Retarding ink, preparation method and application thereof, and retarding film

Abstract

The invention discloses delayed coagulation ink, a preparation method and application thereof and a delayed coagulation film. The formula of the delayed coagulation ink provided by the invention comprises the compound retarder and the solvent type ink. The compound retarder contains a plurality of ester groups, has relatively large steric hindrance, can play an excellent retarding effect, and can prevent the diffusion of the cured retarding ink, avoid the distortion of the pattern formed by the retarding ink and improve the definition of the pattern of the concrete finished product when the concrete finished product is prepared. Solvent type printing ink is adopted as the retarding printing ink, and the manufactured pattern is not prone to distortion in the concrete pouring process. And a solvent type ink-jet printer can be adopted to prepare the delayed coagulation film in a transfer printing manner, so that the preparation efficiency of the delayed coagulation film is improved. The compatibility of the compound retarder and solvent type ink is good, and a retarding film prepared after combined action can be placed for a long time after curing treatment. In addition, a more efficient delayed coagulation membrane preparation process is adopted, the preparation time of the delayed coagulation membrane is shortened, and the preparation efficiency of the delayed coagulation membrane is improved.

Description

Technical Field

[0001] The invention relates to the technical field of building materials, in particular to a retarding ink and a preparation method and application thereof, and a retarding film. Background Art

[0002] Slow-setting ink has important applications in slow-setting imaging concrete technology. The retarder component it contains can delay the hydration process of concrete, thereby obtaining a customized pattern. The specific application scheme is: use the method of spraying slow-setting ink to print the pattern on a specially treated printing medium (base film), which is called a slow-setting film; then place the slow-setting film on a flat and smooth workbench with the slow-setting surface (pattern surface) facing up; then install the frame according to actual requirements and pour concrete; when the concrete reaches the final setting state, remove the slow-setting film and rinse the concrete surface with a high-pressure water gun, then the glue at the original slow-setting ink position will be washed away, exposing the aggregate; the color difference between the different colors of the aggregate and the glue can form a pattern.

[0003] In the related art, most of the retarding film production methods are to use screen printing to transfer the retarding ink coating to the base film, and obtain the retarding film product after the retarding ink coating is dried; or first add the retarder component to the paper pulp, then print the pattern on the surface of the pulp, and then apply a layer of water-soluble resin coating on the pattern surface of the paper to finally obtain the retarding film. The above methods all have the problem of too long cycle, which reduces the efficiency of retarding film preparation; and the retarding layer is prone to damage during storage and transportation. In addition, the retarder components in the existing retarding ink are mostly water-soluble, and the patterns produced by the retarder are prone to distortion during the pouring of concrete, reducing the beauty of the finished concrete product.

[0004] Therefore, providing a retarding ink that can keep the retarding layer from being easily damaged, avoid distortion of the pattern on the retarding film, and improve the clarity of the pattern on the finished concrete product, as well as a more efficient retarding film preparation process, has important practical significance and production value. Summary of the invention

[0005] The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the present invention proposes a slow-setting ink and a preparation method and application thereof, and a slow-setting film, aiming to solve the problems that when the current slow-setting ink is used to prepare the slow-setting film, the cycle is too long, the preparation efficiency is low, the slow-setting layer is easily damaged during storage and transportation, and the pattern of the slow-setting ink is easily distorted during the pouring of concrete.

[0006] In a first aspect of the present invention, a retarding ink is provided, comprising a compound retarder and a solvent-based ink; the compound retarder comprises, by weight, 20 to 30 parts of triethyl citrate, 15 to 40 parts of tributyl citrate, and 35 to 50 parts of trioctyl phosphate; the solvent-based ink comprises, by weight, 40 to 60 parts of epoxy acrylate resin, 5 to 15 parts of 4-methylbenzophenone, 20 to 30 parts of alkoxy acrylate, and 15 to 25 parts of pigment.

[0007] The retarding ink according to the embodiment of the present invention has at least the following beneficial effects: the retarding ink provided by the present invention is a curable retarding ink, and the formula includes a compound retarder and a solvent-based ink. The compound retarder is an ester-based compound retarder (including triethyl citrate, tributyl citrate and trioctyl phosphate). Since it contains multiple ester groups and has a large steric hindrance, the hydrolysis rate is relatively slow, so that a long-term slow release can be achieved. At the same time, the citric acid released by hydrolysis also has a certain retarding effect. The synergistic effect of the two can achieve an excellent retarding effect; when the above-mentioned compound retarder is added to the retarding ink and acts on the concrete surface, its retarding effect is relatively mild, will not react violently, and the retarded area will not spread, so it will not affect the hydration process of the concrete in the non-retarded area; when preparing the finished concrete product, the diffusion of the cured retarding ink can be prevented, and the pattern formed by the retarding ink can be avoided from being distorted, thereby improving the clarity of the pattern of the finished concrete product. In addition, the retarding ink uses solvent-based ink instead of water-soluble ink, so the pattern produced is not easily distorted during the pouring of concrete; and the retarding film can be prepared by transfer printing using a solvent-based inkjet printer, which reduces the preparation time of the retarding film and improves the preparation efficiency of the retarding film. Moreover, the above-mentioned compound retarder has good compatibility with the solvent-based ink, and the retarding film produced by their combined action can be placed for a long time (more than 3 months) after curing, which is more convenient for long-term storage and transportation, and has very important economic benefits and production value.

[0008] In some embodiments of the present invention, the mass ratio of the compound retarder to the solvent-based ink is (1.5-2.5):(7.5-8.5).

[0009] In some embodiments of the present invention, the pigment is an organic pigment.

