CN103756236A - Thermoplastic elastomer composition for preparing flexible printing material for three-dimensional printing rapid prototyping - Google Patents
Thermoplastic elastomer composition for preparing flexible printing material for three-dimensional printing rapid prototyping Download PDFInfo
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- CN103756236A CN103756236A CN201410005541.3A CN201410005541A CN103756236A CN 103756236 A CN103756236 A CN 103756236A CN 201410005541 A CN201410005541 A CN 201410005541A CN 103756236 A CN103756236 A CN 103756236A
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Abstract
The invention discloses a thermoplastic elastomer composition for preparing a flexible printing material for three-dimensional printing rapid prototyping. The thermoplastic elastomer composition comprises the following components in percent by weight: 16.8-90.0% of thermoplastic elastomer, 1.0-49.8% of polyolefin, 0-44.0% of softening agent, 0.1-1.3% of lubricating agent and 0.2-0.3% of antioxidant. The hardness of the thermoplastic elastomer is Shore hardness of 50-90A, and the prepared flexible printing material is low in hardness, has outstanding flexibility and toughness and excellent handfeel and is particularly applied to the fields of special industrial design and consumer applications such as the manufacturing of toys, jewelries and fingerprints.
Description
Technical field
The invention belongs to composition for thermoplastic elastomer field, be specifically related to a kind of composition for thermoplastic elastomer of the soft printed material for the preparation of rapid three dimensional printing forming.The invention still further relates to the method for utilizing this composition for thermoplastic elastomer to prepare soft printed material.
Background technology
3 D-printing (3DP) is the one of rapid shaping technique, it is a kind of take digital model file as basis, use the materials such as metal, pottery or macromolecular material, with powder, liquid or the original shape such as thread, by different printing means, in the mode of successively printing, carry out the technology of constructed object.
3 D-printing normally adopts digital technique file printing machine to realize, past, its field such as mould manufacture, industrial design of being everlasting was used to modeling, now just gradually for jewelry, footwear, industrial design, toy, building, engineering and construction, automobile, aerospace, dentistry and medical industries, education, geographical information system(GIS), civil engineering work, gun with etc. field produce component or directly manufacture a product.
From technical standpoint, existing more than ten plant different rapid three dimensional printing forming methods at present, as stereolithography apparatus method (SLA), selective laser sintering method (SLS), fusion sediment speed forming method (FDM), laminated solid body are manufactured the method for forming (LOM), mask solidification method (SGC) etc., wherein following three kinds of methods most importantly:
(1) stereolithography apparatus method (SLA)
From the First quickly shaping device of 1984, adopted the technique of stereolithograghy.In present rapid forming equipment, the most deep with the research of stereolithography apparatus method, use also extensive.This technology is take the polyreaction of photosensitive resin as basis.Ultraviolet ray under computer control, along the each layering cross section profile of part, liquid towards resin carries out point by point scanning, make the thin resin layer being scanned produce polyreaction, by putting, form gradually line, the curing cross section of a final thin layer that forms part, and the resin not being scanned keeps original liquid state.Curing complete when one deck, self-powered platform moves the distance of a synusia thickness, and the resin surface having cured at last layer covers the liquid resin that one deck is new again, in order to the scanning of carrying out again, solidifies.New curing one deck is bonded on front one deck securely, so moves in circles, until the manufacture of whole part prototype is complete.
(2) selective laser sintering method (SLS)
This technique is take laser apparatus as energy source, the powder that makes plastics, wax, pottery, metal or its mixture by laser beam equably sintering on processing plane.On worktable, the powder of uniform spreading last layer very thin (submillimeter level) is as raw material, and laser beam, under the control of computer, scans by the 2-D data of point aspect with certain speed and energy density by scanning device.After laser beam flying, the powder of corresponding position just sinters certain thickness entity lamella into, and the place of scanning does not still keep loose Powdered.This one deck been scanned, needs lower one deck to scan subsequently.First according to object, cut layer thickness and self-powered platform, paving powder cylinder is paved powder again, can start the scanning of new one deck.So repeatedly, until scanned structure at all levels.Remove unnecessary powder, and through suitable aftertreatments such as polishing, oven dry, can obtain part.At present during this technique of application, more as raw material using wax powder and plastic powders, and not yet obtain practicality by the technique that metal powder or ceramics powder carry out bonding or sintering.
(3) fusion sediment speed forming method (FDM)
Within 1993, U.S. Stratasys company has developed the equipment of First based on fusion sediment rapid shaping.Computer aided design (CAD) (CAD) model is divided into from level to level to cross section as thin as a wafer, generates the two-dimensional geometry information of controlling fusion sediment forming nozzle motion track.The heating head (printhead) of fusion sediment moulding is thermoplastic macromolecule material, such as acrylonitrile-butadiene-styrene copolymer (ABS), poly(lactic acid) (PLA) resin, polycarbonate (PC), nylon (Nylon) plastics etc., be heated to criticality, present semi-fluid character, under computer control, along the definite two-dimensional geometry information movement track of computer aided design (CAD), shower nozzle squeezes out the material of half flow state, solidifies the thin layer that forms outline shape.After one deck, by VTOL (vertical take off and landing) system, fall new form layers, be cured.Pile up so layer by layer bonding, form the 3D solid of a part from bottom to top.The key of fusion sediment moulding process is half mobility that keeps material.These materials do not have fixing fusing point, need accurately to control its temperature.
