JP2601744C - - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording paper used for an ink jet printer or a plotter,
In particular, the present invention provides a recording material having excellent suitability as a second original drawing sheet for CAD. 2. Description of the Related Art In the field of design and drafting, a CAD system using a computer has become widespread from the conventional method of creating a drawing by hand. Accordingly, the use of plotters (printer plotters) as peripheral devices for electronic computers has been increasing. This plotter simultaneously outputs print data and plot data on the same page, and it has become easy to obtain graphic output corresponding to the high-speed and large-capacity processing capabilities of electronic computers. When the above plotters are classified by recording method, pen plotters, electrostatic plotters,
They can be broadly classified into heat-sensitive plotters and inkjet plotters. The ink jet recording system is basically capable of recording on plain paper, noiseless, and developed,
Since full-color printing can be easily performed without the need for a fixing process, it has been rapidly spread in word processors, printers, plotters, and the like in recent years, in conjunction with lower prices. [0004] The basic performance required of ink jet recording paper is as follows: a. High image density, circular dot shape, no spread such as bleeding, sharpness around dots, and high resolution; b. A good ink-absorbing speed, excellent drying properties, and good color recording properties such that the inks do not mix with each other when the inks overlap; c. There is little dimensional change after recording, no curl, waving, deformation, etc., and it is a technical problem to achieve both the absorptivity that governs the dryness of the ink and the contradictory properties of dot spreading (bleeding). It is. [0005] Basic paper such as high quality paper can be basically used as the ink jet recording paper. However, paper such as size, air permeability, density, smoothness, and underwater elongation in accordance with ink and other conditions can be used. Recording paper with various physical property values is used. On the other hand, in order to obtain high-quality drawings for color recording or design, control of these physical properties alone is not enough.Coated paper-type inkjet printing with a coating layer provided on the sheet surface to optimize pigments and binders Recording paper is suitable. As a technical means for solving these problems, Japanese Patent Application Laid-Open No. 55-5830 discloses a technique comprising a support and an ink-absorbing layer provided on the surface thereof.
0 to 97.5%, the absorbency of the ink absorbing layer is 1.5 to 18.0 mm /
Ink-jet recording sheet characterized by the fact that the ink-absorbing layer is formed as white pigments such as clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, and sulfuric acid. Barium, titanium oxide, zinc oxide, zinc sulfide, satin white, aluminum silicate, lithopone, etc. are used alone or as a mixture of two or more types. " However, in the above case, since these white pigments are used in the porous ink absorbing layer, the layer itself is opaque, and the obtained ink jet recording sheet has an opacity of 55.0 to 97.5%. The object is different from the transparent paper for ink jet recording in which the transparency is 60% or more, which is the purpose of the above. On the other hand, a transparent plastic film such as polyethylene terephthalate as an OHP (overhead projector) film is disclosed in JP-A-60-132785.
JP-A-60-145879 and JP-A-60-145879 disclose formation of a coating film composed of a mixture of polyvinyl alcohol and polyvinylpyrrolidone.
