JPH04104055A - Paint film for time discoloration - Google Patents

Abstract

PURPOSE:To facilitate the identification of shapes, thicknesses, densities application irregularity and the like by fixing the discolored coloring matter having a lactone ring or a lactam ring and a solid acidic material, forming a colored paint film, and laminating a paint film comprising a polar organic solvent and a binder on the colored paint film. CONSTITUTION:At least one solid or acidic material is selected out of the groups comprising powder wherein oxide or hydroxide in group III - IV elements of the periodic table is present on the surface of a particle, solid phenols, solid organic acids and solid organic sulfonic acids. The main components of a colored film are the solid acid material described above, discolored coloring matter having a lactone ring or lactan ring and a binder resin. A polar organic solvent has at least one atomic group which is selected from groups comprising hydroxide groups, aldehyde groups, amide groups, ether bonded groups, ketone groups and ester groups. A paint film whose main components are the polar organic solvent and a binder resin is overlapped and formed on the colored paint film. Thus the shapes thicknesses, densities, application irregularity and the like of the films can be readily identified by visual inspection.

Description

[Detailed description of the invention] [Industrial application field]

The present invention deals with the aging of iiJ hostile substances such as aromatics, antifungal agents, disinfectants, insect repellents, and malodor masking agents; Products that need to be evaluated by determining the degree of discoloration, such as the degree of decrease in potency over time and the degree of change due to the balance of aging and atmospheric temperature such as fermentation state and drying state, for example, products containing the above substances. It is widely used for molded products (including sheets and films), printed matter (including paper products, metal products, and plastic products), pellets, powders, and various products that change color over time. It doubles the value.

[Conventional technology]

Conventionally, time-indicating compositions such as volatile substances are disclosed in, for example, JP-A-62-163965 and JP-A-63-60.
According to Publication No. 901, a combination of an electron-donating color-forming organic compound having a lactone ring, a color developer, and a desensitizer is disclosed. The above color-forming organic compound develops color when the lactone ring opens, and becomes colorless when the lactone ring closes. Some of the desensitizers mentioned above are
It has a ring-closing effect. In the above combination, the volatile desensitized side evaporates and changes from colorless to colored, thereby informing the status over time. Also, related to this are JP-A-62-281802, JP-A-62-235562, and JP-A-62-179640.
There is a number.

[Problem to be solved by the invention] However, since the aging indicator composition, which changes color over time from colorless to color, is colorless at the time of application, its shape, thickness, density, coating unevenness, etc. cannot be easily identified by visual inspection, and its reliability over time is poor. It was also difficult to register the colors required to create multiple colors that change color. [Means and actions to solve the problem]

