JP2735679B2 - Photochromic molding - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a photochromic molded article having excellent photochromic action durability.

(Prior art) Photochromism is a phenomenon that has been attracting attention for the past several years. When a compound is irradiated with light containing ultraviolet light such as sunlight or light from a mercury lamp, the color changes rapidly, and the light irradiation is stopped. It is a reversible action that returns to the original color when stopped and put in a dark place. A compound having this property is called a photochromic compound, and compounds having various structures have been conventionally synthesized and proposed, but no special common skeleton is recognized in the structure.

The present inventors have continued research on a series of photochromic compounds and have succeeded in synthesizing a novel spirooxazine compound having an oxazine skeleton, and have found that the spirooxazine compound has an excellent photochromic action, They have been proposed (Japanese Patent Application No. 2-42347 and Japanese Patent Application No. 2-78637).

(Problems to be Solved by the Invention) Further, the present inventors have continued research on producing a photochromic molded product represented by a photochromic lens by dispersing the above spirooxazine compound in a resin. As a result, they have found that the durability of the photochromic action of the spirooxazine compound is improved depending on how the spirooxazine compound is present in the resin.

Therefore, an object of the present invention is to obtain a photochromic molded article having excellent durability.

(Means for Solving the Problems) That is, the present invention provides the following formula [I] A resin layer containing a spirooxazine compound represented by is coated on the surface of the thermosetting resin,
The photochromic molded article further comprises a layer made of a hydrolyzate of an organosilicon compound coated thereon.

Also, the present invention Is a photochromic molded product in which a surface of a thermosetting resin is impregnated with a spirooxazine compound represented by formula (1), and a layer made of a hydrolyzate of an organosilicon compound is further coated thereon.

In the above general formula (I), Is an aromatic hydrocarbon group or an unsaturated heterocyclic group which may be substituted, respectively. Specific examples of the aromatic hydrocarbon group include a divalent group derived from one benzene ring such as a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring or a fused ring of 2 to 4 benzene rings. Further, a hydroxyl group, a nitro group, a cyano group, a fluoroalkyl group, a substituted amino group,
Examples include a substituted aromatic hydrocarbon group in which one or more heterocyclic groups such as a halogen atom, an alkyl group, an alkoxy group, a phenyl group, a thienyl group, a furyl group, and a pyrrolyl group are substituted.

In the above general formula (I), The optionally substituted unsaturated heterocyclic group represented by is a 5- or 6-membered ring containing an oxygen, ion or nitrogen atom, or a heterocyclic group in which a benzene ring is fused thereto. Specifically, it is derived from nitrogen-containing heterocycles such as pyridine ring, quinoline ring, pyrrole ring and indole ring; oxygen-containing heterocycle such as furan ring and benzofuran ring; and sulfur-containing heterocycle such as thiophene ring and benzothiophene ring. Divalent heterocyclic group. In particular, in the case of a bicyclic fused heterocycle of a benzene ring and a 5- or 6-membered heterocycle, a high color density can be obtained.

As the substituent of the unsaturated heterocyclic group, the substituent of the aromatic hydrocarbon group described above is employed without any limitation.

Next, in the general formula [I], Is It is.

Here, R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are the same or different, respectively, a hydrogen atom, a halogen atom, a hydrocarbon group,
An alkoxy group, a cyano group, a halogenoalkyl group, an amino group, a substituted amino group or an alkoxycarbonyl group,
At least one of R ₄ and R ₅ is a cyano group, a halogenoalkyl group or an alkoxycarbonyl group, Is an optionally substituted aromatic hydrocarbon group or an unsaturated heterocyclic group.

Examples of the halogen atom include fluorine, chlorine, and bromine.

Examples of the hydrocarbon group include an alkyl group, an aryl group, and an aralkyl group. Among them, the alkyl group is not particularly limited, but generally has 1 to 10 carbon atoms, preferably 1 to 10 carbon atoms.
It is preferably from 4 to 4. More specific examples of the alkyl group include a methyl group, an ethyl group, and an isopropyl group. Further, the aryl group preferably has 6 to 10 carbon atoms, and specific examples thereof include a phenyl group and a naphthyl group. The aralkyl group preferably has 7 to 14 carbon atoms. Specific examples include a benzyl group, a phenylethyl group, a phenylpropyl group, and a naphthylmethyl group.

Next, the alkoxy group is not particularly limited, but generally preferably has 1 to 10 carbon atoms, and preferably 1 to 4 carbon atoms. Specific examples include a methoxy group, an ethoxy group, and an isopropoxy group. it can.

The halogen atom in the above halogenoalkyl group is fluorine, chlorine, bromine or the like, and the alkyl group preferably has 1 to 4 carbon atoms. Specifically, a trifluoromethyl group,
Trichloromethyl group, tribromomethyl group and the like.

An amino group or a substituted amino group has the general formula Indicated by R ₁₁ and R ₁₂ are preferably the same or different hydrogen atoms and hydrocarbon groups, respectively. As the hydrocarbon group, the same groups as those described for R _{4 to} R ₁₀ are preferably used. Furthermore, the substituted amino group has the general formula In the case shown by R ₁₃ is an alkylene group such as a tetramethylene group or a pentamethylene group; _{-CH 2 OCH 2 CH 2 -,} CH 2 CH 2 OCH 2 CH 2 -, - oxyalkylene groups such as _{CH 2 O (CH 2 3;} -CH 2 SCH 2 CH 2 -, - CH 2 S (CH 2
_{3, -CH 2 CH 2 SCH 2} CH 2 - thioalkylene groups such as; And the like.