[0010] The second aspect of the present invention provides a method for preparing a slow-setting ink, comprising the steps of:

[0011] S10, mixing triethyl citrate, tributyl citrate and trioctyl phosphate in parts by weight, stirring and mixing to obtain a composite retarder;

[0012] S20, mixing epoxy acrylate resin, 4-methylbenzophenone, alkoxy acrylate, and pigment in parts by weight, and stirring to obtain a solvent-based ink;

[0013] S30, mixing the compound retarder and the solvent-based ink, and stirring and mixing to obtain a retarding ink.

[0014] In some embodiments of the present invention, in step S10, 20 to 30 parts of triethyl citrate, 15 to 40 parts of tributyl citrate, and 35 to 50 parts of trioctyl phosphate are mixed, and stirred and mixed by a magnetic stirrer to obtain a composite retarder. Preferably, the rotor speed of the magnetic stirrer is 300 to 700 r / min, more preferably 450 to 500 r / min; the stirring time is 5 to 15 min, more preferably about 10 min.

[0015] In some embodiments of the present invention, in step S20, 40 to 60 parts of epoxy acrylate resin, 5 to 15 parts of 4-methylbenzophenone, 20 to 30 parts of alkoxy acrylate, and 15 to 25 parts of pigment are mixed, and stirred and mixed by a magnetic stirrer to obtain a solvent-based ink. Preferably, the rotor speed of the magnetic stirrer is 600 to 1000 r / min, more preferably 700 to 800 r / min; the stirring time is 10 to 20 min, more preferably about 15 min.

[0016] In some preferred embodiments of the present invention, the pigment is an organic pigment.

[0017] In some embodiments of the present invention, in step S30, the compound retarder and the solvent-based ink are mixed according to the ratio of compound retarder: solvent-based ink = (1.5-2.5): (7.5-8.5), and stirred and mixed by a magnetic stirrer to obtain a retarded ink. Preferably, the rotor speed of the magnetic stirrer is 400-800 r / min, more preferably 500-600 r / min; the stirring time is 5-15 min, more preferably about 10 min.

[0018] According to a third aspect of the present invention, a retarding film is provided, comprising a base film and a retarding ink cured on the surface of the base film; the retarding ink is prepared as described above or by the preparation method described above.

[0019] The retarding ink comprises a compound retarder and a solvent-based ink; the compound retarder comprises, by weight, 20 to 30 parts of triethyl citrate, 15 to 40 parts of tributyl citrate, and 35 to 50 parts of trioctyl phosphate; the solvent-based ink comprises, by weight, 40 to 60 parts of epoxy acrylate resin, 5 to 15 parts of 4-methylbenzophenone, 20 to 30 parts of alkoxy acrylate, and 15 to 25 parts of pigment.

[0020] The retarding film according to the embodiment of the present invention has at least the following beneficial effects: the retarding film provided by the present invention comprises a base film and a retarding ink solidified on the surface of the base film, and the formula of the retarding ink comprises a compound retarder and a solvent-based ink. The retarding ink of the present invention uses a solvent-based ink, rather than a water-soluble one, so it can be prepared by transfer printing using a solvent-based inkjet printer, which reduces the preparation time of the retarding film, improves the preparation efficiency of the retarding film, and keeps the retarding ink from being easily damaged during storage and transportation, and the pattern on the retarding film is not easily distorted during the pouring of concrete. Moreover, the retarding film adopts an ester-based composite retarder (including triethyl citrate, tributyl citrate and trioctyl phosphate), which contains multiple ester groups and has a large steric hindrance, and the hydrolysis rate is relatively slow, so that a long-term slow release can be achieved. At the same time, the citric acid released by hydrolysis also has a certain retarding effect. The synergistic effect of the two can achieve an excellent retarding effect; when the above-mentioned ester-based composite retarder is added to the retarding ink and acts on the concrete surface, its retarding effect is relatively mild, will not react violently, and the retarding area will not spread, and will not affect the hydration process of the concrete in the non-retarding area. The retarding film of the present invention adopts the process of curable retarding ink. When preparing the finished concrete product, the retarding ink after curing can be prevented from spreading, and the pattern on the retarding film is prevented from being distorted, thereby improving the clarity of the pattern of the finished concrete product. Moreover, the retarding film has good compatibility with the solvent-based ink. The retarding film can be placed for a long time (more than 3 months) after curing, which is more convenient for long-term storage and transportation.

[0021] In some embodiments of the present invention, the mass ratio of the compound retarder to the solvent-based ink is (1.5-2):(7.5-8.5).

[0022] In some embodiments of the present invention, the pigment is an organic pigment.

[0023] In some embodiments of the present invention, the base film comprises PP synthetic paper, glass paper, PVC film, or polyester film, preferably PP synthetic paper or glass paper.

[0024] At present, the base film used to prepare the slow-setting film is mostly pulp, which is easy to be damaged and susceptible to moisture. After being damp, the retarder will become ineffective and the slow-setting film cannot be used normally; and the surface of the pulp is relatively rough, which can easily reduce the texture of the pattern surface of the finished concrete product and affect the appearance. Based on this, the slow-setting film of the present invention changes the type of base film and adopts PP synthetic paper, glass paper and other paper with high tensile strength and smooth surface as the base film, which solves the problem of pulp being susceptible to moisture and facilitates the long-term storage and transportation of the slow-setting film; at the same time, PP synthetic paper, glass paper and the like have a smooth surface, which can also improve the smoothness of the surface of the finished concrete product, thereby improving the texture of the finished concrete product.

[0025] In some embodiments of the present invention, the slow-setting ink is cured on the surface of the base film by UV light curing. The present invention adopts a UV light curing slow-setting ink process, which can prevent the slow-setting ink from diffusing after curing when preparing the finished concrete product, avoid the distortion of the pattern on the slow-setting film, and thus improve the clarity of the pattern of the finished concrete product; and the slow-setting film after curing is more convenient for long-term storage and transportation.

