CN117279965A - Photocurable resin composition, cured product thereof, and method for producing three-dimensional article - Google Patents

Photocurable resin composition, cured product thereof, and method for producing three-dimensional article Download PDF

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CN117279965A
CN117279965A CN202180078671.8A CN202180078671A CN117279965A CN 117279965 A CN117279965 A CN 117279965A CN 202180078671 A CN202180078671 A CN 202180078671A CN 117279965 A CN117279965 A CN 117279965A
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resin composition
photocurable resin
radical polymerizable
meth
polymerizable compound
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平谷卓之
和田恭平
小川凉
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Canon Inc
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Canon Inc
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Priority claimed from PCT/JP2021/042349 external-priority patent/WO2022113863A1/en
Publication of CN117279965A publication Critical patent/CN117279965A/en
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Abstract

A photocurable resin composition comprising, as a polyfunctional radical polymerizable compound (a), a polyfunctional urethane (meth) acrylate (a 1) comprising at least two (meth) acryloyl groups and two urethane groups in a molecule and comprising a structure represented by the general formula (1) or (2), wherein the content of the polyfunctional urethane (meth) acrylate (a 1) is 10 to 60 parts by mass relative to 100 parts by mass of the total amount of the polyfunctional radical polymerizable compound (a) and the monofunctional radical polymerizable compound (B), and it contains rubber particles (C) whose content is 2 parts by mass or more and less than 18 parts by mass relative to 100 parts by mass of the total amount of the polyfunctional radical polymerizable compound (a) and the monofunctional radical polymerizable compound (B).

Description

Photocurable resin composition, cured product thereof, and method for producing three-dimensional article
Technical Field
The present disclosure relates to a photocurable resin composition, a cured product of the photocurable resin composition, and a method for producing a three-dimensional article.
Background
There is a known optical manufacturing method of a three-dimensional article (hereinafter referred to as "stereolithography") including repeating a step of selectively irradiating a photocurable resin composition with light to form a cured resin layer based on a three-dimensional geometry of a three-dimensional model, thereby manufacturing an article in which such cured resin layers are stacked and bonded together. Using three-dimensional geometric data of a three-dimensional model, stereolithography can easily manufacture three-dimensional objects even with complex geometries, and has therefore been applied to manufacture prototypes for checking geometries and tooling models or molds for checking functionality. In recent years, stereolithography has been applied to the manufacture of practical products.
Under such circumstances, there is a need for a photocurable resin composition capable of producing an article having high impact resistance similar to general-purpose engineering plastics (such as ABS) and high heat resistance even at relatively high temperatures to prevent deformation. Such articles also desirably have a high hardness that exhibits high stress against deformation, in other words, a high modulus of elasticity.
Patent document 1 discloses a photocurable resin composition comprising a cationically polymerizable compound (a) having two or more bisphenol structures and one or more hydroxyl groups, a cationically polymerizable compound other than component (a), a radically polymerizable compound, and multilayered polymer particles.
CITATION LIST
Patent literature
Patent document 1: japanese patent laid-open No. 2008-266551
Disclosure of Invention
Technical problem
However, the cured product of the photocurable resin composition of patent document 1 is insufficient from the viewpoint of providing mechanical strength and elastic modulus suitable for manufacturing an actual product. The elastic modulus is 2GPa or more, which is high, but the impact resistance is significantly lower than ABS.
Solution to the problem
An object of the present invention is to provide a photocurable resin composition capable of providing a cured product having a high elastic modulus and high impact resistance.
The photocurable resin composition according to the present invention comprises a polyfunctional radical polymerizable compound (a), a monofunctional radical polymerizable compound (B), rubber particles (C) formed of a diene-based compound, and a radical polymerization initiator (D), wherein the photocurable resin composition comprises, as the polyfunctional radical polymerizable compound (a): a multifunctional urethane (meth) acrylate (a 1) including at least two (meth) acryl groups and two urethane groups in a molecule and including a structure represented by the general formula (1) or (2), the content of the multifunctional urethane (meth) acrylate (a 1) being 10 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the total amount of the multifunctional radical polymerizable compound (a) and the monofunctional radical polymerizable compound (B), and the content of the rubber particles (C) being 2 parts by mass or more and less than 18 parts by mass with respect to 100 parts by mass of the total amount of the multifunctional radical polymerizable compound (a) and the monofunctional radical polymerizable compound (B).
[ chemical 1]
[ chemical 2]
[ in the general formulae (1) and (2), R 1 And R is 2 Each independently is a hydrocarbon group including an alkylene group having 1 to 18 carbon atoms, and n is 2 to 50.]
Advantageous effects of the invention
The present disclosure can provide a photocurable resin composition capable of forming a cured product having a high elastic modulus, high impact resistance, and high heat resistance and suitable for three-dimensional manufacturing.
Drawings
Fig. 1 is a schematic diagram of a configuration example of a stereolithography apparatus.
Detailed Description
Hereinafter, embodiments according to the present invention will be described. It should be noted that the embodiments described below are merely examples, and the present invention is not limited to these embodiments without being limited to the description.
Photocurable resin composition
For the photocurable resin composition according to the present invention, appropriate amounts of the polyfunctional radical polymerizable compound (a), the monofunctional radical polymerizable compound (B), the rubber particles (C) and the radical polymerization initiator (D) are placed in a stirring vessel and stirred. Other component (E) may be added as needed. The stirring temperature is usually 20℃to 120℃inclusive, preferably 40℃to 100℃inclusive. Subsequently, the volatile solvent or the like is removed as needed, whereby a composition can be produced.
The photocurable resin composition according to the present invention is suitable as a manufacturing material for stereolithography. When used as a material for producing stereolithography, the photocurable resin composition according to the present invention preferably has a viscosity of 0.050pa·s or more and 5.0pa·s or less, more preferably 0.075pa·s or more and 4.5pa·s or more, and still more preferably 0.075pa·s or more and 2.0pa·s or less at 25 ℃ at a shear rate of 5 s-1.
Hereinafter, the components included in the photocurable resin composition of the present invention will be described in detail.
[ multifunctional radical polymerizable Compound (A) ]
The multifunctional radical polymerizable compound (a) included in the photocurable resin composition is a compound including a plurality of radical polymerizable functional groups in the molecule. Hereinafter, the multifunctional radically polymerizable compound (a) may be simply referred to as compound (a).
The photocurable resin composition according to the present invention includes the following compounds as compound (a): a multifunctional urethane (meth) acrylate (a 1) comprising at least two (meth) acryl groups and at least two urethane groups in a molecule and comprising a structure represented by the general formula (1) or (2).
[ chemical 3]
[ chemical 4]
In the general formulae (1) and (2), R 1 And R is 2 Each independently is a hydrocarbon group including an alkylene group having 1 to 18 carbon atoms, and n is 2 to 50, preferably a hydrocarbon group including an alkylene group having 4 to 9 carbon atoms. R is R 1 And R is 2 Is selected from any one or more than two of the following combinations: - (CH) 2 ) m -(m＝1-18)、-(CH 2 ) h C(CH 3 ) 2 (CH 2 ) i - (h=0-15, i=0-15) and- (CH) 2 ) j CH(CH 3 )(CH 2 ) k - (j=0-16), k=0-16). Among these, R 1 And R is 2 Each particularly preferably comprises- (CH) 2 ) m - (m=4-9). In addition to alkylene, R 1 And R is 2 Aromatic hydrocarbon groups may also be included.
As the polyfunctional urethane (meth) acrylate (a 1), for example, a reaction product of a polyol-based compound, a hydroxyl group-containing (meth) acrylate-based compound, and a polyisocyanate-based compound can be used. Alternatively, a reaction product of a polyol-based compound and an isocyanate group-containing (meth) acrylate-based compound, or a reaction product of a hydroxyl group-containing (meth) acrylate-based compound and a polyisocyanate-based compound may be used. The reaction product of the hydroxyl group-containing (meth) acrylate-based compound, the polyisocyanate-based compound and the polyol-based compound is preferable because of the tendency to provide high impact resistance.
As the polyol-based compound, a polycarbonate-based polyol or a polyester-based polyol including the above structure represented by the general formula (1) or (2) can be used. These may be used alone, or two or more of them may be used in combination. From the viewpoint of tending to achieve both high elastic modulus and high impact strength, the polyfunctional urethane (meth) acrylate (a 1) formed of a polycarbonate-based polyol or a polyester-based polyol is preferable. In particular, polycarbonate-based polyols are preferred because they provide strong intermolecular interactions compared to polyester-based polyols and tend to provide a high elastic modulus without decreasing impact strength.
