Photocurable material composition, cured product of photocurable material composition, and method for producing the same

Abstract

To provide a photocurable material composition capable of simultaneously realizing a deflection temperature under load 40°C or higher and Charpy impact strength (with notch) 20 kJ / m2 or higher in a cured product after ultraviolet ray irradiation and also to provide the cured product.SOLUTION: A photocurable material composition at least includes a monofunctional acrylate having a 5-membered ring skeleton including an ether linkage, and a polycarbonate resin soluble to the monofunctional acrylate. In the photocurable material composition, the content of the monofunctional acrylate having the 5-membered ring skeleton including the ether linkage is 18 wt.% through 80 wt.%, and the content of the polycarbonate resin is 10 wt.% through 40 wt.%.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a photocurable material composition and a cured product obtained using the photocurable material composition. More specifically, the present invention relates to a photocurable composition capable of obtaining a cured product having a high heat distortion temperature and excellent impact resistance. Further, the present invention relates to the production of a three-dimensional cured product or the like using the photocurable composition.

Background Art

[0002] Since the photocurable material composition cures in a short time by light irradiation, it is used as a coating material, paint, sealant, and recently also as a material for the optical stereolithography method. However, although the cured product made of the photocurable material composition has impact resistance, its surface hardness, heat distortion temperature, and strength are insufficient, or it has rigidity but is brittle and prone to cracking when made into a coating film or the like. There are hardly any known materials that can achieve both impact resistance and rigidity. Therefore, in parts that require impact resistance and rigidity, thermoplastic resins are mostly used instead of the composition. Injection molding is generally used to mold thermoplastic resins into part shapes, but the degree of freedom in shape may be limited by the type of material and the type of thermoplastic resin itself.

[0003] Generally, when trying to increase the heat distortion temperature of the cured product of the photocurable material composition, materials having functional groups that can increase the crosslinking density or materials having bulky substituents are selected. However, when curing materials having functional groups that can increase the crosslinking density, such as polyfunctional acrylates and epoxy materials, or materials having bulky substituents, such as isobornyl groups, stress concentration and poor curing occur during the curing process. Therefore, although the heat distortion temperature increases, the impact resistance significantly decreases.

[0004] On the one hand, when attempting to increase the impact resistance of the cured product of a photocurable material composition, materials with a reduced crosslink density or materials with rubber-like properties are selected. However, when curing materials with a reduced crosslink density such as high molecular weight acrylic or epoxy, or materials with functional groups capable of stretching and contracting such as urethane, while the impact resistance is improved due to the low crosslink density and the absorption of impact by the stretching and contracting motion of the molecules, the cured product becomes soft, resulting in a decrease in the heat distortion temperature.

[0005] In order to achieve both a high heat distortion temperature and high impact resistance, it is possible to use a combination of materials that increase the heat distortion temperature and materials that increase the impact resistance. However, most of them result in cured products that compromise their respective advantages. Therefore, a material formulation that achieves both a high heat distortion temperature and high impact resistance has not been found in coating materials, paints, sealants, optically stereolithographed objects, and injection molded objects. As a method for evaluating the heat distortion temperature, there is the deflection temperature under load (°C), and as a method for evaluating the impact resistance value, there is the Charpy impact strength (kJ / m 2 ). However, many materials with high impact resistance have a deflection temperature under load of less than 40 °C (load 1.8 MPa), and materials with high rigidity have a Charpy impact strength of less than 5 kJ / m 2 (with notch). If the heat distortion temperature is low, the shaped object will be distorted by its own weight, and if the impact resistance value is low, defects such as chipping of thin parts will occur with a slight impact. Therefore, a material with a deflection temperature under load of 40 °C or higher and a Charpy impact strength of 20 kJ / m 2 or higher (with notch) is required.

[0006] In recent years, the optically stereolithography method has been actively developed, and cured products with special shapes that are difficult to produce by injection molding or casting have come to be produced. However, the activated energy ray-curable material compositions used in the optically stereolithography method also do not have both high impact resistance and rigidity, and their mechanical properties are insufficient for use as products or components.

[0007] Against the backdrop as described above, Patent Document 1 discloses an attempt to improve an active energy ray-curable composition by compounding polycarbonate with an active energy ray-curable material composition. Further, Patent Document 2 discloses that a cured product obtained by a formulation using a cationically polymerizable organic compound and a radically polymerizable organic compound (B) in combination is excellent in toughness and heat resistance.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0009] However, in the material formulation shown in Patent Document 1, although it is shown that the elastic modulus and breaking energy are high in the film tensile test, it is inferred from the value of the breaking energy that it is difficult for the Charpy impact strength (notched) to exceed 20 kJ / m 2 Moreover, in the material formulation shown in Patent Document 2, although the heat distortion temperature under load exceeds 40 °C, the Charpy impact strength converted from the Izod impact strength does not exceed 20 kJ / m 2 It can be inferred that it will not reach the above value.

[0010] The present invention has been made in view of the above-described background art, and its object is to provide a photocurable material composition and a cured product thereof that achieve both a heat distortion temperature under load of 40 °C or higher and a Charpy impact strength (notched) of 20 kJ / m 2 or higher after curing by ultraviolet irradiation.

Means for Solving the Problems

[0011] The photocurable material composition of the present invention comprises a monofunctional acrylate having a 5-membered ring skeleton containing at least an ether bond, and a polycarbonate resin soluble in the monofunctional acrylate having a 5-membered ring skeleton containing the ether bond. In the photocurable material composition, the content of the monofunctional acrylate having a 5-membered ring skeleton containing the ether bond is 18% by weight to 80% by weight, and the content of the polycarbonate resin is 10% by weight to 40% by weight. By irradiating this photocurable material composition with light, a cured product can be provided.

