JPH10268779A - Tacky adhesive sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a tacky adhesive sheet which is securely adherable by heating after determination of a sticking position and is not easily peelable by adopting the constitution obtd. by successively laminating release paper, a thermosensitive type tacky adhesive layer which develops secure adhesiveness when heated, a base and a coding layer for printing. SOLUTION: This sheet is formed of the structure obtd. by successively laminating the release paper, the thermosensitive type tacky adhesive layer which has weak tacky adhesiveness in a normal state and develops the secure adhesiveness when heated to a specified temp. or above, the base and the coding layer for printing. The resulted sheet is the thermosensitive type tacky adhesive sheet which is printable, is temporally fixable and restickable and is securely adherable by heating. The examples of the solid plasticizer constituting the thermosensitive type tacky adhesive layer include various kinds of ester-based compds., such as diphenyl phthalate, dihexyl phthalate, dicyclohexyl phthalate, dihydroabiethyl phthalate and monoglyceride stearate, having the m.p. within a range of about 40 to 130 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a releasably attachable to an adherend until a sticking position is determined.
The present invention relates to a heat-sensitive adhesive sheet capable of firmly bonding by heating after the position of application is determined.

[0002]

2. Description of the Related Art Conventionally, an adhesive sheet having a structure in which a single-color or multicolor printing layer is laminated on one side of a support and an adhesive layer and a release paper are laminated on the other side, and the release paper is peeled off at the time of laminating, and is simply adhered only by pressure. Widely used because they can be combined. However, when the adhesive sheet is inadvertently pasted on the adherend, if the adhesive sheet is peeled off to reapply, the adhesive sheet may curl or wrinkle. There was a problem of tearing. Recently, a removable adhesive has been developed,
Since the re-peelable pressure-sensitive adhesive has a low basic adhesive performance, there is a dilemma that when it is bonded to an adherend, it can be re-adhered but easily peeled off.

A heat-sensitive adhesive which does not exhibit tackiness at room temperature, exhibits tackiness when heated, and maintains tackiness even after tackiness has been developed has been known. The heat-sensitive adhesive has a solid plasticizer and a thermoplastic resin as essential components,
These materials are mixed with a tackifier and the like, and the mixture is applied to the surface opposite to the printing surface on the support to obtain a heat-sensitive adhesive sheet. The pressure-sensitive adhesive layer surface of the heat-sensitive pressure-sensitive adhesive sheet does not show any tackiness at room temperature, but develops tackiness by heating, and maintains the tackiness for a while even after removing the heat source. First, it is considered that the solid plasticizer is melted and the thermoplastic resin and the tackifier are dissolved to develop the tackiness. However, since the heat-sensitive adhesive sheet does not show any adhesiveness at room temperature, it is impossible to temporarily fix the heat-sensitive adhesive sheet to an adherend.

[0004] Adhesives activated by heating include:
In addition, heat-sealable adhesives and hot-melt adhesives are also known, but these are activated only at high temperatures and lose their adhesive strength when cooled to room temperature, so it is impossible to temporarily fix them to the adherend. It is possible.

On the other hand, as an image forming method capable of obtaining a record comparable to multicolor printing by a plate making method,
Multicolor ink jet recording systems are currently receiving attention.
The ink jet recording system records fine images and characters by flying small droplets of ink by various operating principles and attaching them to a recording sheet such as paper. It is easy to use, has great flexibility in recording patterns, and does not require development-fixing, and is rapidly spreading in various applications as a recording device for various figures including Chinese characters and color images. In addition, in applications requiring a small number of copies, it is being widely applied to the field of full-color image recording because of its low cost.

As recording sheets used in the ink jet recording system, efforts have been made in terms of apparatuses and ink compositions in order to use high-quality paper and coated paper used for ordinary printing and writing. However, with the improvement of the performance of ink jet recording apparatuses such as high-speed, high-definition and full-color apparatuses, and expansion of applications, more advanced characteristics are also required for recording sheets. That is, as the recording sheet, the density of the print dots is high, the color tone is bright and vivid, the ink does not flow out or bleeds even when the print dots overlap quickly, and the print dots are printed in the horizontal direction. Is required to have high image reproducibility such that the diffusion of the image is not unnecessarily large and the periphery is smooth and not blurred. That is, in order to obtain a good image, general high-quality paper or coated paper for printing is insufficient, and a recording paper having a dedicated ink receiving layer of an ink jet recording system is indispensable.

A so-called adhesive layer made of an acrylic resin or the like is provided on the back surface of the ink jet recording sheet, and an adhesive ink jet recording sheet having a release paper attached thereto has also been developed. Can be attached to the body. However, since the so-called adhesive layer has a tack, it is very difficult to handle after peeling off the release paper, and it is going to peel off the adhesive inkjet recording sheet to reapply when it is accidentally pasted on the adherend Then, there is a problem that the adhesive ink jet recording sheet is curled or wrinkled, and in the worst case, the sheet is broken.

