the fading rate and improve the moldability, further, a surfactant, an antioxidant, etc. Additives such as radical supplements, UV stabilizers, UV absorbers, mold release agents, color inhibitors, antistatic agents, fluorescent dyes, dyes, pigments, fragrances, and plasticizers can also be added. In addition, a polymerization initiator described later can be added to cure the curable composition. The polymerization initiator will be described in detail in the description of the method for producing a cured product. Known compounds are used without any limitation as these additives to be blended.

As the surfactant, any of nonionic, anionic and cationic surfactants can be used, but from the viewpoint of solubility in the polymerizable monomer, it is preferable to use a nonionic surfactant. Examples of the nonionic surfactant that can be preferably used include sorbitan fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether and the like. When using a surfactant, two or more kinds may be mixed and used. The blending amount of the surfactant is preferably in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass of the component (B).

In addition, as antioxidants, radical supplements, UV stabilizers and / or UV absorbers, hindered amine light stabilizers, hindered phenol antioxidants, phenolic radical supplements, sulfur-based antioxidants, benzotriazole-based compounds , Benzophenone compounds and the like can be preferably used. These may be used in mixture of 2 or more types. In addition, they may be used in combination with surfactants. The blending amount of these antioxidants, radical supplements, ultraviolet stabilizers and / or ultraviolet absorbers is preferably in the range of 0.001 to 20 parts by mass with respect to 100 parts by mass of the component (B).

The above-mentioned hindered amine light stabilizer can be supplementarily blended to the extent that the effects of the present invention are not impaired.

Further, when the curable composition of the present invention is used as a coating agent, a hindered phenol antioxidant can be blended as another particularly useful stabilizer from the viewpoint of improving the repeated durability of the cured product. As the hindered phenol antioxidant, known compounds can be used without any limitation, but the following are preferable from the viewpoint of exhibiting the deterioration preventing effect of the photochromic compound.

IRGANOX245 from Ciba Specialty Chemicals: Ethylene bis (oxyethylene) bis [3,5-tert-butyl-4-hydroxy-m-toluyl] propionate],
IRGANOX 1076 from Ciba Specialty Chemicals: Octadecil-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate,
IRGANOX1010 from Ciba Specialty Chemicals: Pentaerythritol Tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
The blending amount of the hindered phenol antioxidant may be in the range of 0.001 to 20 parts by mass with respect to 100 parts by mass of the component (B), but is preferably in the range of 0.1 to 10 parts by mass. Preferably, it may be used in the range of 0.5 to 5 parts by mass.

Furthermore, as other radically polymerizable monomers,
Vinyl or allyl compounds such as styrene, α-methylstyrene, α-methylstyrene dimer, divinylbenzene, and allyl diglycol carbonate can also be used.

<Method for preparing photochromic curable composition, method for forming cured product and its use>
Next, a method for preparing the photochromic curable composition of the present invention, a method for forming a cured product, and an application will be described.

The preparation of the photochromic curable composition of the present invention is not particularly limited, and a predetermined amount of each component may be weighed and mixed. The order of addition of each component is not particularly limited, and all the components may be added at the same time, or only the polymerizable monomer component ((meta) acrylate compound component) is mixed in advance, and later, for example, described later. A photochromic compound or other additives may be added and mixed immediately before the polymerization as described above. As will be described later, a polymerization initiator may be further added at the time of polymerization, if necessary.

The photochromic curable composition of the present invention preferably has a viscosity at 25 ° C. of 5 to 2000 cPs. When used as a coating agent, the viscosity is preferably 20 to 500 cPs, particularly preferably 50 to 400 cPs. By setting the viscosity in this range, it becomes easy to adjust the thickness of the coating layer, which will be described later, to a thickness of 10 to 100 μm, and it becomes possible to sufficiently exhibit the photochromic characteristics. On the other hand, when used as a kneading type, the viscosity at 25 ° C. is preferably 5 to 300 cPs, more preferably 10 to 100 cPs. By setting this viscosity range, the work of injecting into the lens mold can be easily performed.

