JP2009120536A - Chromene compounds - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photochromic compound developing a yellow or neutral color by a single compound, having good photochromic characteristics, hardly inhibiting the polymerization curing of a composition when added to the composition to be polymerized and cured by a photoradical, and providing a cured article having excellent photochromic characteristics. <P>SOLUTION: The chromene compound has an elementary structure of 2H-benzo[h]chromene represented by formula (1) and is prepared by condensing the ring of tetrahydronaphthalene having a vinyl bond which may be substituted at a specific position, and a specified substituent bonded to the remaining tetrahydronaphthalene skeleton. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel chromene compound and uses of the chromene compound.

  Photochromism is a reversible action that quickly changes color when a compound is exposed to light containing ultraviolet light, such as sunlight or mercury lamp light, and returns to its original color when the light is turned off and left in the dark. . A compound having this property is called a photochromic compound and is used as a material for a photochromic plastic lens.

  In photochromic compounds used for such applications, (1) the degree of coloring in the visible light region (hereinafter referred to as initial coloring) before irradiation with ultraviolet rays is low, (2) coloring when irradiated with ultraviolet rays Degree (hereinafter referred to as the color density) is high, (3) the speed from the start of UV irradiation until the color density reaches saturation (hereinafter also referred to as high color sensitivity), (4) The speed from the end of irradiation to the return to the original state (hereinafter referred to as the fading speed) is fast, (5) good repetitive durability of this reversible action, and (6) dispersibility in the host material used. Therefore, a property of being dissolved at a high concentration in a monomer composition that becomes a host material after curing is required.

  In addition, in photochromic plastic lenses, intermediate colors such as brown and amber are preferred as the color tone of the color development state. Naturally, what kind of color is developed is an extremely important factor for photochromic compounds. Yes.

  When a desired color tone cannot be realized using a single compound, the color tone is adjusted by mixing a plurality of photochromic compounds having different color tone. In this case, not only the physical properties of each compound to be prepared are excellent, but also the physical property balance as a whole (as a mixture) is important.

  A photochromic compound that develops yellow or an intermediate color as a single compound is important for color tone adjustment, and as such a compound, a chromene compound represented by the following formula (A) {also simply referred to as compound (A). Patent Document 1} and a chromene compound represented by the following formula (B) {also simply referred to as compound (B)}. Patent Document 2} is known. A curable composition obtained by dissolving these photochromic compounds in a radical polymerizable monomer is cured by thermal radical polymerization and molded (cast polymerization) to obtain a photochromic plastic lens having good photochromic characteristics. (See Patent Documents 1 and 2).

  The method of manufacturing a photochromic plastic lens by casting polymerization (also referred to as “in mass” method or kneading method) employed in Patent Documents 1 and 2 is one of typical photochromic plastic lens manufacturing methods. There is, however, a limitation that the polymerizable monomers that can be used to obtain good photochromic properties are limited.

  In recent years, a coating method has attracted attention as a method for producing a photochromic plastic lens without such restrictions (see Patent Document 3). In the coating method, a coating agent made of a polymer curable composition containing a photochromic compound is applied to the surface of the lens substrate, and the coating film is cured to form a photochromic coating layer, thereby providing photochromic properties to the lens substrate. To do. Therefore, if good coating film adhesion is obtained, there is no restriction on the base lens in principle.

US Pat. No. 5,783,116 International Publication No. WO00 / 15628 Pamphlet International Publication No. WO03 / 011967 Pamphlet

  In the coating method, the color tone is adjusted in the same manner as in the kneading method, and a photochromic compound that develops a yellow or intermediate color as a single compound is important. However, it has been found that when the compound (A) and the compound (B) are applied to a coating method, a good photochromic coating layer cannot be obtained.

  Therefore, an object of the present invention is to provide a photochromic compound that can be applied to the coating method without any problem and that develops a yellow or intermediate color as a single compound.

  Means for solving the above-mentioned problems provided by the present invention are as follows.

  The first invention is a chromene compound represented by the following formula (1).

^(Wherein, R ^1, R 2, ^{R 3} and ^{R 4, R 3,} and under the condition that at least one ^{R 4} is a group other than a hydrogen atom, respectively, a hydrogen atom, a hydroxyl group, an alkyl group , A cycloalkyl group, an alkoxy group, an aralkyl group, an aralkoxy group, an aryl group, or a halogen atom, R ¹ and R ² , or R ³ and R ⁴ may be linked to each other to form a ring,
R ⁵ , R ⁶ , R ⁷ and R ⁸ each have a hydrogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an aralkyl group, an aralkoxy group, an aryl group, an amino group, or a nitrogen atom as a hetero atom. And a heterocyclic group, a cyano group, a nitro group, a halogen atom, a halogenoalkyl group, or a halogenoalkoxy group bonded by the nitrogen atom, and a plurality of R ⁵ , R ⁶ , R ⁷ , or R ⁸ are present. 2 R ⁵ , 2 R ⁶ , 2 R ⁷ , or 2 R ⁸ may be bonded to form a ring,
m, n, x, and y represent the number of substituents for R ⁵ , R ⁶ , R ⁷ , and R ⁸ , respectively, m and n are each an integer from 0 to 4, and x and y are each 0 To an integer of 5. ).

