JP2020163840A - Peelable laminate - Google Patents

Abstract

To provide a peelable laminate capable of providing a delivery slip, a three-layered label and a pseudo three-layered label without having problems of stickiness on the surface of the adhesive layer of a slip after peeling, re-bonding by pressing, increase in peel strength with the lapse of time in high temperature and high humidity environment and the like.SOLUTION: A peelable laminate consisting of a substrate sheet 1, a pseudo release layer 2 including a silicone acrylic resin and laminated on the substrate sheet and a resin layer 3 including a carboxyl group containing resin and laminated on the pseudo release layer can be peeled between the pseudo release layer and the resin layer.SELECTED DRAWING: Figure 1

Description

The present invention relates to a peelable laminate, and more particularly to a peelable laminate that can be used for record slips used for delivery and management of goods, application for various insurances, tickets, and the like.

Conventionally, for example, as a delivery slip (recording slip) used by being attached to a delivery article, an adhesive layer and a release paper are provided on the back side of the delivery slip as an information recording unit by providing a thermal coloring agent layer on the front surface side. A heat-sensitive color-developing agent layer is also provided on the surface side of the release paper to serve as an information recording unit, and the release paper is used as a copy of the delivery slip.
The amount of thermal paper used for delivery slips is increasing due to the increase in delivery volume due to the expansion of mail-order usage. Conventionally, three-layer labels (pseudo-adhesive paper such as heat-sensitive paper and crimping paper + release paper for strong adhesion) have been widely used for delivery slips (Patent Documents 1, 2, etc.), but these days, they are easier to handle. Pseudo three-layer labels (heat-sensitive paper + resin layer by extrusion laminating processing + release paper for strong adhesion) are beginning to be used.

JP-A-11-245542 JP-A-2005-139397

In the conventional delivery slip using a combination of the adhesive layer and the release paper, the adhesive layer surface of the slip after peeling is sticky, so that it is difficult to handle the peeled slip. In addition, the manufacturing process of conventional 3-layer labels and pseudo-3-layer labels is complicated, and delivery slips for 3-layer labels that use pseudo-adhesive paper such as crimping are not sticky after peeling, but are pressurized. In some cases, re-adhesion may occur, or in a high-temperature and high-humidity environment, the peeling strength may increase over time, causing a problem of increasing peeling, which makes peeling difficult. Further, the delivery slip of the pseudo three-layer label by the laminating process has a problem that the peel strength is not stable, the peel strength becomes too low, and the slip falls off due to friction or the like.

The present inventors have found that the above problems can be solved by laminating a pseudo-release layer containing a silicone acrylic resin on a base sheet and a resin layer containing a carboxyl group-containing resin on the pseudo-release layer. , The present invention has been completed.
That is, the present invention comprises a base sheet, a pseudo-peeling layer laminated on the base sheet, and a resin layer laminated on the pseudo-peeling layer, and the pseudo-peeling layer contains a silicone acrylic resin. It is a peelable laminate in which the resin layer contains a carboxyl group-containing resin and the pseudo-peeling layer and the resin layer can be peeled off.

It is a figure which shows the structure of the peelable laminate of this invention. (1) shows a basic structure, (2) shows a structure in which an adhesive layer is arbitrarily provided on a resin layer, and (3) shows a structure in which a recording layer is arbitrarily provided in the structure of (2). In the figure, 1 is a base sheet, 2 is a pseudo-release layer, 3 is a resin layer, 4 is an adhesive layer, 5 is a release paper, and 6 is a recording layer.

The peelable laminate of the present invention comprises a base sheet, a pseudo-peeling layer laminated on the base sheet, and a resin layer laminated on the pseudo-peeling layer (see FIG. 1 (1)). By forming the peelable laminate in this order, the layers are adhered to each other in a normal state, but the pseudo-peeling layer and the resin layer can be peeled off. In the pseudo-peeling, two layers (for example, the pseudo-peeling layer and the resin layer) are adhered to each other in a normal use state, but both layers are peeled by pulling by a human hand or the like, and then overlapped. It means that it cannot be re-bonded even if it is pressed together.
The peelable laminate may further include an adhesive layer, which is laminated on a surface of the resin layer opposite to the pseudo-release layer (see FIG. 1 (2)). A release paper may be provided on the layer. In this peelable laminate, at least one recording layer may be further provided on the surface of the base material sheet opposite to the surface on which the pseudo-peeling layer is provided (see FIG. 1 (3)).
The peel strength between the pseudo peeling layer and the resin layer is 400 gf / 18 mm or less, preferably 10 to 200 gf / 18 mm. If the peel strength is less than 10 gf / 18 mm, the adhesion between the pseudo peel layer and the resin layer becomes insufficient, and the resin layer may fall off due to friction or the like.

The base sheet used in the present invention can be appropriately selected from conventionally known base sheets such as paper, recycled paper, synthetic paper, film, plastic film, foamed plastic film, and non-woven fabric according to the quality of the desired application. , Is not particularly limited. Moreover, you may use the composite sheet which combined these as a base material sheet.

The pseudo-release layer of the present invention contains a silicone acrylic resin. In addition to the silicone acrylic resin, the pseudo-release layer may contain any other suitable component as long as it does not impair the desired performance. Examples of other components include binders (resins) other than silicone acrylic resins, pigments, cross-linking agents, and the like.

As the silicone acrylic resin, any suitable silicone acrylic resin is used. As the silicone acrylic resin, a silicone acrylic resin obtained by copolymerizing a polyorganosiloxane represented by the following general formula (1) with a (meth) acrylic acid ester is preferably used.

［式（１）中、Ｒ^１、Ｒ^２、及びＲ^３は、それぞれ同一であっても異なっていてもよく、炭素数１〜２０の炭化水素基、又は、炭素原子に結合した水素原子の少なくとも一つをハロゲン原子で置換した炭素数１〜２０のハロゲン化炭化水素基を表し；Ｙはラジカル反応性基、又は、−ＳＨ基、もしくはその両方を有する有機基を表し；Ｚ^１及びＺ^２はそれぞれ同一であっても異なっていてもよく、水素原子、炭素数１〜４のアルキル基、又は、

（式（２）中、Ｒ^４及びＲ^５はそれぞれ同一であっても異なっていてもよく、炭素数１〜２０の炭化水素基、又は、炭素数１〜２０のハロゲン化炭化水素基を表し；Ｒ^６は炭素数１〜２０の炭化水素基、又は、炭素数１〜２０のハロゲン化炭化水素基、もしくは、ラジカル反応性基又はＳＨ基もしくはその両方を有する有機基を表す）で表されるトリオルガノシリル基を表し；ｍは１０，０００以下の正の整数を表し；ｎは１以上の整数を表し；１分子中で、Ｒ^１〜Ｒ^６、Ｙはそれぞれ同一でも異なっていてもよい］。

[In the formula (1), R ¹ , R ² and R ³ may be the same or different from each other, and may be a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom bonded to a carbon atom. Represents a halogenated hydrocarbon group having 1 to 20 carbon atoms in which at least one is substituted with a halogen atom; Y represents a radical reactive group, an -SH group, or an organic group having both; Z ¹ and Z. ² may be the same or different, respectively, and may be a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or

(In the formula (2), R ⁴ and R ⁵ may be the same or different, respectively, and represent a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms. R ⁶ represents a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a radical reactive group, an SH group, or an organic group having both of them). Represents a triorganosilyl group; m represents a positive integer of 10,000 or less; n represents an integer of 1 or more; in one molecule, R ^{1 to} R ⁶ , Y may be the same or different. Good].

In the above general formula (1), R ^{1 to} R ³ may be the same or different from each other, and a hydrocarbon group having 1 to 20 carbon atoms or at least one hydrogen atom bonded to a carbon atom is used. Represents a halogenated hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom. Specific examples of the hydrocarbon group include alkyl groups such as methyl group, ethyl group, propyl group and butyl group, and aryl groups such as phenyl group, trill group, xsilyl group and naphthyl group.

In the above general formula (1), Y represents an organic group having a radical reactive group, a -SH group, or both. Specific examples of this radical-reactive group include a vinyl group, an allyl group, a γ-acryloxypropyl group, a γ-methacryloxypropyl group, a γ-mercaptopropyl group and the like.