[0012] The photocurable material composition of the present invention can be used for manufacturing a three-dimensional cured product.

Effects of the Invention

[0013] According to the present invention, it is possible to provide a photocurable material composition and a cured product thereof in which the heat distortion temperature of the cured product by light irradiation is 40°C or higher and the Charpy impact strength (notched) is 20 kJ / m 2 or higher. Therefore, by using the photocurable material composition of the present invention, a cured product having mechanical properties that could not be obtained with conventional photocurable material compositions can be obtained, and parts that could not be used due to insufficient strength can also be used. Further, by using the photocurable material composition of the present invention in an optical stereolithography method, it becomes possible to supply not only models but also parts that can be used as products, and it becomes possible to directly produce products without using a mold for small-lot production products.

Brief Description of the Drawings

[0014]

Figure 1

Modes for Carrying Out the Invention

[0015] Hereinafter, the present invention will be described in detail. First, the photocurable material composition of the present invention will be described. The photocurable material composition of the present invention comprises a monofunctional acrylate having at least a five-membered ring skeleton containing an ether bond, and a polycarbonate resin (hereinafter, sometimes simply referred to as "polycarbonate resin") that is soluble in the monofunctional acrylate having a five-membered ring skeleton containing an ether bond, and the content of the monofunctional acrylate having a five-membered ring skeleton containing an ether bond in the photocurable material composition is 18% by weight to 80% by weight, and the content of the polycarbonate resin is 10% by weight to 40% by weight.

[0016] The monofunctional acrylate having a five-membered ring skeleton containing an ether bond is not particularly limited as long as it does not reduce the impact resistance of the cured product obtained by polymerization of the photocurable composition.Preferred are tetrahydrofurfuryl acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate, tetrahydrofurfuryl alcohol acrylic acid polymer ester (e.g., Viscoat #150D manufactured by Osaka Organic Chemical Industry Co., Ltd.), and alkoxylated tetrahydrofurfuryl acrylate (e.g., Sartomer SR611 manufactured by Arkema Co., Ltd.).

[0017] By using a monofunctional acrylate with a five-membered ring skeleton containing an ether bond, the adhesion at the interface with the polycarbonate resin is improved, leading to improved rigidity when made into a film and impact resistance when made into a bulk. The improved adhesion is presumably due to the fact that the oxygen atoms in the five-membered ring skeleton containing an ether bond are more polar than the oxygen atoms in the six-membered ring skeleton. Since polycarbonate resin has a polycarbonate moiety, it is believed that the interaction between the oxygen atoms in the more polar polycarbonate moiety and the oxygen atoms in the five-membered ring skeleton is stronger, improving adhesion. In addition, since acrylates containing three- or four-membered ring skeletons containing ether bonds may undergo ring-opening reactions due to acids or bases, a monofunctional acrylate with a five-membered ring skeleton containing an ether bond is used.

[0018] Furthermore, the compatibility with the polycarbonate resin is also improved by using a monofunctional acrylate having a 5-membered ring skeleton containing an ether bond. By improving the compatibility, the monofunctional acrylate having a 5-membered ring skeleton containing an ether bond and the polycarbonate resin are mixed at the molecular level before curing, so that a phase separation structure at the submicron level is also possible when cured. On the other hand, when the compatibility is low, it is considered that the phase separation structure during curing is also larger than that of the present invention, and it is difficult to achieve high mechanical properties even if the adhesion is improved.

[0019] On the other hand, a polyfunctional acrylate having a 5-membered ring skeleton containing an ether bond is also suitable in terms of improving the adhesion to the polycarbonate resin. However, in the case of a polyfunctional acrylate, the impact resistance of the film or bulk body deteriorates due to defective sites of a size that cannot be observed visually due to a large amount of shrinkage during curing and the influence of residual stress due to an increase in the crosslinking density, so it is not suitable for the present invention.

[0020] In addition, when the monofunctional acrylate having a 5-membered ring skeleton containing an ether bond becomes a monofunctional methacrylate having a 5-membered ring skeleton containing an ether bond, the mechanical properties related to rigidity such as the heat distortion temperature under load are improved. However, since the impact resistance is drastically reduced, in the present invention, it is not possible to use a monofunctional methacrylate having a 5-membered ring skeleton containing an ether bond as the main component instead of the monofunctional acrylate having a 5-membered ring skeleton containing an ether bond.

[0021] The content of the monofunctional acrylate having a 5-membered ring skeleton containing an ether bond in the photocurable material composition is not particularly limited as long as it does not deteriorate the mechanical properties of the cured product obtained by polymerizing the photocurable material composition. Considering the solubility of the polycarbonate resin, the mechanical properties of the cured product obtained by polymerizing the photocurable material composition, the viscosity of the photocurable material composition, etc., it is 18% by weight to 80% by weight.