The present invention relates generally to the thermoplastic macromolecule material for fusion sediment speed forming method.For the formed material of fusion sediment speed forming method, now on market generally take acrylonitrile-butadiene-styrene copolymer (ABS) and poly(lactic acid) (PLA) rigid plastics as main flow, also have other mechanically resistant materials such as part use polycarbonate (PC) and nylon (Nylon).The hardness of product out of these forming materials or parts is generally in Rockwell hardness (Rockwell is called for short R) 100～120 scopes, has stronger rigidity, structure is sturdy, therefore range of application is also limited to, and is difficult to use in some special design, such as crawler belt and decoration chain etc.Because these formed material hardness are high, lack soft feel, and easily because its corner angle damage human body, be difficult to use in other product scopes such as toy, ornament and fingerprint.In addition, make this type of thread printed material, at 3 D-printing, supply, in silk process, because its rigidity is excessively strong, there is no ductility, easily after bending, can not recover or rupture, cause to print to have some setbacks the continuity of impact making.
Therefore, be necessary to develop a kind of soft printed material that is generally applicable to fusion sediment printing speed, make fusion sediment speed forming method can be used in field widely.
Summary of the invention
The object of the present invention is to provide a kind of composition for thermoplastic elastomer of the soft printed material for the preparation of 3 D-printing fusion sediment rapid shaping, to solve the above-mentioned problems in the prior art, soft printed material prepared by this composition for thermoplastic elastomer has very low hardness, outstanding flexibility and toughness, and outstanding feel, greatly expanded the Application Areas of 3 D-printing, particularly special industry design and consumer applications field, such as toy, jewellery and fingerprint etc.
In order to achieve the above object, technical scheme of the present invention is:
For the preparation of a composition for thermoplastic elastomer for the soft printed material of 3 D-printing fusion sediment rapid shaping, comprise by weight percentage following component:
| thermoplastic elastomer | 16.8%～90.0% |
| polyolefine | 1.0%～49.8% |
| tenderizer | 0～44.0% |
| lubricant | 0.1%～1.3% |
| oxidation inhibitor | 0.2%～0.3%. |
The durometer level of described composition for thermoplastic elastomer is at Shore hardness 95A(Shore A95) below, preferably between 50A～90A.This durometer level will be low for the printed material of existing fusion sediment rapid shaping many, but can be not too soft and affect printing and making performance.Too low hardness, below Shore hardness 50A, can easily cause feed unstable and cause print procedure to have some setbacks.Too low hardness is also because of adding more tenderizer, and the parts that print or product, can be from the surface transport of parts or product out after placement for some time, causes the feel of sticky hand and object and the environment of easy Contaminated Parts or product periphery.In order to obtain stable feed and print procedure smoothly, and can be because tenderizer is separated out the feel that causes sticky hand, the durometer level of soft printed material of the present invention is preferably between 50A～90A, for example 50A, 60A, 70A, 80A, any number in the above-mentioned scope such as 90A.
The present invention also provides the purposes of above-mentioned composition for thermoplastic elastomer in the soft printed material for the preparation of 3 D-printing fusion sediment rapid shaping.
Described composition for thermoplastic elastomer is to make take this resin of thermoplastic elastomer based as main body.Described thermoplastic elastomer (being called for short TPE or TPR), also referred to as thermoplastic elastomer, had both had the characteristic of rubber, had again the performance of thermoplastics; Be at room temperature soft, be similar to rubber, have toughness and elasticity, during high temperature, flow, energy plasticizing forming, is the so-called third generation rubber after natural rubber and synthetic rubber.Thermoplastic elastomer of the present invention is selected from one or more in styrene analog thermoplastic elastomer (being called for short TPS, TPE-S or SBC), olefin hydrocarbons thermoplasticity elastic body (being called for short TPO or TPE-O), thermoplastic dynamic perduren (being called for short TPV or TPE-V) and Polyurethane Thermoplastic Elastomer (being called for short TPU or TPE-U).The raw-material durometer level of described thermoplastic elastomer can be 30A～90A, preferably 65A～80A.Preferably, described thermoplastic elastomer starting material do not contain gelinite or gelinite content <1%, by adding other components of suitable amount, prepare the composition that is finally suitable for preparing soft printed material.By research, find, the thermoplastic elastomer starting material of higher hardness, oil number is low, is not easy to reach lower hardness; And lower durometer level can have influence on processibility.And the existence of gelinite, single processibility that can have influence on mixing even and extruding pelletization and wire drawing of each component, more can have influence on the outward appearance that finally prints goods.
Described polyolefine is selected from one or more of polypropylene, polyethylene or other olefines oligopolymer.
