WO2003027728A1

WO2003027728A1 - Composition for optical material, optical material and photochromic lens

Info

Publication number: WO2003027728A1
Application number: PCT/JP2002/009855
Authority: WO
Inventors: Mutsuo Kuwada; Katsuyoshi Tanaka; Toshiaki Takaoka
Original assignee: Nof Corporation
Priority date: 2001-09-25
Filing date: 2002-09-25
Publication date: 2003-04-03

Abstract

A high-refraction photochromic lens exhibiting a quick optical response and a low specific gravity and being excellent in heat resistance, impact resistance and so on; an optical material useful as the material of the lens; and a composition useful as the raw material of the optical material. The composition comprises 100 parts by weight of a monomer composition comprising 15 to 97 wt% of at least one compound (A) represented by the general formula (1) wherein j + n = 5 to 7 and 3 to 50 wt% of at least one compound (B) represented thereby wherein j + n = 9 to 11 and 0.001 to 10 parts by weight of a photochromic compound: (1) wherein R1 and R2 are each H or CH3; Ph is phenylene; j and n are each an integer of 0 to 11, with the proviso that j and n are not simultaneously 0 ; and k, m and p are each 0 or 1.

Description

Specification

Compositions for optical materials, optical materials and photochromic lenses

The present invention relates to a photochromic lens having photochromic properties that is colored by sunlight or ultraviolet light and that fades in a B-tone place, an optical material constituting the lens, and a composition for an optical material that can be used as a raw material of the optical material.

Background art

In recent years, in the field of optical materials, light weight, safety, and fashionability have been increasingly emphasized, and materials have shifted from conventional inorganic glass to synthetic resins. Representative examples of the synthetic resin include polydiethylene glycol bisaryl carbonate, polymethyl methacrylate, and polycarbonate.

Recently, photochromic lenses have been used. Examples of the method for producing the photochromic lens include: (1) a method in which a photochromic compound is kneaded into an optical resin and molded (JP-A-61-161286); and (2) a method in which the photochromic compound is dissolved or dispersed. A method of impregnating an optical resin with the resulting solution and dispersing or coating the photochromic compound on the resin surface (U.S. Pat.No. 3,216,958, JP-A-61-228402), (3) converting the photochromic compound into methyl methacrylate There are known methods of dissolving and curing (JP-A-61-233079, JP-A-1-259013, JP-A-7-2938).

In the method (1), since the optical resin is melted at a high temperature of 200 ° C. or more, the photochromic compound is deteriorated, and a problem occurs in the dispersibility of the compound. However, there is a problem that the optical response is low. In the method (2), the lens manufacturing process becomes complicated, and it is difficult to control the amount of the photochromic compound impregnated.

In the method (3), JP-A-61-233079 discloses a method in which a spiroxazine compound, which is a photochromic compound, is dissolved in methyl methacrylate and cured. This method has disadvantages such as a problem that the photochromic compound is inferior due to the polymerizable monomer and the radical polymerization initiator used, a low optical response of the manufactured optical material, and a low refractive index of about 1.49. is there. JP-A 1-259013 and JP-A 7-2938 disclose a method using a polymerizable aryl carbonate. However, even with this method, the inferiority of the photochromic ridged product cannot be overcome, and the resulting optical material There is a problem that the photoresponse speed of coloring and fading is not sufficient.

JP-A-62-267316 describes an optical material having a high refractive index employing a thiourethane resin which is a polymer of polyisocyanate and polythiol. However, when the photochromic conjugate is dissolved and cured in the polyisocyanate and polythiol for producing the thiourethane resin, there is a problem that the photochromic compound reacts with the isocyanate and cannot exhibit photochromic properties. .

As described above, the performance of photochromic compounds is often not sufficiently exhibited with conventional various photochromic optical materials.

Disclosure of the invention

An object of the present invention is to provide a photochromic lens having a high photoresponsiveness, a low specific gravity, excellent heat and impact resistance and other physical properties, and a high refractive index, an optical material as the lens material, and the optical material. An object of the present invention is to provide a composition for an optical material which is a raw material of the optical material.

According to the present invention, 15 to 97% by weight of at least one compound (A) in which the sum of j and II in the formula (1) is 5 to 7 and the sum of j and n in the formula (1) are at least one compound is 9-11 and (B) 3 to 50 weight ^_0/0 monomer 100 parts by weight of the composition containing a photochromic compound 0.001: optical material composition comprising 10 parts by weight is provided You.