In the above general formula (1), Z ¹ and Z ² may be the same or different, respectively, and are represented by a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or the above general formula (2). Represents a triorganosilyl group. Specific examples of the alkyl group include lower alkyl groups such as a methyl group, an ethyl group, a propyl group and a butyl group.

In the above general formula (2), R ⁴ and R ⁵ may be the same or different from each other, and a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms may be used. Represent. R ⁶ represents a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a radical reactive group, an SH group, or an organic group having both of them. As these hydrocarbon groups and radically reactive groups such as, specifically, those exemplified in R ¹ to R ³ and Y in the general formula (1).

In the above general formula (1), m is a positive integer of 10,000 or less, preferably an integer of 500 to 8000. In the above general formula (1), n is an integer of 1 or more, preferably an integer of 1 to 500.

This polyorganosiloxane can be produced by any suitable method. For example, it can be produced by polymerizing a chain-like or cyclic low molecular weight polyorganosiloxane or alkoxysilane having a functional group exemplified in this description.

Any suitable (meth) acrylic acid ester can be used as the (meth) acrylic acid ester. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, Alkyl (meth) acrylates such as 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate and stearyl (meth) acrylate, alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate and butoxyethyl (meth) acrylate, cyclohexyl. Examples thereof include (meth) acrylate, phenyl (meth) acrylate, and benzyl (meth) acrylate. Only one type of this (meth) acrylic acid ester may be used, or two or more types may be used in combination.

The blending ratio of the polyorganosiloxane represented by the general formula (1) and the (meth) acrylic acid ester at the time of copolymerization is preferably 5/95 to 95/5 by weight.

In addition to this (meth) acrylic acid ester, another monomer copolymerizable with this (meth) acrylic acid ester may be copolymerized. Any suitable monomer can be used as another monomer copolymerizable with this (meth) acrylic acid ester. For example, styrene compounds such as styrene, vinyltoluene and α-methylstyrene, unsaturated nitriles such as acryliconitrile and methacrylonitrile, halogenated olefins such as vinyl chloride and vinylidene chloride, and vinyl esters such as vinyl acetate and vinyl propionate. In addition to monomers having one double bond such as unsaturated amides such as acrylamide, methacrylicamide and N-methylolacrylamide, and unsaturated carboxylic acids such as acrylic acid, methacrylic acid and maleic anhydride, ethylene glycol dimethacrylate, Examples thereof include polyunsaturated monomers such as propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, allyl methacrylate, triallyl cyanurate, and triallyl isocyanurate. As the other monomer, only one kind may be used, or two or more kinds may be used in combination.

The content of the other copolymerizable monomer is 30% by weight or less with respect to 100% by weight of the total amount of the (meth) acrylic acid ester and the other copolymerizable monomer. Is preferable. The compounding ratio of the polyorganosiloxane represented by the general formula (1) at the time of copolymerization is the compounding ratio of the (meth) acrylic acid ester and the total weight of the other monomers. It may be within the range of.

This silicone acrylic resin can be obtained by graft-copolymerizing a polyorganosiloxane represented by the above general formula (1) with a (meth) acrylic acid ester. The polymerization of the polyorganosiloxane represented by the general formula (1) and the (meth) acrylic acid ester can be carried out by any suitable polymerization method. The silicone acrylic resin is preferably a resin obtained by graft-copolymerizing the polyorganosiloxane represented by the general formula (1) and the (meth) acrylic acid ester by an emulsion polymerization method.

This emulsion polymerization can be carried out by any suitable method. For example, a method of emulsifying and dispersing a polyorganosiloxane represented by the general formula (1) and a (meth) acrylic acid ester in water, polymerizing in the presence of a radical polymerization initiator, and performing graft copolymerization can be mentioned. Examples of the emulsifier and radical polymerization initiator used in the emulsion polymerization include any suitable emulsifier or radical polymerization initiator. A specific method for producing a silicone acrylic resin is disclosed in Japanese Patent Publication No. 7-5808. This disclosure is incorporated herein by reference.

As the silicone acrylic resin, a commercially available silicone acrylic resin may be used. For example, the product name "Charine" series manufactured by Nissin Chemical Industry Co., Ltd. can be mentioned.

The pseudo-release layer of the present invention may further contain a long-chain alkyl group-containing resin. When the pseudo release layer of the present invention contains a long-chain alkyl group-containing resin in addition to the silicone acrylic resin, the release strength can be suppressed to be lower, which is preferable. As this long-chain alkyl group-containing resin, a long-chain alkyl acrylate copolymer, a long-chain alkyl vinyl ester copolymer, a long-chain alkyl acrylic amide copolymer, a long-chain alkyl allyl ester copolymer, and stearyl isocyanate modification of polyvinyl alcohol Examples thereof include a copolymer of an alkylated polymer such as a product and a long-chain alkyl compound, and a copolymer of a polymer such as a copolymer of polyethylene and stearic acid amide and a long-chain alkyl compound. The number of carbon atoms of this long-chain alkyl group is preferably 6 or more and 30 or less. Specific examples of the long-chain alkyl group-containing resin used in the present invention include Rezem P-677, Rezem S-310, Rezem K-256 (all manufactured by Chukyo Yushi Co., Ltd.), Peloyl 1010, and Peloyl 406 (all one). (Manufactured by Yushi Kogyo Co., Ltd.) and the like are not particularly limited, and these can be used alone or in combination of two or more.

Examples of the binder other than the silicone acrylic resin and the long-chain alkyl group-containing resin include water-soluble resins and / or emulsions of arbitrary suitable resins. Specifically, fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, acetoacetylated polyvinyl alcohol, carboxy-modified polyvinyl alcohol, amide-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, butyral-modified polyvinyl alcohol, olefin-modified polyvinyl alcohol, nitrile. Polyvinyl alcohols such as modified polyvinyl alcohol, pyrrolidone-modified polyvinyl alcohol, silicone-modified polyvinyl alcohol, and other modified polyvinyl alcohols, (meth) acrylic acid, and monomer components (excluding olefins) that can be copolymerized with (meth) acrylic acid. ) Acrylic resin, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, ethyl cellulose, acetyl cellulose and other cellulose derivatives, oxidized starch, etherified starch, esterified starch and other starches, styrene-maleic anhydride copolymer, Styrene-butadiene copolymer, casein, arabiya rubber, polyvinyl chloride, polyvinyl acetate, polyacrylamide, polyacrylic acid ester, polyvinyl butyral, polyvinyl butylose and their copolymers, polyamide resin, silicone resin, petroleum resin, terpene resin , Ketone resin, kumaron resin and the like can be exemplified. These resins may be used alone or in combination of two or more.

Pigments include, for example, aluminum hydroxide, aluminum oxide, aluminum silicate, heavy calcium carbonate, light calcium carbonate, titanium oxide, barium sulfate, silica gel, active white clay, talc, clay, kaolin, calcined kaolin, silicate soil, white. Examples thereof include inorganic pigments such as carbon, magnesium carbonate, magnesium oxide, magnesium hydroxide, zinc oxide, magnesium silicate, calcium silicate and silica, and organic pigments such as polystyrene resin particles, urea-formalin resin particles and polyolefin resin particles. The pigments may be used alone or in combination of two or more. The content of the pigment can be set to any suitable value. Among these pigments, talc, clay, kaolin, calcined kaolin, and aluminum hydroxide are preferable because the stability of the peel strength and the surface strength of the pseudo peel layer are good.

As the cross-linking agent, any suitable cross-linking agent is used depending on the type of binder used. Examples of the cross-linking agent include dialdehyde-based cross-linking agents such as glioxal, polyaldehyde and amino-formaldehyde, polyamine-based cross-linking agents such as polyethyleneamine, polyimine-based cross-linking agents such as polyethyleneimine, and epoxy such as epichlorohydrin-based resin. Examples thereof include a system cross-linking agent, a diglycidyl-based cross-linking agent such as glycerin diglycidyl ether, and a zirconium salt such as ammonium carbonate. This cross-linking agent may be used alone or in combination of two or more. The content of this cross-linking agent can be set to an arbitrary appropriate value depending on the type and content of the binder used.

