JP2018095700A - Peelable adhesive composition and adhesive body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a peelable adhesive body that effectively prevents adhesive residues, and can be suitably peeled from a container having contents therein, and provide a peelable adhesive composition that can be suitably used for the production of the adhesive body.SOLUTION: A peelable adhesive composition is used for the production of a peelable adhesive body stuck to a container having contents therein. The composition contains an adhesive and a primer.SELECTED DRAWING: None

Description

  The present invention relates to a re-peelable pressure-sensitive adhesive composition and a pressure-sensitive adhesive body.

  A re-peelable pressure-sensitive adhesive sheet (re-peelable pressure-sensitive adhesive sheet) that can be peeled relatively easily after being attached to an adherend is easy to handle and used for various labels (for example, , See Patent Document 1).

  However, when the pressure-sensitive adhesive sheet is affixed to a container containing a content containing a specific component, a problem of adhesive residue tends to occur when the pressure-sensitive adhesive sheet is peeled from the container. In particular, the present inventor has found that the above-described problem is particularly likely to occur when the content contains at least one of a fragrance and a surfactant.

JP 2013-241614 A

  An object of the present invention is to provide a re-peelable pressure-sensitive adhesive body that can be suitably peeled from a container in which contents are contained, while effectively preventing the occurrence of a problem of adhesive residue. An object of the present invention is to provide a re-peelable pressure-sensitive adhesive composition that can be suitably used for producing a body.

Such an object is achieved by the present invention described in the following (1) to (10).
(1) A re-peelable pressure-sensitive adhesive composition used for the manufacture of a re-peelable pressure-sensitive adhesive body that is adhered to a container in which the contents are contained,
A re-peelable pressure-sensitive adhesive composition comprising a pressure-sensitive adhesive and a primer.

  (2) The re-peelable pressure-sensitive adhesive composition according to (1), which contains an olefin-based primer as the primer.

  (3) The re-peelable pressure-sensitive adhesive composition according to (1) or (2), wherein the pressure-sensitive adhesive is an emulsion pressure-sensitive adhesive.

  (4) The re-peelable pressure-sensitive adhesive composition according to any one of (1) to (3), wherein the content of the primer with respect to 100 parts by mass of the pressure-sensitive adhesive is 1 part by mass or more and 50 parts by mass or less.

  (5) The releasable pressure-sensitive adhesive composition according to any one of (1) to (4), wherein the content contains at least one of a fragrance and a surfactant.

  (6) The pressure-sensitive adhesive body includes a base material, a pressure-sensitive adhesive layer formed using the re-peelable pressure-sensitive adhesive composition, and a primer layer provided between the base material and the pressure-sensitive adhesive layer. The re-peelable pressure-sensitive adhesive composition according to any one of (1) to (5) above.

  (7) The re-peelable pressure-sensitive adhesive according to (6), wherein the primer contained in the re-peelable pressure-sensitive adhesive composition is the same type as the primer contained in the composition used for forming the primer layer. Composition.

(8) A re-peelable adhesive that is attached to a container containing the contents,
A substrate;
A pressure-sensitive adhesive body comprising: a pressure-sensitive adhesive layer formed using the re-peelable pressure-sensitive adhesive composition according to any one of (1) to (5) above.

(9) An adhesive that is attached to a container containing the contents,
A substrate;
A pressure-sensitive adhesive layer formed using the re-peelable pressure-sensitive adhesive composition according to the above (6) or (7);
An adhesive body comprising a primer layer provided between the substrate and the adhesive layer.

  (10) The pressure-sensitive adhesive body according to (9), wherein the primer layer is composed of a material containing an olefin-based primer.

  According to the present invention, it is possible to provide a re-peelable pressure-sensitive adhesive body that can be suitably peeled from a container in which contents are contained, while effectively preventing the occurrence of a problem of adhesive residue, and the pressure-sensitive adhesive. A re-peelable pressure-sensitive adhesive composition that can be suitably used for production of a body can be provided.

It is a typical longitudinal cross-sectional view which shows suitable embodiment of the adhesive body (adhesive sheet) of this invention. It is a typical longitudinal cross-sectional view which shows suitable embodiment of the manufacturing method of the adhesive body (adhesive sheet) of this invention.

Hereinafter, preferred embodiments of the present invention will be described in detail.
[Re-peelable pressure-sensitive adhesive composition]
First, the re-peelable pressure-sensitive adhesive composition of the present invention will be described.

  The re-peelable pressure-sensitive adhesive composition of the present invention is used for production of a re-peelable pressure-sensitive adhesive body (re-peelable pressure-sensitive adhesive body) to be stuck to a container in which contents are stored (formation of a pressure-sensitive adhesive layer). It is.

  And when this inventor sticks a re-peelable pressure-sensitive adhesive body (for example, a re-peelable pressure-sensitive adhesive sheet) to a container in which a content containing a certain kind of component is accommodated, when peeling, It has been found that the problem of adhesive residue is likely to occur.

  Therefore, the present inventor has conducted earnest research for the purpose of preventing the occurrence of the above problems. As a result, the problem of the adhesive residue as described above is that a certain component (hereinafter also referred to as “predetermined substance”) contained in the contents is re-peeled to the outside of the container through the container. This is due to the shift to the mold pressure-sensitive adhesive body, resulting in the present invention. That is, the re-peelable pressure-sensitive adhesive composition of the present invention includes a primer in addition to the pressure-sensitive adhesive.

  With such a configuration, even when a predetermined substance is transferred from the inside of the container to the re-peelable adhesive, the paste to the adherend (container) when the re-peelable adhesive is peeled off from the adherend (container) The rest can be effectively prevented.

  The contents of the container may be anything, but examples include low molecular weight materials having a molecular weight of 1,000 or less, and more specifically, fragrances, surfactants, plasticizers, and the like. It is preferable to contain at least one of a fragrance and a surfactant.

  Such a component is easily transferred to a re-peelable adhesive adhered to the outside of the container, particularly among various substances, and conventionally, the contents of the container have such components. In the case of inclusion, problems such as adhesive residue were liable to occur when peeling the adhesive from the container. On the other hand, in the present invention, the above-described problems can be sufficiently prevented even when the contents of the container contain at least one of a fragrance and a surfactant. That is, when the contents of the container include at least one of a fragrance and a surfactant, the effect of the present invention is more remarkably exhibited.

  Hereinafter, the case where the contents of the container contain at least one of a fragrance and a surfactant will be mainly described.

<Adhesive>
The pressure-sensitive adhesive constituting the re-peelable pressure-sensitive adhesive composition of the present invention may be, for example, a solvent type or an emulsion type, but is preferably an emulsion type (emulsion pressure-sensitive adhesive).

  Accordingly, it is possible to obtain the optimum adhesive force for the adhesive body relatively easily, and it is advantageous for ensuring the safety of the operator, being friendly to the environment and the human body.

Examples of the pressure-sensitive adhesive contained in the re-peelable pressure-sensitive adhesive composition of the present invention include acrylic, synthetic rubber and natural rubber, and acrylic pressure-sensitive adhesive is preferred.
Thereby, the adhesiveness with respect to a to-be-adhered body (container) can be made more excellent.

  In particular, the pressure-sensitive adhesive contained in the re-peelable pressure-sensitive adhesive composition preferably satisfies the following conditions.

  That is, the pressure-sensitive adhesive contained in the re-peelable pressure-sensitive adhesive composition of the present invention is derived from a (meth) acrylic acid ester (hereinafter also referred to as “monomer (a1)”) having a Tg of homopolymer of −40 ° C. or lower. The structural unit (a2) is 70% by mass or more and 99.5% by mass or less, and the structural unit (a2) derived from the functional group-containing monomer (hereinafter also referred to as “monomer (a2)”) is 0.5% by mass. It is preferably an emulsion pressure-sensitive adhesive containing 20% by mass or less (hereinafter also referred to as “emulsion copolymer (A)” or “copolymer (A)”).

