CN111448277B - Adhesive composition - Google Patents
Adhesive composition Download PDFInfo
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- CN111448277B CN111448277B CN201880078665.0A CN201880078665A CN111448277B CN 111448277 B CN111448277 B CN 111448277B CN 201880078665 A CN201880078665 A CN 201880078665A CN 111448277 B CN111448277 B CN 111448277B
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- block copolymer
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F13/00—Bandages or dressings; Absorbent pads
- A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F13/00—Bandages or dressings; Absorbent pads
- A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
- A61F13/42—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators with wetness indicator or alarm
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
Abstract
The purpose of the present invention is to provide an adhesive composition having excellent discoloration properties, storage stability and compatibility. The adhesive composition contains an acrylic block copolymer, a surfactant, a coloring agent, and a pH adjuster.
Description
Technical Field
The present invention relates to an adhesive composition for indicating wetness.
Background
A pressure-sensitive adhesive composition containing a coloring agent or the like which changes color by changing pH can be used for disposable nonwoven fabric water-absorbent articles such as diaper pants. The adhesive composition reacts and changes color due to a change in pH when it is soaked in urine or water, and therefore is useful as an indicator for informing the presence of moisture. A binder composition obtained by adding a coloring agent or the like to a water-soluble polymer or a water-insoluble polymer is widely known as the binder composition.
For example, patent document 1 discloses an adhesive composition blend containing a water-sensitive polymer such as a vinylpyrrolidone/vinyl acetate copolymer.
In patent document 2, a hot-melt type wetness indicating adhesive composition is disclosed, which contains a water-soluble polymer or a water-insoluble polymer, and the water-insoluble polymer is Ethylene Vinyl Acetate (EVA), a styrene-isoprene-styrene (SIS) block copolymer, a styrene-butadiene-styrene (SBS) block copolymer, a styrene-ethylene-butylene-styrene (SEBS) block copolymer, a styrene-ethylene/ethylene-propylene-styrene (SEEPS) block copolymer, high density polyethylene, low density polyethylene, chemically modified polyethylene, Amorphous Polyalphaolefin (APAO), ethylene/styrene interpolymer (ESI), APAO using a metallocene catalyst, or the like.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. Sho 64-31884 (published 2.2.1989);
patent document 2: japanese Kokai publication No. 2012-506915 (Japanese Kokai publication No. 3/22 (2012).
Disclosure of Invention
Problems to be solved by the invention
However, the adhesive composition containing a water-sensitive polymer disclosed in patent document 1 is considered to have insufficient storage stability because of its lack of water resistance, heat resistance and oil retention. Therefore, when the diaper using the adhesive composition is exposed to a high-temperature/high-humidity environment for a long period of time during transportation or storage, there is a possibility that the performance as an indicator may be impaired or the design of the diaper may be impaired due to bleeding of components.
Further, the binder composition containing a water-insoluble polymer disclosed in patent document 2 is considered to have poor compatibility with a surfactant for imparting hydrophilicity and an acidic material (such as fatty acid and rosin acid) for adjusting pH, because the water-insoluble polymer as a main component has low polarity. Therefore, the adhesive composition of patent document 2 may leak the active ingredient during storage, and the adhesive composition after application may not be uniform and thus may not sufficiently exhibit the performance.
An object of the present invention is to realize an adhesive composition that can exhibit long-term stability even under high-temperature/high-humidity environments, can withstand changes over time due to severe environments accompanying import and export, and long-term storage periods, and is excellent in quality maintenance.
Means for solving the problems
The present inventors have intensively studied the components constituting the adhesive composition in order to solve the above problems, and have found that the above problems can be solved by adding an acrylic block copolymer (acrylic block copolymer), a surfactant, a coloring agent and a pH adjuster to the adhesive composition, and have completed the present invention. That is, the present invention includes the following configurations.
[ 1] an adhesive composition for indicating humidity, characterized by containing an acrylic block copolymer, a surfactant, a coloring agent, and a pH adjuster.
[ 2] the adhesive composition according to [ 1], which is characterized in that,
the backbone of the acrylic block copolymer has:
a polymer block having a glass transition temperature higher than 40 ℃; and
a polymer block having a glass transition temperature lower than 20 ℃.
[ 3] the adhesive composition according to [ 2],
the backbone of the acrylic block copolymer has:
structures represented by [ A1] - [ B ] - [ A2] or [ A ] - [ B ],
the [ A1], [ A2] and [ A ] are polymer blocks having a glass transition temperature higher than 40 ℃,
the [ B ] is a polymer block having a glass transition temperature lower than 20 ℃.
[ 4 ] the adhesive composition according to [ 3], which is characterized in that,
the [ A1], [ A2] and [ A ] are polymer blocks derived from methyl methacrylate,
and [ B ] is a polymer block derived from an alkyl (meth) acrylate having an alkyl group with 2 to 12 carbon atoms.
[ 5 ] the adhesive composition according to any one of [ 1] to [ 4 ], which is characterized in that,
the acrylic block copolymer is contained in an amount of 5 to 75 wt% based on 100 wt% of the adhesive composition.
[ 6 ] the adhesive composition according to any one of [ 1] to [ 5 ], wherein,
the HLB value of the surfactant is 3-20.
[ 7 ] the adhesive composition according to any one of [ 1] to [ 6 ], wherein,
the proportion of the surfactant is 3 to 30 wt% with respect to 100 wt% of the adhesive composition.
[ 8 ] the adhesive composition according to any one of [ 1] to [ 7 ], wherein,
the color developing reagent has a color changing region at a pH of 3-8.
