Low-viscosity and low-dielectric photosensitive resin capable of being used for UV ink-jet printing as well as preparation method and application of low-viscosity and low-dielectric photosensitive resin

Abstract

The invention discloses a low-viscosity low-dielectric photosensitive resin capable of being used for UV ink-jet printing. The low-viscosity low-dielectric photosensitive resin is prepared from 10 to 40 percent of vinyl polysiloxane, 26 to 43 percent of tri (2-hydroxyethyl) isocyanuric acid triacrylate, 28.5 to 44 percent of isobornyl methacrylate, 1 to 2 percent of a photoinitiator and 0.5 to 1 percent of a dispersing agent, the invention discloses a preparation method of low-viscosity low-dielectric photosensitive resin capable of being used for UV ink-jet printing. The preparation method comprises the following steps: step 1, uniformly mixing vinyl polysiloxane, tris (2-hydroxyethyl) isocyanurate triacrylate and isobornyl methacrylate in raw materials of the photosensitive resin to obtain a mixture; step 2, uniformly mixing the mixture with a photoinitiator and a dispersing agent in the raw materials of the photosensitive resin under a dark condition, keeping the temperature at 50 DEG C, standing for 0.5 hour, and eliminating bubbles to obtain the photosensitive resin; the low-viscosity and low-dielectric photosensitive resin capable of being used for UV ink-jet printing is low in viscosity and low in dielectric, has the performance of high temperature resistance and the like at the same time, and realizes high-precision ink-jet printing.

Description

Technical Field

[0001] The present invention relates to the technical field of photosensitive resins for inkjet 3D printing, and in particular to a low-viscosity, low-dielectric UV inkjet printable photosensitive resin, and a preparation method and application thereof. Background Art

[0002] With the continuous development of industrialization, the requirements for the processing and manufacturing of high-performance special-shaped parts are getting higher and higher, and the unique customization advantages of UV inkjet 3D printing are particularly widely used in industrial manufacturing. As an important material in UV inkjet 3D printing, the performance of photosensitive resin is crucial to the molding quality, printing efficiency and sample performance of printing, but traditional photosensitive resins have problems such as high viscosity, slow curing rate and poor dielectric properties, which cannot meet the needs of application scenarios. Therefore, the development of a low-viscosity, low-dielectric photosensitive resin suitable for UV inkjet 3D printing has important technical significance and market demand.

[0003] Tris(2-hydroxyethyl)isocyanuric acid triacrylate (THEICTA) is an acrylic monomer with strong heat resistance (Tg>250℃) and fast curing rate, but its viscosity is too high (over 20000mp·s at room temperature) and cannot be used in inkjet printing; Isobornyl methacrylate (IBOMA) is an acrylic monomer with ultra-low viscosity (11mp·s), which can effectively reduce the viscosity of the resin while maintaining the glass transition temperature (Tg), molecular weight, and functional group content of the polymer; Vinyl polysiloxane has good electrical insulation properties and low dielectric constant, and is suitable for the manufacture of high-frequency electronic devices and microwave devices. However, due to the low double bond content, the curing rate is slow, and the glass transition temperature of polysiloxane is low, which makes it unable to meet the requirements in high-temperature application scenarios. Therefore, it is necessary to study and develop the above three monomers or resins to organically combine and adjust the proportion of each component and the curing conditions to obtain a photosensitive resin with low viscosity and low dielectric constant suitable for UV inkjet 3D printing.

[0004] UV inkjet 3D printing is a technology that uses ultraviolet light to cure photosensitive resins to print three-dimensional entities layer by layer. Compared with other 3D printing methods, it has the advantages of high printing accuracy, fast curing rate, and large-area manufacturing. It is most widely used in the manufacture of low-dielectric special-shaped parts for aerospace and integrated circuit applications. However, UV inkjet printing has very stringent requirements for photosensitive resins, which need to have properties such as fast curing, ultra-low viscosity (less than 50mp·s), and good adhesion. In order to meet the requirements of inkjet printing and application scenarios, low-viscosity, low-dielectric photosensitive resins are needed to meet printing needs in order to manufacture devices with low dielectric properties for use in electronic devices, microwave devices, optical devices and other fields. Summary of the invention

[0005] The present invention designs and develops a low-viscosity, low-dielectric UV inkjet printable photosensitive resin. One of the inventive purposes of the present invention is to simultaneously solve the problems of high viscosity, poor dielectric properties and unstable performance of UV inkjet printable photosensitive resin in the prior art.

