CN107722188A - 3D printing solidifies super hydrophobic material, composition and preparation method thereof with ultraviolet light - Google Patents
3D printing solidifies super hydrophobic material, composition and preparation method thereof with ultraviolet light Download PDFInfo
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- CN107722188A CN107722188A CN201711130979.4A CN201711130979A CN107722188A CN 107722188 A CN107722188 A CN 107722188A CN 201711130979 A CN201711130979 A CN 201711130979A CN 107722188 A CN107722188 A CN 107722188A
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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
- C08F283/002—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers modified by after-treatment
- C08F283/004—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers modified by after-treatment modified by incorporation of silicium atoms
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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
Abstract
The present invention provides a kind of 3D printing includes 30 60 parts of oligomer component with ultraviolet light solidification super hydrophobic material composition；10 30 parts of reactive diluent；15 parts of light trigger.The present invention also provides a kind of preparation method of 3D printing ultraviolet light solidification super hydrophobic material, and this method, which comprises at least, mixes 30 60 parts of oligomer of parts by weight and 10 30 parts of diluents, obtains the first mixed liquor；15 parts of light triggers of parts by weight are added into the first mixed liquor and are stirred to the light trigger and are dissolved, is kept in dark place, obtains the second mixed liquor.3D printing prepared by the present invention solidifies super hydrophobic material with ultraviolet light, has stronger hydrophobicity, improves the resistance to dirty performance of material, and the other performance such as the hardness of material, tensile strength, viscosity, cubical contraction does not decline.In addition, 3D printing provided by the invention ultraviolet light solidifies, super hydrophobic material preparation technology is simple, and easily realization industrializes.
Description
Technical field
The invention belongs to 3D printing technique field, is related to a kind of 3D printing ultraviolet photocureable material and preparation method thereof,
Solidify super hydrophobic material and preparation method thereof with ultraviolet light more particularly to a kind of 3D printing.
Background technology
3D printing technique, it is to be designed a model with Computerized three-dimensional as source, it is discrete by software hierarchy to be with numerical control shaping
System, using laser beam, hot melt nozzle etc. mode by the special materials such as metal dust, ceramic powders, plastics, cell tissue carry out by
Layer accumulation bonds, and final superposition shaping, produces entity products.
Raw material are shaped by the machining mode such as mould, turnning and milling with traditional manufacture, cut with most lifelong
Finished product is different, and 3D solid is changed into several two dimensional surfaces by 3D printing, is given birth to by being superimposed to material process and successively
Production, greatly reduce the complexity of manufacture.This Digitized manufacturing pattern does not need complicated technique, does not need huge machine
Bed, numerous manpowers is not needed, the part of any shape can be generated directly from computer graphics data, makes to manufacture
To extend to wider array of production crowd scope.
Wherein, ultraviolet (UV) ultraviolet curing process in 3D printing technique is because with curing rate is fast, production efficiency is high, pollution
Less, it is widely used in the industries such as adhesive, coating and ink the features such as energy-conservation, solidified after-product excellent performance.Photocuring
Forming technique is also 3D printing technique practical earliest.
Three-dimensional Quick-forming 3D printing technique using photosensitive resin as raw material, there is the spies such as cost is low, precision is high, shaping is fast
Point, is used widely in every field at present.Chinese patent CN105331115A discloses a kind of 3D printing UV-curing
Change the preparation method and application of transparent silicon resin composite, with organosilicon materials and alkoxy silane with acryloxy,
Under catalyst action, the organic siliconresin prepolymer with acryloxy is prepared through sol-gel process；Will be with acryloxy
Organosilicon materials be added drop-wise at 30~120 DEG C in White Carbon black, react 1~24h, obtain acryloxy be modified reinforcement fill out
Material；Finally both are mixed, processing obtains having splendid ultraviolet light resistant, heat endurance and weatherability, and excellent electricity is absolutely
The silicone resin composite material of edge, hydrophobicity and anti-flammability.
