JP3139508B2 - Record sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording sheet, and more particularly to a recording sheet suitable for use as a slip such as a single sheet or a continuous sheet.

[0002]

2. Description of the Related Art Recording sheets are used for various purposes. For example, in a copy slip, a recording sheet and a recording sheet (usually made of paper) are laminated and the front side of the recording sheet is formed. Type pressure applied to the (receiving layer side),
The required amount of ink is transferred onto the recording sheet in the form of characters or figures from the ink layer provided on the back side of the recording sheet by writing pressure, heat, or the like. As the ink, a hot melt ink is often used. When the base material (support) of such a recording sheet is made of paper, the hot melt ink penetrates well from the paper surface to an appropriate depth, and a desired hot melt ink layer can be formed relatively easily.

[0003] However, in the case of transportation slips such as courier service, since the recording sheet positioned on the surface of the slip is required to have durability and weather resistance, a recording sheet using a plastic film, which is more durable than paper, as a support is required. Sheets are being used. However, although the film support is excellent in durability and weather resistance, the hot melt ink does not penetrate well as it is, and it is difficult to form a desired hot melt ink layer. Therefore, conventionally, various devices have been devised for forming a hot melt ink layer on a film support. The structure of a recording sheet using a conventional film as a support usually employs a layer structure of a receiving layer / film support / hot melt ink receiving layer / hot melt ink layer. The hot-melt ink receiving layer is provided so that the hot-melt ink permeates properly and a desired hot-melt ink layer is formed on the surface of the hot-melt ink, and is coated with a high-ink-receptive polymer resin. Or
It is formed by applying a material containing a roughening substance to the polymer resin. There is also known a method of improving the adhesiveness of a hot melt ink by roughening the surface of the film support itself by sandblasting or the like, or performing corona discharge treatment or the like.

[0004]

However, in the conventional recording sheet, the properties of the hot melt ink receiving layer are not sufficient, so that there is a problem that the adhesiveness of the hot melt ink is not sufficient. Therefore, especially when the handling is rough, the hot melt ink is unnecessarily transferred to the paper as the recording sheet, and the paper may be stained. Further, since the adhesiveness of the hot melt ink is not high, it is difficult to uniformly form an ink layer having a target thickness, and copy recording on a recording sheet may be unclear.

[0005] The present invention solves the above problems,
Good adhesion of hot melt ink, preventing unnecessary transfer to recording sheet, easy formation of desired hot melt ink layer, accurate and clear copying and recording on recording sheet It is another object of the present invention to provide a recording sheet having an excellent hot melt ink receiving layer.

[0006]

According to the present invention, there is provided a recording sheet having a receiving layer on one side of a film support, and a coating layer containing an aqueous ethylene ionomer resin as a main component on the other side, Further, a hot mail ink layer is provided on the coating layer.

The material of the film support of the present invention is not particularly limited, and various known plastic films can be used. Typical examples are polyester film (including paper-like polyester film), polycarbonate film, triacetyl cellulose film, cellophane film, polyamide film, polyimide film, polyphenylene sulfide film, polyether imide film, polyether sulfone film, and aromatic. Examples thereof include a polyamide film, a polysulfone film, a polyolefin film and the like. However, it is preferable to use a polyester film, a polycarbonate film, or a polyphenylene sulfide film from the viewpoints of mechanical properties, thermal properties, price, and the like, and a polyester film is particularly preferable.

[0008] Polyester film is a general term for a polymer film having an ester bond as a main bonding chain. Particularly preferred polyesters are polyethylene terephthalate, polyethylene 2,6-naphthalate, and polyethylene α, β-bis (2 -Chlorphenoxy) ethane 4,4'-dicarboxylate, polybutylene terephthalate, etc. Among them, polyethylene terephthalate (hereinafter sometimes abbreviated as PET) may be considered in view of quality, economy and the like. Is most preferred. Known additives in the PET, for example, heat stabilizers, oxidation stabilizers, weather stabilizers, ultraviolet absorbers,
Organic lubricants, pigments, dyes, organic or inorganic fine particles,
Fillers, release agents, antistatic agents, nucleating agents and the like may be blended.