[0026] In some embodiments of the present invention, the UV light is mainly ultraviolet light, the light source is an LED lamp, and the wavelength range is 320-400nm.

[0027] The role of conventional UV light curing is to isolate the concrete surface from the external environment, thereby improving the durability of the concrete; however, the slow-setting ink of the present invention, after UV light curing, can reduce the slow-setting rate of the slow-setting component in the slow-setting ink, so that the reaction rate of the slow-setting component with the concrete can be controlled, and then in the subsequent high-pressure water flushing process, the lines of the slow-setting area are made smoother, thereby improving the clarity of the slow-setting imaging concrete product.

[0028] The current method for making a retarding film is to transfer the retarder coating onto the base film by screen printing, and the finished retarding film is obtained after the retarder coating dries; or first add the retarder component into the paper pulp, then print the pattern on the surface of the pulp, and then apply a layer of water-soluble resin coating on the pattern surface of the paper to finally obtain the retarding film. The above retarding film production method has a long cycle, which reduces the efficiency of retarding film preparation; and the retarding layer is easily damaged during storage and transportation.

[0029] Based on this, the fourth aspect of the present invention provides a method for preparing the above-mentioned slow-setting film, comprising the steps of:

[0030] S10, mixing triethyl citrate, tributyl citrate and trioctyl phosphate in parts by weight, stirring and mixing to obtain a composite retarder;

[0031] S20, mixing epoxy acrylate resin, 4-methylbenzophenone, alkoxy acrylate, and pigment in parts by weight, and stirring to obtain a solvent-based ink;

[0032] S30, mixing the compound retarder and the solvent-based ink, and stirring and mixing to obtain a retarding ink;

[0033] S40, processing the pattern to be presented and mirror-flipping it to obtain a pattern to be printed;

[0034] S50, using a solvent-based inkjet printer to output the retarded setting ink onto the base film in the style of the pattern to be printed, and after the retarded setting ink is solidified, the retarded setting film is obtained.

[0035] Among them, S10 to S30 are the steps of preparing the slow-setting ink. If the slow-setting ink is already available, the preparation method of the slow-setting film only needs to include the following steps:

[0036] S40, processing the pattern to be presented and mirror-flipping it to obtain a pattern to be printed;

[0037] S50, using a solvent-based inkjet printer to output the retarded setting ink onto the base film in the style of the pattern to be printed, and after the retarded setting ink is solidified, the retarded setting film is obtained.

[0038] The method for preparing a retarding film according to an embodiment of the present invention has at least the following beneficial effects: the present invention eliminates the process step of coating a resin layer, adopts a more efficient retarding film preparation process, and utilizes a solvent-based inkjet printer to transfer and prepare the retarding film, thereby simplifying the process steps, reducing the preparation time of the retarding film, and at the same time reducing energy consumption, improving the preparation efficiency of the retarding film, and can keep the retarding ink from being easily damaged during storage and transportation.

[0039] In some embodiments of the present invention, in step S50, while the slow-setting ink is output onto the base film in the style of the pattern to be printed, the slow-setting ink on the surface of the base film is cured by UV light. The present invention uses a UV light curing process to cure the slow-setting ink pattern, which can prevent the slow-setting ink from diffusing after curing when preparing the finished concrete product, avoid distortion of the pattern on the slow-setting film, and thus improve the clarity of the pattern of the finished concrete product; and the slow-setting film after curing is more convenient for long-term storage and transportation.

[0040] In some embodiments of the present invention, the light source of the UV light (ultraviolet light) is an LED lamp with a wavelength range of 320 to 400 nm.

[0041] In some embodiments of the present invention, the base film comprises PP synthetic paper, glass paper, PVC film, or polyester film, preferably PP synthetic paper or glass paper.

[0042] In some embodiments of the present invention, in step S10, 20 to 30 parts of triethyl citrate, 15 to 40 parts of tributyl citrate, and 35 to 50 parts of trioctyl phosphate are mixed, and stirred and mixed by a magnetic stirrer to obtain a composite retarder. Preferably, the rotor speed of the magnetic stirrer is 300 to 700 r / min, more preferably 450 to 500 r / min; the stirring time is 5 to 15 min, more preferably about 10 min.

[0043] In some embodiments of the present invention, in step S20, 40 to 60 parts of epoxy acrylate resin, 5 to 15 parts of 4-methylbenzophenone, 20 to 30 parts of alkoxy acrylate, and 15 to 25 parts of pigment are mixed, and stirred and mixed by a magnetic stirrer to obtain a solvent-based ink. Preferably, the rotor speed of the magnetic stirrer is 600 to 1000 r / min, more preferably 700 to 800 r / min; the stirring time is 10 to 20 min, more preferably about 15 min.

[0044] In some embodiments of the present invention, in step S30, the compound retarder and the solvent-based ink are mixed according to the ratio of compound retarder: solvent-based ink = (1.5-2): (7.5-8.5), and stirred and mixed by a magnetic stirrer to obtain a retarded ink. Preferably, the rotor speed of the magnetic stirrer is 400-800 r / min, more preferably 500-600 r / min; the stirring time is 5-15 min, more preferably about 10 min.

[0045] In some embodiments of the present invention, in step S40, the pattern to be presented is processed by image processing software, and the pixels are adjusted and the image is flipped to obtain the pattern to be printed. The image processing software can be commonly used software and is not limited here.

