WO2020079948A1 - Adhesive sheet and method for producing same - Google Patents

Adhesive sheet and method for producing same Download PDF

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Publication number
WO2020079948A1
WO2020079948A1 PCT/JP2019/032632 JP2019032632W WO2020079948A1 WO 2020079948 A1 WO2020079948 A1 WO 2020079948A1 JP 2019032632 W JP2019032632 W JP 2019032632W WO 2020079948 A1 WO2020079948 A1 WO 2020079948A1
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WO
WIPO (PCT)
Prior art keywords
adhesive sheet
pressure
sensitive adhesive
coating layer
solvent
Prior art date
Application number
PCT/JP2019/032632
Other languages
French (fr)
Japanese (ja)
Inventor
寛三 清水
英志 桑江
Original Assignee
日榮新化株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by 日榮新化株式会社 filed Critical 日榮新化株式会社
Priority to JP2020552552A priority Critical patent/JP7329857B2/en
Priority to CN201980066352.8A priority patent/CN112823191A/en
Publication of WO2020079948A1 publication Critical patent/WO2020079948A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]

Definitions

  • the technology disclosed in the present specification relates to an adhesive sheet provided with a coating layer and a method for manufacturing the same.
  • Patent Document 1 a package made of a water-soluble film containing polyvinyl alcohol (PVA) resin and denatonium benzoate, which is a bitter component, is used to prevent infants from accidentally ingesting a liquid detergent or the like.
  • PVA polyvinyl alcohol
  • Patent Document 1 discloses an adhesive sheet in which an adhesive layer contains an accidental ingestion inhibitor having an emetic property.
  • Patent Document 2 discloses an adhesive sheet in which an adhesive layer contains an accidental ingestion inhibitor having an emetic property.
  • an adhesive sheet is not exposed unless the pressure-sensitive adhesive sheet is peeled off, and thus accidental ingestion of the toy cannot be prevented.
  • An object of the present invention is to provide an adhesive sheet that can effectively prevent accidental ingestion of an adherend.
  • the pressure-sensitive adhesive sheet disclosed in the present specification includes a base film, a coating layer formed on one surface of the base film, containing a bitter component, and comprising a cured product of a solvent-based paint, and the base film. And an adhesive layer formed on the other surface of the.
  • the coating layer contains 2% by mass or more of the bitterness component with respect to the resin solid content of the solvent-based paint. Particularly, it is preferable that the coating layer contains a curing agent.
  • the production method of the pressure-sensitive adhesive sheet of the present invention on one surface of the substrate film, a solvent-based paint containing a bitterness component and a curing agent is applied, and the resin solid content in the solvent-based paint and the curing agent A step of forming a coating layer by a curing reaction, And a step of providing an adhesive layer on the other surface of the base film.
  • the coating layer made of the cured product of the solvent-based paint containing the bitterness component is provided, it is possible to effectively prevent accidental ingestion of the adherend.
  • FIG. 1 is a cross-sectional view showing an example of the pressure-sensitive adhesive sheet disclosed in this specification.
  • FIG. 2 is a diagram showing results of a wiping test using alcohol for the pressure-sensitive adhesive sheet disclosed in the present specification.
  • FIG. 3 is a diagram showing a wiping test using alcohol for a pressure-sensitive adhesive sheet having a coating layer prepared by adding a curing agent to a solvent-based paint.
  • the inventors of the present invention considered coating the surface of the pressure-sensitive adhesive sheet with a water-soluble resin containing a bitter component in order to prevent accidental ingestion of the adherend.
  • the coating layer having a bitter taste may disappear by washing with water or wiping with water. Therefore, when the adherend is a toy or the like, it is considered that the accidental ingestion prevention effect may be lost by washing with water to remove dirt or licking by an infant. Therefore, the inventors of the present application studied to provide a pressure-sensitive adhesive sheet with a coating layer made of a solvent-based paint so that the bitterness of the coating layer can be maintained even after washing with water, and conceived the present invention.
  • FIG. 1 is a cross-sectional view showing an example of the pressure-sensitive adhesive sheet 10 disclosed in this specification.
  • the pressure-sensitive adhesive sheet 10 of the present embodiment includes a base film 5, a coating layer 7 formed on one surface of the base film 5 and made of a cured product of a solvent-based paint, and a base material.
  • the adhesive layer 3 formed on the other surface of the film 5 and the release liner 1 provided on the surface of the adhesive layer 3 opposite to the base film 5 are provided.
  • the “solvent-based paint” means a paint that is poorly soluble in water but well soluble in an organic solvent.
  • the coating layer 7 contains a bitter ingredient.
  • the bitter component for example, one or a mixture of two or more selected from the group consisting of denatonium salt or its derivative, octaacetylsucrose, quercetin, quassin, hop extract and the like can be used. Since these bitterness components are highly safe, they are preferably used even when the adherend of the pressure-sensitive adhesive sheet 10 is a toy or the like for infants.
  • denatonium benzoate, saccharin denatonium, denatonium chloride or a mixture thereof is used as a bitterness component, even a small amount can exert the effect of preventing accidental ingestion.
  • the pressure-sensitive adhesive sheet 10 can be attached to any adherend by cutting it into an appropriate shape.
  • This pressure-sensitive adhesive sheet 10 may be directly attached to the surface of an article such as a toy, but it is attached to the print layer of a label having a print layer on one surface and an adhesive layer on the other surface. You may be asked.
  • the coating layer 7 is formed of a cured product of a solvent-based paint, so that the coating layer 7 is less likely to be washed out even after being washed with water or wiped with water. Therefore, even if the adherend is a toy or the like, the effect of preventing accidental ingestion can be maintained for a long period of time.
  • a solvent-based paint such as acrylic, epoxy, urethane, silicone, and rubber can be used.
  • the bitterness component may be contained in the coating layer 7 at a concentration sufficient for humans to feel the bitterness. Since the coating layer 7 is formed of the cured product of the solvent-based paint, the bitterness component is less likely to dissolve into saliva as compared with the case where it is formed of the cured product of the water-based paint. For example, in the water-soluble film described in Patent Document 1, bitterness can be felt even when the concentration of denatonium benzoate, which is a bitterness component, added to the PVA resin is 0.001% by mass. On the other hand, in the pressure-sensitive adhesive sheet 10 of the present embodiment, the ratio of the bitterness component to the resin solid content of the coating layer 7 is 2% by mass or more.
  • the sensitivity to bitterness varies from person to person, if the content ratio of the bitterness component to the resin solid content is 2% by mass or more, the effect of preventing accidental ingestion can be sufficiently exerted.
  • the concentration of the bitterness component may be equal to or lower than the upper limit at which the bitterness component can be dissolved in the coating, but in order to avoid precipitation of the bitterness component, the content ratio of the bitterness component to the resin solid content may be 10% by mass or less.
  • the bitterness component may be mixed in the coating layer 7 as it is, or may be encapsulated in a water-soluble fine capsule.
  • the film thickness of the coating layer 7 is not particularly limited, it may be 0.1 ⁇ m or more and 10 ⁇ m or less, or may be 0.5 ⁇ m or more and 5 ⁇ m or less in consideration of ease of manufacturing and manufacturing cost. The thicker the coating layer 7, the longer the coating layer 7 is maintained, and the longer the effect of preventing accidental ingestion is.
  • the constituent material of the base film 5 is not particularly limited, but may be, for example, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene (PP), polyethylene (PE), polyvinyl chloride, or the like.
  • the constituent material of the base film 5 may be translucent, and may be colored or, in the case of lamination, may be matted. If the total light transmittance of the adhesive sheet 10 (measured according to JIS K7361-1) is about 70% or more, the article to which the adhesive sheet 10 is applied without impairing the design of the decorative layer of the underlying label You can prevent accidental ingestion. In this case, since it can be used for a label or an adherend having any pattern, the versatility of the adhesive sheet 10 can be enhanced.
  • total light transmittance of the pressure-sensitive adhesive sheet specifically refers to the “total light transmittance of the main body portion 11 of the pressure-sensitive adhesive sheet 10 with the release liner 1 removed from the pressure-sensitive adhesive sheet 10." Shall be pointed out.
  • the thickness of the base material film 5 is not particularly limited, but may be about 2 ⁇ m or more and 250 ⁇ m or less, or may be about 10 ⁇ m or more and 100 ⁇ m or less from the viewpoint of easy handling and manufacturing cost.
  • the pressure-sensitive adhesive layer 3 may be formed of a cured product of a general pressure-sensitive adhesive.
  • the pressure-sensitive adhesive used for forming the pressure-sensitive adhesive layer 3 may be, for example, a known acrylic pressure-sensitive adhesive, silicone pressure-sensitive adhesive, rubber pressure-sensitive adhesive or polyester pressure-sensitive adhesive.