No. 4,399,91 discloses forming a coating film comprising a mixture of an acrylic cation resin having a quaternary ammonium base. [0008] These contradict each other with respect to the technical problems of ink absorptivity and dot spread. JP-A-60-132785 and JP-A-60-145879 disclose water absorption due to swelling of a water-soluble resin such as polyvinylpyrrolidone. Utilization, JP-A-60-143991
In the publication, it is considered that a direct dye or an acidic dye having an anionic group in the aqueous ink is ionic-bonded to a cation group of the acrylic cation resin in the ink receiving layer to insolubilize the dye. However, these ink jet recording sheets have been devised as OHP films and do not have satisfactory quality as the second original drawing paper for CAD. [0009] The second original sheet for CAD may be a second original sheet for diazo copy,
Alternatively, in the case of a design drawing or a program list whose contents need to be checked, the recording sheet must be transparent, but it is most important to satisfy the following quality characteristics. [0010] 1. Writability with a pencil and re-writability. 2. Erasability with poppy rubber etc. 3. Marking of vermilion, stamp, etc. 4. Mechanical strength such as tension and tear. 5. Long-term storage that can withstand heat, humidity, light, etc. Therefore, in the present invention, it is a technical problem to obtain, as the transparent paper for inkjet recording, a transparent paper having both characteristics of the inkjet recording paper and the second original drawing paper for CAD. Conventionally, as a transparent base material for obtaining the second original drawing paper, I.I. Plastic films such as cellulose acetate and polyethylene terephthalate; II. Tracing paper, III. Synthetic pulp mixed paper, IV. Various materials such as transparent paper impregnated with oils and plasticizers have been tried, but all have the following disadvantages. [0013] Film-based ones are excellent in transparency, dimensional stability and mechanical strength, but have drawbacks in foldability and price, and tracing papers have dimensional stability,
The tear strength and the water resistance are inferior, and the workability of coating and the like is particularly inappropriate.
On the other hand, synthetic pulp-mixed paper generally has large irregularities in formation and transparency due to poor affinity between wood pulp and synthetic pulp, and also has disadvantages of low transparency itself.
In the case of transparent paper impregnated in paper with oils, plasticizers, etc. as a clarifying agent, the clarifying agent migrates to other materials during long-term storage, causing winding blocking and image bleeding, and The strength also decreases. By the way, in general, in order to make paper transparent, it is sufficient to fill the voids in the paper layer with a substance having a refractive index similar to that of cellulose fibers. However, when a polymer substance is used as a clarifying agent, the penetration into the inside of the paper layer is insufficient, and a uniform transparent paper cannot be obtained. Therefore, for the purpose of transparency, use of a transparentizing agent that can be cured by a catalyst, heating or other means, that is, use of a reactive resin, in order to prevent migration after sufficiently penetrating a relatively low-molecular liquid material into the paper layer, that is, using a reactive resin Seems to be the best strategy. From such a viewpoint, Japanese Patent Publication No. 43-25927 discloses a use of an alkanol-modified amino resin and a non-oil type or non-drying oil fatty acid-modified short oil type alkyd resin compatible therewith. It has been described, and Japanese Patent Publication No. 51-363
No. 67, diisocyanate or polyisocyanate as the first component,
A clarifying agent comprising a reactive resin in which a polyester polyol is combined as a second component is described in the claims. Therefore, the present inventors have tried to apply a conventional ink-jet coating liquid using a transparent paper impregnated with the above-described reactive resin as a base material. It was not possible to obtain a second original drawing sheet which was transparent and excellent in correction and correction. The present invention is an ink jet recording material which is excellent in ink drying property at the time of recording and has no bleeding of an image. It is intended to provide. Means for Solving the Problems The present inventors have conducted intensive studies in order to solve such problems, and as a result, impregnated paper with these reactive resins and cured the paper layers in the paper layer. A transparent paper having a chain or network structure formed thereon, coated with silica having an average particle size of 5.5 to 10.0 μm and a hydrophilic polymer compound, and emulsion-type cationic polymer is applied to the hydrophilic polymer compound By including a conductive agent, the transparency of the second original drawing paper is excellent in retouching and correction.
% Or more of transparent paper for ink-jet recording was completed. The reactive resin as a clarifying agent in the present invention is an alkanol-modified amino resin known from JP-B-43-25927 and JP-B-51-36367, and a non-oil compatible with the alkanol-modified amino resin. Saturated fatty acids comprising a combination of modified or non-drying oil fatty acid modified short oil type alkyd resin, or diisocyanate or polyisocyanate as the first component, which is compatible and has 8 to 18 carbon atoms Modified or non-drying oil fatty acid-modified oil length of 30 to 70, molecular weight of 1,000 or less, preferably composed of a combination of both components having a polyester polyol resin having an OH value of 10 or more as a second component, In addition to amino resin or polyurethane, polyamide, polyamine, epoxy resin, UV curable or Electron beam curable resins can be used. These reactive resins have a basis weight of 20 to
Impregnate 100 g / m ² of high quality impregnated base paper or high quality paper. [0020] The adhesion ratio of the reactive resin is preferably 10 to 60% based on the substrate, and a transparent base material having a transparency of 60% or more can be obtained after clearing. An ink-jet coating liquid containing silica and a hydrophilic polymer compound is applied to the resin-impregnated and transparent paper thus obtained. In the present invention, the average particle size is 5.5 to 10.0 for the purpose of imparting the second original drawing paper suitability.
