Composition for Wet Indicator and Wet Indicator

Information

  • Patent Application
  • 20230165730
  • Publication Number
    20230165730
  • Date Filed
    January 27, 2023
    a year ago
  • Date Published
    June 01, 2023
    a year ago
Abstract
To provide a composition for wet indicator excellent in discoloration performance. What is disclosed is a composition for wet indicator comprising an oily gel and a wet-sensitive colorant composition.
Description
TECHNICAL FIELD

The present invention relates to a wet indicator which is a member that notifies the presence of moisture by discoloration.


BACKGROUND ART

Examples of an article that exhibits a function by being in contact with moisture include a moisture exchanger (HEM), a moisture detector, an autoclave (sterilization) tape, a packaging article and an absorbent article. As a device that displays that these articles are in a wet state and exhibit a function, a wet indicator is known. Wetting refers to a state in which a liquid comprising water such as a body fluid, that is, moisture is in contact. The indicator refers to a display tool and a marking tool.


Generally, the wet indicator changes its color to indicate whether the article is dry or wet with moisture. For example, the wet indicator is colored or discolored when the article is wet, thereby displaying a status of wet state of the article.


Patent Documents 1 to 3 describe a composition for wet indicator used in combination with an absorbent article such as a diaper.


Patent Document 1 describes a wet indicator composition that changes color in response to pH change. The wet indicator composition contains a water-insoluble thermoplastic polymer composition, a superabsorbent polymer, a wet indicator and a surfactant. ([Abstract], [Claim 1], [Claim 2]).


Patent Document 2 describes a hot melt damp indicator composition that may be applied using a conventional hot melt applicator device. This hot melt damp indicator composition contains components such as a water-insoluble thermoplastic polymer, an anionic surfactant and a leuco dye ([Abstract], [Claim 1], [0006]).


Patent Document 3 describes a dampness/fluid indicator composition that is colorless in its initial state and may provide various final wet color options in the presence of water. The dampness/fluid indicator composition includes a leuco dye and a color-developing agent in a hot melt adhesive matrix ([Abstract], [0001], [0008]).


PRIOR ART DOCUMENTS
Patent Documents



  • Patent Document 1: JP 2009-511673 A

  • Patent Document 2: JP 2018-515165 A

  • Patent Document 3: JP 2018-517894 A



SUMMARY OF THE INVENTION
Problems to Be Solved by the Invention

However, in a conventional composition for wet indicator, a matrix, that is, a main continuous phase is composed of a thermoplastic resin and permeability of moisture is not sufficiently excellent. Such a conventional composition for wet indicator has a weak degree of discoloration when brought into contact with moisture, and timing of discoloration can be delayed, thus there is still room for improvement in discoloration performance. In addition, the conventional wet indicator has an odor, which causes an unpleasant feeling to a user, and also has a problem that the odor is transferred to an absorbent article.


The present invention solves such problems, and an object thereof is to provide a composition for wet indicator which is excellent in discoloration performance and is suppressed in odor.


Means for Solving the Problems

The present invention provides a composition for wet indicator comprising an oily gel and a wet-sensitive colorant composition.


In one embodiment, the oily gel is a solid having an oily substance that is liquid at room temperature, and at least one gelling agent selected from saturated fatty acids having 16 or more carbon atoms and derivatives of the saturated fatty acids.


In one embodiment, the oily substance that is liquid at room temperature is at least one selected from the group consisting of paraffin oil, naphthene oil and aromatic oils.


In one embodiment, the wet-sensitive colorant composition is a composition comprising a leuco dye or a pH indicator, and an anionic surfactant or a nonionic surfactant.


In addition, the present invention also provides a wet indicator comprising any of the compositions for wet indicator.


Further, the present invention also provides an absorbent article comprising the wet indicator.


Effects of the Invention

According to the present invention, there is provided a composition for wet indicator which is excellent in discoloration performance and is suppressed in odor.







DESCRIPTION OF EMBODIMENTS
Oily Gel

The composition for wet indicator of the present invention comprises an oily gel. The oily gel refers to a solid having a structural body of three-dimensionally crosslinked gelling agent and a liquid oily substance contained in the structural body. When the composition for wet indicator of the present invention contains an oily gel, the composition for wet indicator has moderate hardness that is softer than that of a hot-melt type composition for wet indicator, and moisture so easily penetrates into the composition, that the composition is strongly and quickly discolored. Thereby, with the wet indicator of the present invention, a status of wet state of the article may be accurately displayed. In addition, since the oily gel is able to contain a colorant or a body fluid that causes odor, it is possible to reduce the odor of the absorbent article of the present invention.


The liquid oily substance refers to a lipophilic substance that is liquid at room temperature, is incompatible with water, and is compatible with a nonpolar solvent. For example, wax is an oily substance but is solid at room temperature and thus does not correspond to a liquid oily substance. Since a solid oily substance is poor in water permeability, when used in a matrix of the composition for wet indicator, the solid oily substance is likely to adversely affect discoloration properties of the wet indicator. Examples of the liquid oily substance generally include hydrocarbon oils and liquid polymers.


Hydrocarbon oils include paraffin oil, naphthene oil and aromatic oils. Weight average molecular weight of the hydrocarbon oil is preferably from 200 to 2000, from the viewpoint of improving water permeability. The hydrocarbon oil preferably contains at least one selected from paraffin oil and naphthene oil, and more preferably contains paraffin oil, from the viewpoint of improving compatibility with the wet-sensitive colorant composition.


As the hydrocarbon oil, a commercially available product may be used. Examples of the commercially available hydrocarbon oil include White Oil Broom 350 (trade name) manufactured by Kukdong Oil & Chemicals Co. Ltd., Diana Fresia PW32 (trade name), Diana Process Oil PW-90 (trade name) and Daphne Oil KP-68 (trade name) manufactured by Idemitsu Kosan Co.,Ltd., Nyflex 222B (trade name) manufactured by Nynas AB, SUNPURE N90 manufactured by JAPAN SUN OIL COMPANY,LTD., KN4010 (trade name) manufactured by PetroChina Company Limited, Enerper M1930 (trade name) manufactured by BP Chemicals Ltd., Kaydol (trade name) manufactured by Crompton Corporation and Primol 352 (trade name) manufactured by Esso Standard Oil.