The alkoxycarbonyl group is not particularly limited, but generally has 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms. More specific examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

In the general formula [I], at least one of R ₄ and R ₅ must be a cyano group, a halogenoalkyl group or an alkoxycarbonyl group. By selecting these groups, the spirooxazine compound used in the present invention exhibits a good photochromic action even in a high temperature range.

next Is an aromatic hydrocarbon group or an unsaturated heterocyclic group, each of which may be substituted. These groups are already The groups described for are employed without any limitation.

Is the general formula [I] And the spirooxazine compound used in the present invention exhibits a good photochromic action even at a high temperature range.

Next, in the general formula [I], When R ₁ and R ₂ are a hydrogen atom or an alkyl group, R ₁ and R ₂ may form a ring together,
R ₃ is an alkoxycarbonylalkyl group, When R ₁ and R ₂ are a hydrogen atom or an alkyl group, at least one of which is an alkyl group having 2 or more carbon atoms,
Or they may together form a ring,
R ₃ is a hydrogen atom, a hydrocarbon group, an alkoxycarbonylalkyl group or a cyanoalkyl group.

The alkyl group is not particularly limited, but generally has 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms. Specific examples of the above alkyl group include a methyl group, an ethyl group, and an isopropyl group. Also, R ₁ and R ₂
When they together form a ring, they are not particularly limited, but generally a cycloalkyl ring having 5 to 10 carbon atoms, a bicycloalkyl ring, and a tricycloalkyl ring are preferred.
When these are exemplified more specifically, a cyclopentyl ring,
Examples include a divalent group derived from a cyclohexyl ring, a cycloheptyl ring, a norbornane ring, an adamantane ring, or a bicyclo [3.3.1] nonane ring. These R ₁ and R ₂ are
Either one is an alkyl group having 1 or more carbon atoms and the other is an alkyl group having 2 or more carbon atoms, or a combination of these forms a ring to provide a good color density in a high temperature range. It is suitable for indicating

In the general formula [I], the hydrocarbon group represented by R ₃ is not particularly limited, and the groups described in R _{4 to} R ₁₀ are employed.

The alkoxy group in the alkoxycarbonylalkyl group is not particularly limited, but generally has 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. The alkylene group in the alkoxycarbonylalkyl group is not particularly limited, but generally has 1 to 10, preferably 1 to 4 carbon atoms. More specific examples of the alkoxycarbonylalkyl group include a methoxycarbonylmethyl group, a methoxycarbonylethyl group, a methoxycarbonylpropyl group, an ethoxycarbonylmethyl group, an ethoxycarbonylethyl group, an ethoxycarbonylbutyl group, and a butoxycarbonylethyl group.

The cyanoalkyl group is not particularly limited, but generally has 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples of the cyanoalkyl group include a cyanomethyl group, a cyanoethyl group, and a cyanopropyl group.

The spirooxazine compound represented by the general formula [I] in the present invention generally develops a color from red to blue. Therefore,
When the photochromic molded article of the present invention is used for applications such as decorative articles, the compound of the above general formula [I] may be used alone. In addition, when the photochromic molded article of the present invention is used for applications such as sunglasses, the color tone is generally brown or gray, so that the color tone is preferably adjusted in combination with other photochromic compounds.
As other photochromic compounds, those generally called chromene or derivatives thereof are preferably used in the present invention because they can be adjusted to a brown or gray color by using the compound of the general formula [I] in combination. Can be The amount of the above-mentioned chromene or a derivative thereof may be appropriately selected depending on the required color tone. Generally, in order to obtain a brown or gray color tone, 0.01 to 10,000 based on 100 parts by weight of the compound of the general formula [I]. Parts by weight, preferably 0.05 to 1
It is better to select from the range of 000 parts by weight.

The above chromene has the following formula It is a compound shown by these. Further, as the chromene derivative, the compound having the above chromene skeleton is employed without any limitation. In the present invention, a chromene derivative represented by the following formula [A] is particularly preferably used because it has excellent photochromic properties.

In the general formula [A], An aromatic hydrocarbon group and an unsaturated heterocyclic group represented by
Of the spirooxazine compound represented by the general formula (I) The group described for is employed. Further, the substituents of these aromatic hydrocarbon group and unsaturated heterocyclic group are the same as those in the above general formula [I]. The substituents of the aromatic hydrocarbon group and the unsaturated heterocyclic group represented by are adopted without any limitation.

Further, -R ⁵ -SR ⁶ , [However, R ⁵ is an alkylene group or O-R ⁸ _n (however, R ⁸
Is an alkylene group, and n is a positive integer. R ⁶ and R ⁷ are the same or different alkyl groups, and X is -N <, -P <, It is. ] May be substituted one or more times.
The carbon number of the above alkyl group and alkylene group is preferably in the range of 6 to 20, and _n of OR ⁸ n
Is preferably an integer such that the total number of carbon atoms is 6 to 20.

Next, in the general formula [A], the hydrocarbon group and the substituted amino group represented by R ¹ , R ² , R ³ and R ⁴ correspond to R ₄ to R _{4 of the} spirooxazine compound represented by the general formula [I]. similar hydrocarbon groups and substituted amino groups as described for R ₁₀ is employed.

Further, in the general formula [A], R ¹ and R ² may form a ring together, and in this case, the ring is the same as R ₁ and R ₂ in the general formula [I]. The rings described are employed without any restrictions.

Among the above-mentioned chromene or a derivative thereof, in the general formula (A), Is preferably a condensed ring of two or more rings because of high color density. Among them, compounds in which a ring is condensed at positions 7 and 8 of the chromene skeleton are more preferable. Further, in the general formula [A],
When R ¹ and R ² form a ring, the chromene skeleton
Compounds in which a ring is fused at the 5- or 6-position are also preferably used.

