CN108299602A - 3D printing UV cures high translucent material, prepolymer and preparation method - Google Patents
3D printing UV cures high translucent material, prepolymer and preparation method Download PDFInfo
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- CN108299602A CN108299602A CN201711123282.4A CN201711123282A CN108299602A CN 108299602 A CN108299602 A CN 108299602A CN 201711123282 A CN201711123282 A CN 201711123282A CN 108299602 A CN108299602 A CN 108299602A
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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
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to 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
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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Abstract
The present invention provides a kind of 3D printing ultraviolet lights to cure high translucent material composition, for the prepolymer and preparation method of the composition, the composition includes prepolymer, diluent, photoinitiator, wherein, the prepolymer is the mixed hybridization colloidal sol for including oligomer and organosilicon.Light transmittance that the 3D printing ultraviolet light being prepared using technical solution provided by the invention cures high translucent material is high, mist degree is low, good in optical property, can be applied to the 3D printing technique of transparent artware and optical device.The technological process of the preparation method is simple, it is convenient, of low cost to prepare, and is suitable for industrialized production.
Description
Technical field
The present invention relates to 3D printing Material Field more particularly to a kind of 3D printing ultraviolet light cure high translucent material and its
Preparation method.
Background technology
3D printing is successively to increase material by 3D printing equipment according to designed 3D models to manufacture three-dimensional objects
Technology.This successively stack shaping technological synthesis digital modeling techniques, Electromechanical Control technology, information technology, material science
With the cutting edge technology of the numerous areas such as chemistry, it is one kind of rapid shaping technique, is known as the core of " the third time industrial revolution "
Technology.3D printing material is the important substance basis of 3D printing technique development, and to a certain extent, the development of material decides 3D
Can printing have wider application, and 3D printings at present are widely used to the fields such as craftwork, mold design.
The existing 3D printing material in domestic market, in terms of high molecular material mainly based on thermoplastic material, such as
ABS, nylon etc..It is purple relative to the high energy consumption of thermoplastic material and volatile flavor etc. to the issuable harm of surrounding enviroment
Outer photocuring 3D printing material belongs to more green technology, and without heating and environmental protection, application range is broader, UV light
Change the main trend that 3D printing material has become materials industry development.Although it is rapid that ultraviolet light cures 3D printing Materials, so
And the ultraviolet light solidification 3D printing material of high light transmission is very deficient, this severely limits it in optical instrument, automobile accessories, does
The development of the industries such as utility.
The CN201511015395.3 of Guangxi art exhibition Chemical Industry Science Co., Ltd discloses a kind of urethane acrylate type
Ultraviolet photocureable material and preparation method thereof, the ultraviolet light cured article include urethane acrylate oligomer, activity dilution
The components such as agent, photoinitiator, dodecafluoroheptyl methacrylate, silane coupling agent and levelling agent.The invention develops a kind of tool
There are pollution-free, low volatilization, the ultraviolet photocureable material that solidification rate is fast, glossiness is high, hardness is high, shear strength is high.
The CN201611161848.8 that industrial Science and Technology Ltd. is flown upward in Shenzhen discloses a kind of 3D printing ultraviolet light solidification
Material and preparation method thereof, the ultraviolet photocureable material contain following component：A) aliphatic epoxy acrylate, b) aliphatic poly
Urethane acrylate, c) polyurea monomers, d) reactive diluent, e) initiator and f) auxiliary agent.The invention develops a kind of solidification speed
Degree is fast, shrinking percentage is small, color inhibition, elastic good 3D printing photo-curing material.
Although the 3D printing that above-mentioned technology provides ultraviolet photocureable material has various features, the solidification of these ultraviolet lights
The low defect of material generally existing light transmittance.3D printing technique also fails in fields such as optical device, transparent process designs at present
It is in progress, mainly also in that the 3D printing material of existing high transparency extremely lacks.Therefore, a kind of high light transmission is developed
Rate, low haze ultraviolet light solidification 3D printing material have a very important significance, it may have very wide application prospect, can
To be widely used in the industries such as electronic instrument, automobile exterior, building field and office appliance.
Invention content
To solve the above-mentioned problems, on the one hand, the present invention provides a kind of 3D printing ultraviolet lights to cure high translucent material
Composition, prepared 3D printing ultraviolet light, which cures high translucent material, has light transmittance height, good in optical property, transparency height etc.
Feature can be widely applied to the 3D printing technique of transparent artware, optical instrument；On the other hand, invention additionally provides the 3D
Printing ultraviolet light cures the preparation method of high translucent material composition and the prepolymer for the composition.
First aspect present invention provides a kind of prepolymer curing high translucent material for 3D printing ultraviolet light.
The second aspect of the present invention is to provide a kind of high light transmission material of ultraviolet light solidification of the 3D printing including the prepolymer
Feed composition, diluent, photoinitiator.
Wherein, prepolymer of the present invention is the mixed hybridization colloidal sol for including oligomer and organosilicon.
Preferably, in the prepolymer, the silicon dioxide granule of Nano grade is equably crosslinked in oligomer phase.
As the optimal technical scheme of the present invention, the mixed hybridization colloidal sol is passed through by oligomer and organic silicon sol
Ultrasonic disperse is crossed to be made.It is highly preferred that the organic silicon sol is made under acid catalysis through sol-gal process by organosilicon.