The liquid polymer refers to a polymer that exhibits a liquid state at room temperature. The type of the polymer is not particularly limited, but is generally at least one polymer selected from polybutene, polybutadiene, polyisobutylene and polyisoprene. The liquid polymer preferably has a weight average molecular weight of from 2000 to 100000 and more preferably from 2000 to 80000, from the viewpoint of improving water permeability. The liquid polymer preferably contains polybutene, from the viewpoint of improving compatibility with the wet-sensitive colorant composition.


As the liquid polymer, a commercially available product may be used. Examples of the liquid polymer which is a commercially available product include Nisseki Polybutene HV-300 (trade name) and Nisseki Polybutene HV-1900 (trade name) manufactured by ENEOS Corporation, B-1000 (trade name) and BI-2000 (trade name) manufactured by Nippon Soda Co., Ltd., Tetrax (trade name) and Himol (trade name) manufactured by JX Energy Corporation, LIR-15 (trade name) and LIR-50 (trade name) manufactured by KURARAY CO., LTD. and Nipol IR2200 (trade name) manufactured by Zeon Corporation.


The liquid oily substance is contained in the composition for wet indicator in an amount of 10% by mass or more, preferably from 20 to 95% by mass, and more preferably from 30 to 85% by mass, based on the total amount of the oily gel and the wet-sensitive colorant composition. By adjusting the content of the liquid oily substance in the composition for wet indicator within the above ranges, compatibility between the liquid oily substance and the colorant is improved and protons are easily generated, and the composition for wet indicator of the present invention may exhibit clear and rapid coloration.


The liquid oily substance is contained in the oily gel by being held by the three-dimensionally crosslinked gelling agent. The gelling agent that is three-dimensionally crosslinked in the presence of the liquid oily substance may be a known substance. The gelling agent is preferably a saturated fatty acid having 16 or more carbon atoms and derivatives of the saturated fatty acid, from the viewpoint of improving water permeability.


The saturated fatty acid refers to a fatty acid having no double bond or triple bond in the carbon chain. The fatty acid is an aliphatic carboxylic acid having at least one carboxyl group. A saturated fatty acid having a hydroxyl group is preferable because it is easily crosslinked to show good performance for gelling a composition for indicator entirely. The saturated fatty acid is preferably in the form of a chain. Moreover, the chain saturated fatty acid is preferably a linear saturated fatty acid.


The saturated fatty acid has more preferably from 16 to 36 carbon atoms, and further preferably from 18 to 20 carbon atoms. Specific examples of the saturated fatty acid having 16 or more carbon atoms include arachidic acid having 20 carbon atoms, stearic acid having 18 carbon atoms, 12-hydroxystearic acid having 18 carbon atoms, margaric acid having 17 carbon atoms, palmitic acid having 16 carbon atoms and 16-hydroxyhexadecanoic acid having 16 carbon atoms. Among them, 12-hydroxystearic acid is particularly preferable.


The saturated fatty acid derivative refers to a compound in which a part of the saturated fatty acid is substituted with a coexisting group. The saturated fatty acid derivative may have from 16 or more carbon atoms, preferably from 16 to 36 carbon atoms, and more preferably from 18 to 20 carbon atoms. For example, a fatty acid amide, fatty acid alkyl ester, fatty acid metal salt, monoglyceride, diglyceride, sorbitan fatty acid ester or diglycerin fatty acid ester having 16 or more carbon atoms may be used as the saturated fatty acid derivative. Preferred saturated fatty acid derivative includes saturated fatty acid metal salts.


The saturated fatty acid derivative particularly preferably has a chemical structure derived from stearic acid. The “chemical structure derived from stearic acid” refers to the unit represented by formula




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The saturated fatty acid derivative also includes a chemical structure in which a part of formula (1) is substituted with another coexisting group (for example, a hydroxyl group, an alkyl group, an alkali metal, or an alkaline earth metal) and an oligomer or a polymer having the unit represented by formula (1).


The fatty acid metal salt is preferably a metal salt having a chemical structure derived from stearic acid, and specific examples thereof include sodium stearate and lithium 12-hydroxystearate having 18 carbon atoms, and magnesium stearate having 36 carbon atoms. Among them, lithium 12-hydroxystearate is particularly preferable.


When the composition for wet indicator of the present invention contains 12-hydroxystearic acid and lithium 12-hydroxystearate as a gelling agent, it is easy to solidify the oily substance to prepare an oily gel having appropriate hardness. When the oily gel is formed to have appropriate hardness, moisture easily penetrates into the gel. As the moisture easily permeates, the moisture and the surfactant easily coexist, generation of protons is facilitated, and discoloration of the colorant is promoted.


The gelling agent is blended with the oily substance to form a continuous porous body like tissue, and forms a structure in which the oily substance is confined in voids of the continuous porous body. By blending the liquid oily substance with the gelling agent, an oily gel having appropriate hardness is obtained, and the oily gel has a fine continuous porous body. In the composition for wet indicator of the present invention, since the oily gel has a fine continuous porous structure, for example, moisture such as urine and body fluid is possible to easily permeate therein.


The gelling agent is contained in the composition for wet indicator in an amount of from 2 to 80% by mass, preferably from 5 to 70% by mass, and more preferably from 10 to 50% by mass, based on the total amount of the oily gel and the wet-sensitive colorant composition. By adjusting the content of the gelling agent in the composition for wet indicator within the above ranges, compatibility between the liquid oily substance and the colorant is improved and protons are easily generated, and the composition for wet indicator of the present invention may exhibit clear and rapid coloration.


Wet-Sensitive Colorant Composition

The composition for wet indicator of the present invention comprises a wet-sensitive colorant composition. The wet-sensitive colorant composition refers to a composition comprising a colorant that is substantially discolored when receiving protons and a surfactant that releases protons in the presence of water. As the colorant and the surfactant used in the wet-sensitive colorant composition, known colorants and surfactants may be used in combination.


The colorant includes a dye, an indicator and a pigment. Specific examples of the colorant that may be used include oxazolidine-based dyes, azo-based dyes, methine-based dyes, anthraquinone-based dyes and leuco dyes. The colorant preferably contains a leuco dye and a pH indicator, from the viewpoint of obtaining rapid and clear discoloration. Since the leuco dye or the pH indicator has strong proton sensitivity, use of the leuco dye or the pH indicator improves discoloration performance of the composition for wet indicator.


