JP2019199448A - Photocurable resin composition - Google Patents

Abstract

To provide a photocurable resin composition which has excellent formability, forms a cured product excellent in tenacity, and is particularly suitable for a mouth guard, an occlusal splint and a denture-base material which are formed by optical three-dimensional shaping.SOLUTION: The photocurable resin composition contains a urethanated (meth)acrylic compound (A), a polymerizable monomer (B) having an ionic group, and a photoinitiator (C). The urethanated (meth)acrylic compound (A) is a (meth)acrylate comprising in each molecule a urethane bond and at least one structure selected from the group consisting of a polyester, a polycarbonate, a polyurethane, a polyether, a poly-conjugated diene, and hydrogenated poly-conjugated diene.SELECTED DRAWING: None

Description

  The present invention particularly relates to a photocurable resin composition for optical three-dimensional modeling and a mouth guard, an occlusal splint, and a denture base material made of a cured product of the photocurable resin composition.

  Mouthguard protects the stomatognathic system and the brain by reducing the external trauma caused by the great external force applied to the teeth and jawbone during competition mainly in contact sports such as karate, boxing, American football, rugby or soccer. To be installed in the oral cavity. In recent years, with the expansion of sports promotion, wearing in contact sports has become mandatory, there is a trend to recommend wearing in addition to contact sports, and prevention of oral trauma that occurs during classes such as physical education in schoolchildren's education It is being recommended to use it.

  The occlusal splint is worn day and night to correct the alignment of teeth, or worn at night to sleep to suppress tooth wear due to bruxism, and the form is very similar to a mouth guard.

  A denture base material is a material used for a gingival part at the time of mounting | wearing a denture by loss of a tooth | gear. In recent years, the demand for dentures has increased rapidly with the increase in the elderly population.

  These mouth guards, occlusal splints and denture base materials are commonly required toughness. Toughness is a property having both high rigidity and resistance to breakage due to elongation after yielding, and examples of the polymer having high toughness include polyethylene terephthalate (PET) and polycarbonate. If the toughness is impaired, there is a problem that it is necessary to recreate it frequently when it becomes easy to break due to external force or impact of occlusion.

  In addition, usually when preparing a mouth guard, occlusal splint and denture base material, it is necessary to acquire an impression in the oral cavity, but from that discomfort impression acquisition becomes a burden on the patient, Conventionally, it has been pointed out that it has a problem that it requires skill to perform technical operations. In recent years, due to the development of digital technology, attempts have been made to apply optical intraoral scanning for impression acquisition, and attempts have been made to apply optical three-dimensional modeling in molding. In molding, a photocurable resin composition is used. However, since it tends to use a (meth) acrylic monomer in general, it tends to be a material having brittle properties close to an acrylic resin, and has excellent toughness. It has been difficult to design curable materials.

  In such a background, for example, Patent Literature 1 proposes a photocurable resin composition composed of a monofunctional monomer having an ionic group as a technique that has excellent toughness and enables optical three-dimensional modeling. .

JP, 2006-002704, A

  The photocurable resin composition described in Patent Document 1 has not reached the toughness equivalent to PET or polycarbonate, and has insufficient toughness.

  Accordingly, the present invention provides a photocurable resin composition suitable for mouth guards, occlusal splints, and denture base materials, which are excellent in formability and excellent in toughness of a cured product, and are formed by optical three-dimensional modeling. The purpose is to do. Moreover, an object of this invention is to provide the photocurable resin composition which is excellent in the mechanical strength of hardened | cured material. Furthermore, this invention aims at providing the mouth guard which consists of the hardened | cured material of the said photocurable resin composition, the splint for occlusion, and a denture base material.

That is, the present invention provides the following inventions.
[1] contains a urethanized (meth) acrylic compound (A), a polymerizable monomer having an ionic group (B), and a photopolymerization initiator (C),
The urethanized (meth) acrylic compound (A) is
Photocuring which is a (meth) acrylate containing at least one structure selected from the group consisting of polyester, polycarbonate, polyurethane, polyether, polyconjugated diene, and hydrogenated polyconjugated diene in one molecule, and a urethane bond. Functional resin composition;
[2] The photocurable resin composition according to [1], wherein the polymerizable monomer (B) having an ionic group is a radical polymerizable monomer having an ionic group;
[3] The ionic group of the polymerizable monomer (B) having the ionic group is a carboxylic acid group, a phosphoric acid group, a sulfonic acid group and a metal salt thereof, an ammonium salt thereof, or a first of these. A photocurable resin composition according to [1] or [2], which is at least one selected from the group consisting of ˜quaternary ammonium salts and primary to quaternary ammonium groups;
[4] The ionic group of the polymerizable monomer (B) having the ionic group is at least one selected from the group consisting of a carboxylic acid group, a carboxylate, and a primary to quaternary ammonium group. A photocurable resin composition according to [1] or [2],
[5] The polymerizable monomer (B) having an ionic group is a (meth) acrylate polymerizable monomer having an ionic group, and a (meth) acrylamide polymerizable monomer having an ionic group. The photocurable resin composition according to any one of [1] to [4], which is at least one selected from the group consisting of bodies.
[6] The polymerizable monomer (B) having an ionic group has a (meth) acrylate polymerizable monomer having a carboxylic acid group or a salt thereof, and / or a primary to quaternary ammonium group. The photocurable resin composition according to any one of [1] to [5], which is a (meth) acrylate polymerizable monomer;
[7] Furthermore, N-substituted (meth) acrylamide or N, N-disubstituted (meta) containing (meth) acrylamide compound (D), wherein the (meth) acrylamide compound (D) does not have an ionic group. ) The photocurable resin composition according to any one of [1] to [6], which is acrylamide;
[8] The photocurable resin composition according to [7], wherein the (meth) acrylamide compound (D) is N, N-dialkyl-substituted (meth) acrylamide having no ionic group;
[9] The photocurable resin composition according to any one of [1] to [8], which is for optical three-dimensional modeling;
[10] A mouth guard comprising a cured product of the photocurable resin composition according to any one of [1] to [9];
[11] An occlusal splint comprising a cured product of the photocurable resin composition according to any one of [1] to [9];
[12] A denture base material comprising a cured product of the photocurable resin composition according to any one of [1] to [9];
[13] A method for producing a three-dimensional object by an optical three-dimensional modeling method using the photocurable resin composition according to any one of [1] to [9].

  The photocurable resin composition of the present invention is excellent in formability and further excellent in toughness of the cured product. For this reason, the photocurable resin composition of the present invention is particularly suitable as a mouth guard or occlusal splint formed by optical three-dimensional modeling, and can also be suitably used as a denture base material.

  The photocurable resin composition of the present invention contains a urethanized (meth) acrylic compound (A), a polymerizable monomer (B) having an ionic group, and a photopolymerization initiator (C). . The urethanized (meth) acrylic compound (A) has at least one structure selected from the group consisting of polyester, polycarbonate, polyurethane, polyether, polyconjugated diene, and hydrogenated polyconjugated diene (hereinafter referred to as “one molecule”). These are also referred to as “polymer skeletons”), and (meth) acrylates containing urethane bonds. In the present specification, the upper limit value and the lower limit value of the numerical ranges (content of each component, values calculated from each component, physical properties, etc.) can be appropriately combined. Moreover, in this specification, the numerical value of each symbol in a formula can also be combined suitably.

[Urethaneized (meth) acrylic compound (A)]
The urethanized (meth) acrylic compound (A) is used to impart formability and toughness to the cured product of the photocurable resin composition in the photocurable resin composition of the present invention.

