Ink jet for coiled material pipe in high-temperature and high-humidity environment, coiled material pipe ink jet method and coiled material pipe

Abstract

The invention provides ink jet for a coiled material pipe in a high-temperature and high-humidity environment, an ink jet method for the coiled material pipe and the coiled material pipe. The ink jet for the coiled material pipe in the high-temperature and high-humidity environment comprises organic silicon modified acrylic resin, a reactive diluent, a photoinitiator, color paste, a defoaming agent and a flatting agent, the inkjet ink can be used for direct jet printing in a high-temperature and high-humidity environment, does not block a nozzle, and is quick to dry, relatively good in wear resistance, high in tinting strength, firm in adhesion and low in cost.

Description

Technical Field

[0001] The present disclosure relates to the field of tube inkjet technology, and in particular to an inkjet method for a coiled tube in a high temperature and high humidity environment, and a coiled tube. Background Art

[0002] In the production of pipes, it is usually necessary to inkjet mark the extruded substrate tubes, such as spraying product specifications, production date and other information on the surface of the substrate tube. On the one hand, it is easy for users to identify, and on the other hand, each product has good traceability, realizing effective tracking and recording of products, thereby facilitating manufacturer traceability management.

[0003] However, since the substrate tube needs to be fully cooled and shaped when it is extruded, the formed substrate tube extruded by the extruder not only has a temperature of 60°C to 80°C and a humidity greater than 85%, that is, the substrate tube is in a high humidity and high temperature environment; and there are also some high temperature resistant and stable inks on the market, such as the high temperature resistant ink of Chinese patent document No. CN 111876016B, the high temperature resistant water-based polyurethane ink of Chinese patent document No. CN117986918B and the high temperature resistant UV inkjet printing ink of Chinese patent document No. CN 116285498 B.

[0004] Although the above-mentioned high temperature resistant ink improves its high temperature resistance and thermal stability, its wear resistance is relatively poor, resulting in the identification pattern layer of the pipe after inkjet drying being easily rubbed off by the metal winding wheel when it is rolled up while hot, causing the identification pattern layer of the pipe to wear. Summary of the invention

[0005] The purpose of the present invention is to overcome the shortcomings of the prior art and provide an inkjet for coiled tubes in high temperature and high humidity environments, an inkjet method for coiled tubes, and a coiled tube that can be directly printed in high temperature and high humidity environments, does not clog nozzles, dries quickly, has good wear resistance, high coloring power, adhesion fastness, and is low cost.

[0006] The purpose of this disclosure is achieved through the following technical solutions:

[0007] An inkjet for coiled tubes in high temperature and high humidity environments, comprising an organic silicon modified acrylic resin, an active diluent, a photoinitiator, a color paste, a defoamer and a leveling agent.

[0008] The organosilicon-modified acrylic resin has the following structure:

[0009]

[0010] In one embodiment, the viscosity of the silicone-modified acrylic resin is 300 cps to 500 cps; and / or,

[0011] The n of the organosilicon-modified acrylic resin is 10-15.

[0012] In one embodiment, the preparation method of the organosilicon-modified acrylic resin comprises the following steps:

[0013] Methyl hexahydrophthalic anhydride and neopentyl glycol are subjected to a ring-opening reaction to obtain a hydroxyl-terminated and carboxyl-terminated double-capped intermediate;

[0014] The hydroxyl-terminated and carboxyl-terminated double-capped intermediate is cross-linked with vinyl isocyanate-modified silicone to obtain the silicone-modified acrylic resin.

[0015] In one embodiment, the mass ratio of the methyl hexahydrophthalic anhydride to the neopentyl glycol is 1:1; and / or,

[0016] The temperature of the ring-opening reaction is 60° C. to 120° C., the time of the ring-opening reaction is 1 h to 4 h, and the reaction is terminated when the acid value of the ring-opening reaction is stabilized at 200 mgKOH / g to 210 mgKOH / g.

[0017] In one embodiment, the molecular weight of the silicone in the vinyl isocyanate-modified silicone is 900 g / mol to 1300 g / mol; and / or,

[0018] The mass ratio of the vinyl isocyanate modified silicone to the hydroxyl-terminated and carboxyl-terminated double-capped intermediate is 1:3 to 1:4; and / or,

[0019] The temperature of the cross-linking reaction is 60° C. to 90° C., the time of the cross-linking reaction is 4 hours to 8 hours, and the reaction is terminated when the NCO value of the cross-linking reaction decreases to 0% to 0.05%.

[0020] In one of the embodiments, by mass fraction, the silicone-modified acrylic resin is 20 to 30 parts; the active diluent is 50 to 70 parts; the photoinitiator is 5 to 10 parts; the color paste is 1 to 5 parts; the defoaming agent is 0.1 to 0.5 parts; and the leveling agent is 0.1 to 0.5 parts.

[0021] In one embodiment, the viscosity of the inkjet is 10.0 cps to 50.0 cps; and / or,

[0022] The particle size of the inkjet is 0.1 μm to 1.0 μm.

[0023] In one embodiment, the reactive diluent includes at least one of 3-methyl-1,5-pentanediol diacrylate and 1,6-hexanediol diacrylate; and / or,

[0024] The photoinitiator is a type II photoinitiator; and / or,

[0025] The color paste includes at least one of carbon black, aniline black and iron black; and / or,

[0026] The defoamer comprises at least one of a polysiloxane defoamer and a modified siloxane defoamer; and / or,

[0027] The leveling agent includes a modified siloxane leveling agent.

[0028] A coiled tube inkjet method comprises the following specific steps:

[0029] Obtaining a freshly extruded substrate tube;

[0030] The surface of the substrate tube is subjected to an inkjet operation using the inkjet described in any of the above embodiments to obtain a semi-product;

[0031] Pre-curing and deep-curing the semi-product in sequence to obtain a pipe;

[0032] The pipe is rolled up while hot to obtain a coiled pipe.

[0033] A coiled material tube is prepared by the coiled material tube inkjet method described in any one of the above embodiments.

[0034] Compared with the prior art, the present invention has at least the following advantages:

[0035] Since the side chains of the silicone-modified acrylic resin contain carboxyl hydrophilic groups, while the main chain contains methyl, hexacyclic and silicone hydrophobic groups, the side chains of the silicone-modified acrylic resin are hydrophilic, which facilitates contact with water molecules in the high humidity environment on the surface of the newly extruded substrate tube, thereby improving the adhesion strength of the inkjet in a high humidity environment. Since the main chain has strong hydrophobicity, it can effectively prevent the water absorbed by the side chains from entering the main chain of the silicone-modified acrylic resin, so that the inkjet is not prone to ink dispersion in a high humidity environment. With the subsequent curing operation, the inkjet can be cured on the surface of the substrate tube, which helps the inkjet to form a clear and distinct logo pattern layer in a high humidity environment, thereby improving the high coloring power of the inkjet.

[0036] Since the six-membered ring is a rigid hydrophobic group, it ensures that the inkjet can better resist the wear of the metal winding wheel, and the structure of the six-membered ring is stable and not easy to deform, so as to ensure that the inkjet has good high temperature resistance; since silicone is a flexible hydrophobic group, the silicone has good flexibility and elasticity, so as to ensure that the inkjet can better absorb and disperse the impact of the metal winding wheel, thereby effectively preventing the problem of wear of the logo pattern layer, and the bond energy of the Si-O bond of silicone itself is relatively high, so as to ensure that the inkjet has good high temperature resistance; especially with the use of carboxyl hydrophilic groups, since the carboxyl hydrophilic groups are located on the six-membered ring, the flexible carboxyl hydrophilic groups can provide better buffering for the rigid six-membered ring, effectively avoiding the friction of the metal winding wheel to damage the rigid six-membered ring. Compared with the simple use of flexible silicone, the use of the rigid six-membered ring disclosed in the present invention with flexible silicone and flexible carboxyl hydrophilic groups makes the inkjet have Good wear resistance and high temperature resistance; and, due to the interaction between the Si-O bond in the silicone and the carbon-hydrogen bond in the hexacyclic ring, this interaction can make both more stable at high temperatures, and the introduction of the hexacyclic ring can optimize the molecular structure of silicone, making the molecular structure of the silicone-modified acrylic resin more compact and orderly, thereby enhancing the overall strength of the silicone-modified acrylic resin, and then improving the high temperature resistance, wear resistance, high humidity resistance, adhesion fastness and high tinting strength of the inkjet, so as to ensure that the inkjet can be directly printed on the surface of the newly extruded substrate tube, and can form a logo pattern layer with clear, bright handwriting, high firmness, high temperature resistance, high humidity resistance and wear resistance, effectively avoiding the problem that the logo pattern layer of the tube after inkjet drying is easily rubbed off by the metal winding wheel when it is hot and rolled up, causing the logo pattern layer of the tube to be worn, and reducing the investment in production equipment of the tube, thereby reducing the floor space occupied by the tube.

[0037] Since the side chains of the silicone-modified acrylic resin contain multiple methyl groups, the added methyl groups not only improve the hydrophobic properties of the silicone-modified acrylic resin, but also further improve the high-humidity resistance of the inkjet; the added methyl groups also improve the fluidity of the silicone-modified acrylic resin, making the viscosity of the silicone-modified acrylic resin lower, that is, the viscosity at room temperature is 300cps-500cps, so that the prepared inkjet has good fluidity and does not clog the nozzle in a high temperature and high humidity environment, thereby ensuring long-term continuous normal operation of the inkjet.

[0038] Since the silicone-modified acrylic resin retains active hydrogen, the active hydrogen can further improve the fluidity of the inkjet and improve the viscosity of the inkjet, further reducing the problem of easy nozzle clogging in high temperature and high humidity environments; and the active hydrogen can also supply hydrogen to the photoinitiator, promoting the efficiency of the photoinitiator, thereby increasing the drying speed of the inkjet. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] In order to more clearly illustrate the technical solutions of the embodiments of the present disclosure, the drawings required for use in the embodiments will be briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present disclosure and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without paying creative work.

[0040] Figure 1 A flow chart of a coiled material tube inkjet method according to an embodiment of the present invention;

[0041] Figure 2 The invention is a practical object for cutting off a portion of the marking pattern layer of the pipe according to the first embodiment of the present invention. DETAILED DESCRIPTION

[0042] In order to facilitate the understanding of the present disclosure, the present disclosure will be described more fully below with reference to the relevant drawings. The preferred embodiments of the present disclosure are given in the drawings. However, the present disclosure can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present disclosure more thoroughly and comprehensively understood.

[0043] It should be noted that when an element is referred to as being "fixed to" another element, it may be directly on the other element or there may be a central element. When an element is considered to be "connected to" another element, it may be directly connected to the other element or there may be a central element at the same time. The terms "vertical", "horizontal", "left", "right" and similar expressions used herein are for illustrative purposes only and do not represent the only implementation method.

