Resin composition for photomolding

Abstract

The present invention provides a resin composition for photoforming having excellent strength, toughness and water resistance of a formed object. The present invention relates to a resin composition for photoforming, which comprises a carbamate-containing (meth) acrylic acid compound (A), a (meth) acrylic acid ester compound (B) not containing a carbamate bond and a photopolymerization initiator (C), wherein the compound (A) is a carbamate-containing (meth) acrylic acid compound (A-1) having a polymer structure and / or a carbamate-containing (meth) acrylic acid ester compound (A-2) not having a polymer structure, the weight average molecular weight of the compound (A-1) is less than 1000, the molecular weight of the compound (A-2) is less than 1000, and the compound (B) comprises at least one selected from a (meth) acrylic acid ester compound (b-I) represented by the general formula (I) and a (meth) acrylic acid ester compound (b-II) represented by the general formula (II).

Description

Technical Field

[0001] The present invention relates to a resin composition for optical molding. More specifically, the present invention can obtain a three-dimensional object with excellent strength, toughness and water resistance. It is particularly suitable for denture base materials, dental bite plates, and treatment tools for sleep apnea syndrome. Background Art

[0002] Patent document 1 discloses a method for manufacturing a three-dimensional object by repeatedly performing the following steps, namely, the so-called optical three-dimensional forming method, wherein the steps are: supplying a liquid photocurable resin composition with a controlled amount of light energy to cure it into a thin layer, and further supplying a liquid photocurable resin composition thereon, and then irradiating it with light under control to cure it in a stacked manner into a thin layer. Furthermore, after further proposing its basic practical method based on patent document 2, a number of proposals related to the optical three-dimensional forming technology have been made.

[0003] As a representative method for optically manufacturing three-dimensional objects, a method of liquid tank optical molding is usually used to repeatedly perform the following stacking operation to manufacture a three-dimensional object of the final shape. The stacking operation is: for the liquid surface of the liquid photocurable resin composition placed in the container, a computer-controlled ultraviolet laser is selectively irradiated in a manner that can obtain a desired pattern, so that it is cured to a specified thickness to form a solidified layer, and then, a layer of liquid photocurable resin composition is supplied to the solidified layer, and ultraviolet laser is also irradiated to cure it in the same manner as described above to form a continuous solidified layer. When using this method, even if the shape of the object is very complex, it is possible to simply and in a short time with good precision to manufacture the target three-dimensional object, and therefore, it has received great attention in recent years.

[0004] Furthermore, the three-dimensional objects obtained by the photolithography method have been applied from simple concept models to test models, trial products, etc., and with this, the three-dimensional objects are increasingly required to have excellent shaping accuracy. Moreover, on the basis of such characteristics, the characteristics that match the target are also required to be excellent. In particular, in the field of dental materials, the shapes of denture bases, dental bite plates, and treatment tools for sleep apnea syndrome vary from patient to patient and are complex in shape, so the application of the photolithography method can be expected.

[0005] Denture base material is the material used for the gum part when installing dentures due to tooth loss. In recent years, with the increase in the aging population, the demand for dentures has increased dramatically.

[0006] Dental bite plates are worn to correct jaw position, to suppress tooth wear caused by bruxism, and to protect the jaw and oral system and brain in contact sports to reduce trauma caused by large external forces applied to the teeth and jaws. In recent years, their use in dental correction has been rapidly expanding due to their high aesthetic value and the ability to be removed when desired.

[0007] The therapeutic tool for sleep apnea syndrome targeted by the present invention is a device (oral appliance: OA) worn on the teeth at night while sleeping to treat obstructive sleep apnea syndrome (OSAS), and is rapidly being used as a therapeutic tool for sleep apnea syndrome.

[0008] For these denture base materials, dental bite plates and OA, strength, toughness and water resistance are commonly required. This is especially required in partial denture bases that do not contain metal hooks, commonly known as hookless dentures. When the strength is low, the deflection and deformation during occlusion become larger, and the wearing feeling becomes worse. When the toughness is damaged, it is easy to be damaged due to the impact of occlusion and deformation during wearing, and there is a problem that frequent remaking is required. Furthermore, when water resistance is damaged, the mechanical properties are reduced during use, and it is easy to deform or break when worn, which is impractical.

[0009] In addition, it is usually necessary to obtain an oral impression when making denture base materials, dental bite plates, and treatment tools for sleep apnea syndrome, but it has been pointed out in the past that it is a burden on patients due to its discomfort and that skilled technicians are required to operate it. In recent years, due to the development of digital technology, attempts have been made to apply optical intraoral scanning to impression acquisition, and attempts have been made to apply optical three-dimensional shaping in forming. Resin compositions for optical shaping are used in shaping, but generally, the stronger the resin composition, the more brittle it tends to be. On the other hand, when toughness is also desired, the molecular structure becomes flexible and water easily penetrates, making it difficult to satisfy all the strength, toughness, and water resistance.

[0010] In such a background, there is a technology that has excellent toughness and water resistance of the cured product and can perform optical three-dimensional shaping. For example, Patent Document 3 discloses a photocurable resin composition having as essential components a urethanized (meth) acrylic compound having a specific oligomer skeleton and a specific mono (meth) acrylate compound having two aromatic rings. However, since the resin composition of Patent Document 3 is conceived as a soft material for braces, etc., it has low strength and is sometimes not preferred for applications such as denture bases.

[0011] Prior art literature

[0012] Patent Literature

[0013] Patent Document 1: Japanese Patent Application Laid-Open No. 56-144478

[0014] Patent Document 2: Japanese Patent Application Laid-Open No. 60-247515

[0015] Patent document 3: International Publication No. 2019 / 189566. Summary of the invention

[0016] Problems to be solved by the invention

[0017] Therefore, an object of the present invention is to provide a photomolding resin composition having excellent strength, toughness and water resistance, and is particularly suitable for denture base materials, dental bite plates, and treatment tools for sleep apnea syndrome.

[0018] Solutions to Solve Problems

[0019] That is, the present invention includes the following inventions.

[0020] [1] A resin composition for photomolding, comprising a urethanized (meth)acrylic compound (A), a (meth)acrylate compound not containing a urethane bond (B), and a photopolymerization initiator (C);

[0021] The urethanized (meth)acrylic compound (A) is a urethanized (meth)acrylic compound (A-1) having a polymer structure and / or a urethanized (meth)acrylic compound (A-2) not having a polymer structure.

[0022] The weight average molecular weight of the urethanized (meth)acrylic compound (A-1) having a polymer structure is less than 1000,

[0023] The molecular weight of the urethanized (meth)acrylic compound (A-2) having no polymer structure is less than 1000.

[0024] The (meth)acrylate compound (B) not containing a urethane bond comprises at least one selected from a (meth)acrylate compound (bI) represented by the following general formula (I) and a (meth)acrylate compound (b-II) represented by the following general formula (II).

[0025] [Chemical formula 1]

[0026]

[0027] [Chemical formula 2]

[0028]

[0029] In the above formula, R 1and R 2 Each independently represents a group represented by the following general formula (i) or a group represented by the following general formula (ii), wherein X is a divalent hydrocarbon group having 1 to 6 carbon atoms or an oxygen atom;

[0030] [Chemical formula 3]

[0031]

[0032] [Chemical formula 4]

[0033]

[0034] In the above formula, R 3 and R 5 are each independently a divalent hydrocarbon group having 1 to 10 carbon atoms, R 4 and R 6 are independently a hydrogen atom or a methyl group, k and l are independently an integer of 0 to 6;

[0035] [2] The resin composition for photomolding according to [1], wherein the number of urethane bonds contained in the urethanized (meth)acrylic compound (A-1) having a polymer structure and the urethanized (meth)acrylic compound (A-2) not having a polymer structure is 3 or less per molecule;

[0036] [3] The resin composition for photomolding according to [1] or [2], wherein the urethanized (meth)acrylic compound (A) comprises the urethanized (meth)acrylic compound (A-2) having no polymer structure;

[0037] [4] The resin composition for photomolding according to [3], wherein the urethanized (meth)acrylic compound (A-2) having no polymer structure comprises a (meth)acrylate compound;

[0038] [5] The resin composition for photomolding according to any one of [1] to [4], wherein the urethanized (meth)acrylic compound (A-2) having no polymer structure comprises a polyfunctional (meth)acrylate compound;

[0039] [6] The resin composition for photomolding according to any one of [1] to [5], wherein the urethanized (meth)acrylic compound (A) consists essentially only of a compound (A-2) having no polymer structure;

[0040] [7] The resin composition for photomolding according to any one of [1] to [6], wherein the urethanized (meth) acrylic compound (A-2) having no polymer structure comprises 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate and / or N,N'-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate;

