Cleaning label and method for manufacturing the same

Abstract

To provide a label for cleaning, having sticking suitability for temporary fixing by pressure-sensitive adhesion to an adherend such as clothing, capable of being heat-sensitively adhered to the adherend after being temporarily fixed, and having excellent dry-cleaning resistance of hardly coming off even through dry-cleaning.SOLUTION: A label 1 for cleaning comprises a substrate 10, a heat-sensitive adhesive layer 20 laminated on one surface of the substrate 10, and an adhesive layer 30 laminated on a surface of the heat-sensitive adhesive layer 20, opposite to the surface laminated with the substrate 10. The adhesive layer 30 is formed by using an adhesive composition which contains a polymer component (A), a tackifier resin and a cross-linking agent, and the cross-linking agent form a bridge structure with the tackifier resin.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a cleaning label and a method for manufacturing the cleaning label. [Background technology]

[0002] Various tags are used to display information about clothing and the like. 2. Description of the Related Art Dry cleaning shops attach cleaning tags to collected clothing and the like for the purpose of identifying and classifying the clothing and the like. In addition, clothing and the like are affixed with quality tags that contain information such as care instructions, washing symbols, sizes, handling precautions including washing or dry cleaning methods, material types, and fiber composition. The cleaning tag is attached using a metal pin or stapler, and the quality labeling tag is usually sewn directly onto clothing or the like.

[0003] On the other hand, Patent Document 1 discloses a cleaning tag that can be attached to clothing, etc., which is made up of a substrate / hot melt adhesive layer / adhesive layer, in which the hot melt adhesive layer is present over the entire area of ​​the label, and the adhesive layer is partially present on the surface of the hot melt adhesive layer in a position other than the edge portion of the label.

[0004] Patent Document 2 discloses a cloth-attachable tag that includes a printed layer, a thermal adhesive layer made of a hot melt adhesive provided on the back surface of the printed layer, and a temporary adhesive layer made of a detachable pressure-sensitive adhesive provided on the back surface of the thermal adhesive layer, with the temporary adhesive layer temporarily adhered to a release sheet, and the temporary adhesive layer is provided on a portion of the back surface of the thermal adhesive layer. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-71313 [Patent Document 2] Japanese Patent Application Laid-Open No. 2002-72892 Summary of the Invention [Problem to be solved by the invention]

[0006] The cleaning tags listed above are provided with an adhesive layer (adhesive layer in Patent Document 1, temporary adhesive layer in Patent Document 2) that can pressure-sensitively adhere the cleaning tag to an adherend such as clothing to temporarily secure it, and this tends to interfere with the heat-sensitive adhesion of the heat-sensitive adhesive layer (hot-melt adhesive layer in Patent Document 1, thermal adhesive layer in Patent Document 2). For this reason, in Patent Documents 1 and 2, the adhesive layer is provided partially on the heat-sensitive adhesive layer to strengthen the heat-sensitive adhesive force and improve cleaning resistance. However, there is still room for improvement in cleaning resistance.

[0007] The present invention has been made to solve the above-mentioned problems, and has an object to provide a cleaning label that has adhesive suitability that allows it to be temporarily attached by pressure-sensitive adhesion to an adherend such as clothing, and that can be heat-sensitively adhered to the adherend after being temporarily attached, and that has excellent dry-cleaning resistance that makes it difficult to peel off even after dry-cleaning. [Means for solving the problem]

[0008]

[0003] Conventionally, adhesive layers used to temporarily attach labels to rough surfaces such as clothing generally contain a tackifier resin to enhance adhesive strength. However, the inventors' research has surprisingly revealed that the tackifier resin contained in the adhesive layer affects the dry-cleaning resistance exhibited by the heat-sensitive adhesive layer due to the heat-sensitive adhesion. The inventors have then discovered that the cleaning resistance can be improved by adding a tackifier resin and a crosslinking agent that forms a crosslinked structure with the tackifier resin to the adhesive composition that forms the adhesive layer, and have thus completed the present invention. That is, the present invention includes the following aspects.

[0009] (1) a substrate; a heat-sensitive adhesive layer laminated on one surface of the substrate; a pressure-sensitive adhesive layer laminated on the surface of the heat-sensitive adhesive layer opposite to the surface on which the base material is laminated, the pressure-sensitive adhesive layer is formed using a pressure-sensitive adhesive composition containing a polymer component (A), a tackifying resin, and a crosslinking agent, The cleaning label, wherein the crosslinking agent forms a crosslinked structure with the tackifying resin. (2) The cleaning label according to (1) above, wherein the crosslinking agent further forms a crosslinked structure with the polymer component (A). (3) The cleaning label according to (1) or (2), wherein the content of the tackifier resin in the pressure-sensitive adhesive layer is 10 parts by mass or more relative to 100 parts by mass of the polymer component (A). (4) The cleaning label according to any one of (1) to (3), wherein the tackifier resin is at least one tackifier resin selected from the group consisting of rosin-based tackifier resins and terpene phenol-based tackifier resins. (5) The cleaning label according to any one of (1) to (4) above, wherein the glass transition temperature (Tg) of the polymer component (A) is −40° C. or lower. (6) The cleaning label according to any one of (1) to (5) above, wherein the polymer component (A) contains an acrylic polymer. (7) The cleaning label according to (6) above, wherein the content of structural units derived from 2-ethylhexyl acrylate is 50% by mass or more relative to 100% by mass of the polymer component (A). (8) The cleaning label according to any one of (1) to (7) above, wherein the thickness of the adhesive layer is 15 μm or less. (9) The cleaning label according to any one of (1) to (8) above, wherein the melting point of the heat-sensitive adhesive layer is 130° C. or lower. (10) The heat-sensitive adhesive layer contains a polymer component (B), The cleaning label according to any one of (1) to (9), wherein the crosslinking agent further forms a crosslinked structure with the polymer component (B). (11) The cleaning label according to any one of (1) to (10), wherein the substrate is at least one selected from the group consisting of a foamed resin film, a synthetic paper having micropores, and a resin film having micropores. (12) providing a heat-sensitive adhesive layer on one side of the substrate; providing a pressure-sensitive adhesive layer on a surface of the heat-sensitive adhesive layer opposite to the surface on which the substrate is laminated, using the pressure-sensitive adhesive composition containing a polymer component (A), a tackifying resin, and a crosslinking agent; The method for producing a label for cleaning according to any one of (1) to (11) above, wherein the crosslinking agent forms a crosslinked structure with the tackifier resin. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a cleaning label that is suitable for temporary attachment by pressure-sensitive adhesion to an adherend such as clothing, can be heat-sensitively adhered to the adherend after temporary attachment, and has excellent resistance to dry cleaning. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 1 is a cross-sectional view of a cleaning label according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0012] Hereinafter, embodiments of the cleaning label and the method for producing the cleaning label of the present invention will be described.

[0013] <Cleaning label> A cleaning label (hereinafter, sometimes simply referred to as "label") of an embodiment comprises a substrate, a heat-sensitive adhesive layer laminated on one side of the substrate, and a pressure-sensitive adhesive layer laminated on the side of the heat-sensitive adhesive layer opposite to the side on which the substrate is laminated, the pressure-sensitive adhesive layer being formed using a pressure-sensitive adhesive composition containing a polymer component (A), a tackifier resin, and a crosslinking agent, and the crosslinking agent forms a crosslinked structure with the tackifier resin.

[0014] Fig. 1 is a cross-sectional view of a cleaning label 1 according to an embodiment. As shown in Fig. 1, the label 1 according to this embodiment comprises a substrate 10, a heat-sensitive adhesive layer 20 laminated on one side of the substrate 10, and a pressure-sensitive adhesive layer 30 laminated on the side of the heat-sensitive adhesive layer 20 opposite to the side on which the substrate 10 is laminated. The release liner 40 is peeled off when the label is used, and is not an essential component of the label of the present invention.