R ¹ 0 R ² 0 CH. 0 R ² 0 R ¹

I II I II I II I II I

CH ₂ = C- CO- (CHCH ₂₀ ) j- (CO) k- (Ph-C-Ph) p- (OC) m- (OCH ₂ CH) n-OC- C = CH ₂ (1)

CH ₃

(Wherein, R ¹ and R ² represent a hydrogen atom or a methyl group, Ph represents a phenylene group. J and n are independently integers from 0 to 11. Are not simultaneously 0. k, m and p are independently 0 or 1.)

Further, according to the present invention, there is provided an optical material obtained by polymerizing and curing the composition for optical material.

Further, according to the present invention, there is provided a photochromic lens having the optical material. Preferred embodiments of the invention

Hereinafter, the present invention will be described in more detail.

The composition for an optical material of the present invention (hereinafter, referred to as composition (P)) is a polymerizable monomer containing the compound (A) and the compound (B) represented by the formula (1) in a specific ratio. A composition (hereinafter, referred to as composition (M)) and a specific proportion of a photochromic compound. The compound represented by the formula (1) For example, as disclosed in Japanese Patent Publication No. 58-17527, it is not possible to use a specific compound (A) and a specific compound B) in a specific ratio and use in combination with a photochromic compound. unknown.

In the above formula (1), R ¹ and R ² represent a hydrogen atom or a methyl group, and Ph represents a phenylene group. j and n are each independently an integer from 0 to 11; However, i and n do not become 0 at the same time. k, m and p are independently 0 or 1. The compound (A) which is essentially used in the composition (M) is a compound in which the sum of j and n is 5 to 7, and the compound (B) is a compound in which the sum of j and n is 9 to 11 .

The composition (M) is a composition of a polymerizable monomer.In addition to the compound (A) and the compound (B), if necessary, in the formula (1), the sum of j and n is And a monomer selected from the group consisting of an amide compound having a vinyl group (C :), an amide compound having a vinyl group (D), another vinyl compound (E), and a mixture thereof. And a mixture (F) which can constitute a thiourethane resin composed of an isocyanate compound and a thiolic compound. These can be blended in various combinations according to the desired purpose and the like, and other polymerizable monomers can be blended as long as the desired purpose of the present invention is not impaired.

The compound (A) gives the optical material after curing a fast light response and also provides various properties required for the optical material such as heat resistance, impact resistance, durability, and hardness.

As the compound (A), for example, 2,2-bis (4- (2- (meth) acryloxyshethoxy) jetoxyphenyl) propane (j + n = 6), 2,2-bis (4 -(2- (meth) acryloxypropoxy) dipropoxyphenyl) propane (j + n = 6), hexaethylene glycol di (meth) acrylate (j + n = 6) and the like.

The content ratio of the compound (A) is preferably 15 to 97% by weight in the composition (M). Here, when the composition (M) contains the mixture (F), the content ratio of the compound (A) is 15 to 50% by weight, more preferably 15 to 40% by weight in the composition (M). . When the composition (M) does not contain the mixture (F), the content of the compound (A) is 50 to 97% by weight, more preferably 50 to 90% by weight in the composition (M). . In this case, the compound (A) is less than 50 weight ^_0/0, heat resistance,耐衝撃性, durability and various properties required for optical materials such as hardness tends to decrease.

The compound (B) imparts fast photoresponsiveness to the cured optical material.

As the compound (B), for example, 2,2-bis (4- (2- (meth) ataryloxyethoxy) tetrae Toxipheninole) propane 0 · + η = 1Ο), '2,2-bis (4- (2- (meth) acryloxypropoxy) tetrapropoxyphenyl) propane (j + n = 10), nonaethylene glycol Di (meth) acrylate (j + n = 9), nonapropylene glycol di (meth) acrylate (j + n = 9) and the like.

The content ratio of the compound (B) is 3 to 50% by weight, preferably 4 to 40% by weight in the composition (M). If it exceeds 50% by weight, the heat resistance and hardness of the obtained optical material will be reduced.

The relationship between the compound (A) and the compound (B) is 50 to 95 parts by weight of the compound (A) and 5 to 50 parts by weight of the compound (B) when the total amount of both is 100 parts by weight. It is preferable _.

The fibrous compound (C), which can be blended as necessary in the fibrous composition (II), is a monomer capable of further improving heat resistance and hardness in the cured optical material.

