CN108822491A - A kind of 3D printing material and preparation method - Google Patents
A kind of 3D printing material and preparation method Download PDFInfo
- Publication number
- CN108822491A CN108822491A CN201810444931.9A CN201810444931A CN108822491A CN 108822491 A CN108822491 A CN 108822491A CN 201810444931 A CN201810444931 A CN 201810444931A CN 108822491 A CN108822491 A CN 108822491A
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- reactive diluent
- printing material
- antibacterial agent
- epoxy resin
- benzil
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Dental Preparations (AREA)
Abstract
The invention discloses a kind of 3D printing material and preparation methods, which is characterized in that including following raw material by mass percentage：Photosensitizer 1-5%, phthalidyl phosphorous oxides 1.8%, 1.5% reactive diluent 3.5-8% of benzil, coloured powders 0.1-0.5%, surface modifier 0.1-0.7%, ceramic particle powder 1-1.5%, nano antibacterial agent 2.5-4%, surplus is epoxy resin, using polyhydric aliphatic amine and the acrylate containing polynary double bond passes through Michael addition reaction synthesis of super branched photosensitive resin, again using newly synthesized epoxy resin as basic material, using phthalidyl phosphorous oxides and benzil as photoinitiator, add reactive diluent, coloured powders, surface modifier, ceramic particle powder and nano antibacterial agent, synthesize 3D printing material.3D printing material of the present invention, solidification rate is fast, and mechanical property meets the requirement of 3D printing, has certain industrial application value, and adhesive force is strong, does not have delamination in experiment, and solidification front and back volume change is little.
Description
Technical field
The present invention relates to a kind of printed material and preparation method, specifically a kind of 3D printing material and preparation method.
Background technique
3D printing（English：3D printing）, belong to one kind of rapid prototyping technology, it is a kind of digital model file
Based on, with adhesive materials such as powdery metal or plastics, the skill of object is constructed by way of successively stacking accumulation
Art（That is " lamination appearance method "）.Past, it was often used for modeling in fields such as mold manufacture, industrial designs, now just gradually used
In the direct manufacture of some products.Especially some high value applications have had using components made of the printing of this technology,
Mean the universal of " 3D printing " this technology.The most prominent advantage of 3D printing technique is to be not necessarily to machining or any mold,
The part of any shape can be generated directly from computer graphics data, to greatly shorten the lead time of product, mentioned
High production rate and reduction production cost.
There are also other important advantages for three-dimensional printing technology.Most metals and plastic part design to produce, this
Mean that they can be very heavy, and containing with manufacture in relation to but with the unrelated residue of its function.In 3 D-printing skill
In art, raw material are only to produce required product, borrow three-dimensional printing technology, and the part that his team agglomeration goes out is finer
Merrily and lightheartedly.After material is without restriction of production, it can realize therefore its function is produced with machine in the most optimal way
Part compare, the weight of the product printed wants light by 60%, and same firm.3D printing technique wind clouds up in recent years
It gushes, photosensitive resin also gradually moves towards general marketplace, and at the same time, its performance requirement is also gradually increased, and such as requires low-viscosity, consolidates
Mechanical property is good etc. after change.Foreign countries have the photosensitive resin that many shrinking percentages are small, mechanical property is good and put into production, such as DSM public affairs
It takes charge of the alternative traditional engineering plastics ABS of Somos 14120 of production, and domestic less there are production similar products
Enterprise, so that the companies such as DSM are for a long time with high price（As 14120 price of Somos is up to 2000 yuan/kg）Monopolize me
The photosensitive resin market of state, therefore, it is necessary that high performance photosensitive resin is developed in design.
Stereolithography apparatus method（SLA）One of important technology as 3D printing, at present for 3D material for SLA
For be core technology, it is expensive, limit its use.SLA technology is mainly for the manufacture of multiple kinds of molds, model etc.；May be used also
By the way that other ingredients are added, the wax-pattern in precision-investment casting is replaced with SLA prototype model in the feed.SLA technology forming speed
Degree is very fast, and precision is higher, but due to generating contraction in resin curing process, inevitably results from stress or cause deformation.
Therefore it is its development trend that the high light-sensitive material of small, quick solidifying, intensity is shunk in exploitation.
Summary of the invention
The purpose of the present invention is to provide a kind of 3D printing material and preparation methods, to solve to propose in above-mentioned background technique
The problem of.Ceramic particle powder is added as a kind of of raw material in the present invention simultaneously and enhances the wearability of 3D printing material, receives
The addition of nano antibacterial agent extends the holding time of printing article, and the release performance that reactive diluent increases printed material is added
Power is conducive to the actual use of 3D printing material.
