JP5683405B2 - Thermally active adhesive label - Google Patents

Description

The present invention, thermally active adhesive label adhesive composition on one surface of the supporting lifting member (hereinafter also referred to as "adhesive composition".) It relates to thermally active adhesive label provided with an adhesive layer made of.

  The heat-activatable pressure-sensitive adhesive label provided with a pressure-sensitive adhesive layer containing a heat-active pressure-sensitive adhesive on one side of the support is directly or on the opposite side of the pressure-sensitive adhesive layer of the support, an ink jet recording layer, a heat-sensitive recording layer, a pressure-sensitive recording layer, a thermal transfer Various recording layers such as an ink receiving layer or an electrophotographic recording layer are provided and used for various purposes (Patent Documents 1 to 4).

JP2007-204549 JP2009-037109 JP2009-137220A JP2010-241007

Such thermoactive adhesive labels are required to maintain adhesiveness for a long period of time (adhesion persistence), but if the adhesive persistence is increased, adhesiveness is expressed during storage and the adhesive labels stick to each other A blocking problem may occur (Patent Documents 1 to 3).
The present invention, while having sufficient adhesive persistence, and an object thereof is to provide a thermally activated adhesive label having sufficient blocking resistance.

  In order to solve the above problems, the present inventors added a compound (such as Patent Document 3) that has been conventionally used as a sensitizer for a heat-sensitive recording material to the pressure-sensitive adhesive to maintain the pressure-sensitive adhesive label. As a result of examining the properties and blocking resistance, it was found that when a specific compound was added to the pressure-sensitive adhesive, the thermally active pressure-sensitive adhesive label had sufficient adhesion durability and blocking resistance, and the present invention was completed.

又は下記一般式

（式中、Ｘ^１及びＸ^２は、それぞれ独立して、−ＣＨ_２−、−Ｃ_２Ｈ_４−、−ＯＣＨ_２−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−又は−ＳＯ_２−を表し、Ｒ^１及びＲ^２は、それぞれ独立して、ハロゲン原子、アルキル基、アルケニル基又はアルコキシ基を表し、ｍ及びｎは、それぞれ独立して、０〜３の整数を表し、ｏは０又は１を表す。）で表される化合物から成る熱活性粘着ラベル用粘着組成物から成る熱活性粘着層を設けた熱活性粘着ラベル（但し、感熱記録体ラベルを除く。）である。
That is, the present invention provides a thermally active adhesive and the following general formula on one side of the support.

Or the following general formula

(Wherein, X ¹ and X ² are each independently —CH ₂ —, —C ₂ H ₄ —, —OCH ₂ —CH ₂ O—, —OCH ₂ —, —CH ₂ O— or —SO _2- represents, R ¹ and R ² each independently represent a halogen atom, an alkyl group, an alkenyl group or an alkoxy group, m and n each independently represent an integer of 0 to 3, o Represents a heat-active pressure-sensitive adhesive label (excluding a heat-sensitive recording medium label) provided with a heat-active pressure-sensitive adhesive layer comprising a pressure-sensitive adhesive composition for a heat-active pressure-sensitive adhesive label.

又は下記一般式

で表される化合物（以下「添加剤」ともいう。）から成る。
Viscous adhesive composition of the present invention, thermally active adhesive and Formula

Or the following general formula

(Hereinafter also referred to as “additive”).

In the above formula,
X ¹ and X ² each independently represent —CH ₂ —, —C ₂ H ₄ —, —OCH ₂ —CH ₂ O—, —OCH ₂ —, —CH ₂ O— or —SO ₂ —. .
R ¹ and R ² each independently represents a halogen atom, an alkyl group, an alkenyl group or an alkoxy group. As this halogen atom, a chlorine atom is preferable. As this alkyl group, an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is particularly preferable. As this alkenyl group, a vinyl group or an allyl group is preferable. As this alkoxy group, a C1-C3 alkoxy group is preferable.
m and n each independently represent an integer of 0 to 3, preferably 0 or 1.
o represents 0 or 1.

Of the above compounds, the following compounds are preferred.
1) A compound represented by the general formula (Formula 1), wherein X ² represents —CH ₂ —, —C ₂ H ₄ —, or —OCH ₂ —CH ₂ O—, and R ¹ and R ² represent A compound in which each independently represents an alkyl group having 1 to 3 carbon atoms, m and n represent 1, and o represents 0.
2) A compound represented by the general formula (Formula 1), wherein X ¹ and X ² represent —OCH ₂ — or —CH ₂ O, m and n represent 0, and o represents 1.
3) A compound represented by the general formula (Formula 1), wherein X ² represents —SO ₂ —, and m, n and o represent 0.
4) A compound represented by the general formula (Formula 2), wherein X ² represents —OCH ₂ —, and m, n, and o represent 0.
Among these, the compound of 1) is more preferable.

  The content of the additive in the pressure-sensitive adhesive composition is preferably 5 to 40 parts by weight, more preferably 10 to 30 parts by weight with respect to 100 parts by weight of the thermally active pressure-sensitive adhesive described later. If the amount is less than 5 parts by weight, the effect may not be sufficiently exhibited. If the amount exceeds 40 parts by weight, the blending amount of the thermally active adhesive is relatively lowered, and sufficient adhesion to the adherend cannot be obtained. There is.

