KR101497925B1 - ink fixative, method for manufacturing the same and ink-jet recording paper manufactured using the same - Google Patents

Abstract

The present invention provides an ink fixative, a manufacturing method thereof, and an inkjet recording sheet manufactured by using the same. The ink fixative according to the present invention has high fixation, high whiteness, and high durability. The ink fixative includes a compound of a cationic resin and de-alkali sulfonate fluorescent dye.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to an ink fixer, a method of manufacturing the same, and an inkjet recording paper produced using the ink fixative.

The present invention relates to an ink fixing agent, a method for producing the same, and an inkjet recording paper produced using the same, wherein a cationic resin prepared by reacting epihalohydrin with a compound having at least one amine group and a dealkali sulfonic acid fluorescent dye , A method for producing the same, and an inkjet recording container using the same.

BACKGROUND ART [0002] With the widespread use of inkjet recording paper in recent years, improvement in whiteness and printability is strongly demanded.

In particular, when an anionic dye such as a direct dye is used as an ink, a cationic resin, which is a cationic polymer, is generally used as a fixing agent, and such a cationic resin is prepared by using epichlorohydrin to amine.

Fluorescent dyes have been used to improve whiteness in addition to cationic resins. However, when sulfonic acid type fluorescent dyes, which are fluorescent dyes used for general papers, are used together with cationic resins used as ink fixing agents, sulfonic acid salt type fluorescent dyes and ink fixing agents There is a problem such that precipitation occurs in the treatment liquid and the desired whiteness is not obtained.

For example, Japanese Patent Application Laid-Open No. 2010-83044 discloses an inkjet recording medium comprising a specific polyvinyl alcohol and 4,4'-di (triadinoamino) stilbene-2,2'-disulfonate as a binder .

In addition, Japanese Laid-Open Patent Publication No. 2009-73059 discloses an inkjet recording paper having both high ink drying property and water resistance. However, it has been attempted to solve the problem by containing rogetta-type hard calcium carbonate and alkenyl succinic anhydride in a recording paper other than the ink composition .

Therefore, research on an ink composition which can satisfy whiteness, durability and economical efficiency with a simple process is required.

Patent Document 1. Japanese Patent Application Laid-Open No. 2010-83044 (Apr. 15, 2010) Patent Document 2: Japanese Patent Application Laid-Open No. 2009-73059 (2009.04.09)

The present invention relates to an ink fixing agent, and more particularly, to an ink fixing agent containing a compound of a cationic resin and a dealkali sulfonic acid type fluorescent dye prepared by reacting epihalohydrin with a compound having at least one amine group Lt; / RTI >

The present invention also provides a process for producing the ink fixer of the present invention.

The present invention also provides an inkjet recording paper produced using the ink fixer of the present invention.

It is an object of the present invention to provide an ink fixing agent capable of being produced by a simple process without deteriorating the fluorescence performance and fixation performance, and the ink fixing agent of the present invention can be prepared by adding epihalohydrin to a compound having at least one amine group And a compound of a cationic resin and a dealkali sulfonic acid based fluorescent dye prepared by the reaction.

Preferably, the cationic resin of the first embodiment according to one embodiment of the present invention can be prepared by reacting a primary amine or secondary amine represented by the following formula 2 with epihalohydrin.

(2)

R ₁ - NH - R ₂

Wherein R ₁ is a C ₁ -C 7 alkyl group and R ₂ is H or a C 1 -C 7 alkyl group.

Preferably, the cationic resin of the second embodiment of the present invention is obtained by adding at least one polyalkylene polyamine represented by the following formula (3) to the primary amine or secondary amine represented by the above formula (2) and reacting with epihalohydrin .

(3)

[Wherein R ₃ is an alkylene group having 2 to ₃ carbon atoms and n is an integer of 1 to 6]

The cationic resin of the third embodiment according to an embodiment of the present invention is obtained by reacting a polyalkylenepolyamine represented by the formula 3 with adipic acid or urea in the presence of a primary amine represented by the formula 2 or a secondary Amine and reacting it with an epihalohydrin.

Preferably, the cationic resin of the first, second or third aspect of the present invention can be prepared further comprising an urea.

Preferably, the epihalohydrin of the first, second, or third aspect of the present invention may be epichlorohydrin, and the epihalohydrin according to an embodiment of the present invention may be the above primary amine, Amine, polyalkylene polyamine, and mixed amines thereof, in an amount of 0.5 to 1.5 mols.

The primary amine according to one embodiment of the present invention may be methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine or heptylamine, and the secondary amine may be dimethylamine, diethylamine, dipropylamine , Dibutylamine or diphenylamine.

The polyalkylene polyamine according to one embodiment of the present invention may be ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentaamine or pentaethylene hexaamine.

The dealkali sulfonic acid type fluorescent dye according to an embodiment of the present invention may be represented by the following formula (1).

[Chemical Formula 1]

[In the above formula (1)

X ₁ to X ₄ are independently of each other Na ⁺ , K ⁺ or H, and at least one of X ₁ to X ₄ is H;

이며, R₁₁ 내지 R₁₂는 서로 독립적으로 수소, (C1-C5)알킬 또는 (C1-C5)히드록시알킬이며; n은 1 내지 2의 정수이다.]R is _{-N (R 11) (R 12} ) , or

And R ₁₁ to R ₁₂ are independently of each other hydrogen, (C 1 -C 5) alkyl or (C 1 -C 5) hydroxyalkyl; and n is an integer of 1 to 2.]

The present invention also provides a process for producing an ink fixer of the present invention,

a) preparing a dealkali sulfonic acid fluorescent dye by reacting a sulfonic acid fluorescent dye with an acid;

b) preparing a compound of a cationic resin and a dealkali sulfonic acid based fluorescent dye by adding a cationic resin prepared by reacting the above-mentioned dealkali sulfonic acid type fluorescent dye with a compound having at least one amine group with epihalohydrin; .

In the method for producing an ink fixer according to an embodiment of the present invention, as described above, the cationic resin is firstly mixed with a primary amine or a secondary amine represented by the general formula (2) And then reacting epihalohydrin with a polyamine. Second, one or more polyalkylene polyamines represented by the above formula (3) may be added to the primary amine or secondary amine represented by the above formula (2) Hydrin, and can be prepared further comprising elements in these first or second aspects.

