KR20190034913A - Ceramic/metal slurry composition for digital light processing type 3D printer using surface modified pigment - Google Patents

Abstract

The present invention relates to a 3D printing slurry composition, and more particularly, to a photocurable 3D printing ceramic/metal slurry composition using a surface-treated pigment, which is to improve interlayer adhesion between layers of a sculpture using slurry of high content by increasing reactivity and adhesion properties with a polymer resin through surface treatment of a pigment. To this end, the 3D printing slurry composition comprises 10 to 30 wt % of a photocurable resin and 60 to 90 wt % of a surface-treated pigment, wherein a surface treating agent of the pigment is a silane coupling agent or a monomer including acrylate, methacrylate, epoxy, and glycidyl, and the photocurable resin includes 25 to 55 wt % of oligomer, 25 to 60 wt % of a reactive diluent, 1 to 15 wt % of a photoinitiator and other additives.

Description

Technical Field [0001] The present invention relates to a ceramic / metal slurry composition for 3D printing using a surface-treated pigment,

The present invention relates to a slurry composition for 3D printing, and more particularly, to a slurry composition for 3D printing, and more particularly, to a slurry composition for 3D printing, which comprises a slurry having a high content by increasing the reactivity and adhesion with a polymer resin through surface treatment of the pigment, To a photocurable ceramic / metal slurry composition for 3D printing using a surface treated pigment to improve adhesion.

Photocuring The 3D printing method is a method of manufacturing a complex shape by stacking two-dimensional surfaces by selectively irradiating light in the uv (uv) or visible light region to the composite containing the photocurable material. When the amount of the pigment is increased when the two-dimensional surfaces are laminated, the interlayer adhesion between the layers of the molding can be weakened, making it difficult to form the molding.

A low viscosity ceramic slurry composition for 3D printing has been developed to lower the viscosity of a ceramic slurry composition by realizing an optimal ratio of a ceramic slurry composition and a reactive diluent in order to lower the viscosity of a high-concentration ceramic slurry 1647799).

However, in the prior art, the reactive diluent is added to lower the viscosity of the high-concentration ceramic slurry. However, if the dispersing agent is used, the dispersing agent must be used, and if the pigment content is high, the reactivity with the polymer resin, There is a problem.

KR Patent No. 1551255 (2015.09.02) KR Patent No. 1647799 (Aug. 2016)

Disclosure of the Invention The present invention has been proposed in order to solve the problems of the prior art as described above, and it is an object of the present invention to improve the reactivity and adhesion with the polymer resin through the surface treatment (surface modification) of the pigment to use the ceramic / metal slurry having a high pigment content The present invention relates to a photocurable ceramic / metal slurry composition for 3D printing using a surface-treated pigment that facilitates the formation of a molding by improving interlayer adhesion between the sculptures when the 3D sculpture is formed.

In order to achieve the above object, a photocurable ceramic / metal slurry composition for a 3D printing using a surface-treated pigment of the present invention comprises 10 to 30 wt% of a photocurable resin and 60 to 90 wt% of a surface-treated pigment .

Here, the surface treating agent of the pigment is characterized by being a silane coupling agent containing a methoxy group, ethoxy group, dialkoxy group or trialkoxy group and the functional group X having a vinyl group, an epoxy group, a methacryloxy group or a thiol group.

Alternatively, the surface treating agent of the pigment is a monomer containing acrylate, methacrylate and glycidyl.

The pigment is at least one ceramic pigment selected from the group consisting of aluminum oxide, zirconia, titanium oxide, silicon nitride, silicon carbide, aluminum nitride, silica, zinc oxide and zinc sulfate barium sulfate.

Alternatively, the pigment is one or more metal pigments selected from aluminum, tungsten carbide, titanium, cesium, iron, copper, nickel and cobalt powder.