The method for obtaining a photochromic cured product by curing the photochromic curable composition of the present invention is not particularly limited, and a known polymerization method according to the type of polymerizable monomer used can be adopted. The polymerization initiator can be carried out by using a radical polymerization initiator such as various peroxides or azo compounds, or by irradiating with ultraviolet rays, α rays, β rays, γ rays, or the like, or a combination of both.

The radical polymerization initiator is not particularly limited, and known radical polymerization initiators can be used. Examples of typical ones include the following as thermal polymerization initiators.

Diacyl peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyyl peroxide, lauroyl peroxide, acetyl peroxide and the like;
Peroxy esters such as t-butylperoxy-2-ethylhexanoate, t-butylperoxydicarbonate, cumylperoxyneodecanate, t-butylperoxybenzoate;
Percarbonates such as diisopropylperoxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-sec-butyloxycarbonate;
Azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1' -Azobis (cyclohexane-1-carbonitrile), etc. The amount of these thermal polymerization initiators used varies depending on the polymerization conditions, the type of initiator, and the type and composition of the polymerizable monomer, and cannot be unconditionally limited, but in general, It is preferable to use it in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of all the radically polymerizable monomers other than the component (A). The thermal polymerization initiator may be used alone or in combination of two or more.

Further, in the case of polymerization by irradiation with light such as ultraviolet rays, it is preferable to use, for example, the following as the photopolymerization initiator. Benzoyl, benzoin methyl ether, benzoin butyl ether, benzophenol, aetofenone 4,4'-dichlorobenzophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzylmethyl ketal, 1- (4) -Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-isopropylthiooxanthone, bis (2,6-dimethoxybenzoyl-2,4,4-trimethyl-pentyl) Phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosiphin oxide, 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide, 2-benzyl-2-dimethylamino-1- (4-) Morphorinophenyl) -butanone-1.

These photopolymerization initiators are generally used in the range of 0.001 to 5 parts by mass with respect to 100 parts by mass of the component (B). The photopolymerization initiator may be used alone or in combination of two or more. Further, the above thermal polymerization initiator may be used in combination with the photopolymerization initiator.

A particularly preferable method for obtaining a cured product from the photochromic curable composition of the present invention is to irradiate the photochromic curable composition of the present invention containing the above photopolymerization initiator with ultraviolet rays or the like to cure it, and further heat it if necessary. This is a method of completing the polymerization.

When polymerizing by irradiation with ultraviolet rays, a known light source can be used without any limitation. Examples of the light source include an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a xenon lamp, a carbon arc, a germicidal lamp, a metal halide lamp, and an electrodeless lamp. The time of light irradiation using the light source may be appropriately determined depending on the type of the photopolymerization initiator, the absorption wavelength and the sensitivity, the film thickness of the photochromic layer, and the like. When an electron beam is used as the light source, the photochromic layer can be cured without adding a photopolymerization initiator.

The cured product thus obtained can be used as it is as a photochromic optical material, but is usually coated with a hard coat layer for the purpose of further preventing the occurrence of scratches during wearing. used. Thereby, the scratch resistance can be improved.

As the coating agent (hard coating agent) for forming the hard coat layer, known ones can be used without any limitation. Specifically, a silane coupling agent, a hard coating agent containing a sol of an oxide such as silicon, zirconium, antimony, aluminum, or titanium as a main component, or a hard coating agent containing an organic polymer as a main component can be used. ..

Further, a cured product of the photochromic curable composition of the present invention alone, an optical material having a coat layer composed of the curable composition (coating agent) on the surface of the optical substrate, or a hard coat layer further formed on the coat layer. The surface of the formed optical article is subjected to antireflection treatment, antistatic treatment, etc. by vapor deposition of a thin film of a metal oxide such as _{SiO 2} , TiO ₂ , ZrO _{2, or coating of a thin film of an organic polymer, and secondary processing.} It is also possible to apply processing.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

