KR20170044051A - Resin for ion collision detection and method for manufacturing thereof - Google Patents

Abstract

The present invention relates to a method for preparing a resin for preventing ion collision. The method according to the present invention comprises the steps of: introducing 150 g of purified water and 1.2 mol of a polyhydric alcohol to a flask and heating them to 65C, and introducing 0.5-3.5 mol of boron trichloride etherate as a catalyst in such a manner that it may flow down through the wall of the flask to provide a first solution; warming the first solution to 80C, maintaining the temperature and adding 3.6 mol of epichlorohydrine constantly dropwise thereto for 90 minutes to provide a second solution, followed by agitation for 60 minutes; cooling the second solution to 55-60C and introducing 0.8-2.0 mol of any one selected from primary and secondary amines and ammonia to provide a third solution; warming the third solution to 90C, maintaining the temperature, agitating the third solution for 60 minutes, cooling the third solution to 60-65C, maintaining the temperature and agitating the third solution for 6 hours to obtain a polymerizate.

Description

FIELD OF THE INVENTION The present invention relates to a resin for preventing ion collision and a method for producing a fluorescent dye composition containing the same,

The present invention provides a resin for preventing ion collision and a composition of a fluorescent dye using the resin for application to an ink fixing agent (cationic resin) used for high speed printing and high image quality of paper, and more particularly to a composition for preventing the collision of an epihalohydrin To produce a mixed composition of a cationic resin synthesized by reacting a compound having at least one amine group and a diamino-stilbene fluorescent dye to produce a composition for high-speed printing and high-quality image paper in the paper making industry It can be applied to improve the light fastness of fibers using fluorescent whitening agents and direct dyes, which are vulnerable to light fastness, by processing the mixed composition, which is applicable to the ink fixing resin without shocking of anionic fluorescent dyes, and the synthesized cationic resins to the dyed fibers It is.

BACKGROUND ART [0002] As inkjet recording paper and digital, high-speed printing have become widespread in recent years, the whiteness and printability of printing paper are strongly demanded.

In particular, a cationic polymer resin is used as a fixing agent in order to enhance the fixability of anionic inks on printing paper, and such cationic resins include polyimine.

In addition to high molecular weight cationic resins that enhance ink fixability, fluorescent dyes are used to maintain the basic whiteness of the printing paper, but in addition to cationic polymer resins that use stilbene fluorescent dyes for general paper use as ink fixing agents When anionic fluorescent dyes and cationic ink fixing agents are used as shocks due to ion collision, production of printing paper becomes a cause of defects such as occurrence of strick.

In order to solve such problems, for example, Japanese Patent Application Laid-Open No. 10-147057 provides a method for using as an ink fixing agent using a resin obtained by reacting a secondary amine with epichlorohydrin.

JP-A-2010-83044 discloses an inkjet recording medium containing specific polyvinyl alcohol and stilbene-based fluorescent dyes as a binder. JP-A-2009-73059 discloses an inkjet recording inkjet ink having high ink drying property and water resistance, The present inventors tried to solve the problem by containing rosette type hard calcium carbonate and alkenyl succinic anhydride in a recording paper other than the ink composition.

Therefore, as a countermeasure against this, as fluorescent dye composition and resin application which can satisfy whiteness degree and durability economical efficiency by simple process, it is possible to use ion in case of resin processing during post-treatment process of dyed fluorescent dyes and direct dyes, There is a need to develop a novel and advanced resin for preventing ion collision which can improve the fastness by adding a part of the resin for preventing collision.

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made in view of the above problems, and it is an object of the present invention to provide an ion collision preventing resin that can prevent shock caused by ion collision between a cationic resin and a fluorescent dye.

Another object of the present invention is to provide a cationic resin and a fluorescent dye composition prepared by radical polymerization of epihalohydrin to a polyhydric alcohol, polymerizing an alkoxyalkyl halide, and then substituting the halide with an amine.

It is still another object of the present invention to provide a method for synthesizing a resin for preventing ion collision.

It is a further object of the present invention to provide improved colorfastness of fibers dyed with fluorescent dyes and direct dyes as an application of the ionic collision-resistant resin and color build-up in continuous dyeing.