Preferably, the photocurable resin is composed of 25 to 55 wt% of an oligomer, 25 to 60 wt% of a reactive diluent, 1 to 15 wt% of a photoinitiator, and other additives. And optionally further comprising a dispersing agent in an amount of 5 wt% or less.

The oligomer may be at least one selected from the group consisting of polyester acrylate, epoxy acrylate, urethane acrylate, polyether acrylate, polyacrylate, silicone acrylate, unsaturated polyester, and epoxy containing an organic functional group capable of photo- And is a polymer resin.

The reactive diluent may be at least one selected from the group consisting of monofunctional and bifunctional polyfunctional acrylates, methacrylates, glycidyl ethers, epoxies, vinyl ethers, and styrenes.

Also, the photoinitiator may be selected from the group consisting of benzophenones, α-hydroxy ketones (α-HK), benzyl-dialkylketal (BDK), α-amino ketones, phenyl glyoxylates (PG), thioxanthones (ITX), and acylphosphine oxides Or more.

The other additives may be at least one selected from leveling agents, UV stabilizers, UV absorbers, antioxidants, adhesion promoters, water reducing agents, brighteners, defoamers, dispersants, pigment wetting agents, thickeners and water-repellent additives.

The photocurable ceramic / metal slurry composition for 3D printing using the surface-treated pigment of the present invention having the above-described structure exhibits the following useful effects.

First, by increasing the reactivity and adhesion with the polymer resin through the surface treatment (surface modification) of the pigment, it is possible to improve the interlayer adhesion between the sculptures even when the 3D sculpture is formed using the ceramic / metal slurry having a high pigment content, .

Secondly, by using the surface-modified pigment, it is possible to increase the miscibility with the polymer resin so that the amount of the reactive diluent or other additive (dispersant) can be easily controlled so that the viscosity of the slurry can be controlled to facilitate the formation of the 3D sculpture have.

1 is a diagram showing the polymerization of a ceramic / metal slurry composition for photocuring 3D printing using a surface-treated pigment according to the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. Prior to the detailed description of the present invention, terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms.

Therefore, the embodiments described in the present specification and the configurations shown in the drawings are only a preferred embodiment of the present invention, and not all of the technical ideas of the present invention are expressed. Therefore, at the time of the present application, It should be understood that there are equivalents and variations.

In describing the present embodiment, the same names are used for the same components, and further description thereof will be omitted.

1 is a diagram showing the polymerization of a ceramic / metal slurry composition for photocuring 3D printing using a surface-treated pigment according to the present invention.

The present invention relates to a ceramic / metal slurry for photocurable 3D printing that facilitates the formation of a molding using a surface-treated pigment, and is used in such a manner that a raw material is supplied in a water tank of a photocuring type 3D printer.

Specifically, the present invention comprises 10 to 30 wt% of a photocurable resin containing at least one photocurable organic functional group and 60 to 90 wt% of a surface-treated pigment.

The ceramic pigment includes aluminum oxide, zirconia, titanium oxide, silicon nitride, silicon carbide, aluminum nitride, silica, zinc oxide, zinc sulfate barium sulfate and the like.

The metal pigments include aluminum, tungsten carbide, sulfur, titanium, iron, copper, nickel, and cobalt powder.

The surface treating agent (surface modifying agent) of the pigment includes a group capable of reacting with the curing resin during the curing process. The pigments can thus bind strongly to the matrix of the polymeric resin and can lead to an improvement in the physical properties of the cured 3D sculpture.

Also included is a silane coupling agent containing a vinyl group, an epoxy group, an amino group, a methacryloxy group, and a thiol group as a surface treating agent (surface modifying agent) of the pigment. The structure of the silane coupling agent may be a reactor (a methoxy group, an ethoxy group, a dialkoxy group, or a trialkoxy group) that chemically bonds with an inorganic material and a metal material and a reactor (a vinyl group, an epoxy group, A methacryloyl group, a thiol group).

