JPH022056A - Pressure-sensitive copy adhesive sheet - Google Patents

Abstract

PURPOSE:To obtain a pressure-sensitive copy adhesive sheet excellent in durability by bonding a transfer sheet, which is formed by coating a support with a microcapsule containing a dye and/or color pigment and a release agent, to a receiving sheet wherein a receiving part and an adhesive layer are provided to the rear of a transparent sheet. CONSTITUTION:A receiving sheet 4 and a transfer sheet 8 are bonded by an adhesive layer 3. When usual wood free paper 9 is superposed on said set to directly make an entry by a ball-point pen, the dye and/or color pigment in a microcapsule 6 of the transfer sheet 8 are transferred to the receiving part 2 of the receiving sheet by the writing pressure of the ball-point pen. The receiving sheet 4 is released from the transfer sheet 8 after recording and bonded to other body such as a cargo using the adhesive layer 3 and this pressure- sensitive adhesive sheet is used in a form looking a recorded image through through a transparent sheet 1. The transparent sheet 1 itself may be used as the receiving part 2 but, when a receiving layer 11 is provided on the transparent sheet 1, sharp recording can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a pressure-sensitive copying adhesive sheet having excellent recording durability.

"Prior art" Combination of electron-donating color formers such as crystal violet lactone and benzoyl leucomethylene blue with electron-accepting color developers such as activated clay, phenol-formaldehyde condensates, and polyvalent metal salts of aromatic carboxylic acids. (leuco-based recording material), or carboxylic acid nickel salt and N,
Color development of two types of chromogen substances, such as N'-dibenzyludithiooxamide, a combination of metal salts such as organoiron phosphate and stearyl gallate, and a ligand compound (chelate recording material). Pressure-sensitive copying sheets that utilize reactions are well known.

In general, such pressure-sensitive copying sheets include an upper paper (transfer sheet) in which a support is coated with microcapsules containing a chromogen substance prepared by a method such as a phase separation method, an interfacial polymerization method, or an 1n-situ method, and a A bottom sheet (receiving sheet) in which the support is coated with another chromogen substance that reacts with the original substance to develop color, and an inner sheet in which the microcapsules and the chromogen substance described above are coated on different sides of the support. They are used in combination as appropriate.

In addition, as a pressure-sensitive copying sheet that does not use chromogen substances,
It is known to use a transfer paper (so-called carbon back paper) provided with a colored transfer layer on the back surface, which is superimposed on a receiving paper such as high-quality paper.

Also, as a special structure for these, an adhesive layer is provided on the back side of the bottom paper or receiving paper. ? II1ii1) There is a pressure-sensitive copying adhesive sheet which is used in an appropriate combination of a receiving sheet bonded to paper and clay paper, inner paper, or backing carbon paper.

Although these pressure-sensitive copying sheets are convenient in that copies can be easily recorded on a receiving sheet, when used outdoors, like pressure-sensitive copying adhesive sheets, they have problems with the durability of recording. For example, (1) If the receiving sheet support is made of ordinary paper, it will easily tear if only a weak force is applied to it. Especially when the sheet is wet, it is easily torn. (2) If the recorded image on the receiving sheet is subjected to friction or if oil or the like adheres to it, it may become dirty or the recorded image may become faded and unreadable.

In recent years, in order to solve these problems, measures have been taken such as using synthetic paper or synthetic resin film as the receiving sheet support, and protecting the recording sheet by layering a transparent film over it. However, even if these measures are taken, they are not necessarily sufficient. In other words, when synthetic paper or synthetic resin film is used as a support, it has superior mechanical strength and water resistance compared to paper, and is less likely to tear, but records can still become illegible due to friction or oil adhesion. Problems such as not being able to record or fading of records are not improved at all. On the other hand, although the method of protecting records with a transparent film can solve the problems of tearing of the receiving sheet, contamination and fading of the records, it has the drawback of requiring time and cost due to pasting the transparent sheet on the receiving sheet.