[0008]

The problem to be solved by the present invention is that temporary fixing and re-attachment can be performed as many times as necessary until the position to be attached to the adherend is determined. An object of the present invention is to obtain a pressure-sensitive adhesive sheet which can be strongly adhered by heating and cannot be easily peeled off.

[0009]

The present inventor has conducted various studies on the pressure-sensitive adhesive sheet and found that the pressure-sensitive adhesive layer, which is a component of the pressure-sensitive adhesive sheet, was formed as a heat-sensitive pressure-sensitive adhesive layer. In the normal state, the adhesiveness is weak to the adherend, so it can be temporarily fixed and re-attached as many times as possible, and after the sticking position is determined, strong adhesion can be obtained by heating the adhesive sheet. I found something.

That is, the present invention relates to a release paper, a heat-sensitive adhesive layer which has a weak tackiness in a normal state and exhibits strong adhesiveness when heated to a certain temperature or more, a support,
This is a heat-sensitive adhesive sheet that can be printed having a structure in which printing coating layers are sequentially laminated, can be temporarily fixed and re-attached, and can be firmly bonded by heating.

Further, a release paper, a heat-sensitive adhesive layer, which has a weak tackiness in a normal state and exhibits strong adhesiveness when heated to a certain temperature or higher, a support, and an ink receiving layer are sequentially laminated. This is a heat-sensitive adhesive ink-jet recording sheet capable of performing inkjet recording having a structure, capable of being temporarily fixed and re-attached, and capable of firmly bonding by heating.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the heat-sensitive adhesive sheet and the heat-sensitive adhesive ink-jet recording sheet of the present invention will be described in detail. The heat-sensitive adhesive sheet according to the first aspect of the present invention is a release paper, a heat-sensitive adhesive layer (hereinafter referred to as a heat-sensitive adhesive layer) which has weak tackiness in a normal state and exhibits strong adhesiveness when heated to a certain temperature or more. , Simply referred to as a heat-sensitive adhesive layer), a support, and a printing coating layer.

The heat-sensitive adhesive layer according to the present invention comprises at least a solid plasticizer and a thermoplastic resin. Examples of the solid plasticizer constituting the heat-sensitive adhesive layer include diphenyl phthalate, dihexyl phthalate, dicyclohexyl phthalate, dihydroabiethyl phthalate, dimethyl isophthalate, sucrose benzoate, ethylene glycol dibenzoate, and tribenzoic acid. Catechol dipalmitate, catechol distearate, catechol diester, etc. Various ester compounds having a melting point in the range of about 40 to 130 ° C, such as benzoate, stearyl stearate, behenyl monoglyceride, and stearic monoglyceride, may be used. These are used alone or in combination of two or more.

These solid plasticizers and compounds are atomized by a wet or dry pulverizer such as a ball mill, a sand mill, a paint shaker, a dyno mill, an attritor, a Henchel mixer and used as an aqueous dispersion. It is also possible to use microencapsulated by the method. Particle size of solid plasticizer is 10μm
Or less, more preferably 5 μm or less,
From a practical point of view, it is 1-2 μm.

In addition, liquid plasticizers such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, and dibutyl maleate can be microencapsulated by a conventionally known method and apparently used as a solid plasticizer according to the present invention as a solid plasticizer. It is also possible to use them together. Also in this case, the preferred particle size is 1 to 10 μm.

The thermoplastic resin constituting the heat-sensitive adhesive layer is preferably a resin having a low glass transition temperature such that it has tackiness even at room temperature, and has a glass transition temperature (Tg) of -20 ° C or less, more preferably- A thermoplastic resin emulsion having a temperature of 40 ° C. or lower is used. For example, (meth) acrylate copolymer, styrene-isoprene copolymer, styrene-acrylate copolymer, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, ethylene-vinyl acetate copolymer, Vinyl acetate-acrylic acid ester copolymer, ethylene-vinyl chloride copolymer, ethylene-acrylic acid ester copolymer, ethylene-acrylic acid copolymer, ethylene-vinyl chloride copolymer, vinyl acetate-ethylene-acrylic acid Resins such as copolymers, vinyl acetate-ethylene-acrylate copolymers, vinyl acetate-ethylene-styrene copolymers, vinyl acetate-ethylene-vinyl chloride copolymers, polybutadienes, and polyurethanes are exemplified. These are used alone or in combination of two or more.