[0041] [8] The resin composition for photomolding according to any one of [1] to [5], wherein the urethanized (meth)acrylic compound (A) comprises a urethanized (meth)acrylic compound (A-1) having a polymer structure;

[0042] [9] The resin composition for photomolding according to [8], wherein the urethanized (meth)acrylic compound (A-1) having a polymer structure is a (meth)acrylate compound;

[0043]

[10] The resin composition for photomolding according to [8] or [9], wherein the content of the urethanized (meth)acrylic compound (A-1) having a polymer structure is 51 to 95% by mass in 100% by mass of the polymerizable compound;

[0044]

[11] The resin composition for photomolding according to any one of [1] to

[10] , wherein the polymer structure is a structure selected from polyester, polycarbonate, polyurethane, polyether, polyconjugated diene, and hydrogenated polyconjugated diene;

[0045]

[12] The resin composition for photomolding according to any one of [1] to

[11] , wherein k and l are each independently an integer of 1 to 4;

[0046]

[13] The photomolding resin composition according to any one of [1] to

[12] , wherein the (meth)acrylate compound (B) not containing a urethane bond contains the (meth)acrylate compound (b-II), and X is an oxygen atom;

[0047]

[14] The resin composition for photomolding according to

[13] , wherein R 2 is a group represented by the aforementioned general formula (ii);

[0048]

[15] The resin composition for light shaping according to any one of [1] to

[14] , wherein the (meth)acrylate compound (B) not containing a urethane bond contains the (meth)acrylate compound (bI), R 1 is a group represented by the aforementioned general formula (i);

[0049]

[16] The resin composition for photosynthesis according to any one of [1] to

[15] , wherein the content of the photopolymerization initiator (C) is 0.01 to 20 parts by mass based on 100 parts by mass of the total amount of the urethanized (meth)acrylic compound (A) and the (meth)acrylate compound (B) not containing a urethane bond;

[0050]

[17] The resin composition for photopolymerization according to any one of [1] to

[16] , further comprising a polymerization inhibitor (D), wherein the content of the polymerization inhibitor (D) is 0.1 to 100 parts by mass based on 100 parts by mass of the photopolymerization initiator (C);

[0051]

[18] The resin composition for light shaping according to any one of [1] to

[17] , wherein a cured product of the resin composition for light shaping has a flexural strength of 100 MPa or more and a flexural modulus of 2.1 GPa or more;

[0052]

[19] A dental material comprising a shaped article of the photomolding resin composition according to any one of [1] to

[18] ;

[0053]

[20] A denture base material comprising a shaped article of the photomolding resin composition according to any one of [1] to

[18] ;

[0054]

[21] A dental bite plate comprising a shaped article of the photomolding resin composition described in any one of [1] to

[18] ;

[0055]

[22] A material for treating sleep disorders, comprising a shaped article of the photoforming resin composition described in any one of [1] to

[18] ;

[0056]

[23] A method for producing a three-dimensional structure, comprising producing the three-dimensional structure by an optical three-dimensional structure method using the resin composition for optical structure formation described in any one of [1] to

[18] .

[0057] Effects of the Invention

[0058] The light-molding resin composition of the present invention has excellent strength, toughness and water resistance of the molded object. Therefore, the light-molding resin composition of the present invention is suitable for denture base materials and occlusal plates, and can also be suitably used as a material for a treatment tool for sleep apnea syndrome. DETAILED DESCRIPTION

[0059] The resin composition for photomolding of the present invention comprises: a urethanized (meth) acrylic compound (A), a (meth) acrylate compound (B) not containing a urethane bond, and a photopolymerization initiator (C). It should be noted that in this specification, the upper limit and lower limit of the numerical range (the content of each component, the value calculated from each component, and each physical property, etc.) can be appropriately combined. In addition, in this specification, the numerical values ​​of each symbol in the formula can also be appropriately combined.

[0060] [Urethaned (meth)acrylic acid compound (A)]

[0061] In the resin composition for photoforming of the present invention, the carbamate (meth) acrylic compound (A) is used to give the resin composition for photoforming strength and formability to the object being formed. The carbamate (meth) acrylic compound (A) is a carbamate (meth) acrylic compound (A-1) having a polymer structure (hereinafter also simply referred to as "the compound (A-1) having a polymer structure.") and / or a carbamate (meth) acrylic compound (A-2) not having a polymer structure (hereinafter also simply referred to as "the compound (A-2) not having a polymer structure."). The compound (A-1) having a polymer structure has a molecular weight distribution due to the polymer structure. The determination of the molecular weight distribution can be carried out using gel permeation chromatography (GPC). In this specification, the polymer structure refers to a repeating structure of a monomer having a degree of polymerization of 2 or more.

[0062] The urethane (meth) acrylic compound (A) contains, for example, an alkylene skeleton, a cycloalkylene skeleton, and a phenylene skeleton, and can be easily synthesized by allowing a compound having an isocyanate group to react with a (meth) acrylic compound having a hydroxyl group (-OH). In addition, after the aforementioned compound having multiple isocyanate groups is reacted with a polyol to introduce an isocyanate group at the end of the polyol, it is also easily synthesized by allowing it to react with a (meth) acrylic compound having a hydroxyl group. However, in the case of directly reacting a compound having an isocyanate group with a (meth) acrylic compound having a hydroxyl group, since the number of urethane bonds with high polarity in one molecule becomes small, it is preferred from the viewpoint of water resistance. On the other hand, from the viewpoint of excellent strength, the weight average molecular weight (Mw) of the compound (A-1) having a polymer structure needs to be less than 1000. When the weight average molecular weight is 1000 or more, there is a tendency for the shaped object to be softened. From the viewpoint of strength and water resistance, the weight average molecular weight is preferably less than 950, and more preferably less than 850. It should be noted that the weight average molecular weight referred to herein refers to the weight average molecular weight calculated by gel permeation chromatography (GPC) in terms of polystyrene. It should be noted that when the urethane (meth) acrylic compound (A) is a compound (A-2) having no polymer structure, since there is no concept of weight average molecular weight, the molecular weight is applied, and from the viewpoint of excellent strength, the molecular weight needs to be less than 1000. When the molecular weight is 1000 or more, there is a tendency for the shaped object to become soft. From the viewpoint of strength and water resistance, the molecular weight is preferably less than 750, and more preferably less than 500. The molecular weight can be calculated by determining the structure of the compound (A-2) having no polymer structure and from the atomic weight of the elements constituting the structure. The method for determining the structure of the compound is not particularly limited, and a known method for molecular structure analysis (mass spectrometry (MS spectrum) method; magnetic analysis method such as nuclear magnetic resonance method; X-ray crystal structure analysis method, etc.) can be used.

[0063] Furthermore, the urethanized (meth) acrylic compound (A) preferably includes a compound (A-2) having no polymer structure such as polyester, polycarbonate, polyurethane, polyether, etc. When the urethanized (meth) acrylic compound (A) contains a polymer structure, it not only becomes softer, but also tends to reduce water resistance due to an increase in the concentration of polar functional groups. However, even if the urethanized (meth) acrylic compound (A) includes a photomolding resin composition having a polymer structure in which the urethanized (meth) acrylic compound (A) includes a compound (A-1) having a polymer structure, by making the weight average molecular weight of the compound (A-1) having a polymer structure less than 1000, etc., it is possible to suppress the increase in the concentration of polar functional groups, and obtain a molded object having the desired strength and water resistance. In either the compound (A-1) having a polymer structure or the compound (A-2) having no polymer structure, the number of urethane bonds per molecule is preferably 3 or less, and more preferably 2 or less, from the viewpoint of water resistance. The urethanized (meth) acrylic compound (A) can be used alone or in combination of two or more. As a suitable embodiment (X-1), there can be mentioned a photomolding resin composition in which the urethanized (meth) acrylic compound (A) is substantially composed of only a compound (A-2) having no polymer structure, that is, substantially does not contain a compound (A-1) having a polymer structure. The urethanized (meth) acrylic compound (A) is substantially composed of only a compound (A-2) having no polymer structure, which means that the content of the compound (A-1) having a polymer structure is less than 10.0 parts by mass, preferably less than 5.0 parts by mass, more preferably less than 1.0 parts by mass, further preferably less than 0.1 parts by mass, and particularly preferably less than 0.01 parts by mass in the total amount of urethanized (meth) acrylic compounds (A) contained in the photomolding resin composition. In addition, the compound (A-1) having a polymer structure preferably does not contain a (meth) acrylamide group. As another suitable embodiment (X-2), there can be mentioned a resin composition for photomolding in which the urethanized (meth) acrylic compound (A) includes a compound (A-1) having a polymer structure, and the number of urethan bonds contained in the compound (A-1) having a polymer structure is 3 or less per molecule. The number of urethan bonds can be controlled by a known method, but from the aspect of reducing the number of urethan bonds in one molecule, it can also be adjusted by preferentially performing an addition reaction in which a compound having an isocyanate group and a (meth) acrylic compound having a hydroxyl group are directly reacted.For example, in order to make the number of urethane bonds contained in the urethanized (meth)acrylic compound (A-1) having a polymer structure and the urethanized (meth)acrylic compound (A-2) not having a polymer structure 3 or less per molecule, by substantially using a diisocyanate or a polyisocyanate having three isocyanate groups and a reactant of a (meth)acrylic compound having a hydroxyl group as a raw material, or using the foregoing reactant, the number of urethane bonds contained in the urethanized (meth)acrylic compound (A-1) having a polymer structure and the urethanized (meth)acrylic compound (A-2) not having a polymer structure can be made 3 or less per molecule.

