JPH03234788A - Photochromic material - Google Patents

Abstract

PURPOSE:To form a photochromic material with no bleeding out of the photochromic compd. and excellent hardness and light resistance by curing a polymer contg. a specified photochromic compd. with an alkyl-etherified methylolmelamine. CONSTITUTION:A polymer contg. at least a compd. of formula I as a polymerizable ingredient is cured with an alkyl-etherified methylolmelamine. In formula I, a ring alpha is a pyrrolidine, pyrrole or indole ring and the nitrogen atom in the ring alpha is bound to YmR<2> or an org. group R, R is a substd. group such as a 1-20C alkyl group or a 2-20C alkenyl group and a ring beta is a benzene or naphthalene ring, R<1> is a substituent such as hydrogen, a 0-20C amino group, a 1-20C alkoxy group or a 1-20C alkyl group and R<2> is a radical polymerizable functional group, (n) is an integer of 1 or larger; Y is a 1-20C org. group; (m) is 0 or 1 provided that when YmR<2> is bound to the nitrogen atom in the ring alpha, (m) is 1.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a photochromic material with excellent light resistance and durability.

[Prior Art] In recent years, the use of photochromic substances that reversibly change color tone depending on the presence or absence of ultraviolet irradiation has begun to attract attention in the fields of light control materials, recording materials, etc. It is considered useful because of its good applicability to various materials including resins. but,
When incorporated into resins, etc., only the photochromic compound bleeds out, resulting in low repetition resistance.When applied to various products, problems such as not fully satisfying the hardness, durability, etc. required for the product may occur. Because of this, it has not been put into widespread practical use.

Therefore, among the technologies that have been studied so far, there is a method in which a photochromic compound containing a hydroxyl group is reacted and cured with an epoxy resin or a urethane resin.
It is disclosed in Japanese Patent No.-51492. however,
This technique has problems in that the photochromic compound has poor solubility and the resulting photochromic coating has poor hardness and light resistance.

Furthermore, various techniques have been reported to date for reaction-curing polymers with alkyl etherified methylolmelamine. For example, a film made by curing an acrylic polymer with alkyl etherified methylol melamine can be dyed to any desired color tone using known methods, but it is possible to dye a film made of an acrylic polymer cured with alkyl etherified methylol melamine to any desired color tone. There are no examples of this being considered.

[Problems to be Solved by the Invention] The present invention aims to eliminate the drawbacks of the prior art, and provides a photochromic material that does not have the problem of photochromic compound bleed out and has excellent hardness and light resistance. The purpose is to provide

[Means for Solving the Problems] The present invention has the following configuration to achieve the above object.

``A photochromic material characterized by curing a polymer containing at least a compound represented by the following general formula [I] as a polymerizable component with alkyl etherified methylolmelamine.

(In the formula, the α ring is a type selected from a pyrrolidine ring, a pyrrole ring, a piperidine ring, a tetrahydropyridine ring, a dihydropyridine ring, an indoline ring, a benzindoline ring, a tetrahydroquinoline ring, an acridine ring, a benzoxazoline ring, and a benzothiazoline ring. , and the nitrogen atom in the α ring is bonded to Y, nR2 or an organic group R. Here, R is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkenyl group having 7 to 20 carbon atoms. represents a substituent selected from 20 aralkyl groups and aryl groups having 6 to 19 carbon atoms.

The β ring is a benzene ring, a naphthalene ring, an anthracene ring,
One type selected from a phenanthrene ring, a quinoline ring, a dibenzofuran ring, a dibenzothiophene ring, a carbazole ring, and a benzonaphthothiophene ring.

R1 is hydrogen, an amino group having 0 to 20 carbon atoms, and 1 to 2 carbon atoms.
0 alkoxy group, aralkoxy group having 7 to 20 carbon atoms,
Aryloxy group having 6 to 14 carbon atoms, acyloxy group having 2 to 20 carbon atoms, alkyl group having 1 to 20 carbon atoms, 7 carbon atoms
represents a substituent selected from an aralkyl group having ~20 carbon atoms and an aryl group having 6 to 20 carbon atoms.