[0022] A polycarbonate resin soluble in a monofunctional acrylate having a 5-membered ring skeleton containing an ether bond is not particularly limited as long as it can be uniformly dissolved in the monofunctional acrylate having a 5-membered ring skeleton containing an ether bond, and examples include bisphenol A type polycarbonate, bisphenol AP type polycarbonate, bisphenol AF type polycarbonate, bisphenol B type polycarbonate, bisphenol BP type polycarbonate, bisphenol C type polycarbonate, bisphenol E type polycarbonate, bisphenol F type polycarbonate, bisphenol G type polycarbonate, bisphenol M type polycarbonate, bisphenol S type polycarbonate, bisphenol P type polycarbonate, bisphenol PH type polycarbonate, bisphenol TMC type polycarbonate, bisphenol Z type polycarbonate, bisphenoxyethanol fluorene type polycarbonate, polyethylene glycol-modified bisphenoxyethanol fluorene type polycarbonate, etc. Considering solubility and the like, bisphenol A type polycarbonate, bisphenol B type polycarbonate, bisphenol C type polycarbonate, bisphenol E type polycarbonate, bisphenol F type polycarbonate, bisphenol G type polycarbonate, bisphenol TMC type polycarbonate, bisphenol Z type polycarbonate, bisphenoxyethanol fluorene type polycarbonate, polyethylene glycol-modified bisphenoxyethanol fluorene type polycarbonate are preferred. In order to improve the mechanical properties of the cured product obtained by polymerizing the solubility and the photocurable composition, bisphenol C type polycarbonate, bisphenol G type polycarbonate, bisphenol TMC type polycarbonate, bisphenol Z type polycarbonate, bisphenoxyethanol fluorene type polycarbonate are more preferred.

[0023] The molecular weight of the polycarbonate resin is not limited as long as the mechanical properties of the cured product obtained by polymerizing the photocurable composition do not deteriorate. Preferably, the weight average molecular weight is from 1,000 to 200,000. Considering the mechanical properties of the cured product, the viscosity of the photocurable material composition, the solubility of the polycarbonate resin, etc., a weight average molecular weight of from 4,000 to 50,000 is more preferable.

[0024] The content of the polycarbonate resin in the photocurable material composition is from 10% by weight to 40% by weight in consideration of the mechanical properties of the cured product obtained by polymerizing the photocurable material composition, the solubility of the polycarbonate resin, the viscosity of the photocurable material composition, etc. More preferably, it is from 20% by weight to 33% by weight.

[0025] The photocurable material composition may further contain a monofunctional (meth)acrylate different from the monofunctional acrylate having a 5-membered ring skeleton containing an ether bond (hereinafter, may also be referred to as "other monofunctional (meth)acrylate"). By containing other monofunctional (meth)acrylate or polyfunctional (meth)acrylate, the cured product of the photocurable material composition can improve the heat distortion temperature while maintaining the impact resistance.

[0026] Examples of monofunctional (meth)acrylates different from monofunctional acrylates having a 5-membered ring skeleton containing an ether bond include 4-tert-butylcyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, 3-hydroxy-1-(meth)acryloyloxyadamantane, 1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, dicyclopentenyl (meth)acrylate, 2-isopropyladamantan-2-yl (meth)acrylate, tetrahydrodicyclopentadienyl (meth)acrylate, α-(meth)acryloxy-γ-butyrolactone, 2-hydroxy-o-phenylphenolpropyl (meth)acrylate, acryloylmorpholine, diethylacrylamide, isopropylacrylamide, hydroxyethylacrylamide, cyclohexyl (meth)acrylate, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isooctyl (meth)acrylate, tetrahydrofurfuryl methacrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, phenylglycidyl (meth)acrylate, lauryl (meth)acrylate, isodecyl (meth)acrylate, stearyl (meth)acrylate, isooctyl (meth)acrylate, tridecyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxyditricaprylyl glycol (meth)acrylate, tricyclodecane (meth)acrylate, dicyclopentadieneoxyethyl (meth)acrylate, dicyclopentenyl acrylate, dicyclopentenyl oxyethyl acrylate, dicyclopentenyl oxy methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, etc., but are not limited thereto.Also, only one type may be added or a plurality may be combined simultaneously as long as the mechanical properties of the cured product of the photocurable material composition do not deteriorate.

[0027] When the photocurable material composition contains other monofunctional (meth)acrylates, the content is preferably 48% by weight or less of the whole photocurable material composition, more preferably 8% to 48% by weight.

[0028] When the photocurable material composition contains other monofunctional (meth)acrylates exceeding this range, the impact resistance of the resulting cured product deteriorates.

[0029] Next, the photocurable material composition of the present invention may contain components other than the above components. The photocurable material composition of the present invention may contain a polymerization initiator for copolymerizing the polymerizable functional group of a monofunctional acrylate having a 5-membered ring skeleton containing an ether bond. Further, the photocurable material composition may further contain a polymerization inhibitor, a photosensitizer, a light stabilizer, a heat stabilizer, an antioxidant, a release agent, a fungicide, a filler, a pigment, etc. as necessary.

[0030] Examples of the polymerization initiator that generates radical species by light irradiation include, but are not limited to, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 4-phenylbenzophenone, 4-phenoxybenzophenone, 4,4'-diphenylbenzophenone, 4,4'-diphenoxybenzophenone, etc.

[0031] Also, as the polymerization initiator that generates cationic species by light irradiation, iodonium (4-methylphenyl)[4-(2-methylpropyl)phenyl]-hexafluorophosphate is mentioned as a suitable polymerization initiator, but it is not limited thereto.

[0032] Furthermore, examples of the polymerization initiator that generates radical species by heat include, but are not limited to, azo compounds such as azobisisobutyronitrile (AIBN), benzoyl peroxide, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, tert-hexyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-hexyl peroxyneodecanoate, cumyl peroxyneodecanoate, peroxides such as cumyl peroxyneodecanoate.

[0033] The content of the polymerization initiator in the photocurable material composition is preferably in the range of 0.01% by mass or more and 10.00% by mass or less with respect to the photocurable material composition. The polymerization initiator can be used alone or in combination of two or more. The addition ratio of the polymerization initiator to the photocurable material composition may be appropriately selected according to the light irradiation amount and further the additional heating temperature. It may also be adjusted according to the target average molecular weight of the resulting polymer.