  The second invention is a photochromic curable composition containing a polymerizable monomer and a chromene compound represented by the formula (1).

  The third invention is a photochromic curable composition further comprising a photopolymerization initiator in the second invention.

  A fourth invention is a photochromic optical article having, as a constituent member, a polymer molded body in which a chromene compound represented by the formula (1) is dispersed.

  A fifth invention is an optical article having, as a constituent member, an optical base material in which all or a part of at least one surface is coated with a polymer film in which a chromene compound represented by the formula (1) is dispersed.

  A sixth invention is an optical article in which the polymer film is a polymer film obtained by curing the photochromic curable composition according to the third invention by radical photopolymerization.

  The chromene compound of the present invention represented by the formula (1) is similar to the compound (A) and the compound (B) in that 2H-benzo [h] chromene has its 5-position carbon and 6-position carbon. It has a basic structure that is a 6-membered ring condensed in a shared form. However, unlike the above-described conventional compounds, the chromene compound of the present invention has limited substituents bonded to the 6-membered ring. And it is possible to produce the outstanding effect shown by the effect mentioned later by that. Patent Documents 1 and 2 show general formulas conceptually including the chromene compound of the present invention, but the compounds corresponding to the chromene compound of the present invention are not specifically described, and the chromene of the present invention is not described. The compound is novel.

  In the coating method, since the amount of the photochromic compound soluble in the coating agent is limited, it is necessary to form a coating layer having a thickness of, for example, 30 to 50 μm in order to obtain a sufficient color density. Since the coating agent is a liquid, in order to cure the coating agent applied on a curved surface such as a lens substrate while maintaining such thickness without uneven thickness, It is advantageous to utilize radical polymerization.

  According to studies by the present inventors, when the photo-radical polymerizable composition containing the compound (A) or the compound (B) is irradiated with light to be polymerized and cured, these compounds are combined with a photo-radical polymerization initiator. It has been found that it is easy to react and not only inhibits the polymerization and curing of the polymerizable monomer, but also decomposes itself and the photochromic property is remarkably lowered. (Such a phenomenon is probably due to the difference in the type of polymerization initiator, but does not occur during thermal radical polymerization).

  On the other hand, the chromene compound of the present invention has a basic structure (basic skeleton) common to the compound (A) and the compound (B) as described above, that is, 2H-benzo [h] chromene and its carbon at the 5-position. And a structure (skeleton) in which a 6-membered ring is condensed so as to share the 6-position carbon, but substituents bonded to the 6-membered ring are limited. Therefore, it exhibits excellent photochromic properties, and at the same time, the stability of the compound is dramatically improved, and even when irradiated with light in the presence of photoradical polymerization, it becomes difficult to react with the photoradical polymerization initiator, resulting in good photochromic properties. A coat layer having the same can be formed. Moreover, even when the chromene compound of the present invention is added to a polymerizable monomer to form a cured product by thermal radical polymerization, the repeated durability of the photochromic properties of the cured product is not limited to the compounds (A) and (B). ) Is superior to the case of using. That is, according to the present invention, a good photochromic optical article can be obtained by any method of photo radical polymerization and thermal radical polymerization. Furthermore, the obtained optical article exhibits excellent photochromic properties.

  The chromene compound of the present invention exhibits the same effects as those seen in the compound (A) and the compound (B) in terms of color tone and photochromic properties due to the above-mentioned basic structure (skeleton). Furthermore, in the basic structure (skeleton), the presence of a vinyl bond (double bond) bonded to the condensed 6-membered ring and a specific substituent causes “attack by radicals” on the 6-membered ring. The number of hydrogen atoms is likely to be 1 or 0, and the stability is considered to be improved, especially by having a substituent on the 6-membered ring via a double bond that is likely to react with a radical. It is surprising that the effect of improving the sex is exhibited.

  The chromene compound of the present invention is represented by the following formula (1).

In the formula (1), R ¹ , R ² , R ³ and R ⁴ are respectively (i) a hydrogen atom; (ii) a hydroxyl group; (iii) an alkyl group; (iv) a cycloalkyl group; (v) (Vi) an aralkyl group; (vii) an aralkoxy group; (viii) an aryl group; and (ix) a halogen atom. R ¹ and R ² may be bonded to each other to form a (x) ring, and R ³ and R ⁴ may be bonded to each other to form a (xi) ring. However, at least one of R ³ and R ⁴ needs to be a group other than a hydrogen atom. When both R ³ and R ⁴ are hydrogen atoms, the stability is lowered and the effects of the present invention cannot be obtained. From the viewpoint of effect, it is necessary that one or more of R ³ and R ⁴ are not hydrogen atoms, and it is preferable that both R ³ and R ⁴ are groups other than hydrogen atoms.

