CN100415838C - Resin-free neutral blue ink and its prepn process - Google Patents

Abstract

The present invention relates to blue resin-free neutral ink of which the raw materials have the components by the following weight proportion: 15: 38 to 14 portions of phthalocyanine blue pigment, 0.5 to 1 portion of dispersant, 0.15 to 0.5 portion of wetting agents, 1 to 6 portions of polyvinylpyrrolidone, 0.5 to 2 portions of oleic acid, 20 to 35 portions of water soluble lower carbon alcohol, 0.05 to 0.50 portion of benzotriazole, 1 to 3 portions of triethanolamine, 0.1 to 0.5 portion of preservative, 0.5 to 2 portions of thickening agents and 55 to 65 portions of deionized water. The present invention has the advantages of homogeneous pigment dispersion, stable system and appropriate viscous flow without changing with time, the writing of neutral ink pens made from the black neutral ink is gliding, and the preservation period is long.

Description

Blue Neutral writing ink of no resin and preparation method thereof

Technical field

The invention belongs to a kind of Neutral writing ink, relate in particular to a kind of blue Neutral writing ink that is suitable for ballpoint pen and preparation method thereof.

Technical background

Neutral writing ink pen (gel ink pen) is the novel kind in the ballpoint pen series products, compare with traditional oiliness ballpoint pen, though the appearance time is also not long, because of a Neutral writing ink fluent writing, it is spry and light comfortable to write feel, writing is clear, the color and luster sense is good, and handwriting is water-fast, sun-proof, characteristics such as long preservative period, so accepted by the human consumer rapidly, and obtain widely-used.China produces first big country for the Neutral writing ink pen, but produces the almost whole dependence on import of the used ink of Neutral writing ink pen so far, mainly comes from Japan, Korea S, the U.S. and Germany.

The suspension of Neutral writing ink series pigments particulate, because solid pigment density is obviously greater than fluid density, so in fact Neutral writing ink belongs to Unstable Systems, the present external product quality guaranteed period only is about 1 year.In order to improve the stability of Neutral writing ink, all be added with the aqueous polymer resin in the existing prescription, as polyacrylic acid water-base resin (United States Patent (USP) technology, application number 09/947,191, US2OO2/OO717O9A1, be added with the acrylic resin of the molecular weight ranges 5000-10000 of 2wt% in the prescription), increased the shelf-time of ink to a certain extent, but since the fluoropolymer resin introduced itself or be easy to generate polymerization and crosslinked with organic solvent that system exists, the molecular resin amount is constantly increase with the increase of preservation period, cause ink viscosity to improve, mobile variation, thus cause gel ink pen postpone of a specified duration to go out Mo Buchang, even can't normally write.

Summary of the invention

Purpose of the present invention is exactly in order to overcome the above problems, and a kind of long preservative period is provided, and ink viscosity is stable, blue Neutral writing ink of no resin of good fluidity and preparation method thereof.

The blue Neutral writing ink of no resin of the present invention, its parts by weight of raw materials consists of: pigment phthalocyanine blue 15:3 (molecular formula is as follows) 8-14 part, dispersion agent 0.5-1 part, wetting agent 0.15-0.5 part, polyvinylpyrrolidone 1-6 part, oleic acid (molecular formula C ₁₈H ₃₄O ₂) 0.5-2 part, water-soluble low-carbon alcohol 20-35 part, 1,2,3-benzotriazole (molecular formula C ₆H ₅N ₃) 0.05-0.50 part, trolamine (molecular formula N[CH ₂CH ₂OH] ₃) 1-3 part, sanitas 0.1-0.5 part, thickening material 0.5-2 part, deionized water 55-65 part.

Phthalocyanine blue 15:3 molecular formula:

Aforesaid dispersion agent is AEC ₉-H aqueous dispersant (Chinese detergents and cosmetic research institute), SN-DISPERSANT 5040 water-based systems are with in the dispersion agents (Japan-Sheng Nuo Proclarity Corp.) one or both.

Aforesaid wetting agent is a kind of in the universal wetting agent of Dispersant PE-100 (Shenzhen Haichuan Chemical Technology Co., Ltd), SN-WET 992 wetting agents (Japan-Sheng Nuo Proclarity Corp.).