Chinese patent application CN106749942A discloses a kind of 3D printing ultraviolet photocureable material and preparation method thereof, its
The raw material of use includes aliphatic polyurethane, polyurea monomers, reactive diluent, solidification enzyme, levelling agent, dispersant etc., obtains
The good ultraviolet photocureable material of flexible good, color inhibition, good toughness, adhesive force.
Chinese patent CN103012634A disclose a kind of solidification of ultraviolet light phosphate modified acrylate oligomer and
Its preparation method, the ultraviolet photocureable material contain phosphorus pentoxide, hydroxy acrylate, polymerization inhibitor, antioxidant, the invention pole
The earth improves the adhesive force of ultraviolet light cured film.
But the defects of ultraviolet photocureable material generally existing hydrophobicity that above-mentioned patent provides is bad, the resistance to dirty performance of material
It is bad, it yet there are no the related report of 3D printing ultraviolet light solidification super hydrophobic material then.
The content of the invention
In order to solve the above technical problems, to provide a kind of solidification of 3D printing ultraviolet light super thin for the first aspect of the invention
Water material, the composition and preparation method for preparing the material.
One side of the invention is to provide a kind of 3D printing ultraviolet light solidification super hydrophobic material composition, with parts by weight
Meter, including at least following components：
Oligomer component 30-60 parts, preferably 35-55 parts, more preferably 40-50 parts, such as 43 parts, 45 parts；Activity dilution
Agent 10-30 parts, preferably 15-28 parts, more preferably 18-25 parts, such as 20 parts, 23 parts；Light trigger 1-5 parts, preferably 1.5-
4.5 parts, more preferably 2-4 parts, such as 2.5 parts, 3 parts, 3.5 parts.
As a kind of preferable technical scheme of the present invention, the 3D printing solidifies super hydrophobic material composition with ultraviolet light,
In parts by weight, including at least following components：
Oligomer component 30-60 parts, preferably 35-55 parts, more preferably 40-50 parts, such as 43 parts, 45 parts；Activity dilution
Agent 10-30 parts, preferably 15-28 parts, more preferably 18-25 parts, such as 20 parts, 23 parts；Light trigger 1-5 parts, preferably 1.5-
4.5 parts, more preferably 2-4 parts, such as 2.5 parts, 3 parts, 3.5 parts；Auxiliary agent 0.5-8 parts, preferably 1-6 parts, more preferably 1.5-4
Part, such as 2 parts, 3 parts.
As a kind of preferable technical scheme of the present invention, the original oligomer is selected from：Aliphatic simple function polyurethane third
The multifunctional urethane acrylate of olefin(e) acid ester, aliphatic, PPG aliphatic simple function urethane acrylate, polyethers are more
The multifunctional urethane acrylate of first alcohol aliphatic, monofunctional aromatic urethane acrylate, the multifunctional polyurethane of aromatic series
It is one or more mixed in acrylate, solvent-borne type modified urethane acrylate, organic silicon modified polyurethane acrylate
Compound.
Wherein, solvent-borne type modified urethane acrylate of the present invention, can be simple function urethane acrylate or
The deliquescent functional group of the one or more increase urethane acrylates of multifunctional urethane acrylate link.
Wherein, organic silicon modified polyurethane acrylate of the present invention, can be simple function urethane acrylate or
Multifunctional urethane acrylate links one or more silicone functionalities or organosilicon chain.
As a kind of preferred technical scheme of the present invention, the urethane acrylate is selected from：Aliphatic polyurethane third
Olefin(e) acid ester (such as trade name is 611A-85,6103,611B-85,6115J-80,6130B-80), aliphatic polyurethane dipropyl
Olefin(e) acid ester (such as trade name is 611C-70,6118C-70), (such as trade name is 6145- to the acrylate of aliphatic polyurethane six
100th, 6145-100H, 6150-100), PPG, aliphatic urethane acrylate (such as trade name is 615-100),
Solvent-borne type modified urethane acrylate (such as trade name is 6175-3), not stanniferous aliphatic urethane diacrylate are (such as
Trade name is 611C-70NT, 6112-100NT, 6115J-85NT, 6115T-80), aromatic urethane diacrylate (such as
Trade name is 6117C-70) with it is any one in organic silicon modified polyurethane acrylate (such as trade name is DR-U188C)
Kind or several combinations.