In the chromene compound of the present invention, in the basic structure (skeleton), a condensed 6-membered carbon atom and a carbon atom to which R ¹ and R ² are bonded are bonded by a double bond. It is important that Surprisingly, the chromene compound of the present invention is admixed with a polymerizable monomer to undergo photoradical polymerization or thermal radical polymerization even if a double bond that is considered to react easily with a radical is present at the above position. Even if it is stable, it can be set as the hardening body which has the outstanding photochromic characteristic.

  Hereinafter, among the above substituents, those whose structures are not uniquely determined will be described.

  The alkyl group (iii) is not particularly limited, but generally an alkyl group having 1 to 9 carbon atoms is preferable. Examples of suitable alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl and the like.

  (iv) Although it does not specifically limit as a cycloalkyl group, Generally a C3-C12 alkyl group is preferable. Examples of suitable alkyl groups include cyclopropyl group, cyclobutyl, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and the like.

  (v) Although it does not specifically limit as an alkoxy group, Generally a C1-C5 alkoxy group is preferable. Specific examples of suitable alkoxy groups include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group and the like.

  (vi) Although it does not restrict | limit especially as an aralkyl group, Generally a C7-C11 aralkyl group is preferable. Examples of suitable aralkyl groups include benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group and the like.

  (vii) The aralkoxy group is not particularly limited, but an aralkoxy group having 6 to 10 carbon atoms is preferable. Specific examples of suitable aralkoxy groups include phenoxy groups and naphthoxy groups.

  (viii) The aryl group is not particularly limited, but is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms or an aromatic heterocyclic group having 4 to 12 atoms forming a ring. Examples of suitable aryl groups include phenyl, naphthyl, thienyl, furyl, pyrrolinyl, pyridyl, benzothienyl, benzofuranyl, benzopyrrolinyl and the like. In addition, a substituted aryl group in which one or two or more hydrogen atoms of the aryl group are substituted with a substituent such as an alkyl group, an alkoxy group, an aralkyl group, an aralkoxy group and the like as described above can also be suitably used.

  (ix) Although it does not specifically limit as a halogen atom, A fluorine atom, a chlorine atom, a bromine atom, or an iodine atom can be mentioned. Among these, those substituted with a fluorine atom or a chlorine atom are preferred.

The ring (x) formed by connecting R ¹ and R ² or the ring (xi) formed by connecting R ³ and R ⁴ has 3 to 10 carbon atoms to form the ring. A certain aliphatic hydrocarbon ring is preferred. Further, the ring may be condensed with an aromatic hydrocarbon ring such as benzene, naphthalene or naphthalene. Moreover, this ring may have a C1-C5 alkyl group or a C1-C5 alkoxy group as a substituent, Although the number of the substituents is not specifically limited, Preferably it is 0-10. More preferably, it may have 0 to 4 substituents. A particularly preferable ring is a divalent ring containing a carbon atom (hereinafter simply referred to as “vinyl carbon atom”) in which a ring group (R ¹ and R ² are bonded and bonded to the basic skeleton through a double bond). In the form of a group or a “divalent ring group in which a“ 6-membered ring carbon atom ”to which R ³ and R ⁴ are bonded” is represented by a spiro carbon), the following can be mentioned. In the ring group shown below, the lowermost carbon atom having ^two bonds is a “vinyl carbon atom” in which R ¹ and R ² are bonded, or R ³ and R ⁴ are bonded in “ Corresponds to a “6-membered carbon atom”.

In the formula (1), R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently a hydrogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an aralkyl group, an aralkoxy group, an aryl group, An amino group, a heterocyclic group having a nitrogen atom as a hetero atom and bonded by the nitrogen atom, a cyano group, a nitro group, a halogen atom, a halogenoalkyl group, or a halogenoalkoxy group.

Here, the alkyl group, the alkyl group, the cycloalkyl group, the alkoxy group, the aralkyl group, the aralkoxy group, the aryl group, and the halogen atom are the same as the above-described substituents R ^{1 to} R ⁴ , and suitable groups are also there. The same groups as those exemplified can be mentioned.

  The amino group is not limited to a primary amino group, and may be a secondary amino group or a tertiary amino group having a substituent. The substituent that the amino group has is not particularly limited, but an alkyl group or an aryl group is typical, and examples of the substituted amino group having these substituents include an alkylamino group, a dialkylamino group, an arylamino group, or A diarylamino group is mentioned. Preferable specific examples of such a substituted amino group (secondary amino group or tertiary amino group) include alkylamino groups such as methylamino group and ethylamino group; dialkylamino groups such as dimethylamino group and diethylamino group; An arylamino group such as a phenylamino group; a diarylamino group such as a diphenylamino group;

Further, examples of the heterocyclic group having a nitrogen atom as a heteroatom and bonded by the nitrogen atom include a morpholino group, a 2,6-dimethylmorpholino group, a piperidino group, a 2,6-dimethylpiperidino group, 2, 2 6,6-tetramethylpiperidino group, pyrrolidinyl group, piperazino group, N-methylpiperazino group and indolinyl group. In addition, the nitrogen atom which is a hetero atom of the heterocyclic group is bonded to the “basic structure or a ring condensed thereto” in the group R ⁵ , the group R ⁶ , the group R ⁷ , and the group R ⁸ .