The resin of the resin layer containing the photochromic compound such as the spirooxazine compound or chromene or a derivative thereof dispersed therein is strongly adhered to the surface of the thermosetting resin to be coated, as long as the photochromic compound is uniformly dispersed. , Thermoplastic resins and thermosetting resins. In general, when forming a film of a hydrolyzate of an organosilicon compound described below on the surface of a thermosetting resin, it is used for the purpose of improving the adhesion between the film of the hydrolyzate of an organosilicon compound and the thermosetting resin. The primers used can be used without any restrictions. Examples of such a primer include an epoxy resin-based primer having two or more epoxy groups in one molecule such as a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, and an alicyclic epoxy resin. Silane-based primers such as Tosprim A, Tosprim B, Tosprim C, Tosprim D, Tosprim E and YP9341 (all manufactured by Toshiba Silicone; trade name); Polysol F361, Polysol F341, Polysol FF-450; Kogum HW-7 (all manufactured by Showa Polymer Co., Ltd .: trade name), Sebian A517, Sebian A4716, Sebian A46701, Sebian A
4635, Sebian A4730, Sebian A45000, Sebian A4171
(These are Daicel Chemical Industries; trade name), Nicazole
FL-3000, Nicazole ME-702, Nicazole FX-201, Nicazole FX-322, Nicazole FL-329, Nicazole TS-
444, Nicazole TS-501, Nicazole TS-517, Nicazole TS-542, Nissetsu PC-501, Nissetsu PE-115, Nissetsu PE-118, Nissetsu PE-121 (all manufactured by Nippon Carbide Industrial Co., Ltd .; trade name) An acrylic resin-based primer can be used. Also, polyvinyl alcohol,
A hydrophilic resin such as poly (2-hydroxyethyl methacrylate), polyacrylonitrile, or a cellulose-based natural polymer can also be used as a resin for dispersing the photochromic compound.

The amount of the photochromic compound to be contained in these resins may be determined according to the coloring density of the obtained photochromic molded article.In general, the photochromic compound and 0.001 to 60 parts by weight, particularly 100 parts by weight of the resin,
The content is preferably in the range of 0.1 to 40 parts by weight.

The thickness of the resin layer containing the photochromic compound may be determined according to the color density of the resulting photochromic molded product, but is generally preferably in the range of 0.5 to 10 μm.

On the other hand, as a method of impregnating the surface of a thermosetting resin with a photochromic compound, a commonly used photochromic compound is heated to a melting point or higher, melted, and the thermosetting resin is immersed therein for 1 to 60 minutes to impregnate the compound. Is used. Further, a method in which a photochromic compound is melted in a high boiling point inert liquid and a thermosetting resin is immersed therein, as disclosed in JP-A-61-501145, can also be employed. Here, as the high boiling point inert liquid, silicone oil, perfluoro oil, or the like is used, and the photochromic compound may be used after being dissolved in the high boiling point inert liquid at a concentration of 0.1 to 50% by weight. Further, JP-A-60-
A method of dispersing a photochromic compound in a commercially available lacquer as shown in JP 112880, applying this to a thermosetting resin, heating at 100 to 250 ° C. for 1 to 60 minutes, and impregnating the surface is also adopted. Is done. At this time, the concentration of the photochromic compound in the commercial lacquer is preferably 0.1 to 50% by weight.

In the present invention, a layer containing a photochromic compound is formed on or near the surface of the thermosetting resin by the method described above, and a hydrolyzate of an organosilicon compound is used to further improve the durability of the photochromic property thereon. Is applied.

The hydrolyzate of the organosilicon compound is required to have strong adhesion to the resin layer containing the photochromic compound or the thermosetting resin surface after impregnation with the photochromic compound. Further, considering the durability of the photochromic compound and the surface hardness as a molded article, the hydrolyzate layer preferably has a uniform film thickness of 0.2 to 10 μm.

For forming such a film, a coating agent comprising an organosilicon compound, a surface hardness improver, and a curing catalyst is suitably used.

First, as the organosilicon compound as the first component of the coating agent, the following formulas [II] and / or [III] (However, R ₁₁ is a vinyl group, a methacryloyloxy group,
Mercapto group, an epoxy group, a hydrocarbon group, or an alkyl group having at least one group selected from the group consisting of glycidoxy groups, and amino group, an aryl group, a vinyl group, R ₁₂ is alkyl N is 0 or 1, and R ₁₃ is an alkyl group, an acetyl group or an alkoxyalkyl group. ) Organoalkoxysilane compounds represented by (However, A is a divalent hydrocarbon group whose main chain is composed of at least 4 or more atoms in a straight chain, R ₁₄ and R ₁₅ are the same or different alkyl or alkoxyalkyl groups, R ₁₆ and R
₁₇ is the same or different alkyl group, and l and m are 0 or 1).

Organoalkoxysilane compound represented by the above general formula (II), particularly the carbon number of R ₁₂ is from 1 to 4 carbon atoms in R ₁₃ are those having 1 to 4 are commonly used. Specifically, methyltrimethoxysilane, dimethylmethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyl Trismethoxyethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, β- (3,4-epoxy Cyclohexyl) ethyltrimethoxysilane, γ-aminopropyltriethoxysilane and the like.

Further, typical specific examples of the divalent hydrocarbon group represented by A in the disilane compound represented by the general formula (III) include —CH ₂ CH ₂ CH ₂ CH ₂ —, An alkylene group such as —CH ₂ CH ₂ OCH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂
General formulas such as OCH ₂ CH ₂ CH ₂ — CH ₂ ) _p O [(CH ₂ ) _q O] _r (C
H ₂ ) an ether group represented by _p (where p and q are 2 or 3 and r is an integer of 0 or more); (Where R is CH ₂ CH ₂ O or CH ₂ CH ₂ CH ₂ O, and s is 0 to
4 is an integer. t is 0 when s = 0, and s = 1 to 4
In this case, it is 1. And the like.

