JPH01152182A - Photochromic resin and its preparation - Google Patents

Abstract

PURPOSE:To obtain a photochromic resin which is capable of revealing photochromism with high density and can be applied to various base materials, especially to fibers, by dispersing fine particles of a photochromic polymer in a film-forming resin component. CONSTITUTION:This photochromic resin is formed by dispersing in a film- forming resin component at least a component A comprising fine particles of a photochromic polymer having as its constituent a photochromic compound wherein the mean particle diameter of the polymer is 0.1-100mum. As the film- forming resin component, an organic polymer is preferably used because of the ease of mixing with component A, the especially preferred one being a water-soluble or water-dispersible polymer. Examples of the photchromic compound include a spiropyran compound, a spirooxazine compound, a viologen compound, a triarylmethane compound, and an anil compound.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a photochromic resin having photochromic polymer fine particles dispersed therein and a method for producing the same, and relates to a resin having photochromic properties and a method for producing the same, and is applicable to various containers, fabrics, papers, films, etc. It is useful and can be used in various fields.

[Prior Art] Various types of photochromic compounds are known as compounds that change color when exposed to light, and are introduced in books such as "Photochromism" by G. H. Brown.

Among them, organic photochromic compounds are generally used as a composition dispersed in various materials or polymers.

Conventionally, when used as a light control material for sunglass lenses, etc., in order to apply a film-forming component containing a photochromic compound by dissolving it onto the lens,
There were problems such as insufficient color density.

It is also considered to be applied to textile products, and is particularly desired as chameleon fiber.

Two main methods have been proposed for application to chameleon fibers and the like. One method is to directly impregnate the photochromic compound into fibers, and the other is to apply it onto the fibers by, for example, printing.

Considering economic efficiency, etc., the latter method is more effective.

Conventional methods for printing on fibers and the like generally include adding and dispersing a pigment of a desired color in a binder (mainly a water-soluble polymer or a water-dispersible polymer), and curing the pigment after printing. However, when a conventional photochromic compound is applied to this method, there is a problem that the photochromic compound is not sufficiently molecularly compatible with the binder and sufficient photochromic properties are not expressed. Therefore, when applied to the conventional system,
It becomes difficult to select a binder, and even if a binder that exhibits photochromic properties is selected, there are problems such as applicability to printing and elution of the 7-otochromic compound during washing.

The present invention aims to eliminate the drawbacks of the prior art, and is directed to a photochromic material that can exhibit 7 otochromic properties at high concentrations and can be applied to various substrates, especially fibers. The purpose of the present invention is to provide a resin having properties and a method for producing the same.

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

[(1) A resin having photochromic properties, characterized in that the following component A is contained in a dispersed state in a resin component capable of forming a film.

Component A: Photochromic polymer fine particles, which are polymers having a photochromic compound as one component, and are characterized by having an average particle diameter of 0.1 μm or more and 100 μm or less.

(2) A resin having photochromic properties characterized by coating a base material with a composition in which the following component A is dispersed in a component consisting of at least a film-forming resin and a solvent, and drying or curing the composition. manufacturing method. ” The photochromic polymer fine particles that are component A in the present invention are polymers containing a photochromic compound, and the polymer has a diameter of 0°1 μm or more, 100°
It is characterized by having an average particle diameter of μm or less.

As the polymer forming the polymer fine particles, an organic polymer is preferably used. Specific examples of this organic polymer include ethylene, ethylene derivatives, butadiene,
Isoprene, chlorobrene, styrene, styrene derivative, (meth)acrylic acid alkyl ester, (meth)acrylic acid hydroxyalkyl ester, (meth)acrylic acid, (meth)acrylamide, alkyl-substituted (meth)acrylamide, N-substituted maleimide, anhydride maleic acid,
Homopolymerization or copolymerization of (meth)acrylonitrile, methyl vinyl ketone, vinyl acetate, epoxy-substituted (meth)acrylic ester, divinylbenzene, ethylene glycol di(meth)acrylate, and its tenets functional (meth)acrylic ester, etc. Examples include polyester resins, epoxy resins, polyamide resins, polyurethane resins, and cellulose derivatives.

