JP7413070B2 - Peelable laminate and record sheet - Google Patents

Description

The present invention relates to a peelable laminate and a record slip , and more particularly, a peelable laminate and a record slip that can be used for record slips used for delivery and management of goods, various insurance and ticket applications, etc. Regarding.

Conventionally, for example, delivery slips (record slips) that are attached to delivered goods have been provided with a heat-sensitive coloring agent layer on the front side and an information recording section, and an adhesive layer and release paper on the back side of the delivery slip. A heat-sensitive color forming agent layer is also provided on the surface side of this release paper to form an information recording section, and this release paper is used as a copy of the delivery slip.
The amount of thermal paper used for delivery slips is increasing as the amount of deliveries increases due to the expansion of mail order usage. Conventionally, three-layer labels (fake adhesive paper such as thermal paper or pressure bonding + strong adhesive release paper) have been widely used for delivery slips (Patent Documents 1 and 2, etc.), but recently, labels that are easier to handle have been used. Pseudo three-layer labels (thermal paper + extrusion laminated resin layer + strong adhesive release paper) are beginning to be used.

JP 11-245542 JP2005-139397

With conventional delivery slips that use a combination of adhesive layer and release paper, the surface of the adhesive layer on the slip becomes sticky after being peeled off, making it difficult to handle the peeled slip. In addition, the manufacturing process for conventional 3-layer labels and pseudo-3-layer labels is complicated, and delivery slips made with 3-layer labels using pseudo-adhesive paper, such as pressure bonding, are not sticky after being peeled off, but when pressure is applied There have been cases where re-adhesion occurs due to oxidation, or there has been a problem of increased peel strength in which the peel strength increases over time, making it difficult to peel, especially in a high temperature and high humidity environment. Further, delivery slips with pseudo three-layer labels produced by lamination have problems such as unstable peel strength, and the peel strength becomes too low, causing the slip to fall off due to friction or the like.

The present inventors have discovered 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. , we have completed the present invention.
That is, the present invention comprises a base sheet, a pseudo-release layer laminated on the base sheet, and a resin layer laminated on the pseudo-release layer, the pseudo-release layer containing a silicone acrylic resin, The present invention is a peelable laminate in which the resin layer contains a carboxyl group-containing resin, and the pseudo-peelable layer and the resin layer are peelable.

FIG. 1 is a diagram showing the structure of a peelable laminate of the present invention. (1) shows a basic structure, (2) shows a structure in which an adhesive layer is optionally provided on a resin layer, and (3) shows a structure in which a recording layer is optionally provided in addition to the structure in (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-release layer laminated on the base sheet, and a resin layer laminated on the pseudo-release layer (see FIG. 1 (1)). By forming the peelable laminate in this order, the layers are usually adhered to each other, but the pseudo-peelable layer and the resin layer can be peeled off. In addition, pseudo-peeling refers to two layers (for example, the pseudo-peelable layer and the resin layer) that adhere to each other under normal usage conditions, but when both layers peel off due to manual pulling, etc., and then the layers are overlapped. This refers to a state in which the two pieces cannot be re-adhered even if they are pressed together.
This peelable laminate may further include an adhesive layer, and this adhesive layer is laminated on the surface of the resin layer opposite to the pseudo peeling layer (see FIG. 1 (2)). A release paper may be provided on the layer. This peelable laminate may further include at least one recording layer on the surface of the base sheet opposite to the surface on which the pseudo-peelable layer is provided (see FIG. 1(3)).
The peel strength between this pseudo peel layer and the resin layer is 400 gf/18 mm or less, preferably 10 to 200 gf/18 mm. If this peel strength is less than 10 gf/18 mm, the adhesion between the pseudo-release layer and the resin layer will be insufficient, and there is a possibility that the resin layer will 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 nonwoven fabric, depending on the quality of the desired application. , but is not particularly limited. Further, a composite sheet obtained by combining these may be used as the base sheet.

The pseudo-release layer of the present invention contains a silicone acrylic resin. In addition to the silicone acrylic resin described above, this pseudo-release layer may contain any other appropriate components as long as the desired performance is not impaired. Other components include binders (resins) other than silicone acrylic resins, pigments, crosslinking agents, and the like.

Any suitable silicone acrylic resin can be used as the silicone acrylic resin. As the silicone acrylic resin, preferably used is a silicone acrylic resin obtained by copolymerizing a polyorganosiloxane represented by the following general formula (1) and a (meth)acrylic acid ester.

［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 formula (1), R ¹ , R ² , and R ³ may be the same or different, and each represents 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, at least one of which is substituted with a halogen atom; Y represents an organic group having a radical reactive group, a -SH group, or both; Z ¹ and Z ² may be the same or different, and are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or

(In formula (2), R ⁴ and R ⁵ may be the same or different, and each represents 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, or an organic group having a radical reactive group or an SH group or both; represents a triorganosilyl group; m represents a positive integer of 10,000 or less; n represents an integer of 1 or more; R ¹ to R ⁶ and Y may each be the same or different in one molecule; good].

In the above general formula (1), R ¹ to R ³ may be the same or different, and represent at least one of 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 substituted with a halogen atom. Specific examples of this hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, and butyl, and aryl groups such as phenyl, tolyl, xylyl, and naphthyl.

In the above general formula (1), Y represents a radically reactive group, a -SH group, or an organic group having both. Specific examples of this radically 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, 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 this 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, and each represents a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms. represent. R ⁶ represents a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or an organic group having a radically reactive group or an SH group or both. Specific examples of these hydrocarbon groups and radically reactive groups include those exemplified by R ¹ to R ³ and Y in the above 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 8,000. 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 or cyclic low molecular weight polyorganosiloxane or alkoxysilane having a functional group as exemplified in this description.

Any suitable (meth)acrylic ester can be used as this (meth)acrylic 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, stearyl (meth)acrylate, alkoxyalkyl (meth)acrylates such as methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, cyclohexyl Examples include (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, and the like. Only one type of this (meth)acrylic acid ester may be used, or two or more types may be used in combination.

The mixing ratio of the polyorganosiloxane represented by the above general formula (1) and the (meth)acrylic acid ester during copolymerization is preferably from 5/95 to 95/5 in terms of weight ratio.

