TW446645B - Recording paper - Google Patents

Abstract

The present invention aims to provide a new recording paper on which only a part of the patterns printed by an ink-jet printer may be erased without any effect on other parts and no deterioration of the erasion effect will be shown on the erased part even after a lengthy period of time. The solution is to design a recording paper on which a part of the records can be erased. An ink receiving layer with ink-jet printing patterns printed by dye ink should be supported on at least one surface of the base film and ink-jet printing patterns printed by pigment ink and incompatible with the ink receiving layer should be supported on the surface of the ink receiving layer.

Description

It has the eraser formed by inkjet printing to erase (remove), and then to remove the part, and to popularize printing. A popular printer that will be printed by a computer submachine ", printer) includes, dot printing , Inkjet printers, etc., which generate mechanical noise and are used for printing. The paper used at the time of printing is usually overwritten with a part of the recording paper that uses an ink-receiving layer (ink-receiving layer) made of a base material made of plastic film and has good storage properties. The field recording paper was proposed (under the Japanese patent, 'all the patterns printed by inkjet printers are erased, etc., and sometimes the patterns that do not need to be erased are removed after time', and the patterns are fixed 44664 5 ) [Technical field to which the invention belongs] The present invention relates to a recording paper in which a part of the pattern can be erased when necessary, and a new pattern can be added to the eraser. [Prior Art] In recent years, due to the use of computer technology, The information produced is printed by a printer (also known as " printing out (printing out). At this time, the use of laser printers, laser printers, heating printers, inkjet printers are rarely issued when printing out. The cost associated with rotation is low, and it has been widely used. In addition, in order to use inkjet printers to print paper or coated paper, recently, a recording paper made of a hydrophilic polymer substance on the surface has been used. (Because of its water resistance, on the other hand, it is often necessary to eliminate the printing pattern of this inkjet line, and there are a number of JP-A-8-207395 for this purpose.) However, this is used However, the drawings of recording paper have the following disadvantages: that is, when printing is wiped, they are also wiped off, so 'in addition to this inconvenience,

Page 4 446645

V. Explanation of the invention (2) and cannot be eliminated [· Problems to be solved by the present invention] The present invention is to provide a kind of voucher service A, go to + this t "brother service S know the erasable recording paper The lack of recording paper (such as the following) was created for the purpose: that is, only a part of the printing pattern printed on the Xinji J paper by an inkjet printer can be eliminated, and other parts will not be # ,, Xiao ^ ^ τ is eliminated, and this can be eliminated even if! Excessive time does not show a reduction in its elimination performance. [Means for Solving the Problem]-The inventors of this case, in order to develop a recording paper that can print only a part of the printing pattern that can be selectively eliminated by an inkjet printer, repeatedly researched. R: It was found that two inks were used. That is, a dyeing department that can penetrate the ink receiving layer (ink receiving layer) provided on the substrate film and a pigment ink that does not penetrate the ink receiving layer to be printed by dye ink when printing with an inkjet printer. The fact that a part cannot be divided by 4 and the part printed by the pigment ink may be eliminated and can be long, and the elimination performance is maintained for a while, so the present invention is completed based on the research results. That is, the present invention provides a recording paper capable of erasing a part of a recording, which is characterized in that an ink-receiving layer carrying an ink-receptive printing pattern based on dye ink is provided on at least one side of a substrate film, and The surface of the ink-receiving layer carries an ink-jet printing pattern based on a pigment ink that is not compatible with the ink-receiving layer. 'In the recording paper, the ratio of the content ratio of the (A) component to the (B) component of the ink-receiving layer is 8: 2 to 6: 4, and the content of the (C) component is based on the content of the (A) component Total weight per 100 parts (weight) is 30 ～ i〇 ()

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V. Description of the invention Within the range of (3) parts (weight), especially in the range of 40 to 80 parts (weight is good. It is more advantageous in the range of ^^ 鞑), which is more advantageous, (A) component is borrowed from cellulose. Urea cross-linked polyvinyl alcohol, and component (c) is a compound having an average particle size of 3, a parent linking agent or a synthetic silica with a mean particle size of 60 / zm or more. ^ Mixture of silicon monoxide In addition, a layer of a modifier can be stacked on the ink-receiving layer of this recording paper. 3Small array [Embodiment of the invention]