Other examples of the polyol-based compound include polyether-based polyols, polyolefin-based polyols and (meth) acrylic-based polyols. Such a polyol-based compound may be used in combination with a polycarbonate-based polyol and/or a polyester-based polyol.
When a combination of a polycarbonate-based polyol or a polyester-based polyol and another polyol compound is used, the amount of the polycarbonate-based polyol or the polyester-based polyol is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, based on 100 parts by mass of the total amount of the polyol compounds. The amount of the polycarbonate-based polyol or the polyester-based polyol is preferably 20 parts by mass or more, because both high elastic modulus and high impact strength tend to be provided.
A polycarbonate-series polyol is a compound including a carbonate bond in the molecule and a hydroxyl group at the terminal or side chain, and the compound may include an ester bond in addition to the carbonate bond. Examples of polycarbonate-based polyols include reaction products of polyols with phosgene and ring-opening polymers of cyclic carbonates such as alkylene carbonates.
Polyester polyols are compounds that include ester linkages in the molecule and hydroxyl groups at the terminal or side chains. Examples include: polycondensation products of polyols with polycarboxylic acids, ring-opening polymers of cyclic esters (lactones), and reaction products of three components, polyols, polycarboxylic acids, and cyclic esters.
Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1, 4-tetramethylene glycol, 1, 3-tetramethylene glycol, 2-methyl-1, 3-trimethylene glycol, 1, 5-pentamethylene glycol, neopentyl glycol, 1, 6-hexamethylene glycol, 3-methyl-1, 5-pentamethylene glycol, 2, 4-diethyl-1, 5-pentamethylene glycol, glycerin, trimethylolpropane, trimethylolethane, cyclohexane glycol (e.g., 1, 4-cyclohexane glycol), bisphenol (e.g., bisphenol a), and sugar alcohols (e.g., xylitol and sorbitol).
Examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, and hexamethylene carbonate.
Examples of polycarboxylic acids include: aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid and dodecanedioic acid; alicyclic dicarboxylic acids such as 1, 4-cyclohexanedicarboxylic acid; and aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, 2, 6-naphthalene dicarboxylic acid, terephthalic acid, and trimellitic acid.
Examples of cyclic esters include propiolactone, beta-methyl-delta-valerolactone and epsilon-caprolactone.
Examples of hydroxyl group-containing (meth) acrylic compounds include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and 6-hydroxyhexyl (meth) acrylate, 2-hydroxyethyl acryl phosphate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone-modified 2-hydroxyethyl (meth) acrylate, dipropylene glycol (meth) acrylate, fatty acid-modified glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, glycerol di (meth) acrylate, 2-hydroxy-3-acryl-oxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, ethylene oxide-modified pentaerythritol tri (meth) acrylate, dipentaerythritol (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate and ethylene oxide-modified dipentaerythritol penta (meth) acrylate. These hydroxyl group-containing (meth) acrylate compounds may be used alone or in combination of two or more thereof.
Examples of the polyisocyanate-based compound include: aromatic polyisocyanates such as toluene diisocyanate, diphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate and naphthalene diisocyanate; aliphatic polyisocyanates such as pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate and lysine triisocyanate; alicyclic polyisocyanates such as hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, and 1, 3-bis (isocyanatomethyl) cyclohexane; trimeric or polymeric compounds of these polyisocyanates, allophanate-type polyisocyanates, biuret-type polyisocyanates, and water-dispersible polyisocyanates. These polyisocyanate compounds may be used alone or in combination of two or more of them.
Examples of the isocyanate group-containing (meth) acrylate compound include 2-isocyanatoethyl (meth) acrylate and 1,1- (bisacryloxymethyl) ethyl isocyanate. Such isocyanate group-containing (meth) acrylate compounds may be used alone or in combination of two or more thereof.
The weight average molecular weight of the multifunctional urethane (meth) acrylate (a 1) of the photocurable resin composition is preferably 1000 to 60000, more preferably 2000 to 50000. When the weight average molecular weight is 1000 or more, the cured product tends to have significantly improved impact resistance with a decrease in crosslinking density; when the weight average molecular weight is more than 60000, the curable composition tends to have an increased viscosity. It should be noted that in the present invention, the phrase "above" includes "greater than" and the phrase "below" includes "less than".
The weight average molecular weight (Mw) of the multifunctional urethane (meth) acrylate (a 1) is a weight average molecular weight determined by molecular weight calibration using polystyrene standards. The weight average molecular weight can be measured using high performance liquid chromatography. For example, the weight average molecular weight can be measured using a high performance GPC apparatus "HLC-8220GPC" manufactured by Tosoh corporation and two Shodex GPCLF-804 columns (exclusion limit molecular weight: 2X 106, separation range: 300 to 2X 106) connected in series.
The multifunctional urethane (meth) acrylate (a 1) preferably has a radical polymerizable functional group equivalent of 300g/eq or more. When the radical polymerizable functional group equivalent is less than 300g/eq, the impact resistance tends to decrease as the crosslinking density increases. It should be noted that the radical polymerizable functional group equivalent is a value of the molecular weight of each radical polymerizable functional group.
In the photocurable resin composition, the content of the polyfunctional urethane (meth) acrylate (a 1) is 10 parts by mass or more and 60 parts by mass or less, preferably 15 parts by mass or more and 45 parts by mass or less, more preferably 15 parts by mass or more and 40 parts by mass or less, based on 100 parts by mass of the total amount of the polyfunctional radical polymerizable compound (a) and the monofunctional radical polymerizable compound (B). When the content of the multifunctional urethane (meth) acrylate (a 1) is within such a range, both high impact resistance and high heat resistance can be provided. When the content of the multifunctional urethane (meth) acrylate (a 1) is less than 10 parts by mass, the impact resistance tends to be significantly reduced. When the content of the multifunctional urethane (meth) acrylate (a 1) is more than 60 parts by mass, the heat resistance tends to decrease, and the viscosity of the resin composition tends to become higher than a range suitable for a material for stereolithography.
The photocurable resin composition may contain one or two or more polyfunctional radical polymerizable compounds (a 2) other than the polyfunctional urethane (meth) acrylate (a 1) as the polyfunctional radical polymerizable compound (a). In the photocurable resin composition, the radical polymerizable functional group of the multifunctional radical polymerizable compound (a 2) may be an ethylenically unsaturated group. Examples of ethylenically unsaturated groups include (meth) acryl and vinyl. Examples of the polyfunctional radical polymerizable compound (a 2) include polyfunctional (meth) acrylate-based compounds, vinyl ether group-containing (meth) acrylate-based compounds, polyfunctional (meth) acryl-containing isocyanurate-based compounds, polyfunctional (meth) acrylamide-based compounds, polyfunctional maleimide-based compounds, polyfunctional vinyl ether-based compounds, and polyfunctional aromatic vinyl-based compounds.
Examples of the polyfunctional (meth) acrylate-based compound include: ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, dimethyloltricyclodecane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-hexamethylenedi (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epsilon-caprolactone-adduct hydroxypivalate neopentyl glycol di (meth) acrylate (for example, kayarad HX-220, HX-620, etc. manufactured by Kayarad Co., ltd.), di (meth) acrylate of EO-adduct bisphenol A, multifunctional (meth) acrylate including fluorine atom, multifunctional (meth) acrylic including siloxane structure, polycarbonate diol di (meth) acrylate, polyester di (meth) acrylate, polyethylene glycol di (meth) acrylate, polyether-based multifunctional urethane (meth) acrylate, polyolefin-based multifunctional urethane (meth) acrylate, and (meth) acrylic-based multifunctional urethane (meth) acrylate.
Examples of the vinyl ether group-containing (meth) acrylate-based compound include 2-vinyloxyethyl (meth) acrylate, 4-vinyloxybutyl (meth) acrylate, 4-vinyloxybyclohexyl (meth) acrylate, 2- (vinyloxyethoxy) ethyl (meth) acrylate, and 2- (vinyloxyethoxyethoxy) ethyl (meth) acrylate.
