• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Composition of curable resin by radiation and procedure to obtain it. Being the procedure to obtain three-dimensional objects by means of radiation by means of 3D printing, laser type, DLP or LCD, through successive light-cured layers. The radiation curable resin composition comprises one or more epoxy-acrylic resins and polymethyl methacrylate, graphene, halloysite nanotubes and one or more photoinitiators. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2685280A1
    申请号:ES201700369
    申请日:2017-03-31
    公开日:2018-10-08
    发明作者:Karla Daniela MORA BARRIOS
    申请人:Centro Tecnologico De Nanomateriales Avanzados S L；Centro Tecnologico De Nanomateriales Avanzados SL；
    IPC主号:
    专利说明:

    5
    10
    fifteen
    twenty
    25
    30
    35
    40
    Four. Five
    fifty
    DESCRIPTION
    Composition of radiation curable resin and procedure for obtaining it.
    Object of the invention
    One of the objects of the present invention is a novel radiation curable resin, whose main application is to obtain three-dimensional objects by stereolithography, which comprises at least one epoxy-acrylic resin, polymethylmethacrylate, graphene, halloysite nanotubes and one or more photoinitiators . Another object of the invention is a, also novel, method for obtaining it.
    Background of the invention
    The manufacture of three-dimensional objects in a complex way by means of 3D printing or stereolithography, has long been known, and the radiation-curable liquid compositions (laser-cured, DLP or LCD) used have to meet a number of requirements, such as set forth in the following patent documents.
    U.S. Patent No. 5,476,748. Compositions of hybrid systems, photopolymerizable by free radicals and cationically, have been found in said patent. It was shown that these systems provide the required balance of accuracy, speed and final properties.
    The disclosed compositions comprise at least:
    • From 40% to 80% by weight of a difunctional or more functional liquid epoxy resin or of a liquid mixture consisting of difunctional or more functional epoxy resins.
    • From 0.1% to 10% by weight of a cationic photoinitiator or a mixture of cationic photoinitiators.
    • From 0.1% to 10% by weight of a free radical photoinitiator or a mixture of free radical photoinitiators.
    • From 5% to 40% by weight of a certain hydroxylated compound.
    • From 0% to 15% by weight of at least one liquid poly (meth) acrylate having a functionality of (meth) acrylate greater than 2.
    • From 5% to 40% by weight of at least one aromatic cycloaliphatic liquid diacrylate, the content of component (E) being not greater than 50% by weight of the total content of (meth) acrylate.
    In another U.S. Patent No. 5,972,563, a radiation curable liquid composition is disclosed, which further comprises a free radical polymerizable liquid component, and comprising at least the following additional components:
    • From 40% to 80% by weight of a difunctional or more functional liquid epoxy resin or of a liquid mixture consisting of difunctional or more functional epoxy resins.
    5
    10
    fifteen
    twenty
    25
    30
    35
    40
    Four. Five
    fifty
    • From 0.1% to 10% by weight of a cationic photoinitiator or a mixture of cationic photoinitiators.
    • From 0.1% to 10% by weight of a free radical photoinitiator or a mixture of free radical photoinitiators.
    • From 2% to 40% by weight of a hydroxylated compound.
    • The free radical polymerizable component comprises at least 4% to 30% by weight of at least one liquid poly (meth) acrylate, which has a functionality of (meth) acrylate greater than 2.
    • One or more di (meth) acrylates, preferably in an amount of 5% to 40% by weight.
    In another patent US-A-5,605,941, a methodology for producing three-dimensional objects is disclosed. Each of the photopolymerizable compositions possess excellent crude resistance and excellent balanced thermo-mechanical properties. Applicants of this invention have now surprisingly found that the selected hybrid compositions are capable of producing cured articles in stereolithography process systems with improved properties without the use of a free radical photoinitiator.
    The composition comprises:
    • (A) 40% to 80% by weight of a polyfunctional liquid component; which has at least two groups capable of reacting with a ring opening mechanism to form a polymer lattice.
    • (B) 0.1% to 10% by weight of a cationic photoinitiator or a mixture of cationic photoinitiators.
    • (C) 2% to 30% by weight of a compound having at least one unsaturated group and at least one hydroxy group in its molecule.
    • (D) 0% to 40% by weight of a hydroxylated compound that has no unsaturated group.
    • (E) 0% to 30% by weight of at least one liquid poly (meth) acrylate having a functionality greater than 2 and lacking hydroxy groups.
    • (F) 0% to 40% by weight of at least one cycloaliphatic or aromatic liquid di (meth) acrylate lacking hydroxy groups.
    • (G) 0% to 10% by weight of a reactive diluent, where the sum of components (A), (B), (C), (D), (E), (F) and (G) is 100% by weight, and the components (C), (D), (E), (F) and (G) are different and the composition does not contain any amount of free radical initiator.