In the method for producing an ink fixer according to an embodiment of the present invention, the primary amine may be methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine or heptylamine, The amine may be dimethylamine, diethylamine, dipropylamine, dibutylamine or diphenylamine, and the polyalkylene polyamine may be ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or pentaethylene Lt; / RTI >

In the method for producing an ink fixer according to an embodiment of the present invention, the above-mentioned debalkarboxylic acid type fluorescent dye may be represented by the above-mentioned formula (1), and the epihalohydrin may preferably be epichlorohydrin, It may be reacted at 0.5 to 1.5 moles per mole of primary amine, secondary amine, polyalkylene polyamine and mixed amines thereof.

The acid according to an embodiment of the present invention may be hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, acetic acid, formic acid, and mixtures thereof, and may be added in an amount of 1 to 6 moles per mole of the sulfonic acid fluorescent dye.

The cationic resin: sulfonic acid type fluorescent dye according to an embodiment of the present invention may have a weight ratio of each solid content of 1: 0.005 to 0.2.

The present invention also provides an inkjet recording paper produced by using the ink fixer of the present invention or manufactured by the method of producing the ink fixer of the present invention.

The ink fixing agent containing the fluorescent dye of the present invention can be obtained by dealkalkizing a part or the whole of a sulfonic acid fluorescent dye and reacting the sulfonic acid fluorescent dye with a cationic resin so that a sulfonic acid group of the sulfonic acid type fluorescent dye and a salt compound It is possible to increase whiteness and fixability because there is no clumping phenomenon which is a conventional problem.

That is, conventionally, when a sulfonic acid type fluorescent dye and a cationic resin are mixed, aggregation occurs due to ionic bonding between the sulfonic acid type fluorescent dye and the cationic resin, thereby lowering whiteness and fixability. However, the fixing agent of the present invention is a method in which a sulfonic acid type fluorescent dye is de- A salt compound which is one compound is prepared by mixing a dealkali sulfonic acid type fluorescent dye and a cationic resin so that whiteness, which is a conventional problem, is not generated at all, so that whiteness and fixability are not deteriorated.

In addition, the ink fixing agent of the present invention does not cause aggregation and does not cause deterioration of fluorescence performance and ink fixation performance, so that a separate additive for reinforcing the degraded performance is not required, which is economical and environmentally friendly.

In addition, when a sulfonic acid based fluorescent dye and a cationic resin are mixed with each other as in the prior art, their complexes are formed to deteriorate the fluorescence performance and the ink fixation performance. To solve this problem, they are separately treated. However, The use of a salt compound in which a sulfonic acid group of a dealkali sulfonic acid type fluorescent dye and an amine group of a cationic resin are used as a salt makes it possible to directly apply a fluorescent dye and a fixing agent to the starch without mixing them separately, But it is also excellent in terms of effect.

Further, the method for producing an ink fixer of the present invention is a method for producing an ink fixer by using a salt compound in which a sulfonic acid group of a decarboxylic acid sulfonic acid fluorescent dye and an amine group of a cationic resin form a salt as a fluorescent dye, It is possible to produce an ink fixing agent which can be produced by a simple process which does not require careful attention, while simultaneously satisfying both the fluorescent performance and the fixing performance.

In addition, the inkjet recording paper produced using the ink fixer of the present invention can be processed in one process without separately processing the fluorescent dye and the ink fixer, thereby simplifying the process and making it economical. And has the same whiteness and fixability as in the case of manufacturing.

The present invention provides an ink fixer comprising a compound of a cationic resin and a dealkali sulfonic acid based fluorescent dye prepared by reacting epihalohydrin with a compound having at least one amine group.

More particularly, the present invention relates to an ink fixing agent comprising an amine group of a cationic resin prepared by reacting epihalohydrin with a compound having at least one amine group, and a salt compound in which a sulfonic acid group of a decarboxylic acid type fluorescent dye forms a salt do.

The ink fixing agent of the present invention is a fluorescent dye and, unlike the conventional one, a dealkali sulfonic acid type fluorescent dye is used to prepare a salt compound by mixing with a cationic resin so that there is no aggregation due to complexation thereof, Performance.

The alkali metal sulfonate fluorescent dyes of the present invention are prepared by removing alkali metal or alkaline earth metal ions from sulfonic acid fluorescent dyes. For example, the sulfonic acid fluorescent dyes include those in which a sulfone group in a sulfonic acid fluorescent dye is combined with an alkali metal or an alkali metal, It refers to compounds in which transition to -SO ₃ H in the form of SO ₃ Na, -SO ₃ K.

The dealkali sulfonic acid type fluorescent dye according to an embodiment of the present invention necessarily has two or more sulfonic acid bases, and all or a part of the sulfonic acid bases is dealkarized.

In other words, a sulfonic acid-based fluorescent dyes are generally two or more sulfonic acid base, preferably at least four sulfonic acid base (more than 4 -SO ₃ Na, -SO ₃ K, etc.) of I this de-alkaline acid-based fluorescent dyes for example Means that at least one of the sulfonic acid bases is converted to a sulfonic acid group (-SO ₃ H).

In the ink fixing agent of the present invention, the sulfonic acid group of such a dealkali sulfonic acid type fluorescent dye is dealkoxyated to be a sulfonic acid group, and such sulfonic acid group becomes a salt compound forming a salt with the amine group of the cationic resin according to the present invention.

The sulfonic acid group of the present invention forms a salt compound with the amine group of the cationic resin. Thus, the salt form of the sulfonic acid group and the amine group of the present invention may contain one or more sulfonic acid group .

Since the ink fixing agent of the present invention contains such a salt compound, the conventional sulfonic acid-based fluorescent dye and the cationic resin are not mixed with each other to cause aggregation, so that whiteness as well as deterioration of fixability and durability do not occur.

The dealkali sulfonic acid type fluorescent dye of the present invention can be represented by the following formula (1).

[Chemical Formula 1]

[In the above formula (1)

X ₁ to X ₄ are independently of each other Na ⁺ , K ⁺ or H, and at least one of X ₁ to X ₄ is H;

이며, R₁₁ 내지 R₁₂는 서로 독립적으로 수소, (C1-C5)알킬 또는 (C1-C5)히드록시알킬이며; n은 1 내지 2의 정수이다.]R is _{-N (R 11) (R 12} ) , or

And R ₁₁ to R ₁₂ are independently of each other hydrogen, (C 1 -C 5) alkyl or (C 1 -C 5) hydroxyalkyl; and n is an integer of 1 to 2.]