[0034] Examples of the polymerization inhibitor include hydroquinone-based polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, hydroquinone monoethyl ether, hydroquinone monopropyl ether, hydroquinone monobutyl ether, hydroquinone monopentyl ether, hydroquinone monohexyl ether, hydroquinone monooctyl ether, hydroquinone monoheptyl ether, and phenolic polymerization inhibitors having substituents such as 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate. However, hydroquinone-based polymerization inhibitors such as hydroquinone and benzoquinone-based polymerization inhibitors such as benzoquinone are suitable for obtaining a thin film cured product such as a coating because they may turn yellow upon UV irradiation.

[0035] Examples of the polymerization inhibitor include, but are not limited to, those described above as polymerization inhibitors during reaction or storage. The content of the polymerization inhibitor in the photocurable material composition is preferably in the range of 0.01% by mass or more and 1.00% by mass or less with respect to the photocurable material composition. Also, only one polymerization inhibitor may be used, or two or more polymerization inhibitors may be used in combination. Considering the low coloring property, it is specifically preferable to use a combination of hydroquinone-based polymerization inhibitors.

[0036] Examples of the photosensitizer include benzophenone, 4,4 - diethylaminobenzophenone, 1 - hydroxycyclohexyl phenyl ketone, isoamyl p - dimethylaminobenzoate, methyl 4 - dimethylaminobenzoate, benzoin, benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether, 2,2 - diethoxyacetophenone, methyl o - benzoylbenzoate, 2 - hydroxy - 2 - methyl - 1 - phenylpropan - 1 - one, acylphosphine oxide, and the like. The content of the photosensitizer in the photocurable material composition is preferably in the range of 0.01% by mass or more and 10.00% by mass or less with respect to the photocurable material composition.

[0037] The light stabilizer is not particularly limited as long as it does not significantly affect the properties of the cured product of the photocurable material composition. Examples include benzotriazole-based compounds such as 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-[5-chloro(2H)-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)]-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol; cyanoacrylate-based compounds such as ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate; triazine-based compounds; benzophenone-based compounds such as octabenzone, 2,2'-4,4'-tetrahydrobenzophenone. The above light stabilizer may also serve as a photosensitizer, in which case the photosensitizer does not need to be added. The content of the light stabilizer in the photocurable material composition is preferably in the range of 0.01% by mass or more and 10.00% by mass or less based on the photocurable material composition.

[0038] The heat stabilizer is not particularly limited as long as it does not significantly affect the properties of the cured product of the photocurable material composition, and examples include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)]propionate, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, alkyl esters having 7 to 9 carbon atoms in the side chain of 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, 4,6-bis(octylthiomethyl)-o-cresol, 4,6-bis(dodecylthiomethyl)-o-cresol, ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)]propionate, hexamethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)]propionate and other hindered phenol compounds, tris(2,4-di-tert-butylphenyl) phosphite and other phosphorus compounds, dioctadecyl 3,3'-thiodipropionate and other sulfur compounds. The content of the heat stabilizer in the photocurable material composition is preferably in the range of 0.01% by mass or more and 10.00% by mass or less based on the photocurable material composition.

[0039] The antioxidant is not particularly limited as long as it does not significantly affect the properties of the cured product of the photocurable material composition, and examples include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate and other hindered amine compounds. The content of the antioxidant in the photocurable material composition is preferably in the range of 0.01% by mass or more and 10.00% by mass or less based on the photocurable material composition.

[0040] In addition, other polymerizable materials, dyes, fillers, etc. may be added to the photocurable material composition of the present invention for viscosity adjustment and function imparting within the range where significant performance degradation of the cured product does not occur. There is no particular limitation on the polymerizable material, and it is a monofunctional or bifunctional or higher epoxy compound and / or oxetane compound.

[0041] As the monofunctional or polyfunctional epoxy compound and oxetane compound, there are hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether, hydrogenated bisphenol Z diglycidyl ether, cyclohexanedimethanol diglycidyl ether, tricyclodecanedimethanol diglycidyl ether, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylcyclohexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-methadioxane, bis(3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexanecarboxylate, dicyclopentadiene diepoxide, ethylenebis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, ε-caprolactone-modified 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, bis(3,4-epoxycyclohexyl)methane, 2,2-bis(3,4-epoxycyclohexyl)propane, 1,1-bis(3,Examples include, but are not limited to, (4-epoxycyclohexyl)ethane, alpha-pinene oxide, camphorene aldehyde, limonene monooxide, limonene dioxide, 4-vinylcyclohexene monooxide, 4-vinylcyclohexene dioxide, 3-hydroxymethyl-3-methyloxetane, 3-hydroxymethyl-3-ethyloxetane, 3-hydroxymethyl-3-propyloxetane, 3-hydroxymethyl-3-normal butyloxetane, 3-hydroxymethyl-3-propyloxetane, etc.

[0042] When adding an epoxy compound and / or an oxetane compound, a photoacid generator or a photobase generator may be added to the material composition to promote the polymerization reaction of the epoxy and oxetane compounds. Examples of the photoacid generator include, but are not limited to, triarylsulfonium hexafluoroantimonate, triphenylphenacylphosphonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, bis-[4-(diphenylsulfonio)phenyl]sulfide bisdihexafluoroantimonate, bis-[4-(di4'-hydroxyethoxyphenylsulfonio)phenyl]sulfide bisdihexafluoroantimonate, bis-[4-(diphenylsulfonio)phenyl]sulfide bisdihexafluorophosphate, diphenyliodonium tetrafluoroborate, etc.

