JP2006028499A - Photocurable resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photocurable resin composition which exhibits a small volumetric shrinkage and excellent dimensional accuracy in curing, and gives a three dimensionally shaped article and molded article with excellent softness, elastic recovery, and mechanical characteristics, etc. <P>SOLUTION: The invention relates to the photocurable resin composition comprising (a) a urethanized acrylic compound comprising at least one kind of specific polyether-based urethanized acrylic compound or a urethanized acrylic compound comprising at least one of the polyether-based urethanized acrylic compound and a specific polyester-based urethanized acrylic compound, (b) other radically polymerizable compound, and (c) a photopolymerization initiator, and the weight ratio of the urethanized acrylic compound (a): the radically polymerizable compound (b) is 80:20 to 10:90. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

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

In general, liquid photocurable resin compositions are widely used as coating materials, photoresists, dental materials, etc. In recent years, photocurable resin compositions have been three-dimensionally based on data input to three-dimensional CAD. The method of optical molding is attracting attention.
Regarding the optical three-dimensional modeling technology, the liquid photocurable resin is supplied with a required amount of controlled light energy to be cured into a thin layer, and further supplied with the liquid photocurable resin, then the light is controlled. An optical three-dimensional modeling method for manufacturing a three-dimensional model by repeating the process of irradiating and curing in a thin layer is disclosed (see Patent Document 1), and a basic practical method has been further proposed (patent) Reference 2). Since then, many proposals regarding optical three-dimensional modeling technology have been made (see, for example, Patent Documents 3 to 10).

  As a typical method for optically producing a three-dimensional model, an ultraviolet laser controlled by a computer is selected so that a desired pattern can be obtained on the liquid surface of the liquid photocurable resin composition placed in a container. And then cured to a predetermined thickness, and then a liquid resin composition for one layer was supplied on the cured layer and irradiated with an ultraviolet laser in the same manner to be cured in the same manner as described above to be continuous. A method of manufacturing a three-dimensional modeled object having a final shape by repeating a stacking operation of forming a hardened layer is widely used. In the case of this method, since a desired three-dimensional object can be manufactured easily and in a relatively short time even if the shape of the object is quite complicated, it has attracted much attention in recent years.

  Photocurable resin compositions used for coating materials, photoresists, dental materials, etc. include curable resins such as unsaturated polyester, epoxy (meth) acrylate, urethane (meth) acrylate, and (meth) acrylic acid ester monomers. What added the photoinitiator is used widely.

  Moreover, as a photocurable resin composition used in the optical three-dimensional modeling method, a photopolymerizable modified urethane (meth) acrylate compound, an oligoester acrylate compound, an epoxy acrylate compound, an epoxy compound, a polyimide compound, Examples include those containing one or more photopolymerizable compounds such as aminoalkyd compounds and vinyl ether compounds as a main component and a photopolymerization initiator added thereto, and various improved techniques have been disclosed recently. (See Patent Document 4, Patent Document 6, Patent Documents 11-15, etc.).

  The photocurable resin composition used in the optical three-dimensional modeling method is a low-viscosity liquid material from the viewpoints of handleability, modeling speed, modeling accuracy, etc., low volume shrinkage during curing, photocuring Therefore, it is required that the three-dimensional molded object obtained has good mechanical properties. In recent years, the demand and applications of optical three-dimensional objects have been increasing, and depending on the applications, there are demands for three-dimensional objects having high elongation flexibility and elastic recoverability in addition to the above-mentioned characteristics. For example, three-dimensional shaped objects used for applications such as cushion materials with complicated shapes contained in structures and molds for vacuum forming require high flexibility, high elongation, and elastic recovery. Yes.

As a method for producing a flexible optical three-dimensional object, a photo-curable resin containing a heat-aggregating polymer material composed of a vinyl chloride resin powder, a plasticizer, and the like is photocured and optical three-dimensional modeling is performed. There is known a method of thermally coagulating after forming a product (see Patent Document 14).
However, this method has the disadvantage that the viscosity of the resin composition increases because the heat-aggregating polymer is blended in the photocurable resin, and the handleability and modeling accuracy are reduced. In addition, since the plasticizer is used, the mechanical properties such as tear resistance are inferior, and there are problems such as plasticizer migration and oozing on the surface of the three-dimensional structure, which is sufficiently satisfied. The result is not obtained.
In addition, a urethane acrylate resin composition in which caprolactone units are bonded between urethane groups in order to improve the tensile elongation is known (see Patent Document 16), but the cured product has a certain degree of improvement in tensile elongation. However, the flexibility is not enough.

JP 56-144478 A JP 60-247515 A JP-A-62-35966 JP-A-1-204915 Japanese Patent Laid-Open No. 2-113925 Japanese Patent Laid-Open No. 2-145616 JP-A-2-153722 Japanese Patent Laid-Open No. 3-15520 Japanese Patent Laid-Open No. 3-21432 JP-A-3-41126 JP-A-1-213304 JP-A-2-28261 Japanese Patent Laid-Open No. 2-75617 Japanese Patent Laid-Open No. 3-104626 Japanese Patent Laid-Open No. 3-114732 JP-A 61-185522

The object of the present invention is to exhibit a low-viscosity liquid, excellent handleability, can be cured in a short curing time, and when cured by light, has a small volume shrinkage ratio and excellent dimensional accuracy, and also has flexibility and elastic recovery. It is providing the photocurable resin composition which can obtain the molded article, three-dimensional molded item, and other hardened | cured material which are excellent in mechanical characteristics, such as property, tensile strength, and tensile elongation.
And the objective of this invention is a method of manufacturing a molded article by the optical three-dimensional modeling method using said photocurable resin composition.
Furthermore, the objective of this invention is providing the novel urethane acrylic compound which can be used with said photocurable resin composition.

  The inventors of the present invention have repeatedly studied to achieve the above-described object. As a result, a novel urethanized acrylic compound having a specific chemical structure synthesized by the present inventors is extremely effective in achieving the above-mentioned object, and other radical polymerizable compounds and photopolymerization initiation are added to this urethanized acrylic compound. When a liquid is added, a liquid photocurable resin composition having a low viscosity and excellent handleability can be obtained, and when the photocurable resin composition is irradiated with light, it can be cured in a short time, and the volumetric shrinkage It has been found that a three-dimensional structure having a small size, excellent flexibility and elastic recovery having a desired shape and size, and excellent mechanical properties can be obtained with good dimensional accuracy. And the present inventors have found that the above-mentioned photo-curable resin composition can be effectively used not only for the optical three-dimensional modeling method but also for the production of molded products accompanied by curing by light irradiation and other applications. Based on these findings, the present invention has been completed.

    That is, the present invention provides (i) (i) the following general formula (II);

（式中、Ｒ²およびＲ³はそれぞれ独立して水素原子またはメチル基、ｅは１または２であって、ｅが２のときは一方または両方のＲ²がメチル基であり、Ａ²は２価または３価の非置換または置換された炭化水素基であり、ｆは４〜２０の整数、そしてｇは２または３である）
で表されるウレタン化アクリル化合物；および
下記の一般式（III）；

(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 is a methyl group, and A ² is A divalent or trivalent unsubstituted or substituted hydrocarbon group, f is an integer from 4 to 20, and g is 2 or 3)
A urethanized acrylic compound represented by: and the following general formula (III):

（式中、Ｒ⁴およびＲ⁵はそれぞれ独立して水素原子またはメチル基、Ａ³は２価または３価の非置換または置換された炭化水素基であり、ｈは４〜２０の整数、そしてｊは２または３である）
で表されるウレタン化アクリル化合物；
のうちの少なくとも１種から選ばれるウレタン化アクリル化合物；または、
（ii） 前記一般式（II）で表されるウレタン化アクリル化合物および前記一般式（III）で表されるウレタン化アクリル化合物のうちの少なくとも１種から選ばれるウレタン化アクリル化合物と、下記の一般式（Ｉ）；