The substrate film of the recording paper of the present invention is not specifically selected, and it can be optionally used from the materials used so far as the substrate of the recording paper for the inkjet printer. For this kind of substrate, for example, a material arbitrarily selected from polyphthalic acid = diester, polyethylene, polypropylene, polyamide, and the like can be used. Among them, polyethylene terephthalate is particularly suitable. The thickness of this substrate 臈 is usually set in the range of 25 to 25 0 m, and preferably in the range of 50 to 100 claws. For this purpose, the substrate film can be treated with matte as required β —

In the recording paper of the present invention, an ink-receiving layer is provided on at least one side, that is, one side or both sides of the above-mentioned base film, and in order to improve the adhesion between the ink-receiving layer and the base film, it may also be required. An undercoat layer is provided between the substrate 臈 and the ink receiving layer. For this purpose, a saturated polyester resin, a urethane resin, or the like is usually used as the undercoat layer. Among these, a urethane resin is preferred because the urethane resin and the ink-receiving layer have good adhesion. The thickness of this undercoating layer is usually set within the range of 0.5 to 1.5 ΘΠ1. Secondly, for this ink-receiving layer, for example

Poly (ethylene) cross-linked with (A)

Page 6 446645 V. Description of the invention (4) Enol, (B) polyvinylpyrrolidone, and (C) person, dagger layer. ‘Mouth is made of sulphur dioxide and the main component is polyvinyl alcohol used for this component (A). It ’s better to have a polymer mill above +%’, especially in the range of 10,000 to 3,000. If the degree of polymerization is more than 1000%, the ink dryness (ink absorption) and water-repellency of the film will be insufficient. Moreover, in this polyvinyl alcohol, the preferred order >,

Τ, at λ, the polyvinyl alcohol is, I partially saponified with a degree of saponification of 75 mol.% Or more of polyvinyl acetate: saponification ', especially the degree of saponification of 75 to 90 m. u < Punch points of saponification. When the degree of saponification is less than 75% 1.75%, the ink absorption speed will decrease. This (A) component can also be crosslinked by a cellulose-reactive crosslinking agent or urea. This cellulose-reactive crosslinker is a crosslinker that is reactive with the cellulose base, and examples of such crosslinkers include, for example, dimethyl dimethylene, methane Dihydrogen three-phase, f-basic di-derivatives are derived from cyclic or heterocyclic veins of methyl " m. (Ur〇ne), dimethylol glyoxal mono " ureine " These cellulose-reactive crosslinkers or urea are formed in the presence of catalysts (such as ammonium chloride, ammonium nitrate, sulfuric acid, etc.) and react with functional groups in polyvinyl alcohol to form a three-dimensional structure The ratio of the amount of cellulose reactive plastic crosslinker or vein used is based on 100 parts by weight of polyvinyl alcohol, usually 4-12 parts by weight, preferably 5-10 parts by weight. If the amount used is less than 4 parts by weight, the water resistance cannot be sufficiently improved, and if it exceeds 12 parts by weight, the ink absorption tends to decrease. Furthermore, the catalyst used together with this When the amount ratio is based on the cellulose-reactive cross-linking agent, it is usually preferably 20 to 100% by weight. Secondly, the polyethylene resin used as the (B) component v > ratio Slightly biting nets usually have molecules

V. Description of the invention (5) The amount is more than 40,000, especially in the range of 600,000 to 2,800,000. If the molecular weight is less than 40,000, the absorption rate or capacity of the ink becomes low, and as a result, the drying property of the ink is reduced. Furthermore, among the synthetic silicas used as the component (C), the preferred synthetic monoxide has an oil absorption of 75 to 105 ml and a specific surface area of 500 to 900 m2 / g. Right, if the oil absorption is less than 7.5 m 1 or the specific surface area is less than 500 m 2 / g, it is difficult to make the dye ink fully penetrate and be absorbed when printing with dye ink, and the oil absorption is more than 105 ml. When the specific surface area is greater than 900 m2 / g

