KR102105493B1 - Isosorbide urethane acrylate photo curable resin for 3D print with good heat resisting and printing properties and the photo curable resin composition comprising the same - Google Patents

Abstract

The present invention relates to an isosorbide urethane acrylate photocurable resin for 3D printing which has excellent heat resistance and printability, and a photocurable resin composition for 3D printing including the same. More particularly, the isosorbide urethane acrylate photocurable resin for 3D printing which has excellent heat resistance and printability is a compound represented by [Chemical Formula 1] or [Chemical Formula 2], wherein one hydroxyl group of the two hydroxyl groups of isosorbide undergoes urethane reaction with the isocyanate group of 2-isocyanatoethyl methacrylate (MOI) to form urethane acrylate, the other hydroxyl group of isosorbide undergoes urethane reaction with one isocyanate group of 4,4′-diisocyanatomethylenedicyclohexane (HDMI) or isophorone diisocyanate (IPDI) having two isocyanate groups to form urethane bonding, and the other isocyanate group of HDMI or IPDI is end-terminated.

Description

Isosorbide urethane acrylate photo curable resin for 3D print with good heat resisting and printing properties and the photo curable resin composition comprising the same}

The present invention relates to a 3D-printed isosorbate urethane acrylate photocurable resin having excellent heat resistance and printing properties, and a 3D-printed photocurable resin composition comprising the same, and more specifically, two hydrates of isosorbide. One hydroxyl group of the lock group reacts urethane with the isocyanate group of 2-Isocyanatoethyl methacrylate (MOI) having one isocyanate group to form a urethane acrylate, and the other hydroxyl group of isosorbide has two isocyanate groups Eggplant reacts urethane with one isocyanate of 4,4'-Diisocyanato-methylenedicyclohexane (HMDI) or Isophoron diisocyanate (IPDI) to produce a urethane bond, and the other isocyanate group of the HMDI or IPDI is terminally terminated. ] Or [Formula 2] It is water relates to the heat resistance and the printing properties are excellent photo-eye 3D printing Sound carbide urethane acrylate for resin and for 3D printing the photocurable resin composition comprising the same.

In general, photocuring 3D printing is to form a cured layer by irradiating a photocurable resin composition with image light corresponding to a cross-section of a molded object, and sequentially stacking the formed cured layers to complete an output.

Conventionally, the photocurable resin composition used for the photocurable 3D printing mostly uses an epoxy acrylate, and the epoxy acrylate uses an epoxy resin as a raw material, in particular, an aromatic composition BPA (bispenol-A) series Epoxy resin is used.

The BPA-based epoxy acrylate follows the basic physical properties of the existing BPA epoxy resin, so it has the advantage of being fast, inexpensive, and excellent in heat resistance, hardness, and chemical resistance.

Conventionally, as a BPA epoxy acrylate-based photocurable resin composition for 3D printing, in Korean Patent Publication No. 10-2008-0044303 (published on May 20, 2008) a) 30-80% by weight of an epoxy-containing compound; b) 5-40% by weight of bifunctional (meth) acrylate; c) (1) one or more components of low to medium molecular weight containing at least one epoxy or alcohol functional group; And (2) 5-40% by weight of a polyol-containing mixture comprising at least one polyol different from component (1) and having a higher molecular weight than component (1); d) cationic photoinitiators; e) free radical photoinitiators; And optionally f) one or more stabilizers, wherein the weight percent is based on the total weight of the photocurable composition, and the photocurable composition is known.

In addition, Korean Patent Publication No. 10-2006-0125711 (published on December 6, 2006) includes (a) a cationically curable compound, (b) an acrylate-containing compound, (c) a polyfunctional hydroxyl-containing compound, and (d) a cation. A photocurable composition comprising a photoinitiator, and (e) a free radical photoinitiator, having less than 0.54 equivalents of cationically curable groups per 100 grams, preferably less than 0.10 equivalents of acrylate groups and less than 0.10 equivalents of hydroxyl groups per 100 grams of organic portion. This is known.

However, since the BPA epoxy acrylate has a disadvantage that it is difficult to handle due to its high molecular weight and viscosity, a reactive monomer must be used as a diluent, and there is a problem that yellowing is severe when left outdoors.

The yellowing is caused by the structure of the epoxy resin using bisphenol A as a precursor. As a result of prolonged exposure to sunlight, hydrogen bound to carbon in the main chain of the epoxy resin is released to form radicals in its place. The generated radical forms a quinone ring by oxidation / reduction reaction in the benzene ring. The quinone ring formed in this way acts as a chromophore to display a color, and the color expressed by the quinone ring is yellow, so this phenomenon is generally referred to as yellowing.