The oligomer component is to include the mixture of fluorine-containing propene yl carboxylic acid ester and original oligomer, or fluorine-containing propene
Yl carboxylic acid ester and original oligomer chemically react to obtain oligomer.
Wherein, the fluorinated acrylate is compound shown in structure (I) or (II)：
Wherein：
R1 is H or methyl.
R2 is C1-C6 Asias aliphatic group, preferably C2-C4 Asias aliphatic group, such as ethylidene, propylidene, butylidene.
R3 is the C1-C8 alkyl of perfluor substitution, the C3-C8 cycloalkyl of perfluor substitution, the aryl of perfluor substitution；More preferably
For C2-C6 alkyl, more preferably C2-C4 alkyl, such as ethyl, propyl group, butyl.
R is-(O- (CF2)n)m-；N is the natural number selected from 2-5, preferably 2 or 3；M is the natural number selected from 1-25, excellent
Elect 2-20 as, be more hopeful 3-18, such as 3-15,4-12,4-10, such as 5,6,8.
X and y is natural number, and x+y=3, it is preferable that y=2 or 3, and preferably 3.
The fluorinated acrylate is compound shown in structure (II), wherein, y=3.
As a kind of preferred technical scheme of the present invention, described fluorinated acrylate is perfluoroether difunctional third
Olefin(e) acid ester, perfluoroethyl butyryl acyloxy ethyl ester and one or more mixtures in perfluoroethyl hexylyloxy ethyl ester.
As a kind of preferable technical scheme of the present invention, described oligomer component includes：
Original oligomer (such as organic silicon modified polyurethane acrylate) 15-25 parts；Preferably 18-22 parts；
Compound shown in structure formula (II) (such as perfluoroether bifunctional acrylate) 15-35 parts；Preferably 20-30 parts.
As the present invention a kind of preferable technical scheme, the preparation method of perfluoroether bifunctional acrylate, including
Following steps：
Step 1 ,≤5 DEG C under the conditions of, pentaerythritol triacrylate, triethylamine are dissolved in solvent, obtain the first solution；
Step 2, hexafluoropropylene oxide oligomer solution is added into the first solution, it is molten to obtain second in 10-40 DEG C of reaction
Liquid；
Step 3, by the second solution dry, obtain the perfluoroether bifunctional acrylate.
As the present invention a kind of preferable technical scheme, described reactive diluent be monofunctional reaction monomers and/
Or difunctionality base reaction monomers.
As a kind of preferable technical scheme of the present invention, described monofunctional reaction monomers are 18 to 22 carbon
Base acrylate (such as trade name is EM258A), cyclohexyl methacrylate (such as trade name is EM71), bay acid propylene
Acid esters (such as trade name is EM215), benzyl methacrylate (such as trade name is EM75), bicyclic pentyl first acrylic acid
Ester (such as trade name is EM93), tetrahydrofurfuryl acrylate (such as trade name is EM214), stearic acid acrylate are (such as
Trade name is EM218), isotridecyl first acrylate (such as trade name is EM313) and cyclohexyl methacrylate (such as
Trade name is EM71) in any one or a few combination.
As a preferred embodiment of the present invention, described difunctionality base reaction monomers are the propylene of Tricyclodecane Dimethanol two
Acid esters (such as trade name is EM2204), difunctionality base acrylate monomer (such as trade name is EM2206), DPG two
Acrylate (such as trade name is EM222), neopentylglycol diacrylate (such as trade name is EM225), ethoxylated bisphenol A
Diacrylate (such as trade name is EM2260), ethylene glycol dimethacrylate (such as trade name is EM320), poly- second two
Alcohol dimethylacrylate (such as trade name is EM324), 2-Ethylhexyl Methacrylate (such as trade name is EM96), 1,
4 butanediol diacrylates (such as trade name is EM2241) and the third oxidation neopentylglycol diacrylate (such as trade name
For EM2251) any one or a few combination.
As the present invention a kind of preferable technical scheme, described reactive diluent be cyclohexyl methacrylate (such as
Trade name is EM71) and/or 18 to 20 dicarbonyl acrylate (such as trade name is EM258A).