[0046] In some embodiments of the present invention, in step S50, a base film (e.g., PP synthetic paper) is spread flat on the operating table of a solvent inkjet printer, and the retarding ink is injected into the ink cartridge of the solvent inkjet printer. The solvent inkjet printer is used to output the retarding ink to the base film in the style of a pattern to be printed, with a printing thickness of 1 layer. While the pattern is being printed, UV light (ultraviolet light) is used to perform a unidirectional printing operation to solidify the retarding ink on the surface of the base film, thereby obtaining the retarding film.

[0047] In some embodiments of the present invention, the slow-setting ink can be printed onto the base film once or multiple times, that is, the printing thickness can be ≥ 1 layer, which can be adjusted according to the pattern and is not limited here.

[0048] The fifth aspect of the present invention provides a use of the above-mentioned slow-setting ink or the above-mentioned slow-setting film in the preparation of slow-setting imaging concrete.

[0049] In a sixth aspect of the present invention, a slow-setting imaging concrete is provided, wherein the raw material of the slow-setting imaging concrete is the slow-setting ink or the slow-setting film mentioned above.

[0050] The slow-setting imaging concrete according to the embodiment of the present invention has at least the following beneficial effects: the slow-setting imaging concrete provided by the present invention includes the above-mentioned slow-setting ink or the above-mentioned slow-setting film, and therefore also has the beneficial effects of the above-mentioned slow-setting ink or the slow-setting film: when preparing the finished concrete product, the slow-setting film of the process of curing the slow-setting ink can prevent the slow-setting ink from diffusing after curing, avoid the distortion of the pattern on the slow-setting film, and thus improve the clarity of the pattern of the finished concrete product; the slow-setting film can be prepared by transfer printing using a solvent-based inkjet printer, which reduces the preparation time of the slow-setting film and improves the preparation efficiency of the slow-setting film, and the slow-setting ink is not easily damaged during storage and transportation, and the pattern on the slow-setting film is not easily distorted during the pouring of concrete; and the compound retarder in the slow-setting film has good compatibility with the solvent-based ink, and the slow-setting film can be placed for a long time (more than 3 months) after curing, which is more convenient for long-term storage and transportation.

[0051] The seventh aspect of the present invention provides a method for preparing slow-setting imaging concrete, comprising the steps of:

[0052] S100, printing the above-mentioned slow-setting ink onto the base film to obtain a slow-setting film, with the pattern side of the slow-setting ink facing upwards, laying the slow-setting film flat inside the mold and fixing it, or directly laying the above-mentioned slow-setting film flat inside the mold with the pattern side facing upwards and fixing it;

[0053] S200, mixing and stirring the raw materials of the slow-setting concrete according to a predetermined weight ratio, and pouring the mixture into a mold;

[0054] S300, after a predetermined standard curing period, the mold is removed, the slow-setting film on the concrete surface is removed, and high-pressure water flushing is performed to obtain the slow-setting imaging concrete.

[0055] In some embodiments of the present invention, in step S100, the method for preparing the retarding film may be performed according to steps S10 to S50, or a retarding film obtained by other methods may be used.

[0056] In some embodiments of the present invention, in step S100, the pattern surface of the retarding ink is facing upward, the retarding film is spread flat inside the mold, the air between the retarding film and the mold is exhausted, and the retarding film is fixed to the mold.

[0057] In some embodiments of the present invention, in step S200, the raw materials and weight proportions of the slow-setting imaging concrete can adopt the common concrete formula in the field, or any reasonable formula of self-proportioning, and are not limited here. As one example, the raw materials of the slow-setting imaging concrete include 30-45 parts of white cement, 10-20 parts of metakaolin, 15-30 parts of 0.6-0.7mm corundum, 25-40 parts of 0.3-0.4mm corundum, 5-15 parts of 0.1-0.2mm corundum, 0.05-0.1 parts of thickener, 0.05-0.1 parts of early strength agent, 0.05-0.1 parts of silicon-based defoamer, 0.05-0.1 parts of water reducer, and the water-cement ratio is 0.22-0.30.

[0058] In some embodiments of the present invention, in step S300, the curing is performed in a standard curing room for 6 to 10 hours, preferably about 8 hours. BRIEF DESCRIPTION OF THE DRAWINGS

[0059] The present invention will be further described below with reference to the accompanying drawings and embodiments, wherein:

[0060] Figure 1 The pattern of the retarding film product prepared in Example 1 of the present invention;

[0061] Figure 2 The pattern of the slow-setting imaging concrete product corresponding to the slow-setting membrane prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0062] The following will be combined with the embodiments to clearly and completely describe the concept of the present invention and the technical effects produced, so as to fully understand the purpose, characteristics and effects of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, other embodiments obtained by those skilled in the art without creative work are all within the scope of protection of the present invention.

[0063] In the description of the present invention, the description with reference to the terms "one embodiment", "some embodiments", "illustrative embodiments", "examples", "specific examples", or "some examples" means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner.

[0064] If no specific techniques or conditions are specified in the following examples, the techniques or conditions described in the literature in the art or the product instructions are used. All reagents or instruments without manufacturer specified are conventional products that can be purchased commercially.

[0065] Example 1

[0066] The retarding ink consists of 20 wt. % of a compound retarder and 80 wt. % of a solvent-based ink.

[0067] The composition of the compound retarder is: 50g of triethyl citrate, 50g of tributyl citrate, and 100g of trioctyl phosphate; the composition of the solvent-based ink is: 400g of epoxy acrylate resin, 50g of 4-methylbenzophenone, 200g of alkoxy acrylate, and 150g of organic pigment.