[0043] There is no particular limitation on the filler, as long as it does not deteriorate the mechanical properties of the cured product of the photocurable material composition. Examples of the filler include metal salts, metal oxides, polymer fine particles, inorganic fibers, organic fibers, carbon, etc. Examples of the metal oxide include, but are not limited to, silicon oxide, titanium oxide, aluminum oxide, etc. Examples of the polymer fine particles include, but are not limited to, acrylic fine particles, polystyrene fine particles, nylon particles, etc. Examples of the organic fiber include, but are not limited to, nylon fiber, cellulose nanofiber, etc.

[0044] The method for preparing the photocurable material composition of the present invention is not particularly limited, and the most convenient method is to weigh all the materials and then heat and stir them. However, if there is a concern about polymerization due to heating, a polymerization inhibitor may be added as appropriate. Also, when it is difficult to mix uniformly by heating alone, all the materials may be dissolved in a solvent such as acetone, and then the solvent may be distilled off for preparation. Furthermore, stirring by a disperser such as an ultrasonic homogenizer, a ball mill, or a disk mill may be used.

[0045] In the step of curing the photocurable material composition, the shape of the cured product and the curing method of the photocurable material composition are not particularly limited. Examples of the curing method include a method of irradiating light after applying the photocurable material composition on a substrate, a method of irradiating light after injecting the photocurable material composition into a mold, and an optical stereolithography method of stacking cured products of thin films.

[0046] The method of applying the photocurable material composition on a substrate is not particularly limited. For example, a contact transfer type coating device such as a roll coater, a reverse coater, a bar coater, or a slit coater, or a non-contact type coating device such as a spinner (rotary coating device) or a curtain flow coater may be used to apply the composition containing the above resin on the substrate to form a coating film having a desired film thickness.

[0047] Also, when performing optical stereolithography using the photocurable material composition of the present invention, any of the conventionally known optical stereolithography methods and apparatuses can be used. Preferably, an active energy ray is selectively irradiated to form a cured layer so that a cured layer having a desired pattern is obtained in the photocurable material composition, and then an uncured liquid photocurable resin composition is supplied to this cured layer, and the same active energy ray is irradiated to repeatedly perform a lamination operation of newly forming a cured layer continuous with the above-mentioned cured layer to finally obtain a target three-dimensional shaped object.

[0048] The photocurable material composition of the present invention can be widely used in the field of optical stereolithography, and although it is not limited in any way, typical application fields include models for verifying the appearance design during the design process, models for checking the functionality of parts, resin molds for producing molds, base models for producing dies, direct molds for prototype dies, and the like. In particular, the material composition of the present invention can also be used as parts that require durability because it combines a heat distortion temperature and impact resistance.

[0049] Examples of the active energy ray include ultraviolet rays, electron beams, X-rays, radiation, high frequency, and the like. Among them, ultraviolet rays having a wavelength of 300 to 430 nm are preferably used from an economic point of view. As the light source at that time, ultraviolet lasers (for example, semiconductor-excited solid-state lasers, Ar lasers, He-Cd lasers, etc.), high-pressure mercury lamps, ultra-high-pressure mercury lamps, mercury lamps, xenon lamps, halogen lamps, metal halide lamps, ultraviolet LEDs (light-emitting diodes), fluorescent lamps, and the like can be used.

[0050] When irradiating the shaping surface composed of the photocurable material composition with an active energy ray to form each cured resin layer having a predetermined shape pattern, a cured resin layer may be formed by a dot-drawing or line-drawing method using an active energy ray focused into a point such as laser light, or an active energy ray may be irradiated onto the shaping surface in a planar manner through a planar drawing mask formed by arranging a plurality of micro shutters such as a liquid crystal shutter or a digital micromirror shutter (DMD), and a shaping method for forming a cured resin layer may be adopted.

[0051] Fig. 1 shows a configuration example of a stereolithography apparatus 100 using the free surface method. The stereolithography apparatus 100 has a tank 11 filled with a liquid photocurable resin composition 10. Inside the tank 11, a modeling stage 12 is provided so as to be vertically drivable by a drive shaft 13. The irradiation position of the active energy ray 15 emitted from the light source 14 is changed by a galvanometer mirror 16 controlled by the control unit 18 according to the slice data, and the surface of the tank 11 is scanned. In Fig. 1, the scanning range is exemplarily shown by a thick broken line. The slice data is data generated by slicing the three-dimensional shape data of the three-dimensional model to be modeled at a predetermined thickness in the modeling direction.

[0052] The thickness d of the photocurable resin composition 10 cured by the irradiation of the active energy ray 15 is a value determined based on the settings at the time of generating the slice data, and affects the accuracy (reproducibility of the three-dimensional shape data) of the resulting molded object 17. The thickness d is achieved by the control unit 18 controlling the driving amount of the drive shaft 13.

[0053] First, the control unit 18 controls the drive shaft 13 based on the settings, and supplies the photocurable resin composition 10 with a predetermined thickness d onto the modeling stage 12. When the active energy ray 15 is selectively irradiated onto the liquid photocurable resin composition 10 on the modeling stage 12 based on the slice data, the photocurable resin composition 10 cures to form a cured product according to the slice data. Next, the modeling stage 12 is moved in the direction of the white arrow by a distance corresponding to the thickness d, and the uncured photocurable resin composition 10 with a thickness d is supplied to the surface of the cured product. Then, when the uncured photocurable resin composition 10 is irradiated with the active energy ray 15 based on the slice data, a cured product integrated with the previously formed cured product is formed. In this way, by repeating the process of curing the photocurable resin composition in layers, the target three-dimensional cured product (molded object) 17 can be obtained.