[0064] As a compound having an isocyanate group, for example, methylene diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), trimethylhexamethylene diisocyanate (TMHMDI), tricyclodecane diisocyanate (TCDDI), adamantane diisocyanate (ADI), toluene diisocyanate (TDI), xylene diisocyanate (XDI), and diphenylmethane diisocyanate (MDI), and polyisocyanates having more than 3 isocyanate groups derived from these compounds, etc. They can be used alone or in combination of two or more. Among them, from the viewpoint of excellent strength and toughness of the shaped object of the light shaping resin composition of the present invention, preferably HDI, IPDI, TMHMDI, TCDDI, more preferably IPDI, TMHMDI.

[0065] Examples of the (meth)acrylic compound having a hydroxyl group include hydroxy(meth)acrylate compounds such as 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, glycerol mono(meth)acrylate, 2-hydroxy-3-acryloyloxypropyl(meth)acrylate, 2,2-bis[4-[3-(meth)acryloyloxy-2-hydroxypropoxy]phenyl]propane, 1,2-bis[3-(meth)acryloyloxy-2-hydroxypropoxy]ethane, pentaerythritol tri(meth)acrylate, and tri- or tetra(meth)acrylate of dipentaerythritol; and hydroxy(meth)acrylamide compounds such as N-hydroxyethyl(meth)acrylamide and N,N-bis(2-hydroxyethyl)(meth)acrylamide. These compounds may be used alone or in combination of two or more. Among them, from the viewpoint of excellent toughness of the object of the photoforming resin composition of the present invention, preferably 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-acryloxypropyl (meth)acrylate, N-hydroxyethyl (meth)acrylamide, more preferably 2-hydroxyethyl (meth)acrylate.

[0066] The addition reaction of the compound having an isocyanate group and the (meth)acrylic compound having a hydroxyl group can be performed by a known method and is not particularly limited.

[0067] The compound (A-1) having a polymer structure preferably has a polymer structure selected from polyester, polycarbonate, polyurethane, polyether, polyconjugated diene, and hydrogenated polyconjugated diene, and a urethane bond, and is more preferably a (meth)acrylate compound having the above polymer structure and a urethane bond.

[0068] The compound (A-1) having a polymer structure can be easily synthesized by, for example, subjecting a polyol having a polymer structure selected from polyester, polycarbonate, polyurethane, polyether, polyconjugated diene, and hydrogenated polyconjugated diene to an addition reaction with a compound having an isocyanate group and a (meth)acrylate compound having a hydroxyl group. Examples of the polyester include polymers of dicarboxylic acids (aromatic dicarboxylic acids such as phthalic acid and isophthalic acid; unsaturated aliphatic dicarboxylic acids such as maleic acid) and aliphatic diols having 2 to 18 carbon atoms, polymers of dicarboxylic acids (saturated aliphatic dicarboxylic acids such as adipic acid and sebacic acid) and aliphatic diols having 2 to 18 carbon atoms, polymers of β-propiolactone, polymers of γ-butyrolactone, polymers of δ-valerolactone, polymers of ε-caprolactone, and copolymers thereof. Preferred are polymers of dicarboxylic acids (aromatic dicarboxylic acids such as phthalic acid and isophthalic acid; unsaturated aliphatic dicarboxylic acids such as maleic acid) and aliphatic diols having 2 to 12 carbon atoms, and polymers of dicarboxylic acids (saturated aliphatic dicarboxylic acids such as adipic acid and sebacic acid) and aliphatic diols having 2 to 12 carbon atoms. Examples of polycarbonates include polycarbonates derived from aliphatic diols having 2 to 18 carbon atoms, polycarbonates derived from bisphenol A, and polycarbonates derived from aliphatic diols having 2 to 18 carbon atoms and bisphenol A. Preferred examples include polycarbonates derived from aliphatic diols having 2 to 12 carbon atoms, polycarbonates derived from bisphenol A, and polycarbonates derived from aliphatic diols having 2 to 12 carbon atoms and bisphenol A. Examples of polyurethanes include polymers of aliphatic diols having 2 to 18 carbon atoms and diisocyanates having 1 to 18 carbon atoms. Preferred examples include polymers of aliphatic diols having 2 to 12 carbon atoms and diisocyanates having 1 to 12 carbon atoms. Examples of polyethers include polyethylene glycol, polypropylene glycol, polybutylene glycol, and poly(1-methylbutylene glycol). Examples of the polyconjugated diene and hydrogenated polyconjugated diene include 1,4-polybutadiene, 1,2-polybutadiene, polyisoprene, poly(butadiene-isoprene), poly(butadiene-styrene), poly(isoprene-styrene), polyfarnesene, and hydrogenated products thereof. Among these, a polyester structure is preferred from the viewpoint of excellent toughness. Furthermore, from the viewpoint of excellent water resistance and toughness, the polyester structure preferably contains a polyol moiety and an isophthalic acid ester or a sebacate, wherein the polyol moiety has a structure derived from an aliphatic diol unit having 4 to 18 carbon atoms and a branched structure. From the viewpoint of excellent water resistance and molding properties, it is more preferred to contain a polyol moiety and an isophthalic acid ester or a sebacate, wherein the polyol moiety has a structure derived from an aliphatic diol unit having 4 to 12 carbon atoms and a branched structure. It is further preferred to contain a polyol moiety and an isophthalic acid ester or a sebacate, wherein the polyol moiety has a structure derived from an aliphatic diol unit having 5 to 12 carbon atoms and a branched structure. In the production of the compound (A-1) having a polymer structure, a polyol having the above-mentioned polymer structure can be used.Among these, polyester, polycarbonate and polyconjugated diene structures are preferred from the viewpoint of excellent strength and water resistance. In the production of the compound (A-1) having a polymer structure, the aforementioned polyol having a polymer structure can be used.

[0069] Examples of the aliphatic diol unit having 4 to 18 carbon atoms and having a branched structure include 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 1,3-butanediol, 2-methyl-1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 2,7-dimethyl-1,8-octanediol, 2-methyl-1,9-nonanediol, 2,8-dimethyl-1,9-nonanediol, 2-methyl-1,10-decanediol, 2,9-dimethyl-1,10-decanediol, and 2-methyl-1,11-undecanediol. diol, 2,10-dimethyl-1,11-undecandiol, 2-methyl-1,12-dodecanediol, 2,11-dimethyl-1,12-dodecanediol, 2-methyl-1,13-tridecanediol, 2,12-dimethyl-1,13-tridecanediol, 2-methyl-1,14-tetradecanediol, 2,13-dimethyl-1,14-tetradecanediol, 2-methyl-1,15-pentadecandiol, 2,14-dimethyl-1,15-pentadecandiol, 2-methyl-1,16-hexadecanediol, 2,15-dimethyl-1,16-hexadecanediol, and the like. Among these, from the viewpoint of excellent curability and low viscosity of the resin composition for photoforming, it is preferred to use an aliphatic diol having 5 to 12 carbon atoms and having a methyl group as a side chain, such as 2-methyl-1,4-butanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 2,7-dimethyl-1,8-octanediol, 2-methyl-1,9-nonanediol, and 2,8-dimethyl-1,9-nonanediol as the polyol component, more preferably 2-methyl-1,4-butanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, and 2,7-dimethyl-1,8-octanediol, and even more preferably 3-methyl-1,5-pentanediol and 2-methyl-1,8-octanediol.

[0070] As the compound (A-1) having a polymer structure, there can be cited the aforementioned polyol having at least one polymer structure selected from polyester, polycarbonate, polyurethane, polyether, polyconjugated diene and hydrogenated polyconjugated diene, and the reaction product of any combination of a compound having an isocyanate group and a (meth) acrylic compound having a hydroxyl group, and the aforementioned reactant is preferably a (meth) acrylate compound. The compound (A-1) having a polymer structure can be used alone or in combination of two or more. In a certain embodiment (X-3), for example, the compound (A-1) having a polymer structure does not contain a (meth) acrylamide-based oligomer. The resin composition for light shaping.