[ 9 ] the adhesive composition according to any one of [ 1] to [ 8 ],
the color reagent is at least one selected from the group consisting of methyl red, bromophenol blue, bromocresol green, bromocresol purple, methyl yellow, congo red, methyl orange, litmus, bromothymol blue, Cochineal pigment and anthocyanin pigment.
[ 10 ] the adhesive composition according to any one of [ 1] to [ 9 ], wherein,
the ratio of the coloring agent is 0.01 wt% or more with respect to 100 wt% of the binder composition.
[ 11 ] the adhesive composition according to any one of [ 1] to [ 10 ], wherein,
the pH regulator is an acidic material.
[ 12 ] an absorbent article in which,
at least a part of which is coated with the adhesive composition according to any one of [ 1] to [ 11 ].
Effects of the invention
According to an aspect of the present invention, a pressure-sensitive adhesive composition having excellent discoloration properties, storage stability, and compatibility can be provided.
Drawings
FIG. 1 is a schematic view showing the configuration of a hue change test apparatus for an adhesive composition according to an example of the present invention.
Detailed Description
An embodiment of the present invention will be described below, but the present invention is not limited thereto. The present invention is not limited to the configurations described below, and various modifications are possible within the scope shown in the patent claims, and embodiments or examples obtained by appropriately combining the respective technical means disclosed in different embodiments or examples are also included in the technical scope of the present invention. The academic documents and patent documents described in the present specification are incorporated herein by reference in their entirety.
In addition, "a to B" indicating a range of values in the present specification means "a or more and B or less" unless otherwise specified. In addition, "mass" and "weight" are considered synonyms. In addition, the expression "(meth) acrylic acid" is used when any of "acrylic acid" and "methacrylic acid" is used, and the expression "(meth) acrylate" is used when any of "acrylate" and "methacrylate" is used.
[ 1. adhesive composition ]
The pressure-sensitive adhesive composition according to an embodiment of the present invention is a pressure-sensitive adhesive composition for indicating humidity, and includes a composition containing (a) an acrylic block copolymer, (b) a surfactant, (c) a coloring agent, and (d) a pH adjuster. Thus, the adhesive composition is excellent in discoloration, storage stability and compatibility. Specifically, the acrylic block copolymer is contained, so that the adhesive composition has excellent compatibility with other additives such as a surfactant, a coloring agent, and a pH adjuster, and is less likely to be separated during melting. This is because the acrylic block copolymer has high polarity. Further, the adhesive composition exhibits storage stability by containing the acrylic block copolymer. This is because the acrylic block copolymer can increase the cohesive force of the entire adhesive composition, so that the adhesive composition can have shape stability and is excellent in water resistance, heat resistance and oil retention. By containing the surfactant, the adhesive composition is rendered hydrophilic and can respond to the presence of moisture. The adhesive composition has color change properties by containing the color developing agent. By containing the pH adjuster, the difference in color change between before and after the reaction with moisture in the adhesive composition becomes larger. In the present specification, the term "humidity-indicating adhesive composition" refers to an adhesive composition that changes color in response to the presence of moisture.
The adhesive composition preferably has a viscosity of 150,000 mPas or less at 180 ℃ or less, more preferably 120 ℃ or less, further preferably 100 ℃ or less, more preferably 30,000 mPas or less, further preferably 5,000 mPas or less. With this configuration, the adhesive composition can be directly applied to a material having low heat resistance, such as a polyethylene film, which is a constituent material of a diaper. That is, the adhesive composition exhibits excellent coatability.
Preferably, the adhesive composition is in a state that a solution is not separated at 180 ℃ and precipitates and insoluble components (sludge) are not generated. With this configuration, the yield can be improved without causing variation in quality.
< 1-1. acrylic block copolymer >
In the present specification, "acrylic block copolymer" means a polymer having at least one block structure containing an alkyl (meth) acrylate monomer. That is, the acrylic block copolymer may be an acrylic block copolymer having one block structure, or an acrylic block copolymer having a diblock structure, a triblock structure, or a multiblock structure of four or more. The acrylic block copolymer may be used alone or in combination of two or more. Hereinafter, the "block structure of the alkyl (meth) acrylate-containing monomer" is also referred to as a "polymer block derived from an alkyl (meth) acrylate". Preferably, the alkyl (meth) acrylate monomer is an alkyl (meth) acrylate monomer having an alkyl group with 1 to 12 carbon atoms. The acrylic block copolymer may have two or more acrylic polymer blocks, and may contain a polymer block other than the acrylic polymer block, but is preferably composed of only the acrylic polymer block.
Preferably, the backbone of the acrylic block copolymer has: a polymer block having a glass transition temperature higher than 40 ℃; and a polymer block having a glass transition temperature lower than 20 ℃. According to this configuration, the adhesive composition has a low viscosity at low temperatures (e.g., 100 to 120 ℃), and therefore has excellent coatability. In the present specification, a polymer block having a glass transition temperature higher than 40 ℃ is referred to as a "hard block", and a polymer block having a glass transition temperature lower than 20 ℃ is referred to as a "soft block". The hard block more preferably has a glass transition temperature of 100 to 120 ℃. The soft block more preferably has a glass transition temperature of-80 to-40 ℃.
The proportion of the hard block is preferably 7 to 50 wt%, the proportion of the soft block is preferably 50 to 93 wt%, more preferably 15 to 35 wt%, and the proportion of the soft block is preferably 65 to 85 wt%, based on the total amount of the acrylic block copolymer. When the proportion of the hard block is 7% by weight or more, the adhesive composition is less likely to cause stains or exudation even under a high temperature (50 ℃)/high humidity (60% RH) environment, and therefore exhibits more excellent storage stability. Further, by setting the proportion of the hard block to 50% by weight or less, it is possible to realize an adhesive composition having also excellent coatability.