Described tenderizer is selected from white mineral oil (white oil), paraffin oil, organic silicone oil, Viscotrol C, plam oil, epoxy soybean oil, or one or more of environment-friendly type softening agent in some situation.Be preferably white mineral oil.
Described lubricant is selected from one or more of hydro carbons, fatty acid, fatty acid acyl amine, ester class, alcohols, metal soap or compounded lubricant.
Described oxidation inhibitor is one or more of Hinered phenols, hindered amines, phosphorous acid esters, thio-alcohol or composite antioxidant.The preferably combination of Hinered phenols and phosphorous acid esters.
Described composition for thermoplastic elastomer also can comprise other binder components, and its consumption is enough to make formulation to obtain required working properties or use properties.The amount of additive should not cause waste or the processing to formulation or use properties harmful.The technician in thermoplasticity compounding field, without too much experiment, only must, with reference to some documents, for example, from " the plastics additive database " in " plastic design storehouse ", just can select dissimilar additive to add in formulation of the present invention.The non-limitative example of optional additive comprises: one or more in pigment, spices, adhesion promotor, biocide (antiseptic-germicide, mycocide and mould inhibitor), anti-fog agent, static inhibitor, tackiness agent, whipping agent, dispersion agent, weighting agent, compatilizer, smoke suppressor, impact modifier, initiator, mica, processing aid, releasing agent, separant, stablizer, ultraviolet absorbers, viscosity modifier.
The composition for thermoplastic elastomer of the above-mentioned soft printed material for the preparation of 3 D-printing fusion sediment rapid shaping of the present invention is based on this resin of thermoplastic elastomer based, mix with one or more of polyolefine, tenderizer, lubricant and oxidation inhibitor and other optional conventional plastics additives, and adopted high molecular polymer thermoplastic melt blending extruding technology and technique to be prepared from.
Particularly, the invention provides the method that the above-mentioned composition for thermoplastic elastomer of a kind of use is prepared the soft printed material of 3 D-printing fusion sediment rapid shaping, comprise step:
1) by each component of above-mentioned weight percent, in mixing roll, under normal temperature condition, fully mix, form the material mixing;
2) material mixing being thrown in into length-to-diameter ratio (L/D) is more than 44 parallel double-screw extruders, under 180～220 ℃ of conditions, carries out fusion plastification, forms melt;
3) melt is further evenly mixing, through parallel double-screw extruder mouth, mold pressing goes out, and then uses conventional underwater pelletizer to carry out granulation, makes the soft printed material of soft particle form.
In another embodiment, above-mentioned steps 3) the soft particle that makes can further process, and comprises step:
4) by above-mentioned soft particle by plastifying fusion again under 180～220 ℃ of conditions of conventional single screw extrusion machine, form melt;
5) by described melt through single screw extrusion machine go-no-go mouth mould after, cooling and shaping under the tank of normal temperature, makes strand;
6) described strand is drawn through tractor, by winding machine rolling, make the soft printed material of standard package packing.
Wherein, above-mentioned steps 5) port mould diameter of described single screw extrusion machine, conventional size specification includes but not limited to 1.75mm, 2.0mm and 3.0mm.
Wherein, above-mentioned steps 6) described standard package packing, general packed weight specification includes but not limited to 0.5KG, 1KG and 2KG.
Wherein, above-mentioned steps 1)～6) the soft printed material prepared, be the thread form of certain size size, be generally applicable to sell on market with thread feed, based on fusion sediment printing speed, be shaped to the three-dimensional printer of principle.
In another embodiment, above-mentioned steps 3) the soft particle that makes can be stored through processing, and optionally carries out step 4) again, and treatment process comprises:
I) separant is evenly sprinkling upon on the soft particle that step 3) makes, the amount adding is soft particle weight 0.05%～1%;
Ii) the soft particle that is mixed with separant is carried out to removal moisture drying, 70～90 ℃ of drying temperatures, time of drying is more than 2 hours, until the water content of soft particle, lower than 0.02%, seals and preserves;
Above-mentioned steps i) in, described separant can be the powder of talcum, polyolefin-wax, metallic stearate, silicon-dioxide, starch or other mineral fillers.The size range of described separant is about 100nm～30 μ m.Described separant makes soft particle lay up period before use not adhered to one another.
Above-mentioned steps ii) in dry soft particle can use tank shape packing material, for example iron flask, plastics pot or paper can, carry out subpackage according to certainweight standard, and sealed storage.Described standard can shape packing, can be 0.5KG, 1KG or 2KG, but be not limited to this.
In another embodiment, above-mentioned steps 3) or step I) the soft particle that obtains, also can grind or briquetting with conventional equipment, make powdery or block soft printed material.
Soft printed material prepared by aforesaid method of the present invention, it can be soft particle form, also or powdery or bulk, be applicable to the described extrusion screw rod that utilizes of patent No. ZL200520080240.3 and realize continuous feeding, based on fusion sediment printing speed, be shaped to the three-dimensional printer of principle.
