JP2002060435A - Photocurable resin composition - Google Patents

Abstract

(57) [Problem] A photocurable resin composition capable of producing a three-dimensional molded article having a small volume shrinkage ratio, excellent dimensional accuracy, high heat deformation temperature, excellent heat resistance, and excellent transparency and mechanical properties. Offer. (I) The following general formula (I): (Wherein, R ¹ is an optionally substituted alicyclic group, aromatic group or aliphatic group, R ¹ may have an etheric oxygen atom, and R ² is a divalent diamine residue. R ³ is a divalent amino alcohol residue, R ⁴ is a hydrogen atom or a methyl group, m
Represents an integer of 1 to 6, and n represents an integer of 1 to 5. And (ii) a radically polymerizable compound and / or a cationically polymerizable compound other than the imidized acrylic compound; and (iii) a photocurable composition containing a photopolymerization initiator. Resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocurable resin composition, a method for producing a three-dimensional object using the photocurable resin composition, an imidized acrylic compound used for the photocurable resin composition, and a method for producing the same. It relates to a manufacturing method. More specifically, the present invention has a small volume shrinkage at the time of photocuring, excellent dimensional accuracy, high heat deformation temperature, excellent heat resistance, and excellent transparency, furthermore, tensile strength, tensile elongation, and tensile strength. A photocurable resin composition capable of obtaining a molded article or a three-dimensional molded article having excellent mechanical properties such as elastic modulus, and a method for producing a molded article by optical three-dimensional molding using the photocurable resin composition And an imidized acrylic compound used in the photocurable resin composition and a method for producing the same.

[0002]

2. Description of the Related Art In general, liquid photocurable resin compositions are widely used as coating materials (particularly hard coating agents), photoresists, dental materials, and the like.
A method of three-dimensionally optically molding the photocurable resin composition based on the data input to D has attracted particular attention. Regarding the optical three-dimensional molding technology, a required amount of controlled light energy is supplied to a liquid photo-curable resin to cure it in a thin layer, and then a liquid photo-curable resin is further supplied thereon, and then the light is controlled under control. Japanese Patent Application Laid-Open No. 56-144478 discloses an optical three-dimensional molding method for producing a three-dimensional molded product by repeating a process of irradiating and laminating and hardening into a thin layer, and further discloses a basic practical method. Showa 60-
247515. After that, a number of proposals regarding optical three-dimensional modeling technology have been made, for example, JP-A-62-35966, JP-A-1-204915, JP-A-2-113925, and JP-A-2-145616. Gazette, JP-A-2-153
722, JP-A-3-15520, JP-A-3-15520
Japanese Patent Application Laid-Open No. 21432 and Japanese Patent Application Laid-Open No. 3-41126 disclose techniques relating to an optical three-dimensional printing method.

[0003] A typical method for optically producing a three-dimensional object is a computer-controlled method for obtaining a desired pattern on the liquid surface of a liquid photocurable resin composition in a molding bath. The irradiated ultraviolet laser is selectively irradiated to cure to a predetermined thickness, and then one layer of the liquid resin composition is supplied on the cured layer and irradiated with the ultraviolet laser in the same manner as described above. There is a method of producing a three-dimensional structure having a final shape by repeating a lamination operation of curing to form a continuous cured layer. In the case of this method, even if the shape of the modeled object is considerably complicated, the target three-dimensional modeled object can be easily manufactured in a relatively short time, so that it has been receiving particular attention in recent years.

Photocurable resin compositions used for coatings, photoresists, dental materials and the like include unsaturated polyesters, epoxy (meth) acrylates, urethane (meth) acrylates, (meth) acrylate monomers and the like. The addition of a photopolymerization initiator to a hydrophilic resin is widely used. The photocurable resin composition used in the optical three-dimensional molding method includes a photopolymerizable modified (poly) urethane (meth) acrylate compound, an oligoester acrylate compound, an epoxy acrylate compound, an epoxy compound, and a polyimide. Compounds, one or more of photopolymerizable compounds such as aminoalkyd compounds, vinyl ether compounds, etc. as a main component, and a photopolymerization initiator added thereto, and recently,
JP-A-1-204915, JP-A-1-21330
4, JP-A-2-28261, JP-A-2-7
Various improved techniques are disclosed in JP-A-5617, JP-A-2-145616, JP-A-3-104626, JP-A-3-114732, JP-A-3-1147324, and the like.

[0005] The photocurable resin composition used for optical three-dimensional molding is a low-viscosity liquid material, has a small volume shrinkage upon curing, and has a low light-emitting property, in view of handling properties, molding speed, and molding accuracy. It is required that the three-dimensional structure obtained by curing has good mechanical properties. recent years,
The demand and applications of optical three-dimensional objects are in the direction of expansion, and depending on the application, in addition to the above-mentioned properties, it has a high heat deformation temperature, excellent heat resistance, and excellent transparency. Three-dimensional objects have been required. For example, optical three-dimensional objects used to design complex heat medium circuits and optical three-dimensional objects used to analyze the heat medium behavior of complex structures have small volume shrinkage during photo-curing, Those having high transparency and excellent transparency are regarded as important.

Conventionally, for the purpose of obtaining an optical three-dimensional structure having improved heat resistance, a method of introducing a benzene ring into the molecule of a photocurable resin and a method of increasing the crosslink density in a photocurable product have been proposed. Has been considered. However, even in this case, the heat deformation temperature under a high load is at most 70 to 80 ° C.
And its heat resistance is not sufficient. In addition, when trying to improve the heat resistance of the photocured product, on the other hand, the volume shrinkage during curing is increased, and the dimensional accuracy is reduced.

In general, an increase in the crosslink density of the photocurable resin composition can be expected to improve heat resistance, but at the same time, an increase in the crosslink density tends to increase the volume shrinkage during curing. The improvement in heat resistance and the reduction in volume shrinkage during curing are in a trade-off relationship. As one method for overcoming this trade-off, the present inventors have previously developed and proposed a photocurable resin composition in which a filler is mixed with a specific photocurable resin (Japanese Patent Laid-Open No. 5-1966).
No. 91, Japanese Unexamined Patent Publication No. Hei 5-196692). When using the photocurable resin composition of the present inventors,
It has an excellent effect of overcoming the trade-off relationship described above and obtaining a molded article having excellent heat resistance and a small volume shrinkage. The present inventors have further studied based on the above-mentioned invention, and found that the photocurable resin composition has a high viscosity due to the inclusion of a filler, and has a high flow viscosity. It was found that there was room for improvement in the handleability during molding from the fact that it exhibited thixotropic properties.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a low-viscosity liquid, which is excellent in handleability, can be cured in a short photo-curing time, has a small volume shrinkage when cured by light, and has high dimensional accuracy. Obtain molded products, three-dimensional molded products, and other cured products that are excellent, have high heat distortion temperature, have excellent heat resistance, and also have excellent mechanical properties such as transparency, tensile strength, tensile elongation, tensile elasticity, etc. A photocurable resin composition that can be used and a method for producing a three-dimensional molded article by performing optical three-dimensional modeling using the same, and a non-conventional photocurable compound that can be effectively used for the photocurable resin composition. To provide.