[0071] Examples of the compound (A-2) not having a polymer structure include difunctional (meth)acrylates such as 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate (common name: UDMA), 2,4-toluenebis(2-carbamoyloxyethyl)dimethacrylate, bishydroxyethyl methacrylate-isophorone dicarbamate, 2,4-toluenebis(2-carbamoyloxyethyl)dimethacrylate, and hexamethylenebis{2-carbamoyloxy-3-phenoxypropyl}diacrylate; and (meth)acrylate compounds such as trifunctional or higher-functional (meth)acrylates such as N,N'-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate and 2,4-toluenebis(2-carbamoyloxyethyl)hexaacrylate. These compounds may be used alone or in combination of two or more. Among these, from the viewpoint of strength and toughness, 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate and N,N′-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate are preferred, and 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate is more preferred.

[0072] The content of the urethanized (meth)acrylic compound (A) in the resin composition for photomolding of the present invention (when both the compound (A-1) having a polymer structure and the compound (A-2) not having a polymer structure are included, the total content thereof) is preferably 10 to 99 parts by mass based on 100 parts by mass of the total amount of the urethanized (meth)acrylic compound (A) and the (meth)acrylate compound (B) not containing a urethane bond (hereinafter also simply referred to as the “total amount”), more preferably 30 to 90 parts by mass, and even more preferably 50 to 80 parts by mass from the viewpoint of better moldability and strength of the molded product. In a preferred embodiment (X-4), the urethanized (meth) acrylic compound (A) contained in the resin composition for photomolding includes a compound (A-2) having no polymer structure, and the content of the compound (A-2) having no polymer structure is preferably 10 to 99 parts by mass in the total amount of 100 parts by mass, and is more preferably 30 to 90 parts by mass, and is further preferably 50 to 80 parts by mass from the perspective of better moldability and strength of the molded object. In another preferred embodiment (X-5), the urethanized (meth) acrylic compound (A) contained in the resin composition for photomolding includes a compound (A-1) having a polymer structure, and the content of the compound (A-1) having a polymer structure is preferably 51 to 95 parts by mass in the total amount of 100 parts by mass, and is more preferably 55 to 90 parts by mass, and is further preferably 60 to 85 parts by mass from the perspective of better moldability and strength of the molded object. Furthermore, in the above-mentioned preferred embodiment (X-5), the content of the compound (A-1) having a polymer structure is preferably 51 to 95% by mass in 100% by mass of the polymerizable compound, more preferably 55 to 90% by mass, and more preferably 60 to 85% by mass in terms of better moldability and strength of the molded product. When the photomolding resin composition contains a (meth)acrylamide compound (D), the above-mentioned polymerizable compound 100% by mass refers to the total of 100% by mass of the urethanized (meth)acrylic compound (A), the (meth)acrylate compound (B) not containing a urethane bond, and the (meth)acrylamide compound (D). In another preferred embodiment (X-6), the content of the compound (A-1) having a polymer structure contained in the photomolding resin composition is preferably 51 to 95% by mass in the entire photomolding resin composition, more preferably 55 to 90% by mass, and more preferably 60 to 85% by mass in terms of better toughness.

[0073] [(Meth)acrylate compound (B) not containing a urethane bond]

[0074] The (meth)acrylate compound (B) not containing a urethane bond can reduce the viscosity of the resin composition for photoforming in the present invention, and is used to impart toughness and water resistance to the object. The (meth)acrylate compound (B) not containing a urethane bond can be used alone or in combination of two or more.

[0075] The (meth)acrylate compound (B) not containing a urethane bond may contain at least one selected from the group consisting of a (meth)acrylate compound (bI) represented by the above general formula (I) (hereinafter referred to as “(meth)acrylate compound (bI)”) and a (meth)acrylate compound (b-II) represented by the above general formula (II) (hereinafter referred to as “(meth)acrylate compound (b-II)”). The (meth)acrylate compound (bI) and the (meth)acrylate compound (b-II) are described below.

[0076] The symbols in formula (I) are explained below. In formula (I), R 1 is a group represented by the above general formula (i) or a group represented by the general formula (ii). From the viewpoint of excellent curability of the obtained photomolding resin composition of the present invention, in the formula (i) or (ii), R 4 and R 6 Each of R and R is independently a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of excellent molding properties of the photomolding resin composition and excellent toughness of the cured product. 3 and R 5 Each independently represents a divalent hydrocarbon group having 1 to 10 carbon atoms. As the aforementioned hydrocarbon group, from the viewpoint of low viscosity and excellent molding properties of the obtained resin composition for light molding, the carbon number is preferably 1 to 6, more preferably 1 to 4, and further preferably 1 to 3. Examples of the aforementioned hydrocarbon group include a linear or branched alkylene group having 1 to 10 carbon atoms; a divalent cycloalkylene group having 3 to 10 carbon atoms; and a phenylene group. k and l are each independently an integer of 0 to 6, and from the viewpoint of low viscosity and excellent molding properties of the obtained resin composition for light molding, k is preferably 1 to 4, more preferably 1 to 3, further preferably 1 to 2, and particularly preferably 1. In addition, l is preferably 1 to 4, more preferably 1 to 2, and further preferably 1.

[0077] Examples of the (meth)acrylate compound (bI) include o-phenylphenol (meth)acrylate, m-phenylphenol (meth)acrylate, p-phenylphenol (meth)acrylate, methoxylated o-phenylphenol (meth)acrylate, methoxylated m-phenylphenol (meth)acrylate, methoxylated p-phenylphenol (meth)acrylate, ethoxylated o-phenylphenol (meth)acrylate, ethoxylated m-phenylphenol (meth)acrylate, ethoxylated p-phenylphenol (meth)acrylate, propoxylated o-phenylphenol (meth)acrylate, propoxylated m-phenylphenol (meth)acrylate, propoxylated p-phenylphenol (meth)acrylate, butoxylated o-phenylphenol (meth)acrylate, butoxylated m-phenylphenol (meth)acrylate, and butoxylated p-phenylphenol (meth)acrylate. These may be used alone or in combination of two or more. Among these, from the perspective of excellent molding properties of the resin composition for photomolding and the toughness and water resistance of the cured product, ethoxylated o-phenylphenol acrylate, ethoxylated m-phenylphenol acrylate, ethoxylated p-phenylphenol acrylate, propoxylated o-phenylphenol acrylate, propoxylated m-phenylphenol acrylate, and propoxylated p-phenylphenol acrylate are more preferred; ethoxylated o-phenylphenol acrylate, ethoxylated m-phenylphenol acrylate, and ethoxylated p-phenylphenol acrylate are further preferred; ethoxylated o-phenylphenol acrylate and ethoxylated m-phenylphenol acrylate are particularly preferred; and ethoxylated o-phenylphenol acrylate is most preferred.

[0078] The symbols of formula (II) are explained below. In formula (II), X is a divalent hydrocarbon group having 1 to 6 carbon atoms or an oxygen atom. The viscosity of the obtained photomolding resin composition is low, and from the perspective of excellent molding properties, an oxygen atom is preferred. 2 is a group selected from the group consisting of the above general formula (i) or (ii). In view of the excellent curability of the obtained photoforming resin composition of the present invention, in the formula (i) or (ii), R 4 and R 6 Each of R and R is independently a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of excellent curability of the photoresist composition and flexibility of the cured product. 3 and R 5Each independently represents a divalent hydrocarbon group having 1 to 10 carbon atoms. As the aforementioned hydrocarbon group, from the viewpoint of low viscosity and excellent curability of the obtained resin composition for photoforming, the carbon number is preferably 1 to 6, more preferably 1 to 4, and further preferably 1 to 3. Examples of the aforementioned hydrocarbon group include a linear or branched alkylene group having 1 to 10 carbon atoms; a divalent cycloalkylene group having 3 to 10 carbon atoms; and a phenylene group. k and l are each independently an integer of 0 to 6, and from the viewpoint of low viscosity and excellent shaping of the obtained resin composition for photoforming, k is preferably 1 to 4, more preferably 1 to 3, further preferably 1 to 2, and particularly preferably 1. In addition, l is preferably 1 to 4, more preferably 1 to 2, and further preferably 1.