Be compared with the prior art, the thermoplastic elastomer of the soft printed material of three-dimensional for fusion sediment printing speed moulding (FDM) provided by the invention has following advantage and beneficial effect:
(1) the soft printed material of preparing has low hardness, and produced parts or product have lively sense of touch, and is not easy human body to cause hard thing injury, has higher application security.
(2), due to its toughness, the soft printed material of preparation, with thread feed in the situation that, can not occur because of fracture of wire, and the phenomenon of having to end printing, thereby make print procedure more smooth and easy, and greatly improve printing effect.
(3) the soft printed material of preparing is more because of its outstanding flexibility, going for need to be repeatedly or often bending, folding or press the application scenario becoming, thereby expanded more broadly the Application Areas of 3 D-printing, special special industry design and consumer applications field, such as toy, jewellery and hand are touched etc.
(4) raw material of the soft printed material of preparing obtains in extensive range, and technological operation easily realizes.
(5) in the each 3D printed material critical performance parameters contrast from following table 1, can find out that soft printed material of the present invention has very low hardness, be the scope at Shore hardness 50～90A, and elongation very high (>250%).The inventor finds in print procedure, and bending and fracture easily occur printed material when feed, and the elongation relation of material is very close, and elongation at break <100%, is generally easy to bending and fracture; The skin hardness of human body is in about Shore hardness 30A, uses file printing that Rockwell hardness characterizes goods out, only specially designed mellow and full surface, otherwise be easy to human body to damage.
Table 1: for the performance comparison of the printed material of 3 D-printing fusion sediment rapid shaping
Embodiment
For better understanding the present invention, below in conjunction with the embodiment explanation detailed to the present invention, but the scope of protection of present invention is not limited to the scope that embodiment represents.
Starting material source
this resin of thermoplastic elastomer based
Thermoplastic elastomer of the present invention comprises styrene analog thermoplastic elastomer, polyolefins thermoplastic elastomer, thermoplastic dynamic perduren and thermoplastic polyurethane.
Styrene analog thermoplastic elastomer can be selected from one or more of styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), styrene-butadiene-styrene block copolymer (SBS), styrene isoprene styrene block copolymer (SIS) (SIS), styrene-ethylene-propylene-styrene segmented copolymer (SEPS) etc.For example, can enumerate Kraton G series and the Kraton D series that U.S. Ke Teng high-performance polymer company (Kraton Performance Polymers, Inc.) produces; Septon series and the Hybrar series of Japan Kuraray company (Kuraray Co., Ltd.); Taipol series and the Vector series of Taiwan Tai Xiang Co., Ltd (TSRC Corporation); But be not limited to this.
Polyolefins thermoplastic elastomer can be selected from the superpolymer (POE) of the ethene of metallocene catalyst catalysis and the superpolymer of butylene or ethene and octene, polyolefin block polymkeric substance (OBC) is (as ethene-a-olefin copolymer, hydrogenated butadiene-isoamyl ethene-butadiene block copolymer, stereoblock polypropylene), polyolefin graft copolymer (as polyisobutene-g-polystyrene), one or more of ethylene-propylene-diene terpolymer (EPDM) etc.For example, can enumerate Vistamaxx series and the Exact series of Exxon Mobil company (Exxon Mobil Corporation), Affinity series, Engage series, Infuse series, Nordel series and the Versify series of Dow Chemical company (The Dow Chemical Company); Tafmer series and the Notio series of Mitsui chemical company (Mitsui Chemicals Group); But be not limited to this.
Thermoplastic dynamic perduren can be selected from one or more of dynamic vulcanization terpolymer EP rubber (EPDM), dynamic vulcanization paracril (NBR), dynamic vulcanization natural rubber (NBR), dynamic vulcanization acrylic elastomer (ACM) etc.For example, can enumerate the Santoprene series of Exxon Mobil company (Exxon Mobil Corporation), the Sarlink series of U.S. Ai Peisi company (Teknor Apex Company), the Zeotherm series of Japanese Rui Weng chemical company (Zeon Chemicals L.P.); But be not limited to this.
Thermoplastic polyurethane can be selected from one or more of polyether(poly)urethane, PAUR, polycaprolactone polyurethane and aliphatic polyurethane etc.For example, can enumerate the Elastollan series of BASF Aktiengesellschaft (BASF SE); Desmopan series and the Texin series of Bayer A.G (Bayer AG); Estane series, Pearlstick series and the Pearlthane series of U.S. Lubrizol Corp. (The Lubrizol Corporation); U.S.'s Hensel steps the Irogran series of international corporation (Huntsman International LLC); The Mirathane series of Yantai, Shandong Mei Rui chemical material company limited (Miracll Chemicals Co., Ltd.); But be not limited to this.
polyolefine
There is no particular limitation for polyolefine starting material of the present invention, can use one or more of polypropylene, polyethylene or other olefines oligopolymer.For example, can enumerate the polypropylene series such as Pro-fax, the Moplen of Dutch Li Ande Basel company (LyondellBasell Industries N.V.) and Hifax, and the polyethylene series such as Hostalen, Lucalen and Lupolen; The TotalPPH of company of Total France (Total S.A.) and PPC polypropylene series, and Total polyethylene series; The Globalene polypropylene series of Taiwan Lee Chang Yung Chemical Indust (LCY Chemicals Corp.); But be not limited to this.
