JP2000129253A - Ultraviolet reversibly color changeable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable formation of a coated film which shows excellent durability when applied not only to places and substances insusceptible to friction such as wall surfaces and nails but also even to articles frequently susceptible to friction such as vehicles such as automobiles and trains run by electricity, portable machines such as portable telephones, electronic pocket notebooks and portable electronic computers and, simultaneously, can reversibly change in color upon immediate reaction with the presence or absence of sun light and artificial light, particularly irradiation with ultraviolet rays. SOLUTION: This ultraviolet reversibly color changeable composition comprises 0.1-5 wt.% naphthopyran compound, 0.9-10 wt.% animal or vegetable oil and fat and balance acrylic resin vehicle. The animal or vegetable oil and fat is at least one member selected from the group consisting of a fish liver oil, a vegetable oil and an aliphatic hydrocarbon to be obtained by the isolation from the animal or vegetable oil, and the acrylic resin vehicle is composed of an acrylic resin and an organic solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a UV-chromic composition useful as a printing ink for paints and clothes for vehicles such as automobiles and trains, buildings, mobile phones, electronic notebooks, portable electronic computers and the like. The present invention relates to a reversible ultraviolet discolorable composition which changes to a chromatic color upon irradiation with ultraviolet light contained in sunlight or artificial light and forms a transparent colorless film or a film which reversibly changes to its original color when irradiation with ultraviolet light is stopped. Things.

[0002]

2. Description of the Related Art Conventionally, for the purpose of shading effect and decorative effect, it has been practiced to attach a colored film to the surface of various articles such as eyeglasses and window glass, or to apply a nail polish to nails to form a film. Have been done. Many of these compositions usually have a dye or pigment dissolved or dispersed in a vehicle, but have a drawback in that the color is unchanged.

As a means for solving this problem, attention has been paid to photochromic compounds exhibiting photochromic properties which change reversibly by light or heat, and recently, a product formed by adding a photochromic compound to a synthetic resin to form a film has been tried. Marking films that emit light upon irradiation with near-ultraviolet light (eg, Ole Rainbow, trade name, Lintec Corporation) are commercially available.

On the other hand, Japanese Patent Application Laid-Open No. Hei 10-147776 discloses that if only an organic photochromic compound is added to nitrocellulose, which is used as a vehicle in lacquer paints and nail varnishes, instead of conventional pigments, the mixture is yellow. A photochromic composition in which an aliphatic cyclic epoxy compound is used in combination with nitrocellulose has been proposed to solve the problem that the photochromic composition does not show photochromic property due to discoloration or browning. This photochromic composition includes azobenzene, thioindigo, dithizone,
Spiroran, spirooxazine, fulgide, dihydropyrene, spirothiopyran, benzopyran,
An organic photochromic compound such as a naphthopyran-based compound, a triphenylmethane-based compound, or a porogen-based compound is dissolved or dispersed in a vehicle containing nitrocellulose and an aliphatic cyclic epoxy compound.

[0005]

However, the conventional photochromic composition has no problem when applied to objects or places that do not receive much friction after the film is formed, such as walls and nails. When applied to objects that are frequently subjected to friction or exposed to sunlight, such as vehicles, mobile phones, electronic organizers, portable electronic computers, and other portable devices, there is a problem that deterioration is severe and wear resistance and durability are lacking. Further, it has been clarified that the use of the organic photochromic compound has a problem that it takes a relatively long time from receiving sunlight to discoloring or from being shielded by sunlight to discoloring.

Accordingly, the present invention can be applied not only to objects and places that do not receive friction such as wall surfaces and claws, but also to mobile devices such as vehicles such as automobiles and trains, mobile phones, electronic notebooks, and portable electronic computers. In addition to exhibiting excellent durability even when applied to articles subject to friction, it is possible to form a coating film that can be reversibly discolored in response to the presence or absence of sunlight and artificial light, especially ultraviolet light. The purpose is to:

[0007]

According to the present invention, as a means for solving the above problems, a naphthopyran compound is used as a photochromic material, which is dissolved or dispersed in an acrylic resin-based vehicle together with animal and vegetable fats and oils. Things.

Therefore, according to the present invention, 0.1 to 5% by weight of naphthopyran compound, 0.9 to 10% by weight of animal and vegetable oils and fats,
An ultraviolet reversible color-change composition comprising the remainder of an acrylic resin-based vehicle is obtained.