[0006] The second purpose of the present invention is to solve the problems of poor compatibility with the traditional acrylic resin system and poor molding effect under UV irradiation after mixing by adding vinyl-terminated polysiloxane.

[0007] The third object of the present invention is to provide a method for preparing vinyl-terminated polysiloxane to obtain vinyl-terminated polysiloxane, thereby solving the problem that traditional polysiloxane with Si-O-Si as the main chain is difficult to cure and mold, and has poor molding effect under UV irradiation after mixing with traditional acrylic resin, and at the same time solves the problem of severe reaction conditions and complicated reaction steps.

[0008] The present invention designs and develops a method for preparing a low-viscosity, low-dielectric UV inkjet printable photosensitive resin. The purpose of the present invention is to simultaneously solve the problems of high viscosity, poor dielectric properties and unstable performance of the UV inkjet printable photosensitive resin prepared by the prior art.

[0009] The present invention also relates to the development of a low-viscosity, low-dielectric UV inkjet printable photosensitive resin for use in 3D printing, solving the application demand problem of UV inkjet 3D printing in the prior art.

[0010] The technical solution provided by the present invention is:

[0011] A low-viscosity, low-dielectric, UV inkjet printable photosensitive resin, wherein the raw material weight percentage of the photosensitive resin comprises:

[0012] Vinyl polysiloxane: 10-40%, tris(2-hydroxyethyl)isocyanuric acid triacrylate: 26-43%, isobornyl methacrylate: 28.5-44%, photoinitiator: 1-2%, dispersant: 0.5-1%.

[0013] Preferably, the preparation method of the vinyl polysiloxane comprises the following steps:

[0014] Step 1, weigh hydroxyl-terminated polydimethylsiloxane and isocyanate in a molar ratio of 1:2.5, heat and stir the isocyanate and raise the temperature to 65°C, then slowly drop the hydroxyl-terminated polydimethylsiloxane, adjust the temperature to 80°C after the dropwise addition is completed, add a small amount of dibutyltin dilaurate, and react for 2.5 hours to obtain isocyanate-terminated polysiloxane;

[0015] Step 2: weigh the isocyanate-terminated polysiloxane and 1-ene peroxypropionic acid in a molar ratio of 1:2, slowly heat and stir until the temperature reaches 45°C, add a certain amount of chloroplatinic acid solution, slowly heat to 85°C, react for 4 hours, and then filter and rotary evaporate to obtain vinyl polysiloxane.

[0016] Preferably, the photoinitiator is at least one of 2-hydroxy-2-methylphenylacetone, Irgacure 2959, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide and phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide.

[0017] Preferably, the dispersant is at least one of Disponer 903, TEGO Dispers 686, TEGO 685 and BYKJET-9151.

[0018] A method for preparing a low-viscosity, low-dielectric UV inkjet printable photosensitive resin comprises the following steps:

[0019] Step 1: uniformly mixing vinyl polysiloxane, tris(2-hydroxyethyl)isocyanurate triacrylate and isobornyl methacrylate in the raw materials of the photosensitive resin to obtain a mixture;

[0020] Step 2: Evenly mix the mixture with the photoinitiator and dispersant in the raw materials of the photosensitive resin under light-proof conditions, and then keep the mixture at 50° C. for 0.5 h to obtain the photosensitive resin after eliminating bubbles;

[0021] The raw materials of the photosensitive resin are measured by weight percentage and include:

[0022] Vinyl polysiloxane: 10-40%, tris(2-hydroxyethyl)isocyanuric acid triacrylate: 26-43%, isobornyl methacrylate: 28.5-44%, photoinitiator: 1-2%, dispersant: 0.5-1%.

[0023] Preferably, in the step 1, the temperature is controlled at 60° C. during the mixing process, and the stirring is performed at a speed of 600 r / min for 30 min; and

[0024] In the step 2, the temperature is controlled at 60° C. during the mixing process, and the mixture is stirred at a speed of 600 r / min for 30 min.

[0025] Preferably, the photoinitiator is at least one of 2-hydroxy-2-methylphenylacetone, Irgacure 2959, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide and phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide.

[0026] Preferably, the dispersant is at least one of Disponer 903, TEGO Dispers 686, TEGO 685 and BYKJET-9151.