[0044] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present disclosure. The terms used herein in the specification of the present disclosure are only for the purpose of describing specific embodiments and are not intended to limit the present disclosure. The term "and / or" used herein includes any and all combinations of one or more related listed items.

[0045] The present disclosure provides an inkjet for a coiled tube in a high temperature and high humidity environment, comprising an organosilicon-modified acrylic resin, a reactive diluent, a photoinitiator, a color paste, a defoamer and a leveling agent, wherein the organosilicon-modified acrylic resin has the following structure:

[0046]

[0047] The above-mentioned inkjet for coiled tubes in high temperature and high humidity environments is added with silicone-modified acrylic resin containing carboxyl hydrophilic groups, hexacyclic rings, methyl groups and silicone hydrophobic groups, which improves the inkjet's high temperature resistance, wear resistance, high humidity resistance, adhesion fastness and high tinting strength, so as to ensure that the inkjet can be directly printed on the surface of the freshly extruded substrate tube, and can form a logo pattern layer with clear, vivid handwriting, high firmness, high temperature resistance, high humidity resistance and wear resistance, effectively avoiding the problem that the logo pattern layer of the tube after inkjet drying is easily rubbed off by the metal winding wheel when it is rolled up while hot, causing the logo pattern layer of the tube to be worn, and reducing the investment in tube production equipment, thereby reducing the floor space occupied by the tube.

[0048] In order to better understand the technical solutions and beneficial effects of the present invention, the present invention is further described in detail below in conjunction with specific embodiments:

[0049] One embodiment is used for inkjet printing of coiled tubes in a high temperature and high humidity environment, comprising an organic silicon modified acrylic resin, a reactive diluent, a photoinitiator, a color paste, a defoaming agent and a leveling agent,

[0050] The organosilicon-modified acrylic resin has the following structure:

[0051]

[0052] It is understandable that currently, groups such as siloxane, epoxy, aromatic and polyester are generally introduced to improve the high temperature resistance of acrylic system inkjet, such as Chinese patent document No. CN 112390916 B by introducing polyester, methyl, cycloalkane and carboxyl; and Chinese patent document No. CN113980194A by introducing epoxy and siloxane. Although the above-mentioned inkjet can improve the high temperature resistance, adhesion and thermal stability of the inkjet itself, in some relatively harsh production environments, such as pipe production, the temperature and humidity of the substrate tube when it is extruded are very high, that is, the temperature reaches 60℃~80℃ and the humidity is greater than 85%, and the pipe after the inkjet is dried needs to be rolled up while hot. Since the inkjet is soft and tough, it is easy to wear when it is rubbed by the metal winding wheel.

[0053] Of course, there are some inkjet inks on the market that reduce the viscosity of acrylic acid systems by adding hyperbranched acrylate oligomers so that the inkjet ink can maintain good fluidity, such as disclosed in Chinese patent documents No. CN 113980194 A and CN116769356 B. However, the reaction preparation conditions of hyperbranched acrylate oligomers are relatively harsh, resulting in a high cost of inkjet inks. In addition, hyperbranched acrylate oligomers are easily decomposed at high temperatures, which affects the overall performance of inkjet inks, resulting in most of the inkjet inks on the market being prone to falling off and blurred handwriting when directly spraying on the surface of a coiled tube under a high temperature and high humidity environment. This phenomenon is more obvious, especially after the metal winding wheel is wound up.

[0054] In order to solve the above technical problems, therefore, in the present disclosure, without the need to introduce hyperbranched acrylate oligomers, the characteristics of the functional groups of the silicone-modified acrylic resin itself are used to solve the problems of high temperature and high humidity resistance, wear resistance, good fluidity, low viscosity, fast drying, high tinting strength, and adhesion fastness of inkjet. Specifically, in the present disclosure, by introducing carboxyl hydrophilic groups into the side chains of the silicone-modified acrylic resin, and the main chain containing methyl, hexacyclic ring, and hydrophobic groups of silicone, the side chains of the silicone-modified acrylic resin are made hydrophilic, which is convenient for contacting with water molecules in the high humidity environment on the surface of the substrate tube just extruded, thereby improving the adhesion fastness of the inkjet in a high humidity environment. Since the main chain has strong hydrophobicity, it can effectively prevent the water absorbed by the side chains from entering the main chain of the silicone-modified acrylic resin, so that the inkjet is not easy to scatter ink in a high humidity environment. With the subsequent curing operation, the inkjet can be cured on the surface of the substrate tube, which helps the inkjet to form a clear and distinct logo pattern layer in a high humidity environment, thereby improving the high tinting strength of the inkjet.

[0055] It can also be understood that since the six-membered ring is a rigid hydrophobic group, it ensures that the inkjet can better resist the wear of the metal winding wheel, and the structure of the six-membered ring is stable and not easy to deform, so as to ensure that the inkjet has good high temperature resistance; since silicone is a flexible hydrophobic group, the silicone has good flexibility and elasticity, so as to ensure that the inkjet can better absorb and disperse the impact of the metal winding wheel, thereby effectively preventing the problem of wear of the logo pattern layer, and the bond energy of the Si-O bond of silicone itself is relatively high, so as to ensure that the inkjet has good high temperature resistance; especially with the use of carboxyl hydrophilic groups, since the carboxyl hydrophilic groups are located on the six-membered rings, the flexible carboxyl hydrophilic groups can provide better buffering for the rigid six-membered rings, effectively avoiding the friction of the metal winding wheel to damage the rigid six-membered rings. Compared with the simple use of flexible silicone, the use of the rigid six-membered ring disclosed in the present invention with flexible silicone and flexible carboxyl hydrophilic groups makes the inkjet The ink has good wear resistance and high temperature resistance; and, due to the interaction between the Si-O bond in the organosilicon and the carbon-hydrogen bond in the hexacyclic ring, this interaction can make both more stable at high temperatures, and the introduction of the hexacyclic ring can optimize the molecular structure of the organosilicon, making the molecular structure of the organosilicon-modified acrylic resin more compact and orderly, thereby enhancing the overall strength of the organosilicon-modified acrylic resin, and then improving the high temperature resistance, wear resistance, high humidity resistance, adhesion fastness and high tinting strength of the inkjet, so as to ensure that the inkjet can be directly spray-printed on the surface of the substrate tube that has just been extruded, and can form a logo pattern layer with clear, bright handwriting, high firmness, high temperature resistance, high humidity resistance and wear resistance, effectively avoiding the problem that the logo pattern layer of the tube after the inkjet is dried is easily rubbed off by the metal winding wheel when it is rolled up while hot, causing the logo pattern layer of the tube to be worn, and reducing the investment in production equipment of the tube, thereby reducing the floor space occupied by the tube.

[0056] It can also be understood that, since the side chain of the organosilicon-modified acrylic resin contains multiple methyl groups, the added methyl groups not only improve the hydrophobicity of the organosilicon-modified acrylic resin, but also further improve the high-humidity resistance of the inkjet; and the added methyl groups also improve the fluidity of the organosilicon-modified acrylic resin, making the viscosity of the organosilicon-modified acrylic resin lower, especially when n is 10 to 15, the viscosity of the organosilicon-modified acrylic resin at room temperature is 300cps-500cps, so as to ensure that the prepared inkjet has good fluidity, so that the inkjet does not clog the nozzle in a high temperature and high humidity environment, thereby ensuring that the inkjet can continue to be normal for a long time. In this way, under the premise of reducing the use of hyperbranched acrylate oligomers, only the characteristics of the hydrophilic groups of carboxyl, methyl, hexacyclic rings, and hydrophobic groups of silicone in the silicone-modified acrylic resin and the molecular weight of silicone are used to ensure that the final prepared inkjet has good fluidity, low viscosity, high temperature resistance, wear resistance, high humidity resistance, adhesion fastness and high tinting strength, so that the inkjet of the present invention can be directly printed on the surface of the substrate tube just extruded, and can form a logo pattern layer with clear, bright handwriting, high firmness, high temperature resistance, high humidity resistance and wear resistance, and ensure that the inkjet does not block the nozzle under high temperature and high humidity environment.

[0057] It can also be understood that since the organosilicon-modified acrylic resin retains active hydrogen, the active hydrogen can further improve the fluidity of the inkjet and improve the viscosity of the inkjet, further reducing the problem of easy nozzle clogging of the inkjet under high temperature and high humidity environments; and the active hydrogen can also supply hydrogen to the photoinitiator, promote the efficiency of the photoinitiator, thereby increasing the drying speed of the inkjet.

[0058] In one embodiment, n of the organosilicon-modified acrylic resin is 10 to 15, so as to ensure that the molecular weight of the organosilicon-modified acrylic resin is small, so that the organosilicon-modified acrylic resin has good fluidity and low viscosity, and ensures that the prepared inkjet has good fluidity, so that the inkjet does not block the nozzle in a high temperature and high humidity environment, thereby ensuring the normal operation of the inkjet for a long time. Specifically, in one embodiment, the viscosity of the organosilicon-modified acrylic resin is 300cps to 500cps.

[0059] It should be noted that in the modification process of some acrylic resins at present, solvents are usually required to prepare intermediates, as disclosed in Chinese patent document No. CN113980194A: first, initiator B, soft monomer, functional monomer, hard monomer and solvent A are mixed to obtain a mixed solution 1, and then solvent A containing a chain transfer agent is heated under the protection of an inert gas, and the mixed solution 1 is added dropwise to carry out reaction I, and the hydroxy polyacrylate is obtained after cooling. Not only are the reaction steps cumbersome, but the solvent used is generally an organic solvent with a low boiling point, which leads to the problem that it is easy to generate waste gas during the heating process, causing pollution to the ecological environment.

[0060] Therefore, the present disclosure also provides a method for preparing an organic silicon modified acrylic resin, which comprises the following steps: firstly, subjecting methyl hexahydrophthalic anhydride and neopentyl glycol to a ring-opening reaction to obtain a terminal hydroxyl-terminated carboxyl-terminated diblock intermediate, so that when the methyl hexahydrophthalic anhydride and neopentyl glycol are subjected to a ring-opening reaction, no low-boiling point organic solvent is required, which effectively avoids the problem of waste gas generated by the low-boiling point organic solvent due to excessively high heating temperature, and the methyl hexahydrophthalic anhydride and neopentyl glycol can be subjected to a one-step reaction to obtain the terminal hydroxyl-terminated carboxyl-terminated diblock intermediate, which simplifies the reaction steps of the terminal hydroxyl-terminated carboxyl-terminated diblock intermediate; then, the terminal hydroxyl-terminated carboxyl-terminated diblock intermediate is subjected to a cross-linking reaction with a vinyl isocyanate-modified organic silicon to obtain the organic silicon modified acrylic resin, so that the terminal hydroxyl-terminated diblock intermediate is The carboxyl double-terminated intermediate can be connected to the end of the vinyl isocyanate-modified silicone, so that the terminal carboxyl group can be located on the side chain of the silicone-modified acrylic resin, and the six-membered ring and silicone are located on the main chain of the silicone-modified acrylic resin, so as to ensure that the silicone-modified acrylic resin has good fluidity, low viscosity, high temperature resistance, high humidity resistance, wear resistance, adhesion fastness and high tinting strength, thereby ensuring that the inkjet can be directly printed on the surface of the freshly extruded substrate tube, and form a logo pattern layer with clear, bright, high firmness, high temperature resistance, high humidity resistance and wear resistance, and ensure that the inkjet does not block the nozzle under high temperature and high humidity environment; no waste water, no waste gas and no waste residue are generated in the entire process of the preparation of the silicone-modified acrylic resin, which is more green and environmentally friendly.