  Examples of the halogenoalkyl group include those in which one or more hydrogen atoms of the aforementioned alkyl group are substituted with a fluorine atom, a chlorine atom, or a bromine atom. Among these, those substituted with fluorine atoms are preferred. Examples of suitable halogenoalkyl groups include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, and a pentafluoroethyl group.

  As the halogenoalkoxy group, one in which one or more hydrogen atoms of the aforementioned alkoxy group are substituted with a fluorine atom, a chlorine atom, or a bromine atom is preferable, and among them, those substituted with a fluorine atom are particularly preferable. Is preferred. Specific examples of the halogenoalkoxy group include a fluoromethoxy group, a difluoromethoxy group, and a trifluoromethoxy group.

In the formula (1), m, n, x, y , respectively representing the number of substituents ^{R 5, R 6, R 7} , R 8. m and n are each an integer of 0 to 4, preferably an integer of 0 to 2, and x and y are each an integer of 0 to 5, preferably an integer of 0 to 2.

In addition, when there are a plurality of R ⁵ , R ⁶ , R ⁷ , or R ⁸ , that is, when m, n, x, or y is 2 or more, two R ⁵ , R ⁶ , 2 R ⁷ , or 2 R ⁸ may combine to form a ring. This ring is preferably an aliphatic hydrocarbon ring having 3 to 10 carbon atoms forming the ring or a heterocyclic ring containing an oxygen atom. Specific examples of these rings include the ring represented by the following formula (2). In the following formula (2), a benzene ring to which X and Y are bonded represents a benzene ring to which R ⁵ , R ⁶ , R ⁷ , or R ⁸ is bonded in the basic structure. In addition, the bonding positions shown as R ⁵ , R ⁶ , R ⁷ and R ⁸ are not particularly limited and can be appropriately selected.

(In the formula, X and Y are each O or —C (R ¹⁶ ) (R ¹⁷ ) —, and R ¹⁶ and R ¹⁷ are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Each of R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , or R ¹⁵ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; and R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , or R ¹⁶ and R ¹⁷ may be combined to form a cycloalkyl ring having 3 to 6 carbon atoms. More specifically, the formula (2) preferably used can be exemplified as follows. Incidentally, the benzene ring of the ring group shown below, in the basic ^structure, shows a benzene ring which ^{R 5, R 6, R 7} , R 8 are attached. In addition, the bonding positions shown as R ⁵ , R ⁶ , R ⁷ and R ⁸ are not particularly limited and can be appropriately selected.

  Specific examples of the particularly preferred chromene compound in the present invention include the following compounds.

  The chromene compound of the present invention generally exists as a colorless or light yellow solid or viscous liquid at normal temperature and pressure, and can be confirmed by the following means (I) to (III).

(I) By measuring a proton nuclear magnetic resonance spectrum ( ¹ H-NMR), a peak based on an aromatic proton and an alkene proton in the vicinity of δ 5.0 to 9.0 ppm, and in the vicinity of δ 0.5 to 4.0 ppm. Peaks based on protons of alkyl groups and alkylene groups appear. Moreover, the number of protons of each linking group can be known by relatively comparing the respective spectrum intensities.

  (II) The composition of the corresponding product can be determined by elemental analysis.

(III) ¹³ by measuring the C- nuclear magnetic resonance spectrum ⁽¹³ C-NMR), the peak based on the carbons of an aromatic hydrocarbon group near Deruta110～160ppm, based on the carbon of an alkene and alkyne near δ80~150ppm A peak based on carbon of the alkyl group and the alkylene group appears in the vicinity of δ20 to 80 ppm.

  Although the synthesis | combining method of the chromene compound of this invention is not specifically limited, For example, it can manufacture suitably by the method as shown below. That is, it can be suitably produced by reacting a naphthol derivative represented by the following formula (3) with a propargyl alcohol derivative represented by the following formula (4) in the presence of an acid catalyst.

  First, a naphthol derivative represented by the following formula (3) will be described.

{Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , m, and n have the same meanings as those in formula (1), respectively. }.

  The naphthol derivative represented by the formula (3) is not particularly limited.

(In the formula, R is a hydroxyl group or a phenolic protecting group, and R ⁵ , R ⁶ , m, and n are respectively synonymous with the groups shown in the formula (1)).
The compound represented by the following formula is heated in a solvent in the presence of an acid such as p-toluenesulfonic acid and polyphosphoric acid.

(In the formula, R is a hydroxyl group or a phenolic protecting group, and R ⁵ , R ⁶ , m, and n are respectively synonymous with the groups shown in the formula (1)).
Further, after reacting with a Grignard reagent, a vinylation reaction with an acid is performed, and the substituent R is deprotected as necessary, or a Wittig reaction is performed, and then the substituent R is removed as necessary. By performing the protection, the naphthol derivative represented by the above formula (3), which is the target product, can be synthesized directly. For these methods, a method that is easier to synthesize may be appropriately selected according to the naphthol derivative represented by the above formula (3), which is the target product.