The heat-sensitive adhesive layer of the present invention must be capable of being temporarily fixed and reattached to an adherend any number of times in a normal state. More specifically, the 180 ° adhesive strength to a stainless steel plate according to JIS Z0237 is 10 gf / 25 mm or more and 200 gf / 25 m before heating and fixing.
m, more preferably 20 gf / 25 mm or more and 100
gf / 25 mm or less. In addition, after the sticking position is determined, strong adhesiveness is developed by heating, and it is necessary to increase the adhesive strength before it can be easily peeled off. More specifically, the 180 ° adhesive strength to a stainless steel plate according to JIS Z0237 is 300 gf after heat fixing.
/ 25 mm or more, more preferably 500 gf / 25 mm or more. Such adjustment of the adhesive force can be achieved by changing the mixing ratio of the solid plasticizer in the heat-sensitive adhesive layer.

The mixing ratio of the solid plasticizer in the present invention is as follows:
The content is preferably in the range of 5 to 30% by weight based on the total solid content of the heat-sensitive adhesive composition. More preferably, 1
0 to 20% by weight. If the ratio of the solid plasticizer is less than this range, the adhesive strength before heat fixing is too strong, so that it is difficult to re-attach after temporary fixing to the adherend, or the increase in adhesive strength due to heating is small and the adhesive can be fixed. Or not. On the other hand, if it exceeds this range, the adhesive force before heating is lost, so that temporary fixing for positioning cannot be performed.

A tackifier may be added to the heat-sensitive adhesive layer according to the present invention in order to improve the adhesive strength. Specific examples of the tackifier used in the present invention include terpene resin, aliphatic petroleum resin, aromatic petroleum resin, coumarone indene resin, styrene resin, phenol resin,
Terpene phenol resin, rosin derivative resin and the like are used.

These tackifiers include thermoplastic resin 100
200 parts by weight or less, preferably 50 to 150 parts by weight. If the mixing ratio is less than this range, the effect of the addition is small, and if the mixing ratio is beyond this range, the adhesive strength tends to decrease.

A filler or the like can be added to the heat-sensitive adhesive layer according to the present invention as long as the object of the present invention is not impaired. For example, carbonates and oxides of aluminum, zinc, magnesium, barium, titanium and the like can be used. , Hydroxides, sulfates, etc., and inorganic pigments including viscosities such as natural silica, clay, zeolite, kaolin, calcined kaolin, starch, styrene resin, melamine resin, acrylic resin, paraffin, natural wax, synthetic wax, etc. Can be used.

The heat-sensitive adhesive layer according to the present invention contains an aqueous polymer binder, for example, an aqueous polymer binder, for the purpose of increasing the cohesive force in the heat-sensitive adhesive layer or the support or the heat-sensitive adhesive layer. Polyvinyl alcohol, polyvinyl acetate, oxidized starch, etherified starch, cellulose derivatives such as carboxymethylcellulose, hydroxyethylcellulose, casein, gelatin, sodium alginate and the like can be added. The mixing ratio of the aqueous polymer binder is added within a range that does not impair the original adhesive strength of the heat-sensitive adhesive sheet, and specifically, 30% by weight or less based on the total solid content of the heat-sensitive adhesive layer. Preferably, it is used in a range of 10% by weight or less.

In addition to the above components, the heat-sensitive adhesive layer according to the present invention may contain various additives such as a hardener, a preservative, a dye, an ultraviolet absorber, an antioxidant, a pH adjuster, and a defoamer. Additives can be added.

The coating amount of the heat-sensitive adhesive layer depends on the composition of the heat-sensitive adhesive layer and the material of the adherend to be bonded, but is usually 1 to 50 g / m ² in dry coating amount. Preferably 5
It is applied in a range of 35 g / m ² . If the coating amount of the heat-sensitive adhesive layer is less than 1 g / m ² , a sufficient adhesive force cannot be obtained when the adhesive layer is temporarily fixed to an adherend or bonded by heating. On the other hand, if it exceeds 50 g / m ² , the adhesive function is saturated, which is not economically preferable.

As a coating method for providing a heat-sensitive adhesive layer,
Blade coating method, gravure coating method, gravure offset coating method, bar coating method, roll coating method, knife coating method, air knife coating method, comma coating method, U comma coating method, AK
Known coating methods such as KU coating method, smoothing coating method, microgravure coating method, reverse roll coating method, 4 or 5 roll coating method, dip coating method, drop curtain coating method, slide coating method, die coating method, etc. Is available. Alternatively, printing is performed on a support using various printing methods such as flexo, letterpress, gravure, and offset.

The drying conditions for coating or printing the heat-sensitive adhesive layer on a support must be such that the solid plasticizer used does not melt. As a drying method, a drying method using a heat source by infrared rays, microwaves, or high frequency can be used in addition to hot air drying.