(Structural unit (a1))
The structural unit (a1) is a structural unit derived from a (meth) acrylic acid ester having a glass transition temperature (Tg) of a homopolymer of −40 ° C. or lower.

  Here, the Tg of the homopolymer of (meth) acrylic acid ester constituting the structural unit (a1) is −40 ° C. or lower, preferably −50 ° C. or lower, more preferably −55 ° C. or lower, still more preferably. It is -60 degrees C or less.

  By including the structural unit (a1) derived from a (meth) acrylic acid ester having a Tg of -40 ° C. or less in the copolymer (A), the increase in adhesive strength with time after sticking is more effective. Therefore, the removability of the pressure-sensitive adhesive body can be further improved.

  The lower limit of the Tg of the (meth) acrylate homopolymer is not particularly limited, but the Tg of the (meth) acrylate homopolymer constituting the structural unit (a1) is preferably − It is 100 ° C or higher.

  In addition, as a Tg value of the (meth) acrylic acid ester homopolymer, for example, a value described in “POLYMER HANDBOOK 3rd edition” (published by John Wiley & Sons, Inc.) can be used.

  Examples of the (meth) acrylic acid ester having a homopolymer Tg of −40 ° C. or less include, for example, butyl acrylate (homopolymer Tg = −54 ° C. (hereinafter the same)), n-hexyl acrylate (−45 ° C.), 2- Ethylhexyl acrylate (-70 ° C), isooctyl acrylate (-58 ° C), lauryl methacrylate (-65 ° C), 2-methoxyethyl acrylate (-50 ° C), 2- (2-ethoxyethoxy) ethyl acrylate (-54 ° C) ), Isodecyl acrylate (−60 ° C.), tridecyl acrylate (−55 ° C.), tridecyl methacrylate (−40 ° C.) and the like, and one kind or a combination of two or more kinds can be used.

  Among these, butyl acrylate and 2-ethylhexyl acrylate are preferable, and 2-ethylhexyl acrylate is more preferable from the viewpoint of improving the removability of the pressure-sensitive adhesive body.

Although content of a structural unit (a1) is not specifically limited, It is preferable that it is 70 to 99.5 mass% in all the structural units contained in a copolymer (A), and 74 to 99 mass%. More preferably, it is 77 mass% or less, More preferably, it is 77 mass% or more and 98 mass% or less, Most preferably, it is 89 mass% or more and 97 mass% or less.
Thereby, the removability of an adhesive body can be made more excellent.

(Structural unit (a2))
The structural unit (a2) is a structural unit derived from a functional group-containing monomer.
Here, the “functional group” of the “functional group-containing monomer” refers to a functional group that can react with a cross-linking agent to serve as a cross-linking origin or a functional group having a cross-linking promoting effect.

  Examples of the functional group include a carboxy group, a hydroxy group, an amide group, an amino group, an epoxy group, a cyano group, a keto group, a nitrogen atom-containing ring, and an alkoxysilyl group.

  Examples of functional group-containing monomers include carboxy group-containing monomers, hydroxy group-containing monomers, amide group-containing monomers, amino group-containing monomers, epoxy group-containing monomers, cyano group-containing monomers, keto group-containing monomers, and nitrogen atom-containing rings. And a monomer having an alkoxysilyl group.

  Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid; ethylenically unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid and citraconic acid, and anhydrides thereof. 2-carboxyethyl methacrylate and the like.

  Examples of the hydroxy group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl ( Examples thereof include hydroxyalkyl (meth) acrylates such as meth) acrylate and 4-hydroxybutyl (meth) acrylate; unsaturated alcohols such as vinyl alcohol and allyl alcohol.

  Examples of the amide group-containing monomer include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide, N -Methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, etc. are mentioned. These amide group-containing monomers can serve as starting points for crosslinking.

  Examples of amino group-containing monomers include primary amino group-containing (meth) acrylate monomers, secondary amino group-containing (meth) acrylate monomers, tertiary amino group-containing (meth) acrylate monomers, and amide groups. Examples include tertiary amino group-containing N-substituted (meth) acrylamide monomers in which a substituent containing a tertiary amino group is bonded to a nitrogen atom.

  Examples of the monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and allyl glycidyl ether.

  Examples of the cyano group-containing monomer include acrylonitrile and methacrylonitrile.

  Examples of the keto group-containing monomer include diacetone (meth) acrylamide, acetone (meth) acrylate, vinyl methyl ketone, vinyl ethyl ketone, allyl acetoacetate, vinyl acetoacetate, and acetoacetyl (meth) acrylate.

  Examples of the monomer having a nitrogen atom-containing ring include N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpiperidone, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinylmorpholine, N-vinylcaprolactam, N- (meth) acryloylmorpholine and the like can be mentioned.

  Examples of the alkoxysilyl group-containing monomer include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3-acryloxypropyltriethoxysilane, and 3- (meth) acryloxy. Examples thereof include propylmethyldimethoxysilane and 3- (meth) acryloxypropylmethyldiethoxysilane.

  These functional group-containing monomers can be used alone or in combination of two or more.

  Among these, a carboxy group-containing monomer is preferable, and (meth) acrylic acid is more preferable.

  Thereby, the removability of the obtained pressure-sensitive adhesive body and the coating property of the re-peelable pressure-sensitive adhesive composition (particularly, the coating property in high-speed application) can be further improved.

  Although content of a structural unit (a2) is not specifically limited, It is preferable that it is 0.5 mass% or more and 20 mass% or less in all the structural units contained in a copolymer (A), and 0.8 mass%. It is more preferably 15% by mass or less, more preferably 1.2% by mass or more and 12% by mass or less, and most preferably 1.5% by mass or more and 7.0% by mass or less.

  Thereby, the mechanical stability of the re-peelable pressure-sensitive adhesive composition and the re-peelability of the pressure-sensitive adhesive body can be further improved.

(Structural unit (a3))
In addition, the emulsion copolymer (A) may include a structural unit (a3) derived from another monomer other than the structural units (a1) and (a2).
Thereby, for example, adhesive force and cohesive force can be controlled more suitably.

  The other monomer can be selected from monomers copolymerizable with a (meth) acrylic acid ester having a Tg of -40 ° C. or lower.

  Specific examples of the monomer include (meth) acrylic acid ester having a homopolymer Tg exceeding −40 ° C., vinyl monomers other than those mentioned as the functional group-containing monomer, and the like.

  Examples of the (meth) acrylic acid ester having a homopolymer Tg exceeding −40 ° C. include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, methyl methacrylate, butyl methacrylate and the like. Among these, (meth) acrylic acid ester having an alkyl group having 1 to 3 carbon atoms is preferable.

  Examples of vinyl monomers other than those listed as functional group-containing monomers include styrene, α-methylstyrene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, and the like.

  The content of the structural unit (a3) derived from the other monomer is not particularly limited, but is 0% by mass or more and 29.5% by mass or less in all the structural units included in the copolymer (A). It is preferably 0% by mass to 25% by mass, more preferably 0% by mass to 20% by mass, and most preferably 0% by mass to 8% by mass.

  The average particle diameter of the emulsion copolymer (A) is preferably 80 nm or more, more preferably 200 nm or more and 800 nm or less, and further preferably 300 nm or more and 650 nm or less.

  Thereby, the mechanical stability of the re-peelable pressure-sensitive adhesive composition and the applicability of the re-peelable pressure-sensitive adhesive composition (particularly, the coatability at high-speed application) can be further improved.

  The average particle size of the emulsion copolymer (A) is adjusted by controlling the type of anionic emulsifier used during emulsion polymerization, the amount used, the polymerization start conditions, the stirring device, the stirring conditions, and the like. Can do.