tenderizer
Tenderizer of the present invention can be any conventional tenderizer, for example, be selected from one or more in the environment-friendly type softening agent in white mineral oil, paraffin oil, organic silicone oil, Viscotrol C, plam oil, epoxy soybean oil or some situation.Preferably white mineral oil.For example, can enumerate Britol and the Hydrobrite series of Suo Nuobang company (Sonneborn Inc.); Drakeol series, Calsol series, Duoprime series and the Parol series of U.S. Ka Lumei company (Calumet Specialty Products Partners, L.P.); The Puretol series of Canada petroleum oil company (Petro-Canada Lubricants Inc.); Savonol series and the Technol series of the Savita oil product technology company limited (Savita Oil Technologies Limtied) of India; But be not limited to this.
lubricant
Lubricant of the present invention comprises internal lubricant and external lubricant, be selected from hydro carbons (for example microcrystalline wax, whiteruss, solid paraffin, clorafin, polyethylene wax, oxidized polyethlene wax), fatty acid (for example saturated fatty acid, unsaturated fatty acids and hydroxy fatty acid), fatty acid acyl amine (for example stearic amide, N, N-ethylenebisstearamide (EBS), amine hydroxybenzene, erucicamide, n-butyl stearate, glycerine three hydroxy stearic acid esters), ester class (for example low-carbon-ester, polyol ester, macrogol ester), alcohols (for example fatty alcohol, polyvalent alcohol, polyoxyethylene glycol, polypropylene glycol), one or more of metal soap or compounded lubricant.Preferred fatty acid amides.For example, can enumerate the Kemamide series of U.S. PMC company (PMC Group); The Crodamide series of Britain standing grain major company (Croda International Plc); The Finawax series of U.S. Aakash chemistry and dyestuff company (Aakash Chemicals and Dye-Stuffs, Inc.); But be not limited to this.
oxidation inhibitor
Described oxidation inhibitor is selected from Hinered phenols (four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), 2,6-di-t-butyl-4-methyl
phenol(antioxidant 264), β-(3,5-di-tert-butyl-hydroxy phenyl) positive octadecanol ester of propionic acid (antioxidant 1076), two (tri-grades of butyl-4-hydroxy phenyls of 3,5-) thioether), hindered amines (for example
naphthylamines,
pentanoic,
ursol D), phosphorous acid esters (two (2,4-DI-tert-butylphenol compounds) pentaerythritol diphosphites (oxidation inhibitor 626), three [2.4-di-tert-butyl-phenyl] phosphorous acid esters (irgasfos 168)), thio-alcohol (for example thio-2 acid dilaurate (DLTP), the two lauryl alcohol esters (DLTDP) of thio-2 acid) or composite antioxidant one or more.The preferably combination of hindered phenol and phosphorous acid ester or thio-alcohol.For example, can enumerate the Irganox series of BASF Aktiengesellschaft (BASF SE); The Songnox series of Korea S Sun-won Industry Co., Ltd. (Songwon Industrial Co., Ltd.); But be not limited to this.
optional additive
Described optional additive, conventional filler-calcium carbonate, can enumerate the Vicron series of U.S. specialty minerals company (Specialty Minerals Inc.); SS series and the NS series of Formosa Plastics (Formosa Plastics Corporation); But be not limited to this.
The impact of the hardness of component on soft printed material
The present invention adopts thermoplastic melt blending to extrude modification technology and technique, prepares the composition based on thermoplastic elastomer of the soft printed material of different hardness.Repeatedly result of study shows, the soft durometer of described composition for thermoplastic elastomer is determined by following two kinds of principal elements:
1) this resin of thermoplastic elastomer based.Thermoplastic elastomer has a common feature, be phase-separated system, one be wherein at room temperature plastics phase (hard phase) mutually, and another is rubber phase (soft phase) mutually, the elasticity that such structure has just formed the existing rubber of thermoplastic elastomer has had again intensity and the hot plastic processibility of plastics.Hard mutual-assistance thermoplastic elastomer has intensity, if firmly not mutually, under stress, unrestricted flow will occur rubber phase, thereby loses actual application value.After dissolving when hard phase melted by heating or in solvent, thermoplastic elastomer generation unrestricted flow, now can process; When after cooling or solvent evaporates, hard solidifying, now the intensity of thermoplastic elastomer is recovered.Thus, in some sense, the hard effect of having played mutually traditional vulcanized rubber cross-linking set of thermoplastic elastomer, said process is often called as physical crosslinking.And softly to thermoplastic elastomer, provide elasticity, if there is no soft phase, that thermoplastic elastomer can only be plastics or hard thing the same as plastics.The suitable durometer level of described this resin of thermoplastic elastomer based of the present invention is 65A～80A.More preferably, described thermoplastic elastomer is the thermoplastic elastomer resin that does not contain low gelinite or low gelinite content <1% weight.By adding other components, prepare the composition that is finally suitable for preparing soft printed material.By research, find, this resin of thermoplastic elastomer based of higher hardness, oil number is low, is not easy to reach lower hardness; And lower durometer level can have influence on processibility.And the existence of gelinite, single processibility that can have influence on mixing even and extruding pelletization and wire drawing of each component, more can have influence on the outward appearance that finally prints goods.