Examples of the polyfunctional (meth) acryl-containing isocyanurate-based compound include: tris (acryloyloxyethyl) isocyanurate, tris (methacryloyloxyethyl) isocyanurate, and epsilon-caprolactone-modified tris (2-acryloyloxyethyl) isocyanurate.
Examples of the polyfunctional (meth) acrylamide-based compound include N, N ' -methylenebisacrylamide, N ' -ethylenebisacrylamide, N ' - (1, 2-dihydroxyethylene) bisacrylamide, N ' -methylenebisacrylamide, and N, N ', N "-triacryloyldiethylenetriamine.
Examples of the polyfunctional maleimide-based compound include: 4,4 '-diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3' -dimethyl-5, 5 '-diethyl-4, 4' -diphenylmethane bismaleimide, 4-methyl-1, 3-phenylene bismaleimide and 1, 6-bismaleimide- (2, 4-trimethyl) hexane.
Examples of the polyfunctional vinyl ether-based compound include: ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, polypropylene glycol divinyl ether, butylene glycol divinyl ether, hexylene glycol divinyl ether, bisphenol a alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerol trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether and dipentaerythritol hexavinyl ether.
Examples of the polyfunctional aromatic vinyl compound include divinylbenzene.
When the photocurable resin composition contains the polyfunctional radical polymerizable compound (a 2) having a radical polymerizable functional group equivalent of less than 300g/eq, the content thereof is preferably 20 parts by mass or less, more preferably 18 parts by mass or less, and even more preferably 15 parts by mass or less, relative to 100 parts by mass of the total amount of the polyfunctional radical polymerizable compound (a) and the monofunctional radical polymerizable compound (B).
When the content of the multifunctional radical polymerizable compound (a 2) having a radical polymerizable functional group equivalent of less than 300g/eq is more than 20 parts by mass, the cured product has an increased crosslink density, and the crosslink density tends to become nonuniform. Therefore, the application of impact from the outside may cause the generation of a region where stress is concentrated, so that the effect of improving impact resistance due to the addition of rubber particles cannot be provided, and the Charpy impact strength may be similar to that in the prior art.
When the photocurable resin composition contains the polyfunctional radical polymerizable compound (a 2) having a radical polymerizable functional group equivalent of 300g/eq or more, the content thereof is preferably 40 parts by mass or less, more preferably 35 parts by mass or less, relative to 100 parts by mass of the total amount of the polyfunctional radical polymerizable compound (a) and the monofunctional radical polymerizable compound (B). When the content of the multifunctional radical polymerizable compound (a 2) having a radical polymerizable functional group equivalent of 300g/eq or more is more than 40 parts by mass, the heat resistance tends to be lowered, and the resulting cured product tends to have a significantly lowered elastic modulus.
[ monofunctional radically polymerizable Compound (B) ]
In the photocurable resin composition, the monofunctional radical polymerizable compound (B) is a compound having only a single radical polymerizable functional group in the molecule. Hereinafter, the monofunctional radical polymerizable compound (B) may be simply referred to as compound (B).
Examples of free radically polymerizable functional groups include ethylenically unsaturated groups. Specific examples of the ethylenically unsaturated group include (meth) acryl and vinyl. It should be noted that, in the present specification, (meth) acryl means acryl or methacryl.
Examples of the monofunctional radical polymerizable compound (B) including a (meth) acryloyl group include monofunctional (meth) acrylamide-based compounds and monofunctional (meth) acrylate-based compounds.
Examples of the monofunctional (meth) acrylamide-based compound include (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-t-butyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-diacetone (meth) acrylamide, N-dimethyl (meth) acrylamide, N-diethyl (meth) acrylamide, N-dipropyl (meth) acrylamide, N-dibutyl (meth) acrylamide, N- (meth) acryloylmorpholine, N- (meth) acryloylpiperidine and N- [3- (dimethylamino) propyl ] acrylamide.
Examples of the monofunctional (meth) acrylate-based compound include: methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycidyl (meth) acrylate, 3-methyl-3-oxetanyl-methyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenylglycidyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, phenylcellosolve (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentyloxy ethyl (meth) acrylate, biphenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, phenyloxy (meth) acrylate, furfuryl (meth) acrylate, phenyloxy (meth) acrylate, and (meth) acrylate, phenoxypropyl (meth) acrylate, benzyl (meth) acrylate, butoxytriglycol (meth) acrylate, 2-ethylhexyl polyethylene glycol (meth) acrylate, nonylphenylpolypropylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, glycidyl (meth) acrylate, glycerol (meth) acrylate, trifluoromethyl (meth) acrylate, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, allyl (meth) acrylate, epichlorohydrin-modified butyl (meth) acrylate, epichlorohydrin-modified phenoxy (meth) acrylate, ethylene Oxide (EO) -modified phthalic acid (meth) acrylate, EO-modified succinic acid (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate, N-dimethylaminoethyl (meth) acrylate, morpholino (meth) acrylate, EO-modified phospho (meth) acrylate, japanese (meth) co-polymer, catalyst name, monofunctional (meth) acrylates comprising an imide group (product name: M-140, manufactured by Toyama Synthesis Co., ltd.), and monofunctional (meth) acrylates comprising a siloxane structure.
Examples of the monofunctional radical polymerizable compound including an ethylenically unsaturated group other than a (meth) acryloyl group include: styrene derivatives such as styrene, vinyl toluene, alpha-methyl styrene, chlorostyrene, styrenesulfonic acid and salts of the foregoing; maleimide systems, such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide and cyclohexylmaleimide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and vinyl cinnamate; vinyl cyanide compounds such as (meth) acrylonitrile; and N-vinyl compounds such as N-vinylpyrrolidone, N-vinyl-epsilon-caprolactam, N-vinylimidazole, N-vinylmorpholine, N-vinylacetamide and vinylmethyl oxazolidinone.
Such monofunctional radical polymerizable compounds may be used alone or two or more of them may be used in combination.
In the photocurable resin composition, the content of the monofunctional radical polymerizable compound (B) is preferably 40 parts by mass or more and 85 parts by mass or less, more preferably 45 parts by mass or more and 80 parts by mass or less, relative to 100 parts by mass of the total of the polyfunctional radical polymerizable compound (a) and the monofunctional radical polymerizable compound (B).
From the viewpoint of improving the curing speed, the monofunctional radical polymerizable compound preferably contains at least one compound selected from the group consisting of a monofunctional acrylamide compound, a monofunctional acrylate compound and an N-vinyl compound. In particular, it is preferable to contain a monofunctional acrylamide-based compound or an N-vinyl compound. From the viewpoint of providing both high heat resistance and high impact strength, the monofunctional acrylamide-based compound preferably includes a cyclic structure such as acryloylmorpholine or phenylacrylamide. The N-vinyl compound preferably includes a cyclic structure such as N-vinylpyrrolidone, N-vinyl-epsilon-caprolactam, N-vinylimidazole, N-vinylmorpholine or vinylmethyl oxazolidinone.
When an N-vinyl compound is used as the monofunctional radically polymerizable compound (B), the N-vinyl content relative to the total amount of radically polymerizable functional groups in the photocurable resin composition is preferably 80 mol% or less, more preferably 75 mol% or less. The homopolymerization of the N-vinyl compound is difficult, and the N-vinyl content with respect to the total amount of radical polymerizable functional groups may be set to 80 mol% or less, thereby significantly promoting curing, and a manufacturing material suitable for stereolithography may be provided, which is preferable.
In the case of using a monofunctional methacrylate-based compound as the monofunctional radically polymerizable compound (B), the curing speed tends to be increased when the methacrylate group content is 25 mol% or less relative to the total amount of radically polymerizable functional groups in the photocurable resin composition, which is preferable. The content of the methacrylate group is more preferably 20 mol% or less, or 0 mol%. When the content of the methacrylate group is more than 20 mol%, the curing speed tends to be significantly reduced, and the material of manufacture is not suitable for stereolithography, which is not preferable.
The photocurable resin composition may not include or may include a monofunctional radical polymerizable compound containing an alicyclic hydrocarbon group; when the compound is included, the content thereof is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, relative to 100 parts by mass of the total of the polyfunctional radical polymerizable compound (a) and the monofunctional radical polymerizable compound (B). When the content of the monofunctional radical polymerizable compound containing an alicyclic hydrocarbon group is more than 50 parts by mass, the effect of improving impact resistance is often not provided. Further, during the addition of the rubber particles (C), the photocurable resin composition tends to have an increased viscosity and becomes difficult to handle. For example, in the case of using a photocurable resin composition as a manufacturing material for stereolithography, its high viscosity may cause an increase in manufacturing time or difficulty in realizing the manufacturing itself.