[0015] <Base material> Examples of the substrate 10 of the label 1 according to the embodiment include film, paper, cloth, and nonwoven fabric. The film may be a resin film, preferably a synthetic resin film, such as a polyester film (e.g., polyethylene terephthalate, polybutylene terephthalate, or polyethylene naphthalate), a polyolefin film (e.g., polyethylene or polypropylene), a polyamide film (e.g., nylon), a polyurethane film, a polystyrene film, a polylactic acid film, or a cellulose film.

[0016] The substrate may be a film having micropores. The film having micropores is preferably at least one selected from the group consisting of foamed resin film, synthetic paper having micropores, and resin film having micropores. The presence of micropores makes the film white, improving the visibility of washing instructions and the like.

[0017] The foamed resin film is a porous resin film, and examples thereof include a film obtained by extrusion foaming of a resin, a film obtained by molding a resin composition in which a gas is dispersed, etc. Examples of foamed resin films include a foamed polyester film, a foamed polyethylene terephthalate film, a foamed polypropylene film, a foamed polyethylene film, and a foamed polystyrene film.

[0018] The resin film having micropores is a porous resin film produced using a synthetic resin as a main raw material. Examples of the resin in the resin film having micropores include the same resins as those used in the foamed resin film.

[0019] Synthetic paper with micropores is a porous film with properties similar to those of paper made primarily from synthetic resin. Examples of synthetic resins used as the primary raw material for synthetic paper include polypropylene, polyester, and polystyrene, with polyethylene terephthalate being an example of polyester. Here, the primary raw material refers to a raw material that accounts for 50% or more by mass of the total raw materials used for synthetic paper. Examples of micropores in synthetic paper include micropores generated during the stretching process. For example, when a synthetic resin containing a filler is stretched, microvoids are formed around the filler, imparting a white, paper-like texture. Specific examples of synthetic paper with micropores include Yupo (registered trademark) (containing polypropylene, Yupo Corporation), Crisper (registered trademark) (containing polyester, Toyobo Co., Ltd.), and N-Coat (registered trademark) (containing polypropylene, Nakamoto Pax Co., Ltd.). Products with properties equivalent to these are also included in the category of synthetic paper with micropores. The substrate may be transparent or opaque, but is preferably opaque so that the information printed on the label can be easily identified. The film having micropores is also opaque, making it suitable as a label substrate.

[0020] Examples of the paper include those containing wet strength agents, those coated with synthetic resins, those impregnated with synthetic resins, and those containing oil-resistant agents. Examples of fabrics and nonwoven fabrics include those containing cellulose fibers such as hemp, wool, cotton, pulp, and rayon, as well as fibers such as nylon, polyester, polyurethane, and vinylon.

[0021] The type of weave of the fabric is not particularly limited, and examples thereof include satin such as polyester satin, and taffeta such as polyester taffeta and cotton taffeta.

[0022] The substrate 10 may be made up of a single layer or multiple layers, in which case each layer may be the same or different.

[0023] The thickness of the substrate 10 can be set appropriately and is, for example, preferably 15 to 300 μm, more preferably 30 to 200 μm, and even more preferably 40 to 100 μm. When the thickness of the substrate is within the above range, good dry cleaning resistance can be achieved.

[0024] In this specification, "thickness" refers to a value expressed as the average of thickness measurements at five randomly selected locations, and can be obtained using a constant pressure thickness gauge in accordance with the mechanical scanning measurement method (Method A) specified in JIS K7130.

[0025] Here, the thickness of the substrate means the thickness of the entire substrate, and for example, when the substrate is made up of multiple layers, the thickness means the total thickness of all layers constituting the substrate.

[0026] <Adhesive layer> The adhesive layer 30 in the label 1 according to this embodiment has pressure-sensitive adhesive properties, allowing the label to be attached to an adherend such as clothing by pressure-sensitively adhering to the adherend. "Pressure-sensitive adhesive" refers to the property of being able to adhere to an adherend by applying pressure to the adhesive layer. Note that the terms "pressure-sensitive adhesion" and "adhesion" have the same meaning. The label has an adhesive layer, which allows it to be temporarily attached to clothing, etc., prior to subsequent heat-sensitive bonding using a press or the like, utilizing the heat-sensitive adhesive layer. The ability to temporarily attach makes it easy to accurately attach the label to the desired position on the object to which it is to be heat-bonded.

[0027] The adhesive layer can be formed using an adhesive composition containing the components that make up the adhesive layer. The adhesive layer in the label of this embodiment is formed using an adhesive composition containing a polymer component (A), a tackifier resin, and a crosslinking agent. The polymer component is a component that can be considered to be formed by a polymerization reaction of a polymerizable compound. The adhesive composition can contain, for example, the above-mentioned polymer component (A), a tackifier resin, a crosslinking agent, and optionally other optional components, such that the total content (% by mass) of these components does not exceed 100% by mass. The content of the polymer component (A) relative to the total mass of the solid content of the PSA composition may be 50% by mass or more, 50 to 95% by mass, 55 to 93% by mass, or 60 to 91% by mass. The "solid content" of the PSA composition refers to the non-volatile content remaining in the PSA composition after excluding volatile components such as solvents. Examples of the solid content contained in the PSA composition include a tackifier resin, a polymer component, and a crosslinking agent. The tackifier resin, polymer component, and crosslinking agent will be described below.

[0028] Tackifying resin In this specification, the term "tackifier resin" refers to a resin that has the function of improving the adhesive performance of a pressure-sensitive adhesive layer when added to the pressure-sensitive adhesive layer. Tackifier resins are also called tackifiers.

[0029] The tackifier resin may be a polymer. The weight-average molecular weight of the tackifier resin may be, for example, 5,000 or less, 100 to 5,000, 200 to 3,000, or 300 to 1,000. The weight-average molecular weight may be a polystyrene-equivalent value measured by gel permeation chromatography (GPC).

[0030] In the pressure-sensitive adhesive composition, the proportion of the tackifier resin content relative to 100 parts by mass of the polymer component (A) is not particularly limited, but is preferably 6 parts by mass or more, more preferably 7 parts by mass or more, and even more preferably 10 parts by mass or more. The upper limit of the tackifier resin content is not particularly limited, but in the pressure-sensitive adhesive composition, the proportion of the tackifier resin content relative to 100 parts by mass of the polymer component (A) is preferably 6 to 30 parts by mass, more preferably 7 to 20 parts by mass, and even more preferably 10 to 15 parts by mass. By setting the content of the tackifier resin within the above range, a label having an excellent balance between application suitability and cleaning resistance can be obtained.

[0031] Conventionally, when a label is to be pressure-sensitively adhered to an object having a rough surface such as clothing, a tackifying resin is generally added to the adhesive layer. However, the inventors have clarified that in conventional labels, the inclusion of a tackifier resin in the adhesive layer is a factor that reduces dry cleaning resistance. On the other hand, according to the label of the present embodiment, even when a PSA composition containing a tackifier resin is used, the PSA composition contains a crosslinking agent that forms a crosslinked structure with the tackifier resin, so that a label with excellent dry cleaning resistance can be provided.

[0032] Here, "dry cleaning resistance" refers to the property of a label that, after pressure-sensitive and heat-sensitive adhesion to an adherend, does not or is unlikely to peel off from the adherend due to dry cleaning (for example, in the dry cleaning test using perchloroethylene described below).

[0033] Considering that dry cleaning resistance is mainly exerted by the heat-sensitive adhesion of the heat-sensitive adhesive layer, the fact that the tackifier resin in the adhesive layer affects dry cleaning resistance is a result that exceeds normal expectations. If the PSA composition does not contain a crosslinking agent that forms a crosslinked structure with the tackifier resin, the tackifier resin may dissolve in the solvent used in dry cleaning, or the solvent may penetrate into the PSA layer, causing the label to swell, which may result in peeling of the label during dry cleaning. It is not clear why forming an adhesive layer using an adhesive composition containing a crosslinking agent that forms a crosslinked structure with a tackifier resin can improve the cleaning resistance of a label. However, it is thought that the inclusion of a crosslinking agent in the adhesive composition of the embodiment causes the tackifier resin and the crosslinking agent to react to form a crosslinked structure, thereby preventing the tackifier resin from leaching out into the solvent used in dry cleaning and suppressing peeling of the label.