    JP 20 75,618, discloses mixtures of an epoxy resin, an acrylate, a cationic photoinitiator and a radical one, as well as a polyester with terminal OH groups. The acrylate component used contains at least 50% of an acrylic monomer provided with more than 3 double bonds.
    5
    10
    fifteen
    twenty
    25
    30
    35
    40
    Four. Five
    fifty
    EP-A-360 869, publishes a mixture of resins for molding with light containing a cationic crosslinkable organic compound, as well as a cationic photoinitiator, taking into account that other radical polymerizable components can also be used simultaneously , eg polyacrylates.
    In patent ES2100513, it makes the following mention; 55 g of 3 ', 4'-3,4-epoxycyclohexylmethyl 3,4' epoxycyclohexanecarboxylate was mixed at 60 ° C with 18 g of a trifunctional polycaprolactone with terminal OH groups (TONER Polyol 0301 from Union Carbide) and 12 g of bisphenol diacrylate To ethoxylated (SRR 349 of the Sartomer company). Then, 1 g of 1-hydroxycyclohexylphenyl ketone (Irgacure® 184 from Ciba-Geigy) and 1 g of triarylsulfonium hexafluoroantimonate (Cyracure UVI 6974 from Union Carbide) are added, then stirred until a clear mixture is formed and homogeneous The liquid formulation has a viscosity at 30 ° C of 138 mPa-s. The molded parts are manufactured with a He / Cd laser (radiation energy: 320 mJ / cm2). Then the laser crosslinking (raw parts), said parts have the following properties: modulus of elasticity: 1320 N / mm2 elongation at break: 6.4%. For complete crosslinking, the raw pieces are subjected to UV light for 30 minutes and heated at 130 ° C for 30 minutes. The pieces have these properties:
    Modulus of elasticity: 1580 N / mm2 elongation at break: 4.3% warping factor (curl): CF 6: 0.01 CF 11: 0.02.
    Patent 2345031 mentions that the mechanical resistance of the crude model (modulus of elasticity, resistance to fracture), which is also referred to as crude resistance, constitutes an important property of the crude model and is essentially determined by the nature of the liquid resin composition for 3D or stereolithographic printing used.
    On the other hand, graphene is one of the hardest materials known, becoming the ideal candidate for reinforcement in a high performance curable liquid resin. It has been found that some materials can qualitatively improve their properties by adding graphene and analogs thereof, as in the case of photopolymerizable resins, where it is demonstrated unambiguously that stress transfer takes place from the polymer matrix to the monolayer of graphene, showing that graphene acts as a reinforcement phase. Another significant advantage is that the warping or contracting effect of the nanocomposite during photopolymerization is almost imperceptible when said reinforcement is added.
    Graphene is the most stable allotrope of coal, under standard conditions of pressure and temperature. Its structure is formed by a huge stack of superimposed sheets one after the other, within which atoms form hexagonal cells through covalent bonds of 1.42 A.
    Graphite oxide (GO), is a compound obtained by oxidation of graphite by a strong oxidant and in the presence of nitric acid, whose sheets consist of a two-dimensional carbonaceous skeleton, formed by a large number of sp3 carbons and a small number of sp2 carbons. During oxidation, the graffiti structure is maintained, although the aromatic character is partially lost. The structure contains different amounts of functional groups such as hydroxyl, ether, carboxylic groups, ketone groups, etc. The proposed formula for this compound being C704H2. The GO forms stable dispersions in water, where GO of a single sheet can be detected. Some researchers have observed that interlaminar spacing increases from 0.3 nm to 1.23 nm when the GO is dispersed in 0.05 N NaOH solution, it can be considered fully exfoliated for 0.01 N NaOH solutions. Consequently, the GO presents an interesting intercalation chemistry (GICs), offering many possibilities to obtain different nanocomposites.
    5
    10
    fifteen
    twenty
    25
    30
    35
    40
    Four. Five
    In fact, similar to laminated solids, such as natural silicates, graphite can be exfoliated. The exfoliation consists of the separation of the individual graphite sheets and is achieved by a thermal shock at high temperature (~ 1000 ° C) or with microwaves, eliminating by sudden volatilization the interleaving or the oxidized components of GO, achieving a unidirectional extension of the initial sheets.
    In this sense, recent publications show substantial improvements of some properties, such as, for example, a decrease in the thermal expansion coefficient (CTE) and an increase in the modulus of elasticity. It should be noted that the reinforcement of the nanocomposite, mixed with an appropriate amount of halloysite nanotubes, could significantly increase impact resistance, without sacrificing the flexural modulus, resistance and thermal stability.
    In relation to halloysite nanotubes and in contrast to other inorganic nanomaterials used as fillers in polymeric matrices, these can be easily obtained and are much cheaper. Its unique crystalline structure, similar to that of carbon nanotubes (CNT), as far as geometry is concerned, makes these materials potential substitutes.