Examples of the monofunctional radical polymerizable compound including an alicyclic hydrocarbon group include isobornyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-t-butylcyclohexyl acrylate, 3, 5-trimethylcyclohexyl acrylate, 2-methyl-2-adamantyl (meth) acrylate, and 2-ethyl-2-adamantyl (meth) acrylate.
The homopolymer or copolymer of the monofunctional radically polymerizable compound (B) preferably has a glass transition temperature (Tg) of 70℃or higher, more preferably 80℃or higher. The Tg of the copolymer can be determined by the FOX equation (formula (1)). Tg is described in absolute temperature.
1/Tg＝∑(W i /Tg i ) (1)
In the above formula (1), W i Is the mass ratio of the monofunctional radical polymerizable compound in the copolymer; tg of (Tg) i Is a homopolymer of a monofunctional radical polymerizable compound (in terms of absolute temperatureUnits). Glass transition temperature (Tg) as a homopolymer of radical polymerizable compound for FOX equation i ) Commonly known values of the polymer may be used. Alternatively, the polymer may be actually produced, and a measurement value obtained by Differential Scanning Calorimetry (DSC) or dynamic viscoelasticity measurement (DMA) may be used.
[ rubber particles (C) ]
The photocurable resin composition is allowed to contain rubber particles (C) to provide a cured product having improved impact resistance.
The composition forming the rubber particles included in the photocurable resin composition is a diene compound. Examples of the rubber particles formed of the diene-based compound include butadiene rubber, crosslinked butadiene rubber, styrene/butadiene copolymer rubber, acrylonitrile/butadiene copolymer rubber, isoprene rubber, chloroprene rubber, and natural rubber. The rubber particles are preferably formed from one such composition or a combination of two or more such compositions. In particular, from the viewpoints of improving impact resistance and suppressing an increase in viscosity of the photocurable resin composition, the rubber particles particularly preferably include at least one selected from the group consisting of butadiene rubber, crosslinked butadiene rubber, and styrene/butadiene copolymer rubber.
The composition of the rubber particles preferably has a glass transition temperature of 0 ℃ or less, more preferably-5 ℃ or less. When the glass transition temperature is more than 0 ℃, the effect of improving the impact resistance is not often provided. The glass transition temperature of the composition of the rubber particles may be determined by, for example, differential Scanning Calorimetry (DSC) or dynamic viscoelasticity measurement (DMA).
The rubber particles are more preferably rubber particles having a core-shell structure. Specifically, the rubber particles preferably include a core containing the above rubber, and further include a shell covering the outer surface (surface) of the core and formed of a polymer of a radical polymerizable compound. The use of such rubber particles having a core-shell structure can appropriately improve the dispersibility of the rubber particles in the resin composition, which can further improve the impact resistance.
The polymer of the radically polymerizable compound forming the shell preferably has a form that is graft polymerized to the surface of the core by chemical bond and covers at least a portion of the core. The rubber particles having a core-shell structure formed by graft polymerization of the shell and the core may be formed by: the graft polymerization of the radically polymerizable compound is carried out by a known method in the presence of particles serving as a core. For example, the rubber particles may be prepared in the following manner: to latex particles which can be prepared by emulsion polymerization, microemulsion polymerization, suspension polymerization, seed polymerization, or the like and dispersed in water, a radical polymerizable compound serving as a component material of the shell may be added and polymerized.
It should be noted that when the surface of the core has no or very small amounts of reactive moieties (e.g., ethylenically unsaturated groups) for the graft polymerization of the shell, an intermediate layer containing reactive moieties may be formed on the surface of the particles acting as the core prior to the graft polymerization of the shell. In other words, the form of the rubber particle having the core-shell structure includes such forms: wherein a shell is formed over the core with an intermediate layer disposed therebetween.
As the radical polymerizable compound forming the shell, a monofunctional radical polymerizable compound having a single radical polymerizable functional group in the molecule can be suitably used. In the case of being dispersed in a resin composition including a radical polymerizable compound, rubber particles including a shell of a polymer containing a monofunctional radical polymerizable compound exhibit high dispersibility. Such rubber particles are also preferable from the viewpoint of tending to provide high impact resistance.
The monofunctional radical polymerizable compound used for forming the shell may be appropriately selected in consideration of compatibility with the core-forming composition and dispersibility in the resin composition. For example, one or a combination of two or more selected from the materials described as examples of the monofunctional radical polymerizable compound (B) may be used. When the shell includes a polymer of a (meth) acryl-containing monofunctional radical polymerizable compound, the rubber particles exhibit high dispersibility in the photocurable resin composition, and an increase in viscosity of the photocurable resin composition tends to be suppressed, which is preferable.
As the radical polymerizable compound for forming the shell, a monofunctional radical polymerizable compound and a polyfunctional radical polymerizable compound may be used in combination. When a multifunctional radical polymerizable compound is used to form the shell, the photocurable resin composition tends to have a low viscosity and becomes easy to handle. On the other hand, when the content of the polyfunctional radical polymerizable compound is too high, there is a tendency that the effect of improving the impact resistance by adding the rubber particles having the core-shell structure cannot be provided. Therefore, in the case of forming the shell using the polyfunctional radical polymerizable compound, the amount of the polyfunctional radical polymerizable compound is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and still more preferably 25 parts by mass or less, per 100 parts by mass of the radical polymerizable compound for forming the shell. It should be noted that the polyfunctional radical polymerizable compound for forming the shell may be appropriately selected in consideration of compatibility with the composition forming the core and dispersibility in the resin composition. One or a combination of two or more selected from the materials described as examples of the multifunctional urethane (meth) acrylate (a 1) and the multifunctional radical polymerizable compound (a 2) may be used.
In the rubber particle having a core-shell structure, the core-shell mass ratio of the shell to 100 parts by mass of the core is preferably 1 part by mass or more and 200 parts by mass or less, more preferably 2 parts by mass or more and 180 parts by mass or less. When the core-shell mass ratio is within such a range, the addition to the photocurable resin composition can effectively improve impact resistance. When the amount of the shell is less than 1 part by mass, dispersibility of the rubber particles in the photocurable resin composition is insufficient, and thus an effect of improving impact resistance tends to be not provided. When the amount of the shell exceeds 200 parts by mass, the rubber particles are covered thickly by the shell, which reduces the effect of improving impact resistance due to the rubber component. In order to provide sufficient impact resistance, a large amount of rubber particles needs to be added; the addition of a large amount of rubber particles tends to cause an increase in viscosity of the photocurable resin composition and difficulty in handling.
The average particle diameter of the rubber particles is preferably 20nm to 10 μm, or 50nm to 5 μm. When the average particle diameter is less than 20nm, an increase in viscosity of the photocurable resin composition due to the addition of the rubber particles or the interaction between the rubber particles tends to cause a decrease in heat resistance or a decrease in impact resistance of the cured product due to an increase in the specific surface area of the rubber particles.
When the average particle diameter is more than 10 μm, the surface area (specific surface area) of the contact interface between such rubber particles (rubber component) and the cured product of the photocurable resin composition is excessively reduced, so that the effect of improving impact resistance by the addition of the rubber particles tends to be reduced. The average particle diameter as used herein refers to an arithmetic (numerical) average particle diameter, and can be measured by a dynamic light scattering method. For example, the average particle diameter of rubber particles dispersed in a suitable organic solvent may be measured using a particle size measuring device.
The rubber particles preferably have a gel fraction of 5% or more. When the gel fraction is less than 5%, impact resistance and heat resistance tend to decrease, which is not preferable. The gel fraction can be determined in the following manner. Will W 1 [g]Is immersed in a sufficient amount of toluene and left at room temperature for 7 days. Subsequently, the solid component is separated by centrifugation or the like, and dried at 100 ℃ for 2 hours; the amount of the solid component after drying was measured. The mass of the solid component after drying is W 2 [g]The gel fraction is represented, and may be determined using the following equation.
