CN109401259A - Solid material composition and its preparation method and application - Google Patents
Solid material composition and its preparation method and application Download PDFInfo
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- CN109401259A CN109401259A CN201811101924.5A CN201811101924A CN109401259A CN 109401259 A CN109401259 A CN 109401259A CN 201811101924 A CN201811101924 A CN 201811101924A CN 109401259 A CN109401259 A CN 109401259A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
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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
- B33Y10/00—Processes of additive manufacturing
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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
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Abstract
The present invention relates to 3D printing Material Field, a kind of solid material composition and its preparation method and application is disclosed.On the basis of the total weight of the solid material composition, the solid material composition includes: the acrylate oligomer of 10-40 weight %, the ring trimethylolpropane dimethoxym ethane acrylate of 5-20 weight %, the low viscosity monomer of 15-40 weight %, the polyfunctional monomer of 5-30 weight %, the photoinitiator of 1-5 weight %, the levelling agent of 0.01-1 weight %, the polymerization inhibitor etc. of 0.01-1 weight %.The solid material composition is both able to satisfy the requirement for digitizing micro- spray 3D printer low viscosity, while having the characteristics that printing smell is low, it is high to be formed by solid material comprehensive mechanical property.
Description
Technical field
The present invention relates to 3D printing Material Fields, and in particular to a kind of solid material composition and preparation method thereof and answers
With.
Background technique
Increasing material manufacturing (also known as 3D printing) is successively to accumulate material based on mathematical model and produced physical item
Emerging manufacturing technology will generate profound impact to traditional process flow, production line, factory mode, industrial chain combination, be manufacture
Representative subversiveness technology in industry.
3D printing material is a ring important in 3D printing industry, in the 3D printing of the field of polymers, liquid photocurable
Resin is quickly grown because its curing rate is fast, formed precision is high.Photocuring 3D printing currently on the market is mainly solid with cubic light
Change based on the method for forming (SLA) and digital light processing (DLP), but in both printing types, the component of printing is immersed in always not
In cured resin, the health of user is endangered, raw materials consumption is big, support removal trouble, and can only once print one kind
Material and color greatly limit the application range of 3D printing.
Micro- spray 3D printing method (Polyjet 3D printing) is digitized to be invented by OBJET company, Israel, it is solid with liquid light
Change resin is raw material, and 3D printing is completed by the way of drop on demand ink jet.Due to digitize it is micro- spray have very high formed precision,
Multiple material and multiple color can be printed simultaneously, and the advantages such as raw material are lost less, are environmentally friendly, support removal is simple are increasingly becoming
The trend of photocuring 3D printing.Digitize the printing principle of micro- spray 3D printing method are as follows: the jet printing head of PolyJet is along X-axis
Direction moves back and forth injection photosensitive polymer, and after photopolymer materials are injected on workbench, UV ultraviolet lamp will be along spray
Head operative orientation is launched UV ultraviolet light and is solidified to photopolymer materials, should after completing one layer of jet printing and solidification
Process can repeat progress, and one layer connects one layer, until entire 3D object is formed.
In digitizing micro- spray 3D printing, backing material and at least one solid material are needed, solid material is used to print
Required object, backing material play the role of supporting solid material.
Relative to the 3D printing material of SLA and DLP, the requirement for digitizing micro- spray 3D printing material is higher, and development difficulty is more
Greatly.It under the premise of guaranteeing to print object physical property, needs to meet eject request, thus digitizes micro- spray 3D printing material and exist
Viscosity under print temperature will be lower than 20cps, and surface tension is within the scope of 20-30dyn/cm.
On world market, micro- spray 3D printer and 3D printing material are digitized mainly by external OBJET company monopolizing, valence
Lattice are very expensive.In recent years, as the continuous breakthrough and exploitation, urgent need to resolve digitlization of the micro- spray 3D printer of domestic digitalization are micro-
Spray the exploitation and nationalization of 3D printing resin.Photocuring 3D is developed primarily directed to SLA and DLP printer on domestic market
Printed material, it is less to the research achievement for the 3D printing material for digitizing micro- spray 3D printer.
