CN106647167A - Matte photosensitive resin for photocuring quick molding and preparation method thereof - Google Patents

Abstract

The invention discloses a matte photosensitive resin for light-curing rapid prototyping and a preparation method thereof. The resin is made of the following raw materials in parts by weight: 5-45 parts by weight of polyurethane acrylate, 5-45 parts of epoxy resin, 5-45 parts by weight of Diluent 10~25, cationic photopolymerization initiator 1~8, free radical photopolymerization initiator 1~8, micron silica 1~10, polyethylene wax powder 1~10, nonionic surfactant 1~ 3. The photosensitive resin can have a good matt effect after light-curing rapid prototyping due to the addition of micron silicon dioxide and polyethylene wax powder, and the introduction of the matte effect makes it impossible to observe the surface of the molded parts manufactured by light-curing rapid prototyping Clear print texture, which significantly improves the surface quality of molded parts. It makes the manufactured three-dimensional solid have better mechanical properties, and at the same time can reduce the shrinkage and warpage of the molded parts, improve the printing accuracy, and have stronger practicability.

Description

A kind of matte photosensitive resin for photocuring rapid prototyping and preparation method thereof

technical field

The invention belongs to the technical field of 3D printing, and in particular relates to a matte photosensitive resin for photocuring rapid prototyping and a preparation method thereof.

Background technique

3D printing technology, also known as rapid prototyping technology, is based on digital model files, using powdered metal or plastic and other bondable materials to construct objects by layer-by-layer printing. 3D printing technology is becoming more and more competitive in today's manufacturing industry, so it is called "manufacturing technology with industrial revolution significance". 3D printing technologies include fused deposition modeling, selective laser sintering, photo-curing rapid prototyping (stereolithography solidification rapid prototyping) and other technologies. Among them, light-curing rapid prototyping is to scan light (ultraviolet light, laser, etc.) on the resin liquid surface point by point according to the shape of the two-dimensional cross-section, so that the resin is cured, and the cured resin forms a two-dimensional figure, which is scanned layer by layer. , solidified, and finally a complete three-dimensional entity can be obtained. In light-curing rapid prototyping, photosensitive resin is the basis of the entire technology as a molding material, and the quality of photosensitive resin will determine the precision of the formed part as well as its mechanical and thermal properties.

In recent years, many universities and scientific research institutes in my country have carried out research on light-cured rapid prototyping photosensitive resins. Patent CN200910040526.1 discloses a stereolithography rapid prototyping photosensitive resin and its preparation method and application. The stereolithography rapid prototyping photosensitive resin involved includes epoxy resin, acrylate, free radical initiator, cationic initiator and diluent . Wherein the epoxy resin is a phenolic resin or an alicyclic epoxy resin with a hexyl ring, and the diluent is an epoxy resin diluent, an acrylate diluent or a mixture thereof. Patent CN200910095846.7 discloses a UV-curable photosensitive resin for rapid prototyping injection molds, which mainly consists of epoxy acrylate, epoxy resin, double-tube functional group monomer or trifunctional monomer reactive diluent and other components. On the basis of the above patents, patent CN201110177676.4 provides a high-precision ultraviolet laser curing rapid prototyping photosensitive resin, which contains alicyclic epoxy resin and oxetane compound with high cationic ultraviolet curing activity, which can Manufacture parts with high precision. At present, the photosensitive resins used for light-curing rapid prototyping are mainly composed of epoxy resins, polyurethane acrylates, etc., and the main focus is on the improvement of mechanical properties. More photosensitive resins with special effects or properties need to be further developed.

In addition, photo-curing rapid prototyping is based on a layer-by-layer manufacturing method, which enables clear printing textures to be observed on the surface of the formed three-dimensional solid, and poor surface quality limits the wide application of photo-curing technology. Solvent polishing is usually used to improve the surface quality, but the operation is cumbersome and has a certain impact on the health of the operator.

Matt material refers to a special material with a very fine grained surface. When a beam of parallel light hits the surface of the material, if it is a normal smooth surface, only specular reflection will occur, and 100% of the light will enter the human eye after reflection, but if it is a matte material with uneven surface, diffuse scattering will occur. At this time The light cannot fully enter the human eye due to scattering in all directions, which makes people feel that the light is soft and produces a noble and elegant viewing experience. Gloss is a numerical representation of the degree to which the surface of an object is close to a mirror surface, and can be used to measure the matte effect of a material. The gloss of traditional materials can reach 100% due to the surface finish, while the gloss of matt materials is usually less than 50%.