In order to improve these drawbacks, the present invention aims to convert powders, solid phenols, and solids in which oxides or hydroxides of Group 3 to 4 elements of the periodic table are present on the particle surface into organic acids. and a solid acidic substance selected from the group consisting of organic sulfonic acids, a color-changing dye having a lactone ring or a lactam ring, and a binder resin. A coating film mainly composed of a polar organic solvent and a binder resin having at least one atomic group selected from the group consisting of a hydroxyl group, an aldehyde group, an amide group, an ether bonding group, a ketone group, and an ester group is formed by overlapping each other. It is configured as shown. Powders in which oxides or hydroxides of Group 3 to 4 elements of the periodic table are present on the particle surface as used in the present invention include those in which the powder itself is made of the above-mentioned oxides or hydroxides. ni, no 41! There are powders and plastic powders with the above oxides or hydroxides attached to the surface, or inorganic powders and plastic powders containing the above oxides or hydroxides as a main component. The oxides or hydroxides of Group 3 to 4 elements of the periodic table, which may be used in combination with these powders, include boron, aluminum, scandium, indium, silicon, titanium, zirconium, and tin. Oxides or hydroxides used alone or as a mixture of two or more are preferred, and examples of oxides include alumina, scandium oxide, indium oxide, glue,
Titania, zirconia, tin oxide, etc. are the king ones,
Examples of hydroxides include aluminum hydroxide, alumina gel, alumina hydrate, scandium hydroxide, indium hydroxide, hydroxide, silica gel, titanium hydroxide, and stannyl compounds, natanyl compounds, and hydroxide. Examples include zirconium, zirconyl compounds, and tin hydroxide. In addition, the moisture content of the powder (smaller ones are advantageously used in the present invention. In addition, solid phenols include phenylphenol,
Oquinoacetophenone, nochlohequinolphenol, biphenol, bisphenol 8, bisphenol F, t
-butylphenol, di-butylphenol, di-t
-Butylfuresol, dobnorphenol, 2,2-methylenebis(4-methyl6-1-butylphenol)
, 4.4-dihydroxydiphenylsulfone, biphenol, bicatechol, naphthol, hydroquinone, hydroquinone monomethyl ether, chlorophenol, catechol, pyrogallol, aminephenol, fromphenol, thymol, methylcatechol, ethylcatechol, isopropylcatechol, (-butylcatechol,
Resolunone, p-hydroxybenzo 861 ester, etc. are used. Solid organic acids include benzoic acid, p-hydroxybenzoic acid, p-hydroxybenzoic acid ester, salicylic acid, succinic acid, geltaric acid, adipic acid, zehatic acid, maleic acid, fumaric acid, malic acid, malonic acid, phthalic acid, Isophthalic acid, terephthalic acid, cinnamic acid, chlorbenzoic acid, toluic acid, abietic acid, hydrogenated abietic acid,
Glycolic acid, phenylacetic acid, phenoxyacetic acid, gallic acid, trimetic acid, romellitic acid, naphthalenedicarboxylic acid, anthracenecarboxylic acid, biphenyldicarboxylic acid, diphenolic acid, and the like are used. Solid 119 sulfonic acids include p-toluenesulfonic acid, naphthalenesulfonic acid, benzenesulfonic acid, -
Monohenzendisulfonic acid and the like are used. The above solid acidic substances may be used alone or as a mixture of two or more. Examples of color-changing dyes having a lactone ring or lactam ring include fluoran dyes, triphenylmethanephthalide dyes, and lactam dyes. Examples of fluoran dyes include 2-N N-dihendylamino-〇-diethylaminofluoran, 2-(2-chloroanilino)
-6-ethylaminofluorane, 1,3-dimethyl-
6-ethylaminofluorane, 6-diethylaminofluorane, 2-7nilino-3-methyl-
6-N-Ethyl-N-tetrahydrofurfurylaminofluorane, 2-(2-chloroanilino)-6-sibutylaminofluorane, 3-cyclohexylmethylamino-6-methyl-7-anilite fluorane, 3- Ethyl
Isobutylamino-6-methyl-7anilinofluorane, 3-dimethylamine-5,6-henzofluorane, 3
-diethylamine-7-methylaminofluorane, 3-
Diethylamine-7-phenylaminofluorane, 3-
Diethylamino-7-(N-methyl-N-phenylaminofluorane, 3-diethylamine-6-methyl-7-
Phenylaminofluorane, 3-diethylamino-7-dihendylaminofluorane, 2-(N-phenyl-N-
methylamino)-6-(N-ρ-tolylN-ethylamino)fluoran, 3-(4-diethylamino-2=ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)- 4-Azaphthalide, 3-(4-diethylaminophenyl-3-ethoquinophenyl)-3-(