2) tenderizer, or claim softening agent, plasticizer, is a kind of additive that increases the flexibility of material or make material liquefaction.After tenderizer is absorbed by this resin of thermoplastic elastomer based, can further soften again its hardness.But different types of thermoplastic elastomer has very large difference to the degree of absorption of tenderizer.Styrene analog thermoplastic elastomer and polyolefins thermoplastic elastomer have higher assimilation ratio.
The inventor is at the soft printed material of implementing to be prepared by composition for thermoplastic elastomer, be applied in the process of fusion sediment printing speed moulding, through further investigation, find too low hardness, be Shore hardness 50A when following, can easily cause feed unstable and cause print procedure to have some setbacks.Too low hardness is also because of adding more tenderizer, and the parts that print or product, can be from the surface transport of parts or product out after placement for some time, causes the feel of sticky hand and object and the environment of easy Contaminated Parts or product periphery.In order to obtain stable feed and print procedure smoothly, and can be because tenderizer is separated out the feel that causes sticky hand.Different types of composition for thermoplastic elastomer is suitable for durometer level can be different.Preferably, the Shore hardness of soft printed material of the present invention is 50～90A, such as, any number in the above-mentioned scopes such as 55A, 60A, 65A, 70A, 75A, 80A, 85A.
preferred embodiment
In a kind of exemplary embodiment, the composition for thermoplastic elastomer of the soft printed material for the preparation of 3 D-printing fusion sediment rapid shaping of the present invention, comprises following component by weight percentage:
| Thermoplastic elastomer | 30.0%～43.8% |
| Polyolefine | 11.8%～40.1% |
| Tenderizer | 29.5%～44.0% |
| Lubricant | 0.1% |
| Oxidation inhibitor | 0.3% |
Described thermoplastic elastomer is selected from above-mentioned thermoplastic elastomer arbitrarily, optimization styrene analog thermoplastic elastomer, and for example SEBS, can be the combination of Kraton G1650 and Kraton G1651, the weight ratio of the two can be 1:1, as described in embodiment 1～5.
Described polyolefine is selected from polypropylene, polyethylene and other olefin oligomers.Optimization polypropylene.
Described tenderizer is selected from the environment-friendly type softening agent in white mineral oil, paraffin oil, organic silicone oil, Viscotrol C, plam oil, epoxy soybean oil or some situation.Preferably white mineral oil.
Described lubricant can be above-mentioned any lubricant.Preferably erucicamide.
Described oxidation inhibitor can be above-mentioned any oxidation inhibitor.The preferably combination of hindered phenol and phosphite ester kind antioxidant, the weight ratio of the two can be 1:2.The for example combination of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and three (2,4-di-tert-butyl-phenyl) phosphorous acid ester.
In a kind of exemplary embodiment, the composition for thermoplastic elastomer of the soft printed material for the preparation of 3 D-printing fusion sediment rapid shaping of the present invention, comprises following component by weight percentage:
| Thermoplastic elastomer | 49.8%～82.0% |
| Polyolefine | 7.0%～49.8% |
| Tenderizer | 0～10.6% |
| Lubricant | 0.1% |
| Oxidation inhibitor | 0.3% |
Described thermoplastic elastomer is selected from above-mentioned thermoplastic elastomer arbitrarily.Optimization styrene analog thermoplastic elastomer, for example SEPS, can be Septon2063, as described in embodiment 6～10.
Described polyolefine is selected from polypropylene, polyethylene and other olefin oligomers.Optimization polypropylene.
Described tenderizer is selected from the environment-friendly type softening agent in white mineral oil, paraffin oil, organic silicone oil, Viscotrol C, plam oil, epoxy soybean oil or some situation.Preferably white mineral oil.
Described lubricant can be above-mentioned any lubricant.Preferably erucicamide.
Described oxidation inhibitor can be above-mentioned any oxidation inhibitor.The preferably combination of hindered phenol and phosphite ester kind antioxidant, the weight ratio of the two can be 1:2.The for example combination of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and three (2.4-di-tert-butyl-phenyl) phosphorous acid ester.
In a kind of exemplary embodiment, the composition for thermoplastic elastomer of the soft printed material for the preparation of 3 D-printing fusion sediment rapid shaping of the present invention, comprises following component by weight percentage:
| Thermoplastic elastomer | 16.8%～59.0% |
| Polyolefine | 8.0%～22.0% |
| Tenderizer | 23.7%～32.7% |
| Weighting agent | 0～37.2% |
| Lubricant | 0.1% |
| Oxidation inhibitor | 0.2% |
Described thermoplastic elastomer can be above-mentioned any thermoplastic elastic, is preferably the combination of styrene analog thermoplastic elastomer and polyolefins thermoplastic elastomer.For example, can be the combination of SEBS and polyolefin block copolymer (OBC), the weight ratio of the two is 1:(1～1.05), as described in embodiment 11～15.
