CN109763352B - Dyeing liquid for nylon parts and surface coloring treatment method for nylon parts - Google Patents
Dyeing liquid for nylon parts and surface coloring treatment method for nylon parts Download PDFInfo
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- CN109763352B CN109763352B CN201910021700.1A CN201910021700A CN109763352B CN 109763352 B CN109763352 B CN 109763352B CN 201910021700 A CN201910021700 A CN 201910021700A CN 109763352 B CN109763352 B CN 109763352B
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- 239000004677 Nylon Substances 0.000 title claims abstract description 87
- 229920001778 nylon Polymers 0.000 title claims abstract description 87
- 238000004043 dyeing Methods 0.000 title claims abstract description 28
- 239000007788 liquid Substances 0.000 title claims abstract description 19
- 238000004040 coloring Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims abstract description 15
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 52
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims abstract description 18
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 7
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 17
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical class C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 229960000583 acetic acid Drugs 0.000 claims description 11
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 10
- 239000012362 glacial acetic acid Substances 0.000 claims description 10
- 239000001632 sodium acetate Substances 0.000 claims description 10
- 235000017281 sodium acetate Nutrition 0.000 claims description 10
- 239000000975 dye Substances 0.000 claims description 8
- 239000000980 acid dye Substances 0.000 claims description 5
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 5
- 239000000985 reactive dye Substances 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000000434 metal complex dye Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 3
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 claims description 3
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 3
- KNSXNCFKSZZHEA-UHFFFAOYSA-N [3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical class C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C KNSXNCFKSZZHEA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004386 diacrylate group Chemical group 0.000 claims description 3
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000987 azo dye Substances 0.000 claims description 2
- 239000000986 disperse dye Substances 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 238000005286 illumination Methods 0.000 abstract 1
- 238000010146 3D printing Methods 0.000 description 28
- 238000003756 stirring Methods 0.000 description 24
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 18
- 238000001035 drying Methods 0.000 description 16
- -1 carboxylic acid modified epoxy acrylate Chemical class 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000005498 polishing Methods 0.000 description 10
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 9
- 235000019253 formic acid Nutrition 0.000 description 9
- 239000007853 buffer solution Substances 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003822 epoxy resin Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- ILCRHUJGVUEAKX-UHFFFAOYSA-N butan-1-ol;butyl acetate Chemical compound CCCCO.CCCCOC(C)=O ILCRHUJGVUEAKX-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 210000004243 sweat Anatomy 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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Abstract
The invention discloses a dyeing liquid for a nylon workpiece and a surface coloring treatment method for the nylon workpiece, wherein the dyeing liquid for the nylon workpiece comprises 6.25-12 parts by mass of n-butyl alcohol, 6.25-12 parts by mass of butyl acetate, 26-37.5 parts by mass of acrylate, 10-25 parts by mass of organic carboxylic acid, 15-30 parts by mass of dye, 0.5-1 part by mass of an auxiliary agent and a pH regulator, and the pH regulator is used for regulating the pH of the dyeing liquid to 4-6. The nylon product colored by the dyeing liquid has smooth surface, uniform color and good illumination resistance.
Description
Technical Field
The invention relates to the field of coloring agents, in particular to a coloring solution for a nylon product and a surface coloring treatment method for the nylon product.
Background
The 3D printing technology is a technology for manufacturing a rapid forming part by utilizing the principles of layer-by-layer superposition and accumulation forming. Because of the additive manufacturing, the design of the structure can be designed almost freely without being influenced by the processing mode. Many designers have designed products with a wide variety of 3D structures. On the other hand, with the popularization and the promotion of 3D printing technology, the application of 3D printing supplies is more and more extensive. Nylon is one of 3D printing consumables, has a great deal of advantages such as intensity height, chemical stability are good, wear resistance is good, is the preferred material of industrial grade 3D printing more. However, due to the limitation of the printing principle, the nylon part printed by 3D has more surface pores and poorer roughness; in addition, due to the limitation of the forming process and the forming speed, the model printed by the 3d printer is difficult to overcome the laminated texture formed in the Z-axis direction, and the effects of smooth surface, uniform color and difficult fading after coloring treatment of the product are difficult to achieve, so that the appearance quality and the application of the product are influenced. The existing coloring treatment method usually needs a complicated process and harsh treatment conditions, and is high in time cost and economic cost, so that the popularization and the use of 3D printing nylon parts are not facilitated.
Disclosure of Invention
The invention aims to solve the technical problem of providing a dyeing solution for nylon workpieces and a surface coloring treatment method for the nylon workpieces, wherein the nylon workpieces colored by the dyeing solution have smooth surfaces, uniform colors, good light resistance and difficult fading.
The technical scheme adopted by the invention is as follows:
the invention provides a dyeing liquid for nylon workpieces, which comprises 6.25-12 parts by mass of n-butyl alcohol, 6.25-12 parts by mass of butyl acetate, 26-37.5 parts by mass of acrylate, 10-25 parts by mass of organic carboxylic acid, 15-30 parts by mass of dye, 0.5-1 part by mass of an auxiliary agent and a pH regulator, wherein the pH regulator is used for regulating the pH of the dyeing liquid to 4-6.
Preferably, the pH adjusting agent is a buffer.
Preferably, the organic carboxylic acid is a saturated monocarboxylic acid having C1-C3. The larger the number of carbon atoms in the saturated monocarboxylic acid, the less acidic the saturated monocarboxylic acid is, as compared with the macromolecular organic carboxylic acid, the more unfavorable the experiment under acidic conditions of the present invention is, and therefore, the small molecular organic carboxylic acid, i.e., the saturated monocarboxylic acid of C1 to C3 is preferable.
Still further preferably, the organic carboxylic acid includes any one of formic acid, acetic acid and n-propionic acid.
Preferably, the acrylate includes any one of modified epoxy acrylate, polyethylene glycol (400) diacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated trimethylolpropane triacrylate, 1,6 hexanediol diacrylate, tripropylene glycol diacrylate, and dipropylene glycol diacrylate.
The modified epoxy acrylate refers to chemically modified epoxy acrylate, and the chemical modification is to prepare modified epoxy acrylate with different performances by reacting epoxy groups or hydroxyl (-OH) groups after ring opening in epoxy resin with other modified substances so as to improve the performances of the epoxy acrylate. For example, a part of epoxy groups in the epoxy resin firstly carry out ring-opening reaction with alcohol, carboxylic acid or amine and then are esterified by acrylic acid to prepare modified epoxy acrylate, namely organic compounds of hydroxyl (-OH), carboxyl (-COOH) or amino (-NH2) groups are grafted in the epoxy resin, so that the performance of the epoxy acrylate can be effectively improved.
The modified epoxy acrylate selected by the invention comprises but is not limited to carboxylic acid modified epoxy acrylate (such as succinic acid epoxy acrylate, sebacic acid epoxy acrylate, adipic acid epoxy acrylate or suberic acid epoxy acrylate and the like), alcohol modified epoxy acrylate (such as polyethylene glycol, polybutadiene and triethylene glycol which are obtained by modifying epoxy resin firstly and then acrylating) and amine modified epoxy acrylate (such as diamine which is obtained by modifying epoxy resin firstly and then acrylating), and modified epoxy acrylate prepared by other modification methods which can effectively improve viscosity, glossiness, flexibility, pigment wetting dispersibility and adhesive force of epoxy acrylate. Preferably, the auxiliary agent comprises at least one of a leveling agent, a fixing agent and a dispersing agent.
Preferably, the dye includes any one of an acid dye, a reactive dye, an azo dye, a disperse dye, and a metal complex dye. Further preferably having a sulfonic acid group (-SO)3H) Or a water-soluble group molecular structure such as a carboxyl group (-COOH) because of a sulfonic acid group (-SO)3H) Or water-soluble group molecules such as carboxyl (-COOH) and the like are arranged in a linear type, and the aromatic ring structure is positioned on the same plane, so that the dye has higher affinity to the nylon product, the dye is adsorbed to the surface by the nylon product in the solution and continuously diffuses to the amorphous area of the nylon product to form hydrogen bonds and van der Waals force with nylon macromolecules, and the color fastness of the nylon product is further improved.
The invention also provides a surface coloring treatment method of the nylon product, which comprises the following steps:
(1) preparing the dyeing liquid for the nylon workpiece;
(2) and (2) putting a nylon workpiece into the dyeing liquid prepared in the step (1), and heating for dyeing.
Preferably, step (1) is: mixing 6.25-12 parts by mass of n-butyl alcohol, 6.25-12 parts by mass of butyl acetate, 26-37.5 parts by mass of acrylate, 10-25 parts by mass of organic carboxylic acid, 15-30 parts by mass of dye and 0.5-1 part by mass of auxiliary agent, adding glacial acetic acid to adjust the pH value to 4-6, adding 0.1-0.5 part by mass of sodium acetate, and uniformly mixing.
Preferably, the heating temperature in the step (2) is 96-120 ℃, and the heating time is 30-120 min.
Furthermore, the heating rate in the step (2) is 1-3 ℃/min. Too fast a temperature rise rate easily leads to too fast dye-uptake rate and uneven dyeing.
Preferably, step (2) further comprises a step of pretreating the nylon part before the nylon part is put into the container.
Further, the pretreatment is a polishing treatment.
Preferably, the dyeing in step (2) by heating further comprises a drying step. Further preferably, the drying is any one of natural drying, drying with a blower and drying in a drying oven.
Preferably, the nylon piece is a 3D printing nylon piece.
The invention has the beneficial effects that:
the invention provides a dyeing liquid for nylon products, wherein n-butyl alcohol (boiling point 117.8 ℃) and ethyl acetate (boiling point 126.2 ℃) are mixed to form butanol-butyl acetate azeotrope, the azeotropic point is 117.2 ℃, the melting point of nylon (taking nylon 12 as an example) is 170-180 ℃, and the butanol-butyl acetate azeotrope is adopted to enable the whole coloring experiment to be carried out in a lower temperature environment, so that the coloring treatment is ensured to have less influence on the shrinkage deformation of the nylon products. The method is characterized in that the key part of the method is the proportion of acrylic ester in n-butyl alcohol, butyl acetate and acrylic ester, the proportion of the acrylic ester in the three is always kept at 52-75%, experiments prove that the nylon product with smooth surface, uniform color and good light resistance can be obtained within the proportion range of the acrylic ester, the proportion of the acrylic ester is too high, a layer of grease is not easy to dry after the nylon product is dyed, and the impregnation effect of impregnation liquid formed when the proportion of the acrylic ester is too low is weak, so that the surface of the nylon product is dull and easy to fade.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
Pretreatment of 3D printing nylon parts: adding an abrasive, water and a polishing solution into polishing equipment, uniformly mixing, then putting a proper amount of 3D printing parts, setting the rotating speed of a polishing drum to be 10-2000r/min, setting the polishing time to be 1-30 min, starting the polishing equipment to finish polishing the 3D printing parts, after polishing, closing the polishing equipment, discharging the water and the polishing solution, taking out the 3D printing nylon parts, and cleaning.
Taking 12 parts by weight of n-butyl alcohol and 12 parts by weight of butyl acetate, mixing and stirring at room temperature for 30min, adding 26 parts by weight of succinic acid epoxy acrylate, mixing and stirring uniformly, adding 10 parts by weight of formic acid, 15 parts by weight of acid dye and 0.5 part by weight of leveling agent, adding a proper amount of glacial acetic acid to adjust the pH value to 4-6, adding 0.1 part by weight of sodium acetate as a buffer solution, and stirring uniformly; and (3) putting the pretreated 3D printing nylon workpiece, raising the temperature to 96 ℃ at a speed of 1 ℃ per minute, keeping heating for 30min, taking out the dyed 3D printing nylon workpiece, cleaning the 3D printing nylon workpiece for 3 times by using distilled water, and drying the 3D printing nylon workpiece in an oven at 80 ℃ for 12h to obtain the nylon workpiece with a smooth surface and uniform color.
Example 2
Taking 6.25 parts by weight of n-butanol and 6.25 parts by weight of butyl acetate, mixing and stirring at room temperature for 30min, adding 37.5 parts by weight of adipic acid epoxy acrylate, mixing and stirring uniformly, adding 10 parts by weight of formic acid, 15 parts by weight of acid dye and 0.5 part by weight of leveling agent, adding a proper amount of glacial acetic acid to adjust the pH value to 4-6, adding 0.1 part by weight of sodium acetate as a buffer solution, and stirring uniformly; and (3) putting the pretreated 3D printing part, raising the temperature to 96 ℃ at a speed of 1 ℃ per minute, keeping heating for 30min, taking out the dyed 3D printing nylon part, cleaning the nylon part for 3 times by using distilled water, and drying the nylon part in an oven at 80 ℃ for 12h to obtain the nylon part with a smooth surface and uniform color.
Example 3
Taking 6.25 parts by weight of n-butanol and 6.25 parts by weight of butyl acetate, mixing and stirring at room temperature for 120min, adding 37.5 parts by weight of polyethylene glycol (400) diacrylate, mixing and stirring uniformly, adding 25 parts by weight of formic acid, 30 parts by weight of acid dye and 1 part by weight of leveling agent, adding a proper amount of glacial acetic acid to adjust the pH value to 4-6, adding 0.5 part by weight of sodium acetate as a buffer solution, and stirring uniformly; and (3) putting the pretreated 3D printing workpiece, raising the temperature to 120 ℃ at a speed of 3 ℃ per minute, keeping heating for 120min, taking out the dyed 3D nylon printing workpiece, cleaning the workpiece for 3 times by using distilled water, and drying the workpiece in an oven at 80 ℃ for 12h to obtain the nylon workpiece with a smooth surface and uniform color.
Example 4
Taking 6.25 parts by weight of n-butanol and 6.25 parts by weight of butyl acetate, mixing and stirring at room temperature for 30min, adding 37.5 parts by weight of ethoxylated trimethylolpropane triacrylate, mixing and stirring uniformly, adding 10 parts by weight of formic acid, 15 parts by weight of metal complex dye and 0.5 part by weight of leveling agent, adding a proper amount of glacial acetic acid to adjust the pH value to 4-6, adding 0.1 part by weight of sodium acetate as a buffer solution, and stirring uniformly; and (3) putting the pretreated 3D printing nylon workpiece, raising the temperature to 96 ℃ at a speed of 2 ℃ per minute, keeping heating for 30min, taking out the dyed 3D printing workpiece, cleaning the 3D printing workpiece for 3 times by using distilled water, and drying the 3D printing workpiece in an oven at 80 ℃ for 12h to obtain the nylon workpiece with a smooth surface and uniform color.
Example 5
Taking 6.25 parts by weight of n-butanol and 6.25 parts by weight of butyl acetate, mixing and stirring at room temperature for 30min, adding 37.5 parts of 1,6 hexanediol diacrylate, mixing and stirring uniformly, adding 25 parts of formic acid, 15 parts of metal complex dye and 0.5 part of leveling agent, adding a proper amount of glacial acetic acid to adjust the pH value to 4-6, adding 0.1 part of sodium acetate as a buffer solution, and stirring uniformly; and (3) putting the pretreated 3D printing part, raising the temperature to 105 ℃ at a speed of 2 ℃ per minute, keeping heating for 30min, taking out the dyed 3D printing nylon part, cleaning the nylon part for 3 times by using distilled water, and drying the nylon part in an oven at 80 ℃ for 12h to obtain the nylon part with a smooth surface and uniform color.
Example 6
Taking 10 parts by weight of n-butanol and 10 parts by weight of butyl acetate, mixing and stirring at room temperature for 30min, adding 30 parts by weight of ethoxylated pentaerythritol tetraacrylate, mixing and stirring uniformly, adding 10 parts by weight of formic acid, 15 parts by weight of reactive dye and 0.5 part by weight of leveling agent, adding a proper amount of glacial acetic acid to adjust the pH value to 4-6, adding 0.1 part by weight of sodium acetate as a buffer solution, and stirring uniformly; and (3) putting the pretreated 3D printing part, raising the temperature to 115 ℃ at a speed of 2 ℃ per minute, keeping heating for 30min, taking out the dyed 3D printing nylon part, cleaning the nylon part for 3 times by using distilled water, and drying the nylon part in an oven at 80 ℃ for 12h to obtain the nylon part with a smooth surface and uniform color.
Example 7
Comparative example 1: taking 12.5 parts by weight of n-butyl alcohol and 12.5 parts by weight of butyl acetate, mixing and stirring for 30min at room temperature, adding 25 parts by weight of tripropylene glycol diacrylate, mixing and stirring uniformly, adding 10 parts by weight of formic acid, 15 parts by weight of reactive dye and 0.5 part by weight of leveling agent, adding a proper amount of glacial acetic acid to adjust the pH value to 4-6, adding 0.1 part of sodium acetate as a buffer solution, stirring uniformly, adding a pretreated 3D printing nylon workpiece, raising the temperature to 115 ℃ at a speed of raising the temperature by 2 ℃ per minute, keeping heating for 30min, taking out the dyed 3D printing workpiece, cleaning for 3 times by using distilled water, drying for 12h at 80 ℃ in an oven to obtain a dyed nylon workpiece, and observing the dull surface of the dyed nylon workpiece.
Comparative example 2: taking 6 parts by weight of n-butyl alcohol and 6 parts by weight of butyl acetate, mixing and stirring for 30min at room temperature, adding 38 parts by weight of dipropylene glycol diacrylate, mixing and stirring uniformly, adding 10 parts by weight of formic acid, 15 parts by weight of reactive dye and 0.5 part by weight of leveling agent, adding a proper amount of glacial acetic acid to adjust the pH value to 4-6, adding 0.1 part by weight of sodium acetate as a buffer solution, stirring uniformly, adding a pretreated 3D printed nylon workpiece, raising the temperature to 115 ℃ at a speed of raising the temperature to 2 ℃ per minute, keeping heating for 30min, taking out the dyed 3D printed workpiece, cleaning for 3 times by using distilled water, drying for 12h at the temperature of an oven 80 ℃ to obtain a dyed nylon workpiece, observing that a layer of grease is attached to the surface of the dyed nylon workpiece, showing a non-drying state, and continuously drying the dyed nylon workpiece in the oven at the temperature of 80 ℃ for more than 12 h.
The dyed nylon articles prepared in examples 1 to 6 and comparative examples 1 to 2 were tested for light resistance, water resistance, sweat resistance and color uniformity, wherein the light resistance test was conducted by exposing the test pieces colored with different ratios of the dyeing solutions to natural light under the same test conditions for the same time, and the test results are shown in table 1, and the nylon articles colored with different ratios of the dyeing solutions were exposed under the same test conditions, and the results are shown in table 2. The results in table 1 show that the nylon part prepared by using the acrylic ester in the comparative example 1, which accounts for n-butyl alcohol, butyl acetate and acrylic ester, has obviously light color when the proportion content of the acrylic ester in the n-butyl alcohol, the butyl acetate and the acrylic ester is too low, the nylon part prepared by using the acrylic ester in the comparative example 2, which accounts for n-butyl alcohol, the butyl acetate and the acrylic ester, has obviously dark color, and the nylon part colored by using the dyeing liquid of the invention has no obvious surface after being irradiated for 8 hours and has better light resistance, and the results in table 2 show that the nylon part colored by using the dyeing liquid of the invention has improved light resistance, water resistance, sweat resistance and color uniformity.
TABLE 1 lightfastness of the nylon articles of examples 1-6 and comparative examples 1-2
TABLE 2 comparison of the Properties of the Nylon parts of examples 1-6 and comparative examples 1-2
Claims (8)
1. The dyeing liquid for nylon workpieces is characterized by comprising 6.25-12 parts by mass of n-butyl alcohol, 6.25-12 parts by mass of butyl acetate, 26-37.5 parts by mass of acrylate, 10-25 parts by mass of organic carboxylic acid, 15-30 parts by mass of dye, 0.5-1 part by mass of auxiliary agent and a pH regulator, wherein the pH regulator is used for regulating the pH of the dyeing liquid to 4-6;
the acrylate comprises any one of modified epoxy acrylate, polyethylene glycol (400) diacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated trimethylolpropane triacrylate, 1,6 hexanediol diacrylate, tripropylene glycol diacrylate and dipropylene glycol diacrylate, and the mass ratio of the n-butyl alcohol to the butyl acetate is 1: 1.
2. the dyeing liquid for nylon articles as claimed in claim 1, wherein the organic carboxylic acid is a saturated monocarboxylic acid having C1-C3.
3. The dyeing liquor for nylon articles according to any one of claims 1-2, characterized in that the auxiliary comprises at least one of leveling agent, fixing agent and dispersing agent.
4. The dyeing liquid for nylon articles according to any one of claims 1 to 2, wherein the dye comprises any one of an acid dye, a reactive dye, an azo dye, a disperse dye and a metal complex dye.
5. The surface coloring treatment method of the nylon product is characterized by comprising the following steps:
(1) preparing a dyeing liquor for nylon articles according to any one of claims 1 to 4;
(2) putting a nylon workpiece into the dyeing liquid prepared in the step (1), and heating for dyeing;
wherein the heating temperature in the step (2) is 96-120 ℃, the heating time is 30-120 min, and the heating rate is 1-3 ℃/min.
6. The surface coloring treatment method of the nylon product according to claim 5, wherein the step (1) is: mixing 6.25-12 parts by mass of n-butyl alcohol, 6.25-12 parts by mass of butyl acetate, 26-37.5 parts by mass of acrylate, 10-25 parts by mass of organic carboxylic acid, 15-30 parts by mass of dye and 0.5-1 part by mass of auxiliary agent, adding glacial acetic acid to adjust the pH value to 4-6, adding 0.1-0.5 part by mass of sodium acetate, and uniformly mixing.
7. The method for coloring a surface of a nylon article according to claim 5, wherein the step of pretreating the nylon article is further included before the step (2) of putting the nylon article.
8. The surface coloring treatment method for the nylon product according to any one of claims 5 to 7, wherein the nylon product is a 3D printed nylon product.
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CN101311408A (en) * | 2007-05-23 | 2008-11-26 | 郡是株式会社 | Pigmentation process for sewing thread and the pigmented sewing thread |
CN103276610A (en) * | 2013-06-08 | 2013-09-04 | 太仓市芸芸化纤有限公司 | Nylon fabric dyeing technology |
CN104119754A (en) * | 2014-08-01 | 2014-10-29 | 吴江华诚复合材料科技有限公司 | Acrylate series colorful coating material |
CN105646249A (en) * | 2016-03-24 | 2016-06-08 | 中国科学技术大学 | Acrylate derivative, method for preparing same and unsaturated resin paint |
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CN101311408A (en) * | 2007-05-23 | 2008-11-26 | 郡是株式会社 | Pigmentation process for sewing thread and the pigmented sewing thread |
CN103276610A (en) * | 2013-06-08 | 2013-09-04 | 太仓市芸芸化纤有限公司 | Nylon fabric dyeing technology |
CN104119754A (en) * | 2014-08-01 | 2014-10-29 | 吴江华诚复合材料科技有限公司 | Acrylate series colorful coating material |
CN105646249A (en) * | 2016-03-24 | 2016-06-08 | 中国科学技术大学 | Acrylate derivative, method for preparing same and unsaturated resin paint |
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