JPH0255462B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to thermochromic labeling compositions. Such compositions, in the form of ink or paint, are used for marking in steam sterilization of surgical tools and packaged foods, or in steam heating treatment in production processes such as rubber vulcanization, and are used to mark the markings by heating under certain conditions. The color change indicates that the process has been completed. Conventional compositions have a short color change time and change color as soon as a predetermined temperature is reached, making them unsatisfactory for identification purposes when heating at a constant temperature for a certain period of time is required. The present inventor uses at least one of a methine dye or a cyanine dye as a color-changing pigment component, and uses at least one of a methine dye or a cyanine dye selected from anhydrous aromatic dibasic acid, halogenated aromatic dibasic acid, and halogenated aromatic anhydride dibasic acid. By using at least one of the
Even when a predetermined discoloration temperature is reached by heating, discoloration can be suppressed until a predetermined time, and when a predetermined time has elapsed, discoloration is promoted and the discoloration occurs quickly, and the difference in color before and after discoloration can be clearly discerned. Further, a thermochromic labeling composition whose color change time can be freely controlled within a certain range by adjusting the amount of the specific organic acid added. Furthermore, we have completed a thermochromic marking composition that exhibits particularly good effects when applied directly to a rubber material during rubber vulcanization without peeling off during or after vulcanization even if it adheres. . As the color-changing pigment component used in the present invention, various known methine dyes having a methine group can be used as the methine dye, and various known ones can be used as the cyanine dye. Specifically, the following can be exemplified. That is, the color index basics (C.
I.Basic Red) 12, 13, 14, 15, 27, 35, 36,
37, 45, 48, 49, 52, 53, 66 and 68, color index basic query (CIBasic
Yellow) 11, 12, 13, 14, 21, 22, 23, 24, 28,
29, 33, 35, 40, 43, 44, 45, 48, 49, 51, 52 and 53, Color Index Basic Violet (CIBasic Violet) 7, 15, 16, 20,
21, 39 and 40, Color Index Basic Blue (CIBasic Blue) 62 and 63, Color Index Basic Orange (CIBasic
Examples include Orange) 27, 42, 44, and 46. Among these methine-based or cyanine-based dyes, color index dyes and
Basic Cred 12, 13, 14, 15 and 37, Color Index Basic Yellow 11 and
13, Color index basic violet
I can list 15 mags. The color-changing pigment component consisting of at least one of the above is present in an amount of 0.01 to 10 parts by weight per 100 parts by weight of the composition, preferably 0.5 to 5 parts by weight (hereinafter, parts by weight are simply referred to as parts).
is used. If the pigment component is too small, the color will be unclear and the color will change in a short period of time. Moreover, if it is excessive, the difference between the colors before and after the color change becomes small, making it difficult to distinguish. It should be noted that these dyes have the advantage of improving water resistance when used as a kind of additive by bringing the dye into contact with a phenol resin, rosin, or a rosin derivative in advance, as in Patent No. 878644 (Japanese Patent Publication No. 52-2324). The resin components used in the present invention include rosin, hydrogenated rosin, or derivatives thereof such as glycerin esters and pentaerythritol esters, petroleum resins, phenol-modified alkyd resins, styrenated alkyd resins, alkyd resins such as epoxy esters, and rosin-modified phenolic resins. phenolic resins such as rosin-modified xylene resins, xylene resins such as alkylphenol xylene resins, coumaron resins, acrylic resins such as polymers and copolymers of acrylic esters and methacrylic esters, ketone resins, and styrene-maleic acid. Examples include resins such as cellulose resins such as methoxycellulose, nitrocellulose, and acetylcellulose, polyvinyl butyral, vinyl chloride-vinyl acetate copolymers, ethylene-vinyl acetate copolymers, polyamides, and polyurethanes. Preferred examples include rosin derivatives, petroleum resins, phenolic resins, ketone resins, styrene-maleic acid resins, polyvinyl butyral, and vinyl chloride-vinyl acetate copolymers. At least one resin component can be used in an amount of 1 to 40 parts, more preferably 5 to 20 parts, based on 100 parts of the composition. If the resin component is too small, the adhesiveness of the composition will deteriorate. Moreover, if it is in excess, the viscosity of the composition becomes too high, which is inappropriate. In the present invention, at least one selected from aromatic anhydride dibasic acids, halogenated aromatic dibasic acids, and halogenated aromatic anhydride dibasic acids is used as the component for suppressing discoloration. Specific examples include phthalic anhydride, monochlorophthalic acid, monobrominated phthalic acid, tetrachlorophthalic acid, tetrabrominated phthalic acid, tetrachlorophthalic anhydride, and tetrabrominated phthalic anhydride. These specific organic acids range from 0.1 to 25 parts per 100 parts of the composition.
