JPH0691810A - Recording sheet - Google Patents

Abstract

PURPOSE:To obtain a recording sheet generating no supply mistake or running inferiority and excellent in the close adhesiveness of toner or ink, in the recording sheet wherein an image receiving layer, a plastic film and an easily slidable antistatic layer are laminated in this order, by forming the easily slidable antistatic layer using a silicone modified quaternary ammonium salt polymer. CONSTITUTION:An image receiving layer composed of a compsn. prepared by adding inorg. and/or org. particles and a polymeric electrolyte or conductive powder controlling surface electric resistance to a polymeric binder if necessary is applied to the corona treatment surface of a plastic film, for example, by a gravure coater. A silicone modified quanternary ammonium salt polymer is diluted to be applied to the surface opposite to the image receiving layer of the plastic film, for example, by a gravure coater to form an easly slidable antistatic layer.

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 as a copying base material for electrophotography, ink jet and the like, particularly as an OHP sheet.

[0002]

2. Description of the Related Art In recent years, the demand for creating and printing documents in offices has increased due to the spread of OA, and a copying machine / printer excellent in print quality with low noise has been demanded. Electrophotographic copying machines and ink jet printers have been put into practical use to meet these requirements. Further, in recent years, the color copying technology has reached the completion area, and color copying machines / printers have been gradually spread, and the demand for color OHP sheets has become strong.

[0003]

Various recording sheets used in these systems have been proposed in the past. However, when the recording sheets are continuously fed, the slippage between the recording sheets is poor and the antistatic property is low. Since it is defective, there are problems such as a paper feed error, running failure, and dust adhesion due to static electricity.

In order to solve the above problems, the present invention provides
An object of the present invention is to provide a recording sheet having excellent characteristics such as excellent slipperiness and antistatic property, no paper feeding error or running failure, and less dust adhesion.

[0005]

To achieve this object, the present invention provides a recording sheet comprising an image receiving layer, a plastic film, and an easy-slipping / antistatic layer laminated in this order. A recording sheet, characterized in that the prevention layer comprises a silicon-modified quaternary ammonium salt polymer.

The plastic film in the present invention includes polyolefins such as polyethylene and polypropylene, polyesters, polycarbonates, polyvinyl chlorides, polyamides, polyester amides, polyethers,
Polyimide, polyamide imide, polystyrene, poly-P-phenylene sulfide, polyether ester, poly (meth) acrylic acid ester and the like are preferable. Furthermore, these copolymers, blends, and further crosslinked products can be used. Among them, polyester, preferably polyethylene terephthalate is preferable from the viewpoint of mechanical properties, workability and the like.

The polyester as referred to in the present invention is a well-known one, for example, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, bis-α, β (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid, adipine. Polyester obtained by polycondensing at least one bifunctional carboxylic acid such as acid or sebacic acid with at least one glycol such as ethylene glycol, triethylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol Can be mentioned. Further, the polyester may be blended or copolymerized with another type of polymer within a range that does not impair the object of the present invention, and includes an antioxidant, a heat stabilizer, a lubricant, a pigment, an ultraviolet absorber and the like. It may be. The intrinsic viscosity of the polyester (measured in 25 ° C. orthochlorophenol) is 0.4 to 2.0, preferably 0.5 to 1.
Those in the range of 0 are usually used.

The polyester film used in the present invention may be one in which fine bubbles are contained in the film, and the bubbles are whitened by scattering light. The formation of these fine bubbles is caused by incompatible polymers such as poly-3-methylbutene-1, poly-4-methylpentene-1, polypropylene, polyvinyl t-butane, 1, and the like in a film base material such as polyester.
It is formed by finely dispersing 4-trans-poly-2,3-dimethylbutadiene, cellulose triacetate, cellulose tripropionate, polychlorotrifluoroethylene, etc., and stretching it uniaxially or biaxially. During stretching, voids (air bubbles) are formed around the incompatible polymer particles, and the voids are whitened because they exhibit a light scattering action. Also, since it has fine bubbles, it has a low specific gravity and also has cushioning properties.

Further, in the present invention, a polyester film in which fine particles such as calcium carbonate, amorphous zeolite particles, anatase type titanium dioxide, calcium phosphate, silica, kaolin, talc and clay are used together may be used. In addition to such fine particles, fine particles precipitated by the reaction of the catalyst residue and the phosphorus compound in the polyester polymerization reaction system may be used in combination.