    On the other hand, presenting chemical-physical characteristics similar to lamellar clays, they have the advantage that they do not need to be exfoliated inside the polymer, potentially improving their final properties. Finally, the size of the internal diameter of the nanotubes makes halloysite a material with potential applications as an encapsulant (host system) of small molecules such as different types of drugs, and may be useful for the controlled release of different types of substances
    Halloysite is made up of aluminum-silicate nanotubes. It is a totally natural nanomaterial, composed of a double layer of aluminum, silicon, hydrogen and oxygen. They are geometrically very fine tubular particles (figure 1 right), whose dimensions are about 50 nm internal diameter and 500 nm at 1.2 pm approximately long. Among the advantages of these nanotubes, its biocompatibility, natural origin, low toxicity, have a large surface area, high capacity for cation exchange and are economical.
    Taking into account all these characteristics, it seems reasonable to think that halloysite nanotubes are good candidates to use them as polymer matrix matrices to improve, among other things, their fracture toughness.
    There are studies that demonstrate this improvement in the case that the matrices are thermosetting polymers based on epoxy. However, none of the research papers that have been found are focused on dental applications; which makes it an even more attractive proposal in the production of three-dimensional objects through 3D printing in dental applications.
    The large surface area of these nanotubes, influences the dispersion in the polymeric matrices throughout their processing, favoring the homogenization of the final composite material. In general, they have a great tendency to form aggregates and even agglomerated by favorable interparticle interactions (possibility of forming hydrogen bonds between hydroxyl groups).
    5
    10
    fifteen
    twenty
    25
    30
    35
    40
    Four. Five
    fifty
    Description of the invention
    The radiation curable resin composition, which is one of the objects of the present invention comprises one or more epoxy-acrylic and polymethylmethacrylate, graphene, halloysite nanotubes and one or more photoinitiators resins.
    Brief description of the figures
    Figure 1. Flexural strength. "High impact nanocomposites, of epoxy resin reinforced with natural nanotubes" Polymer, 48: 6426-6433 (2007).
    Figure 2. Geometric structure and dimensions of halloysite nanotubes. Halloysite is made up of aluminum-silicate nanotubes. Its composition comprises a double layer of aluminum, silicon, hydrogen and oxygen (figure 1 left). They are geometrically, very fine tubular particles (figure 1 right), whose dimensions are about 50 nm internal diameter and 500 nm at 1.2 pm approximately long.
    Figure 3. The printing of models printed on DLP is appreciated, with different percentages of nano reinforcement. Where we observe a more transparent model with a 5% load and a grayish model with a 20% percentage of weight content.
    Preferred embodiment
    A preferred embodiment of the radiation curable resin composition is composed of:
    • (A) 40% to 60% by weight of at least one liquid epoxy resin, difunctional or of greater epoxy functionality equal to or greater than 2.
    • (B) 0% to 40% by weight of at least one liquid poly (meth) acrylate, of a (meth) acrylate functionality. (B) shall be a maximum of 50% by weight of the total content of (meth) acrylate.
    • (C) 0.1% to 10% by weight of at least one cationic photoinitiator for the component.
    • (D) 0.1% to 10% by weight of at least one radical photoinitiator for the components.
    • (E) 5% to 15% by weight of at least one polyether, polyester or polyurethane provided with terminal OH groups.
    • (F) 2% to 30% by weight of a compound having at least one unsaturated group and at least one hydroxy group in its molecule.
    • (G) 0% to 30% by weight of a hydroxylated compound that has no unsaturated group.
    • (H) 0.1% to 5% graphene oxide or graphene functionalized with an adhesive component.
    • (I) other reinforcement materials have been included, such as halloysite nanotubes, between 0.1% to 20% by weight.
    5
    10
    fifteen
    twenty
    25
    30
    35
    40
    Four. Five
    fifty
    The total sum of the compounds is equal to 100% by weight.
    The use of functionalized graphene or graphene is related to polymer-graphene-polymer structures and complex multilayer structures with repeated layers of graphene and polymer substrate. The insertion of functionalized graphene or graphene into the nanocomposite of curable liquid resin has advantageous properties. It does not suffer thermal expansion.
    Other reinforcement materials have been included such as halloysite nanotubes, between 0.1% to 20% by weight, which can also be included in the multilayer structure (polymer-graphene-halloysite-polymer nanotubes), as required.
    The invention of the curable liquid polymer matrix resin with epoxy / acrylic resin base, preferably for dental use, reinforced with functionalized graphene or graphene and halloysite nanotubes, has been used to improve the mechanical properties of the polymer matrix.
    The surface of the substrate on which graphene is applied is substantially flat. However, the methods of the present invention are applicable to irregular surfaces, such as surfaces containing peaks, depressions and / or undulations.
