KR101514745B1 - Photocurable resin composition for thermal decomposition master model mold of precision casting - Google Patents
Photocurable resin composition for thermal decomposition master model mold of precision casting Download PDFInfo
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- KR101514745B1 KR101514745B1 KR1020140112915A KR20140112915A KR101514745B1 KR 101514745 B1 KR101514745 B1 KR 101514745B1 KR 1020140112915 A KR1020140112915 A KR 1020140112915A KR 20140112915 A KR20140112915 A KR 20140112915A KR 101514745 B1 KR101514745 B1 KR 101514745B1
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- dimethacrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
Abstract
Description
The present invention relates to a photocurable composition for molding a precision casting pyrolysis master model, and more particularly to a photocuring composition composed of an acrylate or a methacrylate compound necessary for preparing a pyrolysis master model in precision casting, When the master model is pyrolyzed in the mold, pyrolysis must be performed at a high temperature and the pyrolysis rate is slow. In addition, since the residues and gas remain after pyrolysis, the quality of the molded product is lowered. And a photocurable composition for molding a precision casting thermal decomposition master model which is pyrolyzed quickly at a low temperature by introducing a methyl group into the main chain of the acrylate or methacrylate compound to form a propylene group and does not remain after pyrolysis.
In general, casting is a process in which a metal is heated to dissolve and then a molten metal is injected into the mold to produce a certain type of product, or a plastic in a fluid state, a rubber latex, a monomer compounded to be polymerized, Is widely used as a kind of plastic molding method in which a plastic resin such as a polymer is injected into a mold or squeezed and solidified on a mold surface.
Such casting can be divided into general casting and precision casting. In general casting, casting is divided into upper and lower molds, so that the products are formed into a delicate and creative design expression There are limits to this.
However, the precision casting method is a method that can accurately cast shapes, textures, dimensions, and weights to be expressed literally, and is widely used for mass production of precious metal jewelry such as gold, platinum, and silver. (Investment) is also called investment casting.
Especially, products made by precision casting process can get a beautiful surface. Since master model is mainly made of wax, it is called "lost wax casting" In case of casting, the molten metal is introduced to the terminal details by the centrifugal force, the vacuum suction or the suction force according to the suction pressure, and the metal structure is tightened.
The conventional general precision casting method is a method in which the same master model as the product to be molded is manufactured with wax, the mold is molded through refractory molding work of the master model, the master model in the mold is pyrolyzed and removed, .
At this time, the master model can be manufactured by injection molding using a thermally decomposable material such as a thermosetting resin, a thermoplastic resin, or a photo-curing resin as well as wax. Particularly, currently, A method of three-dimensionally printing and photo-curing a master model by using a 3D printer controlled on the basis of the master model is widely used.
Presently, a photopolymerizable composition capable of printing the master model with a 3D printer is a cured product of a composition comprising (i) 100 parts by weight of an organopolysiloxane and ii) 0.01 to 5 parts by weight of a photoinitiator, in Korean Patent No. 10-0357785 , And the organopolysiloxane (i) comprises (A) 30 to 100% by weight of an organopolysiloxane of the following average composition formula (1); R a R 1 b SiO (4 -ab) / 2 (1) wherein R is the same or different monovalent hydrocarbon group which is unsubstituted or substituted with no aliphatic unsaturated bond or an alkoxy; Identical or different R 1 is a photoreactive group selected from a (meth) acryloyl-containing group, a vinyloxyalkyl group and an epoxy-containing group; The letters a and b are positive numbers satisfying 1.90? A <2.40, 0.0003? B? 0.10 and 1.90 <a + b? 2.40 and the organopolysiloxane contains at least two photoreactive groups in the molecule and has a molecular weight of 100-1,000,000 has a viscosity of cp and, and (B) R p R 1 q SiO 1/2 units (M), SiO 2 units (q), and / or XSiO 3/2 0~70% by weight, comprising units (T) Wherein the R and R1 are as defined above and the letters p and q are 0, 1, 2 or 3 and p + q = 3, X is selected from R and R & (Q + T) of from 0.6 to 1.2 and a molar ratio R 1 / Si of from 0.01 to 0.10).