``Problems to be Solved by the Invention'' An object of the present invention is to solve the above-mentioned problems and provide a pressure-sensitive copying adhesive sheet that has sufficient recording durability even when used outdoors.

"Means for Solving the Problems" The present invention provides (a) a receiving part (2) on the back side of a transparent sheet (1).
) and a receptor sheet (4) having an adhesive layer (3) (b)
This is a pressure-sensitive copying adhesive sheet formed by bonding a transfer sheet (8) formed by coating microcapsules (6) containing dyes and/or colored pigments and a release agent (7) on a support (5).

"Function" FIG. 1 is a sectional view illustrating the pressure-sensitive copying adhesive sheet of the present invention. The receiving sheet (4) and the transfer sheet (8) are bonded together with an adhesive layer (3). When you write directly with a ballpoint pen (101, etc.) on top of this set of high-quality paper (9), the dye and/or colored pigment in the microcapsules (6) of the transfer sheet (8) are transferred to the receiving sheet (4). )
transfers to the receiving part (2) of the cell, and a copy record is obtained on the receiving part (2). In the present invention, the receiving sheet (4) is peeled off from the transfer sheet (8) after recording, and is pasted onto other objects such as luggage using the adhesive layer (3), and the transparent sheet H11
It is used to view recorded images through In addition to this, it is also possible to use it in combination with other sheets known in the field of pressure-sensitive copying paper, such as top paper, middle paper, bottom paper, and stand-alone pressure-sensitive copying paper.

Although the transparent sheet (1) itself may be used as the receiving part (2) as shown in FIG. 1, clear recording can be obtained by providing a receiving layer αυ on the transparent sheet (1). Furthermore, even if there is a pattern or record on the baggage to which the receptor sheet is attached, or if the area is darkly colored, by providing the receptor layer aυ, the recorded image and the pattern overlap, making it impossible to identify the recorded image. can also be prevented.

A method of part-coating an adhesive layer (3) using screen printing or the like on the receptor layer αυ provided on the entire surface of the transparent sheet (1), or a method of partially coating the adhesive layer (3) on the release agent layer (2) of the transfer sheet (8). A receptor sheet as shown in FIG. 2 may be formed by part-coating 3) and bonding it to a receptor layer aυ provided on the entire surface of a transparent sheet fl). As a method for providing the receptor layer (2) and the adhesive layer (3) on the transparent sheet (<1), in addition to providing the receptor layer αυ on the entire surface of the transparent sheet as described above, there are two methods for providing the receptor layer αυ and the adhesive layer (3) on the entire surface of the transparent sheet as described above. ) with a part-coated adhesive layer (Figure 3), or an adhesive layer coated on the entire surface (Figure 3).
) on which a receptive layer 0υ is partially provided (FIG. 4) is possible.

Although the receiving layer OD is not an essential element in the present invention, when it is provided, it is provided by printing or coating an aqueous or non-aqueous white pigment-containing ink or coating liquid onto a transparent sheet.

Usually, an aqueous coating liquid is used, and this aqueous coating liquid contains a water-soluble binder or a latex binder similar to that used for white pigments and transfer sheets, and if necessary,
A dispersant, a surfactant, a chromogen substance, etc. are added, and the composition is prepared by dispersing with a propeller stirrer, ball mill, sand grinder, etc.

White pigments used in the receptor layer include aluminum,
Oxides of zinc, magnesium, calcium, titanium, etc.
hydroxides, carbonates, sulfates, and colloidal silica,
Examples include clays such as zeolite, bentonite, kaolin, and calcined kaolin, and organic pigments such as melamine resin and urea resin.

The amount of white pigment to be blended in the receiving layer varies depending on the type of pigment and cannot be determined unconditionally, but from the viewpoint of coloring and hiding properties, it is usually 30 parts by weight per 100 parts by weight of the coating liquid (solid content).
-95 parts by weight, preferably 60-90 parts by weight. In addition, the amount to be applied varies depending on the type and amount of pigment and cannot be determined unconditionally, but from the viewpoint of color development and concealment, it is 3 to 20 g /
m, more preferably 5 to 15 g/m.