[0027] Preferably, the preparation method of the vinyl polysiloxane comprises the following steps:

[0028] Step 1, weigh hydroxyl-terminated polydimethylsiloxane and isocyanate in a molar ratio of 1:2.5, heat and stir the isocyanate and raise the temperature to 65°C, then slowly drop the hydroxyl-terminated polydimethylsiloxane, adjust the temperature to 80°C after the dropwise addition is completed, add a small amount of dibutyltin dilaurate, and react for 2.5 hours to obtain isocyanate-terminated polysiloxane;

[0029] Step 2: weigh the isocyanate-terminated polysiloxane and 1-ene peroxypropionic acid in a molar ratio of 1:2, slowly heat and stir until the temperature reaches 45°C, add a certain amount of chloroplatinic acid solution, slowly heat to 85°C, react for 4 hours, and then filter and rotary evaporate to obtain vinyl polysiloxane.

[0030] The low-viscosity, low-dielectric UV inkjet printable photosensitive resin is used in 3D printing.

[0031] The beneficial effects of the present invention are:

[0032] 1. The vinyl-terminated polysiloxane obtained by the present invention contains a regularly arranged -Si-O-Si structure arrangement. The polysiloxane with Si-O-Si as the main chain has excellent properties such as low dielectricity, hydrophobicity, chemical stability and biocompatibility, and has the performance of both inorganic materials and organic materials, and has excellent properties such as low surface tension, electrical insulation, oxidation stability, weather resistance, physiological inertness, etc.; at the same time, the present invention uses isocyanate to modify polysiloxane, and then reacts with 1-ene peroxypropionic acid to obtain a polysiloxane with a double bond terminal group. Compared with the traditional preparation method of vinyl chloride and dimethyl (siloxane and polysiloxane) reaction, the reaction conditions are mild, and the product can be obtained in two steps. The prepared vinyl polysiloxane has a lower viscosity, can be quickly diffused and mixed in the solution, and is well compatible with the acrylic resin system;

[0033] 2. The vinyl-terminated polysiloxane obtained by the present invention, tris(2-hydroxyethyl)isocyanuric acid triacrylate and isobornyl methacrylate are mixed in different proportions, and after adding a photoinitiator and a dispersant, the low-viscosity, low-dielectric, UV inkjet-printable photosensitive resin of the present invention is obtained. Isobornyl methacrylate is used to reduce the viscosity without reducing the dielectric properties and temperature resistance of the photosensitive resin, thereby achieving low viscosity and low dielectric properties, and having high temperature resistance and other properties;

[0034] 3. The low-viscosity, low-dielectric, UV inkjet printable photosensitive resin obtained by the present invention utilizes isobornyl methacrylate to organically combine polysiloxane with a silicon-oxygen structure and tris(2-hydroxyethyl)isocyanuric acid triacrylate, thereby effectively reducing the surface tension of the photosensitive resin and achieving high-precision inkjet printing. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1a This is a schematic diagram of the thermogravimetric test results of Example 1 described in the present invention.

[0036] Figure 1b This is a schematic diagram of the thermogravimetric test results of Example 2 described in the present invention.

[0037] Figure 1c This is a schematic diagram of the thermogravimetric test results of Example 3 described in the present invention.

[0038] Figure 1d This is a schematic diagram of the thermogravimetric test results of Example 4 described in the present invention.

[0039] Figure 1e This is a schematic diagram of the thermogravimetric test results of Example 5 described in the present invention.

[0040] Figure 1f This is a schematic diagram of the thermogravimetric test results of Example 6 described in the present invention.

[0041] Figure 1g This is a schematic diagram of the thermogravimetric test results of Example 7 described in the present invention.

[0042] Figure 1h This is a schematic diagram of the thermogravimetric test results of Example 8 described in the present invention.

[0043] Figure 1i This is a schematic diagram of the thermogravimetric test results of Comparative Example 2 of the present invention.

[0044] Figure 2a This is a graph showing the viscosity test results of Example 1 described in the present invention.

[0045] Figure 2b This is a graph showing the viscosity test results of Example 2 described in the present invention.

[0046] Figure 2c This is a graph showing the viscosity test results of Example 6 described in the present invention.