[0079] Examples of the (meth)acrylate compound (b-II) include o-phenoxybenzyl (meth)acrylate, m-phenoxybenzyl (meth)acrylate, p-phenoxybenzyl (meth)acrylate, 2-(o-phenoxyphenyl)ethyl (meth)acrylate, 2-(m-phenoxyphenyl)ethyl (meth)acrylate, 2-(p-phenoxyphenyl)ethyl (meth)acrylate, 3-(o-phenoxyphenyl)propyl (meth)acrylate, 3-(m-phenoxyphenyl)propyl (meth)acrylate, 3-(p-phenoxyphenyl)propyl (meth)acrylate, )propyl (meth)acrylate, 4-(o-phenoxyphenyl)butyl (meth)acrylate, 4-(m-phenoxyphenyl)butyl (meth)acrylate, 4-(p-phenoxyphenyl)butyl (meth)acrylate, 5-(o-phenoxyphenyl)pentyl (meth)acrylate, 5-(m-phenoxyphenyl)pentyl (meth)acrylate, 5-(p-phenoxyphenyl)pentyl (meth)acrylate, 6-(o-phenoxyphenyl)hexyl (meth)acrylate, 6-(m-phenoxyphenyl)hexyl (meth)acrylate, and 6-(p-phenoxyphenyl)hexyl (meth)acrylate. These may be used alone or in combination of two or more. Among these, from the viewpoint of excellent molding properties of the resin composition for photomolding and excellent toughness and water resistance of the molded product, o-phenoxybenzyl acrylate, m-phenoxybenzyl acrylate, p-phenoxybenzyl acrylate, 2-(o-phenoxyphenyl)ethyl acrylate, 2-(m-phenoxyphenyl)ethyl acrylate, and 2-(p-phenoxyphenyl)ethyl acrylate are more preferred; o-phenoxybenzyl acrylate, m-phenoxybenzyl acrylate, and p-phenoxybenzyl acrylate are further preferred; o-phenoxybenzyl acrylate and m-phenoxybenzyl acrylate are particularly preferred; and m-phenoxybenzyl acrylate is most preferred.

[0080] The content of the (meth)acrylate compound (B) not containing a urethane bond in the resin composition for photoforming of the present invention is preferably 1 to 90 parts by mass in the total amount of 100 parts by mass of the urethanized (meth)acrylic compound (A) and the (meth)acrylate (B) not containing a urethane bond, more preferably 10 to 70 parts by mass, and further preferably 20 to 50 parts by mass from the viewpoint of better moldability, toughness and water resistance of the molded product. As another preferred embodiment (X-7), in the aforementioned embodiment (X-5) or (X-6), the urethanized (meth)acrylic compound (A) contained in the resin composition for photoforming includes a compound (A-1) having a polymer structure, and the content of the (meth)acrylate compound (B) not containing a urethane bond is preferably 5 to 49 parts by mass in the aforementioned total amount of 100 parts by mass, more preferably 10 to 45 parts by mass, and further preferably 15 to 40 parts by mass from the viewpoint of better moldability, toughness and water resistance of the molded product. Furthermore, in the above-mentioned suitable embodiment (X-7), the content of the (meth)acrylate compound (B) not containing a urethane bond is preferably 5 to 49% by mass in 100% by mass of the polymerizable compound, more preferably 10 to 45% by mass, and even more preferably 15 to 40% by mass in terms of better styling properties, toughness of the shaped object, and water resistance.

[0081] The polymerizable compound contained in the resin composition for photoforming of the present invention may be substantially composed of only the urethanized (meth)acrylic compound (A) and the (meth)acrylate compound (B) not containing a urethanate bond. The polymerizable compound substantially consists of only the urethanized (meth)acrylic compound (A) and the (meth)acrylate compound (B) not containing a urethanate bond, which means that the content of other polymerizable compounds (such as compounds having ethylenically unsaturated groups such as (meth)acrylamide polyurethane oligomers) other than the urethanized (meth)acrylic compound (A) and the (meth)acrylate compound (B) not containing a urethanate bond is less than 10.0 parts by mass, preferably less than 5.0 parts by mass, more preferably less than 1.0 parts by mass, further preferably less than 0.1 parts by mass, and particularly preferably less than 0.01 parts by mass in 100 parts by mass of the total amount of the polymerizable compounds contained in the resin composition for photoforming.

[0082] [Photopolymerization initiator (C)]

[0083] The photopolymerization initiator (C) used in the present invention can be selected from polymerization initiators generally used in the industrial field and used. Among them, photopolymerization initiators used for dental applications are preferred.

[0084] Examples of the photopolymerization initiator (C) include (bis)acylphosphine oxides, thioxanthones or quaternary ammonium salts of thioxanthones, ketals, α-diketones, coumarins, anthraquinones, benzoin alkyl ether compounds, α-aminoketone compounds, etc. The photopolymerization initiator (C) may be used alone or in combination of two or more.

[0085] Among these photopolymerization initiators (C), at least one selected from (bis)acylphosphine oxides and α-diketones is preferably used. Thus, a photoforming resin composition having excellent photocurability in the ultraviolet region and the visible light region and showing sufficient photocurability even when using any light source selected from lasers, halogen lamps, light emitting diodes (LEDs) and xenon lamps can be obtained.

[0086] Among the (bis)acylphosphine oxides, 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-tetramethylbenzoyldiphenylphosphine oxide, benzoylbis(2,6-dimethylphenyl)phosphonate, 2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt, 2,4,6-trimethylbenzoylphenylphosphine oxide potassium salt, and ammonium salt of 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Examples of the bisacylphosphine oxides include bis(2,6-dichlorobenzoyl)phenylphosphine oxide, bis(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, 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, and bis(2,5,6-trimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide. Furthermore, compounds described in Japanese Patent Application Laid-Open No. 2000-159621 are included.

[0087] 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).

[0088] Examples of the α-diketones include diacetyl, benzil, camphorquinone, 2,3-pentanedione, 2,3-octanedione, 9,10-phenanthrenequinone, 4,4′-oxybenzil, and acenaphthenequinone. Among them, camphorquinone is particularly preferred when a light source in the visible light region is used.

[0089] The content of the photopolymerization initiator (C) in the resin composition for light shaping of the present invention is not particularly limited. From the viewpoint of the curability of the obtained resin composition for light shaping, the photopolymerization initiator (C) is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the total amount of the urethanized (meth) acrylic compound (A) and the (meth) acrylic ester compound (B) not containing a urethane bond. When the content of the photopolymerization initiator (C) is less than 0.01 parts by mass, the polymerization cannot proceed sufficiently, and there is a concern that a molded product cannot be obtained. The content of the photopolymerization initiator (C) is more preferably 0.05 parts by mass or more, further preferably 0.1 parts by mass or more, particularly preferably 0.5 parts by mass or more, and most preferably 1.5 parts by mass or more, relative to the total amount of 100 parts by mass. 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, it may cause precipitation from the resin composition for light shaping. The content of the photopolymerization initiator (C) is more preferably 15 parts by mass or less, further preferably 10 parts by mass or less, particularly preferably 5.0 parts by mass or less, and most preferably 3.0 parts by mass or less, based on 100 parts by mass of the total amount.

[0090] The resin composition for photomolding of the present invention is not particularly limited as long as it contains the above-mentioned urethanized (meth) acrylic compound (A), the (meth) acrylate compound (B) not containing a urethane bond, and the photopolymerization initiator (C), and may contain other components. For example, it may contain a (meth) acrylamide compound (D). The (meth)acrylamide compound (D) is not particularly limited as long as it has a (meth)acrylamide skeleton, and examples thereof include 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-(2-hydroxyethyl) (meth)acrylamide, N,N-bis(2-hydroxyethyl) (meth)acrylamide, N-acryloylmorpholine, N,N-dimethylaminoethyl (meth)acrylamide, N,N-dimethylaminoethyl (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-(2-hydroxyethyl) (meth)acrylamide, N-bis- ...bis-(2- The present invention also provides monofunctional (meth)acrylamide compounds such as N,N-diethylaminoethyl (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)acrylamide, N,N-dipropylaminobutyl (meth)acrylamide, and N,N-dibutylaminobutyl (meth)acrylamide. These compounds may be used alone or in combination of two or more. As a preferred embodiment (X-8), for example, the photomolding resin composition in any of the above embodiments (X-1) to (X-7) that does not contain the (meth)acrylamide compound (D) can be mentioned. The photomolding resin composition of the present invention can be produced by a known method.

[0091] In the light shaping resin composition of the present invention, within the scope of not damaging the main idea of ​​the present invention, for the purpose of improving photocurability, a polymerization accelerator may be included. As a polymerization accelerator, for example, 4-(N,N-dimethylamino) ethyl benzoate, 4-(N,N-dimethylamino) methyl benzoate, 4-(N,N-dimethylamino) benzoic acid n-butoxyethyl ester, 4-(N,N-dimethylamino) benzoic acid 2-(methacryloyloxy) ethyl ester, 4-(N,N-dimethylamino) benzophenone, 4-(N,N-dimethylamino) butyl benzoate, etc. can be cited. They can be used alone or in combination of two or more. Among these, from the viewpoint of giving excellent curability to the light shaping resin composition, it is preferred to use at least one selected from 4-(N,N-dimethylamino) ethyl benzoate, 4-(N,N-dimethylamino) benzoic acid n-butoxyethyl ester and 4-(N,N-dimethylamino) benzophenone.