In order to achieve the above object, a method for producing an ion collision-resistant resin and a method for producing a fluorescent dye mixed composition including the same, which comprises the steps of charging 150 g of purified water and 1.2 mol of a polyhydric alcohol into a flask, And then adding 0.5 to 3.5 mol of boron trichloride ethane as a catalyst so as to flow through the flask wall to prepare a first solution; Maintaining and maintaining the primary solution at 80 DEG C and adding 3.6 mol of epichlorohydrine uniformly dropwise for 90 minutes to prepare a secondary solution and maintaining stirring for 60 minutes; Cooling the secondary solution to 55 to 60 ° C and adding 0.8 to 2.0 mols of any one selected from the group consisting of primary amine and ammonia to prepare a tertiary solution; Stirring the mixture for 60 minutes, cooling and maintaining the third solution at 60 to 65 ° C, and stirring for 6 hours to obtain a polymerized product; .

으로 표시되되, n은 알킬렌기이며 2 내지 6의 정수이고, 분자량은 92 이하인 것을 특징으로 한다.In addition, the polyhydric alcohol may be represented by the formula

, Wherein n is an alkylene group and is an integer of 2 to 6 and has a molecular weight of 92 or less.

In addition, the above-mentioned primary and secondary amines can be used in combination with one or more of methylamine, ethylamine, propylamine, isopropylamine, methanolamine, ethanolamine, propanolamine, isopropylamine, dimethylamine, diethylamine, dipropylamine, diisopropyl Amine, dimethanolamine, diethanolamine, dipropanolamine, diisopropanolamine, and ammonia water.

으로 표현되되, R₁은 C₁의 알킬렌기이고, R₂는 H이며, x는 2 내지 5의 정수이고, R₃,R₅는 C₂ 의 알킬렌기이고, R₄, R₆은 C₁ 알킬렌기이며, n은 다가알코올 수-x이며 1 내지 4이고, m은 n과 동일한 숫자 혹은 n-1을 가지며, Z₁, Z₂는 할로겐 원소, 암모늄, 1 내지 4차 알킬아민, 알킬기 C₁~C₃를 포함하는 하이드록시 알킬아민 중 선택된 어느 두 개인 것을 특징으로 한다.In addition,

Wherein R ₁ is an alkylene group of C ₁ , R ₂ is H, x is an integer of 2 to 5, R ₃ and R ₅ are C ₂ alkylene groups, R ₄ and R ₆ are C ₁ N is a number of polyhydric alcohols-x, 1 to 4, m is a number equal to n or n-1, Z ₁ and Z ₂ are halogen elements, ammonium, primary to quaternary alkylamines, alkyl groups C _And hydroxyalkylamines containing ₁ to ₃ carbon atoms.

In addition, the polymer is characterized by having a molecular weight (MW) of 2,000 to 10,000 and a cation density (meq / g) of 0.1 to 0.5.

In addition, the fluorescent dye mixed composition is characterized in that it is prepared by mixing 60 to 70% by weight of the polymer according to claim 1 and 30 to 40% by weight of a fluorescent dye.

으로 표현되되 R₁은 C₁의 알킬렌기이고, R₂는 H이며, x는 2 내지 5의 정수이고, R₃,R₅는 C₂ 의 알킬렌기이고, R₄, R₆은 C₁ 알킬렌기이며, n은 다가알코올 수-x이며 1 내지 4이고, m은 n과 동일한 숫자 혹은 n-1을 가지며, Z₁, Z₂는 할로겐 원소, 암모늄, 1 내지 4차 알킬아민, 알킬기 C₁~C₃를 포함하는 하이드록시 알킬아민 중 선택된 어느 두 개인 중합체 65g을 혼합하는 단계;로 이루어진 것을 특징으로 한다.In addition, 300 ml of purified water, 1 to 5 g of dispersant and 12 g of calcium carbonate were added to the flask, and 40 g of Cynuric chloride was added thereto while maintaining the temperature at 0 to 5 ° C by external cooling to prepare a primary dye solution ; 52 g of Aniline-2,5-Disulfonic acid and 11 g of Soda ash were added to the primary dye solution, and the resultant was dropped for 3 hours at 6 to 8 ° C. The reaction product was stirred and maintained for 1 hour to obtain a secondary dye solution Producing; After the temperature of the secondary dye solution was raised to 20 ° C, 40 g of Disopropanol-amine was added, and the mixture was heated to 100 ° C and stirred for 4 hours to prepare a tertiary dye solution. Filtering the third dye solution to remove impurities and then heating to obtain a dye product; 35 g of the dye product,

Wherein R ₁ is an alkylene group of C ₁ , R ₂ is H, x is an integer of 2 to 5, R ₃ and R ₅ are C ₂ alkylene groups, R ₄ and R ₆ are C ₁ alkyl N is a number of polyvalent alcohol-x, 1 to 4, m is a number equal to n or n-1, Z ₁ and Z ₂ are a halogen element, ammonium, primary to quaternary alkylamine, alkyl group C ₁ And 65 g of a polymer selected from two selected from hydroxyalkylamines including C ₃ .