    In a preferred embodiment, the thickness of the functionalized graphene or graphene and the adhesive component for adhering the functionalized graphene or graphene to the substrate can be as small as 100 nm.
    In another preferred embodiment, the curable liquid resin comprises functionalized graphene or graphene and halloysite nanotubes incorporated into the substrate. Typically, in this embodiment, it is not necessary for said resin to contain an adhesive component. However, ideally to ensure good adhesion and retention of graphene it is important that the polarity of the curable liquid resin is compatible with graphene and halloysite nanotubes.
    In another embodiment, the curable liquid resin may contain graphene that has not been previously chemically modified (virgin graphene), or contain functionalized graphene (graphene that has been chemically modified, such as graphene oxide), the latter being an alternative embodiment.
    In the field of 3D printing (laser, DLP or LCD) or stereolithography, the hybrid composition that translates into chemical mixtures of curable components by free radicals and cationically curable is well understood.
    In this invention, ring opening is cationically activated for epoxides, and for (meth) acrylate it is activated by free radicals. The essential feature of the composition of this invention is the presence of an amount of a compound having at least one terminal and / or pendant unsaturated group and at least one hydroxyl group in its molecule together with a conventional cationically curable component.
    Preferred compounds having at least one terminal and / or pendant unsaturated group and at least one hydroxyl group are mono- and polyhydroxyacrylates, mono- and polyhydroxymethacrylates and mono and polyhydroxyvinyl ethers. There are some examples of cationically conventional curable components that are compounds that are polymerized by a ring opening reaction, such as epoxides, oxetanes, and tetrahydropyran. The liquid, consisting of a polyfunctional compound that has at least two groups capable of reacting by or as a result of a ring opening mechanism to form a polymer lattice,
    5
    10
    fifteen
    twenty
    25
    30
    35
    40
    Four. Five
    fifty
    which is used in the new compositions, are conveniently resins, which are liquid at room temperature and, which are cationically activated.
    The resins may have an aliphatic, aromatic, cycloaliphatic, araliphatic or heterocyclic structure; they contain the cyclic groups as side groups, or the epoxy group, which can be part of a system of alicyclic or heterocyclic rings. Resins of these types are known in general terms and are commercially available, in said resins preferably, component (A) contains oxirane (epoxide) rings in the molecule. Polyglycidyl esters and poly (pmethylglycidyl) are some epoxy resins.
    Poly (glycidyl ethers) or poly [(P-methylglycyl) ethers] can also be used which can be obtained by reacting a compound having at least two free alcoholic hydroxyl groups and / or phenolic hydroxyl groups with a conveniently substituted epichlorohydrin under alkaline conditions or in the presence of an acid catalyst, followed by alkali treatment. Particularly important representatives of poly (glycidyl ethers) or poly (p-methylglycidyl ethers) are based on phenols; either in monocyclic phenols, or polycyclic phenols, for example, in bis (4-hydroxyphenyl) methane (bisphenol F), 2,2-bis (4- hydroxyphenyl) propane (bisphenol a), or in condensation products, obtained in acidic conditions of phenols or cresols with formaldehyde.
    The present invention has been based on bisphenol A and bisphenol F and mixtures thereof. It has been obtained by dehydrochlorination of the reaction products of epichlorohydrin with amines containing at least two amino hydrogen atoms. The poly (S-glycidyl) compound is suitable for component (A) of the new composition, some examples of epoxy compounds that are part of an alicyclic or heterocyclic ring system include, 2- (3,4-epoxycyclohexyl-5 , 5-spiro-3,4-epoxy) cyclohexane-1,3-dioxane, bis (2,3-epoxycyclopentyl) ether, 2,3-epoxycyclopentyl glycidyl ether, 1,2-bis (2,3- epoxycyclopentyloxy) ethane, ethylenebis (3,4-
    epoxycyclohexane) -carboxylate, ethanediol-di (3,4- epoxycyclohexylmethyl) -ether, dioxide
    vinylcyclohexene, dicyclopentadiene diepoxide, bis (4- hydroxycyclohexyl) methane diglycidyl ether, 2,2-bis (4-hydroxycyclohexyl propane diglycidyl ether, 3, 4-epoxycyclohexylmethyl-3, 4-
    poxycyclohexanecarboxylate, 3, 4-epoxy-6-methyl-cyclohexylmethyl-3, 4-epoxy-6-
    methylcyclohexanecarboxylate, di (3,4-epoxycyclohexylmethyl) -hexanedioate, di (3,4-epoxy-6-
    methylcyclohexylmethyl) -hexanedioate.
    Component (A) contains between 40% to 60% by weight. Component (B) contains between 0% and 40% by weight. As for component (C), there is a range of cationic photoinitiators known industrially for curable liquid resins, such as onium salts, with weakly nucleophilic anions. They are found in various inventions such as EP-A-0044274, EP-A-0054509, EP-A-0153904, EP-A-0035969, EP-A-0164314 and US-A-3,708,296.