As the slippery / antistatic layer in the present invention, it is necessary to use a silicon-modified quaternary ammonium salt polymer. The silicon-modified quaternary ammonium salt polymer is a copolymer selected from at least one or more selected from the following groups.

Those having at least one quaternary ammonium salt, for example, 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride, 2-hydroxy-3-methacryloxypropyltriethylammonium chloride, 2-hydroxy-2-acryloxypropyltrimethylammonium. Chloride, 2-hydroxy-3-acryloxypropyltriethylammonium chloride, 2-methacryloxyethyltrimethylammonium chloride, 2-methacryloxyethyltriethylammonium chloride, 2-acryloxyethyltrimethylammonium chloride,
2-acryloxyethyltriethylammonium chloride, dimethylaminoethylmethacrylate salt, diethylaminoethylmethacrylate salt, dimethylaminoethylacrylate salt, diethylaminoethylacrylate salt, vinylbenzyltrimethylammonium chloride, vinylbenzyltriethylammonium chloride, 4-vinyl-N -Methylpyridinium chloride, NN-dimethyl substituted 3,5-methylpiperidinium chloride, dimethyldiallylammonium chloride,
Diethyldiallylammonium chloride, polyethyleneimine hydrochloride, etc. and "Surfactant Handbook"
There are various quaternary ammonium salts and pyridinium salts described in (Industrial Books 1960), but other known various quaternary ammonium salts
Grade ammonium salts can be used.

Particularly, 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride, 2-hydroxy-3-methacryloxypropyltriethylammonium chloride, 2-hydroxy-2-acryloxypropyltrimethylammonium chloride, 2-hydroxy-3-acryloxypropyltriethylammonium chloride, 2 -Methacryloxyethyltrimethylammonium chloride, 2-methacryloxyethyltriethylammonium chloride, 2-acryloxyethyltrimethylammonium chloride, 2-acryloxyethyltriethylammonium chloride, dimethylaminoethylmethacrylate salt, diethylaminoethylmethacrylate salt, dimethylamino Ethyl acrylate salt, di Salts chill aminoethyl acrylate.

[0013] For example, methylsilane described in "silicon resin" (Kihachi Tamura, 1936, published by Nikkan Kogyo Shimbun),
Organosilanes such as phenylsilane, methylsiloxane, methylhydrogensiloxane, organosiloxanes such as phenylsiloxane, and vinyl or allylsiloxane condensates in which a vinyl or allyl group is directly bonded to a silicon atom.

Further, styrene, acrylic acid-based ester or the like can be copolymerized with the above. The acrylic acid ester as used herein refers to an acrylic acid ester and a methacrylic acid ester, and is preferably an ester of an aliphatic alcohol having 1 to 4 carbon atoms, for example,
Examples thereof include methyl acrylate, ethyl acrylate, butyl acrylate, propyl acrylate, 2-hydroxyethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, propyl methacrylate and 2-hydroxyethyl methacrylate.

The image receiving layer in the present invention comprises a layer containing a polymer binder and, if necessary, inorganic and / or organic particles. The polymer binder is composed of a thermoplastic resin or a curable resin, and further a water-soluble polymer or a water-dispersible polymer.

Examples of the thermoplastic resin include polyester, polyamide, polyesteramide, polyvinyl acetal, polyvinyl chloride, poly (meth) acrylic acid ester, polyimide, polyurethane, polycarbonate, polystyrene, polymethylpentene, polyolefin and halogenated polyolefin. , Alkyd resins, polyamideimides, silicon resins, fluororesins and the like, and copolymers and blends thereof. Further, as the curable resin that is cured by light, heat, oxygen, etc., for example, phenol resin, melamine resin, epoxy resin, cross-linked organosilicon resin, poly (meth) acrylic acid ester copolymer containing a reactive monomer can be used. Examples thereof include those obtained by adding a crosslinking agent and crosslinking. Water-soluble polymers and water-dispersible polymers include oxidized starch, etherified starch, esterified starch,
Starches such as dextrin, cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose, casein, gelatin, polyvinyl alcohol and its derivatives, polyvinylpyrrolidone, polyacrylic acid,
Vinyl-based copolymers such as polymethacrylic acid or its esters, salts and copolymers thereof, polyhydroxyethyl methacrylate and copolymers thereof, or functional group-modified polymers such as carboxyl groups of these various polymers, polyesters and Examples thereof include copolymers and other latex.

