CN106243290B - A kind of rubber-type photocuring 3D printing material and preparation method thereof - Google Patents
A kind of rubber-type photocuring 3D printing material and preparation method thereof Download PDFInfo
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- CN106243290B CN106243290B CN201610310909.6A CN201610310909A CN106243290B CN 106243290 B CN106243290 B CN 106243290B CN 201610310909 A CN201610310909 A CN 201610310909A CN 106243290 B CN106243290 B CN 106243290B
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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
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
- C08F283/105—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule on to unsaturated polymers containing more than one epoxy radical per molecule
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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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another
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Abstract
The invention discloses a kind of rubber-type photocuring 3D printing materials and preparation method thereof, are prepared using the following raw material：Silane-modified hydrogenated bisphenol A epoxy acrylate, epoxy resin, photosensitive diluent, polyol compound, cation light initiator, free radical photo-initiation, auxiliary agent.Compared with prior art, the present invention is added using silane-modified hydrogenated bisphenol A epoxy acrylate as prepolymer in 3D printing material, and the tension fracture elongation rate of photocuring 3D printing material is made to increase substantially, and has splendid elasticity, toughness, flexibility.Also, the present invention can adjust material hardness by the change of raw material proportioning, the different product of Shore A hardness 30~95 be obtained, to meet different demands.Therefore, the rubber-type photocuring 3D printing material that prepared by the present invention has the characteristics that high resiliency, high tenacity, hardness are low, flexibility is high, formed precision is high, glossiness is high.
Description
Technical field
The present invention relates to rapid prototyping ＆ manufacturing technology field more particularly to a kind of rubber-type photocuring 3D printing material and its
Preparation method.
Background technology
3D printing is a kind of novel threedimensional model manufacturing technology for phase late 1980s generating and growing up, and is
The Integration ofTechnology of CAD/CAM, precision machinery, laser technology and Materials Science and Engineering, being one has powerful vitality
New technology.3D printing technique is also known as increases material manufacturing technology, is to utilize computer, three-dimensional stereo model is converted into simple two
Dimensional plane model controls molding process by computer, finally obtains the manufacturing technology of the molded part of complicated shape, solve perhaps
More insoluble problems of classical production process greatly improve production efficiency so as to shorten the manufacturing cycle of product.
Introduction To Stereolithography (SLA) is to obtain commercial Application earliest, and most widely used at present, research is most
The most ripe rapid shaping technique of more, technology.The moulding material of SLA is liquid photosensitive resin, and forming principle is using ultraviolet
Photochemical reaction occurs for the photoactive substance in laser resin system, when ultraviolet lighting is mapped on liquid resin, exposure position hair
Third contact of a total solar or lunar eclipse initiated polymerization and cure, while being combined with Computer Control Technology, quickly obtain cured article.The molding side of SLA
Method is to control light source by computer, is scanned along liquid level according to cross section profile above resin storage tank, and the tree in scanned region is made
Fat cures, and then, lifting platform declines the thickness of one layer of thin slice, and ultraviolet light is scanned again, the curing resin layer newly formed and its
One layer of following solidified resin is securely bonded to together, so repeats to finish until molding.
In photocureable rapid shaping (SLA), liquid photosensitive resin is important component, and the quality of photosensitive resin will be certainly
Determine the precision, mechanical property and hot property of molded part.Currently, the 3D printing light that You Duo companies of foreign countries have developed commercialization is solid
Change resin, using it is most be DSM N. V. Somos series plastics, which is similar to ABS, in hardness, bullet
Property, durability is all very outstanding in terms of resistance to water soak.It develops with exploitation SLA photosensitive resins starting than later, in the color of material the country
Pool, mechanical performance make precision, durability aspect and external also larger gap.Currently, the domestic photocuring 3D developed is beaten
The print material overwhelming majority is that hardness is high, flexible low, and with the fast development of SLA technology and large-scale application, this will be limited
Its application range and development.Therefore, photocuring 3D printing material of the exploitation with high resiliency, high flexibility, is playing 3D printing
The flexible materials market expansion such as tool manufacturing industry, medical field is of great significance.