The thermoactive adhesive (delay tack type adhesive) is composed of a thermoplastic resin, a solid plasticizer, and a tackifier, and exhibits adhesiveness when heated.
Examples of the thermoplastic resin include methyl methacrylate (Tg = 105 ° C.), ethyl acrylate (Tg = −22 ° C.), butyl acrylate (Tg = −54 ° C.), 2-ethylhexyl acrylate (Tg = −85 ° C.), carboxy Vinyl aromatic compounds such as polycaprolactone acrylate (Tg = −41 ° C.), monohydroxyethyl acrylate succinate (Tg = −40 ° C.), styrene (Tg = 100 ° C.), vinyl chloride (Tg = 80 ° C.), vinylidene chloride Vinyl halides such as (Tg = −20 ° C.), vinyl acetates such as vinyl acetate (Tg = 30 ° C.), vinyl propionates (Tg = 10 ° C.), ethylene (Tg = −125 ° C.), butadiene (Tg = − 109 ° C) and other monomers such as acrylonitrile (Tg = 130 ° C) Examples thereof include copolymers used singly or in combination of two or more kinds, and two or more kinds of thermoplastic resins may be mixed and used.

As the solid plasticizer, a benzoic acid ester compound, a hindered phenol ester compound, or the like is preferably used.
Examples of the benzoic acid ester compounds include benzoic acid sucrose, benzoic acid diethylene glycol ester, benzoic acid glyceride, benzoic acid pentaerythritol ester, benzoic acid trimethylolethane ester, and benzoic acid trimethylolpropane ester. Among these, benzoic acid trimethylolpropane ester is particularly preferably used.

Examples of the hindered phenol ester compound include triethylene glycol bis [3- (3-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol bis [3- (3-t-butyl-4-hydroxy-). 5-methylphenyl) propionate], triethylene glycol bis [3- (3,5-di-tert-butyl-4-hydroxy-phenyl) propionate], 1,6-hexanediol bis [3- (3-t- Butyl-4-hydroxyphenyl) propionate], 1,6-hexanediol bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate], 1,6-hexanediol bis [3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiobis [eth 3- (3-t-butyl-4-hydroxyphenyl) propionate], thiobis [ethylene 3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate], thiobis [ethylene 3- (3 5-di-t-butyl-4-hydroxyphenyl) propionate]. Among these, triethylene glycol bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate], 1,6-hexanediol bis [3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionate] and thiobis [ethylene 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] are particularly preferably used.
These solid plasticizers can also be used as a mixture of two or more. In addition, the aqueous dispersion of the solid plasticizer is prevented from settling, and from the viewpoint of the surface properties (smoothness) of the coating layer, the dispersion particle size should be less than a certain value by a dispersing / pulverizing machine such as a ball mill or a handy mill. It is preferable to adjust.

  Examples of tackifiers include rosin, hydrogenated rosin and derivatives thereof, rosin resins such as resin acid dimers, terpene resins such as terpene resins, aromatic modified terpene resins, hydrogenated terpene resins, and terpene-phenol resins. , Aliphatic petroleum resins, aromatic petroleum resins, alicyclic petroleum resins, styrene resins, phenol resins, and the like. These resins are used alone or in combination of two or more.

The activation temperature of the thermally active pressure-sensitive adhesive used in the present invention is preferably 50 to 100 ° C. The activation temperature is the minimum temperature necessary for the thermally active adhesive to exhibit adhesiveness, and is a value obtained by measuring the minimum temperature at which adhesiveness has developed. When the activation temperature is less than 50 ° C., a problem of unintentional adhesion between the adhesive layer and the support or various recording layers provided on the support during storage, such as so-called blocking is likely to occur. On the other hand, when the temperature exceeds 100 ° C., problems such as discoloration and unintentional color development may occur in the support and various recording layers provided on the support.
For the measurement of the active temperature, a thermal inclination tester (for example, Toyo Seiki Seisakusho Co., Ltd., settable temperature range 50 to 250 ° C.) is used, and the adhesive coating surface is applied to a hot plate set at an arbitrary temperature for 5 seconds. After the contact, the lowest temperature at which expression of adhesiveness was confirmed by touching with a finger was defined as the activation temperature.

The thermoplastic resin, solid plasticizer, and tackifier can be appropriately selected and used so that the activation temperature of the thermally active adhesive used in the present invention is 50 to 100 ° C. Moreover, it is preferable that the weight ratio of the solid content of a thermoplastic resin, a solid plasticizer, and a tackifier is thermoplastic resin: solid plasticizer: tackifier = 15-45: 45-75: 5-25.
Specific examples of the thermally active adhesive used in the present invention include Heat Magic DW1040W (manufactured by Toyo Ink, active temperature: 50 ° C.), Eco Brid 5610 (manufactured by Daicel Finechem, active temperature: 70 ° C.), Eco Brid TM- 1 (manufactured by Daicel Finechem, active temperature: 100 ° C.), Eco Brid S-1 (manufactured by Daicel Fine Chem, active temperature: 90 ° C.), Eco Brid TM-100 (manufactured by Daicel Fine Chem, active temperature: 70 ° C.), Eco Brid 5635 (Daicel FineChem, active temperature: 70 ° C), Eco Brid 5640 (Daicel FineChem, active temperature: 70 ° C), Dick Seal DLA-820K (Dainippon Ink, active temperature: 80 ° C) , Dick seal ED-920K (Dainippon Ink Co., Ltd., activation temperature: 90 ° C.) It is.

