TW519520B - Resin composition for ink-jet recording sheet, ink-jet recording sheet, method for ink-jet recording and manufacture of ink-jet recording sheet - Google Patents

Abstract

This invention provides a resin composition for ink-jet recording sheet, an ink-jet recording sheet, a method for ink-jet recording and manufacture of ink-jet recording sheet to satisfy various request characteristics such as a restriction in a manufacture, an insufficiency of reactant fixability with a cationic substance and an anionic dye, an ink absorbance and a stain suppressing effect by incorporating a specific water absorbing polymer compound as a main component and a cationic polymer compound. The ink-jet recording sheet comprises a base layer and an ink-receiving layer formed on the base layer. The ink-receiving layer comprises a water-absorbing polymer (1) represented by the chemical formula (I) as the main component and a cationic polymer (2). The polymer (1) and the polymer (2) are mixed in a proportion of from 50/50 to 99/1 by weight. A cationic or nonionic surfactant (3) is incorporated into the ink-receiving layer in an amount of 1 to 10 wt.%. The resin composition contains a water absorbing compound (1) represented by a formula (I) [in which A is (CH2CH2O) and (CH2CHYCHO), and its addition form is (CH2CH2O)m-(CH2CYHO)n-(CH2CH2O)p, in which m, n and p are each integer of 1 or above, a weight ratio calculated by repeating numbers m, n and p is 44(m+p)/(molecular weight of 4 or more C alkylene oxide)n=94/6-80/20, moreover, a weight ratio calculated by repeating numbers m, n and p is set for 44(m+p) being greater than 50% by weight, Y is 2 or more C hydrocarbon group, X1 is a residue of an organic compound having two active hydrogen groups, and R1 is a dicarboxylic acid or the like compound residue] as a main component, and is compatible with a cationic polymer compound, and hence excellent absorbance is maintained and its stain can be suppressed.

Description

519520 A7 B7 V. Description of the invention (丨) [Detailed description of the invention] '[Technical field to which the invention belongs] The present invention relates to a resin composition for an inkjet recording medium, an inkjet recording medium, an inkjet recording method, and inkjet A method for manufacturing a recording medium, and more particularly, to a resin composition for an inkjet recording medium suitable for use in inkjet recording of water-based ink, an inkjet recording medium, an inkjet recording method, and a method for manufacturing an inkjet recording medium. [Known Technology] Since inkjet recording is not noisy, high-speed printing is possible, and multi-color printing can be performed by using a plurality of nozzles, and the cost is low, it has a rapid performance as an image information output device for color photocopiers and computers. Popularity. In the case of inkjet recording media, (1) the ink must be absorbed quickly; (2) the ink must dry quickly; (3) no ink dots should be diffused or the periphery of the ink dots should be blurred when absorbing the ink Unscrupulous phenomenon; (4) Prevent the occurrence of uneven printing; (5) The printing interface between different colors must be clear; Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) (6) The quality is stable even after long-term storage after printing, especially the image deterioration such as bleed rarely occurs even under high humidity; characteristics such as inkjet recording media used so far, are On the ink-absorbing layer using a water-insoluble film as a support, a hydrophilic polymer is mainly laminated. As for these hydrophilic polymers, polyvinyl alcohol and polyethylene can be cited. The paper size applies the Chinese National Standard (CNS) A4 Regulation (210 X 297 Public Love) 519520 A7 B7 V. Description of the Invention (V) Water-soluble polymers such as enol modifiers, polyvinylpyrrolidone, and gelatin. Furthermore, an ink jet recording medium using a combination of the above-mentioned hydrophilic polymer and a water-absorbent resin, or a porous inorganic powder such as silica, alumina, or the like is also proposed. However, it has been questioned that when such inkjet recording media are used, the water-soluble resin laminated on the ink absorbing layer absorbs water during storage, and the problem of ink bleeding may occur. In order to solve the above-mentioned problems, an inkjet recording medium has been proposed which contains a cationic substance in the ink absorbing layer and prevents the ink from oozing out by reacting the cationic substance with an anionic dye used in an aqueous ink. However, in this ink jet recording medium, since the compatibility between the cationic substance and the water-soluble polymer is not good, the cationic substance may leak out of the surface of the ink absorbing layer. In addition, since the cationic substance is not thermoplastic, it has to be applied in a solution to obtain an inkjet recording medium, which poses a limitation on manufacturing. In addition, the fixation between the reactant of the cationic substance and the anionic dye is insufficient, and as a result, the phenomenon of bleeding cannot be prevented. Furthermore, the reaction between a cationic substance and an anionic dye also causes a change in hue. [Problems to be Solved by the Invention] As described above, the current actual situation is that it is impossible to obtain an inkjet recording medium that can satisfy all required characteristics. The present invention is made in view of the above-mentioned problems, and an object thereof is to provide a resin composition for an inkjet recording medium, an inkjet recording medium, an inkjet recording method, and an inkjet recording medium that can satisfy various required characteristics, in particular, satisfying absorption and bleed-out suppression effects. Manufacturing method of inkjet recording medium. 6 This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling out this page)-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-_ _ ϋ n · Ϋ ϋ I n I n ϋ ϋ I n ϋ ϋ n ϋ n I ϋ ϋ 519520 A7 ___ B7 V. Description of the invention (々) [Means to solve the problem] In order to achieve the foregoing object, the inkjet recording medium of the present invention A resin composition is characterized in that a water-absorbing polymer compound (1) represented by the following chemical formula (I) is used as a main component and a cationic polymer compound (2) is contained (the first patent application scope) . [化 6] — [A XlA Rl] — (I) γ [In the above formula (1), A is composed of Hch2ch2o> —and the composition of which is