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 urethanized acrylic compound represented by:
A urethanized acrylic compound selected from at least one of:
(Ii) a urethanized acrylic compound selected from at least one of the urethanized acrylic compound represented by the general formula (II) and the urethanized acrylic compound represented by the general formula (III); Formula (I);

（式中、Ｒ¹は水素原子またはメチル基、ａは１または２であって、ａが２のときは一方または両方のＲ¹がメチル基であり、Ａ¹は２価または３価の非置換または置換された炭化水素基であり、ｂは３〜６の整数、ｃは３〜１４の整数、ｄは２または３である）
で表されるウレタン化アクリル化合物とからなるウレタン化アクリル化合物；
（ロ） 前記（イ）のウレタン化アクリル化合物以外のラジカル重合性化合物;
並びに、
（ハ） 光重合開始剤；
を含有する光硬化性樹脂組成物であって、前記（イ）のアクリルウレタン化合物：前記（ロ）のラジカル重合性化合物の含有割合が８０：２０〜１０：９０（重量比）であることを特徴とする光硬化性樹脂組成物である。

(In the formula, R ¹ is a hydrogen atom or a methyl group, a is 1 or 2, and when a is 2, one or both R ¹ is a methyl group, and A ¹ is a divalent or trivalent non-valent group. A substituted or substituted hydrocarbon group, b is an integer of 3-6, c is an integer of 3-14, d is 2 or 3)
A urethane-modified acrylic compound comprising a urethane-modified acrylic compound represented by:
(B) a radically polymerizable compound other than the urethane-modified acrylic compound of (a);
And
(C) Photopolymerization initiator;
The content ratio of the (a) acrylic urethane compound: (b) radical polymerizable compound is 80:20 to 10:90 (weight ratio). It is the photocurable resin composition characterized.

And this invention is a resin composition for optical three-dimensional model | molding which consists of said photocurable resin composition.
Furthermore, this invention is a method of manufacturing a three-dimensional molded item by the optical three-dimensional modeling method using said resin composition for optical three-dimensional modeling.
And this invention is the following general formula (II);

（式中、Ｒ²およびＲ³はそれぞれ独立して水素原子またはメチル基、ｅは１または２であって、ｅが２のときは一方または両方のＲ²がメチル基であり、Ａ²は２価または３価の非置換または置換された炭化水素基であり、ｆは４〜２０の整数、そしてｇは２または３である）
で表されるウレタン化アクリル化合物；または
下記の一般式（III）；

(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 is a methyl group, and A ² is A divalent or trivalent unsubstituted or substituted hydrocarbon group, f is an integer from 4 to 20, and g is 2 or 3)
Or a urethanated acrylic compound represented by the following general formula (III):

（式中、Ｒ⁴およびＲ⁵はそれぞれ独立して水素原子またはメチル基、Ａ³は２価または３価の非置換または置換された炭化水素基であり、ｈは４〜２０の整数、そしてｊは２または３である）
で表されるウレタン化アクリル化合物である。

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)
It is a urethane-ized acrylic compound represented by these.

The photo-curable resin composition of the present invention exhibits a low-viscosity liquid, is excellent in handleability, and can be cured in a short curing time. It can be effectively used for the production of various molded products by the molding method.
And when the photocurable resin composition of the present invention is used, when it is cured with light, the volume shrinkage rate is small, and a molded article or a three-dimensional modeled article having excellent dimensional accuracy can be obtained, and thereby The cured products such as molded products and three-dimensional molded products are excellent in mechanical properties such as flexibility, elastic recovery, tensile strength, and tensile elongation, and are effective for various applications by taking advantage of these properties. Can be used for

The present invention is described in detail below.
First, the urethanized acrylic compound represented by the above general formula (II) used in the photocurable resin composition of the present invention [hereinafter referred to as “urethane acrylate compound (II)”] and the above general formula (III) The urethanized acrylic compound represented by the following formula [hereinafter referred to as “urethanized acryl compound (III)”].

In the urethanized 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; CH ₂ ═C ( It is necessary that one or both groups R ^{2 of} R ² ) —COO—CH ₂ — is a methyl group. In the urethanized acrylic compound (II), when e is 2, two groups; CH ₂ ═C (R ² ) —COO—CH ₂ — When both groups R ² are hydrogen atoms are extremely toxic in the synthesis Furthermore, it must pass through glycerin diacrylate having carcinogenicity and skin irritation, and it cannot be used substantially, which is not preferable.

  In the urethanized acrylic compound (II), f must be an integer in the range of 4 to 20, preferably an integer in the range of 5 to 14, and an integer in the range of 6 to 10. It is more preferable. When f exceeds 20, the melting point of the urethanized acrylic compound (II) becomes high, and even if a low molecular weight compound is used as the radical polymerizable compound (b), it is excellent in fluidity at room temperature. Further, the tensile elongation and flexibility of a cured product obtained by photocuring are reduced, and a three-dimensional modeled product or a molded product excellent in desired flexibility and elastic recovery property 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 decreased, and a three-dimensional modeled product or molded product having excellent target flexibility and elastic recovery properties can be obtained. It becomes impossible.

  Furthermore, g must be 2 or 3 in the urethanized acrylic compound (II). When the urethane-modified acrylic compound (II) having g of 2 is used, it is obtained from the photocurable resin composition of the present invention as compared with the case of using the urethane-modified acrylic compound (II) having g of 3. There is a tendency that the flexibility and tensile elongation of a photocured product such as a three-dimensional modeled product or a molded product tend to be large, but in any case it has a large tensile elongation and is excellent in flexibility. Products and molded products can be obtained.

In the urethanized acrylic compound (II), the group A ² is a divalent or trivalent unsubstituted or substituted hydrocarbon group, and the group A ² is unsubstituted or substituted having 6 to 20 carbon atoms. It is preferably an aliphatic, aromatic and / or alicyclic divalent or trivalent hydrocarbon group.
The urethanized acrylic compound (II) is preferably a diisocyanate compound or a triisocyanate compound represented by the general formula: A ^2- (NCO) g (A ² and g are the same as described above), as described later. 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 to produce the urethanized acrylic compound (I). Is preferred. More specifically, preferred examples of the group A ² in the urethanized acrylic compound (II) include an isophorone group, a tolylene group, a 4,4′-diphenylmethane group, a naphthylene group, a xylylene group, a phenylene group, and 3,3 ′. -Dichloro-4,4'-phenylmethane group, toluylene group, hexamethylene group, 4,4'-dicyclohexylmethane group, hydrogenated xylylene group, triphenylenemethane group, tetramethylxylene group and the like can be mentioned.

  The production method of the urethanized acrylic compound (II) is not particularly limited. Regardless of the production method, the compound represented by the above general formula (II) and the photocurable resin composition containing the compound are the present ones. Although included in the scope of the invention, the urethanized acrylic compound (II) can be preferably produced by the following method.

《Representative example of urethanized acrylic compound (II)》
(1) The following general formula (iv):

（式中、Ｒ²およびｅは上記と同じ）
で表されるエチレングリコールのモノ（メタ）アクリル酸エステルまたはグリセリンのジ（メタ）アクリル酸エステル１モルに対して、下記の一般式（ｖ）：

(Wherein R ² and e are the same as above)
The following general formula (v): 1 mol of ethylene glycol mono (meth) acrylate or glycerol di (meth) acrylate

（式中、Ｒ³は上記と同じ）
で表されるプロピレンオキサイド［上記の一般式（ｖ）においてＲ³＝ＣＨ₃］またはエチレンオキサイド［上記の一般式（ｖ）においてＲ³＝Ｈ］の少なくとも一方を反応させて、下記の一般式（vi）：

(Wherein R ³ is the same as above)
At least one of propylene oxide [R ³ = CH ₃ in the above general formula (v)] or ethylene oxide [R ³ = H in the above general formula (v)] represented by the following general formula: (Vi):

（式中、Ｒ²、Ｒ³、ｅおよびｆは上記と同じ）
で表されるプロピレンオキサイドおよび／またはエチレンオキサイドの付加化合物をつくり；次いで
（２） 上記（１）で得られる一般式（vi）で表されるプロピレンオキサイドおよび／またはエチレンオキサイドの付加化合物を、前記した一般式：Ａ²−（ＮＣＯ）ｇで表されるジイソシアネート化合物またはトリイソシアネート化合物と反応させることによって、ウレタン化アクリル化合物（II）を製造する。

(Wherein R ² , R ³ , e and f are the same as above)
An addition compound of propylene oxide and / or ethylene oxide represented by the following formula; and then (2) the addition compound of propylene oxide and / or ethylene oxide represented by the general formula (vi) obtained in (1) above, general formula: a ² - by reacting a diisocyanate compound represented by (NCO) g or triisocyanate compound, to produce a urethane acrylate compound (II).