Use μm silica. Pigments generally used in ink jet coating liquids include clay, talc, calcium carbonate, barium sulfate, titanium oxide and the like. However, although these pigments are effective for improving writability, they are white pigments, so that another object of the present invention, a transparent paper for inkjet recording having a transparency of 60% or more, cannot be obtained. Further, silica having an average particle diameter of more than 10.0 μm has a large degree of wear when writing with a pencil, lacks sharpness of an image, and also causes ink bleeding as ink jet recording suitability. On the other hand, when silica having an average particle size of less than 3.0 μm is used, the specific surface area of the coating film is increased and the ink absorption speed is increased, but the transparency is reduced and the transparency of 60% or more cannot be obtained. Further, ultrafine silica typified by colloidal silica has good transparency but does not provide writability. The present invention uses a silica pigment having an average particle size of 5.5 to 10.0 μm,
That goal is achieved. The addition ratio of the silica pigment can be usually in the range of 5 to 80% by weight, preferably 20 to 50% by weight, based on the solid content of the coating solution. Also with respect to the coating amount of the inkjet recording coating liquid, but may range from 0.5~1 5g / m ² (dry weight), the optimum application amount is 1 to 5 g / m ^2. The relationship between the addition ratio of the silica pigment and the coating amount is determined by transparency and pencil writing. That is, when the addition ratio of the silica pigment is high and the coating amount is large, the transparency of 60% or more cannot be obtained. Conversely, when the addition ratio of the silica pigment is low and the coating amount is small, sufficient writing properties cannot be obtained. In the present invention, as another means for achieving the object, 20% or more of an emulsion-type cationic conductive agent is added to a hydrophilic polymer compound. The hydrophilic polymer compound generally used in the ink jet coating liquid is, for example, a water-soluble polymer compound such as oxidized starch, etherified starch, gelatin, casein, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, and ethylene glycol maleic anhydride copolymer. And polyvinyl alcohol. However, these polymer compounds alone cannot overcome the technical problems of ink drying properties and ink bleeding in inkjet recording. In the present invention, a cationic conductive agent is blended with the above-mentioned hydrophilic polymer compound. Polyvinyl alcohol is most suitable because it is limited by a polymer compound compatible with the cationic conductive agent from ionic. In the present invention, an emulsion-type cationic conductive agent is used as the cationic conductive agent. The present inventors have studied various water-soluble cationic conductive agents in the process leading to the present invention, but were unable to obtain a transparent paper for ink jet recording excellent in writing correction as a second original drawing paper. The reason is that when the cationic conductive agent is a water-soluble resin, the coated base material is a transparent paper impregnated with a reactive resin, and therefore lacks adhesion to the base material, and the writing correction as the second original drawing paper is performed. Concluded that no sex could be obtained. Further, the present inventors have conducted various studies based on the above findings. As a result, when forming an inkjet coating on transparent paper impregnated with a reactive resin, an emulsion-type cationic conductive agent was used as the cationic conductive agent. It has been found that when used, the adhesion to the base material becomes good, the writing correctability as the second original drawing paper becomes good, and the object of the present invention is achieved. The emulsion-type cationic conductive agent used in the present invention includes (I) alkyl acrylate, alkyl methacrylate, styrene and the like, and (II) methacryloxyethyltrimethylammonium chloride, methacrylamidopropyltrimethylammonium chloride. And a hydrophilic copolymer resin dispersion obtained by copolymerizing quaternary ammonium salts such as 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride and vinylbenzyltrimethylammonium chloride in an aqueous medium. This quaternary ammonium salt accounts for 30 mol% in the copolymer resin.