In addition to this (meth)acrylic ester, other monomers that can be copolymerized with this (meth)acrylic ester may be copolymerized. Any suitable monomer can be used as the other monomer copolymerizable with this (meth)acrylic ester. For example, styrene compounds such as styrene, vinyltoluene, and α-methylstyrene; unsaturated nitrites such as acrylonitrile and methacrylonitrile; halogenated olefins such as vinyl chloride and vinylidene chloride; vinyl esters such as vinyl acetate and vinyl propionate; In addition to monomers with one double bond such as unsaturated amides such as acrylamide, methacrylamide, and N-methylolacrylamide, and unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and maleic anhydride, ethylene glycol dimethacrylate, Examples include polyunsaturated monomers such as propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, allyl methacrylate, triallyl cyanurate, and triallyl isocyanurate. The other monomers mentioned above may be used alone or in combination of two or more.

The content of this copolymerizable other monomer is 30% by weight or less based on 100% by weight of the total amount of the above (meth)acrylic acid ester and the above copolymerizable other monomer. It is preferable. In addition, the blending ratio with the polyorganosiloxane represented by the above general formula (1) when performing copolymerization is such that the blending ratio with the total weight of the (meth)acrylic acid ester and the above other monomers is as above. It is sufficient if it is within the range of .

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

This emulsion polymerization can be performed by any suitable method. For example, a method may be mentioned in which a polyorganosiloxane represented by the general formula (1) and a (meth)acrylic acid ester are emulsified and dispersed in water, and polymerized in the presence of a radical polymerization initiator to perform graft copolymerization. As the emulsifier and radical polymerization initiator used in emulsion polymerization, any suitable emulsifier or radical polymerization initiator can be mentioned. A specific method for producing silicone acrylic resin is disclosed in Japanese Patent Publication No. 7-5808. This disclosure is incorporated herein by reference.

As this silicone acrylic resin, a commercially available silicone acrylic resin may be used. For example, the product name "Chaline" 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. It is preferable that the pseudo-peel layer of the present invention contains a long-chain alkyl group-containing resin in addition to the silicone acrylic resin, since the peel strength can be suppressed to a lower level. These long-chain alkyl group-containing resins include long-chain alkyl acrylate copolymers, long-chain alkyl vinyl ester copolymers, long-chain alkyl acrylamide copolymers, long-chain alkyl allyl ester copolymers, and stearyl isocyanate-modified polyvinyl alcohol. Examples include copolymers of alkylated polymers such as polyethylene and long-chain alkyl compounds, and copolymers of polymers such as copolymers of polyethylene and stearamide and long-chain alkyl compounds. The number of carbon atoms in this long-chain alkyl group is preferably 6 or more and 30 or less. Specific examples of long-chain alkyl group-containing resins used in the present invention include Rezem P-677, Rezem S-310, Rezem K-256 (all manufactured by Chukyo Yushi Co., Ltd.), Pearoyl 1010, Pearoyl 406 (all manufactured by Chukyo Yushi Co., Ltd.), (manufactured by Yushi Kogyo Co., Ltd.), etc., and these are not particularly limited, and these may be used alone or in combination of two or more.

Examples of binders other than the silicone acrylic resin and long-chain alkyl group-containing resin include water-soluble resins and/or emulsions of any appropriate 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, and 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 copolymerizable with (meth)acrylic acid (excluding olefins) ), cellulose derivatives such as hydroxyethylcellulose, methylcellulose, ethylcellulose, carboxymethylcellulose, ethylcellulose, and acetylcellulose, starches such as oxidized starch, etherified starch, and esterified starch, styrene-maleic anhydride copolymer, Styrene-butadiene copolymer, casein, gum arabic, polyvinyl chloride, polyvinyl acetate, polyacrylamide, polyacrylic acid ester, polyvinyl butyral, polystyrose and their copolymers, polyamide resin, silicone resin, petroleum resin, terpene resin , ketone resin, coumaron resin, etc. These resins may be used alone or in combination of two or more.

Examples of pigments include aluminum hydroxide, aluminum oxide, aluminum silicate, heavy calcium carbonate, light calcium carbonate, titanium oxide, barium sulfate, silica gel, activated clay, talc, clay, kaolin, calcined kaolin, diatomaceous earth, and white. Examples 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 above pigments may be used alone or in combination of two or more. The content of the pigment may be set to any appropriate value. Among these pigments, talc, clay, kaolin, calcined kaolin, and aluminum hydroxide are preferred because they have good stability in peel strength and surface strength of a pseudo peel layer.

Any appropriate crosslinking agent may be used depending on the type of binder used. Examples of the crosslinking agent include dialdehyde crosslinking agents such as glyoxal, polyaldehyde, and amino-formaldehyde, polyamine crosslinking agents such as polyethyleneamine, polyimine crosslinking agents such as polyethyleneimine, and epoxy resins such as epichlorohydrin resin. Examples include diglycidyl-based crosslinking agents, diglycidyl-based crosslinking agents such as glycerin diglycidyl ether, and zirconium salts such as zirconium ammonium carbonate. These crosslinking agents may be used alone or in combination of two or more. The content of this crosslinking agent can be set to any 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 additives in addition to the binder, pigment, and crosslinking agent described above. Examples of such additives include lubricants, dispersants, antifoaming agents, waterproofing agents, and ultraviolet absorbers. These additives may be used alone or in combination of two or more. The content of these additives can be set to any appropriate value depending on desired characteristics and the like.
The pseudo-release layer may be formed by any suitable method. For example, an aqueous dispersion (coating liquid for a pseudo release layer) containing a binder containing the silicone acrylic resin, a pigment, a crosslinking agent, and other additives as necessary is prepared, and the dispersion is coated and dried. It can be formed by

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, even more preferably 40 to 95% by weight, even more preferably Contains 50 to 90% by weight. In addition, when the above-mentioned long-chain alkyl group-containing resin is blended, the above-mentioned silicone acrylic resin and the above-mentioned long-chain alkyl group-containing resin are combined in a total solid content of 40% by weight or more, preferably 50 to 95% by weight. %, more preferably 60 to 85% by weight. When a long-chain alkyl group is blended, it is contained in a solid content of 10% or more, preferably 20% or more, more preferably 30% or more, based on the silicone acrylic resin.
The coating amount of this pseudo-release layer can be set to any appropriate value. For example, the coating amount is 1.0 g/m ² or more, preferably 2.0 g/m ² to 6.0 g/m ² .

The resin layer of the present invention contains a carboxyl group-containing resin. In addition to the carboxyl group-containing resin, this pseudo-peelable layer may contain any other appropriate components as long as the desired performance is not impaired. Other components include binders (resins) other than carboxyl group-containing resins, pigments, crosslinking 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. is preferably at least one selected from acrylic resins and carboxy-modified polyvinyl alcohols.