The leuco dye is a dye that may change between two chemical species (one of which is colorless). Reversible transformations are caused by heat, light or pH; resulting in examples of thermochromism, photochromism and halochromism, respectively. Typical irreversible transformations are caused by reduction or oxidation. The colorless form is sometimes referred to as a leuco form.


The leuco dye is not limited as long as it is sufficiently colored, and a known or commercially available one may be used. For example, the following compounds such as a leuco dye that may develop color by an acid may be suitably used. These may be used singly or two or more kinds thereof.


(a) Fluorans: 2′-[(2-chlorophenyl)amino]-6′-(dibutylamino)-spiro[isobenzofuran-1(3H),9′-(9H)xanthen]-3-one, 3-diethylamino-6-methyl-7-chlorofluoran, 3-dimethylaminobenzo(a)-fluoran, 3-amino-5-methylfluoran, 2-methyl-3-amino-6,7-dimethylfluoran, 2-bromo-6-cyclohexylaminofluoran, 6′-ethyl(4-methylphenyl)amino-2′-(N-methylphenylamino)-spiro(isobenzofuran1(3H),9′-(9H)xanthen)-3-one, 3,6-diphenylaminofluoran, 9-ethyl(3-methylbutyl)amino-spiro[12H-benzo(a)xanthene-12, 1′(3′H)isobenzofuran]-3′-one and 2′-[bis(phenylmethyl)amino]-6′-(diethylamino)-spiro-[isobenzofuran-1(3H),9′-(9H)xanthen]-3-one;

  • (b) Fluorens: 3,6-bis(diethylamino)fluorenespiro(9,3′)-4′-azaphthalide and 3,6-bis(diethylamino)fluorenespiro(9,3′)-4′,7′-diazaphthalide;
  • (c) Diphenylmethane phthalides: 3,3-bis-(p-ethoxy-4-dimethylaminophenyl)phthalide;
  • (d) Diphenylmethane azaphthalides: 3,3-bis-(1-ethoxy-4-diethylaminophenyl)-4-azaphthalide and 3,3-bis(4-diethylamino-2-ethoxyphenyl)-4-azaphthalide;
  • (e) Indolyl phthalides: 3,3-bis(n-butyl-2-methylindol-3-yl)phthalide and 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide;
  • (f) Phenylindolyl phthalides: 3-(1-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide;
  • (g) Phenylindolyl azaphthalides: 3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide and 3-[2-ethoxy-4-(N-ethylanilino)phenyl]-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide;
  • (h) Styrylquinolines: 2-(3-methoxy-4-dodecoxystyryl)quinoline;
  • (i) Diazarhodamine lactones: 2-(dimethylamino)-8-(dimethylamino)-4-methyl-spiro[5H-(1)benzopyrano(2,3-d)pyrimidine-5,1′(3′H)-isobenzofuran];
  • (j) Pyridines: 2,6-diphenyl-4-(6-dimethylaminophenyl)pyridine and 2,6-diethoxy-4-(4-diethylaminophenyl)pyridine;
  • (k) Quinazolines: 2-(4-N-methylanilinophenyl)-1-phenoxyquinazoline and 2-(4-dimethylaminophenyl)-4-(1-methoxyphenyloxy)quinazoline;
  • (1) Bisquinazolines: 4,4′-(ethylenedioxy)-bis[2-(1-diethylaminophenyl)quinazoline] and 4,4′-(ethylenedioxy)-bis[2-(1-di-n-butylaminophenyl)quinazoline];
  • (m) Ethylenophthalides: 3,3-bis[1,1-bis-(p-dimethylaminophenyl)ethyleno-3]phthalide;
  • (n) Ethylenoazaphthalides: 3,3-bis[1,1-bis-(p-dimethylaminophenyl)ethyleno-2]-4-azaphthalide and 3,3-bis[1,1-bis-(p-dimethylaminophenyl)ethyleno-2]-4,7-diazaphthalide; and
  • (o) Aminophthalides: 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (crystal violet lactone).


In addition, at least one of aminophthalides and fluorans may be used as a colorant. As the fluoran, particularly, 2′-[bis(phenylmethyl)amino]-6′-(diethylamino)-spiro-[isobenzofuran-1(3H),9′-(9H)xanthen]-3-one, 2′-[(2-chlorophenyl)amino]-6′-(dibutylamino)-spiro[isobenzofuran-1(3H),9′-(9H)xanthen]-3-one and 3,6-diphenylaminofluoran are more preferable. As the aminophthalides, crystal violet lactone is particularly preferable.


When the composition for wet indicator of the present invention contains a leuco dye as a colorant, the leuco dye is easily ring-opened by protons generated in the presence of a surfactant and urine (moisture), and the composition for wet indicator is quickly colored, which is preferable. The content of the leuco dye may be appropriately determined according to the type of the leuco dye and a desired hue.


The pH indicator refers to a chemical to be added to a reaction liquid in order to know an equivalent point by a change directly visible, such as a change in color or formation of a precipitate in titration. As the pH indicator, an acid-base indicator is used. Specific examples of the pH indicator include phenolphthalein, methyl orange, potassium chromate, bromocresol green and bromophenol blue.


The colorant is contained in the composition for wet indicator in an amount of from 0.01 to 7% by mass, preferably from 0.05 to 5% by mass, and more preferably from 0.1 to 4% by mass, based on the total amount of the oily gel and the wet-sensitive colorant composition. By adjusting the content of the colorant in the composition for wet indicator within the above ranges, color difference between the dry state and the wet state of the composition for wet indicator increases, and discoloration may be easily perceived.


The colorant is used in combination with a surfactant to be a wet-sensitive colorant composition. The surfactant improves compatibility of the colorant with other components, and the colorant is easily included in the oily gel.


The surfactant is a substance exhibiting a function of discoloring the colorant in the presence of moisture. For example, anionic surfactants and nonionic surfactants are preferable because they are easily wetted with water to generate protons, and many colorants are discolored by receiving protons.