The pseudo-release layer of the present invention may further contain any suitable additive in addition to the binder, pigment, and cross-linking agent. Examples of the additive include lubricants, dispersants, defoamers, water resistant agents, ultraviolet absorbers and the like. These additives may be used alone or in combination of two or more. The content of these additives can be set to any suitable value depending on the desired properties and the like.
The pseudo-peeling layer can be formed by any suitable method. For example, an aqueous dispersion (coating solution for a pseudo-release layer) containing the binder containing the silicone acrylic resin, a pigment, a cross-linking agent and, if necessary, other additives is prepared, and the dispersion is coated and dried. This can be formed.

The pseudo-release layer of the present invention contains the silicone acrylic resin in a solid content of 20% by weight or more, preferably 30% by weight or more, more preferably 30 to 95% by weight, still more preferably 40 to 95% by weight, still more preferably. Contains 50-90% by weight. When the long-chain alkyl group-containing resin is blended, the silicone acrylic resin and the long-chain alkyl group-containing resin are contained in the pseudo-release layer in an amount of 40% by weight or more, preferably 50 to 95% by weight in total solid content. %, More preferably 60 to 85% by weight. When a long-chain alkyl group is blended, the solid content is 10% or more, preferably 20% or more, more preferably 30% or more, based on the silicone acrylic resin.
The coating amount of this pseudo-peeling layer can be set to any appropriate value. For example, the coating amount is at 1.0 g / ^{m 2} or more, preferably ^{2.0g / m 2 ~6.0g / m 2} .

The resin layer of the present invention contains a carboxyl group-containing resin. In addition to the above-mentioned carboxyl group-containing resin, the pseudo-release layer may contain any suitable other component as long as it does not impair the desired performance. Examples of other components include binders (resins) other than carboxyl group-containing resins, pigments, cross-linking agents, and the like.

Examples of the carboxyl group-containing resin used in the resin layer of the present invention include acrylic resins, carboxy-modified polyvinyl alcohol in which a carboxyl group is introduced into polyvinyl alcohol, and carboxymethyl cellulose, and the carboxyl group-containing resin used in the present invention. Is preferably at least one selected from an acrylic resin and a carboxy-modified polyvinyl alcohol.

The acrylic resin used in the resin layer of the present invention comprises (meth) acrylic acid and a monomer component (excluding olefins) copolymerizable with (meth) acrylic acid. The (meth) acrylic acid is preferably blended in an amount of 1 to 10 parts by weight based on 100 parts by weight of the acrylic resin.
(Meta) acrylic acid is alkali-soluble and has the property of turning an acrylic resin into a water-soluble resin by adding a neutralizing agent. By changing the acrylic resin to a water-soluble resin, especially when a pigment is contained in the resin layer, the bondability to the pigment is remarkably improved, and a resin layer having excellent strength is formed even when a large amount of pigment is contained. be able to.
Examples of components copolymerizable with (meth) acrylic acid include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, propyl (meth) acrylic acid, butyl (meth) acrylic acid, and isobutyl (meth) acrylic acid. , (Meta) pentyl acrylate, (meth) hexyl acrylate, (meth) -2-ethyl acrylate hexyl, (meth) octyl acrylate and other alkyl acrylate resins and epoxy resins, silicone resins, styrene or derivatives thereof. Modified alkyl acrylate resins such as the above alkyl acrylate resin modified by, (meth) acrylonitrile, acrylic acid ester, hydroxyalkyl acrylate ester can be exemplified, and in particular, (meth) acrylonitrile and / or methyl methacrylate is blended. Is preferable. The (meth) acrylonitrile is preferably blended in an amount of 15 to 70 parts by weight based on 100 parts by weight of the acrylic resin. Further, it is preferable that methyl methacrylate is contained in an amount of 20 to 80 parts by weight based on 100 parts by weight of the acrylic resin. When (meth) acrylonitrile and methyl methacrylate are contained, 15 to 18 parts by weight of (meth) acrylonitrile may be blended in 100 parts by weight of the acrylic resin, and 20 to 80 parts by weight of methyl methacrylate may be blended in 100 parts by weight of the acrylic resin. preferable.

The acrylic resin used in the resin layer of the present invention is preferably a non-core shell type acrylic resin. In general, core-shell type acrylic resins are often used because they have excellent heat resistance as compared with non-core-shell type acrylic resins, and when used in a coating layer, they have excellent printability, particularly stick resistance. However, since the shell portion of the core-shell type acrylic resin has low thermal conductivity, it also has a drawback that the print density and the image quality are inferior.
On the other hand, ordinary non-core shell type acrylic resins have low heat resistance and have a drawback that sticks and head meals are likely to occur, but non-core shell type acrylic resins having a specific range of glass transition points (Tg) are Because of its high heat resistance, it is possible to achieve both print density, image quality and print runnability, which are contradictory to the core-shell type acrylic resin.
The glass transition point (Tg) of the acrylic resin in the present invention is preferably higher than 30 ° C and lower than 100 ° C. When the Tg is 30 ° C. or lower, the water resistance is improved, but the heat resistance is low, and sticks are likely to be formed. On the other hand, if the Tg is high, the heat resistance becomes good and the stick resistance and the scratch resistance are improved, but if the Tg is too high, the resin layer becomes brittle and the water resistance and the plasticizer resistance may decrease. More preferably, Tg is higher than 50 ° C and 95 ° C or lower.
The Tg of the acrylic resin can be measured by differential scanning calorimetry (DSC).

The carboxy-modified polyvinyl alcohol used in the resin layer of the present invention is a reaction product of polyvinyl alcohol and a polyvalent carboxylic acid such as fumaric acid, phthalic acid anhydride, meritonic acid anhydride, and itaconic acid anhydride, or an esterified product of these reactants. Further, it is obtained as a saponified product of vinyl acetate and an ethylenically unsaturated dicarboxylic acid such as maleic acid, fumaric acid, itaconic acid, crotonic acid, acrylic acid and methacrylic acid. Specifically, for example, the production method exemplified in Example 1 or 4 of JP-A-53-91995 can be mentioned. The degree of saponification of the carboxy-modified polyvinyl alcohol is preferably 72 to 100 mol%, and the degree of polymerization is preferably 500 to 2400, more preferably 1000 to 2000.

When a carboxy-modified polyvinyl alcohol is used in the resin layer of the present invention, an epichlorohydrin-based resin and / or a polyamine / polyamide-based resin (excluding those contained in the epichlorohydrin-based resin) may be used in combination. preferable.

This epichlorohydrin-based resin is a resin characterized by containing an epoxy group in the molecule, and examples thereof include polyamide epichlorohydrin resin and polyamine epichlorohydrin resin. These can be used alone or in combination. Further, as the amine present in the main chain of the epichlorohydrin-based resin, primary to quaternary amines can be used, and there is no particular limitation. Further, since the water resistance is good, the degree of cationization and the molecular weight are preferably 5 meq / g · Solid or less (measured value at pH 7) and a molecular weight of 500,000 or more.
Specific examples of the epichlorohydrin-based resin include violet resin 650 (30), violet resin 675A, violet resin 6615 (manufactured by Sumitomo Chemical Corporation), WS4002, WS4020, WS4024, WS4030, WS4046, WS4010, CP8970. (The above is manufactured by Seiko PMC) and the like.