Further, in addition to the above organosilicon compound, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, o-phthalic acid diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether An organic compound having two or more epoxy groups in one molecule can also be used in combination.

As the second component of the coating agent, a tetraalkoxysilane compound represented by the following formula Si (OR ₁₈ ) ₄ (IV) (where R
₁₈ is an alkyl group or an alkoxyalkyl group)
And at least one selected from colloidal silica and a component obtained by hydrolysis of The tetraalkoxysilane compound represented by the general formula (IV) has 1 carbon atom of R _18.
~ 4 are commonly used. Specific examples include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and the like. Further, as the colloidal silica, silica fine powder having a particle size of 1 to 100 μm produced by various conventionally known methods can be used as it is or in the form of a colloidal solution in which this is dispersed in a polar solvent. In the present invention, the colloidal solution in which the colloidal silica is dispersed in a polar solvent, for example, water or an alcoholic solvent such as methanol or isopropanol, is preferably adjusted to be weakly acidic.

The curing catalyst of the third component of the coating agent is used to lower the curing temperature of the coating film and shorten the curing time, and is a compound known as a curing catalyst in the hydrolysis of an organosilicon compound, such as hydrochloric acid, sulfuric acid, and acetic acid. / Sodium acetate mixture, tin chloride, perchloric acid, ammonium perchlorate, zinc perchlorate, perchlorate such as magnesium perchlorate, metal acetylacetonate such as aluminum acetylacetonate, metal naphthenate, It is preferable to use p-toluenesulfonic acid, benzoic acid, alkali metal phosphate, sodium thiocyanate and the like.

Further, in addition to the above-described components, it is possible to add a silicon-based or fluorine-based surfactant to improve the smoothness of the obtained film and form a uniform film of the next inorganic hard material. In addition, other various additives, for example, ultraviolet absorbers, antioxidants, dyes and pigments, or organic carboxylic acids such as formic acid and acetic acid as gelling inhibitors can also be used.

The amount of each component of these coating agents is the first component
10-100 parts by weight of the second component, 100 parts by weight of the third component 1
It is preferably from 10 to 10 parts by weight.

As a method of forming a film of a hydrolyzate of an organosilicon compound using the above-mentioned coating agent, a known method is employed without any limitation.

As the thermosetting resin used in the present invention, ethylene glycol diacrylate, diethylene glycol dimethacrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A dimethacrylate, 2,2-bis (4-methacryloyloxyethoxyphenyl) propane, 2,2 Poly (acrylic acid) and poly (methacrylic acid ester) compounds such as bis (3,5-dibromo-4-methacryloyloxyethoxyphenyl) propane; diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl tartrate, diallyl epoxysuccinate, Diallyl fumarate, diallyl chlorendate,
Polyallyl compounds such as diallyl hexaphthalate, diallyl carbonate, allyl diglycol carbonate, and trimethylolpropane triallyl carbonate; 1,2-
Polyvalent thioacrylic acid and polyvalent thiomethacrylic acid ester compounds such as bis (methacryloylthio) ethane, bis (2-acryloylthioethyl) ether and 1,4-bis (methacryloylthiomethyl) benzene; radical polymerization of divinylbenzene and the like Polymer of functional polyfunctional monomer: or each of these monomers and acrylic acid, methacrylic acid, unsaturated carboxylic acid such as maleic anhydride, methyl acrylate, methyl methacrylate, benzyl methacrylate, phenyl methacrylate, Acrylic acid and methacrylic acid ester compounds such as 2-hydroxyethyl methacrylate; fumaric acid ester compounds such as diethyl fumarate and diphenyl fumarate; thioacrylic acid and thiomethacrylic acid such as methylthioacrylate, benzylthioacrylate and benzylthiomethacrylate Copolymers with radically polymerizable monofunctional monomers such as vinyl compounds such as styrene, chlorostyrene, methylstyrene, vinylnaphthalene, and bromostyrene; and ethanedithiol, propanetriol, hexanedithiol, and pentaerysulfur Addition copolymers of a polyvalent thiol compound such as tall tetrakisthioglycolate, di (2-mercaptoethyl) ether and the above-mentioned radical polymerizable polyfunctional monomer: diphenylethane diisocyanate, xylylene diisocyanate,
An addition polymer of a polyvalent isocyanate compound such as p-phenylene diisocyanate and a polyhydric alcohol compound such as ethylene glycol, trimethylolpropane, pentaerythritol and bisphenol A, or the above-mentioned polyvalent thiol compound may be used. These monomers can be used alone or in combination of two or more.

By adding an ultraviolet stabilizer to the resin layer containing the photochromic compound dispersed in the photochromic molding of the present invention, and by impregnating the ultraviolet stabilizer together when impregnating the photochromic compound, the durability of the photochromic property is improved. Can be further improved. As the ultraviolet stabilizer, a known ultraviolet stabilizer added to various plastics can be used without any limitation.