As the compound (C), for example, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane (j + n = 2), 2,2-bis (4- (2- (meta ) Atari mouth xylethoxycarbonyloxy) phenyl) propane j + n = 2), 2,2-bis (4- (meth) acryloxypropoxyphenyl) propane (j + n = 2), 2 , 2-bis (4- (2- (meth) acryloxypropoxycarbonyloxy) phenyl) lip パン + + η = 2), diethylene glycol di (meth) acrylate (j = 2), triethylene glycol (Meth) acrylate (j = 3), dipropylene dalicol di (meth) acrylate (j = 2), tripropylene dalicol di (meth) acrylate (j = 3) and the like.

When compound (C) is added, the content ratio is usually 3 to 25% by weight, preferably 4 to 20% by weight in composition (M). If the content exceeds 25% by weight, the photoresponsiveness of the cured optical material may be undesirably reduced.

In the composition (M), the amide compound (D), which can be added as required, prevents the composition (P) of the present invention from deteriorating the photochromic compound due to a radical polymerization initiator described below. It prevents reaction with the isocyanate compound in the mixture (F), and further provides faster optical response to the cured optical material.

Examples of the amide compound (D) include, for example, acrylamide, methacrylamide, N-vinylformamide, N-vinylacetamide, N-methyl-N-butylacetamide, N-vinylphthalimide, and 1-viel -2-pyrrolidinone, 1-vinylimidazole, N-isopropylatarylamide, N- (3-dimethylaminopropynole) acrylamide, N- (3-dimethylaminopropyl) methacrylamide, Ν, Ν-dimethylacrylamide Ν, Ν, Ν-dimethyl methacrylamide, Ν, ジェ -ethyl acrylamide, 3-methacrylamide -Ν, Ν-dimethyl Mouth pyramine, N- (l, l-dimethyl-3-oxobutyl) acrylamide, N- (hydroxymethyl) acrylamide and the like. Among them, N, N-dimethylacrylamide, N-isopropylacrylamide, N- (3-dimethylaminopropyl) acrylamide, and N- (3-dimethylaminopropyl) methacrylamide are preferred. When used, two or more kinds may be used in combination.

When the amide compound (D) is used, the content ratio is usually 0.1 to 30% by weight, preferably 0.8 to 20% by weight in the composition (M). If the amount is less than 0.1% by weight, it is difficult to obtain a desired effect by adding the amide compound (D). If the amount exceeds 30% by weight, curing may be poor, which is not preferable. When the composition (M) contains the mixture (F), the content ratio of the amide compound (D) is preferably 0.8 to 5% by weight in the composition (M).

In the composition (M), the other vinyl compound (E), which can be blended as necessary, is a polymerizable bur compound other than the compounds (A) to (C) and the amide compound (D). And, for example, a compound in which the sum of] 'and n in the formula (1) is 1, 4 or 8. Other vinyl compounds (E) can be appropriately selected and used to adjust the refractive index, dyeability, heat resistance, hardness and the like of the obtained optical material.

Examples of the bull-based compound (E) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, s-butyl (meth) acrylate, and i-butyl (meth) acrylate. Rate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyxyl (meth) acrylate, glyceroyl mono (Meth) acrylate, glycidyl (meth) acrylate, 2-methoxethyl (meth) acrylate, diethylene glycol mono (meth) acrylate, methoxy ethoxyxyl (meth) acrylate, triethylene glycol mono (meth) Acrylate, tetraethylene dalicol mono (meth) acrylate, methoxy tetraethyl Nonglycone mono (meth) acrylate, nonaethyleneglycone mono (meth) acrylate, methoxynonaethylene glycol mono (meth) acrylate, methoxytriethylene glycol (meth) acrylate, polyethylene glycolone (meth) atari Rate, methoxypolyethylene glycol (meth) acrylate, propylene glycol mono (meth) acrylate, methoxypropylene glycol (meth) acrylate, styrene, halogen-substituted styrene, methyl-substituted styrene, dibutylbenzene bulnaphthalene , Diaryl orthophthalate, diaryl isophthalate, dia Ryl terephthalate, 2,2-bis (4- (2- (meth) acryloxyethoxy) ethoxyphenyl) propane j + _n = 4), 2,2-bis (4- (2- (meth) acrylic acid) Xhetoxy) triethoxyphenyl) propane j + _n = 8), 2,2-bis (4-((meth) acrylic xylethoxy) polyethoxyphenyl) propane, 2,2-bis (4-(( 2- (meth) acryloxyethoxy) ethoxycarbonyloxy) phenyl) propane (j + n = 4), 2,2-bis (4- (2- (meth) acryloxypropoxy) propoxyphenyl) propane j + n = 4), 2,2-bis (4- (2- (meth) acryloxypropoxy) trip, poxyphenyl) propane (j + n = 8), 2,2-bis (4- ((meta) Acryloxypropoxy) polypropoxyphenyl) propane, 2,2-bis (4-((2- (meth) acryloxypropoxy) propoxyl-propionyloxy) phenyl) propa (j + n = 4), ethylene glycol di (meth) acrylate 0 '= 1), tetraethylene dalichol di (meth) acrylate 0 · = 4), propylene glycol di (meth) acrylate (j = l) ), Tetrapropylene glycol di (meth) phthalate j = 4) and the like. Above all, in order to adjust heat resistance and hardness, it is preferable to use a monomer having three or more (meth) acrylic groups.