    The photoinitiator (C) and (D) is in amounts of 0.1% to 10% by total weight. In 3D or stereolithographic printing, laser beams are normally used, it is essential that the absorption capacity of the composition be adjusted such that the curing intensity for the normal laser rate is approximately 0.1 to 2.5 mm height
    It has been intended that the invention contain various photoinitiators of different sensitivity to light radiation in terms of wavelength. The purpose is that optimal optical absorption occurs. An interesting aspect is that the optimum level of the cationic photoinitiator is between 2% and 8% in relation to the total weight of the photoinitiators.
    Component (E) is present in an amount of at least 5% by weight based on the total weight of the composition.
    5
    10
    fifteen
    twenty
    25
    30
    Success has also been achieved in solving the challenge of a new composition for 3D printing (laser or DLP) or stereolithography, whose cured object-models exhibit greater tensile strength, impact resistance, and elongation at break. This was achieved with the reinforcement of nanoparticles of halloysite and graphene nanotubes or functionalized graphene.
    The amount of graphene or functionalized graphene added to the nanocomposite is 0.1% to 5% of the total weight.
    In the present invention, there is provided a method of improving the mechanical properties of the curable liquid resin, said improvement, including an increase in modulus, strength and hardness. Said increase is increased by 10%, and can even reach 100% or more, therefore, the hardening by deformation of the curable liquid resin involves cycles of tension delivery. In addition, there are also significant improvements in density, crystallinity, light absorption and luminescence as optical properties, damping capacity and stability to PH changes.
    image 1
    Diagram of reaction for the initiator divided by ultraviolet of the liquid resin, when coming into contact with UV light, the photopolomerization occurring.
    In the present invention, it is mentioned that other important properties of this invention, not present in the aforementioned patents are a high sensitivity for the radiation used in the course of curing and an almost imperceptible warping factor, which allows a high definition of the shape of the crude model. In addition, for example, the pre-cured layers of material are easily wettable between layers by the composition of the curable liquid resin and of course not only the crude model but also the final shaped article has superior mechanical properties.
    The process of preparing the radiation curable resin composition was divided into three stages:
    5
    10
    fifteen
    twenty
    25
    30
    35
    40
    Four. Five
    fifty
    I) polymer blend
    II) reinforcement with nanoparticles
    III) 3D printing to obtain the three-dimensional object
    I) To mix the components of (A) to (G), previously weighed in an electronic weight, they are stirred with a magnetic mixer between 200 rpm at 800 rpm, for 3 days, to further improve the Mix magnetic tablets are added. Subsequently, the mixture is taken to an opaque sterile container.
    II) In the context of the present invention, once the initial mixture of the curable liquid resin is obtained, we proceed to weigh the reinforcing materials, in this case the functionalized graphene or graphene and the Halloysite nanotubes, these are taken to ultrasonic agitation to achieve homogenization of the mixture at the percentages already described. The ultrasonic bath was performed with a nominal frequency of between 25 to 45 kHz, at room temperature and for a range of 3 to 6 hours, during which time an average temperature is reached between 35 ° C to 60 ° C, The gel effect was presented and the prepolymerization stage was completed.
    The radiation curable liquid resin composition is a homogeneous mixture with different proportions of reinforcements, which may contain a higher percentage of functionalized graphene or graphene, with halloysite nanotubes on a larger or smaller scale. Thus, the invention is also related to structures such as graphene, halloysite nanotubes, and complex structures with repeated layers of nanorefers and polymer matrix. Thus, the structure offers us a reinforced curable liquid resin, with numerous advantages and with great stability, both thermal and dimensional.
    III) 3D printing is done by means of a 3D printer, so cationic and / or free radical type photoinitiators were used. What they do is absorb ultraviolet (UV) photons, which the 3D printer projector emits at a certain wavelength. The free radicals when exposed to the Light begin to react with the curable liquid resin and start the polymerization. To induce polymerization, it is necessary that the projector light is focused and aligned properly in relation to the polymerization pool.
    The object in 3D, is created from the union of different layers united and photopolymerized with each other as the light strikes. The resolution of the created objects is between 0.02 to 0.05 pm.
    During the exposure of the object to be created in the light, the exothermic reaction must be considered, and that implies what is the nature of the reaction itself. Large cross sections tend to create a warping effect, because due to the increase in temperature a polymerization reaction is caused that causes the object to expand. To avoid this warping effect, curing dynamics parameters must be applied and the exposure time must be reduced in the printing program software, in order to avoid overexposure and obtain the final model.
    The construction or printing of three-dimensional (3D) objects based on computer-designed models use a power source, laser type, DLP or LCD type, to draw a cross-section.