Invention content
Present invention solves the technical problem that it is to provide a kind of rubber-type photocuring 3D printing material and preparation method thereof, it should
Rubber-type photocuring 3D printing material has the characteristics that high resiliency, high flexibility.
The present invention provides a kind of rubber-type photocuring 3D printing materials, are prepared using the following raw material：
Preferably, the silane-modified hydrogenated bisphenol A epoxy acrylate is that the hydrogenation that the first silane compound is modified is double
Phenol A epoxy acrylates, first silane compound include γ-glycidyl ether oxypropyl trimethoxy silane, γ-ammonia third
Ethyl triethoxy silicane alkane, N- β-aminoethyl-γ-aminopropyltriethoxy dimethoxysilane, vinyl three (methoxyethoxy) silane
One or more of [β-(3,4 expoxycyclohexyl) ethyl] trimethoxy silane.
Preferably, the epoxy resin include bisphenol A epoxide resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin,
One or more of cycloaliphatic epoxy resin and novolac epoxy resin.
Preferably, the cycloaliphatic epoxy resin is 3,4- epoxycyclohexyl formic acid -3 ', 4 '-epoxycyclohexanecarboxylates, double
((3,4- epoxycyclohexyls) methyl) adipate ester, 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters, 3,4- epoxies
Cyclohexyl methyl -3 ', one or more of the polymerizate of 4 '-epoxycyclohexyl formic acid esters and caprolactone.
Preferably, the photosensitive diluent includes acrylate monomer, vinyl ether monomers and oxetane compound
One or more of.
Preferably, the polyol compound is polyether polyol and/or polycaprolactone polyol.
Preferably, the cation light initiator includes aryl diazonium salts, triaryl matte hexafluoro antimonate, triaryl matte
One or more of hexafluorophosphate and aryl cyclopentadienyl molysite.
Preferably, the free radical photo-initiation includes dimethoxybenzoin, benzophenone, 1- hydroxy-cyclohexyl benzene first
Ketone, 2- methyl-1s-(4- first mercaptophenyl) -2- morpholines acetone -1,2- hydroxy-2-methyls-phenylacetone -1,2,4,6,-front three
Base benzoyl-diphenyl phosphine oxide, bis- (2,4,6 ,-trimethylbenzoyl) phenyl phosphine oxide 2,4- diethyl thioxanthones
One or more of with 4- benzoyls -4 '-dimethyl diphenyl sulfide.
Preferably, the auxiliary agent include one kind in coupling agent, polymerization inhibitor, levelling agent, antifoaming agent or wetting dispersing agent or
It is several.
Correspondingly, the present invention also provides a kind of preparations of the rubber-type photocuring 3D printing material described in above-mentioned technical proposal
Method, including：By silane-modified hydrogenated bisphenol A epoxy acrylate, epoxy resin, photosensitive diluent, polyol compound, sun
Ionic photoinitiator, free radical photo-initiation and auxiliary agent mixing, stir 30~120 minutes at 20~60 DEG C, obtain rubber-type
Photocuring 3D printing material.
Beneficial effects of the present invention：The present invention provides a kind of rubber-type photocuring 3D printing material and preparation method thereof,
It is prepared using the following raw material：Silane-modified hydrogenated bisphenol A epoxy acrylate, epoxy resin, photosensitive diluent, polyol
Object, cation light initiator, free radical photo-initiation, auxiliary agent.Compared with prior art, the present invention is with silane-modified A Hydrogenated Bisphenol A
A epoxy acrylates are added as prepolymer in 3D printing material, keep the tension fracture elongation rate of photocuring 3D printing material big
Amplitude improves, and has splendid elasticity, toughness, flexibility.Also, the present invention can adjust material by the change of raw material proportioning
Hardness obtains the different product of Shore A hardness 30~95, to meet different demands.Therefore, the rubber-type light that prepared by the present invention is solid
Changing 3D printing material has the characteristics that high resiliency, high tenacity, hardness are low, flexibility is high, formed precision is high, glossiness is high.