The base paper preferably used for the support according to the present invention is composed mainly of wood pulp and filler. As wood pulp, chemical pulp such as LBKP, NBKP, GP, PGW, RMP, TMP, CTMP,
CMP, mechanical pulp such as CGP, pulp such as waste paper pulp such as DIP, if necessary conventionally known pigments and binders and sizing agents and fixing agents, retention improver,
By mixing one or more kinds of additives such as a cationizing agent and a paper-strengthening agent, the support can be manufactured by various apparatuses such as a fourdrinier paper machine, a circular net paper machine, and a twin wire paper machine. It can be made acidic, neutral or alkaline. Further, the base paper may be subjected to on-machine processing of a calender device including a metal roll and a synthetic resin roll. At this time, off-machine processing may be performed, and after processing, flatness may be controlled by further performing calendar processing using a machine calendar, a super calendar, or the like.

Examples of the filler contained in the base paper include light calcium carbonate, heavy calcium carbonate, kaolin, clay, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, satin white, aluminum silicate, and diatomaceous earth. Earth, calcium silicate, magnesium silicate, synthetic silica, aluminum hydroxide, alumina,
White inorganic pigments such as lithopone, zeolite, magnesium carbonate and magnesium hydroxide, styrene-based plastic pigments, acrylic-based plastic pigments, polyethylene, microcapsules, and organic pigments such as urea resin and melamine resin.

Examples of the sizing agent contained in the base paper include a rosin sizing agent for acidic papermaking, a modified rosin sizing agent for neutral papermaking, AKD, ASA, and a cationic polymer type sizing agent.

The support according to the present invention may further include a plastic sheet such as polyethylene, polypropylene, polyethylene terephthalate, or polyamide, and a synthetic paper or nonwoven fabric made of these synthetic fibers, or a synthetic resin laminated on one or both sides of the paper. Laminated paper, metal foil, or metal foil and paper, vapor-deposited paper, opaque sheet subjected to hologram treatment, bonded product of synthetic resin film, mica paper, glass paper, and the like can also be used.

In the present invention, the printing coating layer is a coating layer for improving printability corresponding to printing such as ordinary offset printing, flexographic printing, gravure printing, and the like. It can be used for printing such as a water-based or oil-based pen, and includes so-called slightly coated paper. The printing coating layer is composed of a pigment and a binder. The mixing ratio of pigment and binder is
Generally, the binder is used in an amount of 5 parts by weight or more, preferably 10 to 70 parts by weight, based on 100 parts by weight of the pigment.

The pigment used in the coating layer for printing in the present invention includes kaolin, clay, calcium carbonate, satin white, titanium oxide, aluminum hydroxide, zinc oxide, barium sulfate, calcium sulfate, silica, activated clay, lake, plastic Pigment and the like.

As the binder, starch, casein,
Water-soluble resins such as gelatin, polyvinyl alcohol, carboxymethylcellulose, and hydroxyethylcellulose, and styrene-butadiene-based, acrylic-based, and vinyl acetate-based resin emulsions can be used.

Various additives such as a dispersant, a crosslinking agent, a dye, a fluorescent agent, an ultraviolet absorber, an antioxidant, a preservative, a surfactant, an antifoaming agent, a thickener, and a conductive agent are added to the printing coating layer. Agents can be added.

In the present invention, the coating amount of the coating layer for printing is 1 g / m ² or more on a dry weight basis, preferably
3 to 30 g / m ² is appropriate. If the coating amount of the printing coating layer is less than 1 g / m ² , good printability is not exhibited, and there is no point in providing the printing coating layer.
If it is more than g / m ² , it does not contribute to the improvement of printability, and is not economically preferable.

Further, various known techniques such as conducting a conductive treatment to prevent troubles in paper feeding and stacking, and providing an undercoat layer between the support and the heat-sensitive adhesive layer may be used as necessary. Can be added.

After the heat-sensitive adhesive sheet of the present invention is removably attached to an adherend, the adhesive is fixed by heating. As a method for fixing the adhesive by heating, in addition to the method using hot air, a thermocompression bonding method using an iron or a hot roll, a method using a heat source using infrared rays, microwaves, or high frequency can be used.

Since the heat-sensitive adhesive layer of the heat-sensitive adhesive sheet of the present invention has a weak tackiness even in a normal state, a release paper is provided on the sheet surface facing the heat-sensitive adhesive layer. There is a need.

Examples of the release paper according to the present invention include a film having a releasability itself such as a polyolefin resin film and a fluororesin film, a high-density base paper such as glassine paper, and a silicone as a release agent for paper or film. A resin which has been coated with a release component such as a resin, a fluororesin, or a long-chain alkyl compound in a dry coating amount of about 0.05 to 3 g / m ² and dried is used.