′ Because the penetration of the pigment ink occurs, the pattern printed by the pigment ink is difficult to be erased (erased) by an eraser or the like. For this reason, it is more suitable to synthesize silicon dioxide ', which has an average particle diameter in the range of 0.5 to 15 # m', and is preferably in the range of 0.8 to 9 / zm. If the average particle diameter is less than 0.5 to m, poor ink drying properties are exhibited. If the average particle size exceeds 1 5 m, the dot shape is difficult to form a true circle, and the image resolution tends to decrease. In this (C) component of synthetic silicon dioxide, 'especially suitable synthetic silica' has an average particle size of less than 3. 5 am, and synthetic silicon dioxide with an average particle size of 0 // m or more-an oxide dream Of a mixture. The average particle size of this item is small

When the mixing ratio of t f monoxide to larger synthetic dioxide is calculated by weight t, a range of 8: 2 to 2: 8 is preferred. • When the content ratio of (A.) Chengdao and (b) is calculated by weight ratio, it is better to be within 6.4. If the ratio of (A) component is less than this range * Water resistance will reduce the root & citron ^ is low and cause the adhesion, and if the ratio of (A) component is greater than this range, the absorption of dye ink will be reduce.

Page 8 446645 • · \ ·, V. Description of the invention (6) Secondly, when the content of the component (C) is based on the total weight of the component (A) and the component (B) per 100 parts by weight, it is selected. Within the range of 30 to 100 parts by weight, it is preferable to be within the range of 40 to 80 parts by weight. If the content is less than 30 parts by weight, the absorption of dye inks will be reduced, and if it exceeds 100,000 parts by weight, the financial water will be reduced. The recording paper of the present invention can be produced by a method such as the following method. That is, 'the (A) component, the (B) component, and the (c) component are each dissolved or dispersed in an aqueous medium at a specified ratio to prepare a coating liquid having a solid content concentration of 10 to 15 wt%. After that, it is applied on the base film according to a conventional method or an undercoat layer is set as required, and it is dried to provide an ink-receiving layer. In this case, various additives conventionally used so far such as a surfactant, a lubricant, a stabilizer, a colorant, and the like can be added to the coating liquid. The thickness of this ink-receiving layer is generally within a range of 5 to 30 'and preferably within a range of 10 to 20. In the present invention, a layer containing a dot-shape-adjusting agent may be provided on the ink-receiving layer thus provided as necessary. For this purpose, the dot shape adjusting agent is preferably a fourth-stage ammonium salt type acrylic resin. Specific examples of the fourth-stage ammonium salt type acrylic resins include copolymer salts of alkyl acrylate or alkyl methacrylate and dialkylamino acrylate or dialkylamino alkyl acrylate. Such a fourth-stage ammonium salt-type acrylic resin is a conventional thing, for example, a quaternary salt of a copolymer of butyl methacrylate and dimethylamino ethyl methionate of 1: 1 mole ratio is possible. A commercially available product. In order to form this layer containing the dot matrix shape adjusting agent, the above dot matrix shape adjusting agent is applied in an appropriate solvent such as alcohol or a mixture of alcohol and water, etc., and the solution is applied on the ink receiving layer and then dried. . At this time, you can also

Page 9 446645 V. Description of the invention (7) The adjusting agent is formed in the ink-receiving layer i ', and the dot-shape adjusting agent can be dissolved into the ink-receiving layer in one piece, or penetrate the ink-receiving layer. For two items, the coating amount of the array shape adjusting agent is 3 Η. In the range of *, if the coating amount of the dot matrix shape adjusting agent is less than 3g / m2, the quality (resolution of the image) is insufficient, and if it exceeds 1〇 ^ 2, Ϊ 右 # Eb / 墨Dryness will decrease. The function of forming the shape of the layer containing the lattice shape adjusting agent closer to the true circle and preventing the film ίΪ: Ξ: 丄 Set the ink receiving layer and the layer containing the shape adjusting agent on the substrate = 上 依 昭 Λ 在 基The back of the film (that is, the opposite of the ink-receiving layer, a matt layer or another ink-receiving layer is arranged by the spotter. The above 1 light layer is formed by resin (light :: 1, and the adhesive includes, for example, thermoplastic Examples are C (, heat =.), And ^ # μ series of poly® resins, gas vinyl resins, kaolin, alumina,-:: L silicon, hafnium oxide, clay magnesium hydroxide, calcium phosphate, ^ Li et al. Calcium carbonate, barium sulfate, resins, amines, acid brewing resins, gas B :::: body ... powder of synthetic resin of feminine acid. This item has no f = only 丨 melamine / Formaldehyde condensate, etc. ~ 2, it is better to set the particle size on the back surface of Q.1 substrate film with 2 particle diameters, and it is better to form the substrate. In addition, the same ink receiver is provided on the 2 surface. Two also =: = base = layer, for example, no photoactant or very little