The molecular weight of the acrylic block copolymer is preferably 10,000 to 400,000, more preferably 40,000 to 200,000, and still more preferably 40,000 to 120,000. By making the molecular weight 10,000 or more, the adhesive composition will exhibit such excellent storage stability that stains and oozes are not generated even under a high temperature (50 ℃)/high humidity (60% RH) environment. By making the molecular weight 400,000 or less, the adhesive composition will also have excellent coatability.
The main chain of the acrylic block copolymer preferably has a structure represented by [ A1] - [ B ] - [ A2] or [ A ] - [ B ], more preferably has a structure represented by [ A1] - [ B ] - [ A2 ]. Here, the [ A1], [ A2] and [ A ] are polymer blocks having a glass transition temperature higher than 40 ℃ (hard blocks), and the [ B ] is a polymer block having a glass transition temperature lower than 20 ℃ (soft blocks). Since the acrylic block copolymer is water-insoluble and has a diblock structure or a triblock structure, the adhesive composition is excellent in water resistance, heat resistance, and oil retention, and also excellent in storage stability under a high-temperature (50 ℃) and high-humidity (60% RH) environment. Further, [ A1] and [ A2] may be the same polymer block or different polymer blocks as long as they have a glass transition temperature within the above range. The acrylic block copolymer may contain a polyfunctional coupling agent such as a silane coupling agent as long as it has the above structure, but it is preferable that the acrylic block copolymer is linear.
The polymer blocks [ A1], [ A2] and [ A ] are not particularly limited as long as they have a glass transition temperature within the above range, and include, for example, polymer blocks derived from methyl methacrylate, ethyl methacrylate, acrylonitrile, acrylamide, acrylic acid, and combinations thereof. The above-mentioned [ A1], [ A2] and [ A ] are hard blocks having a high glass transition temperature, and therefore, polymer blocks derived from methyl methacrylate are preferable.
The [ B ] is not particularly limited as long as it is a polymer block having a glass transition temperature within the above range, and is preferably a polymer block derived from an alkyl (meth) acrylate in which the alkyl group has 2 to 12 carbon atoms. Examples of the polymer block derived from an alkyl (meth) acrylate include polymer blocks derived from ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, pentyl acrylate, isopentyl acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl acrylate, lauryl acrylate, isooctyl acrylate, decylmethyl acrylate, cyclohexyl acrylate, nonyl acrylate, n-octyl (meth) acrylate, n-decyl methacrylate, n-dodecyl methacrylate, n-tetradecyl methacrylate, isobornyl methacrylate, and combinations thereof. Since [ B ] is a soft block having a low glass transition temperature, a polymer block derived from n-butyl acrylate, 2-ethylhexyl acrylate, or a combination thereof is preferable.
The same alkyl (meth) acrylate monomer may be contained in both the hard block and the soft block. The acrylic block copolymer may contain one or more other monomers other than the monomers constituting the hard block and the soft block, as long as the hard block and the soft block do not interfere with complete phase separation between the hard block and the soft block during cooling. Examples of the other monomer include a vinyl monomer. In the present specification, the vinyl monomer may further include (meth) acrylic acid esters, vinyl ethers, styrene monomers, and (meth) acrylamides. The other monomers are preferably methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate.
The glass transition temperature (Tg) of the polymer block derived from an alkyl (meth) acrylate is a value obtained from the FOX formula based on the glass transition temperature of each monomer homopolymer constituting the polymer block derived from an alkyl (meth) acrylate and the content ratio (weight fraction) of the monomer. The glass transition temperature of the homopolymer can be, for example, the glass transition point described in "handbook of adhesion technology" of journal industries, news.
Preferably, the acrylic block copolymer has an MFR value, measured according to ISO1133, of from 0g/10min to 150g/10min, more preferably from 1g/10min to 100g/10min, at 190 ℃ under a load of 2.16 kg. By setting the MFR value of the acrylic block copolymer at 190 ℃ under 2.16kg to 0g/10min to 150g/10min, the acrylic block copolymer does not cause stains or bleeding even under a high temperature (50 ℃)/high humidity (60% RH) environment, and exhibits excellent storage stability.
The proportion of the acrylic block copolymer is preferably 5 to 75% by weight, more preferably 10 to 40% by weight, based on 100% by weight of the adhesive composition. By setting the proportion of the acrylic block copolymer to 5% by weight or more, the adhesive composition can exhibit excellent storage stability without causing stains or bleeding even in a high temperature (50 ℃) and high humidity (60% RH) environment. By setting the proportion of the acrylic block copolymer to 75% by weight or less, the adhesive composition will also have excellent coatability.
< 1-2. surfactant >
The HLB value of the surfactant is preferably 3-20, and more preferably 5-19. With this configuration, a pressure-sensitive adhesive composition having more excellent compatibility can be provided. In the present specification, the HLB value is a value calculated by the following Griffin (Griffin) formula.
[ mathematical formula 1]
Examples of the surfactant include nonionic surfactants, ionic surfactants, and amphoteric surfactants.
Examples of the nonionic surfactant include ester type, ether type, ester ether type, alkanolamide type, and fluorine type. Examples of the ester type include glycerin fatty acid esters, sorbitan fatty acid esters, and sucrose fatty acid esters. Examples of the ether type include a polycondensate of a polydimethylsiloxane group and an alkylene oxide adduct, a polysiloxane-polyoxyalkylene copolymer, a polyoxyethylene lauryl ether, a polyoxyethylene alkylphenyl ether, a polyoxyethylene alkyl ether, and a polyoxyethylene polyoxypropylene block polymer. Examples of the ester ether type include polyethylene glycol fatty acid esters and polyoxyethylene sorbitan fatty acid esters. Examples of the alkanolamide type include aliphatic alkanolamides. Examples of the fluorine type include perfluorodecanoic acid-diglyceride and a perfluoroalkoxyalkylene (パーフルオロアルキルアルキレンオキサイド) compound.