The acrylic resin used in the resin layer of the present invention consists of (meth)acrylic acid and monomer components (excluding olefins) copolymerizable with (meth)acrylic acid. (Meth)acrylic acid is preferably blended in an amount of 1 to 10 parts by weight per 100 parts by weight of the acrylic resin.
(Meth)acrylic acid is alkali-soluble and has the property of making an acrylic resin a water-soluble resin by adding a neutralizing agent. By changing the acrylic resin to a water-soluble resin, especially when pigments are contained in the resin layer, the binding to the pigment is significantly improved, forming a resin layer with excellent strength even when containing a large amount of pigment. be able to.
Examples of components copolymerizable with (meth)acrylic acid include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and isobutyl (meth)acrylate. , alkyl acrylate resins such as pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and octyl (meth)acrylate, and epoxy resins, silicone resins, styrene or derivatives thereof. Examples include modified alkyl acrylate resins such as the above-mentioned alkyl acrylate resins, (meth)acrylonitrile, acrylic esters, and hydroxyalkyl acrylic esters, but in particular, (meth)acrylonitrile and/or methyl methacrylate are blended. It is preferable. (Meth)acrylonitrile is preferably blended in an amount of 15 to 70 parts by weight per 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 included, 15 to 18 parts by weight of (meth)acrylonitrile to 100 parts by weight of acrylic resin and 20 to 80 parts by weight of methyl methacrylate to 100 parts by weight of acrylic resin are blended. 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 widely used because they have better heat resistance than non-core-shell type acrylic resins, and when used in coating layers, they have excellent printing runnability, especially stick resistance. However, since the shell portion of the core-shell type acrylic resin has low thermal conductivity, it also has the disadvantage of poor print density and image quality.
On the other hand, normal non-core-shell type acrylic resins have low heat resistance and have the disadvantage of being prone to stick and head scum, but non-core-shell type acrylic resins with a glass transition temperature (Tg) in a specific range Because of its high heat resistance, it is possible to achieve both print density, image quality, and print runnability, which are contradictory to core-shell type acrylic resins.
The glass transition point (Tg) of the acrylic resin in the present invention is preferably higher than 30°C and lower than 100°C. If Tg is 30° C. or lower, water resistance is improved, but heat resistance is low and stick is likely to occur. On the other hand, if the Tg is high, the heat resistance will be good and the stick resistance and scratch resistance will be improved, but if the Tg is too high, the resin layer will become brittle and the water resistance and plasticizer resistance may decrease. More preferably, Tg is higher than 50°C and lower than 95°C.
Note that 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 polyhydric carboxylic acid such as fumaric acid, phthalic anhydride, mellitic anhydride, itaconic anhydride, or an esterified product of these reactants. Furthermore, it is obtained as a saponified copolymer of vinyl acetate and ethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, crotonic acid, acrylic acid, and methacrylic acid. Specifically, for example, the manufacturing method illustrated in Example 1 or 4 of JP-A-53-91995 may be mentioned. Further, 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 2,400, more preferably 1,000 to 2,000.

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

This epichlorohydrin resin is a resin characterized by containing an epoxy group in its molecule, and includes, for example, polyamide epichlorohydrin resin, polyamine epichlorohydrin resin, etc. These can be used alone or in combination. Furthermore, as the amine present in the main chain of the epichlorohydrin resin, primary to quaternary amines can be used, and there are no particular limitations. Furthermore, in order to have good water resistance, the degree of cationization and 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 epichlorohydrin resins include violet resin 650 (30), violet resin 675A, violet resin 6615 (manufactured by Sumitomo Chemical Co., Ltd.), WS4002, WS4020, WS4024, WS4030, WS4046, WS4010, CP8970. (all manufactured by Seiko PMC), etc.

This polyamine/polyamide resin means a polyamine resin and/or a polyamide resin, and does not include those included in the above-mentioned epichlorohydrin resin. Examples of such polyamine/polyamide resins include polyamide urea resins, polyalkylene polyamine resins, polyalkylene polyamide resins, polyamine polyurea resins, modified polyamine resins, modified polyamide resins, and polyamide resins that do not have epoxy groups in their molecules. Examples include alkylene polyamine urea formalin resin, polyalkylene polyamine polyamide polyurea resin, and these can be used alone or in combination.
Specific examples of such polyamine/polyamide-based resins include Sumiraze Resin 302 (manufactured by Sumitomo Chemical Co., Ltd.: polyamine polyurea resin), Sumiraze Resin 712 (manufactured by Sumitomo Chemical Co., Ltd.: polyamine polyurea resin), and Sumiraze Resin 703. (manufactured by Sumitomo Chemical Co., Ltd.: polyamine polyurea resin), Sumiraze Resin 636 (manufactured by Sumitomo Chemical Co., Ltd.: polyamine polyurea resin), Violaze Resin SPI-100 (manufactured by Sumitomo Chemical Co., Ltd.: modified polyamine resin), Violaze Resin SPI- 102A (manufactured by Sumitomo Chemical Co., Ltd.: modified polyamine resin), violet resin SPI-106N (manufactured by Sumitomo Chemical Co., Ltd.: modified polyamide resin), violet resin SPI-203 (50) (manufactured by Sumitomo Chemical Co., Ltd.), violet resin SPI- 198 (manufactured by Sumitomo Chemical Co., Ltd.), Printiv A-700 (manufactured by Asahi Kasei Co., Ltd.), Printiv A-600 (manufactured by Asahi Kasei Co., Ltd.), PA6500, PA6504, PA6634, PA6638, PA6640, PA6644, PA6646, PA6654, PA6702, PA6704 ( The above-mentioned resins include polyalkylene polyamine polyamide polyurea resin manufactured by Seiko PMC, and it is also possible to use these alone or in combination of two or more. Although not particularly limited, it is preferable to use polyamine resins (polyalkylene polyamine resin, polyamine polyurea resin, modified polyamine resin, polyalkylene polyamine urea formalin resin, polyalkylene polyamine polyamide polyurea resin).

