CN114560976B - Try-on model resin for 3D printing and preparation method and application thereof - Google Patents
Try-on model resin for 3D printing and preparation method and application thereof Download PDFInfo
- Publication number
- CN114560976B CN114560976B CN202210319208.4A CN202210319208A CN114560976B CN 114560976 B CN114560976 B CN 114560976B CN 202210319208 A CN202210319208 A CN 202210319208A CN 114560976 B CN114560976 B CN 114560976B
- Authority
- CN
- China
- Prior art keywords
- parts
- weight
- printing
- try
- model
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
Abstract
The invention relates to a 3D printing try-on model resin, and a preparation method and application thereof, wherein the preparation raw materials of the resin comprise the following components in parts by weight: 10-30 parts by weight of polyurethane acrylate prepolymer; 20-50 parts by weight of polyurethane methacrylate cross-linking agent; 10-30 parts by weight of a monomer; 30-50 parts by weight of a reactive diluent; 1-5 parts by weight of a photoinitiator; 0.1-1 part by weight of defoaming agent. The resin provided by the disclosure has excellent mechanical strength stability, color stability and higher bonding strength after photo-curing, and can meet the mechanical and aesthetic requirements when applied to temporary dental restoration treatment.
Description
Technical Field
The disclosure relates to the technical field of photo-curing materials, in particular to a 3D printing try-on model resin and a preparation method and application thereof.
Background
In recent years, a photocurable 3D printing try-on model resin, also referred to as a 3D printing temporary dental model resin or a 3D printing try-on denture model resin, has been increasingly used. The resin is often used for 3D printing of temporary crowns, bridges, inlays and veneering models to manufacture personalized and customized temporary crown-bridge restoration bodies, thereby meeting the temporary restoration treatment requirements. With the progress of industrial technology, 3D printing resins have the potential to completely replace traditional hand-set temporary crown bridge resins. However, the quality of the currently used 3D printing try-on model resin is uneven, and only a few resins can meet the related standards of ISO-10477, ISO-4049 and the like. Therefore, the cost of such a 3D printing try-on model is high.
At present, most of photocuring models prepared from 3D printing resins can reach bending strength of more than 100MPa under the ASTM-D790 standard. However, the photo-curing model is severely discolored and has obviously reduced mechanical strength after long-term soaking, cold and hot circulation and illumination, namely, the color stability, water resistance and mechanical property stability can not meet the market requirements yet. Generally, when a patient wears a temporary crown clinically, the patient needs to stay in the oral cavity for 1-30 days and go through a long-term cold-hot cycle until the permanent crown is replaced or further repair treatment is received; in the period of wearing the temporary crown, the light-cured model is in a humid environment in the oral cavity of a human body, and the material is easy to soften and become brittle after being subjected to cold and hot circulation, so that the temporary crown is at risk of falling off or cracking; and the photo-curing model prepared by 3D printing of the photosensitive resin can be obviously discolored under the conditions of long-term air exposure, soaking and ultraviolet irradiation.
CN112353694 a provides a 3D printed photocurable material for temporary crowns, which improves the properties of rigidity, toughness, etc. of the photocurable model material by introducing an organic-inorganic hybrid UV resin; CN 111728879A provides a high-performance DLP-3D printing material applied to the field of stomatology and a preparation method thereof, which improves the wear resistance and toughness of a photo-curing model by introducing nano silicon dioxide, and the improved photosensitive resin for 3D printing is used for printing and manufacturing dental products such as crown and bridge and the like through a 3D printing technology and is applied to the field of stomatology. The above patent application does not discuss and optimize the color stability of the temporary crown model for 3D printing in detail, while the prior art does not give quantified data for color stability under the ISO-10477 standard. Under the standard of ISO-10477, according to CIELAB theory, if the color difference delta E of a sample is more than or equal to 1, the naked eye can obviously distinguish the color difference, and the distinguishable color difference is difficult to meet the aesthetic requirement of the temporary crown restoration material in the increasingly-improved oral medicine field, and the temporary crown restoration material has better color simulation degree and color stability and is matched with the color of the natural teeth of a patient as much as possible in aesthetic terms.