Photocuring system is divided into free radical type and cationic, and free radical type generally uses acrylic resin as former
Material, cationic generally use epoxylite as raw material.Although cationic has, contraction is small, smell is small, without oxygen inhibition
The advantages that, but cationic system photocuring reaction is very slow, cationic initiator price is very expensive, is easy by humidity
It influences, the shelf-life is short, and there are dark reactions, have the risk of obstruction spray head, are unsuitable to apply to digitize in micro- spray 3D printing.
Currently, free radical type solid material in the market, which usually will use, largely to be had in order to meet the requirement of low viscosity
The low viscosity monomer of penetrating odor, such as isobornyl acrylate (IBOA), phenoxyethyl acrylate (PHEA), tetrahydro
Furanacrylate (THFA), ethoxyethoxyethyl acrylate (EOEOEA) etc. lead to (the print temperature height in printing
In room temperature, generally at 50 DEG C or more), resin can generate penetrating odor, influence working environment, harm health.
Therefore, it is necessary to develop, one kind is new not only to be met low viscosity but also meets the lower 3D printing solid material of smell.
Summary of the invention
The purpose of the present invention is to provide a kind of new solid material compositions and its preparation method and application.It is provided
Solid material composition is both able to satisfy the requirement for digitizing micro- spray 3D printer low viscosity, while having that smell is lower, resultant force
Learn the high feature of performance.
According to the first aspect of the invention, the present invention provides a kind of solid material compositions, with the solid material group
On the basis of the total weight for closing object, the solid material composition includes:
Wherein, the acrylate oligomer is selected from polyester acrylate and/urethane acrylate；
The low viscosity monomer is selected from acryloyl morpholine, dipropylene glycol diacrylate, dipropylene glycol dimethacrylate
At least one of ester, tripropylene glycol diacrylate and tripropylene glycol dimethylacrylate.
According to the second aspect of the invention, the present invention provides a kind of sides for preparing solid material composition of the present invention
Method, this method comprises: by the acrylate oligomer, ring trimethylolpropane dimethoxym ethane acrylate, low viscosity monomer, more
Functional monomer, photoinitiator and polymerization inhibitor are mixed and stirred for, then 20-80 DEG C at a temperature of, be added into gained mixture
The levelling agent, optional antisettling agent and optional mill base simultaneously stir evenly.
According to the third aspect of the invention we, the present invention provides solid material compositions of the present invention in 3D printing
Application.
The present invention, which passes through, introduces ring trimethylolpropane dimethoxym ethane acrylate and the acrylate oligomer, so that with
The ring trimethylolpropane dimethoxym ethane acrylate and low viscosity monomer of low smell replace existing isobornyl acrylate contour
The solid material composition of the invention of smell monomer can satisfy the printing of low viscosity (viscosity at 25 DEG C is less than 120cps)
It is required that.Solid material composition smell in print procedure is small, environmentally friendly, harm is small, is beaten with the solid material composition
Printing, solidifying obtained solidfied material is non-alkali-soluble, requirement of the micro- spray 3D printer of satisfaction digitlization to solid material, Er Qiesuo
Stating solidfied material (i.e. solid material) also has excellent comprehensive mechanical property.
Detailed description of the invention
Fig. 1 is a kind of printing effect figure of the solid material composition A1 of embodiment 1.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
According to the first aspect of the invention, the present invention provides a kind of solid material compositions, with the solid material group
On the basis of the total weight for closing object, the solid material composition includes:
In solid material composition of the invention, the acrylate oligomer is selected from polyester acrylate and/or poly- ammonia
Ester acrylate.
In solid material composition of the invention, the polyester acrylate can be the routine in existing light-cured resin
Selection.It is preferred that the polyester acrylate is the polyester acrylate of 1-6 function.It will be apparent to a skilled person that
The functional group of polyester acrylate refers to the acryloxy in polyester acrylic ester structure.