In addition, when the curing degree of BPA epoxy acrylate increases, shrinkage increases, adhesion decreases, and brittle properties increase, and the material becomes brittle or brittle after curing. At this time, the shrinkage phenomenon damages the adhesive surface, so printing characteristics may deteriorate.

In order to solve the problems of the BPA epoxy acrylate as described above, a non-epoxy watch photocurable resin composition was developed, forming a three-dimensional object in a three-dimensional printer in Korean Patent Publication No. 10-2003-0009435 (published on January 19, 2003). As a chemical composition, the component includes a non-aqueous organic monomer compound, and the compound includes at least one of alcohol, ester, ether, silane, vinyl monomer, acrylic monomer, or methacrylate monomer, wherein the acrylic monomer is a tree ( Propylene glycol) diacrylate, ethylene glycol phenyl ether acrylate or 1,6 hexanediol diacrylate, or the methacrylic monomer is 1,3 butylene glycol dimethacrylate, neopentyl glycol dimethacrylate Acrylate, butyl methacrylate, 1,6 hexanediol dimethacrylate or di (propylene glycol Cole) A photocurable composition for a three-dimensional printer, which comprises at least one of allyl ether methacrylates.

In addition, in Korean Patent Publication No. 10-2012-0055242 (published on May 31, 2012), based on 100 parts by weight of the photocurable resin composition, 50 to 80 parts by weight of an acrylic compound, 10 to 50 parts by weight of silsesquioxane, sight 0.5 to 5 parts by weight of a chemical release agent and 1 to 5 parts by weight of an ultraviolet initiator, and the acrylic compound is selected from the group consisting of monofunctional monomers, bifunctional monomers, trifunctional monomers, polyfunctional monomers, and mixtures thereof. Sesquioxane is known as a photocurable resin composition characterized in that it is selected from the group consisting of silsesquioxane having acrylate or methacrylate groups and mixtures thereof.

In addition, in Korean Patent Publication No. 10-2012-0137258 (published on December 20, 2012), it is a photocurable inkjet ink with excellent wetting developability for substrates such as acrylic resin substrates, and surface liquid repellent curing with excellent adhesion to substrates As a photocurable inkjet ink capable of forming a film, an organic solvent (A), a bifunctional or lower (meth) acrylate (B) having a hydroxyl group, a urethane (meth) acrylate (C), a surfactant (D), and photopolymerization A photocurable inkjet ink containing an initiator (E) and the urethane (meth) acrylate (C) represented by the formula (2) is known.

(In the formula (2), R1, R2 and R3 are each independently a divalent organic group having 1 to 20 carbon atoms, R4 and R5 are each independently hydrogen or alkyl having 1 to 6 carbon atoms, m and n are each independently As an integer from 1 to 3.)

In addition, in Korean Patent Publication No. 10-2016-0058595 (May 25, 2016), a color ink composition for forming a three-dimensional flexible structure by applying an ultraviolet curing inkjet method using a piezo head, an acrylate oligomer 13 to 30% by weight; Acrylate monofunctional and polyfunctional monomers 60 to 80% by weight; Pigment 0.1 to 2.0% by weight; 4 to 12% by weight of photoinitiator; And an additive composition containing a leveling agent and a stabilizer, 1 to 5% by weight, of an ink composition for forming a three-dimensional flexible structure.

However, the above-mentioned curable resin compositions for 3D printing are slow in curing speed and hard to be uniformly cured due to the curing mechanism being cured only by radical curing polymerization by photocuring or UV curing of acrylate or methacrylate double bonds. There was a problem that the strength was low and the heat resistance was weak.

On the other hand, isosorbide (Isosorbide) is a heterocyclic compound derived from glucose, hydrogenated glucose to form sorbitol, which can be obtained by double dehydration.

The isosorbide is a V-shaped structure in which two tetrahydrofuran rings are bonded at an angle of 120 °, and has a hydroxy group at positions 2 and 6 carbon. Isosorbide (Isosorbide) is a compound of a rigid structure having an optical asymmetry, and its derivatives have a unique function, and are useful as a raw material for pharmaceuticals or high-functional industrial materials.

In addition, isosorbide (Isosorbide) has excellent optical properties and thermal properties, and is used in optical electronic members such as optical disk substrates, optical fibers, or lenses. In addition, it can be utilized as a composition of a dental filler by applying an isosorbide (Isosorbide) derivative.