At present, a model printed and molded by commercially available trial model resin is usually subjected to soaking for 1-30 days and 5000 times of cold and hot circulation, so that the mechanical strength of the model is obviously reduced, and the color of the model is also obviously changed; these deficiencies can affect the effectiveness of temporary restorations and, in severe cases, can cause the model to fall off or chip in the mouth, adversely affecting the patient's health. Therefore, it is necessary to provide a new 3D printing try-on model resin capable of satisfying application requirements.
Disclosure of Invention
In order to solve the technical problems, the disclosure provides a 3D printing try-on model resin, and a preparation method and application thereof. The resin provided by the disclosure has excellent mechanical strength stability, color stability and higher bonding strength after photo-curing, and can meet the mechanical and aesthetic requirements when applied to temporary dental restoration treatment.
In a first aspect, the present disclosure provides a 3D printing try-on model resin, wherein the resin comprises the following raw materials in parts by weight:
in the printing process of the resin, when the UV light source irradiates the photoinitiator in the resin, the photoinitiator can be induced to generate free radicals, so that the prepolymer, the monomer and the cross-linking agent are caused to generate polymerization reaction, the resin is solidified, and finally, the solid printing product is formed through layer-by-layer photo-solidification in the Z-axis direction in a stacking mode.
The cross-linking agent defined by the disclosure contains a polycarbonate structure, and the molecular chain contains aliphatic methylene and carbonate group repeating units, so that the cross-linking agent has the advantages of strong rigidity, high temperature resistance, difficult hydrolysis, difficult oxidation, difficult decomposition and aging under ultraviolet irradiation; meanwhile, compared with the acrylate structural unit, the cross-linking agent also contains the methacrylate structural unit, and has higher rigidity, better hydrophobicity and lower skin irritation; the crosslinking agent contains trimethyl hexamethylene structural units, and has good hydrophobicity and high hardness; the monomer contains an aliphatic carbon chain structure and has good hydrophobicity; therefore, the mechanical stability of the material can be remarkably improved by adding the hydrolysis-resistant and aging-resistant methacrylate crosslinking agent and the monomer with hydrolysis resistance into the photosensitive resin for 3D printing, and the material can still maintain good mechanical properties after long-term constant-temperature water bath and cold-hot circulation.
The urethane acrylate prepolymer is 10 to 30 parts by weight, for example, 12 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 22 parts by weight, 25 parts by weight, 28 parts by weight, or the like.
20-50 parts by weight of the polyurethane methacrylate cross-linking agent, for example, 25 parts by weight, 30 parts by weight, 32 parts by weight, 35 parts by weight, 38 parts by weight, 40 parts by weight, 42 parts by weight, 45 parts by weight, 48 parts by weight and the like.
The monomer is 10 to 30 parts by weight, for example, 12 parts by weight, 15 parts by weight, 18 parts by weight, 20 parts by weight, 22 parts by weight, 25 parts by weight, 28 parts by weight, or the like.
The reactive diluent is 30 to 50 parts by weight, for example, 32 parts by weight, 35 parts by weight, 38 parts by weight, 40 parts by weight, 45 parts by weight, or the like.
The photoinitiator is 1 to 5 parts by weight, for example, 2 parts by weight, 3 parts by weight, 4 parts by weight, etc.
The antifoaming agent is 0.1 to 1 part by weight, for example, 0.2 part by weight, 0.5 part by weight, 0.6 part by weight, 0.8 part by weight, and the like.
As a preferred technical solution of the present disclosure, the molecular weight of the urethane acrylate prepolymer is 2000-5000, for example 3000, 4000, 5000, etc., the shore hardness of the cured pure prepolymer is above 90D, preferably the prepolymer is selected from any one or a combination of at least two of etenal 6199, SARTOMER CN9010 NS or SARTOMER CN983 NS.
In the present disclosure, the pure prepolymer curing refers to curing the prepolymer provided in the present disclosure without adding any other reactive monomer, directly adding an initiator.
As a preferred technical scheme of the disclosure, the polyurethane methacrylate cross-linking agent is difunctional polyurethane methacrylate with a molecular weight of 500-2000, preferably polyurethane methacrylate prepared by polyaddition reaction of polycarbonate diol, hydroxyethyl methacrylate and trimethyl hexamethylene diisocyanate, and is preferably selected from SARTOMER CN1963 and RAHN 4205. The crosslinking agents described in this disclosure have molecular weights of 500-2000, e.g., 600, 800, 1000, 1200, 1500, 1800, etc.