In the present invention, considering the improvement in durability of the photochromic compound, among various ultraviolet stabilizers, a singlet oxygen quencher, a hindered amine light stabilizer, a hindered phenol antioxidant, and a sulfur-based antioxidant are preferably used. Is done. More specific examples of these ultraviolet stabilizers include Sheasorb UV1084, Sheasorb 3346 (all manufactured by American Cyanamid Co.), UV-Cek AM101, and UV-Cek A.
M105 (all manufactured by Ferro Corporation), Irgas Tab 2002, Tinuvin 765, Tinuvin 144, Chimasorb 944,
Tinuvin 622, Irganox 1010, Irganox 245
(Manufactured by Ciba-Geigy), Reylex NBC (manufactured by Dupont), Sheasorb 3346 (manufactured by American Cyanamid), Sanol LS-1114, Sanol LS-744, Sanol LS
−2626 (above, manufactured by Sankyo Co., Ltd.), Sumilizer GA-8
0, Sumilizer GM, Sumilizer BBM-S, Sumilizer WX-R, Sumilizer S, Sumilizer BHT, Sumilizer TP-D, Sumilizer TPL-R, Sumilizer T
PS, Sumilizer MB (Sumitomo Chemical Co., Ltd.), Mark AO-
50, mark AO-20, mark AO-30, mark AO-330, mark AO-23 (all manufactured by Adeka Argus), antioxidant HPM-12 (manufactured by SFOS) and the like.
Each of the above names is a trade name.

(Effect) In the photochromic molded article of the present invention, the durability of the photochromic compound is improved by allowing the photochromic compound to be present in the resin.

The photochromic molded article of the present invention can be used in a wide range of fields, for example, various recording memory materials, copying materials, printing photoconductors, cathode ray tube recording materials, laser photosensitive materials, etc. It can be used as a recording material. In addition, the photochromic molded article of the present invention can be used as a material for a photochromic lens material, an optical filter material, a display material, a light meter, a decoration, and the like.

(Examples) Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. “Parts” in the examples is “parts by weight”.

 The symbols in the following examples indicate the following compounds.

・ BMDBP: 2,2-bis (4-methacryloyloxyethoxy-3,5-dibromophenyl) propane ・ Cl-St: chlorostyrene ・ TMP-TAC: trimethylolpropane triallyl carbonate ・ BADBP: 2,2-bis ( 4-allyl carbonate ethoxy-3,5-dibromophenyl) propane ・ ADC: allyl diglycol carbonate ・ DAP: diallyl phthalate ・ St: styrene ・ DCIPF: di (2-chloroisopropyl) fumarate ・ EGDMA: ethylene glycol dimethacrylate ・ PETTP : Pentaerythritol tetrakis (β-thiopropionate) ・ DME: Di (2-methylcaptoethyl) ether ・ DVB: Divinylbenzene ・ XIC: Xylylene diisocyanate ・ HPA: 3- (2,4-dibromophenoxy) -2 -Hydroxypropyl acrylate-MMA: methyl methacrylate-DEGDMA: diethylene glyco Ludi methacrylateTBBM: 3,4,5-tribromobenzyl methacrylateHEMA: 2-hydroxyethyl methacrylateBMA: benzyl methacrylatePVA: polyvinyl alcoholPHEMA: polyhydroxyethyl methacrylatePAN: polyacrylonitrileperbutyl ND: t-butyl peroxy-2-hexanoate Production Example 1 Compound of the following formula 2.01 g (0.0057 mol) and the compound of the following formula 1.4 g (0.0057 mol) and 0.41 g (0.0058 mol) of pyrrolidine
Was dissolved in 50 ml of ethyl alcohol and heated under reflux for 2 hours.

After the reaction, the solvent was removed, and purification was carried out by chromatography on silica gel to obtain 200 mg of a spirooxazine compound represented by the following formula.

Elemental analysis of this compound gave C 65.12%, H 4.90%, N
8.51%, O 9.74%, F 11.73%, which are calculated values for C ₂₇ H ₂₄ N ₃ O ₃ F ₃ C 65.45%, H 4.88%, N 8.48%, O 9.
It was very good agreement with 69% and F 11.50%. When the proton nuclear magnetic resonance spectrum was measured, δ 6.5 to 9 ppm
Near 9H peak based on quinoline ring proton, indoline ring proton and oxazine ring proton, δ 4pp
around m 2H peak based on the proton of
3H peak based on proton of CH ₃ bond, δ 1.3 to 2.1
A broad peak of 10H based on the proton of the cyclohexane ring was shown around ppm. Furthermore, when ¹³ C-nuclear magnetic resonance spectrum was measured, a peak based on carbon of carbonyl at around 170 ppm, a peak based on carbon of benzene ring, quinoline ring and oxazine ring of indoline, around δ 100 to 160 ppm, around δ 125 ppm A peak based on a trifluoromethyl group, a peak based on spiro carbon at around δ99 ppm and δ52 ppm, and a peak based on a methyl group and carbon of a methylene chain near δ20 to 50 ppm were shown.

From the above results, it was confirmed that the isolated product was the compound represented by the above structural formula (1).

Production Example 2 Compound of the Following Formula 2.0 g (0.0057 mol) of the compound of the following formula 1.4 g (0.0057 mol) and 0.41 g (0.0057 mol) of pyrrolidine
Was dissolved in 50 ml of ethyl alcohol and heated under reflux for 2 hours. After the reaction, the solvent was removed and the residue was purified by chromatography on silica gel to obtain 150 mg of a spirooxazine compound represented by the following formula.

Elemental analysis of this compound gave C 65.23%, H 5.21%, N
8.56%, O 9.71%, F 11.29%, which are calculated values for C ₂₇ H ₂₆ N ₃ O ₃ F ₃ C 65.18%, H 5.27%, N 8.45%, O 9.
Very good agreement with 93% and F 11.46%. When the proton nuclear magnetic resonance spectrum was measured, δ 6.5 to 9 ppm
Near the aromatic proton peak, δ
A peak based on the methyl proton of the ethyl group was around 1.0 ppm, a peak based on the methylene proton of the ethyl group was around δ 2 ppm, and a peak based on the proton of N-CH ₂ CH ₂ COOCH ₃ was around δ 3.5 ppm. When ¹³ C-NMR was measured, a peak based on carbon of carbonyl around δ 170 ppm, an aromatic carbon around δ 100 to 160 ppm, a peak based on carbon of oxazine ring and carbon of trifluoromethyl group, δ 99 ppm In the vicinity, a peak based on spiro carbon, a peak near δ 50 ppm based on carbon of methylene bonded to nitrogen, and a peak near δ 20 to 40 ppm based on carbon of methyl group and methylene group bonded to carbon were shown. From the above results, it was confirmed that the isolated product was the compound represented by the above structural formula (2).