<Synthesis of component (A)>
(Synthesis Example 1)
Synthesis of "A-1";
A stirring blade, a thermometer, and a dropping funnel were installed in a 200 mL four-necked flask.
1,2,2,6,6-pentamethyl-4-hydroxypiperidine; 17.0 g (0.1 mol),
Dibutyl tin dilaurate; 7.4 mg
Dibutylhydroxytoluene; 6.1 g (0.05 mol),
Dehydrated toluene; 60 mL
Was prepared. The mixture was heated to 60 ° C. and 17.1 g (0.1 mol) of 2-isocyanatoethyl methacrylate was added in small portions. The mixture was stirred at 60 to 65 ° C. for 1 hour. Then, it was washed 3 times with 50 mL of water and extracted with toluene. After drying with magnesium sulfate, the solvent was distilled off. The obtained white solid was purified by a neutral alumina column {developing solvent: chloroform / ethyl acetate = 3/1 (v / v)} to obtain 35.5 g of the white solid.

The elemental analysis values of this product are C62.45%, H9.16%, N8.28%, O19.81%. This _value, C62.55% calculated values of _{C 17 H 30 N2О 4, H9.26} %, N8.58%, and very good matching O19.61%.

Moreover, when the nuclear magnetic resonance spectrum of protons was measured, a peak of 26 protons was measured at 1 to 5 ppm, a peak of 3 protons based on an acrylic group at 5 to 7 ppm, and a peak of 1 proton based on a hydrogen atom at the 4-position of a piperidyl group. A minute peak was observed.

From the above, the white solid has the following formula (A-1);

It was confirmed that the compound was represented by. The yield was 94%. Hereinafter, this compound may be simply referred to as "A-1" (a is 1 and b is 0).

(Synthesis Example 2)
Synthesis of "A-2";
A stirring blade, a thermometer, and a dropping funnel were installed in a 200 mL four-necked flask.
1,2,2,6,6-pentamethyl-4-hydroxypiperidine; 17.0 g (0.1 mol),
Dibutyl tin dilaurate; 7.4 mg,
Dibutylhydroxytoluene; 6.1 g (0.05 mol),
Dehydrated toluene; 60 mL
Was prepared. The mixture was heated to 60 ° C. and 19.9 g (0.1 mol) of 2- (2-methacryloyloxyethyloxy) ethyl isocyanate was added in small portions. The mixture was stirred at 60 to 65 ° C. for 1 hour. Then, it was washed 3 times with 50 mL of water and extracted with toluene. After drying with magnesium sulfate, the solvent was distilled off. The obtained white solid was purified by a neutral alumina column {developing solvent: chloroform / ethyl acetate = 3/1 (v / v)} to obtain 36.3 g of the white solid.

The elemental analysis values of this product are C65.09%, H9.75%, N7.70%, and O17.47%. This value was in excellent agreement with _{the calculated values of C 20} H _{35 N2O 4} of C 65.19%, H 9.85%, N 7.60% and O 17.37%.

In addition, when the nuclear magnetic resonance spectrum of protons was measured, a peak of 32 protons was measured at 1 to 5 ppm, a peak of 2 protons based on a methacryl group at 5 to 7 ppm, and a peak of 1 proton based on a hydrogen atom at the 4-position of a piperidyl group. A minute peak was observed.

From the above, the white solid has the following formula (A-2);

It was confirmed that the compound (A-2) was represented by. The yield was 92%. Hereinafter, this compound may be simply referred to as "A-2" (a is 2, and the average value of b is 0).

(Synthesis Example 3)
Synthesis of "A-3";
1,2,2,6,6-pentamethyl-4-piperidyl-polyethoxy (b≈4 (the average value of b is 4), a is 1) alcohol according to the description of JP-A-2001-71640. Got Then, according to the synthesis method of Synthesis Example 1, the target product (A-3) represented by the following formula (A-3) was obtained.

When the nuclear magnetic resonance spectrum of the protons of this compound (A-3) was measured, a peak of 43 protons at 1 to 5 ppm, a peak of 2 protons based on a methacryl group at 5 to 7 ppm, and a 4-position of a piperidyl group were observed. A peak for one proton based on a hydrogen atom was observed. Hereinafter, this compound may be simply referred to as "A-3". (A is 1 and the average value of b is 4.)
(Synthesis Example 4)
Synthesis of "A-4";
According to the description in JP-A-2001-71640, 1,2,2,6,6-pentamethyl-4-piperidyl-polypropoxy (b≈8 (the average value of b is 8), a is 1). I got alcohol. Then, according to the synthesis method of Synthesis Example 1, the target product (A-4) represented by the following formula was obtained. The structural formula of the compound is as follows.