The polyester acrylate can be commercially available, for example, the trade mark selected from Sartomer be CN2283NS,
CN2279、CN2273、CN2281、CN8201NS、CN2262、CN2203NS、CN2282、CN2303、CN292、CN293、
The commodity of CN294E, CN3108NS, CN8201NS, the trade mark in South Korea's U.S. source are the commodity such as PS4040, PS420, PS643, DSM-
The trade mark of AGI (Royal DSM company) is the commodity such as 720, P-10, P-20, P-60, P-90, and the trade mark of Changxing chemistry is 6311-
100、6320、6325-100、6333-100、6342、6351、6360、6360D、6361-100、6364-1、6372、6385、
The trade mark of the commodity such as 6390F, DR-E530, DR-E572, DR-E615, DR-E630, DR-E636, DR-E850, double bond chemical industry is
The commodity such as 2315HM35,270,281,284,285,286, B-509B, B-520 of Guangdong Boxing, B-523, B-570, B-574,
The commodity such as B-574C.
In solid material composition of the invention, the urethane acrylate is the urethane acrylate of two functions.
It will be apparent to a skilled person that the functional group of urethane acrylate refers to third in urethane acrylate structure
Alkene acyloxy.
The urethane acrylate can be commercially available, for example, the trade mark selected from Sartomer be CN992,
The commodity such as CN991NS, CN963B80, CN981B88NS, CN985B88, CN9167, the trade mark in South Korea's U.S. source be PU240,
The commodity such as PU2100, PU2061, HR6200, the trade mark of DSM-AGI are the commodity of U-61, and the trade mark of Changxing chemistry is 6115J-
80、6115T-80、6131-1、6150-100、6153-1、6154B-80、6155W、6165H、6172-1、DR-U021、DR-
The commodity such as U050M1, DR-U093-1, DR-U250, DR-U381, the commodity that the trade mark of double bond chemical industry is 850, Guangdong Boxing chemical industry
B-270 commodity.
In solid material composition of the invention, the acrylate oligomer is less than 10000cps in 25 DEG C of viscosity.
In the present invention, when the acrylate oligomer is selected from commercial products, the viscosity of the acrylate oligomer refers to have
Effect component (refers to the component that photocuring reaction can occur in commodity after printing, i.e. oligomer itself, does not include that may be present molten
Other components such as agent) viscosity.
In solid material composition of the invention, the effect of the low viscosity monomer is to reduce the viscosity of composition, tool
Body is selected from acryloyl morpholine (ACMO), dipropylene glycol diacrylate, dipropylene, tripropylene glycol dipropyl
At least one of olefin(e) acid ester and tripropylene glycol dimethylacrylate.
In solid material composition of the invention, the polyfunctional monomer belongs to photocrosslinking agent, can refer to prior art choosing
It selects.For the present invention, under preferable case, the polyfunctional monomer is selected from trimethylolpropane trimethacrylate, trihydroxy methyl third
Alkane trimethyl acrylic ester, ethoxyquin trimethylolpropane trimethacrylate, ethoxyquin trimethylol propane trimethyl acrylic acid
Ester, glycerol propoxylate triacrylate, glycerol propoxylate trimethyl acrylic ester, pentaerythritol tetraacrylate, pentaerythrite
Tetramethyl acrylate, ethoxyquin pentaerythritol tetraacrylate, ethoxyquin pentaerythritol tetramethylacrylate, double three hydroxyls first
At least one of base tetraacrylate and double trimethylolpropane tetramethyl acrylate.It is highly preferred that more officials
Energy monomer is selected from ethoxyquin trimethylolpropane trimethacrylate and/or ethoxyquin pentaerythritol tetraacrylate.