  • the thickness of the pressure-sensitive adhesive layer 3 is not particularly limited, but may be, for example, 5 ⁇ m or more and 50 ⁇ m or less.
  • the adhesive force of the adhesive layer 3 to the adherend may be set arbitrarily, but as a guide, if it is at least about 5 N / 25 mm or more with respect to stainless steel, the user (for example, an infant) is stuck to the adherend.
  • the pressure-sensitive adhesive sheet 10 can be made difficult to peel off, and if it is 8 N / 25 mm or more, the pressure-sensitive adhesive sheet 10 can be made more difficult to peel off.
  • the pressure-sensitive adhesive force of the pressure-sensitive adhesive layer 3 to the adherend may be less than 5 N / 25 mm.
  • the release liner 1 may have a configuration that allows the main body portion 11 of the adhesive sheet 10 to be easily peeled off from the release liner 1 during use.
  • a release liner 1 may be formed by forming a known release agent layer on the surface of the base material such as glassine paper, high-quality paper, or resin film on the side of the pressure-sensitive adhesive layer 3.
  • the paint containing the bitterness component and the solvent-based paint used for forming the coating layer 7 may be directly applied to an article such as a toy to prevent accidental ingestion of the article.
  • the pressure-sensitive adhesive sheet 10 of the present embodiment is superior to the method of directly applying the paint to the article in that it can be peeled off from the adherend or replaced with a new one as needed. This advantage does not change even when the adhesive sheet 10 is attached to the surface of the printed label.
  • the pressure-sensitive adhesive sheet 10 described above is an example of the embodiment, and the configuration of the pressure-sensitive adhesive sheet may be appropriately changed without departing from the spirit of the present invention.
  • a commercially available solvent-based paint is diluted with a solvent such as toluene or ethyl acetate to have an appropriate viscosity to prepare a coating liquid.
  • This coating solution is thinly applied to one surface of the base film 5 using a coater to form a coating layer 7 having a thickness after drying of about 0.1 ⁇ m or more and about 10 ⁇ m or less.
  • the coater used for coating the coating liquid can be appropriately selected from a knife coater, a comma type coater, a micro bar coater, an air knife coater, a reverse roll coater, a reverse gravure coater, a die coater, a curtain coater and the like.
  • a pressure-sensitive adhesive layer 3 is formed by applying a coating liquid containing a commercially available pressure-sensitive adhesive to the release surface of the release liner 1 and drying it.
  • the pressure-sensitive adhesive sheet 10 of the present embodiment is formed by bonding the surface of the base film 5 opposite to the coating layer 7 to the surface of the pressure-sensitive adhesive layer 3 opposite to the release liner 1. be able to.
  • the adhesive sheet 10 can be appropriately processed into a predetermined size by a slitter and a cutting machine.
  • the pressure-sensitive adhesive sheet 10 from which the release liner 1 has been peeled off may be attached to the print layer of the label, for example, the back surface of which is adhesively processed and the print layer is provided on the front surface.
  • the label laminate including the pressure-sensitive adhesive sheet 10 (hereinafter, simply referred to as “label”) may be punched into a predetermined shape. This label is attached to an article such as a toy.
  • the pressure-sensitive adhesive processing step instead of the above method, after applying a coating liquid containing a pressure-sensitive adhesive to the surface of the base film 5 opposite to the coating layer 7, the pressure-sensitive adhesive layer 3 is removed.
  • the base film 5 and the release liner 1 may be attached so as to be sandwiched between.
  • the coating layer 7 may be formed after the adhesive processing step.
  • a known curing agent such as an epoxy type, an isocyanate type, a metal chelate type, or a melamine type may be added to the solvent-based paint used for forming the coating layer 7.
  • the addition amount of the curing agent is not particularly limited, but may be, for example, about 0.1 parts by mass to 10 parts by mass with respect to 100 parts by mass of the resin solid content in the solvent-based paint used for forming the coating layer. Since the crosslinking density in the coating layer 7 can be increased by using the curing agent, it is possible to prevent the coating layer from peeling off when wiping with water. As a result, even if the number of times of wiping with water is increased, bitterness can be maintained more easily than in the case where no curing agent is used.
  • the addition of the curing agent to the solvent-based coating makes it easier to maintain the bitterness even when wiping is repeated using a liquid containing alcohol such as ethanol. Therefore, even if stains are repeatedly wiped off with a liquid containing alcohol for disinfection, the effect of preventing accidental ingestion can be exerted for a long period of time.
  • the pressure-sensitive adhesive sheet 10 of the present embodiment can also be used alone or in the form of a label laminate as an animal repellent sheet. Since dogs, cats, boars, etc. tend to avoid bitterness components like humans, for example, by arranging the adhesive sheet 10 or the label laminate at a place where animal excrement damage or food damage occurs, These damages can be reduced.
  • the animal repellent effect of the pressure-sensitive adhesive sheet 10 is more effective for animals that largely depend on information by taste. Therefore, the adhesive sheet 10 of the present embodiment has a greater repellent effect on cats than dogs, for example.
  • Sensitivity to bitterness varies from person to person, but it is generally less likely to feel bitterness with age, so it can be said that children are more sensitive to bitterness than adults. Also, smokers tend to be less sensitive to bitterness. Therefore, by setting the concentration of the bitterness component blended in the coating layer 7 to a relatively low concentration (for example, 2% by mass or more and less than 6% by mass based on the resin solid content of the solvent-based paint), the pressure-sensitive adhesive sheet according to the present embodiment The accidental ingestion prevention effect of 10 can be easily exerted selectively on the child.
  • the concentration of the bitterness component blended in the coating layer 7 is relatively high (for example, 6% by mass or more and 10% by mass or more with respect to the resin solid content of the solvent-based paint). Mass% or less).
  • a plurality of pressure-sensitive adhesive sheets 10 having different concentrations of bitterness components can be set as one set to serve as an aging checker. For example, if you can feel the bitterness of the adhesive sheet 10 having the lowest bitterness component concentration, it is determined to be “young”, and if you cannot feel the bitterness of the adhesive sheet 10 having the highest bitterness component concentration, it is “aged”. Can be determined.
  • Example 1 In a mixed solvent of 100 parts by mass of toluene, 100 parts by mass of ethyl acetate and 5 parts by mass of methanol, 0.492 parts of denatonium benzoate powder (manufactured by MacFarlan Smith Co., Ltd .; product name "Vitrex”) was dissolved.
  • this denatonium benzoate solution total 205.492 parts by mass
  • a coating liquid was prepared by mixing the same with parts by mass, and the coating liquid was applied to one surface of a transparent PET film (manufactured by Toray Industries, Inc .; product name “Lumirror T11”). Then, the PET film was dried at 100 ° C. for 1 minute to form a coating layer having a thickness of 1 ⁇ m on the PET film.
  • this pressure-sensitive adhesive sheet contains 2.00% by mass of denatonium benzoate with respect to the resin solid content on a mass basis.
  • an adhesive sheet having a structure as shown in FIG. 1 was produced.
  • the total light transmittance of the pressure-sensitive adhesive sheet (measured according to JIS K7361-1) was 91.72%.
  • Example 2 A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1 except that the amount of denatonium benzoate powder mixed with 100 parts by mass of the thermoplastic acrylic acid ester-based polymer solution was changed to 1.23 parts by mass.
  • the coating layer of this pressure-sensitive adhesive sheet contains 5.00% by mass of denatonium benzoate based on the resin solid content.
  • the total light transmittance of this pressure-sensitive adhesive sheet was 91.84%.
  • Example 3 To the coating liquid for forming the coating layer, 0.91 part of a commercially available melamine-based curing agent and 0.45 part of a commercially available isocyanate-based curing agent were added to 100 parts by weight of the thermoplastic acrylic acid ester-based polymer.
  • a pressure-sensitive adhesive sheet was produced by the same method as in Example 2 except for.
  • a pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that the amount of denatonium benzoate powder mixed with 100 parts by mass of the thermoplastic acrylic ester polymer solution was changed to 0.123 parts by mass.
  • the coating layer of this pressure-sensitive adhesive sheet contains denatonium benzoate in an amount of 0.50% by mass based on the resin solid content.
  • the total light transmittance of this pressure-sensitive adhesive sheet was 91.73%.
  • This denatonium benzoate solution (total of 200.00147 parts by mass) and a solution of PVA resin containing water (manufactured by Taisei Kagaku Co., Ltd .; product name "Maltite 150") (resin solid content 14.7% by mass) are mixed.
  • To prepare a coating liquid and the coating liquid was applied to one surface of the transparent PET film. Then, the PET film was dried at 100 ° C. for 1 minute to form a coating layer having a thickness of 1 ⁇ m on the PET film.