As the optimal technical scheme of the present invention, the weight proportion of the oligomer and organosilicon or organic silicon sol
It is 3: (2-1), such as 3: 2,3: 1.5 or 3: 1, the most preferably 3: 2.It ensure that the titanium dioxide of Nano grade so much the betterly
Silicon particle is equably crosslinked in oligomer phase, and microstructure shows a kind of organic and inorganic cross-linked network.
As the optimal technical scheme of the present invention, the oligomer is polyester acrylate oligomers.Preferably,
The oligomer is modified polyester acrylate ester (article number：6315,6316,6319,6319-1,6343, DR-E539), four
Functional group's polyester acrylate (article number：6321-100,6325-100,6325-100), polyester acrylate (article number：
6333-100、6340、6340N、6349、6351、 6353、6353-1、6355、6360、6360D、6371、6372、6385、DR-
One or more of E504, DR-E524, DR-E527, DR-E540A, DR-E636, DR-E650, DR-E750, DR-E850)
Blend.It is highly preferred that the oligomer is modified polyester acrylate ester (article number：6319), modified polyester acrylate ester
(article number：6343), polyester acrylate (article number：DR-E524 one or more blends in).Wherein, of the invention
The modification refers to linking new functional group or organic matter chain (such as in the case where not changing polyester acrylate backbone structure
Organosilicon chain).
As the optimal technical scheme of the present invention, the organosilicon is siloxanes.Preferably, the organosilicon
For：
Wherein, R1, R2, R3, R4 between any two can be identical or different, and are independently selected from C1-C5 alkyl, C1-
C4 alkylacyls, specific such as methyl, ethyl, propyl, acryloyl group, γ-methylacryloyl, butyl.
As the more preferable technical solution of the present invention, the organosilicon is selected from ethyl orthosilicate, tetramethoxy-silicane
With it is one or more in γ-methacryloxypropyl trimethoxy silane.It is highly preferred that the organosilicon is positive silicon
It is one or more in acetoacetic ester and γ-methacryloxypropyl trimethoxy silane.
As the optimal technical scheme of the present invention, the 3D printing cures high translucent material composition with ultraviolet light,
According to weight proportion, the prepolymer, diluent, photoinitiator weight proportion be：
25-50 parts of prepolymer, preferably 30-40 parts, such as 33 parts, 35 parts, 38 parts；15-40 parts of diluent, preferably 20-
38 parts, preferably 25-35 parts, such as 28 parts, 30 parts, 32 parts；0.5-5 parts of photoinitiator, preferably 1-4 parts, preferably 1.5-3.5
Part, such as 2 parts, 2.5 parts, 3 parts.
As the optimal technical scheme of the present invention, the 3D printing cures high translucent material composition with ultraviolet light,
According to weight proportion, including following component：
25-50 parts of prepolymer, preferably 30-40 parts, such as 33 parts, 35 parts, 38 parts；15-40 parts of diluent, preferably 20-
38 parts, preferably 25-35 parts, such as 28 parts, 30 parts, 32 parts；0.5-5 parts of photoinitiator, preferably 1-4 parts, preferably 1.5-3.5
Part, such as 2 parts, 2.5 parts, 3 parts.0.5-5 parts of auxiliary agent, preferably 1-4 parts, preferably 1.5-3.5 parts, such as 2 parts, 2.5 parts, 3 parts.
As the present invention an optimal technical scheme, the diluent can be simple function group or polyfunctional group (such as
Two functional groups) one or more of acrylate.Preferably, the molecular weight of the acrylate diluent is 2000-
5000。
It is highly preferred that monofunctional acrylates' ester is selected from 2- phenoxyethyl acrylates, ethoxyquin phenoxy group
Acrylate (article number：PH2EOA, PH3EOA), 2- phenoxyethyl methacrylates, glycidyl methacrylate,
One or more mixtures in benzyl acrylic methyl esters, benzyl methyl methyl acrylate.
It is highly preferred that the bifunctional acrylate is selected from 1,6- hexanediyl esters, dipropylene glycol dipropyl
Olefin(e) acid ester, 3- methyl-1s, 5- Diacrylates, ethoxyquin 1,6 hexanediol diacrylate, two propylene of tripropylene glycol
One or more mixtures in acid esters, Tricyclodecane Dimethanol diacrylate.Most preferably, the diluent is 1,6-
Hexanediyl ester, it is one or more mixed in 2- phenoxyethyl acrylates, ethoxyquin phenoxy group acrylate
Close object.
As the optimal technical scheme of the present invention, the photoinitiator is preferably free radical polymerization photoinitiator.
Preferably, the free radical polymerization photoinitiator is Dialkoxy acetophenones, alpha-hydroxyalkyl benzophenone, α-amine alkane
Base benzophenone, acylphosphine oxide, esterification oximinoketone compound, aryl peroxide ester compounds, halogenated methyl arone, organic sulfur-containing chemical combination
One or more mixtures in object, benzoyl formiate, thioxanthone and its derivative, anthraquinone, coumarone and camphorquinone.
It is highly preferred that the free radical polymerization photoinitiator is 1- hydroxy-cyclohexyl-phenyls ketone, α, α-diethoxy
One or more mixtures in acetophenone, benzoyl formiate.