Specific implementation mode
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still
It should be appreciated that these descriptions are only the feature and advantage further illustrated the present invention, rather than to the claims in the present invention
Limitation.
In conjunction with specific implementation mode, invention is further explained.
The present invention provides a kind of rubber-type photocuring 3D printing material, is prepared using the following raw material：
The present invention is using silane-modified hydrogenated bisphenol A epoxy acrylate as preparing rubber-type photocuring 3D printing material
Raw material makes the tension fracture elongation rate of photocuring 3D printing material increase substantially, and has splendid elasticity, toughness, flexibility.
The silane-modified hydrogenated bisphenol A epoxy acrylate is preferably 10~20 parts by weight, more preferably 13~18 parts by weight.
Preferably, the silane-modified hydrogenated bisphenol A epoxy acrylate is preferably that the first silane compound changes
The hydrogenated bisphenol A epoxy acrylate of property, first silane compound includes γ-glycydoxy trimethoxy silicon
Alkane (KH-560), gamma-aminopropyl-triethoxy-silane (KH-550), N- β-aminoethyl-γ-aminopropyltriethoxy dimethoxysilane
(KH-602), vinyl three (methoxyethoxy) silane (A-173) and [β-(3,4 expoxycyclohexyl) ethyl] trimethoxy silicon
One or more of alkane (A-186).Present invention preferably employs method of modifying well known to those skilled in the art.The present invention uses
Hydrogenated bisphenol A epoxy acrylate preferably using method well known in the art prepare or it is purchased in market, more preferably using hydrogenation
Bisphenol A epoxide resin and acrylic acid are esterified through epoxy addition under the action of basic catalyst and are made.
Preferably, the epoxy resin preferably includes bisphenol A epoxide resin, bisphenol F epoxy resin, A Hydrogenated Bisphenol A
One or more of A epoxy resin, cycloaliphatic epoxy resin and novolac epoxy resin.The cycloaliphatic epoxy resin is preferably
3,4- epoxycyclohexyl formic acid -3 ', 4 '-epoxycyclohexanecarboxylates, bis- ((3,4- epoxycyclohexyls) methyl) adipate esters, 4,5-
7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters, 3,4- epoxycyclohexyl-methyls 3,4- epoxycyclohexyls formic acid esters and oneself
One or more of polymerizate of lactone.Wherein, 3,4- epoxycyclohexyl-methyls -3 ', 4 '-epoxycyclohexyl formic acid esters and
The polymerizate of caprolactone is long-chain cycloaliphatic epoxy resin, it is preferred to use Jiangsu Tai Teer new materials Science and Technology Ltd.
TTA2083, TTA2081.The epoxy resin is preferably 10~60 parts by weight, more preferably 20-60 parts by weight, more preferably
40-60 parts by weight.
Preferably, the photosensitive diluent is preferably acrylate monomer, vinyl ether monomers and oxa- ring fourth
One or more of hydride compounds, more preferably hydroxy-ethyl acrylate, tri (propylene glycol) diacrylate, 1,6- hexylene glycols
Diacrylate, (9) ethoxyquin trimethylolpropane trimethacrylate, Tetraethylene glycol diacrylate, triethylene glycol diethyl
In alkene ether, 3- ethyls -3- methylols-oxetanes and 3,3- oxygroups two (3 '-ethyls -3 '-methylene) oxetanes
One or more.The photosensitive diluent is preferably 5~30 parts by weight, more preferably 10~20 parts by weight, more preferably 10
~15 parts by weight.
Preferably, the polyol compound is preferably polyether polyol and/or polycaprolactone polyol, more excellent
It is selected as one or more of polytetramethylene glycol, polycaprolactone diols and polycaprolactone trihydroxylic alcohol.The polynary alcoholization
It is preferably 5~15 parts by weight to close object, more preferably 10~15 parts by weight.
