JPH09169827A - Photocurable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a molded item which undergoes a small vol. shrinkage in photocuring, exhibiting a high dimensional accuracy, and is excellent in softness, elastic recovery, and mechanical characteristics by compounding a urethanized acrylic compd., another free-radical-polymerizable compd., and a photopolymn. initiator. SOLUTION: This photocurable resin compsn. is prepd. by compounding at least one compd. (A) selected from among compds. represented by formulas I (wherein (a) is 1 or 2; R<1> is H or methyl provided when (a) is 2, then one or both of R<1> 's are methyl; A<1> is a di- or trivalent hydrocarbon group; (b) is 3-6; (c) is 3-14; and (d) is 2 or 3), II (wherein (e) is 1 or 2; R<2> and R<3> are each H or methyl provided when (e) is 2, then one or both of R<2> 's are methyl; A<2> is a di- or trivalent hydrocarbon group; (f) is 4-20; and (g) is 2 or 3), and III (wherein R<4> and R<5> are each H or methyl; A<3> is a di- or trivalent hydrocarbon group; (h) is 4-20; and (j) is 2 or 3), a free-radical-polymerizable acrylic or allylic compd. (B) other than component A, and a photopolymn. initiator (C) in a wt. ratio of A/B of (80:20)-(10:90) and in a wt. ratio of C/(A+B) of 0.1-10%.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photocurable resin composition, a method for producing a three-dimensional object using the photocurable resin composition, and a urethanated acrylic compound used in the photocurable resin composition. More specifically, the present invention, when cured by light, has a small volume shrinkage ratio and is excellent in dimensional accuracy, and is also excellent in flexibility, elastic recovery and mechanical properties, and a three-dimensional molded object, and further Photocurable resin composition capable of obtaining a cured product of the above, a method for producing a molded article by an optical three-dimensional modeling method using the photocurable resin composition, and urethanization used in the photocurable resin composition It relates to an acrylic compound.

[0002]

2. Description of the Related Art Generally, a liquid photocurable resin composition is widely used as a coating material, a photoresist, a dental material, and the like. In recent years, a photocurable resin composition is based on data input to a three-dimensional CAD. A method of stereoscopically shaping a composition has attracted attention. Regarding the optical three-dimensional modeling technology, a liquid photo-curable resin is supplied with a required amount of controlled light energy to be cured into a thin layer, and then a liquid photo-curable resin is further supplied onto the liquid photo-curable resin to control the light under control. An optical three-dimensional modeling method for producing a three-dimensional model by repeating the steps of irradiating and curing in a thin layer is disclosed in JP-A-56-14.
No. 4478, and its basic practical method was further proposed by JP-A-60-247515. Since then, many proposals regarding optical three-dimensional modeling technology have been made.
-35,966, JP-A-1-204915,
JP-A-2-113925, JP-A-2-14561
No. 6, JP-A-2-153722, JP-A-3-
Japanese Patent No. 15520, Japanese Patent Laid-Open No. 3-21432, Japanese Patent Laid-Open No. 3-41126 disclose techniques relating to an optical three-dimensional modeling method.

[0003] A typical method for optically producing a three-dimensional object is a computer controlled ultraviolet ray so as to obtain a desired pattern on the liquid surface of a liquid photocurable resin composition placed in a container. A 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 similarly irradiated with an ultraviolet laser to be cured as described above. A method of manufacturing a three-dimensional structure having a final shape by repeating a laminating operation of forming a continuous cured layer by using the same is generally used widely. In the case of using this method, even if the shape of the modeled object is quite complicated, the desired three-dimensional modeled object can be easily manufactured in a relatively short time, and thus has attracted great attention in recent years.

As the photocurable resin composition used for coating materials, photoresists, dental materials, etc., curing of unsaturated polyester, epoxy (meth) acrylate, urethane (meth) acrylate, (meth) acrylic acid ester monomer, etc. A resin in which a photopolymerization initiator is added is widely used.

The photocurable resin composition used in the optical three-dimensional molding method is a photopolymerizable modified urethane (meth).
Acrylate compound, oligoester acrylate compound, epoxy acrylate compound, epoxy compound, polyimide compound, aminoalkyd compound,
Examples thereof include one containing one or more photopolymerizable compounds such as vinyl ether compounds as a main component and a photopolymerization initiator added thereto, and recently, JP-A-1-204.
915, JP-A-1-213304, JP-A-2-28261, JP-A-2-75617,
JP-A-2-145616, JP-A-3-10462
No. 6, JP-A-3-114732, and JP-A-3-114732.
Various improved techniques are disclosed in Japanese Patent No. 1147324 and the like.

The photocurable resin composition used in the optical three-dimensional molding method is a low-viscosity liquid material and has little volume shrinkage during curing from the viewpoints of handleability, molding speed, molding accuracy and the like. However, it is required that the mechanical properties of the three-dimensional model obtained by photocuring be good. In recent years, there is a tendency for demand and applications of optical three-dimensional objects to expand, and accordingly, three-dimensional objects having high elongation flexibility and elastic recovery in addition to the above-mentioned properties are required depending on the applications. For example, a cushion material with a complicated shape contained in a structure, a three-dimensional object used for a vacuum molding die, or the like has a high flexibility, a high elongation, and an elastic recovery property. Is needed.

As a method for producing a flexible optical three-dimensional molded article, a photo-curable resin containing a heat-aggregating polymer material such as a vinyl chloride resin powder or a plasticizer is photo-cured to be optically cured. There is known a method of thermally agglomerating after forming a three-dimensional object (Japanese Patent Laid-Open No. 3-104 mentioned above).
626 publication). However, this method has a drawback in that the viscosity of the resin composition is increased because the thermocoagulable polymer is mixed in the photocurable resin, and the handleability and the molding accuracy are reduced. Further, since the plasticizer is used, the mechanical properties such as tear resistance are inferior, and there are problems such as migration of the plasticizer and bleeding on the surface of the three-dimensional structure, which is sufficiently satisfied. No results have been obtained. Further, there is known a urethane acrylate-based resin composition in which a caprolactone unit is bonded between urethane groups in order to improve the tensile elongation (Japanese Patent Laid-Open No. 61-61160).
No. 185522), the cured product has some improvement in tensile elongation, but the flexibility is still insufficient.

[0008]

The object of the present invention is to exhibit a low-viscosity liquid, which is easy to handle, can be cured in a short curing time, and has a small volume shrinkage rate when cured by light, resulting in dimensional accuracy. Provided is a photocurable resin composition which is excellent in flexibility, and has excellent mechanical properties such as flexibility, elastic recovery property, tensile strength, and tensile elongation. Is. And the objective of this invention is a method of manufacturing a molded article by the optical three-dimensional modeling method using the said photocurable resin composition. Further, it is an object of the present invention to provide a novel urethane acrylic compound that can be used in the above photocurable resin composition.

[0009]

Means for Solving the Problems The inventors of the present invention have been studying to achieve the above object. As a result, the novel urethanated acrylic compound having a specific chemical structure synthesized by the present inventors is extremely effective in achieving the above-mentioned object, and this urethanized acrylic compound is added to other radical polymerizable compounds and photopolymerization initiation. Addition of an agent gives a liquid photocurable resin composition with low viscosity and excellent handleability, and when the photocurable resin composition is irradiated with light, it can be cured in a short time, and the volume shrinkage ratio It was found that a three-dimensional object having a small size, a desired shape and size, excellent flexibility and elastic recovery, and excellent mechanical properties can be obtained with good dimensional accuracy. Then, the present inventors have found that the above-mentioned photocurable resin composition can be effectively used not only in an optical three-dimensional modeling method, but also in the production of molded articles involving curing by light irradiation and other applications. The present invention has been completed based on the above findings.