[0034] The tackifier resin may be any resin capable of forming a crosslinked structure with the crosslinking agent contained in the pressure-sensitive adhesive composition. Examples of the tackifier resin include tackifier resins having a functional group capable of forming a crosslinked structure with the crosslinking agent. Examples of the tackifier resin having the functional group include rosin-based tackifier resins such as rosin and rosin derivatives; terpene phenol-based tackifier resins such as terpene phenol resins and hydrogenated terpene phenol resins; and other tackifier resins such as alkylphenol resins and phenolic resins.

[0035] The tackifier resin may be at least one type of tackifier resin selected from the group consisting of rosin-based tackifier resins and terpene phenol-based tackifier resins, each having a functional group capable of forming a crosslinked structure with a crosslinking agent.

[0036] In the present embodiment, "rosin" refers collectively to rosin resins and rosin derivatives. The rosin-based tackifying resin may have a carboxyl group as a functional group capable of forming a crosslinked structure with a crosslinking agent contained in the pressure-sensitive adhesive composition. Such rosins include unmodified rosins such as tall rosin, gum rosin, and wood rosin, which contain resin acids such as abietic acid, neoabietic acid, palustric acid, pimaric acid, isopimaric acid, and dehydroabietic acid as their main components, as well as disproportionated rosin, polymerized rosin, hydrogenated rosin, rosin ester, rosin-containing diol, and other chemically modified rosins. Furthermore, "acid-modified" refers to the addition of carboxyl groups to rosin, and specific examples of acid-modified rosins include those obtained by reacting rosin with an α,β-unsaturated carboxylic acid such as (meth)acrylic acid, maleic acid (anhydride), fumaric acid, itaconic acid, or citraconic acid (anhydride).

[0037] The rosin ester can be, for example, an ester of at least one of rosin and rosin derivatives with an alcohol, such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylene glycol, glycerin, pentaerythritol, or dipentaerythritol.

[0038] The terpene phenol resin may be a copolymer of a terpene monomer and phenol. The hydrogenated terpene phenol resin may be a hydrogenated terpene phenol resin. The terpene phenol tackifier resin may have a hydroxyl group as a functional group capable of forming a crosslinked structure with a crosslinking agent contained in the pressure-sensitive adhesive composition.

[0039] The acid value of the tackifier resin is preferably 10 to 250 mgKOH / g, and is measured in accordance with JIS K0070. The hydroxyl value of the tackifier resin is preferably 10 to 250 mgKOH / g, and is measured in accordance with JIS K0070.

[0040] These tackifying resins may be used alone or in combination of two or more.

[0041] Polymer component Examples of the polymer component (A) include known adhesive resins, such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, and ester resins, with acrylic resins being preferred.

[0042] The acrylic resin may be, for example, an acrylic polymer having at least a structural unit derived from a (meth)acrylic acid alkyl ester, and it is preferable that the polymer component (A) contains an acrylic polymer. The proportion of the acrylic polymer content relative to the total mass of the solid content of the pressure-sensitive adhesive composition may be 50% by mass or more, may be 50 to 95% by mass, may be 55 to 93% by mass, or may be 60 to 91% by mass. The acrylic polymer may have one type of structural unit or two or more types, and when there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0043] In this specification, the term "(meth)acrylic acid" is a concept that encompasses both "acrylic acid" and "methacrylic acid." The same applies to terms similar to (meth)acrylic acid.

[0044] The (meth)acrylic acid alkyl ester may be, for example, one in which the alkyl group constituting the alkyl ester has 1 to 20 carbon atoms, and the alkyl group is preferably linear or branched. More specifically, the (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-butyl (meth)acrylate, -nonyl, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, hexadecyl (meth)acrylate (palmityl (meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate), nonadecyl (meth)acrylate, and eicosyl (meth)acrylate.

[0045] From the viewpoint of improving the adhesive strength of the pressure-sensitive adhesive layer, the acrylic polymer preferably has a structural unit derived from a (meth)acrylic acid alkyl ester in which the alkyl group has 4 or more carbon atoms. From the viewpoint of further improving the adhesive strength of the pressure-sensitive adhesive layer, the alkyl group preferably has 4 to 12 carbon atoms, more preferably 4 to 8. Furthermore, the (meth)acrylic acid alkyl ester in which the alkyl group has 4 or more carbon atoms is preferably an acrylic acid alkyl ester.

[0046] The acrylic polymer preferably further contains a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth)acrylate ester. The functional group-containing monomer serves as a starting point for crosslinking when the functional group reacts with a crosslinking agent described below, for example. The polymer component (A) preferably has a functional group capable of forming a crosslinked structure with the crosslinking agent contained in the pressure-sensitive adhesive composition, and the acrylic polymer preferably has a functional group capable of forming a crosslinked structure with the crosslinking agent contained in the pressure-sensitive adhesive composition.

[0047] Examples of the functional group in the functional group-containing monomer include a hydroxyl group, a carboxyl group, an amino group, and an epoxy group. That is, examples of functional group-containing monomers include hydroxyl group-containing monomers, carboxyl group-containing monomers, amino group-containing monomers, and epoxy group-containing monomers.

[0048] Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth)acrylates such as hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; and non-(meth)acrylic unsaturated alcohols (unsaturated alcohols not having a (meth)acryloyl skeleton) such as vinyl alcohol and allyl alcohol.

[0049] Examples of the carboxyl group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth)acrylic acid and crotonic acid; ethylenically unsaturated dicarboxylic acids (dicarboxylic acids having an ethylenically unsaturated bond) such as fumaric acid, itaconic acid, maleic acid and citraconic acid; anhydrides of the ethylenically unsaturated dicarboxylic acids; and (meth)acrylic acid carboxyalkyl esters such as 2-carboxyethyl methacrylate.

[0050] The functional group-containing monomer is preferably a carboxyl group-containing monomer.

[0051] The functional group-containing monomer constituting the acrylic polymer may be of only one type or of two or more types, and when two or more types are used, the combination and ratio thereof can be selected arbitrarily.

[0052] In the acrylic polymer, the content of the structural units derived from functional group-containing monomers is preferably 1 to 35 mass %, more preferably 2 to 32 mass %, and particularly preferably 3 to 30 mass %, relative to the total amount of structural units.

[0053] The acrylic polymer may further contain structural units derived from other monomers in addition to the structural units derived from the (meth)acrylic acid alkyl ester and the structural units derived from the functional group-containing monomer. The other monomer is not particularly limited as long as it is copolymerizable with the (meth)acrylic acid alkyl ester or the like. Examples of the other monomers include styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, and acrylamide.

[0054] The other monomers constituting the acrylic polymer may be one type only or two or more types, and when two or more types are used, the combination and ratio thereof can be selected arbitrarily.

[0055] The glass transition temperature (Tg) of the polymer component (A) is preferably −40° C. or lower, more preferably −70° C. or higher to −40° C. or lower, and even more preferably −60° C. or higher to −55° C. When the Tg of the polymer component (A) is the above upper limit or lower, the adhesive strength to the adherend is improved. Instead of increasing the content of the tackifier resin in the pressure-sensitive adhesive layer, the pressure-sensitive adhesive property of the pressure-sensitive adhesive layer can be increased by lowering the glass transition temperature (Tg) of the polymer component (A).

[0056] The glass transition temperature (Tg) of the polymer component (A) can be calculated using the Fox formula shown below. 1 / Tg=(W1 / Tg1)+(W2 / Tg2)+...+(Wm / Tgm) (where Tg is the glass transition temperature of the polymer component, Tg1, Tg2,...Tgm are the glass transition temperatures of the homopolymers of the monomers that make up the polymer, and W1, W2,...Wm are the mass fractions of the monomers, where W1+W2+...+Wm=1.) The glass transition temperatures of the homopolymers of each monomer in the Fox formula can be found in the Polymer Data Handbook, Adhesive Handbook, or Polymer Handbook. For example, the Tg of the homopolymer of methyl acrylate is 10°C, the Tg of the homopolymer of 2-hydroxyethyl acrylate is -15°C, the Tg of the homopolymer of 2-ethylhexyl acrylate is -70°C, and the Tg of the homopolymer of 2-ethylhexyl methacrylate is -10°C.