  In the reaction (1), it is preferable to react a mono (meth) acrylate of ethylene glycol or a di (meth) acrylate of glycerine with propylene oxide and / or ethylene oxide using a catalyst. Thereby, an addition compound of propylene oxide and / or ethylene oxide represented by the above general formula (vi) can be obtained smoothly. Moreover, since the addition compound of propylene oxide and / or ethylene oxide represented by the general formula (vi) is already known, a known one may be used as it is.

In addition, the propylene oxide and / or ethylene oxide addition compound represented by the general formula (vi) is reacted with the diisocyanate compound or triisocyanate compound represented by the general formula: A ^2- (NCO) g. In the reaction, when a conventional urethanization catalyst such as an organic tin catalyst or a tertiary amine catalyst is reacted at a temperature of 40 to 90 ° C., the desired urethanized acrylic compound (II) can be smoothly obtained. Can get to.

In the reaction (2), the types of the diisocyanate compound and triisocyanate compound represented by the general formula: A ^2- (NCO) g to be reacted with the addition compound represented by the general formula (vi) are particularly limited. Any of diisocyanate compounds and triisocyanate compounds capable of performing a urethanization reaction can be used. Among them, preferred examples of the diisocyanate compound and the triisocyanate compound include isophorone diisocyanate, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, naphthylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, 3,3′-dichloro-4, 4'-phenylmethane diisocyanate, toluylene diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, triphenylmethane triisocyanate, tetramethylxylene diisocyanate, hydrogenated 4,4'- Diphenylmethane diisocyanate can be mentioned, and these isocyanate compounds can be used alone. It may be used in combination of two or more thereof. Among the above-described isocyanate compounds, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate are particularly preferably used. In this case, a photocured product having a high tensile elongation and excellent flexibility and flexibility is obtained. It can be obtained from the photocurable resin composition of the present invention containing a urethanized acrylic compound (II).

In the urethanized acrylic compound (III), R ⁴ and R ⁵ are each independently a hydrogen atom or a methyl group. And h needs 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 urethanized acrylic (III) becomes high, and even if a low molecular weight compound is used as the radical polymerizable compound (b), a photocurable resin composition having excellent fluidity at room temperature is obtained. Further, it becomes difficult to obtain, and the tensile elongation and flexibility of the cured product obtained by photocuring are lowered, and a three-dimensional modeled product or a molded product having excellent target flexibility and elastic recovery property cannot be obtained. In addition, even when h is less than 4, the tensile elongation and flexibility of a cured product obtained by photocuring are reduced, and a three-dimensional modeled product or a molded product having excellent target flexibility and elastic recovery can be obtained. It becomes impossible.

  Furthermore, j must be 2 or 3 in the urethanized acrylic compound (III). When the urethanized acrylic compound (III) where 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) where j is 3. There is a tendency that the flexibility and tensile elongation of photocured products such as three-dimensional molded products and molded products that are produced tend to be large, but in any case they have large tensile elongation and are excellent in flexibility. Products and molded products can be obtained.

In the urethanized acrylic compound (III), the group A ³ is a divalent or trivalent unsubstituted or substituted hydrocarbon group, and the group A ³ is an unsubstituted or substituted group having 6 to 20 carbon atoms. It is preferably an aliphatic, aromatic and / or alicyclic divalent or trivalent hydrocarbon group.
The urethanized acrylic compound (III) is preferably a diisocyanate compound or a triisocyanate compound represented by the general formula: A ^3- (NCO) j (A ³ and j are the same as described above), as described later. From this point, the group A ³ is a divalent or trivalent residue excluding the isocyanate group of the diisocyanate compound or triisocyanate compound used to produce the urethanized acrylic compound (I). Is preferred. More specifically, preferable 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 ′. -Dichloro-4,4'-phenylmethane group, toluylene group, hexamethylene group, 4,4'-dicyclohexylmethane group, hydrogenated xylylene group, triphenylenemethane group, tetramethylxylene group and the like can be mentioned.

  The production method of the urethanized acrylic compound (III) is not particularly limited. Regardless of the production method, the compound represented by the above general formula (III) and the photocurable resin composition containing the compound are the present ones. Although included in the scope of the invention, the urethanized acrylic compound (III) can be preferably produced by the following method.

《Typical production example of urethanized acrylic compound (III)》
(1) Acrylic acid or methacrylic acid is reacted with at least one of propylene oxide and ethylene oxide, and the following general formula (vii):

（式中、Ｒ⁴、Ｒ⁵およびｈは上記と同じ）
で表されるアクリル酸またはメタクリル酸のプロピレンオキサイドおよび／またはエチレンオキサイド付加化合物をつくり；次いで
（２） 上記（１）で得られる一般式（vii）で表されるプロピレンオキサイドおよび／またはエチレンオキサイド付加化合物を、前記した一般式：Ａ³−（ＮＣＯ）ｊで表されるジイソシアネート化合物またはトリイソシアネート化合物と反応させることによって、ウレタン化アクリル化合物（III）を製造する。

(Wherein R ⁴ , R ⁵ and h are the same as above)
A propylene oxide and / or ethylene oxide addition compound of acrylic acid or methacrylic acid represented by the following formula; then (2) propylene oxide and / or ethylene oxide addition represented by the general formula (vii) obtained in (1) above The urethanized acrylic compound (III) is produced by reacting the compound with a diisocyanate compound or triisocyanate compound represented by the general formula: A ^3- (NCO) j.

  The reaction (1) is preferably carried out by reacting acrylic acid and / or methacrylic acid with propylene oxide and / or ethylene oxide using an appropriate catalyst, and represented by the general formula (vii) described above. The propylene oxide and / or addition compound of ethylene oxide can be obtained smoothly.

The reaction of (2) above, wherein the propylene oxide and / or ethylene oxide addition compound represented by the general formula (vii) is reacted with a diisocyanate compound or triisocyanate compound represented by the general formula: A ^3- (NCO) j In the case of using a conventionally known urethanization catalyst, for example, an organic tin catalyst, a tertiary amine catalyst, etc., when both are reacted at a temperature of 40 to 90 ° C., the desired urethanized acrylic compound (III) is smoothly produced. Obtainable.

In the reaction (2), the types of the diisocyanate compound and triisocyanate compound represented by the general formula: A ^3- (NCO) j to be reacted with the addition compound represented by the general formula (vii) are particularly limited. Any of diisocyanate compounds and triisocyanate compounds capable of performing a urethanization reaction can be used. Among them, preferred examples of the diisocyanate compound and the triisocyanate compound include isophorone diisocyanate, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, naphthylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, 3,3′-dichloro-4, 4'-phenylmethane diisocyanate, toluylene diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, triphenylmethane triisocyanate, tetramethylxylene diisocyanate, hydrogenated 4,4'- Diphenylmethane diisocyanate can be mentioned, and these isocyanate compounds can be used alone. It may be used in combination of two or more thereof. Among the above-described isocyanate compounds, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate are particularly preferably used. In this case, a photocured product having a high tensile elongation and excellent flexibility and flexibility is obtained. It can be obtained from the photocurable resin composition of the present invention containing a urethanized acrylic compound (III).