More specifically, the sulfonic acid-based fluorescent dye to be debalkered according to an embodiment of the present invention may be, for example, C.I. Fluorescent Brighteners 210, 220, 264, 353 and 357. At least one sulfonate salt of the sulfonic acid salt-based fluorescent dye to be used in the present invention should be dealkali to be a sulfonic acid group, and such a dealkalization may be carried out in the presence of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, But it is preferable to carry out the dealkalization to about 40 to 60% which is insoluble in water by the hydrochloric acid. The obtained dealkali sulfonic acid type fluorescent dye may be used in a state in which salt such as salt is present in the precipitated state.

The alkyl described in the present invention includes both straight chain and branched chain. Hydroxyalkyl is a compound having a hydroxyl group at the terminal or side chain of alkyl. Examples thereof include -CH ₂ OH, -CH ₂ CH ₂ OH, -CH (OH ) CH ₃ or -CH ₂ CH ₂ CH ₂ OH.

The cationic resin of the present invention can be prepared by reacting an epihalohydrin with a compound having at least one amine group, and preferably the first aspect of the cationic resin of the present invention is a primary amine represented by the following formula Secondary amine represented by the following general formula (2) and epihalohydrin, and the second embodiment is characterized in that at least one polyalkylene polyamine represented by the general formula (3) is added to a primary amine or a secondary amine represented by the following general formula And a third aspect thereof is a process for preparing a polyamine by reacting a polyalkylene polyamine represented by the following general formula (3) with adipic acid or urea, with a primary amine or a secondary amine represented by the following general formula Followed by reaction with an epihalohydrin.

(2)

R ₁ - NH - R ₂

Wherein R ₁ is a C ₁ -C 7 alkyl group and R ₂ is H or a C 1 -C 7 alkyl group.

(3)

[Wherein R ₃ is an alkylene group having 2 to ₃ carbon atoms and n is an integer of 1 to 6]

The primary amine according to one embodiment of the present invention may be methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine or heptylamine, and the secondary amine may be dimethylamine, diethylamine, dipropylamine , Dibutylamine or diphenylamine, and the polyalkylene polyamine may be ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentaamine or pentaethylene hexaamine.

The epihalohydrin according to an embodiment of the present invention may be epichlorohydrin. Epihalohydrin may be used in an amount of 0.5 to 1 mole of the primary amine, the secondary amine, the polyalkylene polyamine and the mixed amine thereof, To 1.5 mol.

The cationic resin according to an embodiment of the present invention may be adjusted to a certain pH by adding acid and alkali after the reaction, or may be added with a water-soluble solvent, but generally it is not necessary.

The present invention also relates to a method for producing a sulfonic acid-based fluorescent dye, comprising the steps of: a) reacting a sulfonic acid fluorescent dye with an acid to prepare a dealkali sulfonic acid fluorescent dye;

b) preparing a compound of a cationic resin and a dealkali sulfonic acid based fluorescent dye by adding a cationic resin prepared by reacting the above-mentioned dealkali sulfonic acid type fluorescent dye with a compound having at least one amine group with epihalohydrin; And a method for producing the ink fixer.

In the method for producing an ink fixer of the present invention, the dealkali sulfonic acid type fluorescent dye and the cationic resin have already been described above.

The manufacturing method of the present invention will be described in detail below.

First, a sulfonic acid type fluorescent dye is added to deionized water, heated and dissolved, and then reacted with an acid to prepare a dealkali sulfonic acid type fluorescent dye. As described above, the sulfonic acid fluorescent dye of the present invention has at least two or more sulfonic acid groups in the fluorescent dye, and the sulfonic acid fluorescent dye is in the form of a salt in which a sulfonic acid group is combined with an alkali metal or an alkaline earth metal.

These sulfonic acid type fluorescent dyes are used to prepare a dealkali sulfonic acid type fluorescent dye.

Although hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, acetic acid, formic acid, and mixtures thereof may be used, hydrochloric acid is preferable from the viewpoint of efficient dealkalization, and 1 mole of the sulfonic acid fluorescent dye To about 6 moles, and can be dealkalized.

The reaction temperature and time of the sulfonic acid based fluorescent dye and the acid are not particularly limited, but may be preferably from 20 to 90 DEG C for 30 minutes to 2 hours. A cationic resin is added to the thus obtained dealkoxy fluorescent dye and stirred at 20 to 90 캜 for 30 minutes to 5 hours to obtain the ink fixer of the present invention.

The cationic resin and the sulfonic acid-based fluorescent dye according to an embodiment of the present invention may be used in a weight ratio of 1: 0.005 to 0.2 in terms of solids content, and 1: 0.03 to 0.1 in terms of enlarging effect, durability and fixing performance .

Although the solid content of the ink fixer of the present invention affects the viscosity of the ink fixer, it is preferable to control the dialkylamine to about 50% in view of economy and ease of use. In addition, after the production of the alkaline fluorescent dye, the salts generated in the reaction vessel in this state may be blended with the cationic resin immediately without removing the salt, and it is preferable to employ this method in terms of production efficiency.

The ink fixer of the present invention is stable even after being stored for a long period of time and used in the production of inkjet paper by a conventionally known method.

That is, the ink fixer of the present invention is suitable for ink fixing purposes of inkjet recording paper using inkjet pigments and dyes or pigments for dyeing and dyes. As the material of the inkjet recording paper, there are paper, pulp, cotton fiber and the like, and particularly paper and pulp are preferable. When an inkjet recording paper is manufactured using paper or pulp as a raw material, the pulp is dissociated, and the pulp is extruded or extruded through an extrusion process to be added during the process until the paper is papermaking, And an external coating method or an overcoating method in which the coating composition is added to a coating composition comprising a pigment and an organic polymer binder.

The pulverization slurry is prepared by pulp, refiner or the like with a predetermined degree of beating, and the ink fixing agent of the present invention is added to the pulp slurry in an amount of 0.01 to 10 mass% per dry mass of paper, After adding rosin or an AKD sizing agent, a PAM-based wet strength enhancer, an epoxy wetting enhancer, Alum, a fixing agent, a positive starch, a retention agent and the like as necessary, the inkjet paper is subjected to a paper- Can be obtained.