[0054] The shaped article thus obtained is taken out of the tank 11, and after removing the unreacted photocurable resin composition remaining on its surface, post-treatments such as washing or post-curing by heat treatment may be performed as necessary to obtain the final article. By post-curing, the unreacted photocurable resin composition that may remain on the surface and inside of the shaped article can be cured, the stickiness of the surface of the shaped article can be suppressed, and the initial strength of the shaped article can be improved.

[0055] Also, shaping by the regulated liquid surface method is also preferable. In the stereolithography apparatus using the regulated liquid surface method, the shaping stage 12 of the stereolithography apparatus 100 in FIG. 1 is provided so as to lift the cured product above the liquid surface, and the light irradiation means is provided below the tank 11. A typical shaping example of the regulated liquid surface method is as follows. First, a photocurable resin composition is supplied between the support surface of the support stage provided so as to be able to move up and down and the bottom surface of the tank, and the support surface of the support stage and the bottom surface of the tank containing the photocurable resin composition are installed so as to have a predetermined distance d. Next, active energy rays are irradiated based on the slice data onto the photocurable resin composition between the support surface of the support stage and the bottom surface of the tank from the bottom surface side of the tank containing the photocurable resin composition. By irradiating the active energy rays, the photocurable resin composition between the stage support surface and the bottom surface of the tank is cured, and a cured product is formed. Then, the support stage is raised to peel off the cured product from the bottom surface of the tank.

[0056] Next, while adjusting the height of the support stage so that the distance between the cured product formed on the support stage and the bottom surface of the tank becomes a predetermined distance d, an uncured curable resin composition is supplied between the cured product on the support stage and the bottom surface of the tank. Then, in the same manner as before, the uncured photocurable resin composition is selectively irradiated with active energy rays based on the slice data, and a cured product integrated with the previously formed cured product is formed. By repeating such steps a plurality of times, a shaped article in which cured products of the photocurable resin are laminated and integrated can be obtained.

[0057] The above described an example of manufacturing an article by curing the photocurable resin composition according to the present invention using the optical stereolithography method, but the applications are not limited thereto. The photocurable resin composition according to the present invention can be used to manufacture protective films, coating films, sealants, etc. by polymerization upon light irradiation. Alternatively, the article can also be manufactured by pouring the photocurable resin composition according to the present invention as a raw material into a mold, and irradiating the poured resin with light for polymerization after pouring. In any application, the cured product of the photocurable resin composition according to the present invention can achieve both a high heat distortion temperature and high impact resistance.

Examples

[0058] Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the examples described below as long as the gist thereof is not exceeded.

[0059] (Example 1) (1) Preparation of photocurable material composition 28.0 g of tetrahydrofurfuryl acrylate as a monofunctional acrylate having a 5-membered ring skeleton containing an ether bond, 7.0 g of a bisphenol Z-type polycarbonate resin (manufactured by Mitsubishi Gas Chemical Company, average molecular weight 20,000) as a polycarbonate resin, and 0.22 g of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (manufactured by Tokyo Chemical Industry Co., Ltd.) as a polymerization initiator were weighed. These were transferred to a sealable container and heated and stirred at 50 °C for 24 hours (VMRC-5 manufactured by AS ONE Corporation) to prepare a photocurable material composition.

[0060] (2) Preparation of samples for evaluation A mold with a size of 4 mm × 10 mm × 80 mm was placed on a quartz plate coated with a release agent. The photocurable material composition prepared above was poured into the mold and sandwiched and fixed with the quartz plate coated with the release agent. Using an ultraviolet integrated light meter (product name: UTI-250, manufactured by Ushio Inc.), light with a wavelength of 365 nm was irradiated at 10 mW for 120 seconds, twice on each of the front and back surfaces, to cure the photocurable material composition. Then, the prismatic shaped object was demolded from the mold. The obtained shaped object was heat-treated at 50 °C for 1 hour and then at 100 °C for 1 hour to obtain a sample for evaluation.

[0061] (3) Evaluation method The heat distortion temperature (heat deflection temperature) using an HDT tester manufactured by Toyo Seiki Seisaku-sho, Ltd. and the Charpy impact strength (impact resistance) using an impact tester and a notching machine manufactured by Toyo Seiki Seisaku-sho, Ltd. were evaluated for the evaluation samples under the test conditions according to JIS K 7191-1 Method A and JIS K 7111-1, and judged according to the following criteria. The results are shown in Table 1. (Evaluation criteria) A: The heat deflection temperature is 70 °C or higher and the Charpy impact strength is 20 kJ / m 2 or higher B: The heat deflection temperature is 40 °C or higher and less than 70 °C and the Charpy impact strength is 20 kJ / m 2 or higher C: The heat deflection temperature is less than 40 °C or the Charpy impact strength is less than 20 kJ / m 2 less than

[0062] The evaluation sample with evaluation criterion A has a heat deflection temperature and a Charpy impact strength equivalent to those of an ABS resin. Also, the evaluation sample with evaluation criterion B has a performance that combines a heat deflection temperature and a Charpy impact strength that exceed those of a cured product obtained from a conventional photocurable material composition, although not as good as that of an ABS resin. On the other hand, the evaluation sample with evaluation criterion C has a heat deflection temperature and a Charpy impact strength equivalent to those of a cured product obtained from a conventional photocurable material composition.

[0063] (Example 2) A photocurable material composition was prepared in the same manner as in Example 1, except that the polycarbonate resin was changed to 14.0 g. Using this photocurable material composition, an evaluation sample was prepared in the same manner as in Example 1 and evaluated by the method described in Example 1. The evaluation results are shown in Table 1.