Aforesaid water-soluble low-carbon alcohol is polyoxyethylene glycol (molecular formula HO[CH ₂CH ₂O] nH) and propylene glycol (molecular formula C ₃H ₈O ₂), glycerine (molecular formula C ₃H ₈O ₃) or Diethylene Glycol (molecular formula C ₄H ₁₀O ₃) in a kind of by weight than for 1-1.5: 1 mixes and forms.

Aforesaid polyoxyethylene glycol is that molecular-weight average is that 200 Macrogol 200, molecular-weight average are that 400 poly(oxyethylene glycol) 400, molecular-weight average are one or more of 600 Polyethylene Glycol-600.

Aforesaid polyvinylpyrrolidone (molecular formula [C ₆H ₉NO] n) be PVP-K15 (relative molecular weight 8 * 10 ³), PVP-K3O (relative molecular weight 4 * 10 ⁴) in one or both.

Aforesaid sanitas is SN-CIDE 135 (Japan-Sheng Nuo Puli company limited) or SN-CIDE215 (Japan-Sheng Nuo Proclarity Corp.).

Aforesaid thickening material is one or more in the HISOLD 206 association type acrylate thickening materials (this Co., Ltd. of Korea S-rood), HISOLD 105 association type acrylate thickening materials (this Co., Ltd. of Korea S-rood), RHEOLATE 430 (U.S.'s hamming this).

Preparation method of the present invention comprises the steps:

(1) at first 1-6 part polyvinylpyrrolidone is dissolved in the deionized water of equivalent, heats and stirred 0.5-1 hour, obtain polyvinylpyrrolidonesolution solution at 60 ℃-80 ℃;

(2) by trolamine and deionized water by weight than 1: 1-1.5 is mixed with the pH regulator agent;

(3) thickening material, deionized water and trolamine are by weight than 1: 8-18: 1 mix after, stir that it is swelling to is transparent fully, obtain the neutral thickening material;

(4) a kind of by weight than 1-1.5 with in polyoxyethylene glycol and glycerine, Diethylene Glycol or the propylene glycol: 1 is mixed with water-soluble low-carbon alcohol;

(5) polyvinylpyrrolidonesolution solution that makes according to dispersion agent 0.5-1.0 part, wetting agent 0.15-0.5 part, the first step, oleic acid 0.5-2 part, the 4th go on foot the water-soluble low-carbon alcohol, 1 that makes, 2,3-benzotriazole 0.05-0.5 part, deionized water 15-20 part mixed solution add the kneading of phthalocyanine blue 8-14 part after stirring and forming even soup compound;

(6) soup compound after the kneading places high-shear emulsion machine to shear 20-30 minute, and rotating speed is controlled at 1500-4000 rev/min of scope;

(7) material after the high-shear was placed the sand mill continuously grinding 20-30 minute;

(8) adding neutral thickening material, deionized water 20-30 part that pH regulator agent, sanitas 0.1-0.5 part, the 3rd step that second step made make behind the sand milling stirs and formed the mobile hemicolloid in 20-30 minute and get final product;

(9) filtration, vacuum outgas promptly get the Neutral writing ink finished product.

The no resin Neutral writing ink advantage of the present invention's preparation is: rationally cooperate by polyvinylpyrrolidone and water-soluble low-carbon alcohol to replace the employed acrylic acid or the like water-base resin of traditional neutral ink, colo(u)rant dispersion is even, system is stable, the viscosity flow state is suitable and do not change in time, makes a Neutral writing ink fluent writing, long quality-guarantee period.