Conventionally, a dental filler composition using an isosorbide (Isosorbide) is disclosed in Korean Patent Publication No. 10-2016-0123563 (Date of Publication October 26, 2016) represented by the structural formula 1 below.

In Structural Formula 1, m and n may be the same as or different from each other, and each independently is an integer of 1 to 3, R 1 is each independently hydrogen atom, methyl group and ethyl group, and R 2 are each independently It is either a hydrogen atom, a methyl group, or an ethyl group.

In addition, the compound represented by the following structural formula 1 in Korean Patent Publication No. 10-2018-0066548 (published on June 19, 2018); And a compound represented by the following structural formula 2; Dental filler compositions comprising an isosorbide derivative compound are known.

In structural formula 1, R 1 and R 2 may be the same or different from each other, and each independently a hydrogen atom, a C1 to C6 alkyl group, a C2 to C6 alkenyl group, a C2 to C6 alkynyl group, a C5 to C6 cycloalkyl group, and a C6 to C10 It is any one selected from aryl groups.

 In Structural Formula 2, n is any one of 2 to 5, R 3 and R 4 may be the same as or different from each other, and each independently a hydrogen atom, a C1 to C6 alkyl group, a C2 to C6 alkenyl group, and a C2 to C6 alky Any one selected from a nil group, a C5 to C6 cycloalkyl group, and a C6 to C10 aryl group.

In addition, the isosorbide (Isosorbide) is currently being developed as a photocurable resin composition for 3D printing, urethane acrylate (Urethane acrylate) and eye in Korean Patent Registration No. 10-1855122 (Registration Date April 30, 2018) A light source curable material for 3D printing is known, which includes an isosorbide methacrylate in a weight ratio of 6: 4.

In addition, a monomer comprising isosorbide, polytetramethylene glycol (Poly (tetramethylene glycol)) and acrylate on Korean Patent Registration No. 10-1850826 (date of registration April 16, 2018), or It comprises a polymer of the monomer, the monomer is acrylate, polytetramethylene glycol, isosorbide, and acrylate, respectively, characterized in that the synthetic compound is connected via isocyanate, respectively, 3D printing light source curing type Materials are known.

In addition, 2-Isocyanatoethyl methacrylate on isosorbide in International Patent Publication WO 2016/160135 Al (International Publication Date October 6, 2016) and US Registered Patent US 9,580,441 B1 (Registration Date February 28, 2017) (MOI) or Isophorone diisocyanate (IPDI) is reacted and a photocurable resin composition containing the following compounds is known.

However, the conventional isosorbide urethane methacrylate compounds, apart from the increase in glass transition temperature according to the content of isosorbide, present a problem in that mechanical properties, which are impact strenghth, are reduced ( In addition to being published in Korean Patent Publication No. 10-2015-0089625), there is a problem in that workability is significantly lowered due to the increase in room temperature crystallinity and high viscosity due to the chiral structure at room temperature for application to 3D printing.

Accordingly, the present inventors introduced a double bond to utilize an isosorbide material as a photo-curing photo-curing (radical-curing) material for a 3D printer, and complemented the material fragility during precision processing and fine pattern printing, and decided Isosorbide-based urethane by urethane reaction of 2-Isocyanatoethyl methacrylate (MOI) and 4,4'-Diisocyanato-methylenedicyclohexane (HMDI) or Isophoron diisocyanate (IPDI) to the isosorbed nucleus to suppress the increase in sex The acrylate backbone structure branch developed a photocurable resin for 3D printing and completed the present invention.

The photocurable resin for isosorbide-based urethane acrylate 3D printing of the present invention has excellent light source properties (transparency, refractive index, etc.), heat resistance and hardness properties, is eco-friendly, and is suitable as a material for DLP and SLA 3D printing It can be usefully used for manufacturing transparent products such as jewelry, optical lamps, automobile rear combination lamp lenses and glasses using 3D printers.