That is, the present invention provides (a) the following general formula (I);

[0011]

Embedded image (Wherein, R ¹ is a hydrogen atom or a methyl group, a is 1 or 2, and when a is 2, one or both of R ¹ are methyl groups, and A ¹ is a divalent or trivalent non-valent group. A substituted or substituted hydrocarbon group, b is an integer of 3 to 6, c is 3
An integer of from 14 to 14, and d is 2 or 3); a urethane-containing acrylic compound represented by the following general formula (II):

[0012]

Embedded image (Wherein, R ² and R ³ are each independently a hydrogen atom or a methyl group, e is 1 or 2, and when e is 2, one or both R ² are methyl groups, and A ² is A divalent or trivalent unsubstituted or substituted hydrocarbon group,
Is an integer of 4 to 20, and g is 2 or 3); and a general formula (III) below:

[0013]

Embedded image (Wherein, R ⁴ and R ⁵ are each independently a hydrogen atom or a methyl group, A ³ is a divalent or trivalent unsubstituted or substituted hydrocarbon group, h is an integer of 4 to 20, And j is 2 or 3) a urethane acrylate compound selected from at least one of the following urethane acrylate compounds: (b) a radical polymerizable compound other than the urethan acrylate compound of (a) And (c) a photocurable resin composition containing a photopolymerization initiator, wherein the content ratio of the acrylic urethane compound (a): the radical polymerizable compound (b) is 80:20.
It is a photocurable resin composition characterized by being 10:90 (weight ratio).

The present invention is a resin composition for optical three-dimensional modeling, which comprises the above photocurable resin composition. Furthermore, the present invention is a method for producing a three-dimensional molded article by an optical three-dimensional molding method, using the above resin composition for optical three-dimensional molding.

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

[0016]

Embedded image (Wherein, R ¹ is a hydrogen atom or a methyl group, a is 1 or 2, and when a is 2, one or both of R ¹ are methyl groups, and A ¹ is a divalent or trivalent non-valent group. A substituted or substituted hydrocarbon group, b is an integer of 3 to 6, c is 3
An integer of from 14 to 14, and d is 2 or 3); a urethane-containing acrylic compound represented by the following general formula (II):

[0017]

Embedded image (Wherein, R ² and R ³ are each independently a hydrogen atom or a methyl group, e is 1 or 2, and when e is 2, one or both R ² are methyl groups, and A ² is A divalent or trivalent unsubstituted or substituted hydrocarbon group,
Is an integer of 4 to 20, and g is 2 or 3); or a urethanated acrylic compound represented by the following general formula (III);

[0018]

Embedded image (In the formula, R ⁴ and R ⁵ are each independently a hydrogen atom or a methyl group, A ³ is a divalent or trivalent unsubstituted or substituted hydrocarbon group, h is an integer of 4 to 20, And j is 2 or 3).

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. First, the urethanated acrylic compound represented by the above general formula (I) used in the photocurable resin composition of the present invention [hereinafter, referred to as "urethaned acrylic compound (I)"] and the above general formula (II Urethane-ized acrylic compound [hereinafter referred to as "urethane-modified acrylic compound (I
I) ”] and the urethanized acrylic compound represented by the above general formula (III) [hereinafter, referred to as“ urethaned acrylic compound (III) ”].

In the urethanated acrylic compound (I), R ¹ is a hydrogen atom or a methyl group, and a is 1 or 2, and when a is 2, there are two groups; CH ₂ ═C
It is necessary that one or both groups R ^{1 of} (R ¹ ) —COO—CH ₂ — be a methyl group. Two groups when a is 2 in the urethanated acrylic compound (I);
When both groups R ^{1 of} CH ₂ ═C (R ¹ ) —COO—CH ₂ — are hydrogen atoms, it is necessary to go through glycerin diacrylate, which is highly toxic synthetically, carcinogenic and skin irritant. However, it cannot be practically used, which is not preferable.

Further, in the urethanated acrylic compound (I), b is an integer in the range of 3 to 6, and b is 5 among them because the stability of the urethanized acrylic compound (I) and the ease of production. It is preferable from the standpoint of sex. And
In the urethanated acrylic compound (I), c is 3 to 1
4 must be an integer in the range of 4, and c is 3 to 10.
It is preferable that it is the integer of the range of, and it is more preferable that it is the integer of the range of 3-6. When c exceeds 15, the melting point of the urethanized acrylic compound (I) becomes high, and it becomes low as another radical polymerizable compound (hereinafter referred to as “radical polymerizable compound (B)”) of the above (B). It becomes difficult to obtain a photocurable resin composition having excellent fluidity even at room temperature even if a molecular weight one is used, and further, the tensile elongation and flexibility of the cured product obtained by photocuring are lowered, and thus the objective It becomes impossible to obtain a three-dimensional molded article or molded article having excellent flexibility and elastic recovery. Also, when c is less than 3, the tensile elongation and flexibility of the cured product obtained by photocuring are reduced, and the desired three-dimensional modeled article or molded article having excellent flexibility and elastic recovery is obtained. I will not be able to.

In the urethanated acrylic compound (I), d must be 2 or 3. d
When the urethanated acrylic compound (I) in which is 2 is used, the urethanized acrylic compound (I) in which d is 3
Compared with the case of using, the flexibility and tensile elongation of the photocured product such as a three-dimensional molded article or a molded article obtained from the photocurable resin composition of the present invention tends to be large, but Even in such a case, a three-dimensional molded article or molded article having a large tensile elongation and excellent flexibility can be obtained.

In the urethanated acrylic compound (I), the group A ¹ is a divalent or trivalent unsubstituted or substituted hydrocarbon group, and the group A ¹ has 6 to 20 carbon atoms.
Is preferably an unsubstituted or substituted aliphatic, aromatic and / or alicyclic divalent or trivalent hydrocarbon group. The urethane-modified acrylic compound (I) is preferably a diisocyanate compound or a triisocyanate compound represented by the general formula; A ^1- (NCO) d (A ¹ and d are the same as described above), as described later. From this point, the group A ¹ is a divalent or trivalent residue excluding the isocyanate group of the diisocyanate compound or triisocyanate compound used for producing the urethanated acrylic compound (I). Is preferred. More specifically, urethanated acrylic compound (I)
As a preferred example of the group A ¹ in, an isophorone group,
Tolylene group, 4,4'-diphenylmethane group, naphthylene group, xylylene group, phenylene group, 3,3'-dichloro-4,4'-phenylmethane group, toluylene group, hexamethylene group, 4,4'-dicyclohexylmethane Base,
Examples thereof include hydrogenated xylylene group, triphenylene methane group, tetramethyl xylene group and the like.

The method for producing the urethanated acrylic compound (I) is not particularly limited, and the compound represented by the above general formula (I) and the photocurable resin composition containing the compound are not limited by the production method. However, the urethanated acrylic compound (I) can be preferably produced by the following method.

<< Typical Production Method of Urethaned Acrylic Compound (I) >> (1) The following general formula (i):

[0026]

Embedded image (Wherein R ¹ and a are the same as those described above) with respect to 1 mol of ethylene glycol mono (meth) acrylate or glycerin di (meth) acrylate represented by the following general formula (ii) :

[0027]

Embedded image (Where b is the same as above), and reacted with a lactone represented by the following general formula (iii):

[0028]

Embedded image (Wherein R ¹ , a, b and c are the same as described above); and (2) a lactone adduct represented by the general formula (iii) obtained by the above (1) With the general formula: A ^1- (N
By reacting with a diisocyanate compound or a triisocyanate compound represented by (CO) d, a urethanated acrylic compound (I) is produced.

In the above reaction (1), a mono (meth) acrylic acid ester of ethylene glycol or a di (meth) acrylic acid ester of glycerin and a lactone are used, if necessary, with a cation catalyst, an anion catalyst and an organotin. Using a catalyst (for example, dibutyltin, etc.), etc., usually 10
The reaction is preferably carried out at 0 to 140 ° C., whereby the lactone addition compound represented by the general formula (iii) can be smoothly obtained.

In the reaction (2) in which the above-mentioned diisocyanate compound or triisocyanate compound is reacted with the lactone addition compound represented by the above general formula (iii), a conventionally known urethane-forming catalyst such as an organic tin catalyst is used. Using a tertiary amine catalyst or the like, 40 to 90 ° C
By reacting both at the temperature of, the desired urethanated acrylic compound (I) can be obtained smoothly.