[0047] Figure 2d This is a graph showing the viscosity test results of Comparative Example 2 of the present invention. DETAILED DESCRIPTION

[0048] The present invention is further described in detail below in conjunction with the accompanying drawings so that those skilled in the art can implement the invention with reference to the description.

[0049] The present invention provides a low-viscosity, low-dielectric, UV inkjet printable photosensitive resin, the raw materials of which, measured by weight percentage, include:

[0050] Vinyl polysiloxane: 10-40%;

[0051] Tris(2-hydroxyethyl)isocyanurate triacrylate: 26-43%;

[0052] Isobornyl methacrylate: 28.5-44%;

[0053] Photoinitiator: 1-2%;

[0054] Dispersant: 0.5-1%;

[0055] Wherein, the preparation method of vinyl polysiloxane comprises the following steps:

[0056] Step 1: Weigh hydroxyl-terminated polydimethylsiloxane and isocyanate in a molar ratio of 1:2.5, add isocyanate into a four-necked flask equipped with a thermometer, condenser, and magnetic stirrer; under nitrogen protection, heat and stir until the temperature rises to 65°C, then slowly drop hydroxyl-terminated polydimethylsiloxane, adjust the temperature to 80°C after the dropwise addition is complete, and add a small amount of dibutyltin dilaurate as a catalyst. React for 2.5 hours to obtain isocyanate-terminated polysiloxane;

[0057] Step 2: Weigh the isocyanate-terminated polysiloxane and 1-ene peroxypropionic acid produced in the previous step in a molar ratio of 1:2, add them into a four-necked flask equipped with a thermometer, a condenser, and a magnetic stirrer, slowly heat and stir until the temperature reaches 45°C, then add a certain amount of catalyst chloroplatinic acid solution, slowly heat to 85°C, react for 4 hours, and then filter and rotary evaporate to obtain the product, i.e., vinyl polysiloxane.

[0058] In another embodiment, tris(2-hydroxyethyl)isocyanuric acid triacrylate (THEICTA) monomer is purchased from Sartomer, and has a Tg of 272° C. and a viscosity of 22500 mp·s at room temperature after melting.

[0059] In another embodiment, isobornyl methacrylate (IBOMA) monomer is purchased from Sartomer Corporation and has a Tg of 110° C. and a viscosity of 11 mp·s at room temperature.

[0060] In another embodiment, the photoinitiator is at least one of 2-hydroxy-2-methylphenylacetone, Irgacure 2959, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, and phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide.

[0061] In another embodiment, the dispersant is at least one of Disponer 903, TEGO Dispers 686, TEGO 685 and BYKJET-9151.

[0062] The present invention provides a method for preparing a low-viscosity, low-dielectric UV inkjet printable photosensitive resin, comprising the following steps:

[0063] Step 1: Preparation of vinyl polysiloxane:

[0064] Weigh hydroxyl-terminated polydimethylsiloxane and isocyanate at a molar ratio of 1:2.5, add isocyanate into a four-necked flask equipped with a thermometer, condenser, and magnetic stirrer; under nitrogen protection, heat and stir until the temperature rises to 65°C, then slowly drop hydroxyl-terminated polydimethylsiloxane, adjust the temperature to 80°C after the dropwise addition, and add a small amount of dibutyltin dilaurate as a catalyst. React for 2.5 hours to obtain isocyanate-terminated polysiloxane;

[0065] The isocyanate-terminated polysiloxane and 1-ene peroxypropionic acid produced in the previous step were weighed in a molar ratio of 1:2 and added into a four-necked flask equipped with a thermometer, a condenser and a magnetic stirrer. After slowly heating and stirring to 45°C, a certain amount of catalyst chloroplatinic acid solution was added, and the temperature was slowly raised to 85°C. After reacting for 4 hours, the product, i.e., vinyl polysiloxane, was obtained by suction filtration and rotary evaporation.

[0066] Step 2: Preparation of low-viscosity and low-dielectric photosensitive resin:

[0067] Vinyl polysiloxane, tris(2-hydroxyethyl)isocyanurate triacrylate and isobornyl methacrylate were added into a stirring kettle in order according to weight percentage, the temperature was controlled at 60° C., and the stirring speed was 600 r / min for 30 min to obtain a low-viscosity and low-dielectric photosensitive resin;

[0068] Add light stabilizer and photoinitiator, control the temperature to 60°C, adjust the stirring speed to 600r / min and stir for 30min to mix evenly;

[0069] Stop stirring, set the temperature to 50°C, and let it stand for 30 minutes to eliminate bubbles, thereby obtaining a low-viscosity, low-dielectric, UV inkjet printable photosensitive resin;

[0070] The raw materials of the photosensitive resin include, by weight percentage:

[0071] Vinyl polysiloxane: 10-40%, tris(2-hydroxyethyl)isocyanuric acid triacrylate: 26-43%, isobornyl methacrylate: 28.5-44%, photoinitiator: 1-2%, dispersant: 0.5-1%.

