CN112480851A - UV (ultraviolet) adhesive for reducing curing shrinkage and preparation method thereof - Google Patents

UV (ultraviolet) adhesive for reducing curing shrinkage and preparation method thereof Download PDF

Info

Publication number
CN112480851A
CN112480851A CN202011319052.7A CN202011319052A CN112480851A CN 112480851 A CN112480851 A CN 112480851A CN 202011319052 A CN202011319052 A CN 202011319052A CN 112480851 A CN112480851 A CN 112480851A
Authority
CN
China
Prior art keywords
powder
adhesive
nano
diluent
curing shrinkage
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202011319052.7A
Other languages
Chinese (zh)
Inventor
黄延禄
邓鸿信
杨永强
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South China University of Technology SCUT
Original Assignee
South China University of Technology SCUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by South China University of Technology SCUT filed Critical South China University of Technology SCUT
Priority to CN202011319052.7A priority Critical patent/CN112480851A/en
Publication of CN112480851A publication Critical patent/CN112480851A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C09J163/10—Epoxy resins modified by unsaturated compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/103—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing an organic binding agent comprising a mixture of, or obtained by reaction of, two or more components other than a solvent or a lubricating agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • C04B35/111—Fine ceramics
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/26—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on ferrites
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/486—Fine ceramics
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63452—Polyepoxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
    • C04B2235/3212—Calcium phosphates, e.g. hydroxyapatite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3275—Cobalt oxides, cobaltates or cobaltites or oxide forming salts thereof, e.g. bismuth cobaltate, zinc cobaltite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3279—Nickel oxides, nickalates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5454—Particle size related information expressed by the size of the particles or aggregates thereof nanometer sized, i.e. below 100 nm
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2244—Oxides; Hydroxides of metals of zirconium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Civil Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention discloses a UV adhesive for reducing curing shrinkage and a preparation method thereof, wherein the UV adhesive comprises the following components in percentage by weight: 40% -57% of prepolymer, 16% -38% of diluent, 4% -19% of swelling monomer, 0.8% -7% of photoinitiator and 5% -20% of nano-scale powder, wherein the type of nano-scale powder is the same as that of powder bed powder in three-dimensional printing. Adding the prepolymer, the diluent, the expansion monomer and the photoinitiator into the same container according to the weight percentage, and stirring the mixture until a uniform mixed solution A is formed; and selecting the type of the nano-scale powder according to the type of the powder bed powder, adding the nano-scale powder into the mixed solution A according to the weight percentage, uniformly mixing, and removing bubbles to finish the preparation of the UV adhesive. The nano-scale powder which is the same as the powder bed powder is adopted, the mechanical property of the product can be effectively improved, the shrinkage rate is reduced, particularly, when post-treatment such as sintering and the like is required, other impurities are not introduced, and the mechanical properties such as density, strength and the like are obviously improved.