Y

I • iCHaCHaOl __ (CHj CHO) jp— (CHjCHgO ^ -— (where m, n, p is an integer greater than 0; and the weight ratio calculated from repeated numbers m, n, p is set to 44 (m + p) / (Molecular weight of alkylene oxides with a carbon number of 3 or more) n = 94/6 ~ 80/20; Also, in the weight ratio calculated from each repeating unit m, n, p, p / (m + p) It is a hydrocarbon group of 50% by weight or more, a Ygfe number of 1 or more), X1 is a residue of an organic compound having two active hydrogen groups, and R1 is a dicarboxylic acid compound residue)]. The resin composition for an inkjet recording medium of the present invention is mainly composed of the water-absorbing polymer compound (1) represented by the above-mentioned chemical formula (I), and is compatible with the cationic polymer compound (2). Maintains excellent ink absorption and suppresses possible bleeding during storage under high humidity. 7 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) Li: Order --------- line-Qin Ministry of Economy Printed by the Intellectual Property Bureau employee consumer cooperative 519520 A7 B7 Printed by the Intellectual Property Bureau employee consumer cooperative of the Ministry of Economic Affairs 5. Description of the invention (+) In the present invention, as the cationic polymer compound (2), if (a) below is used Or (b) alone or a mixture thereof, since these substances have good affinity with the water-absorbing polymer compound (1), no bleeding phenomenon occurs on the surface of the ink receiving layer, and can be prevented from being used in the ink component Changes in hue caused by the reaction of anionic dyes. (Items 2 and 3 of the scope of patent application) (a) 15 mol% or more of the acrylic structural unit represented by the following chemical formula (Π) and 65 mol% or more and 99 mol% or less of the acrylic structural unit represented by the following chemical formula (melon) Mol% or less, and 1 mole 7 of acrylamide structural unit represented by the following chemical formula (IV). A cationic polymer compound with a weighted average molecular weight of 1,000 or more and 50000 or less in a linear irregular arrangement composed of less than 35 mol% above [Chem 7] — (CH 广 CH2i— [Chem 8] one of CH) —. COOR2 (In the formula, R2 represents the base of carbon number 1 ~ 4) [化 9] — (CH2 一 " CH—— Ruler 4 CONH—R3—N—R5. Χθ 8 (Π) (I) (N) (Please read the precautions on the back before filling in this page) Order --------- line · This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 519520

A7 B7 V. Description of the invention (In the formula, R3 represents a dilute group having 2 to 8 carbons, r4 and R5 each represent an alkyl group having 1 to 4 carbons, R6 represents an alkyl group having 1 to 12 carbons, An aralkyl group having 7 to 12 carbon atoms or an alicyclic alkyl group having 6 to 12 carbon atoms, where XΘκ represents a halogen ion, CH30S03, or C2H50S03, (b) is represented by the above chemical formula (n) 65 mol% or more and 99 mol% or less of ethylene structural unit, 15 mol% or less of acrylate structural unit represented by the above chemical formula (m), and 1 mol of acrylamide structural unit represented by the following chemical formula (V) It is a cationic polymer compound with a weight average molecular weight of 1,000 to 50000 and a linear irregular arrangement composed of not less than 35 mole% and less. [CH2—CHi— / r4 I 3 e / et CONH- R —NH · X (V) (where R3 represents an alkenyl group having 2 to 8 carbon atoms, R4 and R5 are alkyl groups having 1 to 4 carbon atoms, respectively, and ㊀ represents a halogen ion, CH30S03 ·, or C2H5OS ( V.) The cationic polymer compound (2) of the above (a) and (b) may contain an acrylate structural unit represented by the above chemical formula (Π) However, it is not absolutely necessary. The upper limit (15 mole%) is specified only for the Mohr fraction of the acrylate structural unit, and there is no special provision for the lower limit. Among these inventions, as long as The weight mixing ratio of the water-absorbing polymer compound (1) and the cationic polymer compound (2) is set to 50/50 or more 99/1 9 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) — — — — — — — «1ΙΙΙΙΙΙ — — I Win (Please read the notes on the back before filling out this page) Xin. Printed by the Consumers’ Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 519520 Printed by the Consumer ’s Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Explanation of the invention () Below, a better balance can be achieved between the ink collection property and the bleed-out suppression effect. (Item 4 of the scope of patent application) In these inventions, as long as it is cationic or nonionic The active agent (3) can effectively suppress the bleeding when stored under high humidity (the scope of the patent application is the fifth item). The blending amount of the active agent (3) is preferably 1% by weight or more and 10% by weight or less. (apply for patent Scope item 6). An inkjet recording medium is formed by laminating an ink receiving layer and a substrate using the resin composition for the inkjet recording medium (item 7 in the scope of the patent application), as long as small amounts of water-based color ink are ejected. Drop and adhere to the ink receiving layer for inkjet recording (No. 8 in the scope of patent application) to obtain a clear, low-bleed image when stored under high humidity. This inkjet recording medium will constitute the base material layer When the resin composition is pressed into a sheet shape, the resin composition for an inkjet recording medium of the present invention is also pressed into a sheet shape, and the two are laminated at the same time, so that the desired object can be easily obtained. (Item 9 of the scope of patent application). [Embodiment of the invention] The most important feature of the inkjet recording medium of the present invention is that the ink receiving layer is mainly composed of the water-absorbing polymer compound (1) represented by the above-mentioned chemical formula (I). Here, "the water-absorbing polymer compound (1) is a main component" means that the water-absorbing polymer compound (1) is a main polymer. Specifically, the proportion of the water-absorbing polymer compound (1) in the ink receiving layer is preferably 50% by weight or more. In the part represented by A in the above chemical formula (I), the ethylene oxide chain represented by the repeating number m and the ethylene oxide chain represented by the repeating number P will repeat 10 times. The paper standard applies to the Chinese National Standard (CNS). A4 size (210 X 297 mm) (Please read the notes on the back before filling this page)