The pulp slurry is pulverized by a pulper, a refiner, or the like to a predetermined degree of beating, and pulp slurry is prepared. The pulp slurry is pulverized and pulverized using conventional rosin or an AKD sizing agent, a PAM-based strength increasing agent, an epoxy wetting enhancer, A positive press starch, a preservative, and the like are added as needed, followed by a papermaking process by a conventional method, and then the size fixing press machine of the present invention is applied to a size press coating solution containing 0.1 to 100 mass% And then dried to obtain an inkjet paper. The above-mentioned size press coating solution is prepared by appropriately mixing starch, PVA (polyvinyl alcohol), CMC (Carboxyl methyl cellulose), surface sizing agent, water and the like.

In the extrusion-overcoating method, pulp slurry is first pulverized with a pulper, a refiner or the like to a predetermined degree of beating, and a pulp slurry is prepared by adding a conventional sizing agent, soil strength enhancer, wetting enhancer, fixing agent, Thereafter, a papermaking process and a drying process are carried out by a conventional method, and then a coating solution containing the composition of the present invention is coated on the surface of paper and dried to obtain an inkjet paper. The above-mentioned overcoating solution is prepared by appropriately mixing PVA, CMC, a dispersant, water and the like to a white inorganic pigment such as fine silica.

In particular, the ink fixer of the present invention is suitable for an overcoating method using a white pigment inorganic pigment such as a particulate silica and a size press method using starch.

Further, the ink fixer of the present invention is excellent in compatibility with other medicines, and is also capable of imparting superior ink repellency and whiteness.

That is, even if starch is added to prepare a coating solution, the ink fixer according to the present invention is not economically produced because of the complexation of the fluorescent dye and the ionic resin, so that the fluorescence performance and fixing performance are maintained.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

[Synthesis of cationic resin 1]

To a four-necked flask equipped with a thermometer, a stirrer, a dropping device and a reflux condenser was added 90 g of 1 mole of 50% strength dimethylamine to 64 g of deionized water. 92.5 g of 1 mol of epichlorohydrin was slowly added thereto for about 2 hours while keeping the temperature at 50 캜 or lower. Next, the temperature was raised to 65 占 폚 and 15 g of 10% caustic soda solution was added dropwise at 65 占 폚 for about 20 minutes and stirred for 2 hours to obtain cationic resin 1 shown in Table 1.

[Synthesis of cationic resin 2]

Into a four-necked flask similar to the synthesis of the cationic resin 1, 81 g of a 0.9 molar amount of dimethylamine at a concentration of 50%, 10.3 g of 0.1 mol of diethylenetriamine and 74 g of deionized water were added, and 92.5 g of 1 mol of epichlorohydrin was added and reacted 15 g of a 10% caustic soda solution was reacted to obtain the cationic resin 2 shown in Table 1.

[Synthesis of cationic resin 3]

Into a four-necked flask similar to the synthesis of the cationic resin 1, 81 g of dimethylamine at a concentration of 50%, 81 g of dimethylamine, 12.2 g of ethylenediamine, and 76 g of deionized water were added and 83.3 g of epichlorohydrin was added thereto, And 15 g of a caustic soda solution were reacted to obtain the cationic resin 3 shown in Table 1.

[Synthesis of cationic resin 4]

To a four-necked flask similar to the synthesis of the cationic resin 1 were added 65.8 g of diethylamine, 0.13 mol of diethylenetriamine, and 150 g of deionized water, and 92.5 g of 1 mol of epichlorohydrin was added and reacted. % Sodium hydroxide solution was reacted to obtain the cationic resin 4 shown in Table 1.

[Synthesis of cationic resin 5]

In a four-necked flask similar to the synthesis of the cationic resin 1, 72 g of dimethylamine, 6 g of 0.1 mol of urea, 0.1 mol of diethylene triamine, and 120 g of deionized water were added and 92.5 g of 1 mol of epichlorohydrin was added and reacted 15 g of a 10% caustic soda solution was reacted to obtain the cationic resin 5 shown in Table 1.

[Synthesis of cationic resin 6]

In a four-necked flask similar to the synthesis of the cationic resin 1, 70 g of monomethylamine of 0.9 mol, a concentration of 0.1 mol of diethylenetriamine, and 65 g of deionized water were added, and 140 g of 1 mol of epibromohydrin was added and reacted 15 g of a 10% caustic soda solution was reacted to obtain the cationic resin 6 shown in Table 1.

[Synthesis of cationic resin 7]

In a four-necked flask similar to the synthesis of the cationic resin 1, 58 g of monoethylamine in a concentration of 70%, tetraethylenetetramine in an amount of 0.1 mol in 14.6 g, and deionized water in an amount of 101 g were added and 92.5 g of epichlorohydrin was added in an amount of 92.5 g, 15 g of a 10% caustic soda solution was reacted to obtain the cationic resin 7 shown in Table 1.

[Synthesis of cationic resin 8]

103 g of 1 mol of diethylamine and 161 g of deionized water were added to a four-necked flask similar to the synthesis of the cationic resin 1, and 92.5 g of 1 mol of epichlorohydrin was added and reacted. Then, 15 g of 10% To obtain a cationic resin 8 as shown in Fig.

[Synthesis of cationic resin 9]

206 g of 2 mol of diethylene triamine and 146 g of 1 mol of adipic acid were subjected to dehydration reaction at 150 DEG C for 12 hours to obtain a pH 10.5, a viscosity of 300 cps, and a solid content of 50.5% I, 72 g of 50 mol% dimethylamine and 72 g of deionized water were added, and 92.5 g of 1 mol of epichlorohydrin was added to react, and 15 g of 10% caustic soda was reacted to obtain a cationic Resin 9 was obtained.

[Synthesis of cationic resin 10]

206 g of 2 mol of diethylene triamine and 60.6 g of 1 mol of urea were deammoniated at 120 캜 for 5 hours to obtain a pH of 11.6, a viscosity of 50 cps, and a solid content of 50.2% II, 72 g of dimethylamine having a concentration of 50%, 72 g of deionized water, and 92.5 g of 1 mol of epichlorohydrin were added, reacted, and 15 g of 10% caustic soda was reacted, To obtain a cationic resin 10.