Embodiment

Embodiment 1

(1) at first 1 part of PVP-K3O is dissolved in the deionized water of equivalent, heats and stirred 0.5 hour, obtain PVP-K30 solution at 60 ℃; (2) be mixed with the pH regulator agent by 1 part of trolamine and 1 part of deionized water; (3) 16 parts of deionized water dilutions of 2 parts of thickening material HISOLD, 206 usefulness back is added 2 parts of trolamines, it is transparent fully that stirring is swelling to it, obtains neutral HI SOLD 206; (4) get 10 parts of Macrogol 200s, 10 parts of mixed with propylene glycol, make water-soluble low-carbon alcohol; (5) according to 0.5 part of dispersant A EC ₉The water-soluble low-carbon alcohol that the PVP-K30 solution that-H, 0.15 part of wetting agent PE-100, the first step make, 0.5 part of oleic acid, the 4th step make, 0.05 part 1,2,3-benzotriazole, 20 parts of deionized waters are mixed with mixed solution, mediate adding 8 parts of phthalocyanine blues behind its formation soup compound that stirs; (6) soup compound after the kneading places high-shear emulsion machine to shear 20 minutes, and rotating speed is controlled at 1500 rev/mins of scopes; (7) material after the high-shear was placed the sand mill continuously grinding 20 minutes: add 206,27 parts of deionized water and stirring of neutral HISOLD that pH regulator agent that second step made, 0.1 part of SN-CIDE135, the 3rd step make behind (8) sand milling and formed the mobile hemicolloid in 20 minutes and get final product; (9) filtration, vacuum outgas promptly get the Neutral writing ink finished product.Product performance index sees Table 1.

Embodiment 2

(1) at first respectively 2 parts of PVP-K30,1 part of PVP-K15 are dissolved in the deionized water of equivalent, heat and stirred 1 hour, obtain PVP-K30 solution and PVP-K15 solution at 80 ℃; (2) be mixed with the pH regulator agent by 1 part of trolamine and 1 part of deionized water; (3) 4 parts of deionized water dilutions of 0.5 part of thickening material HI SOLD 206 usefulness back is added 0.5 part of trolamine, to add 0.5 part of trolamine after 9 parts of deionized water dilutions of 0.5 part of thickening material HISOLD, 105 usefulness again, it is transparent fully that stirring is swelling to it, obtains neutral HISOLD 206 and neutral HISOLD 105; (4) get 15 parts of polyoxyethylene glycol, 15 parts of mixed with propylene glycol, make water-soluble low-carbon alcohol; (5) according to 1 part of dispersant A EC ₉The water-soluble low-carbon alcohol that the PVP-K30 solution that-H, 0.5 part of wetting agent PE-100, the first step make, PVP-K15 solution, 2 parts of oleic acid, the 4th steps make, 0.5 part 1,2,3-benzotriazole, 15 parts of deionized waters are mixed with mixed solution, mediate adding 14 parts of phthalocyanine blues behind its formation soup compound that stirs; (6) soup compound after the kneading places high-shear emulsion machine to shear 30 minutes, and rotating speed is controlled at 4000 rev/mins of scopes; (7) material after the high-shear was placed the sand mill continuously grinding 30 minutes; (8) adding neutral HISOLD 206 that pH regulator agent that second step made, 0.5 part of SN-CIDE135, the 3rd step make and 105,20 parts of deionized water and stirring of neutral HISOLD behind the sand milling formed the mobile hemicolloid in 30 minutes and gets final product; (9) filtration, vacuum outgas promptly get the Neutral writing ink finished product.Product performance index sees Table 1.

Embodiment 3

(1) at first 6 parts of PVP-K30 is dissolved in the deionized water of equivalent, heats and stirred 0.5 hour, obtain PVP-K30 solution at 70 ℃; (2) be mixed with the pH regulator agent by 1 part of trolamine and 1 part of deionized water; (3) 4 parts of deionized water dilutions of 0.5 part of thickening material HISOLD, 206 usefulness back is added 0.5 part of trolamine, it is transparent fully that stirring is swelling to it, obtains neutral HI SOLD 206; (4) get 10 parts of Macrogol 200s, 5 parts of poly(oxyethylene glycol) 400,10 parts of glycerine and be mixed with water-soluble low-carbon alcohol; (5) according to 0.8 part of dispersant A EC ₉The water-soluble low-carbon alcohol that the PVP-K30 solution that-H, 0.3 part of wetting agent PE-100, the first step make, 1 part of oleic acid, the 4th step make, 1 part 1,2,3-benzotriazole, 15 parts of deionized waters are mixed with mixed solution, mediate adding 10 parts of phthalocyanine blues behind its formation soup compound that stirs; (6) soup compound after the kneading places high-shear emulsion machine to shear 25 minutes, and rotating speed is controlled at 2000 rev/mins of scopes; (7) material after the high-shear was placed the sand mill continuously grinding 25 minutes; (8) adding 206,30 parts of deionized water and stirring of neutral HISOLD that pH regulator agent that second step made, 0.3 part of SN-CIDE135, the 3rd step make behind the sand milling formed the mobile hemicolloid in 25 minutes and gets final product; (9) filtration, vacuum outgas promptly get the Neutral writing ink finished product.Product performance index sees Table 1.

