TWI654246B - Biodegradable and light-cured composition for three dimensional printing - Google Patents

Abstract

The invention discloses a biodegradable photopolymerizable composition for three-dimensional printing, which mainly comprises a material having the following content by weight: 70-90% of a photopolymer resin and a weight percentage greater than 0 and an upper limit of 20% An inorganic compound, wherein the photopolymerizable resin is a photopolymerizable biodegradable polymer having an acrylate functional group, and further, the inorganic compound can be further subjected to a decane reaction with a monodecane crosslinking agent, and the photopolymerization of the present invention The composition is a liquid state at room temperature due to the use of a small molecular weight photopolymerizable resin, which is advantageous as a photocurable material required for three-dimensional printing.

Description

Biodegradable photopolymerizable composition for three-dimensional printing

A biodegradable photopolymerizable composition for three-dimensional printing using a photopolymerizable biodegradable polymer having an acrylate functional group as a host material.

3D-Printing technology is a Rapid Prototyping technology with a wide variety of technologies, including Fused Deposition Modeling (FDM) and Laminated Object Manufacturing (LOM). And Stereolithography (SLA), etc., in which the technical principle of stereoscopic curing technology is to focus on the surface of the "photocurable material" with "light" of specific wavelength and intensity, thereby completing the single layer material. Graphical, because it has the advantage of faster forming speed, it is widely used, and in modern, biodegradable polymer (biodegradable polymer) is often used as light. The material of the solidified material, such as the Chinese Patent Publication No. CN103923470B "a biodegradable material for 3d printing", discloses a rosin containing 10 to 45% of acrylic acid, 10 to 40% of acrylic rosin. derivative, 5~10% lauric acid acrylate, 5~15% ultrafine calcium carbonate, 1-8% vinyl decane crosslinker, 20-50% hydroxy acrylate and 1~5% photoinitiator The biodegradable material composed of 3d printing has a photodegradation rate of up to 95%. Please refer to the following other patents: (1) Republic of China Invention Patent Notice No. I480293B "Photocuring "Resin and photocurable resin composition"; (2) Chinese Patent Publication No. CN103665802A "a polylactic acid material for 3d printing and a preparation method thereof"; (3) Chinese Invention Patent Publication No. CN103980682A "A kind of Polycaprolactone material for 3d printing and its preparation method".

However, the compositions disclosed in the above-mentioned various previous examples for three-dimensional printing can be found to be disadvantageously used in three-dimensional printing pastes, such as biodegradable polymers of large molecular weight. The slurry material mixed into the three-dimensional printing must still be mixed with other monomer or oligomer materials, so that it is urgent to develop a three-dimensional printing material including a small molecular weight polymer.

In view of the above problems, the present inventors have researched and analyzed existing three-dimensional printing materials based on years of experience in related industries, and are able to develop better three-dimensional printing materials; thus, the main features of the present invention The object is to provide a photopolymerizable polymer having an acrylate functional group. A biodegradable polymer, and an unalkylated or decylated inorganic compound is used as a host material to facilitate photopolymerization of a biodegradable photopolymerizable composition for three-dimensional printing.

For the above purposes, the biodegradable photopolymerizable composition for three-dimensional printing of the present invention is mainly composed of a photopolymerizable resin having a weight percentage of 70 to 90%, an inorganic component having a weight percentage greater than 0 and an upper limit of 20%. Compound.

Wherein the photopolymerizable resin is a photopolymerizable biodegradable polymer having an acrylate functional group.

Wherein, the inorganic compound is hydroxyapatite (HA), glass powder such as cerium oxide (SiO ₂ ) or zirconium dioxide (ZrO ₂ ), and mineral trioxide triaggrim (MTA). Not limited to this.

Wherein, the inorganic compound can be further subjected to a cerium grouping reaction by silanization, and the hydrogen atom of the Si-H bond of the decane cross-linking agent is alkoxy. Substituted alkoxy decane, such as Monoalkoxysilane, Diaikoxysilane or Monoalkoxysilane, but not limited thereto .

The biodegradable photopolymerizable composition for three-dimensional printing of the present invention comprises, in addition to a photopolymerizable resin having a weight percentage of 70 to 90%, an inorganic compound having a weight percentage greater than 0 and an upper limit of 20%. In addition, there may be further included at least one other additive.

Wherein, the additive is one or a combination of a photoinitiator, a fluorescent whitening agent or a color additive.