As other components in the resin layer of the present invention, binders (resins) other than carboxyl group-containing resins can be used in combination within a range that does not impede desired performance. Binders (resins) other than carboxyl group-containing resins include fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, acetoacetylated polyvinyl alcohol, amide-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, butyral-modified polyvinyl alcohol, and olefin-modified polyvinyl alcohol. Polyvinyl alcohols such as alcohol, nitrile-modified polyvinyl alcohol, pyrrolidone-modified polyvinyl alcohol, silicone-modified polyvinyl alcohol, and other modified polyvinyl alcohols, cellulose derivatives such as hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, acetyl cellulose, oxidized starch, etherified starch, and esters. Starches such as modified starch, styrene-maleic anhydride copolymer, styrene-butadiene copolymer, casein, gum arabic, polyvinyl chloride, polyvinyl acetate, polyacrylamide, polyacrylic acid ester, polyvinyl butyral, polystyrose, and the like. Examples include copolymers of, polyamide resins, silicone resins, petroleum resins, terpene resins, ketone resins, coumaron resins, and the like. These resins may be used alone or in combination of two or more.

The resin layer of the present invention contains this carboxyl group-containing resin in a solid content of 10% by weight or more, preferably 15 to 50% by weight, and more preferably 20 to 40% by weight.
The coating amount of this resin layer can be set to any appropriate value. For example, the coating amount is 1.0 g/m ² or more, preferably 2.0 g/m ² to 10.0 g/m ² .
The means for applying the pseudo-release layer and resin layer of the present invention is not particularly limited, and can be applied according to well-known and commonly used techniques. 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 bent blade coater, a bevel blade coater, a roll coater, and a curtain coater is appropriately selected and used.

As the adhesive contained in the adhesive layer of the present invention, known adhesives conventionally used mainly for labels can be used. There are two main types of adhesives: those that exhibit adhesiveness at room temperature (room temperature adhesives), and those that do not exhibit adhesiveness at room temperature but become adhesive when heated (hot melt adhesives, heat-activated adhesives). There is an adhesive (delayed tack type adhesive)), and any adhesive may be used in the heat-sensitive recording label of the present invention, but there is no need to use release paper etc., and the additive of the present invention It is preferable to use a heat-activated adhesive in the present invention because of its great effect.

Examples of room-temperature adhesives include emulsion-type and solvent-type adhesives such as rubber-based, acrylic-based, and vinyl ether-based adhesives. The main components of this adhesive are natural rubber latex obtained by graft copolymerization of vinyl monomers, acrylic resin obtained by emulsion polymerization of monomers consisting of (meth)acrylic acid alkyl esters having alkyl groups, and acrylic esters. -styrene copolymer, acrylic ester-methacrylic ester-styrene copolymer, ethylene-vinyl acetate copolymer, and the like. This adhesive also contains penetrants, film-forming aids, antifoaming agents, rust preventives, thickeners, wetting agents, preservatives, ultraviolet absorbers, light stabilizers, pigments, and inorganic fillers. etc. may be blended.

The hot-melt adhesive is preferably one that is composed of a thermoplastic resin, a wax, and a tackifier, and that melts into a liquid state and exhibits tackiness when heated.
This thermoplastic resin includes ethylene-(meth)acrylic acid copolymer, (meth)acrylic acid-(meth)acrylic acid ester copolymer, α-olefin-maleic anhydride copolymer, styrene-(meth)acrylic acid Examples include copolymers.
Waxes include carnauba wax, candelilla wax, montan wax, fatty acids, fatty acid glycerides, polyethylene wax, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polypropylene wax, waxes obtained by oxidizing these waxes, and ethylene-acrylic acid copolymer wax. and ethylene-methacrylic acid copolymer wax.
Tackifiers include rosin, rosin derivatives (hydrogenated 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.). esterified rosin, etc.), terpene resins (α-pinene, β-pinene), terpene phenol resins, aromatic modified terpene resins, hydrogenated terpene resins, aliphatic petroleum resins, aromatic petroleum resins, copolymer resins Examples include petroleum resins, alicyclic petroleum resins, coumaron-indene resins, styrene resins, and phenolic resins.

A heat-activated adhesive (delayed tack type adhesive) is composed of a thermoplastic resin, a solid plasticizer, and a tackifier, and develops tackiness 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), carboxypolymer Vinyl aromatic compounds such as caprolactone acrylate (Tg = -41°C), succinic acid monohydroxyethyl acrylate (Tg = -40°C), styrene (Tg = 100°C), vinyl chloride (Tg = 80°C), vinylidene chloride ( Vinyl halides such as Tg = -20°C), vinyl esters such as vinyl acetate (Tg = 30°C) and vinyl propionate (Tg = 10°C), ethylene (Tg = -125°C), butadiene (Tg = -109 It is a copolymer that uses olefinic monomers such as olefin monomers (Tg = 130°C) and other monomers such as acrylonitrile (Tg = 130°C) alone or two or more types, and can also be used as a mixture of two or more types of thermoplastic resins. It is possible.

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

Examples of the hindered phenol ester compound include triethylene glycol bis[3-(3-t-butyl-4-hydroxyphenyl)propionate], triethylene glycol bis[3-(3-t-butyl-4-hydroxy- 5-methylphenyl)propionate], triethylene glycol bis[3-(3,5-di-t-butyl-4-hydroxy-phenyl)propionate], 1,6-hexanediol bis[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] and thiobis[ethylene 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]. Among these, triethylene glycol bis[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate], 1,6-hexanediol bis[3-(3,5-di-t- butyl-4-hydroxyphenyl)propionate] and thiobis[ethylene 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] are particularly preferably used.
These solid plasticizers can also be used as a mixture of two or more types. In addition, in order to prevent sedimentation and improve the surface properties (smoothness) of the coating layer, the aqueous dispersion of the solid plasticizer is processed using a dispersion/pulverizing machine such as a ball mill or handy mill so that the dispersed particle size is below a certain level. Adjustment is preferred.

Examples of the tackifier include rosin, hydrogenated rosin and their derivatives, rosin resins such as resin acid dimers, terpene resins, aromatic modified terpene resins, hydrogenated terpene resins, and terpene-phenol resins. , aliphatic petroleum resins, aromatic petroleum resins, alicyclic petroleum resins, styrene resins, phenolic resins, and the like. These resins may be used alone or in combination of two or more.
This heat-activated adhesive may further contain thickeners, surfactants, antifoaming agents, lubricants, colorants, pigments, etc., as long as they do not impede the adhesive properties.