  The urethanized (meth) acrylic compound (A) is, for example, an addition reaction between a polyol containing the polymer skeleton, a compound having an isocyanate group (—NCO), and a (meth) acrylate compound having a hydroxyl group (—OH). Can be easily synthesized. In addition, the urethanized (meth) acrylic compound (A) is obtained by subjecting a (meth) acrylate compound having a hydroxyl group to a ring-opening addition reaction with a lactone or alkylene oxide, and then obtaining a compound having a hydroxyl group at one end. It can be easily synthesized by addition reaction with a compound having a group.

  The urethanized (meth) acrylic compound (A) contains a structure selected from the group consisting of polyester, polycarbonate, polyurethane, polyether, polyconjugated diene, and hydrogenated polyconjugated diene. These are not particularly limited as long as they have the structure described above. For example, polyesters include polymers of phthalic acid and alkylene diols having 2 to 12 carbon atoms, polymers of adipic acid and alkylene glycols having 2 to 12 carbon atoms, malein A polymer of an acid and an alkylene diol having 2 to 12 carbon atoms, a polymer of β-propiolactone, a polymer of γ-butyrolactone, a δ-valerolactone polymer, an ε-caprolactone polymer, and a copolymer thereof. Can be mentioned. Examples of the polycarbonate include a polycarbonate derived from an aliphatic diol having 2 to 12 carbon atoms, a polycarbonate derived from bisphenol A, and a polycarbonate derived from an aliphatic diol having 2 to 12 carbon atoms and bisphenol A. Examples of the polyurethane include a polymer of an aliphatic diol having 2 to 12 carbon atoms and a diisocyanate having 1 to 12 carbon atoms. Examples of the polyether include polyethylene glycol, polypropylene glycol, polybutylene glycol, poly (1-methylbutylene glycol) and the like. Polyconjugated dienes and hydrogenated polyconjugated dienes include 1,4-polybutadiene, 1,2-polybutadiene, polyisoprene, poly (butadiene-isoprene), poly (butadiene-styrene), poly (isoprene-styrene), polyfarnesene, And hydrogenated products thereof. Among these, polyesters, polycarbonates, and polyconjugated dienes are preferable because they are excellent in toughness of the cured product. For the production of the urethanized (meth) acrylic compound (A), a polyol having the above-described polymer skeleton can be used. In addition, it is preferable that a urethanized (meth) acrylic compound (A) does not have an ionic group mentioned later.

  Examples of the compound having an isocyanate group include hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), and trimethylhexamethylene diisocyanate (TMHMDI). , Tricyclodecane diisocyanate (TCDDI), adamantane diisocyanate (ADI), and the like.

  Examples of the (meth) acrylate compound having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 10 -Hydroxydecyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerin mono (meth) acrylate, N-hydroxyethyl (meth) acrylamide, N, N-bis (2-hydroxyethyl) (meth) acrylamide, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, 2,2-bis [4- [3- (meth) acryloyloxy-2-hydroxy The Poxy] phenyl] propane, 1,2-bis [3- (meth) acryloyloxy-2-hydroxypropoxy] ethane, pentaerythritol tri (meth) acrylate, dipentaerythritol tri or tetra (meth) acrylate and other hydroxy ( And a (meth) acrylate compound.

  The addition reaction between the compound having an isocyanate group and the (meth) acrylate compound having a hydroxyl group can be carried out according to a known method, and is not particularly limited.

  The resulting urethanized (meth) acrylic compound (A) has at least one structure selected from the group consisting of polyester, polycarbonate, polyurethane, polyether, polyconjugated diene, and hydrogenated polyconjugated diene. A reaction product of an arbitrary combination of a polyol, a compound having an isocyanate group, and a (meth) acrylate compound having a hydroxyl group may be mentioned.

  The weight average molecular weight (Mw) of the urethanized (meth) acrylic compound (A) is preferably 500 to 50000, more preferably 750 to 30000, and still more preferably 1000 to 15000 from the viewpoints of viscosity and strength.

  The content of the urethanized (meth) acrylic compound (A) in the photocurable resin composition of the present invention includes the urethanized (meth) acrylic compound (A), the polymerizable monomer (B) having an ionic group, and It is preferable that it is 10-90 mass% with respect to the total amount of a (meth) acrylamide compound (D), and it is more preferable that it is 20-80 mass% from the point which is excellent by the moldability and the toughness of hardened | cured material, 30 More preferably, it is -70 mass%.

[Polymerizable monomer having ionic group (B)]
The polymerizable monomer (B) having an ionic group provides further toughness to the cured product of the photocurable resin composition while maintaining the formability in the photocurable resin composition of the present invention. Used for. A polymer network via hydrogen bonds formed from the urethanized (meth) acrylic compound (A) and a polymer network via ionic bonds contained in the polymerizable monomer (B) having an ionic group intervene. As a result, the rigidity increases compared to the state in which each single network is formed, and the two types of reversible bonds are split in stages under stress and develop elongation after yielding, improving toughness. Is considered to be seen.

  As the polymerizable monomer (B) having an ionic group, a radical polymerizable monomer having an ionic group is preferably used. Specific examples of the radical polymerizable monomer having an ionic group include α-cyanoacrylic acid, (meth) acrylic acid, α-halogenated acrylic acid, crotonic acid, cinnamic acid, and sorbic acid having an ionic group. , Esters such as maleic acid and itaconic acid, (meth) acrylamide, (meth) acrylamide derivatives, vinyl esters, vinyl ethers, mono-N-vinyl derivatives, styrene derivatives and the like. As the polymerizable monomer (B) having an ionic group, from the viewpoint of miscibility with the urethanized (meth) acrylic compound (A) and formability, a (meth) acrylate-based polymerizable monomer having an ionic group is used. A (meth) acrylamide polymerizable monomer having a monomer and an ionic group is preferred.

  The ionic group in the present invention means a functional group having a positive or negative charge. Examples of ionic groups include carboxylic acid groups, phosphoric acid groups, sulfonic acid groups and their metal salts, ammonium salts thereof, primary to quaternary ammonium salts, primary to quaternary ammonium groups, and the like. included. Among these, carboxylic acid groups and salts thereof, and primary to quaternary ammonium groups are preferable from the viewpoints of solubility and toughness.