The naphthopyran compound has the formula:

Embedded image Wherein, R1 is -C (O) W, wherein W is OR ₄ also -N (R ₅₎
R ₆ ) and R ₄ are hydrogen, an allyl group, a (C ₁ -C ₆ ) alkyl group,
A phenyl group, a mono (C ₁ -C ₆ ) alkyl-substituted phenyl group,
Mono (C ₁ -C ₆ ) alkoxy-substituted phenyl group, phenyl
(C ₁ -C ₃ ) alkyl group, mono (C ₁ -C ₆ ) alkyl-substituted phenyl (C ₁ -C ₃ ) alkyl group, mono (C ₁ -C ₆ ) alkoxy-substituted phenyl (C ₁ -C ₃ ) alkyl Group, (C ₁ -C ₆ ) alkoxy (C ₂ -C ₄ ) alkyl or (C ₁ -C ₆ ) halogenated alkyl group, R ₅ and R ₆ are each hydrogen, (C ₁ -C ₆ ) alkyl group, One selected from the group consisting of a C ₅ -C ₇ cycloalkyl group, a phenyl group, a mono-substituted phenyl group and a di-substituted phenyl group, wherein the phenyl substituent is a (C ₁ -C ₆ ) alkyl group or (C ₁ -C ₆ ) an alkoxy group, wherein the halogen substituent is chlorine or fluorine, and R ₂ and R ₃ are hydrogen, an allyl group, a (C ₁ -C ₆ ) alkyl group, a C ₃ -C ₇ cycloalkyl group, substituted or unsubstituted; phenyl group, -OR ₇ group, R ₇ is hydrogen, (C ₁ -C ₆₎ alkyl group, a phenyl (C ₁ -C ₃ ) Alkyl group, mono (C ₁ -C ₆ ) alkyl-substituted phenyl (C ₁ -C
₃ ) alkyl group, (C ₁ -C ₆ ) alkoxy (C ₂ -C ₄ ) alkyl group, C ₃ -C ₇ cycloalkyl group, mono (C ₁ -C ₄ ) alkyl-substituted (C ₃ -C ₇ ) Cycloalkyl group, (C ₁ -C ₆ ) alkyl halide, allyl group, group —CH (R ₈ ) X, X is CN, CF ₃ , CF ₃ , halogen, or —C (O) W,
R ₈ is a halogen or a (C ₁ -C ₆ ) alkyl group, or R ₇ is a group —C (O) Y (where Y is hydrogen, (C ₁ -C ₆ )
Alkyl group, (C ₁ -C ₆ ) alkoxy group, substituted or unsubstituted aryl group, phenyl group or naphthyl group, phenoxy group, (C ₁ -C ₆ ) mono- or dialkyl-substituted phenoxy group, (C ₁ -C 6 ₆ ) mono- or dialkyl-substituted phenylamino group, (C ₁ -C ₆ ) mono- or di-alkoxy-substituted phenylamino group, wherein the aryl substituent is (C _1-
A group selected from (C ₆ ) alkyl group or (C ₁ -C ₆ ) alkoxy group), the halogen or the halogen substituent is chlorine or fluorine, n is an integer of 0, 1, 2 or 3,
B and B ′ each represent a substituted or unsubstituted aryl phenyl group or naphthyl group, and the aryl substituent is hydrogen, a (C ₁ -C ₆ ) alkyl group, or a (C ₁ -C ₆ ) halogenated alkyl group. A group selected from the group consisting of a (C ₁ -C ₆ ) alkoxy group, a (C ₁ -C ₆ ) alkoxy (C ₁ -C ₄ ) alkyl group, an acryloxy group, a methacryloxy group and a halogen,
The halogen or halogenated group is fluorine or chlorine. At least one of the naphthopyran compounds represented by the formula [1] may be used.

Specifically, naphthopyran compounds include 2,2-bis (4-methoxyphenyl) -5-methoxycarbonyl-6-hydroxy-2H-naphtho [1,2-
6] pyran, 2,2-bis (4-methoxyphenyl) -5
-Methoxycarbonyl-6-methoxy-2H-naphtho
[1,2-6] pyran, 2,2-bis (4-methoxyphenyl) -5-methoxycarbonyl-6- (ethoxycarbonyl) methoxy-2H-naphtho [1,2-6] pyran, 2-
(4-methoxyphenyl) -2-t-butyl-5-methoxycarbonyl-6-acetoxy-2H-naphtho [1,2-
6] pyran, 2- (4-methoxyphenyl) -2-phenyl-5-methoxycarbonyl-6- (cyanomethoxy)-
Others such as 2H-naphtho [1,2-6] pyran, 2,2-bis (4-methoxyphenyl) -5-methoxycarbonyl-6- (methoxycarbonyl) -2H-naphtho [1,2-6] pyran And naphthopyran compounds described in U.S. Pat. No. 5,458,814 and commercially available ones.