When the nuclear magnetic resonance spectrum of the protons of this compound (A-4) was measured, a peak of 57 protons at 1 to 5 ppm, a peak of 2 protons based on a methacryl group at 5 to 7 ppm, and a 4-position of a piperidyl group were observed. A peak for one proton based on a hydrogen atom was observed. Hereinafter, this compound may be simply referred to as "A-4". (A is 1 and the average value of b is 8.)
(Synthesis Example 5)
Synthesis of "A-5";
1,2,2,6,6-pentamethyl-4-piperidyl-polyethoxy (b≈8 (the average value of b is 8), a is 1) alcohol according to the description of JP-A-2001-71640. Got Then, according to the synthesis method of Synthesis Example 1, the target product (A-5) represented by the following formula (A-5) was obtained. The structural formula of the compound is as follows.

When the nuclear magnetic resonance spectrum of the protons of this compound (A-5) was measured, a peak of 59 protons at 1 to 5 ppm, a peak of 2 protons based on a methacryl group at 5 to 7 ppm, and a 4-position of a piperidyl group were observed. A peak for one proton based on a hydrogen atom was observed. Hereinafter, this compound may be simply referred to as "A-5". (A is 1 and the average value of b is 8.)
(Synthesis Example 6)
Synthesis of "A-6" According to the description in Japanese Patent Application Laid-Open No. 2001-71640, 1,2,2,6,6-pentamethyl-4-piperidyl-polyethoxy (b is 2 and a is 2) alcohol is used. Obtained. Then, according to the synthesis method of Synthesis Example 2, the target product (A-6) represented by the following formula (A-6) was obtained. The structural formula of the compound is as follows.

When the nuclear magnetic resonance spectrum of the protons of this compound (A-6) was measured, a peak of 35 protons at 1 to 5 ppm, a peak of 2 protons based on a methacryl group at 5 to 7 ppm, and a 4-position of a piperidyl group were observed. A peak for one proton based on a hydrogen atom was observed. Hereinafter, this compound may be simply referred to as "A-6". (A is 2 and b is 2.).

(Synthesis Example 7)
"A-7"synthesis;
The target product (A-7) was obtained according to the method of Synthesis Example 1 except that 2- (2-methacryloyl (polyethoxy) a = 4) ethyl isocyanate was used instead of 2-isocyanatoethyl methacrylate in Synthesis Example 1. .. The structural formula of the compound is as follows.

When the nuclear magnetic resonance spectrum of the protons of this compound (A-7) was measured, a peak of 39 protons at 1 to 5 ppm, a peak of 2 protons based on a methacryl group at 5 to 7 ppm, and a 4-position of a piperidyl group were observed. A peak for one proton based on a hydrogen atom was observed. Hereinafter, this compound may be simply referred to as "A-7" (a is 4 and b is 0).

<Names and abbreviations of each component>
The abbreviations and names of the compounds used as the component (A), the component (B1), the component (B2), the component (B3), the component (C) and other components are shown below.

(A) component;
Each component synthesized in Synthesis Examples 1 to 7. A-1, A-2, A-3, A-4, A-5, A-6, A-7.

(B) component (B1) component;
TMPT; trimethylolpropane trimethacrylate.
D-TMP; Ditrimethylolpropane tetraacrylate (B2) component;
9G; Polyethylene glycol dimethacrylate (average chain length of ethylene glycol chain 9, average molecular weight 536).
14G; polyethylene glycol dimethacrylate (average chain length 14 of ethylene glycol chains, average molecular weight 736).