    The printing area is carried out along the X and Y axes, creating layer by layer of pixel by pixel, each finished layer moves along the Z axis, which defines the height, creating the following layers with the same sequence . 3D printing or projection stereolithography
    5
    10
    fifteen
    twenty
    25
    30
    35
    40
    (DLP, laser or LCD) uses a data projector to create each layer simultaneously and adheres to the previously cured layer. The thickness of each layer is between 0.2 to 0.5 microns.
    At the end of the three-dimensional object, the sample continues to be removed from the aluminum plate where it is created and taken to a final post-cure, in a curing chamber, at a power of about 100 watts.
    There are many applications for this microscale technique, including microbioreactors, or to support tissue growth, drug microarrays and biochemical integrated circuits that could eventually simulate biological systems.
    The three-dimensional objects obtained from 3D printing, with the composition object of the present invention have very useful functions in various disciplines, which includes the dental and biomedical sector, including from surgical splints, models, aligners (transparent and Vita type colors) , crowns and / or provisional and / or definitive covers.
    Likewise, a method of improving the mechanical properties of the currently used resins is provided, since none have nanorefrequency, which together with the methodology used provides perfect homogenization and adhesion to the curable liquid resin.
    The improvement of the mechanical properties of the composition includes an increase in Young's modulus, strength and hardness. This increase is between 10% to 300% depending on the percentage of reinforcement that is added, also improves the modulus and resistance as would be expected from a high aspect ratio fill. Only 5% by weight improved the interlaminar shear strength (ILSS) by 25% and the hardness was significantly improved at the same time.
    Another interesting advantage is the dimensional stability provided by the invention, since the deformation by contraction of the object obtained by 3D printing is zero, unlike those currently existing that handle error margins due to said contraction.
    In addition, the composition has antibacterial and antifungal properties and has the particularity of significantly improving optical properties, such as opalescence, luminescence and opacity and other intrinsic properties such as density and crystallinity.
    Therefore, the composition has excellent structural applications in the dental field such as discharge splints, bite splints, immediate load splints for implants, provisional, crowns and definitive covers, as well as applications in other fields and fields.
    权利要求:
    Claims (15)
    [1]
    5
    10
    fifteen
    twenty
    25
    30
    35
    40
    Four. Five
    fifty
    1. Radiation curable resin composition characterized in that it comprises one or more epoxy-acrylic and polymethylmethacrylate, graphene, halloysite nanotubes and one or more photoinitiators resins.
    [2]
    2. Radiation curable resin composition according to claim 1, characterized in that it comprises:
    • 40% to 60% by weight of at least one liquid epoxy resin, where the liquid epoxy resins have at least two groups capable of reacting by a ring opening mechanism to form a polymer lattice.
    • 0% to 40% by weight of at least one liquid poly (meth) acrylate, of a (meth) acrylate functionality, wherein said liquid poly (meth) acrylate will be at most 50% by weight of the total content of ( met) acrylate.
    • 0.1% to 10% by weight of at least one cationic photoinitiator.
    • 0.1% to 10% by weight of at least one free radical photoinitiator.
    • 5% to 15% by weight of at least one polyether provided with terminal OH groups.
    • 2% to 30% by weight of a compound that has at least one unsaturated group and at least one hydroxy group in its molecule.
    • 0% to 30% by weight of a hydroxylated compound that does not have any unsaturated groups.
    • 0.1% to 5% graphene.
    • 0.1% to 20% by weight of halloysite nanotubes.
    [3]
    3. Radiation curable resin composition according to claim 2, characterized in that at least one liquid epoxy resin is difunctional.
    [4]
    4. Radiation curable resin composition according to claim 2 or 3, characterized in that at least one liquid epoxy resin has an epoxy functionality of at least 2.
    [5]
    5. Radiation curable resin composition according to any one of the preceding claims, characterized in that it comprises at least one polyester provided with terminal OH groups.
    [6]
    6. Radiation curable resin composition according to any of the preceding claims, characterized in that it comprises 5% to 15% by weight of the at least one polyester provided with terminal OH groups.
    [7]
    7. Radiation curable resin composition according to any of the preceding claims, characterized in that it comprises at least one polyurethane provided with terminal OH groups.
    [8]
    8. Radiation curable resin composition according to any of the preceding claims, characterized in that it comprises 5% to 15% by weight of the at least one polyurethane provided with terminal OH groups.
    5
    10
    fifteen
    twenty
    25
    30
    35
    40
    Four. Five
    [9]
    9. Radiation curable resin composition according to any of claims 6 and 8, characterized in that the total weight percentage of polyether, polyester or polyurethane is between 5% and 15%.
    [10]
    10. Radiation curable resin composition according to any of the preceding claims, characterized in that it comprises an adhesive for adhering graphene to the substrate.
    [11]
    11. Radiation curable resin composition according to any of claims 210, characterized in that graphene is graphene oxide.