으로 표현되되, X는 서로 독립적으로 Na+, K+, H 이며 n은 0 내지 2의 정수이고, NR은 1급 내지 2급의 이미노 알킬 모노아세테이트 및 이미노 알킬 디아세테이트 중 선택된 어느 하나인 것을 특징으로 한다.In addition,

, Wherein X is independently selected from Na +, K +, H, n is an integer of 0 to 2, and NR is any one selected from iminoalkyl monoacetate and iminoalkyldiacetate of a primary to secondary grade .

In addition, the dye product is characterized in that it comprises six sulfonic acid bases (-SO ₃ X).

According to the ionic-impact-preventing resin containing the fluorescent dye of the present invention according to the present invention, the cationic resin used for ink fixing and the resin for preventing the ionic impact are buffered between cations, resulting in collision of ions, which is a problem of general fluorescent dyes (Dye precipitation and lump), which can enhance the whiteness and fixability.

That is, conventionally, when a sulfonic acid based sulfur dye and a cationic resin are mixed, shocking (dye precipitation, lump) occurs due to mutual ionic bonding, resulting in decreased whiteness and fixability. However, The fluorescent dye does not cause a shocking phenomenon even when it is mixed with a cationic resin used as an ink fixing agent without a pretreatment process, and the whiteness and fixability are not deteriorated.

In addition, the ionic-impact-preventing resin of the present invention has a weak acidity with a cationic resin used as an ink fixing agent and a buffering effect, and the fluorescent dye mixed composition prepared using the same has improved fluorescent performance and ink Since no deterioration of fixation performance occurs, it is very economical and environmentally friendly because no additional additive is needed to reinforce degraded performance.

In addition, when a sulfonic acid fluorescent dye and a cation resin are mixed with each other as in the prior art, the fluorescence performance and the ink fixation performance are lowered due to formation of the complex salt thereof. However, in order to solve this problem, By using the resin and the fluorescent dye composition, it is possible to perform sizing immediately by mixing the cationic resin and the fluorescent dye mixed composition contained in the resin for preventing the ion collision, without treating the fluorescent dye and the fixing agent in separate processes, And has an effect of exhibiting physical properties.

In addition, when the fluorescent dye mixed composition of the present invention is mixed with the cationic resin for fixing the ink used in the paper industry, it is not necessary to pay attention to the fine pH control, and it is possible to easily mix and stir the ink, At the same time, it can be satisfied.

In addition, since the fluorescent dye mixed composition of the resin for preventing collision of the present invention can be used as a single process without treating each separate process, the process can be simplified, which is very economical and the same as the product treated with a separate process Whiteness and fixing performance.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a comparative chart comparing the presence or absence of precipitation with the use of the fluorescent dye mixed composition of the present invention. FIG.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. The accompanying drawings are not drawn to scale and wherein like reference numerals in the various drawings refer to like elements.

The main feature of the present invention is to provide a mixed composition of a sulfonic acid fluorescent dye by polymerizing epichlorohydrin in a polyhydric alcohol in the presence of a catalyst and synthesizing a resin for preventing an ion collision by using a primary or secondary amine or ammonia water.

More specifically, polymerization of epichlorohydrin with boron trichloride ethane as a catalyst in a polyhydric alcohol mixture having 3 to 6 hydroxyl groups, a method of polymerizing an end-group chloride of a polymer alcohol chloride intermediate with a primary or secondary amine or ammonia To prepare a resin having a weak cationic property to prevent ion collision.

  The ionic-collision-resistant resin and the fluorescent dye-containing composition of the present invention are free from aggregation with the cationic resin for ink fixation unlike the prior art, and do not cause a high fluorescence performance and a deterioration in the performance of the cationic resin.