Examples of photochromic compounds that can be contained in the polymer fine particles that are component A include spiropyran compounds, spirooxazine compounds, viologen compounds, triarylmethane compounds, dithizone mercury complex compounds, annealing compounds, fulgide compounds, imidazole compounds, and stilbene compounds. It will be done. These compounds can be added as molecularly dispersed or copolymerized components in the polymer. Among these, incorporating it as a copolymerization component is a preferred method because it is excellent in terms of durability, solvent resistance, and physical properties. Photochromic compounds that can be contained as copolymerization components include 1-(meth)acryloxyethyl-3,3-dimethyl-6°-nitroindolinospirobenzopyran, 1.3.3-trimethyl-
8°bemeta)acryloxymethyl-6°-nitroindolinospirobenzopyran, 1-(meth)acrylamidoethyl-3,3-dimethyl-6-nitroindolinospirobenzopyran, 1-(meth)acryloxyethyl- 3
,3-dimethylindolinospironaphthoxazine, 1
-(meth)acrylamidoethyl-3,3-dimethylindolinospironaphthoxazine, 1,3.3-trimethyl-9-(meth)acryloxyindolinospironaphthoxazine, 1.3.3-trimethyl-5°- (meth)acryloxymethylindolinospironaphthoxazine, 1,3,3-trimethyl-9-vinylbenzoyloxyindolinospironaphthoxazine, vinyl viologen, vinyl substituted doarylmethane, vinylphenylfulgimide, (meth) Examples include acryloxyalkylfulgimide. Further, the content of the photochromic compound in the polymer fine particles varies depending on the desired physical properties, but is usually preferably from o.twt% to 50wt%.

The shape of the photochromic polymer fine particles is not particularly limited, but a spherical shape is preferable in consideration of particle characteristics.

The average particle diameter of the polymer fine particles must be in the range of 0.1 μm or more and 100 μm or less. Here, the average particle size is the average value of the particle size of each particle, and the particle size is the diameter in the case of a spherical shape, and the length and short axis of the particle in the case of a scale, rectangular parallelepiped, cube, etc. It is expressed by the average length of the length. If the average particle diameter is less than 0.1 μm, it is difficult to form fine particles.

On the other hand, when the average particle diameter exceeds 100 μm, the efficiency of the photochromic reaction decreases, the color density during color development becomes low, and furthermore, the particles become conspicuous and there is a possibility that the resolution, saturation, and brightness decrease. The maximum diameter of the particles contained in the particles is not particularly limited, but since the present invention uses fine particles to express their photochromic properties to a greater extent and aims to maintain high quality,
The maximum particle size is preferably 500 μm or less.

Conventionally known techniques can be applied to the production of polymer fine particles having such a particle size. As a method using physical force, the polymer containing the photochromic compound can be made into fine particles by a mechanical crushing method or a spray drying method. Methods using chemical processes include polymerizing monomers (Omi
Shinzo, Powder and Industry 11, Vol. 24, 1986) and chemical pulverization method (JP-A-50-6652, JP-A-58)
-219236 Publication, Japanese Patent Publication No. 59-51566, Japanese Patent Application Publication No. 197734-1986, Japanese Patent Publication No. 1987-1977
851, Japanese Patent Publication No. 61-28688). As a method of polymerizing monomers, photochromic compounds (non-polymerizable compounds or polymerizable compounds) are used.
Examples include a method in which the main component is mixed with other monomers, followed by emulsion polymerization, soap-free emulsion polymerization, nonaqueous dispersion polymerization, seed emulsion polymerization, or suspension polymerization. Chemical pulverization methods include a method in which a polymer in which a photochromic compound is dispersed or a polymer in which a photochromic compound is copolymerized is dissolved in a solvent at high temperature and then precipitated by cooling; A method of crystallizing polymer fine particles by adding and mixing a solvent that is compatible with the solvent of the polymer, and a method of crystallizing the polymer fine particles by dissolving the polymer in an organic solvent, and a method of crystallizing the polymer fine particles by adding and mixing a solvent that is compatible with the solvent of the polymer. This is a method in which the polymer particles are added and mixed into a solvent that is incompatible with the organic solvent, and the organic solvent is removed by heating, reduced pressure, etc. to obtain a dispersion of polymer fine particles, which is then taken out. These methods are
It is appropriately selected depending on the target particle size or the characteristics of the photochromic compound.

In addition, for the purpose of imparting durability and coloring density improvement to the polymer fine particles, antioxidants, irritants, etc. may be added to the polymer fine particles, and polyvinyl having high oxygen barrier properties may be added to the surface of the polymer fine particles. Coating with polymers such as alcohols is also a preferred method. Furthermore, it is also possible to prevent blocking and improve fluidity by adsorbing or sprinkling ultrafine powder such as silica or alumina on the surface of the fine polymer particles in a dispersed state and/or dry state. In addition, in order to improve the physical properties of these polymer particles, we also crosslinked them (
Curing) is also a preferred method.