The activation temperature of the heat-activated adhesive used in the present invention is preferably 50 to 100°C. The activation temperature is the lowest temperature required for a heat-activated adhesive to develop tackiness, and is a value obtained by measuring the lowest temperature at which tackiness is developed. If the activation temperature is less than 50° C., problems such as unintended adhesion between the adhesive layer and the heat-sensitive recording layer, so-called blocking, tend to occur during storage. On the other hand, if the temperature exceeds 100° C., the heating temperature required to develop the tackiness of the heat-activated adhesive is high, causing the problem that color develops even to the heat-sensitive recording layer on the opposite side.
In addition, to measure the activation temperature, use a thermal gradient tester (for example, manufactured by Toyo Seiki Seisakusho Co., Ltd., settable temperature range 50 to 250 degrees Celsius), and place the adhesive-coated surface on a hot plate set at an arbitrary temperature for 5 seconds. After contact, the lowest temperature at which the development of tackiness was confirmed when touched with a finger was defined as the activation temperature.

In the heat-activated adhesive used in the present invention, the thermoplastic resin, solid plasticizer, and tackifier can be appropriately selected and used so that the activation temperature is 50 to 100°C. Further, the weight ratio of the solid content of the thermoplastic resin, solid plasticizer, and tackifier is preferably thermoplastic resin: solid plasticizer: tackifier = 15 to 45: 45 to 75: 5 to 25.
Specific examples of the heat-activated 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, active temperature: 70°C), Ecobrid TM- 1 (manufactured by Daicel Finechem, active temperature: 100°C), Ecobrid S-1 (manufactured by Daicel Finechem, active temperature: 90°C), Ecobrid TM-100 (manufactured by Daicel Finechem, active temperature: 70°C), Ecobrid 5635 (manufactured by Daicel Finechem, active temperature: 70°C), Ecobrid 5640 (manufactured by Daicel Finechem, active temperature: 70°C), Dick Seal DLA-820K (manufactured by Dainippon Ink, active temperature: 80°C) , Dick Seal ED-920K (manufactured by Dainippon Ink Co., Ltd., activation temperature: 90° C.).

If the coating amount of the adhesive is too small, the initial adhesion to the adherend will be insufficient, and if it is too large, it will be difficult to obtain a smooth coated surface and the drying properties will also be reduced. The dry coating amount of the room temperature adhesive is preferably 1 to 30 g/m ² , more preferably 2 to 20 g/m ² . The dry coating weight of the hot melt adhesive is preferably 3 to 20 g/m ² , more preferably 7 to 15 g/m ² . The dry coating weight of the heat-activated adhesive is preferably 5 to 50 g/m ² , more preferably 8 to 30 g/m ² , particularly preferably 10 to 20 g/m ² .
The means for applying the adhesive is not particularly limited, and can be applied according to well-known and commonly used techniques. 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 laminate paper, etc. 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 is, but depending on the application and recording method, an inkjet recording layer, a heat-sensitive recording layer, At least one of various recording layers 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 a base sheet. An inkjet recording layer usually contains a pigment and a binder.
As the pigment, inorganic pigments and organic pigments are 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, Examples include titanium dioxide, zinc oxide, alumina, magnesium carbonate, magnesium oxide, calcium silicate, bentonite, zeolite, sericite, and smectite, and one or more of them can be appropriately selected and used.
As the binder, any known binder used in inkjet recording media may be used. Examples of binders include starches such as oxidized starch, etherified starch, and esterified starch; latex such as styrene-butadiene copolymer (SB) latex and acrylonitrile-butadiene copolymer (NB) latex; polyvinyl alcohol; Examples include modified products thereof; casein; gelatin; celluloses such as carboxymethyl cellulose and hydroxyethyl cellulose; polyurethane; vinyl acetate; unsaturated polyester resins; one type or two or more types can be appropriately selected and used.
The inkjet recording layer also contains sizing agents, fixing agents, pigment dispersants, thickeners, water retention agents, lubricants, antifoaming agents, foam inhibitors, mold release agents, foaming agents, coloring dyes, and coloring agents as necessary. Auxiliary agents such as pigments, fluorescent dyes, preservatives, waterproofing agents, surfactants, and pH adjusters can be added as appropriate.

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).
The proportion of the binder is preferably 4 parts by weight or more and 35 parts by weight or less with respect to a total of 100 parts by weight of all pigments contained in the inkjet recording layer.
The coating amount of the inkjet recording layer is usually 1 to 40 g/m ² per side, preferably 3 g/m ² or more and less than 30 g/m ² per side.
The method for forming the inkjet recording layer on the base sheet is not particularly limited, and includes a blade coater, roll coater, air knife coater, bar coater, gate roll coater, curtain coater, gravure coater, flexogravure coater, and 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 recording medium:
When applied to a heat-sensitive recording material, a heat-sensitive recording layer is provided on a base sheet, and optionally a protective layer is provided on the heat-sensitive recording layer, an undercoat layer (under layer) is provided between the base sheet and the heat-sensitive recording layer, An intermediate layer or the like may be provided between the heat-sensitive recording layer and the protective layer.
The coating amount of the heat-sensitive recording layer is usually about 2 to 12 g/m ² , the protective layer is usually about 1 to 5 g/m ² , and the undercoat layer is usually about 1 to 20 g/m ² .

The heat-sensitive recording layer essentially contains an electron-donating leuco dye (leuco dye) and an electron-accepting color developer (color developer), and optionally contains a sensitizer, binder, pigment, crosslinking agent, lubricant, and image forming agent. It may also contain stabilizers and other auxiliaries.
As the leuco dye used in the present invention, all those known in the field of conventional thermal recording paper can be used, and there are no particular limitations, such as triphenylmethane compounds, fluoran compounds, fluorene compounds, Divinyl compounds and the like are preferred. Specific examples of typical colorless to light-colored leuco dyes (dye precursors) are shown below. Further, these leuco dyes may be used alone or in combination of two or more.