  In this specification, the average particle diameter means a volume-based average particle diameter unless otherwise specified. For example, a dispersion liquid of a target particle is measured using a Coulter Counter particle size distribution measuring instrument (manufactured by COULTER ELECTRONICS INS). TA-II type etc.) and can be obtained by measuring using a 50 μm aperture.

  The glass transition temperature (Tg) of the emulsion copolymer (A) is preferably −80 ° C. or higher and −30 ° C. or lower, more preferably −70 ° C. or higher and −35 ° C. or lower, and −66 ° C. or higher. More preferably, it is −40 ° C. or lower.

  Thereby, the cohesive force of an adhesive layer can be made more excellent and the removability of an adhesive body can be made more excellent.

The glass transition temperature (Tg) is a value obtained by converting the glass transition temperature (Tg _K ) of the absolute temperature (unit: K) calculated by the following formula (1) into a Celsius temperature (unit: ° C.).

In the above formula _{(1), W 1, W} 2, W 3, W 4 ··· shows the mass fraction of the monomer component of the emulsion copolymer (A) _(mass%), Tg _1, Tg ₂ , Tg ₃ , Tg ₄ ... Indicate the glass transition temperature in terms of absolute temperature (K) of the homopolymer of the monomer component of the emulsion copolymer (A).

<Primer>
The re-peelable pressure-sensitive adhesive composition of the present invention contains a primer.
Thereby, while being able to make the joining force with the base material 1 excellent, the adherend (container) provided with the adhesive layer formed using the re-peelable adhesive composition of this invention is used. ), It is possible to effectively prevent cohesive failure of the pressure-sensitive adhesive layer and interfacial failure between the pressure-sensitive adhesive layer and the substrate. As a result, it is possible to effectively prevent adhesive residue on the adherend (container) when the adhesive body is peeled from the container. In particular, even when a predetermined component contained in the contents of the container, which is an adherend, is transferred to an adhesive body attached to the outside of the container through the container, the problem of adhesive residue is generated. It can be effectively prevented.

  Examples of the primer include an olefin primer, an acrylic primer, a urethane primer, an ethylene-vinyl acetate primer, a polyester primer, a vinyl chloride primer, a polyurethane primer, etc. It is preferable to include.

  Thereby, the adhesiveness with respect to the base material etc. of the adhesive layer when it is set as an adhesive body can be made further excellent, and generation | occurrence | production of the problem of an adhesive residue can be prevented more effectively.

  In particular, when the base material that the pressure-sensitive adhesive layer comes into contact with when the pressure-sensitive adhesive body is made of polyolefin, the above-described effects are more remarkably exhibited.

  As the olefin-based primer, for example, a polyolefin obtained by subjecting polyolefin to at least one treatment among acid modification, chlorination, and acrylic modification can be used.

  Examples of commercially available olefin-based primers include Hardren 13-LP, 13-LLP, 14-LWP, 15-LP, 15-LLP, 16-LP, DX-526P, CY-9122P, CY-9124P, and HM. -21P, M-28P, F-2P, F-6P, CY-1132, EH-801, EW-5303, EW-8511, TD-15B, NS-2002, NZ-1004, NZ-1015 (above, Toyobo Super Clone 224H, 223M, 240H, 260F, E-415, E-480T, E-604, Auroren AE-202, AE-301 (Nippon Paper Industries, Ltd.), Arrow Base SA-1200, Examples thereof include SB-1200, SE-1200, SB-1010, DA-1010 (manufactured by Unitika).

  As the acrylic primer, for example, an acrylic copolymer containing a (meth) acrylic monomer and an olefin monomer such as styrene as constituent monomers can be used.

  Examples of commercially available acrylic primers include Bonron XPS002 (manufactured by Mitsui Chemicals).

  As the urethane-based primer, for example, a self-crosslinking water-based urethane resin (a urethane resin that forms a crosslinked structure by evaporating water) can be used.

  Examples of commercially available urethane primers include Takelac WS-4000 (manufactured by Mitsui Chemicals).

  Examples of commercially available ethylene-vinyl acetate based primers include Chemipearl EV210H (manufactured by Mitsui Chemicals).

  Examples of the commercially available polyester primer include Vylonal MD-1200 (manufactured by Toyobo Co., Ltd.).

  Examples of commercially available vinyl chloride based primers include Viniblanc 902 (manufactured by Nissin Chemical Industry Co., Ltd.).

  Examples of commercially available polyurethane-based primers include Superflex 210 (Daiichi Kogyo Seiyaku Co., Ltd.).

  The re-peelable pressure-sensitive adhesive composition has a base material, a pressure-sensitive adhesive layer formed using the re-peelable pressure-sensitive adhesive composition, and a primer layer provided between the base material and the pressure-sensitive adhesive layer. It is preferably used for the production of a body.

  Thereby, the adhesiveness (adhesiveness through a primer layer) of a base material and an adhesive layer can be made more excellent, and generation | occurrence | production of the problem of an adhesive residue can be prevented more effectively.

  The primer (first primer) contained in the re-peelable pressure-sensitive adhesive composition is preferably the same type as the primer (second primer) contained in the composition used for forming the primer layer.

  Thereby, the adhesiveness of a primer layer and an adhesive layer can be made further excellent, and generation | occurrence | production of the problem of an adhesive residue can be prevented more effectively.

  In the present invention, the same type of primer means the same series of primers. More specifically, for example, the acid-modified olefin primer and the acrylic-modified olefin primer are the same type of primer (both are olefin primers).

  Although the content of the primer contained in the re-peelable pressure-sensitive adhesive composition is not particularly limited, it is preferably 1 part by mass or more and 50 parts by mass or less, and 5 parts by mass or more and 35 parts by mass with respect to 100 parts by mass of the adhesive. More preferably, it is less than or equal to parts.

  If the primer content is too low, the effect of including the primer as described above may not be sufficiently exerted depending on the type of primer. Moreover, when content of a primer is too high, the content rate of an adhesive will fall relatively and the adhesive force with respect to the to-be-adhered body of the adhesive manufactured using a re-peelable adhesive composition will fall.

<Crosslinking agent>
The re-peelable pressure-sensitive adhesive composition may contain a crosslinking agent.
By including a crosslinking agent, a crosslinked structure can be formed in the pressure-sensitive adhesive described above. In particular, when it contains an emulsion copolymer (A), it can react with the functional group derived from the functional group-containing monomer contained in the structural unit (a2) of the emulsion copolymer (A).

  Examples of the crosslinking agent include isocyanate crosslinking agents, melamine crosslinking agents, aziridine crosslinking agents, epoxy crosslinking agents, oxazoline crosslinking agents, carbodiimide crosslinking agents, and metal crosslinking agents such as metal complexes. An isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, an oxazoline-based crosslinking agent, and a carbodiimide-based crosslinking agent are preferable.

  Thereby, the cohesive force of an adhesive layer can be improved and the removability of an adhesive body can be made more excellent.

  Examples of the isocyanate crosslinking agent include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane-4,4′-diisocyanate, Examples include diphenylmethane-2,4′-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, dicyclohexylmethane-2,4′-diisocyanate, and lysine isocyanate.

  In addition, trimers of these compounds, terminal isocyanate urethane prepolymers obtained by reacting these isocyanate compounds and polyol compounds, self-emulsifying water-dispersed polyisocyanates, blocked isocyanates, and the like can also be used.

  Examples of the melamine-based crosslinking agent include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexaptoxymethyl melamine, hexapentyloxymethyl melamine, hexahexyloxymethyl melamine, and melamine resin.