As the image receiving layer-containing particles, commonly known inorganic and / or organic particles are used. As the inorganic particles, for example, silicon oxide, titanium oxide, alumina, lead oxide, metal oxides such as zirconium oxide, calcium carbonate, barium titanate, salts such as barium sulfate,
The organic particles are appropriately selected from, for example, styrene resin, acrylic resin, styrene-acrylic copolymer, styrene-divinylbenzene copolymer, melamine resin, epoxy resin, phenol resin, fluororesin and the like. You may use these particles in mixture of 2 or more types.

The average particle size of the above-mentioned particles is not particularly limited, but it is generally preferable to appropriately select in the range of 0.1 to 20 μm. The weight ratio of polymer binder and particles is 100/1 to
It is preferably 100/200. If the amount of particles is larger than this, the film strength of the image receiving layer becomes weak, which is not preferable.

In order to adjust the electric resistance of the surface of the image receiving layer, a polymer electrolyte or a conductive powder is usually added. As the polyelectrolyte, cationic polymers such as quaternary ammonium salts, nonionic polymers such as poval, polyethylene glycol and alkylamines, anionic polymers having anionic polar groups such as carboxylic acids and sulfonic acids, and these And the like. As the conductive powder, tin oxide, indium oxide,
Examples thereof include zinc oxide, titanium oxide, and combinations thereof. Among them, quaternary ammonium salt-based cationic polymers are effectively used from the viewpoints of electrical conductivity and compatibility with polymer binders, and among cationic polymers such as quaternary ammonium salts, cationic acrylic polymers are preferred. used.

In the recording sheet of the present invention, the coefficient of static friction between the coated surfaces of the image receiving layer and the easy-slip / antistatic layer is 1.5.
The following is preferable, and 1.2 or less is more preferable. If the coefficient of static friction is higher than the above range, printing errors may occur due to paper feed errors such as heavy running and running defects (recording sheets clogged inside the copier / printer).

The surface electric resistance value of the image receiving layer is 1 × 10.
^{7 to} 5 × 10 ¹³ Ω / □ is preferable, and further 5 × 10 ⁸ to
1 × 10 ¹³ Ω / □ is preferable. When the surface electric resistance value is out of the above range, there is a possibility that printing failure, paper feeding error, and running failure may occur, which is not preferable. The surface electric resistance value of the easily slipping / antistatic layer is preferably 5 × 10 ¹³ Ω / □ or less,
Further, it is preferably 1 × 10 ¹³ Ω / □ or less. If the surface electric resistance value is higher than the above range, a paper feed error, a traveling failure, and dust adhesion may occur, which is not preferable.

The thickness of the image receiving layer is preferably 0.5 to 30 g / m ² as a coating amount after drying. More preferably, the amount is 1 to 20 g / m ² .
If it is less than this range, the adhesion and absorptivity of the image are deteriorated, whereas if it is more than this range, the workability is deteriorated such that the drying time becomes long, which is not preferable. The thickness of the easily slipping / antistatic layer is not particularly limited as long as it satisfies the above-mentioned static friction coefficient and surface electric resistance value, but practically 0.1 g / m ² or more is desirable.

For the coating of the image receiving layer and the easy-slip / antistatic layer, any known method such as gravure coating, reverse coating, kiss coating, die coating or bar coating can be used. In the image-receiving layer and the easy-slip / antistatic layer of the present invention, known additives such as a plasticizer, a lubricant, a surfactant, a cross-linking agent, and an antioxidant are included within a range that does not impair the effects of the present invention. Agents, ultraviolet absorbers, colorants, optical brighteners, leveling agents and the like may be added.

[0024]

EXAMPLES First, a method of measuring various characteristics in the present invention will be described.

(1) Friction coefficient Static friction coefficient μ according to ASTM-D-1894-63
s, the coefficient of dynamic friction μd was measured.