<Triphenylmethane-based 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]

<Fluorane-based 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-chlorofluoran; 3-diethylamino-6-methyl-7-(m-trifluoromethylanilino)fluoran; 3-diethylamino-6-methyl-7-(o-chloroanilino)fluoran; 3- Diethylamino-6-methyl-7-(p-chloroanilino)fluoran; 3-diethylamino-6-methyl-7-(o-fluoroanilino)fluoran; 3-diethylamino-6-methyl-7-(m-methylanilino)fluoran ; 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-chlorofluorane; 3-diethylamino-7-(m-trifluoromethylanilino)fluorane; 3-diethylamino-7-(o-chloroanilino)fluorane; 3-diethylamino-7-(p-chloroanilino)fluorane; 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- Anilinofluoran; 3-dibutylamino-6-methyl-7-(o,p-dimethylanilino)fluoran; 3-dibutylamino-6-methyl-7-(o-chloroanilino)fluoran; 3-dibutylamino- 6-Methyl-7-(p-chloroanilino)fluoran; 3-dibutylamino-6-methyl-7-(o-fluoroanilino)fluoran; 3-dibutylamino-6-methyl-7-(m-trifluoromethyl 3-dibutylamino-6-methyl-chlorofluoran; 3-dibutylamino-6-ethoxyethyl-7-anilinofluoran; 3-dibutylamino-6-chloro-7-anilinofluoran ; 3-dibutylamino-6-methyl-7-p-methylanilinofluorane; 3-dibutylamino-7-(o-chloroanilino)fluoran; 3-dibutylamino-7-(o-fluoroanilino)fluoran; 3-di-n-pentylamino-6-methyl-7-anilinofluorane; 3-di-n-pentylamino-6-methyl-7-(p-chloroanilino)fluoran; 3-di-n-pentylamino -7-(m-trifluoromethylanilino)fluorane; 3-di-n-pentylamino-6-chloro-7-anilinofluorane; 3-di-n-pentylamino-7-(p-chloroanilino) Fluoran; 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-ani Linofluorane; 3-(N-ethyl-N-xylamino)-6-methyl-7-(p-chloroanilino)fluoran; 3-(N-ethyl-p-toluidino)-6-methyl-7-anilinofluoran Orane; 3-(N-ethyl-N-isoamylamino)-6-methyl-7-anilinofluorane; 3-(N-ethyl-N-isoamylamino)-6-chloro-7-anilinofluorane; 3-(N-ethyl-N-tetrahydrofurfurylamino)-6-methyl-7-anilinofluorane; 3-(N-ethyl-N-isobutylamino)-6-methyl-7-anilinofluorane; 3-(N-ethyl-N-ethoxypropylamino)-6-methyl-7-anilinofluorane; 3-cyclohexylamino-6-chlorofluorane; 2-(4-oxahexyl)-3-dimethylamino- 6-Methyl-7-anilinofluorane; 2-(4-oxahexyl)-3-diethylamino-6-methyl-7-anilinofluorane; 2-(4-oxahexyl)-3-dipropylamino- 6-Methyl-7-anilinofluorane; 2-methyl-6-p-(p-dimethylaminophenyl)aminoanilinofluorane; 2-methoxy-6-p-(p-dimethylaminophenyl)aminoanilino Fluoran; 2-chloro-3-methyl-6-p-(p-phenylaminophenyl)aminoanilinofluoran; 2-chloro-6-p-(p-dimethylaminophenyl)aminoanilinofluoran; 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)amino Anilinofluoran; 2-hydroxy-6-p-(p-phenylaminophenyl)aminoanilinofluoran; 3-methyl-6-p-(p-dimethylaminophenyl)aminoanilinofluoran; 3-diethylamino -6-p-(p-diethylaminophenyl)aminoanilinofluorane; 3-diethylamino-6-p-(p-dibutylaminophenyl)aminoanilinofluorane; 2,4-dimethyl-6-[(4- dimethylamino)anilino]-fluorane

<Fluorene-based 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- ]-4,5,6,7-tetrachlorophthalide

<Others>
3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide; 3-(4-diethylamino-2-ethoxyphenyl)-3-( 1-octyl-2-methylindol-3-yl)-4-azaphthalide; 3-(4-cyclohexylethylamino-2-methoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)- 4-Azaphthalide; 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide; 3,6-bis(diethylamino)fluoran-γ-(3'-nitro)anilinolactam; 3,6 -bis(diethylamino)fluoran-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-naphthoylethane ; 1,1-bis-[2',2',2'',2''-tetrakis-(p-dimethylaminophenyl)-ethenyl]-2,2-diacetylethane; bis-[2,2,2 ',2'-tetrakis-(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, such as activated clay, attapulgite, colloidal silica, inorganic acidic substances such as aluminum silicate, and 4,4'-isopropylidene difluoride. Phenol, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 4,4'-dihydroxydiphenyl sulfide, hydroquinone monobenzyl ether, 4-hydroxybenzoin 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'-methyldiphenyl sulfone, 4-hydroxyphenyl-4'-benzyloxyphenylsulfone, 3,4-dihydroxyphenyl-4'-methylphenyl sulfone, 1-[ 4-(4-hydroxyphenylsulfonyl)phenoxy]-4-[4-(4-isopropoxyphenylsulfonyl)phenoxy]butane, phenol condensation composition described in JP-A-2003-154760, JP-A-8-59603 The aminobenzenesulfonamide derivatives described, bis(4-hydroxyphenylthioethoxy)methane, 1,5-di(4-hydroxyphenylthio)-3-oxapentane, bis(p-hydroxyphenyl)butyl acetate, bis(p-hydroxyphenylthio)-butyl -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 diphenylsulfone crosslinked compounds described in WO97/16420, compounds described in WO02/081229 or JP2002-301873, and N,N' - Thiourea compounds such as di-m-chlorophenylthiourea, p-chlorobenzoic acid, stearyl gallate, bis[4-(n-octyloxycarbonylamino)zinc salicylate] dihydrate, 4-[2-(p - Aromatic carboxylic acids such as methoxyphenoxy)ethyloxy]salicylic acid, 4-[3-(p-tolylsulfonyl)propyloxy]salicylic acid, 5-[p-(2-p-methoxyphenoxyethoxy)cumyl]salicylic acid, and these Salts of aromatic carboxylic acids with polyvalent metal salts such as zinc, magnesium, aluminum, calcium, titanium, manganese, tin, and nickel, as well as antipyrine complexes of zinc thiocyanate, terephthalaldehydic acid, and other aromatic carboxylic acids. Composite zinc salts and the like can be mentioned. These color developers 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 Corporation. The phenol condensation composition described in Publication No. 2003-154760 is available, for example, under the trade name TOMILAC224 manufactured by Mitsubishi Chemical Corporation, and the diphenylsulfone crosslinked compound described in International Publication No. WO 97/16420 is available from Nippon Soda Co., Ltd. It is available under the trade name D-90. Furthermore, the compounds described in WO02/081229 and the like are available as trade names NKK-395 and D-100 manufactured by Nippon Soda Co., Ltd.