In addition, in JP-A No. 10-2013-0141561, a monofunctional ethylenically unsaturated monomer (A), a polyfunctional ethylenically unsaturated monomer (B) containing no urethane group, a urethane group-containing polyfunctional ethylenically unsaturated monomer (C) (D) is known as an ink jet stereolithography model material.
Korean Patent Laid-Open No. 2003-0009435 discloses a chemical composition for forming a three-dimensional article in a three-dimensional printer, wherein the composition comprises a non-aqueous organic monomer compound, and the compound is an alcohol, ester, ether, silane, vinyl monomer, Wherein the acrylic monomer comprises at least one of tri (propylene glycol) diacrylate, ethylene glycol phenyl ether acrylate or 1,6 hexanediol diacrylate, or the methacrylic monomer is at least one of 1,3-butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, butyl methacrylate, 1,6 hexanediol dimethacrylate, or di (propylene glycol) allyl ether methacrylate. A photocurable composition for a three-dimensional printer is known.
Korean Patent No. 10-0838878 discloses a fluid composition for selectively adhering a free-flowing particulate material that is not fixed so as to form a three-dimensional object in a three-dimensional printer. The fluid composition includes a polymerizable monomer and a photoinitiator, and has a wavelength of 320-500 nm, / cm < 2 >, wherein the polymerizable monomer comprises at least one of a methacrylate monomer, an acrylic monomer or a vinyl monomer, wherein the acrylic monomer is at least one selected from the group consisting of tri (propylene glycol) diacrylate , Ethylene glycol phenyl ether acrylate or 1,6 hexanediol diacrylate, or the methacrylate monomer is at least one of 1,3-butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, butyl methacrylate 1,6-hexanediol dimethacrylate, or di Propylene glycol) and the fluid composition is known comprising at least one allyl ether methacrylate.
Korean Patent Laid-Open No. 10-2012-0055242 discloses a photocurable resin composition comprising 50 to 80 parts by weight of an acrylic compound, 10 to 50 parts by weight of silsesquioxane, 0.5 to 5 parts by weight of a photocurable release agent, Wherein the acrylic compound is selected from the group consisting of monofunctional monomers, bifunctional monomers, trifunctional monomers, polyfunctional monomers, and mixtures thereof, wherein the silsesquioxane is selected from the group consisting of acrylate or methacrylate A silsesquioxane having a group represented by the following formula (1), and a mixture thereof.
Korean Unexamined Patent Publication No. 10-2013-0140885 discloses an ink composition comprising 3 to 18 parts by mass of an alkyl (meth) acrylate (A) having an alkyl group having 12 or more carbon atoms based on the total 100 parts by mass of the total monomer content, (B) having 3 or more radically polymerizable functional groups in a molecule having an sp value of 20 to 23, which is represented by the following formula (1):
In particular, Korean Patent Laid-Open No. 10-2010-0016451 discloses a photocurable composition for a three-dimensional printer comprising a compound represented by the following formula as a radical photocurable compound.
However, the photocurable composition composed of the acrylate or methacrylate compound has to be pyrolyzed at a high temperature when the master model is produced by injection molding or a 3D printer and pyrolyzed in the mold, and the pyrolysis rate is slow, The present inventors have found that when a methyl group is introduced into the main chain of the acrylate or methacrylate compound to form a propylene group, And it is possible to improve the quality and productivity of the molded product because the residues and the gas do not remain after pyrolysis, and the present invention has been completed.
The present invention relates to a process for producing a molded article of a molded product, which comprises the steps of: (a) preparing a mold for molding a molded article, which is a master model made of a photocurable composition comprising acrylate or methacrylate, In order to solve the problem of deteriorating the quality, a precision casting pyrolysis master model in which a methyl group is introduced into the main chain of the acrylate or methacrylate compound to form a propylene group and is rapidly pyrolyzed at a low temperature, It is an object of the present invention to provide a photocurable composition for molding.