Further, in the photocurable resin composition of the present invention, as the urethanized acrylic compound of (i), together with at least one of the urethanized acrylic compound (II) and the urethanized acrylic compound (III), in some cases, the above-mentioned A urethanized acrylic compound represented by the general formula (I) [hereinafter referred to as “urethanized acryl compound (I)”] is used.
In the urethanized acrylic compound (I), R ¹ is a hydrogen atom or a methyl group, and a is 1 or 2, and when a is 2, two groups; CH ₂ ═C (R ¹ ) —COO—CH ₂ - one or both of the groups R ¹ is required to be a methyl group of the. In the urethanized acrylic compound (I), when a is 2, two groups; CH ₂ ═C (R ¹ ) —COO—CH ₂ — wherein both groups R ¹ are hydrogen atoms are extremely toxic in the synthesis. Carcinogenic and skin irritant glycerin diacrylate must be passed through, which is not preferable because it cannot be used substantially.

Further, in the urethanized acrylic compound (I), b is an integer in the range of 3 to 6, among which b is 5, such as the stability of the urethanized acrylic compound (I) and the ease of production. It is preferable from the point.
In the urethanized acrylic compound (I), c needs to be an integer in the range of 3 to 14, and c is preferably an integer in the range of 3 to 10, and an integer in the range of 3 to 6 It is more preferable that When c exceeds 15, the melting point of the urethanized acrylic compound (I) increases, and the above-mentioned (b) other radical polymerizable compound [hereinafter referred to as “radical polymerizable compound (b)”] is low. Even if molecular weight is used, it becomes difficult to obtain a photocurable resin composition having excellent fluidity at room temperature, and further, the tensile elongation and flexibility of the cured product obtained by photocuring are decreased, which is the target. It is impossible to obtain a three-dimensional molded article or a molded article excellent in flexibility and elastic recovery. In addition, even when c is less than 3, the tensile elongation and flexibility of a cured product obtained by photocuring are decreased, and a three-dimensional modeled product or a molded product having excellent target flexibility and elastic recovery can be obtained. It becomes impossible.

  In the urethanized acrylic compound (I), d must be 2 or 3. When the urethanized acrylic compound (I) in which d 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 (I) in which d is 3 is used. There is a tendency that the flexibility and tensile elongation of a photocured product such as a three-dimensional modeled product or a molded product tend to be large, but in any case it has a large tensile elongation and is excellent in flexibility. Products and molded products can be obtained.

In the urethanized acrylic compound (I), the group A ¹ is a divalent or trivalent unsubstituted or substituted hydrocarbon group, and the group A ¹ is unsubstituted or substituted having 6 to 20 carbon atoms. It is preferably an aliphatic, aromatic and / or alicyclic divalent or trivalent hydrocarbon group. The urethanized 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 to produce the urethanized acrylic compound (I). Is preferred. More specifically, preferable examples of the group A ¹ in the urethanized acrylic compound (I) include 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 group, hydrogenated xylylene group, triphenylenemethane group, tetramethylxylene group and the like can be mentioned.

  The production method of the urethanized acrylic compound (I) is not particularly limited. Regardless of the production method, the compound represented by the above general formula (I) and the photocurable resin composition containing the compound are the present ones. Although included in the scope of the invention, the urethanized acrylic compound (I) can be preferably produced by the following method.

<< Representative examples of urethanized acrylic compound (I) >>
(1) The following general formula (i):

（式中、Ｒ¹およびａは上記と同じ）
で表されるエチレングリコールのモノ（メタ）アクリル酸エステルまたはグリセリンのジ（メタ）アクリル酸エステル１モルに対して、下記の一般式（ii）：

(Wherein R ¹ and a are the same as above)
The following general formula (ii): 1 mol of ethylene glycol mono (meth) acrylate or glycerol di (meth) acrylate

（式中、ｂは上記と同じ）
で表されるラクトンを反応させて、下記の一般式（iii）：

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

（式中、Ｒ¹、ａ、ｂおよびｃは上記と同じ）
で表されるラクトン付加化合物をつくり；次いで
（２） 上記（１）で得られる一般式（iii）で表されるラクトン付加化合物を、前記した一般式：Ａ¹−（ＮＣＯ）ｄで表されるジイソシアネート化合物またはトリイソシアネート化合物と反応させることによって、ウレタン化アクリル化合物（Ｉ）を製造する。

(Wherein R ¹ , a, b and c are the same as above)
Next, (2) The lactone addition compound represented by the general formula (iii) obtained in the above (1) is represented by the general formula: A ^1- (NCO) d. The urethanized acrylic compound (I) is produced by reacting with a diisocyanate compound or triisocyanate compound.

  The above reaction (1) is carried out by converting a mono (meth) acrylic acid ester of ethylene glycol or a di (meth) acrylic acid ester of glycerin and a lactone, if necessary, a cation catalyst, an anion catalyst, an organic tin catalyst (for example, In general, the reaction is preferably performed at 100 to 140 ° C. using a dibutyltin or the like, whereby the lactone addition compound represented by the above general formula (iii) can be obtained smoothly.

  In the reaction (2) in which the above-mentioned diisocyanate compound or triisocyanate compound is reacted with the lactone addition compound represented by the general formula (iii), a conventionally known urethanization catalyst such as an organotin catalyst, tertiary When both are reacted at a temperature of 40 to 90 ° C. using an amine catalyst or the like, the intended urethanized 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 reaction (2) are not particularly limited, and any of the diisocyanate compound and triisocyanate compound capable of performing a urethanization reaction. Can also be used.
Among them, preferred examples of the diisocyanate compound and the triisocyanate compound include isophorone diisocyanate, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, naphthylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, 3,3′-dichloro-4, 4'-phenylmethane diisocyanate, toluylene diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, triphenylmethane triisocyanate, tetramethylxylene diisocyanate, hydrogenated 4,4'- Diphenylmethane diisocyanate can be mentioned, and these isocyanate compounds can be used alone. It may be used in combination of two or more thereof. Among the above-described isocyanate compounds, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate are particularly preferably used. In this case, a photocured product having a high tensile elongation and excellent flexibility and flexibility is obtained. It can be obtained from the photocurable resin composition of the present invention containing the urethanized acrylic compound (I).

Types of groups R ¹ , R ² , R ³ , R ⁴ , R ⁵ , A ¹ , A ² , A ^{3 in} the urethane-modified acrylic compound (I), urethane-modified acrylic compound (II) and urethane-modified acrylic compound (III) , A, b, c, d, e, f, g, h, j, etc., the properties of the urethanized acrylic compound differ depending on the number of the urethanized acrylic compound (I), urethanized acrylic compound ( Both II) and urethanized acrylic compound (III) exhibit a low-viscosity liquid to a high-viscosity liquid at room temperature, and handleability by selecting and combining appropriate ones as radically polymerizable compounds (b) A low-viscosity photocurable resin composition having excellent resistance can be prepared.
The photocurable resin composition of the present invention may contain only one of the urethanized acrylic compound (I) and the urethanized acrylic compound (II) as the urethanized acrylic compound, or two types. May be contained. Moreover, the photocurable resin composition of the present invention may optionally include at least one of a urethanized acrylic compound (II) and a urethanized acrylic compound (III) as a urethanized acrylic compound, and a urethanized acrylic compound ( I) may be contained.