The PET film is unoriented, uniaxially oriented,
Although any of biaxial orientations can be used, a biaxially oriented PET film is preferable because of its excellent mechanical strength. The biaxially oriented PET film is formed by stretching a non-stretched PET sheet or film about 2.5 to 5 times each in so-called biaxial directions of a longitudinal direction and a width direction. It indicates an orientation pattern.

When the PET film is subjected to a surface treatment by a known method, that is, a film subjected to a corona discharge treatment (in air, nitrogen, carbon dioxide gas, etc.) or an easy adhesion treatment, the aqueous ethylene ionomer resin layer Can be more preferably used because the adhesiveness, water resistance, solvent resistance and the like of the resulting product are improved. Various methods known in the art can be used for the easy adhesion treatment, and acrylic, urethane,
Those coated with various types of easy-adhesives such as polyester, or those coated with the various types of easy-adhesives as described above on a film after uniaxial or biaxial stretching can be suitably used.

[0011] The thickness of the plastic film as the film support is not particularly limited, and an appropriate thickness can be set in a range of about 1 to 500 µm, for example, depending on the stiffness required for the recording sheet.

The surface roughness, haze, and the like of the film support are not particularly limited, and are required to be the thickness of the aqueous ethylene ionomer resin layer described later and between the aqueous ethylene ionomer resin layer and the film support. It may be appropriately set to a desired value in consideration of the adhesive strength, transparency and whiteness required as a recording sheet.

In the recording sheet of the present invention, an aqueous ethylene ionomer resin layer is provided on the surface of the film support opposite to the receiving layer. The aqueous ethylene ionomer resin referred to in the present invention is a resin in which a carboxylic acid group of an ethylene / unsaturated carboxylic acid copolymer is at least partially ionized by a metal ion and ion-crosslinked by the metal ion. The unsaturated carboxylic acid forming a copolymer with ethylene is generally an unsaturated carboxylic acid having 3 to 6 carbon atoms, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, and vinyl benzoate. Also,
The copolymer includes unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, butyl methacrylate, butyl maleate, butyl fumarate, and vinyl ester. For example, vinyl acetate, vinyl propionate, vinyl stearate, higher tertiary vinyl ester, vinyl chloride, vinyl bromide, etc.
-As the olefin, for example, propylene, butene, pentene, hexene, heptene, methylbutene, methylpentene and the like may be copolymerized. Furthermore, ethylene /
Styrene or the like may be graft-copolymerized to the unsaturated carboxylic acid copolymer. As metal ions, sodium, potassium, calcium, barium, zinc, cobalt, nickel, magnesium, copper, lead, etc. are formate, acetate, nitrate, carbonate, bicarbonate, oxide, hydroxide, alkoxide. And so on.

Particularly preferred aqueous ethylene ionomer resins in the present invention include ethylene / methacrylic acid copolymer, ethylene / acrylic acid copolymer, ethylene acrylic acid polymer / styrene graft copolymer, and the like. Examples of the ion include sodium, zinc, magnesium and the like.

The ethylene ionomer resin is obtained by a known production method described in, for example, JP-B-46-25624, JP-A-61-9403, etc., and is dispersed in water by a known technique to obtain an aqueous dispersion. It takes shape. In the present invention, it is desirable that the softening point of the obtained ethylene ionomer resin is in the range of 20 to 180 ° C, preferably 40 to 150 ° C by a measuring method based on ASTM-D-1525-70. If the softening point is lower than 20 ° C., the tackiness of the coating layer is increased and the heat resistance is insufficient, so that the handling property of the recording sheet is liable to deteriorate. When the temperature exceeds 180 ° C., the adhesion to the film support deteriorates, and the adhesion to copying on the recording sheet is poor.

The thickness of the aqueous ethylene ionomer resin layer is not particularly limited, but is 0.5 to 50 μm, preferably 1 to 50 μm.
It is preferably about 30 μm, more preferably about 3 to 20 μm. If the thickness is too thin, the absorption of hot melt ink will be insufficient,
If the thickness is too large, the strength of the coating tends to be insufficient.