Page 10 64 5 V. Description of the invention (8) Ink receiving layer etc. The thickness of the light layer is advantageous in view of preventing curling, and the range of a ^ good pen C and so on is here; set at In the range of 1 ~ 1 ..., 3 ~ Jm is added as an interfacial active agent 1 so that the matte layer contains the lubricant, stabilizer, colorant and the like conventionally used in the present invention. Dou θ < 5 has recorded the paper on the two types of inkjet printing with the above structure ^. The brush paper has an inkjet printing pattern formed by the dye ink in the ink layer. The pattern is made by penetrating the brush. The pattern is formed by the ink-receiving layer being carried, and another printing agent layer (which is laminated on the ink-receiving layer = ^ is contained in the inkjet printing pattern with dot-matrix shape adjustment. The pigment ink on the surface is formed by the above The dye ink is not particularly limited. Use of dye ink is optional. This dye is printed on the mouth of ^^, Rhodamine B or G 'Victoria Blue B is not long', and the dagger is made of peacock green. Blue and other dyes are soluble in mineral oil and vegetable oils: dyed tung oil, synthetic dry oil made from jordan, peracid resin oil and other media, and the pigment inks are not particularly affected Pigment inks for printing can be optionally used to synthesize inorganic pigments, azo pigments, and lake pigments from ordinary sprays. For example, the pigments are dispersed in a medium (such as water, interface dyes, and cyan pigments). Pigment liquid or solvent, etc.) pigment ink. And 'agent' dispersing agent, etc. Material I, pigment use particle size of 0.5 ~ 2 _ In these inkjet printing patterns, the pattern formed by the material ink is bleed through the fixing of the ink receiving layer < 0 #, g: Even if it is rubbed with an eraser or the like, M6 64 5 ―Fifth, the description of the invention (9) " ---- The pattern cannot be erased (erased) by rubbing, on the other hand, the pattern formed by the pigment ink does not penetrate In the ink-receiving layer, the pattern is only carried on the ink-receiving layer, and it is wiped off when rubbed with an eraser or the like. This pattern formed by pigment ink can last for a long time. It can still be easily eliminated in the future. Figure 1 is a longitudinal sectional view showing a model of the basic structure of the recording paper of the present invention, in which an ink-receiving layer 2 having a specified composition is provided on one side of the substrate film 1, and here An ink-jet printing pattern 3 using a dye ink as a ^ ^ is formed in a state of penetrating into the ink-receiving layer 2. In addition, an ink-jet printing pattern 4 based on ink is carried on the surface of the ink-receiving layer 2. Further, The ink-jet printing pattern 4 based on pigment ink is formed in a state where it does not penetrate into the ink-receiving layer. Therefore, if it is rubbed with an eraser or a pencil-type eliminator, it will be easy to remove (erase it off). @ [实施 例] Next, the present invention will be described in more detail based on examples. Example 1 Polyvinylpyrrolidone (molecular weight 1 28 0 0 0 0) 6 parts by weight, polyethylene synthesis (polymerization degree 2000 'saponification degree 88.0mol_%) 14 parts by weight, average silica diameter 3.5 synthetic silicon dioxide powder (specific surface area 7〇 〇2 / g) 6 parts by weight of 'cellulose-reactive cross-linking agent dihydroxyamidoglyoxal mono " urine factor " 1.4 parts by weight'gasified ammonium 0.3 part by weight ), 40 parts by weight of ethanol, 20 parts by weight of propylene glycol monomethyl ether, and 103 parts by weight of water were mixed to prepare a coating liquid for forming an ink-receiving layer. On one side of a 50-m-thick polyethylene terephthalate film, an amine