The diisocyanate compound and triisocyanate compound represented by the general formula: A ^1- (NCO) d used in the above reaction (2) are not particularly limited, and the diisocyanate compound and triisocyanate capable of carrying out the urethanization reaction can be used. Any of the compounds can be used. Among them, preferred examples of the diisocyanate compound and the triisocyanate compound include isophorone diisocyanate, tolylene diisocyanate,
4'-diphenylmethane diisocyanate, naphthylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, 3,3'-dichloro-4,
4'-phenylmethane diisocyanate, toluylene diisocyanate, hexamethylene diisocyanate,
4,4′-dicyclohexylmethane diisocyanate,
Examples thereof include hydrogenated xylylene diisocyanate, triphenylmethane triisocyanate, tetramethyl xylene diisocyanate, and hydrogenated 4,4'-diphenylmethane diisocyanate. These isocyanate compounds may be used alone or in combination of two or more. May be used in combination. Among the above isocyanate compounds,
Isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate are particularly preferably used. In this case, a photocured product having a large tensile elongation and excellent flexibility and flexibility is prepared by using a urethanated acrylic compound (I). Can be obtained from the photocurable resin composition of the present invention.

Next, in the urethanated acrylic compound (II), R ² and R ³ are each independently a hydrogen atom or a methyl group, and e is 1 or 2, and when e is 2, two groups are formed. It is necessary that one or both groups R ^{2 of} CH ₂ ═C (R ² ) —COO—CH ₂ — be a methyl group. In the urethanized acrylic compound (II), when e is 2, two groups; CH ₂ ═C (R ² ) —COO—
When both groups R ² of CH ₂ — are hydrogen atoms, it has to pass through glycerin diacrylate, which is a synthetically extremely toxic, carcinogenic and skin irritant, and cannot be used substantially.
Not preferred.

Further, in the urethanated acrylic compound (II), f is required to be an integer in the range of 4 to 20, preferably 5 to 14.
More preferably, it is an integer in the range of 10 to 10. f is 2
When it exceeds 0, the melting point of the urethanized acrylic compound (II) becomes high, and a photocurable resin composition having excellent fluidity at room temperature is obtained even if a radically polymerizable compound (b) having a low molecular weight is used. In addition, the cured product obtained by photocuring has a reduced tensile elongation and flexibility, and the desired three-dimensional molded article or molded article having excellent flexibility and elastic recovery cannot be obtained. In addition, even when f is less than 4, the tensile elongation and flexibility of the cured product obtained by photocuring are reduced, and a desired three-dimensional modeled article or molded article having excellent flexibility and elastic recovery is obtained. I will not be able to.

Further, a urethane-modified acrylic compound (II)
In, it is necessary that g is 2 or 3. When the urethanated acrylic compound (II) in which g is 2 is used, it is obtained from the photocurable resin composition of the present invention as compared with the case where the urethanized acrylic compound (II) in which g is 3 is used. Although the flexibility and tensile elongation of photocured products such as three-dimensional molded objects and molded products tend to be large, in all cases, the three-dimensional modeling has a large tensile elongation and is excellent in flexibility. You can get things and molded products.

In the urethanated acrylic compound (II), the group A ² is a divalent or trivalent unsubstituted or substituted hydrocarbon group, and the group A ² has 6 to 20 carbon atoms.
Is preferably an unsubstituted or substituted aliphatic, aromatic and / or alicyclic divalent or trivalent hydrocarbon group. Then, urethane acrylate compound (II), as described later, the general formula; A ² - preferably with (NCO) g diisocyanate compound (A ² and g are as defined above) represented by or triisocyanate compound From this point, the group A ² is a divalent or trivalent residue excluding the isocyanate group of the diisocyanate compound or triisocyanate compound used for producing the urethanated acrylic compound (I). Is preferred. More specifically, urethanated acrylic compound (II)
As a preferred example of the group A ² in, an isophorone group,
Tolylene group, 4,4'-diphenylmethane group, naphthylene group, xylylene group, phenylene group, 3,3'-dichloro-4,4'-phenylmethane group, toluylene group, hexamethylene group, 4,4'-dicyclohexylmethane Base,
Examples thereof include hydrogenated xylylene group, triphenylene methane group, tetramethyl xylene group and the like.

The method for producing the urethanated acrylic compound (II) is not particularly limited, and the compound represented by the above general formula (II) and the photocurable resin composition containing the compound are not limited by the production method. However, the urethanated acrylic compound (II) can be preferably produced by the following method.

<< Representative Production Example of Urethaned Acrylic Compound (II) >> (1) The following general formula (iv):

[0038]

Embedded image (Wherein R ² and e are the same as those described above) with respect to 1 mol of a mono (meth) acrylate of ethylene glycol or a di (meth) acrylate of glycerin represented by the following general formula (v) :

[0039]

Embedded image (Wherein R ³ is the same as described above) represented by propylene oxide [R ³ ＣＨCH _{3 in the} above formula (v)] or ethylene oxide [R in the above formula (v)
³ = H] and reacting at least one of the following general formula (vi):

[0040]

Embedded image (Wherein R ² , R ³ , e and f are the same as above), an addition compound of propylene oxide and / or ethylene oxide is prepared; and (2) the general formula (vi) obtained in the above (1). ), An addition compound of propylene oxide and / or ethylene oxide represented by the general formula: A ^2- (NCO)
By reacting with a diisocyanate compound or a triisocyanate compound represented by g, a urethanated acrylic compound (II) is produced.

In the above reaction (1), a mono (meth) acrylic acid ester of ethylene glycol or a di (meth) acrylic acid ester of glycerin is reacted with propylene oxide and / or ethylene oxide using a catalyst. Is preferred, whereby propylene oxide represented by the above general formula (vi) and / or
Alternatively, the addition compound of ethylene oxide can be obtained smoothly. Further, since the propylene oxide and / or ethylene oxide addition compound represented by the general formula (vi) is already known, a known one may be used as it is.

Further, the addition compound of propylene oxide and / or ethylene oxide represented by the general formula (vi) is reacted with a diisocyanate compound or triisocyanate compound represented by the general formula: A ^2- (NCO) g. In the reaction 2), a conventionally known urethane-forming catalyst such as an organic tin catalyst or a tertiary amine catalyst is used to react both at a temperature of 40 to 90 ° C. ) Can be obtained smoothly.

Then, in the reaction of the above (2), the compound represented by the general formula: A which is reacted with the addition compound represented by the general formula (vi)
The types of the diisocyanate compound and the triisocyanate compound represented by ^2- (NCO) g are not particularly limited, and both the diisocyanate compound and the triisocyanate compound capable of performing the urethanization reaction can be used. Among them, preferred examples of the diisocyanate compound and the triisocyanate compound include isophorone diisocyanate, tolylene diisocyanate,
4'-diphenylmethane diisocyanate, naphthylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, 3,3'-dichloro-4,
4'-phenylmethane diisocyanate, toluylene diisocyanate, hexamethylene diisocyanate,
4,4′-dicyclohexylmethane diisocyanate,
Examples thereof include hydrogenated xylylene diisocyanate, triphenylmethane triisocyanate, tetramethyl xylene diisocyanate, and hydrogenated 4,4'-diphenylmethane diisocyanate. These isocyanate compounds may be used alone or in combination of two or more. May be used in combination. Among the above isocyanate compounds,
Isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate are particularly preferably used. In that case, a photocured product having a large tensile elongation and excellent flexibility and flexibility, a urethanated acrylic compound (II) is used. Can be obtained from the photocurable resin composition of the present invention.

Further, a urethanated acrylic compound (III)
In, R ⁴ and R ⁵ are each independently a hydrogen atom or a methyl group. Further, h is required to be an integer in the range of 4 to 20, preferably an integer in the range of 5 to 14, and more preferably an integer in the range of 6 to 10. When h exceeds 20, the melting point of the urethanized acrylic (III) becomes high, and a photocurable resin composition having excellent fluidity at room temperature even when a low molecular weight radical polymerizable compound (b) is used is obtained. In addition, it becomes difficult to obtain the product, and the tensile elongation and flexibility of the cured product obtained by photocuring are lowered, and it becomes impossible to obtain the desired three-dimensional molded product or molded product having excellent flexibility and elastic recovery. Also, when h is less than 4, the tensile elongation and flexibility of the cured product obtained by photo-curing are reduced, and the desired three-dimensional molded item or molded article having excellent flexibility and elastic recovery is obtained. I will not be able to.

