High strength water flag film

Abstract

The application provides a high-strength water mark film, relates to the technical field of pattern water transfer printing, and the high-strength water mark film comprises, from bottom to top, a blending base layer, a water-soluble layer, a bonding layer and an image receiving layer. The thickness of the blending base layer is 120-140 microns, and the blending base layer comprises the following components in parts by mass: 10-30 parts of a polar high polymer material, 70-90 parts of a non-polar high polymer material and 2-7 parts of a hydrophilic high polymer material. The high-strength water mark film has high precision and high stability in the water transfer printing process.

Description

Technical Field

[0001] This invention relates to the field of pattern water transfer printing technology, specifically to a high-strength water-marking film. Background Technology

[0002] Water transfer printing is a decorative process that uses water to transfer printed patterns onto the surface of three-dimensional objects. It is widely used for surface decoration of ceramics, glass, plastics, metals, and composite materials. Water transfer film, as the medium carrying the pattern, is one of its most critical consumables. Traditional water transfer films typically use a paper base as a support, coated with a water-soluble adhesive layer. During use, the paper with the printed pattern is immersed in water; after the adhesive layer dissolves and wets, the pattern layer separates from the paper base and is then transferred to the target workpiece surface. However, the paper base of traditional paper-based water transfer films is composed of natural plant fibers. After immersion in water, the fibers absorb water and swell dramatically, causing irreversible deformation and stretching of the pattern. This severely affects the dimensional accuracy and registration accuracy of the transferred pattern, making it difficult to meet high-precision decorative requirements.

[0003] To address the aforementioned issues, some researchers have attempted to use polymer films to replace paper substrates. While pure organic polymer films offer good dimensional stability, they struggle to simultaneously meet the dual requirements of water transfer printing processes for both water permeability and stiffness of the support.

[0004] Therefore, developing a polymer film with both high water permeability and suitable stiffness to replace the existing paper base and achieve high precision, high stability and high efficiency in the water transfer printing process is a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides a high-strength water-marking film, which solves the technical problem that existing pure organic polymer films cannot simultaneously meet the dual requirements of water transfer printing processes for the water permeability and stiffness of the support.

[0006] To achieve the above objectives, the present invention provides the following technical solution:

[0007] This invention provides a high-strength water level membrane, which comprises, from bottom to top: a blended base layer, a water-soluble layer, an adhesive layer, and an image receiving layer;

[0008] The thickness of the blended base layer is 120-140 μm, and the blended base layer comprises the following components in parts by weight:

[0009] 10-30 parts of polar polymer materials;

[0010] 70-90 parts of nonpolar polymer materials;

[0011] 2-7 parts of hydrophilic polymer material.

[0012] Preferably, the blended base layer further includes inorganic particles, the amount of which is 10-15% of the total mass of the polar polymer material and the non-polar polymer material.

[0013] Preferably, the inorganic particles are selected from water-soluble inorganic particles and / or non-water-soluble fibrous inorganic particles.

[0014] Preferably, the mass ratio of the water-soluble inorganic particles to the insoluble fibrous inorganic particles is 2-5:1.

[0015] Preferably, the water-soluble inorganic particles are selected from at least one of sodium carbonate, potassium chloride, ammonium sulfate, magnesium chloride, sodium chloride, potassium nitrate, and sodium sulfate.

[0016] Preferably, the non-water-soluble fibrous inorganic particles are selected from at least one of wollastonite and calcium sulfate whiskers.

[0017] Preferably, the aspect ratio of the non-water-soluble fibrous inorganic particles is 15-20:1.

[0018] Preferably, the polar polymer material is selected from polyethylene terephthalate, polybutylene terephthalate, or polymethyl methacrylate.

[0019] Preferably, the nonpolar polymer material is selected from any one of polypropylene, polyethylene, and polyisobutylene.

[0020] Preferably, the hydrophilic polymer material is selected from any one of polyethylene glycol, polyvinyl alcohol, and polyvinylpyrrolidone.

[0021] Compared with existing technologies, it has the following beneficial effects:

[0022] 1. This invention provides a high-strength water level membrane, comprising, from bottom to top: a blended base layer, a water-soluble layer, an adhesive layer, and an image receiving layer; the thickness of the blended base layer is 120-140 μm, and the blended base layer comprises the following components in parts by weight: 10-30 parts of polar polymer material, 70-90 parts of non-polar polymer material, and 2-7 parts of hydrophilic polymer material; the blended base layer also includes inorganic particles, the amount of which is 10-15% of the total mass of the polar polymer material and the non-polar polymer material.