  Examples of the aziridine-based crosslinking agent include tetramethylolmethane-tri-β-aziridinylpropionate, trimethylolpropane-tri-β-aziridinylpropionate, N, N′-diphenylmethane-4,4 ′. -Bis (1-aziridinecarboxamide), N, N′-hexamethylene-1,6-bis (1-aziridinecarboxyamide) and the like.

  Examples of the epoxy-based crosslinking agent include bisphenol A / epichlorohydrin type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether, Examples include trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl erythritol, diglycerol polyglycidyl ether, and the like.

  Examples of the oxazoline-based crosslinking agent include 2,2′-bis- (2-oxazoline), 2,2′-methylene-bis- (2-oxazoline), and 2,2′-ethylene-bis- (2-oxazoline). ), 2,2′-trimethylene-bis- (2-oxazoline), 2,2′-tetramethylene-bis- (2-oxazoline), 2,2′-hexamethylene-bis- (2-oxazoline), 2 , 2′-octamethylene-bis- (2-oxazoline), 2,2′-ethylene-bis- (4,4′-dimethyl-2-oxazoline), 2,2′-p-phenylene-bis- (2 -Oxazoline), 2,2'-m-phenylene-bis- (2-oxazoline), 2,2'-m-phenylene-bis- (4,4'-dimethyl-2-oxazoline), 2,2'- (1,3-phenylene - bis - (2-oxazoline), bis - (2-oxazolinyl sulfonyl cyclohexane) sulfide, bis - (2-oxazolinyl sulfonyl norbornane) sulfide, and the like.

  In addition, vinyl monomers such as 2-isopropenyl-2-oxazoline and 2-isopropenyl-4,4-dimethyl-2-oxazoline, and other monomers copolymerizable with vinyl monomers These copolymers can also be used.

  Examples of the carbodiimide-based crosslinking agent include poly (4,4′-diphenylmethanecarbodiimide), poly (p-phenylenecarbodiimide), poly (m-phenylenecarbodiimide), poly (diisopropylphenylcarbodiimide), and poly (triisopropylphenylcarbodiimide). Aromatic polycarbodiimides such as poly (dicyclohexyl methane carbodiimide), aliphatic polycarbodiimides such as poly (diisopropylcarbodiimide), and the like.

Examples of the metal complex-based crosslinking agent include multimetallic acetylacetone and acetoacetyl ester coordination compounds such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium. .
These crosslinking agents can be used alone or in combination of two or more.

  The content of the crosslinking agent is preferably 0.01 parts by mass or more and 20 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less, with respect to 100 parts by mass of the pressure-sensitive adhesive. More preferably, it is 2 parts by mass or more and 6 parts by mass or less.

  Thereby, the applicability | paintability (especially coating property in high-speed application | coating) of a re-peeling type adhesive composition and the re-peelability of an adhesive body can be made more excellent.

<Wetting agent>
The re-peelable pressure-sensitive adhesive composition may contain a wetting agent.
By including the wetting agent, it is possible to improve the coating property (particularly, coating property at high speed application) of the re-peelable pressure-sensitive adhesive composition.

  Examples of the wetting agent include anionic surfactants, nonionic surfactants, acrylic compounds, silicone compounds, fluorine compounds, and water-soluble alcohols.

  Examples of anionic surfactants include higher alcohol sulfates and salts thereof, alkylbenzene sulfonates, polyoxyethylene alkylphenyl sulfonates, polyoxyethylene alkyl diphenyl ether sulfonates, alkyl diphenyl ether disulfonates, and succinic acid. Examples include dialkyl ester sulfonates.

  Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, oxyethylene-oxypropylene block polymer, sorbitan fatty acid ester, polyoxyethylene fatty acid, alkyl (amido) betaine, alkyldimethylamine oxide. And ethylene oxide-modified acetylene glycol.

  Examples of acrylic compounds include (meth) acrylic acid copolymers and acrylic surfactants.

  Examples of commercially available acrylic compounds include Polyflow No. 57, no. 95 (above, manufactured by Kyoeisha Chemical Co., Ltd.), Polyty A-530, A-540, A-550, PS-1900 (above, manufactured by Lion), EFKA-4550, EFKA-4560, EFKA-4570, EFKA-4580 ( As described above, manufactured by Fuka Additive Co., Ltd.), BYK-352, BYK-354, BYK-355, BYK-356, BYK-358, BYK-359, BYK-360, BYK-361, BYK-364, BYK-366, BYK -380, BYK-380N, BYK-381, BYK-390 (manufactured by Big Chemie Japan) and the like.

As a silicone type compound, a silicone type surfactant etc. are mentioned, for example.
In addition, examples of commercially available silicone compounds include polyether-modified dimethylsiloxanes such as SILWET FZ-2166 (manufactured by Nihon Unicar), BYK-302, BYK-348 (and above, manufactured by BYK Japan), SN Examples thereof include wet 125 (manufactured by San Nopco).

As a fluorine-type compound, a fluorine-type surfactant etc. are mentioned, for example.
Examples of commercially available fluorine-based compounds include perfluoroalkylethylenes such as Megafac F-142D, Megafac F-1405 (above, manufactured by Dainippon Ink and Chemicals), and ZONYL FSN (manufactured by DuPont). And oxide adducts.

Examples of the water-soluble alcohol include alcohols having 1 to 3 carbon atoms such as methanol, ethanol, 1-propanol, and 2-propanol.
These wetting agents can be used alone or in combination of two or more.

  The content of the wetting agent is preferably 0.01 parts by mass or more and 2.00 parts by mass or less, and more preferably 0.06 parts by mass or more and 1.60 parts by mass or less with respect to 100 parts by mass of the pressure-sensitive adhesive. Preferably, it is 0.10 parts by mass or more and 1.20 parts by mass or less.

  Thereby, the applicability | paintability (especially coating property in high-speed application | coating) of a re-peeling type adhesive composition and the re-peelability of an adhesive body can be made more excellent.

<Associative thickener>
The re-peelable pressure-sensitive adhesive composition may contain an associative thickener.
The associative thickener is a thickener composed of a polymer having a molecular weight of several thousands to several tens of thousands with a hydrophobic portion at both ends and a hydrophilic portion therebetween, and the hydrophobic portions at both ends associate with the hydrophobic portion of the emulsion particles. By doing so, two particles can be connected to each other, and a loose network structure can be formed in the entire system.

  By containing the associative thickener, the re-peelable pressure-sensitive adhesive composition is more excellent in coatability in high-speed coating.

  The associative thickener has a weight average molecular weight (Mw) of preferably 1,000 or more and 500,000 or less, more preferably 2,000 or more and 200,000 or less, and more preferably 3,000 or more and 100,000. More preferably, it is as follows.

  Examples of the associative thickener include polyacrylic acid-based associative thickeners such as sodium polyacrylate and polyacrylic acid- (meth) acrylic acid ester copolymer; polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl benzyl ether Polyvinyl-based thickeners such as polymers; polyether-based thickeners such as pluronic polyethers, polyether dialkyl esters, polyether dialkyl ethers, and polyether-epoxy-modified products; polyglycol-based thickeners; vinyl Maleic anhydride copolymer-based thickeners such as partial esters of methyl ether-maleic anhydride copolymers; Polyamide-based associative thickeners such as polyamidoamine salts; Polyester-based associative thickeners; Hydrophobizing Cellulose ester-based associative thickener; with a hydrophobic group at the end and molecular chain Urethane associative thickener containing urethane bonds; polycarboxylic acid-based associative thickener.

  Commercially available urethane associative thickeners include, for example, Adecanol UH-420, Adecanol UH-462, Adecanol UH-472, Adecanol UH-540, Adecanol UH-752, Adecanol UH-756VF, Adecanol UH-814N (and above) , Manufactured by ADEKA), SN thickener 612, SN thickener 621N, SN thickener 625N, SN thickener 627N, SN thickener 660T (and above, manufactured by San Nopco).