Further, it includes monomers containing acrylate, methacrylate, epoxy and glycidyl as the surface treating agent (surface modifying agent) of the pigment.

The acrylate may include various acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, and octyl acrylate.

Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyldiehoxysilane, styryltrimethoxysilane 3-methacryloxylpropyl trimethoxysilane, 3-methacryloxypropyl triethoxysilane and 3-acryloxypropyl trimethoxysilane.

Examples of the surface modifying monomer include isobornyl acrylate, isodecyl methacrylate, lauryl acrylate, lauryl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, 2-carboxyethyl acrylate, methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, methacrylate, acrylic acid, tert-butyl acrylate, phenoxyethyl acrylate, 4-t-butylcyclohexyl acrylate, butanediol-mono-acrylate, trimethylolpropanformal acrylate, tripropyleneglycol diacrylate, dipropyleneglycol diacrylate, hexanediol diacrylate and trimethyolopropan triacrylate.

If the amount of the photocurable resin is less than 10 wt%, not only the basic properties of the resin are deteriorated but also the photocuring is not properly performed due to the shortage of reaction sites, which makes it difficult to form a laminate of a molding.

On the other hand, if the content exceeds 30wt%, the total content of the pigment is lowered in the post-processing after sintering the finished sculpture, the total volume ratio is decreased, and the distance of the pigment is distant, so that the sintering density is lowered and the performance as a ceramic / metal sculpture is lowered.

Here, the present invention may further contain 5 wt% or less (0 to 5 wt%) of dispersant and 5 wt% or less (0 to 5 wt%) of other additives as required.

As described above, the present invention allows the vinyl resin, the acrylate resin, and the epoxy resin reactive site to exist in the pigment itself through the surface treatment (surface modification) so that the polymer resin and the pigment are directly bonded. Thereby increasing the bonding density and improving the adhesion.

Hereinafter, the details of the photocurable resin will be described in detail.

In one embodiment, the present invention provides a composition comprising 10 to 30 wt% of a (UV) photocurable resin comprising 25 to 55 wt% of an oligomer, 25 to 60 wt% of a reactive diluent, 1 to 15 wt% of a photoinitiator, and 60 to 90 wt% .

Here, the other additives may include 1 to 5 wt% as an example.

The oligomer may be a polymer such as a polyester acrylate, an epoxy acrylate, a urethane acrylate, a polyether acrylate, a polyacrylate, a silicone acrylate, an unsaturated polyester, an epoxy or the like containing at least one photocurable organic functional group (I. E., One or more species).

The reactive diluent may be at least one polyfunctional acrylate, methacrylate, glycidyl ether, epoxy, vinyl ether, and at least one styrene (i.e., one or more) .

For example, the reactive diluent may be selected from the group consisting of Isobornylacrylate (IBOA), Trimethylolpropane-formal-mono-acrylate, Phenoxyethylacrylate (POEA)

Tripropyleneglycoldiacrylate (TPGDA), Dipropyleneglycoldiacrylate (DPGDA), Hexandioldiacrylate (HDDA) Neopentylglycoldiacrylate (NPGDA)

Trimethylolpropanetriacrylate (TMPTA), Ethoxylated / propoxylated Propoxylatedglyceroletriacrylate

Pentaerythritoltriacrylate (PETIA), Pentaerythritol tetraacrylate (PT4A), Dipentaerythritolpenta / hexaacrylate, Hydroxypropyl-Methacrylates, Isobornyl-Methacrylates, Dicyclopentenyl-oxy-ethyl-Methacrylates, N-Vinylcaprolactam, N-Vinylpyrrolidone, N-Vinylformamide, Acrylamidomorpholine, Divinylether of Tripropylenglycol, cyclohexanedimethanol, and Vinylether capped urethanes.

The reactive diluent is used to control skin irritation, adhesion, flexibility, abrasion resistance, and solvent resistance depending on the ingredients, and controls the viscosity and reactivity of the composition according to the content.