The crosslinking agent with the molecular weight of 500-2000 is preferred, and the crosslinking agent is used for replacing the polyurethane acrylate prepolymer commonly used at present, so that the viscosity of the obtained resin is less than 2000cP at 25 ℃, the fluidity and printability of the photosensitive resin are improved, and the photocuring material is endowed with higher precision.
As a preferred technical scheme of the disclosure, the monomer is a multifunctional acrylate monomer, preferably any one or a combination of at least two of 1, 4-butanediol diacrylate, 1, 4-butanediol dimethacrylate, diethylene glycol dimethacrylate, ditrimethylolpropane acrylate or stearyl methacrylate.
The term "bifunctional" and "multifunctional" as used in this disclosure refer to compounds having two or more unsaturated double bonds.
As a preferred technical scheme of the present disclosure, the mass ratio of the polyurethane acrylate prepolymer to the polyurethane methacrylate cross-linking agent is 1 (2-2.5), for example, 1:2.1, 1:2.2, 1:2.3, 1:2.4, and the like, preferably 1:2.2.
In the present disclosure, when the mass ratio of the urethane acrylate prepolymer to the urethane methacrylate cross-linking agent is within the range of 1 (2-2.5) while the addition amount of the monomer is within the limit of the present disclosure, the finally obtained material can exhibit more excellent mechanical properties and adhesive strength, and the color stability thereof can also meet the requirements.
As a preferred embodiment of the present disclosure, the preparation raw materials of the resin further include 0.1 to 2 parts by weight of a light stabilizer, for example, 0.2 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1.0 parts by weight, 1.2 parts by weight, 1.5 parts by weight, 1.8 parts by weight, etc., and/or 0.1 to 2 parts by weight of an ultraviolet absorber, for example, 0.2 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1.0 parts by weight, 1.2 parts by weight, 1.5 parts by weight, 1.8 parts by weight, etc., in terms of parts by weight.
The addition of light stabilizers and/or ultraviolet absorbers to the resins provided by the present disclosure can improve the color stability and mechanical stability of the photocurable materials.
As a preferred embodiment of the present disclosure, the light stabilizer is selected from hindered amine light stabilizers, preferably bis (1, 2, 6-pentamethyl-4-piperidinyl) sebacate and/or bis (1, 2, 6-pentamethylpiperidinol) sebacate.
As a preferred embodiment of the present disclosure, the ultraviolet absorber is selected from any one or a combination of at least two of 2-hydroxy-4-N-octoxybenzophenone, bis (2-hydroxy-4-methoxyphenyl) methanone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, or N- (ethoxycarbonylphenyl) -N '-methyl-N' -phenylformamidine.
In the method, the compatibility of the hindered amine organic matters and the acrylic ester system is high, the hindered amine organic matters can be uniformly dispersed in the resin, free radicals generated by polymer photoexcitation can be effectively captured, and the cured resin material is prevented from being degraded by light, heat or oxidation. Meanwhile, the ultraviolet absorbent provided by the disclosure has strong absorption capacity in a UVB region, has lower absorption capacity in a UVA region, does not absorb ultraviolet light in a 380-420nm wavelength region, and does not affect 3D printing efficiency; the ultraviolet absorber can convert light energy into heat energy, and timely absorb ultraviolet light before the polymer is photodegradation, so that the model after photocuring can be prevented from being discolored and degraded due to long-term natural light irradiation.
As a preferred embodiment of the present disclosure, the reactive diluent is selected from any one or a combination of at least two of triethylene glycol dimethacrylate, 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate and triethylene glycol dimethacrylate.
As a preferred technical scheme of the present disclosure, the photoinitiator is any one or a combination of at least two of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, photoinitiator 819 and 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-acetone.
As a preferred technical scheme of the present disclosure, the defoamer is selected from any one or a combination of at least two of BYK-a515, BYK-a501, BYK-a555 or BYK-1797.
As a preferred technical scheme of the present disclosure, the preparation raw materials of the resin comprise the following components in parts by weight:
in a second aspect, the present disclosure provides a method for preparing the try-on model resin for 3D printing according to the first aspect, the method comprising: and uniformly mixing the polyurethane acrylate prepolymer, the polyurethane methacrylate cross-linking agent, the monomer, the reactive diluent, the photoinitiator, the defoamer and optionally the light stabilizer and/or the ultraviolet absorber according to the formula amount to obtain the 3D printing test-wear model resin.