Order --------- line II 519520 A7 ____B7 V. Description of the invention (7) The oxyalkylene chain having a carbon number of 3 or more represented by the number η is sandwiched between the two and becomes at the ends. Examples of the oxyalkylene chain having a carbon number of 3 or more represented by the above-mentioned repetition number η include, for example, a butylene oxide chain derived from a butylene oxide, and an oxidized α-olefin having a carbon number of 11 or more and a carbon number of 11 or more Oxidized alpha-olefin chain. That is, in the above chemical formula (I), if the repeating number η is an epoxy butane chain derived from butylene oxide, Υ is an ethyl group. When the repeating number η is derived from an oxidized α-olefin chain having 11 or more carbon atoms, 来自 is a hydrocarbon group having 9 or more carbon atoms. In the case of an oxidized α-olefin chain, the oxidized α-olefin having a carbon number of 11 or more is not particularly limited as long as it is an epoxy compound having an alkenyl group with a carbon number of 11 or more, and preferably has a carbon number. Alkenyl epoxy compounds in the range of 12 to 30. Such oxidized? -Olefins can be used alone or in combination of one or more kinds. When the alkylene oxide chain represented by the repeating number η is a butylene oxide chain, two ethylene oxide chains represented by the repeating number m and ρ are present in the part represented by A in the aforementioned chemical formula (I). The ratio is preferably set to 80% by weight or more and 90% or less, and more preferably 82% by weight to 87% by weight. When the oxyalkylene chain represented by the repeat number η is an oxidized α-olefin having a carbon number of 11 or more, the two ethylene oxide chains represented by the repeat number m and ρ are represented by the aforementioned chemical formula (I). The proportion present in the portion A is preferably set to 90% by weight or more and 94% or less, and more preferably 92% by weight or more and 94% by weight or less. That is, in the part where the above chemical formula (I) is expressed as A, the following formula 11 is used. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling in this Page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy S ϋ n ϋ ϋ ϋ ϋ ϋ I ϋ ϋ I n -IH ϋ · 1 if n ϋ ϋ II n II l_i I ϋ n ϋ 1 519520 A7 B7 V. Description of the invention (/) (44 · (m + p)) / ((Molecular weight of alkylene oxide having 3 or more carbon atoms) · n) The calculated actinide is set in a range of 80/20 to 94/6. Here, 44 is the molecular weight of ethylene oxide. If the ratio of the two ethylene oxide chains represented by the number of repetitions m and p does not fall within the above range, the ink absorbency of the inkjet recording medium will decrease. Conversely, if the ratio exceeds the above range, it will absorb moisture and exudate when stored under high humidity. In the above chemical formula (I), the part represented by A 'is calculated as p / (m + p), that is, the repeat number P in the total amount of two ethylene oxide chains (repeated number m and p). It is necessary to set the proportion of 50% or more, especially 60% to 80%. Thereby, the esterification reaction and the ester substitution reaction with the carboxylic acid compound R1 described later can be easily performed. The moiety represented by X1 in the above formula (I) is an organic compound residue having two active hydrogen groups. Examples of the organic compound having two active hydrogen groups include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, and neopentyl alcohol. Amines such as bisphenol A, polytetramethylene glycol, cyclohexane-1,4-dimethanol, amines such as butylamine, laurylamine, octylamine, cyclohexylamine, and aniline. These substances can be used alone or in combination of one or more. The part represented by R1 in the above formula (I) is a residue of a dicarboxylic acid compound. Examples of usable dicarboxylic acid compounds include dicarboxylic acids, dicarboxylic anhydrides, and lower alkyl esters of dicarboxylic acids. As for the above-mentioned dibasic acids, for example, peptidic acid, isophthalic acid, terephthalic acid, malonic acid, and 12 paper sizes are applicable to Chinese National Standard (CNS) A4 (210 X 297 mm). Read the memorandum and fill in two more pages. I w IIIIII Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed 519520 A7 B7 V. Description of the invention (gas) Succinic acid, sebacic acid, maleic acid, transbutene Diacid, adipic acid, itaconic acid, etc. Examples of the dicarboxylic anhydride include fluorene obtained from the above-mentioned various dicarboxylic acids. Examples of the lower alkyl esters of the dicarboxylic acids include methyl, dimethyl, ethyl, diethyl, propyl, and dipropyl esters of the above-mentioned various dicarboxylic acids. These substances can be used alone or in combination of one or more. Among them, the use of a dicarboxylic acid anhydride or a lower alkyl ester of a dicarboxylic acid is particularly preferred from the viewpoint of easiness of reaction. The water-absorbing polymer compound (1) represented by the chemical formula (I) has a water absorption of about 5 to 15 times its own weight. The use of this compound can provide ink absorption to the ink receiving layer. In addition, since the water-absorbing polymer compound (1) is a thermoplastic material, it can be extruded into a sheet shape, and an ink jet recording medium can be easily manufactured. Here, an example of a method for producing the water-absorbing polymer compound (1) represented by the aforementioned chemical formula (I) will be described. First, caustic alkali such as sodium hydroxide and potassium hydroxide is used as a catalyst, and an organic compound having two active hydrogen groups is subjected to addition polymerization using ethylene oxide at a temperature of about 90 to 200 ° C. Then, it is further subjected to oxidative thinning addition polymerization with a carbon number of 3 or more, and further to oxidative addition polymerization with ethylene oxide. That is, an organic compound having two active hydrogen groups is subjected to addition polymerization with ethylene oxide, butylene oxide, or an oxidized α-olefin having a carbon number of 11 or more and ethylene oxide in this order. The weight-average molecular weight of the polyoxylean compound obtained at this stage is preferably 5,000 or more and 30,000 or less, particularly preferably 10,000 or more and 30,000 or less. If the weight average molecular weight is not within the above range, there is a problem that the formability of the ink receiving layer is reduced. Conversely, if the weight average molecular weight exceeds the above range, it will be oxidized. X 297 mm) (Please read the notes on the back before filling out this page).