Properties of cationic resin Cationic resin Exterior pH ⁽¹⁾ Viscosity ⁽²⁾ Solid ⁽³⁾ One Light yellow liquid 8.2 52 53 2 Light yellow liquid 7.8 60 53 3 Light yellow liquid 7.8 58 53 4 Light yellow liquid 8.5 45 52 5 Light yellow liquid 7.8 65 52 6 Light yellow liquid 7.3 50 53 7 Pale yellow liquid 7.5 53 53 8 Light yellow liquid 8.1 48 52 9 Light yellow liquid 7.8 50 53 10 Light yellow liquid 7.7 43 53

⁽¹⁾ pH: Measured with a digital pH meter (Horiba F-52) at 25 ° C

⁽²⁾ Viscosity: Measured in a Brookfield viscometer (LV, DV-I +, Spindle No. 62, 60 rpm) at 25 ° C (unit: cps)

⁽³⁾ Solid content: Weighed pure solids (unit:%) after drying for 8 hours in a forced circulation drier at 105 ° C

[Example 1] Production of ink fixing agent 1

A four-necked flask equipped with a thermometer, a stirrer, a dropping device and a reflux condenser was charged with a fluorescent dye C.I. 116.5 g of Fluorescent Brightener 220 (molecular formula: C40H40N12O16S4Na4) and 252 g of deionized water were added and dissolved by heating at 85 ° C. After the dye was completely dissolved and the liquid became transparent, the solution was cooled to 70 ° C. and 20.9 g of 35 mol% And the mixture was stirred for one hour at the same temperature for one hour to obtain a deblocked yellow particle-derived alkali metal sulfonate fluorescent dye 1. This was cooled to 40 DEG C, 2386 g of the cationic resin 1 was added and stirred at the same temperature for 1 hour to obtain the ink fixer of Example 1 shown in Table 2.

[ Example 2] Production of ink fixing agent 2

An ink fixer of Example 2 shown in Table 2 was prepared in the same manner as in Example 1 except that 2,390 g of cationic resin 2 was used instead of cationic resin 1 in Example 1.

[Example 3] Production of ink fixing agent 3

In the same manner as in the production of the dealkali sulfonic acid type fluorescent dye 1, the fluorescent dye C.I. 130.5 g of Fluorescent Brightener 263 (molecular formula: C40H38N12O18S6Na6) and 282 g of deionized water were added and dissolved by heating at 85 DEG C. When the fluorescent dye had completely dissolved, 31.4 g of 0.3 mol of 35% hydrochloric acid was added thereto three times, To obtain a yellow alkaline sulfonic acid type fluorescent dye 2, and then cooled to 40 DEG C to obtain 3570 g of a cationic resin 3 to obtain an ink fixing agent of Example 3 shown in Table 2. [

[Example 4] Production of ink fixing agent 4

An ink fixing agent 4 of Example 4 shown in Table 2 was prepared in the same manner as in Example 3, except that 3570 g of cationic resin 4 was used instead of cationic resin 3 in Example 3.

[Example 5] Preparation of ink fixing agent 5

In the same manner as in the production of the dealkali sulfonic acid type fluorescent dye 1, the fluorescent dye C.I. 133.4 g of Fluorescent Brightener 353 (molecular formula: C40H34N12O20S6Na6) and 180 g of deionized water were added and dissolved by heating at 85 DEG C. When the fluorescent dye had completely dissolved, 31.4 g of 0.3 mol of 35% hydrochloric acid was added thereto three times, Soluble alkali-soluble fluorescent dye 3 was obtained. Then, the solution was cooled to 40 캜 and 3090 g of cationic resin 5 was added to obtain ink fixer 5 of Example 5 shown in Table 2.

[Example 6] Production of ink fixing agent 6

An ink fixing agent 6 of Example 6 shown in Table 2 was prepared in the same manner as in Example 5 except that 3060 g of cationic resin 6 was used instead of cationic resin 5 in Example 5.

[ Example 7] Production of ink fixing agent 7

In the same manner as in the production of the dealkali sulfonic acid type fluorescent dye 1, the fluorescent dye C.I. 130.5 g of Fluorescent Brightener 357 (molecular formula: C40H38N12O18S6Na6) and 230 g of deionized water were added and dissolved by heating at 85 DEG C. When the fluorescent dye had completely dissolved, 41.7 g of 35 mol% hydrochloric acid was added in three portions, To obtain sulfonic acid-based fluorescent dye 4 having insoluble yellow particles. The solution was cooled to 40 캜 and 2960 g of cationic resin 7 was added to obtain ink fixer 7 of Example 7 shown in Table 2.

[Example 8] Production of ink fixing agent 8

An ink fixing agent 8 of Example 8 shown in Table 2 was obtained in the same manner as in Example 7 except that 3010 g of the cationic resin 8 was used instead of the cationic resin 7 in Example 8.

[Example 9] Production of ink fixing agent 9

In the same manner as in the production of the dealkali sulfonic acid type fluorescent dye 1, the fluorescent dye C.I. After dissolving 112.9 g of Fluorescent Brightener 210 (molecular formula: C40H36N12O16S4Na4) and 205 g of deionized water, the mixture was heated to 85 ° C and dissolved. After the fluorescent dye had completely dissolved, 20.9 g of 35 mol% hydrochloric acid Followed by stirring at the same temperature for one hour to precipitate insoluble yellow particles to obtain an alkali sulfonic acid based fluorescent dye 5. Subsequently, the whole was cooled to 40 占 폚, 2630 g of cationic resin 9 was added and stirred to obtain ink fixer 9 of Example 9 shown in Table 3.

[Example 10] Preparation of ink fixing agent 10

 An ink fixing agent 10 of Example 10 shown in Table 2 was prepared in the same manner as in Example 9, except that 2630 g of cationic resin 10 was used instead of cationic resin 9 in Example 9.