R2 represents a radically polymerizable functional group.

n is an integer of 1 or more.

Y represents an organic group having 1 to 20 carbon atoms.

m represents 0 or 1. However, when Y, R2 is bonded to the nitrogen atom in the α ring, m represents 1. ” The polymer constituting the photochromic material of the present invention (hereinafter, this polymer is referred to as a photochromic polymer) is:
It contains at least a compound represented by the general formula [I] (hereinafter, this compound is referred to as a photochromic compound) as a polymerizable component.

In general formula (I), the α ring is selected from a pyrrolidine ring, a pyrrole ring, a piperidine ring, a tetrahydropyridine ring, a dihydropyridine ring, an indoline ring, a benzindoline ring, a tetrahydroquinoline ring, an acridine ring, a benzoxazoline ring, and a benzothiazoline ring. It is one of a kind.

The nitrogen atom contained in this α ring is present in bond with Y, R2 or an organic group R, and is represented by:

Here, specific examples of the substituent R include a chain alkyl group having 1 to 20 carbon atoms such as a methyl group, ethyl group, and octadecyl group, and a chain alkyl group having 3 to 20 carbon atoms such as a tert-butyl group and a 2-methylpentyl group. Branched alkyl groups, cyclohexyl groups, norbornyl groups, adamantyl groups, etc. with 3 or more carbon atoms
10 cycloalkyl groups, alkenyl groups having 2 to 20 carbon atoms such as vinyl groups, allyl groups, hexenyl groups, 1,3-butadienyl groups, isopropenyl groups, benzyl groups, phenethyl groups, (2-naphthyl)methyl groups, etc. carbon number 7~
20 represents an aryl group having 6 to 19 carbon atoms, such as an aralkyl group, a phenyl group, or a 2-naphthyl group.

R may be substituted, and in such a case, specific examples of the substituent include a hydroxy group; an amino group such as an amino group and a dibenzylamino group; an alkoxy group such as a methoxy group, an ethoxy group, and a propoxy group; Acyloxy groups such as benzoyloxy; alkyl groups such as methyl, ethyl, trifluoromethyl, butyl; benzyl, 4-(
Aralkyl groups such as 2,3-epoxypropyl) phenethyl groups; Aryl groups such as phenyl groups; Halogen groups such as fluoro and chloro groups; Cyano groups; Carboxy groups; Nitro groups;
Acyl group such as acetyl group; ethoxycarbonyl group, 34
-Alkoxycarbonyl groups such as epoxybutyloxycarbonyl groups; carbamoyl groups, carbamoyl groups such as N-phenylcarbamoyl groups, carbamoyloxy groups such as (N-(acetoxy)propylcarbamoyl)oxy groups;
Examples include sulfonic acid groups such as sulfonic acid and its metal salts (eg, sodium, lithium salts, etc.).

Y in R2, which is another substituent that can be bonded to the nitrogen atom of the α ring, is an organic group having 1 to 20 carbon atoms, and specific examples include a methylene group, -(-CH2CH
Alkyleneoxy groups such as 20 x T1-(-CH2CFI-0-+-T (a represents a natural number), phenylene groups,
Examples include arylene groups such as naphthylene groups.

Here, the substituents/bonds represented by Y are present. Also, m must be 1. Furthermore, R2 is a radical polymerizable functional group, and specific examples thereof include acryloxy group, methacryloxy group, methacrylamide group, p-vinylbenzoyloxy group, m-vinylbenzyl group, (2-(meth)acryloxy group, loxyalkyl)amino group, N-(2-(meth)acryloxy)alkylcarbamoyl group, (N-(:3-(meth)acryloxy)alkylcarbamoyl)oxy group, and the like.

The above Y, R2 groups can be substituted on atoms other than the nitrogen atom in the α ring, on each atom in the β ring, or in R1, etc. In that case, even if m is O It may be 1. Further, n, which is the number of functional groups contained in the general formula (I) of Y□R2, is an integer of 1 or more, but when n is 2 or more, the Y, .