[0061] The preparation method of the organosilicon-modified acrylic resin has not only a simple synthesis process, but also no organic solvent is used in the entire preparation process, no waste water, no waste gas and no waste residue is generated, which is more environmentally friendly and low in cost.

[0062] The preparation method of the organosilicon-modified acrylic resin of one embodiment includes some or all of the following steps:

[0063] S101, subjecting methyl hexahydrophthalic anhydride and neopentyl glycol to a ring-opening reaction to obtain a hydroxyl-terminated and carboxyl-terminated double-capped intermediate.

[0064] It can be understood that methyl hexahydrophthalic anhydride can provide a six-membered ring and a methyl group, and the acyloxy group of methyl hexahydrophthalic anhydride can undergo a ring-opening reaction with the hydroxyl group in neopentyl glycol. For details, please refer to the following reaction principle:

[0065]

[0066] It can be seen that when methyl hexahydrophthalic anhydride and neopentyl glycol undergo a ring-opening reaction, there is no need to add a low-boiling-point organic solvent, which effectively avoids the problem of waste gas generation due to excessively high heating temperature of the low-boiling-point organic solvent. In addition, methyl hexahydrophthalic anhydride and neopentyl glycol can obtain a hydroxyl-terminated and carboxyl-terminated dicapped intermediate through a one-step reaction, which not only simplifies the reaction steps of the hydroxyl-terminated and carboxyl-terminated dicapped intermediate, but also ensures that no wastewater and waste residue are generated in the entire ring-opening reaction, which is more green and environmentally friendly.

[0067] Specifically, in one embodiment, the mass ratio of the methyl hexahydrophthalic anhydride to the neopentyl glycol is 1:1, so as to ensure that the added methyl hexahydrophthalic anhydride and the neopentyl glycol can just react to form a double-terminated intermediate with a terminal hydroxyl group and a terminal carboxyl group, and no waste water and no waste residue are generated; and the ring-opening reaction of methyl hexahydrophthalic anhydride and neopentyl glycol does not require the use of an organic solvent, so as to ensure that no waste gas is generated, which is more green and environmentally friendly.

[0068] In one embodiment, the temperature of the ring-opening reaction is controlled to be 60° C. to 120° C., and the time of the ring-opening reaction is 1 h to 4 h, so that the reaction is terminated when the acid value of the ring-opening reaction is stabilized at 200 mgKOH / g to 210 mgKOH / g, thereby ensuring that methyl hexahydrophthalic anhydride and neopentyl glycol can just react to form a terminal hydroxyl group and a terminal carboxyl group double-terminated intermediate without the generation of wastewater, waste gas and waste residue.

[0069] In one embodiment, in the ring-opening reaction of methyl hexahydrophthalic anhydride and neopentyl glycol, a catalyst is further added to accelerate the ring-opening reaction of methyl hexahydrophthalic anhydride and neopentyl glycol. Specifically, the catalyst can be a tertiary amine catalyst. In a preferred embodiment, the catalyst is a quaternary ammonium salt catalyst, and the quaternary ammonium salt catalyst includes at least one of triphenylphosphine and benzyltriethylammonium bromide.

[0070] In one embodiment, the amount of catalyst used is 0.01% to 0.5% of the total mass of the entire reaction system of methylhexahydrophthalic anhydride and neopentyl glycol, so as to achieve a more comprehensive catalysis of methylhexahydrophthalic anhydride and neopentyl glycol.

[0071] S102, cross-linking the hydroxyl-terminated and carboxyl-terminated double-capped intermediate with vinyl isocyanate-modified silicone to obtain the silicone-modified acrylic resin. The specific reaction principle is as follows:

[0072]

[0073] The double-terminated intermediate of terminal hydroxyl group and terminal carboxyl group can be linked to the end of the vinyl isocyanate-modified silicone without generating waste water, waste gas and waste residue, so that the terminal carboxyl group can be located on the side chain of the silicone-modified acrylic resin, and the six-membered ring and silicone are located on the main chain of the silicone-modified acrylic resin.

[0074] It should be noted that, for example, the organosilicon-modified hydroxy epoxy acrylic resin of Chinese patent document No. CN 113980194 A, it is usually necessary to add an inhibitor to prevent the occurrence of free radical polymerization in hydroxy polyacrylate and fatty acid-modified epoxy acrylate, thereby ensuring the stability and fluidity of the mixture of hydroxy polyacrylate and fatty acid-modified epoxy acrylate, and further ensuring the sufficiency and stability of the reaction of hydroxy polyacrylate and fatty acid-modified epoxy acrylate. However, the added inhibitor will affect the jetting performance of the inkjet, especially in a high temperature and high humidity environment. The conventional inkjet with the added inhibitor is more likely to have the problem of nozzle clogging in a high temperature and high humidity environment.

[0075] Therefore, in the present disclosure, the terminal hydroxyl-terminal carboxyl diblocked intermediate and the amount of vinyl isocyanate modified silicone are utilized to ensure that the terminal hydroxyl-terminal carboxyl diblocked intermediate and the vinyl isocyanate modified silicone have good fluidity and stability. In this way, without the need to add additional inhibitors, the terminal hydroxyl-terminal carboxyl diblocked intermediate and the vinyl isocyanate modified silicone have good stability and fluidity in the cross-linking reaction, so that the terminal hydroxyl-terminal carboxyl diblocked intermediate and the vinyl isocyanate modified silicone can just react to obtain a silicone-modified acrylic resin with good fluidity and low viscosity, and the reaction steps are simple, and no waste water, waste gas or waste residue is generated.

[0076] The above-mentioned preparation method of organosilicon-modified acrylic resin simplifies the synthesis process while reducing the use of organic solvents and polymerization inhibitors. The entire preparation process generates no waste water, no waste gas and no waste residue, which is more environmentally friendly and low-cost.

[0077] In one of the embodiments, the molecular weight of the silicone in the vinyl isocyanate-modified silicone is 900 g / mol to 1300 g / mol; in particular, when n is 10 to 15, the molecular weight of the silicone is moderate, which helps to prepare a silicone-modified acrylic resin with fluidity, low viscosity, high temperature resistance, high humidity resistance, abrasion resistance, adhesion fastness and high tinting strength.

[0078] In a preferred embodiment, the mass ratio of the vinyl isocyanate-modified silicone to the hydroxyl-terminated and carboxyl-terminated intermediate is 1:3 to 1:4, so as to ensure that the added vinyl isocyanate-modified silicone and the hydroxyl-terminated and carboxyl-terminated intermediate can just react to obtain silicone-modified acrylic resin, and no waste water, waste gas or waste residue is generated, which is green and environmentally friendly.

[0079] Specifically, in one of the embodiments, the temperature of the cross-linking reaction of the vinyl isocyanate-modified silicone and the hydroxyl-terminated and carboxyl-terminated intermediate is 60°C to 90°C, the time of the cross-linking reaction is 4h to 8h, and the reaction is terminated when the NCO value of the cross-linking reaction decreases to 0% to 0.05%, so as to ensure that the vinyl isocyanate-modified silicone and the hydroxyl-terminated and carboxyl-terminated intermediate can just react to obtain the silicone-modified acrylic resin, and no waste water, waste gas or waste residue is generated, which is green and environmentally friendly.

[0080] In one embodiment, when the vinyl isocyanate modified silicone undergoes a crosslinking reaction with the terminal hydroxyl-terminated carboxyl-terminated intermediate, an organotin catalyst is also added to the reaction of the vinyl isocyanate modified silicone with the terminal hydroxyl-terminated carboxyl-terminated intermediate. Specifically, the amount of the organotin catalyst is 0.01% to 0.5% of the total mass of the entire reaction system of the vinyl isocyanate modified silicone and the terminal hydroxyl-terminated carboxyl-terminated intermediate, so as to achieve a more comprehensive catalysis of the vinyl isocyanate modified silicone and the terminal hydroxyl-terminated carboxyl-terminated intermediate.

[0081] In one of the embodiments, by mass fraction, the silicone-modified acrylic resin is 20 to 30 parts; the reactive diluent is 50 to 70 parts; the photoinitiator is 5 to 10 parts; the color paste is 1 to 5 parts; the defoamer is 0.1 to 0.5 parts and the leveling agent is 0.1 to 0.5 parts.

[0082] It can be understood that due to the addition of silicone-modified acrylic resin containing carboxyl hydrophilic groups, hexacyclic rings, methyl groups and silicone hydrophobic groups, the high temperature resistance, wear resistance, high humidity resistance, adhesion fastness and high tinting strength of the inkjet are improved, so as to ensure that the inkjet can be directly printed on the surface of the freshly extruded substrate tube, and can form a logo pattern layer with clear, bright handwriting, high firmness, high temperature resistance, high humidity resistance and wear resistance, effectively avoiding the problem that the logo pattern layer of the tube after inkjet drying is easily rubbed off by the metal winding wheel when it is rolled up while hot, causing wear of the logo pattern layer of the tube, and reducing the investment in tube production equipment, thereby reducing the floor space occupied by the tube. Furthermore, since the organosilicon-modified acrylic resin has good fluidity and low viscosity, when 20 to 30 parts of the organosilicon-modified acrylic resin are compounded with 50 to 70 parts of an active diluent, 5 to 10 parts of a photoinitiator, 1 to 5 parts of a color paste, 0.1 to 0.5 parts of a defoaming agent, and 0.1 to 0.5 parts of a leveling agent, the prepared inkjet can have good fluidity and low viscosity, so that the inkjet does not clog the nozzle under a high temperature and high humidity environment, thereby ensuring long-term continuous normal operation of the inkjet; and the active hydrogen retained by the organosilicon-modified acrylic resin can supply hydrogen to the photoinitiator, promote the efficiency of the photoinitiator, thereby improving the drying speed of the inkjet, and there is no need to use hyperbranched acrylate oligomers and inhibitors, which not only reduces the use cost, but also further reduces the probability of the inkjet nozzle being clogged under a high temperature and high humidity environment.