  The pressure-sensitive adhesive composition used in the present invention may further contain a thickener, a surfactant, an antifoaming agent, a lubricant, a colorant, a pigment, and the like as long as the adhesiveness is not impaired.

A thermally activated adhesive label can be constructed by providing a thermally active adhesive layer made of this adhesive composition on one side of the support.
There is no restriction | limiting in particular in the support body used by this invention, What is necessary is just to select suitably by a use. Examples of such a support include paper, recycled paper, synthetic paper, film, plastic film, foamed plastic film, non-woven fabric, and a composite sheet obtained by combining these. Further, a paper support that is at least partially water-decomposable or water-soluble may be used depending on the purpose of use (for example, JP-A 2006-299498, JP-A 2007-237634, JP-A 2008-291409, etc.). . Since the heat-activatable pressure-sensitive adhesive label using such a water-decomposable or water-soluble paper support is dissolved or dispersed by being immersed in water, the labor of peeling or disposal is reduced.

When the coating amount of the pressure-sensitive adhesive composition on the support is small, the initial adhesion to the adherend is insufficient, and when it is too large, a smooth coated surface is difficult to obtain and the drying property is also lowered. Although depending on the paper quality of the support, the dry coating amount of the thermally active adhesive is preferably 5 to 50 g / m ² , more preferably 8 to 30 g / m ² , and particularly preferably 10 to 20 g / m ² . .
The heat-activatable pressure-sensitive adhesive label of the present invention is applied to an adherend by appropriately heating with a heater or the like so that the pressure-sensitive adhesive layer has an activation temperature or higher.

  This heat-activatable pressure-sensitive adhesive label may be used as it is, but various recording layers may be provided on the surface of the support opposite to the surface on which the heat-active pressure-sensitive adhesive layer is provided depending on the application and recording method. Examples of such applications include, but are not limited to, the following application examples.

Application to inkjet recording media:
When applied to an inkjet recording medium, an inkjet recording layer is provided on a support. The ink jet recording layer usually contains a pigment and a binder.
As the pigment, an inorganic pigment or an organic pigment is used. Examples of inorganic pigments include kaolin, silica such as synthetic amorphous silica, heavy calcium carbonate, light calcium carbonate, silica-calcium carbonate composite particles, talc, calcined kaolin obtained by calcining the kaolin, calcium sulfate, barium sulfate, Examples thereof include titanium dioxide, zinc oxide, alumina, magnesium carbonate, magnesium oxide, calcium silicate, bentonite, zeolite, sericite, and smectite, and one or more types can be appropriately selected and used.
Any binder may be used as long as it is a known binder used for inkjet recording media. Examples of binders include starches such as oxidized starch, etherified starch and esterified starch; latexes such as styrene / butadiene copolymer (SB) latex and acrylonitrile / butadiene copolymer (NB) latex, polyvinyl alcohol and Examples thereof include casein; gelatin; celluloses such as carboxymethyl cellulose and hydroxyethyl cellulose; polyurethanes; vinyl acetate; unsaturated polyester resins and the like. One or two or more types can be appropriately selected and used.
For the ink jet recording layer, sizing agent, fixing agent, pigment dispersant, thickener, water retention agent, lubricant, antifoaming agent, antifoaming agent, release agent, foaming agent, coloring dye, coloring as necessary Auxiliaries such as pigments, fluorescent dyes, preservatives, water-proofing agents, surfactants, and pH adjusters can be added as appropriate.

The mixing ratio of the pigment in the ink jet recording layer is 65 to 88 parts by weight, preferably 70 to 80 parts by weight with respect to 100 parts by weight of the entire ink jet recording layer (solid content).
The ratio of the binder is preferably 4 parts by weight or more and 35 parts by weight or less with respect to 100 parts by weight in total of all the pigments contained in the ink jet recording layer.
The coating amount of the inkjet recording layer is usually per side 1 to 40 g / ^{m 2,} preferably less than one side per 3 g / ^{m 2} or more 30 g / ^{m 2.}
The method for providing the ink jet recording layer on the support is not particularly limited, but is a blade coater, roll coater, air knife coater, bar coater, gate roll coater, curtain coater, gravure coater, flexographic gravure coater, spray coater. An off-machine coating machine or an on-machine coating machine equipped with various coaters such as a size press is appropriately selected and used.

Application to thermal recording media:
When applied to a thermal recording medium, a thermal recording layer is provided on the support, and optionally a protective layer on the thermal recording layer, an undercoat layer (underlayer) between the support and the thermal recording layer, and thermal recording. An intermediate layer or the like may be provided between the layer and the protective layer. The heat-activatable pressure-sensitive adhesive label produced in this way is called a heat-sensitive recording medium label.
The coating amount of the heat-sensitive recording layer is usually 2~12g / ^{m 2} approximately, the protective layer is usually 1 to 5 g / ^{m 2} approximately, the undercoat layer is generally from 1 to 20 g / ^{m 2} approximately.