[0023] The aforementioned high-strength water level membrane's blended base layer comprises polar polymer materials, non-polar polymer materials, and inorganic particles. It possesses high strength, but the interfacial bonding between the polar and non-polar polymer materials is extremely weak. Microscopic gaps exist at the contact points between the polar and non-polar polymer materials in the blended base membrane. Simultaneously, the interface between the organic polymer materials and inorganic particles is incompatible, also resulting in interfacial gaps in the blended base membrane. Under tensile conditions of 60-70℃ and a stretch of 2-4 times, these microscopic gaps between the polar and non-polar polymer materials are widened, forming a microcrack network. Stress concentrates at the interface between the organic polymer materials and inorganic particles, causing separation between the organic polymer matrix and the inorganic particles, thus forming pores in situ. The microcrack network and pores improve the permeability of the blended base layer. Furthermore, the hydrophilic polymer material enhances the hydrophilicity of the blended base layer.

[0024] 2. The inorganic particles in this invention are selected from water-soluble inorganic particles and / or non-water-soluble fibrous inorganic particles. During pattern transfer, the high-strength water-resistant film is placed in water, and the blended base layer comes into contact with the water. The water-soluble inorganic particles in the blended base layer dissolve upon contact with water, thereby forming continuous micropores in the blended base layer, further improving the permeability of the blended base layer. The non-water-soluble fibrous inorganic particles in the blended base layer act as a skeletal support, thereby significantly improving the stiffness of the blended base layer. In this invention, the mass ratio of water-soluble inorganic particles to non-water-soluble fibrous inorganic particles has a significant impact on the permeability and stiffness of the blended base membrane. Specifically, when the proportion of water-soluble inorganic particles is higher, the water-soluble inorganic particles dissolve in water after the blended base membrane comes into contact with water, forming more pores on the blended base membrane and increasing the permeability of the blended base membrane. However, this results in a decrease in the stiffness of the blended base membrane. Therefore, in order to balance the permeability and stiffness, the preferred mass ratio of water-soluble inorganic particles to non-water-soluble fibrous inorganic particles is 2-5:1. Detailed Implementation

[0025] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are described clearly and completely. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0026] To better understand the above technical solution, the following will provide a detailed explanation of the above technical solution in conjunction with specific implementation methods.

[0027] I. Preparation Method

[0028] The reagents or raw materials mentioned in the following examples and comparative examples, along with their models and manufacturers, are as follows:

[0029] Sodium carbonate: Shandong Haihua, industrial grade;

[0030] Potassium chloride: Shouguang Bangze Chemical Co., Ltd., agricultural grade;

[0031] Ammonium sulfate: Zhongchuang Xingyuan Chemical, industrial grade;

[0032] Wollastonite: Jiangxi Southern Wollastonite Industry Co., Ltd., needle-shaped powder, aspect ratio 15:1;

[0033] Calcium sulfate whiskers: Shanghai Fengzhu Composite New Materials Technology Co., Ltd., aspect ratio 20:1;

[0034] PP: Sinopec Shanghai Petrochemical;

[0035] PET: Sinopec Yizheng Chemical Fiber;

[0036] PEG: Jiangsu Haian Petrochemical Plant, molecular weight 30,000;

[0037] PVA1788: Shanghai Yingjia Industrial Development Co., Ltd.;

[0038] Nano-silica: Lingwei Technology;

[0039] Acrylic resin: Shenzhen Youkete PChem® BM-218;

[0040] PCA90 curing agent: Jiangmen Dongyang Ink Co., Ltd.;

[0041] SA580: Lingwei Technology HOMJET®;

[0042] All materials are commercially available, commonly used products. All raw materials were dried under suitable drying conditions before use. The reagents described above are only for illustrating the source and composition of the reagents used in the experiments of this invention, to ensure full disclosure, and do not imply that the invention cannot be achieved by using other similar reagents or reagents provided by other suppliers.

[0043] Example 1

[0044] This embodiment provides a high-strength water level membrane, which includes, from bottom to top: a blended base layer, a water-soluble layer, an adhesive layer, and an image receiving layer, with thicknesses of 130μm, 8μm, 12μm, and 7μm, respectively.