Description

UV (ultraviolet) adhesive for reducing curing shrinkage and preparation method thereof
Technical Field
The invention relates to the technical field of adhesives, in particular to a UV adhesive for reducing curing shrinkage and a preparation method thereof.
Background
The 3DP method refers to a three-dimensional printing method in which a binder is sprayed onto a powder bed to bind the powder and form the powder layer by layer to obtain a final product. Conventional binders include mainly organic liquid binders, inorganic binders, metal salt binders, hydration binders. However, the conventional adhesives generally have the disadvantages of long curing time and low processing efficiency, and the occurrence of Ultraviolet (UV) curing adhesives solves the problem. The UV adhesive is also called photosensitive resin, can be cured under the irradiation of ultraviolet light, has very short curing time, greatly improves the production efficiency, and simultaneously has the advantages that the reaction conditions are easy to meet, so that the UV adhesive has great brilliance in 3 DP.
The photosensitive resin is a liquid mixture consisting of a prepolymer, a diluent, an ultraviolet light initiator and other auxiliary agents. The prepolymer is a main component of the photosensitive resin, and determines the viscosity of the liquid photosensitive resin before curing, the volume shrinkage generated in the curing process, the hardness, the impact strength, the tensile strength and other important mechanical properties of a cured product. The radical type photosensitive resin is the most commercially available photosensitive resin at the earliest time, and the most widely used photosensitive resin in the field of 3D printing is also the radical type at present. The resin is obtained by polymerizing an acrylate prepolymer and a free radical photoinitiator. The photoinitiator decomposes free radicals under the action of ultraviolet light, and the free radicals initiate the double bonds of the acrylate to break, so that the double bonds are mutually polymerized to form the polymer with larger molecular weight. The main advantages of the radical type photosensitive resin are: the curing speed is high, the variety of the photosensitizer is high, but the problems of large volume shrinkage during polymerization, large internal stress of a product, easy buckling deformation and the like exist, and the application of the photosensitive resin in some fields with high requirements on the precision of workpieces is severely limited. Therefore, reducing the volume shrinkage of photosensitive resins is a constant research focus in this field.
In order to reduce the curing shrinkage of the photosensitive resin, inorganic powder or inert non-reactive resin is generally added.
The inorganic powder occupies a part of the space because of not participating in the reaction, and can significantly reduce the volume shrinkage and enhance the properties such as strength and the like. The common use of the inorganic powder is silicon dioxide, titanium dioxide, aluminum silicate, barium sulfate, nano zinc oxide and the like, but the essential difference between the inorganic powder and the organic photosensitive resin causes that the inorganic powder and the organic photosensitive resin cannot be completely compatible, most of the inorganic powder is suspended in a photosensitive resin system through high-speed dispersion, so that the inorganic powder has high requirements on equipment during dispersion, and the conditions of agglomeration, precipitation and the like are easy to occur during use, thereby seriously affecting the stability of the product. Further, when post-sintering treatment is required, the photosensitive resin needs to be completely decomposed, and the inorganic powder cannot be decomposed, and in such a case, it cannot be used.
The principle of adding the inert resin is the same as that of adding the inorganic powder, and compared with inorganic fillers, the common aldehyde ketone resin, high molecular weight epoxy resin, rosin resin, vinyl chloride-vinyl acetate resin and the like have the advantages that the compatibility of the inert resin and photosensitive resin is greatly improved, the influence on the performance of the whole system is small, and the stability is good, but the types of the inert resin which can be selected at present are not many, and the inert resin is not suitable for all photosensitive resin systems.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a UV adhesive for reducing curing shrinkage rate, and solves the problem of volume shrinkage of the conventional photosensitive resin.
The other technical scheme of the invention is as follows: provides a preparation method of the UV adhesive for reducing curing shrinkage.
The technical scheme of the invention is as follows: a UV bonding agent for reducing curing shrinkage comprises the following components in percentage by weight: 40% -57% of prepolymer, 16% -38% of diluent, 4% -19% of swelling monomer, 0.8% -7% of photoinitiator and 5% -20% of nano-scale powder, wherein the type of nano-scale powder is the same as that of powder bed powder in three-dimensional printing.