As the optimal technical scheme of the present invention, the auxiliary agent can be levelling agent, wetting agent, antifoaming agent, help and draw
Send out one or more of agent and transparent agent.Preferably, the auxiliary agent includes but not limited to levelling agent, wetting agent, antifoaming agent, helps
Initiator and transparent agent.
It is highly preferred that the weight proportion of auxiliary agent each component is：0.1-1 parts of levelling agent, 0.5-2 parts of wetting agent, antifoaming agent
0.1-1 parts, 0.1-1 parts of aided initiating, 0.5-1 parts of transparent agent.
As the optimal technical scheme of the present invention, the antifoaming agent is preferably water-base cement silicone emulsion, higher alcohols
Poly- penta 4 alcohol ether of fatty acid ester compounded object, polyoxyethylene polyoxypropylene, polyoxyethylene polyoxy propyl alcohol amidogen ether, polyoxypropylene glyceryl
One or more mixtures in ether, polyoxyethylene polyoxypropylene glycerin ether, dimethyl silicone polymer；The levelling agent is poly-
Siloxanes-ether copolymer, silicone oil, dimethyl silicone polymer, polyether polyester azo polyether polyeste, alkyl-modified organic silica
One or more mixtures in alkane, acrylate；The wetting agent be silanol class nonionic surfactant, sulfonated oil,
One or more mixtures in soybean lecithin, thio-alcohol, hydrazides, mercaptan acetal；The aided initiating is triethyl group
One or more mixtures in amine, triethanolamine, triphenylphosphine, thiodiglycol；The transparent agent is sorbitol derived
Object to chloromethyl dibenzyl sorbitol (EC-4), double-(p- ethyl dixylyl isopropyl) sorbierite (NC-4), 1,3,2,
4 ,-two (benzal) sorbierite (article numbers：Millad3905), 1,3,2,4 ,-two (4- Methyl-benzylidenes) sorbierite (article numbers：
) and one or more mixtures in novel sorbose alcohols transparent agent (Millad3988) Millad3940.It is further preferred that
The levelling agent is selected as one or more in BYK-333, BYK-306；The antifoaming agent is selected as in BYK-066N, BYK-057
It is one or more；The wetting agent is selected as BYK-167；Aided initiating is selected as triethylamine；Transparent agent is selected as EC-4.
Third aspect of the present invention provides a kind of 3D printing described above high translucent material combination of ultraviolet light solidification
The preparation method of object, including：
Step A：Under acid catalysis colloidal sol is made in organosilicon with sol-gal process；
Step B：Oligomer will be added in the colloidal sol obtained in step A and antifoaming agent, ultrasonic wave minute disperse to obtain transparent
Hybrid collosol；
Step C：To be added in the hybrid collosol obtained in step B photoinitiator, diluent and other that may be present help
Agent, mixing obtain the 3D printing ultraviolet light and cure high translucent material composition.
More specifically, the 3D printing ultraviolet light cures the preparation method of high translucent material composition, including：
Step A：Under the catalytic action of HCl colloidal sol is made in load weighted organosilicon with sol-gal process；
Step B：Oligomer and antifoaming agent will be added in the colloidal sol obtained in step A, ultrasonic wave dispersion in 40-60 minutes obtains
The hybrid collosol of homogeneous transparent；
Step C：Photoinitiator, diluent and other auxiliary agents will be added in the hybrid collosol obtained in step B, in 1000-
It is stirred 15-30 minutes under 3000r/min rotating speeds, obtains evenly dispersed 3D printing and cure high translucent material with ultraviolet light.
As the optimal technical scheme of the present invention, the antifoaming agent being added in step B is the total weight 20- of antifoaming agent
40%.
As the optimal technical scheme of the present invention, in step C, it is preferably 2000r/min to stir speed.
The 3D printing ultraviolet light being prepared using technical solution provided by the invention cures the light transmission of high translucent material
Rate is high, mist degree is low, good in optical property, can be applied to the 3D printing technique of transparent artware and optical device.The preparation method
Technological process it is simple, prepare convenient, of low cost, be suitable for industrialized production.
Specific implementation mode
The detailed description for preferred implementation method of the invention below of participating in the election of 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 fields of the present invention
The normally understood identical meaning of technical staff.When there is a conflict, the definition in this specification shall prevail.
As used herein term " by ... prepare " it is synonymous with "comprising".Term "comprising" used herein, " comprising ",
" having ", " containing " or its any other deformation, it is intended that cover non-exclusionism includes.For example, the combination comprising listed elements
Object, step, method, product or device are not necessarily limited to those elements, but may include not expressly listed other elements or
Such composition, step, method, product or the intrinsic element of device.
Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit
When the Range Representation that choosing value limits, this, which should be understood as, specifically discloses by any range limit or preferred value and any range
Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open
When range " 1 to 5 ", described range should be interpreted as including range " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise range intention includes its end
Value and all integers and score in the range.
Approximate term in specification and claims is used for modifying quantity, and it is specific to indicate that the present invention is not limited to this
Quantity further includes the modified part of the acceptable change without lead to related basic function close to the quantity.Phase
It answers, modifies a numerical value with " about ", " about " etc., mean that the present invention is not limited to the exact numericals.In some examples, approximate
Term likely corresponds to the precision of the instrument of measured value.In present specification and claims, range limits can be with
Combination and/or exchange, these ranges include all subranges contained therebetween if not stated otherwise.