[0045] A method for preparing a high-strength water level membrane is also provided, comprising the following steps:

[0046] S1. Preparation of blended base layer

[0047] S11, Preparation of modified inorganic materials

[0048] The coupling agent isopropyl tris(dioctylphosphoyloxy)titanate was diluted with isopropanol at a mass ratio of 1:1. Water-soluble inorganic particulate sodium carbonate powder was added to a mixer and, under stirring conditions at 40°C, the diluted coupling agent was added to the sodium carbonate powder via spraying. The net mass of the coupling agent accounted for 1.0% of the mass of the sodium carbonate powder. The mixture was stirred at high speed for 5 minutes, and then stirred at 70°C for 15 minutes to obtain modified sodium carbonate.

[0049] The coupling agent isopropyl tris(dioctylphosphoyloxy)titanate was diluted with isopropanol at a mass ratio of 1:1. Insoluble fibrous inorganic wollastonite powder was added to a mixer and, under stirring conditions at 40°C, the diluted coupling agent was added to the wollastonite powder via spraying. The net mass of the coupling agent accounted for 1.0% of the mass of the wollastonite powder. The mixture was stirred at high speed for 2 minutes, and then stirred at 70°C for 20 minutes to obtain modified wollastonite.

[0050] S12, Preparation of blended base film

[0051] PP, PET, and PEG were added to a mixer according to the mass ratio in Table 1. Antioxidant 168 was then added at 0.2% of the total mass of PP and PET. The mixture was stirred for 5 minutes to obtain a premix. Modified sodium carbonate and modified wollastonite were weighed according to Table 1. The premix was added to a co-rotating twin-screw extruder via a weighing scale from the main feed inlet and the modified sodium carbonate and modified wollastonite from the side feed inlets. The conveying section was set to 80°C, the melting and extrusion sections to 180°C, and the screw speed to 350 rpm. After plasticizing, blending, distributing, cooling, drying, and pelletizing, a blend masterbatch was obtained. The screw was cleaned to prevent residual inorganic particles from jamming it after cooling. The blend masterbatch was melt-extruded again at 180°C and cast through a T-die at 190°C onto a quench roller at 30°C to form a blend sheet. The blended thick film was subjected to longitudinal stretching, transverse stretching and shaping treatment in sequence. The longitudinal stretching and transverse stretching conditions were: stretching temperature 70℃ and stretching ratio 3 times. The shaping treatment conditions were: heat treatment at 150℃ for 20 seconds to obtain a blended base film with a thickness of 130μm, which is the blended base layer.

[0052] S2. Preparation of hydrosol

[0053] Weigh the raw materials as follows: 25 parts PVA1788, 55 parts water, 10 parts ethanol, 0.1 parts nano silica, and 0.05 parts sodium hexametaphosphate. Add PVA1788 to 50 parts water and stir thoroughly to disperse. Soak and swell for 30 minutes, then heat to 90°C and maintain the temperature while stirring until PVA1788 is completely dissolved into a transparent solution. In another container, pre-disperse the nano silica with 5 parts water and sodium hexametaphosphate, and sonicate for 15 minutes to obtain a nano silica dispersion. Cool the PVA1788 solution to 65°C, and slowly add the nano silica dispersion while stirring. Then add ethanol and continue stirring for 30 minutes until homogeneous. After standing to remove bubbles, the hydrosol is obtained.

[0054] S3. Preparation of adhesive

[0055] Weigh the raw materials as follows: 60 parts acrylic resin, 20 parts ethyl acetate, 20 parts isopropanol, and 5 parts PCA90 curing agent. Add ethyl acetate and isopropanol to a container, add acrylic resin and mix well, then add PCA90 and mix well to obtain the adhesive.

[0056] S4, Image Receiving Layer Adhesive

[0057] Weigh the raw materials as follows: 100 parts water, 30 parts adsorbent SA580, 30 parts 10% (g / g) PVA solution, 1.0 part dispersant BYK-190, and 1.0 part wetting agent BYK-346. Mix the water, SA580, dispersant BYK-190, and wetting agent BYK-346, and stir evenly using a high-speed disperser. Slowly add 10% PVA solution and stir evenly. Let stand to remove bubbles to obtain the image receiving layer adhesive.