[0009]

Means for Solving the Problems The present inventors have repeatedly studied to achieve the above object. As a result, the imidized acrylic compound having a specific chemical structure newly synthesized by the present inventors is extremely effective in achieving the above object,
When another radical polymerizable compound and / or cationic polymerizable compound and a photopolymerization initiator are added to the imidized acrylic compound, a liquid photocurable resin composition having low viscosity and excellent handleability is obtained, and The photocurable resin composition can be cured in a short time by irradiating it with light, and the volumetric shrinkage during curing is small, and three-dimensional molded articles and other molded articles having desired shapes and dimensions are manufactured with high dimensional accuracy. The present invention was found to be possible, and that the molded product and the three-dimensional molded product obtained by photocuring have a high heat deformation temperature and excellent heat resistance, and furthermore have excellent transparency and mechanical properties. completed.

That is, the present invention provides (1) (i) the following general formula (I):

[0011]

Embedded image (Wherein, R ¹ is an optionally substituted alicyclic group, an optionally substituted aromatic group or an optionally substituted aliphatic group, and R ¹ is an etheric oxygen atom. R ² is a divalent diamine residue, R ³ is a divalent amino alcohol residue, R ⁴ is a hydrogen atom or a methyl group, m is an integer of 1 to 6, n is 1 to At least one kind of an imidized acrylic compound represented by the formula:
(Ii) A photocurable resin composition comprising: a radically polymerizable compound and / or a cationically polymerizable compound other than the imidized acrylic compound; and (iii) a photopolymerization initiator.

In the present invention, the content ratio of (2) [the imidized acrylic compound]: [the radically polymerizable compound and / or the cation polymerizable compound] is 8
0:20 to 10:90 (mass ratio): the photocurable resin composition of the above (1); (3) based on the total mass of the imidized acrylic compound and the radically polymerizable compound and / or the cationically polymerizable compound. (1) or (2), wherein the content of the photopolymerization initiator is 0.1 to 10% by mass.
And (4) the photocurable resin composition according to any one of (1) to (3) above, which is for optical three-dimensional modeling. Further, the present invention is (5) a method for producing a three-dimensional structure by optical three-dimensional molding using the photocurable resin composition of (4).

The present invention provides (6) the following general formula (I):

[0014]

Embedded image (Wherein, R ¹ , R ² , R ³ and R ⁴ represent the same groups as described above, and m and n represent the same numbers as described above).

Further, the present invention provides (7) the following general formula (II):

[0016]

Embedded image (Wherein R ¹ represents the same group as described above), and an acid anhydride (II) represented by the following general formula (III);

[0017]

Embedded image A diamine compound (III) represented by H ₂ N—R ² —NH ₂ (III) (wherein R ² represents the same group as described above) is reacted to obtain a compound represented by the following general formula (III): I
V);

[0018]

Embedded image (Wherein, R ¹ and R ² are the same groups as described above, and n represents the same number as described above.)
Then, the imidized acid anhydride (IV) is added to the following general formula (V):

[0019]

Embedded image An amino alcohol represented by H- (O—R ³ ) m-NH ₂ (V) wherein R ³ represents the same group as described above and m represents the same number as described above. V) to react with the following general formula (VI):

[0020]

Embedded image (Wherein, R ¹ , R ² and R ³ represent the same groups as described above;
And n are the same numbers as above. )) To produce an imidated alcohol compound (VI), wherein the imidized alcohol compound (VI) is (meth) acrylic acid or (meth)
By reacting acrylic acid halide, the above-mentioned general formula (I)
This is a method for producing an imidized acrylic compound represented by the formula: In addition, in this specification, acrylic acid or methacrylic acid is represented as (meth) acrylic acid, acrylate or methacrylate is represented as (meth) acrylate, and acrylamide or methacrylamide is represented as (meth) acrylamide.

[0021]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. First, the imidized acrylic compound represented by the above general formula (I) used in the photocurable resin composition of the present invention [hereinafter referred to as “imidized acrylic compound (I)”] will be described. In the imidized acrylic compound (I), R
¹ is a substituted tetravalent may alicyclic group, optionally substituted 4- to divalent aromatic group or an optionally substituted tetravalent aliphatic group, and R ¹ if May have an etheric oxygen atom in the group described above. R ¹
Examples of an alkyl group, a halogen atom, a residue derived from an alicyclic tetracarboxylic acid or an anhydride thereof substituted or unsubstituted with a substituent such as a nitro group, an alkyl group, a halogen atom, A residue derived from an aromatic tetracarboxylic acid or an anhydride thereof substituted or unsubstituted with a substituent such as a nitro group, substituted or substituted with a substituent such as a halogen atom, a nitro group or the like; And aliphatic tetracarboxylic acids (preferably saturated aliphatic tetracarboxylic acids) or residues derived from their anhydrides.

Preferred examples of R ¹ include substituted or unsubstituted cyclohexyltetracarboxylic acid (tetracarboxylcyclohexane), substituted or unsubstituted hydrogenated biphenyltetracarboxylic acid, and substituted or unsubstituted hydrogenated biphenylethertetracarboxylic acid. Examples thereof include a tetracarboxylic acid residue derived from an acid or an anhydride thereof, or a group represented by the following.

[0023]

Embedded image [Wherein, R ⁵ and R ⁶ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 9 carbon atoms, and X represents —O—, —SO ₂ —, —C (= O)-, -C
(CH _{3) 2} - or -C (CF _{3) 2} - shows a]

[0024]

Embedded image (In the formula, R ⁷ represents a hydrogen atom or a linear or branched alkyl group having 1 to 9 carbon atoms.)

[0025]

Embedded image (In the formula, R ⁸ and R ⁹ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 9 carbon atoms.)

