CN111004355A - DLP (digital light processing) type photocuring 3D printing resin and preparation method thereof - Google Patents

DLP (digital light processing) type photocuring 3D printing resin and preparation method thereof Download PDF

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Publication number
CN111004355A
CN111004355A CN201911084468.2A CN201911084468A CN111004355A CN 111004355 A CN111004355 A CN 111004355A CN 201911084468 A CN201911084468 A CN 201911084468A CN 111004355 A CN111004355 A CN 111004355A
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monomer
printing
dlp
printing resin
acrylate
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董先明
吕展衡
陈品鸿
周武艺
罗颖
杨乐敏
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South China Agricultural University
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South China Agricultural University
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    • C—CHEMISTRY; METALLURGY
    • 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
    • C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
    • 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
    • B33Y10/00—Processes of additive manufacturing
    • 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
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)

Abstract

The invention belongs to the technical field of high polymer materials and 3D printing materials, and particularly relates to DLP (digital light processing) type photocuring 3D printing resin and a preparation method thereof. The photocuring 3D printing resin is a blending liquid containing the following raw materials: the monomer A, the monomer B, the oligomer C, a photoinitiator, a diluent, a defoaming agent and an antioxidant; the monomer A is a mercapto carboxylic ester compound, the monomer B is an allyl or triacrylate compound, and the oligomer C is urethane acrylate. The photocuring 3D printing resin disclosed by the invention is high in curing speed, low in shrinkage rate of a printed finished product, high in glossiness, good in light transmittance, not easy to yellow and age, and the mechanical property of the photocuring 3D printing resin reaches the strength similar to that of an ABS injection molding. The resin is simple in preparation process, easy to operate, low in toxicity, small in smell and environment-friendly, is green and environment-friendly photocuring 3D printing resin, and can be applied to the 3D printing and manufacturing fields of teeth, jewelry, optical lenses, lamps and the like.

Description

DLP (digital light processing) type photocuring 3D printing resin and preparation method thereof
Technical Field
The invention belongs to the technical field of light-cured resin and 3D printing materials, and particularly relates to DLP (digital light processing) type light-cured 3D printing resin and a preparation method thereof.
Background
The photocuring 3D printing technology is a novel material processing and forming method which is based on a three-dimensional model and is a method for directly printing a solid model by adding materials layer by layer. The technology can print parts with diversified shapes and appearances and individuation without manufacturing a die, thereby greatly simplifying the production process of the product. At present, the photocuring 3D printing resin is generally prepared from oligomers such as polyacrylic resin, epoxy acrylic resin, polyurethane acrylic resin and the like as raw materials, active monomers such as acrylates and vinyl ethers, photoinitiators such as cationic type, free radical/cationic hybrid type and the like, and other additives. The cationic photocurable resin has a high cost price, and thus has a great limitation in application. The traditional free radical type light-cured resin has the advantages of low raw material price and relatively mild reaction conditions, but the curing speed of the resin is relatively slow, the time consumption is long when the resin is applied to 3D printing, the shrinkage rate of the cured resin is large, the mechanical property is poor, and the application of the 3D printing is also greatly limited.
At present, by utilizing the advantages of the click reaction of sulfydryl and double bonds in a photosensitive resin structure, a photosensitive resin material with good mechanical property, high curing speed and high molding precision can be obtained. Chinese patent CN101665552A discloses a 3D printing photosensitive resin prepared from six different components, i.e., 2-bis (2-mercaptoethylthio) -3-mercaptopropane, isocyanates, a-methyl methacrylate, tetrabromobisphenol a, 2-hydroxy-3-phenoxyacrylic propyl ester, styrene compounds, etc., which can be used for preparing optical resin lenses with high refractive index by 3D printing. However, the structure composition is relatively complex, styrene compounds with large odor and tetrabromobisphenol A compounds with large harm are contained, the preparation process is complex, and the cost is high, so that the method cannot be used for industrial production on a large scale. In addition, the resin has many additives, requires a long preparation time, and lacks detailed parameters of a printing process in 3D printing, resulting in inconvenience in application. Therefore, the development of a photo-curing 3D printing resin which is simple to prepare, has a small smell and low toxicity, is fast in reaction speed, has high mechanical properties, and is widely applicable is urgently needed.