In addition, indefinite article "an" before element of the present invention or component and "one" quantitative requirement to element or component
(i.e. occurrence number) unrestriction.Therefore "one" or "an" should be read as including one or at least one, and odd number
The element or component of form also include plural form, unless the apparent purport of the quantity refers to singulative.
" blend " means that two or more polymer is mixed by physics or chemical method and formed jointly
Polymer.
The present invention provides a kind of 3D printing ultraviolet lights to cure high translucent material composition, and the present invention uses following skill
Art scheme：It include prepolymer, diluent, photoinitiator and, wherein the prepolymer be include the mixed of oligomer and organosilicon
Hybrid collosol is closed, the wherein silicon dioxide granule of Nano grade is equably crosslinked in oligomer phase.Finally obtained ultraviolet light
Curing materials, finished product has very high light transmittance and very low mist degree after ultraviolet light cures.
The maximum of the present invention is characterized in that carrying by the way that nano silicon dioxide is scattered in hybrid collosol, is introduced into system
Light transmittance is risen, the present invention is using organosilicon and oligomer as the prepolymer of ultraviolet photocureable material, cooperation diluent, primosome
System, auxiliary agent etc. are uniformly mixed under high speed dispersion, and the product light transmittance after being printed with SLA type 3D printers is excellent, and material exists
Light transmittance is up to 98.80% under 2cm thickness, while mist degree is low, and hardness is good, is better than conventional photosensitive material.
As a kind of preferred technical solution of the present invention, prepolymer be the weight ratio of oligomer and organosilicon be 3: 2 it is miscellaneous
Change colloidal sol.
As a kind of technical solution having choosing of the present invention, the oligomer is modified polyester acrylate ester (6319), changes
It is one or more in property polyester acrylate (6343), polyester acrylate (DR-E524).
As a kind of perferred technical scheme, organosilicon is selected as：Ethyl orthosilicate and γ-methacryloxypropyl three
Methoxy silane.
As a kind of perferred technical scheme, diluent is selected as 2- phenoxyethyl acrylates, ethoxyquin phenoxy group third
One in olefin(e) acid ester, 2- phenoxyethyl methacrylates, 1,6 hexanediol diacrylate, dipropylene glycol diacrylate
Kind or two or more mixtures.
As a kind of preferred technical solution of the present invention, the free radical polymerization photoinitiator is selected as：1- hydroxyls-ring
Hexyl-phenyl ketone, α, one or more mixtures in α-diethoxy acetophenone, benzoyl formiate.
As a kind of preferred technical solution of the present invention, the auxiliary agent is 1 part of levelling agent, 1 part of aided initiating, wetting agent 1
Part, 0.5 part of antifoaming agent, 1 part of transparent agent.
As a preferred embodiment of the present invention, levelling agent is selected as one or more in BYK-333, BYK-306；It is described
Antifoaming agent is selected as one or more in BYK-066N, BYK-057；The wetting agent is selected as BYK-167；Aided initiating is selected as three
Ethylamine, transparent agent are selected as EC-4.
Second aspect of the present invention provides the preparation method that a kind of 3D printing ultraviolet light cures high translucent material, at least wraps
Include following steps：
Ethyl orthosilicate, absolute ethyl alcohol and deionized water are added in there-necked flask, the oil bath at 40-50 DEG C, stirring is equal
It is even, hydrochloric acid is added, is reacted 45-60 minutes, then add suitable deionized water and absolute ethyl alcohol, γ-methyl-prop is then added dropwise
Alkene acryloxypropylethoxysilane trimethoxy silane, time for adding are 30 minutes, and 55-65 DEG C is warming up to after being added dropwise, and flow back 3-5h, most
Room temperature is aged 3-5 days afterwards, obtains Ludox.The ethyl orthosilicate being wherein added and γ-methacryloxypropyl trimethoxy
The molar ratio of base silane is：1∶1；The molar ratio of absolute ethyl alcohol and deionized water is：1: 1 to 1: 1.5；Ethyl orthosilicate with
The molar ratio of absolute ethyl alcohol and hydrochloric acid is：1: 3: 0.0001 to 1: 3.5: 0.0002.
By Ludox, vacuum extracts ethyl alcohol and water at 50 DEG C, then sequentially adds acrylate oligomers into Ludox again
The antifoaming agent of object and 20-40%, ultrasonic wave dispersion in 40-60 minutes obtain the hybrid collosol of homogeneous transparent, Ludox and acrylic acid
The weight ratio of ester oligomer is：3: 2 to 3: 1.
The auxiliary agents such as photoinitiator, diluent, remaining antifoaming agent are added in obtained hybrid collosol, turn in 2000r/min
It is stirred evenly under speed, obtains uniform 3D printing ultraviolet light solidification high transparency material.
