JPH0348231B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to thermochromic labeling compositions. Such compositions are applied or printed directly onto objects in the form of ink, paint, or the like. Alternatively, they are processed as printed matter and used as labels during heat treatment in production processes such as rubber vulcanization, or during sterilization of packaged foods and surgical tools. It is possible to recognize that the process has been completed. Although the composition of the present invention 1 does not change color under moist heat,
This is a thermochromic marking composition that irreversibly changes color when heated under certain conditions during dry ripening, and is particularly suitable for dry heat vulcanization treatment in the rubber vulcanization process. Compounds that irreversibly change color due to loss of crystallization water used as the thermochromic pigment component in the present invention include nickel hexamethylenetetramine complex chloride decahydrate salt, cobalt hexamethylenetetramine decahydrate salt, and cobalt hexamethylenetetramine complex chloride decahydrate salt, as a hydrated salt of a heavy metal-hexamethylenetetramine complex compound. Complex chloride decahydrate, cobalt hexamethylenetetramine complex sulfate heptahydrate, cobalt hexamethylenetetramine complex thiocyanate 4
hydrate salt, decahydrate salt of cobalt hexamethylenetetramine complex nitrate, octahydrate salt of cobalt hexamethylenetetramine complex iodide, nonahydrate salt of cobalt hexamethylenetetramine complex bromide salt, 4 salt of cobalt borate as a hydrous form of heavy metal borate. Hydrates of heavy metal phosphates include cobalt phosphate octahydrate, cobalt potassium phosphate monohydrate,
Examples of the hydrous heavy metal sulfate include cobalt ammonium phosphate monohydrate, cobalt sulfate heptahydrate, and copper sulfate pentahydrate. Among these, those based on cobalt phosphate, which exhibit a complete irreversible reaction, are preferably used. A compound that changes color due to loss of crystallization water, which is composed of at least one of the above, is
1 to 50 parts by weight are used per 100 parts by weight (hereinafter, parts by weight are simply referred to as parts), preferably 5 to 40 parts. If these compounds are used in excess, the adhesive properties of the composition will deteriorate, and if they are used in excess, the composition will change color in a short period of time. Moreover, the discoloration becomes unclear and difficult to identify. The rubber used in the present invention is used as a binder that imparts adhesive properties to the composition. In particular, when used in the vulcanization process, it is possible to impart good 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 part will not peel off from the material. Rubber includes natural rubber or synthetic rubber such as isobutylene rubber, styrene-butadiene rubber, nitrile rubber, butyl rubber, urethane rubber, ethylene propylene rubber, chloroprene rubber, chlorosulfonated polyethylene rubber, chloropolyethylene rubber, acrylic rubber, epichlorohydrin rubber, etc. An example is a modified product. At least one of these rubbers is added per 100 parts of the composition.
It can be used from 0.5 to 50 parts, preferably from 1 to 80 parts. When rubber is added in excess, the viscosity of the composition increases, making coating or printing difficult. In addition, when the amount is too small, the adhesiveness deteriorates. The organic solvent used in the present invention is one that dissolves the above-mentioned rubber and the resin described below and disperses the thermochromic compound. Ethylene glycol alkyl ethers, ethylene glycol alkyl esters such as ethylene glycol monopropylate and ethylene glycol monoacetate, ketones such as methyl ethyl ketone, methyl isobutyl ketone, isophorone, and 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; Any material used in paints can be used. The organic solvent is determined by taking into consideration the viscosity of the composition, stability during use and storage, dryness during use, etc., but the solubility varies depending on the rubber or resin, so the organic solvent may be determined depending on the rubber or resin. Select and use as appropriate. Usually, 80 parts to 80 parts out of 100 parts of the composition are
Preferably 40 to 70 parts are used. In addition, by adding various resins to the composition of the present invention 1 as a viscosity imparting and adhesion aid, and as a dispersion aid for a thermochromic compound and/or a pigment described below, the thermochromic label of the present invention 2 can be added. A composition for use can be obtained. The resins used in the composition of the present invention 2 include rosin, hydrogenated rosin, or derivatives thereof such as glycerin ester and bentaerythritol ester, natural resins such as Danmar Sierrak, etc.