[0026]

Embedded image

[0027]

Embedded image (In the formula, R ¹⁰ represents a hydrogen atom or a linear or branched alkyl group having 1 to 9 carbon atoms.)

[0028]

Embedded image

The imidized acrylic compound (I) has 2 to 6 groups R ¹ according to the number of repeating units n, and the plurality of groups R ¹ may be the same or different. If they are the same, the production of the imidized acrylic compound (I) is easy.

In the imidized acrylic compound (I),
R ² may be any diamine residue, that is, any divalent organic group derived from a diamine, such as an aliphatic diamine, an aromatic diamine, an alicyclic diamine, or a (poly) alkylene glycol diamine. Can be Specific examples of R ² include ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, hexamethylenediamine, diaminocyclohexane, isophoronediamine, triethyleneglycoldiamine, diethyleneglycol-bispropyl Diamine residues derived from diamines such as diamine can be mentioned. When two or more groups R ² are present in the imidated acrylic compound (I), they may be the same diamine residue or different diamine residues. The production of the fluorinated acrylic compound (I) is easy. Among them,
R ² is preferably a diamine residue derived from an aliphatic diamine or an alicyclic diamine, particularly a diamine residue derived from an aliphatic diamine, because of the ease of synthesis of the imidated acrylic compound (I), The photocurable product obtained from the photocurable resin composition containing (I) is preferable in terms of toughness, cost, and the like.

In the imidized acrylic compound (I),
R ³ is an amino alcohol residue, that is, a divalent organic group derived from amino alcohol. Among them, R
³ is a general formula: H- (OR ¹¹ ) m-NH ₂ (wherein R ¹¹ is a chain or branched alkylene group having 2 to 10 carbon atoms, and m is an integer of 1 to 6) ) Is a residue of an amino alcohol (that is, a chain or branched alkylene group having 2 to 10 carbon atoms), which makes it easier to synthesize the imidated acrylic compound (I), The photocured product obtained from the photocurable resin composition containing (I) is preferable in terms of toughness and cost, and has 2 carbon atoms.
To 4 alkylene groups (ethylene group, n-propylene group,
(Isopropylene group, n-butylene group).

In the imidized acrylic compound (I), R ⁴ is a hydrogen atom or a methyl group. further,
In the imidated acrylic compound (I), m is an integer of 1 to 6, and is preferably an integer of 1 to 3, which is excellent in compatibility with the component (ii) described below, It is preferable because the synthesis is easy. Further, n is an integer of 1 to 5, and an integer of 1 to 3 facilitates the synthesis of the imidized acrylic compound (I), and has excellent compatibility with the component (ii) described below; It is preferable because it is easy to handle.

The method for producing the imidized acrylic compound (I) used in the photocurable resin composition of the present invention is not particularly limited, but typical examples include the method described in (6) above. That is, (a) the above general formula (II)
An acid anhydride (II) represented by the following general formula (III)
Is reacted to produce an imidated acid anhydride (IV) represented by the above general formula (IV), and then (b) the imidized acid anhydride (IV) Is reacted with an amino alcohol (V) represented by the above general formula (V) to produce an imidated alcohol compound (VI) represented by the above general formula (VI). By reacting compound (VI) with (meth) acrylic acid or (meth) acrylic halide, imidized acrylic compound (I) can be produced smoothly.

Representative examples of the acid anhydride (II) used in the production of the imidized acrylic compound (I) include substituted or unsubstituted cyclohexyltetracarboxylic anhydride (tetracarboxylic cyclohexane acid anhydride), substituted or unsubstituted Substituted hydrogenated biphenyltetracarboxylic anhydride, substituted or unsubstituted hydrogenated biphenylethertetracarboxylic anhydride, tetra having any group R ¹ (tetracarboxylic acid residue) represented by the above formula or Carboxylic anhydrides and the like can be mentioned, and one or more of these can be used. When a tetracarboxylic anhydride having a group R ¹ represented by the above formula or is used as the acid anhydride (II), the imidized acrylic compound (I) which exhibits a liquid state and is excellent in handleability during stereolithography can be obtained. Obtainable.

Representative examples of the diamine compound (III) used for the production of the imidized acrylic compound (I) include:
Ethylenediamine, 1,2-diaminopropane, 1,3
-Diaminopropane, 1,4-diaminobutane, hexamethylenediamine, diaminocyclohexane, isophoronediamine, triethyleneglycoldiamine, diethyleneglycol-bispropyldiamine, and the like, and one or more of these may be used. it can. Among them, ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-
Diaminobutane and hexamethylenediamine are useful for the synthesis and economy of the imidized acrylic compound (I), the toughness of the photocured product obtained from the photocurable resin composition containing the imidated acrylic compound (I), and the like. Preferred from the point.

A typical example of the amino alcohol (V) used in the production of the imidized acrylic compound (I) is represented by the general formula: H- (OR ¹¹ ) m -NH ₂ (wherein R ¹¹ is a chain or branched Represents an alkylene group having 2 to 10 carbon atoms, and m represents an integer of 1 to 6). By using such an amino alcohol, an imidized acrylic compound ( I) can be synthesized easily and economically, and the photocured product obtained from the photocurable resin composition containing the imidized acrylic compound (I) is excellent in toughness and the like. In particular, as the amino alcohol (V), ethylamino alcohol, n-propylamino alcohol, isopropylamino alcohol, n-butylamino alcohol and the like are preferably used.

The (meth) acrylic acid or (meth) acrylic halide to be reacted with the imidated alcohol compound (VI) includes acrylic acid, methacrylic acid, acrylic chloride, methacrylic chloride, acrylic bromide, methacrylic bromide, and the like. And, among them, acrylic acid chloride and / or
Alternatively, methacrylic acid chloride is preferably used because it has good reactivity with the imidated alcohol compound (VI) and the intended imidized acrylic compound (I) can be obtained smoothly.