The heat-sensitive recording layer essentially contains an electron-donating leuco dye (leuco dye) and an electron-accepting developer (developer), and optionally a sensitizer, binder, pigment, cross-linking agent, lubricant, image. Stabilizers and other auxiliaries may be included.
As the leuco dye, those known in the field of conventional thermal recording paper can be used. For example, triphenylmethane compounds, fluorane compounds, fluorene compounds, divinyl compounds and the like are preferably used. Specific examples of the leuco dye include crystal violet lactone, 3-diethylamino-7-chlorofluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-cyclohexylamino-6-chlorofluorane, 3- Diethylamino-7-dibenzylaminofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3-cyclohexylmethylamino-6-methyl- 7-anilinofluorane, 3-ethylisoamylamino-6-methyl-7-anilinofluorane, 3-diethylamino-7- (o-chloroanilino) fluorane, 3-dibutylamino-7- (o-chloroanilino) fluorane Etc.

  As the developer, those known in the field of conventional thermal recording paper can be used. For example, 4,4′-isopropylidenediphenol, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2 , 2-bis (4-hydroxyphenyl) -4-methylpentane, 4,4′-dihydroxydiphenyl sulfide, hydroquinone monobenzyl ether, benzyl 4-hydroxybenzoate, 4,4′-dihydroxydiphenyl sulfone, 2,4 ′ -Dihydroxydiphenylsulfone, 4-hydroxy-4'-isopropoxydiphenylsulfone, 4-hydroxy-4'-n-propoxydiphenylsulfone, 4-hydroxy-4'-allyloxydiphenylsulfone, bis (3-allyl-4- Hydroxyphenyl) sulfone, 4-hydroxy-4'-methyldi Phenylsulfone, 4-hydroxyphenyl-4'-benzyloxyphenylsulfone, 3,4-dihydroxyphenyl-4'-methylphenylsulfone, 3,4-dihydroxyphenyl-4'-methylphenylsulfone, 4,4'-bis (Np-trisulfonylurea) diphenylmethane, Np-tolylsulfonyl-N′-phenylurea, 2,2′-bis [4- (4-hydroxyphenylsulfonyl) phenoxy] diethyl ether, 1- [4- ( 4-hydroxyphenylsulfonyl) phenoxy] -4- [4- (4-isopropoxyphenylsulfonyl) phenoxy] butane, diphenylsulfone cross-linking compounds described in WO 97/16420, compounds described in WO 02/081229, and the like Can be mentioned.

  As the sensitizer, those known in the field of conventional thermal recording paper can be used. For example, fatty acid amides such as stearic acid amide and palmitic acid amide, ethylene bisamide, montanic acid wax, polyethylene wax, 1, 2-di (3-methylphenoxy) ethane, p-benzylbiphenyl, β-benzyloxynaphthalene, 4-biphenyl-p-tolyl ether, m-terphenyl, 1,2-diphenoxyethane, dibenzyl oxalate, oxalic acid Di (p-chlorobenzyl), oxalate di (p-methylbenzyl), dibenzyl terephthalate, benzyl p-benzyloxybenzoate, di-p-tolyl carbonate, phenyl-α-naphthyl carbonate, 1,4-diethoxy Naphthalene, 1-hydroxy-2-naphthoic acid phenyl ester, o -Xylene-bis- (phenyl ether), 4- (m-methylphenoxymethyl) biphenyl, 4,4'-ethylenedioxy-bis-benzoic acid dibenzyl ester, dibenzoyloxymethane, 1,2-di (3 -Methylphenoxy) ethylene, bis [2- (4-methoxy-phenoxy) ethyl] ether, methyl p-nitrobenzoate, phenyl p-toluenesulfonate, and the like.

As the binder, those known in the field of conventional thermal recording paper can be used, for example, water-soluble polymers such as starch, polyvinyl alcohol, methylcellulose, carboxymethylcellulose, styrene / butadiene copolymers, acrylic acid-based binders, and the like. Examples include synthetic resin emulsions such as copolymers.
Examples of the pigment include kaolin, calcined kaolin, calcium carbonate, aluminum oxide, titanium oxide, magnesium carbonate, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, silica, talc, and various organic pigments.

Examples of the crosslinking agent include glyoxal, methylol melamine, melamine formaldehyde resin, melamine urea resin, polyamine epichlorohydrin resin, polyamide epichlorohydrin resin, potassium persulfate, ammonium persulfate, sodium persulfate, ferric chloride, Examples include magnesium chloride, borax, boric acid, alum, and ammonium chloride.
Examples of the lubricant include fatty acid metal salts such as zinc stearate and calcium stearate, waxes, and silicone resins.
In addition, image stabilizers such as 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane, benzophenone and triazole UV absorbers, dispersants, antifoaming agents, oxidation Inhibitors, fluorescent dyes and the like can be used.