Examples of the ionic surfactant include anionic surfactants and cationic surfactants.
Examples of the anionic surfactant include hydrocarbon anionic surfactants, fluorine anionic surfactants, and silicone anionic surfactants having an anionic group. Examples of the hydrocarbon-based anionic surfactant include carboxylic acid type, sulfonic acid type, sulfate type, phosphate type, and borate type surfactants. Examples of the carboxylic acid type include aliphatic monocarboxylic acid salts, and N-acylglutamate (N- アシロイルグルタミン acid salt). Examples of the sulfonic acid type include alkylbenzenesulfonates, naphthalenesulfonate-formaldehyde condensates, and dialkyl sulfosuccinates. Examples of the sulfate type include alkyl sulfate salts and alkyl polyoxyethylene sulfate salts. Examples of the phosphate ester type include alkyl phosphate salts. Examples of the borate type include an alkyl borate and the like. Examples of the fluorine-based anionic surfactant include sodium perfluorodecanoate and sodium perfluorooctyl sulfonate. Examples of the silicone anionic surfactant having the anionic group include polymers having a polydimethylsiloxane group and a carboxylic acid metal salt.
Examples of the cationic surfactant include amine salt type and quaternary ammonium salt type. Examples of the amine salt type include alkylamine salts. Examples of the quaternary ammonium salt type include alkyltrimethylammonium salts, dialkyldimethylammonium salts, and alkyldimethylbenzylammonium salts.
Examples of the amphoteric surfactant include betaine type and imidazoline type. Examples of the betaine type include dimethyl stearyl betaine, dimethyl lauryl betaine, and dihydroxy lauryl betaine. Examples of the imidazoline type include disodium N-lauryl-p-iminodipropionate.
The proportion of the surfactant is preferably 3 to 30% by weight, more preferably 5 to 15% by weight, based on 100% by weight of the adhesive composition. By setting the proportion of the surfactant to 3% by weight or more, the color-changing agent has excellent color-changing properties, in which a significant color change due to moisture can be observed. When the proportion of the surfactant is 30% by weight or less, the adhesive composition exhibits excellent storage stability without causing stains or bleeding even in a high-temperature (50 ℃) and high-humidity (60% RH) environment.
< 1-3. color developing reagent >
In the present specification, the color-developing reagent refers to a chemical agent that changes color with chemical changes, such as a pH indicator that is an indicator that changes color by reacting with a change in pH. The color-developing reagent preferably has a color-changing region at a pH of 3 to 8, and more preferably has a color-changing region at a pH of 3 to 7. With this configuration, when the adhesive composition is acidic, a color change from acidic to neutral is caused upon reaction with moisture. Specifically, the color reagent is preferably a pH indicator, and the pH indicator is preferably at least one selected from the group consisting of methyl red, bromophenol blue, bromocresol green, bromocresol purple, methyl yellow, congo red, methyl orange, litmus, bromothymol blue, cochineal red pigment, and anthocyanin pigment.
The proportion of the coloring agent is preferably 0.01% by weight or more, and more preferably 0.1% by weight or more, based on 100% by weight of the binder composition. According to this configuration, the color change of the color developing reagent can be visually confirmed. The upper limit of the content of the coloring agent is not particularly limited, and is preferably 3% by weight or less based on 100% by weight of the pressure-sensitive adhesive composition, from the viewpoints of maintenance of other properties such as thermal stability, odor property, compatibility, and adhesiveness, and cost.
< 1-4.pH regulator
The pH regulator is preferably an acidic material. The acidic material is not particularly limited as long as the pH of the binder composition can be made smaller than 7, and the acid dissociation constant (pKa) thereof is preferably 2 to 6, and more preferably a material having an acidic group such as a carboxyl group, a phosphate group, a phosphite group, a sulfonate group, or a phenolic hydroxyl group in the molecule. According to this configuration, the pH of the adhesive composition is acidic, and when the adhesive composition reacts with moisture, the pH approaches neutral, and the difference in pH between before and after the reaction with moisture becomes large, so that the color change due to the reaction with moisture becomes large. Examples of the acidic material include fatty acids, hydroxy acids, aromatic carboxylic acids, dicarboxylic acids, tricarboxylic acids, abietic acids, maleic acids, phthalic acids, and malic acids. Examples of the fatty acid include stearic acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, 12-hydroxystearic acid, isostearic acid, undecylenic acid, Tall acid (Tall acids), eicosapentaenoic acid, and docosahexaenoic acid. The pH adjuster may be a material that also functions as a thickener, a softener, and other additives.
The proportion of the pH adjuster is not particularly limited as long as the pH of the binder composition can be adjusted to a desired pH, and is preferably 3 to 90% by weight based on 100% by weight of the binder composition.
< 1-5. other additives >
The pressure-sensitive adhesive composition may further contain additives other than the above components as necessary within a range not impairing the discoloration property, storage stability, compatibility, coatability and the like. Examples of the additive include a thickener, a softener, a stabilizer, a filler, a fluorescent agent, an antioxidant, an ultraviolet absorber, a colorant, and the like.
