WO2022033113A1 - Three-dimensional molding material, and three-dimensional object and slice layer thereof - Google Patents

Abstract

A three-dimensional molding material, and a three-dimensional object and a slice layer thereof, capable of effectively improving the mechanical strength of the three-dimensional object, reducing the porosity of the three-dimensional object, and increasing the compactness of the three-dimensional object. The three-dimensional molding material comprises a liquid material and a powder material. The liquid material comprises an active component, and the active component can undergo a polymerization reaction to form a polymer; the powder material per se does not undergo a polymerization reaction and does not undergo a polymerization reaction with the active component, and the liquid material dissolves at least part of the powder material.

Description

Materials for three-dimensional molding, three-dimensional objects and sliced layers thereof

This application is required to be submitted to the China Patent Office on August 11, 2020, and the application number is 202010803364.9. The priority of the Chinese patent application entitled "Material for Three-Dimensional Forming, Three-Dimensional Object and Sliced Layer thereof", the entire content of which is incorporated herein by reference.

technical field

The present application relates to the technical field of three-dimensional object forming, and in particular, to materials for three-dimensional forming, three-dimensional objects and slice layers thereof.

Background technique

The main process of the three-dimensional object additive manufacturing technology is to obtain the digital model of the three-dimensional object, slice and layer the digital model, and perform data processing and conversion on each slice layer to obtain the printing data of each slice layer. The printing device According to the slice layer printing data, layer-by-layer printing is performed and superimposed to produce three-dimensional objects.

Existing technologies for additive manufacturing of 3D objects include inkjet printing technology and technology that combines powder and inkjet printing. Among them, the inkjet printing technology mainly refers to that the print head on the support platform selectively ejects the photosensitive resin material according to the layer patterning data of the three-dimensional object, also known as the printing data, and the radiation source irradiates the ejected photosensitive resin material to form a cured layer. However, the selection of materials in inkjet printing technology is relatively narrow, and it is difficult to manufacture high-strength objects, which limits its application in the industrial and aerospace fields.

In the existing technology combining powder and inkjet printing, the print head selectively ejects liquid material on the powder material layer according to the layer printing data of the three-dimensional object, wherein the powder material contains a first active component, and the liquid material contains a second active component. The reactive components, the first reactive component and the second reactive component are contacted and chemically reacted to form a cured chip layer. However, this molding method has a relatively narrow selection range of materials, and because the powder material participates in the chemical reaction, it is easy to reduce the molding accuracy due to the uneven reaction.

Application content

The embodiments of the present application provide a three-dimensional molding material, a three-dimensional object, and a slice layer thereof, which can effectively improve the mechanical strength of the three-dimensional object, reduce the porosity of the three-dimensional object, and improve the density of the three-dimensional object.

In a first aspect, an embodiment of the present application provides a material for three-dimensional molding, the material comprising:

a liquid material that includes an active component that can polymerize to form a polymer; and

A powder material that does not polymerize itself and does not polymerize with the active component, and the liquid material dissolves at least a portion of the powder material.

In combination with the first aspect, in a feasible embodiment, the powder material is selected from polystyrene, polyvinyl chloride, polyacrylonitrile, acrylonitrile-styrene-acrylate copolymer, polyamide, polyester, polyurethane , poly(meth)acrylates, polymethyl(meth)acrylates, polyvinyl fluoride, chlorinated polyolefins, block and/or graft copolymers containing At least one of polyvinyl alcohol, cellulose, and modified cellulose.

With reference to the first aspect, in a feasible embodiment, the mass proportion of the active component in the liquid material is 55%-99.5%.

In combination with the first aspect, in a feasible embodiment, the active component has an active group that can participate in the polymerization reaction, and the active group includes a carbon-carbon double bond, a hydroxyl group, a carboxyl group, a thiirane group , at least one of isocyanate group, carbonate group, epoxy group, cyclic amide group, cyclic lactone structure, cyclic acid anhydride structure and cyclic acetal structure.

In combination with the first aspect, in a feasible embodiment, the active component includes a first active component, the first active component has an active group, and the first active component dissolves at least part of the powder material.

In combination with the first aspect, in a feasible embodiment, the mass ratio of the first active component in the liquid material is 10%-95%; and/or,

The first active component is selected from the group consisting of carbon-carbon double bond-containing monomers, epoxy-containing groups and compositions that promote ring-opening polymerization of epoxy groups, cyclic lactones, sulfur heterocyclic compounds, and carbonates At least one of a compound and a cyclic amide compound.

In combination with the first aspect, in a feasible embodiment, the active component further includes a second active component, and the second active component has an active group; the second active component does not dissolve the powder material.

In combination with the first aspect, in a feasible embodiment, the mass ratio of the second active component in the liquid material is 5%-90%; and/or,

The second active component is selected from monomers and/or prepolymers containing carbon-carbon double bonds, diluents and/or prepolymers containing epoxy groups, and monomers that promote ring-opening polymerization of epoxy groups. At least one of the compounds and/or prepolymers, polyols, cyclic lactones, sulfur heterocyclic compounds, and cyclic amide compounds.

In combination with the first aspect, in a feasible embodiment, the first active component and/or the second active component has a swelling group, and the swelling group can participate in a polymerization reaction, and the The swelling group is selected from at least one of spirocyclic ether structure, spirocyclic orthocarbonate structure, spirocyclic orthoester structure, bicyclic orthoester structure and bicyclic lactone structure.

In combination with the first aspect, in a feasible embodiment, the first active component and/or the second active component has a combination of active groups, and the combination of active groups can form the the swelling group.

In combination with the first aspect, in a feasible embodiment, the active group combination includes any of the combination of a polyol group and an orthocarbonic diester group, an epoxy group and a cyclic lactone structure combination. A sort of.

In combination with the first aspect, in a feasible embodiment, the liquid material further includes a first auxiliary agent, and the first auxiliary agent includes at least one of a free radical initiator, an anionic initiator, a cationic initiator and a catalyst and/or, the mass proportion of the first auxiliary agent in the liquid material is 0%-10%.

In combination with the first aspect, in a feasible embodiment, the liquid material further includes a second auxiliary agent, and the second auxiliary agent includes a leveling agent, a defoaming agent, a polymerization inhibitor, a surfactant, and an antioxidant. , at least one of plasticizer and dispersant; and/or, the mass proportion of the second auxiliary agent in the liquid material is 0.1%-30%.

With reference to the first aspect, in a feasible embodiment, the liquid material further includes a colorant, and the colorant accounts for 0%-10% by mass in the liquid material.

With reference to the first aspect, in a feasible embodiment, the average particle size of the powder material is 1 um˜400 um.

In combination with the first aspect, in a feasible embodiment, the powder material further includes an additive, and the additive includes at least one of a flow aid and a filler.