(A) a reactive oligomer which is a glycidyl methacrylate compound represented by the following formula (1) wherein a methyl group is introduced into a main chain and the main chain is composed of a propylene group repeating unit; (B) a reactive diluent; (C) a photopolymerization initiator; And (D) a pigment. The photocurable composition for molding a precision casting pyrolysis master model is a solution to the problem.
[Chemical Formula 1]
(Wherein n is an integer of 1 to 30)
The reactive oligomer (A) is a photo-curing composition for molding a precision casting thermal cracking master model, wherein a methyl group is introduced into a main chain and the main chain is composed of a repeating unit of propylene group and further a methacrylate compound represented by the following formula As a solution to the problem.
(2)
(Wherein n is an integer of 1 to 30)
The reactive diluent (B) is a monomer having at least one radically polymerizable functional group capable of copolymerizing with a reactive oligomer, wherein the reactive diluent (B) is selected from the group consisting of caprolactone acrylate, octyldecyl acrylate, isooctyl acrylate,? -Phenyl phenol (EO) 2 acrylate, phenol (EO) 4 acrylate, phenol (EO) 2 acrylate, benzyl acrylate, lauryl acrylate, behenyl acrylate, isodecyl acrylate, phenol (EO) 8 acrylate, nonylphenol (PO) 2 acrylate, ethoxyethoxyethyl acrylate, stearyl acrylate, stearyl acrylate, stearyl acrylate, Monofunctional acrylates selected from aryl acrylates; Hexanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol (EO) n diacrylate, butanediol diacrylate, hydroxylpivalic acid neopentyl glycol diacrylate, neopentyl glycol (PO) Diethylene glycol diacrylate, bisphenol A (EO) 4 diacrylate, bisphenol A (EO) 3 diacrylate, bisphenol A (EO) 10 di Acrylate, bisphenol A (EO) 20 diacrylate, bisphenol A (EO) 30 diacrylate, tricyclodecane dimethanol diacrylate, tetraethylene glycol diacrylate,
The photopolymerization initiator (C) is an alpha-hydroxy ketone type; Phenylglyoxylate-based; Benzyldimethylketal system; Aminoketone type; Monoacylphosphine system; Bisacylphosphine system; Phosphine oxide system; Metallocene system; And an iodonium salt-based photo-curable composition for molding a precision casting thermal decomposition master model.
The photocurable composition for molding a precision casting pyrolysis master model of the present invention is characterized in that a master model made of a photocurable composition containing acrylate or methacrylate is used for pyrolysis in a mold such as high temperature pyrolysis, To solve the problem of deteriorating the quality of the molded product due to residual residues after the polymerization, a methyl group is introduced into the main chain of the acrylate or methacrylate compound to form a propylene group, which is rapidly pyrolyzed at a low temperature, There is no gas remaining, which is excellent in improving the quality and productivity of the molded product.
BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a comparison of a master model printed with a composition of the present invention and a conventional composition
FIG. 2 is a schematic view of the MiiCraft 3D printer used in the embodiment of the present invention.
Fig. 3 is a schematic view showing a master model pyrolysis test
Fig. 4 is a graph showing the results of the master model pyrolysis test
Fig. 5 is a graph showing the results of a master model pyrolysis test
Fig. 6 is a graph showing the results of a master model pyrolysis test
The present invention relates to: (A) a reactive oligomer which is a glycidyl methacrylate compound represented by the following formula (1) wherein a methyl group is introduced into a main chain and the main chain is composed of a propylene group repeating unit; (B) a reactive diluent; (C) a photopolymerization initiator; (D) pigment, which is characterized by comprising a photocurable composition for molding a precision casting thermal decomposition master model.
[Chemical Formula 1]
(Wherein n is an integer of 1 to 30)
The reactive oligomer (A) is a photo-curing composition for molding a precision casting thermal cracking master model, wherein a methyl group is introduced into a main chain and the main chain is composed of a repeating unit of propylene group and further a methacrylate compound represented by the following formula As a feature of the technical configuration.