Embodiment 4

(1) at first respectively 4 parts of PVP-K30,1 part of PVP-K15 are dissolved in the deionized water of equivalent, heat and stirred 50 minutes, obtain PVP-K30 solution and PVP-15 solution at 70 ℃; (2) be mixed with the pH regulator agent by 1 part of trolamine and 1 part of deionized water; (3) 4 parts of deionized water dilutions of 0.5 part of thickening material RHEOLATE, 430 usefulness back is added 0.5 part of trolamine, it is transparent fully that stirring is swelling to it, obtains neutral RHEOLATE 430; (4) get 15 parts of Macrogol 200s, 15 parts of glycerine are mixed with water-soluble low-carbon alcohol; (5) the water-soluble low-carbon alcohol that makes of the PVP-K30 solution that makes according to 0.5 part of dispersion agent SN-DISPERSANT5040,992, (1) step of 0.2 part of wetting agent SN-WET, PVP-K15 solution, 2 parts of oleic acid, the 4th steps, 0.4 part 1,2,3-benzotriazole, 20 parts of deionized waters are mixed with mixed solution, will add 12 parts of kneadings of phthalocyanine blue behind its formation soup compound that stirs; (6) soup compound after the kneading places high-shear emulsion machine to shear 20 minutes, and rotating speed is controlled at 3000 rev/mins of scopes; (7) material after the high-shear was placed the sand mill continuously grinding 20 minutes; (8) adding 430,30 parts of deionized water and stirring of neutral RHEOLATE that pH regulator agent that second step made, 0.2 part of SN-CI DE135, the 3rd step make behind the sand milling formed the mobile hemicolloid in 30 minutes and gets final product; (9) filtration, vacuum outgas promptly get the Neutral writing ink finished product.Product performance index sees Table 1.

Embodiment 5

(1) at first respectively 4 parts of PVP-K30,1 part of PVP-K15 are dissolved in the deionized water of equivalent, heat and stirred 45 minutes, obtain PVP-K30 solution and PVP-K15 solution at 65 ℃; (2) be mixed with the pH regulator agent by 1 part of trolamine and 1 part of deionized water; (3) with thickening material RHEOLATE 430 and HISOLD 206 each 0.5 part add 0.5 part of trolamine again with 4 parts of deionized waters dilutions respectively, it is transparent fully that stirring is swelling to it, obtains neutral RHEOLATE 430 and HISOLD206; (4) get 10 parts of poly(oxyethylene glycol) 400,5 parts of Polyethylene Glycol-600s, 10 parts of Diethylene Glycols and be mixed with water-soluble low-carbon alcohol; (5) the water-soluble low-carbon alcohol that makes of the PVP-K30 solution that makes according to 0.5 part of dispersion agent SN-DISPERSANT 5040,0.5 part of wetting agent SN-WET 992, the first step, PVP-K15 solution, 2 parts of oleic acid, the 4th steps, 0.1 part 1,2,3-benzotriazole, 20 parts of deionized waters are mixed with mixed solution, mediate adding 10 parts of phthalocyanine blues behind its formation soup compound that stirs; (6) soup compound after the kneading places high-shear emulsion machine to shear 20 minutes, and rotating speed is controlled at 3000 rev/mins of scopes; (7) material after the high-shear was placed the sand mill continuously grinding 20 minutes; (8) adding neutral RHEOLATE 430 and HISOLD206,30 parts of deionized water and stirring that pH regulator agent that second step made, 0.2 part of SN-CIDE215, the 3rd step make behind the sand milling formed the mobile hemicolloid in 20 minutes and gets final product; (9) filtration, vacuum outgas promptly get the Neutral writing ink finished product.Product performance index sees Table 1.