  And the photocurable resin composition of the present invention is used together with at least one of the urethanized acrylic compound (II) and the urethanized acrylic compound (III), or the urethanized acrylic compound (II) and the urethanized acrylic. A radically polymerizable compound (b) is contained together with at least one compound (III) and the urethanized acrylic compound (I). As the radically polymerizable compound (b), carbon-carbon that can react with the urethanized acrylic compound when irradiated with light and can react with the radically polymerizable compound (b) to form a cured product. Any radically polymerizable compound having an intermediate unsaturated bond can be used, but acrylic compounds and / or allyl compounds are preferably used. Further, the radical polymerizable compound (b) may be either a monofunctional compound or a polyfunctional compound, or both a monofunctional compound and a polyfunctional compound may be used in combination. Furthermore, the radically polymerizable compound (b) may be a low molecular weight monomer or an oligomer, or may have a certain molecular weight to some extent. And even if the photocurable resin composition of this invention contains only one type of radically polymerizable compound as a radically polymerizable compound (b), or it contains two or more types of radically polymerizable compounds. Good.

  Examples of radical polymerizable compounds that can be used as the radical polymerizable compound (b) in the photocurable resin composition of the present invention include, but are not limited to, isobornyl (meth) acrylate, bornyl (meth) methacrylate, (Meth) acrylates such as dicyclopentenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (poly) propylene glycol mono (meth) acrylate and t-butyl (meth) acrylate , Monofunctional radically polymerizable compounds such as (meth) acrylamides such as morpholine (meth) acrylamide, N-vinylcaprolactone and styrene; trimethylopropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri ( 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 ( Such as (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 diacrylate, etc. Mention may be made of polyfunctional radically polymerizable compounds.

  In addition to the radically polymerizable compounds described above, urethanization other than epoxy compounds, urethanized acrylic compounds (I) to urethanized acrylic compounds (III) conventionally used in resin compositions for optical three-dimensional modeling, etc. It can be used as a radically polymerizable compound (b) such as an acrylic compound, an epoxy (meth) acrylate compound, or another ester (meth) acrylate.

  In the photocurable resin composition of this invention, 1 type (s) or 2 or more types of the above-mentioned radical polymerizable compounds can be used as a radical polymerizable compound (b). Of the various radical 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. When cured, it can be made into molded products, three-dimensional molded products, and other cured products that have smaller volume shrinkage, better dimensional accuracy, and better flexibility, elastic recovery, and mechanical properties. A photocurable resin composition is obtained.

And in the photocurable resin composition of this invention, it is necessary that {weight of a urethane-ized acrylic compound (i)}: {weight of a radically polymerizable compound (b)} is 80: 20-10: 90. Yes, preferably 65:35 to 25:75, and more preferably 60:40 to 35:65. In the photocurable resin composition, when the ratio of the urethanized acrylic compound (I) is less than 10% by weight based on the total weight of the urethanized acrylic compound (I) and the radical polymerizable compound (B), it is cured by light. When it exceeds 80% by weight, the tear resistance of the cured product obtained by photocuring is reduced, and the elastic recovery is reduced, so that a change stress is externally applied. Even when the stress is removed, the original shape is not restored, and the viscosity of the photocurable resin composition becomes too high, and the handleability, moldability, and formability are lowered. When it is used in the case, the target three-dimensional model cannot be manufactured smoothly.
Here, the “weight of the urethanized acrylic compound (A)” means that the photocurable resin composition is the urethanized acrylic compound (II) and the urethanized acrylic compound (III) as the urethanized acrylic compound of (A). ) Is the weight of the urethanized acrylic compound (II) or urethanized acrylic compound (III), the urethanized acrylic compound (II) and the urethanized acrylic compound (III) When both are contained, the total weight of both is said, and contains at least one of urethane-modified acrylic compound (II) and urethane-modified acrylic compound (III) and urethane-modified acrylic compound (I) If so, it refers to their total weight.

  Furthermore, the photo-curable resin composition of the present invention includes at least one of the urethanized acrylic compound (II) and the urethanized acrylic compound (III), or the urethanized acrylic compound (II) and the urethanized acrylic compound. A photopolymerization initiator is contained together with at least one of (III) and the urethanized acrylic compound (I) and the radical polymerizable compound (b). As the photopolymerization initiator, any radical photopolymerization initiator conventionally used in photocurable resin compositions can be used and is not particularly limited. Examples of the photopolymerization initiator that can be used in the photocurable resin of the present invention include, but are not limited to, 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, pt- Butyldichloroacetophenone, pt-butyltrichloroacetophenone, p-azidobenzalacetophenone, 1-hydroxycyclohexylphenylketono, benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, xanthone, Ruorenon, can be mentioned benzaldehyde, anthraquinone, triphenylamine, carbazole and the like.

  When a compound having a radical polymerizable group and a cationic polymerizable group such as an epoxy group is used as the radical polymerizable compound (b), a photo cationic polymerization initiator is used in combination with the above-mentioned photo radical polymerization initiator. In this case, the type of the photocationic polymerization initiator is not particularly limited, and those conventionally known can be used.

  The amount of photopolymerization initiator used can vary depending on the type of urethanized acrylic compound and radical polymerizable compound (b) in (a), the type of photopolymerization initiator, etc. Based on the total weight of the acrylic compound and the radically polymerizable compound (b), it is preferably 0.1 to 10% by weight, more preferably 1 to 5% by weight.

  The photocurable resin composition of the present invention contains a leveling agent, a surfactant, an organic polymer modifier, an organic plasticizer, organic or inorganic solid fine particles, if necessary, in addition to the above-described components. You may do it. Examples of the organic solid fine particles include cross-linked polystyrene fine particles, cross-linked polymethacrylate fine particles, polyethylene fine particles, and polypropylene fine particles. Examples of inorganic solid fine particles include glass beads, talc fine particles, and oxidized fine particles. Examples thereof include silicon fine particles. When organic solid fine particles and / or inorganic solid fine particles are contained in the photo-curable resin composition of the present invention, a photo-cured resin treated with a silane coupling agent such as aminosilane, epoxy silane, or acrylic silane is used. In many cases, the mechanical strength of the cured product obtained is improved. In the case of containing polyethylene solid particles and / or polypropylene solid particles treated with a silane coupling agent, polyethylene solid particles and / or polypropylene solids obtained by copolymerizing about 1 to 10% by weight of an acrylic acid compound. The use of fine particles is preferable because the affinity with the silane coupling agent is increased.

  The viscosity of the photocurable resin composition of the present invention can be adjusted according to the application and use mode. Generally, when measured using a rotary B-type viscometer, at room temperature (25 ° C.), The viscosity is preferably about 100 to 100,000 centipoise (cp) from the viewpoints of handleability, moldability, and three-dimensional formability, 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 modeling, the above-mentioned viscosity at room temperature is in the range of 300 to 5000 cp. It is desirable from the viewpoint that the property can be improved and the intended three-dimensional model can be manufactured smoothly with high dimensional accuracy. The viscosity of the photocurable resin composition can be adjusted by selecting the types of the urethanized acrylic compounds (I) to (III) and the radical polymerizable compound (b), adjusting the blending ratio thereof, and the like.

When the photocurable resin composition of the present invention is stored in a state where light can be blocked, the modification or polymerization is usually performed at a temperature of 10 to 40 ° C. for a long period of about 6 to 18 months. Can be preserved while maintaining good photocuring performance.
The photo-curable resin composition of the present invention is a molded product or three-dimensional product having its characteristics, particularly when it is cured by light, having a small volume shrinkage ratio and excellent dimensional accuracy, and excellent flexibility, elastic recovery and mechanical properties. It can be used for various purposes by taking advantage of the characteristics that a molded product and other cured products can be obtained. For example, manufacturing of a three-dimensional model by optical three-dimensional modeling, casting molding, casting, etc. Can be used for the production of various molded products such as film-like products and molds, coating, and vacuum forming dies.

Among them, the photo-curable resin composition of the present invention is suitable for use in the above-described optical three-dimensional modeling method, and in that case, the dimensional accuracy is excellent while keeping the volume shrinkage ratio during photo-curing small. In addition, it is possible to smoothly manufacture a three-dimensional structure that 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 conventionally known optical three-dimensional modeling method and apparatus can be used. Among them, in the present invention, it is preferable to use an active energy beam 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. A laser beam 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 modeling time, and obtain a three-dimensional modeled object with high modeling accuracy by utilizing the good light condensing property of the laser beam. be able to.