(B3) component;
A-400; Polyethylene glycol diacrylate (average chain length of ethylene glycol chain 9, average molecular weight 508)
BPE500: 2,2-bis [4-methacryloxy (polyethoxy) phenyl] propane (average chain length of ethylene glycol chain 10).
GMA: Glycidyl methacrylate.
Polyrotaxane monomer; details of the polyrotaxane monomer are shown below. A polyrotaxane monomer in which an acrylic group was introduced into polyrotaxane was produced with reference to the method described in the internationally published WO2015 / 068798 pamphlet.
Molecular weight of shaft; polyethylene glycol with a molecular weight of 35,000.
End of axis molecule; adamantane.
Cyclic molecule; α-cyclodextrin.
Number of inclusions of cyclic molecules; 0.25.
Degree of modification of cyclic molecule; 50% (a state in which a 50% hydroxyl group of α-cyclodextrin is modified with a ring-opened body of the following polycaprolactone).
Side chain molecular weight; polycaprolactone with a molecular weight of 500.
Polymerizable group; acrylate.
Degeneration rate: 85% (state in which an acrylate group is introduced into 85 mol% of terminal OH of the ring-opened body of the polycaprolactone).

Component (C); Photochromic compound The compound shown below.
PC1:

Other ingredients;
Photopolymerization initiator;
CGI1800: A mixture of 1-hydroxycyclohexylphenyl ketone and bis (2,6-dimethoxybenzoyl-2,4,4-trimethyl-pentylphosphine oxide (mass ratio: 3: 1).

Hindered amine light stabilizer;
LS765: Sebacic acid (1,2,2,6,6-pentamethyl-4-piperidyl) diester.
LA-87: 2,2,6,6-tetramethyl-4-piperidyl methacrylate.
HM-19: The structural formula is shown below. The repeating unit of − (OCH ₂ CH ₂ ) − is 6 on average.

Hindered Phenol Antioxidant;
IRGANOX245: Ethylene bis (oxyethylene) bis [3,5-tert-butyl-4-hydroxy-m-toluyl] propionate].

Moisture-curable primer;
Made by Tokuyama Corporation, TR-SC-P.

<Preparation of photochromic curable composition and production / evaluation of cured product>
The following ingredients were mixed to prepare a photochromic curable composition.

(Example 1)
As the component (A), A-1 produced in Synthesis Example 1; 5 parts by mass,
(B) As an ingredient
TMPT; 20 parts by mass,
9G; 50 parts by mass,
A-400; 15 parts by mass,
BPE500; 24 parts by mass,
GMA; 1 part by mass, 100 parts by mass of the above total amount (100 parts by mass of the total amount of the component (B))
On the other hand, 2 parts by mass of PC1 (component (C)) was added as a photochromic compound and mixed sufficiently. In this mixture,
Antioxidant (IRGANOX245); 3 parts by mass,
Polymerization initiator (CGI1800) 0.5 parts by mass,
Was added and mixed thoroughly to obtain a photochromic curable composition (coating agent). The compounding ratio of the coating agent is shown in Table 1.

Using a spin coater (MIKASA, 1H-DX2), a moisture-curable primer TR- The SC-P was coated at 70 rpm for 15 seconds and then at 1000 rpm for 10 seconds. Then, about 2 g of the coating agent obtained by the above method was spin coated at a rotation speed of 60 rpm for 40 seconds and then at 600 rpm for 10 to 20 seconds so that the film thickness of the photocrocoat layer became 40 μm. The surface-coated lens was irradiated with light for 90 seconds using a metal halide lamp having an output of 200 mW / cm ^{2 in a nitrogen gas atmosphere to cure the coating film.} Then, it was further heated at 110 ° C. for 1 hour to produce an optical material having a photochromic coat layer.

The following evaluation was performed using the obtained optical material having a photochromic coat layer. The results are shown in Table 1.

(1) Color development density A xenon lamp {L-2480 (300W) SHL-100, manufactured by Hamamatsu Photonics} is applied to the obtained photochromic cured product via an aeromas filter (manufactured by Corning) at 20 ° C ± 1 ° C, photochromic coating. The beam intensity on the layer surface is 365 nm = 2.4 mW / cm ² , 245 nm = 24 μW / cm ² , and the color is developed by irradiating for 300 seconds. Obtained by multi-channel photodetector MCPD1000}.