The tackifier may be a natural one, a petroleum one, or a combination thereof, and examples thereof include rosin acid, rosin ester, hydrocarbon resin, synthetic polyterpene (polyterpene resin) resin, natural terpene resin, and a combination thereof.
Examples of the tackifier include rosin and modified rosin derivatives such as rosin alcohol, methyl ester rosin, diethylene glycol ester rosin, glycerol ester rosin and partially hydrogenated rosin, fully hydrogenated rosin or polymerized rosin, pentaerythritol ester and partially hydrogenated rosin, fully hydrogenated rosin or polymerized rosin; natural resins commercially available under trade names of gum rosin, wood rosin, tall oil rosin, and the like; modified rosins such as polymerized rosin and partially hydrogenated rosin; polyterpene resins such as polymers of α -pinene, polymers of β -pinene, and dipentene polymers; terpene-modified products such as terpene-phenol copolymer and α -pinene-phenol copolymer; an aliphatic petroleum resin; alicyclic petroleum resins; a cyclopentadiene resin; aromatic petroleum resin; a phenolic resin; an alkylphenol-acetylene-based resin; a styrene resin; a xylene-based resin; a coumarone-indene resin; copolymers of vinyl toluene with alpha-methyl styrene, and the like. In the case where the tackifier has an acidic functional group, a function as a pH adjuster will also be obtained.
The proportion of the tackifier is not particularly limited, and is preferably 90% by weight or less based on 100% by weight of the adhesive composition.
The softening agent has a melting point of 100 ℃ or lower, and a softening point of preferably 90 ℃ or lower, more preferably 80 ℃ or lower, even more preferably 70 ℃ or lower, and most preferably 60 ℃ or lower. With this configuration, the adhesive composition can be directly applied to a material having low heat resistance, such as a polyethylene film, which is a constituent material of a diaper, and thus exhibits excellent coatability. Preferably, the softening agent has good compatibility with the acrylic block copolymer and high polarity. Examples of the softener include fatty acids and derivatives thereof, waxes, oils, and the like. As the fatty acid, for example, the above-mentioned fatty acid as the acidic material can be used. As the wax, for example, vegetable-derived waxes such as carnauba wax, candelilla wax, wood wax, rice wax, and beeswax can be suitably used. Examples of the oils include vegetable oils, animal oils, ester oils, alcohols, alkenyl succinic anhydrides, chlorinated paraffins, and derivatives thereof (including hardened oils). Examples of the vegetable oil include castor oil, hardened castor oil, and the like. Examples of the ester oil include palm aliphatic esters, phthalates, adipates, sebacates, and azelates. Examples of the alcohol include polyalkylene glycols such as polyethylene glycol and polypropylene glycol, and glyceryl diacetylmonolaurate. In the case where the softening agent is a fatty acid, since the functional group has a carboxyl group, a function as a pH adjuster will also be obtained.
Examples of the stabilizer include 1,3, 5-trimethyl 2,4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, pentaerythritol tetrakis-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis (3-laurylthiodipropionate), n-octadecyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 4 '-methylenebis (2, 6-tert-butylphenol), 4' -thiobis (6-tert-butyl-o-cresol), 2, 6-di-tert-butylphenol, 6- (4-hydroxyphenoxy) -2, 4-bis (n-octyl-thio) -1,3, 5-triazine, di-n-octadecyl-3, 5-di-tert-butyl-4-hydroxy-benzyl-phosphonate, 2- (n-octylthio) ethyl-3, 5-di-tert-butyl-4-hydroxy-benzoate, and sorbitol hexa [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) -propionate ], and the like.
Examples of the filler include talc, calcium carbonate, clay silica, mica, wollastonite, feldspar, aluminum silicate, alumina hydrate, glass microspheres, ceramic microspheres, thermoplastic microspheres, barite, and wood flour.
< 1-6. method for producing adhesive composition
The method for producing the adhesive composition is not particularly limited, and examples thereof include a method in which the above materials are kneaded and mixed by heating using a melting tank, a roll, a banbury mixer, a kneader, an extruder, or the like.
[ 2. absorbent article ]
The adhesive composition according to one embodiment of the present invention can be suitably used for water-absorbent articles because it changes color by reacting with moisture such as urine. Therefore, an absorbent article containing the adhesive composition according to one embodiment of the present invention is also included in the present invention. At least a part of the water-absorbent article according to one embodiment of the present invention is coated with a humidity-indicating adhesive composition containing an acrylic block copolymer, a surfactant, a coloring agent and a pH adjuster. The pressure-sensitive adhesive composition is not described in detail in connection with the description of [ 1. pressure-sensitive adhesive composition ].
At least a part of the water-absorbent article according to one embodiment of the present invention is coated with the adhesive composition. Therefore, the water-absorbent article is excellent in discoloration and storage stability. Specifically, the water-absorbent article exhibits storage stability by incorporating the acrylic block copolymer having excellent water resistance, heat resistance and oil retention into the adhesive composition. By making the adhesive composition contain the surfactant, the water-absorbent article will have hydrophilicity. Thus, since moisture can be rapidly diffused in the adhesive composition, the color-developing reagent can react to the presence of moisture. By allowing the adhesive composition to contain the coloring agent, the water-absorbent article will have color-changing properties. By incorporating the pH adjuster in the adhesive composition, the reaction between the water-absorbent article and a trace amount of moisture in the atmosphere is suppressed and the water-absorbent article reacts with a large amount of moisture such as urine, so that the difference in color change between before and after the reaction with moisture becomes larger.
Examples of the water-absorbent article include disposable nonwoven fabric water-absorbent articles. Examples of the disposable nonwoven fabric water-absorbent article include disposable diapers for children and adults, and pet diapers. The moisture of urine or the like changes the pH of the adhesive composition applied to a part of the water-absorbent article. The adhesive composition can be discolored to show the presence of moisture.