  • the coating layer of this pressure-sensitive adhesive sheet contains 0.01% by mass of denatonium benzoate based on the resin solid content. The total light transmittance of this pressure-sensitive adhesive sheet was 91.72%.
  • a pressure-sensitive adhesive sheet was produced in the same manner as in Comparative Example 2 except that the amount of denatonium benzoate contained in the dried coating layer was adjusted to be 1.00% by mass based on the resin solid content of the layer. .
  • the total light transmittance of this pressure-sensitive adhesive sheet was 91.70%.
  • test piece with a size of 2.5 cm ⁇ 2.5 cm was cut out from each produced pressure-sensitive adhesive sheet, and this was used as a test piece before wiping with water.
  • the test piece cut out from each pressure-sensitive adhesive sheet was wiped 10 times in one direction with a cloth impregnated with pure water from the coating layer side, and this was used as a test piece after wiping with water.
  • Whether or not the coating layer of each test piece before and after wiping with water was lightly licked once with a tongue and whether bitterness was felt was confirmed by 5 men, 3 men and 2 women, and evaluated as follows. The cloth was replaced with a new one after each wipe.
  • Table 1 shows the test results for the prevention of accidental ingestion of the adhesive sheet.
  • FIG. 2 is a diagram showing the result of wiping the pressure-sensitive adhesive sheet prepared in Example 2 with ethanol
  • FIG. 3 is a diagram showing the result of wiping the pressure-sensitive adhesive sheet prepared in Example 3 with ethanol.
  • the coating layer formed without using the curing agent began to peel off in a streak shape at the time of wiping three times with ethanol, and after the tenth wiping was completed. The coating layer was completely removed. The bitterness was maintained until after the sixth wiping, but the bitterness disappeared after the tenth wiping.
  • the pressure-sensitive adhesive sheet disclosed in this specification is used to prevent accidental ingestion of adherends that may be accidentally ingested, such as toys.

Abstract

Provided are an adhesive sheet capable of effectively preventing accidental ingestion of an adherend, and a method for producing the adhesive sheet. The adhesive sheet 10 is equipped with: a base film 5; a coating layer 7 composed of a cured product of a solvent-based paint that contains a bitter component, the coating layer 7 being formed on one surface of the base film 5; and an adhesive layer 3 formed on the other surface of the base film 5. The coating layer 7 contains 2 mass% or more of the bitter component relative to the resin solids fraction of the solvent-based paint. The coating layer 7 preferably includes a curing agent.

Description

粘着シート及びその製造方法Adhesive sheet and manufacturing method thereof
　本明細書に開示された技術は、コーティング層が設けられた粘着シート及びその製造方法に関する。 The technology disclosed in the present specification relates to an adhesive sheet provided with a coating layer and a method for manufacturing the same.
　乳幼児が液体洗剤等を誤飲するのを防止するために、ポリビニルアルコール（ＰＶＡ）樹脂と、苦味成分である安息香酸デナトニウムとを含有する水溶性フィルムからなる包装体が用いられることが知られている（特許文献１）。 It is known that a package made of a water-soluble film containing polyvinyl alcohol (PVA) resin and denatonium benzoate, which is a bitter component, is used to prevent infants from accidentally ingesting a liquid detergent or the like. (Patent Document 1).
特開２０１６－１０８４２６号公報JP, 2016-108426, A 特許５７３６７３０号公報Japanese Patent No. 5736730
　しかしながら、玩具等の誤飲を防ぐ目的で特許文献１に記載の包装体を用いる場合、包装体を開封した後、玩具自体の誤飲を防ぐことはできない。
　一方、特許文献２には、粘着剤層に催吐性を有する誤飲防止剤を含有させた粘着シートが開示されている。しかし、玩具にこの粘着シートを貼り付けたとしても、当該粘着シートを剥がさなければ粘着剤層は露出しないので、玩具の誤飲を防ぐことはできない。
　本発明は、被着体の誤飲を効果的に防ぎうる粘着シートを提供することを目的とする。 However, when the package described in Patent Document 1 is used for the purpose of preventing accidental ingestion of a toy or the like, it is not possible to prevent accidental ingestion of the toy itself after opening the package.
On the other hand, Patent Document 2 discloses an adhesive sheet in which an adhesive layer contains an accidental ingestion inhibitor having an emetic property. However, even if this pressure-sensitive adhesive sheet is attached to a toy, the pressure-sensitive adhesive layer is not exposed unless the pressure-sensitive adhesive sheet is peeled off, and thus accidental ingestion of the toy cannot be prevented.
An object of the present invention is to provide an adhesive sheet that can effectively prevent accidental ingestion of an adherend.
　本明細書に開示された粘着シートは、基材フィルムと、前記基材フィルムの一方の面上に形成され、苦味成分を含み、溶剤系塗料の硬化物からなるコーティング層と、前記基材フィルムの他方の面上に形成された粘着剤層とを備えている。前記コーティング層には、前記溶剤系塗料の樹脂固形分に対して２質量％以上の前記苦味成分が含まれている。特に、前記コーティング層が硬化剤を含むことが好ましい。
　又、本発明の粘着シートの製造方法は、基材フィルムの一方の面上に、苦味成分と硬化剤を含む溶剤系塗料を塗布し、前記溶剤系塗料中の樹脂固形分と硬化剤との硬化反応によりコーティング層を形成する工程と、
　前記基材フィルムの他方の面上に粘着剤層を設ける工程と
を含むことを特徴とする。 The pressure-sensitive adhesive sheet disclosed in the present specification includes a base film, a coating layer formed on one surface of the base film, containing a bitter component, and comprising a cured product of a solvent-based paint, and the base film. And an adhesive layer formed on the other surface of the. The coating layer contains 2% by mass or more of the bitterness component with respect to the resin solid content of the solvent-based paint. Particularly, it is preferable that the coating layer contains a curing agent.
Further, the production method of the pressure-sensitive adhesive sheet of the present invention, on one surface of the substrate film, a solvent-based paint containing a bitterness component and a curing agent is applied, and the resin solid content in the solvent-based paint and the curing agent A step of forming a coating layer by a curing reaction,
And a step of providing an adhesive layer on the other surface of the base film.
　本明細書に開示された粘着シートによれば、苦味成分を含む溶剤系塗料の硬化物からなるコーティング層が設けられているので、被着体の誤飲を効果的に防止しうる。 According to the pressure-sensitive adhesive sheet disclosed in the present specification, since the coating layer made of the cured product of the solvent-based paint containing the bitterness component is provided, it is possible to effectively prevent accidental ingestion of the adherend.
図１は、本明細書に開示された粘着シートの一例を示す断面図である。FIG. 1 is a cross-sectional view showing an example of the pressure-sensitive adhesive sheet disclosed in this specification. 図２は、本明細書に開示された粘着シートに対するアルコールを用いた拭き取り試験の結果を示す図である。FIG. 2 is a diagram showing results of a wiping test using alcohol for the pressure-sensitive adhesive sheet disclosed in the present specification. 図３は、溶剤系塗料に硬化剤を加えて作製したコーティング層を有する粘着シートに対するアルコールを用いた拭き取り試験を示す図である。FIG. 3 is a diagram showing a wiping test using alcohol for a pressure-sensitive adhesive sheet having a coating layer prepared by adding a curing agent to a solvent-based paint.
　当初、本願発明者らは、被着体の誤飲を防止するために、粘着シートの表面に苦味成分を含む水溶性樹脂をコーティングすることを考えた。しかし、この粘着シートでは、水洗いや水拭きによって苦味を呈するコーティング層が消失する可能性があることが分かった。従って、被着体が玩具等である場合、汚れを落とすために水洗いしたり、乳幼児が舐めたりすることで、誤飲防止効果が失われる可能性があると考えられた。
　そこで、本願発明者らは、水洗いした場合でもコーティング層の苦味を維持できるように、溶剤系塗料からなるコーティング層を粘着シートに設けることを検討し、本願発明に想到した。 Initially, the inventors of the present invention considered coating the surface of the pressure-sensitive adhesive sheet with a water-soluble resin containing a bitter component in order to prevent accidental ingestion of the adherend. However, in this pressure-sensitive adhesive sheet, it was found that the coating layer having a bitter taste may disappear by washing with water or wiping with water. Therefore, when the adherend is a toy or the like, it is considered that the accidental ingestion prevention effect may be lost by washing with water to remove dirt or licking by an infant.
Therefore, the inventors of the present application studied to provide a pressure-sensitive adhesive sheet with a coating layer made of a solvent-based paint so that the bitterness of the coating layer can be maintained even after washing with water, and conceived the present invention.