Polyester acrylate oligomers
In the present invention, the polyester acrylate oligomers of selection are chosen to be with low viscosity and the good spy of dilution property
Property, can enumerate have modified polyester acrylate ester (6315,6316,6319,6319-1,6343, DR-E539), tetrafunctional base
Polyester acrylate (6321-100,6325-100,6325-100), polyester acrylate (6333-100,6340,6340N,
6349、6351、6353、6353-1、6355、 6360、6360D、6371、6372、6385、DR-E504、DR-E524、DR-
E527, DR-E540A, DR-E636, DR-E650, DR-E750, DR-E850), polyester chloride acrylic ester (6314C-55,
6314C-60、6314C-60L)。
Mono-functional's acrylate
In the present invention, mono-functional's acrylate of selection is chosen to be with low viscosity and the good characteristic of dilution property,
What can be enumerated has：2- phenoxyethyl acrylates, ethoxyquin phenoxy group acrylate (PH2EOA, PH3EOA), 2- benzene oxygen
Base ethylmethyl acrylate, glycidyl methacrylate, benzyl acrylic methyl esters, benzyl methyl methyl acrylate.
Difunctionality acrylate
In the present invention, the difunctionality acrylate of selection is chosen to be with low viscosity and the good characteristic of dilution property,
What can be enumerated has：1,6 hexanediol diacrylate, dipropylene glycol diacrylate, 3- methyl-1s, two propylene of 5- pentanediols
Acid esters, ethoxyquin 1,6 hexanediol diacrylate, tripropylene glycol diacrylate, Tricyclodecane Dimethanol diacrylate
Photoinitiator
In the present invention, the photoinitiator of selection must have good stability and without Yellowing, and what can be illustrated has：1-
Hydroxy-cyclohexyl-phenyl ketone, α, α-diethoxy acetophenone, benzoyl formiate, 2,4,6- trimethylbenzoyls-two
Phenyl phosphine oxide, benzoyl derivatives, benzophenone.
Levelling agent
In the present invention, levelling agent is not particularly limited, and what can be illustrated has：Polysiloxanes-ether copolymer, silicone oil,
Dimethyl silicone polymer, polyether polyester azo polyether polyeste, alkyl-modified organosiloxane, acrylate.
Antifoaming agent
In the present invention, antifoaming agent is not particularly limited, and what can be illustrated has：Water-base cement silicone emulsion, higher alcohols
Poly- penta 4 alcohol ether of fatty acid ester compounded object, polyoxyethylene polyoxypropylene, polyoxyethylene polyoxy propyl alcohol amidogen ether, polyoxypropylene glyceryl
Ether, polyoxyethylene polyoxypropylene glycerin ether, dimethyl silicone polymer.
Wetting agent
In the present invention, wetting agent agent is not particularly limited, and what can be illustrated has：Silanol class non-ionic surface active
Agent, sulfonated oil, soybean lecithin, thio-alcohol, hydrazides, mercaptan acetal.
Aided initiating
In the present invention, aided initiating is not particularly limited, and what can be illustrated has：Triethylamine, triethanolamine, triphen
Base phosphine, thiodiglycol.
Transparent agent
In the present invention, transparent agent is not particularly limited, and what can be illustrated has：Sorbitol derivatives are to chloromethyl two
Benzylidene sorbitol (EC-4), double-(p- ethyl dixylyl isopropyl) sorbierite (NC-4), 1,3,2,4 ,-two (benzals)
Sorbierite (Millad3905), 1,3,2,4 ,-two (4 Methyl-benzylidene) sorbierites (Millad3940) and Millad3988.
Embodiment 1
Embodiment 1 provides a kind of 3D printing ultraviolet light and cures high translucent material, in parts by weight, raw material include with
Lower component：
3D printing ultraviolet light cures the preparation method of high translucent material, includes the following steps：
Ethyl orthosilicate, absolute ethyl alcohol and deionized water are added in there-necked flask, the oil bath at 40 DEG C stirs evenly,
Hydrochloric acid is added, is reacted 60 minutes, then add suitable deionized water and absolute ethyl alcohol, γ-methacryloxypropyl is then added dropwise
Base propyl trimethoxy silicane, time for adding are 30 minutes, and 60 DEG C are warming up to after being added dropwise, and flow back 3h, last room temperature ageing 3
It, obtains Ludox；
By Ludox, vacuum extracts ethyl alcohol and water at 50 DEG C, then sequentially adds acrylate oligomers into Ludox again
Object and 20% antifoaming agent, the dispersion of ultrasonic wave 60 minutes obtains the hybrid collosol of homogeneous transparent, Ludox and acrylate oligomers
The weight ratio of object is：2∶3；
The auxiliary agents such as photoinitiator, diluent, remaining antifoaming agent are added in obtained hybrid collosol, turn in 2000r/min
It is stirred evenly under speed, obtains uniform 3D printing ultraviolet light and cure high translucent material.