Further, the prepolymer is at least one of epoxy acrylic resin, polyester acrylic resin, polyurethane acrylic resin, bisphenol A epoxy acrylic resin, novolac epoxy acrylate and modified epoxy acrylic resin.
Further, the diluent is at least one of a monofunctional diluent, a bifunctional diluent, and a polyfunctional diluent.
Further, the photoinitiator is at least one of a radical photoinitiator and a cationic photoinitiator.
Further, the swelling monomer is at least one of spiro orthocarbonate, bicyclo orthoester and spiro orthoester.
Further, the nanoscale powder is made of a metal material or a ceramic material.
Further, the metal material is one of 304 stainless steel, 316 stainless steel, titanium alloy, nickel and nickel alloy, and the ceramic material is one of alumina, zirconia, cobalt oxide, nickel oxide, iron oxide, calcium phosphate and hydroxyapatite.
The other technical scheme of the invention is as follows: the preparation method of the UV adhesive comprises the following steps:
step S1: adding the prepolymer, the diluent, the expansion monomer and the photoinitiator into the same container according to the weight percentage, and stirring the mixture until a uniform mixed solution A is formed;
step S2: and selecting the type of the nano-scale powder according to the type of the powder bed powder, adding the nano-scale powder into the mixed solution A according to the weight percentage, uniformly mixing, and removing bubbles to finish the preparation of the UV adhesive.
Further, in the step S2, the nano-scale powder and the mixed solution a are uniformly mixed by adopting manual stirring, ultrasonic vibration, magnetic stirring or mechanical rotation stirring, and the mixing time is 0.5 to 2 hours.
Further, in the step S2, the solution obtained by uniformly mixing the nanoscale powder and the mixed solution a is placed in a vacuum oven for drying and degassing, wherein the drying temperature is 30-60 ℃.
Compared with the prior art, the invention has the following beneficial effects:
the UV adhesive for reducing the curing shrinkage rate is prepared by complementing the curing expansion characteristic of an expansion ring-opening monomer UV material with the curing shrinkage characteristic of other types of UV materials and adding a nano-scale powder material, so that the UV adhesive with short curing time, good mechanical property and stable shrinkage property is obtained. The same powder can effectively improve the mechanical property of the product and reduce the shrinkage rate, and particularly when the post-treatment such as sintering and the like is needed, the nano-scale powder which is the same as the powder bed powder is adopted, other impurities cannot be introduced, and the mechanical properties such as density, strength and the like of the powder are obviously improved.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The embodiment provides a UV adhesive for reducing curing shrinkage, which comprises the following components in percentage by weight: 40% -57% of prepolymer, 16% -38% of diluent, 4% -19% of swelling monomer, 0.8% -7% of photoinitiator and 5% -20% of nano-scale powder, wherein the type of nano-scale powder is the same as that of powder bed powder in three-dimensional printing.
The prepolymer is at least one of epoxy acrylic resin, polyester acrylic resin, polyurethane acrylic resin, bisphenol A epoxy acrylic resin, novolac epoxy acrylate and modified epoxy acrylic resin; the diluent is at least one of monofunctional diluent, bifunctional diluent and polyfunctional diluent; the photoinitiator is at least one of a free radical photoinitiator and a cationic photoinitiator; the expansion monomer is at least one of spiro orthocarbonate, bicyclo orthoester and spiro orthoester; the nano-scale powder is made of metal materials or ceramic materials.
Description of the principle of reducing curing shrinkage: most UV adhesives experience varying degrees of volume shrinkage after curing. The volume shrinkage is caused by a change in the intermolecular distance, and before curing, the intermolecular force is van der waals force, and after curing, covalent bonds are formed between the original molecules, and the intermolecular distance is changed from the van der waals distance to the covalent distance. The expansion ring-opening monomer is a monomer which can be subjected to ring-opening polymerization through cations or free radicals, and the monomer does not undergo polymerization shrinkage but also expands in certain volume before and after polymerization. The expansion ring-opening monomer is added into a photosensitive resin system, so that the polymerization shrinkage of the resin can be obviously reduced.
The nano-scale powder is made of metal materials or ceramic materials. The metal material is one of 304 stainless steel, 316 stainless steel, titanium alloy, nickel and nickel alloy, and the ceramic material is one of alumina, zirconia, cobalt oxide, nickel oxide, ferric oxide, calcium phosphate and hydroxyapatite.