The disposable nonwoven fabric water-absorbent article is not particularly limited, and may be, for example, a laminate of a hydrophobic nonwoven fabric, a back sheet of polyethylene or the like, a tissue paper, an absorbent body, a paper towel, and a hydrophilic nonwoven fabric in this order. Preferably, the adhesive composition is coated on at least a portion of the backing sheet. Preferably, the adhesive composition is applied in an area where a color change can be visually confirmed. In the case of using the diaper for children or adults and the diaper for pets, it is preferable that the nonwoven fabric on the side directly contacting the skin is hydrophilic. With this configuration, the disposable nonwoven fabric water-absorbent article absorbs moisture such as urine without irritating the skin, and does not leak within a range not exceeding the absorption amount of the disposable nonwoven fabric water-absorbent article.
As the pH adjuster, a substance that does not irritate the skin is preferably selected as appropriate.
The method for applying the adhesive composition to the disposable nonwoven fabric water-absorbent article is not particularly limited, and a general method for applying a hot-melt adhesive can be used. For example, die coating, spray coating, bead coating, roll coating, flexographic printing and the like can be cited.
The present invention is not limited to the above embodiments, and various modifications can be made within the scope of the claims, and embodiments obtained by appropriately combining the respective technical means disclosed in the different embodiments are also included in the technical scope of the present invention.
Examples
The present invention will be described in further detail below with reference to examples. The present invention is not limited to the following examples.
[ example 1]
A triblock copolymer (hereinafter referred to as PMMA-PnBA-PMMA) (Clarity LA2140(クラリティ LA2140) made by Korea Kabushiki Kaisha クラレ, MFR (190 ℃, 2.16 kg): 31g/10min), 8 wt% of polyoxyethylene lauryl ether (DKS NL-80 made by Korea Kaisha, HLB: 12.9), 0.15 wt% of bromocresol green (Wako pure chemical industries, Ltd., color change range: pH3.8 to 5.4), 7 wt% of stearic acid (stearic acid 48 made by Kaisha (ミヨシ oil Kaisha, acid value: 207mg KOH/g), and 14 wt% of rosin acid (Chinese rosin X, Kaisha chemical industries, Ltd., acid value: 168mg KOH/g) were prepared, A cured castor oil (hydrogenated castor oil, available from Ito oil Co., Ltd.) in an amount of 25 wt% and a rosin ester (super ester A-75, available from Mitsuga chemical Co., Ltd.) in an amount of 25.85 wt% were mixed in a heated mixer at 180 ℃ to prepare a 100 wt% adhesive composition.
[ example 2]
An adhesive composition was prepared in the same manner as in example 1 except that PMMA-PnBA-PMMA (Clarity LA4285, manufactured by Korea, Ltd., MFR (190 ℃, 2.16 kg): 1.5g/10min) was used instead of PMMA-PnBA-PMMA (MFR (190 ℃, 2.16 kg): 31g/10 min).
[ example 3]
An adhesive composition was prepared in the same manner as in example 1 except that the amount of PMMA-PnBA-PMMA was 70.85 wt% and no castor bean hardened oil or rosin ester was added.
[ example 4 ]
An adhesive composition was prepared in the same manner as in example 1 except that 5% by weight of PMMA-PnBA-PMMA and 40.85% by weight of rosin ester were used.
[ example 5 ]
A pressure-sensitive adhesive composition was prepared in the same manner as in example 1 except that 30 wt% of PMMA-PnBA-PMMA was used, 40.85 wt% of a diblock copolymer of PnBA and PMMA (hereinafter referred to as PnBA-PMMA) (Clarity LA1114, manufactured by Korea, viscosity (160 ℃ C.): 5,000mPa · s) was further added, and no castor bean hardened oil or rosin ester was added.
[ example 6 ]
A pressure-sensitive adhesive composition was prepared in the same manner as in example 1, except that the polyoxyethylene lauryl ether was used in an amount of 3 wt% and the rosin ester was used in an amount of 30.85 wt%.
[ example 7 ]
A pressure-sensitive adhesive composition was prepared in the same manner as in example 1, except that 30 wt% of polyoxyethylene lauryl ether was used and 3.85 wt% of rosin ester was used.
[ example 8 ]
An adhesive composition was prepared in the same manner as in example 1 except that PnBA-PMMA (MFR (190 ℃, 2.16 kg): 11.4g/10min) was used instead of PMMA-PnBA-PMMA.
[ example 9 ]
An adhesive composition was prepared in the same manner as in example 1 except that a triblock copolymer of PMMA (hereinafter referred to as PMMA-P (2EHA-co-nBA)) (hereinafter referred to as PMMA-P (2EHA-co-nBA) -PMMA) (MFR (190 ℃, 2.16 kg): 3.8g/10min) and a polymer block (P (2EHA-co-nBA) obtained by randomly copolymerizing 2-ethylhexyl acrylate (2EHA) and n-butyl acrylate (nBA) were used instead of PMMA-PnBA-PMMA.
[ example 10 ]
A pressure-sensitive adhesive composition was prepared in the same manner as in example 1 except that polyoxyethylene lauryl ether (DKS NL-15, manufactured by first Industrial pharmaceutical Co., Ltd., HLB value: 5.1) was used in place of polyoxyethylene lauryl ether (HLB value: 12.9).
[ example 11 ]
An adhesive composition was prepared in the same manner as in example 1 except that polyoxyethylene lauryl ether (DKS NL-600F, first Industrial pharmaceutical Co., Ltd., HLB value: 18.6) was used instead of polyoxyethylene lauryl ether (HLB value: 12.9).
