CN112250802A - DLP (digital light processing) type 3D printing photocuring material with gradual color change and anodic oxidation effect imitation - Google Patents
DLP (digital light processing) type 3D printing photocuring material with gradual color change and anodic oxidation effect imitation Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
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- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
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- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
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Abstract
The invention belongs to the field of 3D printing, in particular to a DLP type 3D printing photocureable material with gradient color and anode oxidation imitating effect, the raw materials comprise the following components in parts by mass: 10-30 parts of high-strength aliphatic urethane acrylate, 10-30 parts of high-toughness aliphatic urethane acrylate, 3-10 parts of monofunctional radical acrylate monomer, 3-10 parts of difunctional radical acrylate monomer, 1-5 parts of pigment, 1-10 parts of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, 1-10 parts of interference color aluminum paste, 1-10 parts of chameleon interference type pearl powder, 1-10 parts of UV curable cellulose ester resin, 1-10 parts of non-floating resin coated aluminum paste, 1-10 parts of electrosilvering resin and 1-10 parts of anti-settling additive. The invention combines two effects of gradient color and anodic oxidation effect, achieves the appearance effects of high metal texture, dazzling color and gradient color, and has excellent mechanical property and good storage stability of the toner.
Description
Technical Field
The invention belongs to the field of 3D printing, and particularly relates to a DLP type 3D printing photocuring material with gradual color change and an anodic oxidation effect imitation.
Background
With the gradual development of the 3D printing industry, the requirement of people on the attractiveness of a formed product is higher and higher, most DLP type 3D printing light-curing materials with 385nm wave bands on the market are monotonous in color appearance, are pure-color 3D printing light-curing materials, do not have good texture, and can be realized only by carrying out post-treatment secondary paint spraying when the effects of high metal texture, colorful color, gradient color and the like are required. The DLP type 3D printing photocuring material with slightly good texture has the problems of poor mechanical property and poor storage stability of color paste toner.
Disclosure of Invention
Aiming at the problems in the prior art, the DLP type 3D printing photocuring material with gradient color and an imitation anodic oxidation effect is provided, two effects of gradient color and imitation anodic oxidation effect are combined, the appearance effects of high metal texture, color dazzling and gradient color changing are achieved, the types of gradient colors are selected more, the mechanical property is excellent, the storage stability of toner is good, and the stability and the sustainable printing property of the gradient color effect are ensured.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
the DLP type 3D printing photocuring material with the gradual color change and the effect of imitating anodic oxidation comprises, by mass, 10-30 parts of high-strength aliphatic polyurethane acrylate, 10-30 parts of high-toughness aliphatic polyurethane acrylate, 3-10 parts of a monofunctional radical acrylate monomer, 3-10 parts of a difunctional radical acrylate monomer, 1-5 parts of a pigment, 1-10 parts of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 1-10 parts of interference color aluminum paste, 1-10 parts of chameleon interference type pearl powder, 1-10 parts of UV curable cellulose ester resin, 1-10 parts of non-floating resin coated aluminum paste, 1-10 parts of electroplated silver resin and 1-10 parts of an anti-settling auxiliary agent.
The preparation method of the material comprises the following steps: the raw material components are mixed according to the weight portion ratio, and then stirred for 30-45 minutes at 25-50 ℃ to obtain uniform liquid.
The interference color aluminum silver is a metal pigment taking flaky aluminum flakes as base materials.
Furthermore, the interference color aluminum paste takes the flaky aluminum flakes as a base material, a silicon dioxide layer is coated on the surface of the flaky aluminum flakes for silicon wrapping treatment, and metal particles are plated on the flaky aluminum flakes to form metal pigments. The metal particles are made of metals with different colors, including nickel, tin, zinc and copper.
The non-floating resin coated aluminum silver paste has the metal luster like silk, and is narrower in particle size distribution, whiter and stronger in metal feeling compared with common aluminum silver powder products.