The sulfonic acid-based fluorescent dye used in the present invention must have at least two sulfonic acid bases, and the sulfonic acid groups are basified with Li, Na, K or the like to increase the solubility in water. Namely, for example, a sulfonic acid fluorescent dye usually has at least two sulfonic acid bases, preferably six sulfonic acid bases (-SO ₃ Na, SO ₃ K).

The fluorescent dye composition containing the ionic-collision-resistant resin of the present invention does not cause aggregation that occurs when a conventional sulfonic acid-based fluorescent dye and a cation resin are simply mixed, and does not cause deterioration in fixability and durability as well as in whiteness

In the present invention, the fluorescent dye of the fluorescent dye mixed composition contained in the resin for preventing ion collision can be represented by the following formula (3).

(3)

(In the above formula (3)

X is independently of each other Na +, K +, H, and n is an integer of 0 to 2.

NR represents a primary or secondary C ₁ -C ₄ alcohol amine, alkylamine, and also includes morpholine. NR is a primary or secondary C2 to C4 iminoalkyl monoacetate or diacetate.)

Specific examples of the fluorescent dye according to one embodiment of the present invention include CI Optical Brightener (Fluorescent brightener) 220, 264, 353, and 357.

[Example 1] Synthesis of resin for preventing ion collision

150 g of water and 1.2 mol of polyol are put into a four-necked flask, and when the temperature of the dissolution reaction becomes 65 ° C., the catalyst boron-trifluoride etherate is fed so as to flow down through the barrier wall.

The reaction solution is heated to 80 ° C. and 3.6 mol of epichlorohydrine is slowly added thereto for 90 minutes (while maintaining the temperature). When the addition is completed, the mixture is stirred at 80 ° C. for 60 minutes. Cool the reaction mixture to 55-60 ° C, add 0.8mol of ammonia slowly, raise the temperature to 90 ° C, and keep stirring for 60 minutes. (The color of the reaction solution changes from transparent to slightly turbid. The reaction solution was maintained at 60 to 65 ° C for 6 hours with stirring, and the reaction was completed to synthesize an ionic-impact-preventing resin 1 having a molecular weight of 4,107 and a cation density of 0.3125 meq / g and a viscosity of 97 cps.

[Example 2] Synthesis of resin for preventing ion collision

After reacting in the same manner as in Example 1, 1.0 mol of ammonia was added to obtain an ionic-impact-preventing resin 2 having a molecular weight of 7,764 and a cation density of 0.6875 meq / g and a viscosity of 124 cps.

(See Table 1)

[Example 3] Synthesis of resin for preventing ion collision

After reacting in the same manner as in Example 1, 2.0 mol of monoethanolamine was added thereto to obtain an ionic-impact-preventing resin 3 having a molecular weight of 2,628 and a density of 0.375 meq / g and viscosity of 159 cps.

(See Table 1)

[Example 4] Synthesis of resin for preventing ion collision

After reacting in the same manner as in Example 1, 1.2 mol of diethylamine was added thereto to obtain an ionic-impact-preventing resin 4 having a molecular weight of 3,405 and a cation density of 0.125 meq / g and a viscosity of 50 cps.

(See Table 1)

[Example 5] Synthesis of resin for preventing ion collision

After reacting in the same manner as in Example 1, 2.0 mol of diethanolamine was added thereto to obtain an ionic-impact-preventing resin 5 having a molecular weight of 2,723 and a density of 0.1875 meq / g and a viscosity of 130 cps.

(See Table 1)

[Example 6] Synthesis of resin for preventing ion collision

After reacting as in Example 1, 1.5 mol of monoisopropylamine was added thereto to obtain an ionic-impact-preventing resin 6 having a molecular weight of 2,970 and a density of 0.25 meq / g of viscosity of 143 cps. (See Table 1)

[Example 7] Synthesis of resin for preventing ion collision

After reacting as in Example 1, 1.5 mol of monoisopropanolamine was added thereto to obtain an ionic-impact-preventing resin 7 having a molecular weight of 3,212 and a density of 0.187 meq / g and a viscosity of 135 cps. (See Table 1)

[Example 8] Synthesis of resin for preventing ion collision

After reacting in the same manner as in Example 1, 1.5 mol of diisopropanolamine was added thereto to obtain an ionic-impact-preventing resin 6 having a molecular weight of 2,429 and a density of 0.125 meq / g and a viscosity of 90 cps. (See Table 1)