In the above-mentioned reaction step (a), the imidized acid anhydride (IV), and consequently the imidized acrylic compound (I) is adjusted by adjusting the use ratio of the acid anhydride (II) and the diamine compound (III). The number of repeating units n
Can be variously changed within the range of 1 to 5. For example,
Theoretically, acid anhydride (II) and diamine compound (III)
Is used in a molar ratio of 2: 1 to obtain an imidated acid anhydride (IV) in which n is 1 and, consequently, an imidized acrylic compound (I) in which n is 1; n is 2
And the imidized acrylic compound (I) in which n is 2 is obtained, and the imidated acid anhydride (IV) in which n is 3 is obtained when used in a molar ratio of 4: 3. Thus, an imidized acrylic compound (I) in which n is 3 is obtained, and when used in a molar ratio of 5: 4, an imidized acid anhydride (IV) in which n is 4 and, consequently, an imidized acrylic compound in which n is 4 Compound (I) is obtained. In addition, the above (a) to (c)
Are dissolved in a hydrocarbon solvent such as toluene or xylene, or an aprotic polar solvent such as dimethylformamide, dimethyl sulfoxide, or diethylene glycol dimethyl ether.
When the reaction is carried out at a temperature of about 0 ° C., the desired compounds can be produced smoothly.

In the photocurable resin composition of the present invention, only a single imidized acrylic compound (I) may be used as the imidized acrylic compound (I), or the degree of polymerization and / or
Alternatively, a mixture of two or more types of imidized acrylic compounds (I) in which the types of the above groups are different may be used. Also,
In the photocurable resin composition of the present invention, the use of the liquid imidized acrylic compound (I) improves the handleability of the photocurable resin composition. However, in some cases, a solid imidized acrylic compound (I) may be used.
When the solid imidized acrylic compound (I) is used, the photocurable resin of the present invention is produced in accordance with the same composition ratio as when the liquid imidized acrylic compound (I) is used. The effect can be fully exhibited.

The photocurable resin composition of the present invention comprises, together with the above-mentioned imidized acrylic compound (I), another radical polymerizable compound (hereinafter sometimes simply referred to as "radical polymerizable compound") and a cationic polymerizable compound. At least one of the following. As the radical polymerizable compound, the imidized acrylic compound (I) when irradiated with light is used.
And any radical polymerizable compound having a carbon-carbon unsaturated bond capable of reacting with each other to form a cured product by reacting with the radical polymerizable compounds. Acrylic compounds, allyl compounds and / or vinyl lactams are preferably used. The radical polymerizable compound may be either a monofunctional compound or a polyfunctional compound, or may be a combination of a monofunctional compound and a polyfunctional compound. Further, the radical polymerizable compound may be a low molecular weight monomer, an oligomer, or, in some cases, a compound having a relatively large molecular weight. The photocurable resin composition of the present invention may contain only one kind of radically polymerizable compound, or may contain two or more kinds of radically polymerizable compounds.

Although not limited, examples of the radical polymerizable compound that can be used in the photocurable resin composition of the present invention include isobornyl (meth) acrylate, bornyl (meth) methacrylate, and dicyclopentenyl (meth). A), acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (poly) propylene glycol mono (meth) acrylate, and t-butyl (meth) acrylate; ) (Meth) acrylamides such as acrylamide, monofunctional radically polymerizable compounds such as N-vinylcaprolactone and styrene; trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth)
Acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate,
Triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, diallyl phthalate, diallyl fumarate, ethylene oxide-modified bisphenol A
Examples thereof include polyfunctional radical polymerizable compounds such as di (meth) acrylate, and one or more of these compounds can be used. Further, in the above general formula (I), an imide acryl compound in which n is 0 can also be used.

In the photocurable resin composition of the present invention, in addition to the above-mentioned radically polymerizable compound, urethane (meth) acrylate, epoxy (meth) ) Acrylate compounds, other ester (meth) acrylates and the like can be used as radically polymerizable compounds.

In the photocurable resin composition of the present invention, morpholine (meth) acrylamide, dicyclopentenyl di (meth) acrylate, N-vinylcaprolactam, urethane (meth) can be used among the various radically polymerizable compounds described above. Acrylates are preferably used, and when using these radically polymerizable compounds, when cured with light,
Smaller volume shrinkage, better dimensional accuracy, higher heat distortion temperature, superior heat resistance, and transparency, tensile strength,
Molded articles, three-dimensional molded articles, and other photo-cured articles having excellent mechanical properties such as rigidity can be obtained.

The cationically polymerizable compounds that can be used in the photocurable resin composition of the present invention include epoxy compounds such as aliphatic diepoxy compounds, alicyclic diepoxy compounds and aromatic diepoxy compounds, and aliphatic divinyl ether compounds. And vinyl ether compounds such as alicyclic divinyl ether compounds and aromatic divinyl ether compounds, and one or more of these can be used. When a cationically polymerizable compound is used, the imidized acrylic compound (I), the radically polymerizable compound and the cationically polymerizable compound are used instead of only the imidized acrylic compound (I) and the cationically polymerizable compound. Is preferred in terms of photocuring properties, heat resistance, mechanical properties and the like.

In the photocurable resin composition of the present invention, the content ratio of [imidized acrylic compound (I)]: [radical polymerizable compound and / or cationic polymerizable compound] is 80: The ratio is preferably from 20 to 10:90, more preferably from 65:35 to 25:75, even more preferably from 60:40 to 35:65. In the photocurable resin composition, the proportion of the imidized acrylic compound (I) is less than 10% by mass based on the total mass of the imidized acrylic compound (I) and the radical polymerizable compound and / or the cationic polymerizable compound. If it is, when cured with light, it may not be possible to obtain a molded article or a three-dimensional molded article having high heat resistance, tensile strength, and rigidity based on an imide group, whereas if it exceeds 80% by mass, the photocurable resin composition If the viscosity of the object becomes too high, the handleability, moldability, and formability are reduced, and particularly when used in an optical three-dimensional molding method, the object and the three-dimensional object may not be produced smoothly.

The photocurable resin composition of the present invention may be used together with the above-mentioned imidized acrylic compound (I) and other radically polymerizable compounds and / or cationically polymerizable compounds.
Contains a photopolymerization initiator. As the photopolymerization initiator, any photoradical polymerization initiator and / or photocationic polymerization initiator conventionally used in photocurable resin compositions can be used and is not particularly limited. Although not limited, examples of the photopolymerization initiator (photoradical polymerization initiator) that can be used in the photocurable resin of the present invention include 2,2.
2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, diethoxyacetophenone, acetophenone, 3-methylacetophenone, 2-hydroxymethyl-1-phenylpropane-
1-one, 4'-isopropyl-2-hydroxy-2-
Propiophenone, 2-hydroxy-2-methyl-propiophenone, p-dimethylaminoacetophenone, p
-T-butyldichloroacetophenone, pt-butyltrichloroacetophenone, p-azidobenzalacetophenone, 1-hydroxycyclohexylphenyl ketone, benzophenone, methyl o-benzoylbenzoate,
Michler's ketone, 4,4'-bisdiethylaminobenzophenone, xanthone, fluorenone, fluorene,
Benzaldehyde, anthraquinone, triphenylamine, carbazole and the like can be mentioned.