The electrosilvering resin is a special multi-component thixotropic acrylic acid modified polymer, and a unique structure and multiple reaction groups are used, so that interference color aluminum silver paste and non-floating resin coated aluminum silver paste obtain a super-bright mirror effect, the super-silver powder is arranged in a metal sense, and is whitened and brightened by several times, and the whiteness of the silver powder and the metal sense of the pearl powder are effectively improved. Further, the electrosilvering resin is a hydroxyl and ethyl cellulose modified acrylate, its macromolecule has many branch structure, there is certain double bond density, and the cellulose in the resin is the macromolecular structure of structural symmetry, after DLP equipment photocuring, macromolecular structure makes the quick shrink solidification of cured layer, with the help of the quick shrink tension of this kind of structure, make interference color aluminium thick liquid and non-superficial type resin parcel type aluminium thick liquid flare-up, help interference color aluminium thick liquid and non-superficial type resin parcel type aluminium thick liquid directional arrangement, the pressurized tends to parallel arrangement, the brightening, obtain the mirror surface effect of a super glittering. And the hydrogen-oxygen bonding network of the resin and the reticular structure of the cellulose generate a special anchoring effect on the non-floating resin coated aluminum silver paste and the interference color aluminum silver paste on the sheet surface modified by the surface modification and the high-molecular complex, so that the movement and rolling of the aluminum silver paste in the material are restrained, the aluminum silver paste is kept in a uniformly dispersed, closely arranged and parallel arrangement state, and the metal feeling of the anodic oxidation is simulated.
The combination of interference color aluminum paste, non-floating resin coated aluminum paste and electro-silvering resin endows the 3D printing material molded workpiece with a high-texture anodic oxidation effect.
The chameleon interference type pearl powder is prepared by taking artificially synthesized transparent flaky silicon dioxide as a substrate, wrapping a metal oxide with a high reflection effect, and wrapping a layer of transparent color pigment capable of absorbing light with certain wavelength. Different color effects, multiple color effects and color flow are presented along with different angles of the observer. The optical phenomena of two different color senses of the application system containing the pigment when observed in the vertical (front) direction and in the side (side direction) direction are caused by the interference and absorption of the incident light by the pigment, and the silica plate crystal with the producible particle size and narrow thickness distribution is made into multilayer light by the transparent SiO2The metal oxide with high reflection effect is wrapped on the crystal plate, and the material shows very pure and bright magic color effect and color-changing property with angle. The color change effect is caused by light interference, and the color generated by light reflection is different due to different thicknesses of the curing layers. Incident light is reflected/refracted by the cured layer, part of the light (e.g., red) passes through the pigment, and the rest (green in this case) is reflected, and since the interference color contains two colors, the background color should be considered. In the case where the background color is white, the complementary color, which is a transmission element, is reflected by it and then the change effect is reduced in order in combination with the original reflected color. In the case where the background is black, the transmitted complementary color is attracted thereto, and the original reflected color is clearly retained.
The combination of the chameleon interference type pearl powder and the interference aluminum paste endows the 3D printing material forming workpiece with a gradient color effect to a certain degree.
The UV-curable cellulose ester resin can increase the setting arrangement of interference aluminum paste, chameleon interference type pearl powder and non-floating type resin-coated aluminum paste, improve the directional arrangement effect, and improve the compatibility of the interference aluminum paste, the chameleon interference type pearl powder and the non-floating type resin-coated aluminum paste with the main resin.
The pigment is a pigment wetting dispersant, and further, the pigment is a polyether phosphate such as digaTEGO Dispers 655.
The anti-settling assistant is a mixture of polyamide wax and oxidized polyethylene wax, such as Japanese Disibulon anti-settling assistant NS-5501.
The high-toughness aliphatic urethane acrylate is selected from the group consisting of molecular weight (Mw) [ measured by GPC ]: 18000 the side chain of the oligomer contains more flexible chain segments of polyether polyol and large molecular segment chains of aliphatic diisocyanate, which brings high notch impact strength and certain tensile strength to the whole material. One of Zhanxin EBECRYL 8413, DIC LUXYDIR ZHU-2047, Yangxing 6113 or DIC UA-230 is used.