When the other vinyl compound (E) is used, the content ratio is usually 3 to 20% by weight, preferably 4 to 15% by weight in the composition (M).

In the composition (M), the mixture (F), which can be blended as required, is a mixture of an isocyanate compound and a thiol compound which can constitute a thiourethane resin, and is used for increasing the refractive index of the obtained optical material. Can be blended.

Examples of the above-mentioned isocyanate compound include 3-isopropenyl-α, α-dimethylbenzyl isocyanate, isocyanateethyl methacrylate, hexamethylene diisocyanate, and 4,4′-dicyclohexyl methacrylate. And m-xylylene diisocyanate, m-tetramethylenolylene diisocyanate, isophorone diisocyanate, and mixtures thereof.

Examples of the thiol compound include ethanedithionole, 1,6-hexanedithiol, 3,3′-dithiodipropionic acid, ethylene glycol dithioglycolate, and 2,2′-thiodiethanethiol , 2,2'-oxyethanethiol, dimercaptotriethylene disulfide, 1,2-dithioglycerin, 1,3-dithioglycerin, 1,4-benzenedithiol, 1,2-bis (mercaptomethylene) Examples include benzene, trimethylolpropane tris (thioglycolate), pentaerythritol tetrakis (thioglycolate), pentaerythritol tetrakis (mercaptopropionate), and mixtures thereof. Content in the case of using the mixture (), the composition (M) Normal 20% to 70% by weight in, rather preferably is 30 to 60 weight ^_0/0. The mixing ratio of the isocyanate compound and the thiol conjugate in the mixture (F) is usually 1.0 to 4.0, preferably 1.1 to 2.0 in terms of a functional group molar ratio (thiol group / isocyanate group).

When the composition (M) does not contain the mixture (F), from the viewpoint of the operability at the time of operation and the refractive index of the obtained optical material, after satisfying the above-mentioned specifications of the respective conjugates, The content of the compound in which p is 1 and j + n is 2 to 11 in k, p, in and n in the formula (1) in the composition (M) is 60 to 90% by weight, and In the formula (1), it is preferable that k, p, m and n are all 0, and the content of the compound in which j is 1 to 11 is 10 to 40% by weight. When the former compound is less than 60% by weight, the refractive index tends to be low, and when the latter compound is less than 10% by weight, the viscosity of the composition (M) may increase and the operability at the time of operation may decrease. This is not desirable.

When the composition (M) does not contain the mixture (F), the content of the compound represented by the formula (1) in the composition (M) is 70 to 99.9% by weight, particularly 80 to 99% by weight. % By weight is preferred. If the content is less than 70% by weight, the obtained optical material is provided with a fast light response, and various properties required for the optical material such as heat resistance, impact resistance, durability, and hardness may be deteriorated. . On the other hand, when the composition (M) contains the mixture (F), the composition (M) satisfies the above-mentioned requirements for each compound and mixture, and further contains the compound represented by the formula (1) in the composition (M). The ratio is 20-70 weight ⁰ /. In particular, 30 to 60% by weight is preferable. If the content is less than 20% by weight, the refractive index may not be sufficiently improved, and if the content is more than 70% by weight, the required optical response may not be provided to the obtained optical material.

The composition (P) of the present invention has such a property that, based on 100 parts by weight of the composition (M), the light transmittance is changed by ultraviolet light or visible light, and the light transmittance is restored when the light source is cut off. 0.001 to 10 parts by weight, preferably 0.01 to 1 part by weight of a photochromic compound. If the amount is less than 0.001 part by weight, the photochromic property of the optical material becomes insufficient, and if the amount exceeds 10% by weight, poor curing of the optical material and light transmittance are remarkably reduced.