Examples of commercially available polyether associative thickeners include SN thickener 601, SN thickener A-801, SN thickener A-806 (manufactured by San Nopco).
These associative thickeners can be used alone or in combination of two or more.

  Among these, a urethane associative thickener and a polyether associative thickener are preferable, and a urethane associative thickener is more preferable.

  Thereby, the re-peelable pressure-sensitive adhesive composition is more excellent in coatability in high-speed application.

  The content of the associative thickener is preferably 0.01 parts by weight or more and 1.80 parts by weight or less, and 0.02 parts by weight or more and 1.20 parts by weight or less with respect to 100 parts by weight of the adhesive. Is more preferably 0.03 parts by mass or more and 0.80 parts by mass or less.

  Thereby, the applicability | paintability of the re-peeling type adhesive composition in high-speed application | coating can be made more excellent.

<Plasticizer>
The re-peelable pressure-sensitive adhesive composition may contain a plasticizer.
Thereby, the softness | flexibility and elasticity of a re-peelable adhesive composition can be made more excellent. Moreover, the removability of the re-peelable pressure-sensitive adhesive composition can be made more excellent, and a pressure-sensitive adhesive body (for example, a pressure-sensitive adhesive sheet) produced using the re-peelable pressure-sensitive adhesive composition can be adhered ( The feeling of turning when peeling from the container can be made more excellent.

  Examples of the plasticizer include citric acid plasticizers such as tributyl acetyl citrate and triethyl acetyl citrate; dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, di-n-octyl phthalate, and phthalic acid Phthalic acid ester plasticizers such as dicyclohexyl; Trimellitic acid ester plasticizers such as trioctyl trimellitic acid, triisononyl trimellitic acid, and triisodecyl trimellitic acid; Plasticizers; Polyester plasticizers such as phthalic polyesters, Phosphate ester plasticizers such as tricresyl phosphate, trioctyl phosphate, triphenyl phosphate; Epoxy types such as epoxidized linseed oil and epoxidized butyl stearate Agent; liquid polybutene, mineral oil, lanolin, wax, liquid polyisoprene, liquid polyacrylates, triethanolamine, alkyl amines, amine alkylene oxide adduct, glycerin, diglycerin, and silicone oil.

  The content of the plasticizer contained in the re-peelable pressure-sensitive adhesive composition is not particularly limited, but is preferably 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the pressure-sensitive adhesive. It is more preferable that the amount is not less than 5 parts by mass.

  If the content of the plasticizer is too low, depending on the type of the plasticizer, the effect of including the plasticizer as described above may not be sufficiently exhibited. Moreover, when content of a plasticizer is too high, content of an adhesive will fall relatively and the function of an adhesive may not fully be exhibited.

<Other ingredients>
The re-peelable pressure-sensitive adhesive composition may contain components other than those described above. Examples of such components include colorants such as dyes and pigments, antioxidants such as anilides and phenols, UV absorbers such as benzophenones and benzotriazoles, light stabilizers, dispersants, and tackifiers. , Antifoaming agents, modifiers, rust inhibitors, solvents, leveling agents, antistatic agents and the like. The content of these components is not particularly limited, but it is preferable not to exceed 10% by mass as a whole of these components excluding the solvent.

  The solid content concentration in the re-peelable pressure-sensitive adhesive composition is preferably 20% by mass to 70% by mass, more preferably 30% by mass to 65% by mass, and 40% by mass to 60% by mass. More preferably, it is as follows.

  Thereby, the applicability | paintability (especially the applicability | paintability in high-speed application | coating) of a re-peelable adhesive composition can be made more excellent.

[Adhesive]
Next, the pressure-sensitive adhesive body of the present invention will be described.
FIG. 1 is a schematic longitudinal sectional view showing a preferred embodiment of the pressure-sensitive adhesive body (pressure-sensitive adhesive sheet) of the present invention.

  As shown in FIG. 1, a pressure-sensitive adhesive sheet (re-peelable pressure-sensitive adhesive sheet) 10 as a pressure-sensitive adhesive body is attached to a container in which contents are stored, and includes a base material 1, a pressure-sensitive adhesive layer 2, and the like. Is provided. And the adhesive layer 2 is formed using the re-peeling type adhesive composition of this invention mentioned above.

  Thereby, it is possible to provide the pressure-sensitive adhesive sheet 10 that can be suitably peeled from the container in which the contents are stored while effectively preventing the occurrence of the adhesive residue problem.

Note that when the pressure-sensitive adhesive sheet 10 is peeled from the container, the container has a history in which the content containing at least one substance (predetermined substance) among the fragrance and the surfactant is stored. In addition, when the pressure-sensitive adhesive sheet 10 is attached to the container or when the pressure-sensitive adhesive sheet 10 is peeled from the container, the container may not be in a state where the contents are accommodated.
Further, in this specification, “film” includes the concept of a sheet.

In the present embodiment, the primer layer 3 is provided between the substrate 1 and the pressure-sensitive adhesive layer 2.
Thereby, the adhesiveness of the base material 1 and the adhesive layer 2 can be made more excellent, the removability of the adhesive sheet 10 can be made more excellent, and the adherend (container) It is possible to more effectively prevent delamination (interfacial failure) and the like on the inner surface side of the pressure-sensitive adhesive layer 2 (the surface opposite to the surface facing the adherend) when the pressure-sensitive adhesive sheet 10 is peeled from it can.

The substrate 1 has a function of supporting the pressure-sensitive adhesive layer 2.
The substrate 1 may be in any form such as a dense film, woven fabric, non-woven fabric, paper, porous body, and the like.

  The constituent material of the substrate 1 is not particularly limited, and examples thereof include resin materials, metal materials, vegetable fibers such as pulp, animal fibers such as wool, and the like, and resin materials are preferably used.

  Examples of the resin material constituting the substrate 1 include polyethylene, polypropylene, ethylene / propylene copolymer, ethylene / vinyl acetate copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, Polyolefins such as ethylene / butyl acrylate copolymer, ethylene / methacrylic acid copolymer, ethylene / methyl methacrylate copolymer; polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate; acetate resin, acrylonitrile -Butadiene-styrene copolymer (ABS) resin, polystyrene, polyvinyl chloride, polyamide, polyesteramide, polyether, polyimide, polyamideimide, poly-p-phenylene sulfide, polyether s Le, and the like, may be used alone or in combination of two or more selected from these.

  Moreover, the base material 1 may contain components other than those described above. Examples of such components include colorants such as dyes and pigments, antioxidants such as anilides and phenols, UV absorbers such as benzophenones and benzotriazoles, light stabilizers, modifiers, and rust prevention. Agents, fillers, surface lubricants, corrosion inhibitors, heat stabilizers, lubricants, antistatic agents, polymerization inhibitors, crosslinking agents, catalysts, plasticizers, leveling agents, thickeners, softeners, dispersants, etc. It is done.

  Moreover, the base material 1 may be comprised from a single layer, and the laminated body provided with a some layer may be sufficient as it. Moreover, the base material 1 may be comprised with the inclination material from which a composition changes in gradient in the thickness direction, for example.

  As the base material 1 as a laminate including a plurality of layers, for example, a film made of a metal material such as aluminum on a base made of a resin material such as polyolefin such as polypropylene or polyester such as polyethylene terephthalate ( For example, the thing provided with the vapor deposition film | membrane etc. is mentioned.

  Conventionally, the base material having such a structure has a problem of adhesive residue particularly when an adhesive layer is formed on the film side made of a metal material. Therefore, even when the base material having such a configuration is used, it is possible to effectively prevent the occurrence of the adhesive residue problem. That is, the effect of the present invention is exhibited more remarkably when a base material made of a metal material is provided on a base portion made of a resin material as a base material. .

