JPH11140339A - Irreversibly temperature-indicating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an irreversibly temperature-indicating material which develops a blue or red color at about 60 deg.C, is desirable for administering the temperature history of e.g. a canned drink and is excellent in storability and safety. SOLUTION: There is provided an irreversibly temperature-indicating material prepared by forming a layer containing a colorless or light-color basic dye, a color developer and a heat-fusible substance, wherein the basic dye used is 3-(1-n-ocryl-2-methylindol-3-yl)-3-(4-diethylamino-2-ethoxyphenyl)-3-a zaphthalide or 3,3'-bis(1-n-octyl-2-methylindol-3-yl)phthalide, and the heat-fusible substance used comprises 1,2-diphenoxyethane and/or dibenzyl oxalate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an irreversible temperature indicating material used for managing the temperature history of, for example, canned beverages.

[0002]

2. Description of the Related Art In the canned beverage industry, for example, it is used for an application label for a canned coffee campaign, to monitor whether a consumer has warmed or drank, or in the case of canned beverages that are altered by heat. There is a strong demand for a temperature-controlling temperature-indicating material that develops color at around 60 ° C. as an indicator for knowing whether the storage conditions are appropriate, whether the consumer has accidentally warmed it, and the like.

[0003] As the irreversible type temperature indicating material for managing the temperature history, a dye type type and an inorganic type type are generally known. The dye-based type utilizes the reaction between a colorless or pale-colored basic dye and a color former, and makes both color components come into contact with heat to form a color.It is relatively inexpensive and can produce various color tones. , And is also highly safe,
It is very advantageous as compared with the inorganic type. However, the conventionally proposed dye-based irreversible temperature indicating material has a color development temperature of about 80 ° C. to 140 ° C., and thus cannot be used for canned beverages.

[0004]

The problem to be solved by the present invention is that
To provide a dye-based irreversible thermosensitive material that develops blue or red at around ° C. and is suitable, for example, for managing the temperature history of canned beverages and the like, and has excellent storage stability and excellent safety. It is in.

[0005]

SUMMARY OF THE INVENTION The present invention provides a method for manufacturing a semiconductor device comprising the steps of:
In an irreversible thermostatic material provided with a layer containing a colorless or light-colored basic dye and a colorant and a heat-fusible substance,
3- (1-n-octyl-2-methylindol-3-yl) -3- (4-diethylamino-) as a basic dye
2-ethoxyphenyl) -4-azaphthalide or 3,
3'-bis (1-n-octyl-2-methylindol-3-yl) phthalide was used and contained 1,2-diphenoxyethane and / or dibenzyl oxalate as a heat-fusible substance. The present invention relates to an irreversible thermometer material characterized in that:

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to 3
-(1-n-octyl-2-methylindol-3-yl) -3- (4-diethylamino-2-ethoxyphenyl) -4-azaphthalide or 3,3'-bis (1-n
-Octyl-2-methylindol-3-yl) phthalide is selectively combined with 1,2-diphenoxyethane and / or dibenzyl oxalate as a heat-fusible substance. By adopting such a combination, a quality suitable for temperature control of a canned beverage or the like, that is, a sharp coloration reaction occurs at a temperature of about 60 ° C., and a dark color is clearly formed, and An irreversible temperature indicating material having excellent preservability such as heat resistance, moisture resistance and light resistance in the uncolored part and the colored part, and also excellent in safety has been obtained.

In the present invention, the amount of 1,2-diphenoxyethane and / or dibenzyl oxalate is not necessarily limited, but is preferably 50 to 500 parts by weight based on 100 parts by weight of the basic dye. , Preferably in the range of 100 to 300 parts by weight.

Although the present invention uses a specific basic dye and a heat-fusible substance as described above, other known basic dyes and heat-fusible substances can be used as long as the desired effect is not impaired. It is also possible to use an active substance together.