（実施形態）
　図１は、本明細書に開示された粘着シート１０の一例を示す断面図である。同図に示すように、本実施形態の粘着シート１０は、基材フィルム５と、基材フィルム５の一方の面上に形成され、溶剤系塗料の硬化物からなるコーティング層７と、基材フィルム５の他方の面上に形成された粘着剤層３と、粘着剤層３の基材フィルム５とは反対側の面上に設けられた剥離ライナー１とを備えている。ここで、「溶剤系塗料」とは、水には難溶性であるのに対して有機溶媒にはよく溶ける塗料を意味する。 (Embodiment)
FIG. 1 is a cross-sectional view showing an example of the pressure-sensitive adhesive sheet 10 disclosed in this specification. As shown in the figure, the pressure-sensitive adhesive sheet 10 of the present embodiment includes a base film 5, a coating layer 7 formed on one surface of the base film 5 and made of a cured product of a solvent-based paint, and a base material. The adhesive layer 3 formed on the other surface of the film 5 and the release liner 1 provided on the surface of the adhesive layer 3 opposite to the base film 5 are provided. Here, the “solvent-based paint” means a paint that is poorly soluble in water but well soluble in an organic solvent.
　コーティング層７には、苦味成分が含まれている。苦味成分としては、例えば、デナトニウム塩もしくはその誘導体、オクタアセチルスクロース、クェルセチン、クァシン、ホップ抽出物等からなる群から選ばれた１つ又は２つ以上の混合物を用いることができる。これらの苦味成分は安全性が高いので、粘着シート１０の被着体が、乳幼児を対象とする玩具等である場合でも、好ましく用いられる。上述の物質のうち、安息香酸デナトニウム、サッカリンデナトニウム、塩化デナトニウム又はこれらの混合物を苦味成分として用いる場合、少量でも誤飲防止効果を発揮できる。 The coating layer 7 contains a bitter ingredient. As the bitter component, for example, one or a mixture of two or more selected from the group consisting of denatonium salt or its derivative, octaacetylsucrose, quercetin, quassin, hop extract and the like can be used. Since these bitterness components are highly safe, they are preferably used even when the adherend of the pressure-sensitive adhesive sheet 10 is a toy or the like for infants. Among the above-mentioned substances, when denatonium benzoate, saccharin denatonium, denatonium chloride or a mixture thereof is used as a bitterness component, even a small amount can exert the effect of preventing accidental ingestion.
　粘着シート１０から剥離ライナー１を剥がしてこの粘着シート１０を被着体に貼付した場合、苦味成分を含むコーティング層７が露出することになるので、特許文献２に記載の粘着シートとは異なり、被着体自体が誤飲されるのを防ぐことができる。また、粘着シート１０は適切な形状に裁断すれば被着体を選ばずに貼り付けることができる。この粘着シート１０は、直接玩具等の物品表面に貼り付けられてもよいが、一方の面に印刷層が設けられ、他方の面に粘着剤層が設けられたラベルの印刷層上に貼り付けられてもよい。 When the release liner 1 is peeled off from the pressure-sensitive adhesive sheet 10 and the pressure-sensitive adhesive sheet 10 is attached to an adherend, the coating layer 7 containing the bitterness component is exposed. Therefore, unlike the pressure-sensitive adhesive sheet described in Patent Document 2, It is possible to prevent the adherend from being accidentally ingested. The pressure-sensitive adhesive sheet 10 can be attached to any adherend by cutting it into an appropriate shape. This pressure-sensitive adhesive sheet 10 may be directly attached to the surface of an article such as a toy, but it is attached to the print layer of a label having a print layer on one surface and an adhesive layer on the other surface. You may be asked.
　本実施形態の粘着シート１０では、コーティング層７が溶剤系塗料の硬化物により形成されているので、水洗いや水拭きを行った後でもコーティング層７が流失しにくくなっている。このため、被着体が玩具等の場合であっても、誤飲防止効果を長期間維持することができる。コーティング層７を形成するための塗料としては、アクリル系、エポキシ系、ウレタン系、シリコーン系、ゴム系等の公知の溶剤系塗料を用いることができる。 In the pressure-sensitive adhesive sheet 10 of the present embodiment, the coating layer 7 is formed of a cured product of a solvent-based paint, so that the coating layer 7 is less likely to be washed out even after being washed with water or wiped with water. Therefore, even if the adherend is a toy or the like, the effect of preventing accidental ingestion can be maintained for a long period of time. As the paint for forming the coating layer 7, known solvent-based paints such as acrylic, epoxy, urethane, silicone, and rubber can be used.
　苦味成分は、ヒトが苦味を感じるのに十分な濃度でコーティング層７に含まれていればよい。コーティング層７は溶剤系塗料の硬化物により形成されているので、水性塗料の硬化物により形成される場合に比べて、唾液に対して苦味成分が溶け出しにくくなっている。例えば、特許文献１に記載の水溶性フィルムでは、苦味成分である安息香酸デナトニウムのＰＶＡ樹脂に対する添加濃度を０．００１質量％としても苦味を感じさせることができる。これに対し、本実施形態の粘着シート１０では、コーティング層７の樹脂固形分に対する苦味成分の割合は、２質量％以上となっている。苦味に対する感度は個人差があるが、樹脂固形分に対する苦味成分の含有割合を２質量％以上とすれば、十分に誤飲防止効果を発揮させることができる。一方、苦味成分の濃度は、当該苦味成分が塗料に溶解できる上限以下であればよいが、苦味成分の析出を避けるために、樹脂固形分に対する苦味成分の含有割合を１０質量％以下としてもよい。苦味成分は、コーティング層７にそのまま混入されていてもよいし、水溶性の微細なカプセル内に封入されていてもよい。 The bitterness component may be contained in the coating layer 7 at a concentration sufficient for humans to feel the bitterness. Since the coating layer 7 is formed of the cured product of the solvent-based paint, the bitterness component is less likely to dissolve into saliva as compared with the case where it is formed of the cured product of the water-based paint. For example, in the water-soluble film described in Patent Document 1, bitterness can be felt even when the concentration of denatonium benzoate, which is a bitterness component, added to the PVA resin is 0.001% by mass. On the other hand, in the pressure-sensitive adhesive sheet 10 of the present embodiment, the ratio of the bitterness component to the resin solid content of the coating layer 7 is 2% by mass or more. Although the sensitivity to bitterness varies from person to person, if the content ratio of the bitterness component to the resin solid content is 2% by mass or more, the effect of preventing accidental ingestion can be sufficiently exerted. On the other hand, the concentration of the bitterness component may be equal to or lower than the upper limit at which the bitterness component can be dissolved in the coating, but in order to avoid precipitation of the bitterness component, the content ratio of the bitterness component to the resin solid content may be 10% by mass or less. . The bitterness component may be mixed in the coating layer 7 as it is, or may be encapsulated in a water-soluble fine capsule.
　コーティング層７の膜厚は特に限定されないが、製造のしやすさ及び製造コストを考慮して、０．１μｍ以上１０μｍ以下としてもよく、０．５μｍ以上５μｍ以下程度としてもよい。コーティング層７が厚い程、コーティング層７は長期間維持され、誤飲防止効果も長持ちする。 Although the film thickness of the coating layer 7 is not particularly limited, it may be 0.1 μm or more and 10 μm or less, or may be 0.5 μm or more and 5 μm or less in consideration of ease of manufacturing and manufacturing cost. The thicker the coating layer 7, the longer the coating layer 7 is maintained, and the longer the effect of preventing accidental ingestion is.
　基材フィルム５の構成材料は特に限定されないが、例えばポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）、ポリプロピレン（ＰＰ）、ポリエチレン（ＰＥ）、ポリ塩化ビニル等であってもよい。 The constituent material of the base film 5 is not particularly limited, but may be, for example, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene (PP), polyethylene (PE), polyvinyl chloride, or the like.
　基材フィルム５の構成材料は、透光性を有していてもよく、着色されたり、ラミネートの場合、マット加工が施されていてもよい。粘着シート１０の全光線透過率（ＪＩＳ　Ｋ７３６１－１に準じて測定）が７０％程度以上であれば、下地となるラベルの装飾層等の意匠性を損なうことなく粘着シート１０が適用される物品の誤飲を防ぐことができる。この場合、どのような模様が施されたラベル又は被着体に対しても使用できるので、粘着シート１０の汎用性を高めることができる。 The constituent material of the base film 5 may be translucent, and may be colored or, in the case of lamination, may be matted. If the total light transmittance of the adhesive sheet 10 (measured according to JIS K7361-1) is about 70% or more, the article to which the adhesive sheet 10 is applied without impairing the design of the decorative layer of the underlying label You can prevent accidental ingestion. In this case, since it can be used for a label or an adherend having any pattern, the versatility of the adhesive sheet 10 can be enhanced.