In a second aspect, an embodiment of the present application provides a slice layer of a three-dimensional object, where the slice layer of the three-dimensional object is formed by printing the three-dimensional object additive manufacturing process using the above-mentioned materials.

In a third aspect, an embodiment of the present application provides a three-dimensional object, wherein the three-dimensional object is formed by printing the three-dimensional object additive manufacturing process using the above-mentioned materials.

The technical solution of the present application has at least the following beneficial effects:

The three-dimensional molding materials provided in the embodiments of the present application include powder materials and liquid materials containing active components, the powder materials and the active components do not undergo contact chemical reaction; the active components dissolve at least part of the powder materials, and the active components Polymerization reaction occurs to form high molecular polymer, and the formed high molecular polymer and powder material form a blend, especially when mixed with dissolved powder material at the molecular level to form a high molecular alloy, which makes the powder material, powder material and active There is a good connection between the polymers of the components and between the printing layers and the layers. In addition, the formed high molecular polymer can be mixed with the powder material to obtain a "sea-island structure" or a homogeneous structure with good interface bonding, which improves the mechanical strength of the three-dimensional object.

The active components in the liquid material of the present application fill the gaps between the powder materials, dissolve the powder materials, further reduce the porosity inside the three-dimensional object, and improve the density of the three-dimensional object. The active components are polymerized to form a molecular-level mixture of high molecular polymers and powder materials, and colorless or light-colored transparent three-dimensional objects can be easily obtained.

The active component in the liquid material of the present application undergoes a polymerization reaction to form a layer of a three-dimensional object and the three-dimensional object obtained by manufacturing basically has no residual small molecular substances, and basically no small molecular substances are precipitated during use, which can meet the requirements of safety and environmental protection. .

Description of drawings

In order to illustrate the technical solutions in the embodiments of the present application more clearly, the following briefly introduces the drawings that are used in the description of the embodiments. Obviously, the drawings in the following description are only some embodiments of the present application. For those of ordinary skill in the art, other drawings can also be obtained from these drawings without creative labor.

FIG. 1 is a schematic structural diagram of a three-dimensional object additive manufacturing device provided by a specific embodiment of the present application;

2 is a schematic flowchart of a method for additive manufacturing of a three-dimensional object provided by a specific embodiment of the present application;

3a-3g are schematic structural diagrams of a three-dimensional object formation process provided by a specific embodiment of the present application.

detailed description

In order to better understand the technical solutions of the present application, the embodiments of the present application are described in detail below with reference to the accompanying drawings.

It should be clear that the described embodiments are only a part of the embodiments of the present application, but not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present application.

The terms used in the embodiments of the present application are only for the purpose of describing specific embodiments, and are not intended to limit the present application. As used in the embodiments of this application and the appended claims, the singular forms "a," "the," and "the" are intended to include the plural forms as well, unless the context clearly dictates otherwise.

It should be understood that the term "and/or" used in this document is only an association relationship to describe the associated objects, indicating that there may be three kinds of relationships, for example, A and/or B, which may indicate that A exists alone, and A and B exist at the same time. B, there are three cases of B alone. In addition, the character "/" in this document generally indicates that the related objects are an "or" relationship.

The embodiment of the present application provides a material for three-dimensional molding, including:

a liquid material that includes an active component that can polymerize to form a polymer; and

A powder material that does not polymerize itself and does not polymerize with the active component, and the liquid material dissolves at least a portion of the powder material.

In this solution, the active components in the liquid material undergo a polymerization reaction to form a high-molecular polymer, and the formed high-molecular polymer forms a blend with the powder material, especially a molecular-level mixture with the powder material dissolved in the liquid material. , forming a polymer alloy, so that there is a good connection between the powder materials, between the powder materials and the polymer of the active component, and between the printing layer and the layer, showing a "sea-island structure" or a homogeneous structure, The mechanical strength of the three-dimensional object can be improved.

It should be noted that the sea-island structure is a two-phase system of blends, in which one phase is a continuous phase and the other is a dispersed phase, and the granular powder material is dispersed in the continuous polymer to form a strong connection , which can improve the mechanical strength of three-dimensional objects.

Specifically, the powder material is a material particle in powder form that does not polymerize with the active components in the liquid material, nor does the powder material itself polymerize. Optionally, the powder material is selected from polystyrene (PS), polyvinyl chloride (PVC), polyacrylonitrile, acrylonitrile-styrene-acrylate copolymer (ASA), polyamide (PA), polyester, polyurethane (PU), poly(meth)acrylates, polymethyl(meth)acrylates, polyvinyl fluoride, chlorinated polyolefins, block and/or graft copolymers containing such as modified nylon, modified olefin polymers, etc.), at least one of hydroxyl-containing polyvinyl alcohol (PVA), cellulose, and modified cellulose.

The melting point or melting temperature of the powder material in this embodiment may be 60°C to 300°C. The particle shape and particle size of the powder material are not particularly limited. When the powder material provided in this embodiment forms the powder material layer, the fluidity of the powder material can meet the usage requirements, the gap formed between the powder materials can be filled with the applied liquid material, and the applied liquid material can wet the powder material The surface and/or at least part of the powder material can be dissolved in the liquid material.

Optionally, according to the difference in the manufacturing process of the powder material, the powder material in this embodiment may be spherical, dendritic, flake, disc, needle, and rod shapes. The average particle size of the powder material is 1 μm to 400 μm, for example, 1 μm, 5 μm, 10 μm, 30 μm, 50 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 350 μm or 400 μm, and the average particle size of the powder material is preferably 30 μm to 200 μm. The particle gap in the powder material is about 5 nm to 100 μm, for example, it can be 5 nm, 10 nm, 100 nm, 250 nm, 500 nm, 1 μm, 5 μm, 10 μm, 25 μm, 50 μm, 75 μm or 100 μm, which is not limited herein. The particle gap of the powder material in this embodiment is in the range of 5 nm to 100 μm. When the liquid material is selectively applied to the powder material layer, the liquid material can quickly penetrate into the powder material layer through the gap and retain part of the surface layer, thereby wetting the surface of the powder material in the selected area and at least partially dissolve the powder material. It should be noted that the dissolution in this example refers to all possible situations except complete insolubility.

The powder material in the present application may also include additives, and the additives include at least one of flow aids and fillers. Among them, flow aids are used to improve the fluidity of powder materials, such as silicon dioxide, talc, etc.; fillers are used to improve the mechanical strength of three-dimensional objects, such as graphene, carbon nanotubes, glass Fiber, kaolin, etc. are not limited in this embodiment.

In this embodiment, the liquid material includes an active component capable of polymerizing, which dissolves at least a portion of the powder material. Preferably, the active ingredient completely dissolves the powder material in contact with the active ingredient.