Various known colorants can be used as the colorant used in the temperature indicator of the present invention. For example, 4,4'-isopropylidenediphenol, 4,4'-cyclohexylidenediphenol, 2,2- Bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,4-bis [α-methyl-α- (4′-hydroxyphenyl) ethyl Benzene, 1,3-bis [α-methyl-α-
(4′-hydroxyphenyl) ethyl] benzene, bis (4-hydroxy-3-methylphenyl) sulfide,
4,4′-dihydroxydiphenyl sulfide, 4,
4'-dihydroxydiphenylsulfone, 2,4'-dihydroxydiphenylsulfone, 4-hydroxy-4 '
-Methyldiphenylsulfone, 4-hydroxy-4'-
Isopropoxydiphenyl sulfone, bis (3-allyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4′-benzyloxyphenyl sulfone,
3,4-dihydroxyphenyl-4′-methylphenylsulfone, 4-hydroxybenzoic acid benzyl ester,
N, N'-di-m-chlorophenylthiourea, 2,4-
Dihydroxy-N- (2′-methoxyphenyl) benzamide, Np-tolylsulfonyl-N′-phenylurea, 4,4′-bis (p-toluenesulfonylaminocarbonylamino) diphenylmethane, 4- [2- (p
-Methoxyphenoxy) ethoxy] zinc salt of salicylic acid, 4- [3- (p-tolylsulfonyl) propoxy]
Zinc salt of salicylic acid, 5- [p- (2-p-methoxyphenoxyethoxy) cumyl] zinc salt of salicylic acid, 4-
And the like. Zinc salt of octyloxyacetylaminosalicylic acid and the like. In addition, two or more color formers can be used in combination as needed.

[0010] Among these colorants, the melting point is 100 to
The use of a compound at 200 ° C. is preferred in terms of color developability and the storage stability of the uncolored portion, and the use of a compound having a melting point of 120 to 160 ° C. is particularly preferred.

The amount of these colorants to be used should be appropriately adjusted according to the type of the colorant to be used, but generally 50 to 500 parts by weight per 100 parts by weight of the basic dye, Preferably it is adjusted in the range of about 100 to 300 parts by weight.

In order to further improve the storability, various known storability improvers may be contained in the color forming layer of the temperature indicating material. Specific examples of the storage stability improver include the following compounds. 2,2′-methylenebis (4-methyl-6-tert-butylphenol),
2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-thiobis (3-methyl-6
-Tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol),
1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,3 5-tris (3,5-di-tert
-Butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1- [α-methyl-α- (4-hydroxyphenyl) ethyl] -4- [α ′, α′-bis (4-hydroxy Phenyl) ethyl] benzene, tetrakis (1,2,2,6,6-pentamethyl-4-piperidinyl) -1,2,3,4-butanetetracarboxylate, 1,3,5-tris (4-tert- Butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid, 4-benzyloxyphenyl-4 ′-(2-methyl-2,3-epoxypropyloxy) phenylsulfone, 2- (2′-hydroxy-5) '-Methylphenyl)
Benzotriazole, bis [2-hydroxy-3-
(2′H-benzotriazol-2′-yl) -5-octylphenyl] methane, sodium salt or magnesium salt of 2,2′-methylenebis (4,6-di-tert-butylphenyl) phosphoric acid, and the like.

The coating solution for a color-forming layer containing these is generally made of a basic dye, a color former, a heat-fusible substance using water as a dispersion medium and a stirring / pulverizing machine such as a ball mill, attritor, sand mill, colloid mill or the like. Are dispersed together or separately, and are prepared by mixing and stirring.

In such a coating solution, starches, cellulose derivatives such as hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, gelatin, casein, gum arabic, polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, sulfone group-modified polyvinyl alcohol are usually used as binders. Various modified polyvinyl alcohols such as acetoacetyl group-modified polyvinyl alcohol, silicon-modified polyvinyl alcohol, styrene / maleic anhydride copolymer salt, styrene / acrylic acid copolymer salt, styrene / butadiene copolymer emulsion, etc. 2 to 40% by weight, preferably 5
About 25% by weight is blended. Of course, two or more of these binders can be used in combination.

Further, various auxiliaries can be added to the coating liquid. Examples of such auxiliaries include sodium dioctyl sulfosuccinate, sodium dodecylbenzene sulfonate, sodium lauryl alcohol sulfate, sodium salt of fatty acid and metal salt of fatty acid. And the like, other antifoaming agents, fluorescent dyes, antioxidants and the like. Also, a dispersion or emulsion of stearic acid, polyethylene, carnauba wax, paraffin wax, zinc stearate, calcium stearate, ester wax, or the like is contained in the coating liquid so that the temperature indicating material does not stick due to contact with a recording device or a recording head. It can also be added.

In addition, inorganic pigments such as kaolin, clay, talc, calcium carbonate, calcined clay, titanium oxide, diatomaceous earth, fine anhydrous silica, activated clay, and organic pigments such as urea formalin resin filler can be added.