[0057] The content of structural units derived from 2-ethylhexyl acrylate relative to 100% by mass of the polymer component (A) is preferably 50% by mass or more, more preferably 50 to 70% by mass, and even more preferably 55 to 65% by mass. As described above, since 2-ethylhexyl acrylate has a low Tg, by ensuring that the content of structural units derived from 2-ethylhexyl acrylate in the polymer component (A) is equal to or greater than the lower limit, the pressure-sensitive adhesive property of the pressure-sensitive adhesive layer can be effectively improved.

[0058] Crosslinking agent The crosslinking agent contained in the PSA composition may be any agent capable of forming a crosslinked structure with the tackifier resin contained in the PSA composition, and examples of such crosslinking agents include crosslinking agents having a functional group capable of forming a crosslinked structure with the tackifier resin. Examples of crosslinking agents include isocyanate-based crosslinking agents (crosslinking agents having an isocyanate group) such as adducts of diisocyanates such as toluene diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate; epoxy-based crosslinking agents (crosslinking agents having a glycidyl group) such as N,N,N',N'-tetraglycidyl-m-xylylenediamine; aziridine-based crosslinking agents (crosslinking agents having an aziridinyl group) such as hexa[1-(2-methyl)-aziridinyl]triphosphatriazine; metal chelate-based crosslinking agents (crosslinking agents having a metal chelate structure) such as aluminum chelate; and isocyanurate-based crosslinking agents (crosslinking agents having an isocyanuric acid skeleton).Other usable crosslinking agents include melamine-based compounds, hydrazide-based compounds, oxazoline-based compounds, carbodiimide-based compounds, urea-based compounds, dialdehyde-based compounds, metal alkoxides, and metal salts.

[0059] Examples of aluminum chelate compounds include diisopropoxyaluminum monooleyl acetoacetate, monoisopropoxyaluminum bisoleyl acetoacetate, monoisopropoxyaluminum monooleate monoethyl acetoacetate, diisopropoxyaluminum monolauryl acetoacetate, diisopropoxyaluminum monostearyl acetoacetate, diisopropoxyaluminum monoisostearyl acetoacetate, monoisopropoxyaluminum mono-N-lauroyl-β-alanate monolauryl acetoacetate, aluminum trisacetylacetonate, monoacetylacetonate aluminum bis(isobutylacetoacetate) chelate, monoacetylacetonate aluminum bis(2-ethylhexylacetoacetate) chelate, monoacetylacetonate aluminum bis(dodecylacetoacetate) chelate, and monoacetylacetonate aluminum bis(oleylacetoacetate) chelate.

[0060] The pressure-sensitive adhesive composition may contain only one type of crosslinking agent, or two or more types. When two or more types are contained, the combination and ratio thereof can be selected arbitrarily.

[0061] For example, when a rosin-based tackifying resin is used as the tackifying resin contained in the PSA composition, any of the crosslinking agents exemplified above can be suitably used.Furthermore, when a terpene phenol-based tackifying resin is used as the tackifying resin contained in the PSA composition, among the crosslinking agents exemplified above, an isocyanate-based crosslinking agent and a metal chelate-based crosslinking agent can be suitably used.

[0062] The content of the crosslinking agent in the pressure-sensitive adhesive composition is preferably 0.1 parts by mass or more and 15 parts by mass or less, more preferably 0.3 parts by mass or more and 10 parts by mass or less, and even more preferably 0.4 parts by mass or more and 5 parts by mass or less, relative to 100 parts by mass of the total content of the polymer compound (A) and the tackifier resin.

[0063] When the pressure-sensitive adhesive composition contains a crosslinking agent, the dry cleaning resistance of the label can be improved.

[0064] By including a crosslinking agent in the PSA composition of the embodiment, the tackifier resin reacts with the crosslinking agent to form a crosslinked structure, which is thought to prevent the tackifier resin from leaching out into solvents used in dry cleaning and suppress peeling of the label.

[0065] The crosslinking agent contained in the pressure-sensitive adhesive composition preferably also forms a crosslinked structure with the polymer component (A). Such a crosslinking agent can form a crosslinked structure between the tackifier resin and the polymer component (A). By crosslinking the tackifier resin with the polymer component (A), the crosslinking agent can more effectively prevent the elution of the tackifier resin.

[0066] Furthermore, the crosslinking agent can, for example, crosslink the polymer components (A) contained in the pressure-sensitive adhesive layer to each other, thereby strengthening the pressure-sensitive adhesive layer and improving dry cleaning resistance.

[0067] The crosslinking agent contained in the pressure-sensitive adhesive composition preferably forms a crosslinked structure with the polymer component (B) contained in the heat-sensitive adhesive layer described below. The crosslinking agent, for example, crosslinks the polymer component (A) contained in the pressure-sensitive adhesive layer with the polymer component (B) contained in the heat-sensitive adhesive layer described below, thereby strengthening the bond at the interface between the pressure-sensitive adhesive layer and the heat-sensitive adhesive layer and improving dry cleaning resistance.

[0068] As an example of a pressure-sensitive adhesive composition, preferably, Examples of pressure-sensitive adhesive compositions include those in which the content of polymer component (A) is 50 to 95% by mass relative to 100% by mass of the total mass of the solid content of the pressure-sensitive adhesive composition, the content of tackifier resin is 6 to 30 parts by mass relative to 100 parts by mass of polymer component (A), and the content of crosslinker in the pressure-sensitive adhesive composition is 0.1 to 15 parts by mass relative to 100 parts by mass of the total content of polymer compound (A) and the tackifier resin.

[0069] More preferably, the pressure-sensitive adhesive composition is An example of a pressure-sensitive adhesive composition is one in which the content of polymer component (A) is 55 to 93 mass% relative to 100 mass% of the total mass of the solid content of the pressure-sensitive adhesive composition, the content of tackifier resin is 7 to 20 mass parts relative to 100 parts by mass of polymer component (A), and the content of crosslinker in the pressure-sensitive adhesive composition is 0.3 to 10 mass parts relative to 100 parts by mass of the total content of polymer compound (A) and the tackifier resin.

[0070] As an example of a more preferred pressure-sensitive adhesive composition, An example of a pressure-sensitive adhesive composition is one in which the content of polymer component (A) is 60 to 91% by mass relative to 100% by mass of the total mass of the solid content of the pressure-sensitive adhesive composition, the content of tackifier resin is 10 to 15 parts by mass relative to 100 parts by mass of polymer component (A), and the content of crosslinker in the pressure-sensitive adhesive composition is 0.4 to 5 parts by mass relative to 100 parts by mass of the total content of polymer compound (A) and the tackifier resin.

[0071] In the label 1 of this embodiment, a pressure-sensitive adhesive layer 30 is provided between the heat-sensitive adhesive layer 20 and the adherend. In Patent Documents 1 and 2, a layer corresponding to the pressure-sensitive adhesive layer is provided on part of the surface of the layer corresponding to the heat-sensitive adhesive layer in order to prevent the layer from interfering with heat-sensitive adhesion. In contrast, the label of the embodiment has improved cleaning resistance of the heat-sensitive adhesive layer by using a crosslinking agent that forms a crosslinked structure with the tackifying resin, so it is not necessarily required to have an adhesive layer only on a portion of the heat-sensitive adhesive layer.

[0072] In the embodiment of the label 1, the pressure-sensitive adhesive layer 30 is preferably provided over 70 to 100 area % of the surface of the heat-sensitive adhesive layer 20 (100 area %), more preferably over 90 to 100 area %, and even more preferably over the entire surface (100 area %). By providing the pressure-sensitive adhesive layer 30 with an area percentage equal to or greater than the lower limit, the thickness of the label is made uniform, adhesion to the adherend is improved, and dry cleaning resistance can be improved.

[0073] The adhesive layer may consist of one layer (single layer), or may consist of two or more layers. When it consists of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited.