The heat-sensitive adhesive sheet of the present invention can be used as a heat-sensitive adhesive label by printing on a coating layer for printing. As a printing method, printing is performed on the printing coating layer using various printing methods such as flexo, letterpress, gravure, and offset. After the heat-sensitive adhesive layer and the release paper are sequentially provided on the support, printing may be performed on the printing coating layer, or after printing on the printing coating layer, the heat-sensitive adhesive layer may be formed on the opposite surface of the support. An adhesive layer and a release paper may be sequentially provided.

The heat-sensitive adhesive / ink-jet recording sheet according to the second aspect of the present invention has an ink-jet recording property composed of a release paper, a heat-sensitive adhesive / adhesive layer, a support and an ink receiving layer, and is temporarily fixed. It is a sheet that can be re-attached and can be firmly bonded by heating. The sheet of the present invention can be used as a label.

One or more known white pigments can be used for the support and the ink receiving layer used in the present invention. For example, light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, synthetic non-crystalline Amorphous silica, colloidal silica, colloidal alumina, pseudoboehmite, aluminum hydroxide, alumina, lithopone, zeolite,
White inorganic pigments such as hydrohaloysite, magnesium carbonate, and magnesium hydroxide; styrene plastic pigments, acrylic plastic pigments; polyethylene, microcapsules, and organic pigments such as urea resins and melamine resins. Among the above, as the white pigment contained as a main component in the ink receiving layer, a porous inorganic pigment is preferable, and a porous synthetic amorphous silica, a porous magnesium carbonate, a porous alumina, and the like, and particularly, a fine pore Large volume porous synthetic amorphous silica is preferred.

It is preferable to add a cationic compound having a quaternary ammonium group or a compound having a tertiary amino group to the ink receiving layer of the present invention. By adding these compounds to the ink receiving layer of the present invention, when the recording surface is wet with water after ink jet recording on the ink receiving layer of the thermosensitive adhesive ink jet recording sheet of the present invention, the ink jet recording is performed. It was found that the phenomenon that the contents did not flow into water and the printing did not bleed (providing water resistance) occurred.

In the ink receiving layer of the present invention, other additives such as a dispersant, a thickener, a flow improver, a defoamer, a foam inhibitor, a release agent, a foaming agent, a penetrant, Color dyes, color pigments, fluorescent whitening agents, ultraviolet absorbers, antioxidants, preservatives, anti-binders, water-proofing agents, wet paper strength agents, dry paper strength agents, antistatic agents, anti-aging agents, etc. Can be appropriately blended.

When the ink receiving layer is provided in the present invention, the coating amount is not particularly limited, but if it is too small, the image density, color and sharpness are low, and the ink diffuses in the surface direction of the support. As a result, deterioration of the dot shape called feathering, which is jagged like a bird's wing, occurs. In addition, if the coating amount is too large, the drying load in the drying step after coating or impregnation increases, and not only does the productivity decrease due to a decrease in the coating or impregnation speed, but also when drying under a high load, the ink receiving layer The binder in the coating composition that constitutes moves to the surface of the ink receiving layer together with the solvent that evaporates,
In order to reduce the amount of voids on the surface, background contamination may occur during recording. The problem that occurs in the ink receiving layer having a large coating amount is affected by the concentration of the coating composition and the ability of the drying step, and the preferable coating amount of the ink receiving layer is 1 to 10 g /.
m ² .

An anchor coat layer of starch, polyvinyl alcohol or the like may be provided between the support of the present invention and the ink receiving layer.

The method for coating the ink receiving layer is to use various apparatuses such as a blade coater, a roll coater, an air knife coater, a bar coater, a rod blade coater, a short dwell coater, and a size press on or off machine. Can be. After coating, machine calendar, TG calendar,
The finishing may be performed using a calendar such as a super calendar or a soft calendar.

The ink used in the present invention includes the following colorants:
This is a recording liquid composed of a liquid medium and other additives.

Examples of the colorant include water-soluble dyes such as direct dyes, acid dyes, basic dyes, reactive dyes, and food dyes.

Examples of the solvent for the ink include water and various water-soluble organic solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, and isobutyl. Alkyl alcohols having 1 to 4 carbon atoms such as alcohol; amides such as dimethylformamide and dimethylacetamide; ketones or ketone alcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; polyethylene glycol and polypropylene glycol Polyalkylene glycols; ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,2,6-hexanetriol, thiodi Recall, hexylene glycol, an alkylene group such as diethylene glycol 2-6
And lower alkyl ethers of polyhydric alcohols such as glycerin, ethylene glycol methyl ether, diethylene glycol methyl (or ethyl) ether, and triethylene glycol monomethyl ether. Among these many water-soluble organic solvents, polyhydric alcohols such as diethylene glycol, triethylene glycol monomethyl ether,
Preferred are lower alkyl ethers of polyhydric alcohols such as triethylene glycol monoethyl ether. Other additives include, for example, pH adjusters, sequestering agents,
Examples include a fungicide, a viscosity modifier, a surface tension modifier, a wetting agent, a surfactant, and a rust inhibitor.