In addition to obtaining a special matte effect, the use of matte materials will make the formed three-dimensional entity not be observed due to the diffuse reflection of the uneven surface. The clear printing texture will improve the surface quality and promote the rapid prototyping technology of light curing. It can be applied in more fields, and avoid the subsequent cumbersome surface treatment procedures. However, there has been no report on matte photosensitive resins applied to light-curing rapid prototyping so far.

Based on the above description, it is necessary to develop a new type of photosensitive resin for light-curing rapid prototyping with matte effect, which can improve the surface quality of the formed three-dimensional solid while enriching the types of photosensitive resin for light-curing rapid prototyping.

Contents of the invention

The purpose of the present invention is to provide a matte photosensitive resin for photocuring rapid prototyping, to improve the surface quality, mechanical properties and printing accuracy of photocuring rapid prototyping parts, and to enrich the types of photosensitive resins for photocuring rapid prototyping. Photosensitive resin enables light-curing rapid prototyping to manufacture molded parts with a matte effect, which has a better viewing experience and promotes the application of light-curing rapid prototyping in more fields.

Another object of the present invention is to provide a method for preparing a matt photosensitive resin for photocuring rapid prototyping, which has a simple process and low cost, and can rapidly and large-scale produce a matt photosensitive resin that meets the requirements of photocuring rapid prototyping.

To achieve the above object, the present invention adopts the following technical solutions:

A matte photosensitive resin for light-curing rapid prototyping, which is made of the following raw materials in parts by weight: urethane acrylate 5-45, epoxy resin 5-45, reactive diluent 10-25, cationic light Polymerization initiator 1~8, free radical photopolymerization initiator 1~8, micron silica 1~10, polyethylene wax powder 1~10, nonionic surfactant 1~3.

The ratio of the parts by weight of the micron silicon dioxide to the polyethylene wax powder is 1:3 to 6:1, the particle diameters of the micron silicon dioxide and the polyethylene wax powder are both 1 to 15 microns, and the refractive indices are both 1 to 15 microns. It is 1.45~1.54.

The viscosity of the matte photosensitive resin for light-curing rapid prototyping is 100-300 mPa·s (25° C.).

The epoxy resin is one of aliphatic glycidyl ether epoxy resin, alicyclic epoxy resin or a mixture thereof.

The cycloaliphatic epoxy resin is 3,4-epoxy-6-methylcyclohexylcarboxylate-3',4'-epoxy-6'-methylcyclohexylmethyl ester.

The reactive diluent is one or a mixture of ethylene glycol diglycidyl ether diacrylate or tripropylene glycol diglycidyl ether diacrylate.

The cationic photopolymerization initiator is one or a mixture of two or more of diaryliodonium hexafluorophosphate, diaryliodonium hexafluoroarsenate or triarylsulfonium hexafluorophosphate.

The free radical photopolymerization initiator is one or a mixture of two or more of benzoin dimethyl ether, chlorinated benzophenone, and 1-hydroxycyclohexylbenzophenone.

The nonionic surfactant is one or a mixture of fatty alcohol polyoxyethylene ether, fatty acid methyl ester ethoxylate, polyoxyethylene sorbitan monostearate.

The preparation method of the water-washable ultraviolet laser curing rapid prototyping photosensitive resin, the steps are as follows: according to the weight ratio, first stir the micron silicon dioxide, polyethylene wax powder and nonionic surfactant, and then add the remaining polyurethane acrylic acid Ester, epoxy resin, reactive diluent, cationic photopolymerization initiator and free radical photopolymerization initiator, and then heated to 60~80°C and stirred for 60~120 minutes to make it into a light yellow uniform liquid.