parts, preferably 0.5 to 25 parts can be used. By adjusting the amount of organic acid added, it is possible to freely control the discoloration time of the composition within a certain range, and when adding synthetic rubber for rubber vulcanization, the synergistic effect between the organic acid and synthetic rubber can be achieved. This greatly improves adhesion to rubber materials. If the amount of organic acid is too small, the discoloration time will be shortened and it will not be effective. Moreover, if it is in excess, the color will not change clearly. The organic solvent used in the present invention is one that can dissolve the above three components, including alcohols such as ethanol, butanol and cyclohexanol, ethylene glycol alkyl ethers such as ethylene glycol monoethyl ether and diethylene glycol monomethyl ether, and ethylene glycol propylene glycol. esters, ethylene glycol alkyl esters such as ethylene glycol monoacetate, ketones such as methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone, benzene,
Aromatic hydrocarbons such as toluene, xylene, and cumene, aliphatic hydrocarbons such as N-hexane, alicyclic hydrocarbons such as cyclohexane, esters such as ethyl acetate and propyl propionate, and other ordinary inks or At least one type of paint used in paints can be used. The organic solvent is determined in consideration of the viscosity of the composition, stability during use and storage, drying property during use, etc., but since the solubility varies depending on the resin, it is appropriately selected and used depending on the resin. Usually 30 out of 100 parts of the composition
~80 parts are used, preferably 40-70 parts. In addition, in the present invention, a pigment with excellent dispersion stability is added in order to make the difference in color before and after discoloration of the composition of the present invention more noticeable, or an oil-soluble dye is added in order to adjust the color before and after discoloration. It's okay. Among these, white pigments such as titanium oxide and zinc white have the effect of sharpening color development and are preferably used. These pigments or oil-soluble dyes
Pigment: 0.5-30 parts, dye: 0.001-5 parts per 100 parts
part can be used. Further, by adding a gelling agent such as benzylidene sorbitol or dibenzylidene sorbitol, a composition can be made into a solid rod-shaped marker having thixotropy. Furthermore, optical brighteners, plasticizers, thickeners, or antifoaming agents may be added as necessary. Furthermore, especially when the composition of the present invention is used for rubber vulcanization, it is desirable to add synthetic rubber. By adding this, it is possible to impart adhesion and flexibility so that even if the rubber material before and after vulcanization is altered or deformed by heating, the coating film of the composition will not peel off from the material. Synthetic rubbers include isobutylene rubber, styrene-butadiene rubber, nitrolyl rubber,
Examples include butyl rubber, urethane rubber, ethylene propylene rubber, chloroprene rubber, chlorosulfonated polyethylene rubber, chloropolyethylene rubber, acrylic rubber, epichlorohydrin rubber, and modified products thereof. At least one type of synthetic rubber can be used in an amount of 0.5 to 20 parts per 100 parts of the composition. Compositions of the invention can be prepared in a variety of ways. For example, a methine dye or a cyanine dye is added to a portion of an organic solvent, and the mixture is stirred and dissolved at room temperature to 80°C. When using dyes or pigments for color adjustment, they may be dissolved or dispersed at the same time.
On the other hand, a resin component or, if necessary, a synthetic rubber is added to the remainder of the organic solvent and dissolved by stirring at room temperature to 80°C. Next, after mixing both solutions, add acid,
Stir and mix at room temperature to 80°C. Alternatively, a methine dye or cyanine dye and a part of the resin component are dissolved in a part of an organic solvent,
This may be mixed with the remainder of the organic solvent, the remainder of the resin component, and, if necessary, a synthetic rubber dissolved therein. Furthermore, the dye, resin component, and synthetic rubber may be added to and dissolved in a mixed solvent that has excellent dissolving power for the methine dye or cyanine dye. The present invention will be explained in detail with reference to Examples below. Example 1 50 parts of vinyl chloride-vinyl acetate copolymer 700 parts of isophorone were immersed and stirred and dissolved to obtain a resin liquid, while 400 parts of toluene was mixed with a finely dispersed red pigment (manufactured by Sanyo Shiki Co., Ltd., ethylene propylene dimonomer processed pigment Pigmo). Texture thread
103E) 100 parts are mixed by immersion, the pigment is dispersed to form a dispersion liquid, and this is mixed with the resin liquid to obtain a mixed solution. Next, phenolic resin (manufactured by Hitachi Chemical, Hytanol 1133)
Add a solution prepared by mixing and dissolving 70 parts of ethylene glycol monobutyl ether, 100 parts of CI Basic Yellow 11, and 30 parts of CI Basic Yellow 11 to the above mixed solution.
The mixture was stirred and mixed, and 120 parts of monobrominated phthalic acid was added and dissolved or dispersed with stirring to obtain an orange-colored composition suitable for rubber vulcanization. The resulting composition was applied to a rubber material that required vulcanization at 150°C for 25 minutes to form a marker, and when heated with steam under the above conditions, the color changed from orange to red after 25 minutes, indicating that vulcanization had not completed. I was able to clearly identify what was completed.