[0072] In another embodiment, tris(2-hydroxyethyl)isocyanuric acid triacrylate (THEICTA) monomer is purchased from Sartomer, and has a Tg of 272° C. and a viscosity of 22500 mp·s at room temperature after melting.

[0073] In another embodiment, isobornyl methacrylate (IBOMA) monomer is purchased from Sartomer Corporation and has a Tg of 110° C. and a viscosity of 11 mp·s at room temperature.

[0074] In another embodiment, the photoinitiator is at least one of 2-hydroxy-2-methylphenylacetone, Irgacure 2959, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, and phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide.

[0075] In another embodiment, the dispersant is at least one of Disponer 903, TEGO Dispers 686, TEGO 685 and BYKJET-9151.

[0076] The present invention provides an application of a low-viscosity, low-dielectric UV inkjet printable photosensitive resin in 3D printing. The low-viscosity, low-dielectric photosensitive resin prepared above is loaded into the ink tank of an array-type UV inkjet 3D printer, and the printing parameters (printing speed, extrusion pressure, layer thickness, temperature, etc.) are adjusted to print a spline of corresponding size.

[0077] Low-viscosity, low-dielectric, UV inkjet printable photosensitive resins were prepared according to the weight percentages in the following examples.

[0078] Example 1

[0079] A raw material of a low-viscosity, low-dielectric, UV inkjet printable photosensitive resin, which is composed of the following components in terms of weight percentage:

[0080] Vinyl polysiloxane: 40%;

[0081] Tris(2-hydroxyethyl)isocyanurate triacrylate: 30%;

[0082] Isobornyl methacrylate: 28.5%;

[0083] The photoinitiator is 2-hydroxy-2-methylphenylacetone: 1%;

[0084] Dispersant: BYKJET-9151: 0.5%;

[0085] Example 2

[0086] A raw material of a low-viscosity, low-dielectric, UV inkjet printable photosensitive resin, which is composed of the following components in terms of weight percentage:

[0087] Vinyl polysiloxane: 36.5%;

[0088] Tris(2-hydroxyethyl)isocyanurate triacrylate: 28%;

[0089] Isobornyl methacrylate: 34%;

[0090] The photoinitiator is 2-hydroxy-2-methylphenylacetone: 1%;

[0091] Dispersant: BYKJET-9151: 0.5%;

[0092] Example 3

[0093] A raw material of a low-viscosity, low-dielectric, UV inkjet printable photosensitive resin, which is composed of the following components in terms of weight percentage:

[0094] Vinyl polysiloxane: 33.5%;

[0095] Tris(2-hydroxyethyl)isocyanurate triacrylate: 26%;

[0096] Isobornyl methacrylate: 39%;

[0097] The photoinitiator is 2-hydroxy-2-methylphenylacetone: 1%;

[0098] Dispersant: BYKJET-9151: 0.5%;

[0099] Example 4

[0100] A raw material of a low-viscosity, low-dielectric, UV inkjet printable photosensitive resin, which is composed of the following components in terms of weight percentage:

[0101] Vinyl polysiloxane: 30.5%;

[0102] Tris(2-hydroxyethyl)isocyanurate triacrylate: 32%;

[0103] Isobornyl methacrylate: 36%;

[0104] The photoinitiator is 1% 2-hydroxy-2-methylphenylacetone;

[0105] Dispersant: BYKJET-9151: 0.5%;

[0106] Example 5

[0107] A raw material of a low-viscosity, low-dielectric, UV inkjet printable photosensitive resin, which is composed of the following components in terms of weight percentage:

[0108] Vinyl polysiloxane: 27%;

[0109] Tris(2-hydroxyethyl)isocyanurate triacrylate: 35%;

[0110] Isobornyl methacrylate: 35%;

[0111] The photoinitiator is 2-hydroxy-2-methylphenylacetone: 2%;