  Examples of the polymerizable monomer having a carboxylic acid group or a salt thereof of the present invention include (meth) acrylic acid, 6- (meth) acryloyloxyhexylcarboxylic acid, 9- (meth) acryloyloxynonylcarboxylic acid, 10 -(Meth) acryloyloxydecylcarboxylic acid, 11- (meth) acryloyloxyundecylcarboxylic acid, 12- (meth) acryloyloxidedecylcarboxylic acid, 13- (meth) acryloyloxytridecylcarboxylic acid, N- (meth) Acryloylglycine, N- (meth) acryloyl aspartic acid, 2- (meth) acryloyloxyethyl hydrogen succinate, 2- (meth) acryloyloxyethyl hydrogen phthalate, 2- (meth) acryloyloxyethyl hydrogen maleate, O -(Meta) a Liloyl tyrosine, N- (meth) acryloyl tyrosine, N- (meth) acryloylphenylalanine, N- (meth) acryloyl-p-aminobenzoic acid, N- (meth) acryloyl-o-aminobenzoic acid, 2- (meta ) Acryloyloxybenzoic acid, 3- (meth) acryloyloxybenzoic acid, 4- (meth) acryloyloxybenzoic acid, N- (meth) acryloyl-5-aminosalicylic acid, N- (meth) acryloyl-4-aminosalicylic acid, 6- (meth) acryloyloxyhexane-1,1-dicarboxylic acid, 9- (meth) acryloyloxynonane-1,1-dicarboxylic acid, 10- (meth) acryloyloxydecane-1,1-dicarboxylic acid, 11- (Meth) acryloyloxyundecane-1,1-dicarboxylic acid, 12- (meta Acryloyl oxide decane-1,1-dicarboxylic acid, 13- (meth) acryloyloxytridecane-1,1-dicarboxylic acid, 4- (meth) acryloyloxyethyl trimellitate, 4- (meth) acryloyloxyethyl trimellitate Tate anhydride, 4- (meth) acryloyloxybutyl trimellitate, 4- (meth) acryloyloxyhexyl trimellitate, 4- (meth) acryloyloxydecyl trimellitate, 4- (meth) acryloyloxyethyl trimellitate Tate nuclear hydrogenated, 4- (meth) acryloyloxyethyl trimellitate anhydride nuclear hydrogenated, 4- (meth) acryloyloxybutyl trimellitate nuclear hydrogenated, 4- (meth) acryloyloxy Nuclear hydrogenated hexyl trimellitate, 4- ( Nuclear hydrogenated product of (meth) acryloyloxydecyl trimellitate, 2- (meth) acryloyloxyethyl-3 ′-(meth) acryloyloxy-2 ′-(3,4-dicarboxybenzoyloxy) propyl succinate, 6 -(Meth) acryloyloxyethylnaphthalene-1,2,6-tricarboxylic acid, 6- (meth) acryloyloxyethylnaphthalene-2,3,6-tricarboxylic acid, 4- (meth) acryloyloxyethylcarbonylpropionoyl- 1,8-naphthalic acid, 4- (meth) acryloyloxyethylnaphthalene-1,8-tricarboxylic acid, and the like, compounds obtained by acid anhydride grouping of carboxylic acid groups of these compounds, and lithium salts and sodium salts thereof , Magnesium salt, potassium salt, calcium salt, zinc salt, ammonium salt First to fourth grade ammonium salt. Among these, from the viewpoint of excellent toughness of the cured product, (meth) acrylic acid, 6- (meth) acryloyloxyhexylcarboxylic acid, 9- (meth) acryloyloxynonylcarboxylic acid, 10- (meth) acryloyloxydecylcarboxylic acid Acid, 11- (meth) acryloyloxyundecylcarboxylic acid, 12- (meth) acryloyloxide decylcarboxylic acid, 13- (meth) acryloyloxytridecylcarboxylic acid, 2- (meth) acryloyloxybenzoic acid, 3- ( (Meth) acryloyloxybenzoic acid, 4- (meth) acryloyloxybenzoic acid, 4- (meth) acryloyloxyethyl trimellitate, 4- (meth) acryloyloxyethyl trimellitate anhydride, 4- (meth) acryloyloxy Butyl trimellitate, -(Meth) acryloyloxyhexyl trimellitate, 4- (meth) acryloyloxydecyl trimellitate, 4- (meth) acryloyloxyethyl trimellitate nuclear hydrogenated product, 4- (meth) acryloyloxyethyl trimellitate Tate anhydride nuclear hydrogenate, 4- (meth) acryloyloxybutyl trimellitate nuclear hydrogenate, 4- (meth) acryloyloxyhexyl trimellitate nuclear hydrogenate, 4- (meth) acryloyloxy Nuclear hydrogenated products of decyl trimellitate and sodium, magnesium, potassium, calcium, zinc and primary to quaternary ammonium salts thereof are preferred, (meth) acrylic acid, 10- (meth) acryloyl Oxydecylcarboxylic acid, 11- (meth) acryloyloxyundecylcarbo Acid, 12- (meth) acryloyloxide decylcarboxylic acid, 2- (meth) acryloyloxybenzoic acid, 4- (meth) acryloyloxybenzoic acid, 4- (meth) acryloyloxyethyl trimellitate, 4- (meth) Acryloyloxyethyl trimellitate anhydride, (meth) acryloyloxyethyl trimellitate nuclear hydrogenation, 4- (meth) acryloyloxyethyl trimellitate anhydride nuclear hydrogenation, and magnesium salts and calcium thereof Salt, zinc salt, and primary to quaternary ammonium salt are more preferable, (meth) acrylic acid, 10- (meth) acryloyloxydecylcarboxylic acid, 4- (meth) acryloyloxybenzoic acid, 4- (meth) acryloyloxy Ethyl trimellitate, 4- (meth) acrylo Iroxyethyl trimellitate anhydride, (meth) acryloyloxyethyl trimellitate nuclear hydrogenated, 4- (meth) acryloyloxyethyl trimellitate anhydride nuclear hydrogenated, and zinc salts thereof, More preferred are primary to quaternary ammonium salts.

  Examples of the polymerizable monomer having a phosphate group or a salt thereof of the present invention include 2- (meth) acryloyloxyethyl dihydrogen phosphate, 3- (meth) acryloyloxypropyl dihydrogen phosphate, 4- ( (Meth) acryloyloxybutyl dihydrogen phosphate, 5- (meth) acryloyloxypentyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 7- (meth) acryloyloxyheptyl dihydrogen phosphate, 8 -(Meth) acryloyloxyoctyl dihydrogen phosphate, 9- (meth) acryloyloxynonyl dihydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 1- (meth) acryloyloxyundecyl dihydrogen phosphate, 12- (meth) acryloyl oxide decyl dihydrogen phosphate, 16- (meth) acryloyloxy hexadecyl dihydrogen phosphate, 20- (meth) acryloyloxyeicosyl Dihydrogen phosphate, 2- (meth) acryloyloxyethylphenyl hydrogen phosphate, 2- (meth) acryloyloxyethyl-2-bromoethyl hydrogen phosphate, 2-methacryloyloxyethyl- (4-methoxyphenyl) hydrogen phosphate 2-methacryloyloxypropyl- (4-methoxyphenyl) hydrogen phosphate, bis [2- (meth) acryloyloxyethyl] hydrogen Bis [4- (meth) acryloyloxybutyl] hydrogen phosphate, bis [6- (meth) acryloyloxyhexyl] hydrogen phosphate, bis [8- (meth) acryloyloxyoctyl] hydrogen phosphate, bis [ 9- (meth) acryloyloxynonyl] hydrogen phosphate, bis [10- (meth) acryloyloxydecyl] hydrogen phosphate, 1,3-di (meth) acryloyloxypropyl dihydrogen phosphate, and lithium salts thereof Sodium salt, magnesium salt, potassium salt, calcium salt, zinc salt, ammonium salt, and primary to quaternary ammonium salt. Among these, from the viewpoint of excellent toughness, 8- (meth) acryloyloxyoctyl dihydrogen phosphate, 9- (meth) acryloyloxynonyl dihydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 11 -(Meth) acryloyloxyundecyl dihydrogen phosphate, 12- (meth) acryloyl oxide decyl dihydrogen phosphate, zinc salts thereof, and primary to quaternary ammonium salts thereof are preferred. 10- (Meth) acryloyl Oxydecyl dihydrogen phosphate and its zinc salt, and its primary to quaternary ammonium salts are more preferred.

  Examples of the polymerizable monomer having a sulfonic acid group or a salt thereof of the present invention include 2- (meth) acrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl (meth) acrylate, and lithium salts thereof. Sodium salts, magnesium salts, potassium salts, calcium salts, zinc salts, ammonium salts, and primary to quaternary ammonium salts are exemplified.