Embodiment 2
Compared with Example 1, modified polyester acrylate ester and organosilicon weight ratio are 3-1 in the prepolymer of embodiment 2,
In parts by weight, raw material includes following components：
3D printing ultraviolet light cures the preparation method of high translucent material, includes the following steps：
Ethyl orthosilicate, absolute ethyl alcohol and deionized water are added in there-necked flask, the oil bath at 40 DEG C stirs evenly,
Hydrochloric acid is added, is reacted 60 minutes, then add suitable deionized water and absolute ethyl alcohol, γ-methacryloxypropyl is then added dropwise
Base propyl trimethoxy silicane, time for adding are 30 minutes, and 60 DEG C are warming up to after being added dropwise, and flow back 3h, last room temperature ageing 3
It, obtains Ludox；
By Ludox, vacuum extracts ethyl alcohol and water at 50 DEG C, then sequentially adds acrylate oligomers into Ludox again
Object and 20% antifoaming agent, the dispersion of ultrasonic wave 60 minutes obtains the hybrid collosol of homogeneous transparent, Ludox and acrylate oligomers
The weight ratio of object is：1∶3；
The auxiliary agents such as photoinitiator, diluent, remaining antifoaming agent are added in obtained hybrid collosol, turn in 2000r/min
It is stirred evenly under speed, obtains uniform 3D printing ultraviolet light and cure high translucent material.
Embodiment 3
Embodiment 3 provides a kind of 3D printing ultraviolet light and cures high translucent material, in parts by weight, raw material include with
Lower component：
3D printing ultraviolet light cures the preparation method of high translucent material, includes the following steps：
Ethyl orthosilicate, absolute ethyl alcohol and deionized water are added in there-necked flask, the oil bath at 50 DEG C stirs evenly,
Hydrochloric acid is added, is reacted 60 minutes, then add suitable deionized water and absolute ethyl alcohol, γ-methacryloxypropyl is then added dropwise
Base propyl trimethoxy silicane, time for adding are 30 minutes, and 60 DEG C are warming up to after being added dropwise, and flow back 5h, last room temperature ageing 5
It, obtains Ludox；
By Ludox, vacuum extracts ethyl alcohol and water at 50 DEG C, then sequentially adds acrylate oligomers into Ludox again
Object and 20% antifoaming agent, the dispersion of ultrasonic wave 60 minutes obtains the hybrid collosol of homogeneous transparent, Ludox and acrylate oligomers
The weight ratio of object is：2∶3；
The auxiliary agents such as photoinitiator, diluent, remaining antifoaming agent are added in obtained hybrid collosol, turn in 2000r/min
It is stirred evenly under speed, obtains uniform 3D printing ultraviolet light and cure high translucent material.
Embodiment 4
Compared with Example 3, in the prepolymer of embodiment 4 modified polyester acrylate ester and organosilicon weight ratio be 3-1 with
Parts by weight meter, raw material include following components：
3D printing ultraviolet light cures the preparation method of high translucent material, includes the following steps：
Ethyl orthosilicate, absolute ethyl alcohol and deionized water are added in there-necked flask, the oil bath at 50 DEG C stirs evenly,
Hydrochloric acid is added, is reacted 60 minutes, then add suitable deionized water and absolute ethyl alcohol, γ-methacryloxypropyl is then added dropwise
Base propyl trimethoxy silicane, time for adding are 30 minutes, and 60 DEG C are warming up to after being added dropwise, and flow back 5h, last room temperature ageing 5
It, obtains Ludox；
By Ludox, vacuum extracts ethyl alcohol and water at 50 DEG C, then sequentially adds acrylate oligomers into Ludox again
Object and 20% antifoaming agent, the dispersion of ultrasonic wave 60 minutes obtains the hybrid collosol of homogeneous transparent, Ludox and acrylate oligomers
The weight ratio of object is：1∶3；
The auxiliary agents such as photoinitiator, diluent, remaining antifoaming agent are added in obtained hybrid collosol, turn in 2000r/min
It is stirred evenly under speed, obtains uniform 3D printing ultraviolet light and cure high translucent material.
Embodiment 5
Embodiment 5 provides a kind of 3D printing ultraviolet light and cures high translucent material, in parts by weight, raw material include with
Lower component：
3D printing ultraviolet light cures the preparation method of high translucent material, includes the following steps：
Ethyl orthosilicate, absolute ethyl alcohol and deionized water are added in there-necked flask, the oil bath at 50 DEG C stirs evenly,
Hydrochloric acid is added, is reacted 50 minutes, then add suitable deionized water and absolute ethyl alcohol, γ-methacryloxypropyl is then added dropwise
Base propyl trimethoxy silicane, time for adding are 30 minutes, and 60 DEG C are warming up to after being added dropwise, and flow back 3h, last room temperature ageing
3-5 days, obtain Ludox；
By Ludox, vacuum extracts ethyl alcohol and water at 50 DEG C, then sequentially adds acrylate oligomers into Ludox again
Object and 20% antifoaming agent, the dispersion of ultrasonic wave 60 minutes obtains the hybrid collosol of homogeneous transparent, Ludox and acrylate oligomers
The weight ratio of object is：2∶3；
The auxiliary agents such as photoinitiator, diluent, remaining antifoaming agent are added in obtained hybrid collosol, turn in 2000r/min
It is stirred evenly under speed, obtains uniform 3D printing ultraviolet light and cure high translucent material.