A hot melt ink layer is provided on the aqueous ethylene ionomer resin layer. Hot melt ink is heated and melted or heated to a certain temperature on a printing machine until the moment when printing and coating is performed on the material to be printed.
It keeps printability such as fluidity, and after printing, forms a strong coating film on the material to be printed at cooling or normal temperature.However, the hot melt ink used for the recording sheet of the present invention is not particularly limited. Known heat-type copying carbon ink, transfer-type heat-sensitive ink, hot-melt type glass ink, and the like can be used. In the case of slips, carbon ink is suitable for transfer recording using a thermal head with a computer or personal computer, and transfer-type thermal ink is suitable, and for transfer to a glass surface, hot-melt glass ink is suitable. The method for forming the hot melt ink layer is not particularly limited, and a known method can be used.

The receiving layer of the present invention is a layer composed of a composition containing a white hidden pay pigment and a polymer resin binder as main components. The layer as the main component refers to a layer which is 50% by weight or more in the receiving layer, and other substances may be appropriately added. In the present invention, such a receiving layer is provided on one surface of the film support.

In the present invention, the polymer resin binder is
Thermoplastic resins, selected from thermosetting resins, resins that are soluble in well-known organic solvents, and those having less hydrophilic groups or hydrophilic components are preferred in terms of water resistance, moisture resistance, etc. of the receiving layer, Specific examples include, for example, acrylic, vinyl, urethane, epoxy, polyester, polypropylene, melamine, carbonate, butyral, etc., and copolymers and mixtures thereof.

In the present invention, the water resistance, solvent resistance,
From the viewpoint of heat resistance, abrasion resistance, mechanical strength, and the like, it is preferable to use a thermosetting resin, and more preferably, a resin which can be crosslinked by using a well-known crosslinking agent. In addition, examples of the organic solvent include, for example, alcohols, carboxylate esters, ketones, aliphatic hydrocarbons, alicyclic or aromatic hydrocarbons, and mixtures thereof, and do not adversely affect coating properties and the like. The choice of one is preferred.

The white hidden pay pigment referred to in the present invention is an inorganic or organic pigment exhibiting a white receiving layer, and examples of the inorganic pigment include zinc carbonate, zinc oxide, zinc sulfide, and the like.
Talc, carion, heavy / light chamber or synthetic calcium carbonate, titanium oxide, silica, lithium fluoride, calcium fluoride, barium sulfate, alumina, zirconia, calcium phosphate, natural or synthetic swelling or non-swelling mica, etc. Examples of organic pigments include, for example, polystyrene, polymethylstyrene, polymethoxystyrene, polyvinyl chloride, polyethylene, polypropylene, polyvinylidene chloride, polymethacrylate, polymethylmethacrylate, polychloroacrylate, and the like. At least one selected from the above is applied, but is not particularly limited. The pigment may be in a hollow porous or non-hollow porous state. Further, the pigment may be subjected to a treatment such as adding a functional group such as glycidyl or methylol group to the surface in order to improve dispersibility in the resin.

The average particle size of the white hidden pay pigment is 0.1 to 25.
μm, preferably in the range of 1.0 to 10 μm, is preferred in terms of handleability, coatability and the like. Further, the content of the white hidden pay pigment in the receiving layer is preferably 0.1 to 70% by weight, more preferably 5 to 50% by weight. Content is 0.
If it is less than 1% by weight, the white concealing payability is sufficient, and if it is 70% by weight or more, the adhesion between the receiving layer and the film base material is liable to decrease.

In the present invention, the adhesiveness of the receiving layer, the solvent resistance,
In order to further improve the heat resistance, it is preferable that the receiving layer contains a crosslinking agent.

The cross-linking agent referred to in the present invention is a functional group present in a polymer resin binder, for example, a hydroxyl group,
It is not particularly limited as long as it is a cross-linking agent for performing a cross-linking reaction with a carboxyl group, a glycidyl group, an amide group, etc., and finally as a receiving layer having a three-dimensional network structure. Examples include urea-based, melamine-based, acrylamide-based, and polyamide-based resins, and epoxy compounds, isocyanate compounds, and aziridine compounds.