[0074] The thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably 16 μm or less, more preferably 15 μm or less, even more preferably 1 to 13 μm, and particularly preferably 5 to 11 μm. In order to improve the pressure-sensitive adhesive strength, it is common to increase the thickness of the adhesive layer, but in the use of the label of the embodiment, it is sufficient to exert adhesive strength sufficient to enable temporary attachment to the object to which it is attached. Furthermore, by keeping the thickness of the adhesive layer at or below the above upper limit, it is unlikely to interfere with the adhesion between the heat-sensitive adhesive layer and the object to which it is attached, such as clothing.

[0075] Here, the thickness of the adhesive layer means the thickness of the entire adhesive layer, and for example, the thickness of an adhesive layer consisting of multiple layers means the total thickness of all layers that make up the adhesive layer.

[0076] From the above viewpoints, the adhesive strength of the adhesive layer is preferably 0.5 to 30 N / 25 mm, more preferably 2 to 20 N / 25 mm, and even more preferably 3 to 15 N / 25 mm, in terms of T-peel adhesive strength with cotton fabric, measured in accordance with JIS K6854-3 at a peel rate of 300 mm / min. Note that the adhesive strength here refers to the adhesive strength of the adhesive layer before the label is heat-sensitively adhered (of the label that is not heat-sensitively adhered). If the adhesive strength of the adhesive layer is equal to or greater than the above lower limit, it is suitable for temporary attachment to an object to be attached, and if it is equal to or less than the above upper limit, it is preferable because it is easy to remove again.

[0077] <Heat-sensitive adhesive layer> The heat-sensitive adhesive layer 20 in the label 1 according to this embodiment has heat-sensitive adhesive properties, and is a layer that enables the label to be attached by heat-sensitively adhering it to an adherend such as clothing. "Heat-sensitive adhesive properties" refer to the property that allows the heat-sensitive adhesive layer to be heated, melted, and then hardened again, thereby adhering it to an adherend. Examples of heat-sensitive adhesion include heat and pressure adhesion (adhesion by application of heat and pressure) to the adherend using an iron, a press, or the like. The label is adhered to the substrate by heating the heat-sensitive adhesive layer to a temperature above its melting point and then cooling it. The use of heat-sensitive adhesion ensures strong adhesion to the substrate, resulting in a label with excellent dry-cleaning resistance.

[0078] In the label 1 of the embodiment, an adhesive layer 30 is provided between the heat-sensitive adhesive layer 20 and the adherend, and it is thought that heating or pressurizing the label causes deformation of the adhesive layer 30, exposing the heat-sensitive adhesive layer 20 and allowing it to adhere to the adherend.

[0079] The composition of the heat-sensitive adhesive layer is not particularly limited as long as it has heat-sensitive adhesive properties. The heat-sensitive adhesive layer does not exhibit adhesive properties at room temperature (23°C), for example, but exhibits adhesive properties when heated. The heating temperature of the heat-sensitive adhesive layer can be appropriately determined depending on the composition of the heat-sensitive adhesive layer, and heat-sensitive adhesion can be exhibited by heating the heat-sensitive adhesive layer to a temperature equal to or higher than the melting point of the heat-sensitive adhesive layer.

[0080] The heat-sensitive adhesive layer preferably contains a polymer component (B). Examples of the polymer component (B) include thermoplastic resins having heat-sensitive adhesive properties, such as polyolefin resins and polyester resins. Examples of polyolefin resins include polyethylene (low density polyethylene, medium density polyethylene, high density polyethylene, etc.), polypropylene, polybutene, polyisobutylene, polybutadiene, polyisoprene, etc. The heat-sensitive adhesive layer may also contain olefin copolymers such as ethylene-α-olefin copolymers and ethylene-propylene copolymers; acrylic polymers such as ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers, ethylene-acrylic acid ester copolymers and ethylene-methacrylic acid ester copolymers; vinyl acetate polymers such as ethylene-vinyl acetate copolymer (EVA); or ionomer resins or acid-modified polyolefins obtained by modifying these with acids.

[0081] The polymer component (B) may have a functional group capable of bonding to other compounds, such as a vinyl group, a (meth)acryloyl group, an amino group, a hydroxyl group, or a carboxyl group. The polymer component (B) preferably has a functional group capable of forming a crosslinked structure with the crosslinking agent contained in the pressure-sensitive adhesive composition. For example, the polymer component (B) having the functional group may be crosslinked with the polymer component (A) contained in the pressure-sensitive adhesive layer via a crosslinking agent. Examples of the crosslinking agent include those exemplified for the pressure-sensitive adhesive layer above, and a crosslinking agent that reacts with and bonds to the polymer component (A) contained in the pressure-sensitive adhesive layer and the polymer component (B) contained in the heat-sensitive adhesive layer is preferred. By crosslinking the polymer component (A) contained in the pressure-sensitive adhesive layer and the polymer component (B) contained in the heat-sensitive adhesive layer, the adhesion at the interface between the pressure-sensitive adhesive layer and the heat-sensitive adhesive layer is strengthened, thereby improving dry cleaning resistance.

[0082] The heat-sensitive adhesive layer preferably has a melting point of 130°C or lower, more preferably 50°C or higher and 120°C or lower, and even more preferably 70°C or higher and 110°C or lower. When the melting point of the heat-sensitive adhesive layer is equal to or lower than the upper limit, the heat-sensitive adhesive strength is appropriately exhibited at practical heating temperatures, and the dry cleaning resistance is improved.

[0083] The heat-sensitive adhesive layer may consist of a single layer or multiple layers, and in the case of multiple layers, each layer may be the same or different.

[0084] The thickness of the heat-sensitive adhesive layer can be appropriately set, and is, for example, preferably 15 to 300 μm, more preferably 30 to 200 μm, and even more preferably 40 to 100 μm. When the thickness of the heat-sensitive adhesive layer is in the above range, good dry cleaning resistance is achieved.

[0085] Here, the thickness of the heat-sensitive adhesive layer means the thickness of the entire heat-sensitive adhesive layer; for example, when the heat-sensitive adhesive layer consists of multiple layers, the thickness means the total thickness of all layers that make up the heat-sensitive adhesive layer.

[0086] <Release liner> The release liner 40 is provided on the surface of the pressure-sensitive adhesive layer 30 opposite to the side on which the heat-sensitive adhesive layer 20 is provided.

[0087] There are no particular limitations on the release liner 40, and in general, any known release liner having a release treatment applied to one side of the sheet can be appropriately selected and used. Examples of liners that can be used for the release liner 40 include paper such as glassine paper, fine paper, and kraft paper, laminated paper obtained by laminating such paper with a thermoplastic resin such as polyethylene, polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and polyolefin films such as polyethylene and polypropylene.

[0088] Examples of release treatment agents for performing the release treatment include silicone, long-chain alkyl resins, and fluorine-based resins. The thickness of the release liner 40 is not particularly limited, but is preferably 10 to 150 μm, and more preferably 20 to 130 μm.

[0089] The total thickness of the layers of the label 1 of this embodiment, excluding the release liner 40, is preferably 60 to 100 μm, more preferably 63 to 90 μm, and particularly preferably 65 to 80 μm.

[0090] <Label manufacturing method> The label manufacturing method according to the embodiment includes providing a heat-sensitive adhesive layer on one side of a substrate, and providing an adhesive layer on the side of the heat-sensitive adhesive layer opposite to the side on which the substrate is laminated, using an adhesive composition containing a polymer component (A), a tackifier resin, and a crosslinking agent, wherein the crosslinking agent forms a crosslinked structure with the tackifier resin.

[0091] Examples of the pressure-sensitive adhesive composition include those exemplified in the description of the pressure-sensitive adhesive layer above.

[0092] The ratio of the contents of the components that do not vaporize at room temperature in the pressure-sensitive adhesive composition is usually the same as the ratio of the contents of the components in the pressure-sensitive adhesive layer. In this specification, "room temperature" means a temperature that is not particularly cooled or heated, i.e., an ordinary temperature, and examples thereof include a temperature of 15 to 25°C.