Properties of the ink fixatives of Examples 1 to 10 Example Exterior pH Viscosity Solids Fluorescence concentration ⁽¹⁾ Storage stability ⁽²⁾ One Light yellow liquid 7.9 49 50.1% 5% ○ 2 Light yellow liquid 7.6 60 50.2% 5% ○ 3 Pale yellow liquid 7.3 54 50.4% 3% ○ 4 Light yellow liquid 7.5 42 50.1% 3% ○ 5 Light yellow liquid 7.5 45 50.8% 4% ○ 6 Light yellow liquid 7.1 50 51.0% 4% ○ 7 Dermal ferric liquor 7.2 49 50.4% 4% ○ 8 Light yellow liquid 7.8 48 50.5% 4% ○ 9 Light yellow liquid 7.7 42 50.8% 4% ○ 10 Light yellow liquid 7.9 40 50.7% 4% ○

⁽¹⁾ Measurement of fluorescence intensity: Each of the purified fluorescent brighteners was used as a standard and absorbance was measured at a wavelength of 350 nm with a UV-VIS Spectrophotometer (Shimadzu UV-2401PC). (unit:%)

⁽²⁾ Storage stability: The samples were allowed to stand for 1 month in a constant temperature oven at 40 占 폚, and changes in viscosity and appearance were observed and evaluated as follows.

 ○: Very stable.

 ?: The viscosity was slightly increased or a small amount of precipitate was formed.

 X: The viscosity has increased significantly or a large amount of precipitate has formed.

  As shown in Table 2, the cationic resin containing fluorescent dyes obtained in Examples 1 to 10 was in a pale yellow liquid state and exhibited excellent storage stability. In addition, DS-Coat and Samyang Genex oxidized starch (Sun Size) 10% aqueous solution, no precipitate was formed, and it was very stable, with no viscosity stability or other changes with time.

[Comparative Example 1]

In a four-necked flask, 116.5 g of 0.1 mol of fluorescent dye CI220 (Shanxi Qingshan Chem, BBU) and 205 g of deionized water were added and completely dissolved at 85 ° C. When the fluorescent dye had completely dissolved, the solution was cooled to room temperature. 2386 g of INK fixer 1 Followed by stirring for a time period to obtain Comparative Example 1 shown in Table 3. In Comparative Example 1, it was observed that a yellow precipitate was formed after 1 day from the addition of 10% aqueous solution of oxidized starch (DS-Coat).

[Comparative Example 2]

130.5 g of a fluorescent dye CI263 (Shanxi Qingshan Chem, CI 263) and 282 g of a fluorescent dye CI263 were placed in a four-necked flask and completely dissolved at 85 ° C. After the fluorescent dye had completely dissolved, the solution was cooled to room temperature and 3570 g of INK fixer 3 And stirred for 1 hour to obtain Comparative Example 2 shown in Table 3. [ In Comparative Example 2, it was observed that a yellow precipitate was formed after 1 day by adding it to a 10% aqueous solution of oxidized starch (DS-Coat).

[Comparative Example 3]

In a four-necked flask, 133.4 g of 0.1 mole of fluorescent dye CI353 (Shanxi Qingshan Chem, CI 353) and 190 g of deionized water were added and completely dissolved at 85 ° C. When the fluorescent dye had completely dissolved, it was cooled to room temperature and 3090 g of INK FIX 5 And the mixture was stirred for 1 hour to obtain Comparative Example 3 shown in Table 3. In Comparative Example 3, it was observed that a yellow precipitate was formed after a lapse of 2 days by adding it to a 10% aqueous solution of oxidized starch (DS-Coat).

[Comparative Example 4]

130.5 g of fluorescent dye CI357 (Shanxi Qingshan Chem, KSM) and 240 g of deionized water were added to a four-necked flask and completely dissolved at 85 ° C. When the fluorescent dye had completely dissolved, the solution was cooled to room temperature. 2960 g of INK fixer 7 Followed by stirring for a time period to obtain Comparative Example 4 shown in Table 3. In Comparative Example 4, it was observed that a yellow precipitate was formed after a lapse of 2 days by adding it to a 10% aqueous solution of oxidized starch (Samyang Genex Sunsize Co., Ltd.).

[Comparative Example 5]

In a four-necked flask, 112.9 g of a fluorescent dye CI 210 (Shanxi Qingshan Chem, CI 210) and 112 g of deionized water were added and completely dissolved at 85 ° C. When the fluorescent dye had completely dissolved, the solution was cooled to room temperature and 2556 g of INK fixer 9 And stirred for 1 hour to obtain Comparative Example 5 shown in Table 3. [ In Comparative Example 5, it was observed that a yellow precipitate was formed after 1 day from the addition to the 10% aqueous solution of the oxidized starch (Samyang Genex Sunsize Co., Ltd.).

[Comparative Example 6] Production of ink fixing agent 11

112.9 g of CI Fluorescent Brightener 210 (molecular formula: C40H36N12O16S4Na4) (0.19 mole) and deionized water (202 g) were added in the same manner as in the preparation of the dealkali sulfonic acid type fluorescent dye 1 and dissolved by heating at 85 캜. When the fluorescent dye had completely dissolved, 20.9 g of 0.2 mol of 35% strength HCl were added in three portions, followed by stirring at the same temperature for one hour. The dye became insoluble and yellow particles were precipitated to obtain a dealkoxy fluorescent dye 5. Next, the whole was cooled to 40 DEG C, and 426 g of the intermediate I obtained in the cationic resin 9 and 50 g of deionized water were added and reacted with 92.5 g of 1 mol of epichlorohydrin, to which 2556 g of a cationic resin, which was a polymer, To obtain ink fixing agent 11 of Example 11 shown in Table 3. [ Example 11 was observed in that a yellow precipitate was formed after a lapse of 2 days by adding it to a 10% aqueous solution of oxidized starch (DS-Coat).

[Comparative Example 7] Production of ink fixing agent 12

112.9 g of CI Fluorescent Brightener 210 (molecular formula: C40H36N12O16S4Na4) (0.19 mole) and deionized water (202 g) were charged in the same manner as in the preparation of the dealkali sulfonic acid type fluorescent dye 1 and dissolved by heating at 85 ° C. After the fluorescent dye was completely dissolved, 20.9 g of 0.2 mol of 35% strength HCl were added in three portions, followed by stirring at the same temperature for one hour. The dye became insoluble and yellow particles were precipitated to obtain a dealkali sulfonic acid type fluorescent dye 5. Next, the whole was cooled to 40 ° C, and 2556 g of a cationic resin, which was a polymer obtained by reacting 1 mole of epichlorohydrin with 927 g of epichlorohydrin, was charged with 257 g of the intermediate 1 obtained in the cationic resin 10 and 56 g of deionized water, The ink fixer 12 of Example 12 shown in Table 3 was obtained. In Example 12, it was observed that a yellow precipitate was formed after 2 days from the addition of 10% aqueous solution of oxidized starch (Samyang Genex Sunsize Co., Ltd.).