[0011] Since simply dissolving or dispersing the naphthopyran compound in an acrylic resin-based vehicle does not provide the expected coloring or discoloration properties, in order to solve this problem, the present invention provides a method for producing a naphthopyran compound using an animal or plant. Fats and oils are added and mixed. As animal and vegetable oils,
At least one selected from the group consisting of fish liver oil, vegetable oil, and aliphatic hydrocarbons that are liquid at room temperature may be used. Examples of the fish liver oil include those collected from the liver of marine animals such as tuna, bonito, oil flounder and shark. Examples of vegetable oils include those collected from sesame oil, olive oil, rapeseed oil, and the like. Furthermore, examples of the aliphatic hydrocarbon include unsaturated aliphatic hydrocarbons isolated from animal and vegetable oils, squalene, and pristane.

As the acrylic resin-based vehicle, an acrylic resin-based paint base comprising an acrylic resin and an organic solvent may be used. In addition, this acrylic resin-based paint base
The color does not necessarily need to be colorless and transparent, and may contain a dye or pigment of a desired color as a colorant. Therefore, a known acrylic resin-based paint employed as an automotive paint may be used.

The above composition is obtained by adding and mixing a naphthopyran compound to 10 parts by weight of animal and vegetable oils and fats, and dissolving or dispersing the compound in an acrylic resin-based paint base. Usually, the composition is set to 0.1 to 5% by weight of a naphthopyran compound, 0.9 to 10% by weight of animal and vegetable oils, and 95 to 99% by weight of an acrylic resin-based paint base. By changing the naphthopyran compound, the color to be developed can be variously changed, but by changing the content of the naphthopyran compound, the color development at the time of ultraviolet irradiation can also be changed.

The organic solvent may be selected from hydrocarbon solvents, ester solvents, and alcohols depending on the animal and vegetable fats and oils used.
At least one solvent selected from the group consisting of toluene solvents and ether ester solvents may be appropriately selected. When using animal and vegetable fats and oils which have not been isolated, usually 10 to 30% of a hydrocarbon solvent, 10 to 30% of an ester solvent, 10 to 30% of an alcohol solvent and 10 to 30% of an ether ester solvent It is preferable to use a mixed solvent consisting of Typical examples of the hydrocarbon solvent include toluene and xylene. Examples of the ester solvent include ethyl acetate, butyl acetate, and isobutyl acetate. Examples of the alcohol-based solvent include lower alcohols such as ethanol, n-butanol and isobutanol, and examples of the ether-ester-based solvent include butyl glycol acetate. Can be

[0015]

EXAMPLE Acrylic resin 23.1%, cellulose resin 5.8
%, Toluene 21.7%, ester solvent 13.1%,
An acrylic resin-based transparent paint base comprising 23.1% of an alcohol-based solvent, 9.7% of an ether ester-based solvent, and 2.9% of a plasticizer is prepared. Separately, naphthopyran compounds (2,2-dimethyl-5-carbomethoxy-6-acetoxy-2H-naphtho [1,2-6] pyran, C ₂₉ H
₂₂ O ₅ ) 1 part by weight was mixed with 10 parts by weight of olive oil, and this mixture was added and mixed with 989 parts by weight of an acrylic resin-based transparent paint base to obtain an ultraviolet reversible discolorable composition.

The ultraviolet reversible color-changing composition was applied to the plastic surface of a dark blue mobile phone and dried to form a colorless and transparent coating film. When this colorless and transparent coating film was exposed to sunlight, it turned reddish pink within a few seconds or within one second depending on the exposure time. Then, after the mobile phone was kept exposed to sunlight for 1 minute, the mobile phone was placed in a container made of ultraviolet-cut glass to block the ultraviolet light and observed. In addition, when the mobile phone was repeatedly exposed to and blocked from sunlight for 60 days, it was confirmed that the reversible changes were repeated stably. In parallel with this, a friction test was conducted in which the surface of the coating film was rubbed with a cloth, and no abrasion of the coating film and no deterioration in reversible discoloration were observed.

Further, the above-mentioned ultraviolet reversible color-changing composition is applied on a white coating film coated with an acrylic resin paint, and dried to form a colorless and transparent coating film, and this coating film is exposed to direct sunlight. When a durability test was conducted for xx days in which the coating film was washed with water and car wax was applied every day, no reversible discoloration of the coating film and no deterioration in gloss were observed, and no abrasion was observed. Irradiation with a commercially available plaque light (near-ultraviolet radiation lamp) resulted in discoloration in the same manner as when exposed to sunlight.