Examples of the anionic surfactant include:

  • alkali metal alkyl sulfates such as sodium dodecyl sulfate and potassium dodecyl sulfate; sodium dodecyl polyglycol ether sulfate;
  • ammonium alkyl sulfates such as ammonium dodecyl sulfate;
  • sodium sulfosinoate;
  • alkyl sulfonates such as alkali metal salts of sulfonated paraffin and ammonium salts of sulfonated paraffin;
  • fatty acid salts such as sodium laurate, triethanolamine oleate and triethanolamine abietate;
  • alkylaryl sulfonates such as sodium dodecylbenzene sulfonate and alkali metal sulfates of alkali phenol hydroxyethylene;
  • high alkyl naphthalene sulfonates;
  • naphthalenesulfonic acid formalin condensate;
  • dialkyl sulfosuccinates;
  • polyoxyethylene alkyl sulfate salts; and
  • polyoxyethylene alkylaryl sulfate salts.


Examples of the nonionic surfactant include:

  • polyoxyethylene alkyl ethers;
  • polyoxyethylene alkylaryl ethers;
  • sorbitan fatty acid ester;
  • polyoxyethylene sorbitan fatty acid ester;
  • fatty acid monoglyceride such as glycerol monolaurate;
  • polyoxyethyleneoxypropylene copolymer; and
  • condensation product of ethylene oxide and aliphatic amine, amide or acid.


The surfactant is preferably an anionic surfactant, more preferably a linear alkylbenzene sulfonate, and further preferably sodium dodecylbenzene sulfonate. When sodium dodecylbenzene sulfonate is used as the surfactant, the colorant is easily dissolved in the oily substance, and the oily substance is so easily brought into contact with water, that protons are easily generated. Since protons are easily provided to the colorant, discoloration of the composition for wet indicator rapidly proceeds.


The surfactant is contained in the composition for wet indicator in an amount of from 1 to 30% by mass, preferably from 3 to 20% by mass, and more preferably from 5 to 15% by mass, based on the total amount of the oily gel and the wet-sensitive colorant composition. By adjusting the content of the surfactant in the composition for wet indicator within the above ranges, sensitivity of the composition for wet indicator to moisture is improved, and a wet state is accurately displayed.


Pigment

In the composition for wet indicator of the present invention, a pigment may be used as necessary. The pigment includes inorganic pigments and organic pigments. The inorganic pigment includes colored inorganic pigments and extender pigments.




  • Examples of the colored inorganic pigment include white titanium oxide, white lead (basic lead carbonate), zinc white (zinc oxide), lithopone (barium sulfate/zinc sulfide);

  • reddish red iron (III) oxide, red lead (lead oxide), silver vermilion (mercury sulfide), molybdenum-red;

  • yellowish chrome yellow (lead chromate), cadmium yellow (cadmium sulfide), zinc chromate, lissajous (lead monoxide);

  • bluish ultramarine blue, prussian blue, cobalt blue (cobalt aluminate); and

  • black pigment includes iron black (iron(II,III) oxide and carbon black.



Examples of the extender pigment include barite (barium sulfate), gypsum (hydrous calcium sulfate), kaolin (white clay), silica (silicon dioxide), white carbon (precipitated silica), talc, barium carbonate and calcium carbonate.


Examples of the organic pigment include lake and colored organic pigments. There are two types of lake, one of which is dyeing lake, which is a pigment obtained by dyeing an extender pigment with a dye. Another lake is one in which a dye is made insoluble by reacting with a divalent or higher metal salt, and examples thereof include azo lake formed from an azo dye.


Examples of the colored organic pigment include insoluble azo pigments, metal phthalocyanine pigments, anthraquinone pigments and vat pigments. Among azo dyes, anthraquinone dyes and indigo dyes shown as representative types of dyes based on chemical structures, substances insoluble in water are used as pigments. Moreover, the metal phthalocyanine pigment has a color tone from blue to green, and is excellent in light resistance.


Tackifier Resin

In the composition for wet indicator of the present invention, a tackifier resin may be used as necessary. Examples of the tackifier resin include natural rosin, modified rosin, hydrogenated rosin, glycerol esters of natural rosin, glycerol esters of modified rosin, pentaerythritol esters of natural rosin, pentaerythritol esters of modified rosin, pentaerythritol esters of hydrogenated rosin, copolymers of natural terpenes, three-dimensional polymers of natural terpenes, hydrogenated derivatives of copolymers of hydrogenated terpenes, polyterpene resins, hydrogenated derivatives of phenol-based modified terpene resins, aliphatic petroleum hydrocarbon resins, hydrogenated derivatives of aliphatic petroleum hydrocarbon resins, aromatic petroleum hydrocarbon resins, hydrogenated derivatives of aromatic petroleum hydrocarbon resins, cyclic aliphatic petroleum hydrocarbon resins and hydrogenated derivatives of cyclic aliphatic petroleum hydrocarbon resins.


As the tackifier resin, a commercially available product may be used. Examples of such a commercially available product include KE-604 (trade name), ARKON P100 (trade name) and ARKON M100 (trade name) manufactured by Arakawa Chemical Industries, Ltd., RHR-101HK manufactured by Wuzhou Sun Shine Forestry & Chemicals Co., Ltd., Foral AX-E (trade name) manufactured by Eastman Chemical Company, FTR6100 manufactured by Mitsui Chemicals, Inc., CLEARON M105 (trade name) manufactured by YASUHARA CHEMICAL CO.,LTD., ECR5600 (trade name) and ECR179EX (trade name) manufactured by Exxon Mobil Corporation and Quinton DX390 (trade name) manufactured by Zeon Corporation. These commercially available tackifier resins may be used alone or in combination.


In consideration of compatibility between the surfactant and the liquid oily substance, RHR-101HK and Foral AX-E, which are rosin-based tackifier resins, are particularly preferable as the tackifier resin.


Other Components

The composition for wet indicator of the present invention may contain, as components other than the above, at least one additive of a thickener (styrene-based polymer, olefin-based polymer), an antioxidant (phenol-based, phosphorus-based and sulfur-based), an ultraviolet absorber, a fluorescent brightening agent, a non-discoloring dye, a fragrance, a disinfectant, an antibacterial agent, a repellent, a skin care component, a non-discoloring pigment, a lubricant and a filler.


Method for Producing Composition for Wet Indicator

The composition for wet indicator of the present invention is prepared by mixing the above-described components with heating as necessary. When the components are mixed until they become uniform and cooled to room temperature, the composition for wet indicator gelates and becomes hard.