The basic principles of the present invention are as follows: urethane acrylate, epoxy resin, active diluent and initiator constitute the main components of the matte photosensitive resin of the present invention. Among them, the polymerization of epoxy resin is ring-opening polymerization, with small shrinkage, and the polymerization of urethane acrylate is the polymerization of carbon-carbon double bond breaking into single bond, with great shrinkage, but the curing rate of urethane acrylate under ultraviolet laser irradiation is faster than The curing rate of epoxy resin, so what the matte photosensitive resin of the present invention uses is the composite resin that epoxy resin and urethane acrylate are formed, while improving mechanical property, guarantee that photosensitive resin shrinkage rate is little when photocuring, molding High precision and high enough photosensitivity. Traditional reactive diluents such as trihydroxypropane triacrylate, tripropylene glycol diacrylate, etc. are highly volatile and irritating, and have certain pollution to the working environment. In the present invention, the glycidyl ether acrylate with less irritation is selected. As a reactive diluent, it can reduce the irritation of photosensitive resin while ensuring the photocuring effect, and reduce the pollution to the working environment.

Micron silica and polyethylene wax powder are used to achieve the matt effect of photosensitive resins. The particle size of 1-15 microns can ensure that the formed three-dimensional entity has a fine granular surface to achieve a matte effect, and the shading rate of 1.45-1.54 is close to the shading rate of the photosensitive resin to ensure the transparency of the photosensitive resin for photo-curing molding. Among them, micron silica has good compatibility with epoxy resin, etc., but it cannot migrate to the surface of the material to achieve a matte effect when used alone, and polyethylene wax powder has poor compatibility with polar epoxy resin, etc. , the combination of the two can achieve the best matte effect. Nonionic surfactants are used to effectively disperse micron silica and polyethylene wax powder in photosensitive resins to prevent precipitation due to long-term storage.

The advantages and beneficial effects that the present invention has are:

1. The present invention unexpectedly finds that by adding micron silicon dioxide and polyethylene wax powder, the three-dimensional entity obtained by photocuring rapid prototyping of the photosensitive resin has a good matte effect.

2. The present invention unexpectedly finds that no clear printing texture can be observed on the surface of the molded parts manufactured by light-curing rapid prototyping using a matt photosensitive resin, which significantly improves the surface quality of the molded parts.

3. The photosensitive resin of the present invention, due to the addition of micron silicon dioxide and polyethylene wax powder, makes the three-dimensional entity of light-cured rapid prototyping have better mechanical properties, and can also reduce the shrinkage and warpage of the molded parts at the same time, and improve the printing quality. Accuracy and practicality are stronger.

4. The preparation method of the matt photosensitive resin of the present invention is easy to operate, requires relatively low process conditions and production equipment, can realize large-scale popularization and production, has broad market prospects, and excellent market benefits.

detailed description

The present invention will be further described below in conjunction with specific embodiments. It should be understood that the following examples are only used to illustrate the present invention rather than limit the scope of the present invention, and those skilled in the art can make some non-essential improvements and adjustments based on the content of the above invention.

Comparative example 1

A matte photosensitive resin for light-curing rapid prototyping, which is made of the following raw materials: 5-45 parts of polyurethane acrylate, 5-45 parts of epoxy resin, reactive diluent (ethylene glycol diglycidyl ether di Acrylate or tripropylene glycol diglycidyl ether diacrylate) 10~25 parts, cationic photopolymerization initiator 1~8 parts, free radical photopolymerization initiator 1~8 parts, micron silicon dioxide 1~10 parts, 1~10 parts of polyethylene wax powder, 1~3 parts of nonionic surfactant.

The preparation method of the above-mentioned curing rapid prototyping matte photosensitive resin is as follows:

According to the weight ratio, first stir the micron silica, polyethylene wax powder and nonionic surfactant, and then add the remaining polyurethane acrylate, epoxy resin, active diluent, cationic photopolymerization initiator and free radical Type photopolymerization initiator, then heated to 60~80°C and stirred for 60~120 minutes to mix evenly.

Comparative example 2

A matte photosensitive resin for light-curing rapid prototyping, which is made of the following raw materials: 45 parts of polyurethane acrylate, epoxy resin (3,4-epoxy-6-methylcyclohexylcarboxylic acid-3' , 4'-epoxy-6'-methylcyclohexyl methyl ester) 30 parts, reactive diluent (tripropylene glycol diglycidyl ether diacrylate) 15 parts, cationic photopolymerization initiator (diaryliodonium Hexafluorophosphate) 2 parts, free radical photopolymerization initiator (benzoin dimethyl ether) 1 part, micron silicon dioxide 3 parts, nonionic surfactant (fatty alcohol polyoxyethylene ether) 1 part.