The above requirement is necessary, and below this value, the copolymer resin has poor hydrophilicity and lacks suitability as an ink jet recording material. Although such an emulsion-type cationic conductive agent may be used alone,
Preferably, it is used in combination with a hydrophilic polymer compound such as polyvinyl alcohol for the purpose of improving coating properties. For the purpose of improving water resistance, polyvinyl alcohol may be used by adding and mixing a water resistance agent such as glyoxal. The mixing ratio of the emulsion-type cationic conductive agent is preferably 20% or more in the hydrophilic polymer compound. If the blending ratio of the emulsion-type cationic conductive agent is less than 20%, the adhesion of the coating film is poor, the writing correction property as the second original drawing paper cannot be obtained, and the drying property of the ink is poor, and bleeding occurs. . Emulsion resins such as SBR latex, acrylic emulsion, vinyl chloride emulsion and vinyl acetate emulsion have good adhesion to the transparentizing base material, but have poor hydrophilicity and ionicity of the coating film. Since it is an anion, it cannot overcome the technical problems of ink drying properties and ink bleeding as an inkjet recording material. That is, when an inkjet coating liquid is applied using a transparent paper impregnated with a reactive resin excellent in processability and the like as a base material, the transparent pigment as the coating liquid has an average particle size of 3.0 to 1
By using 0.0 μm silica and blending 20% or more of an emulsion-type cationic resin with a hydrophilic polymer compound, it is an object of the present invention to be suitable for the second original drawing paper such as writing correctability with a transparency of 60% or more. The transparent paper for inkjet recording having the following is effectively obtained. EXAMPLES The present invention will be described in more detail with reference to the following examples. Example 1 100 parts by weight of a 70% polyester polyol xylene solution having a reaction molar ratio of coconut oil fatty acid 5, phthalic anhydride 6, and glycerin 7 on a base paper for impregnating high-quality wood with a basis weight of 50 g / m ^2. Was mixed with 47 parts by weight of a 60% ethyl acetate solution of triisocyanate having a reaction molar ratio of tolylene diisocyanate 3 and trimethylolpropane 1, and the ratio of ethyl acetate to toluene was diluted by 1: 1 to obtain 61. % Solidified resin composition liquid, and the excess liquid is removed with a pressure cup roll.
Curing was performed at 0 ° C. for 3 minutes to obtain a transparent base material having a transparency of 71.5%. Each component of the inkjet coating liquid was prepared by the following method. 90 parts of water was added to 10 parts of polyvinyl alcohol (trade name: PVA117, manufactured by Kuraray Co., Ltd.), and the mixture was steamed at 100 ° C. for 30 minutes, cooled, and a polyvinyl alcohol solution having a solid concentration of 10% was obtained. To 20 parts of a silica pigment (trade name: Syloid 162) having an average particle size of 5.5 μm, 40 parts of water and 40 parts of methyl alcohol were added, and dispersed by a homomixer for 30 minutes.