As the adhesive used in the present invention, rubber-based, acrylic-based, polyether-based, ethylene-vinyl acetate-based, etc. can be used.
It is used as an emulsion type, solvent type, or solvent-free type (true melt type or electron beam curing type) coating liquid, and is usually
It is applied at a dry weight of 5 to 50 g/l.

On the other hand, as a release agent for the transfer sheet, condensation polymerization type silicone, addition polymerization type silicone can be used, emulsion type silicone,
It is used as a solvent type or solventless type (electron beam curing type) coating liquid, and is usually applied at a dry weight of 0.01 to 10 g/m2.

The transfer sheet is usually obtained by partially or entirely coating a release agent on a microcapsule coating layer, but it may also be partially or entirely coated on a support in a mixed state of microcapsules and a release agent.

Examples of colored pigments or dyes used in the present invention include red pigments such as carbon black, monoazo, disazo, rhodamine, perylene, and quinacridone;
Blue pigments such as copper phthalocyanine and triallylmethane; various pigments such as yellow pigments such as benzidine, monoazo and disazo; and red dyes such as monoazo, disazo, rhodamine and rose bengal. ; Blue dyes such as disazo and triallylmethane; monoazo,
Examples include various dyes such as yellow dyes such as disazo dyes.

These pigments and/or dyes are usually dissolved or dispersed in a hydrophobic medium and microencapsulated. As the hydrophobic medium, for example, various media already known in the field of pressure-sensitive copying paper may be used. It can be selected and used, and vegetable oils, mineral oils, aromatic hydrocarbons, alcohols, organic acids, esters, organic phosphorus compounds, ethers, amides, ketones, carbonate 1, etc. are used. In addition to colored pigments and/or dyes, this hydrophobic medium also contains
Antioxidants, ultraviolet absorbers, resins, chromogen substances, etc. are added as necessary.

As the encapsulation method, conventionally known coacervation method, interfacial polymerization method, 1n-situ method, etc. can be used, but especially melamine formaldehyde resin capsules obtained by 1n-situ method or polyurethane obtained by interfacial polymerization method. -Polyurea resin capsules are particularly preferred.

The amount of the dye and/or colored pigment contained in the capsule varies depending on its dyeing ability, solubility or dispersibility in the medium, etc., and cannot be determined unconditionally, but it is usually o. , 1 to 200 parts by weight, preferably 1 to 1001i1 part.

The microcapsules thus obtained may contain water-soluble or latex binders, capsule protectants, pigments, dispersants,
Antifoaming agents, preservatives, ultraviolet absorbers, release agents, etc. are added as appropriate to prepare a microcapsule coating solution, and the powder capsules obtained by filtering and drying the microcapsule dispersion are mixed with organic solvents, oils, and resins. Dispersed in a vehicle or wax such as, and further added as necessary, pigments, capsule protectants, ultraviolet absorbers, antioxidants, photopolymerization initiators, dryers, surfactants, thickeners, gelling agents, etc. in the ink field. Various auxiliary agents known in the art and release agents are added as necessary to prepare capsule inks of evaporation drying type, radiation curing type, oxidative polymerization type, real melt type, etc., and the inks are coated on a support using a coating device or a printing machine. Ru.

The amount of microcapsule coating liquid or ink applied is not particularly limited, but from the viewpoint of color development and economical efficiency, it is usually 1 to 15 g/rrr, more preferably 2 to 10 g/rrr.
g/m.