When a compound having a cationically polymerizable group such as an epoxy group together with a radically polymerizable group is used as the radically polymerizable compound, a photo-cationic polymerization initiator is used in combination with the above-mentioned photo-radical polymerization initiator. The kind of the cationic photopolymerization initiator in that case is not particularly limited, and a conventionally known one can be used. It is generally known that the cationic photopolymerization initiator is deactivated in the presence of a basic compound, but the imidized acrylic compound (I) used in the present invention deactivates the cationic photopolymerization initiator. I also found it to react without doing it.

The amount of the photopolymerization initiator used can vary depending on the imidized acrylic compound (I), the type of radically polymerizable compound, the type of cationically polymerizable compound, the type of photopolymerization initiator and the like. It is preferably 0.1 to 10% by mass, more preferably 1 to 5% by mass, based on the total mass of the acrylic compound (I) and the radical polymerizable compound and / or the cationic polymerizable compound.

The photocurable resin composition of the present invention may contain, if necessary, a leveling agent, a surfactant, an organic polymer modifier, an organic plasticizer, organic or inorganic solid fine particles in addition to the above-mentioned components. And the like. Examples of the aforementioned organic solid fine particles include crosslinked polystyrene-based fine particles, crosslinked polymethacrylate-based fine particles, polyethylene-based fine particles, polypropylene-based fine particles, and the like.
Examples of the inorganic solid fine particles include glass beads, talc fine particles, and silicon oxide fine particles.
When the photo-curable resin composition of the present invention contains organic solid fine particles and / or inorganic solid fine particles, a photo-curable resin which is treated with a silane coupling agent such as aminosilane, epoxy silane, or acrylic silane can be used. In many cases, the mechanical strength of the cured product obtained by the above-mentioned process is improved, which is preferable. When the polyethylene-based solid fine particles and / or the polypropylene-based solid fine particles that have been subjected to the silane coupling agent treatment are contained in the photocurable resin composition, a polyethylene-based copolymer obtained by copolymerizing about 1 to 10% by mass of an acrylic acid-based compound is used. It is preferable to use solid fine particles and / or polypropylene solid fine particles because the affinity with the silane coupling agent is increased.

When the above-mentioned organic solid fine particles and / or inorganic solid fine particles are contained in the photocurable resin composition of the present invention, the heat resistance of the photocured product is often further improved.
At that time, in order to maintain good transparency while further improving the heat resistance, the solid fine particles are formed into extremely small submicron particles, and a suitable surface treatment is applied to the light-curable resin. It is desirable that the photocurable resin composition is stably dispersed in the composition to suppress an increase in viscosity of the photocurable resin composition.

The viscosity of the photocurable resin composition of the present invention can be adjusted according to the use and the mode of use. Generally, the viscosity is measured at room temperature (25 ° C.) when measured using a rotary B-type viscometer.
Is preferably about 0.1 to 100 Pa · s from the viewpoint of handleability, moldability, three-dimensional molding property, and the like.
More preferably, it is about 3 to 50 Pa · s. In particular,
When the photocurable resin composition of the present invention is used for optical three-dimensional modeling, it is preferable to keep the viscosity at room temperature in the range of 0.3 to 10 Pa · s, so that the handleability at the time of modeling becomes good,
In addition, it is desirable because a target three-dimensional structure can be smoothly manufactured with high dimensional accuracy. The viscosity of the photocurable resin composition can be adjusted by selecting the type of the imidized acrylic compound (I) and the radically polymerizable compound, adjusting the mixing ratio thereof, and the like.

When the photocurable resin composition of the present invention is stored in a state capable of blocking light, it is usually kept at a temperature of 10 to 40 ° C. for a long period of about 6 to 18 months. It can be stored while maintaining good photocuring performance while preventing denaturation and polymerization. The photocurable resin composition of the present invention can be used for various applications, for example, for three-dimensional modeling, molding, coating agents, inks, adhesives, and the like. In particular, the photocurable resin composition of the present invention has excellent properties, that is, a small volumetric shrinkage when cured with light, excellent dimensional accuracy, excellent mechanical properties having high tensile strength, and excellent properties. Utilizing the properties of having heat resistance and transparency, it can be effectively used for the production of various molded articles and three-dimensional molded articles. It can be used for the production and coating of various molded articles such as film-like articles and mold articles using molds and the like.

Among them, the photocurable resin composition of the present invention is suitable for use in an optical three-dimensional molding method, and when used for optical three-dimensional molding, while maintaining a small volume shrinkage during photocuring. It is possible to smoothly produce a three-dimensional structure having excellent dimensional accuracy and excellent heat resistance, rigidity and transparency. In performing optical three-dimensional modeling using the photocurable resin composition of the present invention, any of conventionally known optical three-dimensional modeling methods and apparatuses can be used. Among them, in the present invention, as the light energy for curing the resin, it is preferable to use an active energy ray generated from an Ar laser, a He-Cd laser, a xenon lamp, a metal halide lamp, a mercury lamp, a fluorescent lamp, or the like. Is particularly preferably used. When a laser beam is used as the active energy beam, it is possible to increase the energy level and shorten the molding time, and furthermore, by utilizing the good light-collecting property of the laser beam,
It is possible to obtain a three-dimensional object with high modeling accuracy.

In carrying out optical three-dimensional molding using the photocurable resin composition of the present invention, any of a conventionally known method and a conventionally known stereolithography system apparatus can be adopted, and there is no particular limitation. As a typical example of the preferably used optical three-dimensional molding method, a liquid photocurable resin composition is selectively irradiated with active energy rays so as to obtain a cured layer having a desired pattern to form a cured layer. Then, by supplying an uncured liquid photocurable resin composition to the cured layer, repeating the operation of irradiating active energy rays in the same manner to form a new cured layer continuous with the cured layer. A method for finally obtaining a desired three-dimensional structure can be given. The three-dimensional structure obtained thereby can be used as it is, or in some cases, post-curing by light irradiation or post-curing by heat, etc., to use it after further improving its mechanical properties and shape stability etc. You may do so.