The type and amount of leuco dye, developer, and other various components used in the heat-sensitive recording layer are determined according to the required performance and recording suitability, and are not particularly limited. On the other hand, about 0.5 to 10 parts by weight of the developer and 0.5 to 20 parts by weight of the pigment are used, and the binder is suitably about 5 to 25% by weight in the solid content of the heat-sensitive recording layer.
In the heat-sensitive recording material of the present invention, the leuco dye, the developer, and the material to be added as necessary are until the particle diameter is several microns or less by a pulverizer such as a ball mill, an attritor, a sand glider, or an appropriate emulsifier. Atomized, and various additive materials are added according to the binder and purpose to obtain a coating solution. As a solvent used for this coating liquid, water, alcohol, etc. can be used, The solid content is about 20 to 40 weight%. The coating means is not particularly limited, and can be applied according to well-known conventional techniques. For example, various coaters such as an air knife coater, rod blade coater, vent blade coater, bevel blade coater, roll coater, curtain coater, etc. An off-machine coating machine or an on-machine coating machine provided with is appropriately selected and used.

Application to pressure-sensitive recording media:
When applied to a pressure-sensitive recording medium, a color former composition mainly comprising a capsule containing an oily substance in which an electron-donating leuco dye (leuco dye) is dissolved is usually applied to one side of a base paper. Apply a developer composition mainly composed of an electron-accepting developer (developer) to be colored when contacting the color developer on one side of the upper paper and the base paper (pressure-sensitive recording layer) ), The middle sheet coated with the color former composition on the other side, the developer composition coated on one side of the base paper (pressure-sensitive recording layer), and the adhesive layer of the present invention provided on the other side Prepare paper. These are used in the order of upper paper-middle paper-lower paper or upper paper-lower paper, and the color developer reacts with the developer by destroying the capsule in the upper paper by the pressure of the writing pressure or printer. To develop color.
The capsule is a micro container mainly having a core material such as liquid or solid covered with a film material such as gelatin, polyurea urethane resin, urea-formaldehyde resin, and has a size of about 1 to 200 μm. As a capsule manufacturing method, a coacervation method, an interfacial polymerization method, an in-situ method, or the like is used.

Application to thermal transfer recording media:
When applied to a thermal transfer recording medium, a thermal transfer recording layer mainly composed of a pigment and a binder is provided on a support. A film (ink ribbon) coated with a heat-meltable ink layer containing a color material is heated by heat generated by a thermal head, etc., and the color material is melted, evaporated and sublimated and transferred to a thermal transfer recording layer to obtain a recorded image. be able to.
For the thermal transfer recording layer, in addition to pigments and binders, if necessary, dispersants, thickeners, release agents, surfactants, viscosity modifiers, flocculants, leveling agents for the purpose of improving coating suitability, A water-proofing agent or the like may contain a lubricant, an antistatic agent or the like for the purpose of improving the recording characteristics and improving the transportability of the recording medium.

Application to electrophotographic recording media:
When applied to an electrophotographic recording medium, an electrophotographic recording layer mainly composed of a pigment and a binder is provided on a support. It is possible to obtain a recorded image by exposing the photoreceptor to change the charge on the surface of the photoreceptor, adsorbing the toner colored body according to the charge (residual charge), and transferring and fusing to the electrophotographic recording layer. .
The electrophotographic recording layer may contain a release agent or the like in addition to the pigment and the binder as necessary. The coating amount of the electrophotographic recording layer is appropriately selected depending on the application, but is usually about ² to 40 g / m ² .

  Hereinafter, although the heat-sensitive recording material of the present invention is illustrated by examples and comparative examples, it is not intended to limit the present invention. In the description, “part” means “part by weight” and “%” means “% by weight” unless otherwise specified.

[Example 1]
A mixture having the following composition was mixed and stirred to prepare an adhesive coating solution.
Adhesive coating solution Thermally active adhesive (manufactured by Daicel Finechem Co., Ltd .: Eco Brid S-1, thermoplastic resin:
Solid plasticizer: tackifier = 20: 70: 20, active temperature: 90 ° C., hereinafter referred to as “thermally active adhesive 1”. 100.0 parts 1,2-di (3-methylphenoxy) ethane (manufactured by Sanko Co., Ltd .: KS232, melting point 98 ° C.)
10.0 parts Thickener (manufactured by San Nopco: SN thickener 929S) 0.2 parts Dry coating amount of adhesive coating solution on Mayer bar on one side of fine paper (basic weight 47g / m ² base paper) Coating and drying (blow dryer at 50 ° C., 5 minutes) were performed so as to be 13.0 g / m ² to prepare a thermally activated adhesive label.

[Example 2]
A thermally active adhesive label was prepared in the same manner as in Example 1 except that the amount of 1,2-di (3-methylphenoxy) ethane (manufactured by Sanko Co., Ltd .: KS232) in the adhesive coating solution was 20.0 parts. Produced.
[Example 3]
A thermally activated pressure-sensitive adhesive label was produced in the same manner as in Example 2 except that the dry coating amount of the pressure-sensitive adhesive coating solution was 20.0 g / m ² .
[Example 4]
A thermally activated pressure-sensitive adhesive label was produced in the same manner as in Example 2, except that the dry coating amount of the pressure-sensitive adhesive coating solution was 30.0 g / m ² .