[0068] The specific steps of the preparation process of the slow setting film are:

[0069] 1) Preparation of compound retarder: 50 g of triethyl citrate, 50 g of tributyl citrate and 100 g of trioctyl phosphate were placed in a glass beaker, stirred with a magnetic stirrer, the rotor speed was set to 500 r / min, and stirred for 10 min;

[0070] 2) Prepare solvent-based ink: put 400g of epoxy acrylate resin, 50g of 4-methylbenzophenone, 200g of alkoxy acrylate and 150g of organic pigment in a glass beaker, stir with a magnetic stirrer, set the rotor speed to 800r / min, and stir for 15min;

[0071] 3) Preparation of retarding ink: 200 g of ester-based composite retarder and 800 g of solvent-based ink were placed in a glass beaker, stirred with a magnetic stirrer, the rotor speed was set to 600 r / min, and stirred for 10 min;

[0072] 4) Pattern processing: Use image processing software to process the desired pattern, adjust the pixels and flip the image to obtain the pattern style to be printed;

[0073] 5) Pattern printing and back-end processing: Spread the base film (PP synthetic paper) flat on the operating table of the solvent inkjet printer, inject the retarding ink into the ink cartridge of the solvent inkjet printer, and use the solvent inkjet printer to output the retarding ink to the base film according to the pattern to be printed, with a printing thickness of 1 layer; while printing the pattern, use UV light (ultraviolet light, wavelength range of 350-400nm) for unidirectional printing operation to cure the retarding ink on the surface of the base film to obtain a retarding film, which takes about 5 minutes.

[0074] Example 2

[0075] The retarding ink consists of 17 wt. % of a compound retarder and 83 wt. % of a solvent-based ink.

[0076] The composition of the compound retarder is: 45g of triethyl citrate, 60g of tributyl citrate, and 95g of trioctyl phosphate; the composition of the solvent-based ink is: 440g of epoxy acrylate resin, 65g of 4-methylbenzophenone, 180g of alkoxy acrylate, and 155g of organic pigment.

[0077] The specific steps of the preparation process of the slow setting film are:

[0078] 1) Preparation of compound retarder: 45 g of triethyl citrate, 60 g of tributyl citrate and 95 g of trioctyl phosphate were placed in a glass beaker, stirred with a magnetic stirrer, the rotor speed was set to 450 r / min, and stirred for 10 min;

[0079] 2) Prepare solvent-based ink: put 440g of epoxy acrylate resin, 65g of 4-methylbenzophenone, 180g of alkoxy acrylate and 155g of organic pigment in a glass beaker, stir with a magnetic stirrer, set the rotor speed to 700r / min, and stir for 15min;

[0080] 3) Prepare retarding ink: put 170g of ester-based composite retarder and 830g of solvent-based ink in a glass beaker, stir with a magnetic stirrer, set the rotor speed to 500r / min, and stir for 10min;

[0081] 4) Pattern processing: Use image processing software to process the desired pattern, adjust the pixels and flip the image to obtain the pattern style to be printed;

[0082] 5) Pattern printing and back-end processing: Spread the base film (cellophane) flat on the operating table of the solvent inkjet printer, inject the retarding ink into the ink cartridge of the solvent inkjet printer, and use the solvent inkjet printer to output the retarding ink to the base film according to the pattern to be printed, with a printing thickness of 2 layers; while printing the pattern, use UV light (ultraviolet light, wavelength range of 320 ~ 360nm) for unidirectional printing operation to cure the retarding ink on the surface of the base film to obtain a retarding film, which takes about 6 minutes.

[0083] Example 3

[0084] The retarding ink consists of 25 wt. % of a compound retarder and 75 wt. % of a solvent-based ink.

[0085] The composition of the compound retarder is: 40g of triethyl citrate, 60g of tributyl citrate, and 100g of trioctyl phosphate; the composition of the solvent-based ink is: 430g of epoxy acrylate resin, 70g of 4-methylbenzophenone, 180g of alkoxy acrylate, and 160g of organic pigment.

[0086] The specific steps of the preparation process of the slow setting film are:

[0087] 1) Preparation of compound retarder: 40 g of triethyl citrate, 60 g of tributyl citrate and 100 g of trioctyl phosphate were placed in a glass beaker, stirred with a magnetic stirrer, the rotor speed was set to 450 r / min, and stirred for 10 min;

[0088] 2) Prepare solvent-based ink: put 430g of epoxy acrylate resin, 70g of 4-methylbenzophenone, 180g of alkoxy acrylate and 160g of organic pigment in a glass beaker, stir with a magnetic stirrer, set the rotor speed to 700r / min, and stir for 15min;

[0089] 3) Prepare retarding ink: put 170g of ester-based composite retarder and 830g of solvent-based ink in a glass beaker, stir with a magnetic stirrer, set the rotor speed to 500r / min, and stir for 10min;

[0090] 4) Pattern processing: Use image processing software to process the desired pattern, adjust the pixels and flip the image to obtain the pattern style to be printed;

[0091] 5) Pattern printing and back-end processing: Spread the base film (cellophane) flat on the operating table of the solvent inkjet printer, inject the retarding ink into the ink cartridge of the solvent inkjet printer, and use the solvent inkjet printer to output the retarding ink to the base film according to the pattern to be printed, with a printing thickness of 2 layers; while printing the pattern, use UV light (ultraviolet light, wavelength range of 320 ~ 360nm) for unidirectional printing operation to cure the retarding ink on the surface of the base film to obtain a retarding film, which takes about 6 minutes.

[0092] Comparative Example 1

[0093] The difference between Comparative Example 1 and Example 1 is that the retarder is not an ester-based composite retarder.

[0094] The retarding ink is composed of 20 wt. % of retarder and 80 wt. % of solvent-based ink.