For example, all the components contained in the composition for wet indicator are put into a container, and the components are dissolved or uniformly dispersed, and heated and stirred until a uniform state is obtained. The heating temperature is appropriately adjusted generally in the range of from 50 to 250° C., preferably from 70 to 200° C., and more preferably from 80 to 160° C. The heating time is determined in consideration of the heating temperature, but is generally adjusted between 5 minutes and 1 hour, and preferably between 10 minutes and 40 minutes.


A uniform composition may be prepared by putting each component into a container in turn and sequentially mixing the components.


Wet Indicator

The composition for wet indicator is molded into a suitable shape and is used as a wet indicator, optionally in combination with a component, substance or material that does not impair wet indicator function. The composition for wet indicator may be used as a single material, for example, by being applied onto a substrate material such as a film or paper, or may be used in combination with a water-absorbent substance. The wet indicator of the present invention may be used for various articles in which a wet state needs to be detected, but is particularly preferably used for absorbent articles.




  • When the composition for wet indicator and the water-absorbent substance are combined, examples of embodiment thereof are as follows. That is,

  • positioning a composition for wet indicator and a water-absorbent substance adjacent to each other;

  • mixing the composition for wet indicator and the water-absorbent substance; and heating the composition for wet indicator and the water-absorbent substance to be compatible with each other.



The water-absorbent substance may be a known resin having a water-absorbing property such as polyvinyl alcohol or an acrylic resin or a known substance having a water-absorbing property such as wood, paper or cloth, and shape of the water-absorbent substance may be any shape such as a sheet shape, a lump shape, a granular shape or a fibrous shape.


Absorbent Article

The absorbent article of the present invention includes a water-absorbent substance and the composition for wet indicator of the present invention. Specifically, the absorbent article is a so-called hygienic material such as a sanitary napkin, a urine absorbing liner, puerperal shorts, a breast milk pad, an armpit sweat pad, a paper diaper, a pet sheet, a hospital gown and a surgical white gown.


The absorbent article is composed of at least one member selected from a group consisting of a woven fabric, a nonwoven fabric, a rubber, a resin, paper and a polyolefin film, and the wet indicator according to the present invention. The polyolefin film is preferably a polyethylene film for reasons such as durability and cost.


When the wet indicator of the present invention is used for paper diaper, the wet indicator is preferably attached to the surface of the powder or particles of the water-absorbent resin stored in the disposable diaper. In addition to the paper diaper, by applying the wet indicator of the present invention to a surface of various substrate materials such as resin particles, woven fabric, nonwoven fabric, resin sheet, paper, resin molded article, metal and wood by any means, a moisture wet indicator action may be provided on the surface of various substrate materials.


EXAMPLES

Hereinafter, for the purpose of describing the present invention in more detail and specifically, the present invention will be described using examples, but these examples do not limit the present invention at all.


In Examples and Comparative Examples, components to be blended in a composition for wet indicator are shown below.


Liquid oily substances constituting an oily gel are as follows. <Liquid Oily Substances>

  • Paraffin oil (liquid paraffin (trade name) manufactured by FUJIFILM Wako Pure Chemical Corporation)
  • Paraffin oil (Daphne Oil KP-68 (trade name) manufactured by Idemitsu Kosan Co.,Ltd.)
  • Paraffin oil (Diana Fresia PW-32 (trade name) manufactured by Idemitsu Kosan Co.,Ltd.)
  • Naphthenic oil (KNH4010 (trade name) manufactured by PetroChina Company Limited)
  • Liquid polybutene (Nisseki Polybutene HV-100 (trade name) manufactured by JXTG Nippon Oil & Energy Corporation)


<Wax>

  • Fischer-Tropsch wax (Sasol H1 (trade name) manufactured by Sasol Limited)


Colorants constituting the wet-sensitive colorant composition are as follows. <Colorants>

  • pH Indicator (bromocresol green (trade name) manufactured by FUJIFILM Wako Pure Chemical Corporation)
  • Leuco dye (crystal violet lactone (trade name) manufactured by FUJIFILM Wako Pure Chemical Corporation)
  • Leuco dye (Blue 1 (trade name) manufactured by Yamada Chemical Co., Ltd.)
  • Leuco dye (Blue 203 (trade name) manufactured by Yamada Chemical Co., Ltd.)


Surfactants constituting the wet-sensitive colorant composition are as follows. <Surfactants>

  • Anionic surfactant (sodium dodecylbenzene sulfonate (reagent name) manufactured by KANTO CHEMICAL CO.,INC.)
  • Anionic surfactant (Aerosol QT-100 (trade name) manufactured by SOLVAY)
  • Nonionic surfactant (SURFLIC-AQ250 (trade name) manufactured by Itoh Oil Chemicals Co.,Ltd.)


Gelling agents constituting the oily gel are as follows. <Gelling Agents (Saturated Fatty Acids having 16 or More Carbon Atoms or Derivatives Thereof)>

  • Saturated fatty acid having 18 carbon atoms (stearic acid (reagent name) manufactured by FUJIFILM Wako Pure Chemical Corporation)
  • Saturated fatty acid having 16 carbon atoms (16-hydroxyhexadecanoic acid (reagent name) manufactured by FUJIFILM Wako Pure Chemical Corporation)
  • Saturated fatty acid having 18 carbon atoms (12-hydroxystearic acid (reagent name) manufactured by FUJIFILM Wako Pure Chemical Corporation)
  • Saturated fatty acid derivative having 18 carbon atoms (sodium stearate (reagent name) manufactured by FUJIFILM Wako Pure Chemical Corporation)
  • Saturated fatty acid derivative having 36 carbon atoms (magnesium stearate (reagent name) manufactured by FUJIFILM Wako Pure Chemical Corporation)


<Non-Gelling Agents (Hydrocarbon Not Corresponding to “Gelling Agents”)>

  • Aliphatic alkane having 17 carbon atoms (n-heptadecane (reagent name) manufactured by FUJIFILM Wako Pure Chemical Corporation))
  • Aliphatic alkane having 20 carbon atoms (eicosane (reagent name) manufactured by FUJIFILM Wako Pure Chemical Corporation))
  • Aliphatic alcohol having 18 carbon atoms (1-octadecanol (reagent name) manufactured by FUJIFILM Wako Pure Chemical Corporation)
  • Unsaturated fatty acid having 18 carbon atoms (oleic acid (reagent name) manufactured by FUJIFILM Wako Pure Chemical Corporation)
  • Saturated fatty acid having 10 carbon atoms (decanoic acid (reagent name) manufactured by FUJIFILM Wako Pure Chemical Corporation)
  • Saturated fatty acid having 14 carbon atoms (3-hydroxytetradecanoic acid (reagent name) manufactured by Combi-Blocks Inc.)