Examples of water-soluble binders include proteins such as gelatin, albumin, and casein, cereal starch, pregelatinized starch,
Starches such as oxidized R powder, etherified starch, and esterified starch; water-soluble natural polymer compounds such as celluloses such as carboxymethyl cellulose and hydroxyethyl cellulose; polysaccharides such as agar, sodium alginate, and gum arabic;
There are water-soluble synthetic polymer compounds such as polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, polyacrylamide, maleic acid copolymer, etc. Latex binders include styrene-butadiene latex,
Examples include acrylonitrile-butadiene latex, acrylic ester-based latex, vinyl acetate-based latex, methyl methacrylate-butadiene latex, and carboxy-modified (for example, acrylic acid) latex thereof.

In addition, examples of organic solvents include benzene, toluene,
Xylene, cyclohexane, hexane, ligroin, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, methyl cellosolve, ethyl cellosolve, diethylene glycol monobutyl ether, diethylene glycol motubutyl ether acetate, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n -butanol, n-hexanol, cyclohexanol, 2-ethylhexyl alcohol and the like.

Examples of oils include vegetable oils (drying oils such as linseed oil and safflower oil, semi-drying oils such as soybean oil, and non-drying oils such as castor oil), processed oils (dehydrated castor oil, polymerized oils, maleated oils). , vinylated oil, urethanized oil), mineral oil (machine oil, spindle oil), etc.

Furthermore, examples of the resin include natural resins such as rosin (gum rosin, wood rosin, tall oil rosin) shellac, copal, dallman, giltnite, zein, hardened rosin, ester gum and other rosin esters, maleic acid resin, fumaric acid resin, Double rosin, polymerized rosin,
Rosin-modified phenolic resin, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, cellulose acetate propionate, cellulose acetate butyrate,
Semi-synthetic resins such as nitrocellulose, phenolic resins, quinolene resins, urea resins, melamine resins, ketone resins, coumaron/indene resins, petroleum resins, terpene resins, cyclized rubbers, chlorinated rubbers, alkyd resins, polyamide resins, acrylic resins, Polyvinyl chloride, vinyl chloride/vinyl acetate copolymer, polyvinyl acetate, ethylene/maleic anhydride copolymer, styrene/maleic anhydride copolymer, methyl vinyl ether/maleic anhydride copolymer, isobutylene/maleic anhydride Synthetic resins such as copolymers, polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl butyral (butyral resin), polyvinylpyrrolidone, chlorinated polypropylene styrene resin, epoxy resin, polyurethane, as well as polyethylene glycol diacrylate, propylene glycol dimecrylate, Pentaerythritol triacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate,
Hexanediol diacrylate, 1,2-butanediol diacrylate, reaction product of epoxy resin and acrylic acid, reaction product of methacrylic acid, pentaerythritol and acrylic acid, condensation product of maleic acid, diethylene glycol and acrylic acid, methyl methacrylate , butyl methacrylate, styrene, and other oligomers or prepolymers having ethylenically unsaturated bonds.

Waxes include carnauba wax, montan wax, and paraffin wax.1. Microcrystalline wax, castor wax, stearamide,
Examples include stearic acid, stearyl alcohol, distearyl phosphate, and the like.

In the present invention, known coating machines and printing machines are used to apply each coating liquid or ink onto a support, and the coating machines include air knife coating, roll coating, blade coating, Printing machines such as Rondo Blade Coating are Toppan Printing,
Examples include intaglio (clavier) printing, lithographic (offset) printing, screen printing, and the like. Among these, screen printing is preferred in terms of performance when printing an adhesive or microcapsule-containing layer.

The transparent sheet used as the receiving sheet may be any sheet as long as the records can be read through the sheet, and examples include, but are not limited to, the following synthetic resin sheets. Ethylene resin, propylene resin, styrene resin, vinyl chloride resin, ester resin, polyamide resin, acrylic resin, nitrile resin, urethane resin, cellulose resin, etc.

Examples of the support for the transfer sheet include paper, impregnated paper, synthetic paper, and metal foil.