Properties of Comparative Examples 1 to 7 Exterior pH Viscosity Solids Fluorescence intensity Storage stability Comparative Example 1 Light yellow liquid 7.6 36 50% 4% × Comparative Example 2 Light yellow liquid 7.7 40 51% 4% × Comparative Example 3 Light yellow liquid 7.9 43 51% 3% × Comparative Example 4 Light yellow liquid 7.5 44 51% 3% × Comparative Example 5 Light yellow liquid 7.5 45 50% 3% × Comparative Example 6 Light yellow liquid 7.9 40 51% 2% △ Comparative Example 7 Light yellow liquid 7.9 35 51% 2% △

Note: The measurement method is the same as the method

[Evaluation of ink jet recording paper production and printing characteristics of Examples and Comparative Examples]

  Using the ink fixer of the present invention obtained in Examples and Comparative Examples, an inkjet recording paper was produced by the following method and printing characteristics were evaluated.

①. Inkjet recording paper manufacturing - Size press external method

  First, a pulp slurry was prepared by pulp, refiner, or the like with a predetermined degree of beating to prepare a pulp slurry. The pulp slurry was pulverized with an ordinary AKD sizing agent (Hercules-100A) and a PAM type paper strengthening agent (CP- (EP-WS), Alum (50% aqueous solution of aluminum sulfate), amphoteric starch (Samyang Genex C6060) and PAM-based retention agent (Basf Percol-63) were added as an epoxy wetting enhancer , A sizing press coating solution was coated on a size press machine and dried to obtain an inkjet paper. The size press coating solution was prepared by baking the oxidized starch (DS-Coat) in a 10% aqueous solution at 95 ° C and adding 100 parts by weight of the ink fixing agent of the present invention obtained in Examples and Comparative Examples to the oxidized starch And 10 parts by weight of a surface sizing agent (SF-3000 manufactured by Wuzhen Industry Co., Ltd.) were used to prepare a coating solution for size press, which was left in a 70 ° C water bath for 1 hour and then used.

The coating solution for size press was coated on paper using a bar coater (Bar No. 2) and dried with a drum dryer at 105 ° C to prepare an inkjet recording paper. The above coating solution was prepared so that the dry weight was 2 g / m < ² >

② Inkjet printing

 Black (B), yellow (Y), cyan (C), and magenta (M) were printed with a size of 20 mm x 50 mm using an inkjet printer (Hewlett Packard, Office Jet 6000 Special Edition).

③ Evaluation of stability and printing characteristics of size press coating solution

The stability, whiteness, and ink water resistance of the size press coating solution were evaluated respectively as follows.

(1) Evaluation of the stability of the size press coating solution

The size press coating solution containing the ink fixing agent obtained in Examples and Comparative Examples in an amount of 10 mass% based on the mass of the starch was left in a thermostat at 70 캜 for 3 days, and the viscosity and appearance were observed.

○: Very stable.

 ?: The viscosity was slightly increased or a small amount of precipitate was formed.

 X: The viscosity has increased significantly or a large amount of precipitate has formed.

(2) Whiteness

The whiteness (WI) of the inkjet recording paper produced by the size press extrusion method described above was measured using a Nippon Denshoku Spectrophotometer SA2000.

(3) Water resistance of ink

Inks of black (B), yellow (Y), cyan (C) and magenta (M) were printed on inkjet recording paper produced by the above-mentioned size press extrusion method in a size of 20 mm x 50 mm. Then, the surface of the inkjet recording paper was impregnated with water at room temperature for 5 minutes, the surface was removed, and the optical density of the remaining ink was measured using Dainippon Screen MFG DM-62.

[Evaluation of Stability of Coating Solution for Inkjet Recording Medium]

The coating solution for the inkjet recording medium using the cationic resin obtained from Examples and Comparative Examples was evaluated by the method described above and is shown in Table 4.

Evaluation of Stability of Coating Solution of InkJet Recording Medium Ink jet recording medium application solution stability Example 1 ○ Example 2 ○ Example 3 ○ Example 4 ○ Example 5 ○ Example 6 ○ Example 7 ○ Example 8 ○ Example 9 ○ Example 10 ○ Comparative Example 1 × Comparative Example 2 × Comparative Example 3 × Comparative Example 4 × Comparative Example 5 × Comparative Example 6 △ Comparative Example 7 △

In the results shown in Table 4, Examples 1 to 10 are excellent in mixing stability with 10% aqueous starch solution, Examples 7 to 8 are excellent, and Comparative Examples 1 to 5 produce yellow precipitates.

[Evaluation of printing characteristics using an inkjet recording medium]

  Table 5 shows the printing properties in which the cationic resin obtained from Examples and Comparative Examples were measured for whiteness and water resistance by the method described above.

Printing characteristic measurement result
Whiteness
(CIE) Water resistance Black (B) Yellow (Y) Cyan (C) Magenta (M) Control 60.1 0.9 0.05 0.4 0.01 Example 1 79.5 1.7 0.4 1.2 0.5 Example 2 79.2 1.8 0.4 1.2 0.5 Example 3 75.4 1.7 0.4 1.3 0.6 Example 4 75.1 1.8 0.4 1.2 0.5 Example 5 76.8 1.8 0.3 1.2 0.5 Example 6 76.1 1.7 0.4 1.1 0.6 Example 7 76.5 1.8 0.4 1.2 0.5 Example 8 77.0 1.5 0.3 1.1 0.4 Example 9 78.5 1.8 0.4 1.2 0.5 Example 10 78.2 1.8 0.4 1.2 0.5 Comparative Example 1 67.5 1.3 0.2 0.8 0.09 Comparative Example 2 66.9 1.2 0.2 0.7 0.1 Comparative Example 3 65.3 1.2 0.2 0.7 0.1 Comparative Example 4 64.5 1.1 0.2 0.6 0.09 Comparative Example 5 65.7 1.2 0.2 0.6 0.1 Comparative Example 6 63.8 1.0 0.2 0.5 0.09 Comparative Example 7 64.1 1.0 0.1 0.5 0.08

  As can be seen from the results of Table 5, it was found that the ink fixing agents of Examples 1 to 10 not only greatly improved whiteness but also had excellent ink water resistance.