Examples of the photochromic compound include mercury dithionate, a spiropyran compound, a spiroxazine compound, a spiroindoline compound, a fulgide compound, a fulgimide compound, an adamantylidene compound, a cyclophan compound, a chromene compound, and a mixture thereof. The composition (P) of the present invention may optionally contain an amine compound. By blending the amine compound, the optical response speed of color development and fading of the obtained optical material is maintained, and deterioration of the photochromic compound due to a trace amount of acid contained in the ester compound in the composition (P) is suppressed. Can be suppressed.

As the amine compound, for example, trimethylamine, dimethylamine, triethylene, getylamine, ethylamine, triethanolamine, jetanolamine, rilylamine, Ν, Ν-dimethylaminoethyl methacrylate, Ν, Ν-jetyl Aminoethyl methacrylate, Ν- (3-dimethylaminopropyl) acrylamide, Ν- (3-dimethylaminopropyl) methacrylamide, mercaptoethylamine,) 3-mercaptoethylamine, tetramethylbutanediamine, Examples include triethylenediamine, pyridine, 1,8-diazabicyclo (5,4,0) indene-7 or a mixture thereof. Of these, use of Ν, Ν-dimethylaminoethyl methacrylate, Ν- (3-dimethylaminopropyl) methacrylamide, and 1,8-diazabicyclo (5,4,0) ndecene-7 is preferred.

When the Aminich compound is blended, the content ratio is usually 5 to 50,000 ppm, preferably 100 to 30,000 ppm in the composition (II). If it is less than 5 ppm, the desired effect of the amine compound is insufficient, and if it exceeds 50,000 ppm, curing failure may occur, which is not preferable. When the composition (M) contains the mixture (F), the content ratio of the amine compound in the composition (P) is preferably 10 to 5000 ppm.

The composition (P) of the present invention may further contain an ultraviolet absorber if necessary. By blending the ultraviolet ray absorbent, UV cut performance can be imparted to the obtained optical material, and deterioration of the optical material and influence on eyes can be reduced. Examples of the ultraviolet absorber include a phenyl salicylate compound, a benzophenone compound, a benzotriazole compound, and a cyanoacrylate compound. Specifically, 2- (2'-hydroxy-5'-methylphenyl) benzotriazolone, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chloro -Benzotriazonole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chloromonobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di -t-Amylphenyl) -benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylpheninole) benzotriazole, 2- (2'-hydroxy-5'-t-butylphenyl) ) Benzotriazole, 2- (2'-hydroxy-5'small octylphenyl) benzotriazole or a mixture thereof.

When the ultraviolet absorber is contained, the content ratio is generally 100 parts by weight of the composition (M). It is always 0.001 to 5 parts by weight, preferably 0.01 to 1 part by weight. If the amount is less than 0.001 part by weight, sufficient UV cut performance cannot be imparted to the obtained optical material. If the amount exceeds 5 parts by weight, the optical material tends to yellow due to coloring of the ultraviolet absorber itself, which is not preferable.

The composition (P) of the present invention further contains additives such as an antioxidant, a light stabilizer, a coloring agent, a release agent, a surfactant, and an antibacterial agent in addition to the above-mentioned components in a usual use range. Can be done. The optical material of the present invention is a material obtained by polymerizing and curing the composition (P). As a method for producing the optical material, for example, a curing agent such as a radical polymerization initiator is added to the composition (P), and the composition is injected into a metal or glass or plastic casting having a desired lens shape or the like. After that, a method of polymerizing and demolding, and the like are included. The resulting optical material is a transparent, solvent-insoluble cross-linked resin.

The radical polymerization initiator prevents ^^ of the photochromic compound at the time of curing, and further suppresses coloring at the time of curing when the composition (P) contains a polyol, a thiol compound, or an isocyanate compound. Preferred examples thereof include a peroxyester-based initiator, a peroxyketal-based initiator, and an azo-based initiator.

Examples of the peroxester type initiator include t-hexylperoxynedecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, t-hexylperoxy- 2-ethylhexanoate, 1-cyclohexyl-1-methylethylperoxy neodecanoate, cuminoleperoxy neodecanoate, t-butylpentanoloxy-2-ethylhexanoate T, t-butyl peroxypivalate, t-hexyl phenoloxypivalate, t-butyl oleperoxy neodecanoate, t-butyl peroxyisobutyrate, t-butyl peroxy xylaurate, t -Butylperoxy nonanoate or mixtures thereof. Examples of the peroxyketal initiator include 1,1-bis (t-hexylperoxy) cyclohexane, di-t-butylbutyloxy-2-methylcyclohexane, and 1,1-bis (t-hexylperoxy). Butyl peroxy) -3,3,5-trimethylcyclohexane or a mixture thereof.