[ example 12 ]
A pressure-sensitive adhesive composition was prepared in the same manner as in example 1 except that bromophenol blue (manufactured by Wako pure chemical industries, Ltd., color change range: pH 3.0 to 4.6) was used instead of bromocresol green.
[ example 13 ]
A pressure-sensitive adhesive composition was prepared in the same manner as in example 1 except that methyl red (manufactured by Wako pure chemical industries, Ltd., discoloration range: pH 4.4 to 6.2) was used instead of bromocresol green.
[ comparative example 1]
An adhesive composition was prepared in the same manner as in example 1 except that polyethylene glycol (PEG) (PEG20000, manufactured by seitan chemical co., ltd. キシダ) was used instead of PMMA-PnBA-PMMA.
[ comparative example 2]
An adhesive composition was prepared in the same manner as in example 1 except that a triblock copolymer (SBS) of styrene and butadiene (Asaprene T-420(アサプレン T-420), manufactured by Asahi chemical Co., Ltd., styrene: 30 wt%, MFR (190 ℃ C., 2.16 kg): 1.1g/10min) was used instead of PMMA-PnBA-PMMA.
[ comparative example 3]
An adhesive composition was prepared in the same manner as in example 1 except that PnBA (Alfon UP1000(アルフォン UP1000, manufactured by Toyo chemical Co., Ltd.) was used instead of PMMA-PnBA-PMMA.
[ comparative example 4 ]
An adhesive composition was prepared in the same manner as in example 1 except that a random copolymer (EMMA) of ethylene and methyl methacrylate (Acryft CM5022(アクリフト CM5022), manufactured by Sumitomo chemical Co., Ltd., MFR (190 ℃ C., 2.16 kg): 450g/10min) was used instead of PMMA-PnBA-PMMA.
[ comparative example 5 ]
A pressure-sensitive adhesive composition was prepared in the same manner as in example 1, except that the rosin ester was changed to 33.85% by weight and the polyoxyethylene lauryl ether was not added.
[ comparative example 6 ]
A pressure-sensitive adhesive composition was prepared in the same manner as in example 1, except that the rosin ester was used in an amount of 26 wt% and bromocresol green was not added.
The compositions of the adhesive compositions prepared in examples 1 to 13 and comparative examples 1 to 6 are shown in tables 1 and 2.
[ test method ]
< 1. color Change >
FIG. 1 is a sectional view showing the configuration of a hue change test apparatus for evaluating the discoloration of an adhesive composition. As shown in FIG. 1, a glass plate, a Polyethylene (PE) film having a thickness of 20 μm, a binder composition having a thickness of 20 to 30 μm, and a cotton puff (コットンパフ) (manufactured by Cotton laboratory Co., Ltd.) were arranged in this order from the bottom. 200. mu.L of pure water was dropped onto the cotton puff, and after 1 minute and 2 minutes, the color change of the adhesive composition that had passed through the glass plate and the PE film was visually observed, and evaluated according to the following criteria.
Very good: after 1 minute, the color of the adhesive composition as a whole was changed to a state of a different color from the original color.
O: after 2 minutes, the color of the adhesive composition as a whole was changed to a state of a different color from the original color.
X: after 2 minutes, the color of the adhesive composition was relatively unchanged from the original color.
< 2. storage stability >
The evaluation of < 1. color change > was carried out by using a device used for the evaluation, leaving it at a temperature of 50 ℃ and a humidity of 60 RH%, and observing the state of the solution after 24 hours, and then evaluating the solution according to the following criteria.
Very good: even after 24 hours, the temperature was raised to 60 ℃, and there was no transfer of the binder composition components to the cotton dust-treated surface, no oil stain of the PE film, and no stain of the binder composition components penetrating the PE film.
O: no binder composition component transferred to the cotton dust face, no oil stain of the PE film, and no stain of the binder composition component passed through the PE film.
X: there is at least a state where the binder composition component is transferred to one of the cotton powder puff surface, the oil stain of the PE film, and the binder composition component passing through the PE film.
< 3. compatibility >
A100 mL beaker was charged with 50g of the binder composition, heated to 180 ℃ and allowed to stand in a constant temperature bath. After 2 hours, the molten state of the adhesive composition was visually confirmed, and evaluated according to the following criteria.
O: the separation of the dissolved solution, and the state of the precipitate and sludge did not occur.
X: at least one of the separation of the dissolved solution, the precipitate and the sludge occurs.
[ results ]
The test results of the samples prepared in examples 1 to 13 and comparative examples 1 to 6 are shown in table 3 below.
[ Table 3]
TABLE 3
From the above results, it was confirmed that the adhesive compositions of the examples are excellent in discoloration property, storage stability and compatibility. It was confirmed that the adhesive compositions of examples 3 and 5 have higher oil retention due to a higher proportion of the acrylic block copolymer and are therefore more excellent in storage stability than other adhesive compositions. In addition, it was confirmed that the adhesive compositions of examples 2 and 9 are more excellent in storage stability than the adhesive compositions of other examples because the MFR value of the acrylic block copolymer is small. It was confirmed that the adhesive composition of example 7 is more excellent in discoloration than other adhesive compositions because of a high proportion of surfactant and high hydrophilicity.
The binder compositions of comparative examples 5 and 6 showed no discoloration after dropping for 2 minutes. It was confirmed that the adhesive compositions of comparative examples 1 to 4 were in a state of bleeding and staining to the PE film after 24 hours had elapsed. The separation of the dissolved solution of the adhesive composition of comparative example 2 was confirmed. In particular, in comparative example 4, it is considered that the storage stability is poor because a random copolymer having a large MFR value is used.