(2)
(Wherein n is an integer of 1 to 30)
The reactive diluent (B) is a monomer having at least one radically polymerizable functional group capable of copolymerizing with a reactive oligomer, wherein the reactive diluent (B) is selected from the group consisting of caprolactone acrylate, octyldecyl acrylate, isooctyl acrylate,? -Phenyl phenol (EO) 2 acrylate, phenol (EO) 4 acrylate, phenol (EO) 2 acrylate, benzyl acrylate, lauryl acrylate, behenyl acrylate, isodecyl acrylate, phenol (EO) 8 acrylate, nonylphenol (PO) 2 acrylate, ethoxyethoxyethyl acrylate, stearyl acrylate, stearyl acrylate, stearyl acrylate, Monofunctional acrylates selected from aryl acrylates; Hexanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol (EO) n diacrylate, butanediol diacrylate, hydroxylpivalic acid neopentyl glycol diacrylate, neopentyl glycol (PO) Diethylene glycol diacrylate, bisphenol A (EO) 4 diacrylate, bisphenol A (EO) 3 diacrylate, bisphenol A (EO) 10 di Acrylate, bisphenol A (EO) 20 diacrylate, bisphenol A (EO) 30 diacrylate, tricyclodecane dimethanol diacrylate, tetraethylene glycol diacrylate,
The photopolymerization initiator (C) is an alpha-hydroxy ketone type; Phenylglyoxylate-based; Benzyldimethylketal system; Aminoketone type; Monoacylphosphine system; Bisacylphosphine system; Phosphine oxide system; Metallocene system; And an iodonium salt-based photo-curable composition for molding a precision casting thermal decomposition master model.
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
First, the photocurable composition for molding a precision casting thermal cracking master model of the present invention comprises (A) methacrylic acid represented by the above formulas (1) to (2) wherein a main chain contains a methyl group and the main chain is composed of a repeating unit of propylene group A reactive oligomer composed of at least one late compound; (B) a reactive diluent; (C) a photopolymerization initiator; (D) a pigment.
Conventionally, a master model made of a photocurable composition containing a commonly used acrylate or methacrylate is used as a mold for a mold due to high temperature pyrolysis, retardation of pyrolysis rate, and residual remnants after pyrolysis, There is a problem that the quality of a molded product is deteriorated. However, when a propylene group is formed by introducing a methyl group into the main chain of the acrylate or methacrylate compound, it is thermally decomposed rapidly at a low temperature and remains after the pyrolysis Have been found in the present invention.
That is, the main chain of the acrylate or methacrylate compound usually used has a structure of ethylene group (-CH 2 -CH 2 -), and it is known that pyrolysis takes place through the following four stages of decomposition reaction by heat.
Initially, the initiation reaction proceeds and the radicals are recombined and propagated to produce monomers with double bonds and unit radicals. Next, the chain is subjected to a cleavage process. First, the decomposed monomer radical is combined with a non-decomposed polymer to form a separated polymer and another small unit radical, or a giant radical is generated After the hydrogen transfer takes place, a monomer radical and a stabilized olefin mixture are formed. Therefore, pyrolysis reaction of an acrylate or methacrylate compound having an ethylene group (-CH 2 -CH 2 -) main chain structure is difficult due to radical formation due to heat, and pyrolysis products are obtained as a wax phase.
Therefore, when a master model is prepared with an acrylate or methacrylate compound having an ethylene group (-CH2-CH2-) main chain structure and pyrolysis is carried out in a mold, the pyrolysis temperature is 350 to 470 ° C, It is necessary to leave a residue on the wax or to decompose into a molecule of a certain size through pyrolysis by a catalyst and to suppress the generation of a gigantic radical.
When an acrylate or methacrylate compound having an ethylene group (-CH2-CH2-) backbone structure is pyrolyzed, an aromatic component is produced by Diels-Alder reaction and condensation. This is because the cyclic compound And the back-biting phenomenon, which is converted to polymer, has been pointed out as a problem of pyrolysis.