[Patent Document 001] Korean Patent Publication No. 10-2008-0044303 (Date of publication May 20, 2008) [Patent Document 002] Korean Patent Publication No. 10-2006-0125711 (published on December 6, 2006) [Patent Document 003] Korean Patent Publication No. 10-2003-0009435 (Date of Publication January 19, 2003) [Patent Document 004] Korean Patent Publication No. 10-2012-0055242 (published on May 31, 2012) [Patent Document 005] Korean Patent Publication No. 10-2012-0137258 (published on December 20, 2012) [Patent Document 006] Korean Patent Publication No. 10-2016-0058595 (published on May 25, 2016) [Patent Document 007] Korean Patent Publication No. 10-2016-0123563 (published on October 26, 2016) [Patent Document 008] Korean Patent Publication No. 10-2018-0066548 (published on June 19, 2018) [Patent Document 009] Korean Registered Patent 10-1855122 (Registration Date April 30, 2018) [Patent Document 0010] Korean Registered Patent 10-1850826 (Registration Date April 16, 2018) [Patent Document 0011] International Publication Patent WO 2016/160135 Al (published on October 6, 2016) [Patent Document 0012] US Registered Patent US 9,580,441 B1 (Registration Date February 28, 2017)

In order to solve the above-mentioned conventional problems, the present invention is isosorbide by urethane reaction of 2-Isocyanatoethyl methacrylate (MOI) and 4,4'-Diisocyanato-methylenedicyclohexane (HMDI) or Isophoron diisocyanate (IPDI) to the isosorbide nucleus. An object of the present invention is to solve the problem of providing a photocurable resin for 3D printing and a photocurable resin composition for 3D printing containing the same.

The present invention, in order to solve the above problems, one of the two hydroxyl groups of isosorbide (Isosorbide) hydroxyl group is urethane acrylate by urethane reaction with an isocyanate group of 2-Isocyanatoethyl methacrylate (MOI) having one isocyanate group Form, and the other hydroxy group of isosorbide reacts urethane with one isocyanate of 4,4'-Diisocyanato-methylenedicyclohexane (HMDI) or Isophoron diisocyanate (IPDI) having two isocyanate groups to form urethane bonds. In addition, the other isocyanate group of the HMDI or IPDI is a compound represented by the following [Chemical Formula 1] or [Chemical Formula 2], which is terminally terminated, and an isosorbate urethane acrylate photocurable resin for 3D printing having excellent heat resistance and printing properties. It should be used as a solution to the problem.

[Formula 1]

[Formula 2]

The heat resistance of the compound represented by the following [Formula 1-1] and the urethane acrylate to form a urethane acrylate by reacting 2-Hydroxy propyl acrylate (2-HPA) with the terminal-terminated isocyanate group of the compound represented by [Formula 1] and An isocarbide urethane acrylate photocuring resin for 3D printing with excellent printing characteristics is used as a solution to the problem.

[Formula 1-1]

The heat resistance of the compound represented by the following [Formula 1-2] and the urethane acrylate to form a urethane acrylate by reacting 2-Hydroxy ethyl acrylate (2-HEA) with the terminal-terminated isocyanate group of the compound represented by [Formula 1] and An isocarbide urethane acrylate photocuring resin for 3D printing with excellent printing characteristics is used as a solution to the problem.

[Formula 1-2]

The heat resistance of the compound represented by the following [Chemical Formula 1-3] and urethane acrylate to form a urethane acrylate by reacting the terminal-terminated isocyanate group and 2-Hydroxy ethyl methacrylate (2-HEMA) of the compound represented by [Chemical Formula 1] and An isocarbide urethane acrylate photocuring resin for 3D printing with excellent printing characteristics is used as a solution to the problem.

[Formula 1-3]

The heat resistance of the compound represented by the following [Chemical Formula 2-1] and the urethane acrylate to form a urethane acrylate by reacting the terminal-terminated isocyanate group and 2-Hydroxy propyl acrylate (2-HPA) of the compound represented by [Chemical Formula 2] and An isocarbide urethane acrylate photocuring resin for 3D printing with excellent printing characteristics is used as a solution to the problem.

[Formula 2-1]

The heat resistance of the compound represented by the following [Formula 2-2] and the urethane acrylate to form a urethane acrylate by reacting the terminal-terminated isocyanate group of the compound represented by [Formula 2] with 2-Hydroxy ethyl acrylate (2-HEA) and An isocarbide urethane acrylate photocuring resin for 3D printing with excellent printing characteristics is used as a solution to the problem.

[Formula 2-2]

The heat resistance of the compound represented by the following [Formula 2-3] and the urethane acrylate to form a urethane acrylate by reacting the terminal-terminated isocyanate group and 2-Hydroxy ethyl methacrylate (2-HEMA) of the compound represented by [Formula 2] and An isocarbide urethane acrylate photocuring resin for 3D printing with excellent printing characteristics is used as a solution to the problem.