  Examples of ammonium salt and primary to quaternary ammonium salt are not particularly limited, but ammonium salt, methylammonium salt, ethylammonium salt, propylammonium salt, isopropylammonium salt, butylammonium salt, sec-butylammonium salt, isobutylammonium Salt, tert-butyl ammonium salt, pentyl ammonium salt, hexyl ammonium salt, cyclohexyl ammonium salt, octyl ammonium salt, 2-ethylhexyl ammonium salt, dimethyl ammonium salt, diethyl ammonium salt, dipropyl ammonium salt, diisopropyl ammonium salt, dibutyl ammonium salt Di-sec-butylammonium salt, diisobutylammonium salt, di-tert-butylammonium salt, dipenty Ammonium salt, dihexylammonium salt, dicyclohexylammonium salt, dioctylammonium salt, di-2-ethylhexylammonium salt, trimethylammonium salt, triethylammonium salt, tripropylammonium salt, triisopropylammonium salt, tributylammonium salt, tri-sec-butyl Ammonium salt, triisobutylammonium salt, tri-tert-butylammonium salt, tripentylammonium salt, trihexylammonium salt, tricyclohexylammonium salt, trioctylammonium salt, tri-2-ethylhexylammonium salt, ethylenediamine, butylenediamine, tetra Methylethylenediamine, tetramethylbutylenediamine, tetraethylethylenediamine, Tiger ethyl butylene diamine, pyridinium salts, piperidinium salts, pyrrolidinium salts, piperazinium salts, and imidazolium salts. Among these, ammonium salt, ethylammonium salt, isopropylammonium salt, butylammonium salt, octylammonium salt, 2-ethylhexylammonium salt, diethylammonium salt, diisopropylammonium salt, dibutyl from the viewpoint of excellent solubility and toughness of the cured product Ammonium salt, dioctylammonium salt, di-2-ethylhexylammonium salt, triethylammonium salt, tributylammonium salt, trioctylammonium salt, tri-2-ethylhexylammonium salt, ethylenediamine, butylenediamine, tetramethylethylenediamine, tetramethylbutylenediamine, Tetraethylethylenediamine, tetraethylbutylenediamine, pyridinium salt, piperidinium salt, pyrrolidinium salt Piperazinium salt and imidazolium salt are preferable, ammonium salt, octylammonium salt, 2-ethylhexylammonium salt, diisopropylammonium salt, dioctylammonium salt, di-2-ethylhexylammonium salt, triethylammonium salt, trioctylammonium salt, tri-2 -Ethylhexylammonium salt, tetramethylethylenediamine, tetramethylbutylenediamine, tetraethylethylenediamine, tetraethylbutylenediamine, pyridinium salt, piperidinium salt, pyrrolidinium salt, imidazolium salt are more preferred, diisopropylammonium salt, dioctylammonium salt, di-2-ethylhexyl Ammonium salt, triethylammonium salt, trioctylammonium salt, tri 2-ethylhexyl ammonium salts, tetramethylethylenediamine, tetraethylethylenediamine, pyridinium salts, imidazolium salts are more preferable.

  Although it does not specifically limit as an example of the polymerizable monomer which has the 1st-quaternary ammonium group of this invention, Halogenated 2- (meth) acryloyloxyethylammonium halide, 2- (meth) acryloyloxypropylammonium halide, Halogenated 2- (meth) acryloyloxybutylammonium, halogenated 2- (meth) acryloyloxyhexylammonium, halogenated 2- (meth) acryloyloxyoctylammonium, halogenated 2- (meth) acryloyloxyethyltrimethylammonium, halogen 2- (meth) acryloyloxyethyltriethylammonium halide, 2- (meth) acryloylethyldimethyl (N-benzyl) ammonium halide, 2- (meth) acryloyloxypropyltrimethyl halide Ammonium, halogenated 2- (meth) acryloyloxypropyltriethylammonium, halogenated 2- (meth) acryloyloxybutyltrimethylammonium, halogenated 2- (meth) acryloyloxybutyltriethylammonium, halogenated 2- (meth) acryloyloxy Hexyltrimethylammonium, 2- (meth) acryloyloxyhexyltriethylammonium halide, 2- (meth) acryloyloxyoctyltrimethylammonium halide, 2- (meth) acryloyloxyoctyltriethylammonium halide, 2- (meth) halide Acryloyloxyethylpyridinium, halogenated 2- (meth) acryloyloxyethyl (N-butyl) piperidinium, halogenated 2- ( T) acryloyloxyethyl pyrrolidinium, halogenated 2- (meth) acryloyloxyethyl imidazolium, halogenated (meth) acryloylaminopropyltrimethylammonium, halogenated (meth) acryloylaminopropyl (N-benzyl) dimethylammonium, etc. Examples include (meth) acrylate polymerizable monomers having a primary to quaternary ammonium group. Among these, 2- (meth) acryloyloxyethylammonium halide, 2- (meth) acryloyloxybutylammonium halide, 2- (meth) acryloyloxyhexyl halide, because of its excellent solubility and toughness of the cured product. Ammonium, 2- (meth) acryloyloxyoctylammonium halide, 2- (meth) acryloyloxyethyltrimethylammonium halide, 2- (meth) acryloylethyldimethyl (N-benzyl) ammonium halide, 2- (meta) halide ) Acrylyloxyethyltriethylammonium halide, 2- (meth) acryloyloxybutyltrimethylammonium halide, 2- (meth) acryloyloxybutyldiethylammonium halide, 2-halogenated halide (Meth) acryloyloxyhexyl ditrimethylammonium halide, 2- (meth) acryloyloxyhexyltriethylammonium halide, 2- (meth) acryloyloxyoctyltrimethylammonium halide, 2- (meth) acryloyloxyoctyltriethylammonium halide, halogenated 2- (meth) acryloyloxyethylpyridinium, halogenated 2- (meth) acryloyloxyethyl (N-butyl) pyrrolidinium, halogenated 2- (meth) acryloyloxyethylimidazolium, halogenated (meth) acryloylaminopropyl (N -Benzyl) dimethylammonium is preferred, halogenated 2- (meth) acryloyloxyethylammonium, halogenated 2- (meth) acryloyloxy Tyltrimethylammonium, 2- (meth) acryloylethyldimethyl (N-benzyl) ammonium halide, 2- (meth) acryloyloxyethyltriethylammonium halide, 2- (meth) acryloyloxyethylpyridinium halide, 2-halogenated (Meth) acryloyloxyethyl imidazolium and halogenated (meth) acryloylaminopropyl (N-benzyl) dimethylammonium are more preferred. Examples of halides are not particularly limited and include fluorides, chlorides, bromides, and iodides, but fluorides and chlorides are preferred from the viewpoint of the toughness of the cured product.

  The content of the polymerizable monomer (B) having an ionic group in the photocurable resin composition of the present invention is such that the urethanized (meth) acrylic compound (A) and the polymerizable monomer having an ionic group ( 0.1-90 mass% is preferable with respect to the total amount of B) and the (meth) acrylamide compound (D), 0.5-60 mass% is more preferable from the point which is excellent by toughness, 1.0-30 mass % Is more preferable, and 1.5 to 15% by mass is particularly preferable.

  The polymerizable monomer contained in the photocurable resin composition of the present invention is substantially composed only of the urethanized (meth) acrylic compound (A) and the polymerizable monomer (B) having an ionic group. Or a urethanized (meth) acrylic compound (A), a polymerizable monomer (B) having an ionic group, and a (meth) acrylamide compound (D). That the polymerizable monomer is substantially composed only of the urethanized (meth) acrylic compound (A) and the polymerizable monomer (B) having an ionic group means that the urethanized (meth) acrylic compound ( The content of polymerizable monomers other than A) and the polymerizable monomer having an ionic group (B) is 10 with respect to the total amount of polymerizable monomers contained in the photocurable resin composition. Less than 0.0% by mass, preferably less than 5.0% by mass, more preferably less than 1.0% by mass, still more preferably less than 0.1% by mass, and particularly preferably 0.01% by mass. Means less than%.