(2) Surface electric resistance The surface electric resistance was measured at 20 ° C. and 65% RH using a digital ultra-high resistance / micro ammeter (type R8340) manufactured by Advantest.

(3) Image characteristics Fuji Xerox electrostatic copying machine (type 5055) and Canon inkjet printer (type BJC)
-820J), and the image characteristics were visually evaluated. ◯: The image is clear. X: The image is unclear, the density is low, or the adhesiveness is poor.

(4) Runnability Fuji Xerox electrostatic copying machine (type 5055) and Canon inkjet printer (type BJC)
-820J). ○: Drive without problems. Δ: A paper feed error occurs, but the vehicle runs. X: Driving is impossible.

Next, the present invention will be described more specifically by way of examples. In addition, all compounding parts in the examples are parts by weight.

Example 1 Polyethylene terephthalate homopolymer chips produced by a conventional method (intrinsic viscosity: 0.62, melting point: 259)
(° C.) Was used to obtain a 100 μm biaxially stretched polyester film by a conventional method. Corona discharge treatment was performed on the thus obtained biaxially stretched polyester film.
Next, an image receiving layer having the following composition was coated on the corona discharge treated surface with a gravure coater (the coating amount of the image receiving layer after drying was 5 g / m ² ). The surface electric resistance value of the image receiving layer was 1 × 10 ¹⁰ Ω / □.

Image-Receiving Layer In a flask equipped with a condenser, a thermometer, and a stirrer, 50 parts of xylene, 10 parts of methyl methacrylate, 11 parts of n-butyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate, 18 parts of styrene, and acrylic. 0.5 part of an acid and 0.5 part of azobisisobutyronitrile were charged and stirring polymerization was completed at 80 ° C. for 2 hours to obtain a poly (meth) acrylic acid ester / styrene copolymer. The copolymer 50
Parts, 50 parts of quaternary ammonium salt polymer ("Elekondo" PQ-50B manufactured by Soken Chemical Industry Co., Ltd.), toluene / MIBK =
A coating solution diluted with 1/1 to 20% was obtained.

On the other hand, a silicone-modified quaternary acrylic ammonium salt polymer ("Saftomer" ST-250 manufactured by Mitsubishi Petrochemical Co., Ltd.) was used as an easy-slip / antistatic layer on the opposite side of the image receiving layer.
0) was diluted to 15% with toluene / MEK = 1/1 and coated with a gravure coater (the coating amount after drying was 1.0 g /
It was m ²⁾ to obtain a recording sheet of the present invention.

The thus-obtained image-receiving layer of the recording sheet and the easy-slip / antistatic layer had a static friction coefficient μs of 0.53 and a dynamic friction coefficient μd of 0.25 between the coated surfaces, and the easy-slip / antistatic layer was also used. The surface electric resistance value of was 5 × 10 ¹⁰ Ω / □.

Next, a copy test of the recording sheet of the present invention was carried out by an electrophotographic copying machine. As a result, there were no feeding errors or running defects, the image characteristics were good, and the toner adhesion was good.

Example 2 The biaxially stretched polyester film obtained in Example 1 was subjected to corona discharge treatment. Next, an image receiving layer having the following composition was coated on the surface treated with corona discharge by a reverse coater (the coating amount of the image receiving layer after drying was 10 g / m ² ). The surface electric resistance value of the image receiving layer is 5 × 10 ⁹ Ω /
It was □.

Image Receptive Layer 2-Hydroxy-3-methacryloxypropyltrimethylammonium chloride and 2-hydroxyethyl acrylate were polymerized by a conventional radical polymerization method to prepare a quaternary ammonium salt polymer. Next, trimethyl- (3-methacrylamidopropyl) ammonium chloride and vinyl acetate were copolymerized, and the resulting copolymer was saponified by a conventional method so that the content of the monomer unit having a cationic group was 3 mol%. And saponification degree of vinyl acetate unit is 88
A cation-modified polyvinyl alcohol having a mol% and a degree of polymerization of 1750 was prepared. Water / methyl alcohol = so that the quaternary ammonium salt polymer, the cation-modified polyvinyl alcohol and the water-soluble melamine resin (“Nikalac” MW-22 manufactured by Sanwa Chemical Co., Ltd.) have a solid content ratio of 50/50/10. It was dissolved in a 1/1 solvent to obtain a coating material having a solid content of 10%.