The polyamine / polyamide resin means a polyamine resin and / or a polyamide resin, and does not include those contained in the above epichlorohydrin resin. Examples of such polyamine / polyamide-based resins include polyamide urea resin, polyalkylene polyamine resin, polyalkylene polyamide resin, polyamine polyurea resin, modified polyamine resin, modified polyamide resin, and poly, which do not have an epoxy group in the molecule. Examples thereof include an alkylene polyamine urea formalin resin and a polyalkylene polyamine polyamide polyurea resin, and these can be used alone or in combination.
Specific examples of such polyamine / polyamide resins include violet resin 302 (manufactured by Sumitomo Chemical Co., Ltd .: polyamine polyurea resin), violet resin 712 (manufactured by Sumitomo Chemical Co., Ltd .: polyamine polyurea resin), and violet resin 703. (Sumitomo Chemical Co., Ltd .: Polyamide Polyurea Resin), Sumire's Resin 636 (Sumitomo Chemical Co., Ltd .: Polyamide Polyurea Resin), Sumire's Resin SPI-100 (Sumitomo Chemical Co., Ltd .: Modified Polyamine Resin), Sumire's Resin SPI- 102A (Sumitomo Chemical Co., Ltd .: modified polyamine resin), Sumire's resin SPI-106N (Sumitomo Chemical Co., Ltd .: modified polyamide resin), Sumire's resin SPI-203 (50) (Sumitomo Chemical Co., Ltd.), Sumire's resin SPI- 198 (manufactured by Sumitomo Chemical Co., Ltd.), Printive A-700 (manufactured by Asahi Kasei Co., Ltd.), Principal A-600 (manufactured by Asahi Kasei Co., Ltd.), PA6500, PA6504, PA6634, PA6638, PA6640, PA6644, PA6646, PA6654, PA6702, PA6704 ( As mentioned above, Starlight PMC Co., Ltd .: Polyalkylene polyamine polyamide polyurea resin) and the like can be mentioned, and these can be used alone or in combination of two or more. Although not particularly limited, it is preferable to use a polyamine-based resin (polyalkylene polyamine resin, polyamine polyurea resin, modified polyamine resin, polyalkylene polyamine urea formalin resin, polyalkylene polyamine polyamide polyurea tree).

As another component in the resin layer of the present invention, a binder (resin) other than the carboxyl group-containing resin can be used in combination as long as the desired performance is not impaired. Examples of binders (resins) other than carboxyl group-containing resins include fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, acetacetylated polyvinyl alcohol, amide-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, butyral-modified polyvinyl alcohol, and olefin-modified polyvinyl. Alcohol, nitrile-modified polyvinyl alcohol, pyrrolidone-modified polyvinyl alcohol, silicone-modified polyvinyl alcohol, other polyvinyl alcohols such as modified polyvinyl alcohol, cellulose derivatives such as hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, acetyl cellulose, oxidized starch, etherified starch, ester Stars such as chemical starch, styrene-maleic anhydride copolymer, styrene-butadiene copolymer, casein, arabia rubber, polyvinyl chloride, polyvinyl acetate, polyacrylamide, polyacrylic acid ester, polyvinyl butyral, polystyrose and them. Examples thereof include copolymers, polyamide resins, silicone resins, petroleum resins, terpene resins, ketone resins, and kumaron resins. These resins may be used alone or in combination of two or more.

The resin layer of the present invention contains the carboxyl group-containing resin in an amount of 10% by weight or more, preferably 15 to 50% by weight, and more preferably 20 to 40% by weight in terms of solid content.
The coating amount of this resin layer can be set to any appropriate value. For example, the coating amount is at 1.0 g / ^{m 2} or more, preferably ^{2.0g / m 2 ~10.0g / m 2} .
The means for coating the pseudo-peeling layer and the resin layer of the present invention is not particularly limited, and coating can be performed according to a well-known and commonly used technique. For example, an off-machine coating machine or an on-machine coating machine equipped with various coaters such as an air knife coater, a rod blade coater, a vent blade coater, a bevel blade coater, a roll coater, and a curtain coater is appropriately selected and used.

As the pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer of the present invention, a known pressure-sensitive adhesive conventionally mainly used for labels can be used. These adhesives are mainly those that exhibit adhesiveness at room temperature (normal temperature adhesive) and those that do not exhibit adhesiveness at room temperature and exhibit adhesiveness when heated (hot melt adhesive, thermal activity). There is an adhesive (delayed tack type adhesive)), and any adhesive may be used for the heat-sensitive recording body label of the present invention, but it is not necessary to use a release paper or the like, and the additive of the present invention. It is preferable to use a heat-active adhesive in the present invention because of the large effect of the above.

Examples of the room temperature adhesive include emulsion-type adhesives such as rubber-based, acrylic-based, and vinyl ether-based adhesives, and solvent-based adhesives. The main components of this pressure-sensitive adhesive are a natural rubber latex graft-copolymerized with a vinyl-based monomer, an acrylic resin obtained by emulsion polymerization of a monomer composed of a (meth) acrylic acid alkyl ester having an alkyl group, and an acrylic acid ester. -Styrene copolymer, acrylic acid ester-methacrylic acid ester-styrene copolymer, ethylene-vinyl acetate copolymer and the like can be mentioned. In addition, this adhesive includes penetrants, film-forming aids, defoamers, rust preventives, thickeners, wetting agents, preservatives, UV absorbers, light stabilizers, pigments, and inorganic fillers, if necessary. Etc. may be blended.

The hot melt adhesive is preferably composed of a thermoplastic resin, a wax, and a tackifier, and melts and becomes liquid when heated to exhibit adhesiveness.
This thermoplastic resin includes ethylene- (meth) acrylic acid copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, α-olefin-maleic anhydride copolymer, and styrene- (meth) acrylic acid. Examples include copolymers.
Waxes include carnauba wax, candelilla wax, montan wax, fatty acids, fatty acid glyceride, polyethylene wax, paraffin wax, microcrystallin wax, Fishertropch wax, polypropylene wax, oxidized wax, and ethylene-acrylic acid copolymer wax. And ethylene-methacrylic acid copolymer wax and the like.
Examples of the tackifier include rosin, rosin derivatives (hydrogen rosin, disproportionated rosin, polymerized rosin, acrylic acid modified rosin, fumaric acid modified rosin, maleic acid modified rosin, and their rosin esters (alcohol, glycerin, pentaerythritol, etc.). (Esterated rosin, etc.)), terpene resin (α-pinene, β-pinene), terpene phenol resin, aromatic-modified terpene resin, hydride terpene resin, aliphatic petroleum resin, aromatic petroleum resin, copolymerization Examples thereof include petroleum resin, alicyclic petroleum resin, kumaron-inden resin, styrene resin, and phenol resin.

The thermoactive pressure-sensitive adhesive (delayed tack type pressure-sensitive adhesive) is composed of a thermoplastic resin, a solid plasticizer, and a pressure-sensitive adhesive, and exhibits adhesiveness when heated.
This thermoplastic resin includes methyl methacrylate (Tg = 105 ° C.), ethyl acrylate (Tg = -22 ° C.), butyl acrylate (Tg = -54 ° C.), 2-ethylhexyl acrylate (Tg = -85 ° C.), and carboxylpoly. Vinyl aromatic compounds such as caprolactone acrylate (Tg = -41 ° C), monohydroxyethyl succinate (Tg = -40 ° C), styrene (Tg = 100 ° C), vinyl chloride (Tg = 80 ° C), vinylidene chloride (Tg = 80 ° C). Vinyl halide such as Tg = -20 ° C, vinyl ester such as vinyl acetate (Tg = 30 ° C), vinyl propionate (Tg = 10 ° C), ethylene (Tg = -125 ° C), butadiene (Tg = -109 ° C). It is a copolymer using olefin-based monomers such as (° C.) and other monomers such as acrylonitrile (Tg = 130 ° C.) alone or in combination of two or more, and may be used by mixing two or more types of thermoplastic resins. It is possible.

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 compound include benzoic acid sucrose, benzoic acid diethylene glycol ester, benzoic acid glyceride, benzoic acid pentaerythrite ester, benzoic acid trimethylol ethane ester, and benzoic acid trimethyl propane ester. Of 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] and triethylene glycol bis [3- (3-t-butyl-4-hydroxy-). 5-Methylphenyl) propionate], triethylene glycol bis [3- (3,5-di-t-butyl-4-hydroxy-phenyl) propionate], 1,6-hexanediolbis [3- (3-t-) Butyl-4-hydroxyphenyl) propionate], 1,6-hexanediolbis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate], 1,6-hexanediolbis [3-( 3,5-Di-t-butyl-4-hydroxyphenyl) propionate], thiobis [ethylene 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] can be mentioned. Among these, triethylene glycol bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate] and 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 types. From the viewpoint of preventing sedimentation and the surface property (smoothness) of the coating layer, the aqueous dispersion of the solid plasticizer should have a dispersion particle size of a certain level or less by a dispersion / crusher such as a ball mill or a handy mill. It is preferable to adjust.