[Photoinitiator (C)]
The photopolymerization initiator (C) used in the present invention can be selected from polymerization initiators used in the general industry, and among them, the photopolymerization initiator used for dental use is preferably used.

  Photopolymerization initiators (C) include (bis) acylphosphine oxides, thioxanthones or ammonium salts of thioxanthones, ketals, α-diketones, coumarins, anthraquinones, benzoin alkyl ether compounds, α-amino ketones System compounds and the like.

  Among these photopolymerization initiators (C), it is preferable to use at least one selected from the group consisting of (bis) acylphosphine oxides and α-diketones. As a result, the photo-curing resin has excellent photo-curability in the ultraviolet region and visible light region, and exhibits sufficient photo-curing properties using any light source of laser, halogen lamp, light-emitting diode (LED), and xenon lamp. A composition is obtained.

  Among the (bis) acylphosphine oxides used as the photopolymerization initiator (C), examples of the acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine. Oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenyl Phosphine oxide, benzoyldi (2,6-dimethylphenyl) phosphonate, 2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt, 2,4,6-trimethylbenzoylphenol Le phosphine oxide potassium salt, and ammonium salt of 2,4,6-trimethylbenzoyl diphenylphosphine oxide. Examples of bisacylphosphine oxides include bis (2,6-dichlorobenzoyl) phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, and bis (2,6-dichlorobenzoyl). ) -4-propylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2, 4,4-trimethylpentylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,5,6) -Trimethylbe Benzoyl) -2,4,4-trimethyl pentyl phosphine oxide and the like. Furthermore, the compound described in Unexamined-Japanese-Patent No. 2000-159621 can be mentioned.

  Among these (bis) acylphosphine oxides, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine Oxide and 2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt are particularly preferably used as the photopolymerization initiator (C).

  Examples of the α-diketone used as the photopolymerization initiator (C) include diacetyl, benzyl, camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4,4 ′. -Oxybenzyl, acenaphthenequinone. Among these, camphorquinone is particularly preferable when a light source in the visible light region is used.

  Although content of the photoinitiator (C) in the photocurable resin composition of this invention is not specifically limited, From viewpoints, such as sclerosis | hardenability of the photocurable resin composition obtained, a urethanated (meth) acryl compound ( The photopolymerization initiator (C) is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer (B) having an ionic group and the (meth) acrylamide compound (D). . When content of a photoinitiator (C) is less than 0.01 mass part, superposition | polymerization does not fully advance and there exists a possibility that a molded article may not be obtained. As for content of a photoinitiator (C), 0.05 mass part or more is more preferable with respect to the said total amount of 100 mass parts, and 0.1 mass part or more is further more preferable. On the other hand, when the content of the photopolymerization initiator (C) exceeds 20 parts by mass, when the solubility of the polymerization initiator itself is low, precipitation from the photocurable resin composition may be caused. As for content of a photoinitiator (C), 15 mass parts or less are more preferable with respect to the said total amount of 100 mass parts, 10 mass parts or less are more preferable, and 5.0 mass parts or less are especially preferable.

  The photocurable resin composition of the present invention contains the urethanized (meth) acrylic compound (A), a polymerizable monomer (B) having an ionic group, and a photopolymerization initiator (C). If there is no limitation in particular, for example, components other than this may be included. The photocurable resin composition of this invention can be manufactured according to a well-known method.

[(Meth) acrylamide compound (D)]
It is preferable that the photocurable resin composition of the present invention further contains a (meth) acrylamide compound (D). Polymer network via hydrogen bonds formed from (meth) acrylamide contained in urethanized (meth) acrylic compound (A) and (meth) acrylamide compound (D), polymerizable monomer having ionic group (B ) Included in the polymer network via ionic bonds, the rigidity is increased compared to the case where each single network is formed, and two types of reversible bonds are stepped by stress loading. It is considered that the improvement in toughness is observed because of the elongation after yielding. The (meth) acrylamide compound (D) is N-substituted (meth) acrylamide or N, N-disubstituted (meth) acrylamide, and is not particularly limited as long as it is a compound having no ionic group. The ionic group that the (meth) acrylamide compound (D) does not mean means an ionic group of the polymerizable monomer (B) having an ionic group. Examples of the N-substituted (meth) acrylamide include N-alkyl-substituted (meth) acrylamide. Examples of the N, N-disubstituted (meth) acrylamide include N, N-dialkyl-substituted (meth) acrylamide. The alkyl group which the above-mentioned N-alkyl substituted (meth) acrylamide and N, N-dialkyl substituted (meth) acrylamide have may have a substituent. Although carbon number of the alkyl group which said N-alkyl substituted (meth) acrylamide and N, N-dialkyl substituted (meth) acrylamide have is not specifically limited, 1-10 are preferable, 1-6 are more preferable, 1- 4 is more preferable. Although the number of the substituents is not particularly limited, 1 to 6 is preferable, 1 to 3 is more preferable, and 1 to 2 is more preferable. Examples of the substituent include a hydroxyl group and a cyano group. Moreover, the alkyl group which N, N-dialkyl substituted (meth) acrylamide has may form the heterocyclic ring together.

  Examples of the (meth) acrylamide compound (D) include N-substituted (meth) acrylamides such as N- (2-hydroxyethyl) (meth) acrylamide; N, N-dimethyl (meth) acrylamide, N, N-diethyl (Meth) acrylamide, N, N-di-n-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-di-n-butyl (meth) acrylamide, N, N-di-n-hexyl (Meth) acrylamide, N, N-di-n-octyl (meth) acrylamide, N, N-di-2-ethylhexyl (meth) acrylamide, N, N-bis (2-hydroxyethyl) (meth) acrylamide, N -Acryloylmorpholine, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylamino ester (Meth) acrylamide, N, N-dipropylaminoethyl (meth) acrylamide, N, N-dibutylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl ( (Meth) acrylamide, N, N-dipropylaminopropyl (meth) acrylamide, N, N-dibutylaminopropyl (meth) acrylamide, N, N-dimethylaminobutyl (meth) acrylamide, N, N-diethylaminobutyl (meth) Examples include N, N-disubstituted (meth) acrylamides such as acrylamide, N, N-dipropylaminobutyl (meth) acrylamide, and N, N-dibutylaminobutyl (meth) acrylamide. These may be used alone or in combination of two or more. Among these, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-di-n is the point that the curability of the photocurable resin composition and the toughness of the cured product are excellent. -Propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-di-n-butyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N-acryloylmorpholine, N, N -Dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N, N-dimethylaminobutyl (Meth) acrylamide, N, N-diethylaminobutyl (meth) Kurylamide is more preferable, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N-acryloylmorpholine, N, N-dimethylaminoethyl. (Meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, and N, N-diethylaminopropyl (meth) acrylamide are more preferable, and N, N-dimethylacrylamide, N , N-diethylacrylamide, N-isopropylacrylamide, N- (2-hydroxyethyl) acrylamide, N-acryloylmorpholine, N, N-dimethylaminoethylacrylamide, N, N-diethylaminoethylacrylic Bromide, N, N-dimethylaminopropyl acrylamide, N, N-diethylaminopropyl acrylamide is particularly preferred, N, N-diethyl acrylamide, N, N-dimethylaminopropyl acrylamide is most preferred.