Further, the active components in the liquid material have active groups that can participate in the polymerization reaction, and the active groups include carbon-carbon double bonds, hydroxyl groups, carboxyl groups, thiirane groups, isocyanate groups, and carbonate groups. , at least one of epoxy group, cyclic amide group, cyclic lactone structure, cyclic acid anhydride structure and cyclic acetal structure. It should be noted that the active component does not undergo a polymerization reaction with the powder material.

Optionally, based on the total mass of the liquid material being 100%, the mass ratio of the active component in the liquid material is 55%-99.5%, for example, it may be 55%, 60%, 65%, 70% %, 75%, 80%, 85%, 90%, 95% or 99.5%, of course, the mass ratio of the active component in the liquid material can also be set to other values according to actual needs, which is not limited here. When the mass proportion of the active component in the liquid material exceeds 54%, the active component can dissolve at least part of the powder material, and when the active component undergoes a polymerization reaction to form a high molecular polymer, the high molecular polymer and the powder material form a blend In particular, it can be mixed with dissolved powder materials at the molecular level to form a polymer alloy, so that there is a good connection between powder materials, between powder materials and polymers of active components, and between printing layers and layers.

In addition, the formed high-molecular polymer can be mixed with the powder material to obtain a "sea-island structure" or a homogeneous structure with good interface bonding. The mechanical properties of the three-dimensional objects made of the three-dimensional molding material provided by the application are significantly improved, for example, the tensile strength is improved. The active components are polymerized to form polymers, and there are basically no small molecular substances remaining in the manufactured three-dimensional objects, and no small molecular substances are precipitated during the use process, which meets the requirements of safety and environmental protection; the formed high molecular polymers and powder materials meet molecular Level mixing, easy to obtain colorless or light-colored transparent three-dimensional objects.

The active ingredient includes a first active ingredient having an active group that dissolves at least a portion of the powder material. Specifically, the first active component may be a substance including only one dissolvable powder material, or a mixture of substances including multiple dissolvable powder materials, and the solubility of the multiple substances to the powder material may be different or the same.

It should be noted that the dissolution mentioned in this example refers to all possible situations except complete insolubility. For example, at least 1% of the powdered material dissolves when 1 g of the powdered material is placed in 100 g of the active ingredient. Preferably, the first active component completely dissolves the powder material. The dissolution is not limited to normal temperature, and the active ingredient can also be dissolved in the powder material under the condition of heating and/or stirring; The powder material dissolves slowly upon contact, and the powder material can be heated to increase the rate of dissolution.

In this embodiment, based on the total mass of the liquid material being 100%, the mass proportion of the first active component in the liquid material is 10%-95%. For example, it can be 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% or 95%. Of course, the mass ratio can also be matched according to the actual usage, which is not done here. limited. Preferably, the mass ratio of the first active component in the liquid material is 30%-95%. In this embodiment, the mass proportion of the first active component in the liquid material is greater than or equal to 30%. By increasing the proportion of the first active component in the liquid material, the dissolution rate of the first active component to the powder material and the degree of dissolution, thereby increasing the mechanical strength of the printed object.

The first active component can be selected from the group consisting of monomers containing carbon-carbon double bonds, epoxy-containing groups and compositions that promote ring-opening polymerization of epoxy groups, cyclic lactones, sulfur heterocyclic compounds, carbonates At least one of compounds and cyclic amide compounds. Specifically, the carbon-carbon double bond-containing monomer may be (meth)acrylates, vinyl ethers, allyl ethers, styrene, acryloyl morpholine, N-vinyl pyrrolidone, and the like. The epoxy group-containing and ring-opening-polymerizing-promoting epoxy group-containing compositions may be epoxy diluents and/or hydroxyl-containing small molecules or prepolymers, epoxy diluents and/or carboxyl-containing Small molecules or prepolymers. The cyclic lactone can be γ-butyrolactone, δ-valerolactone, ε-caprolactone, etc.; the thio heterocyclic compound such as thiirane, thietane, etc.; the carbonate Such compounds can be dimethyl carbonate, diethyl carbonate, etc.; cyclic amide compounds can be caprolactam and the like.

Exemplarily, the first active component may be styrene or γ-butyrolactone, and the powder material may be polystyrene that can be dissolved by styrene or γ-butyrolactone.

The first active component may also be a (meth)acrylate monomer, and the powder material may be poly(meth)acrylate, cellulose, modified cellulose, Hydroxyl-containing polyvinyl alcohol, polyester, polyurethane, modified polyamide, etc.

The first active component can also be acryloyl morpholine, and the powder material can be polyurethane, cellulose, modified cellulose, hydroxyl-containing polyvinyl alcohol, etc. that can be partially dissolved by acryloyl morpholine.

The first active component can also be epichlorohydrin, epoxy diluent, and the powder material can also be polycarbonate, modified polyamide, cellulose ester, fiber that can be dissolved by epichlorohydrin or epoxy diluent. ether, etc.

The first active component can be γ-butyrolactone, and the powder material can also be polyacrylonitrile, cellulose acetate, polymethyl methacrylate, polyvinyl fluoride, polystyrene, etc. that can be dissolved by γ-butyrolactone.

The first active component can also be ε-caprolactone, and the powder material can also be chlorinated polyolefin, polyurethane, etc. that can be dissolved by ε-caprolactone.

Further, the active component may also include a second active component, the second active component has an active group; the second active component does not dissolve the powder material, that is, the second active component Completely insoluble powder materials. Optionally, the second reactive component can undergo a polymerization reaction by itself, or can participate in a polymerization reaction together with the first reactive component.

In this embodiment, based on the total mass of the liquid material being 100%, the mass ratio of the second active component in the liquid material is 5%-90%. For example, it can be 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% or 90%. Of course, the mass ratio can also be matched according to the actual usage. This is not limited. Preferably, the mass ratio of the second active component in the liquid material is 20%-70%. By controlling the proportion of the second active component in the liquid material, on the premise of ensuring that the first active component dissolves the powder material, the second active component and the first active component have complementary formation properties, so that the three-dimensional object has a higher ratio than only the first active component. The first active component is higher performance, such as reduced shrinkage.

It should be noted that, during the additive manufacturing process of the three-dimensional object, the second active component can be filled into the voids between particles of the powder material or inside the powder particles, thereby reducing the porosity of the molded object and increasing the molding density of the object. Further, the second active component can also form properties complementary to the first active component, so that the three-dimensional object has higher properties than when only the first active component is contained.

In a specific embodiment, the second active component is selected from monomers and/or prepolymers containing carbon-carbon double bonds, diluents and/or prepolymers containing epoxy groups, promoting epoxy groups At least one of monomers and/or prepolymers, polyols, cyclic lactones, sulfur heterocyclic compounds, and cyclic amide compounds that undergo ring-opening polymerization.