The structure, shape, size, and the like of the three-dimensional structure are not particularly limited, and can be determined according to each use. Typical application fields of the optical three-dimensional modeling method of the present invention include a model for verifying an external design during design, a model for checking the functionality of parts, a resin mold for producing a mold, Examples include a base model for producing a mold, a direct mold for a prototype mold, and the like. More specifically, production of precision parts, electric / electronic parts, furniture, building structures, automobile parts, various containers, castings, molds, models for molds, and models for processing. Can be. Utilizing its excellent heat resistance and transparency properties, it can be used very effectively for prototyping high-temperature components, such as designing complex heat transfer circuits and manufacturing components for analyzing the heat transfer behavior of complex structures. be able to.

[0056]

EXAMPLES The present invention will be specifically described below with reference to examples and the like, but the present invention is not limited to the following examples.

<< Synthesis Example 1 >> [Production of imidized acrylic compound (I)] (1) Into a ³ dm ³ (2 liter) three-necked flask equipped with a stirrer, a temperature controller, a thermometer and a condenser. ,
240 g of 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic anhydride (0.8 mol
l), hydroquinone 0.16 g (2000 ppm),
400 g of xylene and dimethylformamide (hereinafter D
After charging 400 g (referred to as MF) and uniformly dissolving at 60 ° C., 24 g (0.4 mol) of ethylenediamine was added dropwise over about 1 hour, and a dehydration reaction was performed at 130 to 150 ° C. for about 3 hours (dehydration amount: 14). .4g). (2) The reaction solution obtained in the above (1) was cooled to about 80 ° C., and 48.8 g (0.8 mol) of β-aminoethyl alcohol was added thereto.
l) is added dropwise over about 1 hour,
A dehydration reaction was performed for 1 hour (dehydration amount: 14.0 g). (3) The reaction liquid obtained in the above (2) was cooled to about 80 ° C., and 79.6 g (0.88 mol) of acrylic acid chloride was added thereto.
And 88.8 g (0.88 mol) of triethyleneamine were added, and the mixture was heated and stirred at 130 to 150 ° C., and the reaction was terminated after 3 hours. (4) The reaction mixture obtained in (3) was transferred to a separating funnel, 800 g of chloroform was added, and the mixture was washed once with 1600 g of water and 1600 g of a 15% aqueous sodium hydroxide solution. Xylene and DMF in the reaction solution after washing were distilled off under reduced pressure to obtain 212 g of a brown solid (yield 65).
%). (5) IR analysis of the reaction product obtained in the above (4) showed that the absorption derived from an imide bond (1774 cm ^-1 ), an ester bond (1695 cm ^-1 ) and an acryloyl group C ＝ C bond (1634 cm ^-1 ). It was confirmed. Also,
According to the gel permeation chromatography, the reaction product was represented by the general formula (I), wherein R ¹ was a group represented by the formula, R ² and R ³ were ethylene groups, R ⁴ was a hydrogen atom, and m Is a mixture containing a compound in which n is 0 to 4 (a compound in which n = 0 is 12% by mass, a compound in which n = 1 is 45% by mass, a compound in which n = 2 is 20% by mass, and a compound in which n = 3 Compound 12% by mass and n = 4 a compound consisting of 11% by mass).

<< Synthesis Example 2 >> [Production of reaction product containing urethane acrylate and morpholine acrylamide] (1) ^Three internal volume 5 dm ³ (5 liter) equipped with stirrer, temperature controller, thermometer and condenser In the neck flask,
888 g of isophorone diisocyanate, 906 g of morpholine acrylamide and dibutyltin dilaurate
After charging 0 g, the mixture was heated in an oil bath so that the internal temperature became 80 to 90 ° C. (2) A liquid obtained by uniformly mixing and dissolving 0.7 g of methylhydroquinone in 464 g of 2-hydroxyethyl acrylate is charged into a dropping funnel with a side tube that has been kept at 50 ° C. in advance, and the liquid in the dropping funnel is The contents in the flask of (1) were dropped and mixed under stirring in a nitrogen atmosphere while maintaining the temperature of the contents of the flask at 80 to 90 ° C., and reacted by stirring at the same temperature for 2 hours. (3) Then, after lowering the temperature of the contents of the flask to 60 ° C, 137 g of pentaerythritol charged into another dropping funnel was quickly added dropwise, and the temperature of the contents of the flask was maintained at 80 to 90 ° C for 4 hours. The reaction was carried out to produce a reaction product containing urethane acrylate and morpholine acrylamide, and the obtained reaction product was taken out of the flask while being warm. The obtained reaction product was a colorless and viscous liquid at normal temperature (25 ° C.).

Example 1 [Preparation of Photocurable Resin Composition] In a three-necked flask having an internal volume of 1 dm ³ (1 liter) equipped with a stirrer, a cooling tube and a dropping funnel with a side tube, the synthesis example 1 was used. 180 g of the reaction product containing 88% by mass of the obtained imidized acrylic compound and the reaction product 3 obtained in Synthesis Example 2
00 g and dicyclopentanyl diacrylate 120
g, and the atmosphere was replaced by vacuum degassing and nitrogen replacement. Then, in an environment in which ultraviolet rays are blocked, 1-hydroxycyclohexyl phenyl ketone (“Irgacure 18” manufactured by Ciba Geigy) is used.
4 "; a photo-radical polymerization initiator) 18 g was added, and the mixture was stirred at a temperature of 25 ° C until complete dissolution (mixing and stirring time: about 1 hour) to give a photo-curable resin composition as a colorless and transparent viscous liquid (Viscosity at room temperature: about 20 Pa · s).

Example 2 [Production of Photocured Molded Product by Molding Method] (1) A transparent silicon mold having a dumbbell test piece-shaped mold cavity in accordance with JIS 7113 was prepared in Example 1 described above. After injecting the photocurable resin composition,
Using a 30 W ultraviolet lamp, 1
When a molded product in the form of a dumbbell test piece hardened by irradiating ultraviolet rays for 5 minutes to cure the resin composition was obtained, a molded product having excellent transparency (dumbbell-shaped test piece) was obtained.
The molded article was taken out of the mold, and its tensile properties (tensile strength, tensile elongation and tensile modulus) were measured in accordance with JIS K 7113. The results are as shown in Table 1 below. (2) In addition, the heat deformation temperature of the dumbbell-shaped test piece obtained in the above (1) was measured by the method A (load: 18.5 kg / mm ² ) according to JIS K7207, and as shown in Table 1 below. Met. (3) Further, the specific gravity (d ₂ of the light before curing specific gravity of the photocurable resin composition used in the molding of Example 2 and (d _1), the resulting molded article (dumbbell-shaped test piece) ) Was measured, and the volumetric shrinkage (%) was determined by the following equation (1). The results were as shown in Table 1 below.