  The content of the (meth) acrylamide compound (D) in the photocurable resin composition of the present invention is the urethanized (meth) acrylic compound (A), the polymerizable monomer (B) having an ionic group, and (meth) 1) -90 mass% is preferable with respect to the total amount of acrylamide compound (D), 5-80 mass% is more preferable, and 10-70 mass% is further more preferable.

  The photocurable resin composition of the present invention can contain a polymerization accelerator (E) for the purpose of improving photocurability within a range not impairing the gist of the present invention. Examples of the polymerization accelerator (E) include ethyl 4- (N, N-dimethylamino) benzoate, methyl 4- (N, N-dimethylamino) benzoate, 4- (N, N-dimethylamino) benzoate. Acid n-butoxyethyl, 4- (N, N-dimethylamino) benzoic acid 2- (methacryloyloxy) ethyl, 4- (N, N-dimethylamino) benzophenone, 4- (N, N-dimethylamino) benzoic acid Butyl is mentioned. Among these, from the viewpoint of imparting excellent curability to the photocurable resin composition, ethyl 4- (N, N-dimethylamino) benzoate, n-butoxy 4- (N, N-dimethylamino) benzoate At least one selected from the group consisting of ethyl and 4- (N, N-dimethylamino) benzophenone is preferably used.

  The photocurable resin composition of the present invention further contains a filler (F) in order to adjust the paste properties or to increase the mechanical strength of the cured product of the photocurable resin composition. Also good. Examples of the filler (F) include an organic filler, an inorganic filler, and an organic-inorganic composite filler. A filler (F) may be used individually by 1 type, and may use 2 or more types together.

  Examples of the organic filler material include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, cross-linked polymethyl methacrylate, cross-linked polyethyl methacrylate, polyester, polyamide, polycarbonate, Polyphenylene ether, polyoxymethylene, polyvinyl chloride, polystyrene, polyethylene, polypropylene, chloroprene rubber, nitrile rubber, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene A copolymer is mentioned. These may be used alone or in combination of two or more. The shape of the organic filler is not particularly limited, and the particle size of the filler can be appropriately selected and used.

  Examples of the inorganic filler material include quartz, silica, alumina, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, Glass ceramic, aluminosilicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, strontium calcium fluoroaluminosilicate glass It is done. These may also be used alone or in combination of two or more. The shape of the inorganic filler is not particularly limited, and an amorphous filler or a spherical filler can be appropriately selected and used.

  A polymer can be added to the photocurable resin composition of the present invention for the purpose of modifying flexibility, fluidity and the like within a range not impairing the gist of the present invention. For example, natural rubber, synthetic polyisoprene rubber, liquid polyisoprene rubber and hydrogenated product thereof, polybutadiene rubber, liquid polybutadiene rubber and hydrogenated product thereof, styrene-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, acrylic rubber, isoprene- Isobutylene rubber, acrylonitrile-butadiene rubber, or styrenic elastomer can be added. Specific examples of other polymers that can be added include polystyrene-polyisoprene-polystyrene block copolymers, polystyrene-polybutadiene-polystyrene block copolymers, poly (α-methylstyrene) -polybutadiene-poly (α-methylstyrene). ) Block copolymer, poly (p-methylstyrene) -polybutadiene-poly (p-methylstyrene) block copolymer, or a hydrogenated product thereof.

  The photocurable resin composition of the present invention may contain a softener as necessary. Examples of the softener include petroleum softeners such as paraffinic, naphthenic, and aromatic process oils, and vegetable oil softeners such as paraffin, peanut oil, and rosin. These softeners may be used alone or in combination of two or more. The content of the softening agent is not particularly limited as long as the gist of the present invention is not impaired. Usually, the urethanized (meth) acrylic compound (A), the polymerizable monomer (B) having an ionic group, and (meta ) It is 200 parts by mass or less, preferably 100 parts by mass or less with respect to 100 parts by mass of the total amount of the acrylamide compound (D).

  Moreover, a well-known stabilizer can be mix | blended with the photocurable resin composition of this invention for the purpose of suppression of deterioration or adjustment of photocurability. Examples of the stabilizer include a polymerization inhibitor, an ultraviolet absorber, and an antioxidant.

  Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, dibutyl hydroquinone, dibutyl hydroquinone monomethyl ether, 4-t-butylcatechol, 2-t-butyl-4,6-dimethylphenol, 2,6-di-t- Examples include butylphenol and 3,5-di-t-butyl-4-hydroxytoluene. The content of the polymerization inhibitor is 0 with respect to 100 parts by mass of the total amount of the urethanized (meth) acrylic compound (A), the polymerizable monomer (B) having an ionic group, and the (meth) acrylamide compound (D). 0.001 to 1.0 part by mass is preferable.

  Moreover, a well-known additive can be mix | blended with the photocurable resin composition of this invention for the purpose of adjustment of a color tone, or adjustment of paste property. Examples of the additive include pigments, dyes, organic solvents, and thickeners.

  The photocurable resin composition of this invention is excellent in the toughness of hardened | cured material. Therefore, the photocurable resin composition of the present invention can be applied to applications in which such advantages are utilized, and is particularly suitable for mouth guards, occlusal splints and denture base materials. The shape of the cured product using the photocurable resin composition of the present invention can be changed according to each application. In addition, the photocurable resin composition of the present invention may be prepared by using each component (urethane (meth) acrylic compound (A), ionicity) for each use such as a mouth guard, an occlusal splint, and a denture base material as necessary. Group-containing polymerizable monomer (B), polymerization initiator (C), (meth) acrylamide compound (D) and various optional components (polymerization accelerator (E), filler (F), polymer, softener , Stabilizers, additives, etc.)) and the content and content can be adjusted.

  From the point that the photocurable resin composition of the present invention is suitable for uses such as mouth guards, occlusal splints and denture base materials, the bending strength of the cured product is preferably 30 MPa or more, more preferably 40 MPa or more, 50 MPa or more is more preferable. Further, the bending strength of the cured product is preferably 400 MPa or less, more preferably 300 MPa or less, and further preferably 200 MPa or less. The method for measuring the bending strength is as described in Examples described later. In addition, since the photocurable resin composition of the present invention is suitable for uses such as mouth guards, occlusal splints and denture base materials, the flexural modulus of the cured product is preferably 500 to 5000 MPa, and preferably 1000 to 4000 MPa. Is more preferable, and 1400 to 3000 MPa is more preferable. The measuring method of the flexural modulus is as described in the examples described later.

  The photo-curable resin composition of the present invention is a molded product or a three-dimensional modeled product having a small volume shrinkage ratio and excellent dimensional accuracy when cured with light, and excellent in mechanical properties of the cured product, Can be used for various applications taking advantage of the properties that other cured products can be obtained, for example, production of a three-dimensional object by an optical three-dimensional modeling method, a film-like substance by a casting method, casting, etc. It can be used for the production of various molded products such as molds, coating, vacuum forming dies and the like.

  Among them, the photo-curable resin composition of the present invention is suitable for use in the above-described optical three-dimensional modeling method, and in that case, the dimensional accuracy is excellent while keeping the volume shrinkage ratio during photo-curing small. And the three-dimensional molded item which is excellent in a mechanical characteristic can be manufactured smoothly.

  As another embodiment of the present invention, a method of producing a three-dimensional modeled object by an optical three-dimensional modeled method using any one of the above-described photocurable resin compositions can be mentioned.