[0112] Dispersant: BYKJET-9151: 1%;

[0113] Example 6

[0114] A raw material of a low-viscosity, low-dielectric, UV inkjet printable photosensitive resin, which is composed of the following components in terms of weight percentage:

[0115] Vinyl polysiloxane: 25%;

[0116] Tris(2-hydroxyethyl)isocyanurate triacrylate: 33%;

[0117] Isobornyl methacrylate: 39%;

[0118] The photoinitiator is 2-hydroxy-2-methylphenylacetone: 2%;

[0119] Dispersant: BYKJET-9151: 1%;

[0120] Example 7

[0121] A raw material of a low-viscosity, low-dielectric, UV inkjet printable photosensitive resin, which is composed of the following components in terms of weight percentage:

[0122] Vinyl polysiloxane: 22%;

[0123] Tris(2-hydroxyethyl)isocyanurate triacrylate: 38%;

[0124] Isobornyl methacrylate: 37%;

[0125] The photoinitiator is 2-hydroxy-2-methylphenylacetone: 2%;

[0126] Dispersant: BYKJET-9151: 1%;

[0127] Example 8

[0128] A raw material of a low-viscosity, low-dielectric, UV inkjet printable photosensitive resin, which is composed of the following components in terms of weight percentage:

[0129] Vinyl polysiloxane: 18%;

[0130] Tris(2-hydroxyethyl)isocyanurate triacrylate: 40%;

[0131] Isobornyl methacrylate: 39%;

[0132] The photoinitiator is 2-hydroxy-2-methylphenylacetone: 2%;

[0133] Dispersant: BYKJET-9151: 1%;

[0134] Example 9

[0135] A raw material of a low-viscosity, low-dielectric, UV inkjet printable photosensitive resin, which is composed of the following components in terms of weight percentage:

[0136] Vinyl polysiloxane: 15%;

[0137] Tris(2-hydroxyethyl)isocyanurate triacrylate: 38%;

[0138] Isobornyl methacrylate: 44%;

[0139] The photoinitiator is 2-hydroxy-2-methylphenylacetone: 2%;

[0140] Dispersant: BYKJET-9151: 1%;

[0141] Example 10

[0142] A raw material of a low-viscosity, low-dielectric, UV inkjet printable photosensitive resin, which is composed of the following components in terms of weight percentage:

[0143] Vinyl polysiloxane: 10%;

[0144] Tris(2-hydroxyethyl)isocyanurate triacrylate: 43%;

[0145] Isobornyl methacrylate: 44%;

[0146] The photoinitiator is 2-hydroxy-2-methylphenylacetone: 2%;

[0147] Dispersant: BYKJET-9151: 1%;

[0148] The photosensitive resins were prepared according to the weight percentages shown below.

[0149] Comparative Example 1

[0150] A raw material of a photosensitive resin, calculated by weight percentage, is composed as follows:

[0151] Vinyl polysiloxane: 8%;

[0152] Tris(2-hydroxyethyl)isocyanurate triacrylate: 45%;

[0153] Isobornyl methacrylate: 44%;

[0154] The photoinitiator is 2-hydroxy-2-methylphenylacetone: 2%;

[0155] Dispersant: BYKJET-9151: 1%;

[0156] Comparative Example 2

[0157] A raw material of a photosensitive resin, calculated by weight percentage, is composed as follows:

[0158] Vinyl polysiloxane: 50%;

[0159] Tris(2-hydroxyethyl)isocyanurate triacrylate: 30%;

[0160] isobornyl methacrylate, 17%;

[0161] The photoinitiator is 2-hydroxy-2-methylphenylacetone: 2%;

[0162] Dispersant: BYKJET-9151: 1%;

[0163] Test Case

[0164] Under light-proof conditions, low-viscosity, low-dielectric, UV inkjet-printable photosensitive resins were prepared according to the raw materials of the photosensitive resins in Examples 1 to 10, respectively, to obtain 10 kinds of low-viscosity, low-dielectric, UV inkjet 3D-printable photosensitive resins. After testing, the viscosities of the light-cured photosensitive resins obtained in Examples 1 to 10 and Comparative Example 1 were all lower than 50 mp·s, while the viscosity of the photosensitive resin in Comparative Example 2 was too high, at 150 mp·s, and could not be used for inkjet printing.