<Tackifier Resin>

  • Hydrogenated rosin-based tackifier resin (RHR-101HK (trade name) manufactured by Wuzhou Sun Shine Forestry & Chemicals Co., Ltd.)
  • Hydrogenated rosin-based tackifier resin (Foral AX-E (trade name) manufactured by Eastman Chemical Japan Ltd.)
  • Hydrogenated hydrocarbon-based tackifier resin (HD-1100 (trade name) manufactured by Tiajin Luhua Chemical Co.ltd.)
  • Hydrogenated hydrocarbon-based tackifier resin (ARKON P100 (trade name) manufactured by Arakawa Chemical Industries, Ltd.)
  • Hydrogenated hydrocarbon-based tackifier resin (ECR5400 (trade name) manufactured by Exxon Mobil Corporation)
  • Hydrogenated hydrocarbon-based tackifier resin (FTR-6100 (trade name) manufactured by Mitsui Chemicals, Inc.)


The above-described components were blended in ratios shown in Tables 1 to 4, and stirred and mixed to prepare a composition for wet indicator. Specifically, components were placed in a 70 ml container and heated to 130° C. with a glass-col heater, and a compound of the components was stirred using a stirrer at a stirring speed of from 300 to 500 rpm for 20 minutes. All numerical values relating to the composition for wet indicator (composition) shown in Tables 1 to 4 are parts by mass (solid content).


For the compositions for wet indicator of Examples and Comparative Examples, appearance was confirmed whether or not an oily gel was formed, and phase separation, odor, discoloration time and color bleeding were evaluated. Details of the evaluation are shown below.


Appearance

The compositions for wet indicator of Examples and Comparative Examples were allowed to stand at room temperature for 1 day, and appearance of each composition was visually observed to confirm whether or not an oily gel was generated.


Whether or not the composition for wet indicator was a gel was evaluated by fluidity of the composition and oozing-out of the oily substance.


The composition was placed in a container, the composition was not flowable even when the container was tilted, and a commercially available oil blotting paper was pressed against the composition, and when oil exudation was visually recognized, the composition was determined as a gel. The evaluation results are as shown in Tables 1 to 4.


Hardness of the composition for wet indicator was evaluated according to the following criteria. In an environment of 23° C., a cylindrical SUS probe was pressed against the composition for wet indicator of each of Examples and Comparative Examples to apply a load of 1 kg, and after 8 seconds, the degree of penetration of the SUS probe into the composition was confirmed to evaluate hardness of the composition. The evaluation criteria are as follows.




  • Penetration of probe having a diameter of 16 mm is 4 mm or more: Very soft

  • Penetration of probe having a diameter of 16 mm is less than 4 mm: Soft

  • Penetration of the probe having a diameter of 5 mm is less than 4 mm: Hard

  • Penetration of probe having a diameter of 3 mm is less than 4 mm: Very hard



Phase Separation

Using 30 g of the composition for wet indicator of each of Examples and Comparative Examples as an evaluation sample, 30 g of each sample was placed in a 70 ml glass container and allowed to stand in a heating furnace at 100° C. After aging the sample for 24 hours, the presence or absence of phase separation was visually confirmed to evaluate whether the composition was uniform or non-uniform.




  • A: No phase separation is observed, and no turbidity is observed

  • B: Phase separation is not observed and is uniform, but slight turbidity is observed

  • C: A slightly transparent supernatant is observed at the top

  • D: Obvious phase separation is observed



Odor

Using 30 g of the composition for wet indicator of each of Examples and Comparative Examples as an evaluation sample, 30 g of each sample was placed in a 70 ml glass container, covered with an aluminum foil, and then allowed to stand in a dryer at 40° C. for 1 hour. Thereafter, the container was taken out from the dryer, the aluminum foil was removed, and odor was confirmed. The evaluation criteria are as follows.




  • A: No odor is sensed

  • B: A slight odor is sensed

  • C: An obvious odor is sensed but is not unpleasant

  • D: A strong and unpleasant odor is sensed



Discoloration Test

The wet indicator composition of each of Examples and Comparative Examples was placed in a glass bottle, and the glass bottle was heated in a dryer at 100° C. until a uniform liquid was obtained. Subsequently, an appropriate amount of each composition was dropped on a hiding rate test paper (JIS K-5600, manufactured by TP Giken Co., Ltd.), then a uniform film having a thickness of about 27.5 µm was quickly prepared with a bar coater (No. 12 manufactured by Daiichi Rika Co., Ltd.), and color of this coating film was recorded as an initial state (sample). It is to be noted that, for a sample in which no coloration was observed, symbol “-” was shown in the table.


The sample was allowed to stand at room temperature for 30 minutes or more and then placed on a table, and water was sprayed on the sample. Thereafter, final color, the degree of hue change (color difference) and time until color oozed out and changed to the final color were recorded and described in Tables 1 to 4.


Color Difference (Degree of Hue Change)

Evaluation criteria of the hue change are as follows.




  • A: A very clear difference in hue is observed before and after spraying

  • B: A clear difference in hue is observed before and after spraying

  • C: A slight difference in hue is observed before and after spraying

  • D: No difference in hue is observed before and after spraying



Color Bleeding

After color of the sample changed to the final color, the water-applied sample was vertically leaned from a table, and color bleeding associated with moisture dripping was recorded. When the color oozes out due to water, application pattern of the wet indicator applied to a diaper collapses and visibility deteriorates. Therefore, it is preferable as the composition for wet indicator when the color bleeding is less. The evaluation criteria are as follows.




  • A: No color bleeding is observed

  • B: Slight color bleeding is observed, but shape of the applied portion is retained

  • C: Color bleeding is observed, but shape of the applied portion is retained

  • D: Color bleeding is observed, and shape of the applied portion is lost and not retained



Time Until It Became Final Color

Time from spraying of water until it became the final color was measured and described in Tables 1 to 4. It is to be noted that, for compositions in which no color difference was observed, symbol “-” was shown in the table.