[0083] It is understandable that although the fluidity and viscosity of the silicone-modified acrylic resin can improve the fluidity of the inkjet to a certain extent, the degree of improvement is limited, resulting in the problem of nozzle clogging in a long-term high temperature and high humidity environment. Therefore, some scholars believe that the above problem can be solved by improving the particle size of the inkjet; but the particle size of the traditional tube-type inkjet is usually between 1.0μm and 10.0μm. When the particle size of the inkjet is within this range, the accuracy of the inkjet and the clarity of the logo pattern can be ensured, while avoiding problems such as nozzle clogging or uneven inkjet.

[0084] That is to say, when technicians in this field improve the fluidity of tube-type inkjets by adjusting the particle size of inkjet, they usually do not choose an inkjet particle size lower than 1.0 μm to solve the problem of fluidity of tube-type inkjet. This is mainly because the specific surface area of ​​inkjet particles lower than 1.0 μm is large, and inkjet particles lower than 1.0 μm are more likely to evaporate under high temperature and high humidity conditions, which will cause the color of the inkjet to fade, seriously affecting the clarity of the logo pattern layer. However, the present disclosure achieves the effect that inkjet with a particle size of 0.1μm to 1.0μm can be directly printed in a high temperature and high humidity environment, and can form a logo pattern layer with clear and vivid handwriting, high firmness, high temperature resistance, high humidity resistance and wear resistance. The main reason is that the silicone-modified acrylic resin of the present disclosure is used, so that the Si-O bonds of the silicone-modified acrylic resin in the small particle size and the carbon-hydrogen bonds in the hexacyclic ring can be arranged more closely together, reducing the pores and defects of the inkjet, thereby reducing the inkjet volatilization rate, making the inkjet of the present disclosure more stable under high temperature and high humidity conditions. In this way, not only the fluidity of the inkjet is further improved, and the problem of nozzle clogging of the inkjet in a long-term high temperature and high humidity environment is effectively avoided; the volatilization rate of the small particle size inkjet is also reduced to ensure the formation of a logo pattern layer with clear and vivid handwriting, high firmness, high temperature resistance, high humidity resistance and wear resistance.

[0085] Furthermore, the ink droplets of the inkjet with a particle size of 0.1 μm to 1.0 μm are smaller, which is conducive to forming finer patterns and texts on the curved surface of the substrate tube, thereby ensuring the clarity of the logo pattern layer and the accuracy of the printing.

[0086] Furthermore, inkjet with a particle size of 0.1μm to 1.0μm can penetrate more deeply into the curved surface fibers of the substrate tube, forming a more secure bond with the substrate tube, thereby improving the adhesion firmness of the logo pattern layer; and, because the ink droplets of inkjet with a particle size of 0.1μm to 1.0μm are smaller, the amount of inkjet can be controlled more accurately, which can not only reduce ink waste and production costs, but also reduce environmental pollution caused by ink volatilization or leakage.

[0087] Furthermore, for printing on tubular curved surfaces such as substrate tubes, inkjet particles with a diameter of 0.1 μm to 1.0 μm can be more evenly distributed on the curved surface of the substrate tube, avoiding the problem of ink droplets accumulating or flowing at the edge or concave part of the curved surface to affect the clarity of the logo pattern layer. In addition, the ink droplets of inkjet particles with a diameter of 0.1 μm to 1.0 μm are smaller and can be dried and cured faster, thereby improving production efficiency.

[0088] It is worth mentioning that since the curved surface of the substrate tube has a certain curvature, the inkjet with small particle size of 0.1μm~1.0μm can more flexibly adapt to the complex curved surface shape, ensuring the continuity and consistency of the printed pattern on the curved surface, thereby broadening the application of inkjet in tubular materials with a variety of different curved surfaces.

[0089] In one of the embodiments, the material of the substrate tube includes any one of PVC (Polyvinyl Chloride), PA (Polyamide), PP (Polypropylene), ABS (Acrylonitrile Butadiene Styrene), PET (Polyethylene Terephthalate), PC (Polycarbonate) and PMMA (Polymethyl Methacrylate), so that the inkjet with a particle size of 0.1μm to 1.0μm can better adhere to the surface of the substrate tube of PVC, PA, PP, ABS, PET, PC and PMMA, and form a logo pattern layer with clear, bright, high firmness, high temperature resistance, high humidity resistance and wear resistance, and the amount of inkjet used is small.

[0090] In one embodiment, the active diluent includes at least one of 3-methyl-1,5-pentanediol diacrylate and 1,6-hexanediol diacrylate. It can be understood that since both 3-methyl-1,5-pentanediol diacrylate and 1,6-hexanediol diacrylate have the characteristics of rapid curing, they can also reduce the viscosity of the inkjet, so as to ensure that the prepared inkjet has the characteristics of rapid curing, and also ensure that the inkjet has good fluidity and low viscosity, further reducing the probability of the inkjet nozzle being blocked, thereby ensuring that the inkjet can operate normally in a high temperature and high humidity environment for a long time.

[0091] It can be understood that if 1,6-hexanediol diacrylate is used alone, since it can significantly improve the degree of crosslinking and high strength, the logo pattern layer finally prepared will have higher strength and toughness, which will cause the logo pattern layer to easily crack due to the winding effect when it is subsequently rolled up while hot; if 3-methyl-1,5-pentanediol diacrylate is used alone, the introduction of methyl groups will reduce the reaction sites with the surface of the substrate tube, causing the logo pattern layer to easily fall off, especially the silicone-modified acrylic resin of the present invention itself has a large amount of methyl groups introduced, which will make it more likely for the logo pattern layer to fall off. Therefore, in a preferred embodiment, the active diluent is a mixture of 3-methyl-1,5-pentanediol diacrylate and 1,6-hexanediol diacrylate. By mixing 3-methyl-1,5-pentanediol diacrylate and 1,6-hexanediol diacrylate, the added 3-methyl-1,5-pentanediol diacrylate can better compensate for the cracking problem of 1,6-hexanediol diacrylate due to its higher strength and toughness, and the added 1,6-hexanediol diacrylate can better improve the reaction site of inkjet, so as to ensure that the identification pattern layer of the coiled material tube after the final winding has high adhesion firmness, clear writing and is not easy to crack.

[0092] In a more preferred embodiment, the mass ratio of 1,6-hexanediol diacrylate to 3-methyl-1,5-pentanediol diacrylate is (4-8):1, so as to ensure that the added 1,6-hexanediol diacrylate and 3-methyl-1,5-pentanediol diacrylate can play a good synergistic role, so as to ensure that the identification pattern layer of the coiled tube after the final winding has high adhesion firmness, clear writing and is not easy to crack.

[0093] It is understandable that since the tube after inkjet drying needs to be rolled up while hot, in actual production, there is not much time left for the tube after inkjet drying to dry. If a cleavage-type photoinitiator is used, it is necessary to absorb strong ultraviolet light to initiate the polymerization cross-linking reaction, that is, strong ultraviolet light is required, which will cause the identification pattern layer of the tube, which is in a high temperature and high humidity environment, to turn yellow and other undesirable problems; if a cationic photoinitiator is used, it is necessary to absorb ultraviolet light in a longer wavelength range, resulting in a significantly lower curing efficiency using a cationic photoinitiator, which causes the tube to be easily worn when entering the metal winding wheel.

[0094] Therefore, in one embodiment, the photoinitiator is a type II photoinitiator, which has higher efficiency, environmental protection, selectivity and reactivity than cleavage photoinitiators and cationic photoinitiators, so that the inkjet of the present invention can be more quickly and stably induced to undergo chemical reactions. In particular, in combination with the active hydrogen of the organosilicon-modified acrylic resin of the present invention, the type II photoinitiator can more quickly induce the chemical reaction of the inkjet, so as to ensure that the tube is already cured when it enters the metal winding wheel, and further reduce the problem of the logo pattern layer being easily oxidized due to incomplete curing. The problem of wear and tear; and the light energy required by the second type photoinitiator is relatively small, which can better reduce the problem that the temperature of the tube becomes high due to absorbing more light energy, causing the logo pattern layer to turn yellow, etc. In this way, the use of the second type photoinitiator can quickly initiate the active hydrogen of the silicone modified acrylic resin, and effectively reduce the problem that the logo pattern layer turns yellow due to the further heating of the substrate tube caused by the high light intensity, which is conducive to rapid curing to form a logo pattern layer with clear handwriting, not easy to turn yellow and crack, high firmness, high temperature resistance, high humidity resistance and wear resistance.

[0095] In one embodiment, the second type of photoinitiator includes at least one of 2,4,6-trimethylbenzoylphenylphosphonic acid ethyl ester, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide. It can be understood that since 2,4,6-trimethylbenzoylphenylphosphonic acid ethyl ester, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide have good thermal stability, it is ensured that the second type of photoinitiator can quickly initiate the chemical reaction of the active hydrogen of the organosilicon-modified acrylic resin using relatively low light energy in a high temperature and high humidity environment, which is conducive to rapid curing to form a logo pattern layer with clear handwriting, not easy to turn yellow and crack, high firmness, high temperature resistance, high humidity resistance and wear resistance.

[0096] In one embodiment, the color paste includes at least one of carbon black, aniline black and iron black to form a black logo pattern layer on the surface of the substrate tube. Further, in one embodiment, the substrate tube is a white or transparent substrate tube, so that the color paste can form a logo pattern layer with clear handwriting, high brightness and high firmness, high temperature resistance, high humidity resistance and wear resistance on the surface of the white or transparent substrate tube.

[0097] In one embodiment, the defoamer includes at least one of a polysiloxane defoamer and a modified siloxane defoamer. It is understood that the added polysiloxane defoamer and the modified siloxane defoamer can not only achieve the defoaming effect of the inkjet during the mixing preparation process, but also facilitate the preparation of an inkjet with good fluidity, uniform system and low viscosity, so as to further reduce the probability of nozzle clogging during long-term continuous operation of the inkjet.

[0098] In one embodiment, the leveling agent includes a modified silicone leveling agent. The added modified silicone leveling agent is not only conducive to forming a smoother and more uniform logo pattern layer, but also conducive to preparing an inkjet with good fluidity, uniform system and low viscosity, so that the nozzle can form continuous and stable ink droplets during the printing process, which is particularly suitable for the printing operation of a logo pattern layer with a longer length, so that a logo pattern layer with clear writing, high clarity, high firmness, high temperature resistance, high humidity resistance and wear resistance can be formed on the surface of the substrate tube.