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

  In that case, the structure, shape, size, and the like of the three-dimensional structure are not particularly limited, and can be determined according to each application. And as a typical application field of the optical three-dimensional modeling method of the present invention, a model for verifying the appearance design in the middle of the design, a model for checking the functionality of the part, a resin for producing a mold Examples include molds, base models for producing molds, and direct molds for prototype molds. More specifically, mention the production of models for precision parts, electrical / electronic parts, furniture, building structures, automotive parts, various containers, castings, molds, mother molds, and processing models. In particular, by utilizing the properties of flexibility and elastic recovery, it can be used very effectively for applications such as a cushion material having a complicated shape in a structure, a mold for vacuum forming, and the like.

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

<< Synthesis Example 1 >> [Production of Urethane Acrylic Compound (I)]
(1) To a 4-liter four-necked flask equipped with a stirrer, a temperature controller, a thermometer, and a condenser, 400 g of 2-hydroxyethyl acrylate and 1572 g of ε-caprolactone were added, and a temperature of 100 to By reacting at 150 ° C. for 8 hours, the above-mentioned caprolactone adduct represented by the general formula (iii) [a compound of R ¹ = hydrogen, a = 1, b = 5 and c = 4 in the general formula (iii)] Manufactured.
(2) In a four-necked flask with an internal volume of 4 liters equipped with a stirrer, a temperature controller, a thermometer and a condenser, which was different from that used in (1) above, was obtained in (1) above. 1976 g of caprolactone adduct, 0.998 g of hydroquinone monomethyl ether, 0.68 g of dilauric acid di-n-butyltin and 320 g of isophorone diisocyanate were added and reacted at 40 to 50 ° C. for 30 minutes, and further reacted at a temperature of 80 to 90 ° C. I let you. As a result, a colorless product having a viscous liquid at room temperature (25 ° C.) was obtained.
(3) When the chemical structure of the product obtained in the above (2) was determined, it was based on lactone at 1.3839 ppm, 1.6414 ppm, 1.6539 ppm, 2.30555 ppm, 4.0505 ppm by NMR measurement. Absorption, further absorption from 0.8 to 1.8 ppm based on multilet isophorone groups, and absorption from 5.8 to 6.5 ppm based on acrylate double bonds were observed. Further, 1700 cm ^-1 by IR measurement, characteristic absorption of the urethane bond was observed at 1540 cm ^-1, the above formula (I) urethane acrylate compounds represented by (I) [in the general formula (I) R ¹ = Hydrogen, A ¹ = isophorone group, a = 1, b = 5, c = 4 and d = 2 compound].

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

<< Synthesis Example 3 >> [Production of Urethane Acrylic Compound (I)]
(1) To a 4 liter four-necked flask equipped with a stirrer, temperature controller, thermometer and condenser, 400 g of 2-hydroxyethyl acrylate and 2359 g of ε-caprolactone were added, and the temperature was adjusted to 100 to 100 under stirring. By reacting at 150 ° C. for 8 hours, the above-mentioned caprolactone adduct represented by the general formula (iii) [a compound of R ¹ = hydrogen, a = 1, b = 5 and c = 6 in the general formula (iii)] Manufactured.
(2) In a four-necked flask with an internal volume of 4 liters equipped with a stirrer, a temperature controller, a thermometer and a condenser, which was different from that used in (1) above, was obtained in (1) above. 2819 g of caprolactone adduct, 0.63 g of hydroquinone monomethyl ether, 0.94 g of dilauric acid di-n-butyltin and 326 g of isophorone diisocyanate were added and reacted at 40-50 ° C. for 30 minutes, then further reacted at a temperature of 80-90 ° C. The urethanized 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 = 6 And d = 2 compound].

<< Synthesis Example 4 >> [Production of Urethane Acrylic Compound (II)]
To a 4-liter four-necked flask equipped with a stirrer, temperature controller, thermometer and condenser, add 2-hydroxyethyl acrylate propylene oxide adduct [“Blemmer 10APE-550B” manufactured by NOF Corporation; Compound represented by formula (vi) wherein R ² = H, R ³ = CH ₃ , e = 1, f = 9] 1492 g, hydroquinone monomethyl ether 0.63 g, dilaurate di-n-butyltin 0.51 g And 222 g of isophorone diisocyanate, reacted at 40 to 50 ° C. for 30 minutes, further reacted at a temperature of 80 to 90 ° C., and urethanized acrylic compound (II) [in the general formula (II), R ² = hydrogen, R ³ = CH ₃ , A ² = isophorone group, compound with e = 1, f = 9 and g = 2].

<< Synthesis Example 5 >> [Production of Urethane Acrylic Compound (III)]
A four-necked flask with an internal volume of 4 liters equipped with a stirrer, a temperature controller, a thermometer, and a condenser was added with propylene oxide acrylate adduct [“Blemmer AP-550” manufactured by Nippon Oil & Fats Co., Ltd .; in the compound represented by) R ⁴ = H, the compounds of the _{^{R 5 = CH 3, h =}} 10] 1517g, hydroquinone monomethyl ether 1.00 g, put dilaurate di -n- butyltin 0.52g and isophorone diisocyanate 222g , Reacted at 40 to 50 ° C. for 30 minutes, and further reacted at a temperature of 80 to 90 ° C. to obtain a urethane-modified acrylic compound (III) [in the general formula (III), R ⁴ = hydrogen, R ⁵ = CH ₃ , A ³ = compound of isophorone group, h = 10 and j = 2].

<< Synthesis Example 6 >> [Production of Urethane Acrylic Compound]
(1) 382 g of 2-hydroxyethyl acrylate and 751 g of ε-caprolactone were added to a four-necked flask having an internal volume of 4 liters equipped with a stirrer, a temperature controller, a thermometer, and a condenser. A compound having a structure similar to the caprolactone adduct represented by the above general formula (iii) after reacting at 150 ° C. for 8 hours [in the general formula (iii), R ¹ = hydrogen, a = 1, b = 5 and Compound in which c = 2] was produced.
(2) In a four-necked flask with an internal volume of 4 liters equipped with a stirrer, a temperature controller, a thermometer and a condenser, which was different from that used in (1) above, was obtained in (1) above. 1133 g of caprolactone adduct, 0.28 g of hydroquinone monomethyl ether, 0.43 g of dilauric acid di-n-butyltin and 305 g of isophorone diisocyanate were added and reacted at 40 to 50 ° C. for 30 minutes, and further reacted at a temperature of 80 to 90 ° C. I let you. As a result, a colorless product having a viscous liquid at room temperature (25 ° C.) was obtained [in the above general formula (I), R ¹ = hydrogen, A ¹ = isophorone group, a = 1, b = 5. , C = 2 and d = 2, and urethanized acrylic compound not included in any of urethanized acrylic compound (I) to urethanized acrylic compound (III)].

<< Synthesis Example 7 >> [Production of Urethane Acrylic Compound]
(1) 116 g of 2-hydroxyethyl acrylate and 1710 g of ε-caprolactone were added to a 4-liter four-necked flask equipped with a stirrer, a temperature controller, a thermometer, and a condenser, and the temperature was adjusted to 100 to 100 under stirring. A compound having a structure similar to the caprolactone adduct represented by the above general formula (iii) after reacting at 150 ° C. for 8 hours [in the general formula (iii), R ¹ = hydrogen, a = 1, b = 5 and Compound with c = 15] was prepared.
(2) In a four-necked flask with an internal volume of 4 liters equipped with a stirrer, a temperature controller, a thermometer and a condenser, which was different from that used in (1) above, was obtained in (1) above. 1826 g of caprolactone adduct, 0.38 g of hydroquinone monomethyl ether, 0.58 g of dilauric acid di-n-butyltin and 93 g of isophorone diisocyanate were added and reacted at 40 to 50 ° C. for 30 minutes, and further reacted at a temperature of 80 to 90 ° C. I let you. As a result, a colorless product having a viscous liquid at room temperature (25 ° C.) was obtained [in the above general formula (I), R ¹ = hydrogen, A ¹ = isophorone group, a = 1, b = 5. , C = 15 and d = 2, and are not included in any of urethanized acrylic compound (I) to urethanized acrylic compound (III).