As the sensitizer, those known in the field of conventional heat-sensitive recording paper can be used, such as fatty acid amides such as stearic acid amide and palmitic acid amide, ethylene bisamide, montanic acid wax, polyethylene wax, 2-di-(3-methylphenoxy)ethane, p-benzylbiphenyl, β-benzyloxynaphthalene, 4-biphenyl-p-tolyl ether, m-terphenyl, 1,2-diphenoxyethane, 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-dibenzyl Ethoxynaphthalene, 1-hydroxy-2-naphthoic acid phenyl ester, o-xylene-bis-(phenyl ether), 4-(m-methylphenoxymethyl)biphenyl, 4,4'-ethylenedioxy-bis-benzoic acid di Benzyl ester, dibenzoyloxymethane, 1,2-di(3-methylphenoxy)ethylene, bis[2-(4-methoxy-phenoxy)ethyl]ether, methyl p-nitrobenzoate, phenyl p-toluenesulfonate, etc. Examples include, but are not particularly limited to. These sensitizers may be used alone or in combination of two or more.

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

Examples of the crosslinking agent include glyoxal, methylolmelamine, melamine formaldehyde resin, melamine urea resin, polyamine epichlorohydrin resin, polyamide epichlorohydrin resin, potassium persulfate, ammonium persulfate, sodium persulfate, ferric chloride, Examples include magnesium chloride, borax, boric acid, alum, ammonium chloride, and the like.
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 ultraviolet absorbers, dispersants, antifoaming agents, oxidizing 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. Approximately 0.5 to 10 parts by weight of the color developer and 0 to 10 parts by weight of the sensitizer are used per 1 part by weight, and the binder has a solid content of 5 to 50 parts per 100 parts by weight of the heat-sensitive recording layer (solid content). Approximately 0 to 50 parts by weight of the pigment is suitable as a solid content per 100 parts by weight of the heat-sensitive recording layer (solid content).
In the heat-sensitive recording material of the present invention, the leuco dye, color developer, sensitizer, and materials added as necessary are processed into particles of several microns or less by a pulverizer such as a ball mill, attritor, or sand glider, or by a suitable emulsifier. The particles are atomized to a small diameter, and a binder and various additive materials are added depending on the purpose to prepare a coating liquid. As the solvent used in this coating liquid, water, alcohol, etc. can be used, and the solid content thereof is about 20 to 40% by weight. Furthermore, the coating method is not particularly limited, and coating can be performed according to well-known and commonly used techniques, such as various coaters such as an air knife coater, rod blade coater, bent blade coater, bevel blade coater, roll coater, and curtain coater. An off-machine coating machine or an on-machine coating machine equipped with this is appropriately selected and used.

Application to pressure sensitive recording media:
When applied to pressure-sensitive recording media, a color former composition whose main component is a capsule containing an oily substance in which an electron-donating leuco dye (leuco dye) or the like is dissolved is usually coated on one side of the base paper. A color developer composition containing an electron-accepting color developer (color developer) as a main component that develops a color when it comes into contact with the color former is applied to the top paper and one side of the base paper (pressure-sensitive recording layer). ), an inner paper coated with a color former composition on the other side, a base paper coated with a color developer composition on one side (pressure-sensitive recording layer), and an adhesive layer of the present invention on the other side. Prepare paper. These are used in combination in the order of top paper - middle paper - bottom paper or top paper - bottom paper, and by destroying the capsules in the top paper with pressure from a pen or printer, the color forming agent reacts with the color developer. to develop color.
Capsules are microscopic containers in which a core material such as liquid or solid is covered with a membrane material such as gelatin, polyurea urethane resin, or urea-formaldehyde resin, and has a size of approximately 1 to 200 μm. As a method for manufacturing capsules, a coacervation method, an interfacial polymerization method, an in-situ method, etc. are used.

Application to thermal transfer recording media:
When applied to a thermal transfer recording medium, a thermal transfer recording layer mainly consisting of a pigment and a binder is provided on a base sheet. A film (ink ribbon) coated with a heat-melting ink layer containing a coloring material is heated by heat generated by a thermal head, etc., and the coloring material is melted, evaporated, sublimated, and transferred to a thermal 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, release agents, surfactants, viscosity modifiers, flocculants, leveling agents, etc. in order to improve coating suitability, as necessary. A lubricant, an antistatic agent, and the like may be included for the purpose of improving recording characteristics and transportability of the recording medium.

Application to electrophotographic recording media:
When applied to an electrophotographic recording medium, an electrophotographic recording layer consisting mainly of a pigment and a binder is provided on a base sheet. A recorded image can be obtained by exposing the photoreceptor to light to change the charge on the surface of the photoreceptor, adsorbing the colored toner according to the charge (residual charge), and transferring and fusing it to the electrophotographic recording layer. .
The electrophotographic recording layer may contain a release agent and the like in addition to the pigment and the binder, if necessary. The coating amount of the electrophotographic recording layer is appropriately selected depending on the application, but is usually about 2 to 40 g/m ² .

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

EXAMPLES The present invention will be illustrated below with examples, but they are not intended to limit the present invention. In each of the Examples and Comparative Examples, "part" means "part by weight" and "%" means "% by weight" unless otherwise specified.

Coating liquids 1 and 2 for pseudo release layer were prepared by mixing the following formulations.
Coating liquid 1 for pseudo release layer
Aluminum hydroxide dispersion (manufactured by Martinsberg, product name: Martinfin OL,
Solid content 50%) 40.0 parts Silicone acrylic resin (manufactured by Nissin Chemical Co., Ltd., product name: Charine E370,
Solid content 45%) 178.0 parts Water 10.0 parts
Coating liquid 2 for pseudo release layer
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., product name: Rethem S-310,
Solid content 37.5%) 107.0 parts Water 10.0 parts

Coating liquids 1 and 2 for resin layer were prepared by mixing formulations having the following proportions.
Coating liquid 1 for resin layer
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., product name: Hydrin Z-7-30,
Solid content 30%) 2.0 parts
Coating liquid 2 for resin layer
Aluminum hydroxide dispersion (Martifin OL) 20.0 parts Carboxy-modified polyvinyl alcohol aqueous solution (manufactured by Kuraray Co., Ltd., product name: KL318,
Solid content 10%) 35.0 parts Polyamide epichlorohydrin resin (manufactured by Seiko PMC, product name: WS4030,
Solid content: 25%) 4.0 parts Polyamide resin (manufactured by Sumitomo Chemical Co., Ltd., product name: Sumiraze Resin SPI-106N,
Solid content 45%) 2.0 parts Zinc stearate (Hydrin Z-7-30) 2.0 parts