The operation of the present invention will be described below. The heat-sensitive adhesive sheet of the first present invention has a coating layer for printing on one side of the support and a heat-sensitive adhesive layer on the other side, so that printing is possible and the tackiness is weak in a normal state. Temporary fixing and reattachment are possible any number of times, and after the attachment position is determined, strong adhesion can be obtained by heating the sheet. The heat-sensitive adhesive recording sheet of the second aspect of the present invention is provided with an ink-receiving layer on one side of the support and a heat-sensitive adhesive layer on the opposite side, so that ink-jet recording is possible and temporary fixing and reattachment are possible. And strong bonding by heating becomes possible.

[0052]

EXAMPLES The present invention will be described in detail below with reference to examples, but the contents of the present invention are not limited to the examples.
All parts and percentages shown below are based on weight. or,
The value indicating the coating amount is the coating amount after drying unless otherwise specified.

Preliminary operation Preparation of support The support was prepared by mixing 100 parts of wood pulp consisting of 72 parts of LBKP (freeness 420 mlcsf) and 28 parts of NBKP (freeness 440 mlcsf) with light calcium carbonate / heavy calcium carbonate. 25 parts of a pigment having a / talc ratio of 32/33/35, 0.12 parts of a commercially available alkyl ketene dimer,
After preparing 0.03 part of a commercially available cationic acrylamide, 1.2 parts of a commercially available cationized starch, and 0.5 part of a sulfuric acid band, papermaking was performed using a Fourdrinier paper machine at a basis weight of 100 g / m ² .

Preparation of Coating Solution for Printing Coating Layer 50 parts of calcium carbonate (Tamapearl TP-123, manufactured by Okutama Industries) as a pigment and 75 parts of SBR latex (JSR-0668, manufactured by Nippon Synthetic Rubber) as a binder were mixed. The solid content was adjusted to 35% to prepare a coating liquid for a coating layer for printing.

Preparation of Coating Solution for Ink Receiving Layer As a coating solution for the ink receiving layer, 120 parts of synthetic amorphous silica (Fanseal X37B, manufactured by Tokuyama Soda), 35 parts of polyvinyl alcohol (PVA117, manufactured by Kuraray), cationic dye fixing agent (Sumireze Resin 1001, manufactured by Sumitomo Chemical Co., Ltd.) was used, and the mixture was adjusted to have a solid content of 15%.

Preparation of Heat-Sensitive Adhesive Layer Coating Liquid Dicyclohexyl phthalate (melting point 64) as a solid plasticizer
C), 2.4 parts by weight of a nonionic surfactant (trade name: Neugen EA-120, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as a dispersant and 100 parts of water were uniformly mixed to a concentration of 56% to form a ball mill. To obtain an average particle diameter of 2.0 μm to prepare a solid plasticizer dispersion.

A vinyl acetate-ethylene-acrylate copolymer emulsion (Sumikaflex 910, manufactured by Sumitomo Chemical Co., Ltd .; glass transition temperature: -20 ° C.) was used as a thermoplastic resin in 30 parts of the solid plasticizer dispersion liquid.
0 parts and a rosin ester dispersion (Super Ester E-730, manufactured by Arakawa Chemical Industries, Ltd.) as a tackifier 7
And 0 parts by weight to prepare a heat-sensitive adhesive layer coating liquid having a solid content of 50% by weight.

Preparation of Coating Solution for Adhesive Layer As a thermoplastic resin, a vinyl acetate-ethylene-acrylate copolymer emulsion (Sumikaflex 910, manufactured by Sumitomo Chemical Co., Ltd .; glass transition temperature -20)
) And 100 parts of a rosin ester dispersion as a tackifier (Arakawa Chemical Industries, Ltd., Superester E-7)
30) was mixed with 70 parts to prepare an adhesive layer coating liquid.

Example 1 One side of the support prepared in the preliminary operation was coated with the coating liquid for the printing layer prepared in the preliminary operation using an air knife coater so that the coating amount was 15 g / m ² , and dried. A coating layer for printing was formed. Further, a heat-sensitive adhesive layer coating solution was applied to the opposite surface of the printing coating layer by an air knife coater so that the coating amount was 25 g / m ² , dried, and then superimposed on a commercially available release paper, A heat-sensitive adhesive sheet of the present invention was produced. The drying temperature at this time is 40 ° C
Met. The printing coating layer of this heat-sensitive adhesive sheet was printed using an offset printing machine.