1 ethyl-2-methylindol-3-yl) phthalide, 3゜3-bis(1-n-butyl-2-methylindol-3-yl) phthalide, 3.3-bis(1-n-butyl-2 -methylindol-3-yl) phthalide, triphenylmethane phthalide pigments include crystal violet lactone, malachite green lactone, etc., and lactam pigments include 3.
6-bis(diethylamino)fluoran-T-anilinolactam, 3,6-bis(diethylamino)fluoran-γ-(4′-nitro)-anilinolactam, 2-C
3,6bisdiethylamino-9-(o-chloroanilino)xanthyl]hensitukuannodolactam, o
There are tamin lactams, etc. Binder resins are not particularly limited, but include, for example:
Hydrophilic resins include polyvinyl alcohol resins, cellulose resins, starches, acrylic acid resins, modified vinyl acetate resins, polyethylene glycol resins, polyvinylpyrrolidone resins, and polyvinylimidazole resins, while hydrophobic resins include ( Meta) acrylic resin, polyester resin, alkyd resin, polyvinyl chloride resin, polyvinyl acetate resin, polystyrene resin, chlorinated rubber resin, polyolefin resin, polybutashene resin, rubber resin, polyamide resin , epochino resin, melamine resin, urea resin, phenol resin, urethane resin, polyterpene 1d Mu, coumaron indene resin, rosin resin, amber resin,
There are shellac resins, balsam resins, cellulose derivative resins, etc. Among hydrophobic resins, especially (meth)acrylic resins, polyester resins, alkyd resins, polyvinyl acetate resins, polystyrene resins, polyolefin resins, polybutadieno resins, rubber resins, polyamide resins, and urethane resins. , rosin-based resins, cellulose derivative-based resins, etc. are suitable for the present invention because they are less susceptible to the effects of moisture in the air. Typical polar organic sludges having at least one atomic group selected from the group consisting of hydroxyl group, aldehyde group, amide group, ether bonding group, ketone group, and ester group are shown below. Solvents with hydroxyl groups include propatool, butanol, pentanol, hexanol, heptatool, octatool, nonanol, decanol, undecanol, dodecanol, benzyl alcohol, phenylethyl alcohol, cyclohexanol, cyclopentanol, terpineol, ethylene glycol, propylene. glycol, trimethylene glycol, butylene glycol,
In addition to pentamethylene glycol, hequinlene glycol, octylene glycol, glycerin, phenol, cresol, xylenol, ether alcohol, ester alcohol, keto alcohol, methyl cellosolve,
Ethyl cellosolve, propyl cellosolve, butyl cellosolve, hexyl cellosolve, phenyl cellosolve, hensyl cellosolve, diethylene glycol, methyl carpitol, ethyl carpitol, butyl carpitol, triethylene glycol, triethylene glycol monomethyl ether, dipropylene glycol, diethylene glycol dimethyl ether, Examples of solvents with aldehyde groups include propylene glycol monomethyl ether, diacetone alcohol, glycerin-γ-monochlorohydrin, and L2.6-hexanetriol.
Examples include aldol, heptylaldehyde, octylaldehyde, undecylaldehyde, citral, hydroxyntro7ral, benzaldehyde, anisaldehyde, and phenylpropylaldehyde. Examples of the solvent having an amide group (here, imide group is also included) include formamide, acetamide, N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide,
Examples include NN-dimethylacetamide, NN, N'N'-tetramethylurea, 2-pyrrolidone, N-methylpyrrolidone, and ε-caprolactam. Further, examples of the solvent having an ether bonding group include dipropyl ether, dibutyl ether, cyamyl ether, diphenyl ether, anisole, phenetol, butylphenyl ether, amyl phenyl ether, methquintoluene, hensyl ethyl ether, diphenyl ether, diphenyl ether, guaiacol, Dimethoxyhenzene, dioxolane, dioxane, dimethoquinoethane,
Diethoxy, noethane, dibropoquinethane, dibutquinethane, orthoformic acid ester, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, dipropylene glycol ether, glycerin ether, acetal, ketal, etc., and examples of solvents having a ketone group include acetone, Methyl ethyl ketone, methyl propyl ketone, diethyl ketone, hexanone, methyl isobutyl ketone, methyl pentyl ketone, dipropyl ketone, diisobutyl ketone, diisoamyl ketone, acetylacetone, mesityl oxide, holon, isophorone, noclopentanone, nclohexanone, acetophenone, ethyl acetoacetate etc. Examples of solvents having ester groups include ethyl formate, propyl formate, butyl formate, pentyl formate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, and acetic acid. Fatty acid esters such as cyclohexyl, phenyl acetate, hensyl acetate, propionate ester, acetate ester, isovalerate ester, or corresponding benzoate ester, toluate ester, ethyl cinnamate, abietate ester, oxalate ester , malonic acid ester, succinic acid ester, geltaric acid ester, adipic acid ester, pimelic acid ester, cehacylic acid ester, azelaic acid ester, fumaric acid ester, malic acid ester, maleic acid ester, itaconic acid ester, citric acid ester, citric acid ester Acid ether esters, glycolic acid esters, lactic acid esters, tartaric acid esters, phthalic acid noesters, glycol (mono, di) esters, glycerin (mono, n, tri) esters, pentaerythritol (