The pressure-sensitive copying sheet of the present invention is usually printed with ruled lines to form a slip or the like, and the printing ink used at that time is preferably an ultraviolet or electron beam curable ink when used on a transparent sheet.

"Examples" Examples will be given below to further clarify the effects of the present invention, but the present invention is not limited to these Examples. Parts and % in the examples represent parts by weight and % by weight, respectively, unless otherwise specified.

Example 1 Fertility i 300 parts of light calcium carbonate, 15 parts of polyvinyl alcohol aqueous solution (solid content) and 900 parts of water were mixed in a ball mill.
A coating solution prepared by adding 60 parts (solid content) of carboxy-modified styrene-butadiene copolymer latex to the dispersion obtained by grinding for 4 hours was applied to a 100 μm Teflon film (product name: Type HP-7, manufactured by Teijin). The dry weight is 5g/r
It was smeared with an air knife coater so that it became rr. Separately, in order to provide an adhesive layer of 2 cm x 20 cm square with an unsmeared area of 1 Q cm (manufactured by Toyo Ink)
After screen printing so that the dry weight was 30 g/rd, it was bonded to the receiving layer of a receiving sheet to prepare a pressure-sensitive copying adhesive sheet.

Add 5 parts of Ai Wong's Nijo Kosho Carbon Blank to 10 parts of diisopropylnaphthalene.
15 parts of an aromatic polyvalent isocyanate (trade name: Coronato L1 manufactured by Nippon Polyurethane Co., Ltd.) was dissolved in 105 parts of the internal phase oil obtained by dispersing it in 0 parts, and this was added to 600 parts of a 2% polyvinyl alcohol aqueous solution. Emulsified, average particle size 8.0
After μ, this system was reacted at 80° C. for 4 hours to obtain a capsule dispersion. 50 parts of starch particles and 2 parts of carboxy-modified styrene-butadiene copolymer latex were added to this dispersion.
0 parts (solid content) and 5 parts of carboxymethylcellulose were added and diluted to a concentration of 18% to prepare microcapsule coating.

The obtained capsule coating liquid was spread on 60 g/rd glassine gi (manufactured by Kanzaki Paper Industries) using an air knife coater so that the dry weight was 5 g/m, and then a silicone resin release agent was applied on the layer to a dry weight of 1 g/m. It was coated with a bar coater to give a coating density of .5 g/m, and 1) dried at 5°C to obtain a transfer sheet.

■ The receiving sheet and the transfer sheet were joined together, high-quality paper was placed on top of the sheet, and printed with a typewriter, resulting in a size of 10 cm
A clear print was obtained on a cm square area where no adhesive was applied. Furthermore, when the receiving sheet was attached to luggage, it was found to be excellent in terms of durability.

"effect" The present invention was a pressure-sensitive copying adhesive sheet with excellent durability.

[Brief explanation of the drawing]

FIG. 1 is a cross-sectional view illustrating the pressure-sensitive copying adhesive sheet of the present invention. FIG. 2 is a sectional view of the pressure-sensitive copying adhesive sheet of the present invention, which is a combination of a receptor sheet provided with a receptor layer and a transfer sheet. Figure 3 shows a receptor sheet of the present invention in which an adhesive layer and a receptor layer are part-coated, and Figure 4 shows a receptor sheet of the invention in which an adhesive layer is provided on a transparent sheet and a receptor layer is further provided. represent.

Claims (3)

[Claims] (1) (a) A receiving sheet (4) having a receiving area (2) and an adhesive layer (3) on the back side of the transparent sheet (1), and (b) dyes and/or colored pigments on a support (5). A pressure-sensitive copying adhesive sheet formed by joining a transfer sheet (8) coated with a release agent (7) and microcapsules (6) containing the following. (2) The pressure-sensitive copying adhesive sheet according to claim (1), wherein the receiving portion is made of a transparent sheet. (3) The pressure-sensitive copying adhesive sheet according to claim (1), wherein the receiving portion comprises a receiving layer containing a white pigment.