Moreover, the coating film showed good adhesion and flexibility without peeling or cracking. Example 2 Polyamide (manufactured by Daiichi General, Versamide 335)
50 parts butadiene rubber (manufactured by Nippon Zeon, Nitzpol)
BR1441) 60 parts ethylene glycol monoethyl ether 150 parts xylene 650 parts Blue oil-soluble dye (Chuo Gosei Kagaku, Oil Blue #8) 1 part CI Basic Cred 15 10 parts monochlorinated phthalic anhydride 5 parts White pigment (titanium oxide) 270 1 part isophorone 100 parts A red-colored composition suitable for rubber vulcanization was obtained in accordance with Example 1 using the above ingredients. The coating film of the obtained composition changed color from red to white after 5 minutes of steam heating at 145°C. Example 3 Phenol resin (manufactured by Arakawa Chemical, Tamanol 100S)
90 parts Styrene-butadiene rubber (Nippon Zeon, Nitzpol 1006) 90 parts cyclohexanone 500 parts Xylene 400 parts Yellow oil-soluble dye (Celest Yellow GRN, Verdice Dyestuff Chemical) 1 part CI Basic Violet 15 50 parts Finely dispersed white pigment (Manufactured by Dainichiseika Chemical Industry, PAGC-
6806) 250 parts Tetrachlorophthalic anhydride 50 parts Ethylene glycol monobutyl ether 100 parts Using the above, a purple colored composition suitable for rubber vulcanization was obtained according to Example 1. The coating film of the obtained composition changed color from purple to yellow after 20 minutes of steam heating at 140°C. Example 4 Methyl ethyl ketone 300 parts Isophorone 500 parts Nitrile rubber (Nippon Zeon, Nippor 1432J)
90 parts Finely dispersed white pigment (manufactured by Toyo Ink, ethylene-vinyl acetate copolymer processed pigment VRC-A101) 350 parts CI Basic Cred 37 70 parts Phthalic anhydride 70 parts Ethylene glycol monoethyl ether 150 parts Example 1 using the above A composition suitable for rubber vulcanization and exhibiting a red color was obtained. The resulting composition is
The color changed from red to white after 15 minutes of steam heating at 150°C. Example 5 Rosin (manufactured by Tokushima Seisei, Rosin WW) 80 parts Ethanol 100 parts Tortane 800 parts Finely dispersed yellow pigment (Manufactured by Sanyo Color, Pygmotex Yellow 302E) 90 parts CI Basic Cred 12 50 parts Tetrabrominated phthalic anhydride 10 Using the above method and according to Example 1, an orange-colored composition suitable for rubber vulcanization was obtained. The coating film of the obtained composition changed color from orange to yellow after 10 minutes of steam heating at 130°C. Example 6 Phenol resin (manufactured by Arakawa Chemical, Tamanol 526)
100 parts styrene-butadiene rubber (Nippon Zeon, Nitzpol 2001) 70 parts toluene 300 parts xylene 800 parts triethyl phosphate 100 parts blue oil-soluble dye (Neozapon FLE, Verdateshu Dye Chemical) 1 part finely dispersed white pigment (Dainichiseika) Industrially manufactured, methacrylic resin-processed pigment PAPC1806) 200 parts CI Basic Cred 14 15 parts Tetrabrominated phthalic anhydride 100 parts Ethylene glycol monoethyl ether 50 parts A composition suitable for rubber vulcanization that exhibits a red color according to Example 1 using the above I got something. The resulting composition is
After 20 minutes of steam heating at 150°C, the color changed from red to white. Example 7 In the composition of Example 6, the amount of tetrabrominated phthalic acid added was varied as shown in Table 1 to obtain various compositions. In the resulting composition, the relationship between the amount of tetrabrominated phthalic anhydride added and the discoloration time at the heating temperature is also shown. From this table, the greater the amount of a specific organic acid added, the more
It can be seen that it takes a long time to change color after reaching a predetermined temperature, and that the change in color can be suppressed. That is, the color change time can be freely controlled within a certain range by adjusting the amount of the organic acid added. 【table】

Claims (1)

[Claims] 1 In 100 parts by weight of the composition, a) 0.01 to 10 parts by weight of at least one of methine dyes or cyanine dyes, b rosin or rosin derivatives, petroleum resins, phenolic resins, xylene resins, alkyd resins,
Coumaron resin, acrylic resin, epoxy resin,
At least one selected from the group consisting of ketone resin, styrene-maleic acid resin, cellulose resin, polyvinyl butyral resin, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, polyamide, and polyurethane.
~40 parts by weight, c 0.1 to 25 parts by weight of at least one selected from the group consisting of anhydrous aromatic dibasic acids, halogenated aromatic dibasic acids, and halogenated aromatic anhydride dibasic acids, d The above dyes, A thermochromic labeling composition containing 30 to 80 parts by weight of at least one organic solvent that dissolves or disperses a resin and an acid. 2. The thermochromic marking composition according to claim 1, wherein 0.5 to 20 parts by weight of at least one type of synthetic rubber is added to 100 parts by weight of the composition.