As the azo-based initiator, for example, azobisisobutyronitrile, azobisdimethinole parelonitrile or a mixture thereof can be mentioned.

If necessary, another curing agent such as another radical polymerization initiator, dibutyltin dilaurate, or dibutyltin di (2-ethylhexanoate) may be used in combination with the curing agent.

The amount of the radical polymerization initiator to be added is usually 0.01 to 0 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of the composition (M) in the composition (P). Less than 0.01 parts by weight will not cure When the amount is more than 10 parts by weight, the obtained optical material tends to be distorted, which is not preferable.

The polymerization curing can be performed by heating or irradiation with active energy rays. The curing condition is usually a polymerization temperature in the range of 30 to 100 ° C, preferably in the temperature range, and the polymerization time is usually 5 to 72 hours, preferably 1C! ~ 36 hours.

In the production of the optical material of the present invention, it is preferable that after the demolding, annealing treatment is performed in a nitrogen or air atmosphere at a temperature of 80 to 20 ° C. for 1 to 5 hours.

The photochromic lens of the present invention is a lens having the optical material. Usually, the optical material is processed into a lens shape, and if necessary, a hard coat process for improving surface hardness and imparting fashionability are provided. For example, by performing a coloring treatment with a disperse dye.

Example

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto. Each test method in the examples is as follows.

Kumitou Izumi Transmittance and Photomix Performance>

Using a transmittance photometer (manufactured by Nippon Denshoku Industries Co., Ltd.), the light transmittance of the resin plate was measured according to JIS K 7105. After UV irradiation (SOLAX XC-500ESS, manufactured by Celic Co., Ltd.) on the resin plate, time to color development (Rl), light transmittance at that time (T1) and time to extinction (R2), light transmission at that time The photochromic performance was evaluated by the ratio (2).

Refractive index and Abbe number>

Using an Abbe refractometer (manufactured by Atago), a test piece of lcmxl.5 cm was cut out from the resin plate at 25 ° C and measured.

Ku specific gravity>

According to JTS K 7112, specific gravity (gZcm ³ ) was measured at 25 ° C. by an underwater displacement method.

A steel ball with a weight of 16 g was naturally dropped onto a resin plate from a height of 127 cm, and the one without damage was designated as (a) and the one with damage was designated as (b).

A lcmx4cm plate is cut out from a resin plate, and the dynamic viscoelasticity is measured by Toyo Paul Doinne: Leopipelon, and the temperature showing the maximum of tan S is defined as the glass transition temperature (Tg). It was used as an indicator of heat resistance.

The abbreviations in the table are as follows.

(A): Compound (A)

BPE-6EA; 2,2-bis (4- (2-acryloxyethoxy) diethoxypheninole) propane, BPE-6E; 2,2-bis (4- (2-methacrylic xychetoxy) jetoxyphenyl) propane , DA-6EG; Hexaethylene glycol diacrylate,

DM-6EG; Hexaethylene glycol dimethacrylate,

(B): Compound (B)

BPE-10EA; 2,2-bis (4- (2-acryloxyethoxy) tetraethoxyphenyl) propane, BPE-10E; 2,2-bis (4- (2-metharyloxyethoxy) tetraethoxyf Enyl) propane, DA9EG; nonaethyleneglyconoresacrylate,

DM9EG; Nonaethylene glycol dimethacrylate,

(C): Compound (C)

BPE-2EA; 2,2-bis (4-acryloxyethoxyphenyl) propane,

BPE-2E; 2,2-bis (4-methacryloxyshetoxyphenyl) propane,

HE-BP; 2,2-bis (4- (2-methacryloxyethoxycarponoxy) phenyl) propane,

DA2EG; diethylene glycol diacrylate,

DM2EG; diethylene glycol dimethacrylate,

(D): Amide compound (D)

DMAA; N, N-dimethylacrylamide, ΓΡΑΑ; N-isopropylacrylamide, DMAPAA; N- (3-dimethylaminopropyl) acrylamide,

DMAPMA; N- (3-dimethylaminopropyl) methacrylamide.

(E): Other vinyl compounds (E)

MA: Methynoacrylate, MMA: Methyl methacrylate,

BA; n-butynoleacrylate, BMA; n-butynolemethacrylate,

BzMA: Penzinole methacrylate,

A4EG: methoxytetraethylene glycol monoacrylate,

MA4EG; methoxytetraethylene dalicol monomethacrylate,

A9EG; methoxy nona ethylene glycol monoacrylate,

MA9EG: methoxy nona ethylene glycol monomethacrylate. (F): mixture (F)

TMI; 3-Isopropenyl-a, (¾-dimethylbenzyl isocyanate, 'XDI; m-xylylene diisocyanate, ETT; 2,2'-thiojetanethiol,

PETT; pentaerythritol tetrakis (/ 3-thiopropionate).