[0064] (Example 3) A photocurable material composition was prepared in the same manner as in Example 1, except that tetrahydrofurfuryl acrylate was changed to 24.5 g, the polycarbonate resin was changed to 14.0 g, and 3.5 g of cyclic trimethylolpropane formal acrylate was further added as another monofunctional (meth)acrylate. Using this photocurable material composition, an evaluation sample was prepared in the same manner as in Example 1 and evaluated by the method described in Example 1. The evaluation results are shown in Table 1.

[0065] (Example 4) A photocurable material composition was prepared in the same manner as in Example 1, except that tetrahydrofurfuryl acrylate was changed to 8.0 g, the polycarbonate resin was changed to 14.0 g, and 20.0 g of cyclic trimethylolpropane formal acrylate was further added as another monofunctional (meth)acrylate. Using this photocurable material composition, an evaluation sample was prepared in the same manner as in Example 1 and evaluated by the method described in Example 1. The evaluation results are shown in Table 1.

[0066] (Example 5) A photocurable material composition was prepared in the same manner as in Example 1, except that the polycarbonate resin was changed to EP-6000 manufactured by Mitsubishi Gas Chemical Company, Inc. Using this photocurable material composition, an evaluation sample was prepared in the same manner as in Example 1 and evaluated by the method described in Example 1. The evaluation results are shown in Table 1.

[0067] (Example 6) A photocurable material composition was prepared in the same manner as in Example 1, except that the polycarbonate resin was changed to BIS-C manufactured by Mitsubishi Gas Chemical Company, Inc. Using this photocurable material composition, an evaluation sample was prepared in the same manner as in Example 1 and evaluated by the method described in Example 1. The evaluation results are shown in Table 1.

[0068] (Example 7) A photocurable material composition was prepared in the same manner as in Example 1, except that tetrahydrofurfuryl acrylate was changed to alkoxylated tetrahydrofurfuryl acrylate ( Sartomer SR611, manufactured by Arkema Co., Ltd.) and the polycarbonate resin was changed to FPC-0220 manufactured by Mitsubishi Gas Chemical Company, Inc. Using this photocurable material composition, an evaluation sample was prepared in the same manner as in Example 1 and evaluated by the method described in Example 1. The evaluation results are shown in Table 1.

[0069] (Example 8) A photocurable material composition was prepared in the same manner as in Example 1, except that tetrahydrofurfuryl acrylate was changed to (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate. Using this photocurable material composition, an evaluation sample was prepared in the same manner as in Example 1 and evaluated by the method described in Example 1. The evaluation results are shown in Table 1.

[0070] (Example 9) A photocurable material composition was prepared in the same manner as in Example 1, except that tetrahydrofurfuryl acrylate was changed to tetrahydrofurfuryl alcohol acrylic acid multimer ester (Viscoat #150D, manufactured by Osaka Organic Chemical Industry Co., Ltd.). Using this photocurable material composition, an evaluation sample was prepared in the same manner as in Example 1 and evaluated by the method described in Example 1. The evaluation results are shown in Table 1.

[0071] (Example 10) A photocurable material composition was prepared in the same manner as in Example 1, except that the amount of tetrahydrofurfuryl acrylate was changed to 24.5 g and 3.5 g of isobornyl methacrylate was further added as another monofunctional (meth)acrylate. Using this photocurable material composition, an evaluation sample was prepared in the same manner as in Example 1 and evaluated by the method described in Example 1. The evaluation results are shown in Table 1.

[0072] (Example 11) The tetrahydrofurfuryl acrylate was changed to 24.5 g, and 3.5 g of 1-adamantyl acrylate was further added as another monofunctional (meth)acrylate. A photocurable material composition was prepared in the same manner as in Example 1. Using this photocurable material composition, an evaluation sample was prepared in the same manner as in Example 1 and evaluated by the method described in Example 1. The evaluation results are shown in Table 1.

[0073] (Example 12) The tetrahydrofurfuryl acrylate was changed to 25.0 g, the polycarbonate resin was changed to 14.0 g, and 3.0 g of cyclic trimethylolpropane formal acrylate was further added as another monofunctional (meth)acrylate. A photocurable material composition was prepared in the same manner as in Example 1. Using this photocurable material composition, an evaluation sample was prepared in the same manner as in Example 1 and evaluated by the method described in Example 1. The evaluation results are shown in Table 1.

[0074] (Comparative Example 1) A photocurable material composition was prepared in the same manner as in Example 1, except that the tetrahydrofurfuryl acrylate was changed to tetrahydrofurfuryl methacrylate. Using this photocurable material composition, an evaluation sample was prepared in the same manner as in Example 1 and evaluated by the method described in Example 1. The evaluation results are shown in Table 1.

[0075] (Comparative Example 2) A photocurable material composition was prepared in the same manner as in Example 1, except that the tetrahydrofurfuryl acrylate was changed to cyclic trimethylolpropane formal acrylate. Using this photocurable material composition, an evaluation sample was prepared in the same manner as in Example 1 and evaluated by the method described in Example 1. The evaluation results are shown in Table 1.

[0076] (Comparative Example 3) The amount of tetrahydrofurfuryl acrylate was changed to 7.0 g, and the amount of polycarbonate resin was changed to 14.0 g. Further, 21.0 g of cyclic trimethylolpropane formal acrylate was added as another monofunctional (meth)acrylate. A photocurable material composition was prepared in the same manner as in Example 1 except for the above changes. Using this photocurable material composition, an evaluation sample was produced in the same manner as in Example 1 and evaluated by the method described in Example 1. The evaluation results are shown in Table 1.