In a third aspect, the present disclosure provides a method for using the 3D printing try-on model resin of the first aspect, the method comprising: and printing the 3D printing try-on model resin by using a 3D printer, and performing ultraviolet curing molding twice to obtain the try-on model.
The 3D printing try-on model resin provided by the present disclosure can be applied in the existing 3D printer, and the conventional printing parameters can meet the application requirements, and the following list is exemplified:
as a preferred technical solution of the present disclosure, the use method includes: printing the 3D printing try-on model resin by using a 3D printer, wherein the light source of the printer is 2-5mW/cm 2 For example 2.5mW/cm 2 、3mW/cm 2 、3.5mW/cm 2 、4mW/cm 2 、4.5mW/cm 2 Ultraviolet light with wavelength of 380-420nm, such as 390nm, 400nm, 410nm, etc., and then performing secondary curing with light source of 20-100mW/cm 2 For example 30mW/cm 2 、40mW/cm 2 、50mW/cm 2 、80mW/cm 2 And the like, ultraviolet light having a wavelength of 380 to 420nm, such as 390nm, 400nm, 410nm, and the like.
In a fourth aspect, the present disclosure provides the use of the 3D printing try-on model resin of the first aspect for the preparation of temporary crown, bridge, inlay or overlay models.
Compared with the prior art, the technical scheme provided by the embodiment of the disclosure has the following advantages:
(1) The photocuring model prepared by using the 3D printing try-on model resin provided by the disclosure has excellent bending strength and bonding performance;
(2) The obtained light-cured model can still maintain higher bending strength and bending strength stability after long-term soaking and cold-hot circulation;
(3) Meanwhile, the photocuring model prepared by the 3D printing test-wear model resin provided by the disclosure has excellent color stability, and under the ISO-10477 standard, after long-term soaking and cold-hot circulation, the chromatic aberration delta E is smaller, the optimal requirement that delta E is smaller than 1 can be met, chromatic aberration is difficult to distinguish by naked eyes, and the aesthetic requirement of a higher temporary crown repair material can be met.
Detailed Description
In order that the above objects, features and advantages of the present disclosure may be more clearly understood, a further description of aspects of the present disclosure will be provided below. It should be noted that, without conflict, the embodiments of the present disclosure and features in the embodiments may be combined with each other.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present disclosure, but the present disclosure may be practiced otherwise than as described herein; it will be apparent that the embodiments in the specification are only some, but not all, embodiments of the disclosure.
Example 1
The embodiment provides a 3D printing try-on model resin which comprises the following components in parts by weight:
16 parts of ETERNAL 6199, 35 parts of SARTOMER CN1963, 21 parts of 1, 4-butanediol dimethacrylate, 38 parts of tripropylene glycol diacrylate, 1 part of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 1.2 parts of bis (1, 2, 6-pentamethyl-4-piperidinyl) sebacate, 1 part of N- (ethoxycarbonylphenyl) -N '-methyl-N' -phenylformamidine and 0.1 part of BYK-A515.
The preparation method comprises the following steps: and adding the components into a batching kettle, mixing, and stirring at 1500rpm/min for 3 hours at the temperature of 50 ℃ to obtain the 3D printing try-on model resin.
Example 2
The embodiment provides a 3D printing try-on model resin which comprises the following components in parts by weight:
21 parts of ETERNAL 6199, 30 parts of SARTOMER CN1963, 21 parts of 1, 4-butanediol dimethacrylate, 38 parts of tripropylene glycol diacrylate, 1 part of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 1.2 parts of bis (1, 2, 6-pentamethyl-4-piperidinyl) sebacate, 1 part of N- (ethoxycarbonylphenyl) -N '-methyl-N' -phenylformamidine and 0.1 part of BYK-A515.
The preparation method comprises the following steps: and adding the components into a batching kettle, mixing, and stirring at 1500rpm/min for 3 hours at the temperature of 50 ℃ to obtain the 3D printing try-on model resin.
Example 3
The embodiment provides a 3D printing try-on model resin which comprises the following components in parts by weight:
11 parts of ETERNAL 6199, 40 parts of SARTOMER CN1963, 21 parts of 1, 4-butanediol dimethacrylate, 38 parts of tripropylene glycol diacrylate, 1 part of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 1.2 parts of bis (1, 2, 6-pentamethyl-4-piperidinyl) sebacate, 1 part of N- (ethoxycarbonylphenyl) -N '-methyl-N' -phenylformamidine and 0.1 part of BYK-A515.