[0061]

## EQU1 ## Volume shrinkage (%) = {(d ₂ −d ₁ ) / d ₂ } × 100 (1)

<< Example 3 >> [Manufacture of three-dimensional molded article by optical three-dimensional molding method] Using the photocurable resin composition obtained in the above-mentioned Example 1, an ultra-high-speed optical molding system (Teijin Machinery Co., Ltd.) Company-made "SO
LIFORM 500 ”) using a water-cooled Ar laser beam (output: 500 mW; wavelength: 333, 351, 364 n)
m) is irradiated perpendicularly to the surface, and the irradiation energy 2
Under the condition of 0 to 30 mJ / cm ^2, the stereolithography is performed with a slice pitch (lamination thickness) of 0.127 mm and an average molding time of 2 minutes per layer by 2 minutes to obtain a three-dimensional molded article having a dumbbell specimen shape in accordance with JIS 7113. Manufactured. The obtained three-dimensional model was washed with isopropyl alcohol to remove the uncured resin liquid adhering to the three-dimensional model, and then irradiated with 3 KW ultraviolet light for 10 minutes and post-cured to obtain a three-dimensional model having excellent transparency. A shaped object was obtained. The tensile properties (tensile strength, tensile elongation and tensile modulus) of the three-dimensional structure (dumbbell-shaped test piece) were measured in accordance with JIS K 7113, and as shown in Table 1 below. In addition, the heat deformation temperature of the post-cured dumbbell-shaped test piece (three-dimensional molded product) obtained above was measured in the same manner as in Example 2, and the results were as shown in Table 1 below. Further, the specific gravity (d ₁ ) of the photocurable resin composition before photocuring and the specific gravity (d ₂ ) of the three-dimensional molded product after post-curing used in the three-dimensional molding method of Example 3 were measured, respectively. When the volume shrinkage rate (%) was obtained by the above equation (1),
It was as shown in Table 1 below.

<< Comparative Example 1 >> [Production of photocurable resin composition and three-dimensional molded article by optical three-dimensional molding method] (1) Production of photocurable resin composition: stirrer, temperature controller, thermometer, and condensation 0.5 dm ³ (5
(00 ml) three-necked flask was charged with 202 g of the reaction product obtained in Synthesis Example 2 and 202 g of dicyclopentadienyl diacrylate, followed by purging under reduced pressure and nitrogen. Then, in an environment in which ultraviolet rays are blocked, 1-hydroxycyclohexylphenyl ketone (“Irgacure 184” manufactured by Ciba Geigy; photoradical polymerization initiator)
12 g was added, and the mixture was stirred at a temperature of 25 ° C. until it was completely dissolved (mixing and stirring time: about 1 hour).
a · s) was obtained. (2) Using the photocurable resin composition obtained in the above (1), optical three-dimensional modeling, washing of uncured resin, and post-curing are performed in the same manner as in Example 3 to obtain a transparent three-dimensional molded article. (Dumbbell-shaped test piece) was manufactured. Tensile properties of the resulting dumbbell-shaped test specimen (solid object)
The heat deformation temperature and the volume shrinkage were measured in the same manner as in Example 5, and were as shown in Table 1 below.

[0064]

[Table 1]

As is clear from the results in Table 1 above, the photocurable resin composition of Example 1 containing the imidized acrylic compound included in the category of the imidized acrylic compound (I) of the present invention was used. In Example 2 and Example 3 in which molding or optical three-dimensional molding is performed under light irradiation, a three-dimensional molded article is manufactured using a photocurable resin composition containing a urethane acrylate compound. In comparison with, molding with better tensile properties such as tensile strength, tensile elongation and tensile elasticity, higher heat deformation temperature and better heat resistance, and smaller volume shrinkage and better dimensional accuracy A product and an optical three-dimensional object were obtained.

Example 4 [Production of imidized acrylic compound (I), production of photocurable resin composition and optical three-dimensional molding] (1) A stirrer, a temperature controller, a thermometer and a condenser were provided. In a 2 dm ³ (2 liter) three-necked flask,
500 g of dehydrated xylene and 179.3 g (0.8 mol) of cyclohexyltetracarboxylic anhydride (1,2,4,5-tetracarboxylcyclohexanoic anhydride)
l), and 100 g of dehydrated xylene and 29.7 g (0.4 mol) of 1,2-diaminopropane in a dropper.
And stirring at room temperature with stirring with a stirrer.
It was dropped over time. After dropping the whole amount, the mixture was further reacted by stirring at room temperature for 2 hours, followed by a dehydration reaction under xylene reflux for about 3 hours (dehydration amount: 14.1 g). Heat reaction was performed. Removing toluene by fractional distillation from the reaction mixture,
Reaction product 14 (2) The reaction solution of the above (1) was cooled to about 80 ° C., and 48.9 g (0.8 mol) of aminoethyl alcohol was added thereto.
Was added dropwise over about 1 hour, and a dehydration reaction was performed under xylene reflux for about 4 hours (dehydration amount: 14.3 g).

(3) The reaction solution obtained in the above (2) was cooled to about 80 ° C., and 79.6 g of acrylic acid chloride was added thereto.
88 mol) and 89.0 g (0.88) of triethylamine
mol), and the mixture was heated and stirred at 130 ° C., and the reaction was terminated after about 4 hours. (4) The reaction mixture obtained in the above (3) was cooled to room temperature, the precipitated salt was separated by filtration, and the filtrate was transferred to a separating funnel.
1500 g of water and 15% aqueous sodium hydroxide solution 15
Washing was performed once each at 00 g. After washing, xylene was distilled off under reduced pressure to obtain 241.0 g of a reaction product (yield 89).
%). The reaction product thus obtained is 11 Pa at room temperature.
-The viscosity of s was shown.

(5) The reaction product obtained in the above (4) was
R analysis revealed that the imide bond (1774 cm ^-1 ), the ester bond (1695 cm ^-1 ) and the acryloyl group C
= C bond (1634 cm ^-1 ) was observed. Elemental analysis revealed 61.11% by mass of carbon, 5.55% by mass of hydrogen and 8.6% of nitrogen.
It was 4% by mass and oxygen was 24.69% by mass. The purity by high performance liquid chromatography was 96%.
As described above, the reaction product in the above general formula (I) is such that R ¹ is a cyclohexyl group, R ² is a propylene group, R ³
Is an ethylene group, R ⁴ is a hydrogen atom, m is 1 and n is 1.