[0077]

Table 1

[0078] In Table 1, the abbreviations indicate the following compounds. Monofunctional acrylate 1: Tetrahydrofurfuryl acrylate Monofunctional acrylate 2: Alkoxylated tetrahydrofurfuryl acrylate Monofunctional acrylate 3: (2-Methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate Monofunctional acrylate 4: Tetrahydrofurfuryl alcohol acrylic acid multimer ester Other monofunctional (meth)acrylate 1: Cyclic trimethylolpropane formal acrylate Other monofunctional (meth)acrylate 2: Isobornyl methacrylate Other monofunctional (meth)acrylate 3: 1-Adamantyl acrylate Other monofunctional (meth)acrylate 4: Tetrahydrofurfuryl methacrylate Polycarbonate resin 1: Bisphenol Z type polycarbonate resin (average molecular weight 20,000) Polycarbonate resin 2: EP-6000 manufactured by Mitsubishi Gas Chemical Company, Inc. Polycarbonate resin 3: BIS-C manufactured by Mitsubishi Gas Chemical Company, Inc. Polycarbonate resin 4: FPC-0220 manufactured by Mitsubishi Gas Chemical Company, Inc.

Industrial Applicability

[0079] Since the photocurable material composition of the present invention and its cured product have a high heat distortion temperature and strong impact resistance compared to materials cured by conventional active energy rays, they can be used in the production of coating materials and parts that require durability by photocuring.

Explanation of Symbols

[0080] 10: Photocurable resin composition 11: Tank 12: Modeling stage 13: Drive shaft 14: Light source 15: Active energy ray 16: Galvanometer mirror 17: Cured product (modeled object) 18: Control unit 100: Stereolithography apparatus

Claims

1. A photocurable material composition comprising at least a monofunctional acrylate having a 5-membered ring skeleton containing an ether bond and a polycarbonate resin soluble in the monofunctional acrylate having a 5-membered ring skeleton containing an ether bond, wherein the content of the monofunctional acrylate having a 5-membered ring skeleton containing an ether bond is 18% by weight to 80% by weight, the content of the polycarbonate resin is 20% by weight to 40% by weight, the polycarbonate resin is of bisphenol type or bisphenoxyethanol fluorene type, A photocurable material composition.

2. The photocurable material composition according to claim 1, wherein the monofunctional acrylate having a 5-membered ring skeleton containing an ether bond is selected from the group consisting of tetrahydrofurfuryl acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate, tetrahydrofurfuryl alcohol acrylic acid multimer ester, and alkoxylated tetrahydrofurfuryl acrylate.

3. The photocurable material composition according to claim 1 or 2, wherein the polycarbonate resin is at least one selected from the group consisting of bisphenol A type, bisphenol B type, bisphenol C type, bisphenol E type, bisphenol F type, bisphenol G type, bisphenol M type, bisphenol P type, bisphenol PH type, bisphenol TMC type, bisphenol Z type, and bisphenoxyethanol fluorene type.

4. The photocurable material composition according to claim 3, wherein the polycarbonate resin is selected from the group consisting of bisphenol A type, bisphenol B type, bisphenol C type, bisphenol E type, bisphenol F type, bisphenol G type, bisphenol TMC type, bisphenol Z type, and bisphenoxyethanol fluorene type.

5. The photocurable material composition according to claim 4, wherein the polycarbonate resin is at least one selected from the group consisting of bisphenol C type, bisphenol Z type, and bisphenoxyethanol fluorene type.

6. The photocurable material composition according to any one of claims 1 to 5, further comprising a monofunctional (meth)acrylate different from the monofunctional acrylate having a 5-membered ring skeleton containing an ether bond.

7. The photocurable material composition according to claim 6, comprising a monofunctional (meth)acrylate different from the monofunctional acrylate having a 5-membered ring skeleton containing an ether bond in a content of 8% by weight to 48% by weight.

8. The monofunctional (meth)acrylate different from the monofunctional acrylate having a 5-membered ring skeleton containing an ether bond is at least one selected from the group consisting of 4-tert-butylcyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, 3-hydroxy-1-(meth)acryloyloxyadamantane, 1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-isopropyladamantan-2-yl (meth)acrylate, cyclohexyl (meth)acrylate, methyl (meth)acrylate, and tricyclodecane (meth)acrylate. The photocurable material composition according to claim 6 or 7.

9. The photocurable material composition according to any one of claims 1 to 8, which is used in an optical stereolithography method.

10. A cured product obtained by copolymerizing the photocurable material composition according to any one of claims 1 to 9.

11. A method for manufacturing an article using an optical stereolithography method, A step of supplying a photocurable resin composition with a predetermined thickness; A step of irradiating the photocurable resin composition with active energy rays based on slice data of a three-dimensional model to be shaped and curing the composition; comprising; A method for manufacturing an article, characterized in that the photocurable resin composition is the photocurable resin composition according to any one of claims 1 to 8.

12. Furthermore, the method for manufacturing an article according to claim 11, characterized by including a step of performing heat treatment on the shaped article obtained by irradiating the active energy rays.

13. The method for manufacturing an article according to claim 11 or 12, characterized in that the active energy rays are ultraviolet rays having a wavelength of 300 to 430 nm.

14. A method for manufacturing an article using casting, A step of pouring a raw material into a mold; A step of irradiating the raw material poured into the mold with light; comprising; A method for manufacturing an article, characterized in that the raw material is the photocurable resin composition according to any one of claims 1 to 8.

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