Industrial applicability
The present invention can be suitably used for disposable nonwoven absorbent articles such as diapers for children or adults, and pet diapers.
Claims (12)
1. An adhesive composition, which is an adhesive composition indicating humidity, characterized in that,
contains acrylic block copolymer, surfactant, color reagent and pH regulator.
2. The adhesive composition of claim 1,
the backbone of the acrylic block copolymer has:
a polymer block having a glass transition temperature higher than 40 ℃; and
a polymer block having a glass transition temperature lower than 20 ℃.
3. The adhesive composition of claim 2,
the backbone of the acrylic block copolymer has:
structures represented by [ A1] - [ B ] - [ A2] or [ A ] - [ B ],
the [ A1], [ A2] and [ A ] are polymer blocks having a glass transition temperature higher than 40 ℃,
the [ B ] is a polymer block having a glass transition temperature lower than 20 ℃.
4. The adhesive composition of claim 3,
the [ A1], [ A2] and [ A ] are polymer blocks derived from methyl methacrylate,
and [ B ] is a polymer block derived from an alkyl (meth) acrylate having an alkyl group with 2 to 12 carbon atoms.
5. The adhesive composition according to any one of claims 1 to 4,
the acrylic block copolymer is contained in an amount of 5 to 75 wt% based on 100 wt% of the adhesive composition.
6. The adhesive composition according to any one of claims 1 to 4,
the HLB value of the surfactant is 3-20.
7. The adhesive composition according to any one of claims 1 to 4,
the proportion of the surfactant is 3 to 30 wt% with respect to 100 wt% of the adhesive composition.
8. The adhesive composition according to any one of claims 1 to 4,
the color developing reagent has a color changing region at a pH of 3-8.
9. The adhesive composition according to any one of claims 1 to 4,
the color reagent is at least one selected from the group consisting of methyl red, bromophenol blue, bromocresol green, bromocresol purple, methyl yellow, congo red, methyl orange, litmus, bromothymol blue, cochineal red pigment and anthocyanin pigment.
10. The adhesive composition according to any one of claims 1 to 4,
the ratio of the coloring agent is 0.01 wt% or more with respect to 100 wt% of the binder composition.
11. The adhesive composition according to any one of claims 1 to 4,
the pH regulator is an acidic material.
12. An absorbent article in which, in a state in which,
at least a portion of which is coated with the adhesive composition of any one of claims 1 to 11.
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| JP2017-236520 | 2017-12-08 | ||
| JP2017236520 | 2017-12-08 | ||
| PCT/JP2018/040980 WO2019111611A1 (en) | 2017-12-08 | 2018-11-05 | Adhesive composition |
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| JP (1) | JP6721801B2 (en) |
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| CN115812093B (en) * | 2020-07-07 | 2023-10-27 | 株式会社Moresco | Adhesive composition and use thereof |
| JP2022086857A (en) * | 2020-11-30 | 2022-06-09 | 日東電工株式会社 | Variable color pressure sensitive adhesive sheet |
| WO2022113777A1 (en) * | 2020-11-30 | 2022-06-02 | 日東電工株式会社 | Variable color adhesive sheet |
| JP2022170596A (en) * | 2021-04-28 | 2022-11-10 | 日東電工株式会社 | Color-changeable adhesive sheet |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6431884A (en) * | 1987-07-06 | 1989-02-02 | Koron Haaman | Hot melt adhesive presparation having humidity degree indicating property |
| JP2008291130A (en) * | 2007-05-25 | 2008-12-04 | Kaneka Corp | Anionic aqueous dispersion of acrylic block copolymer and method for producing the same |
| JP2012506915A (en) * | 2008-07-03 | 2012-03-22 | ボスティック インコーポレイテッド | Hot-melt wettability indicating adhesive composition containing an ultraviolet fluorescent agent |
| JP2013530287A (en) * | 2010-06-30 | 2013-07-25 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン | Block copolymer in adhesive dispersion |
| JP2016539212A (en) * | 2013-11-26 | 2016-12-15 | エルジー・ケム・リミテッド | Adhesive composition |
| CN106573084A (en) * | 2014-08-07 | 2017-04-19 | 宝洁公司 | Wetness indicator with permanent colorant |
-
2018
- 2018-11-05 WO PCT/JP2018/040980 patent/WO2019111611A1/en active Application Filing
- 2018-11-05 JP JP2019558080A patent/JP6721801B2/en active Active
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6431884A (en) * | 1987-07-06 | 1989-02-02 | Koron Haaman | Hot melt adhesive presparation having humidity degree indicating property |
| JP2008291130A (en) * | 2007-05-25 | 2008-12-04 | Kaneka Corp | Anionic aqueous dispersion of acrylic block copolymer and method for producing the same |
| JP2012506915A (en) * | 2008-07-03 | 2012-03-22 | ボスティック インコーポレイテッド | Hot-melt wettability indicating adhesive composition containing an ultraviolet fluorescent agent |
| JP2013530287A (en) * | 2010-06-30 | 2013-07-25 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン | Block copolymer in adhesive dispersion |
| JP2016539212A (en) * | 2013-11-26 | 2016-12-15 | エルジー・ケム・リミテッド | Adhesive composition |
| CN106573084A (en) * | 2014-08-07 | 2017-04-19 | 宝洁公司 | Wetness indicator with permanent colorant |
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| CN111448277A (en) | 2020-07-24 |
| JP6721801B2 (en) | 2020-07-15 |
| JPWO2019111611A1 (en) | 2020-07-27 |
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