In solid material composition of the invention, the photoinitiator is radical type photoinitiator.Under preferable case, institute
State photoinitiator be selected from 2,4,6- trimethylbenzoy-dipheny phosphine oxide, 2- hydroxy-2-methyl -1- phenyl -1- acetone,
1- hydroxyl-cyclohexyl-phenyl ketone, isopropyl thioxanthone, 2- methyl-1-[4- (methyl mercapto) phenyl]-2- morpholinyl-1- third
Ketone, benzophenone, 4- benzoyl -4 '-methyl-diphenyl sulfide, 2- benzoyl methyl benzoate, methyl benzoylformate,
4- phenyl benzophenone, 2,4- diethyl thioxanthone, 2- hydroxy-2-methyl -1- [4- (2- hydroxyl-oxethyl) phenyl] -1- third
At least one of ketone, camphorquinone and phenyl two (2,4,6- trimethylbenzoyl) phosphine oxide.
In solid material composition of the invention, the effect of the levelling agent is to reduce the surface tension of composition, belongs to
Conven-tional adjuvants in photocuring system.For the present invention, under preferable case, the levelling agent be selected from acrylate leveling agent and
At least one of organosilicon levelling agent.The levelling agent can be specifically commercially available, such as selected from German Bi Ke chemistry
(BYK) company production the trade mark be BYK310, BYK307, BYK333, BYK331, BYK330, BYK378, BYK3500 and
One or more of BYK3505 commodity.
In solid material composition of the invention, the sagging inhibitor is referred to prior art selection, and the present invention is to this
It is not particularly limited, the trade mark of for example, BYK company production is the product of BYK410.
In solid material composition of the invention, the mill base is preferably selected from various colors of the average grain diameter less than 1um
The mill base of the various colors of mill base, more preferably average grain diameter less than 400nm.
In solid material composition of the invention, the polymerization inhibitor can refer to prior art selection, as long as being avoided that combination
Autohemagglutination occurs for double bond contained in object.Under preferable case, the polymerization inhibitor is selected from p-hydroxyanisole and/or 2, bis- uncle of 6-
Butyl paracresol.
In solid material composition of the invention, under preferable case, using the total weight of the solid material composition as base
The content of standard, the acrylate oligomer is 20-35 weight %, and the content of ring trimethylolpropane dimethoxym ethane acrylate is
10-20 weight %, the content of the low viscosity monomer are 20-30 weight %, and the content of the polyfunctional monomer is 10-25 weight
% is measured, the content of the photoinitiator is 3-5 weight %, and the content of the levelling agent is 0.1-0.7 weight %, the anti-settling
The content of agent is 0-0.5 weight %, and the content of the mill base is 0-5 weight %, and the content of the polymerization inhibitor is 0.01-0.7 weight
Measure %.
According to the second aspect of the invention, the present invention also provides a kind of method for preparing the solid material composition,
This method comprises: by the acrylate oligomer, ring trimethylolpropane dimethoxym ethane acrylate, low viscosity monomer, more officials
Can monomer, photoinitiator and polymerization inhibitor be mixed and stirred for, then 20-80 DEG C at a temperature of, institute is added into gained mixture
It states levelling agent, optional antisettling agent and optional mill base and stirs evenly.
According to the method for the present invention, the solid material composition can be protected from light or dark conditions under carry out.Such as institute
The preparation process for stating solid material composition can carry out in opaque stirred tank.
According to the method for the present invention, the levelling agent, antisettling agent and mill base can add during aforementioned component stirs
Enter, mixing speed can control in 300-800rpm.
According to the method for the present invention, in order to avoid blocking 3D printing because of impurity that may be present in composition caused by raw material
The spray head of machine, optionally, the method also includes: product will be stirred and be filtered by the filter membrane that average pore size is 1-10 μm.
According to the third aspect of the invention we, the application the present invention provides the solid material composition in 3D printing.
Printed material of the solid material composition particularly suitable as digitizing micro- spray 3D printing.The solid material composition tool
There is lower viscosity, the solidfied material that is formed is non-alkali solubility (for example, by the entity after being printed, solidifying (photocuring reaction)
Material compositions are digitized the solidfied material formed after micro- spray photocuring 3D printer printing, generation photocuring reaction and are immersed in 20
Do not dissolved in 72h in the NaOH solution of weight %), meet the requirement of solid material.Moreover, preparing solid material group with existing
It closes object to compare, solid material composition of the invention also has printing smell low, environmentally friendly, is formed by the resultant force of solid material
Learn the features such as performance is high.