The preparation method of the above-mentioned light curing rapid prototyping matt photosensitive resin is as follows:

According to the weight ratio, first stir the micron silica and nonionic surfactant evenly, and then add the remaining urethane acrylate, epoxy resin, reactive diluent, cationic photopolymerization initiator and free radical photopolymerization initiator , and then heated to 60°C and stirred for 120 minutes to make it a light yellow homogeneous liquid.

Comparative example 3

A matte photosensitive resin for light-curing rapid prototyping, which is made of the following raw materials: 45 parts of polyurethane acrylate, epoxy resin (3,4-epoxy-6-methylcyclohexylcarboxylic acid-3' , 4'-epoxy-6'-methylcyclohexyl methyl ester) 30 parts, reactive diluent (tripropylene glycol diglycidyl ether diacrylate) 15 parts, cationic photopolymerization initiator (diaryliodonium Hexafluorophosphate) 2 parts, free radical photopolymerization initiator (benzoin dimethyl ether) 1 part, polyethylene wax powder 3 parts, nonionic surfactant (fatty alcohol polyoxyethylene ether) 1 part.

The preparation method of the above-mentioned light curing rapid prototyping matt photosensitive resin is as follows:

According to the weight ratio, first stir the polyethylene wax powder and nonionic surfactant evenly, and then add the remaining polyurethane acrylate, epoxy resin, reactive diluent, cationic photopolymerization initiator and free radical photopolymerization initiator , and then heated to 80°C and stirred for 60 minutes to make it a pale yellow homogeneous liquid.

Example 1

The matte photosensitive resin for photocuring rapid prototyping of the present embodiment is made of the following raw materials: 45 parts of polyurethane acrylate, epoxy resin (3,4-epoxy-6-methylcyclohexylcarboxylic acid- 3',4'-epoxy-6'-methylcyclohexyl methyl ester) 30 parts, reactive diluent (tripropylene glycol diglycidyl ether diacrylate) 15 parts, cationic photopolymerization initiator (diaryl iodonium hexafluorophosphate) 2 parts, free radical photopolymerization initiator (benzoin dimethyl ether) 1 part, micron silicon dioxide 3 parts, polyethylene wax powder 3 parts, nonionic surfactant (fatty alcohol polyoxygen Vinyl ether) 1 part.

The preparation method of the light-curing rapid prototyping matte photosensitive resin of the present embodiment is as follows:

According to the weight ratio, first stir the micron silica, polyethylene wax powder and nonionic surfactant, and then add the remaining polyurethane acrylate, epoxy resin, active diluent, cationic photopolymerization initiator and free radical Type photopolymerization initiator, then heated to 70 ° C and stirred for 100 minutes to make it a light yellow homogeneous liquid.

Example 2

The matte photosensitive resin for photocuring rapid prototyping of the present embodiment is made of the following raw materials: 5 parts of polyurethane acrylate, 45 parts of epoxy resin (aliphatic glycidyl ether epoxy resin), reactive diluent ( Ethylene glycol diglycidyl ether diacrylate) 20 parts, cationic photopolymerization initiator (triarylsulfonium hexafluorophosphate) 1.0 parts, radical photopolymerization initiator (chlorinated benzophenone) 8 parts , 10 parts of micron silicon dioxide, 1 part of polyethylene wax powder, 2 parts of nonionic surfactant (polyoxyethylene sorbitan monostearate).

The preparation method of the light-cured rapid prototyping matte photosensitive resin of the present embodiment is as follows:

According to the weight ratio, first stir the micron silica, polyethylene wax powder and nonionic surfactant, and then add the remaining polyurethane acrylate, epoxy resin, active diluent, cationic photopolymerization initiator and free radical Type photopolymerization initiator, then heated to 80 DEG C and stirred for 60 minutes to make it a pale yellow homogeneous liquid.

Example 3

The matte photosensitive resin for photocuring rapid prototyping of the present embodiment is made of the following raw materials: 40 parts of polyurethane acrylate, 20 parts of epoxy resin (aliphatic glycidyl ether epoxy resin), reactive diluent ( Ethylene glycol diglycidyl ether diacrylate and tripropylene glycol diglycidyl ether diacrylate) 18 parts, cationic photopolymerization initiator (diaryliodonium hexafluorophosphate) 1 part, radical photopolymerization initiator 8 parts of agent (1-hydroxycyclohexyl benzophenone), 6 parts of micron silicon dioxide, 1 part of polyethylene wax powder, non-ionic surfactant (fatty acid methyl ester ethoxylate and polyoxyethylene sorbitan monohard Fatty acid ester) 2 parts.

