JP2020172075A - Active energy ray polymerizable resin composition for optical three-dimensional modelling, three-dimensional object, and base material for cell culture - Google Patents

Abstract

To provide a container for cell culture using a curable material for optical three-dimensional modelling in which protein adsorption is suppressed, and which exhibits excellent cell adhesiveness prevention and oxygen permeability effect, and to provide a medical device such as a microchip, and a method for manufacturing the cell culture equipment.SOLUTION: The problem can be solved by an active energy ray polymerizable resin composition for optical three-dimensional modelling containing an α,β-unsaturated double bond group-containing compound (A) having a property of promoting mutual adhesion of cells and an α,β-unsaturated double bond group-containing compound (B) having silicon (excluding one corresponding to the compound (A)).SELECTED DRAWING: None

Description

INDUSTRIAL APPLICABILITY According to the present invention, an active energy ray-polymerizable resin composition for optical three-dimensional modeling, a three-dimensional model, and a cell culture group, which have a high curing rate by light irradiation, excellent molding accuracy, and an excellent protein and cell adhesion preventing effect. Regarding materials.

In recent years, as a method for manufacturing resin molded products, a liquid photocurable resin composition is used as an ultraviolet laser, which is a kind of active energy ray, based on three-dimensional shape data designed by a three-dimensional design system (three-dimensional CAD) on a computer. An optical three-dimensional modeling method (stereolithography) is used in which a molded product is produced by selectively curing it with light.
Compared to conventional cutting, this stereolithography method has various advantages such as being able to handle complicated shapes that are difficult to cut, being a fully automated process, easy to handle, short manufacturing time, and cost effective. It has come to be widely used in the manufacture of medical models quantified by digital technology, physical models for training and experiments, artificial limbs, and the like. As a typical example of this three-dimensional modeling method, light, for example, a kind of active energy ray is used so that a cured layer having a desired pattern can be obtained on the liquid surface of a liquid photocurable resin composition placed in a container. A cured layer is obtained by selectively irradiating a certain ultraviolet laser beam, then a liquid photocurable resin composition is supplied in a layer on the cured layer, and then light is selectively irradiated in the same manner as described above. To form a cured layer continuous with the cured layer. By repeating this laminating operation, a desired three-dimensional model is finally obtained. This three-dimensional modeling method is attracting attention because it is possible to easily obtain a target modeled object in a short time even when the shape of the modeled object to be manufactured is complicated.

Silicone materials are used in a wide range of applications, including medical materials, due to their excellent safety. In recent years, techniques for measuring cell metabolism and secretion have been developed. Oxygen is indispensable not only for cell survival but also for cell maintenance of physiological activity. For example, a culture vessel with a silicone bottom that is manufactured by Bethel Co., Ltd. and sold by Cosmo Bio Co., Ltd. has higher oxygen permeability than a culture vessel with a glass or polystyrene bottom. , It is known that aerobic respiration of rat primary hepatocytes can be maintained.
In addition, an attempt to observe or measure the chemical reaction of cells held on a silicone substrate of a cell culture substrate called a microchip is expected to bring merits such as shortening of analysis time by simplifying and automating the operation. , Has been popular in recent years. In addition, Non-Patent Document 1 has also conducted research on evaluating the function and response of cells using a culture container such as a plate and a microchip, taking advantage of the culture container made of silicone.

However, many microfabricated products of devices such as culture vessels and microchips using cells are produced by casting a transparent material in a silicone mold using photolithography technology. This method is difficult to control the thickness of the product and is not suitable for mass production.
In addition, there is a problem that the surface of the silicone is adhered by cells or proteins derived from a biological sample, resulting in clogging and deterioration of analysis accuracy and sensitivity.
In order to solve this problem, for example, Patent Document 1 describes a microchannel device coated with a cell adhesion inhibitor containing a polymer having a hydrophilic structure such as polyethylene glycol and / or a betaine structure as an active ingredient. Has been reported. However, the difference in surface tension between the adhesive and the wall surface of the silicone base material flow path is large, and when the adhesive is coated, a large uneven repelling phenomenon occurs on the silicone base material, and the coating is made of the adhesive. There was concern about the durability of the layers.

International Publication No. 2017/022815

The present invention relates to a cell culture container using a curable material for optical three-dimensional modeling, which exhibits excellent cell adhesion prevention and oxygen permeability effects while suppressing protein adsorption, a medical device such as a microchip, and the cell. It is an object of the present invention to provide a method for producing culture equipment.

That is, in the present invention, the α, β-unsaturated double bond group-containing compound (A) having an ability to promote the adhesion between cells and the α, β-unsaturated double bond group-containing compound (B) having silicon However, the present invention relates to an active energy ray-polymerizable resin composition for optical three-dimensional modeling containing (excluding those corresponding to the compound (A)).

Further, in the present invention, the compound (A) is at least one of a compound (Ap) represented by the following general formula 1 and an amine compound (Aa), and the active energy ray-polymerizable property for optical three-dimensional modeling is present. Regarding the resin composition.

（一般式１中、
Ｒ¹は炭素数２〜４のアルキレン基、
Ｒ^２は水素原子又は炭素数１〜４のアルキル基、
Ｘは炭素原子、＊―（Ｃ＝Ｏ）Ｏ−、＊−（Ｃ＝Ｏ）ＮＲ^３又は＊−ＮＲ^３（Ｃ＝Ｏ）−、ｆは２〜１００の整数を示し、
Ｒ^３は水素原子又は炭素数１〜１０の有機基、＊は、一般式１中のＲ^４が結合している炭素原子と結合する位置を示し、
Ｒ^４は水素原子又はメチル基を示す。） General formula 1

(In general formula 1,
R ¹ is an alkylene group having 2 to 4 carbon atoms,
R ² is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
X is a carbon atom, *-(C = O) O-, *-(C = O) NR ³ or * -NR ³ (C = O)-, f is an integer of 2 to 100.
R ³ indicates a hydrogen atom or an organic group having 1 to 10 carbon atoms, and * indicates a position in the general formula 1 where R ⁴ is bonded to a carbon atom.
R ⁴ represents a hydrogen atom or a methyl group. )

（一般式２中、
Ｘは炭素原子、＊―（Ｃ＝Ｏ）Ｏ−、＊−（Ｃ＝Ｏ）ＮＲ^３又は＊−ＮＲ^３−（Ｃ＝Ｏ）−を示し、Ｒ^３は水素原子又は炭素数１〜１０の有機基を示し、
Ｒ^６は、水素原子またはメチル基を示し、
Ｒ^７は、炭素数２〜４のアルキレン基を示し、
Ｒ^８は、炭素数１〜１０のアルキレン基を示し、
Ｒ^９、Ｒ^１０およびＲ^１１はそれぞれ独立して、水素原子または炭素数１〜８の炭化水素基を示し、ｑは、平均値で１〜１０を示す。）
一般式３

（一般式３中、
Ｘは炭素原子、＊―（Ｃ＝Ｏ）Ｏ−、＊−（Ｃ＝Ｏ）ＮＲ^３又は＊−ＮＲ^３−（Ｃ＝Ｏ）−を示し、Ｒ^３は水素原子又は炭素数１〜１０の有機基を示し、
Ｒ^１２は、水素原子またはメチル基を示し、
Ｒ^１３およびＲ^１４はそれぞれ独立して、水素原子、炭素数１〜６のアルキル基またはヒドロキシアルキル基を示す。）

一般式４

（一般式４中、
Ｘは炭素原子、＊―（Ｃ＝Ｏ）Ｏ−、＊−（Ｃ＝Ｏ）ＮＲ^３又は＊−ＮＲ^３（Ｃ＝Ｏ）−を示し、Ｒ^３は水素原子又は炭素数１〜１０の有機基を示し、
Ｒ^１５は、水素原子またはメチル基を示し、
Ｒ^１６およびＲ^１７はそれぞれ独立して、炭素数１〜３のアルキレン基を示す。）

一般式５

（一般式５中、Ｒ^１８は、炭素数１〜５のアルキレン基を示す。）

一般式６

（一般式６中、Ｘは炭素原子、＊―（Ｃ＝Ｏ）Ｏ−、＊−（Ｃ＝Ｏ）ＮＲ^３又は＊−ＮＲ^３（Ｃ＝Ｏ）−を示し、Ｒ^３は水素原子又は炭素数１〜１０の有機基を示し、
Ｙは、−（Ｃ＝Ｏ）Ｏ^-、−（Ｏ＝Ｓ＝Ｏ）Ｏ^-を示し、
Ｒ^１９は、水素原子またはメチル基を示し、
Ｒ^２０は、炭素数１〜１０の２価の有機基を示し、
Ｒ^２１およびＲ^２２はそれぞれ独立して、
炭素数１〜１０の炭化水素基を示し、
Ｒ^２３は、炭素数１〜１０の２価の有機基を示す。）

一般式７

（一般式７中、
Ｒ^２５は、水素原子またはメチル基を示し、Ｒ^２６は、−Ｏ−、＊−（Ｃ＝Ｏ）−Ｏ−、
＊−（Ｃ＝Ｏ）−ＮＲ^３１−、＊−ＮＲ^３１−（Ｃ＝Ｏ）−、
Ｒ^３１は、水素原子または炭素数１〜１０の有機基を示し、
＊は、一般式７中のＲ^２５が結合している炭素原子と結合する位置を示す。
Ｒ^２７は、炭素数１〜１０の２価の有機基を示し、
Ｒ^２８、Ｒ^２９およびＲ^３０はそれぞれ独立して、炭素数１〜１０の炭化水素基を示す。） The present invention also relates to the active energy ray-polymerizable resin composition for optical three-dimensional modeling, wherein the amine compound (Aa) is at least one represented by the following general formulas 2 to 7.

General formula 2

(In general formula 2,
X represents a carbon atom, *-(C = O) O-, *-(C = O) NR ³ or * -NR ^3- (C = O)-, and R ³ is a hydrogen atom or 1 to 10 carbon atoms. Indicates an organic group of
R ⁶ represents a hydrogen atom or a methyl group and represents
R ⁷ represents an alkylene group having 2 to 4 carbon atoms.
R ⁸ represents an alkylene group having 1 to 10 carbon atoms.
R ⁹ , R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and q represents 1 to 10 on average. )
General formula 3

(In general formula 3,
X represents a carbon atom, *-(C = O) O-, *-(C = O) NR ³ or * -NR ^3- (C = O)-, and R ³ is a hydrogen atom or 1 to 10 carbon atoms. Indicates an organic group of
R ¹² represents a hydrogen atom or a methyl group and represents
R ¹³ and R ¹⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group. )

General formula 4

(In general formula 4,
X represents a carbon atom, *-(C = O) O-, *-(C = O) NR ³ or * -NR ³ (C = O)-, and R ³ is a hydrogen atom or 1 to 10 carbon atoms. Shows organic groups
R ¹⁵ represents a hydrogen atom or a methyl group and represents
R ¹⁶ and R ¹⁷ each independently represent an alkylene group having 1 to 3 carbon atoms. )

General formula 5

(In the general formula 5, R ¹⁸ represents an alkylene group having 1 to 5 carbon atoms.)

General formula 6

(In general formula 6, X represents a carbon atom, *-(C = O) O-, *-(C = O) NR ³ or * -NR ³ (C = O)-, and R ³ is a hydrogen atom or It shows an organic group with 1 to 10 carbon atoms.
Y indicates − (C = O) O ⁻ , − (O = S = O) O ⁻ ,
R ¹⁹ represents a hydrogen atom or a methyl group and represents
R ²⁰ represents a divalent organic group having 1 to 10 carbon atoms.
R ²¹ and R ²² are independent of each other
Shows hydrocarbon groups with 1 to 10 carbon atoms
R ²³ represents a divalent organic group having 1 to 10 carbon atoms. )

General formula 7

(In general formula 7,
R ²⁵ represents a hydrogen atom or a methyl group, and R ²⁶ is -O-, *-(C = O) -O-,
^{* - (C = O) -NR} 31 -, * - NR 31 - (C = O) -,
R ³¹ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms.
* Indicates the position where R ²⁵ in the general formula 7 is bonded to the carbon atom to which it is bonded.
R ²⁷ represents a divalent organic group having 1 to 10 carbon atoms.
R ²⁸ , R ²⁹ and R ³⁰ each independently represent a hydrocarbon group having 1 to 10 carbon atoms. )

Further, in the present invention, the optical three-dimensional modeling in which the compound (B) is at least one of a compound having a siloxane structure and a (meth) acrylic group (B1) and a compound having a siloxane structure and a vinyl group (B2). The present invention relates to an active energy ray-polymerizable resin composition.

The present invention further relates to the active energy ray-polymerizable resin composition for optical three-dimensional modeling, which further comprises a photoinitiator (C).

The present invention further relates to the active energy ray-polymerizable resin composition for optical three-dimensional modeling, which further comprises a catalyst (D) having active energy ray activity.

The present invention further relates to the active energy ray-polymerizable resin composition for optical three-dimensional modeling, which further contains another α, β-unsaturated double bond group-containing compound (E).

Further, the present invention relates to 100 parts by weight of the active energy ray-polymerizable composition.
0.01 to 50 parts by weight of α, β-unsaturated double bond group-containing compound (A) having an ability to promote cell-cell adhesion.
0.01 to 95 parts by weight of the α, β-unsaturated double bond group-containing compound (B) having silicon;
0 to 30 parts by weight of photoinitiator (C);
The present invention relates to the above-mentioned active energy ray-polymerizable resin composition for optical three-dimensional modeling, which comprises 0 to 50 parts by weight of another α, β-unsaturated double bond group-containing compound (E).

The present invention also relates to a cured product obtained by curing the active energy ray-polymerizable resin composition for optical three-dimensional modeling with active energy rays.

The present invention also relates to a three-dimensional model made of the cured product.
The present invention also relates to a cell culture substrate made of the three-dimensional model.

According to the present invention, a cell culture container using a curable material for optical three-dimensional modeling, a medical device such as a microchip, and a medical device, which suppresses protein adsorption and exhibits excellent cell adhesion prevention and oxygen permeability effects, and A method for producing the cell culture equipment can be provided.