  Next, the propargyl alcohol derivative represented by the following formula (4) will be described.

{Wherein R ⁷ , R ⁸ , x, and y have the same meanings as those in formula (1), respectively. }.

  The synthesis of the propargyl alcohol derivative represented by the formula (4) is not particularly limited. For example, a ketone derivative having a corresponding structure and a metal acetylene compound such as lithium acetylide and sodium acetylide are combined with dimethyl sulfoxide, tetrahydrofuran, It can be synthesized by reacting in a solvent such as dimethylformamide.

  When the naphthol derivative represented by the formula (3) and the propargyl alcohol derivative represented by the formula (4) are reacted in the presence of an acid catalyst, the formula (3) is used with respect to 1 mol of the naphthol derivative represented by the formula (3). It is preferable to use 0.5 to 2 mol, particularly 0.8 to 1.5 mol, of the propargyl alcohol derivative represented by 4). As the acid catalyst, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfonic acid pyridinium salt, or solid acid such as acidic alumina or silica gel can be used. The amount of the acid catalyst used is in the range of 0.01 to 200 parts by mass with respect to 100 parts by mass of the total of the naphthol derivative represented by the formula (3) and the propargyl alcohol derivative (reaction substrate) represented by (4). do it. The reaction is preferably carried out in the presence of a solvent, and an aprotic organic solvent such as N-methylpyrrolidone, dimethylformamide, tetrahydrofuran, benzene, or toluene is used as the solvent. The reaction is usually performed at 0 to 200 ° C., preferably under reflux of a solvent.

  After performing such a reaction, the target product can be isolated from the obtained crude product by carrying out silica gel column purification and recrystallization as necessary.

  The chromene compound of the present invention is well soluble in common organic solvents such as toluene, chloroform, and tetrahydrofuran. When the chromene compound of the present invention is dissolved in such a solvent, the solution is generally almost colorless and transparent. This solution exhibits a good photochromic phenomenon in which the color is rapidly developed when irradiated with sunlight or ultraviolet light, and when the light is cut off, the original color is rapidly restored.

  Moreover, the chromene compound of the present invention exhibits similar photochromic properties even in a polymer solid matrix. Such a polymer solid matrix is not particularly limited as long as the chromene compound of the present invention is uniformly dispersed, and is preferably a radical polymerization curable composition containing a thermoplastic resin and a radical polymerizable monomer. A hardened body can be mentioned. In addition, what is necessary is just to mix | blend the said thermoplastic resin suitably according to a use. The radical polymerizable monomer may be a monofunctional monomer or a polyfunctional monomer as shown below, or a mixture thereof.

  Examples of the optically preferable thermoplastic resin include polymethyl acrylate, polyethyl acrylate, polymethyl methacrylate, polyethyl methacrylate, polystyrene, polyacrylonitrile, polyvinyl alcohol, polyacrylamide, poly (2- Mention may be made of hydroxyethyl methacrylate), polydimethylsiloxane, and polycarbonate.

  Moreover, if a thing suitable as a radically polymerizable polyfunctional monomer contained in the said radical polymerization curable composition is shown, what is shown by following (a)-(d) can be mentioned.

(A) ethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A dimethacrylate, 2,2-bis (4-methacryloyloxyethoxyphenyl) propane, Polyvalent acrylic acid and polyvalent methacrylate compounds such as 2,2-bis (3,5-dibromo-4-methacryloyloxyethoxyphenyl) propane;
(B) Diaryl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl tartrate, diallyl succinate, diallyl fumarate, diallyl chlorendate, diallyl hexaphthalate, diallyl carbonate, allyl diglycol carbonate, trimethylolpropane triallyl carbonate, etc. (C) 1,2-bis (methacryloylthio) ethane, bis (2-acryloylthioethyl) ether, 1,4-bis (methacryloylthiomethyl) benzene and the like polyvalent thioacrylic acid and polyvalent thio Methacrylic acid ester compounds;
(C) Glycidyl acrylate, glycidyl methacrylate, β-methylglycidyl methacrylate, bisphenol A-monoglycidyl ether-methacrylate, 4-glycidyloxy methacrylate, 3- (glycidyl-2-oxyethoxy) -2-hydroxypropyl methacrylate, 3- ( Acrylic acid ester compounds and methacrylic acid ester compounds such as glycidyloxy-1-isopropyloxy) -2-hydroxypropyl acrylate and 3-glycidyloxy-2-hydroxypropyloxy) -2-hydroxypropyl acrylate; and (d) divinylbenzene .

  Moreover, as another monomer contained in the said radical polymerization curable composition, what is shown by following (e)-(i) can be mentioned.