Production Example 3 Compound of the Following Formula 2.01 g (0.0059 mol) and the following compounds 1.02 g (0.0059 mol) and 0.43 g (0.006 mol) of pyrrolidine
Was dissolved in 50 ml of ethyl alcohol and heated under reflux for 2 hours.

After the reaction, the solvent was removed, and the resulting product was purified by chromatography on silica gel to obtain 400 mg of a spirooxazine compound represented by the following formula.

Elemental analysis of this compound gave C 81.35%, H 6.60%, N
7.62% and O 4.43%, which corresponded very well to the calculated values for C ₂₅ H ₂₄ N ₂ O, C 81.49%, H 6.57%, N 7.60% and O 4.34%. Also, when the proton nuclear magnetic resonance spectrum was measured, the peak of 11H based on the protons of the naphthalene ring, the proton of the indoline ring, and the proton of the oxazine ring was found at around δ 6.5 to 8.0 ppm, and N was found around 2.8 ppm.
Peak of 3H based on -CH ₃ bond protons, [delta] 1.3 to 2.0
A broad peak of 10H based on the proton of the cyclohexane ring was shown around ppm. Furthermore, when ¹³ C-nuclear magnetic resonance spectrum was measured, peaks based on carbons of benzene ring, naphthalene ring and oxazine ring of indoline around δ 100 to 160 ppm, peaks based on spiro carbon around δ 99 ppm and δ 56 ppm, δ The peak based on the cyclohexane group and carbon of the methyl base material was shown around 20 to δ 35 ppm.

From the above results, it was confirmed that the isolated product was a compound represented by the above structural formula (3).

Production Example 4 The following compound 2.0 g (0.0057 mol) and the following compounds 0.98 g (0.0057 mol) and 0.41 g (0.0057 mol) of pyrrolidine
Was dissolved in 50 ml of ethyl alcohol and heated under reflux for 2 hours.

After the reaction, the solvent was removed, and purification was carried out by chromatography on silica gel to obtain 200 mg of a spirooxazine compound represented by the following formula.

Elemental analysis of this compound gave C 78.66%, H 6.09%, N 1
1.05% and O 4.2%, which corresponded very well to the calculated values for C ₂₅ H ₂₃ N ₃ O, C 78.71%, H 6.08%, N 11.02% and O 4.2%. Further, when the proton nuclear magnetic resonance spectrum was measured, a peak of 10H based on a proton of a quinoline ring, a proton of an indoline ring and a proton of an oxazine ring was observed at about δ 6.5 to 9 ppm, and N-CH ₃ was found at about δ 2.7 ppm.
The peak of 3H based on the proton of the bond and the broad peak of 10H based on the proton of the norbornane ring were shown around δ 1.3 to 2.5 ppm. Furthermore, when ¹³ C-nuclear magnetic resonance spectrum was measured, peaks based on carbons of benzene ring, naphthalene ring and oxazine ring of indoline around δ 100 to δ 160 ppm, peaks based on spiro carbon around δ 99 ppm and δ 52 ppm, A peak based on the carbon of the norbornane ring was shown around δ 27 to 52 ppm. From the above results, it was confirmed that the isolated product was a compound represented by the above structural formula (4).

Production Examples 5 to 21 Spirooxazine compounds shown in Table 1 were synthesized in the same manner as in Production Examples 1 to 4.

The obtained product was subjected to structure analysis using the same means for structure confirmation as in Production Example 1, and as a result, was confirmed to be a compound represented by the structural formula shown in Table 1.

Production Example 22 1-hydroxy-2-acetonaphthone 10 g (0.054 mo
l) with 6.6 g (0.06 mol) of norcamphor and 8 g of pyrrolidine
(0.113 mol) was dissolved in 300 cc of toluene to prepare a solution. The mixture was boiled for 10 hours and the water was separated. After the completion of the reaction, the toluene was removed under reduced pressure, and the remaining chromanone compound was crystallized with acetone. Next, this chromanone compound was dissolved in 200 cc of methanol, and sodium borohydride was gradually added to obtain a chromanol compound. By heating 7.47 g of this chromanol compound together with 4.5 g of anhydrous copper sulfate in a stream of carbon dioxide at 150 to 160 ° C. for 10 minutes, and purifying the brown viscous liquid by chromatography on silica gel, a chromene compound of the following formula was obtained. 6.3 g of the derivative were obtained.

Elemental analysis of this compound gave C 86.93%, H 6.89%, O
6.18%, which is the calculated value for C ₁₉ H ₁₈ O, C 87.0
Very good agreement was found with 2%, H 6.87% and O 6.12%. Also,
When the proton nuclear magnetic resonance spectrum was measured, δ
6H around 7.2 to 8.3 ppm based on naphthalene ring proton
, A 2H peak based on the alkene proton near δ 5.6 to 6.7 ppm, and a broad 10H peak based on the norbornylidene group proton near δ 1.2 to 2.5 ppm. Furthermore, when ¹³ C-nuclear magnetic resonance spectrum was measured, the peak based on the carbon of the norbornylidene group at about δ 27 to 52 ppm, the peak based on the carbon of the naphthalene ring at about δ 110 to 160 ppm, and the carbon of the alkene at about δ 80 to 110 ppm. Appears. From the above results, it was confirmed that the isolated product was the compound represented by the above structural formula (22).