Exemplarily, the carbon-carbon double bond-containing prepolymer may be, for example, epoxy or (modified) acrylate prepolymer, polyester acrylate prepolymer, urethane acrylate prepolymer, pure Acrylic prepolymers, etc. The epoxy group-containing prepolymer can be, for example, E-51, E-41, etc.; the polyol prepolymer can be, for example, polyester diol, polyether diol, polycaprolactone diol Polyols, polycarbonate diols, etc. The cyclic lactone can be, for example, lactide, glycolide, etc. The cyclic lactone itself is solid and has poor solubility. Some compounds with a cyclic acetal structure, such as trioxymethylene, are solids themselves. (Meth)acrylate monomers have different solubility for different polymers due to their structural differences, such as isobornyl acrylate, isobornyl methacrylate, lauryl acrylate, lauryl methacrylate, cyclotrimethylol Propane acetal acrylate and the like have poor dissolving effect on polyurethane powder and are basically insoluble.

Optionally, the powder material is selected from at least one of polystyrene, poly(meth)acrylates, cellulose or some modified cellulose, polyvinyl alcohol containing hydroxyl groups, polyester, polyurethane, and modified polyamide. In this case, the second active component is selected from prepolymers containing double bonds, prepolymers containing epoxy groups, polyester diols, polyether diols, polycaprolactone diols, polycarbonates At least one of ester diols, solid lactones (lactide, glycolide, trioxymethylene, etc.); when the powder material is selected from cellulose acetate, the second active component is selected from isobornyl acrylate; When the powder material is selected from polyurethane, the second active component is selected from at least one of isobornyl acrylate, isobornyl methacrylate, lauryl acrylate, lauryl methacrylate and cyclotrimethylolpropane methyl acrylate. kind.

Further, the first active component and/or the second active component has a swelling group, the swelling group can participate in the polymerization reaction, and the swelling group is selected from the spirocyclic ether structure, At least one of spirocyclic orthocarbonate structure, spirocyclic orthoester structure, bicyclic orthoester structure and bicyclic lactone structure. For example, the active ingredient containing an intumescent group can be 3,9-diethyl-3,9propenyloxymethyl-1,5,7,11-tetraoxaspiro[5,5]undecane, 3,9-Dihydroxyethyl-3'9'-benzyl-1,5,7,11-tetraoxaspiro[5,5]undecane, etc.

Alternatively, the first reactive component and/or the second reactive component has a combination of reactive groups that can form the swelling group during the polymerization reaction.

The active group combination includes any one of the combination of a polyhydric alcohol group and an orthocarbonic acid diester group, and a combination of an epoxy group and a cyclic lactone structure.

It can be understood that the first active component and/or the second active component has a swelling group or a combination of active groups that can form a swelling group. During the polymerization reaction, the swellable group also undergoes a chemical reaction, so that the volume of the formed polymer expands, and the volume of the object does not shrink due to the curing process, and the final three-dimensional object has a higher dimensional accuracy. In addition, the volume expansion caused by the intumescent group can reduce the porosity of the powder material, densify the polymer powder, and improve the mechanical properties and mechanical strength of the object.

In this embodiment, the molecular structure of the first active component and/or the second active component may also contain a functional group that does not participate in the polymerization reaction, and the functional group may be a hydrophilic group. It is understood that, The hydrophilic group can improve the water solubility of the first active component and/or the second active component. Specifically, the hydrophilic group may be a hydroxyl group, a carboxyl group, or the like. The functional group can also be a group containing a flame retardant function, such as a phosphate group, etc., and the functional group can also be a group containing a bactericidal function, such as a quaternary ammonium salt group.

Further, the liquid material further includes a first auxiliary agent, the first auxiliary agent is used to initiate or catalyze the polymerization reaction of the active component, and the first auxiliary agent includes a free radical initiator, an anionic initiator, a cationic initiator and at least one of the catalysts. Specifically, based on the total mass of the liquid material being 100%, the mass proportion of the first auxiliary agent in the liquid material is 0%-10%, for example, it can be 0%, 1%, 2%, 3% %, 4%, 5%, 6%, 7%, 8%, 9% or 10%. Of course, the mass ratio can also be matched according to the actual usage, which is not limited here.

The free radical initiator can be a high temperature free radical initiator, such as: tert-butyl benzoyl peroxide, dodecanoyl peroxide, dicumyl peroxide, 2-ethylhexyl peroxide tert-amyl peroxide, tert-butyl 2-ethylhexyl peroxide, tert-butyl peroxide (TBHP), tert-amyl peroxide (TAHP), di-tert-butyl peroxide (DTBP), di-tert-amyl peroxide (DTAP), 3,3-bis(tert-butylperoxy)butyric acid acetic acid, 3,3-bis(tert-amylperoxy)butyric acid ethyl ester, tert-butyl peroxybenzoate (TBPB), 3,3 peroxide One or more of tert-butyl 5-trimethylhexanoate (TBPMH), tert-amyl peroxybenzoate (TAPB), tert-amyl peroxyacetate (TAPA), and the like.

The free radical initiator can also be a light free radical initiator, such as: benzoin ether, benzoin α,α-dimethylbenzyl ketal, α,α-diethoxyacetophenone, 2-hydroxy- 2Methyl-phenylacetone-1,1-hydroxy-cyclohexylbenzophenone, 2-hydroxy-2-methyl-p-hydroxyethyl ether phenylacetone-1, [2-methyl 1-(4 -Methylmercaptophenyl)-2-morpholinoacetone-1], [2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1], benzoylformate , 2,4,6-trimethylphenylacyl-ethoxy-phenylphosphine oxide, 2,4,6-trimethylphenylacyl-diphenylphosphine oxide, bis(2,4,6- One or more of trimethyl phenyl acyl) phenyl phosphine oxide, 4-p-toluene mercaptobenzophenone and the like.

The anionic initiator can be butyllithium, butyllithium oxide and the like.

The cationic initiator can be a mixture of triarylsulfonium hexafluorophosphate, blocked phosphate cationic initiator, 4-(phenylthio)phenyldiphenylsulfonium hexafluorophosphate, 4-isobutylbenzene Base-4'-methylphenyliodonium hexafluorophosphate, η6-cumene ferrocene (II) hexafluorophosphate mixture.

The catalyst can be ethylene glycol, stannous isooctanoate, stannous octoate, dibutyltin dilaurate, methyl fluorosulfonic acid, ethyl fluorosulfonic acid, methyl nitrobenzene sulfonic acid, methyl methanesulfonate Or tetraphenylporphyrin aluminides and so on.

Further, the liquid material also includes a second auxiliary agent, and the second auxiliary agent is selected from at least one of a leveling agent, a defoaming agent, a surfactant, a polymerization inhibitor, an antioxidant, a plasticizer, and a dispersing agent. . Specifically, based on the total mass of the liquid material being 100%, the mass ratio of the second auxiliary agent in the liquid material is 0.1%-30%, for example, it can be 0.1%, 1%, 5%, 10% %, 15%, 20%, 25% or 30%. Of course, the mass ratio can also be matched according to the actual usage, which is not limited here.