Changes in Amine Types and Physical Properties No 물질 Balance Molecular Weight ⁽¹⁾ Cationic density (meq / g) ⁽²⁾ Viscosity (cps) ⁽³⁾ Glycerine (mol) Sorbitol (mol) Epichlorohydrin (mol) Amine (mol) One 0.6 0.6 3.6 Ammonia 0.8 4,107 0.3125 97 2 0.6 0.6 3.6 Ammonia 2.0 7,764 0.6875 124 3 0.6 0.6 3.6 MEA (OH) 2.0 2,628 0.375 159 4 0.6 0.6 3.6 DEA 1.2 3,405 0.125 50 5 0.6 0.6 3.6 DEA (OH) 2.0 2,723 0.1875 130 6 0.6 0.6 3.6 MIPA 1.5 2,970 0.25 143 7 0.6 0.6 3.6 MIPA (OH) 1.5 3,212 0.187 135 8 0.6 0.6 3.6 DIPA (OH) 1.5 2,429 0.125 90

⁽¹⁾ Molecular Weight: GPC condition

    Mobile phase: 0.1 mol NaNO3, Flow rate: 1.0 ml / min, Detector: RID

    Column: TSK-Gel 300 mm * 2, Injection sample: 10% Solution 25 μl,

⁽²⁾ Cation density (meq / g):

⁽³⁾ Viscosity (cps): Measured with a Brookfield viscometer at 25 ° C (Spindle No. 62 60 rpm)

Fluorescent dye synthesis

1) Primary synthesis

300 ml of water, a small amount of dispersant and 12 g of calcium carbonate are put into a four-necked flask, and 40 g of cyanuric chloride is added while maintaining the temperature below 5 ° C. After dissolving in 52 g of aniline-2,5-disulfonic acid and 11 g of Soda ash, the mixture was maintained at 6 to 8 ° C for 3 hours while maintaining stirring for 1 hour. The reaction end point was analyzed by HPLC.

2) Secondary synthesis

After the first reaction was completed, the temperature of the reaction mixture was raised to 20 ° C. 37 g of diaminostilbene was dissolved in 11 g of Soda ash, and the mixture was dropped for 2 hours. The reaction was heated to 60 ° C to complete the second synthesis. The reaction end point is analyzed by HPLC.

3) tertiary synthesis

40 g of Disopropanol-amine is added to the reaction product after completion of the second reaction, and the temperature is raised to 100 ° C. and the mixture is stirred for 4 hours to complete the reaction, and the impurities are filtered.

The mixture was cooled to room temperature, treated with R / O and concentrated by heating to obtain 460 g of a product having an E1 Value of 100.

The fluorescent dyes used in the paper industry were synthesized by changing the reactors of R1 and R2 in the same manner as described above and recorded in Table 2.

이다.The formula of the fluorescent dye is

to be.

Changes in functional groups of fluorescent dyes and maximum absorption λ _max change Sample - (SO ₃ Na) _n R Main pick (λ _max ) A-01 -Aniline-4-SO ₃ Na -NH (CH ₂ CH ₂ OH) ₂ 350 A-02 -Aniline-4-SO ₃ Na _{-NH (CH 2 CH (OH)} CH3) 2 349 B-01 -Anyline-2,5-SO ₃ Na -NH (CH ₂ CH ₂ OH) ₂ 350 B-02 -Anyline-2,5-SO ₃ Na -NH (CH ₂ CH (OH) CH ₃ ) ₂ 341

Fluorescent dye composition manufacturing

The amount of the cationic resin and the degree of shocking (dye precipitation) were confirmed by preparing a composition for preventing collision of the ion produced by the above-described example with a fluorescent dye of each kind. The fluorescent dye B-02 thus synthesized was polymerized in Example 1 Confirmation of precipitation stability of the resin and the mixed composition in the cation resin was attached to the results in Table 3 below.

Preparation of mixed composition: 65 g of the resin for preventing ion collision according to the above Table 1 was added to 35 g of a fluorescent dye (B-6, E1 = 100)

                Were mixed and stirred to prepare 100 g of a fluorescent dye mixed composition.