(Amine compound)

MADM; N, N-dimethylaminoethyl methacrylate,

MADE; N, N-Jetylaminoethyl methacrylate, TMA; Triethylamine,

TEA; triethylenediamine,

DBU; 1,8-diazabicyclo (5,4,0) pandecene-7

(Photochromic compound)

P1; Spiropyran compound (1 ', 3'-dihydro-5'-methoxy-1', 3 ', 3'-trimethyl-6-ditrospi (2H-1-benzovirane-2,2'-2H-indole )),

P2: Spirooxazine compound (1,3-dihydro-1,3,3-trimethyl-spiro (2H-indole-2,3′-3H-phenanthone [9,10-b] [l, 4]] oxazine),

P3; fulgide compound (3-adamantane-2-ylidene-4- (1- (2,5-dimethylthiophen-3-yl) -2-methylinopropylidene) dihydrofuran-2,5-dione),

P4: a chromene compound (4- (3-phenyl-3- (4-piperidine-1-yl-phenylinole) -3H-benzo [f-chromen-6-yl) morpholine).

Examples 1-32

Compositions (P) were prepared by blending the respective raw materials shown in Tables 1 to 3. Here, the unit of the numerical value of each raw material in the table is g. Next, 0.4 g of t-butylbenzyloxyneodecanoate was added, and the mixture was injected into a casting mold composed of two glass disks having a diameter of 7 cm and a gasket made of ethylene-propylene wrapper having a thickness of 2 nm. Then, in a hot-air bath with a programmed temperature controller, the temperature rises from 30 to: L20 ° C over 18 hours, then is maintained at 120 ° C for 2 hours, then cooled to 40 ° C over 2 hours did. After curing, the demolded disk-shaped resin plate was subjected to an annealing treatment at 100 ° C. for another 2 hours to prepare a resin plate as an optical material. Tables 1-1 to 3-1 show the results of each test for the resin plate.

Examples 33-40

A composition (P) was prepared by blending the respective raw materials shown in Table 4. Next, 0.02 g of dibutyltin diperphosphate and 0.4 g of t-butylbenzyloxyneodecanoate were added as curing agents. The resin was cured as in Examples 1 to 32 to prepare a resin plate as an optical material. Table 4-1 shows the results of each test for the resin plate.

Comparative Examples 1 to 6

Each material shown in Table 5 was blended to prepare a composition for an optical material. Next, 0.6 g of diisopropyl peroxyxycarbonate was added as a curing agent, and hardened in the same manner as in Examples 1 to 32 to prepare a resin plate as an optical material. Table 5 shows the results of each test for the resin plate.

In addition, Comparative Examples 1, 2 and 6 did not contain the compounds (A) and (B), Comparative Example 3 did not contain the compound (B), and Comparative Example 4 showed the compound (A). Comparative Example 5 is an example in which the content of the compound (B) containing the compounds (A) and (B) exceeds the content of the present invention. In Comparative Examples 4 and 5, deformation occurred when the mold was released after curing.

table 1

Table 1-1

Example

1 2 3 4 5 6 7 8 9 10 11 Transmittance (%) 88 88 88 87 87 87 86 86 88 86 87 Color Green Purple Purple Main

冃 n 鵷

R Satoshi 10 14 15 16 10 12 13 11 10 12 13

Tl (%) 9 17 13 13 11 14 15 11 15 16 14 R2®>) 60 60 60 60 60 60 60 60 60 60 60

T2 (%) 50 46 44 45 42 48 49 47 48 46 49 Review

Refractive index (25 ° C) 1.533 1.546 1.521 1.544 1.516 1.541 1.541 1.532 1.515 1.521 1.527 Val Abbe number 43 39 41 39 42 39 39 41 43 41 40 Specific gravity 1.18 1.20 1.18 1.19 1.18 1.21 1.20 1.21 1.18 1.20 1.19 (a) (a) (a) (a) (a) (a) (a) (a) (a) (a) Heat resistance CC) 77 103 93 96 95 100 97 98 95 92 93