Exemplarily, the mass ratio of the leveling agent in the liquid material is 0.01%-3%; the mass ratio of the defoaming agent in the liquid material is 0.01%-3%; the mass ratio of the surfactant in the liquid material is 0.01%-3%; The ratio is 0%-5%; the mass ratio of the polymerization inhibitor in the liquid material is 0.05%-3%; the mass ratio of the antioxidant in the liquid material is 0.05%-3%; the plasticizer in the liquid material The mass ratio of the dispersant in the liquid material is 0%-25%; the mass ratio of the dispersant in the liquid material is 0%-5%.

It should be noted that the function of the leveling agent is to improve the fluidity of the liquid material and the wetting performance of the powder material, and at the same time adjust the surface tension of the liquid material to enable normal printing. In this application, as long as the leveling agent used can meet the above performance requirements, there is no restriction on which leveling agent to choose, for example, it can be BYK333, BYK377, BYK1798, BYK-UV3530, BYK-UV3575, BYK-UV3535, etc. , TEGO wet 500, TEGO wet 270, TEGO Glide450, TEGO RAD 2010, TEGO RAD 2011, TEGO RAD 2100, TEGO RAD 2200, etc.

The function of the defoamer is to inhibit, reduce and eliminate the bubbles in the liquid material. In this application, as long as the defoamer used can achieve the above effect, there is no restriction on which defoamer to choose. For example, it can be BYK055 and BYK088 of BYK. , BYK020, BYK025, etc., TEGO Airex 920, TEGO Airex 921, TEGO Airex 986, TEGO Foamex 810, TEGO Foamex N, etc. from Digao Company, Efka 7081, Efka7082, etc. from Efka Company.

The function of the polymerization inhibitor can be to improve the stability of the active component at high temperature, to prevent the active component from polymerizing in a non-printing state, and to improve the storage stability of the liquid material. For example, it can be hydroquinone, p-hydroxyanisole, p-benzoquinone, 2-tert-butyl hydroquinone, phenothiazine, etc., and can be Rayon's GENORAD*16, GENORAD*18, GENORAD*20, GENORAD*22, etc., BASF's Tinuvin234, Tinuvin770, Irganox245, Cytec S100, Cytec 130, etc., Ciba's Irgastab UV10, Irgastab UV 22, etc.

The function of the surfactant is to adjust the surface tension of the active component suitable for inkjet printing, and to improve the fluidity of the composition and the wetting performance of the powder material. For example, it can be BYK333, BYK325N, BYK345, BYK346, BYK370, BYK800D of BYK company, TEGO 4000, TEGO WET 260, TEGO WET 270, TEGO WET KL245, TEGO Airex 920, TEGO Airex 921 of Digao company.

The role of antioxidants is mainly to delay or inhibit the oxidation of polymers, such as 2,6-di-tert-butyl-4-methylphenol, β-tetra[3-(3,5-di-tert-butyl-4- Hydroxyphenyl)propionic acid] pentaerythritol ester, β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid n-octadecyl ester, 1,1,3-tris(2-methyl- 4-Hydroxy-5-tert-butylphenyl)butane, 4-[(4,6-dioctylthio-1,3,5-triazin-2-yl)amino]-2,6-di-tert-butyl Ethyl phenol, dilauryl thiodipropionate, tris(nonylphenyl) phosphite, triphenyl phosphite, 2-mercaptobenzimidazole, etc.

The main function of plasticizers is to improve the toughness of finished three-dimensional objects, such as dioctyl phthalate, butyl benzyl phthalate, diisononyl phthalate, and diisodecyl phthalate. , Diethyl adipate, dibutyl adipate, diisobutyl adipate, bis(2-butoxyethyl) adipate, bis(2-ethylhexyl) adipate , triethyl citrate, acetyl triethyl citrate, tributyl citrate, acetyl tributyl citrate.

The function of the dispersant is mainly to improve and improve the dispersion stability of the colorant. For example, there is no restriction on which dispersant to choose. Currently, there are many products on the market, such as BYK102, BYK108, BYK110, BYK180, BYK9133, BYK9076, BYK9131, Digao Dispers 655, Dispers675, Dispers 688, Dis750, Dispers 670 etc.

Further, the liquid material also includes a colorant, and based on the total mass of the liquid material being 100%, the mass proportion of the colorant in the liquid material is 0-10%, for example, it can be 0%, 1%, 2%, 4%, 6%, 8% or 10%. Of course, the mass ratio can also be matched according to the actual usage, which is not limited here.

When the liquid material does not contain a colorant, since the active component dissolves the powder material, the high molecular polymer formed by the polymerization reaction of the active component and the powder material are mixed at the molecular level. At this time, it is easy to obtain colorless or light-colored transparent three-dimensional objects.

Colored three-dimensional objects can be realized when the liquid material contains colorants. Colorants can be dyes or pigments. Pigment can be selected from CIPigment White 6, CIPigment Red 3, CIPigment Red 5, CIPigment Red 7, CIPigment Red 9, CIPigment Red 12, CIPigment Red 13, CIPigment Red 21, CIPigment Red 31, CIPigment Red 49:1, CIPigment Red 58:1, CIPigment Red 175; CIPigment Yellow 63, CIPigment Yellow 3, CIPigment Yellow 12, CIPigment Yellow 16, CIPigment Yellow 83; CIPigment Blue 1, CIPigment One or more of Blue 10, CI Pigment Blue B, Phthalocyanine Blue BX, Phthalocyanine Blue BS, CI Pigment Blue 61:1, etc.

The dyestuff can specifically be selected from CI acid red 37, CI acid red 89 (weak acid red 3B, 2BS), CI acid red 145 (weak acid scarlet GL), CI acid orange 67 (weak acid yellow RXL), CI acid orange 116 ( Acid orange AGT), CI acid orange 156 (weak acid orange 3G), CI acid yellow 42 (weak acid yellow Rs, acid yellow R), CI acid yellow 49 (acid yellow GR200), CI acid blue 277, CI acid blue 344 , CI Acid Blue 350, CI Acid Blue 9 (Brilliant Blue FCF), CI Green 17, CI Acid Green 28, CI Acid Green 41, CI Acid Green 81, CI Acid Violet 17 (Acid Violet 4BNS), CI Acid Violet 54 ( Weak acid brilliant red 10B), CI acid violet 48, CI acid brown 75, CI acid brown 98, CI acid brown 165, CI acid brown 348, CI acid brown 349, CI acid black 26, CI acid black 63, CI acid black 172, CI acid black 194, CI acid black 210, CI acid black 234, CI acid black 235, CI acid black 242, etc.

In the process of additive manufacturing of the three-dimensional object in this embodiment, the active components undergo a polymerization reaction to form the slice layer of the three-dimensional object, and no small molecular substances remain in the manufactured three-dimensional object, and no small molecular substances are precipitated during use, thus achieving a safe and environmentally friendly environment. Require.