[Formula 2-3]

[Formula 1], [Formula 1-1], [Formula 1-2], [Formula 1-3] and [Formula 2], [Formula 2-1], [Formula 2-2], [Formula 2- 3] isosorbate urethane acrylate photocurable resin for 3D printing, which has excellent heat resistance and printing properties, including any one or more compounds represented by 3] and Benzyl acrylate (BZA), a compound represented by the following [Formula 3] The composition is used as a solution to the problem.

[Formula 3]

Isosorbitic urethane acrylate photocurable resin for 3D printing having excellent heat resistance and printing characteristics of the present invention and a photocurable resin composition for 3D printing comprising the same are 2-Isocyanatoethyl methacrylate (MOI) and 4,4 ' -Isosorbide-based urethane acrylate backbone structure by urethane reaction of diisocyanato-methylenedicyclohexane (HMDI) or Isophoron diisocyanate (IPDI), which complements material fragility during precision processing and fine pattern printing and increases crystallinity In particular, it is eco-friendly with excellent light source characteristics (transparency, refractive index, etc.), heat resistance and hardness characteristics, and is suitable as a material for DLP and SLA 3D printing, so it is suitable for jewelry, optical lamps, automobiles using 3D printers. It has an excellent effect that can be usefully used for manufacturing transparent products such as rear combination lamp lenses and glasses.

1 is FT-IR spectrum data of the compound of the present invention [Formula 1-1]
Figure 2 is GPC data of the compound of the present invention [Formula 1-1]
Figure 3 is a comparative picture of the crystal properties of the compound [Formula 1-1] of the present invention
Figure 4 is a conventional isosorbite urethane acrylate DSC behavior graph
Figure 5 is a DSC behavior graph of the [Formula 1-1] compound of the present invention
6 is a printing characteristic of the composition comprising the compound of the present invention [Formula 1-1]

In the present invention, one hydroxy group of two hydroxy groups of isosorbide reacts urethane with an isocyanate group of 2-Isocyanatoethyl methacrylate (MOI) having one isocyanate group to form urethane acrylate, Another hydroxy group of (Isosorbide) is urethane reacted with one isocyanate of 4,4'-Diisocyanato-methylenedicyclohexane (HMDI) or Isophoron diisocyanate (IPDI) having two isocyanate groups to generate a urethane bond, and the HMDI or IPDI Another isocyanate group of the terminal is terminated, the compound represented by the following [Formula 1] or [Formula 2], the heat resistance and the printing property is excellent for 3D printing isosorbate urethane acrylate photocurable resin is a feature of the technical configuration .

[Formula 1]

[Formula 2]

The heat resistance of the compound represented by the following [Formula 1-1] and the urethane acrylate to form a urethane acrylate by reacting 2-Hydroxy propyl acrylate (2-HPA) with the terminal-terminated isocyanate group of the compound represented by [Formula 1] and Iso carbide urethane acrylate photo-curing resin for 3D printing, which has excellent printing characteristics, is characterized by its technical composition.

[Formula 1-1]

The heat resistance of the compound represented by the following [Formula 1-2] and the urethane acrylate to form a urethane acrylate by reacting 2-Hydroxy ethyl acrylate (2-HEA) with the terminal-terminated isocyanate group of the compound represented by [Formula 1] and Iso carbide urethane acrylate photo-curing resin for 3D printing, which has excellent printing characteristics, is characterized by its technical composition.

[Formula 1-2]

The heat resistance of the compound represented by the following [Chemical Formula 1-3] and urethane acrylate to form a urethane acrylate by reacting the terminal-terminated isocyanate group and 2-Hydroxy ethyl methacrylate (2-HEMA) of the compound represented by [Chemical Formula 1] and Iso carbide urethane acrylate photo-curing resin for 3D printing, which has excellent printing characteristics, is characterized by its technical composition.

[Formula 1-3]

The heat resistance of the compound represented by the following [Chemical Formula 2-1] and the urethane acrylate to form a urethane acrylate by reacting the terminal-terminated isocyanate group and 2-Hydroxy propyl acrylate (2-HPA) of the compound represented by [Chemical Formula 2] and Iso carbide urethane acrylate photo-curing resin for 3D printing, which has excellent printing characteristics, is characterized by its technical composition.

[Formula 2-1]

The heat resistance of the compound represented by the following [Formula 2-2] and the urethane acrylate to form a urethane acrylate by reacting the terminal-terminated isocyanate group of the compound represented by [Formula 2] with 2-Hydroxy ethyl acrylate (2-HEA) and Iso carbide urethane acrylate photo-curing resin for 3D printing, which has excellent printing characteristics, is characterized by its technical composition.