The high-strength urethane acrylate is selected from the group consisting of molecular weight (Mw) [ measured by GPC ]: 2100 the oligomer adopts bulk polymerization technology, has uniform molecular morphology, has a molecular structure of soft and hard segment combination, has a certain double bond density, a moderate crosslinking density, more side chains, long-chain urethane acrylate and bicyclic groups on the side chains, has high TG, a certain toughness, good heat resistance, good bending strength and tensile strength. One of Zhanxin EBECRYL 264, Yangxing material 6165 and DIC UA-700 is adopted.
The monofunctional free radical acrylate monomer adopts 4-tert-butyl cyclohexyl acrylate.
The difunctional radical acrylate monomer is hexamethylenediol diacrylate.
The use method of the photocuring material is that according to a workpiece to be printed, the file to be printed is specially processed by using slicing software in the aspect of parameters of a data file of the printed workpiece, the printing layer thickness of each layer is reasonably designed and cut out on the slicing software, the printing layer thicknesses of 50um and 200um are alternately printed, the printing curing time parameters are matched and changed along with the printing layer thickness of each layer, different layer thicknesses exist inside a formed workpiece, different light transmittance and different refractive indexes exist between the different layer thicknesses, and a more obvious gradient color effect is achieved under the action of the chameleon interference type pearl powder.
From the above description, it can be seen that the present invention has the following advantages:
1. according to the invention, interference color aluminum paste and chameleon interference type pearl powder are used, UV-curable cellulose acetate butyrate, non-floating resin-coated aluminum paste and electrosilvering resin are synergistic, so that two effects of gradual color change and anodic oxidation simulation are organically combined, and a high-metal texture, colorful and gradual color change appearance effect is formed.
2. According to the invention, the combination of interference color aluminum paste, non-floating resin coated aluminum paste and electro-silvering resin endows the 3D printing material molded workpiece with a high-texture anodic oxidation effect.
3. The photocuring material provided by the invention adopts an alternate printing mode in a forming process to form different layer thicknesses, and utilizes different light transmittance and different refractive indexes among different layer thicknesses to achieve a more obvious gradient color effect under the action of chameleon interference type pearl powder.
4. The invention combines two effects of gradient color and anodic oxidation effect, achieves the appearance effects of high metal texture, dazzling color and gradient color, has more kinds of gradient colors, excellent mechanical property and good toner storage stability, ensures the stability and sustainable printing property of the gradient color effect, and has more outstanding effect in 385nm wave band.
Detailed Description
The present invention is described in detail with reference to examples, but the present invention is not limited to the claims.
Example 1
The DLP type 3D printing photocuring material with the gradual color change and the simulated anodic oxidation effect comprises, by mass, 10g of high-strength aliphatic polyurethane acrylate, 10g of high-toughness aliphatic polyurethane acrylate, 3g of a monofunctional radical acrylate monomer, 3g of a difunctional radical acrylate monomer, 1g of a pigment, 1g of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 1g of interference color aluminum paste, 1g of chameleon interference type pearl powder, 1g of UV curable cellulose ester resin, 1g of non-floating resin coated aluminum paste, 1g of electroplated silver resin and 1g of an anti-settling additive.
The interference color aluminum paste takes flaky aluminum flakes as a base material, a silicon dioxide layer is coated on the surface layer of the interference color aluminum paste for silicon wrapping treatment, and silver metal particles are plated to form the metal pigment.
The electrosilvering resin is hydroxyl and ethyl cellulose modified acrylate, and macromolecules of the electrosilvering resin have a multi-branch structure.
The chameleon interference type pearl powder is prepared by taking artificially synthesized transparent flaky silicon dioxide as a substrate, wrapping a metal oxide with a high reflection effect, and wrapping a layer of transparent color pigment capable of absorbing light with certain wavelength.
The pigment is TEGO Dispers 655.
The anti-settling auxiliary agent is NS-5501.
The high-toughness aliphatic polyurethane acrylate is Zhan Xin EBECRYL 8413.
The high-strength polyurethane acrylate is used as a new EBECRYL 264.
The monofunctional free radical acrylate monomer adopts 4-tert-butyl cyclohexyl acrylate.
The difunctional radical acrylate monomer is hexamethylenediol diacrylate.
The preparation method of the material comprises the following steps: the raw material components are mixed according to the weight part ratio, and then stirred for 30 minutes at 25 ℃ to obtain uniform liquid.