Further, a urethanized acrylic compound (II
It is necessary that j is 2 or 3 in I).
When the urethanated acrylic compound (III) in which j is 2 is used, it is obtained from the photocurable resin composition of the present invention as compared with the case where the urethanized acrylic compound (III) in which j is 3 is used. There is a tendency that the flexibility and tensile elongation of photocured products such as three-dimensional molded objects and molded products are large.
In either case, a three-dimensional molded article or molded article having a large tensile elongation and excellent flexibility can be obtained.

Further, a urethanated acrylic compound (III)
Wherein the group A ³ is a divalent or trivalent unsubstituted or substituted hydrocarbon group, and the group A ³ has 6 to 2 carbon atoms.
It is preferably 0 unsubstituted or substituted aliphatic, aromatic and / or alicyclic divalent or trivalent hydrocarbon groups. And urethane-modified acrylic compound (III)
Is a general formula; A ^3- (NCO) j (A ³
And j are the same as those described above) can be preferably produced using a diisocyanate compound or a triisocyanate compound, and from this point, the group A ³ is the diisocyanate used to produce the urethanated acrylic compound (I). It is preferably a divalent or trivalent residue excluding the isocyanate group of the compound or triisocyanate compound. More specifically, preferred examples of the group A ³ in the urethanized acrylic compound (III) include isophorone group, tolylene group, 4,4′-diphenylmethane group, naphthylene group, xylylene group, phenylene group, 3,3 ′. −
Examples thereof include a dichloro-4,4'-phenylmethane group, a toluylene group, a hexamethylene group, a 4,4'-dicyclohexylmethane group, a hydrogenated xylylene group, a triphenylenemethane group, and a tetramethylxylene group.

The method for producing the urethanated acrylic compound (III) is not particularly limited, and the compound represented by the above general formula (III) and the photocurable resin composition containing the compound are not limited by the production method. However, the urethanated acrylic compound (III) can be preferably produced by the following method.

<< Typical Production Example of Urethaned Acrylic Compound (III) >> (1) Acrylic acid or methacrylic acid is reacted with at least one of propylene oxide and ethylene oxide to give the following general formula (vii). :

[0049]

Embedded image Wherein R ⁴ , R ⁵ and h are the same as above, to form a propylene oxide and / or ethylene oxide adduct of acrylic acid or methacrylic acid;
Next, (2) the propylene oxide and / or ethylene oxide adduct represented by the general formula (vii) obtained in the above (1) is converted into the above-mentioned general formula: A ^3- (NCO)
By reacting with a diisocyanate compound or a triisocyanate compound represented by j, a urethane acrylate compound (III) is produced.

In the above reaction (1), it is preferable to react acrylic acid and / or methacrylic acid with propylene oxide and / or ethylene oxide using a suitable catalyst, whereby the above-mentioned general formula (vii It is possible to smoothly obtain an addition compound of propylene oxide and / or ethylene oxide represented by).

Further, the propylene oxide and / or ethylene oxide adduct represented by the general formula (vii) is reacted with the diisocyanate compound or triisocyanate compound represented by the general formula: A ^3- (NCO) j. In the reaction of (1), when both of them are reacted at a temperature of 40 to 90 ° C. using a conventionally known urethanization catalyst such as an organotin catalyst and a tertiary amine catalyst, the desired urethanated acrylic compound (III) is obtained. Can be obtained smoothly.

Then, in the reaction of the above (2), the general formula for reacting with the addition compound represented by the general formula (vii):
The types of the diisocyanate compound and the triisocyanate compound represented by A ^3- (NCO) j are not particularly limited, and both the diisocyanate compound and the triisocyanate compound capable of performing the urethanization reaction can be used. Among them, preferred examples of the diisocyanate compound and the triisocyanate compound include isophorone diisocyanate, tolylene diisocyanate,
4'-diphenylmethane diisocyanate, naphthylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, 3,3'-dichloro-4,
4'-phenylmethane diisocyanate, toluylene diisocyanate, hexamethylene diisocyanate,
4,4′-dicyclohexylmethane diisocyanate,
Examples thereof include hydrogenated xylylene diisocyanate, triphenylmethane triisocyanate, tetramethyl xylene diisocyanate, and hydrogenated 4,4'-diphenylmethane diisocyanate. These isocyanate compounds may be used alone or in combination of two or more. May be used in combination. Among the above isocyanate compounds,
Isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate are particularly preferably used. In that case, a photocured product having a large tensile elongation and excellent flexibility and flexibility, a urethanated acrylic compound (III) is used. Can be obtained from the photocurable resin composition of the present invention.

The groups R ¹ , R ² , R ³ , R ⁴ , R ⁵ in the urethanized acrylic compound (I), the urethanized acrylic compound (II) and the urethanized acrylic compound (III),
Types of A ¹ , A ² , A ³ , a, b, c, d, e, f, g,
The properties and the like of the urethane-modified acrylic compound vary depending on the number of h and j, but generally, the urethane-modified acrylic compound (I), the urethane-modified acrylic compound (II) and the urethane-modified acrylic compound (III) are all at room temperature. Is a low-viscosity liquid to a high-viscosity liquid, and a low-viscosity photocurable resin composition having excellent handleability is prepared by selecting an appropriate radical-polymerizable compound (b) and combining them. You can The photocurable resin composition of the present invention contains, as the urethanized acrylic compound, only one of the urethanized acrylic compound (I), the urethanized acrylic compound (II) and the urethanized acrylic compound (III). Or, you may contain 2 or more types.

The photocurable resin composition of the present invention is
It contains a radical polymerizable compound (b) together with at least one of the urethane-modified acrylic compound (I), the urethane-modified acrylic compound (II) and the urethane-modified acrylic compound (III). Radical polymerizable compound (b)
As, a radical having a carbon-carbon unsaturated bond capable of reacting with a urethanated acrylic compound when irradiated with light and reacting radically polymerizable compounds (b) with each other to form a cured product. Any polymerizable compound can be used, but acrylic compounds and / or allyl compounds are preferably used. Also,
The radically polymerizable compound (b) may be either a monofunctional compound or a polyfunctional compound, or both the monofunctional compound and the polyfunctional compound may be used in combination. Further, the radically polymerizable compound (b) may be a low molecular weight monomer or oligomer, or may have a somewhat high molecular weight in some cases. The photocurable resin composition of the present invention may contain only one kind of radical polymerizable compound as the radical polymerizable compound (b) or may contain two or more kinds of radical polymerizable compounds. Good.

Although not limited, examples of the radically polymerizable compound that can be used as the radically polymerizable compound (b) in the photocurable resin composition of the present invention include isobornyl (meth) acrylate and bornyl (meth). Methacrylate, dicyclopentenyl (meth) acrylate, 2
(Meth) acrylates such as -hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (poly) propylene glycol mono (meth) acrylate, t-butyl (meth) acrylate,
(Meth) acrylamides such as morpholine (meth) 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 (meth) acrylate, triethylene glycol (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth)
Mention may be made of polyfunctional radically polymerizable compounds such as acrylate, dicyclopentenyl di (meth) acrylate, diallyl phthalate, diallyl fumarate and ethylene oxide modified bisphenol A diacrylate.

In addition to the radically polymerizable compounds described above, other than epoxy compounds, urethane-containing acrylic compounds (I) to urethane-containing acrylic compounds (III) which have been conventionally used in resin compositions for optical three-dimensional modeling, etc. Can be used as a radically polymerizable compound (b) such as a urethane-modified acrylic compound, an epoxy (meth) acrylate compound, or another ester (meth) acrylate.

In the photocurable resin composition of the present invention, as the radically polymerizable compound (b), one or more of the above radically polymerizable compounds can be used. Among the various radically polymerizable compounds described above, morpholine (meth) acrylamide and ethylene oxide-modified bisphenol A diacrylate are more preferably used in the photocurable resin composition of the present invention,
In that case, when cured by light, a molded product or a three-dimensional molded product having a smaller volumetric shrinkage ratio and being superior in dimensional accuracy, and further being excellent in flexibility, elastic recovery and mechanical properties,
Furthermore, a photocurable resin composition that can be used as another cured product can be obtained.