[Formula 2-2]

The heat resistance of the compound represented by the following [Formula 2-3] and the urethane acrylate to form a urethane acrylate by reacting the terminal-terminated isocyanate group and 2-Hydroxy ethyl methacrylate (2-HEMA) of the compound represented by [Formula 2] and Iso carbide urethane acrylate photo-curing resin for 3D printing, which has excellent printing characteristics, is characterized by its technical composition.

[Formula 2-3]

[Formula 1], [Formula 1-1], [Formula 1-2], [Formula 1-3] and [Formula 2], [Formula 2-1], [Formula 2-2], [Formula 2- 3] isosorbate urethane acrylate photocurable resin for 3D printing, which has excellent heat resistance and printing properties, including any one or more compounds represented by 3] and Benzyl acrylate (BZA), a compound represented by the following [Formula 3] The composition is characterized by the technical composition.

[Formula 3]

Hereinafter, preferred embodiments and drawings of the present invention will be described in detail so that those skilled in the art to which the present invention pertains may easily practice. However, the present invention may be implemented in various different forms, and is not limited to the embodiments described herein.

First, the 3D printing isosorbate urethane acrylate photocurable resin having excellent heat resistance and printing properties of the present invention is 2-Isocyanatoethyl, which has one isocyanate group and one hydroxyl group among two hydroxyl groups of isosorbide. Urethane acrylate reacts with the isocyanate group of methacrylate (MOI) to form urethane acrylate, and the other hydroxyl group of isosorbide is 4,4'-Diisocyanato-methylenedicyclohexane (HMDI) or Isophoron diisocyanate ( IPDI) is reacted with one isocyanate of urethane to form a urethane bond, and the other isocyanate group of the HMDI or IPDI is a compound represented by the following [Formula 1] or [Formula 2] which is terminally terminated.

[Formula 1]

[Formula 2]

Conventionally, urethane acrylate or urethane acrylate (IPDI) with 2-Isocyanatoethyl methacrylate (MOI) urethane-bonded at both ends of isosorbide is used for 3D printing, and it is a chiral structure at room temperature. Due to the increase in sex and high viscosity, there was a problem that workability was significantly reduced when applied as a 3D printer.

In order to improve this, in the present invention, one hydroxy group of two hydroxy groups of isosorbide reacts with an isocyanate group of 2-Isocyanatoethyl methacrylate (MOI) having one isocyanate group to form a urethane acrylate. , Another hydroxy group of isosorbide reacts with one isocyanate of 4,4'-Diisocyanato-methylenedicyclohexane (HMDI) or Isophoron diisocyanate (IPDI) having two isocyanate groups to generate urethane bonds, The other isocyanate group of the HMDI or IPDI was terminated.

That is, in order to suppress the normal temperature crystallinity due to the chiral structure of the isosorbide (Isosorbide), an alicyclic compound having two isocyanates forming a urethane bond at one end of the isosorbide (Isosorbide) 4,4 Introduced '-Diisocyanato-methylenedicyclohexane (HMDI) or Isophoron diisocyanate (IPDI), the terminally terminated isocyanate group of 4,4'-Diisocyanato-methylenedicyclohexane (HMDI) or Isophoron diisocyanate (IPDI) is excellent while suppressing room temperature crystallinity Exert hardness.

The compound represented by [Chemical Formula 1] or [Chemical Formula 2], an isocarbide urethane acrylate photocurable resin for 3D printing having excellent heat resistance and printing properties, can be synthesized by the following [Reaction Scheme 1] or [Reaction Scheme 2], respectively. have.

[Scheme 1]

[Scheme 2]

At this time, the cycloaliphatic compound having two isocyanates, 4,4'-Diisocyanato-methylenedicyclohexane (HMDI) or Isophoron diisocyanate (IPDI) structurally exhibits common properties as an alicyclic diisocyanate, and one end of isosorbide To form a double bond of the urethane bond.

In addition, the terminal-terminated isocyanate group of the compound represented by [Formula 1] or [Formula 2] of the present invention is 2-Hydroxy propyl acrylate (2-HPA), 2-Hydroxy ethyl acrylate (2-HEA) or 2 -Hydroxy ethyl methacrylate (2-HEMA) reacted with urethane, and the heat resistance and printing properties of compounds represented by the following [Formula 1-1] to [Formula 1-3] or [Formula 2-1] to [Formula 2-3] This excellent 3D printing isosorbate urethane acrylate photocurable resin is formed.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

In addition, the 3D printing isosorbate urethane acrylate photocurable resin composition excellent in heat resistance and printing properties of the present invention is the above [Formula 1], [Formula 1-1], [Formula 1-2], [Formula 1-3] ] And [Chemical Formula 2], [Chemical Formula 2-1], [Chemical Formula 2-2], [Chemical Formula 2-3], any one or more compounds, and the compound represented by the following [Chemical Formula 3] Benzyl It contains acrylate (BZA).