　なお、本明細書において、「粘着シートの全光線透過率」とは、具体的には、粘着シート１０から剥離ライナー１を剥がした状態の粘着シート１０の本体部分１１の全光線透過率」を指すものとする。 In the present specification, the "total light transmittance of the pressure-sensitive adhesive sheet" specifically refers to the "total light transmittance of the main body portion 11 of the pressure-sensitive adhesive sheet 10 with the release liner 1 removed from the pressure-sensitive adhesive sheet 10." Shall be pointed out.
　基材フィルム５の膜厚は特に限定されないが、取り扱い易さや製造コストの面から、２μｍ以上２５０μｍ以下程度であってもよく、１０μｍ以上１００μｍ以下程度としてもよい。 The thickness of the base material film 5 is not particularly limited, but may be about 2 μm or more and 250 μm or less, or may be about 10 μm or more and 100 μm or less from the viewpoint of easy handling and manufacturing cost.
　粘着剤層３は、一般的な粘着剤の硬化物により形成されていればよい。粘着剤層３の形成に用いられる粘着剤は、例えば公知のアクリル系粘着剤、シリコーン系粘着剤、ゴム系粘着剤又はポリエステル系粘着剤等であってもよい。この粘着剤層３の膜厚は特に限定されないが、例えば５μｍ以上５０μｍ以下であってもよい。粘着剤層３の被着体に対する粘着力は任意に設定されてよいが、目安としてステンレス鋼に対して少なくとも５Ｎ／２５ｍｍ程度以上であれば使用者（例えば乳幼児）が被着体に貼り付けられた粘着シート１０を剥がしにくくすることができ、８Ｎ／２５ｍｍ以上であれば粘着シート１０をより剥がしにくくすることができる。粘着シート１０が再剥離可能なタイプである場合には、粘着剤層３の被着体に対する粘着力は５Ｎ／２５ｍｍ未満であってもよい。 The pressure-sensitive adhesive layer 3 may be formed of a cured product of a general pressure-sensitive adhesive. The pressure-sensitive adhesive used for forming the pressure-sensitive adhesive layer 3 may be, for example, a known acrylic pressure-sensitive adhesive, silicone pressure-sensitive adhesive, rubber pressure-sensitive adhesive or polyester pressure-sensitive adhesive. The thickness of the pressure-sensitive adhesive layer 3 is not particularly limited, but may be, for example, 5 μm or more and 50 μm or less. The adhesive force of the adhesive layer 3 to the adherend may be set arbitrarily, but as a guide, if it is at least about 5 N / 25 mm or more with respect to stainless steel, the user (for example, an infant) is stuck to the adherend. The pressure-sensitive adhesive sheet 10 can be made difficult to peel off, and if it is 8 N / 25 mm or more, the pressure-sensitive adhesive sheet 10 can be made more difficult to peel off. When the pressure-sensitive adhesive sheet 10 is a removable type, the pressure-sensitive adhesive force of the pressure-sensitive adhesive layer 3 to the adherend may be less than 5 N / 25 mm.
　剥離ライナー１は、使用時に剥離ライナー１から粘着シート１０の本体部分１１を容易に剥がせる構成を有していればよい。例えば、グラシン紙、上質紙、樹脂フィルム等の基材の粘着剤層３側の面上に公知の離型剤層が形成されたものを剥離ライナー１として用いてもよい。 The release liner 1 may have a configuration that allows the main body portion 11 of the adhesive sheet 10 to be easily peeled off from the release liner 1 during use. For example, a release liner 1 may be formed by forming a known release agent layer on the surface of the base material such as glassine paper, high-quality paper, or resin film on the side of the pressure-sensitive adhesive layer 3.
　なお、コーティング層７の形成に用いた苦味成分及び溶剤系塗料入りの塗料を、直接玩具等の物品に塗布して当該物品の誤飲防止を図ることも考えられる。しかしながら、本実施形態の粘着シート１０は、必要に応じて被着体から剥がしたり、新しいものに貼り替えたりすることができる点で、塗料を物品に直接塗布する方法よりも優れている。この利点は、印刷されたラベルの表面に粘着シート１０を貼り付ける場合であっても変わらない。 The paint containing the bitterness component and the solvent-based paint used for forming the coating layer 7 may be directly applied to an article such as a toy to prevent accidental ingestion of the article. However, the pressure-sensitive adhesive sheet 10 of the present embodiment is superior to the method of directly applying the paint to the article in that it can be peeled off from the adherend or replaced with a new one as needed. This advantage does not change even when the adhesive sheet 10 is attached to the surface of the printed label.
　なお、以上で説明した粘着シート１０は、実施形態の一例であり、粘着シートの構成は、本発明の趣旨を逸脱しない範囲において適宜変更してもよい。 The pressure-sensitive adhesive sheet 10 described above is an example of the embodiment, and the configuration of the pressure-sensitive adhesive sheet may be appropriately changed without departing from the spirit of the present invention.
－粘着シートの製造方法－
　粘着シート１０を製造するためには、まず、市販の溶剤系塗料をトルエンや酢酸エチル等の溶媒により適度な粘度になるように希釈することにより、塗液を調製する。この塗液を基材フィルム５の一方の面にコーターを用いて薄く塗工し、乾燥後の膜厚が０．１μｍ以上１０μｍ以下程度のコーティング層７を形成する。ここで、塗液の塗工に用いるコーターは、ナイフコーター、コンマ型コーター、マイクロバーコーター、エアナイフコーター、リバースロールコーター、リバースグラビアコーター、ダイコーター、カーテンコーター等から適宜選択することができる。 -Production method of adhesive sheet-
In order to manufacture the pressure-sensitive adhesive sheet 10, first, a commercially available solvent-based paint is diluted with a solvent such as toluene or ethyl acetate to have an appropriate viscosity to prepare a coating liquid. This coating solution is thinly applied to one surface of the base film 5 using a coater to form a coating layer 7 having a thickness after drying of about 0.1 μm or more and about 10 μm or less. Here, the coater used for coating the coating liquid can be appropriately selected from a knife coater, a comma type coater, a micro bar coater, an air knife coater, a reverse roll coater, a reverse gravure coater, a die coater, a curtain coater and the like.
　次に、剥離ライナー１の剥離面に市販の粘着剤を含む塗液を塗工し、乾燥させることにより粘着剤層３を形成する。続いて、当該粘着剤層３の剥離ライナー１とは反対側の面に、基材フィルム５のコーティング層７とは反対側の面を貼り合せることにより、本実施形態の粘着シート１０を形成することができる。粘着シート１０は、その後、適宜スリッター及び断裁機によって所定のサイズになるように加工することができる。その後、剥離ライナー１が剥離された粘着シート１０は、例えば、裏面が粘着加工され、表面に印刷層が設けられたラベルの印刷層に貼り付けられてもよい。この場合、粘着シート１０を含むラベル積層体（以下、単に「ラベル」と表記する）は、所定の形状になるよう抜き加工されてもよい。このラベルは、玩具等の物品に貼着される。 Next, a pressure-sensitive adhesive layer 3 is formed by applying a coating liquid containing a commercially available pressure-sensitive adhesive to the release surface of the release liner 1 and drying it. Next, the pressure-sensitive adhesive sheet 10 of the present embodiment is formed by bonding the surface of the base film 5 opposite to the coating layer 7 to the surface of the pressure-sensitive adhesive layer 3 opposite to the release liner 1. be able to. After that, the adhesive sheet 10 can be appropriately processed into a predetermined size by a slitter and a cutting machine. After that, the pressure-sensitive adhesive sheet 10 from which the release liner 1 has been peeled off may be attached to the print layer of the label, for example, the back surface of which is adhesively processed and the print layer is provided on the front surface. In this case, the label laminate including the pressure-sensitive adhesive sheet 10 (hereinafter, simply referred to as “label”) may be punched into a predetermined shape. This label is attached to an article such as a toy.
　なお、粘着加工工程においては上記方法に代えて、粘着剤を含む塗液の塗工を基材フィルム５のコーティング層７とは反対側の面に対して行った後、粘着剤層３を間に挟むようにして基材フィルム５と剥離ライナー１とを貼り合わせてもよい。また、コーティング層７の形成は、粘着加工工程の後に行ってもよい。 In the pressure-sensitive adhesive processing step, instead of the above method, after applying a coating liquid containing a pressure-sensitive adhesive to the surface of the base film 5 opposite to the coating layer 7, the pressure-sensitive adhesive layer 3 is removed. The base film 5 and the release liner 1 may be attached so as to be sandwiched between. The coating layer 7 may be formed after the adhesive processing step.