As a kind of preferable technical scheme of the present invention, in described reactive diluent, cyclohexyl methacrylate is (such as
Trade name is EM71) with the weight ratios of 18 to 20 dicarbonyl acrylate (such as trade name is EM258A) it is (1-3)：
(1-3)。
As the present invention a kind of preferable technical scheme, described reactive diluent be monofunctional reaction monomers and/
Or the one or more in difunctionality base reaction monomers.
As a kind of preferred technical scheme of the present invention, described light trigger is 2- methyl isophthalic acids-(4- first sulfydryl benzene
Base) -2- morpholine -1- acetone (such as trade name is PI-907), 2,4,6- trimethylbenzoyl diphenyl phosphine oxide (such as trade names
Referred to as PI-TPO), 2- hydroxy-2-methyl -1- phenyl -1- acetone (such as trade name is PI-1173), 1- hydroxy-cyciohexyl benzene
Ketone (such as trade name is PI-184), benzoyl derivatives (such as trade name is PI-55), benzophenone (such as trade name
For PI-BP), 4- benzoyls -4 '-methyl-diphenyl sulfide (such as trade name is PI-BMS), 2- benzoyl methyl benzoates
(such as trade name is PI-MBB), isopropyl thioxanthone (such as trade name is PI-ITX) and 4- (N, N- dimethylamino) benzene first
One or more in acetoacetic ester (such as trade name is PI-EDB).
As a kind of preferable technical scheme of the present invention, described light trigger is 1- hydroxy-cyciohexyl benzophenone (such as business
The name of an article is referred to as PI-184) with the mixture of 2,4,6- trimethylbenzoyls diphenyl phosphine oxide (such as trade name is PI-TPO).
As a kind of preferable technical scheme of the present invention, 1- hydroxy-cyciohexyl benzophenones (PI- in described light trigger
184) the weight ratio with 2,4,6- trimethylbenzoyls diphenyl phosphine oxide (such as trade name is PI-TPO) is (1-3)：(1-
3)。
As a kind of preferable technical scheme of the present invention, the super hydrophobic material composition also includes auxiliary agent.
Wherein it is preferred in parts by weight, the super hydrophobic material composition comprises at least following auxiliary component：Defoaming
Agent 0.2-1.0 parts, preferably 0.2-0.8 parts, more preferably 0.3-0.6 parts, such as 0.4 part, 0.5 part；Wetting agent 0.2-1.0 parts,
Preferably 0.3-0.8 parts, more preferably 0.4-0.7 parts, such as 0.5 part, 0.6 part；Resistant auxiliary agent 0.2-2.0 parts, preferably 0.5-
1.8 parts, more preferably 0.8-1.5 parts, such as 1 part, 1.3 parts；Levelling agent 0.2-1.0 parts, preferably 0.3-0.8 parts, more preferably
0.4-0.7 parts, such as 0.5 part, 0.6 part.
As a kind of preferable technical scheme of the present invention, the defoamer is water-base cement silicone emulsion, higher alcohols fat
It is poly- penta 4 alcohol ether of acid esters compound, polyoxyethylene polyoxypropylene, polyoxyethylene polyoxy propyl alcohol amidogen ether, polypropylene glycerol aether, poly-
One or more of combinations in oxypropylene polyoxyethylene glycerol ether, dimethyl silicone polymer.
As wetting agent, it is not particularly limited, what can be enumerated has：Silanol class nonionic surfactant, sulfonated oil, fertilizer
Soap, Nekal BX, soybean lecithin, thio-alcohol, hydrazides class, mercaptan acetals etc..
As resistant auxiliary agent, it is allowed to be not easy the attachment for receiving dirt, infected, here mainly for the protection of surface
Resistant auxiliary agent is fluoropolymer solutions, specially SRC-220.
As levelling agent, it is not particularly limited, what can be enumerated has：Dimethyl silicone polymer and polymethyl-benzene base silica
The levelling agents such as alkane, polyether polyester azo polyether polyeste and alkyl silicon type organosiloxane.