Wherein, the photoinitiator is a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, a diphenylketone compound or a mercaptophosphine oxide, but not limited thereto Specifically, the benzoin compound includes, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether; acetophenone compounds include, for example, acetophenone, 2,2-dimethoxy 2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone; anthracene compounds including, for example, 2-methylindole, 2 -ethyl hydrazine, 2-tert-butyl hydrazine, 1-chloroindole; thioxanthone compounds including, for example, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2 - chlorothioxanthone, 2,4-diisopropylthioxanthone; ketal compounds including, for example, acetophenone dimethyl ketal, benzyl dimethyl ketal; diphenyl ketone compounds including, for example, diphenyl Ketone, 4-benzylidene diphenyl sulfide, 4-benzylidene-4'-methyldiphenyl sulfide, 4-benzylidene-4'-ethyldiphenyl sulfide, 4-benzene Mercapto-4'-propyldiphenyl sulfide; mercaptophosphine oxides include, for example, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide ( Abbreviated as TPO), bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-tri Methyl amylphosphine oxide. In a preferred embodiment, the photoinitiator of the present invention is 2,4,6-trimethylbenzimidyl diphenylphosphine oxide which is a mercaptophosphine oxide.

The photoinitiator may also be Camphorquinone (CQ), 1-phenyl 1,2-propanedione (PPD), 4-dimethylaminobenzene. Ethyl formate (Ethyl-4-4dimethylaminobenzoate, EDAB or EDMAB), Dihydroxyethyl-p-toluidine or 2-(Dimethylamino)ethyl methacrylate.

Wherein, the fluorescent whitening agent is used to absorb ultraviolet light and convert it into light of other wavelengths, which may be product names DOUBLE 127, DOUBLE CBS-1, DOUBLE KCB, DOUBLE KSN, DOUBLE OB, DOUBLE OB -1, DOUBLE OB-80, DOUBLE OB-90 or Fluorescent brightener 28, but not limited to this. In the preferred embodiment, the fluorescent whitening agent of the present invention is the product name DOUBLETEX OB.

Wherein, the color additive is used to change the color of the material, such as titanium oxide, iron oxide or color paste, but not limited thereto.

In order to give a clear understanding of the purpose, technical features and effects of the present invention, the following examples will be described with reference to the drawings.

The biodegradable photopolymerizable composition for three-dimensional printing of the present invention is mainly composed of a photopolymerized resin having a weight percentage of 70 to 90%, and a weight of one hundred The inorganic compound is composed of an inorganic compound having a ratio of more than 0 and an upper limit of 20%. In addition, at least one additive may be further included, wherein the additive is a photoinitiator (Phtoinitiator), a fluorescent whitening One or a combination of the agents or one color additive; in one embodiment, the biodegradable photopolymerizable composition for three-dimensional printing of the present invention is composed of the following materials having a weight percentage of 100%: (1) a photopolymerizable resin having a weight percentage of 70 to 90%; (2) an inorganic compound having a weight percentage greater than 0 and an upper limit of 20%; (3) a photoinitiator having a weight percentage greater than 0 and an upper limit of 5%; a fluorescent whitening agent having a weight percentage greater than 0 and an upper limit of 5%; (5) a color additive having a weight percentage greater than 0 and an upper limit of 10%. However, it is only one of the embodiments of the present invention, and the photopolymerizable composition of the present invention may also be an additive which does not contain a fluorescent whitening agent or a color additive.

The photopolymerizable resin is a photopolymerizable biodegradable polymer having an acrylate functional group, which is reacted with a biodegradable polymer of a polyester compound by a propylene chloride. Specifically, the photopolymerizable resin of the present invention has the following structural formula (I): (In the structural formula (I), n represents an integer of 1 to 99, and Ac represents an acrylonitrile group.) The photopolymerization resin used in the present invention has a smaller molecular weight than a conventional high molecular polymer, and is liquid at room temperature. The state is therefore advantageous as a photocurable material required for three-dimensional printing.

The inorganic compound having a weight percentage greater than 0 and an upper limit of 20% is hydroxyapatite (HA), glass powder such as cerium oxide (SiO2) or zirconium dioxide (ZrO2), and trioxide. (Mineral Trioxide Triaggrigate, MTA), but not limited to this, in addition, the inorganic compound can be further subjected to silanization with a decane cross-linking agent for surface modification, and the surface-modified inorganic compound is decanolated. For example, decyl hydroxyapatite can be used to increase the dispersibility of the particles in the photopolymerization resin, reduce the viscosity of the material, and increase the bonding ability of the particles to the monomer. Further, the decane crosslinker is decane. The alkoxy decane in which the hydrogen atom of the Si—H bond is substituted by an alkoxy group, such as a monoalkoxysilane, a dialkoxysilane or a trialkoxy decane crosslink Monoalkoxysilane, but not limited to this.