　なお、コーティング層７の形成に使用される溶剤系塗料中にエポキシ系、イソシアネート系、金属キレート系、メラミン系等の公知の硬化剤を加えてもよい。硬化剤の添加量は特に限定されないが、例えばコーティング層の形成に使用される溶剤系塗料中の樹脂固形分１００質量部に対して０．１質量部～１０質量部程度であってもよい。硬化剤の使用により、コーティング層７中の架橋密度を上げることができるので、水拭きに際してコーティング層を剥がれにくくすることができる。この結果、水拭き回数を増やしても硬化剤を使用しない場合に比べて苦味を維持しやすくなる。また、溶剤系塗料に硬化剤が添加されることによって、エタノール等のアルコールを含む液を用いて清拭が繰り返される場合にも苦味を維持しやすくなる。このため、消毒のためにアルコールを含む液で繰り返し汚れを拭き取っても、誤飲防止効果を長期間発揮できるようになる。 A known curing agent such as an epoxy type, an isocyanate type, a metal chelate type, or a melamine type may be added to the solvent-based paint used for forming the coating layer 7. The addition amount of the curing agent is not particularly limited, but may be, for example, about 0.1 parts by mass to 10 parts by mass with respect to 100 parts by mass of the resin solid content in the solvent-based paint used for forming the coating layer. Since the crosslinking density in the coating layer 7 can be increased by using the curing agent, it is possible to prevent the coating layer from peeling off when wiping with water. As a result, even if the number of times of wiping with water is increased, bitterness can be maintained more easily than in the case where no curing agent is used. In addition, the addition of the curing agent to the solvent-based coating makes it easier to maintain the bitterness even when wiping is repeated using a liquid containing alcohol such as ethanol. Therefore, even if stains are repeatedly wiped off with a liquid containing alcohol for disinfection, the effect of preventing accidental ingestion can be exerted for a long period of time.
　また、本実施形態の粘着シート１０は、単独又はラベル積層体の形態で動物忌避シートとして利用することも可能である。犬や猫、猪等はヒトと同様に苦味成分を忌避する傾向があるので、例えば動物による糞尿被害や食害が発生している場所に粘着シート１０又はラベル積層体を配置しておくことにより、これらの被害を低減することができる。この粘着シート１０の動物忌避効果は、味覚による情報に大きく依存する動物に対してより有効である。このため、本実施形態の粘着シート１０では、例えば犬よりも猫に対する忌避効果の方がより大きくなっている。 The pressure-sensitive adhesive sheet 10 of the present embodiment can also be used alone or in the form of a label laminate as an animal repellent sheet. Since dogs, cats, boars, etc. tend to avoid bitterness components like humans, for example, by arranging the adhesive sheet 10 or the label laminate at a place where animal excrement damage or food damage occurs, These damages can be reduced. The animal repellent effect of the pressure-sensitive adhesive sheet 10 is more effective for animals that largely depend on information by taste. Therefore, the adhesive sheet 10 of the present embodiment has a greater repellent effect on cats than dogs, for example.
　苦味に対する感受性は人によって異なるが、一般的に加齢とともに苦味を感じにくくなるので、子供は大人よりも苦味に敏感であると言える。また、喫煙者は苦味に対して鈍感になる傾向にある。従って、コーティング層７に配合する苦味成分の濃度を比較的低濃度（例えば、溶剤系塗料の樹脂固形分に対して２質量％以上６質量％未満）とすることにより、本実施形態の粘着シート１０の誤飲防止効果を子供に対して選択的に発揮させやすくすることができる。これに対し、老人に対する誤飲防止効果を期待する場合には、コーティング層７に配合する苦味成分の濃度を比較的高濃度（例えば、溶剤系塗料の樹脂固形分に対して６質量％以上１０質量％以下）にすることができる。上述の苦味の感じ方の違いを利用して苦味成分の濃度が互いに異なる複数の粘着シート１０を１つのセットにして老化チェッカーとすることもできる。例えば、一番苦味成分濃度が低い粘着シート１０の苦味を感じることができれば「若い」と判定し、最も苦味成分濃度が高い粘着シート１０の苦味を感じることができなければ「老化している」と判定することができる。 Sensitivity to bitterness varies from person to person, but it is generally less likely to feel bitterness with age, so it can be said that children are more sensitive to bitterness than adults. Also, smokers tend to be less sensitive to bitterness. Therefore, by setting the concentration of the bitterness component blended in the coating layer 7 to a relatively low concentration (for example, 2% by mass or more and less than 6% by mass based on the resin solid content of the solvent-based paint), the pressure-sensitive adhesive sheet according to the present embodiment The accidental ingestion prevention effect of 10 can be easily exerted selectively on the child. On the other hand, in the case of expecting an accidental ingestion effect for the elderly, the concentration of the bitterness component blended in the coating layer 7 is relatively high (for example, 6% by mass or more and 10% by mass or more with respect to the resin solid content of the solvent-based paint). Mass% or less). By utilizing the above difference in how to feel bitterness, a plurality of pressure-sensitive adhesive sheets 10 having different concentrations of bitterness components can be set as one set to serve as an aging checker. For example, if you can feel the bitterness of the adhesive sheet 10 having the lowest bitterness component concentration, it is determined to be “young”, and if you cannot feel the bitterness of the adhesive sheet 10 having the highest bitterness component concentration, it is “aged”. Can be determined.
＜実施例１＞
　１００質量部のトルエン、１００質量部の酢酸エチル及び５質量部のメタノールの混合溶媒に、安息香酸デナトニウム粉末（マクファランスミス社製；製品名「ビトレックス」）０．４９２部を溶解させた。次に、この安息香酸デナトニウム溶液（合計２０５．４９２質量部）と、トルエン及び酢酸エチルを含む市販の熱可塑性アクリル酸エステル系ポリマー（溶剤系塗料）溶液（樹脂固形分２４．６質量％）１００質量部とを混合して塗液を調製し、当該塗液を透明なＰＥＴフィルム（東レ株式会社製；製品名「ルミラーＴ１１」）の一方の面に塗工した。次いで、１００℃、１分間ＰＥＴフィルムを乾燥させることにより、膜厚が１μｍのコーティング層をＰＥＴフィルム上に形成した。この粘着シートのコーティング層中には、質量基準で樹脂固形分に対して２．００質量％の安息香酸デナトニウムが含まれていることになる。このＰＥＴフィルムを用いて図１に示すような構成を有する粘着シートを作製した。粘着シートの全光線透過率（ＪＩＳ　Ｋ７３６１－１に準じて測定）は９１．７２％であった。 <Example 1>
In a mixed solvent of 100 parts by mass of toluene, 100 parts by mass of ethyl acetate and 5 parts by mass of methanol, 0.492 parts of denatonium benzoate powder (manufactured by MacFarlan Smith Co., Ltd .; product name "Vitrex") was dissolved. Next, this denatonium benzoate solution (total 205.492 parts by mass) and a commercially available thermoplastic acrylate polymer (solvent-based coating) solution containing toluene and ethyl acetate (resin solid content 24.6% by mass) 100 A coating liquid was prepared by mixing the same with parts by mass, and the coating liquid was applied to one surface of a transparent PET film (manufactured by Toray Industries, Inc .; product name “Lumirror T11”). Then, the PET film was dried at 100 ° C. for 1 minute to form a coating layer having a thickness of 1 μm on the PET film. This means that the coating layer of this pressure-sensitive adhesive sheet contains 2.00% by mass of denatonium benzoate with respect to the resin solid content on a mass basis. Using this PET film, an adhesive sheet having a structure as shown in FIG. 1 was produced. The total light transmittance of the pressure-sensitive adhesive sheet (measured according to JIS K7361-1) was 91.72%.
＜実施例２＞
　熱可塑性アクリル酸エステル系ポリマー溶液１００質量部に対して混合する安息香酸デナトニウム粉末を１．２３質量部に変更した以外は実施例１と同様にして、粘着シートを作製した。この粘着シートのコーティング層中には、樹脂固形分に対して５．００質量％の安息香酸デナトニウムが含まれていることになる。この粘着シートの全光線透過率は９１．８４％であった。 <Example 2>
A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1 except that the amount of denatonium benzoate powder mixed with 100 parts by mass of the thermoplastic acrylic acid ester-based polymer solution was changed to 1.23 parts by mass. The coating layer of this pressure-sensitive adhesive sheet contains 5.00% by mass of denatonium benzoate based on the resin solid content. The total light transmittance of this pressure-sensitive adhesive sheet was 91.84%.
＜実施例３＞
　コーティング層を形成するための塗液に、熱可塑性アクリル酸エステル系ポリマー１００質量部に対して市販のメラミン系硬化剤０．９１部と市販のイソシアネート系硬化剤０．４５部とを添加したことを除き実施例２と同一の方法により粘着シートを作製した。 <Example 3>
To the coating liquid for forming the coating layer, 0.91 part of a commercially available melamine-based curing agent and 0.45 part of a commercially available isocyanate-based curing agent were added to 100 parts by weight of the thermoplastic acrylic acid ester-based polymer. A pressure-sensitive adhesive sheet was produced by the same method as in Example 2 except for.