There is no problem whether R2 is of the same type or different types.

On the other hand, β included in general formula (I) like the α ring
The ring is selected from a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a quinoline ring, a dibenzofuran ring, a dibenzothiophene ring, a carbazole ring, and a benzonaphthothiophene ring.

Various substituents can be introduced into the α ring and β ring,
By introducing a substituent, it is possible to control the speed of color development and fading, which is one of the photochromic properties, and further control the color tone of color development. Specific examples of substituents that can be introduced and are preferably applied include those having 1 to 20 carbon atoms;
an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 19 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms including the 3-carbon in the α ring, a hydroxy group, an amino group, organic substituted amino group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, 7 to 20 carbon atoms
20 aralkoxy group, aryloxy group having 6 to 19 carbon atoms, acyloxy group having 2 to 20 carbon atoms, halogen group, cyano group, carboxy group, nitro group, acyl group having 2 to 20 carbon atoms, acyl group having 2 to 20 carbon atoms Substituents selected from alkoxycarbonyl groups, carbamoyl groups, carbamoyloxy groups, and sulfonic acid groups can be mentioned.

Furthermore, those containing a beta atom in the β ring are particularly effective as a means for shortening the wavelength of the coloring species or for including a plurality of absorption maximum wavelengths.

Among them, a carbazole ring containing a nitrogen atom and a dibenzofuran ring containing an oxygen atom are preferably used from the viewpoint that they are relatively easy to synthesize and the above-mentioned properties are significantly exhibited.

The photochromic compound of the present invention described above is
No. 93788, Japanese Patent Application Laid-open No. 199279/1983,
These are disclosed in Japanese Patent Application Laid-Open No. 63-250380 and the like, and naturally these are also photochromic compounds that can be used in the present invention.

These photochromic compounds include not only one type but also two types.
By using more than one species in combination, it is possible to broaden the absorption wavelength of the coloring species, create mixed colors, and further improve the apparent durability.

As the photochromic polymer of the present invention, a polymer consisting only of the above photochromic compound of the present invention may be used, but a copolymer with other copolymerizable monomer components may also be used. When using a copolymer, the proportion of the photochromic compound contained in the copolymer varies depending on the intended function of the use of the copolymer, but should be determined by taking into consideration sufficient color density and economic efficiency. can be,
- For boat fishing, 0. It is preferably contained in a proportion of 2% by weight or more and 60% by weight or less.

If this content is less than 0.2% by weight, it is difficult to obtain a sufficient concentration during color development. Moreover, if it exceeds 60% by weight, the price of the obtained cured product becomes high.

Any polymerizable monomer can be used to form a copolymer with the photochromic compound of the present invention as long as it is copolymerizable, but it is important that the degree of polymerization is easy to control and monomer selection is easy. It is particularly preferable to use a monomer having a radically polymerizable functional group because it can be introduced into the polymer in any desired state.

As the monomer having a radically polymerizable functional group, since the photochromic material of the present invention is obtained by curing the above-mentioned photochromic polymer with alkyl etherified methylolmelamine, a polymer effective for such a curing reaction may be used. Preferred examples include monomers having functional groups that can be formed. Examples of monomers having such functional groups include (1) compounds having a hydroxyl group-containing side chain, and (2) compounds having a carboxyl group.

These functional groups may be included in the photochromic compound, but from the viewpoint of controlling the photochromic properties and ease of synthesizing the compound, it is preferable to include them in other copolymerizable monomers.

Specific examples of such monomers include allyl alcohol, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide,
N-(2-hydroxyethyl)acrylamide, N,N
-dihydroxymethylacrylamide, N,N-di(2
-hydroxyethyl) methacrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 1゜4-butylene glycol monoacrylate, 1゜4-butylene glycol monomethacrylate, Glycerol monomethacrylate, hydroxyallyl methacrylate, hydroxymethylaminomethyl acrylate, hydroxymethylaminomethyl methacrylate, 2-hydroxyethylaminomethyl acrylate, 2-(2-hydroxyethylamino)ethyl methacrylate, N,N-di(hydroxymethyl) Aminomethyl acrylate, N,N-di(hydroxymethyl)aminomethyl methacrylate, N,N
-di(hydroxyethyl)aminomethyl acrylate and the like.