The resin component capable of forming a film may be either an organic or an inorganic compound, but organic polymers are particularly preferred because of their ease of mixing with component A. Specific examples include water-soluble polyester, water-soluble olefin rubber, polyvinyl alcohols, polyacrylamides, cellulose derivatives, polyethylene glycols, water-soluble acrylic resins, polyurethane resins, polyacrylic acids, polyamide resins, and vinyl-based Examples include resins, styrene resins, acrylic resins, polyester resins, and epoxy resins.

Other usable materials include silicone resins. Among the above, the dispersion state is good,
Water-soluble polymers and water-dispersible polymers are particularly preferred from the viewpoint of process suitability. These may be used in combination.

Further, it is also preferable to post-crosslink (cure) the resin component for the purpose of improving the physical properties of the film.

The mixing ratio of component A and resin component can vary depending on the desired properties, but is preferably in the range of 0.1 to 99.9 wt%.

Further, components that can be mixed in addition to component A and the resin component include pigments, weathering stabilizers, various reaction initiators, surfactants, and the like.

Next, as a method for producing a resin having photochromic properties according to the present invention, a composition in which photochromic polymer fine particles as the component A are dispersed in a component consisting of the resin capable of forming a film and a solvent is coated on a substrate. It is characterized by drying or curing.

As the solvent that can be used in the method for producing a photochromic resin of the present invention, any dispersion medium may be used as long as it dissolves the resin component but does not completely dissolve component A.

In particular, when component A is a thermoplastic polymer, a poor solvent such as water or alcohol is preferably used as the dispersion medium; however, when component A is a thermosetting (crosslinked) polymer, various organic Solvents can be used. Also, A
The mixing ratio of the component, resin component, and its solvent component can vary depending on its characteristics, but the ratio of component A to resin component is (
The weight ratio) is preferably in the range of 0.01 to 99.9, and the ratio of the (A+resin) component to the solvent is preferably in the range of 0.01 to 99.9. Moreover, it is also possible to use and mix multiple types of each component. Furthermore, as for the mixed state, it is preferable that the A component is uniformly dispersed in the resin component and the solvent. Further, the dispersion medium also includes a reactive dispersion medium.

Components that can be mixed in addition to component A, resin component, and solvent in the resin of the present invention include pigments, dye weathering stabilizers, various reaction initiators, surfactants, and the like.

As the base material that can be coated with the resin of the present invention, it is possible to use burrs, but particularly preferred ones are fibers <m cloth).
, paper, plastic materials, metal materials, and inorganic materials (glass and ceramics).

Since the photochromic resin of the present invention contains a photochromic compound in the polymer particles in the resin, it has high light absorption efficiency and develops color with high concentration.

Further, the photochromic properties can be controlled in various ways by the properties of the polymer constituting the fine particles, and it is easy to apply the photochromic properties to a range of properties depending on various purposes. When applying,
It can be widely used by coating various base materials. It is possible to produce chameleon fibers, for example by printing on the fibers. In this case, it has the effect of being rich in durability such as washing resistance and dry cleaning resistance. In other words, extraction of the photochromic compound by a solvent or the like is suppressed.

In addition, coatings formed on paper, plastic materials, metal materials, glass materials, etc. are useful and can be widely used as light control materials, recording materials, fashion materials, sensors, etc.

[Examples] Examples of the present invention will be described below, but the present invention is not limited thereto.

Example 1 Polymer fine particles having an average particle size of 2.0 μm and a maximum particle size of 13 μm were obtained using polymethyl methacrylate containing 5 wt % of 1.3.3-trimethyl-6°-nitroindolinospiropyran. 5.0 g of these polymer particles and 10.5 g of water-soluble acrylic binder (product name: Ryu
dye-W Fixer450 10 g and product name: Ryudye-WFixer 150 0.5 g (
(both manufactured by Dainippon Ink Co., Ltd.)) and 20 g of emulsion liquid were mixed and thoroughly stirred to obtain a white composition. This composition is used to print on fibers, 1
Curing treatment was performed by heating at 50° C. for 5 minutes. When this print (colorless) was irradiated with ultraviolet light (or sunlight), the print turned purple and the pattern stood out.It was found that coloring and fading can be repeated many times, and it can be used as chameleon fiber.

Example 2 Using polystyrene containing 10 wt % of 1.3.3-trimethylindolinospironaphthoxazine, polymer fine particles having an average particle size of 3.0 μm and a maximum particle size of 15 μm were obtained. 5.0g of these polymer particles and 26g of binder
(Product name: Dexcel C1ear 3310 2
5 g of Dexcel Agent 2 (both manufactured by Dainippon Ink Co., Ltd.) and water were mixed and thoroughly stirred to obtain a white composition. When the printed material (colorless) in the same manner as in Example 1 was exposed to ultraviolet light (or sunlight), it developed a blue color. Color development and fading could be repeated many times.