In the photocurable resin composition of the present invention, {weight of urethanized acrylic compound (I), urethanized acrylic compound (II) and / or urethanized acrylic compound (III) (containing two or more kinds) In that case, the total weight)}: {Weight of radically polymerizable compound (b)}
Is required to be 80:20 to 10:90, and 6
It is preferably 5:35 to 25:75, and 60: 4.
It is more preferably 0 to 35:65. In the photocurable resin composition, a urethanated acrylic compound (I)
The ratio of (III) is from the urethane-modified acrylic compound (I) to
When it is less than 10% by weight based on the total weight of (III) and the radical-polymerizable compound (B), a cured product having flexibility when cured by light cannot be obtained, while when it exceeds 80% by weight, photocuring occurs. The cured product obtained as a result has reduced tear resistance and reduced elastic recovery so that it does not return to its original shape even when stress is removed from the outside when a modified stress is applied from the outside. If the viscosity of the product becomes too high,
Moldability and formability are reduced, and particularly when used in an optical three-dimensional molding method, a target three-dimensional molded object cannot be produced smoothly.

Further, the photocurable resin composition of the present invention comprises
The above-mentioned urethane-modified acrylic compound (I), urethane-modified acrylic compound (II) and / or urethane-modified acrylic compound (III), and radical-polymerizable compound (II)
In addition, it contains a photopolymerization initiator. As the photopolymerization initiator, any photoradical polymerization initiator conventionally used in photocurable resin compositions can be used and is not particularly limited. Although not limited, examples of the photopolymerization initiator that can be used in the photocurable resin of the present invention include:
2,2-dimethoxy-2-phenylacetophenone, diethoxyacetophenone, acetophenone, 3-methylacetophenone, 2-hydroxymethyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-propiophenone , 2-hydroxy-2-methyl-propiophenone, p-dimethylaminoacetophenone, p-t-butyldichloroacetophenone, p-
t-Butyltrichloroacetophenone, p-azidobenzalacetophenone, 1-hydroxycyclohexylphenylketono, benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, xanthone, fluorenone, benzaldehyde, anthraquinone, triphenyl Examples thereof include amine and carbazole.

When a compound having a radically polymerizable group and a cationically polymerizable group such as an epoxy group is used as the radically polymerizable compound (b), a photocationic polymerization initiator together with the above-mentioned radical photopolymerization initiator is used. May be used in combination, and the type of photocationic polymerization initiator in that case is not particularly limited, and conventionally known ones can be used.

The amount of the photopolymerization initiator to be used may vary depending on the types of the urethanated acrylic compounds (I) to (III) and the radical-polymerizable compound (b), the type of the photopolymerization initiator, etc. Urethaned acrylic compound (I),
It is preferably 0.1 to 10% by weight, and more preferably 1 to 5% by weight, based on the total weight of the urethane acrylate compound (II) and / or the urethan acrylate compound (III) and the radical polymerizable compound (b). Is more preferable.

The photocurable resin composition of the present invention contains, in addition to the above-mentioned components, a leveling agent, a surfactant, an organic polymer modifier, an organic plasticizer, organic or inorganic solid fine particles, if necessary. Etc. may be contained. Examples of the organic solid particles described above include crosslinked polystyrene-based particles, crosslinked polymethacrylate-based particles, polyethylene-based particles, polypropylene-based 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 treated with the silane coupling agent are contained, the acrylic acid-based compound is used in an amount of 1 to 10
It is preferable to use polyethylene-based solid fine particles and / or polypropylene-based solid fine particles that have been copolymerized at about wt% because the affinity with the silane coupling agent is high.

The viscosity of the photocurable resin composition of the present invention can be adjusted according to the application and the mode of use, but it is generally room temperature (25 ° C.) when measured with a rotary B-type viscometer.
Is preferably about 100 to 100,000 centipoise (cp) from the viewpoint of handleability, moldability, three-dimensional molding property, and the like, and more preferably about 300 to 50,000 cp. In particular, when the photocurable resin composition of the present invention is used for optical three-dimensional molding, the viscosity at ordinary temperature described above should be kept in the range of 300 to 5,000 cp, which is an optical handling when producing a three-dimensional molded object. This is desirable in that the properties can be improved and the 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 types of the urethanated acrylic compounds (I) to (III) and the radically polymerizable compound (b) and adjusting the mixing ratio thereof.

When the photocurable resin composition of the present invention is stored in a state where it can block light, it is usually stored 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 is a molded article or a three-dimensional molded article which is excellent in its characteristics, particularly in volume curing when it is cured by light and has excellent dimensional accuracy and flexibility, elastic recovery and mechanical properties. It can be used for various purposes by taking advantage of the property that a molded product, and other cured products can be obtained. For example, production of a three-dimensional molded product by an optical three-dimensional molding method, casting molding method, casting, etc. It can be used for the production of various molded products such as a film-shaped product or a molded product according to the above, coating, and a vacuum molding die.

Among them, the photocurable resin composition of the present invention is suitable for use in the above-mentioned optical three-dimensional molding method. In that case, the dimension of the photocurable resin composition is maintained while keeping the volume shrinkage ratio at the time of photocuring small. It is possible to smoothly manufacture a three-dimensional molded article that is excellent in accuracy and is excellent in flexibility, elastic recovery and mechanical properties. 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, 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 as light energy for curing the resin, Laser beams are 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 modeling time, and furthermore, by utilizing the good condensing property of the laser beam,
It is possible to obtain a three-dimensional object with high modeling accuracy.

As described above, in carrying out optical three-dimensional modeling using the photocurable resin composition of the present invention, any conventionally known method or conventionally known stereolithography system apparatus can be adopted without any particular limitation. However, as a typical example of the optical three-dimensional modeling method preferably used in the present invention, a cured layer is prepared by selectively irradiating the photocurable resin composition with active energy rays so that a cured layer having a desired pattern can be obtained. And then supplying an uncured liquid photocurable resin composition to the cured layer, and similarly irradiating active energy rays to form a cured layer continuous with the above-described cured layer. A method of finally obtaining a desired three-dimensional shaped article by repeating the method can be mentioned. In addition, even if the three-dimensional molded object obtained thereby is used as it is, or in some cases, post-curing by light irradiation or post-curing by heat is performed to further improve its mechanical properties and shape stability. It may be used.

At this time, the structure, shape, size, etc. of the three-dimensional molded article are not particularly limited and can be determined according to each application. Typical application fields of the optical three-dimensional modeling method of the present invention include a model for verifying an external design during a design, a model for checking the functionality of parts, and a resin for producing a mold. Examples include the production of a mold, a base model for producing a mold, and a direct mold for a prototype mold. More specifically, precision parts,
The production of models and processing models for electric / electronic parts, furniture, building structures, automobile parts, various containers, castings, dies, mother dies, etc., especially its flexibility and elasticity Utilizing the property of recoverability, it can be used very effectively in applications such as a cushion material having a complicated shape in a structure and a vacuum molding die.

[0068]

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 Urethaned Acrylic Compound (I)] (1) 2-hydroxy was placed in a four-necked flask having an internal volume of 4 liters equipped with a stirrer, a temperature controller, a thermometer and a condenser. 400 g of ethyl acrylate and 1572 g of ε-caprolactone are added and the temperature is 100-150 with stirring.
C. for 8 hours to give a caprolactone adduct represented by the above general formula (iii) [in the general formula (iii), R ¹ =
Hydrogen, compounds with a = 1, b = 5 and c = 4]. (2) A 4-liter four-necked flask equipped with a stirrer, a temperature controller, a thermometer, and a condenser, which was obtained in the above (1), and which was different from the one used in the above (1). Caprolactone adduct 1976 g, hydroquinone monomethyl ether 0.998 g, di-n-butyltin dilaurate 0.
68 g and isophorone diisocyanate (320 g) were added and reacted at 40-50 ° C. for 30 minutes.
Further reaction was performed at 90 ° C. As a result, it was colorless and at room temperature (2
(5 ° C.) to give a viscous liquid product. (3) When the chemical structure of the product obtained in the above (2) was determined, it was found that the product was obtained by NMR measurement at 1.3839 pp.
m, 1.6414 ppm, 1.6439 ppm, 2.3
At 055 ppm, 4.0505 ppm, absorption based on a lactone, and further, at 0.8 to 1.8 ppm, absorption based on the isophorone group of the multilet was observed, and at 5.8 to 6.5 ppm, absorption based on an acrylate double bond was observed. Also, IR
By measurement, characteristic absorption of urethane bond was observed at 1700 cm ⁻¹ and 1540 cm ^−1, and the urethane-modified acrylic compound (I) represented by the above general formula (I) [in the general formula (I), R ¹ = hydrogen, A ¹ = isophorone group, a = 1, b =
5, c = 4 and d = 2].