Specific examples of the compound (2) include acrylic acid, methacrylic acid, crotonic acid, vinyl acetic acid, maleic acid, and itaconic acid.

Further, as other monomers having a radically polymerizable functional group, various copolymerizable monomers can be mentioned for the purpose of controlling weather resistance, film-forming properties, hardness, coloring and fading properties, etc. Examples include (1) a compound having an amino group-containing side chain, and (2) a compound having a hindered amino group.

Specific examples of the compound (2) include acrylamide, methacrylamide, crotonamide, N-methylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N-propylacrylamide, N-propylmethacrylamide, N, N
-dimethylacrylamide, N,N-dimethylmethacrylamide, N,N-diethylacrylamide, N,N-
Diethylmethacrylamide, N,N-dipropylacrylamide, N,N-dipropylmethacrylamide, N-
Butoxymethylacrylamide, N-1so-butoxymethylmethacrylamide, 2-(N-methylamino)ethyl acrylate, 2-(N-methylamino)ethylmethacryle-I', 2- (N,N-dimethylamino)
Ethyl acrylate, 2-(N,N-diethylamino)ethyl acrylate, 2-(N,N-diethylamino)ethyl acrylate, 1-)N,N-diethylamino)ethyl methacrylate, 3-(N,N-diethylamino)propyl acrylate ,3-(N.

Examples include monomers such as N-diethylamino)propyl methacrylate.

Furthermore, specific examples of the compound (2) include 2,2°6.
6-tetramethyl-4-piperidinyl acrylate, 2
, 2.6.6-tetramethyl-4-piperidinyl methacrylate, I, 2.2.6.6-bentamethyl-4
-piperidinyl-acrylate, l, 2.2.6.6
Monomers such as -pentamethyl-4piperidinyl-methacrylate can be mentioned.

Furthermore, in addition to the above monomers having radically polymerizable functional groups, monomers having acrylic groups, methacryl groups, styryl groups, vinyl groups, etc. as polymerizable functional groups can also be suitably used.

Specific examples include styrene, styrene derivatives, divinylbenzene, acrylic esters, methacrylic esters, ethylene glycol dimethacrylate, acrylonitrile, methacrylatrile, methyl vinyl ketone, butadiene, maleic anhydride, vinylidene chloride, etc. Preferred monomers for imparting a glass transition point include vinylcarbazole, N-substituted maleimide, α
Examples include methylstyrene.

In addition, the above polymerizable compounds can be used alone or in combination with
It is also possible to use more than one species in combination.

Copolymerization can be carried out using various radical initiators, for example, peroxides such as benzoyl peroxide, and azo compounds such as azobisisobutyronitrile. Furthermore, polymerization can also be carried out using actinic light such as ultraviolet rays or electron beams. In particular, azo initiators are preferably used from the viewpoint of preventing decomposition during polymerization.

In the present invention, a polymer containing the above photochromic compound is crosslinked and cured with an alkyl etherified methylol melamine, but the alkyl etherified methylol melamine is not particularly limited, and may range from monomethylol melamine to hexamethylol melamine. In addition, the alkyl group for alkyl etherification is not particularly limited, but among them, the alkyl group has 1 to 1 carbon atoms.
Preferably, the alkyl group of No. 4 is used. Specific examples include hexamethoxymethyl melamine, hexamethylol melamine pentamethyl ether, hexamethylol melamine tetramethyl ether, tetramethylol melamine trimethyl ether, hexakis butoxymethyl melamine, tetramethylol melamine butyl ether, and the like. These alkyl etherified methylol melamines may be used alone or in combination of two or more. Also,
The amount used is generally 10% of the photochromic polymer.
5 to 40 parts by weight, more preferably 10 to 3 parts by weight
It is used in a proportion of 0 parts by weight.