When 3D printing of the ceramic material is carried out, ceramic powder which is the same as the powder bed material is crushed and ground into nanoscale powder, and then the nanoscale powder is added into photosensitive resin; when 3D printing of metal materials is processed, the same metal powder is ground to nanoscale powder and then added into photosensitive resin. The same powder can effectively improve the mechanical property of the product and reduce the shrinkage rate. Especially when post-treatment such as sintering is needed, the nano-scale powder which is the same as the powder bed powder is adopted, other impurities are not introduced, and the mechanical properties such as density, strength and the like of the powder bed powder are obviously improved.
Example 1
When the powder bed powder for three-dimensional printing is Al2O3When ceramic powder is prepared, 100g of di-n-butyltin oxide, 600g of toluene and 60g of trimethylolpropane are uniformly mixed, the mixture is heated to 120 ℃ to react for 12 hours or until no water is generated, heating is stopped, carbon disulfide is slowly dripped after the mixture is cooled to room temperature, the temperature is slowly raised to 100 ℃ after the dripping is finished, stirring and reflux reaction are carried out for 12 hours, the toluene is removed by reduced pressure distillation, sufficient n-hexane is used for 3 times to wash reaction liquid, 150g of toluene is used for heating and dissolving, re-precipitation is carried out, and white solid is obtained after vacuum dryingThe expansion monomer of (1); weighing 600g of epoxy acrylic resin, 200g of tripropylene glycol diacrylate (TPGDA), 100g of the expanded monomer prepared in the previous step and 60g of the photoinitiator 1173, mixing at normal temperature, and stirring with a glass rod until the components are mixed uniformly; 100g of Al having an average diameter of 75nm were added2O3And (3) stirring the ceramic powder for 2 hours at the frequency of 10KHZ by using an ultrasonic stirrer under the dark condition, and then removing air bubbles in a vacuum oven at the temperature of 30 ℃ to obtain the required UV adhesive.
Example 2
When the powder bed powder for three-dimensional printing is 316L stainless steel powder, 500g of epoxy acrylic resin, 200g of tripropylene glycol diacrylate (TPGDA), 80g of spiro orthocarbonate and 50g of photoinitiator 1173 are mixed at normal temperature and stirred by a glass rod until the mixture is initially mixed uniformly; then 80g of 316L stainless steel powder with the average diameter of 40nm is added, the mixture is stirred for 30min under the dark condition by an ultrasonic stirrer at the frequency of 20KHZ, and then air bubbles are removed in a vacuum oven at the temperature of 30 ℃ to obtain the required UV adhesive.
Example 3
When the powder bed powder for three-dimensional printing is Al2O3When the ceramic powder is prepared, 440g of bisphenol A epoxy acrylate, 120g of tripropylene glycol diacrylate (TPGDA), 130g of acryloyl morpholine (ACMO), 120g of spiro orthocarbonate, 70g of bicyclo orthoester and 70g of photoinitiator 261 are mixed at normal temperature and stirred by a glass rod until the materials are uniformly mixed initially; 50g of Al having an average diameter of 20nm were added2O3And (3) stirring the ceramic powder for 60min at the frequency of 50KHZ by using an ultrasonic stirrer under the dark condition, and then removing air bubbles in a vacuum oven at the temperature of 30 ℃ to obtain the required UV adhesive.
Example 4
When the powder bed powder for three-dimensional printing is zirconia ceramic powder, 205g of epoxy acrylic resin, 150g of tripropylene glycol diacrylate (TPGDA), 15g of spiro orthocarbonate, 5g of spiro orthoester and 25g of photoinitiator 1173 are mixed at normal temperature and stirred by a glass rod until the mixture is initially mixed uniformly; then 100g of zirconia ceramic powder with the average diameter of 50nm is added, the mixture is stirred for 30min under the dark condition by an ultrasonic stirrer at the frequency of 50KHZ, and then air bubbles are removed in a vacuum oven at the temperature of 30 ℃ to obtain the required UV adhesive.
Example 5
When the powder bed powder for three-dimensional printing is zirconia ceramic powder, 285g of epoxy acrylic resin, 100g of tripropylene glycol diacrylate (TPGDA), 25g of spiro orthocarbonate, 20g of bicyclo orthoester, 5g of spiro orthoester and 15g of photoinitiator 1173 are mixed at normal temperature and stirred by a glass rod until the mixture is initially mixed uniformly; then adding 50g of zirconia ceramic powder with the average diameter of 50nm, stirring for 30min at the frequency of 50KHZ by using an ultrasonic stirrer under the dark condition, and then removing bubbles in a vacuum oven at the temperature of 30 ℃ to obtain the required UV binder.
As mentioned above, the present invention can be better realized, and the above embodiments are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention; all equivalent changes and modifications made according to the present disclosure are intended to be covered by the scope of the claims of the present invention.