On the other hand, a silicone-modified quaternary acrylic ammonium salt polymer ("Saftomer" ST-250 manufactured by Mitsubishi Petrochemical Co., Ltd.) was used as an easily slipping / antistatic layer on the opposite side of the image receiving layer.
0) was diluted to 15% with toluene / MEK = 1/1 and coated with a gravure coater (the coating amount after drying was 1.0 g /
It was m ²⁾ to obtain a recording sheet of the present invention.

The thus obtained recording sheet had a coefficient of static friction μs of 0.45 and a coefficient of dynamic friction μd of 0.25 between the coated surfaces of the image receiving layer and the easy slipping / antistatic layer. The surface electric resistance value of the easily slipping / antistatic layer was 5 × 10 ¹⁰ Ω / □.

Next, a printing test was conducted on the recording sheet of the present invention with an ink jet printer. As a result, there were no feeding errors and running defects, the image characteristics were good, and the ink absorption was good.

Example 3 Polyethylene terephthalate (Intrinsic viscosity [η] = 0.6
5), 94% by weight, 5% by weight of poly-4-methylpentene-1 (TPX-D820, Mitsui Petrochemical Co., Ltd.), and 1% by weight of polyethylene glycol having a molecular weight of 4000 were fed to the extruder A, and the mixture was fed to the extruder A. Melted at 285 ° C. by the method and introduced into the central layer of the T-die three-layer composite die.

On the other hand, the above-mentioned polyethylene terephthalate 9
0% by weight of calcium carbonate (average particle size 0.8 μm) 1
The raw material added with 0 wt% was supplied to an extruder B, melted at 285 ° C. by a conventional method and laminated on both surface layers of a T-die three-layer composite spinneret, and the melt sheet was kept at a surface temperature of 25 ° C. The solid was cooled and solidified on the cooling drum by the electrostatic charge method. Then, the cast sheet was stretched 3.5 times by a roll group heated to 98 ° C in the longitudinal direction according to a conventional method, and cooled to 25 ° C. Further, the drawn film is guided to a tenter 1
The film was stretched 3.2 times in the width direction in an atmosphere heated to 25 ° C. and heat-set at 225 ° C. to obtain a film having a thickness of 100 μm. The thickness of each film layer was 5 μm on the surface layer and 90 μm on the central layer. Using the biaxially stretched polyester film thus obtained, a recording sheet of the present invention was obtained in the same manner as in Example 1.

Using the recording sheet thus obtained, a thermal printer (Autonics: BC-8MK-II, Ribbon: Toppan Printing HD, printing conditions: 10.5 V, 4.2)
As a result of printing the barcode in 5 ms),
It was found that the ink adhesion was excellent. Further, when a UV offset ink (Toyo Ink FDS-2) was printed, it was found that the ink acceptability and ink adhesion were excellent. From these, it can be seen that the recording sheet of the present invention is also useful for thermal printers and UV offset printing.

Comparative Example 1 In Example 1, a commercially available quaternary acrylic ammonium salt polymer (“Elecond” PQ-10 manufactured by Soken Chemical Co., Ltd.) was used as an easily slipping / antistatic layer in toluene / IPA = 1/1. A recording sheet was obtained in the same manner except that it was diluted to 15% and was coated with a gravure coater (the coating amount after drying was 1.0 g / m ² ). As a result of performing a copy test on the recording sheet with an electrophotographic copying machine, the slipperiness between the coated surfaces of the image receiving layer and the easy-sliding / antistatic layer was poor, causing double running and paper feeding error. A paper jam occurred due to poor running inside.

[0044]

According to the present invention, an image receiving layer, a plastic film, and an easy slip / antistatic layer are laminated in this order, and a special easy slip / antistatic layer is used on the opposite side of the image receiving layer. When printing with a copying machine or a printer, a recording sheet can be obtained which does not cause a paper feed error or a running failure and is excellent in toner and ink adhesion.

Claims (1)

[Claims] 1. A recording sheet comprising an image receiving layer, a plastic film, and an easy-slip / antistatic layer laminated in this order, wherein the easy-slip / antistatic layer comprises a silicone-modified quaternary ammonium salt polymer. Characteristic recording sheet.