Preferably, the cation light initiator preferably includes aryl diazonium salts, triaryl matte hexafluoro-antimonic acid
One or more of salt, triaryl matte hexafluorophosphate and aryl cyclopentadienyl molysite.The cation light initiator is preferably 2~
8 parts by weight, more preferably 4~8 parts by weight.
Preferably, the free radical photo-initiation includes dimethoxybenzoin, benzophenone, 1- hydroxy-cyclohexyls
Benzophenone, 2- methyl-1s-(4- first mercaptophenyl) -2- morpholines acetone -1,2- hydroxy-2-methyls-phenylacetone -1,2,4,6, -
Trimethylbenzoy-dipheny phosphine oxide, bis- (2,4,6 ,-trimethylbenzoyl) phenyl phosphine oxide 2,4- diethyl thias
One or more of anthrone and 4- benzoyls -4 '-dimethyl diphenyl sulfide.The free radical photo-initiation is preferably 2~8
Parts by weight, more preferably 4~8 parts by weight.
Preferably, the auxiliary agent preferably includes coupling agent, polymerization inhibitor, levelling agent, antifoaming agent or wetting dispersing agent
One or more of, the coupling agent is preferably KH-560 or KH-570.The auxiliary agent is preferably 0.1~3 parts by weight, more excellent
It is selected as 0.2~4 parts by weight, more preferably 0.4~2 parts by weight.
After the present invention is added using silane-modified hydrogenated bisphenol A epoxy acrylate as prepolymer in 3D printing material, make
The tension fracture elongation rate of photocuring 3D printing material increases substantially, and has splendid elasticity, toughness, flexibility.Also, this
Invention is with silane-modified hydrogenated bisphenol A epoxy acrylate, epoxy resin, photosensitive diluent, polyol compound, cationic photopolymerization
Initiator, free radical photo-initiation, auxiliary agent are raw material, adjust the proportioning of raw material, make the rubber-type photocuring 3D printing material of preparation
Material has the characteristics that high resiliency, high tenacity, hardness are low, flexibility is high, formed precision is high, glossiness is high.
Correspondingly, the present invention also provides a kind of preparation method of rubber-type photocuring 3D printing material, include the following steps：
By silane-modified hydrogenated bisphenol A epoxy acrylate, epoxy resin, photosensitive diluent, the polyalcohol described in above-mentioned technical proposal
Compound, cation light initiator, free radical photo-initiation and auxiliary agent mixing, stir 30~120 minutes at 20~60 DEG C, obtain
To rubber-type photocuring 3D printing material.Wherein, whipping temp is preferably 30~50 DEG C, more preferably 30~40 DEG C；When stirring
Between preferably 40~100 minutes, more preferably 50~90 minutes.
The present invention mixes raw material by mass percentage, and stirs, that is, prepares with high resiliency, highly-flexible
The rubber-type 3D printing photosensitive resin of property.Photo-cured products prepared by the present invention have the high resiliency of rubber-like materials, high tenacity,
And have the characteristics that hardness is low, flexibility is high, formed precision is high, glossiness is high, also, can be adjusted by the change of raw material proportioning
Material hardness is saved, the different product of Shore A hardness 30~95 is obtained, to meet different demands.
Rubber-type photocuring 3D printing material prepared by the present invention is suitable for a variety of SLA printer models, the product of printing
With formed precision height, the transparency is high, and elasticity is high, and flexibility is high, hardness low the characteristics of being similar to rubber-type material feel.Using
Photosensitive resin prepared by the present invention can directly produce arbitrarily complicated shape, have high-precision high resiliency, high flexibility
Rubber-type product, to meet increasingly increasing of the domestic and international market in fields such as biologic medical, toys for children to high flexibility material
Long demand.
For a further understanding of the present invention, technical solution provided by the invention is carried out specifically with reference to embodiment
Bright, protection scope of the present invention is not limited by the following examples.