According to the above, the photoinitiator having a weight percentage greater than 0 and an upper limit of 5% undergoes a chemical change after receiving or absorbing external energy, and is decomposed into a radical or a cation, thereby initiating polymerization of the photopolymerization resin of the present invention. The photoinitiator is a benzoin compound, an acetophenone compound, a hydrazine compound, a thioxanthone compound, a ketal compound, a diphenyl ketone compound or a mercaptophosphine oxide, but not limited thereto; In the case of a compound, it may include, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether; in the case of an acetophenone compound, it may include, for example, acetophenone, 2,2-di Methoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone; in the case of a ruthenium compound, may include - methyl hydrazine, 2-ethyl hydrazine, 2-tert-butyl hydrazine, 1-chloroindole; in the case of thioxanthone compounds, may include, for example, 2,4-dimethyl thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; in the case of a ketal compound, may include, for example, acetophenone dimethyl ketal, benzyl Dimethyl ketal In the case of a diphenyl ketone compound, it may include, for example, diphenyl ketone, 4-benzylidene diphenyl sulfide, 4-benzylidene-4'-methyldiphenyl sulfonium, 4-benzylformamide Base-4'-ethyldiphenyl sulfide, 4-benzylidene-4'-propyldiphenyl sulfide; in the case of mercaptophosphine oxides, may include, for example, 2,4,6-trimethyl Benzomidine diphenylphosphine oxide (TPO for short), bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, bis(2,6-dimethoxybenzamide) -2,4,4-trimethylpentylphosphine oxide; in addition, the photoinitiator can also be Camphorquinone (CQ), 1-phenyl-1,2-propanedione (1-phenyl) 1,2-propanedione, PPD), ethyl 4-dimethylaminobenzoate (Ethyl-4-4dimethylaminobenzoate, EDAB or EDMAB), Dihydroxyethyl-p-toluidine or 2-(Dimethylamino)ethyl methacrylate. In a preferred embodiment, the photoinitiator of the present invention is 2,4,6-trimethylbenzimidyldiphenylphosphine oxide which is a mercaptophosphine oxide.

The fluorescent whitening agent having a weight percentage greater than 0 and an upper limit of 5% is mainly used for absorbing ultraviolet light and converting it into light of other wavelengths, which may be the product name DOUBLE 127, DOUBLE CBS- 1. One of DOUBLE KCB, DOUBLE KSN, DOUBLE OB, DOUBLE OB-1, DOUBLE OB-80, DOUBLE OB-90 or Fluorescent brightener 28, but not limited thereto. In the preferred embodiment, the fluorescent whitening agent of the present invention is the product name DOUBLETEX OB.

The color additive having a weight percentage greater than 0 and an upper limit of 10% is mainly used to change the color of the material, such as titanium oxide, iron oxide or color paste, but not limited thereto.

In summary, the biodegradable photopolymerizable composition for three-dimensional printing of the present invention is mainly composed of a photopolymerizable resin having a weight percentage of 70 to 90%, and a weight percentage greater than 0 and an upper limit of 20%. The inorganic compound is composed of, furthermore, a photoinitiator having a weight percentage greater than 0 and an upper limit of 5%, a fluorescent whitening agent having a weight percentage greater than 0 and an upper limit of 5% or a weight percentage greater than 0 and an upper limit being One or a combination of 10% of one color additive, wherein the inorganic compound may be undecylated or subjected to a decaneization reaction, and the photopolymerized resin has the following structural formula (I): (In the structural formula (I), n represents an integer of 1 to 99, and Ac represents an acryloyl group.)

Therefore, after the present invention is implemented, it is indeed achieved that the object of the present invention is to provide a photopolymerizable biodegradable polymer having an acrylate functional group, and an unalkylated or decylated inorganic compound as a main component. A biodegradable photopolymerizable composition for three-dimensional printing for the photopolymerization.

The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention; any changes and modifications made by those skilled in the art without departing from the spirit and scope of the invention All should be covered by the patent of the present invention.

In summary, the effects of the present invention are patents such as "industry availability," "novelty," and "progressiveness" of the invention; According to the provisions of the Patent Law, an application for an invention patent is filed with the bureau.

Claims (2)

A biodegradable photopolymerizable composition for use as a three-dimensionally printed paste comprising a photopolymerizable resin having a weight percentage of 70 to 90% and an inorganic compound having a weight percentage greater than 0 and an upper limit of 20%, wherein The photopolymerizable resin has the following structural formula (I): In the structural formula (I), n represents an integer of 1 to 99, and Ac represents an acryloyl group. A biodegradable photopolymerizable composition for use as a three-dimensionally printed paste comprising a photopolymerizable resin having a weight percentage of 70 to 90% and an inorganic compound having a weight percentage greater than 0 and an upper limit of 20%, and The inorganic compound can be subjected to a decane reaction with a monodecane crosslinking agent.