[0095] The retarder composition is: 70g of ethylene glycol and 130g of propylene glycol; the solvent-based ink composition is: 400g of epoxy acrylate resin, 50g of 4-methylbenzophenone, 200g of alkoxy acrylate and 150g of organic pigment.

[0096] The specific steps of the preparation process of the slow setting film are:

[0097] 1) Preparation of retarder: Place 70 g of ethylene glycol and 130 g of glycerol in a glass beaker, stir with a magnetic stirrer, set the rotor speed to 500 r / min, and stir for 10 min;

[0098] 2) Prepare solvent-based ink: put 400g of epoxy acrylate resin, 50g of 4-methylbenzophenone, 200g of alkoxy acrylate and 150g of organic pigment in a glass beaker, stir with a magnetic stirrer, set the rotor speed to 800r / min, and stir for 15min;

[0099] 3) Preparation of retarding ink: 200 g of retarder and 800 g of solvent-based ink were placed in a glass beaker, stirred with a magnetic stirrer, the rotor speed was set to 600 r / min, and stirred for 10 min;

[0100] 4) Pattern processing: Use image processing software to process the desired pattern, adjust the pixels and flip the image to obtain the pattern style to be printed;

[0101] 5) Pattern printing and back-end processing: Spread the base film (PP synthetic paper) flat on the operating table of the solvent inkjet printer, inject the retarding ink into the ink cartridge of the solvent inkjet printer, and use the solvent inkjet printer to output the retarding ink to the base film according to the pattern to be printed, with a printing thickness of 1 layer; while printing the pattern, use UV light (ultraviolet light, wavelength range of 350-400nm) for unidirectional printing operation to cure the retarding ink on the surface of the base film to obtain a retarding film, which takes about 5 minutes.

[0102] Comparative Example 2

[0103] The difference between Comparative Example 2 and Example 1 is that the ink is not a solvent-based ink but a water-based ink.

[0104] The retarding ink consists of 20 wt.% of a compound retarder and 80 wt.% of an aqueous ink.

[0105] The composition of the compound retarder is: 50g of triethyl citrate, 50g of tributyl citrate, and 100g of trioctyl phosphate; the composition of the water-based ink is: 30g of epoxy acrylate resin, 30g of 4-methylbenzophenone, 30g of alkoxy acrylate, 700g of ethanol, and 10g of water-based pigment.

[0106] The specific steps of the preparation process of the slow setting film are:

[0107] 1) Preparation of compound retarder: 50 g of triethyl citrate, 50 g of tributyl citrate and 100 g of trioctyl phosphate were placed in a glass beaker, stirred with a magnetic stirrer, the rotor speed was set to 500 r / min, and stirred for 10 min;

[0108] 2) Prepare water-based ink: put 30g of epoxy acrylate resin, 30g of 4-methylbenzophenone, 30g of alkoxy acrylate, 700g of ethanol and 10g of water-based pigment in a glass beaker, stir with a magnetic stirrer, set the rotor speed to 800r / min, and stir for 15min;

[0109] 3) Preparation of retarding ink: 200 g of ester-based composite retarder and 800 g of water-based ink were placed in a glass beaker, stirred with a magnetic stirrer, the rotor speed was set to 600 r / min, and stirred for 10 min;

[0110] 4) Pattern processing: Use image processing software to process the desired pattern, adjust the pixels and flip the image to obtain the pattern style to be printed;

[0111] 5) Pattern printing and back-end processing: Spread the base film (PP synthetic paper) flat on the operating table of the solvent inkjet printer, inject the retarding ink into the ink cartridge of the solvent inkjet printer, and use the solvent inkjet printer to output the retarding ink to the base film according to the pattern to be printed, with a printing thickness of 1 layer; while printing the pattern, use UV light (ultraviolet light, wavelength range of 350-400nm) for unidirectional printing operation to cure the retarding ink on the surface of the base film to obtain a retarding film, which takes about 5 minutes.

[0112] Comparative Example 3

[0113] The difference between Comparative Example 3 and Example 1 is that the ratio of the compound retarder to the solvent-based ink is 30:70.

[0114] The retarding ink consists of 30 wt. % of a compound retarder and 70 wt. % of a solvent-based ink.

[0115] The composition of the compound retarder is: 100g of triethyl citrate, 100g of tributyl citrate, and 200g of trioctyl phosphate; the composition of the solvent-based ink is: 400g of epoxy acrylate resin, 50g of 4-methylbenzophenone, 200g of alkoxy acrylate, and 150g of organic pigment.

[0116] The specific steps of the preparation process of the slow setting film are:

[0117] 1) Preparation of compound retarder: 100 g of triethyl citrate, 100 g of tributyl citrate and 200 g of trioctyl phosphate were placed in a glass beaker, stirred with a magnetic stirrer, the rotor speed was set to 500 r / min, and stirred for 10 min;

[0118] 2) Prepare solvent-based ink: put 400g of epoxy acrylate resin, 50g of 4-methylbenzophenone, 200g of alkoxy acrylate and 150g of organic pigment in a glass beaker, stir with a magnetic stirrer, set the rotor speed to 800r / min, and stir for 15min;

[0119] 3) Preparation of retarding ink: 300 g of ester-based composite retarder and 700 g of solvent-based ink were placed in a glass beaker, stirred with a magnetic stirrer, the rotor speed was set to 600 r / min, and stirred for 10 min;

[0120] 4) Pattern processing: Use image processing software to process the desired pattern, adjust the pixels and flip the image to obtain the pattern style to be printed;

[0121] 5) Pattern printing and back-end processing: Spread the base film (PP synthetic paper) flat on the operating table of the solvent inkjet printer, inject the retarding ink into the ink cartridge of the solvent inkjet printer, and use the solvent inkjet printer to output the retarding ink to the base film according to the pattern to be printed, with a printing thickness of 1 layer; while printing the pattern, use UV light (ultraviolet light, wavelength range of 350-400nm) for unidirectional printing operation to cure the retarding ink on the surface of the base film to obtain a retarding film, which takes about 5 minutes.