  Moreover, the base material 1 may be subjected to a surface treatment for improving the adhesion with the primer layer 3.

  Thereby, generation | occurrence | production of the adhesive residue at the time of peeling the adhesive sheet 10 from a to-be-adhered body (container) can be prevented more effectively.

As such a surface treatment, for example, an oxidation method, a concavo-convex method or the like can be cited.
Examples of the oxidation method include corona discharge treatment (corona treatment), chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like. Method, solvent treatment method and the like.

  These surface treatment methods are appropriately selected according to the material constituting the substrate 1, but in general, corona treatment is preferable from the viewpoints of effects and operability.

  Although the thickness of the base material 1 is not specifically limited, It is preferable that they are 15 micrometers or more and 300 micrometers or less, and it is more preferable that they are 20 micrometers or more and 50 micrometers or less.

  The thickness of the pressure-sensitive adhesive layer 2 is not particularly limited, but is preferably 1 μm or more and 100 μm or less, more preferably 3 μm or more and 50 μm or less, and further preferably 5 μm or more and 30 μm or less.

As a primer used for formation of the primer layer 3, the thing similar to the primer mentioned above as a structural component of a re-peeling type adhesive composition is mentioned, for example.
Thereby, the same effect as described above can be obtained.

  The primer used for forming the primer layer 3 and the primer as a constituent component of the re-peelable pressure-sensitive adhesive composition may be different types, but preferably include the same type in common, and the same It is more preferable that these compounds are included in common.

  Thereby, the adhesiveness of the adhesive layer 2 and the primer layer 3 can be made more excellent, and generation | occurrence | production of the problem of an adhesive residue can be prevented more effectively.

  The primer layer 3 is preferably formed using a material containing an olefin-based primer.

  Thereby, the adhesiveness between the primer layer 3 and the base material 1 and the adhesiveness between the primer layer 3 and the pressure-sensitive adhesive layer 2 can be further improved, and the occurrence of an adhesive residue problem can be further effectively prevented. can do. In particular, when the substrate 1 is composed of polyolefin, or when the pressure-sensitive adhesive layer 2 contains a polyolefin-based compound (for example, the pressure-sensitive adhesive layer 2 is formed using a material containing an olefin-based primer) In such a case, the above-described effects can be exhibited particularly remarkably.

  The thickness of the primer layer 3 is preferably 0.05 μm or more and 3 μm or less, and more preferably 0.1 μm or more and 1 μm or less.

[Method for producing adhesive]
Next, the manufacturing method of the adhesive body of this invention is demonstrated.
FIG. 2 is a schematic longitudinal sectional view showing a preferred embodiment of the method for producing a pressure-sensitive adhesive body (pressure-sensitive adhesive sheet) of the present invention.

  The manufacturing method of the present embodiment includes a base material preparing step (1a) for preparing the base material 1, a primer layer forming step (1b) for forming the primer layer 3 on the base material 1, and adhesion to the surface of the primer layer 3. A pressure-sensitive adhesive layer forming step (1c) for forming the adhesive layer 2.

  First, the base material 1 as described above is prepared (1a). Prior to the primer layer forming step described later, the prepared substrate 1 may be subjected to the surface treatment as described above.

Next, the primer layer 3 is formed on the surface of the substrate 1 (1b).
The primer layer 3 can be formed, for example, by applying a liquid composition (primer layer forming composition) containing a primer onto the substrate 1 by a gravure method, a Meyer bar method, or the like. After application of the primer layer forming composition, treatment such as heating and drying may be performed as necessary.

Thereafter, the pressure-sensitive adhesive layer 2 is formed so as to come into contact with the primer layer 3 (1c).
Although the formation method of the adhesive layer 2 is not specifically limited, It can form suitably by providing the re-peeling-type adhesive composition mentioned above on the surface of the primer layer 3 of the prepared base material 1. FIG. Alternatively, the pressure-sensitive adhesive layer 2 may be formed on the release treatment surface of the release liner, and the pressure-sensitive adhesive layer 2 may be bonded to the primer layer 3 of the substrate 1.

  Application of the re-peelable pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer 2 is performed by, for example, applying a liquid re-peelable pressure-sensitive adhesive composition (coating liquid) to a roll coat, a gravure coat, a reverse coat, a roll brush, The coating can be performed on the substrate 1 by various coating methods such as spray coating, knife coating, die coating, comma coating, and bar coating.

  In forming the pressure-sensitive adhesive layer 2, the re-peelable pressure-sensitive adhesive composition and other components may be mixed to prepare a coating liquid. For example, when the pressure-sensitive adhesive layer 2 is formed, the re-peelable pressure-sensitive adhesive composition may be mixed with water or a solvent.

  The pressure-sensitive adhesive layer 2 may be once formed on a release material (release liner) and then bonded to the substrate 1.

[Adherent (container)]
Next, the container as an adherend to which the pressure-sensitive adhesive sheet of the present invention is attached will be described.
The pressure-sensitive adhesive sheet 10 is attached to a container in which contents are stored.

  Although the constituent material of a container is not specifically limited, It is preferable that it is comprised with the material containing polyolefin, such as polyethylene and a polypropylene.

  These materials have a feature of high stability against acids and alkalis. On the other hand, when a predetermined substance such as a fragrance or a surfactant is easy to permeate and the predetermined substance permeates the adhesive layer of the adhesive sheet and reaches the interface between the adhesive layer and the substrate, the adhesive residue as described above is obtained. The inventor has found that this problem is likely to occur. Therefore, when the container is made of a material containing polyolefin, the effects of the present invention can be exhibited more remarkably while taking advantage of the characteristics of the material.

  The thickness (wall thickness) of the container is preferably 5 mm or less, and more preferably 3 mm or less.

  When the thickness is relatively small as described above, a predetermined substance such as a fragrance or a surfactant is likely to permeate, and usually the above-mentioned problem of adhesive residue is likely to occur. On the other hand, in the present invention, when the thickness is small and the predetermined substance such as the fragrance or the surfactant is easily transmitted (when the permeation amount of the predetermined substance such as the fragrance or the surfactant is large), The problem of adhesive residue as described above can be effectively prevented. Therefore, when the thickness of the container is relatively small as described above, the effect of the present invention is more remarkably exhibited.

  The shape of the container is not particularly limited, and may be any shape such as a tube shape or a bottle shape.

The contents are accommodated in the container (accommodating portion) of the adherend.
The contents may be in any state, for example, solids such as powder, liquids (including a state absorbed in an absorbent body such as a sheet), pastes, and gases. When the product is liquid or pasty, the above problem has occurred more remarkably. However, in the present invention, even when the content is liquid or pasty, the above problem occurs. It can be effectively prevented. Therefore, when the contents are liquid or paste, the effect of the present invention is more remarkably exhibited.

  Specific examples of contents include various detergents, face wash, lotion, makeup remover, cleansing oil, milky lotion, serum, hand cream, body lotion, body cream, lip balm, antiperspirant deodorant, UV care products (sun tanning) Stopper, etc.), perfume, shampoo, hair rinse, conditioner, hair nourishing agent, hair restorer, permanent agent, hair color, hair wax, shaving agent, hair remover, bath oil, toothpaste, liquid toothpaste, mouthwash (mouthwash), Examples include pharmaceuticals, foods (including drinks and supplements), and the like.

  As the fragrance, for example, “Perfume and Flavor Chemicals”, Vol. Iand II, Steffen Arctander, Allured Pub. Co. (1994) and "Synthetic fragrance chemistry and commercial knowledge", Motoichi Into, Chemical Industry Daily (1996) and "Perfume and Flavor Materials of Natural Origin", Stephen Arctander, Allred Pub. Co. (1994) and "Encyclopedia of Scents", edited by Japan Fragrance Association, Asakura Shoten (1989) and "Performer Material Performance V.3.3", Boelens Aroma Chemical Information Service (1996) and "Flower oil". , Danute Lajaujis Anonis, Allured Pub. Co. (1993) can be used.