These crosslinking agents may be used alone or in combination of two or more in some cases. The amount of the cross-linking agent to be added is appropriately selected depending on the type of the cross-linking agent, but is usually preferably 0.01 to 50 parts by weight, more preferably 0.1 to 30 parts by weight, per 100 parts by weight of the solid content of the polymer resin. preferable. Further, it is more preferable to use a crosslinking catalyst in combination with the crosslinking binder because crosslinking proceeds more. Known catalysts such as salts, inorganic substances, organic substances, acid substances, and alkaline substances can be used as the crosslinking catalyst. The amount of the crosslinking catalyst to be added is 0.001 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the solid content of the polymer resin. The polymer resin to which the cross-linking agent is added is cross-linked by heating, ultraviolet rays, electron beams or the like after being applied to the film support, but the heating method is generally used.

The receiving layer constituting the recording sheet of the present invention comprises:
Its smoothness is 2 to 3000 seconds, preferably 10 to 150 seconds.
Desirably, the range is 0 seconds. When the smoothness is out of this range, for example, when printing is performed using a fabric ribbon, the ink permeability does not match, the printing becomes lighter, and the ink tends to remain on the surface of the receiving layer. In the present invention, the hunter whiteness of the receiving layer is 40% or more,
Preferably, it is 60% or more. If the Hunter whiteness is less than 40%, the hidden payability becomes insufficient, and the resolution and sharpness of the type and the like on the surface of the receiving layer are reduced, and reading errors such as in the case of a bar code are liable to occur. The layer thickness of the receiving layer is not particularly limited, but is preferably 0.5 to 50 μm,
Those having a size within the range of from 20 to 20 μm are desirable from the viewpoint of uniform formation of the receiving layer, adhesion and the like. In addition, if necessary, known additives such as an antifoaming agent, a coating improver, a thickener, an antistatic agent, an ultraviolet absorber, and a dye may be added to the receiving layer in an amount that does not impair the effects of the present invention. May be contained.

[0027]

According to the recording sheet of the present invention, a hot melt ink receiving layer made of a specific resin is formed on a film support, so that the following excellent effects can be obtained.

First, since the recording sheet of the present invention is excellent in the adhesiveness and abrasion resistance of the hot melt ink layer, the hot melt ink layer is easily formed in a desired layer, and the copy record is clear and easy to see.

Further, since the recording sheet of the present invention has excellent adhesiveness of the hot melt ink layer, it has excellent handling properties in post-processing.

Further, the receiving layer of the recording sheet of the present invention comprises a fabric ribbon, an electrophotographic toner, an oil-based ink,
Excellent printability with various inks such as V ink.

The recording sheet of the present invention has such excellent characteristics as described above, and thus can be applied to various uses for which copying and recording is required. Among them, it is particularly suitable for delivery slips for business use, home delivery service and the like. It is suitable.

[Measurement and Evaluation Methods] The characteristic values in the present invention are based on the following measurement methods and evaluation criteria. (1) Smoothness Smoothness was determined by measuring with an Oken type air permeability smoothing tester “Model KB15” (Asahi Seiko Co., Ltd.).

(2) Hunter whiteness Using Macbeth 2000 manufactured by Kolmorgen, L
a and b were measured, and Hunter whiteness (W) was calculated by the following formula (measured at 550 nm). W = 100 [(100−L) ² + a ² + b ² ] ^1/2

(3) Recording Property of Receptive Layer Serial printer “PC-PR20” manufactured by NEC Corporation
1U ", and the character pattern is changed to the fabric ribbon" O
AR-NF-2 "(manufactured by Pilot Co., Ltd.), and the print quality and ink absorbency were evaluated, and the recordability was determined as follows.The print quality was evaluated by visual observation and the ink absorption was evaluated. Immediately after printing, the character pattern was rubbed back and forth five times with a finger, and evaluated based on the degree of contamination of the receiving layer with the ink: O: Both print quality and ink absorbency were good Δ: Print quality and ink absorbency were slightly inferior. ×: Both printing quality and ink absorbency are poor

(4) Adhesiveness of ink [I] Cellotape: CT-24 (Nichiban Co., Ltd.) on the ink layer
Was adhered and pressed back and forth 5 times with a load of 2 kg using a hand roller. Then, the cellophane tape was forcibly peeled by hand in the 180 ° direction, and the degree of peeling of the ink layer was observed and evaluated. The criteria were: ：: good (peeling area less than 5%), Δ: slightly poor (peeling area 5% or more and less than 20%), ×: bad (peeling area 20% or more).