In addition, in the curing reaction between the photochromic compound and the alkyl etherified methylol melamine, for example, hydrochloric acid, ammonium chloride, ammonium nitrate, ammonium thiocyanate, etc. can be used as appropriate for the purpose of promoting the crosslinking reaction.

Furthermore, although the curing reaction can usually be achieved by heating,
As for the temperature and reaction time, it is preferable to carry out reaction curing for 10 to 400 minutes at usually 50°C or higher, more preferably 100°C or higher.

The photochromic material of the present invention can be used in various ways, but the range of use is particularly wide.
From the viewpoint of ease of use, it is preferable to use it by applying it to the surface of the object to be coated.

When applied to an object to be coated, ie, used as a so-called coating agent, it is preferable to add various surfactants as surface smoothing agents to the coating composition, although they do not participate in crosslinking. Also, photochromic properties, e.g.
Addition of various sensitizers and ultraviolet absorbers is also preferably used for the purpose of improving color density.

In addition, various organic solvents can be used as the solvent when applied as a coating composition, specifically various alcohols, ketones, ethers, esters, aromatic (halogenated) carbonized It is not particularly limited as long as it can dissolve the matrix resin and other components, such as hydrogens, aliphatic (halogenated) hydrocarbons, cellosolves, various formamides, and sulfoxides.

The photochromic material obtained by the present invention preferably has a thickness of 0.5 μm to 50 μm from the viewpoint of color density and the like. From the viewpoint of weather resistance, 5.0μ
It is particularly preferable that it is at least m. Moreover, various materials such as inorganic glass, fabric, wood, paper, metal, plastic, and ceramics can be used as the base material to be coated. Further, the shape of the substrate to be coated is not particularly limited, and may be a film, sheet, molded product, or the like. Application methods include conventional coating methods used in the coating industry, such as dip coating, spin coating, flow coating, roll coating, curtain flow coating, barcoding,
Methods such as brush coating and screen printing are also applicable.

On the other hand, in order to further increase light resistance with ingredients other than those mentioned above, and further to improve heat resistance and antioxidant properties, antioxidants, stacked oxygen quenchers, etc. are added to further improve practical performance. It is also possible.

For the purpose of further improving the practicality of the photochromic material in the present invention, it is also preferable to provide a coating having hard coat properties on the material to improve the scratch resistance of the article.

A preferred embodiment of the present invention includes a photochromic molded product in which a lens or the like is coated with the photochromic material of the present invention as a film. Furthermore, it is also preferable to laminate the photochromic material of the present invention in a sandwich-like manner using inorganic glass plates or the like.

The photochromic material of the present invention is preferably used in optical articles such as sunglasses and corrective lenses, and window glass for automobiles, homes, offices, etc., and in particular for purposes that require light regulation related to sunlight. It is.

[Examples] Examples are shown below to clarify the gist of the present invention, but the present invention is not limited to these Examples.

Example 1 (1) Preparation of photochromic polymer 40 parts by weight of octyl methacrylate, 19 parts by weight of n-butyl methacrylate, 10 parts by weight of methyl methacrylate, 2,2,6.6 parts by weight
-tetramethyl-4-piperidinyl-methacrylate 1
Using an azobis-based initiator, Polymerization was carried out in a nitrogen atmosphere at a polymerization temperature of 70 to 80°C and a polymerization time of about 7 hours to prepare a photochromic polymer having a solid content of 50% by weight.

(2) Preparation of coating composition For 100 parts by weight of the photochromic polymer in (1) above, 20 parts of "Kneepan 122" (melamine resin manufactured by Mitsui Toatsu Chemical Co., Ltd.)
Parts by weight were blended to prepare a coating composition for photochromic coating.

(3) Coating and heat curing The coating composition obtained in 2) above was coated to a thickness of 1,000
It was applied to a thickness of about 20 μm on a glass plate with a flow coating method. The coated glass plate was heat-cured at 130°C for 1 hour.

(4) Performance tests and results The following tests were conducted. The results are shown in Table 1.