Gel fraction (%) =w 2 /W 1 ×100
In the photocurable resin composition, the content of the rubber particles is 2 parts by mass or more and less than 18 parts by mass, preferably 3 parts by mass or more and 16 parts by mass or less, based on 100 parts by mass of the total amount of the radical polymerizable compounds. When the content of the rubber particles is less than 2 parts by mass, the effect of improving the impact resistance by adding the rubber particles cannot be provided. When the content of the rubber particles is 18 parts by mass or more, the elastic modulus of the resulting cured product is significantly reduced. Further, the rubber particles are close to each other and thus interact more strongly, so that the viscosity of the photocurable resin composition increases significantly, thereby becoming difficult to handle.
[ radical polymerization initiator (D) ]
As the radical polymerization initiator (D), a photo radical polymerization initiator or a thermal radical polymerization initiator may be used.
Photo radical polymerization initiators are mainly classified into intramolecular cleavage type and hydrogen extraction type. In the case of intramolecular cleavage type photo-radical polymerization initiators, such initiators absorb light of a specific wavelength, causing bonds in specific structural portions to be broken; at the broken structural portion, a radical is generated and acts as a polymerization initiator to initiate polymerization of the (meth) acryl-containing ethylenically unsaturated compound. On the other hand, in the case of the hydrogen extraction type, absorption of light of a specific wavelength occurs, which results in an excited state; the excited species cause a reaction that extracts hydrogen from surrounding hydrogen donors, thereby generating free radicals; the radical acts as a polymerization initiator to initiate polymerization of the radical polymerizable compound.
As the intramolecular cleavage type photo-radical polymerization initiator, an alkylbenzene ketone type photo-radical polymerization initiator, an acyl phosphine oxide type photo-radical polymerization initiator, and an oxime ester type photo-radical polymerization initiator are known. Such initiators may undergo alpha cleavage of the bond adjacent to the carbonyl group, thereby generating a radical species. Examples of the alkyl benzophenone-based photo radical polymerization initiator include: benzyl methyl ketal-based photo-radical polymerization initiator, alpha-hydroxy alkyl benzophenone-based photo-radical polymerization initiator, and amino alkyl benzophenone-based photo-radical polymerization initiator. For non-limiting specific compounds, examples of the benzyl methyl ketal-based photo radical polymerization initiator include 2,2' -dimethoxy-1, 2-diphenylethan-1-one (IRGACURE (registered trademark) 651, manufactured by BASF); examples of the α -hydroxyalkylphenone-based photo radical polymerization initiator include: 2-hydroxy-2-methyl-1-phenylpropan-1-one (DAROCUR 1173, manufactured by BASF), 1-hydroxycyclohexylphenyl ketone (IRGACURE 184, manufactured by BASF), 1- [4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methyl-1-propan-1-one (IRGACURE 2959, manufactured by BASF), and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropanoyl) benzyl ] phenyl } -2-methylpropan-1-one (IRGACURE 127, manufactured by BASF); examples of aminoalkylphenone-based photo-radical polymerization initiators include: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (IRGACURE 907, manufactured by BASF) and 2-benzyl methyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone (IRGA CURE 369, manufactured by BASF). Non-limiting examples of acyl phosphine oxide-based photo-radical polymerization initiators include: 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide (Lucirin TPO, manufactured by BASF) and bis (2, 4, 6-trimethylbenzoyl) -phenyl phosphine oxide (IRGACURE 819, manufactured by BASF). Non-limiting examples of oxime ester-based photo-radical polymerization initiators include (2E) -2- (benzoyloxy imino) -1- [4- (phenylthio) phenyl ] oct-1-one (IRGACURE OXE-01, manufactured by BASF). In brackets, examples of trade names are also described.
Non-limiting examples of hydrogen-extracting radical polymerization initiators include: anthraquinone derivatives such as 2-ethyl-9, 10-anthraquinone and 2-tert-butyl-9, 10-anthraquinone, and thioxanthone derivatives such as isopropylthioxanthone and 2, 4-diethylthioxanthone. Such a photo radical polymerization initiator may be used alone, or two or more thereof may be used in combination. They may be used in combination with a thermal radical polymerization initiator described later.
The amount of the photo radical polymerization initiator to be added is preferably 0.1 part by mass or more and 15 parts by mass or less, more preferably 0.1 part by mass or more and 10 parts by mass or less, per 100 parts by mass of the radical polymerizable compound included in the photocurable resin composition. When the amount of the photo radical polymerization initiator is small, the polymerization tends to become insufficient. In the case of excessively adding the polymerization initiator, the molecular weight may not be increased, and the heat resistance or impact resistance may be lowered. The radically polymerizable compound as used herein refers collectively to the polyfunctional radically polymerizable compound (a) and the monofunctional radically polymerizable compound (B).
The thermal radical polymerization initiator may be (without particular limitation) any known compound that generates radicals upon heating; preferred examples include azo compounds, peroxides and persulfates. Examples of the azo-based compound include: 2,2 '-azobisisobutyronitrile, 2' -azobis (methyl isobutyrate), 2 '-azobis-2, 4-dimethylvaleronitrile and 1,1' -azobis (1-acetoxy-1-phenylethane). Examples of peroxides include: benzoyl peroxide, di-tert-butylbenzoyl peroxide, tert-butyl perpivalate and di (4-tert-butylcyclohexyl) peroxydicarbonate. Examples of persulfates include persulfates, such as ammonium persulfate, sodium persulfate, and potassium persulfate.
The amount of the thermal radical polymerization initiator to be added is preferably 0.1 part by mass or more and 15 parts by mass or less, more preferably 0.1 part by mass or more and 10 parts by mass or less, per 100 parts by mass of the radical polymerizable compound included in the photocurable resin composition. In the case of excessively adding the polymerization initiator, the molecular weight does not increase, which may result in a decrease in heat resistance or impact resistance.
[ other Components (E) ]
The photocurable resin composition may contain other component (E) as long as the objects and advantages of the present invention are not impaired.
As the other component (E), a property modifier for imparting desired properties to the cured product, a photosensitizer, a polymerization initiator aid, a leveling agent, a wettability improver, a surfactant, a plasticizer, an ultraviolet absorber, and a silane coupling agent may be included. Inorganic fillers, pigments, dyes, antioxidants, flame retardants, thickeners, defoamers, and the like may be included.
The amount of the other component (E) to be added is preferably 0.05 parts by mass or more and 25 parts by mass or less, more preferably 0.1 parts by mass or more and 20 parts by mass or less, based on 100 parts by mass of the total amount of the polyfunctional radical polymerizable compound (a) and the monofunctional radical polymerizable compound (B). When such a range is satisfied, the desired properties can be imparted to the cured product or the photocurable resin composition without decreasing the elastic modulus or impact resistance of the resulting cured product.
Examples of the property modifiers for imparting desired properties to the cured product include: resins such as epoxy resin, polyurethane, polychloroprene, polyester, polysiloxane, petroleum resin, xylene resin, ketone resin and cellulose resin, engineering plastics such as polycarbonate, modified polyphenylene ether, polyamide, polyacetal, polyethylene terephthalate, polybutylene terephthalate, ultra-high molecular weight polyethylene, polyphenylsulfone, polysulfone, polyacrylate, polyetherimide, polyetheretherketone, polyphenylene sulfide, polyethersulfone, polyamideimide, liquid crystal polymer, polytetrafluoroethylene, polychlorotrifluoroethylene and polyvinylidene fluoride, fluorine-based oligomer, silicone-based oligomer, polysulfide-based oligomer, soft metals such as gold, silver and lead, and layered crystal structure substances such as graphite, molybdenum disulfide, tungsten disulfide, boron nitride, graphite fluoride, calcium fluoride, barium fluoride, lithium fluoride, silicon nitride and molybdenum selenide.
Examples of the photosensitizer include polymerization inhibitors such as phenothiazine and 2, 6-di-t-butyl-4-methylphenol, benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds.
Preparation method of article
As a method of curing the photocurable resin composition of the present invention to provide an article, known stereolithography can be suitably used. A representative example of preferred stereolithography is a method comprising repeating the step of curing the photocurable resin composition of a predetermined thickness based on slice data generated from three-dimensional geometric data of a production target (three-dimensional model). Stereolithography can be broadly divided into two methods, free surface and constraint surface.