[0092] In order to adjust the paste properties or to improve the mechanical strength of the object formed by the light-forming resin composition, a filler may be further blended into the light-forming resin composition of the present invention. Examples of fillers include organic fillers, inorganic fillers, and organic-inorganic composite fillers. One filler may be used alone, or two or more fillers may be used in combination.

[0093] As the material of organic filler, for example, polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, cross-linked polymethyl methacrylate, cross-linked polyethyl methacrylate, polyester, polyamide, polycarbonate, polyphenylene oxide, polyoxymethylene, polyvinyl chloride, polystyrene, polyethylene, polypropylene, chloroprene rubber, nitrile rubber, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene copolymer can be cited. They can 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 for use.

[0094] As the material of inorganic filler, for example quartz, silica, aluminum oxide, silica-titania, silica-titania-barium oxide, silica-zirconium oxide, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, glass ceramics, aluminosilicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, strontium calcium fluoroaluminosilicate glass can be enumerated. In addition, they can be used alone or in combination of two or more. The shape of the inorganic filler is not particularly limited, and irregular shape fillers or spherical fillers can be appropriately selected to use.

[0095] In the light shaping resin composition of the present invention, a polymer may be added for the purpose of modifying flexibility, fluidity, etc., without damaging the main purpose of the present invention. For example, natural rubber, synthetic polyisoprene rubber, liquid polyisoprene rubber and its hydride, polybutadiene rubber, liquid polybutadiene rubber and its hydride, styrene-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, acrylic rubber, isoprene-isobutylene rubber, acrylonitrile-butadiene rubber or styrene elastomer may be added. As specific examples of other polymers that may be added, polystyrene-polyisoprene-polystyrene block copolymers, polystyrene-polybutadiene-polystyrene block copolymers, poly(α-methylstyrene)-polybutadiene-poly(α-methylstyrene) block copolymers, poly(p-methylstyrene)-polybutadiene-poly(p-methylstyrene) block copolymers or their hydrides, etc. may be cited.

[0096] The resin composition for light shaping of the present invention may contain a softener as needed. Examples of the softener include petroleum-based softeners such as paraffin-based, cycloalkane-based, and aromatic-based process oils; and plant oil-based 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 softener is not particularly limited as long as it does not impair the purpose of the present invention. Generally, the total amount of urethane-containing (meth) acrylic compounds (A) and (meth) acrylic ester compounds (B) not containing urethane bonds is 100 parts by mass or less, preferably 100 parts by mass or less.

[0097] In addition, the resin composition for photomolding of the present invention may be blended with a known stabilizer for the purpose of suppressing the degradation of physical properties or adjusting the photocurability, thereby improving the strength and elastic modulus. Examples of the stabilizer include polymerization inhibitors (D), ultraviolet absorbers, and antioxidants. The stabilizer may be used alone or in combination of two or more.

[0098] Examples of the polymerization inhibitor (D) include hydroquinone, hydroquinone monomethyl ether, dibutyl hydroquinone, dibutyl hydroquinone monomethyl ether, 4-tert-butylcatechol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butylphenol, and 3,5-di-tert-butyl-4-hydroxytoluene. From the viewpoint of the effect of suppressing the deterioration of physical properties and the curability, the content of the polymerization inhibitor (D) is preferably 0.001 to 5.0 parts by mass, more preferably 0.05 to 2.5 parts by mass, and even more preferably 0.1 to 1.0 parts by mass relative to 100 parts by mass of the total amount of the urethanized (meth)acrylic compound (A) and the (meth)acrylate compound (B) not containing a urethane bond. Furthermore, from the viewpoint of the effect of improving strength and elastic modulus, the content of the polymerization inhibitor (D) is preferably 0.1 to 100 parts by mass, more preferably 1.0 to 60 parts by mass, and even more preferably 10 to 40 parts by mass based on 100 parts by mass of the photopolymerization initiator (C).

[0099] In addition, the resin composition for photoforming of the present invention may be mixed with known additives in order to adjust the color tone or adjust the paste properties. Examples of the aforementioned additives include solvents such as pigments, dyes, organic solvents, and thickeners. The additives may be used alone or in combination of two or more.

[0100] The light shaping resin composition of the present invention has excellent shapeability and excellent strength, toughness and water resistance of the shaped object. Therefore, the light shaping resin composition of the present invention can be applied to applications that can exert such advantages, and in particular, is most suitable for denture base materials, occlusal plates and therapeutic tools for sleep apnea syndrome. The shape of the shaped object using the light shaping resin composition of the present invention can be changed according to each application. In addition, the light shaping resin composition of the present invention can adjust the type and content of each component (urethanized (meth) acrylic compound (A), (meth) acrylate compound (B) not containing urethanate bond, polymerization initiator (C) and various arbitrary components ((meth) acrylamide compound (D), polymerization accelerator, filler, polymer, softener, stabilizer, additive, etc.)) as needed for each application of denture base materials, occlusal plates and therapeutic tools for sleep apnea syndrome.

[0101] The bending modulus of the cured product of the light shaping resin composition of the present invention is preferably in the range of 2.1 to 4.0 GPa, more preferably in the range of 2.5 to 3.5 GPa, and further preferably in the range of 2.75 to 3.25 GPa. In addition, the bending strength (3-point bending strength) of the cured product of the light shaping resin composition of the present invention is preferably 80 MPa or more, more preferably 90 MPa or more, further preferably 100 MPa or more, and particularly preferably 120 MPa or more. The determination methods of the bending modulus and the bending strength are described in the examples described below. In the case of the cured product of the resin composition for photomolding of the present invention, from the viewpoint of strength and toughness, when the hardness of the cured product at 23° C. (A hardness, A type durometer hardness) is measured using a test piece (molded product) of a sheet having a thickness of 2 mm×a length of 11 cm×a width of 5 cm with a type A durometer (Askagomu durometer type A manufactured by Kobunsu Keiki Co., Ltd.) in accordance with JIS K 7215:1986, the A hardness at 23° C. is preferably 86 or more, more preferably 90 or more, and even more preferably 95 or more. When the hardness of the cured product at 23° C. (D hardness) is measured using the test piece with a type D durometer (Askagomu durometer type D manufactured by Kobunsu Keiki Co., Ltd.) in accordance with JIS K 7215:1986, the D hardness at 23° C. is more preferably 40 to 95, and even more preferably 50 to 90.

[0102] The resin composition for photoforming of the present invention can fully utilize its characteristics, especially when cured by light, it can obtain a molded product or three-dimensional shape with a small volume shrinkage and excellent shaping accuracy, and the shape has excellent flexibility and mechanical properties, and further the characteristics of other cured products, and can be used for various purposes. For example, it can be used for the production of three-dimensional shapes using optical three-dimensional molding methods, the production of various molded products such as film-like objects or model objects using cast molding or casting, covering purposes, vacuum molding molds, etc.

[0103] Among them, the resin composition for photoforming of the present invention is suitable for use in the above-mentioned optical three-dimensional forming method. In this case, it is possible to smoothly produce a three-dimensional object that maintains a small volume shrinkage during photocuring and has excellent forming accuracy and excellent toughness and mechanical properties.

[0104] As another embodiment of the present invention, there is mentioned a method of producing a three-dimensional object by using any of the above-mentioned resin compositions for optical shaping by a conventionally known optical three-dimensional shaping method (for example, a hanging liquid tank optical shaping method).

[0105] When the optical stereoscopic forming resin composition of the present invention is used for optical stereoscopic forming, the previously known optical stereoscopic forming method (such as the hanging liquid tank optical forming method) and the device (such as the optical forming machine such as DIGITALWAX (registered trademark) 028J-Plus manufactured by DWS) can be used. Among them, in the present invention, as the light energy for curing the resin, it is preferred to use active energy light. "Active energy light" refers to energy rays such as ultraviolet rays, electron rays, X-rays, radiation, high frequency, etc. that can cure the optical stereoscopic forming resin composition. For example, the active energy light can be ultraviolet rays with a wavelength of 300 to 400 nm. As the light source of the active energy light, lasers such as Ar lasers and He-Cd lasers can be cited; halogen lamps, xenon lamps, metal halide lamps, LEDs, mercury lamps, fluorescent lamps, etc. are particularly preferably lasers. When a laser is used as a light source, the energy level can be increased and the forming time can be shortened, and the good focusing property of the laser light can be used to obtain a three-dimensional object with high forming accuracy.