Mono, di, tri, tetra) esters, trimethylolpropane esters, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diphenyl carbonate, butyrolactone, caprolactone, methyl salicylate, propyl salicylate, butyl salicylate, benzyl salicylate, cellosolve These include acetates, carpitol acetates, phosphoric acid esters, etc. Various methods are used as the coating means for placing the coating film, and examples include coating methods such as roll coating, reverse coating, and gravure coating; printing methods such as screen printing, gravure printing, letterpress printing, and offset printing; Spinner coating methods, spray coating methods, day coating methods, brush coating methods, etc. are often used. In particular, printing methods are useful for patterning. Examples of methods for forming coating films include powders in which oxides or hydroxides of Group 3 to 4 elements of the periodic table are present on the particle surface, solid phenols, solid organic acids, and solid organic sulfonic acids. Discoloration by adding an appropriate diluting solvent as necessary to a mixture whose main components are at least one acidic substance selected from the group consisting of a color-changing dye having a lactone ring or a lactam ring, and a binder resin. A color ink is prepared, applied to a substrate using any of the above-mentioned coating means, and then dried to form a coating film with sufficient color development. On the other hand, if necessary, a mixture mainly composed of a polar organic solvent having at least one atomic group selected from the group consisting of a hydroxyl group, an aldehyde group, an amide group, an ether bonding group, a ketone group, and an ester group and a binder resin can be used. An ink is prepared by adding an appropriate diluting solvent and applied over the colored coating film. Through this application, the polar organic solvent of the latter ink penetrates into the underlying layer, erasing the previously developed color. Thereafter, the faded color develops as the polar organic solvent evaporates when the product having the coating film is used. In addition, by taking into account differences in boiling point and vapor pressure of polar organic solvents, type of binder resin (molecular weight, type and number of substituents, etc.), film thickness, type of solid acidic substance, storage conditions of the product, etc. It is possible to adjust the time period from the final coating film formation to the time when color development occurs over time. Of course, the time it takes for the color to develop over time changes depending on the environment in which it is used, especially the temperature. In addition, if necessary, dispersants, antifoaming agents, extender pigments, dyes and pigments, ultraviolet absorbers, antioxidants,
Surfactants, zinc carbonate, thiourea compounds, etc. may be added, and in particular, to improve light resistance, ultraviolet absorbers,
It is recommended to mix in antioxidants, zinc carbonate, and thiourea compounds. If the solubility of the binder resin in the solvent of the coating film containing a color-changing pigment is different from the solubility of the binder resin in the solvent of the coating film containing a organic solvent, it is possible to When the films are stacked, the binder resin of the paint film containing the color-changing pigment is less likely to be redissolved.
A more stable coating film can be obtained. In addition, coating films containing color-changing pigments are
When there is a powder in which oxides or hydroxides of group elements exist on the particle surface, the particle surface often retains color-changing pigments, so it is preferable to use a powder containing a polar organic solvent and a binder resin as the main components. When two ink layers are placed one on top of the other, undesirable effects such as a decrease in color density are less likely to occur.