Cationic resin: D-emulsion: DH-FR (pH = 1.9)

Test method: Fluorescent dye mixed composition 10 ml + DH-FR 10 ml Mix for 10 minutes

Results: Though precipitation occurred by shocking when treated with fluorescent dye alone, precipitation did not occur in the mixed composition (see FIG. 1)

Stability of resin and fluorescent dye composition for preventing ion collision against cationic resin Example of resin for preventing ion collision Amount of fluorescent dye composition used (ml) ⁽¹⁾ Fluorescent dye usage (ml) ⁽²⁾ Cationic resin DH-FR
Usage (ml) stability
(Presence or absence of precipitation) B-2 - 10 10 White precipitation occurs Example 1 10 - 10 No sedimentation Example 2 10 - 10 No sedimentation Example 3 10 - 10 No sedimentation Example 4 10 - 10 No sedimentation Example 5 10 - 10 No sedimentation Example 6 10 - 10 No sedimentation Example 7 10 - 10 No sedimentation Example 8 10 - 10 No sedimentation Example 9 10 - 10 No sedimentation Example 10 10 - 10 No sedimentation

^{(1) In the} example, 65 g of the polymer for preventing collision of ion and 35 g of fluorescent dye B-6 (E1 = 100) were mixed to prepare a fluorescent dye mixed composition (concentration E1 = 35)

⁽²⁾ Fluorescent dye concentration E1 = 35

As shown in Table 3, the fluorescent dye alone can not be used due to precipitation when mixed with the cation resin, but when mixed with a resin for preventing collision with a fluorescent dye, precipitation due to shocking does not occur even when used in combination with a cation resin Is a fluorescent dye composition suitable for a cationic resin used for high speed printing or high image printing paper.

[Comparative Example 1] Sizing test and whiteness measurement

Manufacture of 10% starch solution

Using oxidized starch (subject DS-55), 10% starch aqueous solution is cooked at 95 ° C.

Fluorescent dye whiteness test without resin for preventing ion collision

Sizing was performed by adding 2.5 g / L (0.01 g), 5 g / L (0.02 g) and 10 g / L (0.4 g) of fluorescent dyes (B-2) to 20 g of a 10% starch solution in a beaker, Sizing whiteness of the resin-free fluorescent dye was measured.

Sizing and whiteness measurement of a fluorescent dye composition containing a resin for preventing ion collision

4% (0.8 g) of a cationic resin (DH-FR) and 2, 4, and 5 resins for preventing ion collision were selected to prepare fluorescent light dye compositions containing fluorescent dyes (B-02) g / L, 5 g / L, and 10 g / L, and then attached to Table 4 below.

Sizing whiteness measurement result Cationic resin
(DH-FR) Whiteness (CIE-Whiteness) 2.5 g / L 5.0 g / L 10.0 g / L B-2 - 140.6 141.21 143.26 B-2 + Example 2 0.4% 140.28 141.58 143.08 B-2 + Example 3 0.4% 140.56 142.35 146.14 B-2 + Example 4 0.4% 140.87 142.01 146.85 B-2 + Example 5 0.4% 140.65 142.43 146.62

As can be seen from the results of Table 4, all the results except for Example 2 show that whiteness is greatly improved.

Therefore, it can be seen that the mixed composition of the resin for preventing ion collision and the fluorescent dye of the present invention is excellent not only in the cationic resin for high-speed printing but also in the whiteness.

[Comparative Example 2] Application of resin for preventing ion collision (synergy effect of sunlight degree)

Fluorescent Brightener CI No 86 Fluorescent dye 0.5% was dyed at 80 ° C for 40 minutes and then dried at 140 ° C for 120 seconds to measure CIE-Whiteness.

CIE-Whiteness was measured after a 6-hour light-fastness tester after treatment with glyoxal resin and resin for preventing ion collision. As a result, the fastening effect was improved about 2.5 ~ 2.7 points than the untreated product,

Light fastness effect of resin for prevention of ion collision Early UV exposure
After 6 hours Difference C.I.No.86 0.5% 133.23 123.74 9.49 C.I No. 86 0.5% + Glyoxal resin 30 g / L 132.55 124.05 8.50 CI No. 86 0.5% + Example 2 30 g / L 134.43 127.12 7.31 CI No. 86 0.5% + Example 3 30 g / L 134.26 127.35 6.91 C.I.No.86 0.5% + Example 4 30 g / L 134.48 127.10 7.38 CI No. 86 0.5% + Example 5 30 g / L 134.55 127.76 6.79

As described above, the structure and action of the ionic-impact-preventing resin according to the present invention are described in the above description and drawings, but the present invention is not limited to the above description and drawings, It will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit of the invention.