Examples of the tackifier include rosin, hydrogenated rosin and derivatives thereof, rosin-based resin such as resin acid dimer, terpene resin, aromatic-modified terpene resin, hydrogenated terpene resin, and terpene-based resin such as terpene-phenol resin. , An aliphatic petroleum resin, an aromatic petroleum resin, an alicyclic petroleum resin, a styrene resin, a phenol resin and the like. These resins are used alone or in admixture of two or more.
A thickener, a surfactant, an antifoaming agent, a lubricant, a colorant, a pigment and the like may be appropriately added to the heat-active pressure-sensitive adhesive as long as it does not impair the stickiness.

The active temperature of the thermally active pressure-sensitive adhesive used in the present invention is preferably 50 to 100 ° C. The active temperature is the minimum temperature required for the thermally active pressure-sensitive adhesive to develop tackiness, and is a value obtained by measuring the minimum temperature at which the tackiness is developed. If the active temperature is less than 50 ° C., a problem of unintended adhesion between the adhesive layer and the thermal recording layer, so-called blocking, tends to occur during storage or the like. On the other hand, if the temperature exceeds 100 ° C., the heating temperature required to develop the adhesiveness of the heat-active pressure-sensitive adhesive is high, which causes a problem that the heat-sensitive recording layer on the opposite side is also colored.
A thermal tilt tester (for example, manufactured by Toyo Seiki Seisakusho Co., Ltd., settable temperature range of 50 to 250 ° C.) is used to measure the active temperature, and the adhesive-coated surface is applied to the hot plate set to an arbitrary temperature for 5 seconds. After the contact, the lowest temperature at which the development of stickiness was confirmed by touching with a finger was defined as the active temperature.

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

If the amount of the adhesive applied is small, the initial adhesion to the adherend is insufficient, and if it is too large, it is difficult to obtain a smooth coated surface, and the drying property is also lowered. Dry coating amount of cold adhesive is preferably 1 to 30 g / ^{m 2,} more preferably at 2 to 20 g / ^{m 2.} The dry coating amount of the hot melt adhesive is preferably 3 to 20 g / m ² , and more preferably 7 to 15 g / m ² . The dry coating amount of the heat-active pressure-sensitive 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 means for applying the pressure-sensitive adhesive is not particularly limited, and the pressure-sensitive adhesive can be applied according to a well-known conventional technique. Various coaters and laminators are appropriately selected and used.

Further, in the present invention, a release paper may be provided on the adhesive layer. Examples of the release paper include glassine paper, clay coated paper, polyethylene laminated paper, and the like coated with a release agent such as a silicone compound or a fluorine compound.

The peelable laminate of the present invention may be used as it is, but an inkjet recording layer, a heat-sensitive recording layer, etc. At least one various recording layer such as a pressure-sensitive recording layer, a thermal transfer ink receiving layer, or an electrophotographic recording layer may be provided. 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 the base sheet. The inkjet 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 above kaolin, calcium sulfate, barium sulfate, etc. Examples thereof include titanium dioxide, zinc oxide, alumina, magnesium carbonate, magnesium oxide, calcium silicate, bentonite, zeolite, sericite and smectite, and one type or two or more types can be appropriately selected and used.
As the binder, any known binder used for an inkjet recording medium may be used. 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 modified products; casein; gelatin; celluloses such as carboxymethyl cellulose and hydroxyethyl cellulose; polyurethane; vinyl acetate; unsaturated polyester resin and the like, and one or more of them can be appropriately selected and used.
The inkjet recording layer may include sizing agents, fixing agents, pigment dispersants, thickeners, water retention agents, lubricants, defoaming agents, defoaming agents, mold release agents, foaming agents, coloring dyes, and coloring as required. Auxiliary agents such as pigments, fluorescent dyes, preservatives, water resistant agents, surfactants and pH adjusters can be appropriately added.

The blending ratio of the pigment in the inkjet recording layer is 65 to 88 parts by weight, preferably 70 to 80 parts by weight, based on 100 parts by weight of the entire inkjet recording layer (solid content).
It is preferable that the ratio of the binder is 4 parts by weight or more and 35 parts by weight or less with respect to 100 parts by weight of all the pigments contained in the inkjet 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 of providing the inkjet recording layer on the base sheet is not particularly limited, and is limited to a blade coater, a roll coater, an air knife coater, a bar coater, a gate roll coater, a curtain coater, a gravure coater, a flexo gravure coater, and a spray. Off-machine coating machines and on-machine coating machines equipped with various coaters such as coaters and size presses are appropriately selected and used.

Application to thermal recorders:
When applied to a heat-sensitive recording body, a heat-sensitive recording layer is provided on the base sheet, and a protective layer is optionally provided on the heat-sensitive recording layer, and an undercoat layer (under layer) is optionally provided between the base sheet and the heat-sensitive recording layer. An intermediate layer or the like may be provided between the thermal recording layer and the protective layer.
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 color developer (color developer), and optionally a sensitizer, a binder, a pigment, a cross-linking agent, a lubricant, and an image. Stabilizers and other auxiliaries may be included.
As the leuco dye used in the present invention, all known in the field of conventional thermal recording paper can be used, and the leuco dye is not particularly limited, but a triphenylmethane compound, a fluorene compound, a fluorene compound, etc. Dye vinyl compounds and the like are preferable. Specific examples of typical colorless or light-colored leuco dyes (dye precursors) are shown below. Moreover, these leuco dyes may be used alone or in mixture of 2 or more types.

<Triphenylmethane leuco dye>
3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide [also known as crystal violet lactone]; 3,3-bis (p-dimethylaminophenyl) phthalide [also known as malachite green lactone]