As the support, paper (acid paper, neutral paper),
A plastic film, a synthetic paper, a plastic film or a synthetic paper bonded to a coated paper or a high quality paper via an adhesive, a plastic laminated on a paper, or the like is used. As such a plastic film, for example, polyethylene, polyester,
Examples include films of polypropylene, polyvinyl chloride, polystyrene, nylon and the like. As the synthetic paper, for example, a synthetic paper manufactured by a film method or a fiber method is used. In the film method, an internal paper is formed by melt-kneading a synthetic resin, a filler and additives, and extruding to form a film. There are a coating method, a surface coating method in which a pigment coating layer is provided, a surface treatment method, and the like. Examples of the fiber synthetic paper include synthetic pulp paper and spunbond paper.

The method for forming the color-forming layer is not particularly limited, and it can be formed according to a conventionally known and commonly used technique. For example, bar coating, air knife coating, rod blade coating, pure blade coating, short dwell coating And a method of applying and drying a coating liquid on the entire surface of the support by curtain coating or the like, or a method of forming a color-forming layer in a partial or desired pattern, character, or the like by a printing method. When using a plastic film as the support, corona discharge on the surface,
A treatment such as electron beam irradiation can be performed to increase the coating efficiency. The coating amount of the coating liquid is not particularly limited, but is usually ^{2 to} 10 g / m ² , preferably 3 to 10 g / m ² .
It is adjusted in the range of 7 g / m ² .

Further, by providing a protective layer composed of an adhesive, a lubricant, a pigment and the like on the color-forming layer, a temperature-indicating material with further improved storage stability and printability can be obtained. Specific examples of the adhesive used for the protective layer include, for example, polyvinyl alcohols having various degrees of saponification, acetoacetyl group-modified polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, polyvinyl alcohols such as silicon-modified polyvinyl alcohol, acrylic resins, and polyurethane-based adhesives. Resins. These adhesives are used in an amount of 10 to 95% by weight, preferably 30 to 95% by weight, based on the total solid content of the protective layer.
It is desirable to adjust in the range of 90% by weight. The amount of the protective layer applied was 0.5 to 10 g / dry weight.
m ² , preferably in the range of about 1 to 7 g / m ² .

Further, a layer containing a water-soluble resin, a water-dispersible resin, an electron beam-curable resin, or an ultraviolet-curable resin may be provided on the protective layer for the purpose of imparting high gloss. A protective layer may be provided on the back surface of the support, or an undercoat layer may be provided on the support. Further, various known techniques in the field of heat-sensitive recording material production can be applied as appropriate by applying a pressure-sensitive adhesive treatment to the back surface of the support of the temperature indicating material and processing it into a pressure-sensitive adhesive label.

The pressure-sensitive adhesive layer at the time of processing the pressure-sensitive adhesive label is formed on the release layer of the release sheet and then transferred to the back surface of the support or directly applied and dried on the back surface of the support. The coating amount of the adhesive layer is 3 to 50 g / dry weight.
m ² , preferably about 5 to 30 g / m ² .

The pressure-sensitive adhesive layer includes various known rubber-based pressure-sensitive adhesives, butyl (meth) acrylate as a monomer component,
An acrylic resin-based pressure-sensitive adhesive containing 2-ethylhexyl (meth) acrylate is contained as a main component. Specific examples of the rubber-based adhesive include, for example, natural rubber, isopropylene rubber, styrene / butadiene block copolymer, styrene / isoprene / styrene block copolymer, butyl rubber, styrene / ethylene / butylene / styrene block copolymer, Examples thereof include polyisobutylene, polyvinyl isobutyl ether, chloroprene rubber, and nitrile rubber.

The pressure-sensitive adhesive layer further includes a natural resin such as rosin, modified rosin, a derivative of rosin and modified rosin, a polyterpene resin, a modified terpene, an aliphatic hydrocarbon resin, a cyclopentadiene resin, and an aromatic petroleum resin. Resin,
Phenol resin, alkyl-phenol-acetylene resin, chroman / indene resin, vinyl toluene / α
A tackifier such as a methylstyrene copolymer, an antioxidant, a stabilizer, a filler and the like can be added as necessary. These auxiliaries can be used in combination of two or more as necessary.

As described above, the irreversible thermosensitive material of the present invention produces a color reaction with a high sensitivity at a temperature of about 60 ° C. and develops a dark color, and has excellent preservability in uncolored portions and colored portions. It is also excellent in safety and can be used not only for temperature control of canned drinks and the like but also for a wide range of uses.