Page 12 V. Description of the invention (1〇) After the coating is formed below the thickness of 1.0 #m, the acid coating is applied to the undercoating layer with a line | It was heated at a temperature of 0 t for 5 minutes to form an ink receiving layer having a thickness of about 15 vm. Secondly, "under the use of an inkjet plotter (model number: JET750C) manufactured by HP (Hewlett Packard)", the basic design drawing of the building is borrowed from dye ink (manufactured by HP, trade name 51 6 4 4 C "). The structural part is ink-jet printed on the ink-receiving layer, and then the auxiliary structural part of the figure is ink-jet printed by pigment ink (manufactured by HP, trade name " 5 1 645A "). After standing for 1 hour ', as a result of rubbing the printed pattern with an eraser, the auxiliary structural part was completely wiped off, but the basic structural part was not lost at all. In addition, as a result of performing the same operation after standing for 2 months, the erasing performance of the inkjet printing pattern based on the pigment ink is almost unchanged. For comparison, the same pattern was ink-jet printed on commercially available ink-jet printing paper by the pigment ink. Although the elimination test was performed after 1 hour, it was completely impossible after 2 months. eliminate. Example 2 6 parts by weight of polyvinylpyrrolidone (molecular weight 1 28,000) and 14 parts by weight of polyvinyl alcohol (degree of polymerization 2000, degree of saponification 88.0 mol.%) Were averaged. 6 parts by weight of synthetic silicon dioxide powder (specific surface area 700 m2 / g) with a particle size of 3.5, 4 parts by weight of calcium carbonate powder with an average particle size of 2.0 μm, and two hydroxyl groups of a cellulose-reactive crosslinking agent Fluorenylglyoxal mono 11 urine factor "1.4 parts by weight, 0.3 parts by weight of ammonium vaporized, 40 parts by weight of ethanol, 20 parts by weight of propylene glycol monomethyl ether, and water 108. 3 parts by weight are mixed to prepare an ink-receiving layer

Page 13 446 64 5 V. Description of the invention (II) Coating liquid for formation β On one side of a polyethylene terephthalate film having a thickness of 50 m, a thickness of urethane S resin is provided. After coating under the #m, the coating liquid was applied on the undercoating layer with a wire ingot, and heated at a temperature of 30t for 5 minutes to form an ink receiving layer having a thickness of about 15. " Then 'preparation of a fourth-stage ammonium salt type acrylic resin (" Mitsubishi Petrochemical / Division products' inch 7 ^ ^ a (sahotoma) MCP-2000) 1, 0 parts (weight I), ethanol 10. 0 parts by weight, and 89. 0 parts by weight of a matrix-shape-adjusting-agent-layer-forming liquid, which is coated on the ink-receiving layer and dried to form a dot-shape-adjusting agent. Dosage layer containing 4g / m2 of lattice shape modifier. Secondly, an adhesive copolymer acrylic resin) 20 parts (weight) of tongue, actinizer (synthetic arsenic dioxide, average particle size 3 5 " m) 10 parts (=), and water 70 The coating liquid for forming a matte layer composed of parts by weight is applied on the back surface of the ink-receiving layer. U 拟 士, ® rr, heating for 2 minutes at JUC / plate degree to make a matte layer of 5 # πι thick. Regarding the recording paper thus obtained, a printing pattern based on "dye ink and a method based on pigment ink: 2 and the test was erased with an eraser, and the same pattern as in Example u / brush, and chain grass were obtained. Example 3.4 In Example 2, except that the coating liquid for forming the soil layer is Λ 1 _, ,, ^, the coating liquid not used in Table 1 is used, and the coating liquid is used. Jin Xingguan's target example 2 is exactly the same method _ making recording paper 'and using the same method as in Example 2 π Shiqi Qing π ζ phase 形成 to form a dye ink as