[0122] Comparative Example 4

[0123] The retarding ink ratio is: 25wt% water-based pigment and 75wt% retarder.

[0124] The composition of the retarder is as follows: 13 g of sodium gluconate, 15 g of sodium citrate, 2 g of sodium metaphosphate, and 75 g of distilled water;

[0125] The specific steps of the preparation process of the slow setting film are:

[0126] 1) Preparation of retarder: Place 13g sodium gluconate, 15g sodium citrate, 2g sodium metaphosphate and 75g distilled water in a glass beaker, stir with a magnetic stirrer, set the rotor speed to 500r / min, and stir for 15min;

[0127] 2) Make slow-setting ink: put 75g of retarder and 25g of water-based pigment in a glass beaker, stir with a magnetic stirrer, set the rotor speed to 450r / min, and stir for 10min;

[0128] 3) Digital image processing: Use image processing software to process the digital image to be presented, adjust the pixels and flip the image to obtain the pattern style;

[0129] 4) Making a slow-setting film: Outputting the slow-setting ink onto the base film (PP synthetic paper) according to the pattern to obtain a slow-setting film;

[0130] 5) Dry the slow-setting film: Place the slow-setting film in a ventilated and dry environment for 4 hours to dry the surface.

[0131] Comparative Example 5

[0132] The retarder is added into paper pulp to be made into a retarding base film through papermaking, and a pattern is added on the surface of the retarding base film to make a retarding film.

[0133] The composition of the retarder is as follows: 6 g sodium phosphate, 6 g sodium gluconate, 2 g sodium lignin sulfonate, and 80 g distilled water.

[0134] The specific steps of the preparation process of the slow setting film are:

[0135] The compounded retarder is added into the paper pulp at 0.5% of the pulp mass, and then made into 200g / m 2 The retarding base film is a retarding base film. During production, a UV printer is used to print the pattern to be transferred on the base film, and the pattern area is smaller than the base film area. A layer of acrylic resin coating is applied on the UV printed surface of the paper (to increase the time for the moisture in the concrete to wet the base film), and the retarding film is obtained.

[0136] Comparative Example 6

[0137] The super slow-release water-reducing agent is used as a slow-setting ink. A printer is used to transfer the super slow-release water-reducing agent to the surface of PP synthetic paper in the form of a pattern to obtain a slow-setting film.

[0138] The specific steps of the preparation process of the slow setting film are:

[0139] 1) First, place 15g of triethyl citrate in a three-necked flask, use dichloromethane (DCM) as solvent, then add triethylamine (the mass of triethylamine is equimolar to methacryloyl chloride), slowly drop acryloyl chloride (dissolved in dichloromethane) in an ice bath, the molar ratio of acryloyl chloride to triethyl citrate is 1:1.3; about 1 hour after the dropwise addition, raise the temperature to 25°C, stir for 5 hours, and filter. The product after the above reaction is washed with distilled water 3 times, then dehydrated with anhydrous magnesium sulfate, filtered, and distilled. The reddish-brown liquid obtained at this time is triethyl citrate with polymerizable double bonds;

[0140] 2) Add 0.3g of H2O2 to a three-necked flask containing 25g of methyl allyl polyoxyethylene ether and 44.7g of water, and heat to 45°C. Slowly drop a certain proportion of mixed solution A (0.15g of thioglycolic acid, 0.12g of Vc and a small amount of water) and a certain proportion of mixed solution B (3g of acrylic acid (AA, 9% to 15% of the mass of the polyether macromonomer), 1.82g of triethyl citrate with polymerizable double bonds and a small amount of water) into the above device at the same time, and finally obtain a super slow-release water reducer with a solid content of 40%;

[0141] 3) Use the super slow-release water reducer as the retarding ink, and use a printer to transfer the super slow-release water reducer to the surface of the PP synthetic paper in the form of a pattern to obtain a retarding film. Place the retarding film in a cool place for 6 hours until the water in the super slow-release water reducer is dried.

[0142] Test Case

[0143] The retarding films of Examples 1-3 and Comparative Examples 1-6 were laid flat inside the mold with the patterned surface facing upwards, the air between the retarding film and the mold was exhausted, and the retarding film was fixed to the mold, and then concrete was poured; after curing in a standard curing room for 8 hours, the mold was removed, the retarding film on the concrete surface was torn off, and the concrete surface was flushed with high-pressure water to obtain the corresponding retarding imaged concrete.

[0144] The preparation process of concrete is as follows: put 1275g of white cement, 225g of metakaolin, 450g of corundum with a size of 0.6-0.7mm, 900g of corundum with a size of 0.3-0.4mm, and 150g of corundum with a size of 0.1-0.2mm into a mixer and pre-mix the dry powder at a low speed (100r / min) for 3min; add 840g of water and 24g of water reducer and stir at a medium speed (166r / min) for 1min; finally, add 4.5g of hydroxypropyl methylcellulose, 15g of nanocrystalline nucleating agent and 15g of silicon-based defoaming agent and stir quickly (360r / min) for 2min; and slowly pour the stirred concrete into a mold.

[0145] The picture of the finished slow-setting film prepared in Example 1 is as follows: Figure 1 As shown, the pattern of the corresponding slow-setting concrete is as follows Figure 2 As shown in the figure, the lines in the slow-setting area of ​​the image are smooth, the slow-setting ink has not spread, the pattern on the slow-setting film has not been distorted, and the clarity of the finished concrete pattern is high, and the quality is good.