[0093] First, a method for manufacturing a label according to the present invention will be described below, taking a method for manufacturing label 1 as an example. The manufacturing method of the label 1 of this embodiment includes providing a heat-sensitive adhesive layer 20 on one side of the substrate 10, and providing a pressure-sensitive adhesive layer 30 on the side of the heat-sensitive adhesive layer 20 opposite the side on which the substrate 10 is laminated.

[0094] For example, a heat-sensitive adhesive composition containing components constituting a heat-sensitive adhesive layer and, if desired, a solvent is applied onto the substrate 10 using a coating machine such as a roll coater, knife coater, roll knife coater, air knife coater, die coater, bar coater, gravure coater, or curtain coater, and then dried to obtain a laminate A in which the substrate 10 and the heat-sensitive adhesive layer 20 are laminated. As the heat-sensitive adhesive composition, a commercially available heat-sealing agent can be used.

[0095] Furthermore, a pressure-sensitive adhesive composition containing the components constituting the pressure-sensitive adhesive layer 30 and, if desired, a solvent is prepared on the release liner 40, and the pressure-sensitive adhesive composition is applied to the release-treated surface of the release liner 40 using a coating machine and dried to obtain a laminate B in which the release liner 40 and the pressure-sensitive adhesive layer 30 are laminated.

[0096] Next, the exposed surface of the heat-sensitive adhesive layer 20 of the laminate A produced above and the exposed surface of the pressure-sensitive adhesive layer 30 of the laminate B are pressed together to produce a label 1 in which the substrate 10, the heat-sensitive adhesive layer 20, and the pressure-sensitive adhesive layer 30 are laminated in this order.

[0097] After the pressure-sensitive adhesive layer is formed, for example, by leaving it to stand at room temperature for about 7 days, a crosslinked structure can be formed by the crosslinking agent contained in the pressure-sensitive adhesive composition.

[0098] <How to use the label> The label of the embodiment can be used by being attached to an object that can be dry cleaned. Examples of items to be dry cleaned include clothing such as shirts, skirts, pants, hats, scarves, and socks, bedding such as pillows and sheets, as well as covers, curtains, lap blankets, shoes, and bags. The fabric surface of the above items is preferred as the surface to which the label is affixed. Fabric refers to any material woven from natural or synthetic fibers.

[0099] In this specification, "dry cleaning" refers to a general cleaning method using a solvent other than water. The solvent is not particularly limited as long as it can be used for dry cleaning, and examples thereof include petroleum-based solvents such as perchloroethylene and gasoline, with perchloroethylene being preferred.

[0100] An example of a method for using the label of the embodiment includes a step of contacting the adhesive layer with an adherend, which is an object that can be dry cleaned, to pressure-sensitively adhere the label, and a step of heating the pressure-sensitively adhered label to heat-adhere the label to the adherend.

[0101] An example of a method for using the label of the embodiment is a method including a step of dry-cleaning an adherend and a label heat-adhered to the adherend.

[0102] The heating temperature can be determined appropriately depending on the composition of the heat-sensitive adhesive layer, and may be a temperature equal to or higher than the melting point of the heat-sensitive adhesive layer. For example, the heating temperature may be 80 to 250°C, 130 to 200°C, or 140 to 170°C.

[0103] In addition, when heating, heat and pressure bonding (adhesion by applying heat and pressure) using an iron or press machine can be used. The pressure on the label is 0.5 to 10 kg / cm. 2 The extent can be exemplified.

[0104] The label of the embodiment may have a surface that is printed or imprinted. The printing or imprinting may be applied to the surface of the substrate. A known printing device may be used for the printing or imprinting. The printing or imprinting may be performed before or after the label of the embodiment is attached to an adherend.

[0105] The following configurations can be exemplified as preferred uses of the cleaning label of the embodiment.

[0106] In the cleaning label of the embodiment, the substrate is printed with characters or prints, The printed or printed information is one or more dry cleaning information selected from the group consisting of owner information of the object to be dry cleaned with the cleaning label attached, information of the dry cleaning shop, a control code of the object, and a control number of the object, or It is preferable that the information on the object be one or more items selected from the group consisting of care instructions, washing symbols, sizes, washing or dry cleaning methods, material type, fiber composition, and the name of the person displaying them, regarding the object.

[0107] The label having the above-mentioned dry cleaning information can be used as a cleaning label that is attached to an article to be dry cleaned and then used together with the article after dry cleaning.

[0108] The label having the above-mentioned object information can be used as a quality label that is attached to an item to be dry cleaned and then used together with the item after dry cleaning.

[0109] Cleaning labels and quality labels are included in the cleaning label of the embodiment.

[0110] <Tag manufacturing method> The label embodiments described above can be applied to a structure including a second substrate and used to manufacture cleaning tags.

[0111] The method for manufacturing the cleaning tag of the embodiment includes pressure-sensitively adhering a second substrate to a second surface side of the cleaning label of the embodiment, the second surface side being opposite to a first surface side on which the first substrate of the adhesive layer is laminated, to obtain a laminate including the first substrate, the heat-sensitive adhesive layer, the adhesive layer, and the second substrate in this order; and heat-treating the laminate to heat-bond the first substrate and the second substrate via the heat-sensitive adhesive layer.

[0112] Examples of the first substrate include those exemplified as the substrate in the above embodiment. Examples of the heat-sensitive adhesive layer and the pressure-sensitive adhesive layer include those exemplified in the above embodiment.

[0113] Examples of the second substrate include those exemplified above as the first substrate. The second substrate is preferably a film, a cloth, or a nonwoven fabric.

[0114] The first substrate and the second substrate may each be a combination of the same materials, or a combination of different materials. For example, a combination in which the first substrate is fabric and the second substrate is fabric, or a combination in which the first substrate is fabric and the second substrate is film can be exemplified.

[0115] The total thickness of the layers of the tag of the embodiment is preferably 25 to 2000 μm, more preferably 50 to 1000 μm, and even more preferably 100 to 500 μm. [Example]

[0116] The present invention will now be described in more detail with reference to examples, but the present invention is not limited to the following examples.

[0117] <Creating labels> [Comparative Example 1] A polyester synthetic paper (Toyobo Co., Ltd., model number: Crisper K2411, thickness 50 μm) was prepared as a substrate. Next, a polyolefin-based water-based dispersion (Sumitomo Seika Chemicals Co., Ltd., ZAIKXEN AC, containing carboxyl groups, melting point 90°C) was applied as a polyolefin-based heat-sensitive adhesive composition to a thickness of 15 μm and dried to form a heat-sensitive adhesive layer on the substrate, thereby obtaining the label of Comparative Example 1. The label of Comparative Example 1 did not have an adhesive layer.

[0118] Comparative Example 2 As a substrate, polyester synthetic paper (Toyobo Co., Ltd., model number: Crisper K2411, thickness 50 μm) was prepared. An acrylic adhesive composition [a mixture of a polymer of 2-ethylhexyl acrylate (60 parts by mass), n-butyl acrylate (30 parts by mass), methyl acrylate (7 parts by mass), and acrylic acid (3 parts by mass), and a solvent: toluene (30 parts by mass)] (calculated Tg of polymer component = -52.7°C) was prepared, applied to a release liner using a knife coater so that the thickness after drying would be 10 μm, and dried at 100°C for 1 minute to form an adhesive layer. The exposed surface of the pressure-sensitive adhesive layer thus formed was placed on the exposed surface of the substrate and pressure-bonded to obtain a label of Comparative Example 2. The label of Comparative Example 2 did not have a heat-sensitive adhesive layer.

[0119] [Reference example 1] A polyester synthetic paper (Toyobo Co., Ltd., model number: Crisper K2411, thickness 50 μm) was prepared as a substrate. Next, a polyolefin-based water-based dispersion (Sumitomo Seika Chemicals Co., Ltd., Zaixen AC, containing carboxyl groups, melting point 90°C) was applied as a polyolefin-based heat-sensitive adhesive composition to a thickness of 15 μm and dried to form a heat-sensitive adhesive layer on the substrate. An acrylic adhesive composition [a mixture of a polymer of 2-ethylhexyl acrylate (60 parts by mass), n-butyl acrylate (30 parts by mass), methyl acrylate (7 parts by mass), and acrylic acid (3 parts by mass), and a solvent: toluene (30 parts by mass)] (calculated Tg of polymer component = -52.7°C) was prepared, applied to a release liner using a knife coater so that the thickness after drying would be 10 μm, and dried at 100°C for 1 minute to form an adhesive layer. The exposed surface of the pressure-sensitive adhesive layer thus formed was placed on the exposed surface of the heat-sensitive adhesive layer of the laminate of the substrate and the heat-sensitive adhesive layer and pressure-bonded to obtain a label of Reference Example 1.