From the measurement results, the color density was calculated by the following formula.

Color density = ε (300) -ε (0)
During the ceremony
ε (300) is the absorbance at the maximum absorption wavelength after light irradiation for 300 seconds, and ε (0) is the absorbance at the wavelength of the cured product without light irradiation.
The higher this value, the better the photochromic characteristics.

(2) Fading half-life After irradiating the photochromic cured product with light for 300 seconds, the irradiation of light is stopped, and the absorbance of the cured product at the maximum wavelength is 1/2 of the {ε (300) -ε (0)}. The time required for the decrease to {t1 / 2 (min)} was measured. The shorter this time, the faster the fading speed and the better the photochromic characteristics.

(3) Repeated durability The following deterioration acceleration test was conducted to evaluate the repeated durability of color development by light irradiation. The test method is as follows.

That is, the obtained photochromic cured product was accelerated and deteriorated for 200 hours by a xenon weather meter {manufactured by Suga Test Instruments Co., Ltd., X25}. Before and after this deterioration, the above-mentioned color development density was evaluated, and the color development density before the test (A ₀ ) and the color development density after the test (A ₂₀₀ ) were measured.

From this measurement result, the residual rate, which is a measure of repeatability, was calculated.

Residual rate (%) = {(A ₂₀₀ / A ₀ ) x 100}
During the ceremony
A ₀ is the color density before the test.
A ₂₀₀ is the color density after the test.

Further, the value of the degree of yellowing (ΔYI) was determined using a color difference meter {SM-4 manufactured by Suga Test Instruments Co., Ltd.}.

ΔYI = YI _{200 -YI 0}
During the ceremony
YI ₂₀₀ is YI after 200 hours of accelerated deterioration.
YI ₀ is YI before accelerated deterioration.

The higher the residual rate and the smaller the degree of yellowing, the higher the repeatability and the better the photochromic characteristics. The evaluation results obtained are summarized in Table 2.

(4) Turbidity The following storage acceleration test was conducted to evaluate the surface turbidity when stored for a long period of time. That is, the obtained photochromic cured product was placed in a constant temperature and humidity chamber at 60 ° C. and 98% RH for 72 hours. Using a haze meter, the difference in HAZE values (ΔHAZE) before and after the test was determined.

ΔHAZE = HAZE _{72 -HAZE 0}
During the ceremony
HAZE ₇₂ represents HAZE after 72 hours.
HAZE ₀ represents HAZE before being placed in a constant temperature and humidity chamber.

(5) Vickers hardness The Vickers hardness was measured using a micro Vickers hardness tester PMT-X 7A (manufactured by Matsuzawa Co., Ltd.). A quadrangular pyramid diamond indenter was used as the indenter, and evaluation was performed under the conditions of a load of 10 gf and an indenter holding time of 30 seconds. The measurement results are shown by the average value of a total of 3 times after performing a total of 4 measurements and excluding the first value with a large measurement error.

(Examples 2 to 7)
The photochromic curable composition was prepared in the same manner as in Example 1 except for the blending ratios of the photochromic curable compositions shown in Table 1, and a photochromic laminate was prepared in the same manner as in Example 1. Evaluation was performed. The evaluation results are shown in Table 2.

(Comparative Example 1)
The same operation as in Example 1 was performed except that LS765 5 parts by mass was used instead of A-15 parts by mass. Table 3 shows the blending ratio of the photochromic curable composition, and Table 2 shows the obtained evaluation results.

(Comparative Example 2)
The same operation as in Example 1 was performed except that LA-875 parts by mass was used instead of A-15 parts by mass. Table 1 shows the blending ratio of the photochromic curable composition, and Table 2 shows the obtained evaluation results.

(Comparative Example 3)
The same operation as in Example 1 was performed except that HM-19 5 parts by mass was used instead of A-15 parts by mass. Table 1 shows the blending ratio of the photochromic curable composition, and Table 2 shows the obtained evaluation results.