<Synthesis Example 2> [Production of Urethaned Acrylic Compound (I)] A four-necked flask having an internal volume of 4 liters equipped with a stirrer, a temperature controller, a thermometer and a condenser was used. 1972 g of the caprolactone adduct obtained in), 0.44 g of hydroquinone monomethyl ether, and di-n-dilauryl acid.
After adding 0.67 g of butyltin and 250 g of tolylene diisocyanate, the mixture was reacted at 40 to 50 ° C for 30 minutes and then further reacted at a temperature of 80 to 90 ° C. As a result, a colorless product having a viscous liquid state at room temperature (25 ° C.) was obtained [in the urethanated acrylic compound (I) represented by the general formula (I), R ¹ = hydrogen, A ¹ = Tolylene group,
Compounds in which a = 1, b = 5, c = 4 and d = 2]

<< Synthesis Example 3 >> [Production of Urethaned Acrylic Compound (I)] (1) 2-hydroxy was placed in a four-necked four-necked flask equipped with a stirrer, a temperature controller, a thermometer and a condenser. 400 g of ethyl acrylate and 2359 g of ε-caprolactone are added and the mixture is stirred at a temperature of 100-150.
C. for 8 hours to give a caprolactone adduct represented by the above general formula (iii) [in the general formula (iii), R ¹ =
Hydrogen, compounds with a = 1, b = 5 and c = 6]. (2) A 4-liter four-necked flask equipped with a stirrer, a temperature controller, a thermometer, and a condenser, which was obtained in the above (1), and which was different from the one used in the above (1). Caprolactone adduct 2819 g, hydroquinone monomethyl ether 0.63 g, di-n-butyltin dilaurate 0.9
4 g and 326 g of isophorone diisocyanate were added and reacted at 40 to 50 ° C. for 30 minutes.
By further reacting at 90 ° C., the urethanated acrylic compound (I) represented by the above general formula (I) [in the general formula (I), R ¹ = hydrogen, A ¹ = isophorone group, a = 1, b = 5,
Compounds with c = 6 and d = 2] were prepared.

<< Synthesis Example 4 >> [Production of Urethane-Contained Acrylic Compound (II)] 2-Hydroxyethyl acrylate propylene was placed in a 4-liter four-necked flask equipped with a stirrer, a temperature controller, a thermometer and a condenser. Oxide adduct [Nippon Yushi-Seiyaku Co., Ltd. "Blenmer 10APE-550B"; in the compound represented by the above general formula (vi), R ² = H, R ³ =
CH ₃ , compound with e = 1, f = 9] 1492 g, hydroquinone monomethyl ether 0.63 g, di-n-butyltin dilaurate 0.51 g and isophorone diisocyanate 222 g were added and reacted at 40 to 50 ° C. for 30 minutes. Then, the reaction is further carried out at a temperature of 80 to 90 ° C. to give a urethane-modified acrylic compound (II) [in the general formula (II), R
² = _{^{hydrogen, R 3 = CH 3, A}} 2 = isophorone group, e = 1, f
= 9 and compounds of g = 2] were prepared.

[Synthesis Example 5] [Production of urethane-modified acrylic compound (III)] A propylene oxide adduct of acrylic acid was added to a 4-necked four-necked flask equipped with a stirrer, a temperature controller, a thermometer and a condenser. [Nippon Oil & Fat Co., Ltd. "Blemmer A
P-550 "; a compound represented by the above general formula (vii) wherein R ⁴ ＨH, R ⁵ ＣＨCH ₃ , and h = 10] 1
517 g, hydroquinone monomethyl ether 1.00
g, di-n-butyltin dilaurate (0.52 g) and isophorone diisocyanate (222 g).
After reacting at 50 ° C. for 30 minutes, the reaction is further allowed to proceed at a temperature of 80 to 90 ° C. to give a urethane-modified acrylic compound (III) [in the general formula (III), R ⁴ = hydrogen, R ⁵ = CH ₃ , A ³ = isophorone. Groups, compounds with h = 10 and j = 2] were prepared.

<< Synthesis Example 6 >> [Production of Urethane-Contained Acrylic Compound] (1) 382 g of 2-hydroxyethyl acrylate was placed in a 4-necked 4-necked flask equipped with a stirrer, a temperature controller, a thermometer and a condenser. And ε-caprolactone 751 g are added, and the temperature is 100 to 150 ° C. with stirring.
For 8 hours to obtain a compound having a structure similar to the caprolactone adduct represented by the above general formula (iii) [in the general formula (iii), R ¹ = hydrogen, a = 1, b = 5 and c = 2) was produced. (2) A 4-liter four-necked flask equipped with a stirrer, a temperature controller, a thermometer, and a condenser, which was obtained in the above (1), and which was different from the one used in the above (1). Caprolactone adduct 1133 g, hydroquinone monomethyl ether 0.28 g, di-n-butyltin dilaurate 0.4
3 g and 305 g of isophorone diisocyanate were added and reacted at 40 to 50 ° C. for 30 minutes.
Further reaction was performed at 90 ° C. As a result, it is colorless and at room temperature (25
A product having a viscous liquid state was obtained at [° C.] [in the above general formula (I), R ¹ = hydrogen, A ¹ = isophorone group, a
= 1, b = 5, c = 2 and d = 2, and is not included in any of the urethanated acrylic compound (I) to urethanated acrylic compound (III) of the present invention].

[Synthesis Example 7] [Production of urethane-modified acrylic compound] (1) 116 g of 2-hydroxyethyl acrylate was placed in a four-necked four-necked flask equipped with a stirrer, a temperature controller, a thermometer and a condenser. And 1710 g of ε-caprolactone are added and the temperature is kept at 100-150 with stirring.
A compound having a structure similar to the caprolactone adduct represented by the above-mentioned general formula (iii) by reacting at 8 ° C. for 8 hours [in the general formula (iii), R ¹ = hydrogen, a = 1, b = 5 and c = 15] was produced. (2) Obtained in (1) above in a four-liter four-necked flask having an internal volume of 4 liters equipped with a stirrer, a temperature controller, a thermometer and a condenser different from the one used in (1) above. Caprolactone adduct 1826 g, hydroquinone monomethyl ether 0.38 g, dilaurylate di-n-butyltin 0.5
After adding 8 g and 93 g of isophorone diisocyanate and reacting at 40 to 50 ° C. for 30 minutes, a temperature of 80 to
Further reaction was performed at 90 ° C. As a result, it is colorless and at room temperature (25
A product having a viscous liquid state was obtained at [° C.] [in the above general formula (I), R ¹ = hydrogen, A ¹ = isophorone group, a
= 1, b = 5, c = 15 and d = 2, which are not included in any of the urethanated acrylic compound (I) to urethanated acrylic compound (III) of the present invention].

Example 1 [Preparation of Photocurable Resin Composition] The urethane obtained in Synthesis Example 1 was placed in a three-necked flask having an internal volume of 5 liters equipped with a stirrer, a cooling tube and a dropping funnel with a side tube. 1300 g of the acrylic compound (I) and 1200 g of morpholine acrylamide (“NK Ester A-MO” manufactured by Shin-Nakamura Chemical Co., Ltd.) were charged, and the atmosphere was replaced by degassing under reduced pressure. Then, 120 g of 2,2-dimethoxy-2-phenylacetophenone (“Irgacure 651” manufactured by Ciba-Geigy; photo-radical polymerization initiator) was added in an environment shielded from ultraviolet rays, and the temperature was 25 ° C. until completely dissolved.
And agitating (mixing and agitating time of about 1 hour), and a photocurable resin composition containing a urethanated acrylic compound (I), which is a colorless transparent viscous liquid (viscosity of about 390 at room temperature).
cp) was obtained.