---- Order --------- Line J Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 519520 A7 B7 V. Invention Description (0) The reaction rate of the suspected addition reaction will be significantly reduced. Next Then, add a dicarboxylic acid compound to the polyoxidizing compound. After heating up, reduce the pressure to 0.1 ~ 2.7X103Pa for dehydration or dealcoholization while heating at 80 ~ 250 ° C. The reaction time is usually 30 Minutes to 10 hours. Thus, a water-absorbing polymer compound was obtained. When a dicarboxylic acid compound was added to the polyoxyalkylene compound, the blending ratio of the two was in the range of equivalent ratio 1/3 · 5 to 1 / 0.5. The weight-average molecular weight of the water-absorbing polymer compound (1) obtained in this way is preferably set to a range of 10,000 to 300,000, and more preferably to a range of 50,000 to 200,000. The obtained water-absorbent polymer has a high water absorption. The weight average molecular weight of the molecular compound (1) divided by 値 of the weight average molecular weight of the polyoxyalkylene compound used in the production is preferably 2 or more, more preferably 2 or more and 21 or less, and most preferably 4 or more and 21 or less. invention Another characteristic of the inkjet recording medium is that the ink receiving layer contains a cationic polymer compound (2). The cationic polymer compound (2) reacts with anionic dyes generally used in water-based inks, thereby Can prevent the bleeding of ink. In addition, since the cationic polymer compound (2) is a polymer, it does not bleed out of the surface of the ink receiving layer. The cationic polymer compound (2) is a weight average molecular weight. A cationic substance of 1000 or more, preferably 5000 or more. The compounding amount of the cationic polymer compound (2) is smaller than the weight mixing ratio of the water-absorbing polymer compound (1) and the cationic polymer compound (2). It is preferably 50/50 or more and 99/1 or less, and more preferably 65/35 or more and 90/10 or less. If the compounding amount of the cationic polymer compound (2) does not fall within the above range, 14 Chinese paper standards ( CNS) A4 specification (210 X 297 mm) (Please read the notes on the back before filling out this page) #: Order --------- Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 519520 Ministry of Economic Affairs Printed by the Consumer Property Cooperative of the Intellectual Property Bureau A7 B7 V. Description of the Invention (U) The inkjet recording medium will absorb moisture and bleed out when stored under high humidity. Conversely, if the blending amount exceeds the above range, the ink The ink absorptivity of the receiving layer will decrease. The cationic polymer compounds (2) that can be suitably used are: (a) 65 mol% or more and 99 mol or more of the ethylene structural unit represented by the above chemical formula (Π). 〇, 15 mol% or less of the acrylate structural unit represented by the above-mentioned chemical formula (II), and 1 mol of acrylamide structural unit represented by the above-mentioned chemical formula (IV). /. A cationic polymer compound having a linear irregular arrangement with a weight average molecular weight of 1,000 or more and 50000 or less composed of 35 mole% or less; and (b) 65 moles of ethylene structural unit represented by the above chemical formula (Π) Over 99 Moore. / 〇 or less, an acrylic ester structural unit represented by the above chemical formula (ΠI) of 15 mol% or less, and an acrylamide structural unit represented by the above chemical formula (V) of 1 mol% or more and 35 mol% or less A cationic polymer compound having a linear irregular arrangement with a weight average molecular weight of 1,000 to 50,000. These cationic polymer compounds (2) can be used alone or in combination. As long as the cationic polymer compounds (2) of these rhenium and rhenium are used, the bleeding of the ink can be prevented more, and the change in hue caused by the reaction with the anionic dye in the ink component can be suppressed. The cationic polymer compound (2) in the above (a) should contain 65 moles of ethylene structural unit represented by the above chemical formula (Π). /. The content is preferably 99 mol% or more and more preferably 65 mol% or more and 80 mol% or less. If the content is less than the above range, it will not be possible to obtain water-absorbing polymer compounds U) 15 Chinese paper standard (CNS) A4 (210 X 297 mm) applicable to each paper size -------- ^- -------- ^ 1 ^ (Please read the notes on the back before filling this page) 519520 A7 B7 V. Description of the invention) Conversely, if the content exceeds the above range, then provide to The acrylamide structural unit for which the dye reacts will be insufficient, and as a result, it cannot react with the dye and cause bleeding. The cationic polymer compound (2) in the above (a) should contain 15 mol% or less of the acrylate structural unit represented by the above chemical formula (melon), particularly 5 mol% or more and 10 mol ° / °. The following is better. If the content is less than the above range, compatibility with the water-absorbing polymer compound (1) cannot be obtained; on the contrary, if the content exceeds the above range, the production of the cationic polymer compound (2) will become difficult. The cationic polymer compound (2) in the above (a) should contain acrylamide structural unit represented by the above-mentioned chemical formula (IV) in an amount of 1 mol% or more and 35 mol% or less, and in particular, it contains mol. It is preferably at least 30% by mole. If the content is less than the above range, the reaction equivalent with the dye will be insufficient. As a result, the unreacted dye will bleed out. On the contrary, if the content exceeds the above range, the Miscibility will be extremely reduced. The cationic polymer compound (2) of the above (b) should contain 65 mole% or more and 99 mole% or less of the ethylene structural unit represented by the above chemical formula (Π), and particularly contain 65 mole% or more and 80 moles or less. It is preferably less than%. If the content is less than the above range, the compatibility with the water-absorbing polymer compound (1) will decrease; on the contrary, if the content exceeds the above range, the acrylamide structural unit provided to the dye for reaction will be insufficient As a result, it was unable to react with the dye and caused bleeding. The cationic polymer compound (2) in the above (b) should contain the above-mentioned 16 paper sizes applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling in this Page) # Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs δ- · 1 —1 II · 1 ϋ- n I ϋ ϋ n Hi in 1 ϋ 1 'ϋ I ϋ n am— · ϋ Hi nn 1 nn I _ 519520 A7 B7 V. Description of the invention (q) The acrylate structural unit not shown in the formula (m) is 15 mol% or less', and it is particularly preferable to contain 5 mol% or more and mol% or less. If the content is less than the above range, the compatibility with the water-absorbing polymer compound (1) will be reduced; on the contrary, if the content exceeds the above range, the production of the cationic polymer compound (2) will become difficult. The cationic polymer compound (2) in the above (b) should contain 1 mol% or more of 35 mol of the acrylamide structural unit represented by the above-mentioned chemical formula (V). /. Below, especially, it contains 10 mol ° /. Over 30 moore. /. The following is better. If the content is less than the above range, the reaction equivalent with the dye will be insufficient, and as a result, the unreacted dye will bleed out; on the contrary, if the content exceeds the above range, it will be in phase with the water-absorbing polymer compound (1). Capacities will be extremely reduced. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, the cationic polymer compounds (2) (a) and (b) above, each structural unit is linearly irregularly arranged. Thermoplasticity can be obtained by this, coupled with the thermoplasticity of the water-absorbing polymer (2), which makes it possible to thermoform the absorption layer. The weight average molecular weight of the cationic polymer compound (2) is preferably 1,000 or more and 50,000 or less, particularly preferably 5,000 or more and 30,000 or less. If the weight average molecular weight is less than the above range, the cationic polymer compound (2) will bleed out of the surface of the ink receiving layer. Conversely, if the weight-average molecular weight exceeds the above range, it becomes difficult to mix with the water-absorbing polymer compound (1) due to an increase in the melt viscosity. In the ink-receiving layer of the inkjet recording medium of the present invention, it is desirable to mix a cationic or nonionic active agent (3). Based on this reason, based on the reason that the hydrophilicity of the ink receiving layer is increased, the ink absorption speed can be increased. 17 @ 张 平面 Applicable Chinese National Standard (CNS) A4 is a grid (210 X 297 public love)-519520 A7 __ B7 V. Description of the invention (), and can prevent the bleeding of ink. The cationic active agent (3) that can be suitably used includes, for example, a second-stage ammonium salt-type cationic agent, a third-stage ammonium salt-type cationic agent, and a fourth-stage ammonium salt-type cationic agent. Examples of the nonionic active agent (3) that can be suitably used include alkanol type nonionic active agents, higher alcohol type nonionic active agents, higher fatty acid based nonionic active agents, and plurcmic. Type nonionic active agent, propylene glycol fatty acid ester, glycerin fatty acid ester and the like. The blending amount of the cationic or nonionic active agent (3) in the ink receiving layer is preferably 1% by weight or more and 10% by weight or less, and more preferably 2% by weight or more and 5% by weight or less. If the blending amount does not fall within the above range, the ink absorption speed will decrease, and the phenomenon of ink bleeding will easily occur. Conversely, if the compounding amount exceeds the above range, bleeding on the surface of the ink-receiving layer may occur and the surface may become sticky. The thickness of the ink-receiving layer is not particularly limited as long as it can absorb the ink, and is generally 10 // m to 50 // m, and more particularly, 20 / zm to 30 / zm. The inkjet recording medium of the present invention is constituted by stacking an ink receiving layer on a substrate layer. The material of the substrate layer is not particularly limited, and for example, a film made of a water-insoluble plastic such as a polyester resin, polyamide, or polyolefin can be used. In particular, a polyester resin excellent in film hardness and adhesion of the absorbent layer is preferred. The thickness of the base material layer is not particularly limited, but is generally 50 / zm or more and 100 # m or less, and more particularly, 70 // rn or more and 100 / zm or less. 18 This paper size is in accordance with Chinese National Standard (CNS) A4 (21〇 X 297 public love) (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