The preparation method of the light-curing rapid prototyping matte photosensitive resin of the present embodiment is as follows:

According to the weight ratio, first stir the micron silica, polyethylene wax powder and nonionic surfactant, and then add the remaining polyurethane acrylate, epoxy resin, active diluent, cationic photopolymerization initiator and free radical Type photopolymerization initiator, then heated to 70 DEG C and stirred for 90 minutes to make it a pale yellow homogeneous liquid.

Example 4

The matte photosensitive resin for photocuring rapid prototyping of the present embodiment is made of the following raw materials: 42 parts of polyurethane acrylate, epoxy resin (3,4-epoxy-6-methylcyclohexylcarboxylic acid- 3',4'-epoxy-6'-methylcyclohexyl methyl ester) 28 parts, reactive diluent (ethylene glycol diglycidyl ether diacrylate) 10 parts, cationic photopolymerization initiator (diaryl iodonium hexafluoroarsenate and triarylsulfonium hexafluorophosphate) 2 parts, radical photopolymerization initiator (benzoin dimethyl ether and chlorinated benzophenone) 4 parts, micron silica 6 parts , 5 parts of polyethylene wax powder, 3 parts of nonionic surfactant (fatty alcohol polyoxyethylene ether and fatty acid methyl ester ethoxylate).

The preparation method of the matte photosensitive resin for light-curing rapid prototyping in this embodiment is the same as that in Embodiment 2.

Example 5

The matte photosensitive resin for light-curing rapid prototyping of the present embodiment is made of the following raw materials: 38 parts of polyurethane acrylate, epoxy resin (aliphatic glycidyl ether epoxy resin and 3,4-epoxy resin -6-Methylcyclohexyl carboxylic acid-3',4'-epoxy-6'-methylcyclohexyl methyl ester) 20 parts, reactive diluent (tripropylene glycol diglycidyl ether diacrylate) 25 parts, cationic Type photopolymerization initiator (diaryliodonium hexafluorophosphate and diaryliodonium hexafluoroarsenate) 3.5 parts, free radical type photopolymerization initiator (benzoin dimethyl ether and 1-hydroxycyclohexylbenzene Ketone) 5.5 parts, micron silicon dioxide 4 parts, polyethylene wax powder 3 parts, nonionic surfactant (fatty alcohol polyoxyethylene ether) 1 part.

The preparation method of the matte photosensitive resin for light-curing rapid prototyping in this embodiment is the same as that in Embodiment 3.

Example 6

The matte photosensitive resin for photocuring rapid prototyping of the present embodiment is made of the following raw materials: 32 parts of polyurethane acrylate, epoxy resin (3,4-epoxy-6-methylcyclohexylcarboxylic acid- 3',4'-epoxy-6'-methylcyclohexyl methyl ester) 22 parts, reactive diluent (ethylene glycol diglycidyl ether diacrylate and tripropylene glycol diglycidyl ether diacrylate) 23 parts , cationic photopolymerization initiator (triarylsulfonium hexafluorophosphate) 5.6 parts, free radical photopolymerization initiator (chlorinated benzophenone) 4.4 parts, micron silicon dioxide 1 part, polyethylene wax powder 3 3 parts, nonionic surfactant (polyoxyethylene sorbitan monostearate).

The preparation method of the matte photosensitive resin for light-curing rapid prototyping in this embodiment is the same as that in Embodiment 1.

Example 7

The matte photosensitive resin for photocuring rapid prototyping of the present embodiment is made of the following raw materials: 45 parts of polyurethane acrylate, epoxy resin (3,4-epoxy-6-methylcyclohexylcarboxylic acid- 3',4'-epoxy-6'-methylcyclohexyl methyl ester) 5 parts, reactive diluent (tripropylene glycol diglycidyl ether diacrylate) 25 parts, cationic photopolymerization initiator (diaryl iodonium hexafluoroarsenate) 8 parts, free radical photopolymerization initiator (benzoin dimethyl ether) 1 part, micron silicon dioxide 4 parts, polyethylene wax powder 9 parts, nonionic surfactant (fatty acid methyl ester ethoxylates) 3 parts.