[0099] The present disclosure also provides a method for preparing an inkjet, which comprises the following steps: firstly preparing materials according to a formula; then mixing an organosilicon-modified acrylic resin, a photoinitiator and a color paste to obtain a first mixture, so as to perform ball milling together in the subsequent step, so as to ensure that an inkjet having a particle size of 0.1 μm to 1.0 μm can be prepared in the subsequent step, and the efficiency of ball milling is improved; ball milling is performed on the first mixture to ensure that the particle size of the first mixture is within the range of 0.1 μm to 1.0 μm, so as to ensure that an inkjet having a particle size of 0.1 μm to 1.0 μm can be prepared; then, ultrasonically mixing the first mixture, an active diluent, a defoaming agent and a leveling agent to obtain a second mixture, so as to ensure that a second mixture having a uniform system is prepared, and effectively reducing the problem that the particle size of the inkjet is less than 0.1 μm due to the shear force of the second mixture by a stirring member in the conventional method; finally, filtering the second mixture to effectively remove solid particles and impurities with larger particle sizes in the second mixture, so as to obtain an inkjet having a particle size of 0.1 μm to 1.0 μm.

[0100] The above-mentioned method for preparing inkjet ink, by ball milling the first mixture, ensures that an inkjet with a particle size of 0.1μm to 1.0μm can be prepared subsequently, and the efficiency of ball milling is improved; in particular, in conjunction with ultrasonic mixing and filtering operations, a non-contact ultrasonic mixing method is adopted, which not only effectively reduces the problem of the inkjet particle size being less than 0.1μm due to the shear force of the second mixture by the stirring element in the traditional method, but also facilitates the preparation of a second mixture with a stable system, and the filtering operation can effectively remove solid particles and impurities with larger particle sizes in the second mixture to obtain an inkjet with a particle size of 0.1μm to 1.0μm, and in particular, in conjunction with the use of silicone-modified acrylic resin, the prepared inkjet has a small particle size, good fluidity, low viscosity, high firmness, high temperature resistance, high humidity resistance and wear resistance, and is particularly suitable for the inkjet process of substrate tubes in high temperature and high humidity environments.

[0101] See also Figure 2 The inkjet preparation method of one embodiment includes some or all of the following steps:

[0102] S201, prepare materials according to the recipe;

[0103] Specifically, according to the inkjet formula, 20 to 30 parts of silicone-modified acrylic resin, 50 to 70 parts of active diluent, 5 to 10 parts of photoinitiator, 1 to 5 parts of color paste, 0.1 to 0.5 parts of defoaming agent, and 0.1 to 0.5 parts of leveling agent are weighed and set aside.

[0104] S202, mixing the organosilicon-modified acrylic resin, the photoinitiator, and the color paste to obtain a first mixture, so as to subsequently ball-mill the first mixture, thereby ensuring that an inkjet with a particle size of 0.1 μm to 1.0 μm can be prepared subsequently. In addition, the added organosilicon-modified acrylic resin helps to prepare an inkjet with good fluidity, low viscosity, high firmness, high temperature resistance, high humidity resistance, and wear resistance.

[0105] S203, ball milling the first mixture to ensure that the particle size of the first mixture is within 0.1 μm to 1.0 μm, thereby ensuring that the inkjet with a particle size of 0.1 μm to 1.0 μm is prepared. Specifically, the ball milling speed is 200 r / min to 350 r / min, and the time is 10 min to 20 min.

[0106] S204, ultrasonically mixing the first mixture, the active diluent, the defoaming agent and the leveling agent to obtain a second mixture, so as to ensure that the first mixture can be fully and evenly mixed with the active diluent, the defoaming agent and the leveling agent, thereby obtaining a second mixture with a stable system; since ultrasonic mixing adopts a non-contact vibration mixing method, it can effectively reduce the problem of the inkjet particle size being less than 0.1 μm caused by the shear force of the second mixture by the stirring element in the traditional method.

[0107] In one embodiment, the ultrasonic mixing conditions are: the ultrasonic frequency is 40kHz to 60kHz, the ultrasonic power is 2W / cm 2 ~8W / cm 2 The mixing time is 5 to 20 minutes to achieve comprehensive mixing of the first mixture, the active diluent, the defoaming agent and the leveling agent.

[0108] S205, filtering the second mixture to effectively remove solid particles and impurities with larger particle sizes in the second mixture, so as to obtain inkjet with a particle size of 0.1 μm to 1.0 μm.

[0109] The present disclosure also provides a coiled tube inkjet method, comprising the following specific steps: obtaining a substrate tube that has just been extruded; using the inkjet described in any of the above embodiments to perform inkjet operation on the surface of the substrate tube to obtain a semi-product; pre-curing and deep-curing the semi-product in sequence to obtain a tube; and coiling the tube while it is hot to obtain a coiled tube.

[0110] See also Figure 1The coiled tube inkjet method of one embodiment includes some or all of the following steps:

[0111] S301, obtaining a substrate tube that has just been extruded.

[0112] It is understandable that since the newly extruded substrate tube needs to be cooled and shaped in the extruder, the temperature of the newly extruded substrate tube is as high as 60℃~80℃ and the humidity is greater than 85%, resulting in a relatively harsh environment for the printing process of the newly extruded substrate tube, which traditional general inkjet cannot adapt to.

[0113] S302, using the inkjet method described in any of the above embodiments to perform inkjet operation on the surface of the substrate tube to obtain a semi-product.

[0114] It can be understood that, since the inkjet of the present invention is compounded with 20 to 30 parts of silicone-modified acrylic resin, 50 to 70 parts of active diluent, 5 to 10 parts of photoinitiator, 1 to 5 parts of color paste, 0.1 to 0.5 parts of defoaming agent, and 0.1 to 0.5 parts of leveling agent, the prepared inkjet has good fluidity and low viscosity, so that the inkjet does not clog the nozzle under high temperature and high humidity environment, thereby ensuring the long-term continuous normal operation of the inkjet; and the active hydrogen retained by the silicone-modified acrylic resin can supply hydrogen to the photoinitiator, promote the efficiency of the photoinitiator, thereby improving the drying speed of the inkjet, and there is no need to use hyperbranched acrylate oligomers and inhibitors, which not only reduces the cost of use, but also further reduces the probability of the inkjet nozzle being clogged under high temperature and high humidity environment.

[0115] It can also be understood that due to the use of type II photoinitiator, the type II photoinitiator can trigger the chemical reaction of inkjet more quickly to ensure that the tube is already cured when it enters the metal winding wheel, further reducing the problem of easy wear of the logo pattern layer due to incomplete curing; and the light energy required by type II photoinitiator is relatively small, which can better reduce the problem of yellowing of the logo pattern layer due to the tube temperature rising due to absorbing more light energy. In this way, the use of type II photoinitiator can quickly trigger the active hydrogen of the silicone modified acrylic resin, and effectively reduce the problem of yellowing of the logo pattern layer due to further heating of the substrate tube caused by high light intensity, which is conducive to rapid curing to form a logo pattern layer with clear handwriting, not easy to yellow and crack, high firmness, high temperature resistance, high humidity resistance and wear resistance.

[0116] It can also be understood that the inkjet preparation method disclosed in the present invention can ensure that the inkjet with a particle size of 0.1μm to 1.0μm can be directly printed in a high temperature and high humidity environment, and can form a logo pattern layer with clear, vivid, high firmness, high temperature resistance, high humidity resistance and wear resistance, while reducing ink waste, reducing production costs, and facilitating faster drying and curing. It can also effectively avoid the problem of ink droplets accumulating or flowing on the edge of the curved surface or in the depression to affect the clarity of the logo pattern layer. It is particularly suitable for the inkjet process of the substrate tube in a high temperature and high humidity environment.

[0117] It can also be understood that the preparation method of the organosilicon-modified acrylic resin disclosed in the present invention not only has a simple synthesis process, but also does not use organic solvents, does not generate waste water, waste gas, and waste residues during the entire preparation process, which is more environmentally friendly and low-cost.

[0118] S303, pre-curing and deep curing are performed on the semi-product in sequence to obtain a pipe, so as to achieve rapid, stable and comprehensive curing of the inkjet.

[0119] In one embodiment, the pre-curing conditions are: irradiation light power 10W / cm 2 ~20W / cm 2 ; The condition for deep curing is radiant light power of 20W / cm 2 ~25W / cm 2 ; To ensure that the inkjet can quickly form a logo pattern layer on the surface of the substrate tube that is clear, not easy to turn yellow or crack, has high firmness, is resistant to high temperature, high humidity and wear, so as to ensure that the tube is completely cured when entering the hot winding and is not easily worn away by the metal winding wheel. Specifically, in one embodiment, the pre-curing conditions are: irradiation with a UVLED wavelength of 395nm, and the light power is 15W / cm 2 , time 0.1s~5s; deep curing conditions: irradiation with 395nm band of UVLED, light power 20W / cm 2 The time is 0.5s to 5s to achieve rapid drying of the inkjet. On the one hand, it ensures that the logo pattern layer has reached a completely solidified state when the tube enters the metal winding wheel to improve the wear resistance of the logo pattern layer. On the other hand, it effectively reduces the radiation time and causes the white substrate tube or logo pattern layer to turn yellow.

[0120] In a preferred embodiment, the 395nm band of UVLED is used for radiation, and the optical power is 15W / cm 2 , time 1s; deep curing conditions: irradiation with UVLED at 395nm band, light power 20W / cm 2 Time: 1.5s.

[0121] S304, coiling the pipe while hot to obtain a coiled pipe, so as to achieve coiling of the pipe while hot, thereby obtaining a wound coiled pipe.

[0122] The above-mentioned coiled tube inkjet method, by applying the inkjet with a particle size of 0.1μm to 1.0μm obtained by the inkjet preparation method disclosed in the present invention to the inkjet process of the newly extruded substrate tube, not only realizes the direct printing operation on the surface of the newly extruded substrate tube, but also ensures the normal operation of the inkjet for a long time, is not easy to block the nozzle in a high temperature and high humidity environment, and can quickly induce the active hydrogen of the silicone-modified acrylic resin to effectively reduce the problem of yellowing of the logo pattern layer caused by further heating of the substrate tube due to high light intensity, which is conducive to rapid curing to form a logo pattern layer with clear handwriting, not easy to yellow and crack, high firmness, high temperature resistance, high humidity resistance and wear resistance, and low cost. For details, please refer to Figure 2 As shown, it is particularly suitable for the inkjet process of substrate tubes in high temperature and high humidity environments.

[0123] It is understandable that although high humidity can effectively eliminate static electricity on the surface of the substrate tube, since there are many water droplets condensed on the surface of the newly extruded substrate tube, the water droplets will be unevenly distributed on the surface of the newly extruded substrate tube. In addition, the temperature of the newly extruded substrate tube is high, resulting in low humidity in the areas without water droplets on the surface of the newly extruded substrate tube, which causes high static electricity, while the static electricity in the areas with water droplets is relatively small, which makes the static electricity on the surface of the newly extruded substrate tube unevenly distributed. If the extruded substrate tube is directly inkjetted, the inkjet will be unevenly distributed during the printing process, resulting in a blurred logo image layer.