The present invention will be described in detail by way of examples below.
In following embodiment and comparative example,
The viscosity of solid material composition is detected using the DV2T type vertebral plate viscosimeter of Brookfield.
The BZY-101 type surface tension instrument of the auspicious instrument in surface tension use side measures.
Embodiment 1
The present embodiment is for illustrating solid material composition and preparation method thereof of the invention.
1) formula (parts by weight) of solid material composition
Wherein, urethane acrylate is the PU240 (viscosity that 2,25 DEG C of degree of functionality is 7000cps) in South Korea's U.S. source.
2) preparation of solid material composition
By urethane acrylate, acryloyl morpholine, ring trimethylolpropane dimethoxym ethane acrylate, tripropylene glycol dipropyl
Olefin(e) acid ester, 3 ethoxyquin trimethylolpropane trimethacrylates, 1- hydroxycyclohexyl phenyl ketone, 2,4,6- trimethylbenzoyl
Base-diphenyl phosphine oxide and p-hydroxyanisole are added in stirred tank, are heated to 60 DEG C, under the at the uniform velocity stirring of 500r/min,
Levelling agent BYK307 and antisettling agent BYK410 is added, continues to stir 1.5h, obtains solid material composition A1.
The solid material composition A1 is 116cps, surface tension 23dyn/cm in 25 DEG C of viscosity.
Embodiment 2
The present embodiment is for illustrating solid material composition and preparation method thereof of the invention.
1) formula (parts by weight) of solid material composition
Wherein, polyester acrylate is the CN2281 of Sartomer (viscosity that 2,25 DEG C of degree of functionality is 1000cps).
2) preparation of solid material composition
By polyester acrylate, acryloyl morpholine, ring trimethylolpropane dimethoxym ethane acrylate, two propylene of dipropylene glycol
Acid esters, trimethylolpropane trimethacrylate, 1- hydroxycyclohexyl phenyl ketone, 2,4,6- trimethylbenzoy-dipheny
Phosphine oxide and p-hydroxyanisole are added in stirred tank, are heated to 80 DEG C, and under the at the uniform velocity stirring of 500r/min, levelling agent is added
BYK307 and antisettling agent BYK410 continues to stir 1.5h, obtains solid material composition A2.
The solid material composition is 105cps, surface tension 24dyn/cm in 25 DEG C of viscosity.
Embodiment 3
The present embodiment is for illustrating solid material composition and preparation method thereof of the invention.
1) formula (parts by weight) of solid material composition
Wherein, urethane acrylate is the PU2100 (viscosity that 2,25 DEG C of degree of functionality is 6000cps) in South Korea's U.S. source,
Polyester acrylate is the B-570 of Guangdong Boxing (viscosity that 6,25 DEG C of degree of functionality is 550cps).
2) preparation of solid material composition
By urethane acrylate, polyester acrylate, acryloyl morpholine, ring trimethylolpropane dimethoxym ethane acrylic acid
Ester, tripropylene glycol diacrylate, four ethoxyquin pentaerythritol tetraacrylates, 1- hydroxycyclohexyl phenyl ketone and 2,6- bis-
Butylated Hydroxytoluene be added stirred tank in, be heated to 60 DEG C, under the at the uniform velocity stirring of 500r/min, be added levelling agent BYK307 and
Antisettling agent BYK410 continues to stir 1h, obtains solid material composition A3.
The solid material composition A3 is 110cps, surface tension 23dyn/cm in 25 DEG C of viscosity.
Embodiment 4
The present embodiment is for illustrating solid material composition and preparation method thereof of the invention.