  Examples of the surfactant include ionic surfactants such as anionic surfactants, cationic surfactants, and amphoteric surfactants; nonionic surfactants and the like.

  Examples of the anionic surfactant include alkyl sulfates such as sodium lauryl sulfate and potassium lauryl sulfate or salts thereof; alkyl ether sulfates such as polyoxyethylene lauryl sulfate triethanolamine; or salts thereof; N- such as sodium lauroyl sarcosine. Acyl sarcosine or a salt thereof; alkyl phosphoric acid or a salt thereof such as sodium monostearyl phosphate; polyoxyethylene alkyl ether phosphoric acid or a salt thereof such as sodium polyoxyethylene oleyl ether phosphate or sodium polyoxyethylene stearyl ether phosphate; Dialkylsulfosuccinic acid or a salt thereof such as sodium di-2-ethylhexylsulfosuccinate; N-alkyloylmethyl such as N-stearoyl-N-methyltaurine sodium Urine or a salt thereof; sodium dilauroyl glutamate, monosodium N-lauroyl glutamate, sodium N-stearoyl-L-glutamate, arginine N-stearoyl-L-glutamate, sodium N-stearoyl glutamate, sodium N-myristoyl-L-glutamate, etc. N-acyl glutamic acid or a salt thereof.

  As the cationic surfactant, for example, a quaternary ammonium salt is preferable. For example, alkyltrimethylammonium such as stearyltrimethylammonium chloride or lauryltrimethylammonium chloride or a salt thereof; dialkyldimethylammonium chloride, trialkylmethylammonium chloride, alkyl Examples thereof include amines and salts thereof.

  Examples of the amphoteric surfactant include alkyl dimethylamine oxide, alkyl carboxy betaine, alkyl sulfo betaine, amide amino acid salt, alkyl amide propyl betaine and the like.

  Nonionic surfactants include, for example, ethylene glycol fatty acid esters such as ethylene glycol monostearate; polyethylene glycol fatty acid esters such as polyethylene glycol monostearate; polyalkylene glycol alkyl ethers such as polyethylene glycol decyl pentadecyl ether. Polyethylene glycol hydrogenated castor oil monoisolaurate and other polyethylene glycol hydrogenated castor oil; propylene glycol fatty acid ester; glycerol monoisostearic acid ester and other monoglycerin monofatty acid ester; glycerol distearic acid ester and glycerin dilauric acid ester and other monoglycerin Difatty acid esters; Glycerin alkyl ethers such as glycerol monoisostearyl ether Le; sorbitan sorbitan fatty acid esters such as monostearate; fatty acid alkanolamides; fatty acid dialkanolamide such as lauric diethanolamide and the like.

  The sum of the content of the fragrance and the content of the surfactant in the contents is preferably 0.01% by mass or more, and more preferably 0.03% by mass or more.

  Thus, when the content rate of the predetermined component in the contents is relatively high, the effect of the present invention is more remarkably exhibited.

  As mentioned above, although preferred embodiment of this invention was described, this invention is not limited to these.

  For example, the pressure-sensitive adhesive body (for example, pressure-sensitive adhesive sheet) may have at least one coating layer on the surface opposite to the surface facing the pressure-sensitive adhesive layer of the substrate. For example, the printed layer may be provided on the surface of the substrate opposite to the surface facing the pressure-sensitive adhesive layer. Moreover, in order to improve adhesiveness with a printing layer, the coating layer for printing etc. may be provided. Moreover, the coat layer which has functions, such as protecting the surface of an adhesive sheet, may be provided.

  Further, in the above-described embodiment, the case where the pressure-sensitive adhesive body is a pressure-sensitive adhesive sheet including a film-like base material and forming a film shape as the whole pressure-sensitive adhesive body has been representatively described. The shape is not limited to a film shape and may be any shape.

  Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited to these examples. In the following description, various measurement conditions that do not particularly indicate temperature conditions are values at room temperature (23 ° C.).

[1] Production of adhesive sheet (Example 1)
In a container equipped with a stirrer, a thermometer, and a dropping funnel, as raw material monomers, 2-ethylhexyl acrylate (2EHA) 70.0 parts by mass, butyl acrylate (BA) 28.0 parts by mass, acrylic acid (AA) 1 A raw material monomer mixture of 1.0 part by mass and 1.0 part by mass of methacrylic acid (MAA) was charged, and “Adekalia soap SR-10 (product name, manufactured by ADEKA, anionic emulsifier, allyloxymethyl) as an emulsifier was further added. (Alkoxyethyl polyoxyethylene sulfate salt, solid content concentration 100% by mass) "2.0 parts by mass (solid content ratio), 0.1 parts by mass of lauryl mercaptan as a chain transfer agent, and 35.0 masses of ion-exchanged water An emulsion of the raw material monomer mixture was prepared in advance by stirring at room temperature (23 ° C.).

  Separately, 28.0 parts by mass of ion-exchanged water is charged into a reactor equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen introduction tube, and a dropping funnel, and the temperature is increased to 80 ° C. by filling nitrogen. Then, while maintaining the temperature at 80 ° C., 2.0 parts by mass of 10 mass% ammonium persulfate aqueous solution (solid content conversion: 0.20 parts by mass) was added. And the emulsion of said monomer mixture was moved to the dropping funnel, and was dripped over 4 hours. At the same time, 4.0 parts by mass of a 5% by mass aqueous ammonium persulfate solution (solid content: 0.20 parts by mass) was added dropwise, and emulsion polymerization was performed at an internal temperature of 80 ° C.

  After completion of these droppings, the mixture was aged at 80 ° C. for 4 hours, and the emulsion copolymer (A) (structural unit: 2EHA / BA / AA / MAA = 70.0 / 28.0 / 1.0 / 1.0). (Mass part)) was synthesized. Then, after cooling to room temperature, neutralize with ammonia water to pH 8.5, and further add ion exchange water to prepare an aqueous dispersion of an emulsion copolymer (emulsion adhesive) having a solid content concentration of 55% by mass. did. The average particle size of the emulsion copolymer was 450 nm.

  10 parts by mass of an olefin primer (manufactured by Toyobo Co., Ltd., Hardren NZ-1004) and an epoxy-based cross-linking agent (Nagase ChemteX Corporation) with respect to 100 parts by mass of the aqueous dispersion of the emulsion copolymer obtained as described above. Manufactured by Denacol EX-313), 1 part by mass, acrylic compound as a wetting agent (BYK-380N, BYK-380N) 0.2 part by mass (both solid content ratio), urethane associative type as a thickener A thickener (Adeka UH-540, manufactured by ADEKA) and ion-exchanged water are added and sufficiently stirred to obtain a pressure-sensitive adhesive composition (re-peelable pressure-sensitive adhesive composition) having a solid content concentration of 45% by mass. It was.

  Next, the thickness of the pressure-sensitive adhesive layer after drying is 20 μm by a roll coater on the release treatment surface of a release liner (release paper) (manufactured by Lintec, SP-8K Ao, glassine paper release-treated with silicone). Thus, the above-mentioned pressure-sensitive adhesive composition (re-peelable pressure-sensitive adhesive composition) was applied and dried at 90 ° C. for 2 minutes to form a pressure-sensitive adhesive layer on the release liner.

  On the other hand, a polyethylene terephthalate (PET) film (manufactured by Toray Film Processing Co., Ltd., Metal Me TS # 50) provided with an aluminum vapor deposition film to be used as a substrate is prepared, and dried on a surface provided with the aluminum vapor deposition film by a gravure coater. Hardlen NZ-1004 (Toyobo Co., Ltd. emulsion containing an olefin-based primer) was applied as a primer layer forming composition so that the thickness of the subsequent primer layer was 0.1 μm, and the primer layer was formed on the substrate. Formed.