Example 2 Preparation of Photocurable Resin Composition Example 1 except that 1300 g of the urethanized acrylic compound (I) obtained in Synthesis Example 2 was used as the urethanized acrylic compound (I). When a photocurable resin composition was prepared in the same manner, a photocurable resin composition (viscosity at room temperature, about 430 cp) which was a colorless transparent viscous liquid containing the urethanated acrylic compound (I) was obtained.

Example 3 Preparation of Photocurable Resin Composition Example 1 except that 1300 g of the urethanized acrylic compound (I) obtained in Synthesis Example 3 was used as the urethanized acrylic compound (I). When a photocurable resin composition was prepared in the same manner, a photocurable resin composition (viscosity at room temperature, about 600 cp) which was a colorless transparent viscous liquid containing the urethanated acrylic compound (I) was obtained.

Example 4 Preparation of Photocurable Resin Composition The urethane obtained in Synthesis Example 4 was placed in a three-necked flask having an internal volume of 5 liters equipped with a stirrer, a cooling tube and a dropping funnel with a side tube. Acrylic compound (II) 1300 g, Example 1
Same morpholine acrylamide 1200 used in
g was charged and degassed with nitrogen under reduced pressure. Then, under the environment where ultraviolet rays are blocked, the same 2,2 used in Example 1 is used.
-Add 120 g of dimethoxy-2-phenylacetophenone (photoradical polymerization initiator), stir at a temperature of 25 ° C. until completely dissolved (mixing stirring time about 1 hour),
A photocurable resin composition (viscosity of about 430 cp at room temperature), which was a colorless and transparent viscous liquid containing the urethanated acrylic compound (II), was obtained.

Example 5 [Preparation of Photocurable Resin Composition] Synthesis Example 5 was used instead of the urethanated acrylic compound (II).
Urethaned acrylic compound (III) 1300 obtained in
A photocurable resin composition was prepared in the same manner as in Example 4 except that g was used.
A photocurable resin composition (viscosity at room temperature of about 380 cp) which was a colorless and transparent viscous liquid containing I) was obtained.

Comparative Example 1 [Preparation of Photocurable Resin Composition] Instead of the urethanated acrylic compound (I) used in Example 1, 1300 g of the urethanized acrylic compound obtained in Synthesis Example 6 was used. A photocurable resin composition was prepared in the same manner as in Example 1 except that the photocurable resin composition was a colorless transparent viscous liquid (viscosity at room temperature was about 400c.
p) was obtained.

Comparative Example 2 [Preparation of Photocurable Resin Composition] Instead of the urethanized acrylic compound (I) used in Example 1, 1300 g of the urethanized acrylic compound obtained in Synthesis Example 7 was used. A photocurable resin composition was prepared in the same manner as in Example 1 except that the obtained photocurable resin composition was in the form of a thick paste and had no fluidity.

Example 6 [Production of Photocured Molded Article by Molding Method] (1) Prepared in Example 1 above into a transparent silicon mold having a mold cavity in the form of a dumbbell test piece conforming to JIS 7113. Urethaned acrylic compound (I)
After injecting a photo-curable resin composition containing the above, a dumbbell-shaped molded article in which the resin composition is cured by irradiating the entire surface of the silicon mold with ultraviolet rays for 15 minutes using a 30 W ultraviolet lamp to cure the resin composition Manufactured. The obtained molded product (dumbbell-shaped test piece) was taken out from the mold, and JIS K 7
The tensile properties (tensile strength, tensile elongation and tensile elastic modulus) were measured according to 113, and Table 1 below was obtained.
It was as shown in. (2) Further, when the elastic recovery of the dumbbell-shaped test piece obtained in (1) above was evaluated as follows, it was as shown in Table 1 below.

Evaluation of elastic recovery of dumbbell-shaped test pieces
Method : After dumbbell-shaped test piece (molded product or three-dimensional molded item) is completely folded in half by hand at the center in the lengthwise direction and kept as it is for 10 minutes,
When the bent state is released and the original flat dumbbell shape is restored at that time, it is good (○), and when the original flat dumbbell shape is not restored and the bent state remains, or when it cannot be bent. It was evaluated as defective (x).

(3) Furthermore, the specific gravity (d ₁ ) of the photocurable resin composition used for molding in Example 6 before photocuring and the specific gravity of the obtained molded product (dumbbell-shaped test piece). Each (d ₂ ) was measured, and the volumetric shrinkage rate (%) was determined by the following mathematical expression (1). The results are shown in Table 1 below.

[0086]

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

<Example 7> [Production of three-dimensional model by optical three-dimensional model] Using the photocurable resin composition containing the urethanated acrylic compound (I) obtained in Example 1 above, Ultra-fast stereolithography system ("SOLIFOR" manufactured by Teijin Seiki Co., Ltd.
M500 "), water-cooled Ar laser light (output 5
00 mW; wavelength 333, 354, 364 nm) and perform stereolithography under the conditions of irradiation energy of 20 to 30 mJ / cm ^{2 with} a slice pitch (lamination thickness) of 0.127 mm and an average shaping time of 2 minutes per layer. JIS 71
A dumbbell test piece-shaped three-dimensional object conforming to No. 13 was manufactured. The obtained three-dimensional molded product was washed with isopropyl alcohol to remove the uncured resin liquid adhering to the three-dimensional molded product, and then post-cured by irradiating 3 KW of ultraviolet light for 10 minutes. The tensile properties (tensile strength, tensile elongation and tensile modulus) of the resulting three-dimensional model (dumbbell-shaped test piece) were measured according to JISK 7113, and the results are shown in Table 1 below. . The elastic recovery of the post-curing dumbbell-shaped test piece (three-dimensional molded article) obtained as described above was evaluated in the same manner as in Example 6, and the results are shown in Table 1 below. Furthermore, the specific gravity (d ₁ ) of the photocurable resin composition before photocuring and the specific gravity (d ₂ ) of the three-dimensional model after post-curing used in the three-dimensional modeling method of Example 7 were measured, When the volumetric shrinkage rate (%) was calculated by the above mathematical formula (1), the following Table 1 was obtained.
It was as shown in.

<Example 8> [Production of three-dimensional model by optical three-dimensional model] Other than using the photocurable resin composition containing the urethanated acrylic compound (I) obtained in Example 2 above. In the same manner as in Example 7, optical three-dimensional modeling, uncured resin washing and post-curing were performed to manufacture a three-dimensional model (dumbbell-shaped test piece). The resulting dumbbell-shaped test piece (three-dimensional molded article) was measured or evaluated for tensile properties, elastic recovery and volumetric shrinkage in the same manner as in Example 7, and the results are shown in Table 1 below.

<Example 9> [Production of three-dimensional object by optical three-dimensional method] Other than using the photocurable resin composition containing the urethanated acrylic compound (I) obtained in Example 3 above. In the same manner as in Example 7, optical three-dimensional modeling, uncured resin washing and post-curing were performed to manufacture a three-dimensional model (dumbbell-shaped test piece). The resulting dumbbell-shaped test piece (three-dimensional molded article) was measured or evaluated for tensile properties, elastic recovery and volumetric shrinkage in the same manner as in Example 7, and the results are shown in Table 1 below.

Example 10 Production of Photocured Molded Article by Molding Method Using the photocurable resin composition containing the urethanated acrylic compound (II) obtained in Example 4 above, a photocurable resin composition was prepared. Dumbbell test piece-shaped molds conforming to JIS 7113 were filled in the same manner as in Example 6 and filled in a transparent silicone mold having cavities, and light-cured in the same manner as in Example 6 to obtain dumbbell test piece-shaped molded articles. Manufactured. The resulting dumbbell-shaped test piece (molded article) was evaluated for tensile properties, elastic recovery and volumetric shrinkage in the same manner as in Example 6, and the results are shown in Table 1 below.