Example 3 3.0 g of 1.3.3-trimethyl-9°-methacryloxyindolinospironaphthoxazine, 15 g of n-butyl methacrylate, and 2.0 g of ethylene glycol dimethacrylate were mixed, and surfactant and water-soluble polymerization were initiated. Emulsion polymerization was carried out using the polymer and 50 ml of water to obtain 18 g of crosslinked polymer fine particles. 5.0 g of these polymer particles and 20 g of binder (product name: DiCnalK-255)
1G (manufactured by Dainippon Ink Co., Ltd.) was mixed and sufficiently stirred to obtain a white composition.

When printed in the same manner as in Example 1, it turned blue when exposed to ultraviolet light (or sunlight). Color development and fading could be repeated many times.

Comparative Example 1 1.3.3-trimethylindolinospirooxazine 2
．． 0g and 10g of the binder used in Example 2 (product name:
, 5 g of Dexcel C1ear 33109 and 0.5 g of Dexcel Agent 2 (manufactured by Dainippon Ink Co., Ltd.) and a small amount of water were mixed and sufficiently stirred to obtain a white composition. When this was printed in the same manner as in Example 2 and exposed to ultraviolet light, no color developed. This is considered to be because the photochromic compound was not molecularly dissolved in the binder.

[Effects of the Invention] The photochromic composition of the present invention had the following effects.

1. Develops color with high concentration.

2. Excellent solvent resistance and durability.

3. It can be applied to substrates that were previously difficult to coat.

4. It can be used for various purposes as chameleon fiber or paint.

Claims (18)

[Claims] (1) In the resin component capable of forming a film, at least the following A
A resin having photochromic properties characterized by containing components in a dispersed state. Component A: Photochromic polymer fine particles, which are polymers having a photochromic compound as one component, and are characterized by having an average particle diameter of 0.1 μm or more and 100 μm or less. (2) A resin having photochromic properties according to claim (1), wherein component A is uniformly dispersed in the resin component. (3) The resin having photochromic properties according to claim (1), wherein the resin component is a water-soluble polymer. (4) A resin having photochromic properties according to claim (1), wherein the resin component is crosslinked. (5) The resin having photochromic properties according to claim (1), wherein the resin component is a water-dispersible polymer. (6) A resin having photochromic properties according to claim (1), wherein the resin component is post-curable. (7) A patent claim characterized in that the photochromic compound is at least one selected from a spiropyran compound, a spirooxazine compound, a viologen compound, a triarylmethane compound, an annealing compound, a fulgide compound, and a dithizone mercury complex compound. Range number (1)
A resin having photochromic properties as described in Section 1. (8) A resin having photochromic properties according to claim (1), wherein component A contains 0.1 to 50 wt% of a photochromic compound. (9) A component is 0.01 to 99.9 relative to the resin component
A resin having photochromic properties according to claim (1), wherein the resin is mixed in a proportion of % by weight. (10) A resin having photochromic properties characterized by coating a base material with a composition in which the following component A is dispersed in a component consisting of at least a film-forming resin and a solvent, and drying or curing the composition. manufacturing method. Component A: Photochromic polymer fine particles, which are polymers having a photochromic compound as one component, and are characterized by having an average particle diameter of 0.1 μm or more and 100 μm or less. (11) Claim (10) characterized in that the A component is uniformly dispersed in the resin component and the solvent.
A method for producing a resin having photochromic properties as described in 1. (12) The method for producing a resin having photochromic properties according to claim (10), wherein the resin component is a water-soluble polymer. (13) The method for producing a resin having photochromic properties according to claim (10), wherein the resin component is a water-dispersible polymer. (14) The method for producing a resin having photochromic properties according to claim (10), wherein the resin component is post-curable. (15) A patent claim characterized in that the photochromic compound is at least one selected from spiropyran compounds, spirooxazine compounds, viologen compounds, triarylmethane compounds, annealed compounds, fulgide compounds, and dithizone mercury complex compounds. Range No. 1
0) A method for producing a resin having photochromic properties as described in item 0). (16) The method for producing a resin having photochromic properties according to claim (10), wherein component A contains 0.1 to 50 wt% of a photochromic compound. (17) The method for producing a resin having photochromic properties according to claim (10), wherein the solvent is a dispersion medium containing 20 wt% or more of water. (18) Component A is 0.01 to 99% relative to the resin component.
A method for producing a resin having photochromic properties according to claim 10, wherein the resin is mixed at a ratio of 9% by weight.