The second aspect of the invention provides one kind and prepares 3D printing ultraviolet light solidification super hydrophobic material as described above
The method of composition, this method comprise at least following steps：
Step 1, parts by weight 30-60 parts oligomer and 10-30 parts reactive diluent mixed, obtain the first mixing
Liquid；
Step 2, add parts by weight 1-5 part light triggers into the first mixed liquor and stir to the light trigger and dissolve, keep away
Light preserves, and obtains the 3D printing ultraviolet light solidification super hydrophobic material composition.
In a preferred embodiment, step 2 stirs and 1-4 parts first to add part light trigger into the first mixed liquor
Auxiliary agent to the light trigger dissolves, then adds remaining light trigger thereto, is stirred until homogeneous five bubbles, is kept in dark place,
Obtain the 3D printing ultraviolet light solidification super hydrophobic material composition.
3D printing prepared by the present invention solidifies super hydrophobic material with ultraviolet light, has stronger hydrophobicity, improves material
Resistance to dirty performance, and the other performance such as the hardness of material, tensile strength, viscosity, cubical contraction does not decline.In addition, this
It is simple with ultraviolet light solidification super hydrophobic material preparation technology to invent the 3D printing provided, easily realizes industrialization.
Embodiment
Participate in the election of the detailed description of the invention below for being preferable to carry out method and including embodiment this hair can be more easily understood
Bright content.Unless otherwise defined, all technologies used herein and scientific terminology have common with art of the present invention
The identical implication that technical staff is generally understood that.When contradiction be present, the definition in this specification is defined.
Term "comprising" used herein or its any other deformation, it is intended that cover including for non-exclusionism.For example, bag
Composition, step, method, product or device containing listed elements are not necessarily limited to those key elements, but can include being not known
The other key elements listed or such a composition, step, method, product or the intrinsic key element of device.
Equivalent, concentration or other values or parameter are excellent with scope, preferred scope or a series of upper limit preferred values and lower limit
During the Range Representation that choosing value limits, this, which is appreciated that, specifically discloses by any range limit or preferred value and any scope
All scopes that any pairing of lower limit or preferred value is formed, regardless of whether the scope separately discloses.For example, when open
During scope " 1 to 5 ", described scope should be interpreted as including scope " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When number range is described herein, unless otherwise indicated, otherwise the scope is intended to include its end
Value and all integers and fraction within the range.
In addition, indefinite article " one kind " before key element of the present invention or component and "one" to key element or the quantitative requirement of component
(i.e. occurrence number) unrestriction.Therefore "one" or " one kind " should be read as including one or at least one, and odd number
The key element or component of form also include plural form, unless the obvious purport of the quantity refers to singulative.
Embodiment one solidifies the preparation of super hydrophobic material to the 3D printing of embodiment eight with ultraviolet light
Oligomer and diluent are mixed by a certain percentage at room temperature first, stirred under 1000-3000r/min rotating speed
5-10min is mixed, makes it well mixed, after system is well mixed, adds initiator, part defoamer and remaining auxiliary agent with identical
Mixing speed is stirred to the complete solvent of initiator, is then added remaining initiator, stirring at low speed to uniform bubble-free, is kept in dark place
After a period of time, constant weight is dried under vacuum at 40 DEG C, obtains 3D printing ultraviolet light solidification super hydrophobic material, wherein, prepare
During each material ratio it is as shown in table 1.
The content (kg) of table 1, each component into embodiment 8 of embodiment 1
Wherein, adjuvant component is as follows：
Wherein, defoamer is water-base cement silicone emulsion, the fatty acid ester compounded thing of higher alcohols and polyoxyethylene polyoxypropylene
The mixture of poly- penta 4 alcohol ether；
Wetting agent is soybean lecithin, thio-alcohol, hydrazides class, the mixture of mercaptan acetals；
Levelling agent is dimethyl silicone polymer and PSI, the mixing of polyether polyester azo polyether polyeste
Thing；
The preparation method of perfluoroether bifunctional acrylate, comprises the following steps：
Pentaerythritol triacrylate and triethylamine are added in 250ml three-necked flasks according to 3 ︰ 1 mol ratio, and poured into
100ml dichloroethanes.The stirring under conditions of ice bath is until pentaerythritol triacrylate is completely dissolved, then hexafluoro is slowly added dropwise
Expoxy propane oligomer solution, wait to be added dropwise, solution is kept room temperature, stir and allow it to react 2h, it is finally true at 40 DEG C
Sky is dried, and obtains perfluoroether bifunctional acrylate.