<Example 11> [Production of three-dimensional model by optical three-dimensional model] Other than using the photocurable resin composition containing the urethanated acrylic compound (II) obtained in Example 4 above. In the same manner as in Example 7, optical three-dimensional modeling, uncured resin washing and post-curing were performed to manufacture a three-dimensional model (dumbbell-shaped test piece). The resulting dumbbell-shaped test piece (three-dimensional molded article) was measured or evaluated for tensile properties, elastic recovery and volumetric shrinkage in the same manner as in Example 7, and the results are shown in Table 1 below.

Example 12 Production of Photocured Molded Article by Molding Method The photocurable resin composition containing the urethanated acrylic compound (III) obtained in Example 5 was used. Dumbbell test piece-shaped molds conforming to JIS 7113 were filled in the same manner as in Example 6 and filled in a transparent silicone mold having cavities, and light-cured in the same manner as in Example 6 to obtain dumbbell test piece-shaped molded articles. Manufactured. The resulting dumbbell-shaped test piece (molded product) was tested for tensile properties, elastic recovery and volumetric shrinkage in Example 6
It was as shown in Table 1 below.

<Example 13> [Production of three-dimensional object by optical three-dimensional method] Other than using the photocurable resin composition containing the urethanated acrylic compound (III) obtained in Example 5 above. In the same manner as in Example 7, optical three-dimensional modeling, uncured resin washing and post-curing were performed to manufacture a three-dimensional model (dumbbell-shaped test piece). The resulting dumbbell-shaped test piece (three-dimensional molded article) was measured or evaluated for tensile properties, elastic recovery and volumetric shrinkage in the same manner as in Example 7, and the results are shown in Table 1 below.

<Comparative Example 3> [Production of three-dimensional modeled article by optical three-dimensional modeling method] Optically produced in the same manner as in Example 7 except that the photocurable resin composition obtained in Comparative Example 1 was used. Three-dimensional modeling, washing of uncured resin, and post-curing were performed to manufacture a three-dimensional model (dumbbell-shaped test piece). The resulting dumbbell-shaped test piece (three-dimensional molded article) was measured or evaluated for tensile properties, elastic recovery and volumetric shrinkage in the same manner as in Example 7, and the results are shown in Table 1 below.

Comparative Example 4 [Production of Photocured Molded Article by Molding Method] Using the thick paste-like photocurable resin composition obtained in Comparative Example 2 as in Example 6. Similarly, a transparent silicon mold having a mold cavity in the shape of a dumbbell test piece conforming to JIS 7113 was filled, and Example 6 was used.
Light curing was carried out in the same manner as described above to produce a dumbbell test piece-shaped molded article. The tensile properties, elastic recoverability and volumetric shrinkage of the resulting dumbbell-shaped test piece (molded product) were determined in the same manner as in Example 6,
The results are shown in Table 1 below.

[0096]

[Table 1]

From the results shown in Table 1 above, the photocurable resins of Examples 1 to 5 containing the urethanized acrylic compound (I), the urethanized acrylic compound (II) or the urethanized acrylic compound (III). Examples 6 to 13 in which a molded article or a three-dimensional molded article is manufactured using the composition
In the case of, the molded product or three-dimensional molded product of high quality, which has a large tensile elongation, excellent flexibility, elastic recovery, and tensile strength, has a low volumetric shrinkage and dimensional accuracy. It turns out that you can get it well.

On the other hand, in the case of Comparative Example 3, c = 2 in the urethanated acrylic compound represented by the above general formula (I), and the urethanated acrylic compound (I) to urethane of the present invention were used. By using the photocurable resin composition of Comparative Example 1 containing a urethanized acrylic compound that is not included in any of the acrylated acrylic compounds (III), the three-dimensional molded article obtained there has a very small tensile elongation. And lacks flexibility, is hard and brittle, and has a large volume shrinkage.

Further, from the results of Comparative Examples 2 and 4 described above, in the urethanated acrylic compound represented by the above general formula (I), c = 15 and the urethanated acrylic compound (I) of the present invention is obtained. ~ The photocurable resin composition of Comparative Example 2 containing a urethanized acrylic compound that is not included in any of the urethanized acrylic compounds (III) has high viscosity and does not exhibit a liquid state, and thus is difficult to mold. Moreover, it cannot be used in the optical three-dimensional molding method, and in addition, the molded product obtained from the photocurable resin composition of Comparative Example 2 has a very small tensile elongation and is not flexible, and further has a tensile elastic modulus. It can be seen that is low and brittle.

[0100]

EFFECTS OF THE INVENTION The photocurable resin composition of the present invention exhibits a low-viscosity liquid, has excellent handleability, and can be cured in a short curing time. Therefore, various molded products and three-dimensional molded products produced by the light irradiation method can be used. And the production of various molded products by the molding method. And, when the photocurable resin composition of the present invention is used, the volume shrinkage is small when cured by light, it is possible to obtain a molded article or a three-dimensional molded article excellent in dimensional accuracy, and thereby The obtained cured products such as molded products and three-dimensional molded products are also excellent in flexibility, elastic recovery and mechanical properties such as tensile strength and tensile elongation. Can be used for

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yasushi Ishihama 687 Arimoto, Wakayama, Wakayama Shin-Nakamura Kagaku Kogyo Co., Ltd. Industry Co., Ltd.

Claims (5)

[Claims] 1. (a) The following general formula (I); (Wherein, R ¹ is a hydrogen atom or a methyl group, a is 1 or 2, and when a is 2, one or both of R ¹ are methyl groups, and A ¹ is a divalent or trivalent non-valent group. A substituted or substituted hydrocarbon group, b is an integer of 3 to 6, c is 3
An integer of from 1 to 14, and d is 2 or 3); a urethane-containing acrylic compound represented by the following general formula (II): (Wherein, R ² and R ³ are each independently a hydrogen atom or a methyl group, e is 1 or 2, and when e is 2, one or both R ² are methyl groups, and A ² is A divalent or trivalent unsubstituted or substituted hydrocarbon group,
Is an integer of 4 to 20, and g is 2 or 3); and a urethanated acrylic compound represented by general formula (III) below; (Wherein, R ⁴ and R ⁵ are each independently a hydrogen atom or a methyl group, A ³ is a divalent or trivalent unsubstituted or substituted hydrocarbon group, h is an integer of 4 to 20, And j is 2 or 3) a urethane acrylate compound selected from at least one of the following urethane acrylate compounds: (b) a radical polymerizable compound other than the urethan acrylate compound of (a) And (c) a photocurable resin composition containing a photopolymerization initiator, wherein the content ratio of the acrylic urethane compound (a): the radical polymerizable compound (b) is 80:20.
10:90 (weight ratio), The photocurable resin composition characterized by the above-mentioned. 2. Based on the total weight of the acrylic urethane compound of (a) and the radical polymerizable compound of (ii),
The photocurable resin composition according to claim 1, wherein the proportion of the photopolymerization initiator is 0.1 to 10% by weight. 3. The photocurable resin composition according to claim 1, which is a resin composition for optical three-dimensional modeling. 4. A method for producing a three-dimensional object by the optical three-dimensional method using the photocurable resin composition according to claim 3. 5. The following general formula (I); (Wherein, R ¹ is a hydrogen atom or a methyl group, a is 1 or 2, and when a is 2, one or both of R ¹ are methyl groups, and A ¹ is a divalent or trivalent non-valent group. A substituted or substituted hydrocarbon group, b is an integer of 3 to 6, c is 3
To an integer of 14 and d is 2 or 3); a urethanated acrylic compound represented by the following general formula (II); (Wherein, R ² and R ³ are each independently a hydrogen atom or a methyl group, e is 1 or 2, and when e is 2, one or both R ² are methyl groups, and A ² is A divalent or trivalent unsubstituted or substituted hydrocarbon group,
Is an integer of 4 to 20 and g is 2 or 3); or a urethanated acrylic compound represented by the following general formula (III); (In the formula, R ⁴ and R ⁵ are each independently a hydrogen atom or a methyl group, A ³ is a divalent or trivalent unsubstituted or substituted hydrocarbon group, h is an integer of 4 to 20, And j is 2 or 3).