  In performing optical three-dimensional modeling using the photocurable resin composition of the present invention, a conventionally known optical three-dimensional modeling method and apparatus (for example, DIGITIALWAX (registered trademark) 028J-Plus, 020D manufactured by DWS, etc.) Any of the modeling machines can be used. Among them, in the present invention, it is preferable to use an active energy ray as light energy for curing the resin. The “active energy beam” means an energy beam that can cure the photocurable resin composition such as ultraviolet ray, electron beam, X-ray, radiation, high frequency and the like. For example, the active energy ray may be an ultraviolet ray having a wavelength of 300 to 400 nm. Examples of the light source of the active energy ray include lasers such as Ar laser and He—Cd laser; illumination such as halogen lamp, xenon lamp, metal halide lamp, LED, mercury lamp, and fluorescent lamp, and laser is particularly preferable. When a laser is used as the light source, it is possible to increase the energy level and shorten the modeling time, and to obtain a three-dimensional modeled object with high dimensional accuracy using the good condensing property of the laser beam. it can.

  As described above, when performing optical three-dimensional modeling using the photocurable resin composition of the present invention, any of a conventionally known method and a conventionally known stereolithography system apparatus can be employed, but the present invention is not particularly limited. As a representative example of the optical three-dimensional modeling method preferably used in the invention, a cured layer is formed by selectively irradiating a photocurable resin composition with active energy rays so that a cured layer having a desired pattern is obtained. A step of supplying an uncured liquid photocurable resin composition to the cured layer and then irradiating the same with active energy rays to form a new cured layer continuous with the cured layer. By repeating, the method of finally obtaining the target three-dimensional molded item can be mentioned. In addition, even if the three-dimensional shaped object obtained as it is used as it is, or in some cases, post-curing by light irradiation or post-curing by heat, etc., to further increase its mechanical properties or shape stability, etc. It may be used.

  The structure, shape, size, and the like of the three-dimensional structure obtained by the optical three-dimensional modeling method are not particularly limited, and can be determined according to each application. Typical application fields of the optical three-dimensional modeling method of the present invention include a model for verifying the appearance design during the design; a model for checking the functionality of the part; a resin mold for producing a mold; Examples include a base model for producing molds; production of direct molds for prototype molds, and the like. More specifically, the production of models for precision parts, electrical / electronic parts, furniture, building structures, automotive parts, various containers, castings, molds, molds, etc. In particular, taking advantage of the excellent toughness of the photo-curable resin composition, it can be used extremely effectively for applications such as cushioning materials with complex shapes in structures (for example, building structures), vacuum molding dies, etc. can do.

  EXAMPLES Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples, and many modifications are possible within the scope of the technical idea of the present invention. This is possible by those with ordinary knowledge in the field.

<Synthesis Example 1> [Production of Urethane (Meth) acrylic Compound (A-1)]
(1) 250 g of isophorone diisocyanate and 0.15 g of di-n-butyltin dilaurate were added to a 5 L four-necked flask equipped with a stirrer, a temperature controller, a thermometer, and a condenser, and stirred. At a temperature of 70 ° C.
(2) On the other hand, a dropping funnel with a side tube of 2500 g of polyester polyol ("Kuraray polyol (registered trademark) P-5010" manufactured by Kuraray Co., Ltd .; polymer consisting of adipic acid and 3-methylpentanediol, weight average molecular weight Mw5000) Was added dropwise to the flask of (1) above. While stirring the solution in the flask of (1) above, the flask was added dropwise at a constant rate over 4 hours while maintaining the internal temperature of the flask at 65 to 75 ° C. Furthermore, after completion | finish of dripping, it was made to react by stirring at the same temperature for 2 hours.
(3) Next, a solution obtained by uniformly dissolving 150 g of 2-hydroxyethyl acrylate and 0.4 g of hydroquinone monomethyl ether added to another dropping funnel was taken for 2 hours while maintaining the internal temperature of the flask at 55 to 65 ° C. After dropwise addition at a constant speed, the urethanized (meth) acrylic compound (A-1) was obtained by reacting for 4 hours while maintaining the temperature of the solution in the flask at 70 to 80 ° C.

<Synthesis Example 2> [Production of Urethane (Meth) acrylic Compound (A-2)]
(1) 250 g of isophorone diisocyanate and 0.15 g of di-n-butyltin dilaurate were added to a 5 L four-necked flask equipped with a stirrer, a temperature controller, a thermometer, and a condenser, and stirred. At a temperature of 70 ° C.
(2) On the other hand, a polycarbonate polyol ("Kuraray Polyol (registered trademark) C-1090" manufactured by Kuraray Co., Ltd .; polymer consisting of 1,6-hexanediol / 3-methylpentanediol = 9/1 (mass ratio), weight 500 g of average molecular weight Mw 1000) was added to a dropping funnel with a side tube, and the liquid in the dropping funnel was dropped into the flask of the above (1). While stirring the solution in the flask of (1) above, the flask was added dropwise at a constant rate over 4 hours while maintaining the internal temperature of the flask at 65 to 75 ° C. Furthermore, after completion | finish of dripping, it was made to react by stirring at the same temperature for 2 hours.
(3) Next, a solution obtained by uniformly dissolving 150 g of 2-hydroxyethyl acrylate and 0.4 g of hydroquinone monomethyl ether added to another dropping funnel was taken for 2 hours while maintaining the internal temperature of the flask at 55 to 65 ° C. After dropwise addition at a constant speed, the urethanized (meth) acrylic compound (A-2) was obtained by reacting for 4 hours while maintaining the temperature of the solution in the flask at 70 to 80 ° C.

<Synthesis Example 3> [Production of Urethane (Meth) acrylic Compound (A-3)]
(1) Add 195 g of 2,4-tolylene diisocyanate and 0.15 g of di-n-butyltin dilaurate to a 5 L four-necked flask equipped with a stirrer, temperature controller, thermometer and condenser And heated to 70 ° C. with stirring.
(2) On the other hand, 1250 g of polybutylene glycol (“UNIOL (registered trademark) PB-1000” manufactured by NOF Corporation, weight average molecular weight Mw1000) is added to a dropping funnel with a side tube, and the liquid in the dropping funnel is added to the above. It was dripped in the flask of (1). While stirring the solution in the flask of (1) above, the flask was added dropwise at a constant rate over 4 hours while maintaining the internal temperature of the flask at 65 to 75 ° C. Furthermore, after completion | finish of dripping, it was made to react by stirring at the same temperature for 2 hours.
(3) Next, a solution obtained by uniformly dissolving 150 g of 2-hydroxyethyl acrylate and 0.4 g of hydroquinone monomethyl ether added to another dropping funnel was taken for 2 hours while maintaining the internal temperature of the flask at 55 to 65 ° C. After dropping at a constant speed, the reaction was carried out for 4 hours while maintaining the temperature of the solution in the flask at 70 to 80 ° C. to obtain a urethanized (meth) acrylic compound (A-3).

<Synthesis Example 4> [Production of Urethane (Meth) acrylic Compound (A-4)]
In a 5 L SUS autoclave, 390 g of isophorone diisocyanate, 3.5 g of aluminum chelate M (aluminum alkyl acetoacetate diisopropylate) and 200 g of 2-hydroxyethyl acrylate are mixed and reacted at 60 ° C. for 1 hour. Reaction A was synthesized. Next, under an air atmosphere, 600 g of the reaction product A synthesized earlier, hydrogenated polybutadiene having a terminal modified with a hydroxyl group (“GI-1000” manufactured by Nippon Soda Co., Ltd., number average molecular weight Mn 1500, Mw / Mn 1.15, Content of 1,2-bond units (ratio of moles of 1,2-bond units to total moles of 1,2-bond units and 1,4-bond units) 7 mol%, hydrogenation by iodine value measurement (Rate 96 mol%) 1500 g and aluminum chelate M 12.0 g were mixed and reacted at 60 ° C. for 2 hours. The reaction solution is diluted with 1 L of toluene, washed with 0.5 L of distilled water three times, reprecipitated with a 50/50 (volume ratio) solvent of distilled water / methanol, dried under reduced pressure, and urethanized (meth) acrylic. Compound (A-4) was obtained.