<Fluorine leuco dye>
3-diethylamino-6-methylfluorane; 3-diethylamino-6-methyl-7-anilinofluorane; 3-diethylamino-6-methyl-7- (o, p-dimethylanilino) fluorane; 3-diethylamino- 6-Methyl-7-Chlorofluorane; 3-diethylamino-6-methyl-7- (m-trifluoromethylanilino) fluorane; 3-diethylamino-6-methyl-7- (o-chloroanilino) fluorane; 3- Diethylamino-6-methyl-7- (p-chloroanilino) fluorane; 3-diethylamino-6-methyl-7- (o-fluoroanilino) fluorane; 3-diethylamino-6-methyl-7- (m-methylanilino) fluorane 3-Diethylamino-6-methyl-7-n-octylanilinofluorane; 3-diethylamino-6-methyl-7-n-octylaminofluorane; 3-diethylamino-6-methyl-7-benzylaminofluorane 3-Diethylamino-6-methyl-7-dibenzylaminofluorane; 3-diethylamino-6-chloro-7-methylfluorane; 3-diethylamino-6-chloro-7-anilinofluorane; 3-diethylamino- 6-Chloro-7-p-methylanilinofluorane; 3-diethylamino-6-ethoxyethyl-7-anilinofluorane; 3-diethylamino-7-methylfluorane; 3-diethylamino-7-chlorofluorine; 3-Diethylamino-7- (m-trifluoromethylanilino) fluorane; 3-diethylamino-7- (o-chloroanilino) fluorane; 3-diethylamino-7- (p-chloroanilino) fluorane; 3-diethylamino-7- (3-diethylamino-7- ( o-fluoroanilino) fluorane; 3-diethylamino-benzo [a] fluorane; 3-diethylamino-benzo [c] fluorane; 3-dibutylamino-6-methyl-fluorane; 3-dibutylamino-6-methyl-7- Anilinofluolane; 3-dibutylamino-6-methyl-7- (o, p-dimethylanilino) fluorane; 3-dibutylamino-6-methyl-7- (o-chloroanilino) fluorane; 3-dibutylamino- 6-Methyl-7- (p-chloroanilino) fluorane; 3-dibutylamino-6-methyl-7- (o-fluoroanilino) fluorane; 3-dibutylamino-6-methyl-7- (m-) Trifluoromethylanilino) Fluolan; 3-dibutylamino-6-methyl-chlorofluorane; 3-dibutylamino-6-ethoxyethyl-7-anilinofluorane; 3-dibutylamino-6-chloro-7-ani Renofluorane; 3-dibutylamino-6-methyl-7-p-methylanilinofluorane; 3-dibutylamino-7- (o-chloroanilino) fluorane; 3-dibutylamino-7- (o-fluoroanilino) ) Fluolane; 3-di-n-pentylamino-6-methyl-7-anilinofluorane; 3-di-n-pentylamino-6-methyl-7- (p-chloroanilino) fluorane; 3-di-n -Pentylamino-7- (m-trifluoromethylanilino) fluorane; 3-di-n-pentylamino-6-chloro-7-anilinofluorane; 3-di-n-pentylamino-7- (p) -Chloroanilino) fluorane; 3-pyrrolidino-6-methyl-7-anilinofluorane; 3-piperidino-6-methyl-7-anilinofluorane; 3- (N-methyl-N-propylamino) -6- Methyl-7-anilinofluorane; 3- (N-methyl-N-cyclohexylamino) -6-methyl-7-anilinofluorane; 3- (N-ethyl-N-cyclohexylamino) -6-methyl- 7-Anilinofluorane; 3- (N-ethyl-N-xylamino) -6-methyl-7- (p-chloroanilino) fluorane; 3- (N-ethyl-p-toluidino) -6-methyl-7- Anilinofluorane; 3- (N-ethyl-N-isoamylamino) -6-methyl-7-anilinofluoran; 3- (N-ethyl-N-isoamylamino) -6-chloro-7-anilino Fluolan; 3- (N-ethyl-N-tetrahydrofurfurylamino) -6-methyl-7-anilinofluorane; 3- (N-ethyl-N-isobutylamino) -6-methyl-7-anilino Fluoran; 3- (N-ethyl-N-ethoxypropylamino) -6-methyl-7-anilinofluorane; 3-cyclohexylamino-6-chlorofluoran; 2- (4-oxahexyl) -3-3 Dimethylamino-6-methyl-7-anilinofluorane; 2- (4-oxahexyl) -3-diethylamino-6-methyl-7-anilinofluorane; 2- (4-oxahexyl) -3-di Propylamino-6-methyl-7-anili Nofluolane; 2-methyl-6-p- (p-dimethylaminophenyl) aminoanilinofluorane; 2-methoxy-6-p- (p-dimethylaminophenyl) aminoanilinofluorane; 2-chloro-3- Methyl-6-p- (p-Phenylaminophenyl) Aminoanilinofluorane; 2-Chloro-6-p- (p-Dimethylaminophenyl) Aminoanilinofluorane; 2-Nitro-6-p-(p) -Diethylaminophenyl) aminoanilinofluorane; 2-amino-6-p- (p-diethylaminophenyl) aminoanilinofluorane; 2-diethylamino-6-p- (p-diethylaminophenyl) aminoanilinofluorane; 2-Phenyl-6-methyl-6-p- (p-Phenylaminophenyl) aminoanilinofluorane; 2-benzyl-6-p- (p-phenylaminophenyl) aminoanilinofluorane; 2-hydroxy- 6-p- (p-Phenylaminophenyl) aminoanilinofluorane; 3-methyl-6-p- (p-dimethylaminophenyl) aminoanilinofluorane; 3-diethylamino-6-p- (p-diethylamino) Phenyl) aminoanilinofluorane; 3-diethylamino-6-p-(p-dibutylaminophenyl) aminoanilinofluorane; 2,4-dimethyl-6-[(4-dimethylamino) anilino] -fluorane

<Fluorene leuco dye>
3,6,6'-tris (dimethylamino) spiro [fluorene-9,3'-phthalide];3,6,6'-tris (diethylamino) spiro [fluorene-9,3'-phthalide]
<Divinyl leuco dye>
3,3-bis- [2- (p-dimethylaminophenyl) -2- (p-methoxyphenyl) ethenyl] -4,5,6,7-tetrabromophthalide; 3,3-bis- [2- (P-Dimethylaminophenyl) -2- (p-methoxyphenyl) ethenyl] -4,5,6,7-tetrachlorophthalide; 3,3-bis- [1,1-bis (4-pyrrolidinophenyl) ) Ethylene-2-yl] -4,5,6,7-tetrabromophthalide; 3,3-bis- [1- (4-methoxyphenyl) -1- (4-pyrrolidinophenyl) ethylene-2- Il] -4,5,6,7-tetrachlorophthalide

<Others>
3- (4-Diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindole-3-yl) -4-azaphthalide; 3- (4-diethylamino-2-ethoxyphenyl) -3- ( 1-octyl-2-methylindole-3-yl) -4-azaphthalide; 3- (4-cyclohexylethylamino-2-methoxyphenyl) -3- (1-ethyl-2-methylindole-3-yl)- 4-Azaphthalide; 3,3-bis (1-ethyl-2-methylindole-3-yl) phthalide; 3,6-bis (diethylamino) fluoran-γ- (3'-nitro) anilinolactam; 3,6 -Bis (diethylamino) fluorane-γ- (4'-nitro) anilinolactam; 1,1-bis- [2', 2', 2'', 2''-tetrakis- (p-dimethylaminophenyl)- Ethenyl] -2,2-dinitrile ethane; 1,1-bis- [2', 2', 2'', 2''-tetrakis- (p-dimethylaminophenyl) -ethenyl] -2-β-naphthylethane 1,1-bis- [2', 2', 2'', 2''-tetrakis- (p-dimethylaminophenyl) -ethenyl] -2,2-diacetylethane; bis- [2,2,2 ', 2'-Tetrax- (p-dimethylaminophenyl) -ethenyl] -methylmalonic acid dimethyl ester

As the color developer, those known in the field of conventional heat-sensitive recording paper can be used. For example, an inorganic acidic substance such as active white clay, attapulsite, colloidal silica, aluminum silicate, 4,4'-isopropyridende. Phenol, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 4,4'-dihydroxydiphenylsulfide, hydroquinone monobenzyl ether, 4-hydroxybenzo Benzyl acid, 4,4'-dihydroxydiphenylsulfone, 2,4'-dihydroxydiphenylsulfone, 4-hydroxy-4'-isopropoxydiphenylsulfone, 4-hydroxy-4'-n-propoxydiphenylsulfone, bis (3-) Allyl-4-hydroxyphenyl) sulfone, 4-hydroxy-4'-methyldiphenylsulfone, 4-hydroxyphenyl-4′-benzyloxyphenylsulfone, 3,4-dihydroxyphenyl-4′-methylphenylsulfone, 1-[ 4- (4-Hydroxyphenylsulfonyl) phenoxy] -4- [4- (4-isopropoxyphenylsulfonyl) phenoxy] butane, the phenol condensation composition described in JP-A-2003-154760, JP-A-8-59603. Aminobenzenesulfonamide derivative, bis (4-hydroxyphenylthioethoxy) methane, 1,5-di (4-hydroxyphenylthio) -3-oxapentane, bis (p-hydroxyphenyl) butyl acetate, bis (p). -Hydroxyphenyl) Methyl acetate, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,4-bis [α-methyl-α- (4'-hydroxyphenyl) ethyl] benzene, 1,3 -Bis [α-methyl-α- (4'-hydroxyphenyl) ethyl] benzene, di (4-hydroxy-3-methylphenyl) sulfide, 2,2'-thiobis (3-tert-octylphenol), 2,2 '-Thiobis (4-tert-octylphenol), phenolic compounds such as the diphenylsulfone cross-linked compound described in WO97 / 16420, compounds described in WO02 / 081229 or JP-A-2002-301873, and N, N'. Thiouurea compounds such as -di-m-chlorophenylthiourea, p-chlorobenzoic acid, stearyl gallate, bis [4- (n-octyloxycarbonylamino) salicylic acid Zinc] dihydrate, 4- [2- (p-methoxyphenoxy) ethyloxy] salicylic acid, 4- [3- (p-tolylsulfonyl) propyloxy] salicylic acid, 5- [p- (2-p-methoxyphenoxy) Ethoxy) cumil] Aromatic carboxylic acids of salicylic acid, salts of these aromatic carboxylic acids with polyvalent metal salts such as zinc, magnesium, aluminum, calcium, titanium, manganese, tin, nickel, and even zinc thiosocyanate. Examples thereof include antipyrine complexes, composite zinc salts of terephthalaldehyde acids and other aromatic carboxylic acids. These color developeres can be used alone or in combination of two or more. 1- [4- (4-Hydroxyphenylsulfonyl) phenoxy] -4- [4- (4-isopropoxyphenylsulfonyl) phenoxy] butane is available, for example, under the trade name TOMILAC214 manufactured by Mitsubishi Chemical Co., Ltd. The phenol condensation composition described in Kai 2003-154760 is available, for example, under the trade name TOMILAC224 manufactured by Mitsubishi Chemical Co., Ltd., and the diphenyl sulfone cross-linked compound described in International Publication WO 97/16420 is Nippon Soda Co., Ltd. It is available under the trade name D-90. Further, the compound described in WO02 / 081229 etc. is available under trade names NKK-395 and D-100 manufactured by Nippon Soda Corporation.