Disclosure of Invention
In order to overcome the defects of large smell, high toxicity, multiple components, complex preparation process and the like of the existing 3D printing resin, the invention provides the DLP type photocuring 3D printing resin which is small in smell, low in toxicity, good in mechanical property and printing property and can be prepared through a simple process.
In order to solve the technical problems, the invention is realized by the following technical scheme:
the DLP type photocuring 3D printing resin comprises the following raw materials: monomer A, monomer B, oligomer C, photoinitiator, diluent, defoaming agent and antioxidant.
Preferably, the DLP type light-curing 3D printing resin comprises the following raw materials in parts by weight: 9-30 parts of monomer A, 40-120 parts of monomer B, 5-20 parts of oligomer C, 0.2-0.8 part of photoinitiator, 10-25 parts of diluent, 0.05-0.5 part of defoaming agent and 0.1-1 part of antioxidant.
More preferably, the DLP type light-curing 3D printing resin comprises the following raw materials in parts by weight: 9-16 parts of monomer A, 60-80 parts of monomer B, 6-10 parts of oligomer C, 0.4-0.6 part of photoinitiator, 13-18 parts of diluent, 0.2-0.3 part of defoaming agent and 0.4-0.6 part of antioxidant.
Preferably, the monomer A is a mercapto-containing carboxylic acid ester compound, and the mercapto-containing carboxylic acid ester compound is at least one of pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), ethylene glycol dimercaptoacetate, and tridecyl 3-mercaptopropionate.
Preferably, the monomer B is an allyl compound or a triacrylate compound, wherein the allyl compound is at least one of allyl vinyl ester, 1,3, 5-triallyl cyanurate, 1,3, 5-tri-2-propenyl-1, 3, 5-triazine-2, 4,6(1H, 3H, 5H) -trione, and allyl 10-undecenoate, and the triacrylate compound is at least one of trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, and pentaerythritol triacrylate.
Preferably, the oligomer C is at least one of pentadecafunctional urethane acrylate and nonadecanofunctional urethane acrylate, and is available from good chemical (china) ltd, germany.
Preferably, the photoinitiator is at least one of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), 1-hydroxycyclohexylphenylketone (184), 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173), phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide (819), 2-methyl-1- (4-methylthiophenyl) -2-morpholine-1-propanone (907).
Preferably, the diluent is one or two of acrylic acid and acrylate compounds, wherein the acrylate compounds are at least one of butyl acrylate, isooctyl acrylate, isobornyl acrylate, tetrahydrofuryl acrylate, 2-methoxyethyl acrylate, hydroxyethyl acrylate and hydroxypropyl acrylate.
Preferably, the defoaming agent is a UV special defoaming agent, more preferably a defoaming agent JY-821, which is purchased from Jiangsu Jianyu auxiliary agent science and technology limited company.
Preferably, the antioxidant is one of jiedengying antioxidants 1726 and 1010, which are available from jiede new material science and technology limited.
Another object of the present invention is to provide a method for preparing the DLP type photocurable 3D printing resin, comprising the steps of:
(1) uniformly mixing the monomer A and the monomer B, adding the oligomer C, and uniformly mixing to obtain a mixed solution;
(2) and sequentially adding the photoinitiator, the diluent, the defoaming agent and the antioxidant into the obtained mixed solution, and continuously stirring for 15-20min under the shading condition to obtain the DLP type photocuring 3D printing resin.
Compared with the existing DLP type photocuring 3D printing resin, the invention has the following positive beneficial effects:
(1) the product printed by the DLP type photocuring 3D printing resin has the advantages of low shrinkage, high precision, good mechanical property, high glossiness, good light transmittance, yellowing resistance and aging resistance. Mechanical property tests show that the bending strength of the 3D printed sample strip reaches 95 MPa, the tensile strength reaches 53 MPa, and the notch impact strength reaches 7 KJ/m2The strength similar to ABS injection molding is achieved.