To achieve the above object, the present invention provides the following technical solutions：
A kind of 3D printing material, which is characterized in that including following raw material by mass percentage：Photosensitizer 0.5-6.5%, phthalidyl
Phosphorous oxides 1.2-2.2%, benzil 1-2%, reactive diluent 3-10%, coloured powders 0.1-0.8%, surface modifier
0.1-1%, ceramic particle powder 1-1.5%, nano antibacterial agent 2.5-4%, surplus is epoxy resin.
A kind of 3D printing material, which is characterized in that including following raw material by mass percentage：Photosensitizer 0.75-6%, phthalein
Base phosphorous oxides 1.5-1.8%, benzil 1.3-1.7%, reactive diluent 3-10%, coloured powders 0.1-0.8%, surface changes
Property agent 0.1-0.5%, ceramic particle powder 1-2%, nano antibacterial agent 2.5-4%, surplus is epoxy resin.
A kind of 3D printing material, which is characterized in that including following raw material by mass percentage：Photosensitizer 1-5%, phthalidyl
Phosphorous oxides 1.8%, benzil 1.5%, reactive diluent 3.5-8%, coloured powders 0.1-0.5%, surface modifier 0.1-
0.7%, ceramic particle powder 1-1.5%, nano antibacterial agent 2.5-4%, surplus is epoxy resin.
Preferably, the reactive diluent be simple function group, difunctional and polyfunctional group reactive diluent in extremely
Few one kind；
The single functionality reactive diluent includes (methyl) cyclohexyl acrylate, 2- benzene oxygen ethyl (methyl) acrylate, first
At least one of base benzyl acrylate, bicyclic decane acrylate；
The bifunctionality reactive diluent includes ethoxylated bisphenol A (methyl) acrylate, alkoxide 1,6- hexylene glycol dipropyl
At least one of olefin(e) acid ester, tripropylene glycol diacrylate；
Polyfunctionality reactive diluent includes alkoxide trimethylolpropane trimethacrylate, double trimethylolpropane tetrapropylene acid
At least one of ester.
Preferably, the coloured powders include any one in organic pigment and inorganic pigment, and wherein machine pigment is
Pigment scarlet powder, even yellowish, any one in phthalocyanine blue, inorganic pigment is titanium white, lithopone, lead cadmium yellow, any one in barba hispanica
Kind.
A kind of preparation method of 3D printing material, which is characterized in that include the following steps：
Using polyhydric aliphatic amine and the acrylate containing polynary double bond passes through Michael addition reaction synthesis of super branched photosensitive resin,
It is added again using newly synthesized epoxy resin as basic material using phthalidyl phosphorous oxides and benzil as photoinitiator
Reactive diluent, coloured powders, surface modifier, ceramic particle powder and nano antibacterial agent synthesize 3D printing material.
As further scheme of the invention：The Michael addition reaction refers to electrophilic conjugated system（Electronics by
Body）With the carbanion of nucleophilic（Electron donor）The conjugate addition reaction of progress.
Compared with prior art, the beneficial effects of the invention are as follows：
（1）Solidification rate is fast, and mechanical property meets the requirement of 3D printing, has certain industrial application value；
（2）Adhesive force is strong, does not have delamination in experiment；
（3）Solidification front and back volume change is little；
（4）It is wear-resisting, it is used in actual use；
（5）Release ability is good, is conducive to actually use.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
Embodiment 1
A kind of 3D printing material, which is characterized in that including following raw material by mass percentage：Photosensitizer 0.5%, phthalidyl phosphorus oxygen
Compound 1.2%, benzil 1%, reactive diluent 3%, coloured powders 0.8%, surface modifier 0.1%, ceramic particle powder 1%,
Nano antibacterial agent 2.5%, surplus are epoxy resin.
Using polyhydric aliphatic amine and the acrylate containing polynary double bond is photosensitive by Michael addition reaction synthesis of super branched
Resin, and in subsequent research process, using newly synthesized epoxy resin as basic material, with phthalidyl phosphorous oxides and hexichol
Second diketone is photoinitiator, adds reactive diluent, coloured powders, surface modifier, ceramic particle powder and nano antibacterial agent,
To synthesize the more superior 3D printing material of performance.