By using the curable material for optical three-dimensional modeling of the present invention, it is possible to provide a container for cell culture capable of maintaining oxygen supply. As a result, hepatocyte spheroid culture can be performed, and the culture environment of hepatocytes can be imitated in vitro, which is useful for basic research such as liver metabolism.

<Active energy ray-polymerizable resin composition for optical three-dimensional modeling>
The active energy ray-polymerizable resin composition for optical three-dimensional modeling of the present invention comprises an α, β-unsaturated double bond group-containing compound (A) having an ability to promote adhesion between cells and α, having silicon. It is characterized by containing a β-unsaturated double bond group-containing compound (B) (excluding those corresponding to the compound (A)) as an essential component, and is cured by curing with active energy rays. And provide three-dimensional shaped objects.
Here, the "active energy ray" means an energy ray in a broad sense capable of providing the energy required for activation for causing a chemical reaction, including ultraviolet rays, visible rays, infrared rays, electron beams, and radiation. .. In the active energy ray-polymerizable resin composition of the present invention (hereinafter referred to as "resin composition"), the polymerization reaction proceeds by irradiation with the above-mentioned active energy rays to form a cured product. Although not particularly limited, in one embodiment of the present invention, the active energy ray is preferably a light energy ray containing ultraviolet rays.

Hereinafter, the constituent components of the active energy ray-polymerizable resin composition for optical three-dimensional modeling will be specifically described.
A feature of the active energy ray-polymerizable resin composition for optical three-dimensional modeling is that it has a quick-curing property that cures in a short time as compared with thermosetting, and is energy-saving. It is a one-component system and is also characterized by excellent workability.
The curable composition for optical three-dimensional modeling of the present application has an α, β-unsaturated double bond-containing compound (A) having an ability to promote adhesion between cells and an α, β-unsaturated double having silicon. It is characterized by containing a binding group-containing compound (B).
Further, the curable composition for optical three-dimensional modeling is a radical reaction type curable composition for optical three-dimensional modeling (R) and an addition reaction type curable composition for optical three-dimensional modeling using a platinum catalyst, depending on the curing type. It is classified into (Ad).
The composition (R) of the present application includes an α, β-unsaturated double bond group-containing compound (A) having an ability to promote the adhesion between cells, and a compound (B1) having a siloxane structure and a (meth) acrylic group. ) Is contained, and if necessary, a photoinitiator (C) is contained. Further, it may further contain a photosensitizer (F), another α, β-unsaturated double bond group-containing compound (E), and a compound having a vinyl group bonded to siloxane (B2). By conducting a radical polymerization reaction, the reaction has a relatively high activity.
The composition (Ad) of the present application includes an α, β-unsaturated double bond group-containing compound (A) having an ability to promote the adhesion between cells, and a compound (B2) having a siloxane structure and a vinyl group. By further containing the catalyst (D) having active energy ray activity, it is possible to crosslink and cure by an addition reaction, and it is excellent in heat resistance and insulating property. The composition (Ad) preferably contains a siloxane (G) having a hydrogen atom bonded to silicon.

In the present application, especially when it is described as "(meth) acryloyl", "(meth) acrylic acid", "(meth) acrylate", "(meth) acryloyloxy", and "(meth) allyl". Unless otherwise stated, "acryloyl and / or methacrylic acid", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", "acryloyloxy and / or methacryloyloxy", and "allyl and / or metalyl", respectively. It shall represent.

<Α, β-unsaturated double bond group-containing compound (A) that promotes adhesion between cells>
As one of the methods for forming a tissue having a three-dimensional structure closer to that of a living body, a spheroid (cell aggregate) culture method using the original agglutination reaction of adhesive cells has been known from the beginning. The formed spheroids are closer to the living tissue than the monolayer of cells attached to the scaffold, and therefore, by using the spheroids, for example, the effect of the drug on the living tissue can be more easily evaluated.
The facilitation of cell-to-cell adhesion is the promotion of spheroid formation by culturing adherent cells on a non-adhesive scaffold or without using a scaffold in the spheroid culture method. For example, it means preventing adhesion between adherent cells such as scaffold-dependent cells, which have low protein adsorption properties such as betaine and PEG, and various substrate surfaces to which such cells come into contact. ..
The α, β-unsaturated double bond group-containing compound (A) having the ability to promote the adhesion between cells of the present application has the ability to promote the adhesion between cells and is an α, β-unsaturated double. It is not particularly limited as long as it contains a binding group.

In the present application, it is preferable that the compound (A) is an amine compound (Aa) or a compound represented by the following general formula 1 (Ap) as a compound having an adhesive action between cells. Only one of these may be used, or a plurality of types may be used in combination.

（一般式１中、
Ｒ¹は炭素数２〜４のアルキレン基、
Ｒ^２は水素原子又は炭素数１〜４のアルキル基、
Ｘは炭素原子、＊―（Ｃ＝Ｏ）Ｏ−、＊−（Ｃ＝Ｏ）ＮＲ^３又は＊−ＮＲ^３（Ｃ＝Ｏ）−、ｆは２〜１００の整数を示し、
Ｒ^３は水素原子又は炭素数１〜１０の有機基、＊は、一般式１中のＲ^４が結合している炭素原子と結合する位置を示し、
Ｒ^４は水素原子又はメチル基を示す。） General formula 1

(In general formula 1,
R ¹ is an alkylene group having 2 to 4 carbon atoms,
R ² is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
X is a carbon atom, *-(C = O) O-, *-(C = O) NR ³ or * -NR ³ (C = O)-, f is an integer of 2 to 100.
R ³ indicates a hydrogen atom or an organic group having 1 to 10 carbon atoms, and * indicates a position in the general formula 1 where R ⁴ is bonded to a carbon atom.
R ⁴ represents a hydrogen atom or a methyl group. )

f-number of R ¹ may be the same or different, a plurality of R ¹ contained in the repeating units may be the same or different. Hereinafter, as for other codes in each structural unit, a plurality of groups having the same code contained in the repeating unit may be the same or different.
f is preferably an average value of 2 to 90, more preferably an average value of 8 to 85, still more preferably an average value of 8 to 60, and even more preferably an average value of 8 to 50. Particularly preferably, the average value is 10 to 45.

In addition, each "mean value" in this specification can be measured by NMR. For example, for the structure of the following general formula 1, ^{1 1} H-NMR is measured, and the alkylene group having 2 to 4 carbon atoms of R ¹ and the methyl group at the end of the alkyl group having 1 to 4 carbon atoms of R ² are determined. The average value of f can be calculated by comparing the integrated values of the respective proton peaks.
The carbon number of the alkylene group represented by R ¹ is preferably 2 or 3, and more preferably 2. The alkylene group represented by R ¹ may be linear or branched, and specifically, ethane-1,2-diyl group, propane-1,2-diyl group, propane-1,3-diyl. Examples thereof include a group, a propane-2,2-diyl group, a butane-1,2-diyl group, a butane-1,3-diyl group, a butane-1,4-diyl group and the like.
The number of carbon atoms in the alkyl group in R ² is preferably 1 to 3, more preferably 1 or 2, more preferably 1. The alkyl group represented by R ² may be linear or branched, and specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl. Groups include tert-butyl groups.
The carbon number of the organic group in R ³ is preferably 1 to 6. Examples of the organic group include a hydrocarbon group. Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group. The aliphatic hydrocarbon group for R ³ may be either linear or branched, and specific examples thereof include a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, isobutyl group, sec- butyl group , Tart-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and other alkyl groups.
Among X, *-(C = O) -O- is preferable.
Examples of the compound (Ap) represented by the following general formula 1 include compounds obtained by using these alone or by using two or more kinds thereof.

In the present invention, the compound (Ap) represented by the general formula 1 has a polyoxyalkylene hydrophilic skeleton. Examples of the compound having a polyoxyalkylene structure include polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polyethylene glycol polypropylene glycol (meth) acrylate, polyethylene glycol polytetramethylene glycol (meth) acrylate, and polypropylene glycol poly. Examples thereof include tetramethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, and ethoxypolyethylene glycol (meth) acrylate. Among these, polyethylene glycol (meth) acrylate and methoxypolyethylene glycol (meth) acrylate are preferable. Examples of the compound (Ap) include repeating units obtained by using these alone or by using two or more kinds thereof.
Examples of commercially available compounds (Ap) include NOF's Bremer series, and examples thereof include PME-1000, PME-400, and PME-200.

In the present invention, it is preferable to use at least one of the following general formulas 2 to 7 as the amine compound (Aa). Only one of these may be used, or a plurality of types may be used in combination.

General formula 2

(In general formula 2,
X is a carbon atom, *-(C = O) O-, *-(C = O) NR ³ or * -NR ^3- (C = O)-, R ³ is a hydrogen atom or an organic having 1 to 10 carbon atoms. Show the group,
R ⁶ represents a hydrogen atom or a methyl group and represents
R ⁷ represents an alkylene group having 2 to 4 carbon atoms.
R ⁸ represents an alkylene group having 1 to 10 carbon atoms.
R ⁹ , R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and q represents 1 to 10 on average. )

The carbon number of the alkylene group in R ⁷ is preferably 2 or 3, and more preferably 2.
The alkylene group in R ⁷ may be linear or branched, and examples thereof include groups similar to the group exemplified in R ¹ .
In the case where R ⁷ is more, R ⁷ may be the same or different.
The carbon number of the alkylene group in R ⁸ is preferably 1 to 6, more preferably 1 to 4, still more preferably 2 or 3, and particularly preferably 2.
The alkylene group in R ⁸ may be linear or branched, and a suitable specific example thereof is a group similar to the alkylene group in R ⁷ .
R ⁹ , R ¹⁰ and R ¹¹ are each independently preferably a hydrocarbon group having 1 to 8 carbon atoms. The number of carbon atoms of such a hydrocarbon group is preferably 1 to 4, more preferably 1 or 2, and particularly preferably 1. Examples of the hydrocarbon group include an alkyl group; an aryl group such as a phenyl group; and an aralkyl group such as a benzyl group, and an alkyl group is preferable.
The alkyl group may be linear or branched, and suitable specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-. Butyl group is mentioned.
q is preferably an average value of 1 to 7, more preferably an average value of 1 to 4, and particularly preferably 1.

The compound (Aa-1) represented by the general formula 2 includes alkali metal ions such as sodium ion and potassium ion, alkaline earth metal ions such as calcium ion and magnesium ion, ammonium ion, hydrogen ion and hydroxide. It may have a counter ion such as an ion.

In the present invention, the compound (Aa-1) represented by the general formula 2 is 2- (meth) acryloyloxyethyl-2'-(trimethylammonio) ethyl phosphate (2- (meth) acryloyloxyethyl phosphorylcholine). , 3- (Meta) acryloyloxypropyl-2'-(trimethylammonio) ethyl phosphate, 4- (meth) acryloyloxybutyl-2'-(trimethylammonio) ethyl phosphate, 2- (meth) acryloyloxyethoxyethyl -2'-(trimethylammonio) ethyl phosphate, 2- (meth) acryloyloxydiethoxyethyl -2'-(trimethylammonio) ethyl phosphate, 2- (meth) acryloyloxyethyl -2'-(triethylammonio) ) Ethyl phosphate, 2- (meth) acryloyloxyethyl-2'-(tributylammonio) ethyl phosphate and the like.

Examples of the compound (Aa-1) represented by the general formula 2 include repeating units obtained by using these alone or by using two or more kinds thereof.
Examples of commercially available products of the compound compound (Aa-1) represented by the general formula 2 include 2-methacryloyloxyethyl phosphorylcholine manufactured by Tokyo Kasei.

General formula 3

(In general formula 3,
X is a carbon atom, *-(C = O) O-, *-(C = O) NR ³ or * -NR ^3- (C = O)-,
R ³ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms.
R ¹² represents a hydrogen atom or a methyl group and represents
R ¹³ and R ¹⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group. )

The compound (Aa-2) represented by the general formula 3 preferably has an amide group.
The number of carbon atoms of the alkyl group in R ¹³ and R ¹⁴ is preferably 1 to 3. Further, the alkyl group may be linear or branched, and suitable specific examples thereof include a methyl group, an ethyl group, an n-propyl group and an isopropyl group. The number of carbon atoms of the hydroxyalkyl group in R ¹³ and R ¹⁴ is preferably 1 to 6, and more preferably 1 to 3. The alkyl group contained in the hydroxyalkyl group may be linear or branched, and preferred specific examples of the hydroxyalkyl group include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxyisopropyl group. The substitution position of the hydroxy group in the hydroxyalkyl group is arbitrary.
Examples of the compound (Aa-2) represented by the general formula 3 include compounds obtained by using these alone or by using two or more kinds thereof.

In the present invention, the compound (Aa-2) represented by the general formula 3 includes dimethyl (meth) acrylamide, diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and N- (hydroxymethyl) (meth) acrylamide. , N- (2-Hydroxyethyl) (meth) acrylamide and the like.
Examples of commercially available products of the compound (Aa-2) include dimethylacrylamide (DMAA) manufactured by KJ Chemicals.

General formula 4

(In general formula 4,
X is a carbon atom, *-(C = O) O-, *-(C = O) NR ³ or * -NR ³ (C = O)-, R ³ is a hydrogen atom or an organic group having 1 to 10 carbon atoms. Shows,
R ¹⁵ represents a hydrogen atom or a methyl group and represents
R ¹⁶ and R ¹⁷ each independently represent an alkylene group having 1 to 3 carbon atoms. )

The carbon number of the alkylene group in R ¹⁶ and R ¹⁷ is preferably 1 to 2.
Further, the alkylene group may be linear or branched, but linear is preferable. Suitable specific examples include a methane-1,1-diyl group and an ethane-1,2-diyl group.
Examples of the compound (Aa-3) represented by the general formula 4 include compounds obtained by using the monomer alone or by using two or more kinds of the monomers.
In the present invention, examples of the compound (Aa-3) represented by the general formula 4 include 4- (meth) acryloyl morpholine and the like.
Examples of commercially available compounds (Aa-3) include acryloyl morpholine (ACMO) manufactured by KJ Chemicals.