(2) The DLP type photocuring 3D printing resin disclosed by the invention is simple in preparation process, easy to operate, low in toxicity, small in smell and environment-friendly, is an environment-friendly photocuring 3D printing resin, and can be applied to the fields of 3D printing and manufacturing of teeth, jewelry, optical lenses, lamps and the like.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The reagents used in the examples are, unless otherwise specified, commercially available reagents or starting materials, and the test methods used in the examples are, unless otherwise specified, conventional in the art. The specific method for testing the mechanical property of the cured photocuring 3D printing resin is as follows: the tensile test is carried out according to the national standard GB/T1040-. The bending test is carried out according to the national standard GB/T9341-. The notch impact test is carried out according to the national standard GB/T1043-2008 standard.
Example 1
A DLP type photocuring 3D printing resin is prepared by the following steps:
(1) 11.94g pentaerythritol tetrakis (3-mercaptopropionate) ester (monomer A) and 64.72g 1,3, 5-tri-2-propenyl-1, 3, 5-triazine-2, 4,6(1H, 3H, 5H) -trione (monomer B) were weighed and stirred for 100 seconds, respectively; then 8.16g of polyurethane acrylate (oligomer C) with fifteen functionality is added and mixed for 5min until the solution is mixed evenly;
(2) 0.526 g of photoinitiator TPO, 15.73 g of diluent butyl acrylate, 0.25g of antifoaming agent JY-821 and 0.52g of antioxidant 1726 are sequentially added into the mixed solution, and stirred for 15 min on a magnetic stirrer under the condition of shading to obtain the DLP type photocuring 3D printing resin.
And (3) putting the obtained 3D printing resin into a liquid tank of a DLP type 3D printer, setting printer parameters, wherein the number of printing layers is 80, and the thickness of the printing layers is 0.05 mm. Printing under the conditions that the wavelength is 405 nm and the ultraviolet lamp power is 80W, wherein the printing time is 18s at the bottom layer and 6s at each layer to obtain a 3D printing test standard sample strip, and the detection result of the mechanical property after curing is shown in Table 1.
Example 2
A DLP type photocuring 3D printing resin is prepared by the following steps:
(1) 9.27g of tridecyl 3-mercaptopropionate (monomer A) and 75.85g of triallyl 1,3, 5-cyanurate (monomer B) were weighed out and stirred for 100 seconds; then adding 9.17g of polyurethane acrylate (oligomer C) with fifteen functionality, mixing and stirring for 5min until the solution is uniformly mixed;
(2) 0.475 g of photoinitiator 819, 16.74 g of isooctyl acrylate serving as a diluent, 0.28g of antifoaming agent JY-821 and 0.55g of antioxidant 1726 are sequentially added into the mixed solution, and the mixture is stirred for 15 min on a magnetic stirrer under the shading condition, so that the DLP type photocuring 3D printing resin is obtained.
And (3) putting the obtained 3D printing resin into a liquid tank of a DLP type 3D printer, setting printer parameters, wherein the number of printing layers is 80, and the thickness of the printing layers is 0.05 mm. Printing under the conditions that the wavelength is 405 nm and the ultraviolet lamp power is 80W, wherein the printing time is 18s at the bottom layer and 6s at each layer to obtain a 3D printing test standard sample strip, and the detection result of the mechanical property after curing is shown in Table 1.
Example 3
A DLP type photocuring 3D printing resin is prepared by the following steps:
(1) weighing 11.48g trimethylolpropane tri (3-mercaptopropionate) (monomer A) and 63.61g trimethylolpropane triacrylate (monomer B) and stirring for 100 s; then 6.78g of nine-functionality-degree polyurethane acrylate (oligomer C) is added and mixed for 5min until the solution is mixed evenly;
(2) 0.482 g of photoinitiator 184, 13.69 g of tetrahydrofuran acrylate serving as a diluent, 0.22g of antifoaming agent JY-821 and 0.53g of antioxidant 1010 are sequentially added into the mixed solution, and stirring is carried out for 15 min on a magnetic stirrer under the shading condition, so that the DLP type photocuring 3D printing resin is obtained.
And (3) putting the obtained 3D printing resin into a liquid tank of a DLP type 3D printer, setting printer parameters, wherein the number of printing layers is 80, and the thickness of the printing layers is 0.05 mm. Printing under the conditions that the wavelength is 405 nm and the ultraviolet lamp power is 80W, wherein the printing time is 18s at the bottom layer and 6s at each layer to obtain a 3D printing test standard sample strip, and the detection result of the mechanical property after curing is shown in Table 1.
Example 4
A DLP type photocuring 3D printing resin is prepared by the following steps:
(1) 12.28g of pentaerythritol tetrakis (3-mercaptopropionate) (monomer A) and 65.93g of ethoxylated trimethylolpropane triacrylate (monomer B) were weighed out and stirred for 100 s. Then adding 9.06g of polyurethane acrylate (oligomer C) with fifteen functionality, mixing and stirring for 5min until the solution is uniformly mixed;
(2) 0.47 g of photoinitiator 907, 17.24 g of diluent hydroxyethyl acrylate, 0.27g of defoaming agent JY-821 and 0.46g of antioxidant 1726 are sequentially added into the mixed solution, and stirred for 15 min on a magnetic stirrer under the condition of shading to obtain the DLP type photocuring 3D printing resin.
And (3) putting the obtained 3D printing resin into a liquid tank of a DLP type 3D printer, setting printer parameters, wherein the number of printing layers is 80, and the thickness of the printing layers is 0.05 mm. Printing under the conditions that the wavelength is 405 nm and the ultraviolet lamp power is 80W, wherein the printing time is 18s at the bottom layer and 6s at each layer to obtain a 3D printing test standard sample strip, and the detection result of the mechanical property after curing is shown in Table 1.
Example 5
A DLP type photocuring 3D printing resin is prepared by the following steps:
(1) 15.87g trimethylolpropane tris (2-mercaptoacetic acid) ester (monomer A) and 74.94g propoxylated trimethylolpropane triacrylate (monomer B) were weighed and stirred for 100 s. Then 10.06g of nine-functionality polyurethane acrylate (oligomer C) is added and mixed for 5min until the solution is mixed evenly;
(2) 0.49 g of photoinitiator 907, 17.29 g of diluent hydroxyethyl acrylate, 0.27g of antifoaming agent JY-821 and 0.58g of antioxidant 1726 are sequentially added into the mixed solution and stirred for 15 min on a magnetic stirrer under the condition of shading to obtain the DLP type photocuring 3D printing resin.
And (3) putting the obtained 3D printing resin into a liquid tank of a DLP type 3D printer, setting printer parameters, wherein the number of printing layers is 80, and the thickness of the printing layers is 0.05 mm. Printing under the conditions that the wavelength is 405 nm and the ultraviolet lamp power is 80W, wherein the printing time is 18s at the bottom layer and 6s at each layer to obtain a 3D printing test standard sample strip, and the detection result of the mechanical property after curing is shown in Table 1.
Comparative example 1
This comparative example was carried out under the same process conditions and in the same procedure as example 1, except that oligomer C was not added. The test results of the mechanical properties of the test standard sample strips of the DLP type photocuring 3D printing resin prepared by the comparative example after curing are shown in Table 1.
Comparative example 2
This comparative example was conducted under the same conditions and in the same manner as example 1 except that monomer B was replaced with monofunctional Acrylate (ACMO). The test results of the mechanical properties of the test standard sample strips of the DLP type photocuring 3D printing resin prepared by the comparative example after curing are shown in Table 1.
Comparative example 3
This comparative example was conducted under the same conditions and in the same manner as example 1 except that the monomer B was replaced with a difunctional acrylate (HDDA). The test results of the mechanical properties of the test standard sample strips of the DLP type photocuring 3D printing resin prepared by the comparative example after curing are shown in Table 1.
Comparative example 4
This comparative example was conducted under the same process conditions and in the same procedure as in example 1 except that the monomer A was replaced with an epoxy resin. The test results of the mechanical properties of the test standard sample strips of the DLP type photocuring 3D printing resin prepared by the comparative example after curing are shown in Table 1.
TABLE 1 comparison of mechanical Properties
Figure DEST_PATH_IMAGE001
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. The DLP type photocuring 3D printing resin is characterized by comprising the following raw materials: the monomer A, the monomer B, the oligomer C, a photoinitiator, a diluent, a defoaming agent and an antioxidant; the monomer A is a mercapto carboxylic ester compound, the monomer B is an allyl or triacrylate compound, and the oligomer C is urethane acrylate.
2. The DLP type photocuring 3D printing resin as defined in claim 1, comprising the following raw materials in parts by weight: 9-30 parts of monomer A, 40-120 parts of monomer B, 5-20 parts of oligomer C, 0.2-0.8 part of photoinitiator, 10-25 parts of diluent, 0.05-0.5 part of defoaming agent and 0.1-1 part of antioxidant.
3. The DLP type photocuring 3D printing resin as defined in claim 2, comprising the following raw materials in parts by weight: 9-16 parts of monomer A, 60-80 parts of monomer B, 6-10 parts of oligomer C, 0.4-0.6 part of photoinitiator, 13-18 parts of diluent, 0.2-0.3 part of defoaming agent and 0.4-0.6 part of antioxidant.
4. The DLP-type photocurable 3D printing resin according to claim 1, characterized in that: the mercapto carboxylic ester compound is at least one of pentaerythritol tetra (3-mercaptopropionic acid) ester, trimethylolpropane tri (2-mercaptoacetic acid) ester, trimethylolpropane tri (3-mercaptopropionic acid) ester, ethylene glycol dimercaptoacetate and tridecyl 3-mercaptopropionate.
5. The DLP-type photocurable 3D printing resin according to claim 1, characterized in that: the allyl compound is at least one of allyl vinyl ester, 1,3, 5-triallyl cyanurate, 1,3, 5-tri-2-propenyl-1, 3, 5-triazine-2, 4,6(1H, 3H, 5H) -trione and allyl 10-undecylenate, and the triacrylate compound is at least one of trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate and pentaerythritol triacrylate.
6. The DLP-type photocurable 3D printing resin according to claim 1, characterized in that: the oligomer C is at least one of pentadecafunctionality polyurethane acrylate and nonafunctionality polyurethane acrylate.
7. The DLP-type photocurable 3D printing resin according to claim 1, characterized in that: the photoinitiator is at least one of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide and 2-methyl-1- (4-methylthiophenyl) -2-morpholine-1-acetone.
8. The DLP-type photocurable 3D printing resin according to claim 1, characterized in that: the diluent is one or two of acrylic acid and acrylate compounds, wherein the acrylate compounds are at least one of butyl acrylate, isooctyl acrylate, isobornyl acrylate, tetrahydrofuran acrylate, 2-methoxyethyl acrylate, hydroxyethyl acrylate and hydroxypropyl acrylate.
9. The DLP-type photocurable 3D printing resin according to claim 1, characterized in that: the defoaming agent is a defoaming agent JY-821; the antioxidant is one of Jerusalem's jelly antioxidants 1726 and 1010.
10. The method for preparing the DLP type photocurable 3D printing resin according to any one of claims 1 to 9, characterized by comprising the steps of:
(1) uniformly mixing the monomer A and the monomer B, adding the oligomer C, and uniformly mixing to obtain a mixed solution;
(2) and sequentially adding the photoinitiator, the diluent, the defoaming agent and the antioxidant into the obtained mixed solution, and continuously stirring for 15-20min under the shading condition to obtain the DLP type photocuring 3D printing resin.
CN201911084468.2A 2019-11-08 2019-11-08 DLP (digital light processing) type photocuring 3D printing resin and preparation method thereof Pending CN111004355A (en)

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