[0025]

The present invention will be described in more detail with reference to the following Examples, but it should be understood that the present invention is by no means restricted thereto. Unless otherwise specified, parts and% in examples are parts by weight and% by weight, respectively.

Example 1 Preparation of Solution A 3- (1-n-octyl-2-methylindole-3-
A composition consisting of 10 parts of yl) -3- (4-diethylamino-2-ethoxyphenyl) -4-azaphthalide, 5 parts of a 5% aqueous solution of methylcellulose, and 15 parts of water has an average particle size of 1.0 μm by a sand mill. Until ground.

Preparation of Solution B A composition comprising 15 parts of dibenzyl oxalate, 7 parts of a 5% aqueous solution of methylcellulose, and 28 parts of water was pulverized by a sand mill until the average particle size became 1.5 μm.

Solution C Preparation A composition comprising 20 parts of 4-hydroxy-4'-isopropoxydiphenylsulfone, 10 parts of a 5% aqueous solution of methylcellulose, and 30 parts of water is pulverized by a sand mill until the average particle size becomes 1.4 μm. did.

Preparation of temperature indicating material 30 parts of liquid A, 50 parts of liquid B, 60 parts of liquid C, 150 parts of a 10% aqueous solution of polyvinyl alcohol, and 1 part of calcium carbonate
0 parts were mixed and stirred to obtain a coating solution for a coloring layer. The obtained coating solution was coated on a synthetic paper having a thickness of 80 μm [trade name: YUPO FPG # 80,
(Oji Yuka Co., Ltd.)] to obtain a thermochromic material that develops a blue color by drying and drying to a dry weight of 4 g / m ² .

Preparation of temperature indicating label 100 parts of acrylic pressure-sensitive adhesive (trade name: Alloset 8600, solid content: 45%, manufactured by Nippon Shokubai Co., Ltd.), crosslinking agent (trade name: Coronate L-55E, manufactured by Nippon Shokubai Co., Ltd.) 25
And 125 parts of toluene were mixed and stirred, and a coating liquid obtained by coating and drying on a commercially available release paper with a reverse roll coater so that the coating amount after drying was 15 g / m ² was obtained. The back surface side of the temperature indicating material and the pressure-sensitive adhesive layer were stuck together so that a temperature indicating label colored in blue was obtained.

Example 2 A thermochromic label was obtained in the same manner as in Example 1 except that 1,2-diphenoxyethane was used instead of dibenzyl oxalate in the preparation of Solution B.

Example 3 Bis (3-allyl-4) was used instead of 4-hydroxy-4'-isopropoxydiphenylsulfone in the preparation of solution C.
Except for using (-hydroxyphenyl) sulfone, a thermochromic label was obtained in the same manner as in Example 1 to give a blue color.

Example 4 Bis (3-allyl-4) was used instead of 4-hydroxy-4'-isopropoxydiphenylsulfone in the preparation of solution C.
Except for using (-hydroxyphenyl) sulfone, a temperature indicating label colored blue was obtained in the same manner as in Example 2.

Comparative Example 1 In the preparation of solution A, 3- (1-n-octyl-2-methylindol-3-yl) -3- (4-diethylamino-
Except that 3,3-bis (4-dimethylaminophenyl) -6-dimethylaminophthalide was used in place of 2-ethoxyphenyl) -4-azaphthalide, the same temperature label as in Example 1 was used to give a blue color. I got

Comparative Example 2 A thermochromic label was developed in the same manner as in Example 1 except that 1,2-di (3-methylphenoxy) ethane was used instead of dibenzyl oxalate in Preparation of Solution B. Obtained.

Comparative Example 3 A thermochromic label was obtained in the same manner as in Example 1 except that diphenyl phthalate was used in place of dibenzyl oxalate in the preparation of solution B.

The following evaluations were performed on the seven types of temperature indicating labels that emit blue light, and the obtained results are shown in Table 1.

[Color-forming property]
After leaving for 30 minutes each in the environment of ℃, return to room temperature,
A Macbeth densitometer [RD-914,
Using a blue filter, manufactured by Macbeth Co., Ltd.].