4 4 6 6 4 5 V. Explanation of the invention (12) When the erasure test was performed with an eraser based on the printed pattern based on pigment ink and the printed pattern based on pigment ink, the same results were obtained. Comparative Examples 1, 2 In Example 2, except that the coating liquid for forming the ink-receiving layer was used as the coating liquid having the composition shown in Table 1, recording paper was produced in the same manner as in Example 2. When a printing scheme based on dye ink and a printing pattern based on pigment ink were formed in the same manner as in Example 2, when the erasure test was performed with an eraser, the result was that the pigment ink could not be eliminated. Table 1 1 f The package example is lighter than the weight 1 2 3 4 1 2 Composition (weight) of the coating liquid for ink-receiving layer formation Polyvinyl stilboxazone 6 6 6 8 6 6 Polyvinyl alcohol 14 14 14 12 14 14 Synthetic digassed silicon powder 6 6 9 6 5 — Synthetic digassed silicon powder ~ — 1 — 1 — 5 Calcium carbonate powder too — 4 6 4 5 5 Diethyl methyl ethylene glycol: Li Chengmin 1.4 1.4 1.4 0.9 1.4 — Witm-0.3 0.3 0. 3 0.3 0.3 --- Ethanol ~ 40 40 40 40 40 40 Early age of propylene glycol · 20 20 20 20 20 20 108.3 108.3 108.3 108.3 108. 3 110 Dot matrix The use of the whole agent — 4 4 4 4 4 (note) particle size 3.5 / zm 'oil absorption 95ml, than the table size of 3, 5 μ m' oil absorption 21〇ml, ratio 1) synthetic dioxide hair powder Area 7 0 0m2 / g 2) Synthetic dioxide; ε powder surface area 300m2 / g [Effect of the invention]

Page 15 46 64 5 V. Description of the invention (13) Since the recording paper of the present invention is ink-jet printed with dye ink by a pattern that does not need to be erased, the pattern that needs to be erased according to need is ink-jet printed with pigment ink. Benefits described: That is to say, at any time, you can use an eraser or the like to modify the pattern. Furthermore, there is also an advantage that the print pattern portion based on the pigment ink can be kept for a long time without deteriorating the erasing performance. [Brief description of the drawings] FIG. 1 is a longitudinal sectional view of a model of a recording paper of the present invention. [Description of element number] 1 ... substrate film 2 ... ink-receiving layer 3 ... inkjet printing pattern based on dye ink 4 ... inkjet printing pattern based on pigment ink

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Claims (1)

4 46 6 4 5 Case No. 88109782 The scope of the patent application is a record that can eliminate a part of the record 1… on one side, it contains: (A) the eight series of cross-linking on the substrate film-pyridine I, and (C) oil absorption 75 ~ Enol, (B) Polyvinylpyrene 2 / g synthetic silicon dioxide ink-receiving layer, the characteristic specific surface area of 50 ~ 900m is contained in the ink-receiving layer with dye ink 1 | The ink-jet printing maps based on pigments carried in the ink-receiving layer; Ye Dong ''s ink-jet printing maps based on (A) and (B) components of the ink-receiving layer are 8: 2 to 6: 4, and the ratio of the component (C) is calculated by weight ratio, and the total weight per 100 parts (weight) of A t * A) component and (B) component is as the first part (weight) of the scope of the patent application. The vitamin-reactive cross-linking agent or the polyvinyl alcohol 交 cross-linked by the service is the borrowed fiber. 3. If the scope of the patent application is the first, the synthesis with a particle size of 3,5 ρ or less _ shell = \ recording paper, where (C) component is Average synthetic dioxide ... combined with oxidation seconds and average particle size 6 ·. — On top? Please 2 Fan: The recording paper of item 2, in which the ⑹ component is a flat ancestral diameter 3.5 synthesized from m or less-with " a knife 'ten-synthesized synthetic dioxide dream mixed oxidation seconds and average particle size 6. 5 on ° ♦ If the recording paper containing any one of% 蹯 is laminated on the ink-receiving layer in the first patent application scope, there are 3 dot-matrix shape adjusting agent layers. Short-tailed bird \\ 326 \ d \ 2D- \ 90-01 \ 88109782.ptc page 18] | 20〇1-〇2.〇1.〇18