[Formula 3]

[Synthesis of compound represented by [Chemical Formula 1] of the present invention]

After dissolving 146 g of isosorbide in THF (Tetra Hydro furan), 0.182 g of dibutyltin dilaurate (DBTL) as a catalyst and 0.092 g of Hydroquinone monomethyl ether (MEHQ) as a polymerization inhibitor were homogeneously stirred at room temperature, and then 2-Isocyanatoethyl methacrylate (MOI) 155 g, 4,4'-Diisocyanato-methylenedicyclohexane (HMDI) 262 g was added dropwise to the homogeneously stirred mixture, and the temperature was raised while dropping reaction at 50-70 ° C. to display as [Formula 1] of the present invention. Compound was synthesized.

When the synthesized compound represented by [Formula 1] was confirmed through FT-IR Spectrum shown in [FIG. 1], there were no -NCO peaks around 2,250 cm ^-1 and -OH peaks around 3,200 ~ 3,550cm ^-1 . is a 1713 and 3,320 cm ^-1 -NH peak near 1634cm ^-1 and C = C peak was confirmed.

In addition, the molecular weight measurement of the compound represented by the [Formula 1] was measured by GPC method, the measurement results, as shown in Figure 2, Mw812 ~ 860 / Mn810 ~ 856 / DPI 1.003 distribution was confirmed.

[Synthesis of compound represented by [Formula 1-1] in which 2-HPA is urethane-reacted to the compound represented by [Formula 1] of the present invention]

130 g of 2-HPA was added to the compound represented by [Chemical Formula 1] synthesized in [Example 1], and when NCO was checked with FT-IR, the reaction was terminated when there was no -OH group, and represented by [Chemical Formula 1-1] Compound was synthesized.

[Crystalline properties of the compound represented by [Chemical Formula 1-1] of the present invention]

The crystal properties of the compound represented by [Chemical Formula 1-1] synthesized in [Example 2] were compared with the isosorbate urethane acrylate disclosed in the conventional international publication WO 2016/160135 Al, and it was 3 days at room temperature. After standing, the crystal states respectively generated were confirmed and shown in [FIG. 3].

As shown in FIG. 3, the isosorbate urethane acrylate of the present invention (photo on the right) shows that crystals are not generated and are transparent compared to the isosorbed urethane acrylate having a chiral structure (photo on the left). have.

[Physical properties of a composition comprising a compound represented by [Chemical Formula 1-1] of the present invention]

RV-214: Epoxy Acrylate (Bisphenol A Type) (Aekyung chemical Co. Ltd.) as a comparative example with a photocurable resin composition for 3D printing containing the compound represented by [Chemical Formula 1-1] synthesized in [Example 2] Acid Value 1 or less, Mw 520) and Stratasy's 3D-printed photocurable composition are mixed with BZA to prepare the composition to measure flexural strength, HDT, Shore hardness and printing properties according to the following measurement methods, and the results are as follows. It is shown in [Table 1] and [Fig. 4] to [Fig. 6].

-Shore hardness (A, D): ASTM D2240

Durometer was used to measure the hardness of the specimen during initial indentation or constant indentation time. Durometer setting was selected according to the material of the specimen to be measured. Specimens were prepared with a thickness of at least 6 mm and a width and length of 12 mm. The surface of the specimen was flat and parallel to the pedestal of the instrument.

-Flexural Strength: ASTM D790

A specimen with a rectangular cross-section was mounted on two supports and a load was applied to the middle of the specimen. The test was performed until a load was applied to the surface of the specimen until rupture or a maximum strain was applied.

Flexural strength = 3PL / 2bd2

P: Max Load, Unit N

L: Support gap, unit mm

b: width of the specimen, unit mm

d: thickness of the specimen, unit mm

-HDT (0.45 MPa): ASTM D648

A constant load (0.455 MPa) was applied to the middle portion of the rectangular bar specimen, and the specimen was mounted in a container containing a medium for heat transfer. The test measured the temperature at which the specimen was deformed below 0.25 mm while raising the temperature to 2 ° C / min.