(E) unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride;
(F) Acrylic acid and methacrylic acid ester compounds such as methyl acrylate, methyl methacrylate, benzyl methacrylate, phenyl methacrylate, 2-hydroxyethyl methacrylate;
(G) fumaric acid ester compounds such as diethyl fumarate and diphenyl fumarate;
(H) thioacrylic acid and thiomethacrylic acid ester compounds such as methylthioacrylate, benzylthioacrylate, benzylthiomethacrylate; and (i) styrene, chlorostyrene, methylstyrene, vinylnaphthalene, α-methylstyrene dimer, bromostyrene, etc. Vinyl compound.

  The chromene compound of the present invention can be made into a photochromic curable composition by mixing with the polymerizable monomer and the like, and a cured product (molded product) obtained by curing the curable composition is excellent. Show photochromic properties.

  The chromene compound of the present invention alone develops a yellow or intermediate color, exhibits not only good photochromic properties, but also extremely high stability, so even when irradiated with light in the presence of photoradical polymerization, photoradical polymerization is initiated. It is difficult to react with the agent. For this reason, even if it disperse | distributes in the curable composition hardened | cured by radical photopolymerization, the hardening body which does not inhibit hardening and shows a favorable photochromic characteristic can be given. Therefore, it is extremely useful as a component of a photochromic coating agent used when producing a photochromic plastic lens by a coating method. In addition, due to its high stability, even when it is dispersed and polymerized and cured in a curable composition of a type that is cured by thermal radical polymerization, it also has a feature that the repeated durability of its photochromic properties is excellent. . Therefore, its usefulness is also high as a material for producing a photochromic plastic lens by a kneading method.

  When the chromene compound of the present invention is mixed with the radical polymerization curable composition and the photo radical initiator, as a photo radical polymerization composition (photo chromic coating agent), when applied to a photochromic plastic lens obtained by a coating method, These polysynthetic compositions (photochromic curable compositions) can be prepared and used in the same manner as before except that the chromene compound of the present invention is used as a photochromic compound component. In addition, when the chromene compound of the present invention is mixed with the radical polymerization curable composition, as a thermopolymerizable composition (photochromic curable composition), as a raw material for producing a photochromic plastic lens by a kneading method, It can be carried out by a method similar to the conventional method.

  For example, when the photo-radical curable composition is used, the chromene compound of the present invention is added in an amount of 0.01 to 20 mass parts, Preferably 0.1-10 mass parts is added, Furthermore, 0.001-10 mass parts, Preferably 0.01-5 mass parts of radical photopolymerization initiators should just be added. It is of course possible to mix a photochromic compound other than the chromene compound of the present invention in the composition in order to adjust the color tone.

  Examples of suitable radical photopolymerization initiators used at this time are benzoin, benzoin methyl ether, benzoin butyl ether, benzophenol, aethofenone 4,4′-dichlorobenzophenone, diethoxyacetophenone, 2-hydroxy-2-methyl. -1-phenylpropan-1-one, benzylmethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-isopropylthiooxane, Bis (2,6-dimethoxybenzoyl-2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiph Cycloalkenyl - phosphine oxide, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) - can be exemplified butanone -1.

  When such a photo-radical curable composition is used as a photochromic coating agent, a preferable composition is described in, for example, International Publication No. 03/011967 pamphlet, and even when the chromene compound of the present invention is used, these patent documents are also disclosed. According to the description, the composition may be optimized.

  In addition, for the application of the photochromic coating agent thus prepared, the lens base material is appropriately pretreated, then spin-coated with a coating solution containing the chromene compound of the present invention, and irradiated with light in a nitrogen atmosphere. What is necessary is just to harden. As the pretreatment of the lens substrate, surface cleaning with an organic solvent or an aqueous alkali solution, corona treatment, and primer treatment are known, and are appropriately selected according to the type of the substrate. Further, a hard coat layer and an antireflection layer are formed on the formed photochromic coat layer as necessary.

  Using the chromene compound of the present invention, a photochromic plastic lens can be produced by a method other than the kneading method and the coating method. For example, the above-described thermoplastic resin and the chromene compound of the present invention can be kneaded in a molten state, dispersed in the resin, and molded. Also, a method of sandwiching a polymer film in which the photochromic material of the present invention is uniformly dispersed in a lens; a solution in which the chromene compound of the present invention is dissolved in, for example, silicone oil, and the resulting solution and a plastic lens Can be employed at a temperature of 150 to 200 ° C. to diffuse and permeate the chromene compound of the present invention into the plastic lens matrix, and the surface thereof is coated with a curable material (impregnation method).

  Moreover, the chromene compound of the present invention can be used in a wide range of applications other than photochromic plastic lenses. For example, it can be used as various storage materials such as various storage materials, copy materials, printing photoconductors, cathode ray tube storage materials, laser photosensitive materials, and holographic photosensitive materials in place of silver salt photosensitive materials. In addition, the photochromic material using the chromene compound of the present invention can also be used as a material such as a photochromic lens material, an optical filter material, a display material, a light meter, and a decoration.