[0058] S3. Preparation of high-strength water level membrane

[0059] The blended base film was corona treated to achieve a surface energy of 38 dyne / cm. A hydrosol was applied to the corona-treated blended base film using a 120 lines / inch anilox roller with a surface depth of 20 μm and a 0.15 mm thick thin steel blade at a coating speed of 10 m / min. The drying process consisted of three stages: a first stage at 45°C, a second stage at 75°C, and a third stage at 100°C, for a total drying time of 2 minutes. The film was then cured in a 50°C curing chamber for 5 hours to prepare a water-soluble layer. This water-soluble layer was further corona treated to achieve a surface energy of 50 dyne / cm. Finally, a 2-layer coating was applied to the water-soluble layer. Adhesive was applied using a 50 mesh / inch screen and a 0.25 mm thick steel blade at a coating speed of 10 m / min, resulting in a wet film thickness of 30 μm. The film was then dried at 60°C for 1 minute to obtain the adhesive layer. An image receiving layer was then coated onto the adhesive layer using a microgravure process. The ratio of the microgravure roller linear speed to the substrate travel speed was 1.0, the blade pressure was 3 kg, and the contact angle between the substrate and the coating roller was 15°. The film was then dried at three stages: 60°C in the first stage, 80°C in the second stage, and 100°C in the third stage, with each stage drying time being 1 minute, resulting in a high-strength water-marking film.

[0060] Example 2

[0061] The difference between this embodiment and Embodiment 1 is that the mass ratio of PP and PET is different and the types of water-soluble inorganic particles are different, as detailed in Table 1. Otherwise, they are the same as in Embodiment 1.

[0062] Example 3

[0063] The difference between this embodiment and Example 1 lies in the different mass ratios of PP and PET, as well as the different types of water-soluble inorganic particles, as detailed in Table 1. The preparation process of the modified ammonium sulfate is as follows: The coupling agent isopropyl tris(dioctylphosphoyloxy)titanate is diluted with isopropanol at a mass ratio of 1:1. Ammonium sulfate powder is added to a mixer, and under stirring conditions at 40°C, the diluted coupling agent is slowly and evenly added to the ammonium sulfate powder via spraying. The net mass of the coupling agent accounts for 1.0% of the mass of the ammonium sulfate powder. The mixture is stirred at high speed for 15 minutes to obtain modified ammonium sulfate. Other steps are the same as in Example 1.

[0064] Example 4

[0065] The difference between this embodiment and Embodiment 1 is that the ratio of the total mass of water-soluble inorganic particles and non-water-soluble fibrous inorganic particles to the total mass of PP and PET is different, the mass ratio of water-soluble inorganic particles and non-water-soluble fibrous inorganic particles is different, and the longitudinal and transverse stretching processes of the blended thick sheets are different, as detailed in Table 1. Other aspects are the same as in Embodiment 1.

[0066] Example 5

[0067] The difference between this embodiment and Embodiment 1 is that the ratio of the total mass of water-soluble inorganic particles and non-water-soluble fibrous inorganic particles to the total mass of PP and PET is different, the mass ratio of water-soluble inorganic particles to non-water-soluble fibrous inorganic particles is different, the types of non-water-soluble fibrous inorganic particles are different, and the longitudinal and transverse stretching processes of the blended thick sheets are different, as detailed in Table 1. Other aspects are the same as in Embodiment 1.

[0068] Comparative Examples 1-2

[0069] The difference between this comparative example and Example 1 is that the mass ratio of water-soluble inorganic particles to non-water-soluble fibrous inorganic particles is different, as detailed in Table 1. Otherwise, it is the same as Example 1.

[0070] How to use high-strength water level membrane

[0071] Taking the transfer of a pattern onto the surface of a ceramic cup as an example, the high-strength water-resistant film prepared in Example 1 is placed in an inkjet printer to print a pattern on the image receiving layer. After cutting, the patterned high-strength water-resistant film is taken out and placed in water. After 20 seconds, it is taken out and attached to the area of ​​the ceramic cup to be transferred, with the pattern facing up and the blended base layer in contact with the ceramic cup surface. At this time, the water-soluble inorganic particles in the blended base layer dissolve in water, forming continuous micropores in the blended base layer. Water enters the water-soluble layer through the micropores. Under the action of water, the water-soluble layer dissolves, causing the blended base layer to separate from the adhesive layer of the high-strength water-resistant film. The blended base layer is pulled out parallel to the surface of the ceramic cup. The blended base layer is relatively stiff and easy to pull out. The adhesive layer of the high-strength water-resistant film adheres to the surface of the ceramic cup to be transferred. The water on the surface of the pattern is gently wiped dry. After standing at room temperature for 5 hours, the adhesive layer is completely dry, and the pattern is fixed on the surface of the ceramic cup, completing the pattern transfer.