The preparation method of the matte photosensitive resin for light-curing rapid prototyping in this embodiment is the same as that in Embodiment 3.

The units of the above-mentioned Examples 1-7 and Comparative Examples 1-3 are g.

In Examples 1-7 and Comparative Examples 1-3, the particle diameters of micron silica and polyethylene wax powder are both 1-15 microns, and the refractive index is 1.45-1.54.

Table 1 is the material formulation and viscosity of Examples 1-7 and Comparative Examples 1-3.

Table 1 Embodiment 1 ~ 7 and comparative example 1 ~ 3 material formula and viscosity (weight/part)

1. Test methods for mechanical properties and shrinkage of light-cured rapid prototyping photosensitive resin

The prepared light-cured rapid prototyping matte photosensitive resin was printed as a sample sample strip for testing by using a Form1 3D printer from Formlabs in the United States. The specific printing conditions are: the thickness of the forming layer is 0.10 mm, the scanning speed is 20 cm ³ /h, and other parameters such as scanning line width are formed with the default parameters of the system.

Mechanical property tests include tensile property test, bending property test and impact strength test. The tensile performance test is carried out in accordance with GB/T 1040, and the printed sample sample size is 150×10×4 mm, and the tensile speed is 50 mm/min; the bending performance test is carried out in accordance with GB/T 9341, and the printed sample sample The strip size is 80×10×4 mm, the bending speed is 2 mm/min, and the span is 64 mm; the Charpy impact strength is tested according to GB/T 1043, and the printed sample spline size is 80×6×4mm, The depth of the notch is one third of the thickness of the specimen. The comprehensive mechanical performance test of the material is judged by the values of tensile strength, elongation at break, flexural modulus and impact strength obtained from the test.

The shrinkage test is to use a vernier caliper to accurately measure the actual width W2 of the printed sample sample for tensile testing (the design sample width W1=10 mm), and the ratio of the absolute value of the difference between W2 and W1 to W1 is Shrinkage. The smaller the shrinkage, the higher the printing accuracy.

2. Test method for glossiness of matte photosensitive resin curing molding for light-curing rapid prototyping

The gloss test of the photosensitive resin after curing and molding is carried out according to GB/T 8807-1988. The length, width and height of the printed sample are 50×50×1 mm, and the gloss of the sample is measured with a specular gloss meter. Place the sample horizontally on a flat plate, use a D65 light source for the specular gloss meter, adjust the incident angle irradiated on the sample to 45°, repeat the test three times, count the test values and calculate the average value, that is, the final glossiness of the sample. Table 2 is the test results of mechanical properties, shrinkage rate and gloss of the samples of Examples 1-7 and Comparative Examples 1-3.

Table 2 Examples 1-7 and comparative examples 1-3 sample mechanical properties, shrinkage and gloss test results

As can be seen from Table 2, compared with Comparative Example 1, after adding micron silicon dioxide in the photosensitive resin in Comparative Example 2, the mechanical properties have been significantly enhanced, and the shrinkage rate has also significantly decreased. After adding polyethylene wax powder in Comparative Example 3, The mechanical properties are improved compared with Comparative Example 1, and the shrinkage rate is reduced, but the effect is not much different from that of Comparative Example 2. Micron silicon dioxide and polyethylene wax powder are added together in Example 1 (the amount of micron silicon dioxide and polyethylene wax powder After the dosage ratio is 1:1), the mechanical properties of the photosensitive resin after curing and molding have been further improved under the joint action of micron silica and polyethylene wax powder, and the tensile strength, elongation at break and notched impact strength are relatively good. Both ratio 2 and comparative example 3 are significantly improved, the shrinkage rate is further reduced, the printing accuracy is improved, and the practicability is stronger.

The materials of Comparative Examples 1-3 and Examples 1-7 were printed as samples of 50×50×1 mm, and the light transmittance of the samples was tested according to the above-mentioned glossiness test method. It can be seen from Table 2 that in Comparative Example 1, the surface of the sample is smooth and the gloss is high, reaching 92.3%. The addition of micron silica in Comparative Example 2 resulted in a matte effect after the photosensitive resin was cured and molded, and the gloss decreased to 45.2%. The addition of polyethylene wax powder in Comparative Example 3 is beneficial to reduce the gloss, and a photosensitive resin molded part with uneven surface is obtained. At this time, the gloss of the sample is reduced to 48.1%. After micron silicon dioxide and polyethylene wax powder were added together in Example 1, the glossiness of the sample was significantly further reduced, and the glossiness was 35.6%. It can be seen from this that the glossiness of the material has been significantly reduced due to the addition of micron silicon dioxide and polyethylene wax powder, which is conducive to the formation of the matte effect of the material.