Production Example 23 A solution prepared by dissolving 10 g (0.054 mol) of 1-acetyl-2-naphthol, 8.29 g (0.06 mol) of bicyclo [3.3.1] nonan-9-one, and 8.7 g (0.10 mol) of morpholine in 300 cc of toluene was prepared. Prepared. The mixture was boiled for 5 hours and the water was separated. After the reaction, the toluene was removed under reduced pressure,
The remaining chromanone compound was recrystallized from acetone. Next, this chromanone compound was dissolved in 200 cc of methanol, and lithium aluminum hydride was added to obtain a chromanol compound. 6.49 g of this chromanol compound was heated with anhydrous copper sulfate at 170-180 ° C. for 10 minutes in a stream of carbon dioxide, and the brown viscous liquid was purified by chromatography on silica gel to give the chromene derivative 5.
8 g were obtained.

Elemental analysis of this compound gave C 86.81%, H 7.62%, O
5.57%, calculated for C ₂₁ H ₂₂ O, C 87.9
Very good agreements were obtained with 0%, H 7.59% and O 5.52%. When the proton nuclear magnetic resonance spectrum was measured,
δ 7.2-8.3 ppm based on naphthalene ring proton
The peak of 6H, the peak of 2H based on the proton of the alkene near δ 6.0 to 7.0 ppm, and the broad peak of 14H based on the proton of the bicyclo [3.3.1] 9-nonylidene group near δ 1.2 to 2.5 ppm were shown. Further measurement of ¹³ C-nuclear magnetic resonance spectrum, bicyclo [3.
3.1] Peak based on carbon of 9-nonylidene group, δ 110
A peak based on naphthalene ring carbon around ~ 160 ppm, δ
A peak based on the carbon of the alkene appears around 80 to 110 ppm. From the above results, it was confirmed that the isolated product was the compound represented by the above structural formula (23).

Production Example 24 3.06 g (0.01 mol) of a chromanone compound represented by the following formula Was dissolved in 50 cc of anhydrous ether, the solution was cooled to 0 ° C., and a freshly prepared Grignard reagent CH ₃ MgCl (0.012 mol) was added dropwise to the solution over 50 minutes in 50 cc of anhydrous ether. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours, the ether solution was gently poured into cold water, the product was extracted with ether, the solution was dried over magnesium sulfate, and the ether was removed under reduced pressure. The compound was changed to a chromanol compound. Then, the chromanol compound was mixed with anhydrous copper sulfate in a stream of carbon dioxide at 200 ° C. for about 1 hour.
After heating for 0 minutes, a brown viscous liquid is generated by chromatography on silica gel, and a chromene derivative of the following formula
2.47 g were obtained.

By elemental analysis, proton nuclear magnetic resonance spectrum, and measurement of ¹³ C-nuclear magnetic resonance spectrum as in Production Example 22,
This compound was confirmed to be the compound represented by the above structural formula (24).

Production Example 25 1-acetyl-2-naphthol 10 g (0.054 mol), norcamphor 6.6 g (0.06 mol), and morpholine 8.7 g (0.10 m
ol) was dissolved in 300 cc of toluene, boiled for 15 hours, and water was separated. After the reaction, the toluene was removed under reduced pressure,
The remaining product was recrystallized from acetone to obtain 7.53 g of a compound represented by the following formula.

Next, 7.53 g of this compound was dissolved in 100 cc of methanol and reacted with methyl iodide to obtain 6.95 g of a chromanone compound represented by the following formula.

Next, the produced chromanone compound was changed to a chromanol compound in the same manner as in Production Example 24, and a dehydration reaction was performed. After separation and purification, 5.84 g of a chromene derivative represented by the following formula was obtained.

As in Production Example 22, it was confirmed by an elemental analysis, a proton nuclear magnetic resonance spectrum and a ¹³ C-nuclear magnetic resonance spectrum measurement that this compound was the compound represented by the above structural formula (25).

Production Example 26 10 g (0.0318 mol) of 5-n-octyloxy-1-hydroxy-2-acetonaphthone and 2.77 g (0.0477 m) of acetone
ol) and 1.13 g (0.0159 mol) of pyrrolidine in 100 ml of toluene
Was prepared. The mixture was boiled for 10 hours and the water was separated. After completion of the reaction, toluene was removed under reduced pressure, the remaining chromanone compound was dissolved in 100 ml of methanol, and sodium borohydride was gradually added to obtain a chromanol compound. 6.0 g of this chromanol compound was mixed with 4.0 g of anhydrous copper sulfate in a stream of carbon dioxide at 150 to 160 ° C.
The mixture was heated for 10 minutes, and the brown viscous liquid was purified by chromatography on silica gel to obtain 3.8 g of a chromene derivative represented by the following formula.

As in Production Example 22, it was confirmed by an elemental analysis, a proton nuclear magnetic resonance spectrum and a ¹³ C-nuclear magnetic resonance spectrum measurement that this compound was the compound represented by the above structural formula (26).

Production Examples 27 to 35 The chromene derivatives shown in Table 2 were synthesized in the same manner as in Production Examples 22 to 26.

The obtained product was subjected to structure analysis using the same means for structure confirmation as in Production Example 22, and as a result, it was confirmed to be a compound represented by the structural formula shown in Table 2.

Example 1 (1) Production of thermosetting resin 70 parts of chlorostyrene, 2,2-bis (3,5-dibromo-4)
-Methacryloyloxyethoxy-phenyl) propane
One part of perbutyl ND as a radical polymerization initiator was added to a composition consisting of 30 parts and mixed well. This mixture was poured into a mold composed of a gasket composed of a glass plate and an ethylene-vinyl acetate copolymer, and cast polymerization was performed.
The polymerization was carried out using an air furnace at 30 ° C. to 90 ° C. for 18 hours, gradually increasing the temperature, and maintaining the temperature at 90 ° C. for 2 hours. After the polymerization was completed, the mold was taken out of the air furnace, and after standing to cool, the polymer was removed from the glass of the mold.

(2) Preparation of primer coating solution and coating curing Spiro of Preparation Example 1 was prepared using 111 parts of commercially available primer solution SEvian A46701 (manufactured by Daicel Chemical Industries, Ltd .; trade name) (resin concentration was adjusted to 90% by weight). 5 parts of the oxazine compound and 3 parts of the chromene derivative of Production Example 22 were added and dissolved with sufficient stirring. This primer solution was filtered through a membrane filter having a pore size of 1 μm, applied to the base material obtained in (1) by an immersion method, and the lifting speed was adjusted so that the primer film thickness after curing became 1 μm. . After application, the coating was dried at 60 ° C. for 1 hour to obtain a photochromic substrate having a good appearance.

(3) Preparation of coating agent and application curing 20 parts by weight of bis (γ-triethoxysilylpropyl) carbonate, 10 parts by weight of γ-glycidoxypropyltrimethoxysilane, 30 parts by weight of colloidal silica (Nissan Chemical Industries methanol sol) , Methicero 30 parts by weight, 0.05N hydrochloric acid 10
The photochromic substrate obtained in (2) was immersed in a coating agent comprising 0.25 parts by weight of ammonium perchlorate as a curing catalyst and coated as a curing catalyst, and this was air-dried at room temperature. After curing for a time, a film having a thickness of 3 μm was formed.

The photochromic properties of the molded article thus obtained were measured as follows. Xenon Long Life Fade Meter FAL-25AX-H manufactured by Suga Test Machine Co., Ltd.
The fatigue life was measured by C.

Further, a change in color tone was visually observed. The fatigue life (T _1/2 ) was represented by the time required for the absorbance at the maximum absorption wavelength based on the spirooxazine compound to fall to half of the initial (T ₀ ) absorbance. However, the absorbance of T ₀ and T _1/2 is a value obtained by subtracting the absorbance of the unirradiated film at the maximum absorption wavelength based on the spirooxazine compound, and the absorbance of T ₀ was measured 60 seconds after light irradiation. .

 The results are shown in Table 3.

In addition, the performance of the coating made of the hydrolyzate of the organosilicon compound on the outermost surface of the thermosetting resin was evaluated as follows.

(1) Adhesion test 1 mm x 1 mm on the sample surface with a sharp-tipped cutter knife
After 100 squares were attached, a commercially available cellophane tape was attached, and then, if there was no peeling due to the peeling state of the coating when it was quickly peeled off, ○, partially peeled off, △, all Those that were peeled were indicated by x.

(2) Scratch resistance test A # 0000 steel wool was attached to a scratch resistance tester manufactured by Fukuda Machinery Co., Ltd.
The degree of damage on the surface after reciprocating 0 times was visually observed, A was a state where no damage was found, and E was a state where the polymethyl methacrylate fabric was very easily damaged.
The evaluation was made in five stages of A to E.

(3) Hot water test The film was left standing in boiling water for 2 hours, and the appearance of the film was visually observed. When the coating was good in appearance without cracking, peeling, blistering, whitening, etc., it was evaluated as ○. Also,
The above adhesion test was performed, and evaluated based on the same criteria.

 The results are shown in Table 3.

Examples 2 to 14 Except that the thermosetting resin, photochromic compound, primer and coating agent containing an organosilicon compound used in Example 1 were changed to those shown in Table 3,
All were performed in the same manner as in Example 1. The results are shown in Table 3. The film thickness of the film formed by the hydrolyzate of the organosilicon compound was in the range of 1 to 5 μm. Table 4 shows the types of the coating agent containing the organosilicon compound.

Comparative Example 1 The same procedure as in Example 1 was carried out except that no film was formed by the hydrolyzate of the organosilicon compound, and the results are shown in Table 3.

Example 15 To 100 parts of allyl diglycol carbonate, 3 parts of diisopropyl peroxycarbonate was added as a radical polymerization initiator, mixed well, and polymerized in the same manner as in Example 1 to obtain a thermosetting resin. 5 parts of the spirooxazine compound obtained in Production Example 15 and 3 parts of the chromene derivative obtained in Production Example 33 were dispersed in 100 parts of silicone oil, and 200 parts of the poly (allyl diglycol carbonate) obtained above were dispersed on the surface of the plate.
C. for one hour. Thereafter, the plate was cooled with cold water, washed with methanol and acetone, and a 2 μm-thick film made of a hydrolyzate of an organosilicon compound was formed on the surface of the plate in the same manner as in Example 1. Further, the evaluation of the photochromic performance and the evaluation of the film performance of the film made of the hydrolyzate were performed in the same manner as in Example 1.

 The results are shown in Table 5.

Examples 16 to 24 The same procedures as in Example 15 were carried out except that the used thermosetting resin, photochromic compound, impregnating oil and organosilicon compound were changed.

The results are shown in Table 5. In addition, the film thickness of the coating film of the hydrolyzate of the organosilicon compound was in the range of 1 to 5 μm.

Claims (2)

(57) [Claims] 1. The following formula A resin layer containing a spirooxazine compound represented by is coated on the surface of the thermosetting resin,
A photochromic molded article further comprising a layer made of a hydrolyzate of an organosilicon compound coated thereon. 2. The following formula: A photochromic molded article comprising a thermosetting resin impregnated with a spirooxazine compound represented by the formula (1), and a layer made of a hydrolyzate of an organosilicon compound coated thereon.