Claims (9)

As a method for producing an ion collision-resistant resin,
150 g of purified water and 1.2 mol of polyhydric alcohol were charged into a flask, and the mixture was heated to 65 캜. Then, 0.5 to 3.5 mol of boron trichloride ethane was added as a catalyst to prepare a first solution so as to flow through the flask wall.
Maintaining and maintaining the primary solution at 80 DEG C and adding 3.6 mol of epichlorohydrine uniformly dropwise for 90 minutes to prepare a secondary solution and maintaining stirring for 60 minutes;
Cooling the secondary solution to 55 to 60 ° C and adding 0.8 to 2.0 mols of any one selected from the group consisting of primary amine and ammonia to prepare a tertiary solution;
Stirring the mixture for 60 minutes, cooling and maintaining the third solution at 60 to 65 ° C, and stirring for 6 hours to obtain a polymerized product; Wherein the ionic-impact-preventing resin is an ion-exchange resin. The method according to claim 1,
The polyhydric alcohol may be,
The

Lt; / RTI >
n is an alkylene group and is an integer of 2 to 6, and the molecular weight is 92 or less. The method according to claim 1,
The primary, secondary,
Examples of the amines include methylamine, ethylamine, propylamine, isopropylamine, methanolamine, ethanolamine, propanolamine, isopropylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, dimethanolamine, diethanolamine, Dipropanolamine, dipropanolamine, diisopropanolamine, ammonia water, and the like. The method according to claim 1,
The polymer,
The

Lt; / RTI >
R ₁ is an alkylene group of C ₁ , R ₂ is H, x is an integer of 2 to 5, R ₃ and R ₅ are C ₂ alkylene groups, R ₄ and R ₆ are C ₁ alkylene groups, n is the number of polyhydric alcohols-x, 1 to 4, m is a number equal to n or n-1, and Z ₁ and Z ₂ are halogen atoms, ammonium, primary to quaternary alkylamines, alkyl groups C ₁ to C ₃ Wherein the hydroxyalkylamine is selected from the group consisting of hydroxyalkylamines and hydroxyalkylamines. 5. The method of claim 4,
The polymer,
Wherein the polymer has a molecular weight (MW) of 2,000 to 10,000 and a cation density (meq / g) of 0.1 to 0.5. A fluorescent dye mixed composition prepared by mixing 60 to 70% by weight of the polymeric material according to any one of claims 1 to 4 with 30 to 40% by weight of a fluorescent dye. 7. A method for producing a fluorescent dye mixed composition according to claim 6,
300 ml of purified water, 1 to 5 g of dispersant and 12 g of calcium carbonate were added to the flask, and 40 g of Cynuric chloride was added to maintain the temperature of 0 to 5 ° C by external cooling to prepare a primary dye solution.
52 g of Aniline-2,5-Disulfonic acid and 11 g of Soda ash were added to the primary dye solution, and the resultant was dropped for 3 hours at 6 to 8 ° C. The reaction product was stirred and maintained for 1 hour to obtain a secondary dye solution Producing;
After the temperature of the secondary dye solution was raised to 20 ° C, 40 g of Disopropanol-amine was added, and the mixture was heated to 100 ° C and stirred for 4 hours to prepare a tertiary dye solution.
Filtering the third dye solution to remove impurities and then heating to obtain a dye product;
35 g of the dye product,

Wherein R ₁ is an alkylene group of C ₁ , R ₂ is H, x is an integer of 2 to 5, R ₃ and R ₅ are C ₂ alkylene groups, R ₄ and R ₆ are C ₁ alkyl N is a number of polyvalent alcohol-x, 1 to 4, m is a number equal to n or n-1, Z ₁ and Z ₂ are a halogen element, ammonium, primary to quaternary alkylamine, alkyl group C ₁ To 65 g of a polymer selected from two selected from the group consisting of hydroxyalkylamines containing C ₃ to C ₃ . 8. The method of claim 7,
The dye product,
The

, Wherein X is independently selected from Na +, K +, H, n is an integer of 0 to 2, and NR is any one selected from iminoalkyl monoacetate and iminoalkyldiacetate of a primary to secondary grade By weight based on the total weight of the composition. 9. The method of claim 8,
The dye product,
(6) a sulfonic acid group (-SO ₃ X).

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