  Thereafter, the pressure-sensitive adhesive layer formed on the release liner as described above is brought into contact with the surface of the primer layer and aged for one week under conditions of a temperature of 23 ° C. and a relative humidity of 50%. Was obtained.

  That is, the pressure-sensitive adhesive sheet produced in this example has a structure in which a base material, a primer layer, and a pressure-sensitive adhesive layer are laminated in this order.

(Examples 2 to 7)
A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that the composition of the pressure-sensitive adhesive sheet was changed as shown in Table 1 by adjusting the conditions of the re-peelable pressure-sensitive adhesive composition.

(Comparative Example 1)
A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that a primer was not used for adjusting the re-peelable pressure-sensitive adhesive composition and the formation of the primer layer was omitted.

  About each said Example and a comparative example, the monomer structure of the emulsion adhesive contained in a re-peelable adhesive composition and the structure of an adhesive sheet were put together in Table 1, and were shown.

  In Table 1, Hardene NZ-1004 (manufactured by Toyobo Co., Ltd.) as the olefin primer is NZ1004, and Aurolen AE-301 (Nippon Paper Industries Co., Ltd.) as the olefin primer (specially modified polyolefin) is AE-301, olefin. Arrowbase DA-1010 (manufactured by Unitika) as a system primer (modified polyolefin) is DA-1010, Chemipearl EV210H (manufactured by Mitsui Chemicals) as an ethylene-vinyl acetate primer is EV210H, and Bironal MD as a polyester primer -1200 (manufactured by Toyobo Co., Ltd.) as MD-1200, Superflex 210 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as a polyurethane-based primer as S210, vinyl chloride-based primer (acrylic ester-vinyl chloride copolymer) VINYBLAN 902 (manufactured by Nissin Chemical Industry Co., Ltd.) V902, shown SUPERCHLON 223M as an olefin-based primer (acrylic modified chlorinated polyolefin) (manufactured by Nippon Paper Industries Co., Ltd.) at 223M. Moreover, the value of the average particle diameter was calculated | required by the measurement using a 50 micrometer aperture with the Coulter counter particle size distribution measuring device (TA-II type made from COULTER ELECTRONICS INS).

[2] Evaluation [2.1] Removability from a container having no storage history The pressure-sensitive adhesive sheets (pressure-sensitive adhesive sheets protected with a release liner) of each of the examples and comparative examples were 25 mm wide and 150 mm long. Then, it was cut into a test piece.

The release liner was peeled from the obtained test piece, the exposed pressure-sensitive adhesive layer was brought into close contact with the surface of a polyethylene container (tube) having no storage history, and a pressure-sensitive adhesive sheet was adhered.
The thickness of the polyethylene container (tube) was 0.5 μm.

  Next, after standing for 1 day in an environment of 23 ° C. and 50% RH (relative humidity), left for 7 days in an environment of 60 ° C. and again to an environment of 23 ° C. and 50% RH (relative humidity). And left to stand for 1 day.

  Then, the adhesive sheet was peeled off by hand at a speed of 0.3 m / min, and the site where the adhesive sheet of the container was peeled was observed and evaluated based on the following criteria.

A: The area ratio of the part with the adhesive residue in the part where the adhesive sheet of the container is adhered is less than 5%.
B: The area ratio of the part with the adhesive residue in the part where the adhesive sheet of the container is adhered is 5% or more and less than 10%.
C: The area ratio of the portion where the adhesive residue is present in the portion where the adhesive sheet of the container is adhered is 10% or more and less than 25%.
D: The area ratio of the portion having the adhesive residue in the part where the adhesive sheet of the container is adhered is 25% or more and less than 50%.
E: The area ratio of the part with the adhesive residue in the part where the adhesive sheet of the container is pasted is 50% or more.

<Removability from container containing contents (container with storage history)>
A container similar to that used in [2.1] above was prepared except that a makeup remover was contained. As the makeup remover in the container, a commercially available makeup remover (containing a surfactant and a fragrance) was used.

  Next, the adhesive sheet was attached in the same manner as in [2.1] except that the container containing the contents was used as the adherend to which the adhesive sheet was attached.

  Next, in the same manner as in [2.1] above, the sample was allowed to stand for 1 day in an environment of 23 ° C. and 50% RH (relative humidity), and then left for 7 days in an environment of 60 ° C. Return to the environment of% RH (relative humidity) and let stand for 1 day, then peel off the adhesive sheet by hand at a speed of 0.3 m / min, and observe the part where the adhesive sheet of the container was peeled off. Evaluation was made based on the following criteria.

A: The area ratio of the part with the adhesive residue in the part where the adhesive sheet of the container is adhered is less than 5%.
B: The area ratio of the part with the adhesive residue in the part where the adhesive sheet of the container is adhered is 5% or more and less than 10%.
C: The area ratio of the portion where the adhesive residue is present in the portion where the adhesive sheet of the container is adhered is 10% or more and less than 25%.
D: The area ratio of the portion having the adhesive residue in the part where the adhesive sheet of the container is adhered is 25% or more and less than 50%.
E: The area ratio of the part with the adhesive residue in the part where the adhesive sheet of the container is pasted is 50% or more.
These results are summarized in Table 2.

  As is apparent from Table 2, excellent results were obtained in the present invention, whereas satisfactory results were not obtained in the comparative example.

10 ... Adhesive sheet (removable adhesive sheet)
DESCRIPTION OF SYMBOLS 1 ... Base material 2 ... Adhesive layer 3 ... Primer layer

Claims (10)

A re-peelable pressure-sensitive adhesive composition used for the manufacture of a re-peelable pressure-sensitive adhesive body that is adhered to a container in which contents are contained,
A re-peelable pressure-sensitive adhesive composition comprising a pressure-sensitive adhesive and a primer.   The re-peelable pressure-sensitive adhesive composition according to claim 1, comprising an olefin-based primer as the primer.   The re-peelable pressure-sensitive adhesive composition according to claim 1 or 2, wherein the pressure-sensitive adhesive is an emulsion pressure-sensitive adhesive.   The re-peelable pressure-sensitive adhesive composition according to any one of claims 1 to 3, wherein a content ratio of the primer with respect to 100 parts by mass of the pressure-sensitive adhesive is 1 part by mass or more and 50 parts by mass or less.   The re-peelable pressure-sensitive adhesive composition according to any one of claims 1 to 4, wherein the content contains at least one of a fragrance and a surfactant.   The pressure-sensitive adhesive body has a base material, a pressure-sensitive adhesive layer formed using the re-peelable pressure-sensitive adhesive composition, and a primer layer provided between the base material and the pressure-sensitive adhesive layer. The re-peelable pressure-sensitive adhesive composition according to any one of claims 1 to 5.   The re-peelable pressure-sensitive adhesive composition according to claim 6, wherein the primer contained in the re-peelable pressure-sensitive adhesive composition is the same type as the primer contained in the composition used for forming the primer layer. It is a re-peelable adhesive that is attached to a container containing the contents,
A substrate;
A pressure-sensitive adhesive body comprising: a pressure-sensitive adhesive layer formed using the re-peelable pressure-sensitive adhesive composition according to any one of claims 1 to 5. It is an adhesive that is attached to a container containing the contents,
A substrate;
A pressure-sensitive adhesive layer formed using the re-peelable pressure-sensitive adhesive composition according to claim 6 or 7,
An adhesive body comprising a primer layer provided between the substrate and the adhesive layer.   The pressure-sensitive adhesive body according to claim 9, wherein the primer layer is composed of a material containing an olefin-based primer.

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