The preparation method comprises the following steps: and adding the components into a batching kettle, mixing, and stirring at 1500rpm/min for 3 hours at the temperature of 50 ℃ to obtain the 3D printing try-on model resin.
Example 4
The embodiment provides a 3D printing try-on model resin which comprises the following components in parts by weight:
16 parts of ETERNAL 6199, 35 parts of SARTOMER CN1963, 21 parts of 1, 4-butanediol dimethacrylate, 38 parts of tripropylene glycol diacrylate, 1 part of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide and 0.1 part of BYK-A515.
The preparation method comprises the following steps: and adding the components into a batching kettle, mixing, and stirring at 1500rpm/min for 3 hours at the temperature of 50 ℃ to obtain the 3D printing try-on model resin.
Example 5
The embodiment provides a 3D printing try-on model resin which comprises the following components in parts by weight:
11 parts of SARTOMER CN983 NS, 40 parts of RAHN 4205, 21 parts of diethylene glycol dimethacrylate, 38 parts of tripropylene glycol diacrylate, 1 part of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 1.2 parts of bis (1, 2, 6-pentamethylpiperidinol) sebacate, 1 part of N- (ethoxycarbonylphenyl) -N '-methyl-N' -phenylformamidine and 0.1 part of BYK-A515.
The preparation method comprises the following steps: and adding the components into a batching kettle, mixing, and stirring at 1500rpm/min for 3 hours at the temperature of 50 ℃ to obtain the 3D printing try-on model resin.
Example 6
The embodiment provides a 3D printing try-on model resin which comprises the following components in parts by weight:
28 parts of SARTOMER CN9010 NS, 50 parts of RAHN 4205, 10 parts of 1, 4-butanediol diacrylate, 50 parts of 1, 6-hexanediol diacrylate, 5 parts of photoinitiator 819, 2 parts of bis (1, 2, 6-pentamethyl-4-piperidinyl) sebacate, 0.5 part of bis (2-hydroxy-4-methoxyphenyl) methanone, 0.5 part of BYK-1797.
The preparation method comprises the following steps: and adding the components into a batching kettle, mixing, and stirring at 1500rpm/min for 3 hours at the temperature of 50 ℃ to obtain the 3D printing try-on model resin.
Example 7
The embodiment provides a 3D printing try-on model resin which comprises the following components in parts by weight:
12 parts of SARTOMER CN9010 NS, 20 parts of RAHN 4205, 30 parts of 1, 4-butanediol diacrylate, 30 parts of trimethylolpropane triacrylate, 3 parts of 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinyl-1-propanone, 1.2 parts of bis (1, 2, 6-pentamethylpiperidinol) sebacate, 1 part of N- (ethoxycarbonylphenyl) -N '-methyl-N' -phenylformamidine, 0.5 part of BYK-1797.
The preparation method comprises the following steps: and adding the components into a batching kettle, mixing, and stirring at 1500rpm/min for 3 hours at the temperature of 50 ℃ to obtain the 3D printing try-on model resin.
Comparative example 1
The comparative example provides a 3D printing try-on model resin which comprises the following components in parts by weight:
16 parts of ETERNAL 6199, 35 parts of SARTOMER CN991 NS (acrylic cross-linking agent), 21 parts of 1, 4-butanediol dimethacrylate, 38 parts of tripropylene glycol diacrylate, 1 part of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 1.2 parts of bis (1, 2, 6-pentamethyl-4-piperidinyl) sebacate, 1 part of N- (ethoxycarbonylphenyl) -N '-methyl-N' -phenylformamidine and 0.1 part of BYK-A515.
The preparation method comprises the following steps: and adding the components into a batching kettle, mixing, and stirring at 1500rpm/min for 3 hours at the temperature of 50 ℃ to obtain the 3D printing try-on model resin.
Comparative example 2
The comparative example provides a 3D printing try-on model resin which comprises the following components in parts by weight:
16 parts of ETERNAL 61857 (molecular weight less than 1000, shore hardness of the pure prepolymer after curing 82D), 35 parts of SARTOMER CN1963, 21 parts of 1, 4-butanediol dimethacrylate, 38 parts of tripropylene glycol diacrylate, 1 part of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 1.2 parts of bis (1, 2, 6-pentamethyl-4-piperidinyl) sebacate, 1 part of N- (ethoxycarbonylphenyl) -N '-methyl-N' -phenylformamidine and 0.1 part of BYK-A515.