-«^ 1 — ^ 1 · ϋ n ϋ 1__1 Bn one:» J · nn > ϋ _1 1 II ϋ I ϋ I ϋ l ϋ ϋ ί ϋ 1 I— nnn ϋ ϋ nn ϋ ϋ ϋ n ϋ —i I 519520 A7 B7 V. Description of the Invention (β) Here, a method for manufacturing the inkjet recording medium of the present invention will be described. First, melt and mix the water-absorbing polymer compound (1) and the cationic polymer compound (2) by a known method, and if necessary, mix the cationic or nonionic active agent (3) to obtain a resin composition. . Next, it was pulverized, melted and extruded into a film-like layer on a substrate layer to obtain an ink recording layer. When the base material layer is made of plastic, the ink-absorbing recording medium is produced by laminating both the ink absorbing layer and the base material layer, that is, by so-called co-extrusion. By this co-extrusion, the manufacturing process of the ink jet recording medium can be simplified. In addition, the resin composition may be dissolved in a solvent (for example, a mixed solution of xylene and methanol) in which the resin composition used in the ink receiving layer can be dissolved, and then the resin composition may be applied to the base material layer. Manufacture of inkjet recording media. For coating, various known methods such as bar coating, roll coating, blade coating, and kiss roll coating can be used. When the ink receiving sheet is laminated or coated on the substrate layer as described above, if necessary, in order to improve the adhesion strength of the two layers, a primer treatment may be applied to the surface of the substrate sheet. If the conventional inkjet recording medium is used for inkjet recording, the water-based ink can be quickly absorbed by the ink receiving layer, and a sharp image can be obtained. Also, even after the inkjet recording medium is stored under high humidity for a long time after printing is completed, no bleeding of ink occurs. [Examples] Hereinafter, the effects of the present invention will be shown based on the examples. However, the present invention is not limited to the contents described in the examples. 19 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)