[Effect]

In the present invention, first, a color-changing dye having a lactone ring or a lactam ring and a solid acidic substance are fixed with a binder resin, and the lactone ring or lactam ring is opened with the solid acidic substance to form a colored coating film. . Next, by layering a coating film made of a polar organic solvent and a binder on top of the coating, a reaction occurs in which the polar organic solvent penetrates into the underlying coating film and closes the lactone or lactam ring of the color-changing dye, resulting in colorlessness. It happens. The polar organic solvent gradually evaporates from the coating film depending on the time and ambient temperature, the lactone ring or lactam ring opens, color develops, and the entire reaction is completed.

【Example】

After thoroughly mixing a methacrylate resin (30 g) with an average molecular weight of 95.000 and an acid value of 0, 6-diethylaminobenzo(a)-fluoran (8 g) as a discoloring dye and methyl ethyl ketone (140 g), surface area 200
Fine silica powder (20 g) of ±25 vol/g and bisphenol A (2 g) are added and thoroughly mixed to prepare a uniform red ink. Meanwhile, a blue ink was prepared using 3-(4-dienalaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide as a color-changing dye. Using the gravure printing method, red ink is used to first print a hala flower pattern on a high-quality paper card with a tack sticker on the back, and the hala flower pattern is dried and colored. The pattern was printed, dried, and colored. This operation makes it easy to visually align the flowers, stems, and leaves, creating a beautiful floral pattern. Next, a methallyrylate resin (60 g) with an average molecular weight of 25,000 and an acid value of 10.5 was dissolved in a high-boiling aromatic hydrocarbon solvent (240 g), and this was divided into two parts. Ink A was prepared by adding glycol (15 g), and ink B was prepared by adding 2-pyrrolidone (10 g) to the other half, and by screen printing,
Overprint ink A on the red flower pattern above, -
After drying and erasing the color, apply ink B to the blue stems above.
I overprinted it on top of the leaf-shaped zelkova, dried it again, and erased the color. With this method, the printing condition can be easily determined by the way the color fades, so it is easy to obtain products with stable quality over time. When the label with the tack sticker obtained in this way was attached to deodorizing Bonks and placed on the floor indoors, the stems and leaves turned blue after 22 days, when the deodorizing effect of the main island reached half the time. After 48 days, when the deodorant's effectiveness wears off, the red hala flower pattern will develop and completely bloom, indicating that the deodorant's effectiveness has disappeared, making it easy to recognize that it is time to replace it. It's convenient. 60g of polyester resin with an average molecular weight Is of 000-20,000, a glass transition temperature of 67°C, and a specific surface area of 30
0±3Onf/g of silica fine powder <10g) and a mixed solvent of toluene and methyl ethyl ketone in a ratio of 8:2 (24
0g) and stirred for t4', then 2-anilino-3-
Methyl 6-N-ethyl N~tetrahydrofurf + J fluoraminofluorane (10 g) was added and thoroughly mixed to create a uniform monochromatic ink, which was printed using the gravure printing method.
The characters are printed on a polyester film sort and dried to develop color so that the shape and density of the characters can be easily inspected visually.The average molecular weight is 1360.000 and the acid value is 1.
Mix well methacrylate resin (60g), butylcarbitol (20g) and toluene (240g), coat the top layer of the letters with a bar and dry.The letters disappear and the quality of the product is determined by the decolored state. After inspecting the guarantee, a cover film of polyethylene film was layered to create a sheet with a coating that changes color over time to prevent volatilization of butylcarpitol.This sheet was attached to the barrel in which the pickles were pickled, and the cover coat was removed. When I left it for a while, it took about 2 hours for the pickles to pickle properly.
After 18 hours in an atmosphere of 5°C, the letter "J" clearly appears.In this case, the degree of pickling of pickles is a balance between temperature and time, so it is very useful. Yuethyl cellulose resin (100 g), a high boiling point hydrocarbon solvent, and a mixed solvent of 2:1 ethyl cellosolve were thoroughly kneaded, and then ρ-hydroquine benzoic acid (lOg) and crystalline violet lactone (40 g) were kneaded. and further knead it to create blue ink, which is printed on the flower part of a calendar with a pattern of pale pink tulips using screen printing, and dried to develop a blue color to create the register and shape of the flowers. A pattern of blue flower tulips was created by visually inspecting the concentration of blue color and blue color.Meanwhile, hydroxypropyl cellulose resin (60 g) and isopropyl alcohol (4
40g) and diethylene glycol (log) and butylcarpitol (10g) and 2-pyrrolidone (10g)
The mixture was thoroughly mixed and roll coated onto the tulip pattern, dried to erase the blue color to form a pale pink flower tulip pattern, and covered with polyethylene film. When the cover coat was removed when using the calendar, the tulip flowers changed from pale pink to pale violet, pale blue, and dark blue over time, enhancing the design effect of the calendar. One vessel contains methacrylate resin (200g) with a soil molecular weight of 70.000 and an acid value of 3.5, 150g of silica fine powder with a specific surface area of 130 soil and 25rrf/g, zinc carbonate (3g), and a high boiling point hydrocarbon solvent (500g). and 3,3-bis(1-n-butyl-2methyl-indol-3-yl)phthalide (10
0g) to make a red ink, screen print a polka dot pattern on a plus thousand molded product containing room air freshener, dry it to develop a red color, and visually inspect the shape and red density. Acrylate resin (300g) with a molecular weight of 65,000 and an acid value of 3 and dipropylene glycol (100g). 2.4-Dividroxybenzophenone (13 g) and toluene were thoroughly mixed and applied over the polka dot pattern to erase the red color. As the scent of the air freshener fades, the polka dots turn red, and when they turn bright red, the scent has weakened, clearly indicating that it is time to replace the room air freshener-containing plastic molded product.