Therefore, it can be seen that the ink fixing agent of the present invention has excellent compatibility with the raw materials of the inkjet recording medium, and improves whiteness and ink fixing performance.

Claims (22)

An ink fixer comprising a compound of a cationic resin and a dealkali sulfonic acid type fluorescent dye prepared by reacting epihalohydrin with a compound having at least one amine group. An inkjet recording paper produced using the ink fixer of claim 1. The method according to claim 1,
Wherein the cationic resin is prepared by reacting a primary or secondary amine represented by the following formula (2) with epihalohydrin.
(2)
R ₁ - NH - R ₂
Wherein R ₁ is a C ₁ -C 7 alkyl group and R ₂ is H or a C 1 -C 7 alkyl group. The method according to claim 1,
Wherein the cationic resin is prepared by adding at least one polyalkylene polyamine represented by the formula (3) to a primary amine or a secondary amine represented by the following formula (2) and reacting with epihalohydrin.
(2)
R ₁ - NH - R ₂
Wherein R ₁ is a C ₁ -C 7 alkyl group and R ₂ is H or a C 1 -C 7 alkyl group.
(3)

[Wherein R ₃ is an alkylene group having 2 to ₃ carbon atoms and n is an integer of 1 to 6] The method according to claim 1,
The cationic resin is prepared by reacting an adipic acid or urea with a polyalkylene polyamine represented by the following formula (3) and then adding a primary amine or secondary amine represented by the following formula (2) to the product and reacting with epihalohydrin Wherein the ink fixing agent is an organic solvent.
(2)
R ₁ - NH - R ₂
Wherein R ₁ is a C ₁ -C 7 alkyl group and R ₂ is H or a C 1 -C 7 alkyl group.
(3)

[Wherein R ₃ is an alkylene group having 2 to ₃ carbon atoms and n is an integer of 1 to 6] 4. A compound according to any one of claims 1 and 3 to 5,
Wherein the cationic resin is produced by further comprising an element. 4. The method of claim 3,
The primary amine is methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine or heptylamine,
Wherein the secondary amine is selected from the group consisting of dimethylamine, diethylamine, dipropylamine, dibutylamine or diphenylamine. 5. The method of claim 4,
Wherein the polyalkylene polyamine is ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentaamine, or pentaethylene hexaamine. The method according to claim 1,
Wherein the dealkali sulfonic acid type fluorescent dye is represented by the following general formula (1).
[Chemical Formula 1]

[In the above formula (1)
X ₁ to X ₄ are independently of each other Na ⁺ , K ⁺ or H, and at least one of X ₁ to X ₄ is H;
R is _{-N (R 11) (R 12} ) , or

And R ₁₁ to R ₁₂ are independently of each other hydrogen, (C 1 -C 5) alkyl or (C 1 -C 5) hydroxyalkyl; and n is an integer of 1 to 2.] 4. A compound according to any one of claims 1 and 3 to 5,
Wherein the epihalohydrin is characterized by epichlorohydrin. 4. A compound according to any one of claims 1 and 3 to 5,
Wherein the epihalohydrin is reacted at 0.5 to 1.5 moles per mole of the primary amine, the secondary amine, the polyalkylene polyamine or the mixed amine thereof. a) preparing a dealkali sulfonic acid fluorescent dye by reacting a sulfonic acid fluorescent dye with an acid;
b) preparing a compound of a cationic resin and a dealkali sulfonic acid based fluorescent dye by adding a cationic resin prepared by reacting the above-mentioned dealkali sulfonic acid type fluorescent dye with a compound having at least one amine group with epihalohydrin; ≪ / RTI > 13. The method of claim 12,
The cationic resin is prepared by reacting an epihalohydrin with a primary amine or secondary amine represented by the following formula (2) by adding at least one polyalkylene polyamine represented by the following formula (3) Way.
(2)
R ₁ - NH - R ₂
Wherein R ₁ is a C ₁ -C 7 alkyl group and R ₂ is H or a C 1 -C 7 alkyl group.
(3)

[Wherein R ₃ is an alkylene group having 2 to ₃ carbon atoms and n is an integer of 1 to 6] 13. The method of claim 12,
The cationic resin is prepared by reacting a polyalkylene polyamine represented by the following formula (3) with adipic acid or urea and then reacting the resulting product with epihalohydrin by adding a primary amine or a secondary amine represented by the formula (2) ≪ / RTI >
(3)

[Wherein R ₃ is an alkylene group having 2 to ₃ carbon atoms and n is an integer of 1 to 6] 13. The method of claim 12,
Wherein the cationic resin is produced further comprising an urea. 14. A compound according to any one of claims 13 to 14,
The primary amine is methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine or heptylamine;
Wherein said secondary amine is dimethylamine, diethylamine, dipropylamine, dibutylamine or diphenylamine;
Wherein the polyalkylene polyamine is ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentaamine, or pentaethylene hexaamine. 13. The method of claim 12,
Wherein the dealkali sulfonic acid type fluorescent dye is represented by the following formula (1).
[Chemical Formula 1]

[In the above formula (1)
X ₁ to X ₄ are independently of each other Na ⁺ , K ⁺ or H, and at least one of X ₁ to X ₄ is H;
R is _{-N (R 11) (R 12} ) , or

And R ₁₁ to R ₁₂ are independently of each other hydrogen, (C 1 -C 5) alkyl or (C 1 -C 5) hydroxyalkyl; and n is an integer of 1 to 2.] 15. A compound according to any one of claims 12 to 15,
Wherein the epihalohydrin is characterized by epichlorohydrin. 15. A compound according to any one of claims 13 to 14,
Wherein the epihalohydrin is reacted at 0.5 to 1.5 moles per mole of the primary amine, the secondary amine, the polyalkylene polyamine or the mixed amine thereof. 13. The method of claim 12,
Wherein the acid is hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, acetic acid, formic acid or a mixture thereof. 13. The method of claim 12,
Wherein the acid is added in an amount of 1 to 6 moles per mole of the sulfonic acid fluorescent dye. 13. The method of claim 12,
Wherein the solid weight ratio of the cationic resin: sulfonic acid based fluorescent dye is 1: 0.005 to 0.2.