The following are examples of components of several liquid materials provided in the examples of this application:

Embodiment 1:

Example 2:

Example 3:

Example 4:

Example 5:

Example 6:

Example 7:

Comparative Example 1:

Performance Testing:

Using the liquid materials provided in Examples 1-5 and Comparative Example 1 and the same powder material-polyurethane powder (TPU powder) and using the same three-dimensional object additive manufacturing process to print 6 test samples, remember S1~S5 and Ref1 respectively ;

Using the liquid material and powder material-cellulose acetate provided in Example 6 and using the same three-dimensional object additive manufacturing process to print 1 test strip, denoted as S6;

Using the liquid material and powder material-polyurethane powder provided in Example 7 and using the same three-dimensional object additive manufacturing process to print 1 test strip, denoted as S7;

The above-mentioned 8 test specimens are subjected to tensile strength test, elongation at break test, and shrinkage test, and the test results are shown in Table 1; wherein

The tensile strength test is determined according to GB/T 1040.2-2006 Determination Standard of Plastic Tensile Properties.

The elongation at break test is determined according to GB/T 1040.2-2006 Determination Standard of Plastic Tensile Properties.

Shrinkage rate test method, print 100mm×10mm×3mm cuboid objects, measure the length of the cuboid, shrinkage rate=((cuboid length-100mm)/100)*100%.

Density test: Using the pycnometer method, with water as the reference, test the density of the sample at 25°C.

Table 1. Summary table of test data for each embodiment

Test items	S1	S2	S3	S4	S5	S6	S7	Ref1
Tensile strength (MPa)	6.91	6.93	6.12	6.16	1.23	10	8.81	0.87

Elongation at break (%)	261	259	235	241	57	twenty one	236	41
Shrinkage(%)	-5.55	-4.85	-1.51	-0.87	-0.73	-0.71	-1.13	-0.65
Density (g/cm 3 )	1.164	1.164	1.107	1.108	0.966	1.211	1.164	0.897

The test strips obtained by printing the same powder material (polyurethane powder) in combination with the liquid materials provided in Examples 1-5 and Example 7 and Comparative Example 1 can be seen from Table 1. The liquid materials provided in Examples 1-5 contain the first An active component (acryloyl morpholine), the first active component dissolves the polyurethane powder, the liquid material provided in Example 7 contains the first active component (ε-caprolactone), and the ε-caprolactone dissolves the polyurethane powder , the liquid material provided in Comparative Example 1 does not contain the first active component (acryloyl morpholine), but only contains the second active component. The second active component does not dissolve the polyurethane powder, and the final printed test strip S1～ The tensile strength and elongation at break of S5 and S7 are higher than those of Ref1. It can be seen that the liquid material contains the first active component that can dissolve the powder material, and the high molecular polymer formed by the polymerization reaction of the first active component forms a blend with the powder material, especially with the dissolved powder material reaching the molecular level. Mixed to form a polymer alloy, which can effectively improve the mechanical strength of the final shaped object.

In addition, the liquid materials provided in Examples 1-5 are combined with test strips printed from the same powder material (polyurethane powder). The liquid materials provided in Examples 1-5 contain the same first active component (acryloyl morpholine). ); Wherein, the tensile strength, the elongation at break of the test specimen S5 are all lower than the tensile strength and the elongation at break of the test specimen S1～S4, according to the liquid composition table of embodiment 5, it can be seen that in the liquid material, the The mass proportion of the first active component is 10%, which is less than the mass proportion of the first active component in Examples 1-4. Understandably, due to the small proportion of the first active component, it is difficult to dissolve the powder material as much as possible, and the content of the formed polymer alloy is small, resulting in the mechanical strength of the final formed test strip S5 is lower than that of S1-S4. .

It can be seen from Examples 2 to 4 that under the premise that the first active component is both acryloyl morpholine, the proportion of the second active component in Example 2 is less than 20%, and Examples 3 and 2 The proportion of the second active component in 4 is between 20% and 70%. Under the condition that the tensile strength and the elongation at break are basically the same, the shrinkage rate is reduced and the printing accuracy is improved.

The first active component (ε-caprolactone) in the liquid material provided in Example 6 can dissolve the powder material (cellulose acetate), effectively reducing the molding temperature of the existing cellulose acetate powder for three-dimensional printing. The melting temperature of cellulose acetate is about 240°C. The liquid material provided in Example 6 is combined with cellulose acetate for three-dimensional molding printing. The molding temperature is 100°C to 140°C, which reduces the molding temperature; The tensile strength is higher than that of the test strips printed when the improved liquid material of Comparative Example 1 does not contain the first active component.

The liquid material provided in Example 7 can also dissolve the chlorinated polyolefin powder material.

The liquid material provided in Example 1 contains only the first active component, and Examples 2 to 7 contain both the first active component and the second active component, and the test strips obtained by printing the liquid materials provided in Examples 2 to 7 The shrinkage rate is lower than the shrinkage rate of the test strip obtained by printing the liquid material provided in Example 1.

From the density data of Examples 1-7 and Comparative Example 1 above, it can be seen that the density of the three-dimensional object printed from the liquid material containing the first active component is higher than that of the three-dimensional object printed from the liquid material not containing the first active component. Since the first active component dissolves the powder material, the porosity of the printed object is reduced, and the molding density of the object is improved.

FIG. 1 is a schematic structural diagram of a three-dimensional object additive manufacturing device provided by the application. As shown in FIG. 1 , an embodiment of the present application further provides a three-dimensional object additive manufacturing device. The device includes:

A powder supply part 2 for supplying powder material to form a powder material layer;

a forming platform 3 for carrying the powder material layer;

a material dispenser 6 for applying a liquid material on the powder material layer according to the layer printing data, the liquid material dissolving at least part of the powder material, the liquid material comprising an active component capable of polymerizing;

An energy supply device 8 for supplying energy to the powder material layer, so that the active component in the liquid material undergoes a polymerization reaction, and the powder material does not undergo a polymerization reaction and does not undergo a polymerization reaction with the active component , the region where the liquid material is applied in the powder material layer is formed to obtain a slice layer of a three-dimensional object.

In this embodiment, the powder supply component 2 includes a powder storage chamber 23 , a lifter 22 and a powder spreader 21 . The powder storage chamber is used to store powder materials 0 . The powder storage chamber 23 has a movable support plate 231 inside. The lifter 22 It is connected with the support plate 231, which can drive the support plate 231 to rise or fall in the Z direction; the powder spreader 21 is used to spread the powder material 0 in the powder storage cavity 23 onto the forming platform 3 to form the powder material layer L0. The pulverizer 21 can be a pulverizing stick or a scraper.