[0072] Table 1. Amounts of each raw material used in the blended base film of the examples and comparative examples.

[0073]

[0074] II. Testing Methods

[0075] The performance of the blended base films prepared in the examples and comparative examples was tested. The specific test items and test methods are as follows:

[0076] 1. Water permeability: Referring to GB / T1540 "Determination of water absorption of paper and paperboard (Cobb method)", the blended base films prepared in the examples and comparative examples were immersed in water for 15 seconds, and the amount of water absorbed by the blended base films was tested, with the unit being g / m³. 2 .

[0077] 2. Average bending stiffness value: Tested according to QB / T5056-2017, the unit is mN·m. The higher the average bending stiffness value, the stronger the ability to resist bending deformation.

[0078] 3. Tensile strength: Tested according to GB / T 1040.3-2006, with a specimen width of 15mm and a length of 150mm.

[0079] The test results are shown in Table 2.

[0080] Table 2. Performance test results of the blended base films prepared in the examples and comparative examples.

[0081]

[0082] Table 2 shows that in S12 of Examples 1-5, the ratio of the total mass of water-soluble inorganic particles and non-water-soluble fibrous inorganic particles to the total mass of PP and PET is (10-15):100, and the mass ratio of water-soluble inorganic particles to non-water-soluble fibrous inorganic particles is (2-5):1. The prepared blended base film has better water permeability and better resistance to bending deformation. In Comparative Example 1, the mass ratio of water-soluble inorganic particles to non-water-soluble fibrous inorganic particles is 1:1, and the prepared blended base film has poor water permeability. In Comparative Example 2, the mass ratio of water-soluble inorganic particles to non-water-soluble fibrous inorganic particles is 6:1, and the prepared blended base film has poor resistance to bending deformation. It can be seen that the mass ratio of water-soluble inorganic particles to non-water-soluble fibrous inorganic particles of (2-5):1 can balance the water permeability and resistance to bending deformation of the blended base film, so that the prepared high-strength water-resistant membrane meets the usage conditions.

[0083] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitations, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0084] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

[0085] The present invention has been illustrated with the above embodiments to describe the detailed process flow of the present invention. However, the present invention is not limited to the above detailed process flow, that is, it does not mean that the present invention must rely on the above detailed process flow to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A high-strength water level indicator membrane, characterized in that, From bottom to top, it includes: a blended base layer, a water-soluble layer, an adhesive layer, and an image receiving layer; The thickness of the blended base layer is 120-140 μm, and the blended base layer comprises the following components in parts by weight: 10-30 parts of polar polymer materials; 70-90 parts of nonpolar polymer materials; 2-7 parts of hydrophilic polymer material.

2. The high-strength water level membrane as described in claim 1, characterized in that, The blended base layer also includes inorganic particles, the amount of which is 10-15% of the total mass of the polar polymer material and the non-polar polymer material.

3. The high-strength water level membrane as described in claim 2, characterized in that, The inorganic particles are selected from water-soluble inorganic particles and / or non-water-soluble fibrous inorganic particles.

4. The high-strength water level membrane as described in claim 3, characterized in that, The mass ratio of the water-soluble inorganic particles to the insoluble fibrous inorganic particles is 2-5:

1.

5. The high-strength water level membrane as described in claim 3, characterized in that, The water-soluble inorganic particles are selected from at least one of sodium carbonate, potassium chloride, ammonium sulfate, magnesium chloride, sodium chloride, potassium nitrate, and sodium sulfate.

6. The high-strength water level membrane as described in claim 3, characterized in that, The non-water-soluble fibrous inorganic particles are selected from at least one of wollastonite and calcium sulfate whiskers.

7. The high-strength water level membrane as described in claim 3, characterized in that, The aspect ratio of the non-water-soluble fibrous inorganic particles is 15-20:

1.

8. The high-strength water level membrane as described in claim 1, characterized in that, The polar polymer material is selected from polyethylene terephthalate, polybutylene terephthalate, or polymethyl methacrylate.

9. The high-strength water level membrane as described in claim 1, characterized in that, The non-polar polymer material is selected from any one of polypropylene, polyethylene, and polyisobutylene.

10. The high-strength water level membrane as described in claim 1, characterized in that, The hydrophilic polymer material is selected from any one of polyethylene glycol, polyvinyl alcohol, and polyvinylpyrrolidone.

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