(Examples 8 to 11)
Using (A-1) as the component (A), the photochromic curable composition was adjusted by performing the same operation as in Example 1 as the blending ratio in Table 3, and then the photochromic cured product was prepared by the same method as in Example 1. Obtained. Table 3 shows the blending ratio of the photochromic curable composition, and Table 4 shows the obtained evaluation results.

(Examples 12 to 15)
The blending amount of the component (A) is 2 parts by mass, and the photochromic curable composition is adjusted by performing the same operation as in Example 1 as the blending ratio in Table 5, and then the photochromic cured product is prepared by the same method as in Example 1. Obtained. Table 5 shows the blending ratio of the photochromic curable composition, and Table 6 shows the obtained evaluation results.

(Comparative Example 4)
The same operation as in Example 12 was performed except that LS765 2 parts by mass was used instead of A-12 2 parts by mass. Table 5 shows the blending ratio of the photochromic curable composition, and Table 6 shows the obtained evaluation results.

(Comparative Example 5)
The same operation as in Example 12 was performed except that LA-87 2 parts by mass was used instead of A-12 2 parts by mass. Table 5 shows the blending ratio of the photochromic curable composition, and Table 6 shows the obtained evaluation results.

(Comparative Example 6)
The same operation as in Example 12 was performed except that HM-19 2 parts by mass was used instead of A-12 2 parts by mass. Table 5 shows the blending ratio of the photochromic curable composition, and Table 6 shows the obtained evaluation results.

Claims (8)

The following formula (1)

[During the ceremony,
R ¹ is a hydrogen atom or a methyl group,
R ² is a hydrogen atom or a methyl group.
R ³ is a linear or branched alkylene group having 1 to 5 carbon atoms.
a is a number from 2 to 20 on average,
X is the following formula (2)

(During the ceremony,
R ⁴ is a linear or branched alkylene group having 1 to 5 carbon atoms,
b is a number from 0 to 20 on average. ) Is the group
However, a + b is a number of 2 to 20 on average. ]
Hindered amine (meth) acrylate compound indicated by. The hindered amine (meth) acrylate compound (A) according to claim 1, the (meth) acrylate compound (B) other than the hindered amine (meth) acrylate compound (A) according to claim 1, and
Photochromic compound (C)
A photochromic curable composition comprising. 0.01 to 20 parts by mass of the hindered amine (meth) acrylate compound (A),
100 parts by mass of the (meth) acrylate compound (B) and
The photochromic curable composition according to claim 2, which contains 0.01 to 20 parts by mass of the photochromic compound (C). The (meth) acrylate compound (B)
The following formula (3)

(During the ceremony,
R ⁵ and R ⁶ are independently hydrogen atoms or methyl groups, respectively.
R ⁷ is a 3- to hexavalent organic group having 1 to 10 carbon atoms.
c is a number from 0 to 10 on average,
d is an integer of 3 to 6. )
Trifunctional or higher functional (meth) acrylate compound (B1), indicated by
The following formula (4)

(During the ceremony,
R ⁸ , R ⁹ , and R ¹⁰ are independently hydrogen atoms or methyl groups, respectively.
e and f are each independently an integer of 0 or more, and e + f is an integer of 2 or more on average. )
Glycol-based (meth) acrylate compound (B2) represented by, and
Other (meth) acrylate compounds (B3) other than the trifunctional or higher functional (meth) acrylate compound (B1) represented by the formula (3) and the glycol-based (meth) acrylate compound (B2) represented by the formula (4). The photochromic curable composition according to claim 2 or 3. The (meth) acrylate compound (B)
With respect to 100 parts by mass of the trifunctional or higher (meth) acrylate compound (B1)
The photochromic curable composition according to claim 4, which contains 100 to 10000 parts by mass of the glycol-based (meth) acrylate compound (B2) and 30 to 300 parts by mass of the other (meth) acrylate compound (B3). A coating agent containing the photochromic curable composition according to any one of claims 2 to 5. An optical material having a photochromic coat layer obtained by curing the coating agent according to claim 6 on at least one surface of an optical base material. A photochromic cured product obtained by curing the photochromic curable composition according to any one of claims 2 to 5.