As the sensitizer, those known in the field of conventional heat-sensitive recording paper can be used. For example, fatty acid amides such as stearate 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-diphenoxyetane, dibenzyl oxalate, shu Di (p-chlorobenzyl) acid, di (p-methylbenzyl) oxalate, dibenzyl terephthalate, benzyl p-benzyloxybenzoate, di-p-tolyl carbonate, phenyl-α-naphthyl carbonate, 1,4-di Ethoxynaphthalene, 1-hydroxy-2-naphthoic acid phenyl ester, o-xylene-bis- (phenyl ether), 4- (m-methylphenoxymethyl) biphenyl, 4,4'-ethylenedioxy-bis-dibenzoate Benzyl ester, dibenzoyloxymethane, 1,2-di (3-methylphenoxy) ethylene, bis [2- (4-methoxy-phenoxy) ethyl] ether, methyl p-nitrobenzoate, phenyl p-toluenesulfonate, etc. However, the present invention is not particularly limited to these. These sensitizers may be used alone or in combination of two or more.

As the binder, those known in the field of conventional heat-sensitive recording paper can be used, for example, water-soluble polymers such as starch, polyvinyl alcohol, methyl cellulose and carboxymethyl cellulose, styrene-butadiene copolymers, and acrylic acid-based binders. Examples thereof 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 cross-linking agent include glioxal, methylol melamine, melamine formaldehyde resin, melamine urea resin, polyamine epichlorohydrin resin, polyamide epichlorohydrin resin, potassium persulfate, ammonium persulfate, sodium persulfate, ferric chloride, and the like. Examples thereof include magnesium chloride, boar sand, 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-based and triazole-based UV absorbers, dispersants, defoamers, and oxidations. Inhibitors, fluorescent dyes, etc. can be used.

The types and amounts of leuco dyes, color developers, sensitizers, 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, but are usually leuco dyes. About 0.5 to 10 parts by weight of the color developer and 0 to 10 parts by weight of the sensitizer are used for 1 part by weight, and the binder is 5 to 50 parts by weight of the heat sensitive recording layer (solid content). About 0 to 50 parts by weight is appropriate for the pigment with respect to 100 parts by weight of the thermal recording layer (solid content).
In the heat-sensitive recorder of the present invention, the leuco dye, the color developer, the sensitizer, and the material to be added as needed are grains of several microns or less by a crusher such as a ball mill, an attritor, a sand glider, or an appropriate emulsifying device. It is atomized to a diameter, and a binder and various additive materials are added depending on the purpose to prepare a coating liquid. Water, alcohol, or the like can be used as the solvent used in this coating liquid, and the solid content thereof is about 20 to 40% by weight. Further, the coating means is not particularly limited, and coating can be performed according to a well-known conventional technique, for example, various coaters such as an air knife coater, a rod blade coater, a bent blade coater, a bevel blade coater, a roll coater, and a curtain coater. Off-machine coating machines and on-machine coating machines equipped with the above are appropriately selected and used.

Application to pressure-sensitive recording media:
When applied to a pressure-sensitive recording medium, a color-developing agent composition containing 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. A developer composition containing an electron-accepting developer (color developer) as a main component, which develops color when in contact with this color former, is applied to one side of the upper paper and the base paper (pressure sensitive recording layer). ), The inner paper coated with the color-developing agent composition on the other surface, and the developer composition coated on one side of the base paper (pressure-sensitive recording layer), and the adhesive layer of the present invention is provided on the other surface. Prepare the paper. These are used in the order of upper paper-middle paper-lower paper or upper paper-lower paper, and the color former reacts with the developer by destroying the capsules in the upper paper by the pressure of the writing pressure or the printer. And develop color.
The capsule is a micro-container in which a core substance such as a liquid or a solid is covered with a film substance such as gelatin, polyurea urethane resin, or urea-formaldehyde resin, and has a size of about 1 to 200 μm. As a method for producing capsules, a core selvation method, an interfacial polymerization method, an in-situ method and the like are 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 the base sheet. A film (ink ribbon) coated with a heat-meltable ink layer containing a color material is heated by heat generated by a thermal head or the like, and the color material is melted, evaporated, and sublimated and transferred to a heat transfer recording layer to obtain a recorded image. be able to.
In addition to pigments and binders, the thermal transfer recording layer may contain dispersants, thickeners, mold release agents, surfactants, viscosity modifiers, flocculants, leveling agents, etc. for the purpose of improving coating suitability. A water resistant agent or the like may be contained in a lubricant, an antistatic agent or the like for the purpose of improving the recording characteristics and 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 base sheet. A recorded image can be obtained by exposing the photoconductor to change the charge on the surface of the photoconductor, adsorbing the toner colored body according to the charge (residual charge), and transferring and fusing the toner to the electrophotographic recording layer. ..
If necessary, the electrophotographic recording layer may contain a release agent or the like in addition to the pigment and the binder. The coating amount of the electrophotographic recording layer is appropriately selected depending on the intended use, but is usually about ² to 40 g / m ² .

The peelable laminate of the present invention can be used as a delivery slip (record slip) used for delivery and management of goods, a record slip used for applying for various insurances and tickets, and the like.

Hereinafter, the present invention will be illustrated in Examples, but it is not intended to limit the present invention. In each of the Examples and Comparative Examples, "parts" indicates "parts by weight" and "%" indicates "% by weight" unless otherwise specified.

The formulations consisting of the following formulations were mixed to prepare coating liquids 1 and 2 for a pseudo-release layer.
Coating liquid for pseudo release layer 1
Aluminum hydroxide dispersion (manufactured by Martinsberg, trade name: Martin Fin OL,
Solid content 50%) 40.0 parts Silicone acrylic resin (manufactured by Nissin Chemical Co., Ltd., trade name: Charine E370,
Solid content 45%) 178.0 parts Water 10.0 parts
Coating liquid for pseudo release layer 2
Aluminum hydroxide dispersion (Martifin OL) 40.0 parts Silicone acrylic resin (Charine E370) 89.0 parts Long-chain alkyl group-containing resin (acrylonitrile / acrylic acid ester copolymer emulsion, manufactured by Chukyo Yushi Co., Ltd., trade name: Resem S-310,
Solid content 37.5%) 107.0 parts Water 10.0 parts

The coating liquids 1 and 2 for the resin layer were prepared by mixing the formulations having the following ratios.
Coating liquid for resin layer 1
Aluminum hydroxide dispersion (Martifin OL) 20.0 parts Acrylic resin (manufactured by Mitsui Chemicals, trade name ASN1004K, solid content 18%)
19.0 parts Zinc stearate (manufactured by Chukyo Yushi Co., Ltd., trade name: Hydrin Z-7-30,
Solid content 30%) 2.0 parts
Coating liquid for resin layer 2
Aluminum hydroxide dispersion (Martifin OL) 20.0 parts carboxy-modified polyvinyl alcohol aqueous solution (manufactured by Kuraray, trade name: KL318,
Solid content 10%) 35.0 parts Polyamide epichlorohydrin resin (manufactured by Seiko PMC, trade name: WS4030,
Solid content 25%) 4.0 parts Polyamide resin (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumirace Resin SPI-106N,
Solid content 45%) 2.0 parts Zinc stearate (Hydrin Z-7-30) 2.0 parts