[Example 1]
Coating liquid 1 for pseudo release layer was applied to one side of a base sheet (high-quality paper with a basis weight of 54 g/m ² ) using a rod blade method so that the solid content was 4.0 g/m ² . After that, it was dried.
Next, resin layer coating liquid 1 was applied onto this pseudo-release layer using a rod blade method so that the coating amount was 3.0 g/ ^m2 in terms of solid content, and then dried to obtain a laminate. Ta.
[Example 2]
A laminate was produced in the same manner as in Example 1, except that Coating Liquid 1 for pseudo-release layer was changed to Coating Liquid 2 for 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 Coating Liquid 1 for Pseudo Peeling Layer.
[Example 3]
In Coating Liquid 1 for pseudo release layer, the aluminum hydroxide dispersion was changed to 100.0 parts, the silicone acrylic resin was changed to 111.0 parts, and Coating Liquid 1 for resin layer was changed to Coating Liquid 2 for resin layer. A laminate was produced in the same manner as in Example 1 except for the following.

[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 ratio below so that the dry coating amount is 15 g/ ^m2 . The adhesive sheet was prepared by processing and drying.
<Room temperature adhesive coating liquid>
Butyl acrylate (manufactured by Nacalai Tesque Co., Ltd.) 98.0 parts Acrylic acid (manufactured by Nippon Shokubai Co., Ltd.) 1.0 parts Methyl acrylate (manufactured by Kuraray Co., Ltd.) 1.0 parts Ammonium persulfate 0.5 parts Isocyanate-based crosslinking agent (manufactured by Nippon Polyurethane Co., Ltd.) , Coronate L) 3.0 parts Ethyl acetate 30.0 parts The laminate prepared in Example 1 and this adhesive sheet were laminated together so that the resin layer of this laminate and the adhesive layer of the adhesive sheet were in contact with each other. The body was created.
When the release paper was peeled off from this laminate, it was pasted on a separately prepared cardboard box, and the base sheet was peeled off, the pseudo release layer and the resin layer were separated.

[Comparative example 1]
Coating liquid 1 for pseudo release layer was prepared in the same manner as in Example 1, except that 800.0 parts of a fully saponified polyvinyl alcohol aqueous solution (PVA117, solid content 10%) was blended without silicone acrylic resin. A laminate was produced.
[Comparative example 2]
In coating liquid 1 for pseudo release layer, no silicone acrylic resin was blended, and 167.0 parts of styrene-butadiene copolymer latex (manufactured by Nippon Zeon Co., Ltd., trade name: ST5526, solid content 48%) was blended. A laminate was produced in the same manner as in Example 1.
[Comparative example 3]
Lamination was carried out 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 Coating Solution 1 for resin layer without blending the acrylic resin. The body was created.

The following evaluations were performed on the laminates produced in Examples 1 to 4 and Comparative Examples 1 to 3.
<Adhesiveness of each layer>
Regarding the produced laminate, commercially available copy paper was placed on the resin layer, and the copy paper was moved back and forth on the resin layer 10 times under a load of 0.3 g/m ² . Thereafter, the adhesion of each layer was evaluated based on the following criteria.
○: Each layer is adhered without any problem.
Δ: One of the layers peeled off.
×: Peeling occurs especially between the resin layer and the pseudo-peelable layer.
<Peeling test>
Regarding the produced laminate, cellophane tape with a width of 18 mm was pasted on the resin layer, and a roller (diameter 10 cm, width 13 cm, weight 2000 g) was made to reciprocate 5 times on the cellophane tape.
After standing for 1 hour in an environment of 23°C and 50% RH, the cellophane tape was pulled using a digital force gauge (Nidec-Shimpo, FGX-2) at a tensile force of 4.9 N and a tensile angle of 90°. Ta. The evaluation was performed as follows:
○: Peeling occurred between the resin layer and the pseudo peeling layer.
×: No peeling occurred between the resin layer and the pseudo-peelable layer, and other interlayer peeling or layer destruction was observed.
When this evaluation was 0, the peel strength at the interface between the resin layer and the pseudo peel layer was measured.
If the peel strength at the interface between the resin layer and the pseudo-release layer is 400 gf/18 mm or less, it can be said that the resin layer can be peeled off from the pseudo-release layer without any problem.

<Acceleration>
The produced laminate was placed under the conditions of 50° C. and 90% RH for 24 hours, and left standing under the conditions 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)

Consisting of a base sheet, a pseudo-release layer laminated on the base sheet, and a resin layer laminated on the pseudo-release layer, the pseudo-release layer contains a silicone acrylic resin, and the resin layer contains a carboxyl group. A peelable laminate, which contains a resin, and in which the pseudo-peelable layer and the resin layer are peelable. The peelable laminate according to claim 1, wherein the pseudo-peelable 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 acrylic resins and carboxy-modified polyvinyl alcohols. 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) and a (meth)acrylic acid ester. The peelable laminate described in .

(In the formula, R ¹ , R ² and R ³ may be the same or different, and represent at least one of 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 substituted with a halogen atom, Y represents a radically reactive group or an organic group having -SH group, or both, Z ¹ and Z ² are each the same may be different from each other, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or

(In the formula, R ⁴ and R ⁵ may be the same or different, and each represents 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, or an organic group having a radical reactive group or an SH group or both. represents an organosilyl group, m represents a positive integer of 10,000 or less, n represents an integer of 1 or more, and in one molecule, R ¹ to R ⁶ and Y may be the same or different; Good too. ) According to any one of claims 1 to 4 , the coating amount of the pseudo release layer is 1.0 g/m ² or more, and the pseudo release layer contains the silicone acrylic resin in a solid content of 30% by weight or more. Peelable laminate. 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 described in . The resin layer 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 a solid content of 10% by weight or more. Peelable laminate. The peelable laminate according to any one of claims 1 to 7, wherein the peel strength between the pseudo peel 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, and the adhesive layer is laminated on a surface of the resin layer opposite to the pseudo peeling layer. The peelable laminate according to claim 9, further comprising 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 sheet opposite to the surface on which the pseudo peeling 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 thermal transfer ink-receiving layer, or an electrophotographic recording layer. A record slip comprising the peelable laminate according to any one of claims 1 to 12.

Images