TABLE 1















Examples


Component composition
1
2
3
4
5
6
7
8
9




Oily substance
Paraffin oil (liquid paraffin)
66
0
0
64
64
64
64
83
81


Paraffin oil (KP-68)
0
0
0
0
0
0
0
0
0


Paraffin oil (PW-32)
0
63
34
0
0
0
0
0
0


Naphthene oil (KN4010)
0
0
0
0
0
0
0
0
0


Polybutene (HV-100)
0
0
0
0
0
0
0
0
0


Colorant
pH Indicator (bromocresol green)
0
0
0
2
2
2
2
2
0


Leuco dye (crystal violet lactone)
1
0.4
1
0
0
0
0
0
2


Leuco dye (Blue 1)
0
0
0
0
0
0
0
0
0


Leuco dye (Blue 203)
0
0
0
0
0
0
0
0
0


Surfactant
Anionic (Na dodecylbenzene sulfonate)
11
8
22
11
11
11
11
11
11


Anionic (Na dioctyl sulfosuccinate)
0
0
0
0
0
0
0
0
0


Nonionic (AQ250)
0
0
0
0
0
0
0
0
0


Gelling agent
Stearic acid
0
0
0
22
0
0
0
0
0


16-Hydroxyhexadecanoic acid
0
0
0
0
22
0
0
0
0


12-Hydroxystearic acid
22
28
43
0
0
0
0
3
6


Na stearate
0
0
0
0
0
22
0
0
0


Mg stearate
0
0
0
0
0
0
22
0
0


Tackifier resin
Hydrogenated gum rosin (RHR-101HK)
11
9
9
10
10
10
10
10
10


Hydrogenated rosin (AX-E)
0
0
0
0
0
0
0
0
0


Hydrogenated hydrocarbon (HD-1100)
0
0
0
0
0
0
0
0
0


Hydrogenated hydrocarbon (P100)
0
0
0
0
0
0
0
0
0


Hydrogenated hydrocarbon (ECR5400)
0
20
45
0
0
0
0
0
0


Hydrogenated hydrocarbon (FTR-6100)
0
0
0
0
0
0
0
0
0


Total
111
129
154
110
110
110
110
110
110









TABLE 1 (cont.)














Composition applied sample





Performance evaluation results
Appearance (presence or absence of oily gel)
Presence of gel
Presence of gel
Presence of gel
Presence of gel
Presence of gel
Presence of gel
Presence of gel
Presence of gel
Presence of gel


Appearance (hardness of composition for indicator)
Hard
Very hard
Very hard
Soft
Soft
Soft
Soft
Very Soft
Soft


Phase separation (100° C. for 24 hours)
A
A
A
A
A
B
A
A
A


Odor
A
A
A
B
B
B
B
B
A


Initial hue
-
-
-
Dark yellow
Yellow
Light blue
Light green
Yellow
-


Hue (final color) after water wetting
Blue
Blue
Blue
Blue
Light blue
Dark blue
Dark blue
Blue
Blue


Color difference
A
A
A
B
B
A
A
A
B


Color bleeding
B
A
A
B
B
B
B
B
B


Time until discoloration
Immediate
Immediate
Immediate
Immediate
Immediate
Immediate
Immediate
Immediate
Immediate









TABLE 2














Examples


Component composition
10
11
12
13
14
15
16
17




Oily substance
Paraffin oil (liquid paraffin)
20
0
0
0
0
0
0
0


Paraffin oil (KP-68)
0
67
0
66
57
76
69
69


Paraffin oil (PW-32)
0
0
0
0
0
0
0
0


Naphthene oil (KN4010)
0
0
0
0
0
0
0
0


Polybutene (HV-100)
0
0
66
0
0
0
0
0


Colorant
pH Indicator (bromocresol green)
0
0
0
0
0
0
0
1


Leuco dye (crystal violet lactone)
0
0
0
1
1
1
0
0


Leuco dye (Blue 1)
0
0.06
1
0
0
0
1
0


Leuco dye (Blue 203)
2
0
0
0
0
0
0
0


Surfactant
Anionic (Na dodecylbenzene sulfonate)
11
11
11
11
14
0
0
0


Anionic (Na dioctyl sulfosuccinate)
0
0
0
0
0
3
10
0


Nonionic (AQ250)
0
0
0
0
0
0
0
10


Gelling agent
Stearic acid
0
0
0
0
0
0
0
0


16-Hydroxyhexadecanoic acid
0
0
0
0
0
0
0
0


12-Hydroxystearic acid
67
22
22
22
28
20
20
20



Na stearate
0
0
0
0
0
0
0
0


Mg stearate
0
0
0
0
0
0
0
0


Tackifier resin
Hydrogenated gum rosin (RHR-101HK)
10
10
10
0
0
0
0
0









TABLE 2 (cont.)














Hydrogenated rosin (AX-E)
0
0
0
10
0
0
0
0


Hydrogenated hydrocarbon (HD-1100)
0
0
0
0
0
0
0
0


Hydrogenated hydrocarbon (P100)
0
0
0
0
0
0
0
0


Hydrogenated hydrocarbon (ECR5400)
0
0
0
0
0
0
0
0


Hydrogenated hydrocarbon (FTR-6100)
0
0
0
0
28
0
0
0


Total
110
110
110
110
128
100
100
100
















Composition applied sample





Performance evaluation results
Appearance (presence or absence of oily gel)
Presence of gel
Presence of gel
Presence of gel
Presenc e of gel
Presence of gel
Presence of gel
Presence of gel
Presence of gel


Appearance (hardness of composition for indicator)
Hard
Soft
Soft
Soft
Hard
Soft
Soft
Soft


Phase separation (100° C. for 24 hours)
A
A
A
A
B
B
B
C


Odor
A
A
A
A
A
A
A
B


Initial hue
Light blue
-
-
-
-
-
-
Yellow


Hue (final color) after water wetting
Dark blue
Light purple
Purple
Dark blue
Dark blue
Light blue
Blue
Light blue