[0106] As described above, when the optical stereoscopic formation is performed using the optical stereoscopic formation resin composition of the present invention, the conventionally known methods (e.g., hanging liquid tank optical formation method) and the conventionally known optical formation system devices can be used without special limitation. As a representative example of the optical stereoscopic formation method preferably used in the present invention, a method of finally obtaining the target stereoscopic formation object by repeatedly performing the following steps can be cited, wherein the steps are: selectively irradiating the optical stereoscopic formation resin composition with active energy light in a manner that can obtain a solidified layer having a desired pattern to form a solidified layer; and then further supplying the uncured liquid optical stereoscopic formation resin composition to the solidified layer, irradiating the active energy light in the same manner, forming a new solidified layer continuous with the aforementioned solidified layer and laminating the layer. In addition, the thus obtained stereoscopic formation object can be used directly, or, depending on the situation, can be further post-cured by light irradiation or post-cured by heat, etc., to make a product with higher mechanical properties or shape stability before use.

[0107] The structure, shape, size, etc. of the three-dimensional object obtained by the optical three-dimensional molding method are not particularly limited and can be determined according to various uses. As representative application fields of the optical three-dimensional molding method of the present invention, there can be cited models for verifying the appearance design during the design process; models for checking the functionality of parts; resin models for making castings; basic models for making molds; direct models for trial molds, etc. More specifically, there can be cited the production of models or processing models for precision parts, electrical / electronic parts, furniture, building structures, automotive parts, various containers, castings, molds, master molds, etc. In particular, the strength and excellent toughness of the objects of the optical molding resin composition are fully utilized, and it can be extremely effectively used for the formation of complex-shaped cushioning materials in structures (such as building structures), vacuum forming molds, etc. Example

[0108] Next, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples at all, and a person having ordinary knowledge in the art can make various modifications within the scope of the technical idea of ​​the present invention.

[0109] Hereinafter, each component used in the resin composition for photoforming according to the examples or comparative examples will be described together with the abbreviated symbols.

[0110] [Urethaned (meth)acrylic acid compound (A)]

[0111] UDMA: 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl) dimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., molecular weight: 471)

[0112] U4TH: N,N'-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., molecular weight: 673).

[0113] [(Meth)acrylate compound (B) not containing a urethane bond]

[0114] POBA: m-Phenoxybenzyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd.)

[0115] EPPA: Ethoxylated o-phenylphenol acrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).

[0116] [Photopolymerization initiator (C)]

[0117] TPO: 2,4,6-Trimethylbenzoyldiphenylphosphine oxide

[0118] BAPO: bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

[0119] [Polymerization inhibitor (D)]

[0120] BHT: 3,5-di-tert-butyl-4-hydroxytoluene.

[0121] <Synthesis Example 1> [Production of urethanized (meth)acrylic acid compound (A-1)-a having a polymer structure]

[0122] (1) In a 5 L four-necked flask equipped with a stirrer, a temperature regulator, a thermometer, and a condenser, 500 g of 2,4-toluene diisocyanate and 0.2 g of di-n-butyltin dilaurate were added, and the mixture was heated to 70° C. with stirring.

[0123] (2) On the other hand, 600 g of polyethylene glycol ("PEG#200 (registered trademark) manufactured by NOF Corporation, weight average molecular weight Mw: 200) was added to a dropping funnel with a side tube, and the liquid in the dropping funnel was dropped into the flask in (1) above. The solution in the flask in (1) above was stirred and the internal temperature of the flask was maintained at 65 to 75° C. while dropping at a constant rate over 4 hours. After the dropwise addition was completed, the mixture was stirred at the same temperature for 2 hours to allow the mixture to react.

[0124] (3) Next, while the temperature inside the flask was maintained at 55 to 65° C., a liquid prepared by uniformly dissolving 400 g of 2-hydroxyethyl acrylate and 0.4 g of hydroquinone monomethyl ether added to another dropping funnel was added dropwise at a constant rate over 2 hours, and then the solution in the flask was reacted for 4 hours while the temperature was maintained at 70 to 80° C., thereby obtaining a urethanized (meth)acrylic compound (A-1)-a having a polymer structure (weight average molecular weight: 800, number of urethanic acid bonds per molecule: 4). The weight average molecular weight is a weight average molecular weight measured by GPC and converted to polystyrene.

[0125] <Reference Example 1> [Production of urethanized (meth)acrylic acid compound 1]

[0126] (1) In a 5 L four-necked flask equipped with a stirrer, a temperature regulator, a thermometer, and a condenser, 250 g of isophorone diisocyanate and 0.15 g of di-n-butyltin dilaurate were added, and the mixture was heated to 70° C. with stirring.

[0127] (2) On the other hand, 500 g of a polycarbonate polyol ("Kuraray Polyol (registered trademark) C-1090" manufactured by Kuraray Co., Ltd.; a polymer formed from 1,6-hexanediol / 3-methyl-1,5-pentanediol = 9 / 1 (mass ratio), weight average molecular weight: 1000) was added to a dropping funnel with a side tube, and the liquid in the dropping funnel was dropped into the flask in the above (1). It should be noted that the solution in the flask in the above (1) was stirred and dropped at a constant rate for 4 hours while maintaining the internal temperature of the flask at 65 to 75°C. Furthermore, after the dropwise addition was completed, the mixture was stirred at the same temperature for 2 hours to allow the mixture to react.

[0128] (3) Next, while the internal temperature of the flask was maintained at 55 to 65° C., a liquid prepared by uniformly dissolving 150 g of 2-hydroxyethyl acrylate and 0.4 g of hydroquinone monomethyl ether added to another dropping funnel was added dropwise at a constant rate over 2 hours, and then the solution in the flask was reacted for 4 hours while the temperature was maintained at 70 to 80° C., thereby obtaining a urethanized (meth)acrylic compound 1 (weight average molecular weight: 1500, number of urethanate bonds per molecule: 4). The weight average molecular weight is a weight average molecular weight measured by GPC and converted to polystyrene.

[0129] [Determination of weight average molecular weight]

[0130] The weight average molecular weight of the urethanized (meth) acrylic acid compound (A-1)-a and the urethanized (meth) acrylic acid compound 1 was determined by GPC measurement. Tetrahydrofuran was used as the eluent, and two columns of "TSK-gel SuperMultipore HZM-M" manufactured by Tosoh Corporation and "TSKgel SuperHZ4000" connected in series were used as the chromatographic column. In addition, as the GPC apparatus, "HLC-8320GPC" manufactured by Tosoh Corporation equipped with a differential refractive index detector (RI detector) was used. In the measurement, 4 mg of the sample was first dissolved in 5 mL of tetrahydrofuran to prepare a sample solution. Then, the temperature of the column oven was set to 40°C, 20 μL of the sample solution was injected at an eluent flow rate of 0.35 mL / min, and the chromatogram of the sample was measured. On the other hand, GPC measurement was performed on 10 points of standard polystyrene with a molecular weight in the range of 400 to 5,000,000, and a standard curve showing the relationship between retention time and molecular weight was prepared. Based on this calibration curve, the weight average molecular weight (n=1) is determined from the chromatogram of the sample measured as described above.

[0131] [Examples 1 to 9 and Comparative Examples 1 to 2]

[0132] The components were mixed in the amounts shown in Tables 1 and 2 at room temperature (20°C ± 15°C, JIS (Japanese Industrial Standards) Z8703: 1983) to prepare pastes in the form of photomolding resin compositions according to Examples 1 to 9 and Comparative Examples 1 to 2.

[0133] The obtained photomolding resin composition was molded into a test piece (length 64.0 mm, width 10.0 mm, thickness 3.3 mm) having the dimensions described in JIS T 6501:2012 (acrylic resin for denture base) using a photomolding machine (DIGITALWAX (registered trademark) 020D manufactured by DWS).

[0134] <Strength (flexural modulus, flexural strength), toughness (flexural fracture point displacement)>

[0135] For the cured product of the light shaping resin composition involved in each embodiment and each comparative example, after the above-mentioned test piece is kept in the air for 1 day, the test piece is used to perform a 3-point bending test and evaluate, which is used as the initial value. That is, using a universal testing machine (manufactured by Shimadzu Corporation, Autograph AG-I 100kN), under the conditions of a fulcrum distance of 50mm and a crosshead speed of 5mm / min, the test piece is used to implement a 3-point bending test (n=5). The average value of the measured values ​​is shown in Table 1 and Table 2. As the bending modulus of the test piece, it is preferably in the range of 2.1 to 4.0GPa, more preferably in the range of 2.5 to 3.5GPa, and further preferably in the range of 2.75 to 3.25GPa. As a bending strength, it is preferably more than 80MPa, more preferably more than 90MPa, more preferably more than 100MPa, and particularly preferably more than 120MPa. As a breaking point displacement, it is preferred that no fracture occurs. Regarding the displacement of the breaking point, the case where the fracture occurred when the displacement was more than 10 mm was recorded as good toughness "○", the case where the fracture occurred when the displacement exceeded 5 mm and was less than 10 mm was recorded as medium toughness "△", the case where the fracture occurred when the displacement was less than 5 mm was recorded as poor toughness "×", and above △ was recorded as qualified.