Examples of the photoinitiator include benzophenones, α-hydroxy ketones (α-HK), benzyl-dialkylketal (BDK), α-amino ketones, phenyl glyoxylates (PG), thioxanthones (ITX), and acylphosphine oxides .

For example, benzophenone (Genocure® BP), 1-Hydroxy-cyclohexylphenyl-ketone (Irgacure® 184), 2-Hydroxy- 1- [4- (2-hydroxyethoxy) phenyl] -2-methyl-1propanone 2959), 2-Hydroxy-2-methyl1-phenyl-1-propanone (Darocure® 1173), .alpha.,. Alpha.-Dimethoxy-.alpha.phenylacetophenone (Irgacure® 651), 2-Benzyl-2dimethylamino- phenyl] -1-butanone (Irgacure 369)

Methyl-benzoylformate (Genocure® MBF), Isopropyl-thioxanthone (Genocure® ITX), 2,4,6-Trimethylbenzoyl) -diphenyl phosphine oxide (Lucirin® TPO), Phenyl-bis- (2,4,6trimethylbenzoyl) phosphine oxide Irgacure (R) 819).

When the amount of the photoinitiator is less than 1 wt%, the curability is lowered. When the amount of the photoinitiator is more than 15 wt%, the yellowing or crystalline material remains, which may cause discoloration and brittleness of color.

Examples of the other additives include at least one selected from a leveling agent, a UV stabilizer, a UV absorber, an antioxidant, an adhesion promoter, a water reducing agent, a polishing agent, a defoaming agent, a dispersant, a pigment wetting agent, a thickener, Or more) can be used.

When the amount of the other additive is more than 5 wt%, there arises a problem that the yellowing and the crystalline material remain so that the color may be deteriorated and brittle may be caused.

Example 1)

Surface treatment of pigments -silane coupling agent

≪ Method of giving methacrylate functional group as a reaction site to pigment >

100 g of zirconia pigment is dispersed in 1 L of ethanol. After dispersion, 100 mL of distilled water is added. 0.1NM ammonia solution is added to adjust the acidity of the reaction solution to 11, and the reaction temperature is set to 50 degrees. 5 g of trimethoxysilyl propyl methacrylate is added for surface modification. After 12 hours of reaction, wash the reaction solution several times until the acidity of the reaction solution drops below 9, and then dry it in the oven at 50 degrees for 24 hours.

Example 2)

Surface treatment of pigments -monomer

≪ Method of giving various functional groups to pigments >

100 g of zirconia pigment is dispersed in 1 L of ethanol. After dispersion, 100 mL of distilled water is added. 0.1NM ammonia solution is added to adjust the acidity of the reaction solution to 11, and the reaction temperature is set to 50 degrees. 5 g of trimethoxysilyl propyl methacrylate is added for surface modification. After 12 hours of reaction, wash the reaction solution several times until the acidity of the reaction solution drops below 9, and then dry it in the oven at 50 degrees for 24 hours. 100 g of the dried pigment is dispersed in xylene. After setting the reaction temperature to 60 ° C, add 10 g of 4-hydroxbutyl acrylate as a monomer. To proceed the reaction, 0.5 g of initiator V-601 is added. After completing the reaction for about 20 hours, use a surface treated pigment after washing with water. Depending on the desired physical properties of the polymer resin and slurry, the monomer should be selected appropriately. Likewise, a monomer having good compatibility with the polymer resin and the reactive diluent can be selected to improve the dispersibility.

Example 3)

≪ Preparation of ceramic slurry using surface-treated pigment >

Polymer Resin A photocurable resin is prepared by mixing 35wt% of reactive urethane acrylate, 30wt% of reactive diluent, 10wt% of isobonyl acrylate, 10wt% of ethyl acrylate, 10wt% of ethylene glycol dimethacrylate and 5wt% of initiator irgacure 184.