[0120] Comparative Example 3 A polyester synthetic paper (Toyobo Co., Ltd., model number: Crisper K2411, thickness 50 μm) was prepared as a substrate. Next, a polyolefin-based water-based dispersion (Sumitomo Seika Chemicals Co., Ltd., Zaixen AC, containing carboxyl groups, melting point 90°C) was applied as a polyolefin-based heat-sensitive adhesive composition to a thickness of 15 μm and dried to form a heat-sensitive adhesive layer on the substrate. An acrylic adhesive composition containing a petroleum resin-based tackifying resin (Arakawa Chemical Industries, Ltd., Alcon P-90, hydrogenated petroleum resin, softening point 90°C) [a polymer of 2-ethylhexyl acrylate (60 parts by mass), n-butyl acrylate (30 parts by mass), methyl acrylate (7 parts by mass), and acrylic acid (3 parts by mass), the tackifying resin (10 parts by mass), a crosslinking agent: toluene diisocyanate-based polyisocyanate (Tosoh Corporation, Coronate L) (3 parts by mass), and a solvent: a mixture of toluene (30 parts by mass)] (calculated Tg of polymer component = -52.7°C) was prepared, and the resulting coating was applied to a release liner using a knife coater to a dry thickness of 10 μm. The coating was then dried at 100°C for 1 minute to form an adhesive layer. The exposed surface of the pressure-sensitive adhesive layer thus formed was placed on the exposed surface of the heat-sensitive adhesive layer of the laminate of the substrate and the heat-sensitive adhesive layer and pressure-bonded to obtain a label of Comparative Example 3.

[0121] Comparative Example 4 The label of Comparative Example 4 was obtained by the same procedure as in Comparative Example 3, except that the tackifying resin used in Comparative Example 3 was replaced with a petroleum resin-based tackifying resin (Arakawa Chemical Industries, P-140, hydrogenated petroleum resin, softening point 140°C).

[0122] Comparative Example 5 The label of Comparative Example 5 was obtained by the same procedure as in Comparative Example 3, except that the tackifying resin used in Comparative Example 3 was replaced with a styrene-based tackifying resin (Yasuhara Chemical, YS Resin SX100, styrene resin, softening point 100°C).

[0123] Comparative Example 6 The label of Comparative Example 6 was obtained by the same procedure as in Comparative Example 3, except that the tackifying resin used in Comparative Example 3 was replaced with a terpene-based tackifying resin (Yasuhara Chemical, YS Resin PX1000, terpene resin, softening point 100°C).

[0124] Comparative Example 7 The label of Comparative Example 7 was obtained by the same procedure as in Comparative Example 3, except that the tackifying resin used in Comparative Example 3 was replaced with a terpene-based tackifying resin (Yasuhara Chemical, YS Resin PX1250, terpene resin, softening point 125°C).

[0125] [Comparative Example 8] The label of Comparative Example 8 was obtained by the same procedure as in Comparative Example 3, except that the tackifying resin used in Comparative Example 3 was replaced with a terpene-based tackifying resin (Yasuhara Chemical, YS Resin TO105, aromatic modified terpene resin, softening point 105°C).

[0126] [Example 1] The label of Example 1 was obtained by the same procedure as in Comparative Example 3, except that the tackifying resin used in Comparative Example 3 was replaced with a terpene phenol-based tackifying resin (Yasuhara Chemical, YS Polystar T100, terpene phenol resin, softening point 100°C).

[0127] [Example 2] The label of Example 2 was obtained by the same procedure as in Comparative Example 3, except that the tackifying resin used in Comparative Example 3 was replaced with a terpene phenol-based tackifying resin (Yasuhara Chemical, YS Polystar T160, terpene phenol resin, softening point 160°C).

[0128] [Example 3] The label of Example 3 was obtained by the same procedure as in Comparative Example 3, except that the tackifying resin used in Comparative Example 3 was replaced with a rosin-based tackifying resin (Superester A-100, rosin ester, softening point 100°C, manufactured by Arakawa Chemical Industries, Ltd.).

[0129] [Example 4] The label of Example 4 was obtained by the same procedure as in Comparative Example 3, except that the tackifying resin used in Comparative Example 3 was replaced with a rosin-based tackifying resin (Superester A-125, rosin ester, softening point 125°C, manufactured by Arakawa Chemical Industries, Ltd.).

[0130] [Example 5] The label of Example 5 was obtained by the same procedure as in Comparative Example 3, except that the tackifying resin used in Comparative Example 3 was replaced with a rosin-based tackifying resin (Ester Gum HP, hydrogenated rosin ester, softening point 80°C, manufactured by Arakawa Chemical Industries, Ltd.).

[0131] [Example 6] The label of Example 6 was obtained by the same procedure as in Comparative Example 3, except that the tackifying resin used in Comparative Example 3 was replaced with a rosin-based tackifying resin (Arakawa Chemical Industries, Ltd., Pencel D-125, polymerized rosin ester, softening point 125°C).

[0132] [Example 7] The label of Example 7 was obtained by the same procedure as in Comparative Example 3, except that the tackifying resin used in Comparative Example 3 was replaced with a rosin-based tackifying resin (Arakawa Chemical Industries, Ltd., Pencel D-160, polymerized rosin ester, softening point 160°C).

[0133] [Example 8] The label of Example 8 was obtained by the same procedure as in Comparative Example 3, except that the tackifying resin used in Comparative Example 3 was replaced with a rosin-based tackifying resin (Arakawa Chemical Industries, Ltd., Pine Crystal KR-140, ultra-light-colored polymerized rosin, softening point 140°C).

[0134] [Example 9] The label of Example 9 was obtained by the same procedure as in Comparative Example 3, except that the tackifying resin used in Comparative Example 3 was replaced with a rosin-based tackifying resin (Arakawa Chemical Industries, Ltd., Pine Crystal KE-359, ultra-light-colored rosin ester, softening point 99°C).

[0135] [Example 10] The label of Example 10 was obtained by the same procedure as in Comparative Example 3, except that the tackifying resin used in Comparative Example 3 was replaced with a rosin-based tackifying resin (Arakawa Chemical Industries, Ltd., Pine Crystal D-6011, rosin-containing diol, softening point 91.5°C).

[0136] [Example 11] The label of Example 11 was obtained by the same procedure as in Comparative Example 3, except that the tackifying resin used in Comparative Example 3 was replaced with a rosin-based tackifying resin (Arakawa Chemical Industries, Ltd., Pine Crystal KE-604, acid-modified rosin, softening point 129°C).

[0137] [Example 12] The label of Example 12 was obtained by the same procedure as in Comparative Example 3, except that the tackifying resin used in Comparative Example 3 was replaced with a rosin-based tackifying resin (Tamanol 803L, phenol-modified rosin resin, softening point 150°C, manufactured by Arakawa Chemical Industries, Ltd.).

[0138] [Example 13] The label of Example 13 was obtained by the same procedure as in Comparative Example 3, except that the tackifying resin used in Comparative Example 3 was replaced with a rosin-based tackifying resin (Tamanol 901, phenol-modified rosin resin, softening point 130°C, manufactured by Arakawa Chemical Industries, Ltd.).

[0139] The label configurations of the above Examples, Reference Examples, and Comparative Examples are shown in Tables 1 to 3. In the tables, "-" indicates that the corresponding component is not contained.

[0140] [Table 1]

[0141] [Table 2]

[0142] [Physical property evaluation] The labels produced in the above Examples, Reference Examples and Comparative Examples were evaluated for the following physical properties.