(6) A photocurable resin was prepared in the same manner as in Example 1 except that the imidized acrylic compound obtained in the above (4) was used instead of the imidized acrylic compound obtained in the synthesis example 1. When a composition was manufactured and optical three-dimensional modeling was performed in the same manner as in Example 3 using the photocurable resin composition, tensile strength, tensile elongation, tensile elasticity and other tensile properties were excellent. In addition, a three-dimensional structure having a high heat deformation temperature and excellent heat resistance can be manufactured with small volume shrinkage and high dimensional accuracy.

[0070]

The photocurable resin composition of the present invention exhibits a relatively low-viscosity liquid and has excellent handleability, and can be cured in a short curing time.
It can be used effectively for the production of three-dimensional objects and other products. Since the photocurable resin composition of the present invention has a small volume shrinkage at the time of photocuring, a molded article or a three-dimensional molded article having excellent dimensional accuracy can be smoothly obtained by light irradiation molding or optical three-dimensional molding. Photocured products such as molded products and three-dimensional molded products obtained by photocuring the photocurable resin composition of the present invention,
It has a high heat deformation temperature exceeding 250 ° C. and is extremely excellent in heat resistance, and also has high tensile strength, tensile elongation, tensile elastic modulus, etc., and excellent mechanical properties.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court ゛ (Reference) // C08L 33:14 C08L 33:14 (72) Inventor Junichi Tamura 3-3 Nishishinbashi, Minato-ku, Tokyo No. 1 Teijin Machinery Co., Ltd. (72) Inventor Tsuneo Hagiwara 3-3-1 Nishi-Shimbashi, Minato-ku, Tokyo Teijin Machinery Co., Ltd. (72) Inventor Shin Otake 3-3-1, Nishi-Shimbashi, Minato-ku, Tokyo No. 1 Teijin Machinery Co., Ltd. (72) Inventor Eiichi Okazaki 1 in Funami-cho, Minato-ku, Nagoya-shi, Aichi Prefecture Inside Nagoya Research Institute, Toagosei Co., Ltd. (72) Inventor Yasunori Muramatsu Funami, Minato-ku, Nagoya-shi, Aichi 1 in Togosei Co., Ltd., Nagoya Research Institute, Inc. (72) Inventor Toshiharu Suzuki 2-5 Minatomachi, Gamagori-shi, Aichi Prefecture Takemoto Yushi Co., Ltd. (72) Inventor Minoru Shinoda, Aichi Prefecture 2-5, Minato-machi, Kori-shi Takemoto Yushi Co., Ltd. F-term (reference) 4C063 AA05 BB03 CC06 DD04 EE10 4F071 AA31 AA33 AA76 AF15 AF30 AF54 AH12 AH19 BA02 BB01 BB02 BB12 BC01 BC07 4J011 AA05 AC04 QA01 QA01 SA12A UA02 WA07 4J027 AA02 AC02 AD03 AJ02 BA05 BA07 BA08 BA14 BA19 BA20 BA24 BA26 CB10 CC05 CD01 CD10 4J100 AL08P AL08Q AL09Q AM15Q BA07Q BA08P BA08Q BC03Q BC42Q BC64P CA04 CA23 FA03 JA37 JA38

Claims (7)

[Claims] (I) The following general formula (I): (Wherein, R ¹ is an optionally substituted alicyclic group, an optionally substituted aromatic group or an optionally substituted aliphatic group, and R ¹ is an etheric oxygen atom. R ² is a divalent diamine residue, R ³ is a divalent amino alcohol residue, R ⁴ is a hydrogen atom or a methyl group, m is an integer of 1 to 6, n is 1 to At least one kind of an imidized acrylic compound represented by the formula:
A photocurable resin composition comprising (ii) a radically polymerizable compound and / or a cationically polymerizable compound other than the above imidized acrylic compound; and (iii) a photopolymerization initiator. 2. The content ratio of [the imidized acrylic compound]: [the radically polymerizable compound and / or the cationically polymerizable compound] is 80:20 to 10:90 (mass ratio). Photocurable resin composition. 3. The content of the photopolymerization initiator is from 0.1 to based on the total mass of the imidized acrylic compound and the radical polymerizable compound and / or the cationic polymerizable compound.
The photocurable resin composition according to claim 1, wherein the content is 10% by mass. 4. The photocurable resin composition according to claim 1, which is for optical three-dimensional modeling. 5. A method for producing a three-dimensional structure by optical three-dimensional molding using the photocurable resin composition according to claim 4. 6. The following general formula (I): (Wherein, R ¹ is an optionally substituted alicyclic group, an optionally substituted aromatic group or an optionally substituted aliphatic group, and R ¹ is an etheric oxygen atom. R ² is a divalent diamine residue, R ³ is a divalent amino alcohol residue, R ⁴ is a hydrogen atom or a methyl group, m is an integer of 1 to 6, n is 1 to An imidized acrylic compound represented by the formula: 7. The following general formula (II): (Wherein, R ¹ is an optionally substituted alicyclic group, an optionally substituted aromatic group or an optionally substituted aliphatic group, and R ¹ is an etheric oxygen atom. An acid anhydride (II) represented by the following general formula (III): H ₂ N—R ² —NH ₂ (III) wherein R ² Represents a divalent organic group), and reacted with a diamine compound (III) represented by the following general formula (I
V); (Wherein, R ¹ and R ² are the same groups as described above, and n is 1 to
Indicates an integer of 5. Imidized acid anhydride (IV) represented by
Then, the imidized acid anhydride (IV) is added to the following general formula (V): H- (OR ³ ) m -NH ₂ (V) (wherein R ³ is 2 Wherein m represents an integer of 1 to 6), and reacted with an amino alcohol (V) represented by the following general formula (VI): (Wherein, R ¹ , R ² and R ³ represent the same groups as described above;
And n are the same numbers as above. )), And (meth) acrylic acid or (meth) is added to the imidated alcohol compound (VI).
By reacting acrylic acid halide, the following general formula (I): (Wherein, R ^1, R ² and R ³ have the same group as the, R ⁴
Represents a hydrogen atom or a methyl group, and m and n represent the same numbers as described above. A method for producing the imidized acrylic compound represented by the formula (1).