<< Reference Example 1 >> [Preparation of Photocurable Resin Composition]
In a three-necked flask having an internal volume of 5 liters equipped with a stirrer, a condenser tube and a dropping funnel with side tubes, 1300 g of the urethanized acrylic compound (I) obtained in Synthesis Example 1 and morpholine acrylamide (manufactured by Shin-Nakamura Chemical Co., Ltd. “ NK Ester A-MO ")) 1200 g, and vacuum deaeration and nitrogen substitution were performed. Next, 120 g of 2,2-dimethoxy-2-phenylacetophenone (“Irgacure 651” manufactured by Ciba Geigy Inc .; photoradical polymerization initiator) is added under an environment where ultraviolet rays are blocked, and the temperature is 25 ° C. until it is completely dissolved. The mixture was stirred (mixing stirring time: about 1 hour) to obtain a photocurable resin composition (viscosity at about 390 cp at room temperature) containing a urethanized acrylic compound (I), which was a colorless and transparent viscous liquid.

<< Reference Example 2 >> [Preparation of Photocurable Resin Composition]
A photocurable resin composition was prepared in the same manner as in Reference 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). A photocurable resin composition (viscosity of about 430 cp at room temperature), which is a colorless and transparent viscous liquid containing (I), was obtained.

<< Reference Example 3 >> [Preparation of Photocurable Resin Composition]
A photocurable resin composition was prepared in the same manner as in 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). A photocurable resin composition (viscosity of about 600 cp at room temperature), which is a colorless and transparent viscous liquid containing (I), was obtained.

<< Example 1 >> [Preparation of photocurable resin composition]
1300 g of urethanized acrylic compound (II) obtained in Synthesis Example 4 and the same morpholine used in Reference Example 1 in a three-necked flask having an internal volume of 5 liters equipped with a stirrer, a condenser tube and a dropping funnel with side tubes The acrylamide 1200g was prepared and vacuum deaeration nitrogen substitution was carried out. Subsequently, 120 g of the same 2,2-dimethoxy-2-phenylacetophenone (photo radical polymerization initiator) used in Reference Example 1 was added under an environment where ultraviolet rays were blocked, and the temperature was 25 ° C. until completely dissolved. After mixing and stirring (mixing and stirring time of about 1 hour), a photocurable resin composition (viscosity of about 430 cp at room temperature) was obtained as a colorless and transparent viscous liquid containing the urethanized acrylic compound (II).

<< Example 2 >> [Preparation of Photocurable Resin Composition]
A photocurable resin composition was prepared in the same manner as in Example 1 except that 1300 g of the urethanized acrylic compound (III) obtained in Synthesis Example 5 was used instead of the urethanized acrylic compound (II). A photocurable resin composition (viscosity of about 380 cp at room temperature), which is a colorless and transparent viscous liquid containing the fluorinated acrylic compound (III), was obtained.

<< Comparative Example 1 >> [Preparation of Photocurable Resin Composition]
A photocurable resin composition was prepared in the same manner as in Reference Example 1 except that 1300 g of the urethanized acrylic compound obtained in Synthesis Example 6 was used instead of the urethanized acrylic compound (I) used in Reference Example 1. However, a photocurable resin composition (viscosity of about 400 cp at room temperature), which is a colorless and transparent viscous liquid, was obtained.

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

<< Reference Example 4 >> [Production of photo-cured molded product by molding method]
(1) A photocurable resin composition containing a urethanized acrylic compound (I) prepared in Reference Example 1 above is injected into a transparent silicon mold having a mold cavity of a dumbbell specimen shape conforming to JIS 7113. After that, the resin composition was cured by irradiating with ultraviolet rays for 15 minutes from the entire surface of the silicon mold using a 30 W ultraviolet lamp to produce a photocured dumbbell specimen-shaped molded product. The obtained molded product (dumbbell-shaped test piece) was taken out of the mold, and its tensile properties (tensile strength, tensile elongation and tensile modulus) were measured according to JIS K 7113. It was as shown.
(2) Moreover, when the elastic recoverability of the dumbbell-shaped test piece obtained in the above (1) was evaluated as follows, it was as shown in Table 1 below.

Evaluation method for elastic recovery of dumbbell-shaped specimens:
The dumbbell-shaped test piece (molded product or three-dimensional model) is completely folded in half by hand at the center in the length direction and kept in that state for 10 minutes, and then the folded state is released. A case where the original flat dumbbell shape was returned to the original flat dumbbell shape was evaluated as good (◯), and a case where the bent state remained without returning to the original flat dumbbell shape was evaluated as defective (x).

(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 6 and (d _1), the resulting molded article (dumbbell-shaped test piece) ) Were measured and the volume shrinkage (%) was determined by the following mathematical formula (1), and as shown in Table 1 below.

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

<< Reference Example 5 >> [Manufacture of a three-dimensional object by optical three-dimensional modeling]
Using the photocurable resin composition containing the urethanized acrylic compound (I) obtained in Reference Example 1 above, using an ultrahigh-speed stereolithography system (“SOLIFORM500” manufactured by Teijin Seiki Co., Ltd.), Irradiation with water-cooled Ar laser light (output: 500 mW; wavelength: 333, 354, 364 nm) and an irradiation energy of 20 to 30 mJ / cm ² , a slice pitch (lamination thickness) of 0.127 mm, and an average modeling time of 2 per layer Stereolithography was performed in minutes, and a three-dimensionally shaped article in the shape of a dumbbell specimen conforming to JIS 7113 was produced. The obtained three-dimensional model was washed with isopropyl alcohol to remove the uncured resin liquid adhering to the three-dimensional model, and then post-cured by irradiating with 3 KW ultraviolet rays for 10 minutes. The tensile properties (tensile strength, tensile elongation, and tensile elastic modulus) of the three-dimensional modeled object (dumbbell-shaped test piece) obtained as a result were measured according to JIS K 7113, and as shown in Table 1 below. It was.
Moreover, when the elastic recovery property of the post-cure dumbbell-shaped test piece (three-dimensional model) obtained above was evaluated in the same manner as in Reference Example 4, it was as shown in Table 1 below.
Furthermore, the specific gravity (d ₁ ) of the photocurable resin composition before photocuring used in the three-dimensional modeling method of Reference Example 5 and the specific gravity (d ₂ ) of the three-dimensional modeled material after post-curing were respectively measured. When the volume shrinkage (%) was determined by the above mathematical formula (1), it was as shown in Table 1 below.

<< Reference Example 6 >> [Manufacture of a three-dimensional structure by optical three-dimensional modeling]
Optical three-dimensional modeling, washing of uncured resin and post-cure in the same manner as in Reference Example 5 except that the photocurable resin composition containing the urethanized acrylic compound (I) obtained in Reference Example 2 was used. The three-dimensional modeled object (dumbbell shape test piece) was manufactured. As a result, the tensile properties, elastic recoverability, and volume shrinkage of the dumbbell-shaped test piece (three-dimensional modeled object) obtained as a result were measured or evaluated in the same manner as in Example 7. The results were as shown in Table 1 below.

<< Reference Example 7 >> [Manufacture of a three-dimensional object by optical three-dimensional modeling]
Optical three-dimensional modeling, washing of uncured resin and post-cure in the same manner as in Reference Example 5 except that the photocurable resin composition containing the urethanized acrylic compound (I) obtained in Reference Example 3 was used. The three-dimensional modeled object (dumbbell shape test piece) was manufactured. As a result, the tensile properties, elastic recoverability, and volume shrinkage of the dumbbell-shaped test piece (three-dimensional modeled object) obtained as a result were measured or evaluated in the same manner as in Example 7. The results were as shown in Table 1 below.

<< Example 3 >> [Manufacture of a photo-cured molded article by a molding method]
Using the photocurable resin composition containing the urethanized acrylic compound (II) obtained in Example 1 above, a mold cavity having a dumbbell specimen shape conforming to JIS 7113 in the same manner as in Reference Example 4. And filled with a transparent silicon mold and photocured in the same manner as in Example 6 to produce a dumbbell specimen-shaped molded product. The tensile properties, elastic recovery and volumetric shrinkage of the dumbbell-shaped test piece (molded product) obtained as a result were determined in the same manner as in Example 6 and were as shown in Table 1 below.

<< Example 4 >> [Manufacture of a three-dimensional molded article by an optical three-dimensional modeling method]
Optical three-dimensional modeling, washing of uncured resin and post-cure in the same manner as in Reference Example 5 except that the photocurable resin composition containing the urethanized acrylic compound (II) obtained in Example 1 above was used. The three-dimensional modeled object (dumbbell shape test piece) was manufactured. The tensile properties, elastic recovery properties, and volume shrinkage of the resulting dumbbell-shaped test piece (three-dimensional model) were measured or evaluated in the same manner as in Reference Example 5 and were as shown in Table 1 below.

<< Example 5 >> [Production of photo-cured molded product by molding method]
Using the photocurable resin composition containing the urethanized acrylic compound (III) obtained in Example 3 above, a mold cavity having a dumbbell specimen shape conforming to JIS 7113 in the same manner as in Reference Example 4. And filled with a transparent silicon mold and photocured in the same manner as in Reference Example 4 to produce a dumbbell specimen-shaped molded product. The tensile properties, elastic recoverability, and volume shrinkage of the dumbbell-shaped test piece (molded product) obtained as a result were determined in the same manner as in Reference Example 4, and as shown in Table 1 below.

<< Example 6 >> [Manufacture of a three-dimensional object by optical three-dimensional modeling]
Optical three-dimensional modeling, washing of uncured resin and post-cure in the same manner as in Reference Example 5 except that the photocurable resin composition containing the urethanized acrylic compound (III) obtained in Example 2 above was used. The three-dimensional modeled object (dumbbell shape test piece) was manufactured. The tensile properties, elastic recovery properties, and volume shrinkage of the resulting dumbbell-shaped test piece (three-dimensional model) were measured or evaluated in the same manner as in Reference Example 5 and were as shown in Table 1 below.

<< Comparative Example 3 >> [Manufacture of a three-dimensional object by optical three-dimensional modeling]
Except for using the photocurable resin composition obtained in Comparative Example 1 above, optical three-dimensional modeling, uncured resin washing and post-curing were performed in the same manner as in Reference Example 5 to obtain a three-dimensional model (dumbbell shape) Specimen) was manufactured. The tensile properties, elastic recovery properties, and volume shrinkage of the resulting dumbbell-shaped test piece (three-dimensional model) were measured or evaluated in the same manner as in Reference Example 5 and were as shown in Table 1 below.

<< Comparative Example 4 >> [Manufacture of a photo-cured molded article by a molding method]
Using the thick paste-like photocurable resin composition obtained in Comparative Example 2 above, transparent silicon having a dumbbell test piece-shaped mold cavities conforming to JIS 7113 in the same manner as in Reference Example 4 The mold was filled and photocured in the same manner as in Reference Example 4 to produce a molded product having a dumbbell test piece shape. The tensile properties, elastic recovery and volumetric shrinkage of the dumbbell-shaped test piece (molded product) obtained as a result were determined in the same manner as in Example 6 and were as shown in Table 1 below.

  From the results of Table 1 above, using the photocurable resin composition of the present invention of Example 1 or Example 2 containing urethanized acrylic compound (II) or urethanized acrylic compound (III), In the case of Examples 3 to 6 where a three-dimensional model is manufactured, a molded article having a good quality that has a high tensile elongation, excellent flexibility, excellent elastic recovery, and excellent tensile strength. Or it turns out that a three-dimensional molded item is obtained with a low volumetric shrinkage rate with a sufficient dimensional accuracy.

  On the other hand, in the case of Comparative Example 3, c = 2 in the urethanized acrylic compound represented by the general formula (I), and the urethanized acrylic compound (I) to the urethanized acrylic compound (III). By using the photocurable resin composition of Comparative Example 1 containing a urethanized acrylic compound that is not included in any of the above, the three-dimensional molded article obtained there has a very low tensile elongation and lacks flexibility. In addition, it is hard and brittle, and the volumetric shrinkage is large.

  Further, from the results of Comparative Example 2 and Comparative Example 4 above, c = 15 in the urethanized acrylic compound represented by the general formula (I), and urethanized acrylic compound (I) to urethanized acrylic compound. Since the photocurable resin composition of Comparative Example 2 containing a urethanized acrylic compound not included in any of (III) has a high viscosity and does not exhibit a liquid state, it is difficult to perform molding and optical three-dimensional modeling. In addition, the molded product obtained from the photo-curable resin composition of Comparative Example 2 has a very low tensile elongation and no flexibility, and has a low tensile modulus and is brittle. I understand.

The photo-curable resin composition of the present invention exhibits a low-viscosity liquid, is excellent in handleability, and can be cured in a short curing time. It can be used effectively for the production of various molded products by the molding method, and the molded product and three-dimensional model obtained by using the photocurable resin composition of the present invention have a small volume shrinkage ratio and excellent dimensional accuracy, Excellent mechanical properties such as flexibility, elastic recovery, tensile strength, and tensile elongation.
Therefore, the photocurable resin composition of the present invention is used for models and processing for precision parts, electrical / electronic parts, furniture, building structures, automotive parts, various containers, castings, molds, mother molds, etc. It can be effectively used for various applications such as production of models.

Claims (5)

(I) (i) 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 is a methyl group, and A ² is A divalent or trivalent unsubstituted or substituted hydrocarbon group, f is an integer from 4 to 20, and g is 2 or 3)
A urethanized acrylic compound represented by: and the following general formula (III):

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 urethanized acrylic compound represented by:
A urethanized acrylic compound selected from at least one of:
(Ii) a urethanized acrylic compound selected from at least one of the urethanized acrylic compound represented by the general formula (II) and the urethanized acrylic compound represented by the general formula (III); Formula (I);

(In the formula, R ¹ is a hydrogen atom or a methyl group, a is 1 or 2, and when a is 2, one or both R ¹ is a methyl group, and A ¹ is a divalent or trivalent non-valent group. A substituted or substituted hydrocarbon group, b is an integer of 3-6, c is an integer of 3-14, d is 2 or 3)
A urethane-modified acrylic compound comprising a urethane-modified acrylic compound represented by:
(B) a radically polymerizable compound other than the urethane-modified acrylic compound of (a);
And
(C) Photopolymerization initiator;
The content ratio of the (a) acrylic urethane compound: (b) radical polymerizable compound is 80:20 to 10:90 (weight ratio). A photocurable resin composition.   The photocurable resin composition according to claim 1, wherein the ratio of the photopolymerization initiator is 0.1 to 10% by weight based on the total weight of the acrylic urethane compound (a) and the radical polymerizable compound (b).   The photocurable resin composition according to claim 1, which is a resin composition for optical three-dimensional modeling.   The method to manufacture a three-dimensional molded item by the optical three-dimensional modeling method using the photocurable resin composition of Claim 3. 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 is a methyl group, and A ² is A divalent or trivalent unsubstituted or substituted hydrocarbon group, f is an integer from 4 to 20, and g is 2 or 3)
Or a urethanated acrylic compound represented by the following general formula (III):

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)
Urethane acrylic compound represented by