[Preservation property] The untreated temperature indicating label and the temperature indicating label treated at 60 ° C. were allowed to stand in an environment of 40 ° C. and 90% RH for 24 hours (moisture resistance), followed by 24 hours in an environment of 50 ° C. After standing (heat resistance) and after exposure to direct sunlight for 5 hours (light resistance), the density of the coloring layer was measured with a Macbeth densitometer.

[0040]

[Table 1]

Example 5 Preparation of Solution D A composition comprising 10 parts of 3,3'-bis (1-n-octyl-2-methylindol-3-yl) phthalide, 5 parts of a 5% aqueous solution of methylcellulose, and 15 parts of water The product was pulverized with a sand mill until the average particle size became 1.0 μm.

Preparation of temperature indicating material 30 parts of solution D, 50 parts of solution B, 60 parts of solution C, 150 parts of 10% aqueous solution of polyvinyl alcohol, and 1 part of calcium carbonate
0 parts were mixed and stirred to obtain a coating solution for a coloring layer. The obtained coating solution was coated on a synthetic paper having a thickness of 80 μm [trade name: YUPO FPG # 80,
(Manufactured by Oji Yuka Co., Ltd.) so as to have a dry weight of 4 g / m ² and dried to obtain a thermochromic material which develops a red color.

Preparation of a temperature indicating label A temperature indicating label colored red was obtained in the same manner as in Example 1 except that the temperature indicating material obtained above was used in the preparation of the temperature indicating label of Example 1.

Example 6 A thermochromic label was obtained in the same manner as in Example 5 except that 1,2-diphenoxyethane was used instead of dibenzyl oxalate in the preparation of Solution B.

Example 7 In the preparation of solution C, bis (3-allyl-4) was used instead of 4-hydroxy-4'-isopropoxydiphenylsulfone.
Except for using (-hydroxyphenyl) sulfone, a temperature indicating label colored red was obtained in the same manner as in Example 5.

Example 8 In the preparation of solution C, bis (3-allyl-4) was used instead of 4-hydroxy-4′-isopropoxydiphenylsulfone.
Except that (-hydroxyphenyl) sulfone was used, a temperature indicating label colored red was obtained in the same manner as in Example 6.

Comparative Example 4 In the preparation of solution A, 3,3'-bis (1-n-octyl-
Except that 3-diethylamino-7-chlorofluorane was used in place of 2-methylindol-3-yl) phthalide, a red thermochromic label was obtained in the same manner as in Example 5.

Comparative Example 5 A thermochromic label was developed in the same manner as in Example 5 except that 1,2-di (3-methylphenoxy) ethane was used instead of dibenzyl oxalate in the preparation of Solution B. Obtained.

Comparative Example 6 A thermochromic label was obtained in the same manner as in Example 5, except that diphenyl phthalate was used instead of dibenzyl oxalate in the preparation of Solution B.

The following evaluations were performed on the seven types of temperature indicating labels that emit red light, and the obtained results are shown in Table 2.

[Coloring property]
After leaving for 30 minutes each in the environment of ℃, return to room temperature,
Using a Macbeth densitometer [RD-914,
Using a magenta filter, manufactured by Macbeth Co., Ltd.].

[Preservation property] The untreated temperature indicating label and the temperature indicating label treated at 60 ° C. were allowed to stand for 24 hours in an environment of 40 ° C. and 90% RH (moisture resistance), followed by 24 hours in an environment of 50 ° C. After standing (heat resistance) and after exposure to direct sunlight for 5 hours (light resistance), the density of the coloring layer was measured with a Macbeth densitometer.

[0053]

[Table 2]

[0054]

As is clear from Tables 1 and 2, the temperature-indicating material (temperature-indicating label) of the present invention exhibits excellent coloring at 60 ° C. and has good storage stability such as moisture resistance, heat resistance and light resistance. Was also an excellent temperature indicating material (temperature indicating label).

Claims (2)

[Claims] 1. An irreversible temperature-indicating material comprising a support and a layer containing a colorless or light-colored basic dye, a coloring agent and a heat-fusible substance, wherein 3- (1-
n-octyl-2-methylindol-3-yl) -3
-(4-diethylamino-2-ethoxyphenyl) -4
Using azaphthalide or 3,3'-bis (1-n-octyl-2-methylindol-3-yl) phthalide, and 1,2-diphenoxyethane and / or dibenzyl oxalate as the heat-fusible substance An irreversible thermoelectric material characterized by containing an ester. 2. The irreversible thermostatic material according to claim 1, wherein an adhesive layer mainly comprising an adhesive is provided on the back surface of the support.