Claims (10)

1. The UV adhesive for reducing the curing shrinkage rate is characterized by comprising the following components in percentage by weight: 40% -57% of prepolymer, 16% -38% of diluent, 4% -19% of swelling monomer, 0.8% -7% of photoinitiator and 5% -20% of nano-scale powder, wherein the type of nano-scale powder is the same as that of powder bed powder in three-dimensional printing.
2. The UV adhesive for reducing curing shrinkage according to claim 1, wherein the prepolymer is at least one of epoxy acrylic resin, polyester acrylic resin, polyurethane acrylic resin, bisphenol A epoxy acrylic resin, novolac epoxy acrylate, and modified epoxy acrylic resin.
3. The UV adhesive for reducing curing shrinkage according to claim 1, wherein the diluent is at least one of a monofunctional diluent, a difunctional diluent, and a multifunctional diluent.
4. The UV adhesive for reducing curing shrinkage according to claim 1, wherein the photoinitiator is at least one of a radical photoinitiator and a cationic photoinitiator.
5. The UV adhesive for reducing curing shrinkage according to claim 1, wherein the swelling monomer is at least one of a spiro orthocarbonate, a bicyclo orthoester and a spiro orthoester.
6. The UV adhesive for reducing curing shrinkage according to claim 1, wherein the nanoscale powder is made of a metal material or a ceramic material.
7. The UV adhesive for reducing curing shrinkage according to claim 6, wherein the metal material is one of 304 stainless steel, 316 stainless steel, titanium alloy, nickel and nickel alloy, and the ceramic material is one of alumina, zirconia, cobalt oxide, nickel oxide, iron oxide, calcium phosphate and hydroxyapatite.
8. A method for preparing the UV adhesive according to any one of claims 1 to 7, comprising the steps of:
step S1: adding the prepolymer, the diluent, the expansion monomer and the photoinitiator into the same container according to the weight percentage, and stirring the mixture until a uniform mixed solution A is formed;
step S2: and selecting the type of the nano-scale powder according to the type of the powder bed powder, adding the nano-scale powder into the mixed solution A according to the weight percentage, uniformly mixing, and removing bubbles to finish the preparation of the UV adhesive.
9. The method according to claim 8, wherein in step S2, the nanoscale powder and mixed solution a are uniformly mixed by manual stirring, ultrasonic vibration, magnetic stirring or mechanical rotation stirring, and the mixing time is 0.5-2 hours.
10. The preparation method according to claim 8, wherein in step S2, the solution obtained by uniformly mixing the nanoscale powder and the mixed solution a is placed in a vacuum oven for drying and degassing, and the drying temperature is 30-60 ℃.
CN202011319052.7A 2020-11-23 2020-11-23 UV (ultraviolet) adhesive for reducing curing shrinkage and preparation method thereof Pending CN112480851A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011319052.7A CN112480851A (en) 2020-11-23 2020-11-23 UV (ultraviolet) adhesive for reducing curing shrinkage and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011319052.7A CN112480851A (en) 2020-11-23 2020-11-23 UV (ultraviolet) adhesive for reducing curing shrinkage and preparation method thereof

Publications (1)