Fig. 1 shows an example of a configuration of a stereolithography apparatus 100 using a free surface method. The stereolithography apparatus 100 comprises a tank 11 containing a photocurable resin composition 10 in liquid form. Within the groove 11, a manufacturing table 12 is provided so that it can be driven in the vertical direction by a drive shaft 13. For the light energy ray 15 emitted from the light source 14 and used for curing the photocurable resin composition 10, the irradiation position is changed by the galvano mirror 16 controlled by the control unit 18 according to the slice data, and the surface of the photocurable resin composition 10 is scanned. Fig. 1 shows a scanning range indicated by a thick dotted line.
The thickness d of the photocurable resin composition 10 cured with the light energy ray 15 is a value determined according to the setting during generation of slice data and affects the accuracy of the resulting article (reproducibility of three-dimensional geometric data of the manufactured article). The thickness d is provided by a control unit 18 that controls the driving amount of the driving shaft 13.
First, the control unit 18 controls the drive shaft 13 based on the setting so as to supply the photocurable resin composition to the stage 12 at a thickness d. Based on the slice data, the photocurable resin composition in liquid form on the stage 12 is selectively irradiated with light energy rays so as to provide a cured layer having a desired pattern, thereby forming a cured layer. Subsequently, the stage 12 is moved in the direction of the white arrow, thereby providing the uncured photocurable resin composition onto the surface of the cured layer at a thickness d. Subsequently, irradiation of the light energy ray 15 based on the slice data is performed to form a cured product bonded to the previously formed cured layer. The layer curing step may be repeated to provide the target three-dimensional article of manufacture 17.
During irradiation of the surface formed of the photocurable resin composition with the actinic energy ray to form a cured layer having a predetermined geometric pattern, the resin may be cured by a point-by-point drawing process or a line-by-line drawing process using the light energy rays converged into a dot or line shape. Alternatively, a planar photolithographic mask formed by arranging a plurality of micro-optical shutters, such as liquid crystal shutters or digital micromirror shutters, actinic energy rays may be applied in planar form to cure the resin.
As with the free surface method, the constrained surface method is preferably employed for fabrication. A stereolithography apparatus using the constrained surface method has the following configuration: stage 12 of stereolithography apparatus 100 in fig. 1 is arranged such that the article being manufactured is above the liquid level, while the light irradiation apparatus is arranged below tank 11. Representative examples of fabrication by the constrained surface method are as follows. First, a support surface of a support table provided in a vertically freely movable manner and a bottom surface of a tank containing a photocurable resin composition are positioned with a predetermined distance therebetween; a photocurable resin composition is supplied to a gap between a support surface of a support table and a bottom surface of the groove. Subsequently, the photocurable resin composition between the support surface of the stage and the bottom surface of the tank is selectively irradiated with light according to dicing data using a laser light source or a projector from the bottom surface side of the tank containing the photocurable resin composition. The light irradiation cures the photocurable resin composition between the support surface of the stage and the bottom surface of the tank, thereby forming a solid cured layer. Subsequently, the support table is moved upward so that the solidified layer is separated from the bottom surface of the groove.
Subsequently, the height of the support table is adjusted so that there is a predetermined distance between the solidified layer formed on the support table and the bottom surface of the groove. Subsequently, as in the above-described process, the photocurable resin composition is supplied to the gap between the bottom surface of the groove and the cured layer, and irradiated with light according to the dicing data, thereby forming a new cured layer between the photocurable layer and the bottom surface of the groove. This step is repeated a plurality of times to provide an article of manufacture in which a plurality of cured layers are stacked and bonded together.
The manufactured article obtained in this way is taken out of the tank 11; the unreacted photocurable resin composition remaining on the surface is removed, followed by post-treatment as needed, thereby providing a target article.
Examples of post-treatments include washing, post-curing, grinding, polishing, and assembly.
Examples of the detergent for washing include alcohol-based organic solvents typified by alcohols such as isopropyl alcohol and ethyl alcohol. Other examples include ketone-based organic solvents typified by acetone, ethyl acetate, and methyl ethyl ketone, and aliphatic organic solvents typified by terpenes.
After washing, post-curing may be performed by light irradiation, heat irradiation, or both, as needed. Post-curing can cure the unreacted photocurable resin composition (which may remain on or within the surface of the article of manufacture), thereby inhibiting tackiness of the surface of the three-dimensional article of manufacture, and also increasing the initial strength of the three-dimensional article of manufacture.
Examples of light energy rays used to fabricate three-dimensional articles of manufacture include ultraviolet radiation, electron beams, X-rays, and radiation. In particular, from the viewpoint of economy, ultraviolet radiation having a wavelength of 300nm or more and 450nm or less is preferably used. Examples of light sources configured to generate ultraviolet radiation include ultraviolet lasers (e.g., ar lasers and he—cd lasers), mercury lamps, xenon lamps, halogen lamps, and fluorescent lamps. In particular, the laser light source has a high convergence capability, can shorten the manufacturing time at an increased energy level, and can achieve high manufacturing accuracy, so that the laser light source is preferably used.
Examples
Hereinafter, embodiments according to the present invention will be described; however, the present invention is not limited to these examples.
< Material used >
The following is a list of materials used in examples and comparative examples.
[ multifunctional radical polymerizable Compound (A) ]
(multifunctional urethane (meth) acrylate (a 1))
a1-1: a polycarbonate urethane acrylate; "CN9001NS" (difunctional, number average molecular weight/weight average molecular weight (measured value): 1.3X10) 3 /5.4×10 3
a1-2: polyester urethane acrylate; "KAYARAD UXT-6100" (difunctional, number average molecular weight/weight average molecular weight (measured value) manufactured by Japanese Kagaku Co., ltd.: 2.7X10) 3 /6.0×10 3 )
(multifunctional radical polymerizable Compound (a 2) other than component (a 1))
a2-1: polyether urethane acrylate; "KAYARAD UX-6101" (difunctional, number average molecular weight/weight average molecular weight (measured value): 1.0X10) 3 /6.7×10 3 Radical polymerizable functional group equivalent: 500g/eq, manufactured by Japanese Kaikovia Co., ltd
a2-2: ethoxylated isocyanurate triacrylate "A-9300" (molecular weight: 423, free radical polymerizable functional group equivalent: 141g/eq, manufactured by Xinzhongcun chemical Co., ltd.)
a2-3: polycarbonate diol diacrylate "UM-90 (1/3) DM" (molecular weight: about 900, free radical polymerizable functional equivalent: about 450g/eq, manufactured by Yu Xingxing Co., ltd.)
[ monofunctional radically polymerizable Compound (B) ]
N-vinyl-epsilon-caprolactam
B-2: acryloylmorpholine; "ACMO" (manufactured by KJ chemical Co., ltd.)
B-3: diacetone acrylamide; "DAAM" (manufactured by KJ chemical Co., ltd.)
B-4: vinyl methyl oxazolidinone; "VMOX" (manufactured by BASF)
B-5: isobornyl acrylate
[ rubber particles (C) ]
C-1 Kane Ace M-511 (produced by Brillouin chemical Co., ltd.); rubber particles having a core-shell structure wherein the core is formed of crosslinked butadiene rubber and the shell is formed of polymethyl methacrylate
C' -1 METABLEN W-600A (Mitsubishi chemical Co., ltd.); rubber particles having a core-shell structure, wherein the core is formed of an acrylic rubber and the shell is formed of polymethyl methacrylate
An acetone dispersion of rubber particles C-1 and C' -1 was prepared in the following manner.
(preparation of acetone Dispersion of rubber particles C-1)
Rubber particles C-1 (20 parts by mass) and 80 parts by mass of acetone were mixed together and dispersed using an ultrasonic homogenizer until primary particles were formed, thereby providing an acetone dispersion of core-shell rubber particles C-1. The core-shell rubber particle C-1 was measured by a dynamic light scattering method and found to have an average particle diameter of 0.23. Mu.m.
(preparation of acetone Dispersion of rubber particles C' -1)
Rubber particles C '-1 (20 parts by mass) and 80 parts by mass of acetone were mixed together and dispersed using an ultrasonic homogenizer until primary particles were formed, thereby providing an acetone dispersion of core-shell rubber particles C' -1. The core-shell rubber particle C' -1 was measured by a dynamic light scattering method and found to have an average particle diameter of 0.36. Mu.m.