Order --------- Line J Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 519520 A7 B7 V. Description of the invention (4) [Example 1] 'Prepare m in the above formula (I) to be 52, η is 14, P is 155, Y is ethyl, X1 is an ethylene glycol residue, and R1 is an itaconic acid diacid residue, a water-absorbing polymer compound (1). With respect to this water-absorbing polymer compound (1), the polyoxyalkylene compound has a polyoxyalkylene compound having a carbon number of 4 or more and an occupancy ratio of 11% by weight. The average molecular weight of the polyalkylene glycol residue represented by AX! A was 20,294. The weight average molecular weight of this water-absorbing polymer compound (1) was 154,800. The molecular weight was measured by using water-based GPC and a 1: 1 mixed solution of acetonitrile and water as a solution in which the water-absorbing polymer compound (1) was dissolved, and measured in terms of PE0. On the other hand, R2 is C2H5 in the chemical formula (m), R3 is vinyl, R4, R5, and R6 are methyl groups, and X · is C2H5OSCV. (2). In this cationic polymer compound (2), the Mohr fraction (measured by NMR) is based on an ethylene structure unit represented by the above chemical formula (Π) of 65 mole% and an acrylate structure represented by the above chemical formula (M). The unit is 5 mole%, and the acrylamide structural unit represented by the chemical formula (IV) is 30 mole%. The weight average molecular weight (measured by GPC) of the cationic polymer compound (2) was 23,000. Next, 80 parts by weight of the water-absorbing polymer compound (1) and 20 parts by weight of the cationic polymer compound (2) were mixed in a biaxial extruder under extrusion conditions of 150 ° C to pelletize them. It was then extruded at 150 ° C with a uniaxial extruder to make a thick film. Next, overlap the film with the ethylene terephthalate film (thickness 100 / zm), 20 (Please read the precautions on the back before filling this page)