1) formula (parts by weight) of solid material composition
Wherein, urethane acrylate is that (viscosity that 2,25 DEG C of degree of functionality is by the 6165H of Changxing chemical company
6500cps)。
2) preparation of solid material composition
By urethane acrylate, ring trimethylolpropane dimethoxym ethane acrylate, tripropylene glycol diacrylate, 3 second
Aoxidize trimethylolpropane trimethacrylate, 1- hydroxycyclohexyl phenyl ketone, 2,4,6- trimethylbenzoy-dipheny oxygen
Change phosphine and p-hydroxyanisole is added in stirred tank, be heated to 60 DEG C, under the at the uniform velocity stirring of 500r/min, levelling agent is added
BYK307 and mill base continue stirring 1.5h and obtain solid material composition A4 then after 1 μm of membrane filtration.
The solid material composition A4 is 112cps, surface tension 24dyn/cm in 25 DEG C of viscosity.
Embodiment 5
The present embodiment is for illustrating solid material composition and preparation method thereof of the invention.
1) formula (parts by weight) of solid material composition
Wherein, polyester acrylate is the P-20 of DSM-AGI company (viscosity that 2,25 DEG C of degree of functionality is 3500cps).
2) preparation of solid material composition
By polyester acrylate, ring trimethylolpropane dimethoxym ethane acrylate, tripropylene glycol diacrylate, 3 ethoxies
Change trimethylolpropane trimethacrylate, 1- hydroxycyclohexyl phenyl ketone, the oxidation of 2,4,6- trimethylbenzoy-dipheny
Phosphine and p-hydroxyanisole are added in stirred tank, are heated to 60 DEG C, and under the at the uniform velocity stirring of 500r/min, levelling agent is added
BYK307, antisettling agent BYK410 and mill base continue to stir 2h, then after 1 μm of membrane filtration, obtain solid material combination
Object A5.
The solid material composition A5 is 113cps, surface tension 24dyn/cm in 25 DEG C of viscosity.
Embodiment 6
The present embodiment is for illustrating solid material composition and preparation method thereof of the invention.
Solid material composition is prepared according to the method for embodiment 1, the difference is that by ring trimethylolpropane dimethoxym ethane
The dosage of acrylate is adjusted to 5 parts by weight, and the dosage of tripropylene glycol diacrylate, urethane acrylate is adjusted
For 30 parts by weight, to obtain solid material composition A6.
The solid material composition A6 is 105cps, surface tension 23dyn/cm in 25 DEG C of viscosity.
Embodiment 7
The present embodiment is for illustrating solid material composition and preparation method thereof of the invention.
1) formula (parts by weight) of solid material composition
Wherein, urethane acrylate is the PU240 (viscosity that 2,25 DEG C of degree of functionality is 7000cps) in South Korea's U.S. source.
2) preparation of solid material composition
By urethane acrylate, acryloyl morpholine, ring trimethylolpropane dimethoxym ethane acrylate, tripropylene glycol dipropyl
Olefin(e) acid ester, 3 ethoxyquin trimethylolpropane trimethacrylates, 1- hydroxycyclohexyl phenyl ketone, 2,4,6- trimethylbenzoyl
Base-diphenyl phosphine oxide and p-hydroxyanisole are added in stirred tank, are heated to 60 DEG C, under the at the uniform velocity stirring of 500r/min,
Levelling agent BYK307, antisettling agent BYK410 and mill base is added, continues stirring 2h and obtains reality then after 1 μm of membrane filtration
Body material composition A7.
The solid material composition A7 is 85cps, surface tension 23dyn/cm in 25 DEG C of viscosity.
Comparative example 1
Solid material composition is prepared according to the method for embodiment 1, the difference is that being added without ring trimethylolpropane first
Acetal acrylate, and the dosage of tripropylene glycol diacrylate is adjusted to 40 parts by weight, to obtain solid material combination
Object D1.
The solid material composition D1 is 109cps, surface tension 24dyn/cm in 25 DEG C of viscosity.
Comparative example 2
Solid material composition is prepared according to the method for embodiment 1, the difference is that being added without ring trimethylolpropane first
Acetal acrylate, and tripropylene glycol diacrylate is replaced with the isobornyl acrylate of 40 parts by weight, to obtain reality
Body material composition D2.
The solid material composition D2 is 106cps, surface tension 24dyn/cm in 25 DEG C of viscosity.