Raw material used in the embodiment of the present invention is purchased in market.
Embodiment 1-6
100g hydrogenated bisphenol A epoxies acrylate is added in three-necked flask and 2g dibutyltin dilaurate catalysts stir
It mixes, the KH-560 of 4g is slowly dropped in flask, be heated to 75-85 DEG C, then 0.1-10g distilled water is added dropwise, reacted at 90 DEG C
5-6 hours, obtain silane-modified hydrogenated bisphenol A epoxy acrylate；
Using raw material and weight percent shown in table 1, each raw material is mixed, under the conditions of 20~60 DEG C, machinery
Stirring is uniformly mixed for 30~120 minutes to each component, obtains rubber-type photocuring 3D printing material.
The performance of the embodiment 1-6 rubber-type photocuring 3D printing materials prepared is detected respectively, as a result such as 1 institute of table
Show.
The raw material and properties of product of rubber-type photocuring 3D printing material prepared by 1 1-6 of the embodiment of the present invention of table
The explanation of above example is only intended to facilitate the understanding of the method and its core concept of the invention.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvement and modification are also fallen within the protection scope of the claims of the present invention.
Claims (3)
1. a kind of rubber-type photocuring 3D printing material, which is characterized in that prepared using the following raw material：
The epoxy resin includes bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, cycloaliphatic epoxy resin and epoxy novolac
One or more of resin, the cycloaliphatic epoxy resin are 3,4- epoxycyclohexyl formic acid -3 ', 4 '-epoxycyclohexyl first
Ester, bis- ((3,4- epoxycyclohexyls) methyl) adipate esters, 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters, 3,
4- epoxycyclohexyl-methyls -3 ', one or more of the polymerizate of 4 '-epoxycyclohexyl formic acid esters and caprolactone,
The photosensitive diluent includes one kind or several in acrylate monomer, vinyl ether monomers and oxetane compound
Kind,
The polyol compound be polyether polyol and/or polycaprolactone polyol,
The cation light initiator includes one kind in aryl diazonium salts, triaryl matte hexafluoro antimonate and aryl cyclopentadienyl molysite
Or it is several,
The silane-modified hydrogenated bisphenol A epoxy acrylate is the hydrogenated bisphenol A epoxy propylene that the first silane compound is modified
Acid esters, first silane compound include γ-glycidyl ether oxypropyl trimethoxy silane, gamma-aminopropyl-triethoxy
Silane, N- β-aminoethyl-γ-aminopropyltriethoxy dimethoxysilane, (methoxyethoxy) silane of vinyl three and [β-(3,4 rings
One or more of oxygroup cyclohexyl) ethyl] trimethoxy silane,
The free radical photo-initiation includes dimethoxybenzoin, benzophenone, 1- hydroxy cyclohexyl phenylketones, 2- methyl-1s-
(4- first mercaptophenyl) -2- morpholines acetone -1,2- hydroxy-2-methyls-phenylacetone -1,2,4,6,-trimethylbenzoyl-two
Phenyl phosphine oxide, bis- (2,4,6 ,-trimethylbenzoyl) phenyl phosphine oxide 2,4- diethyl thioxanthones and 4- benzoyls-
One or more of 4 '-dimethyl diphenyl sulfides.
2. rubber-type photocuring 3D printing material according to claim 1, which is characterized in that the auxiliary agent includes coupling
One or more of agent, polymerization inhibitor, levelling agent, antifoaming agent or wetting dispersing agent.
3. a kind of preparation method of the rubber-type photocuring 3D printing material described in claim 1-2 any one, feature exist
In, including：
By silane-modified hydrogenated bisphenol A epoxy acrylate, epoxy resin, photosensitive diluent, polyol compound, cationic photopolymerization
Initiator, free radical photo-initiation and auxiliary agent mixing, stir 30~120 minutes at 20~60 DEG C, obtain rubber-type photocuring
3D printing material.
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