[Example 5]
A thermoactive adhesive label was produced in the same manner as in Example 1 except that the amount of 1,2-di (3-methylphenoxy) ethane (manufactured by Sanko Co., Ltd .: KS232) as the adhesive coating solution was 35.0 parts. did.
[Example 6]
A thermoactive adhesive label was produced in the same manner as in Example 1 except that the amount of 1,2-di (3-methylphenoxy) ethane (manufactured by Sanko Co., Ltd .: KS232) as the adhesive coating solution was changed to 45.0 parts. did.
[Example 7]
Example 1 except that diphenylsulfone (UCB, DPS, melting point 126 ° C.) was used instead of 1,2-di (3-methylphenoxy) ethane (manufactured by Sanko: KS232) in the adhesive coating solution. In the same manner as described above, a thermoactive adhesive label was produced.
[Example 8]
A thermoactive adhesive label was produced in the same manner as in Example 7 except that the amount of diphenylsulfone (UCB: DPS) in the adhesive coating solution was 20.0 parts.

［実施例１０］
粘着剤塗工液中の２−ベンジルオキシナフタレン（上野製薬社製：ＢＯＮ）の配合量を２０．０部とした以外は実施例９と同様にして熱活性粘着ラベルを作製した。 [Example 9]
Instead of 1,2-di (3-methylphenoxy) ethane (manufactured by Sanko Co., Ltd .: KS232) in the adhesive coating solution, 2-benzyloxynaphthalene (manufactured by Ueno Pharmaceutical Co., Ltd .: BON, melting point 101 ° C., represented by the following formula: Was used in the same manner as in Example 1 except that was used.

[Example 10]
A thermally active adhesive label was produced in the same manner as in Example 9 except that the amount of 2-benzyloxynaphthalene (manufactured by Ueno Pharmaceutical Co., Ltd .: BON) in the adhesive coating solution was changed to 20.0 parts.

[Example 11]
1,2-bis (phenoxymethyl) benzene (manufactured by Nikka Chemical Co., Ltd .: PMB2, melting point 92) instead of 1,2-di (3-methylphenoxy) ethane (manufactured by Sanko Co., Ltd .: KS232) in the adhesive coating solution A thermoactive pressure-sensitive adhesive label was produced in the same manner as in Example 1 except that (° C., represented by the following formula) was used.

[Example 12]
A thermally active adhesive label was prepared in the same manner as in Example 11 except that the amount of 1,2-bis (phenoxymethyl) benzene (manufactured by Nikka Chemical Co., Ltd .: PMB2) in the adhesive coating solution was 20.0 parts. Produced.
[Example 13]
Instead of the thermally active adhesive (Eco Brid S-1) in the adhesive coating liquid, a thermoactive adhesive (Daicel Finechem Co., Ltd .: Eco Brid 5610, activation temperature: 70 ° C., hereinafter referred to as “thermally active adhesive 2”) .) Was used in the same manner as in Example 2 except that a thermoactive adhesive label was produced.
[Example 14]
1,2-bis (phenoxymethyl) benzene (manufactured by Nikka Chemical Co., Ltd .: PMB2) is used instead of 1,2-di (3-methylphenoxy) ethane (manufactured by Sanko Co., Ltd .: KS232) in the adhesive coating solution A thermally activated adhesive label was produced in the same manner as in Example 13 except that.

[Example 15]
Instead of the thermally active adhesive (Eco Brid S-1) in the adhesive coating solution, a thermally active adhesive (manufactured by Toyo Ink Manufacturing Co., Ltd .: Heat Magic DW1040W, activation temperature: 50 ° C., hereinafter “thermally active adhesive 3” A heat-activatable pressure-sensitive adhesive label was produced in the same manner as in Example 2 except that the above was used.
[Example 16]
1,2-bis (phenoxymethyl) benzene (manufactured by Nikka Chemical Co., Ltd .: PMB2) is used instead of 1,2-di (3-methylphenoxy) ethane (manufactured by Sanko Co., Ltd .: KS232) in the adhesive coating solution A thermally activated adhesive label was produced in the same manner as in Example 15 except that.
[Example 17]
Instead of the thermally active adhesive (Eco Brid S-1) in the adhesive coating solution, a thermally active adhesive (Dick Graphics, Inc .: Dick Seal DLA820K, activation temperature: 80 ° C., hereinafter “thermally active adhesive 4” A heat-activatable pressure-sensitive adhesive label was produced in the same manner as in Example 2 except that the above was used.
[Example 18]
1,2-bis (phenoxymethyl) benzene (manufactured by Nikka Chemical Co., Ltd .: PMB2) is used instead of 1,2-di (3-methylphenoxy) ethane (manufactured by Sanko Co., Ltd .: KS232) in the adhesive coating solution A thermally activated adhesive label was produced in the same manner as in Example 17 except that.

［比較例３］
粘着剤塗工液中のシュウ酸ジ−ｐ−クロルベンジルエステル（大日本インキ社製：ＨＳ３５１９）の配合量を２０．０部とした以外は比較例２と同様にして熱活性粘着ラベルを作製した。 [Comparative Example 1]
A thermoactive adhesive label was produced in the same manner as in Example 1 except that 1,2-di (3-methylphenoxy) ethane (manufactured by Sanko Co., Ltd .: KS232) was not blended in the adhesive coating solution.
[Comparative Example 2]
Instead of 1,2-di (3-methylphenoxy) ethane (manufactured by Sanko Co., Ltd .: KS232) in the adhesive coating liquid, oxalic acid di-p-chlorobenzyl ester (manufactured by Dainippon Ink Co., Ltd .: HS3519, melting point 80 ° C. A heat-activatable pressure-sensitive adhesive label was produced in the same manner as in Example 1 except that the following formula was used.