    [12]
    12. Radiation curable resin composition according to any of claims 210, characterized in that graphene is functionalized graphene.
    [13]
    13. Method for obtaining the radiation curable resin composition defined in any of the preceding claims characterized in that it comprises the following steps:
    a) Mixing of the following components: liquid epoxy resins, liquid poly (meth) acrylate, cationic photoinitiator, free radical photoinitiator, a compound that has at least one unsaturated group and at least one hydroxy group in its molecule, a hydroxylated compound that it has no unsaturated group and at least one of the following polyether, polyester or polyurethane components; The mixing is carried out by means of a magnetic mixer and the introduction into the mixture of magnetic tablets.
    b) The mixture obtained in step a) is poured into a sterile and opaque container.
    c) Addition of graphene and halloysite nanotubes to the mixture contained in the sterile and opaque container.
    d) Closed of the container with a sterile and opaque lid.
    e) Agitation of the mixture in a bath by ultrasound for prepolymerization of the mixture obtained in step c), obtaining the radiation curable resin composition.
    [14]
    14. Method for obtaining the radiation curable resin composition according to claim 13, characterized in that mixing with a magnetic mixer is performed between 200 rpm and 800 rpm for 3 days.
    [15]
    15. Procedure for obtaining the radiation curable resin composition according to claim 13 or 14, characterized in that the nominal frequency of the ultrasound is between 25 to 45 kHz, the bath is at room temperature and the mixing process is hard 3 to 6 hours, time in which an average temperature is reached between 35 ° C to 60 ° C.
    类似技术:
    公开号 | 公开日 | 专利标题
    ES2685280B2|2019-06-21|Radiation curable resin composition and procedure for obtaining it
    CN109503761B|2022-02-01|Stable matrix-filled liquid radiation curable resin compositions for additive fabrication
    KR101800370B1|2017-11-22|Photo-curable resin compositions and method of using the same in three-dimensional printing for manufacturing artificial teeth and denture base
    JP5250776B2|2013-07-31|Photocurable resin composition not containing antimony and three-dimensional article
    JP5559033B2|2014-07-23|Binary photoinitiators, photocurable compositions, their use in three-dimensional article manufacture, and manufacturing methods
    JP5210645B2|2013-06-12|Optical three-dimensional resin composition
    JP5266131B2|2013-08-21|Optical three-dimensional resin composition
    JP5478016B2|2014-04-23|Optical three-dimensional resin composition
    JP4925900B2|2012-05-09|Optical three-dimensional resin composition
    JP4969137B2|2012-07-04|Optical three-dimensional resin composition
    JP2005060673A|2005-03-10|Stereo lithography resin filled with nano-particle
    JPH11100378A|1999-04-13|Epoxy compound and polymerizable composition containing the compound
    JP6410158B2|2018-10-24|Ultraviolet curable resin composition, organic EL light emitting device manufacturing method, and organic EL light emitting device
    JP5376124B2|2013-12-25|Reactive monomer-dispersed silica sol, method for producing the same, curable composition, and cured product thereof
    JP5111774B2|2013-01-09|Optical three-dimensional resin composition
    WO2009145167A1|2009-12-03|Resin composition for optical three-dimensional molding
    RU2408627C2|2011-01-10|Antimony-free photocurable polymeric composition and three-dimensional article
    JP2007238828A|2007-09-20|Resin composition for optically formed three-dimensional article
    JP4014420B2|2007-11-28|Photosensitive resin composition and mold using the same
    JP2013151703A|2013-08-08|Resin composition for three-dimensional shaping
    WO2018043512A1|2018-03-08|Resin composition for optical three-dimensional molding
    WO2019009063A1|2019-01-10|Photoshaping composition
    KR20160041661A|2016-04-18|Composition for optical three-dimensional molding
    JP2003251620A|2003-09-09|Mold-releasing agent for concrete form
    KR20160046095A|2016-04-28|Composition for optical three-dimensional molding
    同族专利:
    公开号 | 公开日
    WO2018178423A3|2018-11-22|
    WO2018178423A2|2018-10-04|
    BR112019020296A2|2020-06-16|
    EP3604375A4|2020-12-02|
    CN110650986A|2020-01-03|
    RU2019134903A3|2021-07-14|
    AU2018242233A1|2019-11-07|
    US20200026185A1|2020-01-23|
    ES2685280B2|2019-06-21|