[ radical polymerization initiator (D) ]
D-1: a photo radical generator; "Irgacure819" (manufactured by BASF)
Preparation of photocurable resin composition
The materials were formulated and mixed to achieve uniformity at the mixing ratios in table 1. These mixtures were mixed with an acetone dispersion of rubber particles C-1 or C' -1 and a volatile component, and acetone was removed, thereby providing photocurable resin compositions of examples 1-8 and comparative examples 1-6.
< preparation of sample >
A cured product was prepared using the prepared photocurable resin composition in the following manner. Firstly, placing a mold with the length of 80mm, the width of 10mm and the thickness of 4mm between two quartz glass plates; such a photocurable resin composition is injected into a mold. The injected photocurable resin composition was alternately irradiated with ultraviolet radiation of 5mW/cm2 from both sides of the mold for 180 seconds each using an ultraviolet irradiation apparatus (manufactured by HOYA CANDEO OPTRONICS CORPORATION under the trade name "LIGHT SOURCE EXECURE 3000"). The resulting cured product was placed in a heating oven at 70℃and heat-treated for 2 hours, thereby providing a specimen having a length of 80mm, a width of 10mm and a thickness of 4 mm.
< evaluation >
[ weight average molecular weight ]
In a gel permeation chromatography (Gel Permeation Chromatography; GPC) apparatus (HLC-8220 GPC manufactured by Tosoh corporation), two Shodex GPC LF-804 columns (rejection limit molecular weight: 2X 106, separation range: 300 to 2X 106 manufactured by Showa electric corporation) connected in series were set, and measurement was performed at 40℃using THF as a developing solvent and an RI (refractive index, differential refractive index) detector. The weight average molecular weight determined is a value corrected using a polystyrene standard.
[ average particle diameter of rubber particles ]
Using a granulometry device (manufactured by Malvern Panalytical, zetasizer Nano ZS); in a glass tank, about 1ml of rubber particles (C-1, C-2) was placed to dilute the acetone dispersion, and the average particle diameter (Z-average) was measured at 25 ℃.
[ viscosity of photocurable resin composition ]
The viscosity of the photocurable resin composition was measured by a rotational rheometer method. Specifically, measurement was performed in the following manner using a viscoelasticity measuring instrument (Physica MCR302, manufactured by Anton Paar GmbH).
A measuring instrument equipped with a conical plate measuring clamp (CP 25-2, manufactured by Anton Paar GmbH; diameter: 25mm,2 ℃) was filled with about 0.5mL of sample and controlled at 25 ℃. Measurements were made at data intervals of 6 seconds at a constant shear rate of 5s-1 and the value at 120 seconds was determined as viscosity. This viscosity was evaluated according to the following scale. Grades a and B correspond to viscosities suitable for stereolithography, while grade C corresponds to too high a viscosity not suitable for stereolithography.
A: viscosity of 2.0 Pa.s or less
B: viscosity of more than 2.0 Pa.s and less than 5.0 Pa.s
C: viscosity of more than 5.0 Pa.s
[ deflection temperature under load ]
The sample was treated in accordance with JIS K7191-2: the sample was heated from room temperature at 2℃per minute under a bending stress of 1.80MPa using a thermal deformation Tester (manufactured by Toyo Seiki Seisakusho Co., ltd., trade name "No.533HDT Tester 3M-2"). The temperature at which the deflection amount of the sample reached 0.34mm was determined as the deflection temperature under load, and this temperature was used as an index of heat resistance. The results will be described in table 1. The heat resistance was evaluated according to the following scale. The grades a and B correspond to deflection temperatures under load acceptable for an actual product, while the grade C corresponds to deflection temperatures under load unsuitable for an actual product.
A: deflection temperature under load of 70 ℃ or higher
B: deflection temperature under load of 50 ℃ or more and less than 70 DEG C
C: deflection temperature under load of less than 50 DEG C
[ Charpy impact Strength ]
A45℃notch (notch) having a depth of 2mm was formed in the center of the sample according to JIS K7111 using a Notching apparatus (trade name "Notching Tool A-4", manufactured by Toyo Seisakusho-Sho). The sample was broken with energy of 2J from the back of the notch using an impact tester (manufactured by Toyo Seiyaku Co., ltd., "IMPACT TESTER IT"). The energy required to achieve breakage was calculated from the swing angle of the hammer (after the sample breakage) that has been swung up to 150 degrees, and was defined as the Charpy impact strength, which was an index of impact resistance. The results will be described in table 1. Impact resistance was evaluated according to the following scale. The Charpy impact strength of the cured product far higher than the existing photocurable composition was evaluated as grade A; the Charpy impact strength of the cured product higher than that of the conventional photocurable composition was evaluated as grade B. The charpy impact strength of the cured product similar to or less than the existing photocurable composition was evaluated as grade C.
A: charpy impact strength of 10kJ/m2 or more
B: a Charpy impact strength of 7kJ/m2 or more and less than 10kJ/m2
C: charpy impact strength of less than 7kJ/m2
[ flexural modulus of elasticity ]
As evaluation of mechanical properties, a flexural test was conducted according to JISK6911-1995 "test method for thermosetting plastics" to measure flexural modulus of elasticity. The measurement was performed using a tensile testing instrument (manufactured by A & D Company, limited, trade name "TENSLON Universal Material testing instrument RTF-1250"). The elastic modulus was evaluated according to the following scale. The grades A and B correspond to flexural moduli similar to or higher than the flexural modulus of a generic ABS, while the grade C corresponds to flexural modulus lower than the flexural modulus of an ABS.
A: flexural modulus of elasticity of 2.2GPa or more
B: flexural modulus of elasticity of 1.7GPa or more and less than 2.2GPa
C: flexural modulus of elasticity of less than 1.7GPa
As shown in table 1, the viscosities of the photocurable resin compositions prepared in examples 1 to 17 are within a range suitable as a manufacturing material for stereolithography. The obtained cured product has high elastic modulus, high impact resistance and high heat resistance.
The cured product according to comparative example 1 formed from the photocurable resin composition containing no polycarbonate-based urethane acrylate but only polyether-based urethane acrylate was not significantly different in impact strength from the cured product of example 1. However, both the elastic modulus and the heat resistance are low. The cured product of comparative example 2 formed of the photocurable resin composition having a high content of rubber particles (C) of 18.5 parts by mass had a very high viscosity, and was not suitable for production by stereolithography. The cured product of comparative example 3 formed of the photocurable resin composition having a low content of rubber particles (C) of 1.5 parts by mass did not have sufficiently improved impact resistance.
The photocurable resin composition containing the acrylic rubber particles has a very high viscosity, which is impractical for production by stereolithography. The resulting cured product, comparative example 4, had a low flexural temperature under load and a low flexural modulus of elasticity.
Both comparative example 5 not comprising the rubber particles (C) and comparative example 6 not comprising the polycarbonate-series urethane acrylate have low impact resistance.
The cured product of comparative example 7, which was formed from the photocurable resin composition having a rubber particle (C) content of 18 parts by mass or more, also had a low flexural modulus and a high viscosity.
Comparative example 8, which is formed of the photocurable resin composition in which the content of the multifunctional urethane (meth) acrylate (a 1) is less than 10 parts by mass with respect to 100 parts by mass of the total of the multifunctional radical polymerizable compound (a) and the monofunctional radical polymerizable compound (B), has low impact resistance. In contrast, comparative example 9, which is formed of a photocurable resin composition having a content of the polyfunctional urethane (meth) acrylate (a 1) of more than 60 parts by mass, has low heat resistance.
The above results have confirmed that: the present invention provides a photocurable resin composition having a viscosity suitable for stereolithography and a cured product provided by curing the photocurable resin composition, the cured product having a high elastic modulus, a high impact resistance and a high heat resistance.
The present invention is not limited to the above-described embodiments, and may be changed or modified in various ways without departing from the spirit and scope of the present invention. Accordingly, to disclose the scope of the invention, the claims are attached below.
The present application claims the following priorities: japanese patent application nos. 2020-194435, filed 24 at 11 in 2020, and 2021-184896, filed 12 at 11 in 2021, are incorporated herein by reference in their entireties.