Order --------- Line J Printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 519520 A7 B7 V. Description of the invention (q ) The lamination process was performed under the condition of 160 ° C to obtain the inkjet recording medium of Example 1. [Example 2] In the above formula (I), m is 28, η is 2, p is 118, Y is a hydrocarbon group having 12 to 14 carbon atoms, X1 is an ethylene glycol residue, and R1 is a peptidic acid residue. Water-absorbing polymer compound (1). In this water-absorbing polymer compound (1), the polyoxyalkylene compound has a polyoxyalkylene compound having a carbon number of 4 or more and a occupancy ratio of 6% by weight. The average molecular weight of the polyalkylene glycol residue represented by AX! A was 13,873. The weight average molecular weight of this water-absorbing polymer compound (1) obtained by the same measurement method as in Example (1) was 97111. On the other hand, it is prepared that in the above chemical formula (melon), R2 is 0: 2: «5, in the above chemical formula (IV), R3 is a vinyl group, R4 and R5 are methyl groups, R6 is a lauryl group, and I is a chloride ion. (a) a cationic polymer compound (2). In this cationic polymer compound (2), the Mohr fraction (measured by NMR) is based on an ethylene structure unit represented by the above chemical formula (Π) of 70 mole% and an acrylate structure represented by the above chemical formula (melon). The unit is 10 Moore. /. The acrylamide structural unit represented by the chemical formula (IV) is 20 mole%. The weight-average molecular weight (as measured by GPC of GPC) of this cationic polymer compound (2) was 23,000. Next, 75 parts by weight of a water-absorbing polymer compound (1) and 25 parts by weight of a cationic polymer compound (2) were used in the same manner as in Example 1 to obtain an inkjet recording medium of Example 2. [Example 3] In the above formula (I), m is 42, η is 23, p is 168, and Y is 21 (Please read the precautions on the back before filling this page)

Order --------- Line J Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 519520 A7 B7 V. Description of the invention (彳) Ethyl, X1 is ethyl and diol residues, and R1 is itaconic acid diacid residue water-absorbing polymer compound (1). With respect to the water-absorbing polymer compound (1), the polyoxyalkylene compound has a polyoxyalkylene compound having a carbon number of 4 or more and an occupation ratio of 18% by weight. The weight average molecular weight of the polyalkylene glycol residue represented by AX! A was 21854. The weight average molecular weight of this water-absorbing polymer compound (1) obtained by the same measurement method as in Example (1) was 139,860. Next, an inkjet recording medium of Example 3 was obtained by using 85 parts by weight of a water-absorbing polymer compound (1) and 15 parts by weight of a cationic polymer compound (2). [Example 4] Instead of using 20 parts by weight of the cationic polymer compound (2) of Example 1, 10 parts by weight of the cationic polymer compound (2) and the cationic active agent (3) were used instead. The lauryl trimethyl ammonium chloride was mixed in advance with a hot roll at 15 ° C. and pelletized, and the others were the same as in Example 1 to obtain the ink jet recording medium of Example 4. [Comparative Example 1] Except for using 100 parts by weight of the water-absorbing polymer compound (1) of Example 1 in the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the rest was not implemented except for the cationic polymer compound (2). Example 1 was the same, and an inkjet recording medium of Comparative Example 1 was obtained. [Comparative Example 2] 20 parts by weight of the cationic polymer compound (2) of Example 1 was not used, and 20 parts by weight of lauryltrimethylammonium chloride was used as the cationic active agent (3). Example 1 was the same, and an ink jet recording medium of Comparative Example 2 was obtained. 22 This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) 519520 Α7 Β7 V. Invention Description (β) [Ink Absorption Test] Use an inkjet printer (brand name "Epson PM750" "And the brand name" Canon BJC-455J ") were printed on the inkjet recording media of each example and each comparative example. One minute after the end of printing, the printed portion of the ink-receiving layer was gently rubbed 3 times' to evaluate the ink absorbency visually. The ink absorption is very good, and the printed part has no change at all. It is judged as "◎", the good thing is judged as "0", the slightly worse thing is judged as "△", and the ink will stain the printed part. "X". The results are shown in Table 1 below. [Ink bleedability test] The inkjet recording medium performing the same printing as described above was left at room temperature for 3 hours after the printing was completed. Next, it was placed in a thermostat-humidifier at a temperature of 35 ° C and a humidity of 90%, and the bleeding of the ink was visually observed 24 hours after the insertion and 120 hours after the insertion. If the exudation is not seen at all, it is judged to be "1". If a small amount of exudation is seen, it is judged to be "2". You can see the exudate 4 (please read the precautions on the back before filling this page)- ------- Order ------------- The thing printed by the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is judged to be "3", and it is almost impossible to judge the thing printed. The results are shown in Table 1 below. Table 1 Guo Senggu of each inkjet recording media Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Ink absorbency PM750C 〇〇〇 △ 〇BJC-455J ◎ ◎ ◎ ® ○ ◎ Ink bleedability (after 24 hours) PM750C 1 1 1 —1 4 2 BJC-455J 1 1 1 3 2 Ink bleedability (120 / J fiber PM750C 2 2 23 2 2 4 3

This paper size applies to China National Standard (CNS) A4 specifications (210 X 519520 A7 B7) V. Description of the invention (/) BJC-45 ^ J 1 1 1 ~~ 1 4 3 In Table 1, the inkjet recording media of each embodiment Compared with the inkjet recording medium of each comparative example, 'the ink absorbency and the ink exudation are superior, so that the superiority of the present invention can be proved. [Effects of the Invention] As described above, according to the present invention, it is possible to Improve ink absorption during inkjet recording, and solve the problems encountered when using hydrophilic polymers in the conventional ink receiving layer. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs S) N (C Standard) A moderate ruler, one piece of paper, 24 cm, T7 12 X 10 2 / fv