Performance detection
In order to illustrate the performance of 3D printing ultraviolet light provided by the invention solidification super hydrophobic material, the present invention is main do as
Lower detection and analysis：
1st, product hardness, the relevant criterion according to as defined in GB/T531-1999, using instead of peak science and technology limited public affairs during Beijing
The hardness of product after the TH210 shore D type hardness testers meter measurement of department's production is dried.
2nd, tensile strength, the relevant criterion according to as defined in GB/T1040.1-2006, expanding precious detection device using Dongguan City has
The tensile strength of product before the HB-7000 type electronics measurer for pulling force measurement of limit company production is dried.
3rd, viscosity, according to relevant criterion as defined in GB 10247-1988, instrument is reached using Tianjin Hua Yixin at 25 DEG C
The viscosity of product before the NDJ-1D types Brookfield viscometer measurement of finite instrument company production is dried.
4th, cubical contraction, using the regulation of DIN16901 in DIN, i.e., with 23 DEG C ± 0.1 DEG C when when shaping
Size is 23 DEG C in temperature with being placed 24 hours after shaping, the corresponding product chi that relative humidity is measured under the conditions of being 50 ± 5%
The shrinkage factor of product before very little difference calculating is dried.
5th, water contact angle, cured film are in OCA40 according to ASTM D5946-1996 testing standards to water contact angle test
Determined under (Dataphysics Co., Germany) normal temperature, droplet size is 0.5 μ L, is tested at least ten times, takes it average
Value.
Test result is as shown in table 2.
Table 2, properties of product characterization test
In general, water contact angle and hydrophobicity are positive correlation, water contact angle is bigger, illustrates the hydrophobic performance of product
More excellent, hydrophilicity is weaker.
Observe table 1, table 2, comparing embodiment 1-3 and embodiment 4-8, it is known that, the 3D printing prepared in embodiment 4-8 is purple
108 ° -113 ° apparently higher than 60 ° -62 ° in embodiment 1-3 of the water contact angle of outer photocuring super hydrophobic material, illustrates oligomeric
Fluoro-containing group is introduced in thing can significantly improve the hydrophobic performance of product.
It is respectively compared embodiment 1-3 and embodiment 4-6, it is found that the 3D printing prepared using the proportioning for implementing 2 is purple
The water contact angle of outer photocuring super hydrophobic material is more than the 3D printing ultraviolet light prepared using embodiment 1, the proportioning of embodiment 3
Solidify the water contact angle of super hydrophobic material；3D printing prepared by the proportioning of embodiment 5 solidifies the water of super hydrophobic material with ultraviolet light
Contact angle is more than to be contacted using 3D printing prepared by embodiment 4, the proportioning of embodiment 6 with the water of ultraviolet light solidification super hydrophobic material
Angle, illustrate that each raw material has an optimal proportion between each other, or in oligomer be 40-50 parts, reactive diluent 15-25
Part, light trigger is 2-4 parts and auxiliary agent is in the range of 2-3 parts or so, and synergistic function is generated between each component, is played
Unexpected technique effect.
In addition, the hardness of each product prepared in comparing embodiment 1-8, stretching is slight, viscosity and cubical contraction etc., can
To find, 3D printing prepared by each embodiment is little with the above-mentioned performance difference of ultraviolet light solidification super hydrophobic material, illustrates to add
Influence of the fluorine-containing functional group to other performances of product is smaller.
The specific embodiment of the present invention is described in detail above, but it is intended only as example, it is of the invention and unlimited
It is formed on particular embodiments described above.To those skilled in the art, it is any to the equivalent modifications that carry out of the present invention and
Substitute also all among scope of the invention.Therefore, the impartial conversion made without departing from the spirit and scope of the invention and
Modification, all should be contained within the scope of the invention.