Claims (27)

1. A photocurable resin composition comprising:
a polyfunctional radical polymerizable compound (A);
a monofunctional radical polymerizable compound (B);
rubber particles (C) formed of a diene compound; and
a radical polymerization initiator (D),
wherein the photocurable resin composition comprises, as the polyfunctional radical polymerizable compound (a): a multifunctional urethane (meth) acrylate (a 1) comprising at least two (meth) acryl groups and two urethane groups in a molecule and comprising a structure represented by the general formula (1) or (2),
the content of the multifunctional urethane (meth) acrylate (a 1) is 10 to 60 parts by mass based on 100 parts by mass of the total amount of the multifunctional radical polymerizable compound (A) and the monofunctional radical polymerizable compound (B), and
The content of the rubber particles (C) is 2 parts by mass or more and less than 18 parts by mass relative to 100 parts by mass of the total of the polyfunctional radical polymerizable compound (A) and the monofunctional radical polymerizable compound (B),
[ chemical 1]
[ chemical 2]
[ in the general formulae (1) and (2), R 1 And R is 2 Each independently is a hydrocarbyl group comprising an alkylene group having 1 to 18 carbon atoms, and n is 2 to 50]。
2. The photocurable resin composition according to claim 1, wherein the content of the multifunctional urethane (meth) acrylate (a 1) is 15 parts by mass or more and 45 parts by mass or less relative to 100 parts by mass of the total amount of the multifunctional radically polymerizable compound (a) and the monofunctional radically polymerizable compound (B).
3. The photocurable resin composition according to claim 1 or 2, wherein in the above general formulae (1) and (2), R1 and R2 are each independently selected from any one or a combination of two or more of the following: - (CH) 2 ) m -(m＝1-18)、-(CH 2 ) h C(CH 3 ) i - (h=0-15, i=0-15) and- (CH) 2 ) j CH(CH 3 )(CH 2 ) k -(j＝0-16，k＝0-16)。
4. The photocurable resin composition according to claim 3, wherein R is represented by the general formulae (1) and (2) 1 And R is 2 Each includes- (CH) 2 ) m -(m＝4-9)。
5. The photocurable resin composition according to any one of claims 1-4, wherein the multifunctional urethane (meth) acrylate (a 1) has a weight average molecular weight of 1000 or more and 60000 or less as determined by molecular weight calibration using a polystyrene standard.
6. The photocurable resin composition according to claim 5, wherein the weight average molecular weight of the multifunctional urethane (meth) acrylate (a 1) determined by molecular weight calibration using a polystyrene standard is 2000 or more and 50000 or less.
7. The photocurable resin composition according to any one of claims 1-6, wherein the multifunctional urethane (meth) acrylate (a 1) has a radically polymerizable functional group equivalent of 300g/eq or more.
8. The photocurable resin composition according to any one of claims 1-7, which comprises a multifunctional radically polymerizable compound (a 2) other than the multifunctional urethane (meth) acrylate (a 1) as the multifunctional radically polymerizable compound (a).
9. The photocurable resin composition according to claim 8, wherein the multifunctional radical polymerizable compound (a 2) comprises an ethylenically unsaturated group.
10. The photocurable resin composition according to claim 9, comprising as the polyfunctional radical polymerizable compound (a 2) at least one selected from the group consisting of: polyfunctional (meth) acrylate compounds, vinyl ether group-containing (meth) acrylate compounds, polyfunctional (meth) acryl-containing isocyanurate compounds, polyfunctional (meth) acrylamide compounds, polyfunctional maleimide compounds, polyfunctional vinyl ether compounds and polyfunctional aromatic vinyl compounds.
11. The photocurable resin composition according to any one of claims 8-10, wherein when a compound having a radical polymerizable functional group equivalent of less than 300g/eq is contained as the multifunctional radical polymerizable compound (a 2), the content of the compound is 20 parts by mass or less with respect to 100 parts by mass of the total amount of the multifunctional radical polymerizable compound (a) and the monofunctional radical polymerizable compound (B).
12. The photocurable resin composition according to any one of claims 8-11, wherein when a compound having a radical polymerizable functional group equivalent of 300g/eq or more is contained as the multifunctional radical polymerizable compound (a 2), the content of the compound is 40 parts by mass or less with respect to 100 parts by mass of the total amount of the multifunctional radical polymerizable compound (a) and the monofunctional radical polymerizable compound (B).
13. The photocurable resin composition according to any one of claims 1-12, wherein the content of the monofunctional radical polymerizable compound (B) is 40 parts by mass or more and 85 parts by mass or less relative to 100 parts by mass of the total amount of the multifunctional radical polymerizable compound (a) and the monofunctional radical polymerizable compound (B).
14. The photocurable resin composition according to any one of claims 1 to 13, which comprises at least one compound selected from the group consisting of a monofunctional acrylamide-based compound, a monofunctional acrylate-based compound and an N-vinyl compound as the monofunctional radical polymerizable compound (B).
15. The photocurable resin composition according to claim 14, comprising an N-vinyl compound as the monofunctional radical polymerizable compound (B), wherein the N-vinyl group content is 80 mol% or less with respect to the total amount of radical polymerizable functional groups in the photocurable resin composition.
16. The photocurable resin composition according to claim 14 or 15, which comprises an N-vinyl compound as the monofunctional radical polymerizable compound (B), wherein the N-vinyl compound comprises a cyclic structure.
17. The photocurable resin composition according to claim 16, wherein the N-vinyl compound is at least one compound selected from the group consisting of: n-vinylpyrrolidone, N-vinyl-epsilon-caprolactam, N-vinylimidazole, N-vinylmorpholine and vinylmethyl oxazolidinone.
18. The photocurable resin composition according to any one of claims 14-17, comprising a monofunctional acrylamide-based compound as the monofunctional radical polymerizable compound (B), wherein the monofunctional acrylamide-based compound comprises a cyclic structure.
19. The photocurable resin composition according to claim 18, wherein the monofunctional acrylamide-based compound is acryloylmorpholine or phenylacrylamide.
20. The photocurable resin composition according to any one of claims 14 to 19, which comprises a monofunctional methacrylate-based compound as the monofunctional radical polymerizable compound (B), wherein the content of methacrylate groups is 25 mol% or less relative to the total amount of radical polymerizable functional groups in the photocurable resin composition.
21. The photocurable resin composition according to any one of claims 1-20, which does not include or includes a alicyclic hydrocarbon group-containing compound as the monofunctional radical polymerizable compound (B), wherein in the case of including an alicyclic hydrocarbon group-containing compound, the content of the compound is 50 parts by mass or less with respect to 100 parts by mass of the total amount of the polyfunctional radical polymerizable compound (a) and the monofunctional radical polymerizable compound (B).
22. The photocurable resin composition according to any one of claims 1-21, wherein the rubber particles (C) comprise at least one selected from the group consisting of: butadiene rubber, crosslinked butadiene rubber, and styrene/butadiene copolymer rubber.
23. The photocurable resin composition according to any one of claims 1-22, wherein the rubber particles (C) have a core-shell structure in which at least a portion of a core comprising rubber is covered with a shell formed from a polymer of a radically polymerizable compound.
24. The photocurable resin composition according to any one of claims 1-23, wherein the rubber particles have an average particle diameter of 20nm or more and 10 μm or less.
25. A cured product formed by polymerizing the photocurable resin composition according to any one of claims 1-24.
26. A method of preparing an article by stereolithography, the method comprising:
a step of placing the photocurable resin composition to a predetermined thickness; and
a step of irradiating the photocurable resin composition with light energy based on slice data of a three-dimensional model to cure the photocurable resin composition,
wherein the photocurable resin composition is the photocurable resin composition according to any one of claims 1-24.
27. The method of making an article according to claim 26, wherein the light energy is light emitted by a laser light source or projector.
CN202180078671.8A 2020-11-24 2021-11-18 Photocurable resin composition, cured product thereof, and method for producing three-dimensional article Pending CN117279965A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2020-194435 2020-11-24
JP2021184896A JP2022083414A (en) 2020-11-24 2021-11-12 Photocurable resin composition and cured product of the same, and method for manufacturing three-dimensional article
JP2021-184896 2021-11-12
PCT/JP2021/042349 WO2022113863A1 (en) 2020-11-24 2021-11-18 Photocurable resin composition, cured object obtained therefrom, and method for producing three-dimensional object

Publications (1)

Publication Number Publication Date
CN117279965A true CN117279965A (en) 2023-12-22

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ID=89212885

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202180078671.8A Pending CN117279965A (en) 2020-11-24 2021-11-18 Photocurable resin composition, cured product thereof, and method for producing three-dimensional article

Country Status (1)

Country Link
CN (1) CN117279965A (en)

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