Embodiment 6
Compared with Example 5, modified polyester acrylate ester and organosilicon weight ratio are 3-1 in the prepolymer of embodiment 6,
In parts by weight, raw material includes following components：
3D printing ultraviolet light cures the preparation method of high translucent material, includes the following steps：
Ethyl orthosilicate, absolute ethyl alcohol and deionized water are added in there-necked flask, the oil bath at 50 DEG C stirs evenly,
Hydrochloric acid is added, is reacted 50 minutes, then add suitable deionized water and absolute ethyl alcohol, γ-methacryloxypropyl is then added dropwise
Base propyl trimethoxy silicane, time for adding are 30 minutes, and 60 DEG C are warming up to after being added dropwise, and flow back 3h, last room temperature ageing
3-5 days, obtain Ludox；
By Ludox, vacuum extracts ethyl alcohol and water at 50 DEG C, then sequentially adds acrylate oligomers into Ludox again
Object and 20% antifoaming agent, the dispersion of ultrasonic wave 60 minutes obtains the hybrid collosol of homogeneous transparent, Ludox and acrylate oligomers
The weight ratio of object is：1∶3；
The auxiliary agents such as photoinitiator, diluent, remaining antifoaming agent are added in obtained hybrid collosol, turn in 2000r/min
It is stirred evenly under speed, obtains uniform 3D printing ultraviolet light and cure high translucent material.
Embodiment 7
Embodiment 7 provides a kind of 3D printing ultraviolet light and cures high translucent material, in parts by weight, raw material include with
Lower component：
3D printing ultraviolet light cures the preparation method of high translucent material, includes the following steps：
Tetramethoxy-silicane, absolute ethyl alcohol and deionized water are added in there-necked flask, the oil bath at 50 DEG C, stirring is equal
It is even, hydrochloric acid is added, is reacted 50 minutes, then add suitable deionized water and absolute ethyl alcohol, γ-methacryl is then added dropwise
Oxygroup propyl trimethoxy silicane, time for adding are 30 minutes, and 60 DEG C are warming up to after being added dropwise, and flow back 3h, and last room temperature is old
Change 3-5 days, obtains Ludox；
By Ludox, vacuum extracts ethyl alcohol and water at 50 DEG C, then sequentially adds acrylate oligomers into Ludox again
Object and 20% antifoaming agent, the dispersion of ultrasonic wave 60 minutes obtains the hybrid collosol of homogeneous transparent, Ludox and acrylate oligomers
The weight ratio of object is：2∶3；
The auxiliary agents such as photoinitiator, diluent, remaining antifoaming agent are added in obtained hybrid collosol, turn in 2000r/min
It is stirred evenly under speed, obtains uniform 3D printing ultraviolet light and cure high translucent material.
Embodiment 8
Compared with Example 7, modified polyester acrylate ester and organosilicon weight ratio are 3-1 in the prepolymer of embodiment 8,
In parts by weight, raw material includes following components：
3D printing ultraviolet light cures the preparation method of high translucent material, includes the following steps：
Tetramethoxy-silicane, absolute ethyl alcohol and deionized water are added in there-necked flask, the oil bath at 50 DEG C, stirring is equal
It is even, hydrochloric acid is added, is reacted 50 minutes, then add suitable deionized water and absolute ethyl alcohol, γ-methacryl is then added dropwise
Oxygroup propyl trimethoxy silicane, time for adding are 30 minutes, and 60 DEG C are warming up to after being added dropwise, and flow back 3h, and last room temperature is old
Change 3-5 days, obtains Ludox；
By Ludox, vacuum extracts ethyl alcohol and water at 50 DEG C, then sequentially adds acrylate oligomers into Ludox again
Object and 20% antifoaming agent, the dispersion of ultrasonic wave 60 minutes obtains the hybrid collosol of homogeneous transparent, Ludox and acrylate oligomers
The weight ratio of object is：1∶3；
The auxiliary agents such as photoinitiator, diluent, remaining antifoaming agent are added in obtained hybrid collosol, turn in 2000r/min
It is stirred evenly under speed, obtains uniform 3D printing ultraviolet light and cure high translucent material.
Embodiment 9
Embodiment 9 provides a kind of 3D printing ultraviolet light and cures high translucent material, in parts by weight, raw material include with
Lower component：
3D printing ultraviolet light cures the preparation method of high translucent material, includes the following steps：
The auxiliary agents such as photoinitiator, diluent, antifoaming agent will be added in prepolymer, are stirred evenly under 2000r/min rotating speeds,
It obtains uniform 3D printing ultraviolet light and cures high translucent material.
Embodiment 10
Embodiment 10 provides a kind of high translucent material of 3D printing ultraviolet light solidification, and in parts by weight, raw material includes
Following components：
3D printing ultraviolet light cures the preparation method of high translucent material, includes the following steps：
The auxiliary agents such as photoinitiator, diluent, antifoaming agent will be added in prepolymer, are stirred evenly under 2000r/min rotating speeds,
It obtains uniform 3D printing ultraviolet light and cures high translucent material.
Performance evaluation
All 3D printings ultraviolet light is cured high translucent material fortune and is cured with 110W ultraviolet lights in 3D printer, solidification temperature
Degree：65 DEG C, cures 5 minutes, be printed as sheet material (thickness：2cm), it is tested.Viscosity is then to be tested in collosol state.
Light transmittance/mist degree：According to the method for GB2410-80 defineds, using light transmittance mist degree analyzer, at room temperature
(humidity is less than 80%) is tested.
Hardness：The pencil hardness of finished product is determined according to the method for GB/T6739-1996 defineds.
Stability:It is placed 72 hours under material normal temperature and pressure environment, has seen whether Yellowing.