General formula 5

(In general formula 5,
R ¹⁸ represents an alkylene group having 1 to 5 carbon atoms. )

The number of carbon atoms of the alkylene group for R ¹⁸ is preferably 3-5.
Further, the alkylene group may be linear or branched, but linear is preferable. Suitable specific examples include a propane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1,5-diyl group.
Examples of the compound (Aa-4) represented by the general formula 5 include compounds obtained by using the monomer alone or by using two or more kinds of the monomers.
In the present invention, examples of the compound (Aa-4) represented by the general formula 5 include 1-vinyl-2-pyrrolidone, N-vinyl-ε-caprolactam and the like.
Examples of commercially available compounds (Aa-4) include N-vinylpyrrolidone manufactured by Wako Pure Chemical Industries, Ltd.

General formula 6

(In general formula 6,
X is a carbon atom, *-(C = O) O-, *-(C = O) NR ³ or * -NR ³ (C = O)-, R ³ is a hydrogen atom or an organic having 1 to 10 carbon atoms. Show the group,
Y indicates − (C = O) O ⁻ , − (O = S = O) O ⁻ ,
R ¹⁹ represents a hydrogen atom or a methyl group and represents
R ²⁰ represents a divalent organic group having 1 to 10 carbon atoms.
R ²¹ and R ²² are independent of each other
Shows hydrocarbon groups with 1 to 10 carbon atoms
R ²³ represents a divalent organic group having 1 to 10 carbon atoms. )

As Y, − (C = O) O− is preferable.
The number of carbon atoms of the divalent organic group in R ²¹ and R ²² is preferably 1 to 8, and more preferably 1 to 6. Further, as the divalent organic group, a divalent hydrocarbon group is preferable, and a divalent aliphatic hydrocarbon group is more preferable. The divalent aliphatic hydrocarbon group may be linear or branched. Further, as the divalent aliphatic hydrocarbon group, an alkanediyl group is preferable. For example, methane-1,1-diyl group, ethane-1,2-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-1,3-diyl group, propane-2. , 2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group.
The number of carbon atoms of the hydrocarbon group in R ²¹ and R ²² is preferably 1 to 6, and more preferably 1 to 4.
Examples of the hydrocarbon group in R ²¹ and R ²² include an alkyl group; an aryl group such as a phenyl group; an aralkyl group such as a benzyl group, and an alkyl group is preferable. The alkyl group may be linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group. Be done. The compound (Aa-5) represented by the general formula 6 includes alkali metal ions such as sodium ion and potassium ion, alkaline earth metal ions such as calcium ion and magnesium ion, ammonium ion, hydrogen ion, and hydroxide. It may have a counter ion such as an ion.

In the present invention, the compound (Aa-5) represented by the general formula 6 includes N- (meth) acryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine, and N- (meth) acryloyl. Examples thereof include (meth) acrylate-based monomers such as oxyethyl-N and N-dimethylammonium-α-N-propylsulfobetaine, vinyl-based monomers, and the like.
Examples of commercially available products of the compound (Aa-5) include FAM-101 manufactured by Fujifilm.

General formula 7

(In general formula 7,
R ²⁵ represents a hydrogen atom or a methyl group, and R ²⁶ is -O-, *-(C = O) -O-,
^{* - (C = O) -NR} 31 -, * - NR 31 - (C = O) -, R 3 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms,
R ³¹ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms.
* Indicates the position where R ²⁵ in the general formula 7 is bonded to the carbon atom to which it is bonded.
R ²⁷ represents a divalent organic group having 1 to 10 carbon atoms.
R ²⁸ , R ²⁹ and R ³⁰ each independently represent a hydrocarbon group having 1 to 10 carbon atoms. )

The carbon number of the organic group in R ³¹ is preferably 1 to 6. Examples of the organic group include a hydrocarbon group.
As the compound (Aa-6) represented by the general formula 7, these can be used alone or in combination of two or more.

In the present invention, the compound (Aa-6) represented by the general formula 7 includes ((meth) acryloyloxy C1-10 alkyl) tri-C1-10 alkylammonium chloride such as (meth) acryloyloxyethyl) trimethylammonium chloride. , ((Meta) acryloyloxyethyl) dimethylbenzylammonium chloride and the like ((meth) acryloyloxy C1-10 alkyl) di C1-10 alkyl C6-10 aralkylammonium chloride. Examples of the monomer species of (meth) acrylamides include (3- (meth) acrylamide C1-10 alkyl) tri-C1-10 alkylammonium chlorides such as (3- (meth) acrylamidepropyl) trimethylammonium chloride, and (3- (meth) acrylamides. ) Acrylamide) Di dimethylbenzylammonium chloride and the like (3- (meth) acrylamide C1-10 alkyl) di C1-10 alkyl C6-10 aralkylammonium chloride and the like.
Examples of commercially available products of the compound (Aa-6) include dimethylamine propyl acrylamide salt methyl quaternary salt (DMAPAA-Q) manufactured by KJ Chemicals.

The total content of compound (A) is preferably 0.01 to 50% by mass, more preferably 5 to 95% by mass, based on the total amount of the composition.
When the total content of the compound (A) is within the above range, it has the ability to promote the adhesion between cells, is more excellent in the cell adhesion prevention performance, and is more excellent in the biological sample adhesion prevention performance.

<Α, β-unsaturated double bond group-containing compound (B) having silicon>
The α, β-unsaturated double bond group-containing compound (B) having silicon excludes the compound (A). Silicon is preferably contained as a siloxane structure, and it is preferable to use at least one of a compound having a siloxane structure and a (meth) acrylic group (B1) and a compound having a siloxane structure and a vinyl group (B2). .. The α, β-unsaturated double bond group-containing compound (B) having silicon is contained in the active energy ray-polymerizable resin composition for optical three-dimensional modeling to provide oxygen permeability to the three-dimensional model made of a cured product. Can be granted. The α, β-unsaturated double bond group-containing compound (B) having silicon may be used alone or in combination of two or more.

<Curing composition for radical reaction type optical three-dimensional modeling (R)>
[Compound with siloxane structure and (meth) acrylic group (B1)]
The compound (B1) having a siloxane structure and a (meth) acrylic group is not particularly limited as long as it has at least one siloxane structure and a (meth) acrylic group in one molecule.
Polysiloxane having any structure used as a curable resin, such as linear, branched, and cyclic, can be used. The (meth) acrylic group may be present at any position in the polysiloxane structure, and may be located at any position at the end of the molecule or inside the molecular chain.
However, the compound (B1) preferably does not contain a mercapto group.
Preferred compounds (B1) include linear polysiloxanes having one (meth) acrylic group at the end of the molecule. Examples of such a preferable compound (B1) include, but are not limited to, organopolysiloxane represented by the following general formula 8.

General formula 8

(In general formula 8,
W is an independently unsubstituted or substituted C1-6 alkyl group or C6-12 aryl group, and l is 5 ≦ l ≦ 10,000.
G is independently the following general formula (Ia):

−Q ¹ −Si (W ² ) _p (W ³ ) _3-p (Ia)

In the general formula (Ia),
Q ¹ is a C2-4 alkylene group or an oxygen atom.
W ² is independently an acrylic or methacrylic group and
W ³ is an independently unsubstituted or substituted C1-9 alkyl group, C1-9 alkoxy group or C6-12 aryl group.
p is 1, 2 or 3)

(Ia) In general formula 8, W independently represents a C1-6 alkyl group (eg, methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, s-butyl group, tert-butyl group, It is a pentyl group, a hexyl group, etc.) or a C6-12 aryl group (for example, a phenyl group, a tolyl group, a naphthyl group, etc.). W may have a substituent. Examples of substituents include, but are not limited to, halogens, hydroxys, aminos, carbonyls and the like.
A methyl group is preferable from the viewpoint of ease of synthesis and economy, and a phenyl group is preferable from the viewpoint of optical viewpoint and high refractive index. To provide a high refractive index to the composition (B) is preferably the number of the phenyl groups is 5% or more of the total number of groups W ^1, and more preferably in the range of 5-50%.
l is in the range of 5 ≦ l ≦ 10,000. From the viewpoint of compatibility with other components, l is preferably 3,000 or less, more preferably 1,500 or less.
The compound (B1) represented by the general formula 8 has two groups represented by the formula (Ia) bonded to the silicon atom at the end of the organopolysiloxane structure as G. The groups represented by the two formulas (Ia) may be the same or different from each other.
Q ¹ is a site that connects two silicon atoms, and is a C2-4 alkylene group or an oxygen atom. When Q ¹ is a C2-4 alkylene group, it may be linear or branched. Further, the two silicon atoms to which Q ¹ is bonded may be bonded by the same carbon atom in the C2-4 alkylene group.
The group represented by the formula (Ia) has a p of 1, 2 or 3, and the group represented by the formula (Ia) contains at least one acrylic group or a methacrylic group as W ² .
When the group represented by the formula (Ia) has two or three (meth) acrylic groups, all of them may be acrylic groups, all of them may be methacrylic groups, and both acrylic groups and methacrylic groups may be used. You may have.
In the group represented by formula (Ia), W ³ is an independently unsubstituted or substituted C1-9 alkyl group, C1-9 alkoxy group or C6-12 aryl group. The number of W ³ per group represented by the formula (Ia) is 0, 1 or 2, and varies depending on the value of p. When two W ^3s are contained in the group represented by the formula (Ia), each W ³ may be the same or different from each other.

The compound (B1) may be used alone or in combination of two or more. When two or more types are used in combination, the polysiloxane represented by the general formula 8 and other polysiloxanes can be used in combination. The amount of the compound (B1) contained in the composition of the present invention is preferably in the range of 0.01 to 90 parts by mass with respect to 100 parts by mass of the entire resin composition.
Examples of commercially available products of compound (B1) include (Silaplane) FM-0711, FM-0721, FM-0725, TM-0701T manufactured by JNC Corporation, and X-22-2445 manufactured by Shin-Etsu Chemical Co., Ltd.

[Photoinitiator (C)]
The curable composition of the present invention can accelerate the polymerization reaction by using the photoinitiator (C). In one embodiment of the present invention, the activation energy is preferably ultraviolet rays, and when the polymerization reaction is allowed to proceed by irradiation with ultraviolet rays, it is preferable to include a photoinitiator (C).
In the present invention, as the photoinitiator (C), a compound arbitrarily selected from known compounds as an active energy ray polymerization initiator can be used.

Specific examples include the following. 2,2-Dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthofluorenone, benzaldehyde, anthraquinone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4-diaminobenzophenone, benzoinpropyl ether, benzoin ethyl ether, benzyldimethyl Ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4-thioxanthone, phenylquinone, and 2 A photoradical generator such as −methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one.
In addition, examples of commercially available products include the following. Irgacure 184,907,651,1700,1800,819,369, and 261 (BASF), DAROCUR-TPO (BASF, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide), DaroCure-1173 Photoradical generators such as (Merck), EzaCure KIP150, and TZT (Nippon Kayaku Hegner), KayaCure BMS, and KayaCure DMBI (Nippon Kayaku Co., Ltd.).
It is also possible to use a photopolymerization initiator having at least one (meth) acryloyl group in the molecule.

In the present invention, the above-mentioned compounds can be used alone or in combination of two or more as the above-mentioned photoinitiator (C). From the viewpoint of reactivity, the blending ratio of the photoinitiator (C) is preferably in the range of 0.01 to 20 parts by weight, with the total amount of the active energy ray-polymerizable resin composition for optical three-dimensional modeling being 100 parts by weight. , More preferably in the range of 0.5 to 10 parts by weight. The curable material of the present invention is substantially free of organic solvents. The curable material preferably does not contain any organic solvent, but the photoinitiator (C) is often poorly soluble in the polymerizable component. Therefore, a small amount of organic solvent may be contained to dissolve the photoinitiator (C). The content of the organic solvent in the curable material is preferably 5% by weight or less.

[Sensitizer (F)]
Further, in order to improve the performance of the photoinitiator (C), a sensitizer (F) may be used in combination. Typical examples of the active energy ray sensitizer include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, and nitriles or other nitrogen-containing compounds. Among them, compounds such as anthracene-based or benzophenone-based, thioxanthone-based or perylene, phenothiazine, and rose bengal are preferably used.

To the composition (R), a compound (B2) having a siloxane structure and a vinyl group described later may be added. The addition of (B2) is preferable because the oxygen permeability is improved.

<Curing composition for addition reaction type optical three-dimensional modeling using platinum catalyst (Ad)>
[Compound having a siloxane structure and a vinyl group (B2)]
The compound (B2) having a siloxane structure and a vinyl group means a polysiloxane having a vinyl group bonded to a silicon atom. The content of the vinyl group is not particularly limited.
The compound (B2) having a siloxane structure and a vinyl group may have a substituent (organo group) bonded to a silicon atom, and for example, an alkyl group having 1 to 8 carbon atoms substituted or unsubstituted. , Substituent or unsubstituted alkoxy group having 1 to 8 carbon atoms, substituted or unsubstituted aryl group, substituted or unsubstituted aralkyl group and the like. Examples of the alkyl group having 1 to 8 carbon atoms include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. , Hexyl group, octyl group and the like. Of these, a methyl group is preferable.
Alkoxy groups having 1 to 8 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, hexyloxy group and Examples include the octyloxy group. Examples of the aryl group include a phenyl group and a methylphenyl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, a diphenylmethyl group and the like.
Examples of the group that can be substituted with the alkenyl group, alkyl group, alkoxy group, aryl group, or aralkyl group include a halogen atom, an acyl group, an alkyl group, a phenyl group, an alkoxyl group, an amino group, and an alkylamino group. Examples thereof include a carbonyl group and a cyano group.
The compound (B2) having a siloxane structure and a vinyl group may be linear, branched, or cyclic. In addition, these may be used alone or in combination of two or more.
Examples of commercially available products of the compound (B2) having a siloxane structure and a vinyl group include both-terminal vinylpolydimethylsiloxane PDV-1631Gelest manufactured by Azmax.