Described tenderizer is selected from the environment-friendly type softening agent in white mineral oil, paraffin oil, organic silicone oil, Viscotrol C, plam oil, epoxy soybean oil or some situation.Preferably white mineral oil.
Described polyolefine is selected from polypropylene, polyethylene and other olefin oligomers.Optimization polypropylene.
Described weighting agent can be above-mentioned any weighting agent.Preferably calcium carbonate.
Described lubricant can be above-mentioned any lubricant.Preferably erucicamide.
Described oxidation inhibitor can be above-mentioned any oxidation inhibitor, is preferably the combination of Hinered phenols and phosphite ester kind antioxidant, and the weight ratio of the two can be 1:1.The combination of for example four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and two (2,4-DTBP) pentaerythritol diphosphites.
In a kind of exemplary embodiment, the soft printed material for 3 D-printing fusion sediment rapid shaping of the present invention, comprises following component by weight percentage:
| Thermoplastic elastomer | 23.8%～34.6% |
| Polyolefine | 8.0%～29.0% |
| Tenderizer | 24.8%～35.0% |
| Weighting agent | 22.0% |
| Lubricant | 0.1% |
| Oxidation inhibitor | 0.3% |
Described thermoplastic elastomer can be above-mentioned any thermoplastic elastic.Preferred thermoplastic dynamic perduren, for example terpolymer EP rubber, as described in embodiment 16～20.
Described tenderizer is selected from the environment-friendly type softening agent in white mineral oil, paraffin oil, organic silicone oil, Viscotrol C, plam oil, epoxy soybean oil or some situation.Preferably white mineral oil.
Described polyolefine is selected from polypropylene, polyethylene and other olefin oligomers.Optimization polypropylene.
Described weighting agent can be above-mentioned any weighting agent.Preferably calcium carbonate.
Described lubricant can be above-mentioned any lubricant.Preferably erucicamide.
Described oxidation inhibitor can be above-mentioned any oxidation inhibitor.The preferably combination of hindered phenol and sulfo-alcohol kind antioxidant, the weight ratio of the two can be 1:2.The combination of the two lauryl alcohol esters of for example four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and thio-2 acid.
In a kind of exemplary embodiment, the composition for thermoplastic elastomer of the soft printed material for the preparation of 3 D-printing fusion sediment rapid shaping of the present invention, comprises following component by weight percentage:
| Thermoplastic elastomer | 46.5%～88.0% |
| Polyolefine | 1.0%～2.5% |
| Tenderizer | 2.0%～18.0% |
| Weighting agent | 3.0%～4.5% |
| Compatilizer | 2.5%～5.0% |
| Lubricant | 1.3% |
| Oxidation inhibitor | 0.2% |
Described thermoplastic elastomer can be above-mentioned any thermoplastic elastomer.The combination of optimization polyurethane thermoplastic elastomer and styrene analog thermoplastic elastomer can be the combination of polyether(poly)urethane and SEBS.The combination of for example Lubrizol Estane58219 and Kraton G1641H, as described in embodiment 21～25.
Described tenderizer is selected from the environment-friendly type softening agent in white mineral oil, paraffin oil, organic silicone oil, Viscotrol C, plam oil, epoxy soybean oil or some situation.Preferably white mineral oil.
Described polyolefine is selected from polypropylene, polyethylene and other olefin oligomers, for example olefin oligomer, Exxon Mobil Oppera100A.
Described weighting agent can be above-mentioned any weighting agent.Preferably calcium carbonate.
Described compatilizer is SEBS maleic anhydride grafts, for example Kraton FG1901.
Described lubricant can be above-mentioned any lubricant, the combination of for example montanin wax and erucicamide.The weight ratio of montanin wax and erucicamide can be 1:0.3.
Described oxidation inhibitor can be above-mentioned any oxidation inhibitor, the preferably combination of Hinered phenols antioxidant and phosphite antioxidant, and the weight ratio of the two can be 1:1.The combination of for example four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and two (2,4-DTBP) pentaerythritol diphosphites.
Embodiment
Embodiment 1～embodiment 5:
1, material and source thereof: as shown in table 2.
Table 2:
2, formula, preparation method and performance test
Formula and performance test: as shown in table 2.
Preparation method: according to the amount ratio shown in table 3, each component is placed in mixing roll, under normal temperature condition, fully mix, the material that formation mixes, throwing in into length-to-diameter ratio (L/D) is more than 44 parallel double-screw extruders, under 180～220 ℃ of conditions, carry out fusion plastification, form melt; Melt is further evenly mixing, and through parallel double-screw extruder mouth, mold pressing goes out, and then uses conventional underwater pelletizer to carry out granulation, makes the soft printed material of soft particle form.