The material distributor 6 is an inkjet print head, and the print head can be a single-pass print head or a multi-channel print head. In this embodiment, the number of print heads is related to the type of liquid material used and the amount of liquid material to be applied, For example, when the liquid material includes functional materials of different colors, the liquid materials of different colors are ejected through different print heads or different channels of the same print head. For example, when the amount of liquid material that needs to be applied is larger than the volume of a single ink droplet to meet the demand, in order to improve printing efficiency, multiple print heads or multiple channels can be used to eject the same kind of material at the same time.

The energy provided by the energy supply device 8 may be radiant energy or thermal energy, and the energy supply device may be selected from at least one of ultraviolet lamps, infrared lamps, microwave emitters, heating wires, heating sheets, and heating plates. It should be noted that the specific choice of which form of energy supply device and the type of active components in the liquid material is related to the type of active components and the type of the first auxiliary, when the active components in the liquid material undergo photopolymerization. During the reaction, the energy supply device 8 provides radiant energy such as ultraviolet radiation at this time, and the photopolymerization reaction of active components is triggered by ultraviolet radiation; when the thermal polymerization reaction of the active components occurs in the liquid material, the energy supply device provides thermal energy at this time. Such as infrared lamps, microwaves, heating wires, heating sheets, and heating plates, which can initiate thermal polymerization of active components through thermal energy.

Optionally, the device for additive manufacturing of three-dimensional objects further includes a lifting mechanism 4, which is connected to the forming platform 3 and drives the forming platform 3 to ascend or descend in a vertical direction.

Optionally, the apparatus for additive manufacturing of three-dimensional objects further comprises a preheating part 5 and/or a heating part 10, and the preheating part 5 is used for preheating the powder material layer to promote active groups in the liquid material. Dissolving the powder material; the heating component 10 is used for heating the powder material layer after the liquid material is applied, so as to promote the active components in the liquid material to dissolve the powder material. The preheating part 5 and the heating part 10 can be selected from at least one of ultraviolet lamps, infrared lamps, microwave emitters, heating wires, heating sheets, and heating plates, respectively.

In this embodiment, the preheating part 5 , the material distributor 6 , the heating part 10 and the energy supply device 8 can be installed on the guide rail 11 in sequence and can move on the guide rail 11 . In this embodiment, when the energy supply device 8 is a device for providing thermal energy, the heating component 10 can be eliminated, and the energy supply device 8 is used to heat the powder material layer applied with the liquid material and initiate a polymerization reaction.

The three-dimensional object additive manufacturing apparatus may further comprise a temperature monitor (not shown in the figures) for monitoring the temperature of the powder material layer.

Further, the three-dimensional object additive manufacturing device further includes a controller 9, which is used to control the powder supply part 2, the material distributor 6, the energy supply device 8, the preheating part 5, the operation of at least one of the heating component 10 and the temperature monitor. For example, the temperature monitor feeds back the monitored temperature to the controller 9, and the controller controls the amount of energy provided by the preheating part 5 and/or the heating part 10 and the energy supply device 8 according to the information fed back by the temperature monitor.

FIG. 2 is a schematic flowchart of the method for additive manufacturing of a three-dimensional object provided by the application, as shown in FIG. 2 , and the method for additive manufacturing of a three-dimensional object is further explained in detail below in conjunction with a device for additive manufacturing of a three-dimensional object:

Step S01 , acquiring a digital model of a three-dimensional object, slicing and layering the digital model of the three-dimensional object, obtaining a plurality of slice layers and layer image data, and generating layer print data according to the layer image data.

In a specific implementation manner, the original data of the three-dimensional object can be obtained by scanning and three-dimensional modeling can be performed to obtain a digital model of the three-dimensional object, or the digital model of the three-dimensional object can be obtained by designing and constructing a three-dimensional object model, and the digital model can be formatted. Conversion, such as converting into STL format, PLY format, WRL format and other formats that can be recognized by slicing software, and then use slicing software to slice and layer the model to obtain slice layer image data, and process the layer image data to obtain the representation of the object. layer print data. The layer print data includes information representing the shape of the object, and/or information representing the color of the object.

In step S10, a powder material layer is formed by using a powder material. As shown in FIG. 3 a , in a specific embodiment, the powder supply part 2 may be used to provide powder material 0 to the forming platform 3 to form a powder material layer L0 .

Step S11, preheating the powder material layer. As shown in FIG. 3b, in a specific embodiment, after the powder material layer L0 is formed, the preheating component 5 preheats the powder material layer L0 to increase the temperature of the powder material, which is helpful for the powder material layer L0 in step S20. The rate of dissolution of the active ingredient into the powder material is facilitated when the liquid material is applied. The preheating temperature is related to the properties of the powder material used, preferably the preheating temperature is below the melting point or melting temperature of the powder material. It can be understood that by controlling the preheating temperature to be lower than the melting point or melting temperature of the powder material in this embodiment, the powder material can be prevented from sticking, which is conducive to the penetration of the liquid material into the gaps between the powder material particles, thereby improving the active component’s effect on the powder. Dissolution rate of powder material.

Step S20, applying a liquid material on the powder material layer according to the layer printing data. As shown in FIG. 3c, in a specific embodiment, the material dispenser 6 can apply the liquid material 7 on the powder material layer L0 according to the layer printing data to form a layer patterned area 31; the liquid material 7 penetrates into the gap of the powder material and covers The surface layer of the powder material, thereby wetting the surface of the powder material.

The liquid material 7 includes an active component capable of polymerizing, which dissolves at least part of the powder material. As shown in FIG. 3d, the powder material in the layer patterned region 31 is dissolved by the active component, so that the powder material and the active component are mixed at the molecular level.

Step S21, heating the powder material layer after applying the liquid material to promote the active components in the liquid material to dissolve the powder material. As shown in Fig. 3e, the heating member 10 heats the powder material layer L0 on the powder material layer L0 applied with the liquid material 7, which further promotes the active components to dissolve the powder material, so that the powder material can be completely dissolved in a short time, and the powder material and the The active components are mixed at the molecular level and mixed evenly, so that the active components undergo a polymerization reaction, and the formed polymer and powder materials also reach the molecular level mixing, thereby forming a polymer alloy and improving the mechanical strength of the formed three-dimensional object.

Step S30 , supplying energy to the powder material layer to cause a polymerization reaction of the active components in the liquid material, and forming the region where the liquid material is applied in the powder material layer to obtain a slice layer of a three-dimensional object. As shown in FIG. 3f , in a specific embodiment, the energy supply device 8 provides energy to the powder material layer L0 to polymerize the active components to form a high molecular polymer to form the slice layer Lw of the three-dimensional object.