[0018]

As is apparent from the above description, the present invention shows excellent durability even when applied to a portable device, a car or a train such as a train, which is frequently subjected to friction, and at the same time, exhibits sunlight and artificial light. In particular, an excellent effect of forming a reversible discolorable coating film having good responsiveness to the presence or absence of ultraviolet irradiation can be obtained.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C09D 11/10 C09D 11/10 133/00 133/00 F term (reference) 4J002 BG001 EA017 EL086 FD206 FD207 GP00 4J038 BA202 CG141 JA73 KA08 MA07 MA09 NA18 4J039 AB04 AB05 AD10 BC31 BC68 BC71 BC72 BC73 BC75 BC76 BC77 BE12 CA04 CA07 EA29 FA03

Claims (5)

[Claims] 1. A naphthopyran compound in an amount of 0.1 to 5% by weight,
An ultraviolet-reversible discoloring composition comprising 0.9 to 10% by weight of animal and vegetable oils and fat, the balance being an acrylic resin-based vehicle. 2. The ultraviolet-reversible color-changing composition according to claim 1, wherein the animal or vegetable fat is at least one selected from the group consisting of fish liver oil, vegetable oil, and aliphatic hydrocarbons obtained by isolation from these animal and vegetable oils. . 3. The ultraviolet reversible color-changing composition according to claim 1, wherein the acrylic resin-based vehicle comprises an acrylic resin and an organic solvent. 4. The composition according to claim 1, wherein the composition comprises a naphthopyran compound.
The UV-reversible discolorable composition according to any one of claims 1 to 3, wherein the composition is 1 to 5% by weight, 0.9 to 10% by weight of animal and vegetable fats and oil, and the balance is an acrylic resin-based vehicle. 5. The method of claim 1, wherein the naphthopyran compound has the formula:[Wherein, R₁Is -C (O) W, where W is OR_FourAlso, -N (R_Five) R
₆), R_FourIs hydrogen, an allyl group, (C1-C₆) Alkyl group,
Enyl group, mono (C₁-C₆) Alkyl-substituted phenyl group,
No (C₁-C₆) Alkoxy substituted phenyl group, phenyl (C₁
-C_Three) Alkyl group, mono (C₁-C₆) Alkyl substituted phenyl
Le (C₁-C_Three) Alkyl group, mono (C₁-C₆) Alkoxy
Substituted phenyl (C₁-C_Three) Alkyl group, (C₁-C₆) Alkoki
Shi (C_Two-C _Four) Alkyl or (C1-C₆) Alkyl halide
And R5 and R6 are each hydrogen, (C1-C6) alkyl
Group, C_Five-C₇Cycloalkyl group, phenyl group, mono-substituted
Selected from the group consisting of phenyl and disubstituted phenyl
And the phenyl substituent is (C₁-C₆) Alkyl group
Or (C₁-C₆) Alkoxy group, the halogen substituent is
Chlorine or fluorine; R_TwoAnd R_ThreeIs hydrogen, allyl group, (C₁-C₆) Alkyl group,
C_Three-C₇Cycloalkyl group, substituted or unsubstituted phenyl
Group, -OR₇Group, R₇Is hydrogen, (C₁-C₆) Alkyl group,
Phenyl (C₁-C_Three) Alkyl group, mono (C₁-C₆) Archi
Substituted phenyl (C₁-C_Three) Alkyl group, (C₁-C₆) Al
Koxy ・ (C_Two-C_Four) Alkyl group, C_Three-C₇Cycloalkyl
Group, mono (C₁-C_Four) Alkyl-substituted (C_Three-C₇) Cycloa
Alkyl group, (C₁-C₆) Alkyl halide, allyl group,
Group -CH (R₈) X, X is CN, CF_Three, CF_Three, Haloge
Or -C (O) W, R₈Is halogen or (C₁
-C₆) Alkyl group, or R₇Is a group -C (O) Y (but
And Y is hydrogen, (C₁-C₆) Alkyl group, (C₁-C₆) Al
Coxy group, substituted or unsubstituted aryl group, phenyl group
Or naphthyl group, phenoxy group, (C₁-C₆)
Or a dialkyl-substituted phenoxy group, (C₁-C₆)
Or a dialkyl-substituted phenylamino group, (C₁-C₆)
A no- or di-alkoxy substituted phenylamino group,
The aryl substituent is (C₁-C₆) Alkyl group or (C₁
-C₆) Groups selected from alkoxy groups);
Or the halogen substituent is chlorine or fluorine, n is 0,
An integer of 1, 2 or 3, B and B ′ each represent a substituted or unsubstituted aryl group;
Phenyl or naphthyl, the aryl substituent is water
Element, (C₁-C₆) Alkyl group, (C₁-C₆) Halogenated al
Kill group, (C₁-C₆) Alkoxy group, (C₁-C₆) Alkoki
Shi (C₁-C_Four) Alkyl group, acryloxy group,
A group selected from the group consisting of a riloxy group and a halogen,
The halogen or the halogenated group is fluorine or a salt;
Is prime. At least the naphthopyran compound represented by
The ultraviolet ray according to any one of claims 1 to 4, wherein the ultraviolet ray is also a kind.
Reversible discolorable composition.