Embodiment 6

(1) at first 5 parts of PVP-K30 is dissolved in the deionized water of equivalent, heats and stirred 50 minutes, obtain PVP-K30 solution at 80 ℃; (2) be mixed with the pH regulator agent by 1 part of trolamine and 1 part of deionization; (3) 0.5 part of thickening material HISOLD206 is added 0.5 part of trolamine with 4 parts of deionized water dilution backs, it is transparent fully that stirring is swelling to it, obtains neutral HISOLD 206; (4) get 20 parts of poly(oxyethylene glycol) 400,15 parts of Diethylene Glycols are mixed with water-soluble low-carbon alcohol; (5) the water-soluble low-carbon alcohol that makes of the PVP-K30 solution that makes according to 0.5 part of dispersant A EC9-H, 0.5 part of SN-DISPERSANT 5040,0.15 part of wetting agent PE-100, the first step, 1 part of oleic acid, the 4th step, 1 part 1,2,3-benzotriazole, 15 parts of deionized waters are mixed with mixed solution, mediate adding 8 parts of phthalocyanine blues behind its formation soup compound that stirs; (6) soup compound after the kneading places high-shear emulsion machine to shear 25 minutes, and rotating speed is controlled at 2500 rev/mins of scopes; (7) material after the high-shear was placed the sand mill continuously grinding 20 minutes; (8) adding 206,30 parts of deionized water and stirring of neutral HISOLD that pH regulator agent that second step made, 0.3 part of SN-CIDE215, the 3rd step make behind the sand milling formed the mobile hemicolloid in 25 minutes and gets final product; (9) filtration, vacuum outgas promptly get the Neutral writing ink finished product.Product performance index sees Table 1.

Embodiment 7

(1) at first respectively 2 parts of PVP-K30,1 part of PVP-K15 are dissolved in the deionized water of equivalent, heat and stirred 1 hour, obtain PVP-K30 solution and PVP-KIS solution at 60 ℃; (2) be mixed with the pH regulator agent by 1.5 parts of trolamines and 1.5 parts of deionized waters; (3) with thickening material RH EOLATE 430 and HISOLD 206 each 0.5 part dilute with 4 parts of deionized waters respectively and add 0.5 part of trolamine again, again 7 parts of deionized water dilutions of 0.5 part of thickening material HISOLD, 105 usefulness back is added 0.5 part of trolamine, it is transparent fully that stirring is swelling to it, obtains neutral HISOLD 206, RHEOLATE 430 and H1SOLD 105; (4) get 15 parts of Macrogol 200s, 15 parts of propylene glycol are mixed with water-soluble low-carbon alcohol; (5) the water-soluble low-carbon alcohol that makes of the PVP-K30 solution that makes according to 0.5 part of dispersant A EC9-H, 0.15 part of wetting agent PE-100, the first step, PVP-K15 solution, 1 part of oleic acid, the 4th step, 0.5 part 1,2,3-benzotriazole, 15 parts of deionized waters are mixed with mixed solution, mediate adding 12 parts of phthalocyanine blues behind its formation soup compound that stirs; (6) soup compound after the kneading places high-shear emulsion machine to shear 30 minutes, and rotating speed is controlled at 4000 rev/mins of scopes; (7) material after the high-shear was placed the sand mill continuously grinding 30 minutes; (8) the pH regulator agent that second step of adding makes behind the sand milling, 0.5 part of SN-CIDE the 215, the 3rd go on foot neutral HISOLD 206, the HISOLD 105 and 430,23 parts of deionized water and stirring of RHEOLATE formation in the 20 minutes mobile hemicolloid that make and get final product; (9) filtration, vacuum outgas promptly get the Neutral writing ink finished product.Product performance index sees Table 1.

Table-1 product performance index

Place placement in 1 year half 2 years during finished product

Example

The viscosity pH value is write situation viscosity pH value and is write situation viscosity pH value and write situation

Embodiment 1 23 8.2 good 23 8.0 good 23 82 is good

Embodiment 2 38 81 good 38 7.9 good 39 8.1 is good

Embodiment 3 28 8.0 good 28 7.8 good 28 80 is good

Embodiment 4 26 8.0 good 27 7.8 good 27 80 is good

Embodiment 5 40 81 good 42 7.9 good 42 8.1 is good

Embodiment 6 30 80 good 30 7.8 good 32 8.0 is good

Embodiment 7 48 82 good 50 8.0 good 50 8.2 is good

Claims (10)

1. blue Neutral writing ink of no resin is characterized in that parts by weight of raw materials consists of:

Pigment phthalocyanine blue 15:3 8-14 part, dispersion agent 0.5-1 part, wetting agent 0.15-0.5 part, polyvinylpyrrolidone 1-6 part, oleic acid 0.5-2 part, water-soluble low-carbon alcohol 20-35 part, 1,2,3-benzotriazole 0.05-0.50 part, trolamine 1-3 part, sanitas 0.1-0.5 part, thickening material 0.5-2 part, deionized water 55-65 part.