＜比較例１＞
　熱可塑性アクリル酸エステル系ポリマー溶液１００質量部に対して混合する安息香酸デナトニウム粉末を０．１２３質量部に変更した以外は実施例１と同様にして、粘着シートを作製した。この粘着シートのコーティング層中には、樹脂固形分に対して０．５０質量％の安息香酸デナトニウムが含まれていることになる。この粘着シートの全光線透過率は９１．７３％であった。 <Comparative Example 1>
A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that the amount of denatonium benzoate powder mixed with 100 parts by mass of the thermoplastic acrylic ester polymer solution was changed to 0.123 parts by mass. The coating layer of this pressure-sensitive adhesive sheet contains denatonium benzoate in an amount of 0.50% by mass based on the resin solid content. The total light transmittance of this pressure-sensitive adhesive sheet was 91.73%.
＜比較例３＞
　２００質量部の水に安息香酸デナトニウム粉末０．００１４７質量部を溶解させた。この安息香酸デナトニウム溶液（合計２００．００１４７質量部）と、水を含むＰＶＡ樹脂（大成化薬株式会社製；製品名「マルタイト１５０」）の溶液（樹脂固形分１４．７質量％）とを混合して塗液を調製し、当該塗液を透明なＰＥＴフィルムの一方の面に塗工した。次いで、１００℃、１分間ＰＥＴフィルムを乾燥させることにより、膜厚が１μｍのコーティング層をＰＥＴフィルム上に形成した。この粘着シートのコーティング層中には、樹脂固形分に対して０．０１質量％の安息香酸デナトニウムが含まれていることになる。この粘着シートの全光線透過率は９１．７２％であった。 <Comparative example 3>
0.00147 parts by mass of denatonium benzoate powder was dissolved in 200 parts by mass of water. This denatonium benzoate solution (total of 200.00147 parts by mass) and a solution of PVA resin containing water (manufactured by Taisei Kagaku Co., Ltd .; product name "Maltite 150") (resin solid content 14.7% by mass) are mixed. To prepare a coating liquid, and the coating liquid was applied to one surface of the transparent PET film. Then, the PET film was dried at 100 ° C. for 1 minute to form a coating layer having a thickness of 1 μm on the PET film. The coating layer of this pressure-sensitive adhesive sheet contains 0.01% by mass of denatonium benzoate based on the resin solid content. The total light transmittance of this pressure-sensitive adhesive sheet was 91.72%.
＜比較例３＞
　乾燥後のコーティング層に含まれる安息香酸デナトニウムが、同層の樹脂固形分に対して０．０５質量％となるように調整したことを除き、比較例２と同様の方法によって粘着シートを作製した。この粘着シートの全光線透過率は９１．６９％であった。 <Comparative example 3>
A pressure-sensitive adhesive sheet was produced in the same manner as in Comparative Example 2 except that the amount of denatonium benzoate contained in the dried coating layer was adjusted to 0.05% by mass with respect to the resin solid content of the layer. . The total light transmittance of this adhesive sheet was 91.69%.
＜比較例４＞
　乾燥後のコーティング層に含まれる安息香酸デナトニウムが、同層の樹脂固形分に対して０．１０質量％となるように調整したことを除き、比較例２と同様の方法によって粘着シートを作製した。この粘着シートの全光線透過率は９１．７７％であった。 <Comparative example 4>
A pressure-sensitive adhesive sheet was produced in the same manner as in Comparative Example 2 except that the amount of denatonium benzoate contained in the dried coating layer was adjusted to 0.10 mass% with respect to the resin solid content of the layer. . The total light transmittance of this pressure-sensitive adhesive sheet was 91.77%.
＜比較例５＞
　乾燥後のコーティング層に含まれる安息香酸デナトニウムが、同層の樹脂固形分に対して０．５０質量％となるように調整したことを除き、比較例２と同様の方法によって粘着シートを作製した。この粘着シートの全光線透過率は９１．７９％であった。 <Comparative Example 5>
A pressure-sensitive adhesive sheet was produced in the same manner as in Comparative Example 2 except that the amount of denatonium benzoate contained in the dried coating layer was adjusted to 0.50% by mass with respect to the resin solid content of the layer. . The total light transmittance of this pressure-sensitive adhesive sheet was 91.79%.
＜比較例６＞
　乾燥後のコーティング層に含まれる安息香酸デナトニウムが、同層の樹脂固形分に対して１．００質量％となるように調整したことを除き、比較例２と同様の方法によって粘着シートを作製した。この粘着シートの全光線透過率は９１．７０％であった。 <Comparative example 6>
A pressure-sensitive adhesive sheet was produced in the same manner as in Comparative Example 2 except that the amount of denatonium benzoate contained in the dried coating layer was adjusted to be 1.00% by mass based on the resin solid content of the layer. . The total light transmittance of this pressure-sensitive adhesive sheet was 91.70%.
－誤飲防止効果の確認試験－
　作製された各粘着シートから２．５ｃｍ×２．５ｃｍのサイズの試験片を切り出し、これを水拭き前の試験片とした。次に、各粘着シートから切り出された試験片を、コーティング層側から純水を含ませた布を用いて一方向に１０回拭き、これを水拭き後の試験片とした。水拭き前及び水拭き後の各試験片のコーティング層を舌で１回軽く舐めて苦味を感じるか否かを男性３名、女性２名の計５名で確認し、下記の通り評価した。布は一度の水拭きのたびに新しいものに交換した。 -Test to confirm accidental ingestion effect-
A test piece with a size of 2.5 cm × 2.5 cm was cut out from each produced pressure-sensitive adhesive sheet, and this was used as a test piece before wiping with water. Next, the test piece cut out from each pressure-sensitive adhesive sheet was wiped 10 times in one direction with a cloth impregnated with pure water from the coating layer side, and this was used as a test piece after wiping with water. Whether or not the coating layer of each test piece before and after wiping with water was lightly licked once with a tongue and whether bitterness was felt was confirmed by 5 men, 3 men and 2 women, and evaluated as follows. The cloth was replaced with a new one after each wipe.
　苦味を感じた人数が４人及び５人である場合を「優」、２人及び３人である場合を「不十分」、０人及び１人である場合を「不良」と評価した。味覚には個人差があることを考慮に入れ、乳幼児の誤飲を確実に防止するためには大多数の者が苦味を感じる必要があると考えてこのような基準を設定した。
　また、「苦味維持の度合い」は、水拭きの前後で苦味に変化が無い場合には「良」と判定し、水拭き後に苦味評価が低下している場合には「不良」と判定した。 When the number of people who felt bitterness was 4 and 5, it was evaluated as "excellent", when 2 and 3 were evaluated as "insufficient", and when 0 and 1 were evaluated as "poor". Taking into consideration that there are individual differences in taste, we set such a standard because it is necessary for most people to feel bitterness in order to prevent accidental ingestion by infants.
Further, the "degree of bitterness maintenance" was determined to be "good" when the bitterness did not change before and after wiping with water, and "bad" when the bitterness evaluation was lowered after wiping with water.
－エタノール拭きに対するコーティング層の耐久性試験－
　実施例２、３で作製された粘着シートから２．５ｃｍ×２．５ｃｍのサイズの試験片を複数枚切り出した後、この試験片のコーティング層に対し、濃度９９．５％のエタノールを含ませた布を用いて一方向に向かって最小で０回、最大で５０回までの所定の回数拭き取りを繰り返した。布は一度拭くたびに新しいものに交換した。拭き取りの際の荷重は約３００ｇとした。次いで、拭き取りが終わった各試験片のコーティング層の状態を光学顕微鏡を用いて観察するとともに、コーティング層を舌で１回軽く舐めて苦味を感じるか否かを男性１名により確認し、評価した。苦味の評価は「有り」と「無し」の二種類のみとした。 -Durability test of coating layer against ethanol wiping-
After cutting out a plurality of 2.5 cm × 2.5 cm size test pieces from the pressure-sensitive adhesive sheets prepared in Examples 2 and 3, the coating layer of the test pieces was impregnated with ethanol having a concentration of 99.5%. Using the above cloth, the wiping was repeated in one direction at a minimum of 0 times and at a maximum of 50 times. Every time I wiped the cloth, I replaced it with a new one. The load during wiping was about 300 g. Then, the state of the coating layer of each test piece that had been wiped off was observed using an optical microscope, and whether or not the coating layer was lightly licked once with a tongue was confirmed by one man and evaluated. . Only two types of bitterness were evaluated, "yes" and "no".