A pigment dispersion having a solid content of 0% was obtained. The emulsion-type cationic conductive agent was charged with 50 parts of deionized water and 2 parts of a 3% aqueous solution of ammonium persulfide as an initiator in a four-necked flask equipped with a stir bar and a nitrogen gas tube, and replaced with nitrogen for 30 minutes. Then, the temperature was raised to 75 ° C. Thereafter, 130 parts of deionized water, 1 part of nonionic NS-240 (manufactured by NOF Corporation) as an emulsifier, 150 parts of methacryloxyethyltrimethylammonium chloride, and 15:50 of 2-hydroxyethyl acrylate, acrylonitrile, butyl acrylate : 35 parts (weight ratio) of monomer and 1 part of t-dodecyl mercaptan as a chain transfer agent were mixed, and the mixture was dropped into the above four-necked flask over 3 hours using a dropping funnel to carry out polymerization. Thirty minutes after the completion of the dropwise addition, the temperature was raised to 85 ° C., 1 part of a 3% aqueous solution of ammonium persulfide was added, and the mixture was kept for 3 hours and cooled. Thereafter, the pH was neutralized to 7 with aqueous ammonia, and after filtration, an emulsion-type cationic conductive agent having a solid content of 30% and a viscosity of 200 cps was obtained. Coating liquid Pigment dispersion 50 parts Polyvinyl alcohol solution 100 parts Emulsion-type cationic conductive agent 30 parts Glyoxal 1 part Water 60 parts Methyl alcohol 60 parts Ink jet with a solid content concentration of 10% in the above composition. An application liquid was obtained. This liquid was applied to the above-mentioned transparent substrate by bar rod coating, and dried at 120 ° C. for 1 minute with a Safeven dryer to obtain an ink-jet transparent recording paper having a coating amount of 3.5 g / m ² . <Comparative Example 1> Example 1 Example 1 except that the silica pigment was removed from the inkjet coating liquid of Example 1. Under the same conditions as above, a transparent paper for inkjet recording was produced. <Comparative Example 2> Example 1 Example 1 except that a silica pigment having an average particle size of 1.4 μm (trade name: Syloid 150) was used as the silica pigment in the inkjet coating liquid of Example 1. Under the same conditions as above, a transparent paper for inkjet recording was produced. <Comparative Example 3> Example 1 Example 1 except that a silica pigment having an average particle diameter of 12.0 μm (trade name: Syloid 620) was used as the silica pigment in the inkjet coating liquid of Example 1. Under the same conditions as above, a transparent paper for inkjet recording was produced. <Comparative Example 4> Example 1 Example 1 except that the emulsion type cationic conductive agent was removed from the ink jet coating liquid of Example 1. Under the same conditions as above, a transparent paper for inkjet recording was produced. <Comparative Example 5> Example 1 Example 1 except that SBR latex was used in place of the emulsion-type cationic conductive agent in the ink jet coating liquid of Example 1. Under the same conditions as above, a transparent paper for inkjet recording was produced. The characteristics of each of the transparent papers for inkjet recording were evaluated by the evaluation method described below, and the results are shown in Table 1. [0046] will be described below evaluation evaluation methods. (1) Recording method: Inkjet printer HG-5130 (Epson)
Recorded. (2) Transparency: Measured using a transparency tester manufactured by Toyo Seiki Seisaku-sho. (3) Ink drying property: The time required for the ink to completely dry was evaluated by ○ to ×. (4) Ink bleeding: The dot shape and the edge portion observed with a stereoscopic microscope were evaluated as 〜 to ×. (5) Pencil writing: using Mitsubishi Pencil Uni 0.5mm, HB, pencil writing,
The pencil abrasion and the sharpness of the image were evaluated as 〜 to ×. In addition, as to whether or not the writing was possible, writing → erasing the eraser → writing was repeated five times, and the sliding of the pencil and the removal of the coating film were evaluated. [Table 1] As can be seen from the examples, according to the present invention, a recording material having a fast drying property of an ink and having no bleeding, and having a transparency of 60% or more and good pencil writing properties. Thus, it is possible to obtain a transparent paper for ink jet recording which has a suitable second original drawing paper.

Claims (1)

Claims 1. A transparent paper impregnated with a reactive resin is provided with a second paper on at least one surface thereof.
A transparent pigment and a hydrophilic polymer compound for imparting suitability to the original drawing paper are applied, the transparent pigment is silica having an average particle size of 5.5 to 10.0 μm, and the hydrophilic polymer compound includes 20% or more of the emulsion-type cationic conductive agent, and 30% by mole or more of the hydrophilic copolymer resin in the emulsion-type cationic conductive agent is the fourth component.
A transparent paper for inkjet recording having a transparency of 60% or more, which is a quaternary ammonium salt.