[0143] (Measurement of adhesive strength of adhesive layer of label before heat-sensitive adhesion) The release liner was peeled from each label obtained in the above Examples, Reference Examples, and Comparative Examples, and the label was placed on cotton cloth (Kanakin No. 3, Japan Standards Association, JIS L0803 compliant) and laminated by rolling it back and forth with a 2000 g rubber roller. After leaving it for 30 minutes in an environment with a humidity of 23°C and 50% RH, the T-type peel adhesive strength between the label and the cotton cloth was measured at a peel rate of 300 mm / min in accordance with JIS K6854-3. The measurement results are shown in Tables 1 to 3.

[0144] (Evaluation of dry cleaning resistance) After a dry cleaning test according to JIS L 0860 A1 method was carried out, it was visually determined whether peeling of the label had occurred. ×: Label peeling occurred over the entire surface of the applied area. △: The label peeled off in a part of the affixed area. ○: Almost no peeling occurred at the affixed area, but peeling was observed in part of the edge of the label. ◎: No peeling of the label was observed over the entire surface of the affixed area.

[0145] Test specimen Each label obtained in the above Examples, Reference Examples, and Comparative Examples was cut to a width of 20 mm and a length of 30 mm, after which the release liner was peeled off and the label was attached to an adherend (Kanakin No. 3) using the same method as used to measure the adhesive strength before heat-sensitive bonding. Then, a pressure cooker is used to apply a load of 1 kg / cm 2 The mixture was heated under pressure at 140°C for 5 seconds. Test solution To 1 L of perchloroethylene, 5 g of anionic surfactant (di-2-ethylhexyl sodium sulfosuccinate), 5 g of nonionic surfactant (polyoxyethylene alkyl ether), and 1 mL of water were added and stirred well to dissolve the mixture, and the resulting homogeneous, transparent solution was used as the test solution. ·test 100 mL of the test liquid prepared above and 20 stainless steel balls were placed in a test bottle, and the test liquid was adjusted to 30°C ± 2°C. The test specimen was placed in the bottle, sealed, and attached to a washing test machine, which was run for 30 minutes at 30°C ± 2°C. The test specimen was removed from the test bottle, lightly rinsed with 100 mL of perchloroethylene, and then the excess liquid was removed and the specimen was dried in a dryer at 60°C or below. The evaluation results are shown in Tables 1 to 3.

[0146] The label of Comparative Example 1 did not have an adhesive layer and had no adhesive strength, meaning that the label of Comparative Example 1 lacked the adhesiveness required for pressure-sensitive adhesion to the target position before heat-sensitive adhesion was performed.

[0147] The label of Comparative Example 2 did not have a heat-sensitive adhesive layer and lacked dry cleaning resistance.

[0148] The label of Reference Example 1 had a heat-sensitive adhesive layer and a pressure-sensitive adhesive layer, and had good adhesion properties and dry-cleaning resistance. It is believed that the label of Reference Example 1 had excellent dry-cleaning resistance because the pressure-sensitive adhesive layer did not contain a tackifier resin.

[0149] The labels of Comparative Examples 3 to 8 had a heat-sensitive adhesive layer and a pressure-sensitive adhesive layer and had good adhesion properties, but it was thought that the tackifying resin contained in the pressure-sensitive adhesive layer had an effect that resulted in poor dry-cleaning resistance.

[0150] On the other hand, the labels of Examples 1 to 13 had improved adhesive strength, excellent application suitability, and very good dry-cleaning resistance due to the inclusion of a tackifier resin in the adhesive layer. The reason why the dry-cleaning resistance was very good despite the inclusion of a tackifier resin in the adhesive layer is thought to be because, in the labels of Examples 1 to 13, the adhesive layer was formed from an adhesive composition containing a crosslinking agent that forms a crosslinked structure with the tackifier resin, and the tackifier resin contained in the adhesive layer formed a crosslinked structure with the crosslinking agent.

[0151] The table indicates the presence or absence of carboxyl groups and hydroxyl groups as functional groups possessed by the tackifier resin. The tackifier resin contained in the labels of Examples 1 to 13 contained carboxyl groups and / or hydroxyl groups. It is presumed that these functional groups react with the toluene diisocyanate polyisocyanate of the isocyanate crosslinking agent contained in the adhesive composition to form a crosslinked structure, which is then crosslinked with the polymer component (A) via the crosslinking agent, thereby preventing the tackifier resin from eluting in solvents used in dry cleaning and suppressing label peeling.

[0152] Furthermore, in the labels of Examples 1 to 13, the polymer component (B) contained in the heat-sensitive adhesive composition of the heat-sensitive adhesive layer has a carboxyl group, and the polymer component (A) contained in the adhesive composition of the adhesive layer has a carboxyl group derived from acrylic acid. These functional groups serve as crosslinking points and are crosslinked by the crosslinking agent, which strengthens the adhesion at the interface between the adhesive layer and the heat-sensitive adhesive layer and prevents peeling at the interface, thereby increasing strength against solvents. This is also thought to have improved dry cleaning resistance.

[0153] The configurations and combinations thereof in each embodiment are merely examples, and additions, omissions, substitutions, and other modifications of the configurations are possible without departing from the spirit of the present invention. Furthermore, the present invention is not limited to each embodiment, but is limited only by the scope of the claims. [Explanation of symbols]

[0154] 1... cleaning label, 10... substrate, 20... heat-sensitive adhesive layer, 30... adhesive layer, 40... release liner

Claims

1. A substrate; a heat-sensitive adhesive layer laminated on one surface of the substrate; a pressure-sensitive adhesive layer laminated on the surface of the heat-sensitive adhesive layer opposite to the surface on which the base material is laminated, the pressure-sensitive adhesive layer is formed using a pressure-sensitive adhesive composition containing a polymer component (A), a tackifying resin, and a crosslinking agent, The heat-sensitive adhesive layer contains a polymer component (B), the crosslinking agent forms a crosslinked structure with the tackifier resin, The crosslinking agent further forms a crosslinked structure with the polymer component (A), The crosslinking agent further forms a crosslinked structure with the polymer component (B), the polymer component (A) contains an acrylic polymer, and the content of structural units derived from 2-ethylhexyl acrylate relative to 100% by mass of the polymer component (A) is 50% by mass or more, and the acrylic polymer further contains structural units derived from a carboxyl group-containing monomer, The polymer component (B) contains a polyolefin resin having a carboxyl group, The pressure-sensitive adhesive composition includes an isocyanate-based crosslinking agent as the crosslinking agent.

2. 2. The cleaning label according to claim 1, wherein the content of the tackifier resin relative to 100 parts by mass of the polymer component (A) in the pressure-sensitive adhesive layer is 10 parts by mass or more.

3. 3. The cleaning label according to claim 1, wherein the tackifier resin is at least one type of tackifier resin selected from the group consisting of rosin-based tackifier resins and terpene phenol-based tackifier resins.

4. The cleaning label according to any one of claims 1 to 3, wherein the glass transition temperature (Tg) of the polymer component (A) is -40°C or lower.

5. The cleaning label according to any one of claims 1 to 4, wherein the adhesive layer has a thickness of 15 µm or less.

6. The cleaning label according to any one of claims 1 to 5, wherein the melting point of the heat-sensitive adhesive layer is 130°C or lower.

7. The cleaning label according to any one of claims 1 to 6, wherein the substrate is at least one selected from the group consisting of a foamed resin film, a synthetic paper having micropores, and a resin film having micropores.

8. a heat-sensitive adhesive layer containing the polymer component (B) provided on one surface of a substrate; providing a pressure-sensitive adhesive layer on a surface of the heat-sensitive adhesive layer opposite to the surface on which the substrate is laminated, using the pressure-sensitive adhesive composition containing the polymer component (A), the tackifier resin, and the crosslinking agent; the crosslinking agent forms a crosslinked structure with the tackifier resin, The crosslinking agent further forms a crosslinked structure with the polymer component (A), The method for producing a label for cleaning according to any one of claims 1 to 7, wherein the crosslinking agent further forms a crosslinked structure with the polymer component (B).

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