Claims (1)

519520 A8 B8 C8 D8 6. Scope of patent application: A resin composition for inkjet recording media, which uses the water-absorbing polymer compound (1) represented by the following chemical formula (I) as the main component and contains cations Polymer compound (2): [化 1]-[AX! A Rl] (I) [In the above formula (1), A is composed of 4ch2ch2o>, and the addition form is γ ch2 cho ^ — (Please read the notes on the back before filling in the ^^ page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy Y ^ CH2CH2〇 ^-(CH2 CHO ^; iCH2CH2〇 ^ — (where m, n, p are 0 The above integer; again, the weight ratio calculated from the repeated number m, n, p is set to 44 (m + p) / (molecular weight of alkylene oxide with a carbon number of 3 or more) n = 94/6 ~ 80/20; Moreover, in the weight ratio calculated from each repeating unit m, n, P, p / (m + p) is set to 50% by weight or more; Y is a hydrocarbon group having a carbon number of 1 or more), and X1 has two activities Residue of a hydrogen-based organic compound, R1 is a dicarboxylic acid compound residue)]. 2. The resin composition for an inkjet recording medium according to the scope of application for a patent, wherein the cationic polymer compound (2) is 65 moles of ethylene structural unit represented by the following chemical formula (Π). / 0 or more and 99 mol% or less, an acrylate structural unit represented by the following chemical formula (melon) of 15 mol% or less, and an acrylamide structural unit represented by the following chemical formula (IV) 1 mol ° /. The weight of the linearly irregular arrangement constituted by the above 35 mol% ------- Order ·! I ---- Line— ^ ^ The paper size applies the Chinese National Standard (CNS) A4 specification (21〇 x 297) 519520 A8 B8 C8 D8 VI. Cationic polymer compounds with an average molecular weight ranging from 5,000 to 50,000: [Chem 2] — (ch2—ch2) — (H) [Chem 3] — ( CH.—CH) I 2 COOR ^ (¢) (where R2 represents an alkyl group having 1 to 4 carbon atoms) [Chem. 4] CONH—Κ3—Ν—Κ5 * χθ Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (In the formula, R3 represents an alkenyl group having 2 to 8 carbon atoms, R4 and R5 represent an alkyl group having 1 to 4 carbon atoms, R6 represents an alkyl group having 1 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms. , Or an alicyclic alkyl group having 6 to 12 carbon atoms, and XΘκ represents a halogen ion, CHbOSCX, or C2H50S03). 3. The resin composition for an inkjet recording medium according to item 1 of the patent application range, wherein the cationic polymer compound (2) is 65 mol% or more from an ethylene structural unit represented by the above chemical formula (Π) 99 Moire% or less, and the acrylate structural unit represented by the above-mentioned chemical formula (melon) is 15 moles 7. The following, and the acrylamide structural unit represented by the following chemical formula (V): 1 Mo 2 This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm)-519520 A8§ --- --- P8 _ 6 A cationic polymer compound having a weight average molecular weight of 10,000 to 50,000 and having a linear irregular arrangement, which is composed of a patent application range of mol% to 35mol%: [Chem. 5] — (CH, a CH *) — / R 4 I 3 · / β CONH—R —ΝΗ · X (V) (Please read the notes on the back before filling in the printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (where R3 represents an alkenyl group with 2 to 8 carbon atoms, R4 and R5 represent an alkyl group with 1 to 4 carbon atoms, χΘΚ Table halogen ion, CH3〇S (X, or C2H50SOO.) 4. The resin composition for inkjet recording media as described in any one of the claims 1 to 3, wherein the water absorption is high The weight mixing ratio of the molecular compound (1) and the cationic polymer compound (2) is 50/50 or more and 99/1 or less. 5. For an inkjet recording medium according to any one of claims 1 to 3 The resin composition further contains a cationic or nonionic active agent (3). 6. If the resin composition for an inkjet recording medium according to item 4 of the patent application, further contains a cationic or nonionic activity 7. The resin composition for inkjet recording media according to item 5 of the patent application, wherein the compounding amount of the cationic or nonionic active agent (3) is 1% by weight or more and 10% by weight or less. The following: 8. Resins for inkjet recording media, such as the scope of patent application No. 6 The finished product, in which the compounding amount of the above-mentioned cationic or non-ionic active agent (3) is 3 ^ The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 519520 Printed by A8 B8 C8 D8 of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 6. The scope of patent application is 1% min. To 10% min. 9. An inkjet recording medium with a base material layer and a laminated layer here An ink-receiving layer on a substrate layer; characterized in that the ink-receiving layer is composed of a resin composition according to any one of claims 1 to 8 of the scope of patent application. 10.10. An inkjet recording method, The process of using the inkjet recording medium with the scope of patent application No. 9 and including the process of ejecting droplets of water-based color ink and attaching to the ink receiving layer. 11. A method for manufacturing an inkjet recording medium, comprising a substrate The process of extruding the resin composition of the layer into a sheet, and the process of extruding the resin composition for an inkjet recording medium according to any one of claims 1 to 8 into a sheet, and then laminating both. Applicable in China Home Standard (CNS) A4 size (210 X 297 mm)