Claims (10)
1. a kind of 3D printing with ultraviolet light solidify super hydrophobic material composition, it is characterised in that in parts by weight, including at least with
Lower component：
Oligomer component 30-60 parts；
Reactive diluent 10-30 parts；
Light trigger 1-5 parts；
Wherein, described oligomer component is to include the mixture of fluorine-containing propene yl carboxylic acid ester and original oligomer, or fluorine-containing
Acrylic carboxylate and original oligomer chemically react to obtain oligomer.
2. super hydrophobic material composition according to claim 1, it is characterised in that the fluorinated acrylate is structure
(II) compound shown in：
Wherein, R1 is H or methyl, and R is-(O- (CF2)n)m-, x+y=3, n are the natural number selected from 2-5, and m is selected from 1-25's
Natural number.
3. super hydrophobic material composition according to claim 2, it is characterised in that described oligomer component includes：
Original oligomer 15-25 parts；
Compound 15-35 parts shown in structure formula (II)；
Or the described oligomer component original oligomer chemically reacts to obtain with compound shown in structure formula (II)
Fluorine-containing oligomer.
4. the super hydrophobic material composition according to any one in claim 1-3, it is characterised in that described initial oligomeric
Thing is selected from：Aliphatic simple function urethane acrylate, the multifunctional urethane acrylate of aliphatic, PPG aliphatic
Simple function urethane acrylate, the multifunctional urethane acrylate of PPG aliphatic, monofunctional aromatic polyurethane
The multifunctional urethane acrylate of acrylate, aromatic series, solvent-borne type modified urethane acrylate, organic silicon modified polyurethane
One or more mixtures in acrylate.
5. the super hydrophobic material composition according to any one in Claims 2 or 3, it is characterised in that y=2 or 3；R2
For ethylidene, one or more of the R3 in ethyl, propyl group, butyl.
6. super hydrophobic material composition according to claim 1, it is characterised in that described reactive diluent is simple function
One or more in base reaction monomers and/or difunctionality base reaction monomers.
7. super hydrophobic material composition according to claim 1, it is characterised in that described light trigger is selected from ultraviolet
One or more of compounds of free radical and/or cation are produced under light irradiation.
8. super hydrophobic material composition according to claim 1, it is characterised in that the super hydrophobic material also includes helping
Agent, in parts by weight, including at least following auxiliary component：
9. a kind of 3D printing as claimed in claim 1 solidifies the preparation method of super hydrophobic material composition, its feature with ultraviolet light
It is, methods described comprises at least following steps：
Step 1, parts by weight 30-60 parts oligomer and 10-30 parts reactive diluent mixed, obtain the first mixed liquor；
Step 2, add parts by weight 1-5 part light triggers into the first mixed liquor and stir to the light trigger and dissolve, lucifuge is protected
Deposit, obtain the 3D printing ultraviolet light solidification super hydrophobic material composition.
10. preparation method according to claim 9, it is characterised in that step 2 adds part to be first into the first mixed liquor
Light trigger stirs and 1-4 parts auxiliary agent to the light trigger dissolves, then adds remaining light trigger thereto, stirs to equal
Even five bubble, is kept in dark place, and obtains the 3D printing ultraviolet light solidification super hydrophobic material composition.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020013765A1 (en) * | 2018-07-11 | 2020-01-16 | Structo Pte Ltd | Methods and composition of a dental model for the manufacture of orthodontic appliances without the use of separator |
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| CN114479052A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Photocuring diluent and preparation method and application thereof |
| CN113980192A (en) * | 2021-10-11 | 2022-01-28 | 深圳市纵维立方科技有限公司 | Photocuring three-dimensional printing resin and preparation method thereof |
| CN116426214A (en) * | 2023-02-15 | 2023-07-14 | 广东希贵光固化材料有限公司 | Ultraviolet light curing dispensing coating for LED lattice module |
| CN116426214B (en) * | 2023-02-15 | 2024-03-15 | 广东希贵光固化材料有限公司 | Ultraviolet light curing dispensing coating for LED lattice module |
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