After mixing 5 g of dispersant efka 4609 with 35 g of the photocurable resin, 80 g of pigment treated with trimethoxysilyl propyl methacrylate and 80 g of pigment treated with hydroxbutyl acrylate were dispersed to prepare a ceramic slurry using the surface treated pigment.

Accordingly, the present invention can improve the miscibility with the binder by dispersing the pigment surface-modified using a surface treatment agent (surface modifier) such as an oligomer, a reactive diluent and a silane or a monomer having good compatibility with the binder without a dispersant, The bonding density between the pigment and the binder is increased through the reaction sites.

It will be apparent to those skilled in the art that the present invention may be embodied in other specific forms without departing from the spirit or scope of the invention as defined in the appended claims. It is self-evident to those who have.

Therefore, the above-described embodiments are to be considered as illustrative rather than restrictive, and the present invention is not limited to the above description, but may be modified within the scope of the appended claims and equivalents thereof.

Claims (11)

And 10 to 30 wt% of a photocurable resin and 60 to 90 wt% of a surface-treated pigment. The ceramic / metal slurry composition for photocuring 3D printing using the surface-treated pigment. The method according to claim 1,
Wherein the surface treating agent of the pigment is a silane coupling agent containing a methoxy group, ethoxy group, dialkoxy group or trialkoxy group and the functional group X having a vinyl group, an epoxy group, an amino group, a methacryloxy group or a sialic group A ceramic / metal slurry composition for photocurable 3D printing using a surface treated pigment. The method according to claim 1,
Wherein the surface treating agent of the pigment is a monomer including acrylate, methacrylate, epoxy, and glycidyl. The ceramic / metal slurry composition for photocuring 3D printing using the surface-treated pigment. The method according to claim 1,
Wherein the pigment is at least one ceramic pigment selected from aluminum oxide, zirconia, titanium oxide, silicon nitride, silicon carbide, aluminum nitride, silica, zinc oxide and zinc sulfate barium sulfate. Of a ceramic / metal slurry composition for 3D printing. The method according to claim 1,
Wherein the pigment is at least one metal pigment selected from the group consisting of aluminum, tungsten carbide, sulfur, titanium, iron, copper, nickel and cobalt powder. Composition. The method according to claim 1,
Wherein the photocurable resin is composed of 25 to 55 wt% of an oligomer, 25 to 60 wt% of a reactive diluent, 1 to 15 wt% of a photoinitiator, and other additives. . 7. The method according to claim 1 or 6,
And a dispersing agent in an amount of 5 wt% or less based on the weight of the pigment. The method according to claim 6,
Wherein the oligomer is at least one polymer resin selected from the group consisting of polyester acrylate, epoxy acrylate, urethane acrylate, polyether acrylate, polyacrylate, silicone acrylate, unsaturated polyester, and epoxy containing an organic functional group capable of photo- Wherein the photoresist composition is a photocurable three-dimensional photoresist composition. The method according to claim 6,
Wherein the reactive diluent is at least one selected from the group consisting of monofunctional and bifunctional polyfunctional acrylates, methacrylates, glycidyl ethers, epoxies, vinyl ethers and styrene. Ceramic / metal slurry composition for photocurable 3D printing. The method according to claim 6,
The photoinitiator may be one or more selected from benzophenones,? -Hydroxy ketones (? -HC), benzyl-dialkylketal (BDK),? -Amino ketones, phenyl glyoxylates (PG), thioxanthones (ITX) and acylphosphine oxides Characterized in that the photocurable ceramic / metal slurry composition for 3D printing using the surface treated pigment. The method according to claim 6,
Wherein the other additive is at least one selected from a leveling agent, a UV stabilizer, a UV absorber, an antioxidant, an adhesion promoter, a water reducing agent, a polish agent, a defoaming agent, a dispersant, a pigment wetting agent, a thickener, Ceramic / metal slurry composition for photocurable 3D printing.

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