Publication Number Publication Date
CN112480851A true CN112480851A (en) 2021-03-12

Family

ID=74932948

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011319052.7A Pending CN112480851A (en) 2020-11-23 2020-11-23 UV (ultraviolet) adhesive for reducing curing shrinkage and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112480851A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113387614A (en) * 2021-05-21 2021-09-14 浙江杨艺园林工程有限公司 Artificial stone protection box and preparation method thereof

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2405539A1 (en) * 2000-04-14 2001-10-25 Z Corporation Compositions for three-dimensional printing of solid objects
WO2005108344A1 (en) * 2004-05-02 2005-11-17 Ashland Licensing And Intellectual Property Llc Radiation-curable coatings for metal substrates from multifunctional acrylate oligomers
CN104570603A (en) * 2013-10-22 2015-04-29 青岛中科新材料有限公司 Preparation method and application of photosensitive resin for ultrasonic curing 3D printing
CN104932197A (en) * 2015-05-26 2015-09-23 南方科技大学 Expansion polymerization imprinting adhesive for nanoimprint
CN105219339A (en) * 2015-11-11 2016-01-06 华南农业大学 A kind of UV solidifies liquid optical cement, its preparation method and application thereof
CN106495670A (en) * 2016-10-13 2017-03-15 深圳市撒比斯科技有限公司 For the adhesive of photocuring pottery 3D printing, its preparation method and application
CN107245314A (en) * 2017-05-26 2017-10-13 苏州汉力新材料有限公司 A kind of 3D printing powder ultraviolet light curing adhesive and preparation method thereof
CN107377976A (en) * 2017-07-06 2017-11-24 苏州恒久光电科技股份有限公司 The 3D printing of metal slurry is without mould gel forming method
WO2018214612A1 (en) * 2017-05-23 2018-11-29 昆山卡德姆新材料科技有限公司 Feed material for 3d printing, and preparation method and usage thereof
CN109133917A (en) * 2018-11-02 2019-01-04 华南农业大学 A kind of ceramic slurry of DLP increasing material manufacturing and preparation method thereof and the method that finished product is prepared using the slurry
CN109400177A (en) * 2018-10-30 2019-03-01 西安点云生物科技有限公司 For the ceramic material of 3D Stereolithography printing and the preparation method of ceramic objects
CN110143815A (en) * 2019-06-19 2019-08-20 中南大学深圳研究院 A kind of high-compactness ceramics and preparation method thereof
CN111690096A (en) * 2020-05-20 2020-09-22 广西春景环保科技有限公司 Preparation method of 3D printing photosensitive resin material

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2405539A1 (en) * 2000-04-14 2001-10-25 Z Corporation Compositions for three-dimensional printing of solid objects
WO2005108344A1 (en) * 2004-05-02 2005-11-17 Ashland Licensing And Intellectual Property Llc Radiation-curable coatings for metal substrates from multifunctional acrylate oligomers
CN104570603A (en) * 2013-10-22 2015-04-29 青岛中科新材料有限公司 Preparation method and application of photosensitive resin for ultrasonic curing 3D printing
CN104932197A (en) * 2015-05-26 2015-09-23 南方科技大学 Expansion polymerization imprinting adhesive for nanoimprint
CN105219339A (en) * 2015-11-11 2016-01-06 华南农业大学 A kind of UV solidifies liquid optical cement, its preparation method and application thereof
CN106495670A (en) * 2016-10-13 2017-03-15 深圳市撒比斯科技有限公司 For the adhesive of photocuring pottery 3D printing, its preparation method and application
WO2018214612A1 (en) * 2017-05-23 2018-11-29 昆山卡德姆新材料科技有限公司 Feed material for 3d printing, and preparation method and usage thereof
CN107245314A (en) * 2017-05-26 2017-10-13 苏州汉力新材料有限公司 A kind of 3D printing powder ultraviolet light curing adhesive and preparation method thereof
CN107377976A (en) * 2017-07-06 2017-11-24 苏州恒久光电科技股份有限公司 The 3D printing of metal slurry is without mould gel forming method
CN109400177A (en) * 2018-10-30 2019-03-01 西安点云生物科技有限公司 For the ceramic material of 3D Stereolithography printing and the preparation method of ceramic objects
CN109133917A (en) * 2018-11-02 2019-01-04 华南农业大学 A kind of ceramic slurry of DLP increasing material manufacturing and preparation method thereof and the method that finished product is prepared using the slurry
CN110143815A (en) * 2019-06-19 2019-08-20 中南大学深圳研究院 A kind of high-compactness ceramics and preparation method thereof
CN111690096A (en) * 2020-05-20 2020-09-22 广西春景环保科技有限公司 Preparation method of 3D printing photosensitive resin material