Table 2

Table 2- Implementation \ column

12 13 14 15 16 17 18 19 20 21

88 88 87 87 86 86 86 86 87 87 Color Purple Purple Purple Blue Blue

Object R1 chute) 13 15 9 10 10 10 9 11 10 12

Tl (%) 11 12 8 10 12 12 9 10 12 13 Sex β2 60 60 60 60 60 60 60 60 60 60 60

Τ2 (%) 49 46 48 43 43 51 50 48 51 49 Refractive index (25 C) 1.538 1.544 1.511 1.516 1.516 1.538 1.528 1.532 L522 1.527 Val Abbe number 40 39 43 42 42 40 42 41 42 40 Specific gravity 1.19 1.19 1.18 1.18 1.18 1.20 1.21 1.21 1.19 1.19 Fermentation resistance (a) (a) (a) (a) (a) (a) (a) (a) (a) (a) Heat resistance (° C) 91 96 91 95 95 93 95 98 87 93 Table 3

Example

22 23 24 25 26 27 28 29 30 31 32

BPE-6EA 8 8 12

(A) BPE-6E 14 16 10 14 10 12 10

DA6EG 4

DM6EG 4 2 12 4

BPE-IOEA 4 4 2

(B) BPE-IOE 2 4 4 2 4

DA9EG 6 2 DM9EG 4 2

BPE-2EA 2

BPE-2E 4 2 2

(C) HE-BP 2

DA2EG 2 4 2

DM2EG 2 2

DMAA 0.2

(D) IPAA 0.2

DMAPAA 0.2

DMAPMA 0.2

MA MMA 2

BA 2

BMA 2

(E) BzMA 2

A4EG 2

MA4EG 2

A9EG 2

MA9EG 2

,

Fan compound

MADM 0.03 0.06

MADE 0.03 0.06

TMA 0.03 0.06

TEA 0.03 0.03 0.06

DBU 0.001 0.002 Photoc p-mic compound

PI 0.02 0.02 0.02

P2 0.02 0.02 0.02

P3 0.02 0.02

P4 0.02 0.02 0.02 Table 3-1

Example

22 23 24 25 26 27 28 29 30 31 32 Transmittance (H /) 88 88 88 87 87 87 86 86 88 86 87

—:

Color green green green purple purple η n 赫赫物物物 R 12 8 12 12 12 9 10 10 9 10 10 10

Tl (%) 7 14 12 10 7 10 11 8 10 12 11 Characteristic R2 (sec) 60 60 60 60 60 60 60 60 60 60 60

T2 (%) 52 48 46 50 49 51 52 51 51 50 52 Refractive index (25 ° C) 1.528 1.539 1.518 1.538 1.511 L538 1.538 1.528 1.511 1.517 1.522 Val 43 40 42 40 43 40 39 42 44 42 42 Specific gravity 1.18 1.20 1.18 1.19 1.18 1.21 1.20 1.21 1.18 1.20 1.19 Impact resistance (a) (a) (a) (a) (a) (a) (a) (a) (a) (a) (a) Heat resistance I4 (° C) 74 96 90 91 91 95 93 95 92 88 87

W 03

18 Table 4

Table 4-]

The resin plate obtained in the examples has not only the basic properties required for optical materials and lenses, but also has excellent photoresponse speed and color stability of the photochromic compound as compared with the resin plate of the comparative example. It was found that the following physical properties were obtained.

Claims

The scope of the claims

In 1) (1);) 'and at least one compound the total of n is 5 to 7 (A) from 15 to 97 weight ^_0/0, and total 9 of j and n in the formula (1) A composition for an optical material comprising 100 parts by weight of a monomer composition containing 3 to 50% by weight of at least one compound (B) which is L1, and 0.001 to 10 parts by weight of a photochromic compound.

(Wherein, R ¹ and R ² represent a hydrogen atom or a methyl group, Ph represents a phenylene group.] 'And n are independently an integer of 0 to: L1, provided that j and n are simultaneously It is not 0. k, m and p are independently 0 or 1.)

2) The monomer composition is a compound (C) in which the sum of j and n in the formula (1) is 2 to 3, an amide compound having a vinyl group (D), another Bier compound (E), and 2. The composition for an optical material according to claim 1, further comprising a monomer selected from the group consisting of these mixtures.

3) The composition for an optical material according to claim 1, further comprising a mixture (F) capable of forming a thioethane resin comprising the cisocyanate compound and a thiol conjugate.

4) The composition for an optical material according to claim 1, further comprising an amine compound.

5) The composition for an optical material according to claim 4, wherein the content of the amine compound is 5 to 50,000 ppm in the composition for an optical material.

6) An optical material obtained by polymerizing and curing the composition for an optical material according to claim 1.

7) A photochromic lens comprising the optical material according to claim 6.