2. the blue Neutral writing ink of a kind of no resin as claimed in claim 1 is characterized in that the molecular formula of described phthalocyanine blue 15:3 is:

3. the blue Neutral writing ink of a kind of no resin as claimed in claim 1 is characterized in that described dispersion agent is AEC ₉One or both in the dispersion agent of-H aqueous dispersant, SN-DISPERSANT 5040 water-based systems.

4. the blue Neutral writing ink of a kind of no resin as claimed in claim 1 is characterized in that described wetting agent is a kind of in the universal wetting agent of DisPersant PE-100, SN-WET 992 wetting agents.

5. the blue Neutral writing ink of a kind of no resin as claimed in claim 1 is characterized in that described water-soluble low-carbon alcohol is a kind of by weight than being 1-1.5 in polyoxyethylene glycol and propylene glycol, glycerine or the Diethylene Glycol: 1 mixes and forms.

6. the blue Neutral writing ink of a kind of no resin as claimed in claim 5 is characterized in that described polyoxyethylene glycol is that molecular-weight average is that 200 Macrogol 200, molecular-weight average are that 400 poly(oxyethylene glycol) 400, molecular-weight average are one or more of 600 Polyethylene Glycol-600.

7. the blue Neutral writing ink of a kind of no resin as claimed in claim 1 is characterized in that described polyvinylpyrrolidone is one or both among PVP-K15, the PVP-K30.

8. the blue Neutral writing ink of a kind of no resin as claimed in claim 1 is characterized in that described sanitas is SN-CIDE135 or SN-CIDEZ15.

9. the blue Neutral writing ink of a kind of no resin as claimed in claim 1 is characterized in that described thickening material is one or more among HISOLD 206 association type acrylate thickening materials, HISOLD 105 association type acrylate thickening materials, the RHEOLATE 430.

10. as each described a kind of preparation method who does not have the blue Neutral writing ink of resin of claim 1-9, it is characterized in that comprising the steps:

(1) at first 1-6 part polyvinylpyrrolidone is dissolved in the deionized water of equivalent, heats and stirred 0.5-1 hour, obtain polyvinylpyrrolidonesolution solution at 60 ℃-80 ℃;

(2) by trolamine and deionized water by weight than 1: 1-1.5 is mixed with the pH regulator agent;

(3) thickening material, deionized water and trolamine are by weight than 1: 8-18: 1 mix after, stir that it is swelling to is transparent fully, obtain the neutral thickening material;

(4) a kind of by weight than 1-1.5 with in polyoxyethylene glycol and glycerine, Diethylene Glycol or the propylene glycol: 1 is mixed with water-soluble low-carbon alcohol;

(5) polyvinylpyrrolidonesolution solution that makes according to dispersion agent 0.5-1.0 part, wetting agent 0.15-0.5 part, the first step, oleic acid 0.5-2 part, the 4th go on foot the water-soluble low-carbon alcohol, 1 that makes, 2,3-benzotriazole 0.05-0.5 part, deionized water 15-20 part mixed solution add the kneading of phthalocyanine blue 8-14 part after stirring and forming even soup compound;

(6) soup compound after the kneading places high-shear emulsion machine to shear 20-30 minute, and rotating speed is controlled at 1500-4000 rev/min of scope;

(7) material after the high-shear was placed the sand mill continuously grinding 20-30 minute;

(8) adding neutral thickening material, deionized water 20-30 part that pH regulator agent, sanitas 0.1-0.5 part, the 3rd step that second step made make behind the sand milling stirs and formed the mobile hemicolloid in 20-30 minute and get final product;

(9) filtration, vacuum outgas promptly get the Neutral writing ink finished product.