As shown in Figure 3f, the energy provided by the energy supply device 8 can further promote the active components to dissolve the powder materials, the active components undergo a polymerization reaction to form high molecular polymers, and the formed high molecular polymers are blended with the powder materials. In particular, it is mixed with dissolved powder materials at the molecular level to form polymer alloys, so that there is a good connection between powder materials, between powder materials and polymers of active components, and between printing layers and layers. . In addition, the formed high molecular polymer can be mixed with the powder material to obtain a "sea-island structure" or a homogeneous structure with good interface bonding, which improves the mechanical strength of the three-dimensional object.

In the process of additive manufacturing of the three-dimensional object in this embodiment, the material distributor 6 applies the liquid material 7 on the powder material layer L0 according to the layer printing data, and the spray amount of the liquid material can be adjusted to realize three-dimensional objects with different properties in different regions.

After step S30, the method further includes: step S40, confirming whether the current slice layer is the last layer.

When it is confirmed that the current slicing layer is not the last layer, forming the powder material layer and applying the liquid material are repeated, and energy is supplied to at least part of the powder material layer applied with the liquid material, and the obtained multiple slicing layers are stacked layer by layer to form a three-dimensional object.

As shown in Figure 3g, in the process of printing a three-dimensional object, after each slice layer L _W of a three-dimensional object is formed, the forming platform 3 is driven by the lifting mechanism 4 to descend by at least one layer thickness, and the powder supply part 2 provides a new The powder material layer L0 is on top of the previously formed layer, the liquid material dispenser 6 applies the liquid material 7 according to the layer printing data to form a new layer patterned area 31 on the powder material layer L0, the energy supply device 8 supplies energy to the layer pattern The region 31 is processed to form a new slice layer of the three-dimensional object; this process is repeated to form the three-dimensional object W.

Step S50, when it is confirmed that the current slice layer is the last layer, heat treatment is performed on the formed three-dimensional object to improve the mechanical strength of the three-dimensional object.

In a specific embodiment, after the three-dimensional object w is obtained, the whole three-dimensional object w is heated by using the preheating part 5 and/or the heating part 10, or the whole three-dimensional object w is taken out and placed in a heating furnace for heating (Fig. Not shown), on the one hand, the powder dissolution effect is better, the porosity between powder materials is reduced, and the compactness of the molded object is higher, and on the other hand, the active component is further polymerized, thereby improving the tensile strength of the three-dimensional object w.

The embodiment of the present application further provides a slice layer of a three-dimensional object, where the slice layer of the three-dimensional object is formed by printing the three-dimensional object additive manufacturing process using the above-mentioned three-dimensional molding material.

An embodiment of the present application further provides a three-dimensional object, wherein the three-dimensional object is formed by printing the three-dimensional object additive manufacturing process using the above-mentioned material for three-dimensional forming.

The above are only preferred embodiments of the present application, and are not intended to limit the present application. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present application shall be included in the protection of the present application. within the range.

Claims (18)

1. A material for three-dimensional molding, characterized in that the material comprises:

   a liquid material that includes an active component that can polymerize to form a polymer; and

   A powder material that does not polymerize itself and does not polymerize with the active component, and the liquid material dissolves at least a portion of the powder material.
2. The material according to claim 1, wherein the powder material is selected from the group consisting of polystyrene, polyvinyl chloride, polyacrylonitrile, acrylonitrile-styrene-acrylate copolymer, polyamide, polyester, polyurethane, Poly(meth)acrylates, polymethyl(meth)acrylates, polyvinyl fluoride, chlorinated polyolefins, block and/or graft copolymers containing At least one of vinyl alcohol, cellulose, and modified cellulose.
3. The material according to claim 1, wherein the mass ratio of the active component in the liquid material is 55%-99.5%.
4. The material according to claim 1, wherein the active component has an active group that can participate in a polymerization reaction, and the active group includes a carbon-carbon double bond, a hydroxyl group, a carboxyl group, a thiirane group, At least one of an isocyanate group, a carbonate-based group, an epoxy group, a cyclic amide group, a cyclic lactone structure, a cyclic acid anhydride structure, and a cyclic acetal structure.
5. 5. The material of claim 4, wherein the active component comprises a first active component having a reactive group, the first active component dissolving at least a portion of the powder Material.
6. The material according to claim 5, wherein the mass ratio of the first active component in the liquid material is 10%-95%; and/or,

   The first active component is selected from the group consisting of carbon-carbon double bond-containing monomers, epoxy-containing groups and compositions that promote ring-opening polymerization of epoxy groups, cyclic lactones, sulfur heterocyclic compounds, and carbonates At least one of a compound and a cyclic amide compound.
7. The material according to claim 5, wherein the active component further comprises a second active component, the second active component has an active group; the second active component does not dissolve the powder Material.
8. The material according to claim 7, wherein the mass ratio of the second active component in the liquid material is 5%-90%; and/or,

   The second active component is selected from monomers and/or prepolymers containing carbon-carbon double bonds, diluents and/or prepolymers containing epoxy groups, and monomers that promote ring-opening polymerization of epoxy groups. At least one of the compounds and/or prepolymers, polyols, cyclic lactones, sulfur heterocyclic compounds, and cyclic amide compounds.
9. The material according to claim 7, wherein the first active component and/or the second active component has a swelling group, the swelling group can participate in a polymerization reaction, and the swelling The sexual group is selected from at least one of spirocyclic ether structure, spirocyclic orthocarbonate structure, spirocyclic orthoester structure, bicyclic orthoester structure and bicyclic lactone structure.
10. The material according to claim 9, characterized in that the first active component and/or the second active component has a combination of active groups that can form the Expansion group.
11. The material according to claim 10, wherein the active group combination comprises any one of a combination of a polyol group and an orthocarbonic acid diester group, and a combination of an epoxy group and a cyclic lactone structure kind.
12. The material according to claim 1, wherein the liquid material further comprises a first auxiliary agent comprising at least one of a free radical initiator, an anionic initiator, a cationic initiator and a catalyst and/or, the mass proportion of the first auxiliary agent in the liquid material is 0%-10%.
13. The material according to claim 1, wherein the liquid material further comprises a second adjuvant, and the second adjuvant comprises a leveling agent, a defoaming agent, a polymerization inhibitor, a surfactant, an antioxidant, At least one of plasticizer and dispersant; and/or, the mass proportion of the second auxiliary agent in the liquid material is 0.1%-30%.
14. The material according to claim 1, wherein the liquid material further comprises a colorant, and the colorant accounts for 0%-10% by mass in the liquid material.
15. The material according to claim 2, wherein the average particle size of the powder material is 1 um to 400 um.
16. The material according to claim 2, wherein the powder material further comprises an additive, and the additive comprises at least one of a flow aid and a filler.
17. A sliced layer of a three-dimensional object, characterized in that, the sliced layer of the three-dimensional object is formed by using the material according to any one of claims 1 to 16 by printing a three-dimensional object additive manufacturing process.
18. A three-dimensional object, characterized in that, the three-dimensional object is formed by printing a three-dimensional object additive manufacturing process using the material according to any one of claims 1 to 16.

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