Example 2 One side of the support prepared in the preliminary operation was coated with the coating liquid for the printing layer prepared in the preliminary operation using an air knife coater so that the coating amount was 15 g / m ² , and dried. A coating layer for printing was formed. After printing was performed on the printing coating layer using an offset printing machine, the coating amount of the heat-sensitive adhesive layer coating solution prepared by the preliminary operation was applied to the opposite surface of the printing coating layer by an air knife coater so that the coating amount was 25%.
g / m ² , and then dried and then superimposed on a commercially available release paper to produce a heat-sensitive adhesive sheet of the present invention.
The drying temperature at this time was 40 ° C.

Example 3 One side of the support prepared in the preliminary operation was supported by using an ink receiving layer coating liquid prepared in the preliminary operation by an air knife coater so as to have a dry coating amount of 5.5 g / m ^2. One side of the body was coated and dried to form an ink receiving layer. Further, the coating amount of the heat-sensitive adhesive layer prepared by the preliminary operation was applied to the opposite surface of the ink receiving layer by an air knife coater at a coating amount of 25 g / g.
After coating and drying so as to obtain m ² , the resultant was overlaid with a commercially available release paper to prepare a heat-sensitive adhesive ink-jet recording sheet of the present invention. The drying temperature at this time was 40 ° C. An image was recorded on the ink receiving layer of the heat-sensitive adhesive recording ink-jet recording sheet using a commercially available ink-jet printer.

Comparative Example 1 A heat-sensitive adhesive layer coating solution prepared by the preliminary operation was applied to one side of the support prepared by the preliminary operation using an air knife coater so that the coating amount became 25 g / m ² . After drying, it was overlaid with a commercially available release paper to produce a heat-sensitive adhesive sheet. The drying temperature at this time was 40 ° C. Printing was performed on the surface of the heat-sensitive adhesive sheet opposite to the heat-sensitive adhesive layer using an offset printing machine.

Comparative Example 2 An image was recorded on the opposite side of the heat-sensitive adhesive layer of the heat-sensitive adhesive sheet prepared in Comparative Example 1 by a commercially available ink jet printer.

Comparative Example 3 An adhesive was prepared in the same manner as in Example 1 except that the heat-sensitive adhesive layer coating liquid prepared in the preliminary operation was replaced with the adhesive layer coating liquid prepared in the preliminary operation. A functional sheet was produced.

Comparative Example 4 In Example 1, a heat-sensitive adhesive layer coating solution (Heat Magic DW) was used instead of the heat-sensitive adhesive layer coating solution prepared by the preliminary operation.
2000, manufactured by Toyo Ink, solid content: 52%), and a heat-sensitive adhesive sheet was produced in the same manner as in Example 1 except that no release paper was used.

Comparative Example 5 In Example 1, a heat-sealable adhesive layer coating solution (Aquatex AC2010, manufactured by Chuo Rika Kogyo, solid content: 45%) was used instead of the heat-sensitive adhesive layer coating solution prepared by the preliminary operation. A heat-sealable adhesive sheet was prepared in the same manner as in Example 1, except that no release paper was used.

Comparative Example 6 An adhesive was prepared in the same manner as in Example 3 except that the adhesive layer coating liquid prepared by the preliminary operation was used instead of the heat-sensitive adhesive layer coating liquid prepared by the preliminary operation. An ink jet recording sheet was prepared. Image recording was performed on the ink receiving layer of the adhesive ink jet recording sheet using a commercially available ink jet printer.

Comparative Example 7 In Example 3, a heat-sensitive adhesive layer coating solution (Heat Magic DW) was used instead of the heat-sensitive adhesive layer coating solution prepared in the preliminary operation.
2000, manufactured by Toyo Ink Co., Ltd., solid content: 52%), and a heat-sensitive adhesive inkjet recording sheet was produced in the same manner as in Example 3 except that no release paper was used. An image was recorded on the ink receiving layer of the heat-sensitive adhesive inkjet recording sheet by a commercially available inkjet printer.

Comparative Example 8 In Example 3, a heat-sealable adhesive layer coating solution (Aquatex AC2010, manufactured by Chuo Rika Kogyo, solid content 45%) was used instead of the heat-sensitive adhesive layer coating solution prepared in the preliminary operation. A heat seal adhesive inkjet recording sheet was prepared in the same manner as in Example 3 except that no release paper was used. An image was recorded on the ink receiving layer of the heat-sealable adhesive inkjet recording sheet by a commercially available inkjet printer.

The sheets and sheets obtained in the above Examples and Comparative Examples were evaluated by the following test methods, and the results are shown in Table 1.