[0165] The photosensitive resins prepared according to the raw materials of the photosensitive resins in the above-mentioned Examples 1 to 10 and Comparative Examples 1 and 2 are respectively prepared into discs with a diameter of 50 mm and a thickness of 2 mm and rectangular parallelepiped strips with sizes of 14×4×2 mm according to dielectric tests and thermodynamic tests.

[0166] Viscosity test: using Discovery HR-30 rheometer, at 25℃ and 60℃, shear rate 100-2000S -1 Test the viscosity of photosensitive resin under conditions.

[0167] Thermogravimetric test: TA Q500 thermogravimetric analyzer was used to test the thermal decomposition of the cured specimens.

[0168] Dynamic thermal analysis: NETZSCH DMA 242C dynamic thermal analyzer was used to test the glass transition temperature of the cured specimens.

[0169] Surface tension: According to the determination of surface tension in GB / T 22237-2008, the surface tension of low-viscosity, low-dielectric UV inkjet 3D printable photosensitive resin is tested.

[0170] Inkjet smoothness: Use an array inkjet printer to print on the printing platform and use UV curing to observe the print line accuracy and inkjet smoothness.

[0171] Printing accuracy: Select the printed lines and place them on the sample plate. After gold spraying, use a scanning electron microscope (SEM) S-4700 to observe the line width.

[0172] Dielectric constant: Tested in accordance with GB / T 29306.2-2012 Determination of dielectric properties of insulating materials at frequencies above 300MHz Part 2: Resonance method.

[0173] Dielectric loss: Determined in accordance with GB / T 29306.2-2012 Dielectric properties of insulating materials at frequencies above 300 MHz Part 2: Resonance method.

[0174] As shown in Table 1, it can be seen from the data in Table 1 that the low-viscosity, low-dielectric UV inkjet printable photosensitive resins prepared according to the raw materials of the photosensitive resins in Examples 1 to 10 of the present invention all have low dielectric constants and dielectric losses, while the dielectric constant in Comparative Example 1 is large, the dielectric loss is high, and the dielectric properties are poor. The low-viscosity, low-dielectric UV inkjet 3D printable photosensitive resins prepared by Examples 1 to 10 have good printability, dielectricity and temperature resistance, low dielectric constant, and can be used for high-precision inkjet 3D printing; as the proportion of isobornyl methacrylate monomer increases, the viscosity of the photosensitive resin decreases, and as the content of vinyl polysiloxane increases, the dielectric properties improve, proving that the prepared photosensitive resin has low viscosity and low dielectric properties; the photosensitive resin is applied to array-type UV inkjet 3D printing, the printed lines are high in precision, the inkjet is smooth, the prepared strips have good temperature resistance, and can be used to manufacture devices with low dielectric properties for electronic devices, microwave devices, optical devices and other fields.

[0175]

[0176] like Figures 1a to 1i As shown, Examples 1 to 8 and Comparative Example 2 all have good thermal stability, and when the content of vinyl polysiloxane is reduced, the thermal decomposition temperature of the cured sample decreases, proving that vinyl polysiloxane can improve the heat resistance of photosensitive resin. Figure 2a to 2d As shown, the viscosity of Example 1, Example 2, and Example 6 are all lower than 50 mp·s, which can be well applied to UV inkjet 3D printing, while the viscosity of the system is increased in Comparative Example 2 due to the 50% mass percentage of vinyl polysiloxane, resulting in failure to spray out good lines, proving that the mass percentage of the components set in the present invention is reasonable and effective. This result also suggests that those skilled in the art should not ignore the reasonable setting of the component content during the preparation process.

[0177] Although the embodiments of the present invention have been disclosed as above, they are not limited to the applications listed in the specification and the implementation modes, and they can be fully applied to various fields suitable for the present invention. For those familiar with the art, additional modifications can be easily implemented. Therefore, without departing from the general concept defined by the claims and the scope of equivalents, the present invention is not limited to the specific details and the illustrations shown and described herein.

Claims

1. A low-viscosity, low-dielectric, UV inkjet printable photosensitive resin, characterized in that: The raw materials of the photosensitive resin are measured by weight percentage and include: Vinyl polysiloxane: 10-40%, tris(2-hydroxyethyl)isocyanuric acid triacrylate: 26-43%, isobornyl methacrylate: 28.5-44%, photoinitiator: 1-2%, dispersant: 0.5-1%.