The preparation method comprises the following steps: and adding the components into a batching kettle, mixing, and stirring at 1500rpm/min for 3 hours at the temperature of 50 ℃ to obtain the 3D printing try-on model resin.
Comparative example 3
The comparative example provides a 3D printing try-on model resin which comprises the following components in parts by weight:
16 parts of ETERNAL 6199, 35 parts of SARTOMER CN1963, 21 parts of (10) ethoxylated bisphenol A diacrylate (monomer of aromatic chain), 38 parts of tripropylene glycol diacrylate, 1 part of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 1.2 parts of bis (1, 2, 6-pentamethyl-4-piperidinyl) sebacate, 1 part of N- (ethoxycarbonylphenyl) -N '-methyl-N' -phenylformamidine and 0.1 part of BYK-A515.
The preparation method comprises the following steps: and adding the components into a batching kettle, mixing, and stirring at 1500rpm/min for 3 hours at the temperature of 50 ℃ to obtain the 3D printing try-on model resin. Comparative example 4
The comparative example provides a 3D printing try-on model resin, SAREMCO Crowntec 3.0.
Comparative example 5
The comparative example provides a 3D printing try-on model resin, namely D002-10.
Application example
The application example provides a use method of a try-on model resin for 3D printing, which comprises the following steps:
(1) Pouring the resin into a 3D printer for printing, and performing ultraviolet light curing molding at 23+ -2deg.C and 50+ -20% humidity with a light source of 4mW/cm 2 Ultraviolet light with a wavelength of 405 nm;
(2) Then placing the model under 80 ℃ and secondary curing light source for 10min for secondary ultraviolet curing, and placing at 23+ -2 ℃ and 50+ -20% humidity for 24h to obtain the light curing model with light source of 60mW/cm 2 Ultraviolet light with a wavelength of 405 nm.
Performance test:
the methods provided by the resin reference application examples provided by examples and comparative examples were printed while performance tests were performed with reference to the following methods:
the photo-cured models printed from the resins provided in examples and comparative examples were immersed in artificial saliva (ISO/TR 10271) for 30 days and subjected to a cold and hot cycle 5000 times, followed by taking out the wiping dry, cold and hot cycle conditions: placing the photo-curing model in water baths at 5+/-1 ℃ and 55+/-1 ℃, respectively carrying out 35s at high and low temperatures, and circulating 5000 times;
(1) Mechanical strength testing according to ASTM-D790;
(2) Flexural strength testing was performed according to ISO-10477 and ASTM-D790;
(3) Color stability testing was performed according to ISO-10477;
(4) Bond strength testing was performed according to ISO-10477;
the test results are shown in Table 1:
TABLE 1
According to the embodiment and the performance test, the photo-curing model prepared by the resin provided by the disclosure has excellent mechanical stability and color stability, the bending strength can still keep higher bending strength after long-term soaking and cold and hot circulation, and chromatic aberration is difficult to distinguish by naked eyes.
As is clear from the comparison of examples 1 to 3, when the mass ratio of the urethane acrylate prepolymer to the urethane methacrylate-based crosslinking agent is in the range of 1 (2-2.5), the photo-curing model obtained by using the resin has more excellent mechanical strength and adhesive strength, and at the same time, also has more excellent color stability. As can be seen from a comparison of examples 1 to 3 and example 4, the addition of the light stabilizer and the ultraviolet absorber to the resin provided in the present disclosure can provide the photo-curing model with excellent color stability; from a comparison of example 1 with comparative examples 1-3, it is seen that the components of the present disclosure need to meet the limitations in order to be able to have excellent mechanical and color stability; as can be seen from the comparison of examples and comparative examples 4-5, the resins provided by the present disclosure have excellent mechanical stability and color stability, and can meet application requirements, as compared with the current commercial products.