Petroleum resins, phenol-modified alkyd resins, styrenated alkyd resins, alkyd resins such as epoxy esters, phenolic resins such as rosin-modified phenolic resins, xylene resins such as rosin-modified xylene resins, alkylphenol xylene resins, coumaron resins, acrylic acid esters, and methane resins. Acrylic resins such as acrylic acid ester polymers and copolymers, ketone resins and styrene maleate resins, cellulose resins such as methoxycellulose, nitrocellulose, acetylcellulose, polyvinyl butyral, vinyl chloride-vinyl acetate copolymers, ethylene -Resins such as vinyl acetate copolymers and polyamides can be exemplified. 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 from these groups can be used in an amount of 1 to 40 parts, preferably 5 to 20 parts, per 100 parts of the composition of the present invention. 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 addition, a pigment with excellent dispersion stability may be added to the composition of the present invention to make the difference in color before and after discoloration more noticeable, or an oil-soluble dye may be added to adjust the color before and after discoloration. Among these, white pigments such as titanium oxide and zinc white have the effect of sharpening color development and can be preferably used. These pigments or oil-soluble dyes are
0.5 to 30 parts of pigment and 0001 to 20 parts of dye 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. The rubber, organic solvent, resin, and pigments used to adjust the color before and after discoloration may be commercially available individually, but organic solvent solutions of rubber, rubber, organic solvents, and pigments may be used. It is convenient to use commercially available products that are already processed, such as kneaded into a paste, or kneaded with resin, organic solvent, and pigment, or pigment coated with resin. Compositions of the invention can be prepared by a variety of methods. For example, when using rubber and resin as an organic solvent, the resin is added and dissolved. Next, if a thermochromic compound and pigment are used, they are added at the same time and stirred, and then kneaded with a roll or homomixer to sufficiently disperse the thermochromic compound and pigment to obtain the composition of the present invention. It can be prepared by conventional methods in the same way as inks and paints. If the obtained compositions of Inventions 1 and 2 are applied or printed on an object requiring heat treatment, the color changes when heated under certain conditions under dry heat, and the heat treatment is seemingly completed. This can be confirmed. Moreover, it is advantageous in terms of work since it is possible to identify at a glance whether the product has been heat-treated or not. In particular, the composition of the present invention 2 has good adhesion to rubber, so it can be used for dry heat vulcanization of rubber with good effects. In addition, especially silicone rubber, butyl rubber, or acrylic rubber, which undergoes moist heat heat treatment in the first step,
When performing dry heat heat treatment in the second step, a methine-based dye is added to the thermochromic compound, rubber, and organic solvent, which are essential components of the present invention, as a resin and a color-changing pigment component that changes color when heated with moist heat. Alternatively, when at least one cyan dye is added, the color changes continuously from the wet heat heat treatment process to the dry heat heat treatment process, and the thermochromic label of the present invention 3 is capable of confirming the completion of the treatment in each process. The composition can be obtained by adding the resin used in the composition of the present invention 2 to the composition of the present invention 3, in other words, the resin used in the composition of the present invention 2 can be obtained.
The thermochromic labeling composition of the present invention 4 can be obtained by adding at least one methine dye or cyanine dye to the composition. The same applies to the case where dry heat heat treatment is performed in the first step and moist heat heat treatment is performed in the second step. Furthermore, by adding at least one organic acid to the above 4 or 5 components, discoloration is suppressed until a predetermined time during moist heat treatment, and when the time is reached, the discoloration is rapid and the difference in color before and after discoloration is more noticeable. It is possible to obtain a thermochromic labeling composition that can be identified by the color of the target and can lengthen the time until discoloration depending on the amount of organic acid added, and can also adjust the time within a certain range. . As the color-changing pigment component used in the present invention that changes color due to moist heat heating, well-known methine dyes and polymethine dyes having a methine group can be used as methine dyes, and various well-known cyanine dyes can be used as cyanine dyes. I can do it. Specifically, the following can be exemplified. That is, color index basics (CIBasic
Red) 12, 13, 14, 15, 27, 35, 36, 37, 45,
48, 49, 52, 53, 66 and 68, color index basic yellow (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 (Orange)
Examples include 27, 42, 44, and 46.
Among these methine-based or cyanine-based dyes, particularly desirable are Color Index Basic Cret 12, 13, 14, 15 and 37, Color Index Basic Yellow 11 and 13, and Color Index Basic Violet. I can list 15 mags. Methine dyes and cyanine dyes are present invention 1
Or, 0.01 to 10 parts, preferably 0.1 to 5 parts, are used per 100 parts of the composition. If the amount of methine dye and cyanine dye is too small, the color development will be unclear and the color will change in a short time. Moreover, if it is excessive, the difference between the colors before and after the color change becomes small, making it difficult to distinguish. These dyes are patented in Patent No. 878644 (Special Publication No. 52
-2324), the dye and phenolic resin or rosin or rosin derivative are brought into contact with each other in advance.
When used as an additive to seeds, it improves water resistance. Organic acids (including acid anhydrides) used in the present invention
Aliphatic monocarboxylic acids including halogen derivatives, oxy derivatives and amino derivatives include valeric acid, lauric acid, stearic acid, oleic acid, linoleic acid and methacrylic acid, and aliphatic dicarboxylic acids include oxalic acid, succinic acid and adipine. Acid, malonic acid, maleic acid, malic acid, tartaric acid, mandelic acid, maleic anhydride, and aspartic acid are aromatic monocarboxylic acids, and benzoic acid, toluic acid, α-naphthoic acid, salicylic acid, sulfosalicylic acid, etc. are aromatic dicarboxylic acids. Acids include phthalic acid, phthalic anhydride, and their halogen derivatives, aromatic sulfonic acids include benzenesulfonic acid, naphthalenesulfonic acid, G-acid, R-acid, sulfanilic acid, naphthionic acid, etc., and alicyclic sulfonic acids include Examples of the phenols include cyclohexylsulfamic acid and the like, and examples include phenol, naphthol, catechol, and hydroquinone. Among them, aliphatic dicarboxylic acids, aromatic monocarboxylic acids, aromatic dicarboxylic acids, aromatic sulfonic acids, and phenols are preferably used, and particularly phthalic anhydride and its halogen derivatives bring about good effects. Organic acid in 100 parts of composition
0.1 to 35 parts, preferably 0.5 to 25 parts can be used. By adjusting the amount of organic acid added, the discoloration time of the composition can be freely controlled within a certain range, and the synergistic effect between organic acid and rubber greatly improves the adhesion to rubber materials. It is particularly effective when used in the rubber vulcanization process. If the amount of organic acid is too small, the discoloration time will be shortened and there will be no effect. Moreover, if it is in excess, the color will not change clearly. The present invention will be explained in detail with reference to Examples below. Example 1 Add 200 parts of cobalt phosphate octahydrate to a solution containing 400 parts of a 20% solution of rubber modified rubber (Clya EX-1226, manufactured by Sakai Chemical Co., Ltd., and 150 parts of isophorone), and mix it thoroughly with a homomixer. The composition of the present invention 1 having a pink color was obtained by kneading. The resulting composition was applied to white drawing paper and heated at 160°C.
When heated with dry heat, the color changed from pink to blue, and the difference in color before and after the change was clearly distinguishable, and it showed complete irreversibility. Furthermore, the coating showed good adhesion without cracking or peeling. Example 2 Styrene-butadiene rubber (Nippon Zeon Co., Ltd. Nitzpol 1006 30 parts cyclohexanone 170 parts mixed and dissolved in a solution of 130 parts xylene butyl cellosolve 40 parts phenolic resin (Arakawa Chemical Co. Tamanol 100S)
Add a solution of 30 parts of white pigment (made by Dainichiseika Chemical Co., Ltd., rosin-based resin processed pigment).
PAGC-6806) 20 parts nickel hexamethylenetetramine complex chloride
175 parts of decahydrate salt was added and mixed, and the mixture was sufficiently kneaded in a kneader to obtain a green composition of the second invention. The obtained composition is applied as a marker to a rubber material that requires vulcanization treatment, and the first step is a wet heat treatment at 150℃ for 30 minutes, and the second step is a continuous dry heat treatment at 180℃ for 120 minutes. When subjected to wet heat treatment, the green color was maintained without any color change, and during dry heat treatment, the color clearly changed from green to purple, confirming that the dry heat treatment was completed. Ta. Furthermore, the applied sign exhibited good adhesion without cracking or peeling from the rubber material. Example 3 prepared according to Example 1 or 2 below
Items 1 to 13 are shown in Attached Table 1. The compositions obtained in these Examples exhibited good effects similar to those in Example 1 or 2. Example 14 5 parts of CI Basic Cred 37 was added to the solution of the composition obtained in Example 3 and stirred to obtain an orange-colored composition of the present invention 3. If CI Basic Cred 37 is difficult to dissolve, alcohol or esters may be added. The obtained composition was applied to a rubber material that required vulcanization treatment to make a mark, and when wet heat and dry heat heat treatments were performed continuously, the color rapidly changed from orange to yellow in 30 minutes by moist heat heating at 145°C. It was confirmed that the moist heat heat treatment was completed by a change in color, and then by dry heat heating at 200°C for 180 minutes, the color changed from yellow to green, confirming that the dry heat heat treatment was completed. Prepared according to Example 14 by adding a methine dye or cyanine dye to Examples 1, 2, and 4 to 11, respectively, so that it can be used for wet heat and dry heat, or dry heat and wet heat continuous heat treatment. Examples 15 to 24 of the compositions of Invention 3 or 4 are shown in Attached Table 2. Example 27 15 parts of sulfosalicylic acid was added to the solution of the composition obtained in Example 14 and stirred to obtain an orange-colored composition of the present invention. The obtained composition was applied to a rubber material that required vulcanization treatment and used as a marker. When wet heat heating and dry heat heat treatment were performed continuously, the color quickly changed to orange after 45 minutes due to wet heat heating at 150°C. Turns yellow and then heats to 180℃
After dry heat heating for 240 minutes, the color changed from yellow to green. It was confirmed that each treatment was completed. Comparing the effects of the composition of this example and the composition of example 14, which does not contain sulfosalicylic acid, in the moist heat treatment, the time until discoloration at the same temperature of 150°C was 30 minutes for example 14. However, in this example, the heating treatment time was 1.5 times longer, at 45 minutes.
It became possible to use it for things that required twice as much.
In addition, discoloration occurred more quickly, completion could be more easily confirmed, and better adhesion to the material was observed. Example 28 was prepared by adding an organic acid to each of the solutions of the compositions obtained in Examples 15 to 26 according to Example 27.
to 39 are shown in Attached Table 3. The compositions of the present invention obtained in these Examples had a longer time to discoloration and faster discoloration than compositions to which no organic acid was added, and also had better adhesion to rubber materials. Good performance and remarkable effects were observed.

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Claims (1)

[Scope of Claims] 1. Irreversible loss of crystal water selected from hydrated salts of heavy metal-hexamethylenetetramine complex compounds, hydrated forms of heavy metal borates, hydrated forms of heavy metal phosphates, and hydrated forms of heavy metal sulfates. A thermochromic labeling composition comprising 1 to 50 parts by weight of at least one thermochromic metal complex compound that changes color, 0.5 to 50 parts by weight of at least one rubber, and 30 to 80 parts by weight of at least one organic solvent. 2 A thermochromic metal that irreversibly changes color due to loss of crystal water, selected from a hydrated salt of a heavy metal-hexamethylenetetramine complex compound, a hydrated form of a heavy metal borate, a hydrated form of a heavy metal phosphate, and a hydrated form of a heavy metal sulfate. For 100 parts by weight of a composition consisting of 1 to 50 parts by weight of at least one kind of complex compound, 0.5 to 50 parts by weight of at least one kind of rubber, and 30 to 80 parts by weight of at least one kind of organic solvent, rosin or rosin derivative/petroleum From the group consisting of resins, phenolic resins, xylene resins, alkyd resins, coumaron resins, acrylic resins, epoxy resins, ketone resins, styrene maleic acid resins, cellulose resins, polyvinyl butyral, vinyl chloride-vinyl acetate copolymers, polyamides and polyurethanes A thermochromic labeling composition containing 1 to 40 parts by weight of at least one selected one. 3. A thermochromic metal that irreversibly changes color due to loss of crystal water, selected from a hydrated salt of a heavy metal-hexamethylenetetramine complex compound, a hydrated heavy metal borate, a hydrated heavy metal phosphate, and a hydrated heavy metal sulfate. Methine-based dyes and cyanine-based A thermochromic marking composition comprising 0.01 to 10 parts by weight of at least one dye. 4. A thermochromic metal that irreversibly changes color due to loss of crystal water, selected from a hydrated salt of a heavy metal-hexamethylenetetramine complex compound, a hydrated heavy metal borate, a hydrated heavy metal phosphate, and a hydrated heavy metal sulfate. For 100 parts by weight of a composition consisting of 1 to 50 parts by weight of at least one kind of complex compound, 0.5 to 50 parts by weight of at least one kind of rubber, and 30 to 80 parts by weight of at least one kind of organic solvent, rosin or rosin derivative/petroleum From the group consisting of resins, phenolic resins, xylene resins, alkyd resins, coumaron resins, acrylic resins, epoxy resins, ketone resins, styrene maleic acid resins, cellulose resins, polyvinyl butyral, vinyl chloride-vinyl acetate copolymers, polyamides and polyurethanes Thermochromic labeling comprising adding 0.01 to 10 parts by weight of at least one of a methine dye and a cyanine dye to 100 parts by weight of a composition containing 1 to 40 parts by weight of at least one selected one. Composition.