Color difference
A
B
B
A
A
C
B
B


Color bleeding
A
B
B
B
A
A
B
B


Time until discoloration
Immediate
Immediate
Immediate
Immediate
Immediate
Immediate
Immediate
Immediate









TABLE 3











Comparative Examples


Component composition
1
2
3
4
5




Wax
Fischer-Tropsch (H1)
0
0
0
0
0


Liquid oily substance
Paraffin oil (liquid paraffin)
64
64
64
64
64


Paraffin oil (KP-68)
0
0
0
0
0


Paraffin oil (PW-32)
0
0
0
0
0


Colorant
pH Indicator (bromocresol green)
2
2
2
2
2


Leuco dye (crystal violet lactone)
0
0
0
0
0


Surfactant
Anionic (Na dodecylbenzene sulfonate)
11
11
11
11
11


n-Heptadecane
22
0
0
0
0


Eicosane
0
22
0
0
0


1-Octadecanol
0
0
22
0
0


Non-gelling agent
Oleic acid
0
0
0
22
0


Decanoic acid
0
0
0
0
22


3-Hydroxytetradecanoic acid
0
0
0
0
0


Gelling agent
12-Hydroxystearic acid
0
0
0
0
0


Tackifier resin
Hydrogenated gum rosin (RHR-101HK)
10
10
10
10
10


Hydrogenated hydrocarbon (ECR5400)
0
0
0
0
0


Total
110
110
110
110
110













Composition applied sample









Performance evaluation results
Appearance (presence or absence of oily gel)
Absence of gel
Absence of gel
Absence of gel
Absence of gel
Absence of gel


Appearance (hardness of composition for indicator)
Liquid
Liquid
Soft solid
Liquid
Heterogeneo us solid


Phase separation (100° C. for 24 hours)
A
A
A
A
A


Odor
B
D
C
C
C


Initial hue
Dark yellow
Yellow
Yellow
Yellow
Yellow


Hue (final color) after water wetting
Dark yellow
Light blue
Yellow
Yellow
Yellow


Color difference
D
B
D
D
D


Color bleeding
D
D
D
D
B


Time until discoloration
-
30 Seconds or more
-
-
-









TABLE 4











Comparative Examples


Component composition
6
7
8
9
10




Wax
Fischer-Tropsch (H1)
0
64
0
0
0


Liquid oily substance
Paraffin oil (liquid paraffin)
64
0
0
87
76


Paraffin oil (KP-68)
0
0
0
0
0


Paraffin oil (PW-32)
0
0
0
0
0


Colorant
pH Indicator (bromocresol green)
2
2
6
2
2


Leuco dye (crystal violet lactone)
0
0
0
0
0


Surfactant
Anionic (Na dodecylbenzene sulfonate)
11
11
31
11
0


n-Heptadecane
0
0
0
0
0


Eicosane
0
0
0
0
0


1-Octadecanol
0
0
0
0
0


Non-gelling agent
Oleic acid
0
0
0
0
0


Decanoic acid
0
0
0
0
0


3-Hydroxytetradecanoic acid
22
0
0
0
0


Gelling agent
12-Hydroxystearic acid
0
22
63
0
22


Tackifier resin
Hydrogenated gum rosin (RHR-101HK)
10
10
68
10
10


Hydrogenated hydrocarbon (ECR5400)
0
0
0
0
0


Total
110
110
168
110
110













Composition applied sample









Performance evaluation results
Appearance (presence or absence of oily gel)
Absence of gel
Absence of gel
Absence of gel
Absence of gel
Presence of gel


Appearance (hardness of composition for indicator)
Liquid
Hard solid
Liquid
Hard solid
Hard Gel


Phase separation (100° C. for 24 hours)
D
D
A
A
A


Odor
C
C
D
D
D


Initial hue
Yellow
Yellow
Dark yellow
Yellow
Light yellow


Hue (final color) after water wetting
Yellow
Yellow
Dark yellow
Yellow
Light yellow


Color difference
D
D
D
D
D


Color bleeding
D
A
D
A
B


Time until discoloration
-
-
-
-
-






As shown in Tables 1 and 2, the compositions for wet indicator of Examples have an oily gel, the components are not separated, and a strong odor is not generated. Further, in the compositions for wet indicator of Examples, a change in color is clear, time from the initial stage to the final discoloration is short, and the color is not blurred.


On the other hand, since the compositions for wet indicator of Comparative Examples 1 to 9 do not have an oily gel as shown in Tables 3 and 4, phase separation occurs and the compositions are non-uniform, odor is generated, or a change in discoloration (color difference) is small. The composition for wet indicator of Comparative Example 10 had an oily gel, but did not contain a surfactant, so that protons were hardly generated, and color difference was not able to be clearly shown.


Without the surfactant, the colorant is hardly compatible with the oily substance and other components, and the colorant is not included in the gel. The composition for wet indicator of Comparative Example 10 was not able to suppress odor of the colorant.


INDUSTRIAL APPLICABILITY

The composition for wet indicator of the present invention provides a wet indicator to be attached to an absorbent article such as a diaper or a napkin.

Claims
  • 1. A composition for wet indicator comprising an oily gel and a wet-sensitive colorant composition.
  • 2. The composition for wet indicator according to claim 1, wherein the oily gel is a solid having an oily substance that is liquid at room temperature, and at least one gelling agent selected from saturated fatty acids having 16 or more carbon atoms and derivatives of the saturated fatty acids.
  • 3. The composition for wet indicator according to claim 1, wherein the oily substance that is liquid at room temperature is at least one selected from the group consisting of paraffin oil, naphthene oil and aromatic oils.
  • 4. The composition for wet indicator according to claim 1, wherein the wet-sensitive colorant composition is a composition comprising a leuco dye or a pH indicator, and an anionic surfactant or a nonionic surfactant.
  • 5. A wet indicator comprising the composition for wet indicator according to claim 1.
  • 6. An absorbent article comprising the wet indicator according to claim 5.
Priority Claims (1)
Number Date Country Kind
2020-129591 Jul 2020 JP national
CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation of International Application No. PCT/JP2021/026603, filed Jul. 15, 2021, which claims benefit of Japanese Patent Application No. 2020-129591 filed in Japan on Jul. 30, 2020, incorporated herein by reference in their entirety.

Continuations (1)
Number Date Country
Parent PCT/JP2021/026603 Jul 2021 WO
Child 18160431 US