Example 2
The DLP type 3D printing photocuring material with the gradual color change and the simulated anodic oxidation effect comprises, by mass, 30g of high-strength aliphatic polyurethane acrylate, 30g of high-toughness aliphatic polyurethane acrylate, 10g of a monofunctional radical acrylate monomer, 10g of a difunctional radical acrylate monomer, 5g of a pigment, 10g of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 10g of interference color aluminum paste, 10g of chameleon interference type pearl powder, 10g of UV curable cellulose ester resin, 10g of non-floating resin coated aluminum paste, 10g of electroplated silver resin and 10g of an anti-settling auxiliary agent.
The interference color aluminum paste takes flaky aluminum flakes as a base material, a silicon dioxide layer is coated on the surface layer of the interference color aluminum paste for silicon wrapping treatment, and silver metal particles are plated to form the metal pigment.
The electrosilvering resin is hydroxyl and ethyl cellulose modified acrylate, and macromolecules of the electrosilvering resin have a multi-branch structure.
The chameleon interference type pearl powder is prepared by taking artificially synthesized transparent flaky silicon dioxide as a substrate, wrapping a metal oxide with a high reflection effect, and wrapping a layer of transparent color pigment capable of absorbing light with certain wavelength.
The pigment is TEGO Dispers 655.
The anti-settling auxiliary agent is NS-5501.
The high-toughness aliphatic polyurethane acrylate DIC LUXYDIR ZHU-2047.
The high-strength polyurethane acrylate is made of Changxing material 6165.
The monofunctional free radical acrylate monomer adopts 4-tert-butyl cyclohexyl acrylate.
The difunctional radical acrylate monomer is hexamethylenediol diacrylate.
The preparation method of the material comprises the following steps: the raw material components are mixed according to the weight part ratio, and then stirred for 45min at 50 ℃ to obtain uniform liquid.
Example 3
The DLP type 3D printing photocuring material with the gradual color change and the effect of imitating anodic oxidation comprises, by mass, 20g of high-strength aliphatic polyurethane acrylate, 20g of high-toughness aliphatic polyurethane acrylate, 8g of a monofunctional radical acrylate monomer, 7g of a difunctional radical acrylate monomer, 3g of a pigment, 7g of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 5g of interference color aluminum paste, 6g of chameleon interference type pearl powder, 5g of UV curable cellulose ester resin, 4g of non-floating resin coated aluminum paste, 5g of electroplated silver resin and 3g of an anti-settling additive.
The interference color aluminum paste takes flaky aluminum flakes as a base material, a silicon dioxide layer is coated on the surface layer of the interference color aluminum paste for silicon wrapping treatment, and silver metal particles are plated to form the metal pigment.
The electrosilvering resin is hydroxyl and ethyl cellulose modified acrylate, and macromolecules of the electrosilvering resin have a multi-branch structure.
The chameleon interference type pearl powder is prepared by taking artificially synthesized transparent flaky silicon dioxide as a substrate, wrapping a metal oxide with a high reflection effect, and wrapping a layer of transparent color pigment capable of absorbing light with certain wavelength.
The pigment is TEGO Dispers 655.
The anti-settling auxiliary agent is NS-5501.
The high-toughness aliphatic polyurethane acrylate is also known as DIC UA-230.
DIC UA-700 is adopted as the high-strength polyurethane acrylate.
The monofunctional free radical acrylate monomer adopts 4-tert-butyl cyclohexyl acrylate.
The difunctional radical acrylate monomer is hexamethylenediol diacrylate.
The preparation method of the material comprises the following steps: the raw material components are mixed according to the weight part ratio, and then stirred for 30min at the temperature of 35 ℃ to obtain uniform liquid.
Performance detection
The products of examples 1-3 were tested for performance according to national standards, as follows:
in summary, the invention has the following advantages:
1. according to the invention, interference color aluminum paste and chameleon interference type pearl powder are used, UV-curable cellulose acetate butyrate, non-floating resin-coated aluminum paste and electrosilvering resin are synergistic, so that two effects of gradual color change and anodic oxidation simulation are organically combined, and a high-metal texture, colorful and gradual color change appearance effect is formed.