Embodiment 2
A kind of 3D printing material, which is characterized in that including following raw material by mass percentage：Photosensitizer 6.5%, phthalidyl phosphorus oxygen
Compound 2.2%, benzil 2%, reactive diluent 10%, coloured powders 0.8%, surface modifier 1%, ceramic particle powder 1.5%,
Nano antibacterial agent 4%, surplus are epoxy resin.
Using polyhydric aliphatic amine and the acrylate containing polynary double bond is photosensitive by Michael addition reaction synthesis of super branched
Resin, and in subsequent research process, using newly synthesized epoxy resin as basic material, with phthalidyl phosphorous oxides and hexichol
Second diketone is photoinitiator, adds reactive diluent, coloured powders, surface modifier, ceramic particle powder and nano antibacterial agent,
To synthesize the more superior 3D printing material of performance.
Embodiment 3
A kind of 3D printing material, which is characterized in that including following raw material by mass percentage：Photosensitizer 0.75%, phthalidyl phosphorus oxygen
Compound 1.5%, benzil 1.3%, reactive diluent 3%, coloured powders 0.1%, surface modifier 0.1%, ceramic particle powder
1%, nano antibacterial agent 2.5%, surplus is epoxy resin.
Using polyhydric aliphatic amine and the acrylate containing polynary double bond is photosensitive by Michael addition reaction synthesis of super branched
Resin, and in subsequent research process, using newly synthesized epoxy resin as basic material, with phthalidyl phosphorous oxides and hexichol
Second diketone is photoinitiator, adds reactive diluent, coloured powders, surface modifier, ceramic particle powder and nano antibacterial agent,
To synthesize the more superior 3D printing material of performance.
Embodiment 4
A kind of 3D printing material, which is characterized in that including following raw material by mass percentage：Photosensitizer 6%, phthalidyl phosphorus oxidation
Object 1.8%, benzil 1.7%, reactive diluent 10%, coloured powders 0.8%, surface modifier 0.5%, ceramic particle powder 2%,
Nano antibacterial agent 4%, surplus are epoxy resin.
Using polyhydric aliphatic amine and the acrylate containing polynary double bond is photosensitive by Michael addition reaction synthesis of super branched
Resin, and in subsequent research process, using newly synthesized epoxy resin as basic material, with phthalidyl phosphorous oxides and hexichol
Second diketone is photoinitiator, adds reactive diluent, coloured powders, surface modifier, ceramic particle powder and nano antibacterial agent,
To synthesize the more superior 3D printing material of performance.
Embodiment 5
A kind of 3D printing material, which is characterized in that including following raw material by mass percentage：Photosensitizer 1-5%, phthalidyl phosphorus oxygen
Compound 1.8%, benzil 1.5%, reactive diluent 8%, coloured powders 0.5%, surface modifier 0.7%, ceramic particle powder
1.5%, nano antibacterial agent 4%, surplus is epoxy resin.
Using polyhydric aliphatic amine and the acrylate containing polynary double bond is photosensitive by Michael addition reaction synthesis of super branched
Resin, and in subsequent research process, using newly synthesized epoxy resin as basic material, with phthalidyl phosphorous oxides and hexichol
Second diketone is photoinitiator, adds reactive diluent, coloured powders, surface modifier, ceramic particle powder and nano antibacterial agent,
To synthesize the more superior 3D printing material of performance.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case where without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power
Benefit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent elements of the claims
Variation is included within the present invention.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
The other embodiments being understood that.
Claims (7)
1. a kind of 3D printing material, which is characterized in that including following raw material by mass percentage：Photosensitizer 0.5-6.5%, phthalein
Base phosphorous oxides 1.2-2.2%, benzil 1-2%, reactive diluent 3-10%, coloured powders 0.1-0.8%, surface modifier
0.1-1%, ceramic particle powder 1-1.5%, nano antibacterial agent 2.5-4%, surplus is epoxy resin.
2. a kind of 3D printing material according to claim 1, which is characterized in that including following original by mass percentage
Material：Photosensitizer 0.75-6%, phthalidyl phosphorous oxides 1.5-1.8%, benzil 1.3-1.7%, reactive diluent 3-10%, color
Powder 0.1-0.8%, surface modifier 0.1-0.5%, ceramic particle powder 1-2%, nano antibacterial agent 2.5-4%, surplus is asphalt mixtures modified by epoxy resin
Rouge.