(a) Photochromic performance: 2.8 mW/cm using a chemical lamp (Measured using ORC Ultraviolet Illuminometer Model UV-302A, Oak Seisakusho ■)
The color density when irradiated with ultraviolet rays was measured and expressed as total light transmittance.

(b) Hardness Using a Mitsubishi pencil "Uni", the film was scratched under a load of 500 g, and the ease of scratching was expressed as pencil hardness.

In Table 1, ◯ indicates that there were almost no scratches in 5 tests, and × indicates that scratches occurred two or more times.

(c) Hot water resistance After being immersed in hot water at 90'C for 2 hours, the presence or absence of any change in appearance was observed. In Table 1, ○ indicates that there was no change in appearance.
X indicates that there was a change in appearance.

(d) Bleed-out resistance The coated and heat-cured glass plates were stored for one month at 40° C. and 90% RH, and then evaluated. In Table 1, ◯ indicates that there was no change in appearance, and × indicates that change in appearance was observed due to bleed-out of the photochromic compound.

Example 2 In Example 1, except that methacrylic acid was not used as the monomer for the photochromic polymer, and 0.1 part by weight of "Catalyst 6000" (curing catalyst manufactured by Mitsui Toatsu Chemical Co., Ltd.) was added as a coating composition. A glass plate having a photochromic coating was obtained in the same manner as in Example 1, and a performance test was conducted in the same manner. The results are shown in Table 1.

Comparative Example 1 A glass substrate having a photochromic coating was obtained in the same manner as in Example 1, except that "Kneepan 122" was not used as the coating composition, and its performance was evaluated in the same manner. The results are shown in Table 1.

Comparative Example 2 A glass substrate having a photochromic coating was obtained in the same manner as in Example 2, except that "Kneepan 122" was not used as the coating composition, and its performance was evaluated in the same manner. The results are shown in Table 1.

Comparative Example 3 In Example 1, when preparing a photochromic polymer, 1,3,3-trimethyl-9'-methacryloxyindolinospironaphthoxazine was replaced with 1,3,3-trimethyl which does not have a polymerizable functional group. - A glass substrate having a photochromic coating was obtained in the same manner as in Example 1 except that indolinospironaphthoxazine was used, and the performance was evaluated in the same manner. The results are shown in Table 1.

[Effect of the invention] Photochromia of the present invention The tough material is hardness, Endurance Light and durable.

Furthermore, it has excellent hot water resistance.

Claims (1)

[Claims] (1) As a polymerizable component, at least the following general formula [I
] A photochromic material characterized in that it is made by curing a polymer containing a compound represented by the following with alkyl etherified methylolmelamine. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] (In the formula, α ring is a pyrrolidine ring, pyrrole ring, piperidine ring, tetrahydropyridine ring, dihydropyridine ring, indoline ring, benzindoline ring, tetrahydroquinoline ring, acridine ring, It is a type selected from a benzoxazoline ring and a benzothiazoline ring, and the nitrogen atom in the α ring is bonded to Y_mR^2 or an organic group R. Here, R is an alkyl group having 1 to 20 carbon atoms, It represents a substituent selected from an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aryl group having 6 to 19 carbon atoms. The β ring is a benzene ring, a naphthalene ring, an anthracene ring,
One type selected from a phenanthrene ring, a quinoline ring, a dibenzofuran ring, a dibenzothiophene ring, a carbazole ring, and a benzonaphthothiophene ring. R^1 is hydrogen, an amino group having 0 to 20 carbon atoms, and 1 to 20 carbon atoms.
20 alkoxy groups, C7-20 aralkoxy groups, C6-14 aryloxy groups, C2-20 acyloxy groups, C1-20 alkyl groups, C7-20 aralkyl groups, and Represents a substituent selected from aryl groups having 6 to 20 carbon atoms. R^2 represents a radically polymerizable functional group. n is an integer on one side. Y represents an organic group having 1 to 20 carbon atoms. m represents 0 or 1. However, when Y_mR^2 is bonded to the nitrogen atom in the α ring, m represents 1.