[Comparative Example 3]
A thermoactive adhesive label was produced in the same manner as in Comparative Example 2 except that the amount of di-p-chlorobenzyl oxalate ester (Dainippon Ink Co., Ltd .: HS3519) in the adhesive coating solution was changed to 20.0 parts. did.

[Comparative Example 4]
Instead of 1,2-di (3-methylphenoxy) ethane (manufactured by Sanko Co., Ltd .: KS232) in the pressure-sensitive adhesive coating solution, benzyl parabenzyloxybenzoate (manufactured by API Corporation: BZB, melting point 117-119 ° C., A thermally activated adhesive label was produced in the same manner as in Example 1 except that (represented by the following formula) was used.

[Comparative Example 5]
Stearic acid amide (CH ₃ (CH ₂ ) ₁₆ CONHCH ₂ OH, manufactured by Chukyo Yushi Co., Ltd.): Hydrin instead of 1,2-di (3-methylphenoxy) ethane (manufactured by Sanko Co., Ltd .: KS232) in the adhesive coating solution A thermoactive adhesive label was produced in the same manner as in Example 1 except that D-757, melting point 109 to 113 ° C) was used.
[Comparative Example 6]
A thermoactive adhesive label was produced in the same manner as in Example 13 except that 1,2-di (3-methylphenoxy) ethane (manufactured by Sanko Co., Ltd .: KS232) was not blended in the adhesive coating solution.
[Comparative Example 7]
A thermoactive adhesive label was produced in the same manner as in Example 15 except that 1,2-di (3-methylphenoxy) ethane (manufactured by Sanko Co., Ltd .: KS232) was not blended in the adhesive coating solution.
[Comparative Example 8]
A thermally activated adhesive label was produced in the same manner as in Example 17 except that 1,2-di (3-methylphenoxy) ethane (manufactured by Sanko Co., Ltd .: KS232) was not blended in the adhesive coating solution.

The following evaluation was performed about the heat activated adhesive label obtained above.
<Adhesiveness>
Using a thermal printer (manufactured by Zebra: 140XiIII, brightness +20, printing speed 51 mm / second), heat energy was applied to the pressure-sensitive adhesive surface of the produced thermally activated pressure-sensitive adhesive label, and after 10 seconds, polyolefin wrap ( It was bonded to Nippon Paper Pack Co., Ltd. (one wrap).
A peel test was conducted immediately after bonding and after treatment for 7 days in an environment of 23 ° C. and 50% RH, and the adhesion durability was evaluated according to the following criteria. If the evaluation is Δ or more, there is no practical problem.
○: Adhered △: Adhered, but can be peeled off with slight force ×: Not adhered

<Blocking resistance>
The prepared heat-activatable pressure-sensitive adhesive label was wound around a 3-inch paper tube so that the surface of the pressure-sensitive adhesive was in contact with the surface of the paper tube, and treated in an environment of 50 ° C. or 50 ° C. and 90% RH for 24 hours. The blocking resistance was evaluated according to the following criteria. If the evaluation is Δ or more, there is no practical problem.
A: When the heat-activatable adhesive label is peeled off from the paper tube, it peels off without feeling of resistance.
○: When the thermally activated adhesive label is peeled off from the paper tube, there is a slight resistance, but no fluffing occurs on the surface of the paper tube.
Δ: There is a resistance when the thermally activated adhesive label is peeled off from the paper tube, and fluffing occurs on the surface of the paper tube, but the surface of the paper tube is not peeled off or the thermally activated adhesive label is not broken.
×: There is a sense of resistance when the thermally activated adhesive label is peeled off the paper tube, and if it is forcibly removed, the surface of the paper tube is peeled off or the thermally activated adhesive label is broken.

The results are shown in the table below.

The heat-activatable pressure-sensitive adhesive label containing the additive of the present invention in the heat-activatable pressure-sensitive adhesive layer has high adhesiveness (adhesion persistence) over time (after 7 days), while no problem occurs in blocking (Example 1). To 18). In particular, when 1,2-di (3-methylphenoxy) ethane (KS232) is used as an additive, the balance between adhesion persistence and blocking resistance is balanced (Examples 1-6, 13, 15). 17).
On the other hand, when the additive of the present invention is not used or when a compound that is not the additive of the present invention is added, the adhesive strength (adhesion persistence) (Comparative Examples 1-3, 5-8) or resistance Any of blocking properties (Comparative Examples 4, 6, and 7) is inferior.