3. a kind of 3D printing material according to claim 1, which is characterized in that including following original by mass percentage
Material：Photosensitizer 1-5%, phthalidyl phosphorous oxides 1.8%, benzil 1.5%, reactive diluent 3.5-8%, coloured powders 0.1-
0.5%, surface modifier 0.1-0.7%, ceramic particle powder 1-1.5%, nano antibacterial agent 2.5-4%, surplus is epoxy resin.
4. a kind of 3D printing material according to claim 1 or 2 or 3, which is characterized in that the reactive diluent is single
At least one of functional group, difunctional and polyfunctional group reactive diluent；
The single functionality reactive diluent includes (methyl) cyclohexyl acrylate, 2- benzene oxygen ethyl (methyl) acrylate, first
At least one of base benzyl acrylate, bicyclic decane acrylate；
The bifunctionality reactive diluent includes ethoxylated bisphenol A (methyl) acrylate, alkoxide 1,6- hexylene glycol dipropyl
At least one of olefin(e) acid ester, tripropylene glycol diacrylate；
Polyfunctionality reactive diluent includes alkoxide trimethylolpropane trimethacrylate, double trimethylolpropane tetrapropylene acid
At least one of ester.
5. a kind of 3D printing material according to claim 1 or 2 or 3, which is characterized in that the coloured powders include
Any one in machine pigment and inorganic pigment, wherein machine pigment is pigment scarlet powder, even yellowish, any one in phthalocyanine blue, nothing
Machine pigment is titanium white, lithopone, lead cadmium yellow, any one in barba hispanica.
6. one kind 3D printing material and preparation method as described in claim 1-3 is any, which is characterized in that include the following steps：
Using polyhydric aliphatic amine and the acrylate containing polynary double bond passes through Michael addition reaction synthesis of super branched photosensitive resin,
It is added again using newly synthesized epoxy resin as basic material using phthalidyl phosphorous oxides and benzil as photoinitiator
Reactive diluent, coloured powders, surface modifier, ceramic particle powder and nano antibacterial agent synthesize 3D printing material.
7. a kind of 3D printing material according to claim 6 and preparation method, which is characterized in that the Michael's addition is anti-
It should refer to electrophilic conjugated system（Electron acceptor）With the carbanion of nucleophilic（Electron donor）The conjugate addition reaction of progress.
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| CN201810444931.9A CN108822491A (en) | 2018-05-10 | 2018-05-10 | A kind of 3D printing material and preparation method |
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| CN201810444931.9A CN108822491A (en) | 2018-05-10 | 2018-05-10 | A kind of 3D printing material and preparation method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112334539A (en) * | 2020-08-13 | 2021-02-05 | 香港理工大学 | Three-dimensional printing antibacterial product |
| WO2022032817A1 (en) * | 2020-08-13 | 2022-02-17 | The Hong Kong Polytechnic University | Three-dimensional printing antimicrobial products |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101497630A (en) * | 2009-03-09 | 2009-08-05 | 安徽恒远化工有限公司 | Phosphoric acrylic ester monomer, hyperbranched polymer flame retardant and preparation thereof |
| CN104311783A (en) * | 2014-11-11 | 2015-01-28 | 合肥思敬齐化工材料有限责任公司 | Unsaturated hyperbranched polyurethane prepolymer as well as preparation method and application thereof |
| CN106928467A (en) * | 2017-04-19 | 2017-07-07 | 珠海飞扬新材料股份有限公司 | A kind of synthetic method of acrylate of ultraviolet light polymerization and application |
-
2018
- 2018-05-10 CN CN201810444931.9A patent/CN108822491A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101497630A (en) * | 2009-03-09 | 2009-08-05 | 安徽恒远化工有限公司 | Phosphoric acrylic ester monomer, hyperbranched polymer flame retardant and preparation thereof |
| CN104311783A (en) * | 2014-11-11 | 2015-01-28 | 合肥思敬齐化工材料有限责任公司 | Unsaturated hyperbranched polyurethane prepolymer as well as preparation method and application thereof |
| CN106928467A (en) * | 2017-04-19 | 2017-07-07 | 珠海飞扬新材料股份有限公司 | A kind of synthetic method of acrylate of ultraviolet light polymerization and application |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112334539A (en) * | 2020-08-13 | 2021-02-05 | 香港理工大学 | Three-dimensional printing antibacterial product |
| WO2022032817A1 (en) * | 2020-08-13 | 2022-02-17 | The Hong Kong Polytechnic University | Three-dimensional printing antimicrobial products |
| GB2611971A (en) * | 2020-08-13 | 2023-04-19 | Univ Hong Kong Polytechnic | Three-dimensional printing antimicrobial products |
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