2. According to the invention, the combination of interference color aluminum paste, non-floating resin coated aluminum paste and electro-silvering resin endows the 3D printing material molded workpiece with a high-texture anodic oxidation effect.
3. The photocuring material provided by the invention adopts an alternate printing mode in a forming process to form different layer thicknesses, and utilizes different light transmittance and different refractive indexes among different layer thicknesses to achieve a more obvious gradient color effect under the action of chameleon interference type pearl powder.
4. The invention combines two effects of gradient color and anodic oxidation effect, achieves the appearance effects of high metal texture, dazzling color and gradient color, has more kinds of gradient colors, excellent mechanical property and good toner storage stability, ensures the stability and sustainable printing property of the gradient color effect, and has more outstanding effect in 385nm wave band.
It should be understood that the detailed description of the invention is merely illustrative of the invention and is not intended to limit the invention to the specific embodiments described. It will be appreciated by those skilled in the art that the present invention may be modified or substituted equally as well to achieve the same technical result; as long as the use requirements are met, the method is within the protection scope of the invention.
Claims (9)
1. The utility model provides a gradual change look and have imitative anodic oxidation effect DLP type 3D and print photocuring material which characterized in that: the material quality proportion is that 10-30 parts of high-strength aliphatic polyurethane acrylate, 10-30 parts of high-toughness aliphatic polyurethane acrylate, 3-10 parts of monofunctional free radical acrylate monomer, 3-10 parts of difunctional free radical acrylate monomer, 1-5 parts of pigment, 1-10 parts of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, 1-10 parts of interference color aluminum silver paste, 1-10 parts of chameleon interference type pearl powder, 1-10 parts of UV curable cellulose ester resin, 1-10 parts of non-floating type resin coated aluminum silver paste, 1-10 parts of electroplated silver resin and 1-10 parts of anti-sinking auxiliary agent.
2. The DLP type 3D printing light curing material with the gradient and the simulated anode oxidation effect according to claim 1, is characterized in that: the interference color aluminum silver is a metal pigment taking flaky aluminum flakes as base materials.
3. The DLP type 3D printing light curing material with the anti-anode oxidation effect and the gradient color as claimed in claim 1, wherein: the monofunctional free radical acrylate monomer adopts 4-tert-butyl cyclohexyl acrylate.
4. The DLP type 3D printing light curing material with the anti-anode oxidation effect and the gradient color as claimed in claim 1, wherein: the difunctional radical acrylate monomer is hexamethylenediol diacrylate.
5. The DLP type 3D printing light curing material with the anti-anode oxidation effect and the gradient color as claimed in claim 1, wherein: the high-strength urethane acrylate is selected from the group consisting of molecular weights: 2100 difunctional cyclic ether alicyclic urethane acrylate oligomer.
6. The DLP type 3D printing light curing material with the anti-anode oxidation effect and the gradient color as claimed in claim 1, wherein: the high-toughness aliphatic urethane acrylate is selected from the group consisting of molecular weight (Mw) [ measured by GPC ]: 18000A difunctional polyurethane acrylate oligomer.
7. The DLP type 3D printing light curing material with the anti-anode oxidation effect and the gradient color as claimed in claim 1, wherein: the pigment adopts a pigment wetting dispersant.
8. The DLP type 3D printing light curing material with the anti-anode oxidation effect and the gradient color as claimed in claim 1, wherein: the anti-settling auxiliary agent is a mixture of polyamide wax and oxidized polyethylene wax.
9. The DLP type 3D printing light curing material with the anti-anode oxidation effect and the gradient color as claimed in claim 1, wherein: the preparation method comprises the following steps: the raw material components are mixed according to the weight portion ratio, and then stirred for 30-45 minutes at 25-50 ℃ to obtain uniform liquid.
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CN114149726A (en) * | 2021-08-25 | 2022-03-08 | 惠州市华阳光学技术有限公司 | Dynamic optical effect layer and preparation method thereof |
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CN107522827A (en) * | 2017-09-20 | 2017-12-29 | 杨军 | A kind of photocuring 3D printing photosensitive resin and its preparation method and application |
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