    KR20190128086A|2019-11-14|
    RU2019134903A|2021-04-30|
    ZA201907156B|2021-08-25|
    EP3604375A2|2020-02-05|
    JP2020512477A|2020-04-23|
    CA3058543A1|2018-10-04|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US5476748A|1992-12-21|1995-12-19|Ciba-Geigy Corporation|Photosensitive compositions|
    EP1385055A1|2002-07-18|2004-01-28|3D Systems, Inc.|Stereolithographic resins with high temperature and high impact resistance|
    WO2011146154A2|2010-02-04|2011-11-24|Drexel University|Room temperature ionic liquid-epoxy systems as dispersants and matrix materials for nanocomposites|
    CN103819656A|2014-02-18|2014-05-28|青岛科技大学|Graphene oxide/light cured resin composite and its preparation method and application|
    US3708296A|1968-08-20|1973-01-02|American Can Co|Photopolymerization of epoxy monomers|
    US4339567A|1980-03-07|1982-07-13|Ciba-Geigy Corporation|Photopolymerization by means of sulphoxonium salts|
    US4383025A|1980-07-10|1983-05-10|Ciba-Geigy Corporation|Photopolymerization by means of sulfoxonium salts|
    US4398014A|1980-11-04|1983-08-09|Ciba-Geigy Corporation|Sulfoxonium salts and their use as polymerization catalysts|
    DE3565013D1|1984-02-10|1988-10-20|Ciba Geigy Ag|Process for the preparation of a protection layer or a relief pattern|
    GB8414525D0|1984-06-07|1984-07-11|Ciba Geigy Ag|Sulphoxonium salts|
    WO1989007620A1|1988-02-19|1989-08-24|Asahi Denka Kogyo K.K.|Resin composition for optical modeling|
    JPH07103218B2|1988-09-13|1995-11-08|旭電化工業株式会社|Resin composition for optical modeling|
    AT193532T|1993-09-16|2000-06-15|Ciba Sc Holding Ag|VINYLETHER COMPOUNDS WITH ADDITIONAL FUNCTIONAL GROUPS DIFFERENT FROM VINYLETHER GROUPS AND THE USE THEREOF FOR THE FORMULATION OF CURABLE COMPOSITIONS|
    EP0822445B2|1996-07-29|2005-02-09|Huntsman Advanced Materials GmbH|Liquid radiation-curable compositions, in particular for stereolithography|
    US6136497A|1998-03-30|2000-10-24|Vantico, Inc.|Liquid, radiation-curable composition, especially for producing flexible cured articles by stereolithography|
    CN1422394B|2000-02-08|2012-08-22|范蒂科股份公司|Liquid, radiation-curable composition, especially for stereolithography|
    TWI406086B|2004-03-22|2013-08-21|3D Systems Inc|Photocurable compositions|TWI674976B|2018-11-12|2019-10-21|三緯國際立體列印科技股份有限公司|Three-dimensional printing device having stirring mechanism|
    CN109627689B|2018-11-23|2021-04-30|贵州航天天马机电科技有限公司|Preparation method of graphene-epoxy resin composite material|
    WO2020232662A1|2019-05-22|2020-11-26|Henkel Ag & Co. Kgaa|Method for cleaning and post processing 3d printed light cure silicones|
    法律状态:
    2018-10-08| BA2A| Patent application published|Ref document number: 2685280 Country of ref document: ES Kind code of ref document: A1 Effective date: 20181008 |
    2019-06-21| FG2A| Definitive protection|Ref document number: 2685280 Country of ref document: ES Kind code of ref document: B2 Effective date: 20190621 |
    优先权:
    申请号 | 申请日 | 专利标题
    ES201700369A|ES2685280B2|2017-03-31|2017-03-31|Radiation curable resin composition and procedure for obtaining it|ES201700369A| ES2685280B2|2017-03-31|2017-03-31|Radiation curable resin composition and procedure for obtaining it|
    CA3058543A| CA3058543A1|2017-03-31|2018-04-02|Radiation-curable resin composition and production method thereof|
    EP18775975.8A| EP3604375A4|2017-03-31|2018-04-02|Radiation-curable resin composition and production method thereof|
    CN201880031566.7A| CN110650986A|2017-03-31|2018-04-02|Composition of radiation-curable resin and method for obtaining the same|
    PCT/ES2018/000039| WO2018178423A2|2017-03-31|2018-04-02|Radiation-curable resin composition and production method thereof|
    BR112019020296-0A| BR112019020296A2|2017-03-31|2018-04-02|COMPOSITION AND PRODUCTION PROCESS OF RADIATION CURABLE RESIN|
    AU2018242233A| AU2018242233A1|2017-03-31|2018-04-02|Radiation-curable resin composition and production method thereof|
    JP2020503367A| JP2020512477A|2017-03-31|2018-04-02|Radiation curable resin composition and acquisition method|
    KR1020197032138A| KR20190128086A|2017-03-31|2018-04-02|Composition and obtaining method of radiation curable resin|
    US16/499,414| US20200026185A1|2017-03-31|2018-04-02|Radiation-Curable Resin Composition and Production Method Thereof|
    RU2019134903A| RU2019134903A3|2017-03-31|2018-04-02|
    ZA2019/07156A| ZA201907156B|2017-03-31|2019-10-29|Radiation-curable resin composition and production method thereof|
    [返回顶部]