2. The low-viscosity, low-dielectric UV inkjet printable photosensitive resin according to claim 1, characterized in that: The preparation method of the vinyl polysiloxane comprises the following steps: Step 1, weigh hydroxyl-terminated polydimethylsiloxane and isocyanate in a molar ratio of 1:2.5, heat and stir the isocyanate and raise the temperature to 65°C, then slowly drop the hydroxyl-terminated polydimethylsiloxane, adjust the temperature to 80°C after the dropwise addition is completed, add a small amount of dibutyltin dilaurate, and react for 2.5 hours to obtain isocyanate-terminated polysiloxane; Step 2: weigh the isocyanate-terminated polysiloxane and 1-ene peroxypropionic acid in a molar ratio of 1:2, slowly heat and stir until the temperature reaches 45°C, add a certain amount of chloroplatinic acid solution, slowly heat to 85°C, react for 4 hours, and then filter and rotary evaporate to obtain vinyl polysiloxane.

3. The low-viscosity, low-dielectric UV inkjet printable photosensitive resin according to claim 1 or 2, characterized in that: The photoinitiator is at least one of 2-hydroxy-2-methylphenylacetone, Irgacure 2959, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide and phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide.

4. The low-viscosity, low-dielectric UV inkjet printable photosensitive resin according to claim 3, characterized in that: The dispersant is at least one of Disponer 903, TEGO Dispers 686, TEGO 685 and BYKJET-9151.

5. A method for preparing a low-viscosity, low-dielectric, UV inkjet printable photosensitive resin, characterized in that: The steps include: Step 1: uniformly mixing vinyl polysiloxane, tris(2-hydroxyethyl)isocyanurate triacrylate and isobornyl methacrylate in the raw materials of the photosensitive resin to obtain a mixture; Step 2: Evenly mix the mixture with the photoinitiator and dispersant in the raw materials of the photosensitive resin under light-proof conditions, and then keep the mixture at 50° C. for 0.5 h to obtain the photosensitive resin after eliminating bubbles; The raw materials of the photosensitive resin are composed of the following components in terms of weight percentage: Vinyl polysiloxane: 10-40%, tris(2-hydroxyethyl)isocyanuric acid triacrylate: 26-43%, isobornyl methacrylate: 28.5-44%, photoinitiator: 1-2%, dispersant: 0.5-1%.

6. The method for preparing a low-viscosity, low-dielectric UV inkjet printable photosensitive resin according to claim 5, characterized in that: In the step 1, the temperature is controlled at 60° C. during the mixing process, and the mixture is stirred at a speed of 600 r / min for 30 min; as well as In the step 2, the temperature is controlled at 60° C. during the mixing process, and the mixture is stirred at a speed of 600 r / min for 30 min.

7. The method for preparing a low-viscosity, low-dielectric UV inkjet printable photosensitive resin according to claim 5 or 6, characterized in that: The photoinitiator is at least one of 2-hydroxy-2-methylphenylacetone, Irgacure 2959, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide and phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide.

8. The method for preparing a low-viscosity, low-dielectric UV inkjet printable photosensitive resin according to claim 7, characterized in that: The dispersant is at least one of Disponer 903, TEGO Dispers 686, TEGO 685 and BYKJET-9151.

9. The method for preparing a low-viscosity, low-dielectric UV inkjet printable photosensitive resin according to claim 5, 6 or 8, characterized in that: The preparation method of the vinyl polysiloxane comprises the following steps: Step 1, weigh hydroxyl-terminated polydimethylsiloxane and isocyanate in a molar ratio of 1:2.5, heat and stir the isocyanate and raise the temperature to 65°C, then slowly drop the hydroxyl-terminated polydimethylsiloxane, adjust the temperature to 80°C after the dropwise addition is completed, add a small amount of dibutyltin dilaurate, and react for 2.5 hours to obtain isocyanate-terminated polysiloxane; Step 2: weigh the isocyanate-terminated polysiloxane and 1-ene peroxypropionic acid in a molar ratio of 1:2, slowly heat and stir until the temperature reaches 45°C, add a certain amount of chloroplatinic acid solution, slowly heat to 85°C, react for 4 hours, and then filter and rotary evaporate to obtain vinyl polysiloxane.

10. Use of the low-viscosity, low-dielectric UV inkjet printable photosensitive resin according to any one of claims 1 to 4 in 3D printing.

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