"Siloxane (G) having a hydrogen atom bonded to silicon"
The composition (Ad) preferably further contains a siloxane (G) having a hydrogen atom bonded to silicon.
The siloxane (G) having a hydrogen atom bonded to silicon is a polysiloxane having at least two hydrogen atoms bonded to a silicon atom. The two hydrogens are added to the double bond of the vinyl group of the compound (B2) having a siloxane structure and a vinyl group by irradiation with active energy rays to form a crosslinked structure, and an addition reaction type using a platinum catalyst is used. A curable composition (Ad) for optical three-dimensional modeling can be obtained.

Further, the siloxane (G) having a hydrogen atom bonded to silicon may have a substituent (organo group) other than the hydrogen atom, and the substituent is the same as that exemplified in the above polysiloxane. Can be mentioned.
The proportion of the compound (B2) having a siloxane structure and a vinyl group and the siloxane (G) having a hydrogen atom bonded to silicon used in producing the curable composition (Ad) is not particularly limited, but the siloxane is not particularly limited. The number of hydrogen atoms bonded to the silicon atom contained in the siloxane (G) having a hydrogen atom bonded to silicon is 0.5 to 3 with respect to 1 mol of the alkenyl group contained in the compound (B2) having a structure and a vinyl group. The ratio is preferably 0 mol.
Examples of commercially available products of siloxane (G) having a hydrogen atom bonded to silicon include methylhydrogenpolysiloxane HMS-031 manufactured by Azmax.

[Catalyst (D)]
The curable composition for addition-reaction type optical three-dimensional modeling (Ad) using a catalyst includes the compound (B2) having the above-mentioned siloxane structure and vinyl group and the above-mentioned siloxane (G) having a hydrogen atom bonded to silicon. May further include a catalyst catalyst (D) for cross-linking.
The catalyst is not particularly limited, but is preferably a platinum-based catalyst. Specifically, platinum black, silica-supported platinum, carbon-supported platinum, chloroplatic acid, chloroplatinate alcohol solution, platinum / olefin complex, and platinum. / Alkenylsiloxane complex, platinum / β-diketone complex, platinum / phosphine complex and the like can be mentioned. In the present application, a (methylcyclopentadienyl) trimethyl platinum catalyst or a bisacetylacetonato platinum (II) catalyst is preferably used.
The catalyst is added so as to be about 0.1 to 500 ppm (Pt equivalent) with respect to the total amount of the compound (B2) having a siloxane structure and a vinyl group and the siloxane (G) having a hydrogen atom bonded to silicon. It is preferable to do so.
Examples of commercially available products of the catalyst (D) include platinum-divinyltelolamethyldisiloxane complex SIP6831.2 manufactured by Azmax.

[Other α, β-unsaturated double bond group-containing compounds (E)]
In the curable composition for optical three-dimensional modeling of the present invention, in addition to the above essential components, other α, β-unsaturated double bond group-containing compound (E) (however, the compound (A), the compound ( B) is to be excluded.) May be included.
By using other α, β-unsaturated double bond group-containing compound (E), the glass transition point (Tg) of the modeled product can be improved to develop high cohesive force, and heat resistance, water resistance, etc. It is possible to form a three-dimensional model having good resistance to the above.
In particular, any compound containing one or more α, β-unsaturated double bond groups can be used without particular limitation, but α, β-ethylene containing one or more hydroxyl groups in its structure can be used. It is preferable to contain the sex-unsaturated double bond group-containing compound (e1) in terms of improving the reaction rate and suppressing curing shrinkage. The compound (e1) is divided into a compound (e1-1) having a hydroxyl group and not having a cyclic structure and a compound (e1-2) having a hydroxyl group and having a cyclic structure, all of which have a hydroxyl group. Therefore, it shows a great effect in reducing the curing shrinkage associated with the polymerization reaction.
Further, in terms of improving durability such as heat resistance or moisture heat resistance, an α, β-ethylenically unsaturated double bond group-containing compound having no hydroxyl group in the molecule and having one or more cyclic structures. It is preferable to contain (e2). Further, other than (e1) and (e2), an α, β-ethylenically unsaturated double bond group-containing compound (e3) having no hydroxyl group and cyclic structure in the molecular structure can also be contained. Although not particularly limited, examples of the compound that can be used as the compound (E) include the following.

Among the α, β-ethylenically unsaturated double-bonding group-containing compound (e1) containing one or more hydroxyl groups, the compound (e1-1) having a hydroxyl group and not having a cyclic structure has a structure thereof. However, there is no particular limitation as long as it does not have a cyclic structure. For example, 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 2-hydroxy (meth) acrylate. Propyl, 3-hydroxypropyl (meth) acrylate, 1-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxy (meth) acrylate Butyl, (meth) acrylic acid 6-hydroxyhexyl, (meth) acrylic acid 8-hydroxyoctyl, cyclohexanedimethanol mono (meth) acrylic acid ester, (meth) acrylic acid 10-hydroxydecyl, (meth) acrylic acid 12- Hydroxylauryl, ethyl (meth) acrylate-α- (hydroxymethyl), monofunctional (meth) glycerol acrylate, or (meth) glycidyl lauric acid ester, (meth) glycidyl oleic acid ester, (meth) A fatty acid ester-based (meth) acrylic acid ester such as glycidyl stearate acrylate, or the hydroxyl group-containing α, β-ethylenically unsaturated double-bonding group such as 2- (acryloyloxy) ethyl 6-hydroxyhexanonate. Hydrophilic (meth) acrylic acid esters containing hydroxyl groups such as (meth) acrylic acid esters having a hydroxyl group at the terminal by ring-opening addition of ε-caprolactone to the contained compound; for example, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxy Butyl vinyl ether, hydroxyhexyl vinyl ether, hydroxyoctyl vinyl ether, hydroxydecyl vinyl ether, hydroxydodecyl vinyl ether, hydroxyoctadecyl vinyl ether, glyceryl vinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, trimethylolpropane monovinyl ether, pentaerythritol monovinyl ether, etc. Acrylic vinyl ethers containing hydroxyl groups; for example, (meth) allyl alcohol, isopropenyl alcohol, dimethyl (meth) allyl alcohol, hydroxyethyl (meth) allyl ether, hydroxy Propyl (meth) allyl ether, hydroxybutyl (meth) allyl ether, hydroxyhexyl (meth) allyl ether, hydroxyoctyl (meth) allyl ether, hydroxydecyl (meth) allyl ether, hydroxydodecyl (meth) allyl ether, hydroxyoctadecyl ( Hydroxyl-containing aliphatic (meth) allyl alcohols or (meth) allyl ethers such as meta) allyl ether and glyceryl (meth) allyl ether; for example, propenediol, butenediol, heptenediol, octenediol, di (meth) acrylic. Α, β-ethylenic unsaturated double bond group-containing compounds having multiple hydroxyl groups such as glucerol acid;
Only one of these may be used, or a plurality of types may be used in combination.

Among the compounds (e1), the compound (e1-2) having a hydroxyl group and having a cyclic structure can be used without particular limitation as long as it has both a hydroxyl group and a cyclic structure. Since the compound (e1-2) has one or more ring structures in the molecule, it is preferable in terms of water resistance, etc., in addition to durability such as heat resistance and moisture heat resistance, even if it has a hydroxyl group. ..

The compound (e1-2) is not particularly limited as long as it has both a hydroxyl group and a cyclic structure in its structure. For example, (meth) acrylic acid 1,2-cyclohexanedimethanol and (meth) acrylic acid. 1,3-Cyclohexanedimethanol, (meth) acrylate 1,4-cyclohexanedimethanol, (meth) acrylate 2-hydroxy-3-phenoxymethyl, (meth) acrylate 2-hydroxy-3-phenoxyethyl, ( 2-Hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-phenoxybutyl (meth) acrylate, 2-hydroxy-3-phenoxydecyl (meth) acrylate, 2-hydroxy-hydroxy (meth) acrylate (Meta) acrylic acid having a cyclic structure other than a heterocycle with a hydroxyl group such as 3-phenoxyoctadecyl, monohydroxyethylphthalate (meth) acrylate, and 2- (4-benzoyl-3-hydroxyphenoxy) ethyl (meth) acrylate. Esters; for example, 2-hydroxy-4- {2- (meth) acryloyloxy} ethoxybenzophenone, 2-hydroxy-4- {2- (meth) acryloyloxy} butoxybenzophenone, 2,2'-dihydroxy-4- A hydroxyl group-containing benzophenone-based (meth) acrylic acid ester such as {2- (meth) acryloyloxy} ethoxybenzophenone, 2hydroxy-4- {2- (meth) acryloyloxy} ethoxy-4'-(2-hydroxyethoxy) benzophenone. Kind; for example, 2- (2'-hydroxy-5'-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-5'-(meth) acryloyloxyethylphenyl) -5 -Chloro-2H-benzotriazole, 2- (2'-hydroxy-5'-(meth) acryloyloxypropylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-5'-(meth) acryloyloxypropylphenyl) Phenyl) -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, and 2- (2' Hydroxyl-containing benzotriazole-based (meth) acrylic acid esters such as -hydroxy-3'-tert-butyl-5'-(meth) acryloyloxyethylphenyl) -5-chloro-2H-benzotriazole; for example, 2,4 -Diphenyl-6- [2-Hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2-methylphenyl) -6- [2-Hydroxy-4- { 2- (Meta) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2-methoxyphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S- Triazine, 2,4-bis (2-ethylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2-ethoxyphenyl) -6- [2-Hydroxy-4- {2- (meth) acryloyloxyethoxy}] -S-triazine, 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- { 2- (Meta) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2,4-diethoxylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}] -S-triazine and 2,4-bis (2,4-diethylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy})]-hydroxyl group-containing triazine such as -S-triazine Examples thereof include system (meth) acrylic acid esters, and these may be used alone or in combination of two or more.

The α, β-ethylenically unsaturated double bond group-containing compound (e2), which does not have a hydroxyl group in the molecule and has one or more cyclic structures, has a ring structure containing no hetero atom in the molecule. α, β-ethylenically unsaturated double bond group-containing compound (e2-1) and α, β-ethylenically unsaturated double bond group-containing compound (e2-2) having a ring structure containing a hetero atom in the molecule. ), But is not particularly limited, but (e2-1) is preferable in terms of heat-resistant yellowing.

The compound (e2-1) is not particularly limited as long as it has a ring structure other than the heterocycle in its structure. For example, cyclohexyl (meth) acrylate and 1-methyl-1 (meth) acrylate. Cyclopentyl, 1-ethyl-1-cyclopentyl (meth) acrylate, 1-isopropyl-1-cyclopentyl (meth) acrylate, 1-methyl-1-cyclohexyl (meth) acrylate, 1-ethyl-ethyl (meth) acrylate- 1-Cyclohexyl, 1-isopropyl-1-cyclohexyl (meth) acrylate, 1-ethyl-1-cyclooctyl (meth) acrylate, benzyl (meth) acrylate, iso-bornyl (meth) acrylate, (meth) Phenyl acrylate, 2-phenoxyethyl (meth) acrylate, 2-oxo-1,2-phenylethyl (meth) acrylate, 2-oxo-1,2-diphenylethyl (meth) acrylate, (meth) acrylic 1-naphthyl acid, 2-naphthyl (meth) acrylate, 1-naphthylmethyl (meth) acrylate, 1-anthryl (meth) acrylate, 2-anthryl (meth) acrylate, 9-anthryl (meth) acrylate , (Meta) 9-anthrylmethyl acrylate, 2-methyladamantyl-2-yl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, (meth) acrylic acid Dicyclopentenyloxyethyl, 2-ethyladamantyl-2-yl (meth) acrylate, 2-n-propyl adamantyl-2-yl (meth) acrylate, 2-isopropyladamantyl-2-yl (meth) acrylate, (Meta) Acrylic Acid 1- (adamantan-1-yl) -1-methylethyl, (meth) Acrylic Acid 1- (adamantan-1-yl) -1-ethylethyl, (meth) Acrylic Acid 1- (adamantan-1) -Il) -1-methylpropyl, (meth) acrylate 1 (adamantan-1-yl) -1-ethylpropyl, (meth) acrylate-5-oxo-4-oxa-tricyclonona-2-yl, (meth) ) Acrylic acid-5-oxo-4-oxa-tricyclodeca-2-yl, (meth) acrylate dihydro-α-turpinyl, (meth) acrylic acid-6-oxo-7-oxa-bicycloocta-2-yl, (Meta) Acrylic Acid-7-oxo-8-Oxa-bicycloocta-2-yl, 2- (meth) Acryloyloxyethylphthalate, 2- (Meta) Acryloy Luoxypropylphthalate, 2- (meth) acryloyloxybutylphthalate, 2- (meth) acryloyloxyhexylphthalate, 2- (meth) acryloyloxyoctylphthalate, 2- (meth) acryloyloxydecylphthalate, 2- (meth) Acryloyloxyethyl hexahydrophthalate, (meth) acrylic acid (3,4-epoxycyclohexyl) methyl, (meth) acrylic acid-o-2-propenylphenyl, (meth) cyclohexylglycidyl ester acrylate, phenyl (meth) acrylate (Meta) acrylic acid cyclic esters such as glycidyl ether;

For example, N- (4-carbamoylphenyl) (meth) acrylamide, β- (2-furyl) (meth) acrylamide, 2,3-bis (2-furyl) acrylamide, N- (9H-fluoren-2-yl). (Meta) acrylamide, N-[(R) -1-phenylethyl] (meth) acrylamide, N-[(S) -1-phenylethyl] (meth) acrylamide, (Z) -N-methyl-3-( Phenyl) (meth) acrylamide, (Z) -3- (fel) (meth) acrylamide, N, N-diethyl-3-phenyl (meth) acrylamide, (Z) -N, N-dimethyl-3- (phenyl) (Meta) acrylamides containing cyclic structures such as (meth) acrylamide. For example, (meth) acrylic acid cyclic esters containing a sulfonyl group such as sulfophenoxyethyl (meth) acrylate, sulfocyclohexyl (meth) acrylate, sulfobenzyl (meth) acrylate; for example, styrene, α-methylstyrene. , 2-Methylstyrene, 3-Methylstyrene, 4-Methylstyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, 4-t-butoxystyrene, 4-t-butoxy-α-methylstyrene, 4 -(2-Ethyl-2-propoxy) styrene, 4- (2-ethyl-2-propoxy) -α-methylstyrene, 4- (1-ethoxyethoxy) styrene, 4- (1-ethoxyethoxy) -α- Aromatic vinyl monomers such as methylstyrene, 1-butylstyrene, 1-chloro-4-isopropenylbenzene; for example, cyclohexyl vinyl ether, cycloxylmethyl vinyl ether, cyclohexyl ethyl vinyl ether, menthyl vinyl ether, tetrahydrofurfuryl vinyl ether, Cyclic vinyl ethers such as norbornenyl vinyl ether, 1-adamantyl vinyl ether, 2-adamantyl vinyl ether, phenyl vinyl ether, benzyl vinyl ether, 1-naphthyl vinyl ether, 2-naphthyl vinyl ether;

For example, vinylphenylpentyl ether, vinylphenylhexyl ether, vinylphenylheptyl ether, vinylphenyloctyl ether, vinylphenylnonyl ether, vinylphenyldecyl ether, vinylphenylundecyl ether, vinylphenyldodecyl ether, vinylphenyltridecyl ether, vinyl. Phenyltetradecyl ether, vinylphenyl pentadecyl ether, vinyl phenyl hexadecyl ether, vinyl phenyl heptadecyl ether, vinyl phenyl octadecyl ether, vinyl phenyl nonadecyl ether, vinyl phenyl eikosyl ether, vinyl phenyl hen eikosyl ether, vinyl phenyl doco Syl ether, vinyl phenyl methyl butyl ether, vinyl phenyl methyl pentyl ether, vinyl phenyl methyl hexyl ether, vinyl phenyl methyl heptyl ether, vinyl phenyl methyl octyl ether, vinyl phenyl methyl nonyl ether, vinyl phenyl methyl decyl ether, vinyl phenyl methyl undecyl ether , Vinylphenylmethyl dodecyl ether, vinylphenylmethyltridecyl ether, vinylphenylmethyltetradecyl ether, vinylphenylmethylpentadecyl ether, vinylphenylmethylhexadecyl ether,
Fragrance with long-chain alkyl groups such as vinylphenylmethylheptadecyl ether, vinylphenylmethyloctadecyl ether, vinylphenylmethylnonadecil ether, vinylphenylmethyleicosyl ether, vinylphenylmethylheneicosyl ether, vinylphenylmethyldocosyl ether, etc. Group vinyl ether-based monomers;

For example, hexyl 4-vinylbenzoate, octyl 4-vinylbenzoate, nonyl 4-vinylbenzoate, decyl 4-vinylbenzoate, dodecyl 4-vinylbenzoate, tetradecyl 4-vinylbenzoate, hexadecyl 4-vinylbenzoate, for example. , 4-decyl benzoate, 4-ecocil vinyl benzoate, docosyl 4-vinyl benzoate, 4-isopropenyl hexyl benzoate, 4-isopropenyl octyl benzoate, 4-isopropenyl nonyl benzoate, 4-isopropenyl Decyl benzoate, 4-isopropenyl dodecyl benzoate, 4-isopropenyl tetradecyl benzoate, 4-isopropenyl hexadecyl benzoate, 4-isopropenyl octadecyl benzoate, 4-isopropenyl benzoate eicosyl, 4-isopropenyl benzoic acid Vinyl benzoic acid ester-based or isopropenyl benzoic acid ester-based monomers having a long-chain alkyl group such as docosyl;

For example, isopropenylphenylmethylbutyl ether, isopropenylphenylmethylpentyl ether, isopropenylphenylmethylhexyl ether, isopropenylphenylmethylheptyl ether, isopropenylphenylmethyloctyl ether,
Isopropenylphenylmethylnonyl ether, isopropenylphenylmethyldecyl ether, isopropenylphenylmethylundecyl ether, isopropenylphenylmethyldodecyl ether, isopropenylphenylmethyltridecyl ether, isopropenylphenylmethyltetradecyl ether, isopropenylphenylmethylpenta Decyl ether, isopropenyl phenylmethyl hexadecyl ether, isopropenyl phenyl methyl heptadecyl ether, isopropenyl phenyl methyl octadecyl ether,
Isopropenylphenyl-based monomers having a long-chain alkyl group such as isopropenylphenylmethyl nonadesyl ether, isopropenylphenylmethyleicosyl ether, isopropenylphenylmethylheneicosyl ether, isopropenylphenylmethyldocosyl ether;

For example, monolong alkyl ester cyclic monomers of dicarboxylic acids such as vinylphenyl phenylnonyl succinate, vinyl phenylmethyl decyl hexahydrophthalate, vinyl phenylethyl dodecyl terephthalate;
Further, for example, if o-di (meth) allyl bisphenol A, hydrogenated bisphenol A having an aromatic ring structure, or the like also has an α, β-unsaturated double bond group, the compound (e2-1) can be used. included. Only one of these may be used, or a plurality of types may be used in combination.

As the compound (e2-1), cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-phenoxyethyl acrylate, iso-bornyl acrylate, di acrylate, from the viewpoint of durability such as heat resistance and water resistance. Cyclopentanyl, dicyclopentanyl diacrylate, dicyclopentenyl acrylate, dicyclopentenyl diacrylate, 2-ethyladamantyl-2-yl acrylate are particularly preferred.

The compound (e2-2) is not particularly limited as long as it has a heterocyclic structure in its structure. For example, pentamethylpiperidinyl (meth) acrylate and 4- (pyrimidine-2-yl) piperazine. Heterocyclic (meth) acrylic acid esters containing nitrogen atoms such as -1-yl (meth) acrylate;

For example, 1-vinylpyrrole, 1-vinyl-2-imidazoline, 1-vinyl-2-methyl-2-imidazoline, 1-vinylimidazole, 1-vinyl-1H-pyrazole, 1-vinyl-3,5-dimethyl- 1H-pyrazole, 3-methyl-5-phenyl-1-vinylpyrazole, 1-vinylindole, 1-vinyl-2-methyl-1H-indole, 1-vinylisoindole, 1-vinyl-1H-benzoimidazole, 1 -Vinyl Indazole, 1-Vinyl Pyrazole, 1-Vinyl Isoxalin, 1-Vinyl Kynazoline, 1-Vinyl Synnoline, 1-Vinyl Carbazole, 1,1'-Divinyl-2,2'-Bi (1H-Imidazole) , N-Vinyl-2-pyrrolidone, N-vinyl-ε-caprolactam, 1-vinylpyridine-2 (1H) -one, 1-vinyl-2 (1H) -pyridinethione and other nitrogen atom-containing heterocycles. Vinyl group-containing compounds;

For example, 1- (meth) allyl-1H-imidazole, 1- (meth) allyl-2-methyl-1H-imidazole, 1- (meth) allyl-3-methyl-1H-imidazole-3-ium, 1-( Meta) Allyl-3-ethyl-1H-imidazole-3-ium, 5-bromo-1- (meth) allyl-1H-pyrazole, 1- (meth) allyl piperazine, 1- (meth) allyl-5,5- Diethylpyrimidine, N- (meth) allyl-s-triazine-2,4,6-triamine, N- (meth) allyl-4,6-dichloro-1,3-5-triazine-2-amine, 1-benzyl -2-Vinyl piperazine, 1-benzyl-3-vinyl piperazine, 1,4-dimethyl-3-vinyl piperazine, 2-vinyl-4,6-diamino-1,3,5-triazine, 6-vinyl-1, Vinyl group-containing compounds having a 6-membered ring containing nitrogen atoms such as 3,5-dimethyl-2,4-diamine and 3-vinyl-1,2,4,5-tetrazine;

For example, 1-vinyl-1H-benzoimidazole, 1-vinyl-5,6-dimethyl-1H-benzoimidazole, 1-vinylindazole, 1-vinylquinolin, 1-vinylquinolin, 1-vinylisoquinolin, 1-vinyliso Xalin, 1-vinylquinoxalin, 1-vinylquinazoline, 1-vinylcinnoline, 1- (meth) allyl-1H-benzoimidazole, 1- (meth) allyl-3-methyl-1H-indazole, 1- (meth) ) Allyl-4-methyl-1H-indazole, N- (meth) allylquinolin-4-amine, di (meth) allylquinoline, 1,2-di (meth) allyl-1,2-dihydroisoquinolin and other nitrogen atoms. Heteropolycyclic ethenyl group-containing compounds containing; for example, 1- (meth) allyl-3,5-dimethyl-1H-pyrazol, 1- (1-methylpropyl) -5- (meth) allylpyrimidine, 1-. It has a heterocyclic structure containing nitrogen atoms such as (meth) allyl-5-isopropylpyrimidine, 1- (meth) allylpyridine, 1- (meth) allylpyridine, and 3,6-dihydro-1- (meth) allylpyridine. (Meta) allyl group-containing compounds;

For example, compounds having a nitrogen atom-containing heterocyclic structure such as 1-methyl-4,5-divinyl-1H-imidazole and two or more vinyl groups;
For example, 2- (meth) allyl-1H-indole, 3- (meth) allyl-1H-indole, 2- (meth) allyl indazole, 3-phenyl-4- (meth) allyl isoquinolin, 9- (meth) allyl. (Meta) allyl group-containing compounds having a heteropolycyclic structure containing nitrogen atoms such as -9H-carbazole;
For example, 2- (4-oxazoline-3-yl) ethyl (meth) acrylate, di (meth) acrylate-ethoxylated isocyanuric acid, tri (meth) acrylate-ethoxylated isocyanuric acid, ε-caprolactone-modified tris- (2-) Acryloyloxyethyl) isocyanurate, di (meth) acrylic acid isocyanuric acid ethylene oxide modification, tri (meth) acrylic acid isocyanuric acid ethylene oxide modification, etc. (meth) acrylic acid having a heterocyclic structure containing oxygen atoms in addition to nitrogen atoms Esters;

For example, 2-vinyloxazole, 2-phenyl-4-vinyloxazole, 2-phenyl-5-vinyloxazole, 5-ethoxy-2-vinyloxazole, 3-vinyl-5-nitrosooxazole, 2-vinyl-4,5 It has a heterocyclic structure containing an oxygen atom in addition to a nitrogen atom such as −diphenyloxazole, 2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-2-oxazoline-5-one, and 2-vinylbenzoxazole. Vinyl group-containing compounds;

For example, glycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ( -2-oxotetrahydropyran-4-yl acrylate, (meth) -4-methyl-2-oxotetrahydropyran-4-yl acrylate, -4-ethyl-2-oxotetrahydropyran (meth) acrylate -4-yl, (meth) acrylic acid-4-propyl-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-5-oxo tetrahydrofuran-3-yl, (meth) acrylic acid-2,2- Dimethyl-5-oxo tetrahydrofuran-3-yl, (meth) acrylic acid-4,4-dimethyl-5-oxotetra-3-yl, (meth) acrylic acid-2-oxotetra-3-yl, (meth) Acrylic acid-4,4-dimethyl-2-oxo tetrahydrofuran-3-yl, (meth) acrylic acid-5,5-dimethyl-2-oxotetra-3-yl, (meth) acrylic acid-2-oxo tetrahydrofuran- 3-Il, (meth) acrylic acid-5-oxo tetrahydrofuran-2-ylmethyl, (meth) acrylic acid-3,3-dimethyl-5-oxo tetrahydrofuran-2-ylmethyl, (meth) acrylic acid-4,4- Heterocycle-containing (meth) acrylic acid esters having an oxygen atom such as dimethyl-5-oxo tetrahydrofuran-2-ylmethyl;

For example, glycidyl group-containing vinyl esters such as glycidyl cinnamate, allyl glycidyl ether, and 1,3-butadiene monooxylane;
As the compound (e2-2), glycidyl acrylate, glycidyl methacrylate, methyl methacrylate (3,4-epoxycyclohexyl), 4-acryloylmorpholin, and 1-vinyl are used in terms of durability such as heat resistance and water resistance. Imidazole, 1-vinylpyridin-2 (1H) -one, di (meth) acrylic acid ethoxylated isocyanuric acid, and tri (meth) acrylic acid ethoxylated isocyanuric acid are particularly preferable.

The compound (e3) other than (e1) or (e2) is not particularly limited as long as it has an α, β-ethylenically unsaturated double bond group in its structure. For example, (meth). ) Methyl acrylate, ethyl (meth) acrylate, 1-propyl (meth) acrylate, 2-propyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, (meth) ) Iso-butyl acrylate, tert-butyl (meth) acrylate, n-amyl (meth) acrylate, iso-amyl (meth) acrylate, n-hexyl (meth) acrylate, 2-amyl (meth) acrylate Ethylhexyl, n-octyl (meth) acrylate, iso-octyl (meth) acrylate, n-nonyl (meth) acrylate, (meth) iso-nonyl acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate , (Meta) octadecyl acrylate, (meth) lauryl acrylate, (meth) stearyl acrylate and other (meth) acrylic acid alkyl esters;
For example, (meth) acrylic acid (meth) allyl, (meth) acrylic acid 1-butenyl, (meth) acrylic acid 2-butenyl, (meth) acrylic acid 3-butenyl, (meth) acrylic acid 1,3-methyl- 3-Butenyl, 2-Chlor 2-propenyl (meth) acrylate, 3-Chlor 2-propenyl (meth) acrylate, 2- (2-propenyloxy) ethyl (meth) acrylate, 2-2-propenyl (meth) acrylate Propenyllactyl, (meth) acrylic acid 3,7-dimethylocta-6-ene-1-yl, (meth) acrylic acid (E) -3,7-dimethylocta-2,6-diene-1-yl, (Meta) acrylic acid esters containing further unsaturated groups such as (meth) acrylateyl, cinnamyl (meth) acrylate, and (meth) vinyl acrylate;

For example, perfluoromethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoropropyl (meth) acrylate, perfluorobutyl (meth) acrylate, perfluorooctyl (meth) acrylate, (meth) Trifluoromethylmethyl acrylate, 2-trifluoromethylethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoroethyl ethyl (meth) acrylate, 2-per (meth) acrylate Fluoromethyl-2-perfluoroethylmethyl, triperfluoromethylmethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate , (Meta) acrylic acid perfluoroalkyl esters such as (meth) acrylic propenate 2-perfluorodecylethyl, (meth) acrylic acid 2-perfluorohexadecylethyl;
For example, (meth) acrylic acid (methoxycarbonyl) methyl, (meth) acrylic acid (methoxycarbonyl) propyl, (meth) acrylic acid (methoxycarbonyl) butyl, (meth) acrylic acid (methoxycarbonyl) decyl, (meth) acrylic. Acid (ethoxycarbonyl) methyl, (meth) acrylic acid (ethoxycarbonyl) ethyl, (meth) acrylic acid (ethoxycarbonyl) propyl, (meth) acrylic acid (ethoxycarbonyl) butyl, (meth) acrylic acid (ethoxycarbonyl) hexyl , (Meta) Acrylic Acid (ethoxycarbonyl) Octyl, (Meta) Acrylic Acid 2- (ethoxycarbonyloxy) Ethyl, (Meta) Acrylic Acid 2- (ethoxycarbonyloxy) propyl, (Meta) Acrylic Acid 2- (ethoxycarbonyloxy) Oxy) butyl, 2- (ethoxycarbonyloxy) hexyl (meth) acrylate, 2- (ethoxycarbonyloxy) octyl (meth) acrylate, 2- (propoxycarbonyloxy) ethyl (meth) acrylate, (meth) acrylic 2- (Butoxycarbonyloxy) ethyl acid, 2- (meth) acrylate 2- (butoxycarbonyloxy) butyl, 2- (meth) acrylate 2- (octyloxycarbonyloxy) ethyl, (meth) acrylate 2- (octyloxycarbonyl) An aliphatic (meth) acrylic acid ester having one carbonyl group such as oxy) butyl;

For example, 2-oxobutanoylethyl (meth) acrylate, 2-oxobutanoylpropyl (meth) acrylate, 2-oxobutanoylbutyl (meth) acrylate, 2-oxobutanoylhexyl (meth) acrylate, 2-oxobutanoyloctyl (meth) acrylate, 2-oxobutanoyldecyl (meth) acrylate, 2-oxobutanoyldodecyl (meth) acrylate, 3-oxobutanoylethyl (meth) acrylate, (meth) ) 3-oxobutanoylpropyl acrylate, 3-oxobutanoylbutyl (meth) acrylate, 3-oxobutanoylhexyl (meth) acrylate, 3-oxobutanoyloctyl (meth) acrylate, (meth) acrylic 3-oxobutanoyldecyl acid, 3-oxobutanoyldodecyl (meth) acrylic acid, 4-cyanooxobutanoylethyl (meth) acrylic acid, 4-cyanooxobutanoylpropyl (meth) acrylic acid, (meth) acrylic Acid 4-cyanooxobutanoylbutyl, (meth) acrylic acid 4-cyanooxobutanoylhexyl, (meth) acrylic acid 4-cyanooxobutanoyloctyl, (meth) acrylic acid 2,3-di (oxobutanoyl) Propyl, 2,3-di (oxobutanoyl) butyl (meth) acrylic acid, 2,3-di (oxobutanoyl) hexyl (meth) acrylic acid, 2,3-di (oxobutanoyl) (meth) acrylic acid ) An aliphatic (meth) acrylic acid ester having two carbonyl groups such as octyl;

For example, (meth) acrylic acid-9-methoxycarbonyl-5-oxo-4-oxa-tricyclo [4.2.1.03,7] nona-2-yl, (meth) acrylic acid-10-methoxycarbonyl- 5-Oxo-4-oxa-tricyclo [5.2.1.03,8] nona-2-yl, (meth) acrylate-4-methoxycarbonyl-6-oxo-7-oxa-bicyclo [3.2] .1] Octa-2-yl, (meth) Acrylic acid-4-methoxycarbonyl-7-oxo-8-oxa-bicyclo [3.3.1] Octa-2-yl, etc. (meth) Acrylic acid cyclic esters;
For example, vinyl acetoacetate, vinyl acetopropionate, vinyl acetoisobutyrate, vinyl acetobutyrate, vinyl acetovalerate, vinyl acetohexanate, vinyl aceto2-ethylhexanate, vinyl aceton-vinyl octanate, vinyl acetodecanoate, acetododecane. Vinyl acetate, vinyl acetooctadecanoate, vinyl acetopivalate, vinyl acetocaprate, vinyl acetocrotonate, vinyl acetosorbate, vinyl propanoyl acetate, vinyl butyryl acetate, vinyl isobutyryl acetate, vinyl palmitoyl acetate, vinyl stearoyl acetate, vinyl pyruboyl acetate , Propanoyl Valephosphate Vinyl, Butyryl Valephosphate Vinyl, Isobutyryl Valephosphate Vinyl, Palmitoyl Valephosphate Vinyl, Stearoyl Valephosphate Vinyl, Pyrvoyl Valerate Vinyl, 2-Acetacetoxyethyl Vinyl Ether, 2-Acetacetoxybutyl Vinyl Ether, 2- Alibo-based vinyl compounds having an acyl group such as acetoacetoxyhexyl vinyl ether and 2-acetoacetoxyoctyl vinyl ether;

For example, vinyl benzoyl acrylate, vinyl benzoyl acetate, vinyl benzoyl propionate, vinyl benzoyl butyrate, vinyl benzoyl valerate, vinyl benzoyl hexanoate, vinyl benzoyl dodecanoate, vinyl 1-naphthoyl acetate, vinyl vinyl naphthoyl propionate, 1- Vinyl naphthoyl butyrate, vinyl vinyl 1-naphthoyl valerate, vinyl vinyl naphthoyl hexanoate, vinyl 2-naphthoyl acetate, vinyl 2-naphthoyl propionate, vinyl vinyl naphthoyl butyrate, vinyl vinyl naphthoyl valerate, 2- Vinyl naphthoyl hexaneate, vinyl nicotinoyyl acetate, vinyl nicotinoyyl propionate, vinyl nicotinoyyl butyrate, vinyl nicotineol ballephosphate, vinyl nicotinoyle hexanoate, vinyl nicotinoyle decanoate, vinyl nicotinoid decanoate, vinyl isonicotinoyl acetate Vinyl noylpropionate, vinyl isonicotinoylbutyrate, vinyl isonicotinoylvalephosphate, vinyl isonicotinoylhexanate, vinyl isonicotinoyldecanoate, vinyl isonicotinoyldodecanoate, vinyl 2-floyl acetate, vinyl 2-floylpropionate , 2-Floyl Butyrate Vinyl, 2-Floyl Valephosphate Vinyl, 2-Floyl Hexanate Vinyl, 2-Floyl Decanoate Vinyl, 2-Floyled Decanoate Vinyl, 3-Floyl Vinyl Acetate, 3-Floyl Propionate Vinyl , 3-Floyl Butyrate Vinyl, 3-Floyl Valephosphate Vinyl, 3-Floyl Hexanoate Vinyl, 3-Floyl Decanoate Vinyl, 3-Floiled Decanoate Vinyl, Anthraniloyl Acetate Vinyl Acetate, Anthraniloyl Propionate Vinyl, Anthraniloyl Butyric Acid Vinyl, anthraniloyl valerate vinyl, anthraniloyl hexanoate vinyl, anthraniloyl decanoate vinyl, anthraniloyl decanoate vinyl, 4- (2-t-ethoxycarbonylethyloxy) styrene, 4- (2-t Aromatic vinyl compounds having an acyl group such as −butoxycarbonylethyloxy) styrene and 4- (2-t-butoxycarbonylpropyloxy) styrene;
For example, acetoacetate (meth) allyl, acetopropionic acid (meth) allyl, acetoisobutyrate (meth) allyl, acetobutyrate (meth) allyl, acetovalerate (meth) allyl, acetohexanoic acid (meth) allyl, aceto2- Ethylhexanoic acid (meth) allyl, aceton-octanoic acid (meth) allyl, acetodecanoic acid (meth) allyl, acetododecanoic acid (meth) allyl, acetooctadecanoic acid (meth) allyl, acetopivalic acid (meth) allyl, acetocaprin Acid (meth) allyl, acetocrotonate (meth) allyl, acetosorbic acid (meth) allyl, propanoyl acetate (meth) allyl, butyryl acetate (meth) allyl, isobutyryl acetate (meth) allyl, palmitoyl acetate (meth) allyl, An aliphatic (meth) allyl compound having an acyl group such as stearoylacetic acid (meth) allyl, (meth) allylaldehyde;

For example, di (meth) acrylic acid ethylene oxide, di (meth) acrylic acid triethylene oxide, di (meth) acrylic acid tetraethylene oxide, di (meth) acrylic acid polyethylene oxide, di (meth) acrylic acid propylene oxide, di. Dipropylene oxide of (meth) acrylic acid, tripropylene oxide of di (meth) acrylic acid, polypropylene oxide of di (meth) acrylic acid, butene oxide of di (meth) acrylic acid, penten oxide of di (meth) acrylic acid, di (meth) 2,2-Dimethylpropyl Acrylic Acid, Di (Meta) Acrylic Acid Hydroxypivalyl hydroxypivalate, Di (Meta) Acrylic Acid Hydroxy Pivalyl Hydroxypivalate Dicaprolactonate, Di (Meta) Acrylic Acid 1,6-hexane Diol, di (meth) acrylic acid 1,2-hexanediol, di (meth) acrylic acid 1,5-hexanediol, di (meth) acrylic acid 2,5-hexanediol, di (meth) acrylic acid 1,7 -Heptanediol, di (meth) acrylic acid 1,8-octanediol, di (meth) acrylic acid 1,2-octanediol, di (meth) acrylic acid 1,9-nonanediol, di (meth) acrylic acid 1 , 2-Decandiol, Di (meth) acrylic acid 1,10-decanediol, Di (meth) acrylic acid 1,2-decanediol, Di (meth) acrylic acid 1,12-dodecanediol, Di (meth) acrylic Acid 1,2-dodecanediol, di (meth) acrylic acid 1,14-tetradecanediol, di (meth) acrylic acid 1,2-tetradecanediol, di (meth) acrylic acid 1,16-hexadecanediol, di (meth) ) Acrylic acid 1,2-hexadecanediol, di (meth) acrylic acid 2-methyl-2,4-pentanediol, di (meth) acrylic acid 3-methyl-1,5-pentanediol, di (meth) acrylic acid 2-Methyl-2-propyl-1,3-propanediol, di (meth) acrylic acid 2,4-dimethyl-2,4-pentanediol, di (meth) acrylic acid 2,2-diethyl-1,3- Propanediol, di (meth) acrylic acid 2,2,4-trimethyl-1,3-pentanediol, dimethylol octane di (meth) acrylic acid, 2-ethyl-1,3-hexanediol di (meth) acrylic acid , Di (meth) acrylic acid 2,5-dimethyl-2,5-hexanediol, di (meth) acrylic acid 2-methi Lu-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, 2,4 diethyl-1,5-pentanediol di (meth) acrylate, di ( 2-Methyl-2-propyl-1,3-propanediol meta) acrylic acid, 2,4-dimethyl-2,4-pentanediol di (meth) acrylic acid, 2,2-diethyl-di (meth) acrylic acid 1,3-Propanediol, di (meth) acrylate 2,2,4-trimethyl-1,3-pentanediol, dimethylol octane di (meth) acrylate, 2-ethyl-1,di (meth) acrylate, 3-Hexanediol, di (meth) acrylic acid 2,5-dimethyl-2,5-hexanediol, di (meth) acrylate 2-butyl-2-ethyl-1,3-propanediol, di (meth) acrylic Bifunctional (meth) acrylic acid esters such as acid 2,4diethyl-1,5-pentanediol, di (meth) acrylic acid 1,1,1-trishydroxymethylethane;

For example, tri (meth) acrylic acid 1,2,3-propanetriol, tri (meth) acrylic acid 2-methylpentane-2,4-diol, tri (meth) acrylic acid 2-methylpentane-2,4-diol. Tricaprolactonate, tri (meth) acrylic acid 2,2-dimethylpropane-1,3-diol, tri (meth) acrylic acid trimethylol hexane, tri (meth) acrylic acid trimethylol octane, tri (meth) acrylic acid 2,2-bis (hydroxymethyl) 1,3-propanediol, tri (meth) acrylic acid 1,1,1-trishydroxymethylethane, tri (meth) acrylic acid 1,1,1-trishydroxymethylpropane, Trifunctional (meth) acrylates such as pentaerythritol tri (meth) acrylate;
For example, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxylated tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tetra (meth) acrylate 2, 2-Bis (Hydroxymethyl) 1,3-Propanediol, Tetra (Meta) Acrylic Acid 2,2-Bis (Hydroxymethyl) 1,3-Propandiol Tetracaprolactonate, Tetra (Meta) Acrylic Acid Di1, 2,3-Propanetriol, di2-methylpentane tetra (meth) acrylate-2,4-diol, di2-methylpentane tetra (meth) acrylate-2,4-diol tetracaprolactonate, tetra ( Di,2-dimethylpropane-1,3-diol acrylate, ditrimethylolbutane tetra (meth) acrylate, ditrimethylolhexane tetra (meth) acrylate, ditrimethylol octane tetra (meth) acrylate, etc. Functional (meth) acrylic acid esters;

For example, vinyl esters of carboxylic acids such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caprate, vinyl laurate, vinyl versatic acid, vinyl pivalate, vinyl palmitate, vinyl stearate;
For example, methyl vinyl ether, ethyl vinyl ether, 2-chlorovinyl ether, n-propyl vinyl ether, allyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, isopentyl vinyl ether, tert. -Pentyl vinyl ether, n-hexyl vinyl ether, isohexyl vinyl ether, 2-ethylbutyl vinyl ether, 2-ethylhexyl vinyl ether, n-heptyl vinyl ether, n-octyl vinyl ether, isooctyl vinyl ether, nonyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, hexane decyl vinyl ether , Octadecyl vinyl ether, ethoxymethyl vinyl ether, 2-methoxyethyl vinyl ether, 2-ethoxyethyl vinyl ether, 2-butoxyethyl vinyl ether, acetoxymethyl vinyl ether, 2-acetoxyethyl vinyl ether, 3-acetoxypropyl vinyl ether, 4-acetoxybutyl vinyl ether, 4- Aliper vinyl ethers such as ethoxybutyl vinyl ether, 2- (2-methoxyethoxy) ethylvir ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether;

For example, ethylene glycol divinyl ether, diethylene glycol divinyl ether (DEGVE), triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, polypropylene glycol. Divinyl ether, butanediol divinyl ether, neopentyl glycol divinyl ether, hexanediol divinyl ether, nonanediol divinyl ether, hydroquinone divinyl ether, 1,4-cyclohexanediol divinyl ether (CHODVE), 1,4-cyclohexanedimethanol divinyl ether ( CHDVE), Trimethylol Propane Trivinyl Ether, Dipentaerythritol Tetravinyl Ether, Ditrimethylol Propanetetravinyl Ether, Dipentaerythritol Hexavinyl Ether and other polyfunctional vinyl ethers;
For example, alkenyl group-containing sulfonic acids such as vinyl sulfonic acid, 2-propenyl sulfonic acid, 2-methyl-2-propenyl sulfonic acid, vinyl sulfuric acid;
For example, nitrile group-containing α, such as (meth) acrylonitrile, α-chloroacrylonitrile, crotonnitrile, maleinenitrile, fumaronitrile, mesaconnitrile, citraconnitrile, itaconenitrile, 2-propennitrile, 2-cyanoethyl (meth) acrylate, etc. β-Unsaturated double bond group-containing compounds;
For example, saturated carboxylic acids such as acetic acid (meth) allyl, propionic acid (meth) allyl, butyrate (meth) allyl, capric acid (meth) allyl, laurate (meth) allyl, allyl octylate, coconut oil fatty acid, vinyl pivalate, etc. Acid (meth) allyl esters;
For example, vinyl halides such as vinyl chloride, vinylidene chloride, allyl chloride;
Dienes such as allenes, 1,2-butadiene, 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene;
For example, cis-diallyl succinate, diallyl 2-methidylene succinate, (E) -vinyl-buta-2-enoate, (Z) -octadeca-9-vinyl enoate, (9Z, 12Z, 15Z) -octadeca-9, Α, β-unsaturated double bond group-containing compounds containing polyfunctional unsaturated bonds such as 12,15-vinyl trieneate;

For example, ethylene, propylene, 1-butene, 2-butene, 2-methylpropene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene. , 1-Dodecene, 1-Tetracosen, 1-Hexacosen, 1-Octacosen, 1-Triacontene, 1-Dodecene, 1-Tetratoacontene, 1-Hexatoriaconten, 1-Octatoriaconten, 1-Tetracontene Etc. and their mixtures and alkenes such as polybutene-1, polypentene-1, poly4-methylpentene-1 and the like;

For example, (meth) acrylic acid, 2-carboxyethyl (meth) acrylic acid, 2-carboxypropyl (meth) acrylic acid, 3-carboxypropyl (meth) acrylic acid, 4-carboxybutyl (meth) acrylic acid, (meth). ) Acrylic acid dimer, maleic acid, fumaric acid, monomethylmaleic acid, monomethylfumaric acid, aconitic acid, sorbic acid, silicic acid, α-chlorosorbic acid, glutaconic acid, citraconic acid, mesaconic acid, itaconic acid, tigric acid, Acrylic acid, senesioic acid, crotonic acid, isoccrotonic acid, mucobromic acid, mucochloric acid, sorbic acid, muconic acid, acrylic acid, penicic acid, gelanic acid, citronellic acid, 4-acrylamide butanoic acid, 6-acrylamidehexanoic acid, 2- Polylactone-based (meth) acrylic acid ester, ethylene oxide, etc., which have a carboxyl group at the end due to the ring-opening addition of the lactone ring, such as (meth) acryloyloxyethyl succinate and mono (meth) acrylic acid ω-carboxypolycaprolactone ester. A carboxyl group-containing aliphatic α, β-unsaturated acid such as an ester of an alkylene oxide-added succinic acid having a carboxyl group at the terminal and (meth) acrylic acid to which an alkylene oxide such as propylene oxide is repeatedly added. Double-bonding group-containing carboxylic acids and their acid anhydrides;
For example, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropylphthalate, 2- (meth) acryloyloxybutylphthalate, 2- (meth) acryloyl. Oxyhexylphthalate, 2- (meth) acryloyloxyoctylphthalate, 2- (meth) acryloyloxydecylphthalate, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 4-isopropenylbenzenecarboxylic acid, Α, β-unsaturated double-bonding group-containing carboxylic acids having acryloyl or aromatic ring containing carboxyl groups such as lauric acid and 7-amino-3-vinyl-3-cephem-4-carboxylic acid and their acid anhydrides. Kind;

As the above-mentioned other α, β-ethylenically unsaturated double bond group-containing compound (e3), a compound having a (meth) acryloyl group is preferable from the viewpoint of reactivity, and the resin composition of the present invention has a photothree-dimensional modeling composition. When used as a compound, it is preferable to contain bifunctional or higher functional (meth) acrylic acid esters from the viewpoint of active energy ray polymerization rate.

In the other α, β-unsaturated double bond group-containing compound (E) of the present invention, curability by irradiation with active energy rays, curing shrinkage of a three-dimensional model described later, heat resistance, moisture heat resistance and water resistance. The advantage of compound (E) in terms of durability is that it contains a hydroxyl group (e1), but it is a good curable material by blending it in a timely manner so that it contains both a hydroxyl group and a cyclic structure. Can be.

In the present invention, the compound (E) is 0.01 to 50 parts by weight, preferably 5 to 99 parts by weight, based on 100 parts by weight of the compound (A). If it is less than 0.01 parts by weight, the expression of high cohesive force, which is the effect of the compound compound (E), and the improvement of resistance such as heat resistance and water resistance cannot be obtained. On the contrary, if it is more than 90 parts by weight, the compound ( When a cured product, which is a feature of A), is produced, the effect of imparting flexibility while maintaining hardness is not exhibited.

In the active energy ray-polymerizable resin composition for optical three-dimensional modeling of the present invention, the content of the α, β-unsaturated double bond group-containing compound (A) having an ability to promote the adhesive action between cells is the composition. 0.01 to 50 parts by weight is preferable, and 1 to 20 parts by weight is more preferable with respect to the total amount of.
The α, β-unsaturated double bond group-containing compound (B) having silicon is preferably 0.01 to 95 parts by weight.
The photoinitiator (C) is preferably 0.01 to 30 parts by weight, more preferably 1 to 20 parts by weight.

A preferable form of the active energy ray-polymerizable resin composition for optical three-dimensional modeling of the present invention is an α, β-unsaturated double bond group-containing compound (A) having a factor that can act on cells in an amount of 0.01 to 50 weight. Department;
0.01 to 90 parts by weight of the α, β-unsaturated double bond group-containing compound (B) having silicon;
0 to 30 parts by weight of photoinitiator (C);
0 to 50 parts by weight of the other α, β-unsaturated double bond group-containing compound (E);
Examples thereof include a form containing.

Further, as the composition (Ad), the content of (A) is preferably 1 to 50 parts by weight, more preferably 1 to 20 parts by weight, based on the total amount of the composition.
The content of (B2) is preferably 1 to 95 parts by weight, more preferably 50 to 95 parts by weight.
The catalyst (D) having active energy ray activity is preferably 0.01 to 10 parts by weight, more preferably 0.01 to 1 part by weight.
Further, the siloxane (G) having a hydrogen atom bonded to silicon is preferably 1 to 20 parts by weight, more preferably 1 to 10 parts by weight.
The other α, β-unsaturated double bond group-containing compound (E) is preferably not added. ,

Further, as the composition (R), the content of (A) is preferably 1 to 50 parts by weight, more preferably 1 to 20 parts by weight, based on the total amount of the composition.
The content of (B1) is preferably 0.01 to 95 parts by weight, more preferably 0.01 to 50 parts by weight.
The other α, β-unsaturated double bond group-containing compound (E) is preferably 0 to 50 parts by weight, more preferably 1 to 50 parts by weight. It is preferable that the catalyst (D) having active energy ray activity is not added.
It is preferable that siloxane (G) having a hydrogen atom bonded to silicon is not added.

Next, the properties of the curable composition for optical three-dimensional modeling will be described.
The curable composition for optical three-dimensional modeling of the present invention comprises the above-mentioned α, β-unsaturated double bond-containing compound (A) having an ability to promote the adhesion between cells and α, β- having silicon. An unsaturated double bond group-containing compound (B) (excluding those corresponding to the compound (A)) is an essential component, and if necessary, a sensitizer (F) and a hydrogen atom bonded to silicon are added. It can be produced by blending the contained siloxane (G) or the like and then uniformly mixing them. When stirring and mixing, it may be prepared by stirring and mixing using a general-purpose device such as a single-screw or multi-screw extruder equipped with a decompression device, a kneader, and a solver. The temperature at the time of stirring and mixing is usually preferably set to 10 to 60 ° C. If the set temperature at the time of preparation is less than 10 ° C, the viscosity may be too high and uniform stirring / mixing work may be difficult. On the contrary, if the temperature at the time of preparation exceeds 60 ° C, a curing reaction due to heat occurs. In some cases, a normal curable material may not be obtained, which is not preferable.
The curable composition for optical three-dimensional modeling of the present invention can be used in any of liquid, paste and film forms.

The curable composition for optical three-dimensional modeling in the present invention preferably contains substantially no organic solvent, but it can also contain a machine solvent. For example, organic solvents such as methanol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, cyclohexane, toluene, xylene and other hydrocarbon solvents, and water are further added. The viscosity of the curable material can be adjusted, or the curable material can be heated to reduce its viscosity.

Next, the molding process (optical three-dimensional modeling method) of the cured product and the curable composition for optical three-dimensional modeling will be described.

The curable composition for optical three-dimensional modeling of the present invention is suitably used as a photocurable liquid resin substance in an optical three-dimensional modeling method (hereinafter, also referred to as a stereolithography method). That is, it is possible to produce a cured product having a desired three-dimensional shape by a stereolithography method in which the curable material of the present invention is selectively irradiated with active energy rays such as ultraviolet rays to supply the energy required for curing. it can.
The curable composition for optical three-dimensional modeling of the present invention is suitably used as a curable liquid substance in the optical three-dimensional modeling method. That is, a three-dimensional model having a desired shape is obtained by selectively irradiating a specific portion of the curable material with light such as visible light, ultraviolet light, or infrared light to supply the active energy required for curing. be able to.

The light source for irradiating active energy rays is mainly light in the wavelength range of 150 to 550 nm. Low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, chemical lamp, black light lamp, microwave-excited mercury lamp, LED In addition to lamps, xenon lamps, metal halide lamps, and the like, semiconductor laser beams, electron beams, and the like can also be used as active energy rays for exposure. An ultraviolet laser beam is preferable in terms of cost, directivity, and convergence.
The irradiation intensity of the active energy ray is preferably 0.1 to 500 mW / cm ² .
If the light irradiation intensity is less than 0.1 mW / cm ² , it takes a long time to cure, and if it exceeds 500 mW / cm ² , it is an uncured curable composition for optical three-dimensional modeling due to the heat radiated from the lamp. It is not preferable because it may cause deterioration of the object. The integrated irradiation amount expressed as the product of the irradiation intensity and the irradiation time is preferably ¹ to 5,000 mJ / cm ² . If the cumulative irradiation amount is less than 1 mJ / cm ² , it takes a long time to cure, and if it is larger than 5,000 mJ / cm ² , the irradiation time becomes very long and the productivity is poor, which is not preferable.

The method of selectively irradiating a specific portion of the curable material with light, which is an active energy ray for curing, is not particularly limited, and various methods can be used. For example, a method of irradiating a specific portion with focused light obtained by using a laser beam, a lens, a mirror, or the like, a method of irradiating unfocused light through a mask having a constant pattern, or the like can be adopted. However, when microfabrication or processing accuracy is required, it is desirable to minimize the magnitude of focused light, and in such a case, it is preferable to use laser light. Further, the specific portion of the curable material to be irradiated with light may be the liquid surface of the curable material placed in the container, the surface of the resin composition in contact with the side wall or the bottom wall of the container, or the liquid. To irradiate the liquid surface of the curable material or the contact surface with the container wall, the light may be radiated directly from the outside or through a transparent vessel wall, and when irradiating a specific part in the liquid, an optical fiber is used. Irradiation may be performed using a light guide body such as.
Further, in the above-mentioned optical three-dimensional modeling method, usually, after curing a specific portion of the curable material, the irradiated position is continuously or stepwise moved from the already cured portion to the uncured portion. , The cured portion can be grown into a desired three-dimensional shape. This movement of the irradiated position can be performed by various methods, for example, moving at least one of a light source, a container containing a curable material, or a cured portion of the curable material, or uncured in the container. It can be carried out by a method such as adding a curable material (liquid curable substance) of.

Next, the three-dimensional model will be described.
As a typical method for obtaining a three-dimensional model using the curable material for optical three-dimensional modeling of the present invention, light is applied so that a cured layer having a desired pattern can be obtained from the curable material of the present invention which is liquid. To form a cured layer by selectively irradiating the cured layer, and then irradiating the uncured composition layer adjacent to the cured layer with light in the same manner to form a new cured layer continuous with the previously formed cured layer. By repeating this laminating operation, a method of finally producing a desired three-dimensional shaped object can be mentioned. As a more specific aspect of this method, the following methods can be mentioned.
The formed three-dimensional model is taken out from the container used for the reaction, the unreacted compound remaining on the surface of the model is removed, and then washed if necessary. Examples of this cleaning agent include organic solvents typified by alcohols such as isopropyl alcohol and ethyl alcohol, organic solvents typified by acetone, ethyl acetate, methyl ethyl ketone and the like, terpenes, and aliphatic typified by glycol ether esters. A low-viscosity liquid resin of an organic solvent, thermocurable or photocurable (meaning curability by light which is an active energy ray) can be used. Further, when it is desired to impart transparency to a three-dimensional model, it is desirable to use the thermosetting or photocurable liquid resin as a cleaning agent. In this case, depending on the type of resin used for cleaning, it is necessary to dry with heat or light (also referred to as post-cure) after cleaning. Since post-cure has the effect of not only curing the resin on the surface but also curing the unreacted curable material that may remain inside the three-dimensional model, it is washed with an organic solvent. It is also preferable to carry out this case.
The cured product of the curable material for optical three-dimensional modeling of the present invention is a variety of resin molded products for electronic products that require complicated and fine processing; for design examination of new products, for presentations, for advertisements and for exhibitions. Models such as; Development prototypes for performance testing and production suitability confirmation; Can be preferably used as three-dimensional models such as medical models for surgical simulation.

Next, the base material for cell culture will be described.
The form of the cell culture substrate is not particularly limited as long as it is a member used for cell culture and having a surface that serves as a scaffold for cell growth. Examples of the cell culture substrate include a cell culture container and a microchannel device. For example, in the cell culture substrate in the form of a film or a plate, a medium containing cells is placed on one surface of the substrate for cell culture, or the substrate is used for culturing such as a single or multi-well plate. The cells can be cultured by accommodating and fixing them in various cell culture containers such as plates, petri dishes, dishes, flasks, and culture bags, and adding a medium containing cells to the containers. In addition, the cell culture substrate itself may be in the form of a culture plate such as a single or multi-well plate, and various cell culture containers such as a culture dish, a culture dish, a flask, and a culture bag. The culture bag can be used when culturing floating cells, stem cells, or the like in a floating state.
Examples of the microchannel device include microreaction devices (specifically, microreactors, microplants, etc.), integrated nucleic acid analysis devices, microelectrophoresis devices, microchromatography devices, and other microanalytical devices; mass spectra and the like. Microdevices for preparing analytical samples such as liquid chromatography; Physicochemical processing devices used for extraction, membrane separation, dialysis, etc .; Environmental analysis chips, clinical analysis chips, gene analysis chips (DNA chips), protein analysis chips (proteome chips) , Sugar chain chips, chromatograph chips, cell analysis chips, pharmaceutical screening chips and other microchannel chips. Among these, the microchannel tip is preferable.
The microchannel device is a portion through which a small amount of sample (preferably a liquid sample) flows, and the width and depth of the channel are not particularly limited, but all of them are usually about 0.1 μm to 1 mm. , Preferably 10 μm to 800 μm. The channel width and depth of the microchannel may be the same over the entire length of the channel, or may have partially different sizes and shapes.

The cell culture equipment may be subjected to plasma treatment, UV ozone treatment, internal infiltration agent treatment, or the like. Since the surface of the silicone base material subjected to these treatments is hydrophilic, it may be difficult for the polymer to be adsorbed. However, the cell culture equipment treatment agent used in the present invention is subjected to such plasma treatment. It also adsorbs to the silicone substrate, and has excellent hydrophilicity and an effect of suppressing the adsorption of biological samples.

The present invention will be described in more detail with reference to the following examples, but the following examples do not limit the scope of rights of the present invention in any way. In the examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively.

<Composition composition>
[Synthesis Examples 1 to 15, Comparative Synthesis Examples 1 and 2]
In a shielded 300 cc mayonnaise bottle in which the oxygen concentration is substituted to 10% or less, the compounds (A) and (B) shown in Table 1, and if necessary, a photoinitiator (C) and a catalyst ( D), other α, β-unsaturated double bond group-containing compound (E), sensitizer (F), and curing agent (G) were charged at the ratios shown in Table 2 and sufficiently stirred by a three-one motor. , And after sufficient defoaming, the compositions (P-1 to 17) shown in the formulation example were obtained.
The evaluation was performed according to the following method, and the results are shown in Table 3-5.

<Manufacturing and evaluation of cell culture equipment>
The above composition (P-1 to 17) is injected into a glass U-shaped bottom 96-well plate mold, and UV light (illuminance: 800 mW / cm ² , integrated light amount:) is used in this mold using a metal highlight lamp. 1000mJ / ^cm 2, 10 seconds) by irradiating was photopolymerization. After the polymerization, it was taken out from the mold to obtain a cured product (C-1 to 17) having a U-shaped bottom 96-well plate shape. The cured product (C-1 to 17) was immersed in water and released from the mold.

[Evaluation of spheroid formation]
[Examples 1 to 15, Comparative Example 1, Comparative Example 2]
After sterilizing the cured product (C-1 to 17) with ethylene oxide gas, a human liver cancer-derived cell line (HepG2) was prepared by adding 10% of fetal bovine serum (FBS) to Dulbecco's modified Eagle's medium (DMEM). the cells) were seeded 1 × 10 ⁴ cells per well, and cultured until day 5 with 5% CO _2/37 ℃ incubator, the cell culture conditions after 5 days and photographed with a transmission type optical microscope 40 times, cells It was evaluated by observing the morphology of. The results are shown in Table 3.
(Evaluation criteria)
◯: Form one spheroid (good)
Δ: Multiple spheroids are formed (defective)
×: Does not form spheroids (extremely poor)

The above composition (P-1 to 17) is applied to a glass plate with a resin composition to a thickness of 250 μm using an applicator, and irradiated with ultraviolet rays of 500 mJ / cm ² (wavelength: 350 nm) to cure a film. Got Next, the cured product (C-18 to 34) was peeled off from the glass plate, and the state was adjusted at 23 ° C. and a relative humidity of 50% for 24 hours to obtain a cured product (C-18 to 34).

[Evaluation of protein adsorption]
[Examples 16 to 30, Comparative Examples 3 and 4]
The cured product (C-18 to 34) was cut into 11 mm squares and placed in a flat-bottomed 24-well plate, and 1 ml of an HRP-IgG solution diluted 10000 times with phosphate buffered saline (PBS) was added and immersed. It was. After incubating for 1 hour at room temperature, each well was washed 4 times with PBS-T (0.1% Tween 20). After dispensing 1 ml of the stain solution into each well and incubating at room temperature for 10 minutes, 1 ml of the reaction terminator solution was dispensed into each well, and then the absorbance Aλ of 450 nm (secondary wavelength 650 nm) was measured by MITHRAS2LD943-M2M microplate reader. Was measured using. The smaller the absorbance Aλ, the lower and better the antibody protein adsorptivity. Evaluation was made based on the following criteria. The results are shown in Table 4.

Staining solution: TMBZ solution (3,3', 5,5'-tetramethylbenzidine)
Reaction terminator: WASH and Stop Solution ForELISA With Solution for ELISA manufactured by Takara Bio Inc. Sulfuric Acid
HRP-IgG: enzyme, antibody (HORSERADIH PEROXIDASE IMMUNOGLOBULING)
PBS-T: PBS with 0.1% Tween 20 added (evaluation criteria)
◯: Aλ ≦ 0.6 (good)
Δ: 0.6 <Aλ ≦ 0.8 (usable)
×: 0.8 <Aλ (defective)
The results are shown in Table 4.

[Oxygen permeability]
[Examples 31 to 45, Comparative Examples 5 and 6 Using the plane electrode cells of the oxygen permeability measuring device (201T, Rehder), the oxygen permeability coefficient (FATT method) is determined by the method specified in ISO18369-4 (FATT method). Dk) was measured. The results are shown in Table 5. _{^{(1Barrer = 1 × 10 -11 O}} 2 (STP) cm / cm 2 mmHg)

◯: Dk ≧ 150 (good)
Δ: 150> Dk ≧ 20 (usable)
X: 20> Dk (defective)
The results are shown in Table 5.

As shown in Tables 3 to 5, the α, β-unsaturated double bond-containing compound (A) having the ability to promote the adhesion between cells of the present invention and the α, β-unsaturated double having silicon. A cured product using an active energy ray-polymerizable resin composition for optical three-dimensional modeling containing a binding group-containing compound (B) (excluding those corresponding to the compound (A)) as an essential component forms spheroids. It showed high properties, low protein adsorption, and high oxygen permeability.
On the other hand, Comparative Example 1 which does not have an α, β-unsaturated double bond group-containing compound having a factor that can act on cells, or does not have an α, β-unsaturated double bond group-containing compound having silicon. The composition of Comparative Example 2 was inferior in spheroid forming property, protein adsorption suppression and oxygen permeability.

Claims (11)

An α, β-unsaturated double bond group-containing compound (A) having an ability to promote the adhesion between cells and an α, β-unsaturated double bond group-containing compound (B) having silicon (however, the compound An active energy ray-polymerizable resin composition for optical three-dimensional modeling containing (excluding those corresponding to (A)). The active energy ray-polymerizable resin for optical three-dimensional modeling according to claim 1, wherein the compound (A) is at least one of a compound (Ap) represented by the following general formula 1 and an amine compound (Aa). Composition.
General formula 1

(In general formula 1,
R ¹ is an alkylene group having 2 to 4 carbon atoms,
R ² is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
X is a carbon atom, *-(C = O) O-, *-(C = O) NR ³ or * -NR ³ (C = O)-, f is an integer of 2 to 100.
R ³ indicates a hydrogen atom or an organic group having 1 to 10 carbon atoms, and * indicates a position in the general formula 1 where R ⁴ is bonded to a carbon atom.
R ⁴ represents a hydrogen atom or a methyl group. ) The active energy ray-polymerizable resin composition for optical three-dimensional modeling according to claim 2, wherein the amine compound (Aa) is at least one represented by the following general formulas 2 to 7.

General formula 2

(In general formula 2,
X represents a carbon atom, *-(C = O) O-, *-(C = O) NR ³ or * -NR ^3- (C = O)-, and R ³ is a hydrogen atom or 1 to 10 carbon atoms. Indicates an organic group of
R ⁶ represents a hydrogen atom or a methyl group and represents
R ⁷ represents an alkylene group having 2 to 4 carbon atoms.
R ⁸ represents an alkylene group having 1 to 10 carbon atoms.
R ⁹ , R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and q represents 1 to 10 on average. )

General formula 3

(In general formula 3,
X represents a carbon atom, *-(C = O) O-, *-(C = O) NR ³ or * -NR ^3- (C = O)-, and R ³ is a hydrogen atom or 1 to 10 carbon atoms. Indicates an organic group of
R ¹² represents a hydrogen atom or a methyl group and represents
R ¹³ and R ¹⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group. )

General formula 4

(In general formula 4,
X represents a carbon atom, *-(C = O) O-, *-(C = O) NR ³ or * -NR ³ (C = O)-, and R ³ is a hydrogen atom or 1 to 10 carbon atoms. Shows organic groups
R ¹⁵ represents a hydrogen atom or a methyl group and represents
R ¹⁶ and R ¹⁷ each independently represent an alkylene group having 1 to 3 carbon atoms. )

General formula 5

(In the general formula 5, R ¹⁸ represents an alkylene group having 1 to 5 carbon atoms.)

General formula 6

(In general formula 6, X represents a carbon atom, *-(C = O) O-, *-(C = O) NR ³ or * -NR ³ (C = O)-, and R ³ is a hydrogen atom or It shows an organic group with 1 to 10 carbon atoms.
Y indicates − (C = O) O ⁻ , − (O = S = O) O ⁻ ,
R ¹⁹ represents a hydrogen atom or a methyl group and represents
R ²⁰ represents a divalent organic group having 1 to 10 carbon atoms.
R ²¹ and R ²² are independent of each other
Shows hydrocarbon groups with 1 to 10 carbon atoms
R ²³ represents a divalent organic group having 1 to 10 carbon atoms. )

General formula 7

(In general formula 7,
R ²⁵ represents a hydrogen atom or a methyl group, and R ²⁶ is -O-, *-(C = O) -O-,
^{* - (C = O) -NR} 31 -, * - NR 31 - (C = O) -,
R ³¹ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms.
* Indicates the position where R ²⁵ in the general formula 7 is bonded to the carbon atom to which it is bonded.
R ²⁷ represents a divalent organic group having 1 to 10 carbon atoms.
R ²⁸ , R ²⁹ and R ³⁰ each independently represent a hydrocarbon group having 1 to 10 carbon atoms. ) The invention according to any one of claims 1 to 3, wherein the compound (B) is at least one of a compound having a siloxane structure and a (meth) acrylic group (B1) and a compound having a siloxane structure and a vinyl group (B2). Active energy ray-polymerizable resin composition for optical three-dimensional modeling. The active energy ray-polymerizable resin composition for optical three-dimensional modeling according to any one of claims 1 to 4, further comprising a photoinitiator (C). The active energy ray-polymerizable resin composition for optical three-dimensional modeling according to any one of claims 1 to 4, further comprising a catalyst (D) having active energy ray activity. The active energy ray-polymerizable resin for optical three-dimensional modeling according to any one of claims 1 to 6, further comprising another α, β-unsaturated double bond group-containing compound (E). Composition. With respect to 100 parts by weight of the active energy ray-polymerizable composition
0.01 to 50 parts by weight of α, β-unsaturated double bond group-containing compound (A) having an ability to promote cell-cell adhesion.
0.01 to 95 parts by weight of the α, β-unsaturated double bond group-containing compound (B) having silicon;
0 to 30 parts by weight of photoinitiator (C);
The active energy ray-polymerizable resin composition for optical three-dimensional modeling according to claim 7, wherein the other α, β-unsaturated double bond group-containing compound (E) is contained in an amount of 0 to 50 parts by weight. .. A cured product obtained by curing the active energy ray-polymerizable resin composition for optical three-dimensional modeling according to any one of claims 1 to 8 with active energy rays. A three-dimensional model made of the cured product according to claim 9. A cell culture substrate comprising the three-dimensional model according to claim 10.