Tensile strength/：Testing standard is GB/T 1040.2-2006, and sample is dumbbell shaped, shape size 150mm
X20mm x4mm, distance is 115 scholar 5.0mm between fixture, and tensile speed is set as 2mm/min.
Cubical contraction：The solidification cubical contraction of ultraviolet photocureable material is printed by following public affairs according to ISO 3521,3D
Formula is calculated：
Wherein, the density of dissolved colloidal state material sample when ρ 1 is uncured, ρ 2 are the density after solidification.
Table 1
| Embodiment | Light transmittance | Mist degree | Hardness | Stability | Tensile strength | Cubical contraction |
| Embodiment 1 | 97.70% | 0.5 | 4H | Without xanthochromia | 16.45MPa | 4.65% |
| Embodiment 2 | 96.10% | 0.5 | 5H | Without xanthochromia | 16.12MPa | 5.12% |
| Embodiment 3 | 96.60% | 0.4 | 4H | Without xanthochromia | 17.65MPa | 4.32% |
| Embodiment 4 | 95.80% | 0.5 | 5H | Without xanthochromia | 17.83MPa | 4.96% |
| Embodiment 5 | 99.20% | 0.2 | 5H | Without xanthochromia | 18.53MPa | 3.64% |
| Embodiment 6 | 98.80% | 0.2 | 6H | Without xanthochromia | 18.25MPa | 4.25% |
| Embodiment 7 | 96.10% | 0.5 | 5H | Without xanthochromia | 15.67MPa | 4.65% |
| Embodiment 8 | 94.30% | 0.4 | 5H | Without xanthochromia | 16.23MPa | 5.23% |
| Embodiment 9 | 89.10% | 1.7 | 2H | Without xanthochromia | 14.35MPa | 8.12% |
| Embodiment 10 | 90.70% | 1.8 | 2H | Without xanthochromia | 14.83MPa | 8.64% |
According to table 1, embodiment 1-8 is compared with embodiment 9,10 it is found that the colloidal sol for being added to organic-silicon hybridization colloidal sol possesses
Better light transmittance and mist degree, while hardness is also risen.And the ratio of different oligomer and organosilicon is also largely
Affect its performance, the weight ratio of organosilicon and oligomer is 2:When 3, the ultraviolet photocureable material of gained is prepared through UV light
The light transmittance highest of product after change, while mist degree is minimum, is suitble to that the 3D printing of opaque products is made, can be applied to craftwork and
Optical device.
The example of front is merely illustrative, some features for explaining the method for the invention.Appended right is wanted
It asks and is intended to require range as wide as possible, and embodiments as presented herein is only the combination according to all possible embodiment
The explanation of the embodiment of selection.Therefore, the purpose of applicant is the feature that the attached claims are not illustrated the present invention
Exemplary selectional restriction.Some numberical ranges used also include subrange within the scope of its in the claims, this
Variation in a little ranges should also be construed to be covered by the attached claims in the conceived case.
Claims (11)
1. a kind of 3D printing UV cures the prepolymer of high translucent material, which is characterized in that the prepolymer is：Including oligomer and
The mixed hybridization colloidal sol of organosilicon.
2. prepolymer according to claim 1, which is characterized in that the mixed hybridization colloidal sol is by oligomer and organosilicon
Colloidal sol is made by ultrasonic disperse.
3. prepolymer according to claim 1, which is characterized in that the weight ratio of the oligomer and organic silicon sol is 3:
(2-1)。
4. according to the prepolymer described in any one of claim 1-3, which is characterized in that the oligomer is polyester
Acid esters oligomer.
5. according to the prepolymer described in any one of claim 1-3, which is characterized in that the organosilicon is siloxanes.
6. a kind of 3D printing UV cures high translucent material, which is characterized in that including：Prepolymer, diluent described in claim 1,
Photoinitiator.
7. 3D printing UV according to claim 6 cures high translucent material, which is characterized in that the prepolymer, diluent,
The weight proportion of photoinitiator is：
25-50 parts of prepolymer；
15-40 parts of diluent；
0.5-5 parts of photoinitiator.
8. 3D printing UV according to claim 6 cures high translucent material, which is characterized in that the diluent is simple function
One or more of the acrylate of group, two functional groups.
9. 3D printing UV according to claim 6 cures high translucent material, which is characterized in that the photoinitiator is certainly
By base polymerization photoinitiator.
10. 3D printing UV according to claim 6 cures high translucent material, which is characterized in that the 3D printing is with ultraviolet
The high translucent material composition of photocuring further includes auxiliary agent, the auxiliary agent include levelling agent, wetting agent, antifoaming agent, aided initiating and
Any one or the combination of several of them in transparent agent.
11. a kind of 3D printing UV as described in any one of claim 6-10 cures the preparation method of high translucent material,
It is characterized in that, including：
Step A：Under acid catalysis colloidal sol is made in organosilicon with sol-gal process；
Step B：Oligomer and antifoaming agent will be added in the colloidal sol obtained in step A, ultrasonic wave minute disperses to obtain transparent miscellaneous
Change colloidal sol；
Step C：Photoinitiator, diluent and other auxiliary agents that may be present will be added in the hybrid collosol obtained in step B, mixes
It closes, obtains the 3D printing ultraviolet light and cure high translucent material composition.
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