[Example 1]
On one side of the base sheet (high-quality paper with a basis weight of 54 g / m ² ), the coating liquid 1 for the pseudo-peeling layer is applied by the rod blade method so that the coating amount is 4.0 g / m ^{2 in} terms of solid content. After that, it was dried.
Next, the resin layer coating liquid 1 is applied onto the pseudo-peeling layer by the rod blade method so that the coating amount is 3.0 g / m ^{2 in} terms of solid content, and then dried to obtain a laminate. It was.
[Example 2]
A laminate was produced in the same manner as in Example 1 except that the coating liquid 1 for the pseudo-release layer was changed to the coating liquid 2 for the pseudo-release layer.
[Example 2]
A laminate was produced in the same manner as in Example 1 except that the aluminum hydroxide dispersion was changed to 130.0 parts and the silicone acrylic resin was changed to 78.0 parts in the coating liquid 1 for the pseudo release layer.
[Example 3]
In the pseudo peeling layer coating liquid 1, the aluminum hydroxide dispersion liquid was changed to 100.0 parts, the silicone acrylic resin was changed to 111.0 parts, and the resin layer coating liquid 1 was changed to the resin layer coating liquid 2. A laminate was produced in the same manner as in Example 1 except for the above.

[Example 4]
On a silicone-treated release paper (thickness 0.08 mm), apply a room temperature adhesive (solvent type acrylic adhesive) coating solution mixed in the following ratio so that the dry coating amount is 15 g / m ^2. It was dried and an adhesive sheet was prepared.
<Room temperature adhesive coating liquid>
Butyl acrylate (manufactured by Nacalai Tesque) 98.0 parts Acrylic acid (manufactured by Nippon Catalyst) 1.0 parts Methyl acrylate (manufactured by Kuraray) 1.0 parts Ammonium persulfate 0.5 parts Isocyanate cross-linking agent (manufactured by Nippon Polyurethane) , Coronate L) 3.0 parts Ethyl acetate 30.0 parts Laminated by laminating the laminate prepared in Example 1 and this adhesive sheet so that the resin layer of this laminate and the adhesive layer of the adhesive sheet are in contact with each other. The body was made.
When the release paper was peeled off from this laminate, attached to a separately prepared corrugated cardboard box, and the base material sheet was peeled off, the space between the pseudo release layer and the resin layer was peeled off.

[Comparative Example 1]
In the pseudo-peeling layer coating liquid 1, 800.0 parts of a completely saponified polyvinyl alcohol aqueous solution (PVA117, solid content 10%) was blended in the same manner as in Example 1 except that the silicone acrylic resin was not blended. A laminate was produced.
[Comparative Example 2]
In the coating liquid 1 for the pseudo-release layer, 167.0 parts of styrene-butadiene copolymer latex (manufactured by Nippon Zeon Co., Ltd., trade name: ST5526, solid content 48%) was blended without blending the silicone acrylic resin. Made a laminate in the same manner as in Example 1.
[Comparative Example 3]
Lamination in the same manner as in Example 1 except that 35.0 parts of a completely saponified polyvinyl alcohol aqueous solution (PVA117, solid content 10%) was blended in the resin layer coating liquid 1 without blending an acrylic resin. The body was made.

The laminates prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were evaluated as follows.
<Adhesion of each layer>
With respect to the produced laminate, commercially available copy paper was layered on the resin layer, and a load of 0.3 g / m ² was applied to reciprocate the copy paper 10 times on the resin layer. Then, the adhesiveness of each layer was evaluated according to the following criteria.
〇: Each layer is adhered without any problem.
Δ: One of the layers is peeled off.
X: In particular, the resin layer and the pseudo-peeling layer are peeled off.
<Peeling test>
A cellophane tape having a width of 18 mm was attached onto the resin layer of the produced laminate, and a roller (diameter 10 cm, width 13 cm, weight 2000 g) was reciprocated 5 times on the cellophane tape.
After allowing to stand for 1 hour in a 23 ° C. 50% RH environment, pull the cellophane tape with a tensile force of 4.9 N and a tensile angle of 90 ° using a digital force gauge (manufactured by Nidec Symposium, FGX-2). It was. The evaluation was done as follows:
〇: Peeled between the resin layer and the pseudo-peeling layer.
X: No peeling was observed between the resin layer and the pseudo-peeling layer, and other delamination or layer breakage was observed.
When this evaluation was 〇, the peel strength at the interface between the resin layer and the pseudo peeling layer was measured.
If the peel strength at the interface between the resin layer and the pseudo-peeling layer is 400 gf / 18 mm or less, it can be said that the resin layer can be peeled from the pseudo-peeling layer without any problem.

<Enhancement>
The prepared laminate was placed under the conditions of 50 ° C. and 90% RH for 24 hours and allowed to stand in an environment of 23 ° C. and 50% RH for 1 hour, and then the above evaluation was performed.

The results are shown in the table below.

1 Base sheet 2 Pseudo-release layer 3 Resin layer 4 Adhesive layer 5 Release paper 6 Recording layer

Claims (13)

It is composed of a base sheet, a pseudo-peeling layer laminated on the base sheet, and a resin layer laminated on the pseudo-peeling layer. The pseudo-peeling layer contains a silicone acrylic resin, and the resin layer is a carboxyl group. A peelable laminate containing a containing resin and capable of peeling between the pseudo-peeling layer and the resin layer. The heat-sensitive recorder according to claim 1, wherein the pseudo-release layer further contains a long-chain alkyl group-containing resin. The peelable laminate according to claim 1 or 2, wherein the carboxyl group-containing resin is at least one selected from an acrylic resin and a carboxy-modified polyvinyl alcohol. Any one of claims 1 to 3, wherein the silicone acrylic resin is a silicone acrylic resin obtained by copolymerizing a polyorganosiloxane represented by the following general formula (1) with a (meth) acrylic acid ester. The peelable laminate according to.

(In the formula, R ¹ , R ² and R ³ may be the same or different, respectively, and may contain at least one hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom bonded to a carbon atom. It represents a halogenated hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom, Y represents a radical reactive group, an -SH group, or an organic group having both, and Z ¹ and Z ² are the same, respectively. It may be different or different, a hydrogen atom, an alkyl radical having 1 to 4 carbon atoms, or

(In the formula, R ⁴ and R ⁵ may be the same or different, respectively, and represent a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms, and R ⁶ Represents a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a radical reactive group, an SH group, or an organic group having both of them). It represents an organosilyl group, m represents a positive integer of 10,000 or less, n represents an integer of 1 or more, and R ^{1 to} R ⁶ and Y are different even if they are the same in one molecule. May be good. ) The method according to any one of claims 1 to 5, wherein the amount of the pseudo-peeling layer applied is 1.0 g / m ² or more, and the pseudo-peeling layer contains the silicone acrylic resin in a solid content of 30% by weight or more. Detachable laminate. 5. When the pseudo-release layer contains the long-chain alkyl group-containing resin, the pseudo-release layer contains the silicone acrylic resin and the long-chain alkyl group-containing resin in a total solid content of 40% by weight or more. The peelable laminate according to. The invention according to any one of claims 1 to 6, wherein the coating amount of the resin layer is 1.0 g / m ² or more, and the resin layer contains the carboxyl group-containing resin in an amount of 10% by weight or more in terms of solid content. Detachable laminate. The peelable laminate according to any one of claims 1 to 7, wherein the peel strength between the pseudo peeling layer and the resin layer is 400 gf / 18 mm or less. The peelable laminate according to any one of claims 1 to 8, further comprising an adhesive layer, wherein the adhesive layer is laminated on a surface of the resin layer opposite to the pseudo-peelable layer. The peelable laminate according to claim 9, which has a release paper on the adhesive layer. The peelable laminate according to any one of claims 1 to 10, wherein at least one recording layer is provided on a surface of the base material sheet opposite to the surface on which the pseudo-release layer is provided. The peelable laminate according to claim 11, wherein the recording layer is an inkjet recording layer, a heat-sensitive recording layer, a pressure-sensitive recording layer, a heat transfer ink receiving layer, or an electrophotographic recording layer. A record sheet made of the peelable laminate according to any one of claims 1 to 12.

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