However, an acrylate or methacrylate compound in which a methyl group is introduced into a main chain and the main chain is composed of a repeating unit of a propylene group has a propylene group (
Therefore, in the present invention, the propylene group (
Examples of the reactive diluent (B) include caprolactone acrylate, octyldecyl acrylate, isooctyl acrylate,? -Phenylphenol (EO) acrylate, 2-ethylhexyl acrylate, (EO) 2 acrylate, phenol (EO) 4 acrylate, phenol (EO) 2 acrylate, benzyl acrylate, lauryl acrylate, behenyl acrylate, isodecyl acrylate, phenol (EO) 8 acrylate, nonylphenol (PO) 2 acrylate, ethoxyethoxyethyl acrylate, stearyl acrylate, stearyl acrylate, stearyl acrylate, Monofunctional acrylates selected from aryl acrylates; Hexanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol (EO) n diacrylate, butanediol diacrylate, hydroxylpivalic acid neopentyl glycol diacrylate, neopentyl glycol (PO) Diethylene glycol diacrylate, bisphenol A (EO) 4 diacrylate, bisphenol A (EO) 3 diacrylate, bisphenol A (EO) 10 di Acrylate, bisphenol A (EO) 20 diacrylate, bisphenol A (EO) 30 diacrylate, tricyclodecane dimethanol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol 400 diacrylate, polyethylene glycol di Acrylate, polyethylene glycol 300 diacrylate, polyethylene glycol 600 diacrylate, polypropylene glycol 400 diacrylate, polypropylene glycol 750 diacrylate Bifunctional acrylate selected from tris (2-hydroxyethyl) isocyanurate diacrylate; Trimethylol propane triacrylate, trimethylol propane (EO) 3 triacrylate, trimethylol propane (EO) 6 triacrylate, trimethylol propane (EO) 9 triacrylate, trimethylol propane (EO) 15 triacrylate , Trifunctional acrylate selected from glycerin (PO) 3 triacrylate, pentaerythritol triacrylate, and tris (2-hydroxyethyl) isocyanurate triacrylate; Polyfunctional acrylates selected from pentaerythritol (EO) n tetraacrylate, pentaerythritol tetraacrylate, ditrimethylol propane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate; Benzyl methacrylate, lauryl methacrylate, lauryltetradecyl methacrylate, isodecyl methacrylate, tetradecyl methacrylate, phenoxy methacrylate, tetrahydrofurfuryl methacrylate, cetyl (C16) metha Monofunctional (meth) acrylate selected from acrylate, methacrylate, acrylate, methacrylate, acrylate, acrylate, acrylate, acrylate, Methacrylate; 1,6-hexanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-propanediol dimethacrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol (EO) 3 dimethacrylate, bisphenol A (EO) 2 di (meth) acrylate, dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, bisphenol A Methacrylate, bisphenol A (EO) 10 dimethacrylate, bisphenol A (EO) 17 dimethacrylate, bisphenol A (EO) 30 dimethacrylate, 1,3-butylene glycol dimethacrylate, polyethylene Bifunctional methacrylate selected from glycol 400 dimethacrylate and polyethylene glycol 200 dimethacrylate; And trifunctional methacrylate selected from trimethylolpropane trimethacrylate. These may be used alone, or two or more of them may be used in combination.
The photopolymerization initiator (C) is an alpha-hydroxy ketone type (
[Molding for Precision Casting Pyrolysis Master Model
Photocuring
Preparation of the composition]
Referring to the following Table 1, the photocurable composition for molding the precision casting thermal cracking master model of the present invention was prepared as in Examples 1 and 2, and the conventional compositions were prepared as in Comparative Examples 1 to 3.
Oligomer
(n = 15)
(n = 30)
Monomer
- BPA (EO) 4DA: Bisphenol A (EO) 4 Diacrylate
- HDDA: 1,6-hexanediol diacrylate
- TPGDA: Tripropylene Glycol diacrylate
- PEG400DA:
- TPO: (2,4,6-trimethylbenzoyl) -phosphine oxide
- ir 250: iodonium (4-methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophosphate (1-
[Manufacturing precision casting pyrolysis master model by 3D printer]
The resultant product obtained by printing a master model using the MiiCraft 3D Printer described in [Example 2] and Comparative Example 1 to Comparative Example 3 described in [Example 2] and [Comparative Example 3] .