[Example 19]
(Example in which an inkjet recording layer is provided)
A composition having the following composition was stirred and dispersed to prepare an ink jet recording layer coating solution.
Inkjet recording layer coating liquid Synthetic amorphous silica (manufactured by Tokuyama: X-60) 100.0 parts Completely saponified polyvinyl alcohol aqueous solution (manufactured by Kuraray: PVA117,
200.0 parts styrene / butadiene copolymer latex (manufactured by Nippon Zeon Co., Ltd .: LX438C)
Solid content 45%) 10.0 parts Styrene acrylic sizing agent (Arakawa Chemical Industries, Ltd .: Polymeron 360,
6.0% polyamine dye fixing agent (manufactured by Starlight PMC: DK6872)
(Solid content 50%) 5.0 parts water 320.0 parts

On one side of high-quality paper (basis paper with a basis weight of 47 g / m ² ), this ink jet recording layer coating liquid is applied and dried with a Meyer bar so that the dry coating amount is 15.0 g / m ² (blow drying) Machine, 60 ° C., 2 minutes). This sheet was processed with a calendar so as to have a smoothness of 20 seconds to obtain an ink jet recording material.
The amount of 1,2-di (3-methylphenoxy) ethane (manufactured by Sanko Co., Ltd .: KS232) in the pressure-sensitive adhesive coating solution is 20.0 on the surface opposite to the ink jet recording layer of the obtained ink jet recording material. The pressure-sensitive adhesive coating solution was applied and dried with a Meyer bar so that the dry coating amount was 13.0 g / m ² (fan dryer at 50 ° C., 5 minutes) to prepare a thermally activated pressure-sensitive adhesive label. .
[Comparative Example 9]
A thermally active adhesive label was produced in the same manner as in Example 19 except that 1,2-di (3-methylphenoxy) ethane was not blended in the adhesive coating solution.

The following evaluation was performed about the obtained heat activation adhesive label.
<Inkjet printing density>
Black (BK), cyan (C), magenta (M), and yellow (Y) solid images with dye ink using an inkjet printer (PM-970C, manufactured by Seiko Epson) on the inkjet recording surface of the thermally activated adhesive label. Is printed. The recording paper after printing was left in a constant temperature and humidity room for one day, and then the printing density of each color was measured using a Macbeth densitometer (Macbeth RD915), and the average value was taken as the average density.
<Anti-fading property>
A solid image of magenta (M) was printed on the ink jet recording surface of the thermally activated adhesive label with a dye ink using an ink jet printer (PM-970C, manufactured by Seiko Epson Corporation). Two printed heat-active adhesive labels are overlapped and sandwiched between quartz glass plates so that the adhesive surface and the inkjet recording surface are in contact with each other, and processed in an environment of 50 ° C or 50 ° C and 90% RH for 24 hours. After that, the recording density of the printed portion of each color was measured using a Macbeth densitometer (Macbeth RD915), the residual ratio was calculated from the values before and after the treatment, and the anti-fading property was evaluated.
Residual rate (%) = (recording density after processing / recording density before processing) × 100
◎: 95% or more ○: 85 to less than 95% △: less than 75 to 85% ×: less than 75%

The results are shown in the table below.

Claims (10)

Thermally active adhesive and the following general formula on one side of the support

Or the following general formula

(Wherein, X ¹ and X ² are each independently —CH ₂ —, —C ₂ H ₄ —, —OCH ₂ —CH ₂ O—, —OCH ₂ —, —CH ₂ O— or —SO _2- represents, R ¹ and R ² each independently represent a halogen atom, an alkyl group, an alkenyl group or an alkoxy group, m and n each independently represent an integer of 0 to 3, o Represents 0 or 1.) A heat-active pressure-sensitive adhesive label provided with a heat-active pressure-sensitive adhesive layer comprising a pressure-sensitive adhesive composition for a heat-active pressure-sensitive adhesive label (excluding a heat-sensitive recording medium label). The heat activation adhesive label according to claim 1, wherein the activation temperature of the heat activation adhesive is 50 to 100 ° C. The thermoactive adhesive comprises a thermoplastic resin, a solid plasticizer, and a tackifier, and is thermoplastic resin: solid plasticizer: tackifier (weight ratio) = 15-45: 45-75: 5-25 Item 3. The thermally activated adhesive label according to item 1 or 2 . The compound is represented by the general formula (Formula 1), X ² represents —CH ₂ —, —C ₂ H ₄ —, or —OCH ₂ —CH ₂ O—, and R ¹ and R ² each independently represent: The thermally active adhesive label as described in any one of Claims 1-3 in which a C1-C3 alkyl group is represented, m and n represent 1, and o represents 0. The compound is represented by the general formula (Formula 1), X ¹ and X ² each independently represent —OCH ₂ — or —CH ₂ O, m and n represent 0, and o represents 1. The heat-activatable adhesive label as described in any one of Claims 1-3. The thermally activated adhesive label according to claim 1, wherein the compound is represented by the general formula (Formula 1), X ² represents —SO ₂ —, and m, n, and o represent 0. The thermally activated adhesive label according to claim 1, wherein the compound is represented by a general formula (Formula 2), X ² represents —OCH ₂ —, and m, n, and o represent 0. The content of the compound of the thermal active adhesive label adhesive composition is thermally active adhesive label according to any one of claims 1 to 7 5 to 40 parts by weight relative to the adhesive 100 weight parts . The thermally activated adhesive label according to any one of claims 1 to 8 , wherein at least one recording layer is provided on a surface of the support opposite to the surface on which the thermally active adhesive layer is provided. The recording layer, an ink jet recording layer, pressure-sensitive recording layer, thermally active adhesive label according to claim 9, which is a thermal transfer ink-receiving layer or an electrophotographic recording layer.