Above-mentioned soft particle, by plastifying fusion again under 180～220 ℃ of conditions of conventional single screw extrusion machine, is formed to melt; By melt, after the mouth mould of single screw extrusion machine go-no-go, cooling and shaping under the tank of normal temperature, makes strand; Described strand, through tractor traction, by winding machine rolling, is made to the soft printed material of standard package packing.
The soft printed material of above-mentioned package packing is carried out to performance test, and test result is as shown in table 3.
Table 3:
Embodiment 6～10:
1, material and source thereof: as shown in table 4.
Table 4:
| Purposes | Chemical name/popular name | Trade(brand)name/source |
| Thermoplastic elastomer | SEPS | Septon2063 |
| Polyolefine | Polypropylene | Formalene1102KR |
| Tenderizer | White mineral oil | Calumet?Calsol5550 |
| Lubricant | Erucicamide | PMC?Kemamide?B?Powder |
| Oxidation inhibitor | Four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester | BASF?Irganox1010 |
| Oxidation inhibitor | Three (2.4-di-tert-butyl-phenyl) phosphorous acid ester | BASF?Irganox168 |
2, formula and performance test: as shown in table 5.Preparation method: similar embodiment 1～5.
Table 5:
Embodiment 11～15:
1, material and source thereof: as shown in table 6.
Table 6:
2, formula and performance test: as shown in table 7.Preparation method: similar embodiment 1～5.
Table 7:
Embodiment 16～20:
1, material and source thereof: as shown in table 8.
Table 8:
2, formula and performance test: as shown in table 9.Preparation method: similar embodiment 1～5.
Table 9:
Embodiment 21～25:
1, material and source thereof: as shown in table 10.
Table 10:
2, formula and performance test: as shown in table 11.Preparation method: similar embodiment 1～5.
Table 11:
Claims (10)
1. for the preparation of a composition for thermoplastic elastomer for the soft printed material of 3 D-printing fusion sediment rapid shaping, it is characterized in that, the hardness of described composition for thermoplastic elastomer is Shore hardness 50A～90A, comprises by weight percentage following component:
2. composition for thermoplastic elastomer as claimed in claim 1, wherein said thermoplastic elastomer is selected from one or more in styrene analog thermoplastic elastomer, polyolefins thermoplastic elastomer, thermoplastic dynamic perduren, Polyurethane Thermoplastic Elastomer; Described polyolefine is selected from one or more of polypropylene, polyethylene or other olefines oligopolymer; Described tenderizer is selected from one or more of white mineral oil, paraffin oil, organic silicone oil, Viscotrol C, plam oil, epoxy soybean oil; Described lubricant is selected from one or more of hydro carbons, fatty acid, fatty acid acyl amine, ester class, alcohols, metal soap or compounded lubricant; Described oxidation inhibitor is selected from one or more of Hinered phenols, hindered amines, phosphorous acid esters, thio-alcohol or composite antioxidant.
3. composition for thermoplastic elastomer as claimed in claim 2, wherein said styrene analog thermoplastic elastomer is selected from one or more in styrene-ethylene-butylene-styrene block copolymer, styrene-ethylene-ethylene-propylene-styrene block copolymer, styrene-butadiene-styrene block copolymer, styrene isoprene styrene block copolymer (SIS), styrene-ethylene-propylene-styrene segmented copolymer; Wherein said polyolefins thermoplastic elastomer is selected from one or more of superpolymer, polyolefin block polymkeric substance, polyolefin graft copolymer, ethylene-propylene-diene terpolymer of the ethene of metallocene catalyst catalysis and the superpolymer of butylene or ethene and octene; Wherein said thermoplastic dynamic perduren dynamic vulcanization terpolymer EP rubber, dynamic vulcanization paracril, dynamic vulcanization natural rubber, dynamic vulcanization acrylic elastomer; Wherein said Polyurethane Thermoplastic Elastomer is selected from one or more of polyether(poly)urethane, PAUR, polycaprolactone polyurethane and aliphatic polyurethane.
4. composition for thermoplastic elastomer as claimed in claim 1, further comprise other additives, described additive is selected from one or more of pigment, spices, adhesion promotor, biocide, anti-fog agent, static inhibitor, tackiness agent, whipping agent, dispersion agent, weighting agent, compatilizer, smoke suppressor, impact modifier, initiator, mica, processing aid, releasing agent, separant, stablizer, ultraviolet absorbers, viscosity modifier.
5. composition for thermoplastic elastomer as claimed in claim 1, comprises following component by weight percentage:
6. composition for thermoplastic elastomer as claimed in claim 1, comprises following component by weight percentage:
7. composition for thermoplastic elastomer as claimed in claim 4, comprises following component by weight percentage:
8. composition for thermoplastic elastomer as claimed in claim 4, comprises following component by weight percentage:
9. the purposes of the composition for thermoplastic elastomer described in claim 1 to 8 any one in the soft printed material for the preparation of 3 D-printing fusion sediment rapid shaping.
10. composition for thermoplastic elastomer as claimed in claim 1, wherein said composition for thermoplastic elastomer can be prepared strand, particle, powdery or block soft printed material.
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