Examples 2-7 are photocurable rapid prototyping matt photosensitive resins prepared within the scope of the components described in the present invention. The manufactured samples have obvious matt effects, significantly improved mechanical properties, low shrinkage, and high printing accuracy. High, indicating that the matte photosensitive resin of the present invention can be well applied to the light-curing rapid prototyping technology, which is conducive to the popularization and use of the light-curing rapid prototyping technology.

The basic principles and main features of the present invention and the advantages of the present invention have been shown and described above. Those skilled in the industry should understand that the present invention is not limited by the above-mentioned embodiments, and what described in the above-mentioned embodiments and the description only illustrates the principles of the present invention, and the present invention will also have other functions without departing from the spirit and scope of the present invention. Variations and improvements all fall within the scope of the claimed invention. The protection scope of the present invention is defined by the appended claims and their equivalents.

Claims (10)

1. A light-curing rapid prototyping matt photosensitive resin is characterized in that it is made of the following raw materials in parts by weight: urethane acrylate 5~45, epoxy resin 5~45, reactive diluent 10~ 25. Cationic photopolymerization initiator 1~8, free radical photopolymerization initiator 1~8, micron silicon dioxide 1~10, polyethylene wax powder 1~10, nonionic surfactant 1~3. 2. the light-curing rapid prototyping matte photosensitive resin according to claim 1, is characterized in that: the ratio of the parts by weight of the micron silicon dioxide and polyethylene wax powder is 1:3 ~ 6:1, so Both the micron silicon dioxide and the polyethylene wax powder have a particle diameter of 1-15 microns, and a refractive index of 1.45-1.54. 3. The matte photosensitive resin for light-curing rapid prototyping according to claim 1, characterized in that: the viscosity of the matt photosensitive resin for light-curing rapid prototyping is 100-300 mPa·s. 4. light-curing rapid prototyping according to claim 1 is characterized in that: described epoxy resin is a kind of in aliphatic glycidyl ether epoxy resin, alicyclic epoxy resin or its mixture. 5. The light-curing rapid prototyping matte photosensitive resin according to claim 4, characterized in that: the cycloaliphatic epoxy resin is 3,4-epoxy-6-methylcyclohexylcarboxylic acid-3' , 4'-epoxy-6'-methylcyclohexyl methyl ester. 6. The light-curing rapid prototyping matte photosensitive resin according to claim 1, characterized in that: the reactive diluent is one of ethylene glycol diglycidyl ether diacrylate or tripropylene glycol diglycidyl ether diacrylate one or a mixture of both. 7. The matte photosensitive resin for light-curing rapid prototyping according to claim 1, characterized in that: the cationic photopolymerization initiator is diaryliodonium hexafluorophosphate, diaryliodonium hexafluoroarsenic One or a mixture of two or more of triarylsulfonium hexafluorophosphate or triarylsulfonium hexafluorophosphate. 8. The light-curing rapid prototyping matte photosensitive resin according to claim 1, characterized in that: the radical photopolymerization initiator is benzoin dimethyl ether, chlorinated benzophenone, 1-hydroxycyclohexyl One or a mixture of two or more of benzophenones. 9. The light-curing rapid prototyping matt photosensitive resin according to claim 1, characterized in that: the nonionic surfactant is fatty alcohol polyoxyethylene ether, fatty acid methyl ester ethoxylate, polyoxyethylene sorbate One or more mixtures of alcohol anhydride monostearate. 10. According to any one of claims 1 to 9, the preparation method of water-washable ultraviolet laser curing rapid prototyping photosensitive resin is characterized in that the steps are as follows: according to the weight ratio, first micron silicon dioxide, polyethylene wax powder and non- Stir the ionic surfactant evenly, then add the remaining urethane acrylate, epoxy resin, reactive diluent, cationic photopolymerization initiator and free radical photopolymerization initiator, then heat to 60~80°C and stir for 60~120 Minutes to make it a light yellow homogeneous liquid.