As shown in [Table 1] and [FIG. 4] to [FIG. 5], the 3D photocurable resin ink composition according to the present invention is stratasys, the world's best competitor in terms of flexural strength, HDT (heat resistance), Shore hardness properties When compared with the material of the company, it can be seen that it appears to be similar, so it can be used as a high-strength and high-heat-resistance 3D photocurable resin ink composition, in particular, as shown in Figure 6, the photocurable photocurable for 3D printing of the present invention It can be seen that the printing resolution output by using the resin composition is also very excellent.

The above description is merely illustrative of the technical idea of the present invention, and those skilled in the art to which the present invention pertains may make various modifications and variations without departing from the essential characteristics of the present invention. Therefore, the embodiments and drawings disclosed in the present invention are not intended to limit the technical spirit of the present invention, but to explain them, and the scope of the technical spirit of the present invention is not limited by the embodiments and the drawings. The scope of protection of the present invention should be interpreted by the claims below, and all technical spirits within the scope equivalent thereto should be interpreted as being included in the scope of the present invention.

Claims (8)

Of the two hydroxy groups of isosorbide, one hydroxyl group reacts urethane with an isocyanate group of 2-Isocyanatoethyl methacrylate (MOI) having one isocyanate group to form urethane acrylate, and of isosorbide (Isosorbide) Another hydroxy group is urethane reacted with one isocyanate of 4,4'-Diisocyanato-methylenedicyclohexane (HMDI) or Isophoron diisocyanate (IPDI) having two isocyanate groups to generate a urethane bond, and the other of the HMDI or IPDI The isocyanate group is an end-terminated isocompound urethane acrylate photocurable resin for 3D printing, which is characterized by being a compound represented by the following [Chemical Formula 1] or [Chemical Formula 2]
[Formula 1]

[Formula 2]

According to claim 1,
Characterized in that the compound represented by the following [Formula 1-1] to form a urethane acrylate by urethane reaction of the terminal-terminated isocyanate group and 2-Hydroxy propyl acrylate (2-HPA) of the compound represented by [Formula 1] Iso carbide urethane acrylate photo-curing resin for 3D printing with excellent heat resistance and printing characteristics
[Formula 1-1]

According to claim 1,
Characterized in that the compound represented by the following [Formula 1-2] to form a urethane acrylate by urethane reacting the terminal-terminated isocyanate group and 2-Hydroxy ethyl acrylate (2-HEA) of the compound represented by [Formula 1] Iso carbide urethane acrylate photo-curing resin for 3D printing with excellent heat resistance and printing characteristics
[Formula 1-2]

According to claim 1,
Characterized in that the compound represented by the following [Formula 1-3] to form a urethane acrylate by urethane reaction of the terminal-terminated isocyanate group and 2-Hydroxy ethyl methacrylate (2-HEMA) of the compound represented by [Formula 1] Iso carbide urethane acrylate photo-curing resin for 3D printing with excellent heat resistance and printing characteristics
[Formula 1-3]

According to claim 1,
Characterized in that the compound represented by the following [Formula 2-1] to form a urethane acrylate by urethane reaction of the terminal-terminated isocyanate group and 2-Hydroxy propyl acrylate (2-HPA) of the compound represented by [Formula 2] Iso carbide urethane acrylate photo-curing resin for 3D printing with excellent heat resistance and printing characteristics
[Formula 2-1]

According to claim 1,
Characterized in that the compound represented by the following [Formula 2-2] to form a urethane acrylate by urethane reaction of the terminal-terminated isocyanate group and 2-Hydroxy ethyl acrylate (2-HEA) of the compound represented by [Formula 2] Iso carbide urethane acrylate photo-curing resin for 3D printing with excellent heat resistance and printing characteristics
[Formula 2-2]

According to claim 1,
Characterized in that the compound represented by the following [Formula 2-3] to form a urethane acrylate by urethane-reacting 2-Hydroxy ethyl methacrylate (2-HEMA) with the terminal-terminated isocyanate group of the compound represented by [Formula 2] Iso carbide urethane acrylate photo-curing resin for 3D printing with excellent heat resistance and printing characteristics
[Formula 2-3]

The following [formula 1], [formula 1-1], [formula 1-2], [formula 1-3] and [formula 2], [formula 2-1], [formula 2-2], [formula 2- 3] isosorbide urethane acrylic for 3D printing with excellent heat resistance and printing characteristics, comprising one or more of the compounds represented by 3] and a compound represented by the following [Formula 3], Benzyl acrylate (BZA) Late photocurable resin composition
[Formula 1]

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 2]

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 3]

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