As shown in FIG. 1, the products printed with the compositions of Examples 1 to 2 of the present invention are excellent in the surface printing state, and the products printed with the compositions of Comparative Examples 1 to 3 Are rough and poor in surface condition.
As mentioned in the detailed description of the present invention, the master model prepared from the compositions of Comparative Examples 1 to 3 has the following problems: high-temperature pyrolysis, pyrolysis rate delay, pyrolysis A master model prepared from the compositions of Examples 1 and 2 in which propylene groups were formed by introducing a methyl group into the main chain of the acrylate compound, Is thermally decomposed rapidly at a low temperature in the mold and remnants and gas do not remain after pyrolysis, and thus the surface condition is excellent.
[Precision casting thermal cracking master model
In mold
Pyrolysis Comparative Test]
The master model was printed using the composition of Example 1 and Comparative Examples 1 to 3 using a MiiCraft 3D Printer as shown in FIG. 2, and the thermal decomposition behavior of the master model in the mold was measured by TGA ) As shown in [Figure 3] to [Figure 6].
As shown in FIG. 3 to FIG. 6, the master model of the composition of Formula 1 of the present invention started to be pyrolyzed at 315.70 ° C and completely pyrolyzed at 432.06 ° C, and the master model of the composition of Comparative Examples 1 to 3 Are thermally decomposed at 353.46 to 474.43 캜, 384.65 to 473.13 캜, and 400.99 to 473.51 캜, respectively, so that the master model of the composition of the formula (1) is pyrolyzed at a temperature about 50 캜 lower than the master model of the composition of the comparative examples 1 to 3, Is fast.
The foregoing description is merely illustrative of the technical idea of the present invention and various changes and modifications may be made by those skilled in the art without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed in the present invention are intended to illustrate rather than limit the scope of the present invention, and the scope of the technical idea of the present invention is not limited by these embodiments. The scope of protection of the present invention should be construed according to the following claims, and all technical ideas within the scope of equivalents should be construed as falling within the scope of the present invention.
Claims (4)
[Chemical Formula 1]
(Wherein n is an integer of 1 to 30)
(B) a monomer having at least one radically polymerizable functional group copolymerizable with the reactive oligomer (A) is at least one selected from the group consisting of caprolactone acrylate, octyldecyl acrylate, isooctyl acrylate,? -Phenyl phenol (EO) (EO) 2 acrylate, phenol (EO) 4 acrylate, phenol (EO) 2 acrylate, benzyl acrylate, lauryl acrylate, behenyl acrylate, isodecyl acrylate, phenol (EO) 8 acrylate, nonylphenol (PO) 2 acrylate, ethoxyethoxyethyl acrylate, stearyl acrylate, stearyl acrylate, stearyl acrylate, Monofunctional acrylates selected from aryl acrylates; Hexanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol (EO) n diacrylate, butanediol diacrylate, hydroxylpivalic acid neopentyl glycol diacrylate, neopentyl glycol (PO) Diethylene glycol diacrylate, bisphenol A (EO) 4 diacrylate, bisphenol A (EO) 3 diacrylate, bisphenol A (EO) 10 di Acrylate, bisphenol A (EO) 20 diacrylate, bisphenol A (EO) 30 diacrylate, tricyclodecane dimethanol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol 400 diacrylate, polyethylene glycol di Acrylate, polyethylene glycol 300 diacrylate, polyethylene glycol 600 diacrylate, polypropylene glycol 400 diacrylate, polypropylene glycol 750 diacrylate Bifunctional acrylate selected from tris (2-hydroxyethyl) isocyanurate diacrylate; Trimethylol propane triacrylate, trimethylol propane (EO) 3 triacrylate, trimethylol propane (EO) 6 triacrylate, trimethylol propane (EO) 9 triacrylate, trimethylol propane (EO) 15 triacrylate , Trifunctional acrylate selected from glycerin (PO) 3 triacrylate, pentaerythritol triacrylate, and tris (2-hydroxyethyl) isocyanurate triacrylate; Polyfunctional acrylates selected from pentaerythritol (EO) n tetraacrylate, pentaerythritol tetraacrylate, ditrimethylol