[0146] The slow-setting inks, slow-setting films and slow-setting imaging concrete prepared in Examples 1-3 and Comparative Examples 1-6 were tested, including the following test items:

[0147] 1. Test the diffusion of retarding ink: Use a solvent-based inkjet printer to print a circle with a diameter of 10 mm on the retarding film. After pouring concrete and curing for 8 hours, remove the film and flush with water to obtain a retarding imaging concrete product. Use a vernier caliper to measure the diameter and depth of the circle on the surface of the finished product to reflect the diffusion of the retarding ink;

[0148] 2. Test the moisture resistance of the slow-setting film: Use a solvent-based inkjet printer to apply the slow-setting ink to the slow-setting film to prepare an A4-sized slow-setting film. Place the prepared slow-setting film in a curing room with a humidity of 95±5% and a temperature of 20±2℃. At the same time, place a blank slow-setting film base film as a reference sample. The standing time is 24 hours. Weigh the mass of the reference sample base film before standing, the mass of the reference sample base film after standing, and the mass of the test sample slow-setting film before standing, m0. x And the mass M of the retarding film of the test sample after standing x , then the water absorption rate of the slow setting film = [(M x -M0)-(m x -m0)]÷m0×100%;

[0149] 3. Test the adsorption between the retarding ink and the base film: Use a solvent-based inkjet printer to apply the retarding ink to the retarding film, prepare an A4-sized retarding film, pour concrete on the retarding film, and place the concrete in a curing room with a humidity of 95±5% and a temperature of 20±2°C for 24 hours. After curing, slowly tear off the retarding film, observe the surface of the finished concrete, observe the residual retarding ink on the surface of the finished concrete, and use the residual retarding ink area percentage to refer to the adsorption between the retarding ink and the base film (the less the retarding ink residue, the higher the adsorption). The clarity, surface texture and other properties are the observation results.

[0150] The performance test results obtained are shown in Tables 1, 2 and 3 below:

[0151] Table 1:

[0152]

[0153] Table 2:

[0154]

[0155] Table 3:

[0156]

[0157] In summary, the slow-setting ink formula provided by the present invention is not easy to spread, and the formed pattern is not easy to be distorted; the obtained slow-setting film is not easy to be affected by moisture, and the adsorption force between the slow-setting ink and the base film is relatively high. When used to prepare finished concrete products, the slow-setting area will not spread, the exposed aggregate is small, the touch is gentle, and the texture is excellent; the pattern of the finished concrete product has high clarity, the pattern boundary is smooth, and the surface texture is excellent. In addition, the present invention also reduces the preparation time of the slow-setting film and improves the preparation efficiency of the slow-setting film.

[0158] The above-mentioned embodiments only express several implementation methods of the present invention, and the description thereof is relatively specific and detailed, but it cannot be understood as limiting the scope of the present invention. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention.

Claims

1. A slow-setting ink, characterized in that: Including compound retarders and solvent-based inks; The composition of the composite retarder includes, by weight: 20 to 30 parts of triethyl citrate, 15 to 40 parts of tributyl citrate, and 35 to 50 parts of trioctyl phosphate; The solvent-based ink comprises, by weight, 40 to 60 parts of epoxy acrylate resin, 5 to 15 parts of 4-methylbenzophenone, 20 to 30 parts of alkoxy acrylate, and 15 to 25 parts of pigment.

2. The slow-setting ink according to claim 1, characterized in that: The mass ratio of the compound retarder to the solvent-based ink is (1.5-2.5):(7.5-8.5).

3. A method for preparing the slow-setting ink according to any one of claims 1 to 2, characterized in that: Includes steps: Mix triethyl citrate, tributyl citrate and trioctyl phosphate according to weight proportions, and stir to obtain a composite retarder; Mix epoxy acrylate resin, 4-methylbenzophenone, alkoxy acrylate and pigment according to weight proportions, and stir to obtain solvent-based ink; The compound retarder and the solvent-based ink are mixed and stirred to obtain the retarded ink.

4. A slow-setting film, characterized in that: It comprises a base film and a slow-setting ink solidified on the surface of the base film; the slow-setting ink is prepared as described in any one of claims 1-2 or by the preparation method described in claim 3.

5. The slow-setting film according to claim 4, characterized in that: The base film includes PP synthetic paper, glassine paper, PVC film, or polyester film.

6. The slow-setting film according to claim 4, characterized in that: Using UV light curing to cure the slow-setting ink on the surface of the base film; Preferably, the light source of the UV light is an LED lamp with a wavelength range of 320 to 400 nm.

7. A method for preparing a retarding film according to any one of claims 4 to 6, characterized in that: Includes steps: After processing the pattern to be presented and mirror-flipping it, a pattern to be printed is obtained; The retarding ink according to any one of claims 1 to 2 is output onto the base film according to the pattern to be printed by using a solvent-based inkjet printer, and the retarding film is obtained after the retarding ink is solidified.

8. The method for preparing a slow-setting film according to claim 7, characterized in that: Outputting the slow-setting ink onto the base film in the style of the pattern to be printed, and curing the slow-setting ink on the surface of the base film by using UV light; Preferably, the light source of the UV light is an LED lamp with a wavelength range of 320 to 400 nm.

9. Use of the slow-setting ink as claimed in any one of claims 1 to 2 or the slow-setting film as claimed in any one of claims 4 to 6 in preparing slow-setting imaging concrete.

10. A slow-setting concrete, characterized in that: The raw material of the slow-setting imaging concrete includes the slow-setting ink as described in any one of claims 1 to 2 or the slow-setting film as described in any one of claims 4 to 6.

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