【Effect of the invention】

Contains color-changing pigment! ! ! The paint film is colored from after the film is applied until before the paint film containing the polar organic solvent is applied, and its shape, thickness, density, coating unevenness, etc. can be easily identified by visual inspection. It has good reliability over time, and it is also easy to make the necessary registration when changing discolored colors to multiple colors, making it easy and effective to detect changes over time in fragrances, drugs, foods, and other substances. The display can be applied to industrial products, household goods, agricultural supplies, etc., and the effects of the present invention can be said to be tremendous in the industrial field. Patent applicant Nissha Printing Co., Ltd.

Claims (1)

[Scope of Claims] 1. Consists of powder, solid phenols, solid organic acids, and solid organic sulfonic acids in which oxides or hydroxides of Group 3 to 4 elements of the periodic table are present on the particle surface. A hydroxyl group, an aldehyde group, an amide group, or an ether bond is formed on a coating film mainly consisting of at least one solid acidic substance selected from the group consisting of a color-changing dye having a lactone ring or a lactam ring, and a binder resin. Discoloration over time, characterized in that a coating film mainly composed of a binder resin and a polar organic solvent having at least one atomic group selected from the group consisting of a radical, a ketone group, and an ester group is formed. coating film. 2. The element according to claim 1, wherein the element of Groups 3 to 4 of the periodic table is at least one element selected from the group consisting of boron, aluminum, scandium, indium, silicon, titanium, zirconium, and tin. Coating film for discoloration over time. 3. The binder resin is (meth)acrylic resin, polyester resin, alkyd resin, polyvinyl acetate resin, polystyrene resin, polyolefin resin, polybutadiene resin, rubber resin, polyamide resin,
The coating film for discoloration over time according to claim 1, which is at least one hydrophobic resin selected from the group consisting of urethane resin, rosin resin, and cellulose derivative resin.