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
VAN-QUYET NGUYEN: "Bi-based lead-free ceramic multilayer actuators using AgPd-(Na0.51K0.47Li0.02)(Nb0.8Ta0.2)O-3 composite inner electrodes", 《SENSORS AND ACTUATORS A-PHYSICAL》 *
余彪等: "基于硫醇/甲基丙烯酸酯的3D打印用光敏树脂的制备及性能研究", 《塑料工业》 *
叶青: "《土木工程材料》", 30 September 2013 *
李小笠: "《快速成型制造实训教程》", 30 November 2016, 东南大学出版社 *
王延庆等: "3D打印材料应用和研究现状", 《航空材料学报》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113387614A (en) * 2021-05-21 2021-09-14 浙江杨艺园林工程有限公司 Artificial stone protection box and preparation method thereof
CN113387614B (en) * 2021-05-21 2022-07-01 浙江杨艺园林工程有限公司 Artificial stone protection box and preparation method thereof

Similar Documents

Publication Publication Date Title
US4251576A (en) Inorganic reinforcing phase dispersed and bonded to polymer matrix
DE2449656A1 (en) NEW MOLDABLE AND HARDENABLE COMPOSITION, METHOD OF MANUFACTURING THE SAME AND MANUFACTURING MULTI-COMPONENT COMPOSITES
DE68908324T2 (en) Granite-like artificial stone.
US5972272A (en) Unsaturated polyester resin composition and process for molding the composition
JP5605825B2 (en) Liquid resin composition and cured product using the liquid resin composition
CN102181115B (en) Polymethyl methacrylate product and preparation method thereof
JPS61197639A (en) Formable composition
EP3932671A1 (en) Dual-curing phase separation type continuous 3d printing high-precision photosensitive resin composition
JPH0615677B2 (en) Powder coating agent for in-mold coating
US3953657A (en) Method for coating particulate solids with polymers
WO2013118697A1 (en) Toughness modifier for curable resin, and curable resin composition
CN112480851A (en) UV (ultraviolet) adhesive for reducing curing shrinkage and preparation method thereof
CN109438632B (en) 3D printing photosensitive resin with ultralow volume shrinkage and preparation method thereof
GB2108987A (en) In-mold coating composition and method of in-mold coating
DE4234324A1 (en) Curable molding compound
JPH07118620A (en) Epoxy-based adhesive composition
JPS6144747A (en) Manufacture of artificial marble
JPH10279819A (en) Optical stereolithographic resin composition
CN109971294B (en) Self-initiated organic/inorganic hybrid material and preparation method and application thereof
CN107429089B (en) Filler material
CN115490522B (en) Photo-curing molding silicon carbide ceramic slurry and application thereof
CN111592620B (en) Photocuring material for 3D printing
KR102437001B1 (en) Manufacturing method of polymer beads and magsand including polymer beads
EP4382575A1 (en) Milled silica and liquid radiation curable compositions comprising same
JPH07233242A (en) Coating composition for in-mold coating molding

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20210312

RJ01 Rejection of invention patent application after publication