Comparative example 3
Solid material composition is prepared according to the method for embodiment 1, the difference is that by the dosage of urethane acrylate
It adjusts to 50 parts by weight, is added without acryloyl morpholine, and the dosage of tripropylene glycol diacrylate is adjusted to 5 parts by weight, from
And obtain solid material composition D3.
The solid material composition D3 is 223cps in 25 DEG C of viscosity, and surface tension 25dyn/cm, viscosity is excessive, nothing
Method is printed.
Test case
Test case is used to illustrate that solid material composition A1-A7, D1-D2 of above embodiments and comparative example to carry out 3D printing
The performance of the solid material (solidfied material) formed afterwards.
Used 3D printer is that the DC501A type of the honest selectron Science and Technology Ltd. in Jiangsu digitizes micro- spray photocuring
3D printer, print temperature are 65 DEG C, and ultraviolet light uses the UV-LED light source of wavelength 395nm.
A kind of printing effect of solid material composition A1 is as shown in Figure 1.
Alkali-soluble test method are as follows: solid material composition is printed as having a size of 1cm (length) × 1cm on glass slide
Then glass slide is put into the NaOH solution of 20 weight % and impregnates 72 hours by the blocky solidfied material of (width) × 0.5cm (thickness), see
Examine whether the solidfied material on glass slide dissolves.
Tensile strength and elongation at break are tested according to the test method of GB/T1040-1992, by solid material composition
The test bars of II type sample of GB/T1040-1992 defined are printed as, are tried using 2366 type pulling force of Instron LEGEND
Test the tensile strength and elongation at break of machine test bars.
Shore hardness according to GB/T2411-1980 test method test, by solid material composition be printed as having a size of
The blocky solidfied material of 5cm (length) × 5cm (width) × 0.5cm (thickness) tests its shore using mountain degree instrument SLX-D Shore durometer
D hardness.
Test result is as shown in table 1.
Table 1
| Number | Smell when printing | Alkali solubility | Tensile strength/MPa | Elongation at break/% | Shore D hardness |
| Embodiment 1 | Basically odorless | It is insoluble | 47.6 | 8.0 | 84 |
| Embodiment 2 | Basically odorless | It is insoluble | 45.1 | 12.1 | 82 |
| Embodiment 3 | Basically odorless | It is insoluble | 48.3 | 9.2 | 84 |
| Embodiment 4 | Basically odorless | It is insoluble | 45.4 | 14.7 | 81 |
| Embodiment 5 | Basically odorless | It is insoluble | 45.7 | 10.2 | 84 |
| Embodiment 6 | Basically odorless | It is insoluble | 42.6 | 8.2 | 83 |
| Embodiment 7 | Basically odorless | It is insoluble | 41.9 | 8.0 | 82 |
| Comparative example 1 | Basically odorless | It is insoluble | 35.2 | 5.6 | 75 |
| Comparative example 2 | Penetrating odor | It is insoluble | 42.2 | 12.2 | 80 |
| Comparative example 3 | It cannot print | - | - | - | - |
It can be seen that print the solid material to be formed complete using solid material composition of the present invention by the result of table 1
Insoluble in alkali, when printing basically odorless, has the characteristics that environmental protection, and prepared solid material has excellent synthesis mechanics
Performance.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made including each technical characteristic with it is any its
Its suitable method is combined, it should also be regarded as the disclosure of the present invention, belongs to for these simple variants and combination
Protection scope of the present invention.
Claims (10)
1. a kind of solid material composition, on the basis of the total weight of the solid material composition, the solid material combination
Object includes:
Wherein, the acrylate oligomer is selected from polyester acrylate and/or urethane acrylate；
The low viscosity monomer is selected from acryloyl morpholine, dipropylene glycol diacrylate, dipropylene, three
At least one of propylene glycol diacrylate and tripropylene glycol dimethylacrylate.