(5) Ink Adhesion [II] The ink layer was evaluated by a Gakushin type friction fastness test. The number of times of abrasion was set to once and five times, and the ink layer after abrasion was visually observed and determined as follows. Good adhesion: ○, slightly poor adhesion:
Δ, poor adhesion: ×.

[0037]

The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these examples. Example 1 A film support had a center line average roughness of 0.053 μm,
One side of a biaxially stretched polyethylene terephthalate film having a whiteness of 93% and a thickness of 50 μm and both surfaces of which are subjected to corona discharge treatment is coated with “Chemipearl” SA-100 (manufactured by Mitsui Petrochemical Co., Ltd.) as an aqueous ethylene ionomer resin. An aqueous medium-based coating material adjusted to 15% by weight was applied by a reverse method, and the applied layer was dried at 130 ° C. for 1 minute to form a coating layer having a thickness of 2.0 μm.

Next, toluene / ethyl acetate (mixing ratio: 1: 1) was used as a diluting solvent on the non-coated surface of the film, and this was crosslinked with a heat-crosslinkable acrylic resin "Cotax" LH-613.
(Manufactured by Toray Industries, Inc.) and a white hidden pay pigment having an average particle size of 1.
A uniformly dispersed coating material having a concentration of 25% by weight in which 0 μm of titanium oxide was added at 40% by weight based on the solid content was applied.
After drying at 0 ° C. for 1 minute, a receiving layer having a thickness of 3.0 μm was provided. After setting the thus obtained film on a hot plate set at 125 ± 5 ° C., a hot-melt ink “HTS66S” manufactured by Teikoku Ink Co., Ltd. was applied to the coating layer by using a rubber convex black bar method. A recording sheet having 0 μm was prepared. The properties of the recording sheet were as shown in Table 1 and were excellent in ink adhesion.

Examples 2 and 3 On the basis of Example 1, "Chemipearl" SA-300 (Example 2) and "Chemipearl" S-100 (Example 3) were used as aqueous ethylene ionomer resins. A recording sheet was produced in the same manner as in Example 1. The recording sheet was excellent in ink adhesion as shown in Table 1.

Example 4 Titanium oxide having an average particle size of 0.5 μm was used as a receiving layer in the same polymer resin binder as in Example 1 as a white opaque pigment, and was 30% by weight based on solid content and porous having an average particle size of 4.0 μm. A recording sheet was prepared in the same manner as in Example 1 except that a uniformly dispersed coating material having a concentration of 30% by weight in which amorphous silica was added at 10% by weight per solid content was used. As shown in Table 1, the properties of the recording sheet were all excellent.

Comparative Example 1 A recording sheet was obtained in Example 1 without providing a coating layer composed of an aqueous ethylene ionomer resin. As shown in Table 1, the recording sheet had insufficient adhesion of the ink layer, indicating that the durability was uneasy.

[0042]

[Table 1]

Continuation of front page (58) Fields investigated (Int.Cl. ⁷ , DB name) B32B 27/16 B32B 27/20 B42D 11/00 B42D 15/00 B42D 15/04 C09D 11/00 C09D 11/02

Claims (3)

(57) [Claims] 1. A film support comprising a receiving layer on one surface, a coating layer mainly composed of an aqueous ethylene ionomer resin on the other surface, and a hot melt ink layer provided on the coating layer. Characteristic recording sheet. 2. The recording sheet according to claim 1, wherein the receiving layer has a smoothness of 2 to 3000 seconds. 3. The recording sheet according to claim 1, wherein the hunter whiteness of the receiving layer is 40% or more.