[0136] <Water resistance>

[0137] For the cured products of the light shaping resin compositions involved in each embodiment and each comparative example, which were prepared in the same manner as the cured products prepared in the toughness measurement, the bending strength was measured in the same manner as the above bending strength test after being immersed in water at 37°C for 168 hours (n=5). The average values ​​of the measured values ​​are shown in Tables 1 and 2. The measurement results of the bending strength in the toughness are taken as the initial bending strength. If the change rate (reduction rate) of the bending strength after immersion in water at 37°C for 168 hours relative to the initial bending strength is 5% or less, the water resistance is excellent, and if it is 2% or less, the water resistance is even better.

[0138] The change rate (reduction rate) of the flexural strength (%) = [{initial flexural strength (MPa) - flexural strength after immersion in water at 37°C for 168 hours (MPa)} / initial flexural strength (MPa)] × 100.

[0139] <Hardness>

[0140] For the cured product of the photomolding resin composition involved in each example and each comparative example, the hardness of the cured product at 23°C was measured using the above-mentioned bending test piece based on JIS K7215:1986 using an A-type durometer (Ascagem durometer A-type manufactured by Kobunsu Keiki Co., Ltd., manufacturing number 32330) and a D-type durometer (Ascagem durometer D-type manufactured by Kobunsu Keiki Co., Ltd., manufacturing number 35318) as an index of hardness. The results are shown in Tables 1 and 2, respectively. In this measurement, when the A hardness at 23°C is 86 or more or the D hardness is 40 to 95, the cured product has a hardness suitable for occlusion, and therefore it can be said that it is suitable as a denture base material, a dental bite plate, and a treatment tool for sleep apnea syndrome.

[0141]

Table 1

[0142] .

[0143]

Table 2

[0144]

[0145] TEGDMA: triethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0146] As shown in Tables 1 and 2, the shapes of the resin compositions for light shaping in Examples 1 to 9 are excellent in strength, toughness, and water resistance. In particular, the strength of the shapes of the resin compositions for light shaping according to Examples 1 to 9 is superior to the strength of the shapes of the resin composition of Comparative Example 1. In addition, the toughness of the shapes of the resin compositions for light shaping according to Examples 1 to 9 is superior to the toughness of the shapes of the resin composition of Comparative Example 2. The water resistance of the shapes of the resin compositions for light shaping according to Examples 1 to 9 is superior to the water resistance of Comparative Example 2.

[0147] Industrial Applicability

[0148] The photomolding resin composition of the present invention is suitable for oral applications such as various dental materials (particularly denture base materials, dental bite plates) or various sleep disorder treatment materials (particularly treatment tools for sleep apnea syndrome) because the molded product has excellent strength, toughness and water resistance.

Claims

1. A resin composition for photomolding, comprising a urethanized (meth)acrylic compound (A), a (meth)acrylate compound not containing a urethane bond (B), a photopolymerization initiator (C) and a polymerization inhibitor (D), The urethanized (meth)acrylic compound (A) contains a urethanized (meth)acrylic compound (A-2) having no polymer structure and, if necessary, a urethanized (meth)acrylic compound (A-1) having a polymer structure. The content of the compound (A-2) having no polymer structure is 10 to 99 parts by mass in 100 parts by mass of the total amount of the urethanized (meth)acrylic compound (A) and the (meth)acrylate compound (B) having no urethane bond, The content of other polymerizable compounds other than the urethanized (meth)acrylic compound (A) and the (meth)acrylate compound (B) not containing a urethane bond is less than 10.0 parts by mass in 100 parts by mass of the total amount of the polymerizable compounds contained in the resin composition for photoforming, The content of the polymerization inhibitor (D) is 0.1 to 100 parts by mass based on 100 parts by mass of the photopolymerization initiator (C). The weight average molecular weight of the urethanized (meth)acrylic compound (A-1) having a polymer structure is less than 1000, The molecular weight of the urethanized (meth)acrylic compound (A-2) having no polymer structure is less than 1000, The urethanized (meth)acrylic compound (A-2) having no polymer structure includes a polyfunctional (meth)acrylate compound. The (meth)acrylate compound (B) not containing a urethane bond comprises at least one selected from a (meth)acrylate compound (bI) represented by the following general formula (I) and a (meth)acrylate compound (b-II) represented by the following general formula (II). [Chemical formula 1] [Chemical formula 2] In the formula, R 1 and R 2 Each independently represents a group represented by the following general formula (i) or a group represented by the following general formula (ii), and X represents a divalent hydrocarbon group having 1 to 6 carbon atoms or an oxygen atom; [Chemical formula 3] [Chemical formula 4] In the formula, R 3 and R 5 are each independently a divalent hydrocarbon group having 1 to 10 carbon atoms, R 4 and R 6 Each of them is independently a hydrogen atom or a methyl group, and k and l are each independently an integer of 0-6.

2. The resin composition for light shaping according to claim 1, wherein The number of urethane bonds contained in the urethanized (meth)acrylic compound (A-1) having a polymer structure and the urethanized (meth)acrylic compound (A-2) not having a polymer structure is 3 or less per molecule.

3. The resin composition for light shaping according to claim 1 or 2, wherein: The urethanized (meth)acrylic compound (A) is substantially composed of only the compound (A-2) having no polymer structure.

4. The resin composition for light shaping according to claim 1 or 2, wherein The urethanized (meth)acrylic compound (A-2) having no polymer structure includes 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate and / or N,N′-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate.

5. The resin composition for light shaping according to claim 1 or 2, wherein: The urethanized (meth)acrylic compound (A) contains a urethanized (meth)acrylic compound (A-1) having a polymer structure.

6. The resin composition for photoforming according to claim 5, wherein The urethanized (meth)acrylic compound (A-1) having a polymer structure is a (meth)acrylate compound.

7. The resin composition for photoforming according to claim 5, wherein The content of the urethanized (meth)acrylic compound (A-1) having a polymer structure is 51 to 95% by mass in 100% by mass of the polymerizable compound.

8. The resin composition for light shaping according to claim 1 or 2, wherein: The aforementioned polymer structure is a structure selected from polyester, polycarbonate, polyurethane, polyether, polyconjugated diene, and hydrogenated polyconjugated diene.

9. The resin composition for light shaping according to claim 1 or 2, wherein: k and l are each independently an integer of 1-4.

10. The resin composition for photoforming according to claim 1 or 2, wherein: The (meth)acrylate compound (B) not containing a urethane bond contains the (meth)acrylate compound (b-II), and X is an oxygen atom.

11. The resin composition for photoforming according to claim 10, wherein R 2 It is a group represented by the aforementioned general formula (ii).

12. The resin composition for light shaping according to claim 1 or 2, wherein: The aforementioned (meth)acrylate compound (B) not containing a urethane bond comprises the aforementioned (meth)acrylate compound (bI), R 1 It is a group represented by the aforementioned general formula (i).

13. The resin composition for light shaping according to claim 1 or 2, wherein: The content of the photopolymerization initiator (C) is 0.01 to 20 parts by mass based on 100 parts by mass of the total amount of the urethanized (meth)acrylic compound (A) and the (meth)acrylate compound (B) not containing a urethane bond.

14. The resin composition for photoforming according to claim 1 or 2, wherein: The content of the polymerization inhibitor (D) is 1.0 to 60 parts by mass based on 100 parts by mass of the photopolymerization initiator (C).

15. The resin composition for photoforming according to claim 1 or 2, wherein: The cured product of the photoforming resin composition has a flexural strength of 100 MPa or more and a flexural modulus of 2.1 GPa or more. 16 . A dental material comprising a shaped article of the photomolding resin composition according to claim 1 .

17. A denture base material comprising a shaped article of the photomolding resin composition according to any one of claims 1 to 15.

18. A dental bite plate comprising a shaped article of the photomolding resin composition according to any one of claims 1 to 15.

19. A material for treating sleep disorders, comprising a shaped article of the photoforming resin composition according to any one of claims 1 to 15.

20. A method for manufacturing a three-dimensional object, wherein: A three-dimensional object is produced by an optical three-dimensional forming method using the resin composition for optical forming according to any one of claims 1 to 15.

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