<Test Method> 1) Temporary Fixing Property After the sheet was cut to a width of 25 mm, the release paper was peeled off and attached to a stainless steel plate. One day after application, the 180-degree dynamic peel strength (300 mm / min) was measured with a Tensilon universal testing machine. Measured value is 10 gf / 25 mm or more and 100 gf / 2
When it is within the range of less than 5 mm, it can be sufficiently temporarily fixed and can be re-peeled, so that the temporary fixing property is good and excellent. 10
If it is 0 gf / 25 mm or more and less than 200 gf / 25 mm, it can be used because it can be peeled off, and the temporary fixing property is acceptable. 2
In the case of not less than 00 gf / 25 mm, a problem such as curling of the heat-sensitive adhesive recording ink-jet recording sheet occurs when the temporarily-fixed heat-sensitive adhesive recording ink-jet recording sheet is peeled off. Judgment can be made and the temporary fixability is poor. If it is less than 10 gf / 25 mm, it cannot be temporarily fixed. However, the unit in Table 1 is gf / 25 mm.

2) Heat Adhesion After the sheet was cut to a width of 25 mm, the release paper was peeled off and affixed to a stainless steel plate.
The adhesion was fixed by spraying from the printing coating layer or the ink receiving layer side for 2 seconds. One day after bonding, the 180-degree dynamic peel strength (300 mm / min) was measured with a Tensilon universal testing machine. When the measured value is 500 gf / 25 mm or more, it is considered that the adhesiveness to the adherend is sufficient, and the heat adhesion is excellent. 300gf / 25mm or more 500g
If it is less than f / 25 mm, it can be used and the heat adhesion is acceptable. If it is less than 300 gf / 25 mm, the heat-sensitive adhesive ink-jet recording sheet can be peeled off from the adherend, so that the heat-adhesive property is inferior. However, Table 1
The unit in the middle is gf / 25 mm.

3) Image clarity before heat bonding The image-recorded portion of the sheet on which printing or ink jet recording was performed before heat bonding was observed with a magnifying loupe. When the image has no bleeding and has sharpness, the image sharpness is excellent, and when the image is slightly sharp but the image is sufficiently clear, the image clarity is average, when bleeding occurs and the image is disturbed Was judged as poor image clarity.

4) Image clarity after heat bonding The release paper of the sheet on which printing or ink jet recording was performed was peeled off, and the sheet was adhered to a stainless steel plate and heated to fix the adhesion. The image recorded portion after the heat bonding was observed with a magnifying loupe. When the image has no bleeding and has sharpness, the image sharpness is excellent, and when the image is slightly sharp but the image is sufficiently clear, the image clarity is average, when bleeding occurs and the image is disturbed Was judged as poor image clarity.

[0075]

[Table 1]

<Evaluation> As shown in Examples 1 to 3, the support was actually used as a label or the like by using a printing coating layer or an ink receiving layer on one side and a heat-sensitive adhesive layer on the other side. In this case, it was possible to temporarily fix it, and it was possible to peel it off again, and strong bonding was made possible by heating. On the other hand, as shown in Comparative Examples 1 and 2, in the configuration in which the heat-sensitive adhesive layer is merely provided on one surface of the support, although the temporary fixing property and the heat adhesive property are excellent, the image after printing or ink jet recording is not obtained. The image was slightly blurred and poor in sharpness. Further, as shown in Comparative Examples 3 and 6, when a normal pressure-sensitive adhesive was used for the pressure-sensitive adhesive layer, the adhesive force before heating was too strong, resulting in poor removability, and no increase in the adhesive force due to heating was observed. I couldn't. In addition, as shown in Comparative Examples 4, 5, 7, and 8, when a heat-sensitive adhesive or a heat-sealing adhesive was used for the adhesive layer, there was no adhesiveness before heating, so that I couldn't make a temporary stop.

[0077]

The heat-sensitive adhesive sheet according to the first aspect of the present invention comprises:
By providing a printing coating layer on one side of the support and a heat-sensitive adhesive layer on the other side, printing is possible and the tackiness is weak in the normal state, so it can be temporarily fixed and re-attached any number of times. After the position is determined, strong adhesion can be obtained by heating the sheet. The heat-sensitive adhesive recording sheet of the second aspect of the present invention is provided with an ink-receiving layer on one side of the support and a heat-sensitive adhesive layer on the opposite side, so that ink-jet recording is possible and temporary fixing and reattachment are possible. And strong bonding by heating becomes possible.

Claims (2)

[Claims] 1. A release paper, in which a heat-sensitive adhesive layer, a support, and a coating layer for printing, which have weak tackiness in a normal state and exhibit strong adhesiveness when heated to a certain temperature or higher, are sequentially laminated. A heat-sensitive adhesive sheet that can be printed with a structured structure, can be temporarily fixed and re-attached, and can be firmly bonded by heating. 2. A release paper, in which a heat-sensitive adhesive layer, a support, and an ink-receiving layer, which have a weak tackiness in a normal state and exhibit strong adhesiveness when heated to a certain temperature or higher, are sequentially laminated. A heat-sensitive adhesive recording sheet capable of performing inkjet recording having a structure, capable of being temporarily fixed and re-attached, and capable of firmly bonding by heating.