  In addition, when using the chromene compound of this invention for the said use, in order to set it as the desired color development color tone, it can be used in mixture with another photochromic compound.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

Example 1
The following naphthol derivatives

3.16 g (10 mmol) and the following propargyl alcohol derivative

2.95 g (11 mmol) was dissolved in 150 ml of toluene, 0.10 g of p-toluenesulfonic acid was further added, and the mixture was stirred at reflux temperature for 30 minutes. After the reaction, the solvent was removed and the residue was purified by chromatography on silica gel to obtain 3.40 g of a white powder product.

The elemental analysis values of this product are C: 82.09%, H: 6.06%, O: 11.25%, and C: 82.06%, which is a calculated value of C ₃₉ H ₃₄ O ₄ , The values agreed well with H: 6.05% and O: 11.29%.

  Further, when proton nuclear magnetic resonance spectrum was measured, it was found that a peak of 15H based on an alkylene group in the vicinity of δ 1.0 to 4.5 ppm, an aromatic proton in the vicinity of δ 5.0 to δ 9.0 ppm, and 19H based on the proton of an alkene. The peak was shown.

Furthermore, when the ¹³ C-nuclear magnetic resonance spectrum was measured, a peak based on the carbon of the aromatic ring in the vicinity of δ110 to 160 ppm, a peak based on the carbon of the alkene in the vicinity of δ80 to 140 ppm, and a peak based on the carbon of the alkyl in δ20 to 60 ppm. Indicated.

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

Examples 2-13
The chromene compounds shown in Tables 1 to 4 were synthesized in the same manner as Example 1. The obtained product was subjected to structural analysis using the same structure confirmation means as in Example 1. As a result, it was confirmed that the compounds having the structural formulas shown in Tables 1 to 4 were obtained.

  Example 14 2,2-bis (4-methacryloyloxypentaethoxyphenyl) propane / polyethylene glycol diacrylate (average molecular weight 532) / trimethylolpropane trimethacrylate / polyester oligomer hexaacrylate (Daicel UCB, EB-1830) / It is obtained in Example 1 with respect to 90 parts by mass of the radical polymerizable monomer composition in which glycidyl methacrylate is blended at a blending ratio of 50 parts by weight / 10 parts by weight / 10 parts by weight / 10 parts by weight / 10 parts by weight. CGI1800 {1-hydroxycyclohexyl phenyl ketone and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine as polymerization initiators after adding 1 part by mass of chromene compound and mixing well Oxide mix Product (weight ratio 3: 1)} is 0.5 parts by mass, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate as a stabilizer is 5 parts by mass, and a silane coupling agent. 7 parts by mass of γ-methacryloyloxypropyltrimethoxysilane and 3 parts by mass of N-methyldiethanolamine were added and mixed thoroughly to prepare a photo radical polymerization curable composition (photochromic curable composition).

Next, about 2 g of the composition obtained by the above method was spin-coated on the surface of a lens substrate (CR39: allyl resin plastic lens; refractive index = 1.50) using a MIKASA spin coater 1H-DX2. The surface-coated lens was irradiated for 3 minutes in a nitrogen gas atmosphere using a metal halide lamp with an output of 120 mW / cm ² to cure the coating film, thereby producing a photochromic plastic lens.

In order to evaluate the cured state of the photochromic cured thin film (film thickness 40 μm) of the obtained photochromic plastic lens, the surface of the coating film was rubbed with a cloth moistened with acetone, and the lens substrate was irradiated with a projector. The projection surface was observed and evaluated. If the curing is good, the surface is not violated by acetone, so that no irregularities or scratches appear on the surface. The evaluation criteria are shown below.
A: It is flat, has no irregularities and scratches, and the cured thin film is sufficiently cured.
B: There are very slight unevenness and scratches.
C: There are unevenness and scratches partially.
D: The coating film is dissolved.

  The evaluation of the cured state of the photochromic plastic lens produced by the method described above was A.

  Moreover, the item shown below was evaluated about the photochromic characteristic of the obtained photochromic plastic lens.

  Maximum absorption wavelength (λmax): This is the maximum absorption wavelength after color development determined by a spectrophotometer (instant multi-channel photodetector MCPD3000) manufactured by Otsuka Electronics Co., Ltd. The maximum absorption wavelength is related to the color tone at the time of color development.

  Color density {ε (120) −ε (0)}: The difference between the absorbance {ε (120)} after the light irradiation for 120 seconds and the above ε (0) at the maximum absorption wavelength. It can be said that the higher this value, the better the photochromic properties.

  Fading half-life [t1 / 2 (min.)]: When light irradiation is stopped after 120 seconds of light irradiation, the absorbance at the maximum absorption wavelength of the sample is 1 of {ε (120) −ε (0)}. Time required to drop to / 2. The shorter the time, the faster the fading speed and the better the photochromic properties.