2. solid material composition according to claim 1, wherein using the total weight of the solid material composition as base
The content of standard, the acrylate oligomer is 20-35 weight %, and the content of ring trimethylolpropane dimethoxym ethane acrylate is
10-20 weight %, the content of the low viscosity monomer are 20-30 weight %, and the content of the polyfunctional monomer is 10-25 weight
% is measured, the content of the photoinitiator is 3-5 weight %, and the content of the levelling agent is 0.1-0.7 weight %, the anti-settling
The content of agent is 0-0.5 weight %, and the content of the mill base is 0-5 weight %, and the content of the polymerization inhibitor is 0.01-0.7 weight
Measure %.
3. solid material composition according to claim 1 or 2, wherein the urethane acrylate is two functions
Urethane acrylate.
4. solid material composition according to claim 1 or 2, wherein the degree of functionality of the polyester acrylate is 1-
6。
5. solid material composition according to claim 1 or 2, wherein the photoinitiator is 2,4,6- trimethylbenzenes
Formoxyl-diphenyl phosphine oxide, 2- hydroxy-2-methyl -1- phenyl -1- acetone, 1- hydroxycyclohexyl phenyl ketone, isopropyl sulphur
Miscellaneous anthrone, 2- methyl-1-[4- (methyl mercapto) phenyl]-2- morpholinyl-1- acetone, benzophenone, 4- benzoyl-4 '-methyl-
Diphenyl sulfide, 2- benzoyl methyl benzoate, methyl benzoylformate, 4- phenyl benzophenone, 2,4- diethyl thioxanthene
Ketone, 2- hydroxy-2-methyl -1- [4- (2- hydroxyl-oxethyl) phenyl] -1- acetone, camphorquinone and (2,4,6- trimethyl of phenyl two
At least one of benzoyl) phosphine oxide.
6. solid material composition according to claim 1 or 2, wherein the polyfunctional monomer is selected from trihydroxy methyl third
Alkane triacrylate, trimethylol-propane trimethacrylate, ethoxyquin trimethylolpropane trimethacrylate, ethoxyquin three
Methylolpropane trimethacrylate, glycerol propoxylate triacrylate, glycerol propoxylate trimethyl acrylic ester, Ji Wusi
Alcohol tetraacrylate, pentaerythritol tetramethylacrylate, ethoxyquin pentaerythritol tetraacrylate, ethoxyquin pentaerythrite four
At least one in methacrylate, double trimethylolpropane tetraacrylate and double trimethylolpropane tetramethyl acrylate
Kind.
7. solid material composition according to claim 1 or 2, wherein the levelling agent is selected from acrylate leveling agent
At least one of with organosilicon levelling agent.
8. solid material composition according to claim 1 or 2, wherein the average particle size of the mill base is excellent less than 1 μm
Choosing is less than 400nm.
9. a kind of method for preparing solid material composition described in any one of claim 1-8, this method comprises: will be described
Acrylate oligomer, ring trimethylolpropane dimethoxym ethane acrylate, low viscosity monomer, polyfunctional monomer, photoinitiator and
Polymerization inhibitor is mixed and stirred for, then 20-80 DEG C at a temperature of, the levelling agent, optional anti-is added into gained mixture
Sedimentation agent and optional mill base simultaneously stir evenly.
10. application of the solid material composition in 3D printing described in any one of claim 1-8.
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| CN201811101924.5A CN109401259A (en) | 2018-09-20 | 2018-09-20 | Solid material composition and its preparation method and application |
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| CN110527033A (en) * | 2019-09-18 | 2019-12-03 | 东莞市神说科技有限公司 | A kind of pure tough resin of 3D printing |
| CN110669163A (en) * | 2019-10-15 | 2020-01-10 | 常州增材制造研究院有限公司 | 3D printing photopolymer composition |
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| CN110437385A (en) * | 2019-07-09 | 2019-11-12 | 湖南昇微新材料有限公司 | A kind of 3D printing photochromic material and preparation method thereof and its application method |
| CN110527033A (en) * | 2019-09-18 | 2019-12-03 | 东莞市神说科技有限公司 | A kind of pure tough resin of 3D printing |
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Application publication date: 20190301 |