[0124] Therefore, in one of the embodiments, before the step of performing inkjet operation on the surface of the substrate tube by using the inkjet described in any of the above embodiments to obtain a semi-product, and after the steps of pre-curing and deep curing the semi-product in sequence, the following step is also included: blowing ion wind on the newly extruded substrate tube to effectively remove water droplets and static electricity on the surface of the substrate tube, thereby reducing the problem of uneven static electricity distribution on the surface of the newly extruded substrate tube, so as to ensure the uniformity of the inkjet during the printing process, thereby ensuring a logo pattern layer with clearer, brighter, high firmness, high temperature resistance, high humidity resistance and wear resistance.

[0125] It can also be understood that since the generated ion wind can effectively drive away the water droplets on the surface of the substrate tube, so as to effectively reduce the moisture on the surface of the newly extruded substrate tube, it is beneficial for the subsequent inkjet to adhere more evenly to the surface of the newly extruded substrate tube, thereby facilitating the preparation of a logo pattern layer with good uniformity, clear writing, more vividness, high firmness, high temperature resistance, high humidity resistance and wear resistance.

[0126] It can also be understood that the ion wind can quickly blow away the water droplets, and the higher temperature of the steel extruded substrate tube can evaporate the blown away water droplets more quickly. In this way, the water droplets can be effectively removed without adding drying equipment.

[0127] In one embodiment, the ion wind blowing operation is performed by an ion blower. Specifically, in one embodiment, the ion blower is arranged near the outlet of the newly extruded substrate tube, so that the ion wind blown by the ion blower can more comprehensively remove water droplets and static electricity from the newly extruded substrate tube.

[0128] In one embodiment, the ion blower is disposed at the top of the outlet and is located directly above the substrate tube that has just been extruded. The air outlet of the ion blower is U-shaped, and the orthographic projection area of ​​the U-shaped air outlet is larger than the orthographic projection area of ​​the substrate tube that has just been extruded.

[0129] It can be understood that since the ion fan is arranged at the top of the outlet and is located directly above the newly extruded substrate tube, the ion wind generated by the ion fan can better drive away the water droplets on the upper part of the substrate tube. Since the air outlet of the ion fan is U-shaped and the positive projection area of ​​the U-shaped air outlet is larger than the positive projection area of ​​the newly extruded substrate tube, the ion wind generated by the U-shaped air outlet can more comprehensively blow away the water droplets and static electricity on the top and both sides of the newly extruded substrate tube. In this way, part of the water droplets on the substrate tube can be evaporated by the high temperature of the newly extruded substrate tube, and part of the water droplets can fall to the bottom of the outlet under the action of gravity, and a very small part of the water droplets gather at the very bottom of the newly extruded substrate tube, so as to ensure that the static electricity on the top and both sides of the newly extruded substrate tube is relatively uniform and has very little water, which is conducive to the subsequent inkjet to be more evenly attached to the surface of the newly extruded substrate tube, thereby facilitating the preparation of a logo pattern layer with good uniformity, clear handwriting, more vividness, high firmness, high temperature resistance, high humidity resistance and wear resistance.

[0130] In one embodiment, the U-shaped air outlet includes a vertical ion air duct, a first inclined ion air duct and a second inclined ion air duct, the vertical ion air duct is arranged at the top of the U-shaped air outlet, the first inclined ion air duct is arranged obliquely at the first side of the U-shaped air outlet, the second inclined ion air duct is arranged obliquely at the second side of the U-shaped air outlet, and the first side and the second side are arranged opposite to each other.

[0131] It can be understood that in actual applications, in order to fully and quickly remove water droplets and static electricity on the surface of the newly extruded substrate tube, ion winds are usually set on the four sides of the outlet. However, this will cause the ion winds at the top and bottom of the outlet to interfere with each other, resulting in low utilization of the ion wind and residual water droplets on both sides of the surface of the substrate tube. Therefore, in the present disclosure, a vertical ion duct, a first inclined ion duct and a second inclined ion duct are respectively arranged on the top of the U-shaped air outlet, the first side of the U-shaped air outlet and the second side of the U-shaped air outlet to ensure that the vertical ion duct, the first inclined ion duct and the second inclined ion duct can continuously drive away the water droplets on the top and both sides of the surface of the substrate tube that has just been extruded and eliminate the static electricity on the top and both sides of the surface of the substrate tube, so as to quickly remove the water droplets and static electricity on the surface of the substrate tube that has just been extruded, and at the same time, the utilization rate of the vertical ion duct, the first inclined ion duct and the second inclined ion duct is improved, the energy of the ion blower is saved, so as to effectively reduce the cost; and the water droplets on the top and both sides of the surface of the substrate tube that has just been extruded will prevent subsequent inkjet from being affected by the water droplets on the top and both sides of the surface of the extruded substrate tube.

[0132] It can also be understood that the vertical ion wind blown out by the vertical ion wind duct can ensure that the vertical ion wind can better drive the water droplets on the top surface of the newly extruded substrate tube to the two sides, and at the same time enable the vertical ion wind to effectively remove the static electricity on the top surface of the substrate tube, while the first inclined ion wind duct and the second inclined ion wind duct can more comprehensively remove the water droplets and static electricity on both sides of the surface of the newly extruded substrate tube, thereby facilitating the subsequent inkjet to adhere more evenly to the surface of the newly extruded substrate tube.

[0133] In one of the embodiments, the angle between the inclined ion wind of the first inclined ion wind duct and the length direction of the substrate tube just extruded is 15°~55°, and the angle between the inclined ion wind of the second inclined ion wind duct and the length direction of the substrate tube just extruded is 15°~55°, so as to ensure that the first inclined ion wind duct and the second inclined ion wind duct can more comprehensively remove water droplets and static electricity on both sides of the surface of the substrate tube just extruded.

[0134] In one embodiment, there are multiple first inclined ion ducts, and each first inclined ion duct is arranged in a matrix along the first side of the U-shaped air outlet; there are multiple second inclined ion ducts, and each second inclined ion duct is arranged in a matrix along the second side of the U-shaped air outlet; there are multiple vertical ion ducts, and each vertical ion duct is arranged in a matrix along the top of the U-shaped air outlet. In this way, multiple first inclined ion ducts, multiple second inclined ion ducts, and multiple vertical ion ducts are arranged in an inner U shape to ensure that the multiple first inclined ion ducts, multiple second inclined ion ducts, and multiple vertical ion ducts can more comprehensively remove water droplets and static electricity on the top and both sides of the surface of the newly extruded substrate tube.

[0135] In one embodiment, the electrostatic neutralization rate of the ion blower when the ion blower is in operation is 400V / s to 600V / s, the action distance of the vertical ion duct is 0.3m to 0.5m, and the action distance of the first inclined ion duct and the action distance of the second inclined ion duct are both 0.6m to 0.8m.

[0136] It is understandable that if the static neutralization rate of the ion blower is less than 400V / s, the static electricity on the surface of the newly extruded substrate tube cannot be completely removed. If the static neutralization rate of the ion blower is greater than 600V / s, although the static neutralization rate is very high, it will cause a high residual voltage and affect the static electricity removal effect. Therefore, in the present disclosure, by controlling the static neutralization rate of the ion blower to operate at 400V / s to 600V / s, while ensuring that the ion wind can completely remove the static electricity on the surface of the newly extruded substrate tube, the problem of residual voltage of the newly extruded substrate tube is avoided.

[0137] It can also be understood that if the action distance of the vertical ion duct is less than 0.3m, the vertical ion duct is closer to the top of the newly extruded substrate tube, causing the water droplets on the top of the newly extruded substrate tube to splash. If the action distance of the vertical ion duct is greater than 0.5m, the vertical ion duct is farther from the top of the newly extruded substrate tube, and it is impossible to achieve a more comprehensive expulsion of the water droplets on the top of the newly extruded substrate tube. Therefore, in the present disclosure, by controlling the action distance of the vertical ion duct to be 0.3m to 0.5m, it is ensured that the wind blown out by the vertical ion duct can more comprehensively drive the water droplets on the top of the substrate tube to both sides, effectively avoiding the problem of splashing of the water droplets on the top to cause more water accumulation at the bottom of the outlet and affecting the service life of the equipment.

[0138] It can also be understood that if the effective distance of the first inclined ion duct or the effective distance of the second inclined ion duct is less than 0.6m, the first inclined ion duct or the second inclined ion duct will be closer to the side of the substrate tube that has just been extruded, causing the water droplets on the side of the substrate tube to splash back to the top of the substrate tube to increase the difficulty of driving away the water droplets on the top. If the effective distance of the first inclined ion duct or the effective distance of the second inclined ion duct is greater than 0.8m, the first inclined ion duct or the second inclined ion duct will be far away from the side of the substrate tube that has just been extruded, and it will be impossible to achieve a more comprehensive driving of the water droplets on the side of the substrate tube that has just been extruded. Therefore, in the present disclosure, by controlling the effective distance of the first inclined ion duct and the effective distance of the second inclined ion duct to be 0.6m~0.8m, it is ensured that the wind blown out by the first inclined ion duct and the second inclined ion duct can more comprehensively drive the two sides of the substrate tube and the water droplets to the bottom of the substrate tube, and effectively avoid the water droplets on the sides splashing back to the top of the substrate tube to increase the difficulty of driving the water droplets on the top, especially in conjunction with the operation of the ion fan with an electrostatic neutralization rate of 400V / s~600V / s and an effective distance of 0.3m~0.5m of the vertical ion duct, so as to more comprehensively remove the static electricity and water droplets on the top and two sides of the substrate tube that has just been extruded, and effectively avoid the splashing of water droplets, which causes more water accumulation at the bottom of the outlet and affects the service life of the equipment, and the splashing of water droplets on the sides back to the top of the substrate tube to increase the difficulty of driving the water droplets on the top.

[0139] In one embodiment, each vertical ion duct includes a vertical ion duct body and a plurality of first nozzles, and the first nozzles are staggered along the length direction of the vertical ion duct body, so that the plurality of staggered first nozzles can more comprehensively remove water droplets and static electricity on the top of the substrate tube that has just been extruded.

[0140] In one embodiment, each first inclined ion duct includes a first inclined ion duct body and a plurality of second nozzles, the second nozzles are evenly distributed along the length direction of the first inclined ion duct body, and each second nozzle is obliquely arranged on the first inclined ion duct body to ensure that the first inclined ion duct blows out inclined ion wind.

[0141] In one embodiment, the inclination angle θ1 between the second nozzle and the first inclined ion wind duct body is (180°-θ2), wherein θ2 is the angle between the inclined ion wind of the first inclined ion wind duct and the length direction of the just extruded substrate tube, thereby ensuring that the angle between the inclined ion wind blown out by the second nozzle and the length direction of the just extruded substrate tube is 15°~55°.

[0142] Likewise, in one embodiment, each second inclined ion wind duct has the structure of the first inclined ion wind duct to ensure that the angle between the inclined ion wind blown out by the second inclined ion wind duct and the length direction of the newly extruded substrate tube is 15° to 55°.

[0143] In one of the embodiments, the inclined ion wind of the first inclined ion duct adjacent to the top of the U-shaped air outlet portion and the ion wind of the vertical ion duct adjacent to the first side of the U-shaped air outlet portion intersect at the top of the first side of the substrate tube that has just been extruded. In this way, the first inclined ion duct and the vertical ion duct can just completely remove the water droplets and static electricity on the top and the first side of the substrate tube that has just been extruded, that is, the utilization rate of the ion wind of the first inclined ion duct and the vertical ion duct is fully improved, and the problem of excess or insufficient ion wind in the first inclined ion duct and the vertical ion duct is effectively avoided.

[0144] Similarly, in one of the embodiments, the inclined ion wind of the second inclined ion duct adjacent to the top of the U-shaped air outlet and the ion wind of the vertical ion duct adjacent to the second side of the U-shaped air outlet intersect at the top of the second side of the substrate tube that has just been extruded, so as to ensure that the second inclined ion duct and the vertical ion duct can just completely remove the water droplets and static electricity on the top and second side of the substrate tube that has just been extruded, that is, fully improve the utilization rate of the ion wind of the second inclined ion duct and the vertical ion duct, and effectively avoid the problem of excess or insufficient ion wind in the second inclined ion duct and the vertical ion duct.

[0145] In one embodiment, the power of the ion blower is 10W to 20W to ensure that the ion blower can provide a static neutralization rate of 400V / s to 600V / s for multiple vertical ion ducts, multiple first inclined ion ducts, and multiple second inclined ion ducts during operation, so as to quickly remove water droplets and static electricity on the surface of the newly extruded substrate tube.

[0146] In one embodiment, the inkjet printer is positioned on the top or both sides of the substrate tube that has just been extruded.

[0147] The present disclosure also provides a coiled material tube, which is prepared by the coiled material tube inkjet method described in any of the above embodiments. It can be understood that since the coiled material tube inkjet method of the present disclosure uses an inkjet with a particle size of 0.1μm to 1.0μm to print on the surface of the substrate tube that has just been extruded, the normal operation of the inkjet is guaranteed to last for a long time, and the problem of nozzle clogging is not easy in a high temperature and high humidity environment, and the active hydrogen of the silicone-modified acrylic resin can be quickly triggered to effectively reduce the problem of yellowing of the logo pattern layer caused by further heating of the substrate tube due to high light intensity, which is conducive to rapid solidification to form a logo pattern layer with clear handwriting, not easy to turn yellow and crack, high firmness, high temperature resistance, high humidity resistance and wear resistance, and low cost, which is particularly suitable for the inkjet process of the substrate tube in a high temperature and high humidity environment, and effectively avoids the problem of metal winding wheel abrading the logo pattern layer.

[0148] Compared with the prior art, the present invention has at least the following advantages:

[0149] 1) Since the side chains of the silicone-modified acrylic resin contain carboxyl hydrophilic groups, while the main chain contains methyl, hexacyclic and silicone hydrophobic groups, the side chains of the silicone-modified acrylic resin are hydrophilic, which facilitates contact with water molecules in the high humidity environment on the surface of the newly extruded substrate tube, thereby improving the adhesion strength of the inkjet in a high humidity environment. Since the main chain has strong hydrophobicity, it can effectively prevent the water absorbed by the side chains from entering the main chain of the silicone-modified acrylic resin, so that the inkjet is not prone to ink dispersion in a high humidity environment. With the subsequent curing operation, the inkjet can be cured on the surface of the substrate tube, which helps the inkjet to form a clear and distinct logo pattern layer in a high humidity environment, thereby improving the high coloring power of the inkjet.

[0150] 2) Since the six-membered ring is a rigid hydrophobic group, it ensures that the inkjet can better resist the wear of the metal winding wheel, and the structure of the six-membered ring is stable and not easy to deform, so as to ensure that the inkjet has good high temperature resistance; since silicone is a flexible hydrophobic group, the silicone has good flexibility and elasticity, so as to ensure that the inkjet can better absorb and disperse the impact of the metal winding wheel, thereby effectively preventing the problem of wear of the logo pattern layer, and the bond energy of the Si-O bond of silicone itself is relatively high, so as to ensure that the inkjet has good high temperature resistance; especially with the use of carboxyl hydrophilic groups, since the carboxyl hydrophilic groups are located on the six-membered ring, the flexible carboxyl hydrophilic groups can provide a better buffer for the rigid six-membered ring, effectively avoiding the metal winding wheel from rubbing and damaging the rigid six-membered ring. Compared with the simple use of flexible silicone, the use of the rigid six-membered ring disclosed in the present invention with flexible silicone and flexible carboxyl hydrophilic groups makes the inkjet have It has good wear resistance and high temperature resistance; and, due to the interaction between the Si-O bond in the silicone and the carbon-hydrogen bond in the hexacyclic ring, this interaction can make both more stable at high temperatures, and the introduction of the hexacyclic ring can optimize the molecular structure of silicone, making the molecular structure of the silicone-modified acrylic resin more compact and orderly, thereby enhancing the overall strength of the silicone-modified acrylic resin, and then improving the high temperature resistance, wear resistance, high humidity resistance, adhesion fastness and high tinting strength of the inkjet, so as to ensure that the inkjet can be directly printed on the surface of the newly extruded substrate tube, and can form a logo pattern layer with clear, bright handwriting, high firmness, high temperature resistance, high humidity resistance and wear resistance, effectively avoiding the problem that the logo pattern layer of the tube after inkjet drying is easily rubbed off by the metal winding wheel when it is hot and rolled up, causing the logo pattern layer of the tube to be worn, and reducing the investment in production equipment of the tube, thereby reducing the floor space occupied by the tube.

[0151] 3) Since the side chains of the silicone-modified acrylic resin contain multiple methyl groups, the added methyl groups not only improve the hydrophobic properties of the silicone-modified acrylic resin, but also further improve the high-humidity resistance of the inkjet; and the added methyl groups also improve the fluidity of the silicone-modified acrylic resin, making the viscosity of the silicone-modified acrylic resin lower, that is, the viscosity at room temperature is 300cps-500cps, so that the prepared inkjet has good fluidity, and the inkjet does not clog the nozzle in a high temperature and high humidity environment, thereby ensuring long-term and continuous normal operation of the inkjet.

[0152] 4) Since the silicone-modified acrylic resin retains active hydrogen, the active hydrogen can further improve the fluidity of the inkjet and improve the viscosity of the inkjet, further reducing the problem of easy nozzle clogging in a high temperature and high humidity environment; and the active hydrogen can also supply hydrogen to the photoinitiator, promoting the efficiency of the photoinitiator, thereby increasing the drying speed of the inkjet.

[0153] Some specific examples are listed below, and if % is mentioned, it means percentage by weight. It should be noted that the following examples do not exhaust all possible situations, and the materials used in the following examples can be obtained from commercial sources unless otherwise specified.

[0154] Example 1

[0155] Preparation of silicone-modified acrylic resin: Methyl hexahydrophthalic anhydride and neopentyl glycol are mixed in a mass ratio of 1:1, and triphenylphosphine catalyst (accounting for 0.01% of the total mass of the reaction system) is added to react at a temperature of 100°C for 2 hours until the acid value in the reaction system stabilizes at 205 mgKOH / g to terminate the reaction and obtain a terminal hydroxyl group and a terminal carboxyl group double-capped intermediate.

[0156] The terminal hydroxyl group and the terminal carboxyl group double-terminated intermediate were mixed with vinyl isocyanate-modified silicone (n is 10, and the molecular weight of the silicone in the vinyl isocyanate-modified silicone is 900 g / mol) in a mass ratio of 1:3, and an organic tin catalyst (accounting for 0.02% of the total mass of the reaction system) was added to react at a temperature of 90° C. for 6 hours until the NCO value in the reaction system was reduced to 0.01%, and the reaction was terminated to obtain an organosilicon-modified acrylic resin. The viscosity of the organosilicon-modified acrylic resin was 300 cps.

[0157] Mixing 30 kg of the organosilicon-modified acrylic resin obtained in step 2), 5 kg of ethyl 2,4,6-trimethylbenzoylphenylphosphonate, and 1 kg of carbon black to obtain a first mixture;

[0158] The first mixture was ball-milled at a speed of 280 r / min for 15 min;

[0159] The first mixture obtained in step 4), 10 kg 3-methyl-1,5-pentanediol diacrylate, 50 kg 1,6-hexanediol diacrylate, 0.1 kg modified siloxane defoamer and 0.1 kg modified siloxane leveling agent were ultrasonically mixed. The ultrasonic mixing conditions were as follows: the ultrasonic frequency was 45 kHz and the ultrasonic power was 6 W / cm 2 ; The mixing time is 10 min to obtain a second mixture;

[0160] The second mixture is filtered, wherein the filter membrane is 0.25 μm, to obtain inkjet with a particle size of 0.25 μm for use.

[0161] Obtain a substrate tube that has just been extruded; wherein the substrate tube is a white PVC substrate tube;

[0162] The surface of the substrate tube is subjected to inkjet operation by the inkjet in step 6) to obtain a semi-finished product;

[0163] The semi-product is pre-cured and deep-cured in sequence to obtain a pipe; wherein the pre-curing condition is: irradiation is carried out using the 395nm band of UVLED, and the light power is 15W / cm 2 , time is 1s; deep curing conditions: irradiation is carried out using the 395nm band of UVLED, and the light power is 20W / cm 2 , time is 1.5s;

[0164] The pipe is coiled while hot to obtain a coiled pipe.

[0165] Example 2

[0166] The difference from Example 1 is that n in step 2) is different, that is, n in step 2) of Example 2 is 15, the molecular weight of the silicone in the vinyl isocyanate-modified silicone is 1300 g / mol, and the viscosity of the obtained silicone-modified acrylic resin is 500 cps, and the rest remains unchanged.

[0167] Example 3

[0168] The difference from Example 1 is that n in step 2) is different, that is, n in step 2) of Example 3 is 13, the molecular weight of the silicone in the vinyl isocyanate-modified silicone is 1100 g / mol, and the viscosity of the obtained silicone-modified acrylic resin is 400 cps, and the rest remains unchanged.

[0169] Example 4

[0170] The difference from Example 1 is that the ball milling conditions in step 4) are different and the pore size of the filter membrane in step 6) is different, that is, the ball milling speed in step 4) of Example 4 is 300r / min, and the time is 20min; the pore size of the filter membrane in step 6) is 0.1μm, and an inkjet with a particle size of 0.1μm is obtained, and the rest remains unchanged.