Residual rate = {(A ₅₀ / A ₀ }, or (A ₂₀₀ / A ₀ )}: The following deterioration promotion test was conducted to evaluate the durability of color development by light irradiation, that is, the obtained polymer (Sample) was accelerated and deteriorated for 50 hours or 200 hours with a Xenon Weather Meter X25 manufactured by Suga Test Instruments Co., Ltd. Thereafter, the color density was evaluated before and after the test, and the color density (A ₀ ) before the test and The developed color density (A ₅₀ or A ₅₀ ) after the test was measured, and the value of (A ₅₀ / A ₀ } or (A ₂₀₀ / A ₀ ) was defined as the residual rate, which was used as an index of color durability. The higher the rate, the higher the durability of coloring.

  These results are shown in Table 5.

Examples 15-26
A photochromic plastic lens was prepared in the same manner as in Example 14 except that the compounds obtained in Examples 2 to 13 were used as the chromene compound, and the characteristics thereof were evaluated. The results are summarized in Table 5.

Comparative Examples 1 and 2
For comparison, the following formulas (A) and (B)

An attempt was made to produce a photochromic plastic lens in the same manner as in Example 14 except that the compound represented by (Comparative Examples 1 and 2) was used, but the coating film was not cured. Moreover, the comparative example 3 and the comparative example 4 hardened by increasing the addition amount of a photoinitiator. In Comparative Example 4 using the compound (B), it was partially cured, but its photochromic properties were poor. These results are summarized in Table 6.

Examples 27-39 and Comparative Examples 5-6
Next, the photochromic cured body was evaluated by the kneading method as follows. That is, first, 0.04 part by mass of the chromene compound obtained in Example 1, 13 parts by mass of tetraethylene glycol dimethacrylate, 48 parts by mass of 2,2-bis [4- (methacryloxyethoxy) phenyl] propane, polyethylene glycol 2 parts by mass of monoallyl ether, 20 parts by mass of trimethylolpropane trimethacrylate, 9 parts by mass of glycidyl methacrylate, and 1 part by mass of t-butylperoxy 2-ethylhexanate are mixed thoroughly, and thermal radical polymerization is performed. Composition (photochromic curable composition) was prepared. Next, the obtained composition was poured into a mold composed of a glass plate and a gasket made of an ethylene-vinyl acetate copolymer, and cast polymerization was performed. The polymerization was carried out using an air furnace, gradually increasing the temperature from 30 ° C. to 90 ° C. over 18 hours, and maintaining at 90 ° C. for 2 hours. After completion of the polymerization, the polymer was removed from the mold glass mold. The obtained polymer (thickness 2 mm) was used as a sample, and photochromic properties were evaluated using the same method as described above.

  Moreover, the photochromic polymer was obtained like the above except having used the compound obtained in Examples 2-13 as a chromene compound, and the characteristic was evaluated. The results are summarized in Table 7.

  For further comparison, a photochromic polymer was obtained in the same manner using the compound represented by the above formula (A) (Comparative Example 5) and the compound represented by the above formula (B) (Comparative Example 6). evaluated. The results are shown in Table 8.

  Also in the evaluation of the photochromic cured body in the kneading method, the cured bodies obtained in Examples 27 to 39 have higher repetition durability of photochromic characteristics than the cured bodies obtained in Comparative Examples 5 and 6. Further, the cured bodies obtained in Examples 27 to 39 have a shorter fading half-life (faster fading speed) than the cured bodies obtained in Comparative Examples 5 and 6, and are excellent in this respect.

Claims (6)

The chromene compound shown by following formula (1).

(Wherein R ¹ , R ² , R ³ , and R ⁴ are each a hydrogen atom, a hydroxyl group, an alkyl group under the condition that at least one of R ³ and R ⁴ is a group other than a hydrogen atom, respectively. A cycloalkyl group, an alkoxy group, an aralkyl group, an aralkoxy group, an aryl group, or a halogen atom, and R ¹ and R ² , or R ³ and R ⁴ may be linked to each other to form a ring. ,
R ⁵ , R ⁶ , R ⁷ and R ⁸ each have a hydrogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an aralkyl group, an aralkoxy group, an aryl group, an amino group, or a nitrogen atom as a hetero atom. And a heterocyclic group, a cyano group, a nitro group, a halogen atom, a halogenoalkyl group, or a halogenoalkoxy group bonded by the nitrogen atom, and a plurality of R ⁵ , R ⁶ , R ⁷ , or R ⁸ are present. 2 R ⁵ , 2 R ⁶ , 2 R ⁷ , or 2 R ⁸ may be bonded to form a ring,
m, n, x, and y represent the number of substituents for R ⁵ , R ⁶ , R ⁷ , and R ⁸ , respectively, m and n are each an integer from 0 to 4, and x and y are each , An integer from 0 to 5. ) A photochromic curable composition comprising a polymerizable monomer and the chromene compound according to claim 1. Furthermore, the photochromic curable composition of Claim 2 formed by containing a photoinitiator. A photochromic optical article having, as a constituent member, a polymer molded body in which the chromene compound according to claim 1 is dispersed. An optical article having, as a constituent member, an optical base material in which at least one surface is coated with a polymer film in which the chromene compound according to claim 1 is dispersed. The optical article according to claim 5, wherein the polymer film is a polymer film obtained by curing the photochromic curable composition according to claim 3 by radical photopolymerization.