propane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate; Benzyl methacrylate, lauryl methacrylate, lauryltetradecyl methacrylate, isodecyl methacrylate, tetradecyl methacrylate, phenoxy methacrylate, tetrahydrofurfuryl methacrylate, cetyl (C16) metha Monofunctional (meth) acrylate selected from acrylate, methacrylate, acrylate, methacrylate, acrylate, acrylate, acrylate, acrylate, Methacrylate; 1,6-hexanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-propanediol dimethacrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol (EO) 3 dimethacrylate, bisphenol A (EO) 2 di (meth) acrylate, dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, bisphenol A Methacrylate, bisphenol A (EO) 10 dimethacrylate, bisphenol A (EO) 17 dimethacrylate, bisphenol A (EO) 30 dimethacrylate, 1,3-butylene glycol dimethacrylate, polyethylene Bifunctional methacrylate selected from glycol 400 dimethacrylate and polyethylene glycol 200 dimethacrylate; Trifunctional methacrylate selected from trimethylolpropane trimethacrylate; A reactive diluent comprising at least one member selected from the group consisting of:
(C) a photopolymerization initiator;
(D) a pigment; and a photo-curing composition for molding a precision casting thermal cracking master model
Wherein the reactive oligomer (A) is a mixture of a methacrylate compound represented by the following formula (2) wherein a methyl group is introduced into a main chain and the main chain is composed of a repeating unit of a propylene group, Light curing composition
(2)
(Wherein n is an integer of 1 to 30)
The photopolymerization initiator (C) is an alpha-hydroxy ketone type; Phenylglyoxylate-based; Benzyldimethylketal system; Aminoketone type; Monoacylphosphine system; Bisacylphosphine system; Phosphine oxide system; Metallocene system; And an iodonium salt-based photo-curable composition for molding a precision casting thermal cracking master model.
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020140112915A KR101514745B1 (en) | 2014-08-28 | 2014-08-28 | Photocurable resin composition for thermal decomposition master model mold of precision casting |
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| KR1020140112915A KR101514745B1 (en) | 2014-08-28 | 2014-08-28 | Photocurable resin composition for thermal decomposition master model mold of precision casting |
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| KR101514745B1 true KR101514745B1 (en) | 2015-04-23 |
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| KR1020140112915A KR101514745B1 (en) | 2014-08-28 | 2014-08-28 | Photocurable resin composition for thermal decomposition master model mold of precision casting |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109153765A (en) * | 2016-03-31 | 2019-01-04 | 路博润先进材料公司 | Thermoplastic polyurethane composite for solid freeform manufacture oral care and medical device and component |
| EP3418782B1 (en) * | 2016-12-26 | 2023-05-03 | LG Chem, Ltd. | Polarizer protection film, polarizing plate comprising the same, liquid crystal display comprising the polarizing plate, and coating composition for polarizer protecting film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040026122A (en) * | 2002-07-12 | 2004-03-27 | 다이요 잉키 세이조 가부시키가이샤 | Photocurable/Thermosetting Resin Composition, and Cured Article Prepared Therefrom |
| KR20060046616A (en) * | 2004-04-09 | 2006-05-17 | 다이요 잉키 세이조 가부시키가이샤 | Curable resin composition and cured film thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040026122A (en) * | 2002-07-12 | 2004-03-27 | 다이요 잉키 세이조 가부시키가이샤 | Photocurable/Thermosetting Resin Composition, and Cured Article Prepared Therefrom |
| KR20060046616A (en) * | 2004-04-09 | 2006-05-17 | 다이요 잉키 세이조 가부시키가이샤 | Curable resin composition and cured film thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109153765A (en) * | 2016-03-31 | 2019-01-04 | 路博润先进材料公司 | Thermoplastic polyurethane composite for solid freeform manufacture oral care and medical device and component |
| EP3418782B1 (en) * | 2016-12-26 | 2023-05-03 | LG Chem, Ltd. | Polarizer protection film, polarizing plate comprising the same, liquid crystal display comprising the polarizing plate, and coating composition for polarizer protecting film |
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