  Each component used for the photocurable resin composition which concerns on an Example or a comparative example is demonstrated below with an abbreviation.

[Polymerizable monomer having ionic group (B)]
METMAC: Methacryloyloxyethyltrimethylammonium chloride (Kyoeisha Chemical Co., Ltd. Light Ester DQ-100)
ZA: Zinc acrylate (manufactured by Asada Chemical Industry Co., Ltd.)

[Photoinitiator (C)]
TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide

[(Meth) acrylamide compound (D)]
ACMO: N-acryloylmorpholine (manufactured by KJ Chemicals)
DEAA: N, N-diethylacrylamide (manufactured by KJ Chemicals)

[Polymerization inhibitor]
BHT: 3,5-di-tert-butyl-4-hydroxytoluene

[Examples 1-7 and Comparative Examples 1-5]
According to Examples 1-7 and Comparative Examples 1-5, each component is mixed under the amounts shown in Table 1 and Table 2 at room temperature (20 ° C. ± 15 ° C., JIS (Japanese Industrial Standards) Z 8703: 1983). A paste as a photo-curable resin composition was prepared.

<Formability>
About the photocurable resin composition which concerns on each Example and each comparative example, modeling of the rectangular parallelepiped test piece of thickness 5mm * length 20mm * width 10mm was performed using the optical modeling machine (DIGITALWAX 020D by DWS). . If the error can be modeled within ± 0.1mm on all sides of the test piece, it can be modeled as “○”, and if the error on either side exceeds ± 0.1mm, it is determined as “Δ”. The case where the model was not obtained was determined as “X”.

<Strength (bending strength, flexural modulus)>
About the photocurable resin composition which concerns on each Example and each comparative example, the test piece of thickness 3.3mm x width 10.0mm x length 64mm was modeled using the optical modeling machine (DIGITALWAX 020D by DWS). Then, α-light V (manufactured by Morita Co., Ltd.) was used for both side irradiation for 3 minutes on one side to obtain a test piece. The obtained test piece was evaluated by performing a bending strength test and a bending elastic modulus test in accordance with JIS T 6501: 2012 “acrylic resin for denture base”. That is, using a universal testing machine (manufactured by Shimadzu Corporation, Autograph AG-I 100 kN), a bending test was performed at a crosshead speed of 5 mm / min. The bending strength of the cured product is preferably 30 MPa or more, more preferably 40 MPa or more, and even more preferably 50 MPa or more from the viewpoint that it is suitable for mouth guards, occlusal splints and denture base materials. The flexural modulus is preferably 500 to 5000 MPa, more preferably 1000 to 4000 MPa, and even more preferably 1400 to 3000 MPa because it is suitable for mouth guards, occlusal splints and denture base materials.

<Toughness (total fracture work)>
About the photocurable resin composition which concerns on each Example and each comparative example, thickness 8.0mm, width 3.0mm, length 39mm, notch depth 3 using an optical modeling machine (DIGITALWAX 020D by DWS) A test piece of .0 mm was formed and irradiated on both sides for 3 minutes on one side using α-light V (manufactured by Morita Co., Ltd.) to obtain a test piece. The obtained test piece was subjected to a fracture toughness test in accordance with JIS T 6501: 2012 “acrylic resin for denture base”, measured with Autograph AG-I 100 kN (manufactured by Shimadzu Corporation), and completely destroyed. Evaluated work. If the total fracture work is a value exceeding 10.0 kJ / m ² , the cured product is excellent in toughness, and is preferably 15.0 kJ / m ² or more because it is suitable for mouth guards, occlusal splints and denture base materials.

  As shown in Table 1 and Table 2, the photocurable resin compositions in Examples 1 to 7 are excellent in the formability as compared with Comparative Examples 1 to 5, and further, the photocurable resin compositions in Examples 1 to 7 are used. The cured product was superior in strength and toughness as compared with Comparative Examples 1-5. Especially the intensity | strength of the hardened | cured material of the photocurable resin composition which concerns on Examples 1-7 was superior to the hardened | cured material of the photocurable resin composition which concerns on Comparative Examples 3 and 5. The toughness of the cured product of the photocurable resin composition according to Examples 1 to 7 was superior to the cured product of the photocurable resin composition according to Comparative Examples 2 to 5. The moldability of the photocurable resin compositions according to Examples 1 to 7 was superior to the photocurable resin compositions according to Comparative Examples 1, 2, and 5. The photocurable resin composition according to Comparative Example 1 could not measure each characteristic because the test piece could not be formed.

  The photocurable resin composition of the present invention is particularly suitable for mouth guards, occlusal splints, and denture base materials that are excellent in modeling properties and excellent in toughness of cured products, and are formed by optical three-dimensional modeling. .

Claims (13)

Containing a urethanized (meth) acrylic compound (A), a polymerizable monomer having an ionic group (B), and a photopolymerization initiator (C);
The urethanized (meth) acrylic compound (A) is
In one molecule, light is a (meth) acrylate containing at least one structure selected from the group consisting of polyester, polycarbonate, polyurethane, polyether, polyconjugated diene, and hydrogenated polyconjugated diene, and a urethane bond. Curable resin composition.   The photocurable resin composition according to claim 1, wherein the polymerizable monomer (B) having an ionic group is a radical polymerizable monomer having an ionic group.   The ionic group of the polymerizable monomer (B) having the ionic group is a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, and a metal salt thereof, an ammonium salt thereof, a primary to a quaternary thereof. The photocurable resin composition according to claim 1 or 2, which is at least one selected from the group consisting of an ammonium salt and a primary to quaternary ammonium group.   The ionic group of the polymerizable monomer (B) having the ionic group is at least one selected from the group consisting of a carboxylic acid group, a carboxylate salt, and a primary to quaternary ammonium group. Item 3. The photocurable resin composition according to Item 1 or 2.   The polymerizable monomer (B) having an ionic group includes a (meth) acrylate polymerizable monomer having an ionic group and a (meth) acrylamide polymerizable monomer having an ionic group. The photocurable resin composition of any one of Claims 1-4 which is at least 1 sort (s) chosen from a group.   The polymerizable monomer (B) having an ionic group has a (meth) acrylate polymerizable monomer having a carboxylic acid group or a salt thereof, and / or a primary to quaternary ammonium group (meth). The photocurable resin composition according to any one of claims 1 to 5, which is an acrylate polymerizable monomer.   Furthermore, N-substituted (meth) acrylamide or N, N-disubstituted (meth) acrylamide containing (meth) acrylamide compound (D), wherein the (meth) acrylamide compound (D) does not have an ionic group. The photocurable resin composition of any one of Claims 1-6 which exists.   The photocurable resin composition of Claim 7 whose said (meth) acrylamide compound (D) is N, N-dialkyl substituted (meth) acrylamide which does not have an ionic group.   The photocurable resin composition according to claim 1, which is for optical three-dimensional modeling.   The mouth guard which consists of a hardened | cured material of the photocurable resin composition of any one of Claims 1-9.   The occlusal splint which consists of hardened | cured material of the photocurable resin composition of any one of Claims 1-9.   The denture base material which consists of hardened | cured material of the photocurable resin composition of any one of Claims 1-9.   The method to manufacture a three-dimensional molded item by the optical three-dimensional modeling method using the photocurable resin composition of any one of Claims 1-9.