It should be noted that in this document, relational terms such as "first" and "second" and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The foregoing is merely a specific embodiment of the disclosure to enable one skilled in the art to understand or practice the disclosure. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the disclosure. Thus, the present disclosure is not intended to be limited to the embodiments shown and described herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The try-on model resin for 3D printing is characterized by comprising the following raw materials in parts by weight:
10-30 parts by weight of polyurethane acrylate prepolymer;
20-50 parts by weight of polyurethane methacrylate cross-linking agent;
10-30 parts by weight of a monomer;
30-50 parts by weight of a reactive diluent;
1-5 parts by weight of a photoinitiator;
0.1-1 parts by weight of a defoaming agent;
0.1-2 parts by weight of a light stabilizer;
0.1-2 parts by weight of an ultraviolet absorber;
the molecular weight of the polyurethane acrylic ester prepolymer is 2000-5000, and the Shore hardness of the pure prepolymer after curing is above 90D;
the polyurethane methacrylate cross-linking agent is polyurethane methacrylate prepared by polyaddition reaction of polycarbonate dihydric alcohol, hydroxyethyl methacrylate and trimethyl hexamethylene diisocyanate;
the monomer is selected from any one or a combination of at least two of 1, 4-butanediol diacrylate, 1, 4-butanediol dimethacrylate, diethylene glycol dimethacrylate, ditrimethylolpropane acrylate or stearyl methacrylate;
the light stabilizer is selected from hindered amine lightA stabilizer selected from 2-hydroxy-4-n-octoxybenzophenone, bis (2-hydroxy-4-methoxyphenyl) methanone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, orN- (ethoxycarbonylphenyl) room-heatingN'Methyl-)N'-any one or a combination of at least two of the phenyl formamidines.
2. The 3D printing try-on model resin according to claim 1, wherein the molecular weight of the polyurethane methacrylate-based crosslinking agent is 500-2000.
3. The 3D printing try-on model resin according to claim 1, wherein the mass ratio of the polyurethane acrylate prepolymer to the polyurethane methacrylate cross-linking agent is 1 (2-2.5).
4. The 3D printing try-on model resin according to claim 3, wherein the mass ratio of the polyurethane acrylate prepolymer to the polyurethane methacrylate cross-linking agent is 1:2.2.
5. The 3D printing try-on model resin according to claim 1, characterized in that the light stabilizer is selected from bis (1, 2, 6-pentamethyl-4-piperidinyl) sebacate and/or bis (1, 2, 6-pentamethylpiperidinyl) sebacate.
6. The 3D printing try-on model resin according to claim 1, wherein the reactive diluent is selected from any one or a combination of at least two of triethylene glycol dimethacrylate, 1, 6-hexanediol diacrylate, trimethylolpropane propoxylate triacrylate, tripropylene glycol diacrylate or triethylene glycol dimethacrylate;
and/or the photoinitiator is any one or a combination of at least two of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, a photoinitiator 819 and 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-acetone;
and/or the defoamer is selected from any one or a combination of at least two of BYK-A515, BYK-A501, BYK-A555 or BYK-1797.
7. The 3D printing try-on model resin according to any one of claims 1 to 6, wherein the preparation raw materials of the resin comprise the following components in parts by weight:
15-20 parts by weight of polyurethane acrylate prepolymer;
30-50 parts by weight of polyurethane methacrylate cross-linking agent;
10-30 parts by weight of a monomer;
30-50 parts by weight of a reactive diluent;
1-5 parts by weight of a photoinitiator;
0.1-1 parts by weight of a light stabilizer;
0.5-1 parts by weight of an ultraviolet absorber;
0.1-1 part by weight of defoaming agent.
8. The method for producing a try-on model resin for 3D printing according to any one of claims 1 to 7, characterized in that the method comprises: and uniformly mixing the polyurethane acrylate prepolymer, the polyurethane methacrylate cross-linking agent, the monomer, the reactive diluent, the photoinitiator, the defoamer, the light stabilizer and the ultraviolet absorber according to the formula amount to obtain the 3D printing try-on model resin.
9. The method of using a try-on model resin for 3D printing according to any one of claims 1 to 7, characterized in that the method of using comprises: and printing the 3D printing try-on model resin by using a 3D printer, and performing ultraviolet curing molding twice to obtain the try-on model.