－試験結果－
　粘着シートの誤飲防止効果についての試験結果を表１に示す。 -Test results-
Table 1 shows the test results for the prevention of accidental ingestion of the adhesive sheet.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　実施例１、２と比較例１との水拭き前の結果から、溶剤系塗料を用いた場合、コーティング層において、樹脂固形分に対する苦味成分の割合が少なくとも２質量％以上であれば、十分な誤飲防止効果があることが確認できた。この結果から、樹脂固形分に対する苦味成分の割合が２％程度以上であれば、誤飲防止効果があるものと考えられた。 From the results of Examples 1 and 2 and Comparative Example 1 before wiping with water, when the solvent-based paint is used, it is sufficient if the ratio of the bitterness component to the resin solid content in the coating layer is at least 2% by mass or more. It was confirmed that it has the effect of preventing accidental ingestion. From this result, it was considered that if the ratio of the bitterness component to the resin solid content is about 2% or more, there is an effect of preventing accidental ingestion.
　また、実施例１、２と比較例１～６の水拭き前の結果との比較から、コーティング層の形成に水性塗料を用いる場合には、溶剤系塗料を用いる場合に比べて苦味成分の含有濃度が低くても苦味を感じさせられることが分かった。しかし、１０回の水拭き後の試験結果から、水性塗料を用いた場合には、苦味成分の濃度を比較的高くした場合であっても水拭きによって容易に誤飲防止効果が失われることが分かった。これに対し、実施例１、２の結果から、溶剤系塗料を用いる場合には、水拭きを繰り返しても苦味成分は除去されにくく、誤飲防止効果が保持されていることが確認できた。 Further, from the comparison between the results of Examples 1 and 2 and the results of Comparative Examples 1 to 6 before wiping with water, when the water-based paint is used for forming the coating layer, the bitterness component is contained as compared with the case where the solvent-based paint is used. It was found that bitterness can be felt even at low concentrations. However, from the test results after 10 times wiping with water, when the water-based paint is used, even if the concentration of the bitterness component is relatively high, the effect of preventing accidental ingestion can be easily lost by wiping with water. Do you get it. On the other hand, from the results of Examples 1 and 2, it was confirmed that when the solvent-based paint was used, the bitterness component was difficult to remove even after repeated wiping with water, and the effect of preventing accidental ingestion was maintained.
　また、図２は、実施例２で作製された粘着シートをエタノール拭きした結果を示す図であり、図３は、実施例３で作製された粘着シートをエタノール拭きした結果を示す図である。 2 is a diagram showing the result of wiping the pressure-sensitive adhesive sheet prepared in Example 2 with ethanol, and FIG. 3 is a diagram showing the result of wiping the pressure-sensitive adhesive sheet prepared in Example 3 with ethanol.
　図２に示すように、硬化剤を使用せずに形成させたコーティング層では、エタノールを用いて３回拭き取りを行った時点でコーティング層が筋状に剥がれ始め、１０回目の拭き取りが終わった時点でコーティング層は完全に除去された。また、６回目の拭き取り後までは苦味が維持されていたが、１０回目の拭き取り後には苦味も無くなっていた。 As shown in FIG. 2, in the coating layer formed without using the curing agent, the coating layer began to peel off in a streak shape at the time of wiping three times with ethanol, and after the tenth wiping was completed. The coating layer was completely removed. The bitterness was maintained until after the sixth wiping, but the bitterness disappeared after the tenth wiping.
　これに対し、図３に示すように、硬化剤を使用した場合には、２０回目の拭き取り後までコーティング層の外観に変化はなく、４０回目の拭き取り後まで苦味を維持できることが確認された。 On the other hand, as shown in FIG. 3, when the curing agent was used, the appearance of the coating layer did not change until after the 20th wiping, and it was confirmed that the bitterness could be maintained after the 40th wiping.
　表１、図２及び図３に示す結果から、エタノールを用いた拭き取りの方が水を用いた拭き取りに比べてコーティング層が除去されやすいことと、コーティング層を形成する際に硬化剤を用いることにより、エタノール拭きに対する耐久性を大幅に向上させることができることとが確認できた。 From the results shown in Table 1, FIG. 2 and FIG. 3, the wiping with ethanol is easier to remove the coating layer than the wiping with water, and the curing agent is used when forming the coating layer. It was thus confirmed that the durability against wiping with ethanol can be significantly improved.
　本明細書に開示された粘着シートは、玩具等、誤飲される可能性がある被着体の誤飲防止に用いられる。 The pressure-sensitive adhesive sheet disclosed in this specification is used to prevent accidental ingestion of adherends that may be accidentally ingested, such as toys.
１　　剥離ライナー
３　　粘着剤層
５　　基材フィルム
７　　コーティング層
１０　粘着シート
１１　本体部分 1 Release Liner 3 Adhesive Layer 5 Base Film 7 Coating Layer 10 Adhesive Sheet 11 Body Part

Claims (9)

  1. 　基材フィルムと、
    　前記基材フィルムの一方の面上に形成され、苦味成分を含み、溶剤系塗料の硬化物からなるコーティング層と、
    　前記基材フィルムの他方の面上に形成された粘着剤層とを備え、
    　前記コーティング層には、前記溶剤系塗料の樹脂固形分に対して２質量％以上の前記苦味成分が含まれている粘着シート。     A base film,
    A coating layer formed on one surface of the base film, containing a bitterness component, and comprising a cured product of a solvent-based paint,
    With a pressure-sensitive adhesive layer formed on the other surface of the base film,
    An adhesive sheet in which the coating layer contains 2% by mass or more of the bitterness component with respect to the resin solid content of the solvent-based paint.
  2. 　請求項１に記載の粘着シートにおいて、
    　前記コーティング層には、前記溶剤系塗料の樹脂固形分に対して１０質量％以下の前記苦味成分が含まれていることを特徴とする粘着シート。     The pressure-sensitive adhesive sheet according to claim 1,
    The pressure-sensitive adhesive sheet, wherein the coating layer contains 10% by mass or less of the bitterness component with respect to the resin solid content of the solvent-based paint.
  3. 　請求項１又は２に記載の粘着シートにおいて、
    　前記コーティング層が硬化剤を含むことを特徴とする粘着シート。     The pressure-sensitive adhesive sheet according to claim 1 or 2,
    The pressure-sensitive adhesive sheet, wherein the coating layer contains a curing agent.
  4. 　請求項１～３のうちいずれか１つに記載の粘着シートにおいて、
    　前記苦味成分は、安息香酸デナトニウム、サッカリンデナトニウム、塩化デナトニウムからなる群から選ばれた少なくとも１種又は２種以上の混合物であることを特徴とする粘着シート。     The pressure-sensitive adhesive sheet according to any one of claims 1 to 3,
    The pressure-sensitive adhesive sheet, wherein the bitter ingredient is at least one selected from the group consisting of denatonium benzoate, saccharin denatonium, and denatonium chloride, or a mixture of two or more thereof.
  5. 　請求項１～４のうちいずれか１つに記載の粘着シートにおいて、
    　全光線透過率が７０％以上であることを特徴とする粘着シート。     The pressure-sensitive adhesive sheet according to any one of claims 1 to 4,
    An adhesive sheet having a total light transmittance of 70% or more.
  6. 　請求項１～５のうちいずれか１つに記載の粘着シートにおいて、
    　前記コーティング層の膜厚は、０．１μｍ以上１０μｍ以下であることを特徴とする粘着シート。     The pressure-sensitive adhesive sheet according to any one of claims 1 to 5,
    The pressure-sensitive adhesive sheet, wherein the coating layer has a thickness of 0.1 μm or more and 10 μm or less.
  7. 　請求項１～６のうちいずれか１つに記載の粘着シートにおいて、
    　貼付された物品の誤飲を防止するために用いられることを特徴とする粘着シート。     The pressure-sensitive adhesive sheet according to any one of claims 1 to 6,
    An adhesive sheet, which is used to prevent accidental ingestion of an attached article.
  8. 　請求項１～６のうちいずれか１つに記載の粘着シートにおいて、
    　動物を忌避するために用いられることを特徴とする粘着シート。     The pressure-sensitive adhesive sheet according to any one of claims 1 to 6,
    A pressure-sensitive adhesive sheet, which is used to repel animals.
  9. 　請求項３に記載の粘着シートを製造する方法であって、基材フィルムの一方の面上に、苦味成分と硬化剤を含む溶剤系塗料を塗布し、前記溶剤系塗料中の樹脂固形分と硬化剤との硬化反応によりコーティング層を形成する工程と、
    　前記基材フィルムの他方の面上に粘着剤層を設ける工程と
    を含むことを特徴とする粘着シートの製造方法。     The method for producing the pressure-sensitive adhesive sheet according to claim 3, wherein a solvent-based paint containing a bitterness component and a curing agent is applied on one surface of the base film to obtain a resin solid content in the solvent-based paint. A step of forming a coating layer by a curing reaction with a curing agent,
    A step of providing an adhesive layer on the other surface of the base film, the method for producing an adhesive sheet.
PCT/JP2019/032632 2018-10-17 2019-08-21 Adhesive sheet and method for producing same WO2020079948A1 (en)

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