[0171] Example 5

[0172] The difference from Example 1 is that the ball milling conditions in step 4) are different and the pore size of the filter membrane in step 6) is different, that is, the ball milling speed in step 4) of Example 5 is 220r / min, and the time is 10min; the pore size of the filter membrane in step 6) is 1.0μm, and an inkjet with a particle size of 1.0μm is obtained, and the rest remains unchanged.

[0173] Comparative Example 1

[0174] The difference from Example 1 is that n in step 2) is different, that is, n in step 2) of Comparative Example 1 is 9, and the rest remains unchanged.

[0175] Comparative Example 2

[0176] The difference from Example 1 is that n in step 2) is different, that is, n in step 2) of Comparative Example 2 is 16, and the rest remains unchanged.

[0177] Comparative Example 3

[0178] The difference from Example 1 is that the formula in step 5) is different. In Comparative Example 3, "10 kg 3-methyl-1,5-pentanediol diacrylate, 50 kg 1,6-hexanediol diacrylate" in step 5) of Example 1 is directly replaced by "60 kg 3-methyl-1,5-pentanediol diacrylate", and the rest remains unchanged.

[0179] Comparative Example 4

[0180] The difference from Example 1 is that the formula in step 5) is different. In Comparative Example 4, the "10 kg 3-methyl-1,5-pentanediol diacrylate, 50 kg 1,6-hexanediol diacrylate" in Example 1 is directly replaced by "60 kg 1,6-hexanediol diacrylate", and the rest remains unchanged.

[0181] Comparative Example 5

[0182] The difference from Example 1 is that the ball milling conditions in step 4) are different and the pore size of the filter membrane in step 6) is different, that is, the ball milling speed in step 4) of comparative example 5 is 200r / min, and the time is 10min; the pore size of the filter membrane in step 6) is 1.2μm, and a 1.2μm inkjet is obtained, and the rest remains unchanged.

[0183] Comparative Example 6

[0184] The difference from Example 1 is that the ball milling conditions in step 4) are different and the pore size of the filter membrane in step 6) is different. The ball milling speed in step 4) of comparative example 6 is 300r / min, the time is 25min, the pore size of the filter membrane in step 6) is less than 0.1μm, and an inkjet with a particle size of less than 0.1μm is obtained. The rest remains unchanged.

[0185] Comparative Example 7

[0186] The difference from Example 1 is that, in Comparative Example 7, an ion wind blowing operation is added between step 7) and step 8) of Example 1, wherein the ion wind blowing operation is performed by an ion blower, which is arranged at the top of the outlet and directly above the substrate tube just extruded, and the air outlet of the ion blower is U-shaped;

[0187] Each vertical ion air duct is arranged in a matrix along the top of the U-shaped air outlet. Each vertical ion air duct includes a vertical ion air duct body and a plurality of first nozzles. Each first nozzle is staggered along the length direction of the vertical ion air duct body, and the action distance of the first nozzle of the vertical ion air duct is controlled to be 0.3m.

[0188] The first inclined ion ducts are arranged in a matrix along the first side of the U-shaped air outlet, and each first inclined ion duct includes a first inclined ion duct body and a plurality of second nozzles. The second nozzles are evenly distributed along the length direction of the first inclined ion duct body, and the inclination angle of each second nozzle to the first inclined ion duct body is 145°, so that the angle between the inclined ion wind blown out by the second nozzle and the length direction of the substrate tube just extruded is 35°;

[0189] The second inclined ion ducts are arranged in a matrix along the second side of the U-shaped air outlet; each second inclined ion duct includes a second inclined ion duct body and a plurality of third nozzles, and the third nozzles are evenly distributed along the length direction of the second inclined ion duct body, and each third nozzle is inclined at an angle of 135° to the second inclined ion duct body, so that the angle between the inclined ion wind blown out by the third nozzle and the length direction of the just extruded substrate tube is 45°; and the action distance between the second nozzle and the third nozzle is controlled to be 0.8m; the power of the ion fan is 15W, and the electrostatic neutralization rate of the ion fan is 500V / s; and the inkjet position is set on the side of the just extruded substrate tube, and the rest remains unchanged.

[0190] The viscosity, average particle size, adhesion, friction resistance times of the inkjet prepared in the above Examples 1 to 5 and Comparative Examples 1 to 7 and the appearance of the marking pattern layer of the rolled pipe were tested to obtain the experimental data in the following table:

[0191] Viscosity: The inkjet was tested at 25°C using a rotational viscometer;

[0192] Average particle size: The average particle size of the inkjet is measured using a particle size analyzer;

[0193] Adhesion: 3M810 tape was used for testing;

[0194] Friction resistance times: tested with a wear tester;

[0195] Appearance inspection of the marking pattern layer of the coiled pipe: randomly select pipes from the production line for visual inspection.

[0196]

[0197]

[0198]

[0199]

[0200] From the comparison between Examples 1 to 3 and Comparative Examples 1 to 2, it can be seen that since n of the vinyl isocyanate-modified silicone in Examples 1 to 3 is 10 to 15, the marking pattern layer of the prepared rolled pipe has the characteristics of clear handwriting, high vividness, not easy to turn yellow, not cracked, not falling off, and not worn, and the nozzle is not blocked during the inkjet process, so that the comprehensive indicators of Examples 1 to 3 are significantly better than those of Comparative Examples 1 to 2, among which the comprehensive indicators of Example 1 are better. For details, please refer to Figure 2 .

[0201] From the comparison between Examples 1 to 3 and Comparative Examples 3 to 4, it can be seen that since the active diluents used in Examples 1 to 3 are 3-methyl-1,5-pentanediol diacrylate and 1,6-hexanediol diacrylate, and the mass ratio of 3-methyl-1,5-pentanediol diacrylate to 1,6-hexanediol diacrylate is (4 to 8): 1, it is ensured that the marking pattern layer of the prepared rolled pipe has the characteristics of clear writing, high brightness, not easy to turn yellow, and not cracked, not falling off, and not worn, and it is ensured that the nozzle is not blocked during the inkjet process, so that the comprehensive indicators of Examples 1 to 3 are significantly better than those of Comparative Examples 3 to 4.

[0202] From the comparison between Examples 1, 4, 5 and Comparative Examples 5 to 6, it can be seen that since the particle size of the inkjet of Examples 1, 4, and 5 is between 0.1 μm and 1.0 μm, it can ensure that the marking pattern layer of the prepared rolled pipe has the characteristics of clear writing, high vividness, not easy to turn yellow, and not cracked, not falling off, and not worn, and ensure that the nozzle is not blocked during the inkjet process, so that the comprehensive indicators of Examples 1, 4, and 5 are significantly better than those of Comparative Examples 5 to 6.

[0203] From the comparison between Example 1 and Comparative Example 7, it can be seen that since Comparative Example 7 adds the operation of blowing ion wind, especially in conjunction with the use of multiple vertical ion wind ducts, multiple first inclined ion wind ducts and multiple second inclined ion wind ducts, it is ensured that the identification pattern layer of the rolled pipe prepared in Comparative Example 7 has higher clarity and vividness of the writing, does not turn yellow, crack or fall off, and is not easy to wear, and ensures that the nozzle is not blocked during the inkjet process, so that the clarity and vividness indicators of the writing of Comparative Example 7 are significantly better than those of Example 1.

[0204] The above-mentioned embodiments only express several implementation methods of the present disclosure, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the disclosed patent. It should be pointed out that, for a person of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present disclosure, and these all belong to the protection scope of the present disclosure. Therefore, the protection scope of the disclosed patent shall be subject to the attached claims.

Claims

1. An inkjet printer for coiled tubes in high temperature and high humidity environments, characterized in that: Including silicone modified acrylic resin, active diluent, photoinitiator, color paste, defoamer and leveling agent, The organosilicon-modified acrylic resin has the following structure:

2. The inkjet according to claim 1, characterized in that The viscosity of the silicone-modified acrylic resin is 300 cps to 500 cps; and / or, The n of the organosilicon-modified acrylic resin is 10-15.

3. The inkjet according to claim 1, characterized in that The preparation method of the organosilicon-modified acrylic resin comprises the following steps: Methyl hexahydrophthalic anhydride and neopentyl glycol are subjected to a ring-opening reaction to obtain a hydroxyl-terminated and carboxyl-terminated double-capped intermediate; The hydroxyl-terminated and carboxyl-terminated double-capped intermediate is cross-linked with vinyl isocyanate-modified silicone to obtain the silicone-modified acrylic resin.

4. The inkjet according to claim 3, characterized in that The mass ratio of the methyl hexahydrophthalic anhydride to the neopentyl glycol is 1:1; and / or, The temperature of the ring-opening reaction is 60° C. to 120° C., the time of the ring-opening reaction is 1 h to 4 h, and the reaction is terminated when the acid value of the ring-opening reaction is stabilized at 200 mgKOH / g to 210 mgKOH / g.

5. The inkjet according to claim 3, characterized in that The molecular weight of the silicone in the vinyl isocyanate-modified silicone is 900 g / mol to 1300 g / mol; and / or, The mass ratio of the vinyl isocyanate modified silicone to the hydroxyl-terminated and carboxyl-terminated double-capped intermediate is 1:3 to 1:4; and / or, The temperature of the cross-linking reaction is 60° C. to 90° C., the time of the cross-linking reaction is 4 hours to 8 hours, and the reaction is terminated when the NCO value of the cross-linking reaction decreases to 0% to 0.05%.

6. The inkjet according to claim 1, characterized in that In terms of mass fraction, the silicone-modified acrylic resin is 20 to 30 parts; the active diluent is 50 to 70 parts; the photoinitiator is 5 to 10 parts; the color paste is 1 to 5 parts; the defoamer is 0.1 to 0.5 parts; and the leveling agent is 0.1 to 0.5 parts.

7. The inkjet according to claim 6, characterized in that The viscosity of the inkjet is 10.0 cps to 50.0 cps; and / or, The particle size of the inkjet is 0.1 μm to 1.0 μm.

8. The inkjet according to claim 1, characterized in that The reactive diluent includes at least one of 3-methyl-1,5-pentanediol diacrylate and 1,6-hexanediol diacrylate; and / or, The photoinitiator is a type II photoinitiator; and / or, The color paste includes at least one of carbon black, aniline black and iron black; and / or, The defoamer comprises at least one of a polysiloxane defoamer and a modified siloxane defoamer; and / or, The leveling agent includes a modified siloxane leveling agent.

9. A coiled tube inkjet method, characterized in that: The specific steps include: Obtaining a freshly extruded substrate tube; The surface of the substrate tube is subjected to inkjet operation using the inkjet according to any one of claims 1 to 7 to obtain a semi-finished product; Pre-curing and deep-curing the semi-product in sequence to obtain a pipe; The pipe is rolled up while hot to obtain a coiled pipe.

10. A coiled tube, characterized in that: The invention is prepared by the coiled tube inkjet method as claimed in claim 9.

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