10. Use of the 3D printing try-on model resin of any one of claims 1-7 in the preparation of a temporary crown, bridge, inlay or overlay model.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210319208.4A CN114560976B (en) | 2022-03-29 | 2022-03-29 | Try-on model resin for 3D printing and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210319208.4A CN114560976B (en) | 2022-03-29 | 2022-03-29 | Try-on model resin for 3D printing and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114560976A CN114560976A (en) | 2022-05-31 |
| CN114560976B true CN114560976B (en) | 2023-07-25 |
Family
ID=81718890
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210319208.4A Active CN114560976B (en) | 2022-03-29 | 2022-03-29 | Try-on model resin for 3D printing and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114560976B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011157419A (en) * | 2010-01-29 | 2011-08-18 | Yokohama Rubber Co Ltd:The | Curable resin composition |
| WO2014172716A1 (en) * | 2013-04-18 | 2014-10-23 | Dentca, Inc. | Photo-curable resin compositions and method of using the same in three-dimensional printing for manufacturing artificial teeth and denture base |
| CN106752316A (en) * | 2016-12-26 | 2017-05-31 | 武汉长盈鑫科技有限公司 | A kind of resistant to elevated temperatures optical fiber coloring ink |
| CN109517111A (en) * | 2018-09-30 | 2019-03-26 | 先临三维科技股份有限公司 | 3D printing method, 3D printing photocuring discoloration instruction resin and preparation method thereof |
| CN111116833A (en) * | 2019-12-30 | 2020-05-08 | 先临三维科技股份有限公司 | Resin composition for 3D printing, anti-oxygen polymerization-resistant resin, 3D printing product and preparation method |
| CN111378074A (en) * | 2020-04-17 | 2020-07-07 | 阜阳师范大学 | Three-arm acrylate polyurethane 3D printing photosensitive resin and preparation method thereof |
| WO2021176023A1 (en) * | 2020-03-04 | 2021-09-10 | Arkema France | Curable composition comprising a photoinitiator |
-
2022
- 2022-03-29 CN CN202210319208.4A patent/CN114560976B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011157419A (en) * | 2010-01-29 | 2011-08-18 | Yokohama Rubber Co Ltd:The | Curable resin composition |
| WO2014172716A1 (en) * | 2013-04-18 | 2014-10-23 | Dentca, Inc. | Photo-curable resin compositions and method of using the same in three-dimensional printing for manufacturing artificial teeth and denture base |
| CN106752316A (en) * | 2016-12-26 | 2017-05-31 | 武汉长盈鑫科技有限公司 | A kind of resistant to elevated temperatures optical fiber coloring ink |
| CN109517111A (en) * | 2018-09-30 | 2019-03-26 | 先临三维科技股份有限公司 | 3D printing method, 3D printing photocuring discoloration instruction resin and preparation method thereof |
| CN111116833A (en) * | 2019-12-30 | 2020-05-08 | 先临三维科技股份有限公司 | Resin composition for 3D printing, anti-oxygen polymerization-resistant resin, 3D printing product and preparation method |
| WO2021176023A1 (en) * | 2020-03-04 | 2021-09-10 | Arkema France | Curable composition comprising a photoinitiator |
| CN111378074A (en) * | 2020-04-17 | 2020-07-07 | 阜阳师范大学 | Three-arm acrylate polyurethane 3D printing photosensitive resin and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114560976A (en) | 2022-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112074262B (en) | Curable composition for high Wen Guangke-based photopolymerization process and method of preparing crosslinked polymer therefrom | |
| US10925693B2 (en) | Dental materials using thermoset polymers | |
| CA2919550C (en) | Method for producing artificial teeth | |
| EP3360907B1 (en) | Photocurable composition, denture base, and plate denture | |
| CN113677718B (en) | Radiation curable compositions for rapid prototyping or rapid manufacturing processes | |
| JP2018501191A (en) | Stereolithography method and composition | |
| CN110799168B (en) | Radiation curable composition for additive manufacturing process | |
| WO2018025943A1 (en) | Photocurable composition, denture base, and removable denture | |
| EP0753028A1 (en) | Radiation curable molding compositions | |
| CN117580543A (en) | Multivalent polymerizable compositions and methods of making and using the same | |
| CN110128655A (en) | One kind being based on mercaptan-alkene selfreparing photosensitive resin composition and application | |
| CN114560976B (en) | Try-on model resin for 3D printing and preparation method and application thereof | |
| DE102019106151A1 (en) | Radiation curable composition for use in rapid prototyping or rapid manufacturing processes | |
| WO2020003133A1 (en) | Hydrated orthodontic articles, kits, and methods of making same | |
| CN112689646B (en) | Radiation curable composition for rapid prototyping or rapid manufacturing processes | |
| CN118344532B (en) | Photosensitive resin composition and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |