Method for producing hardened product, composition, hardened product, and three-dimensional structure

Abstract

To provide a manufacturing method of a cured product capable of manufacturing a cured product having difference of more detailed mechanical characteristics (contrast) in the cured product.SOLUTION: A method for manufacturing a cured product by curing a composition to obtain a cured product comprises: irradiating light in pattern on a composition containing a monomer A having at least one dynamic covalent bond selected from the group consisting of a disulfide bond, a diselenide bond, and a ditelluride bond in a molecule, a monomer B having at least two or more ethylenically unsaturated groups in a molecule, and a curing agent; and heating the composition, wherein the monomer A and the curing agent have at least two or more in each molecule of a pair of curable groups capable of reacting with each other, and the pair of curable groups are selected from a predetermined combination.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a method for producing a cured product, a composition, a cured product, and a three-dimensional structure.

Background Art

[0002] There is known a cured product obtained by curing a composition obtained by mixing a monomer having a disulfide bond, a monomer having an amino group, a monomer having a vinyl group, and a monomer having a glycidyl group (Non-Patent Document 1).

Prior Art Documents

Non-Patent Documents

[0003]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] Since the cured product described in Non-Patent Document 1 has disulfide bonds introduced into the polymer network, even after curing, when heated to a predetermined temperature, it behaves like a thermoplastic resin due to the exchange reaction of the disulfide bonds. Furthermore, since the cured product contains a monomer having a vinyl group, when further heated, an irreversible bond between the thiyl radical and the vinyl group is formed, and when completely cured, it behaves like a thermosetting resin.

[0005] By utilizing the above properties, the heating temperature can be adjusted to soften or irreversibly cure. Furthermore, for example, when a sheet-shaped cured product is obtained and a two-dimensional gradient is given to the heating temperature, a two-dimensional mechanical property contrast corresponding to the above gradient can be imparted to the cured product obtained after cooling again.

[0006] However, when attempting to more finely control the positional mechanical property contrast, there was room for improvement in control by temperature gradient. Therefore, an object of the present invention is to provide a method for producing a cured product that can produce a cured product with a more finely differentiated mechanical property (contrast) in the cured product. Another object of the present invention is also to provide a composition, a cured product, and a three-dimensional structure.

Means for Solving the Problems

[0007] As a result of intensive studies to achieve the above problems, the present inventors have found that the above problems can be achieved by the following configuration.

[0008] [1] A method for producing a cured product, comprising curing a composition to obtain a cured product, wherein the composition contains a monomer A having at least one dynamic covalent bond selected from the group consisting of a disulfide bond, a diselenide bond, and a ditelluride bond in the molecule, a monomer B having at least two or more ethylenically unsaturated groups in the molecule, and a curing agent, and irradiating the composition with light in a pattern and heating the composition, wherein the monomer A and the curing agent each have at least two or more of one of a pair of curable groups that can react with each other in their respective molecules. The pair of curable groups are as follows (a) to (d): (a) A glycidyl group and at least one group selected from the group consisting of a hydroxy group, a carboxy group, and an acid anhydride group for the glycidyl group. (b) A hydroxy group and at least one group selected from the group consisting of a carboxy group and an acid anhydride group for the hydroxy group. (c) An isocyanate group and a hydroxy group for the isocyanate group. (d) A phenol group or a furyl group and a formyl group for the phenol group or the furyl group. A method for producing a cured product, selected from the group consisting of the above. [2] A method for producing a cured product, which comprises curing a composition to obtain a cured product, the method comprising: irradiating a composition containing monomer C having at least one dynamic covalent bond selected from the group consisting of disulfide bonds, diselenide bonds, and ditelluride bonds in the molecule, and monomer B having at least two or more ethylenically unsaturated groups in the molecule, in a pattern with light; and heating the composition, wherein monomer C has two or more benzoxazine rings or alkoxysilyl groups in the molecule. [3] The method for producing a cured product according to [1], wherein the pair of curable groups is at least one group selected from the group consisting of a glycidyl group and at least one group selected from the group consisting of a hydroxy group, a carboxy group, and an acid anhydride group with respect thereto. [4] The method for producing a cured product according to any one of [1] to [3], further comprising irradiating the light before heating. [5] The method for producing a cured product according to any one of [1] to [4], wherein the dynamic covalent bond is a disulfide bond. [6] A composition comprising monomer A having at least one dynamic covalent bond selected from the group consisting of disulfide bonds, diselenide bonds, and ditelluride bonds in the molecule, monomer B having at least two or more ethylenically unsaturated groups in the molecule, and a curing agent, wherein monomer A and the curing agent each have at least two or more of one of a pair of curable groups capable of reacting with each other in their respective molecules. The pair of curable groups is as follows (a) to (d): (a) A glycidyl group and at least one group selected from the group consisting of a hydroxy group, a carboxy group, and an acid anhydride group with respect thereto. (b) A hydroxy group and at least one group selected from the group consisting of a carboxy group and an acid anhydride group with respect thereto. (c) An isocyanate group and a hydroxy group with respect thereto. (d) A phenol group or a furyl group and a formyl group with respect thereto. The composition is selected from the group consisting of. [7] The composition according to [6], wherein the pair of curable groups is at least one group selected from the group consisting of a glycidyl group and at least one group selected from the group consisting of a hydroxy group, a carboxy group, and an acid anhydride group relative thereto. [8] A composition comprising a monomer C having at least one dynamic covalent bond selected from the group consisting of a disulfide bond, a diselenide bond, and a ditelluride bond in the molecule, and a monomer B having at least two or more ethylenically unsaturated groups in the molecule, wherein the monomer A has two or more benzoxazine rings or alkoxysilyl groups in the molecule. [9] The composition according to any one of [6] to [8], wherein the dynamic covalent bond is a disulfide bond.

[10] The composition according to any one of [6] to [9], which is for forming a sheet for assembling a three-dimensional structure by folding.

[11] A composition comprising a monomer A having at least one dynamic covalent bond selected from the group consisting of a disulfide bond, a diselenide bond, and a ditelluride bond in the molecule, a monomer B having at least two or more ethylenically unsaturated groups in the molecule, and a curing agent, wherein the monomer A and the curing agent each have at least two or more of one of a pair of curable groups capable of reacting with each other in their respective molecules. The pair of curable groups is as follows (a) to (d): (a) A glycidyl group and at least one group selected from the group consisting of a hydroxy group, a carboxy group, and an acid anhydride group relative thereto. (b) A hydroxy group and at least one group selected from the group consisting of a carboxy group and an acid anhydride group relative thereto. (c) An isocyanate group and a hydroxy group relative thereto. (d) A phenol group or a furyl group and a formyl group relative thereto. A cured product obtained by irradiating the composition with light in a pattern and heating for curing.

[12] A cured product obtained by irradiating a composition in a pattern with light and heating it to cure, the composition comprising a monomer C having at least one dynamic covalent bond selected from the group consisting of a disulfide bond, a diselenide bond, and a ditelluride bond in the molecule, and a monomer B having at least two or more ethylenically unsaturated groups in the molecule, wherein the monomer A has a benzoxazine ring or two or more alkoxysilyl groups in the molecule.

[13] The cured product according to

[11] , wherein the pair of curable groups is at least one group selected from the group consisting of a glycidyl group and at least one group selected from the group consisting of a hydroxy group, a carboxy group, and an acid anhydride group with respect thereto.

[14] The cured product according to any one of

[11] to

[13] , wherein the dynamic covalent bond is a disulfide bond.

[15] A three-dimensional structure assembled by heating the cured product according to any one of

[11] to

[14] and bending it about the non-exposed portion as an axis. [Advantages of the Invention]

[0009] According to the present invention, a method for producing a cured product can be provided, which can produce a cured product having a finer difference (contrast) in mechanical properties in the cured product. Further, the present invention can also provide a composition, a cured product, and a three-dimensional structure. [Brief Description of the Drawings]

[0010]

Figure 1

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Figure 24

Mode for Carrying Out the Invention

[0011] Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. In this specification, the numerical range represented by "~" means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value. In addition, the description with (meth)acryloyl represents at least one of methacryloyl and acryloyl, and the description with (meth)acrylic represents at least one of methacrylic and acrylic.

[0012] [Method for Producing Cured Product] A method for producing a cured product according to an embodiment of the present invention (hereinafter also referred to as "this production method") includes irradiating a composition containing a monomer A, a monomer B, and a curing agent, which will be described later, with light in a pattern and heating the composition. Hereinafter, first, the components contained in the composition used in this production method will be described for each component. Furthermore, the presumed mechanism by which the desired effect is obtained by the cured product obtained by irradiating the composition with light in a pattern and heating it will be described.

[0013] (Composition) The composition used in this production method includes a monomer A having at least one dynamic covalent bond selected from the group consisting of a disulfide bond, a diselenide bond, and a ditelluride bond in the molecule, a monomer B having at least two or more ethylenically unsaturated groups in the molecule, and a curing agent. The monomer A and the curing agent each have at least two or more of one of a pair of curable groups that can react with each other in the molecule.

[0014] The above composition is obtained by mixing each component. Next, each component contained in the composition will be described in detail.

[0015] ·Monomer A The monomer A is a compound contained in the composition and contributing to the formation of a network in the cured product formed by light irradiation and heating. The monomer A has at least one dynamic covalent bond selected from the group consisting of a disulfide bond (-S-S-), a diselenide bond (-Se-Se-), and a ditelluride bond (-Te-Te-) in the molecule.

[0016] Furthermore, the monomer A has at least two or more curable groups in the molecule. This curable group is in a relationship that can react with the curable group of the curing agent. That is, the curable group of the monomer A and the curable group of the curing agent form "a pair of curable groups that can react with each other".

[0017] Here, "a pair of curable groups that can react with each other" means, for example, a curable group X 1and a curable group X 2 when it can react with this X 1 and X 2 means a combination with X For example, when monomer A has at least one of the curable groups (X 1 , X 2 ), the curing agent has the other curable group. Also, the number thereof is 2 or more in one molecule.

[0018] This combination of a pair of curable groups is selected from the group consisting of (a) to (d) shown in Table 1 below.

[0019]

Table 1

[0020] The above table represents the combination of curable groups (X 1 , X 2 ), and the curable group that monomer A has may be either X 1 , or X 2 . For example, in the case of combination (a), monomer A may have 2 or more glycidyl groups in the molecule. At this time, the curing agent to be described later has 2 or more of at least one curable group selected from the group consisting of the hydroxy group, carboxy group, and acid anhydride group of X 2 in the molecule.

[0021] Also, when monomer A has 2 or more of at least one curable group selected from the group consisting of the hydroxy group, carboxy group, and acid anhydride group of X 2 in the molecule (combination (a)), the curing agent may have 2 or more glycidyl groups in the molecule. The above is the same for (b) to (d).

[0022] Since monomer A has a dynamic covalent bond in the molecule, it is cleaved by light irradiation and radicals are generated. As will be described in detail later, since the above composition contains monomer B having at least two or more ethylenically unsaturated groups in the molecule, the reaction with the ethylenically unsaturated group (for example, the enethiol reaction) proceeds by the radicals generated by light irradiation (for example, thioyl radicals).

[0023] On the other hand, the combination of the above curable groups (X 1 , X 2 ) is a combination in which the reaction hardly proceeds (or does not proceed) upon light irradiation. The combination of the above curable groups (X 1 , X 2 ) is such that the curing reaction easily proceeds by another method different from light irradiation (typically heating). Therefore, when the curable groups of monomer A and the curing agent are selected as described above, a difference occurs in the molecular structure of the final cured product between the exposed portion and the unexposed portion, which is a factor in expressing the specific properties of the cured product produced by this manufacturing method.

[0024] The structure of monomer A is not particularly limited, but typically, a compound represented by the following formula (1) is preferred.

[0025]

Chemical formula

[0026] In formula (1), Z 1 is a group having a curable group, R 1 is a hydrogen atom or a monovalent organic group, L 1 is a (p + q)-valent group containing a dynamic covalent bond, p represents an integer of 0 or more, and q represents an integer of 2 or more.

[0027] In formula (1), a plurality of Z 1 may be the same or different, but when Z 1 is different, it is within the range in each combination of (a) to (d) in Table 1. That is, "when a plurality of Z 1 are different" means that Z 1 is (a)(b), or X 2In the case where it is within that range, it is a group within that range.

[0028] In formula (1), p is an integer of 0 or more, preferably 10 or less, more preferably 8 or less, still more preferably 6 or less, particularly preferably 4 or less, and most preferably 2 or less. Among them, p is preferably 0.

[0029] In formula (1), q is an integer of 2 or more, preferably 10 or less, more preferably 8 or less, still more preferably 6 or less, and particularly preferably 4 or less.

[0030] In formula (1), R 1 is a hydrogen atom or a monovalent organic group. As the monovalent organic group, it is a group different from any of the pair of curable groups (a group that is not any of a glycidyl group, a hydroxy group, a carboxy group, an acid anhydride group, a carboxy group, an isocyanate group, a phenol group, a furyl group, and a furyl group). More specifically, a cyclic or chain alkyl group, an aryl group, or a combination of a plurality of these is preferable. Among them, an alkyl group having 1 to 4 carbon atoms is preferable. Among them, R 1 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. In addition, a plurality of R 1 may be the same or different, and may be bonded to each other to form a ring.

[0031] In formula (1), L 1 is a (p + q)-valent group containing a dynamic covalent bond. When L 1 is a divalent group, it has at least one dynamic covalent bond (-S-S-, -Se-Se-, and -Te-Te-) selected from the group consisting of a disulfide bond, a diselenide bond, and a ditelluride bond, and further, -C(O)-, -C(O)O-, -OC(O)-, -O-, -NR 20 -(R 20represents a hydrogen atom or a monovalent organic group), -N=, an alkylene group (preferably having 1 to 20 carbon atoms, including cyclic and linear forms), an alkenylene group (preferably having 2 to 20 carbon atoms, including cyclic and linear forms), an arylene group, a heteroarylene group, a poly(oxyalkylene) group, and combinations thereof, etc. may be included. In addition, the rings of the cyclic alkylene group, the cyclic alkenylene group, the arylene group, and the heteroarylene group may each form a condensed ring.

[0032] Among these, examples of the arylene group include a 1,2-phenylene group, a 1,2-naphthylene group, a 2,3-naphthylene group, a 1,8-naphthylene group, a 1,2-anthrylene group, a 2,3-anthrylene group, a 1,2-phenanthrylene group, a 3,4-phenanthrylene group, and a 9,10-phenanthrylene group, etc., and any of them may have a substituent.

[0033] Examples of the heteroarylene group include a group obtained by removing any two hydrogen atoms from thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, and quinoxaline, etc.

[0034] Among them, in terms of obtaining a composition having more excellent effects of the present invention, L 1 As the divalent group of L, a dynamic covalent bond (among them, -S-S- is preferable), or in addition to the dynamic covalent bond, a group having -O-, a linear or cyclic alkylene group, an arylene group, or a poly(oxyalkylene) group is preferable.

[0035] Also, L 1When it is a trivalent or higher-valent group, there is no particular limitation, and examples thereof include groups represented by the following (3a) to (3d). In the following formulas, “*” represents the bonding position.

[0036]

Chemical formula

[0037] In formula (3a), Q 3 represents a trivalent group. T 3 represents a single bond or a divalent group, and the three Ts 3 may be the same as or different from each other. Note that at least one or more of the Ts 3 are divalent groups. Examples of Q 3 include a tertiary amino group, a trivalent hydrocarbon group (preferably having 1 to 10 carbon atoms. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group.), or a trivalent heterocyclic group (preferably a 5-membered to 7-membered heterocyclic group), and the hydrocarbon group may contain a hetero atom (for example, -O-). Specific examples of Q 3 include a glycerin residue, a trimethylolpropane residue, a phloroglucinol residue, a cyanuric acid residue, a xanthine residue, and a cyclohexanetriol residue, etc.

[0038] Note that the divalent group of T 3 may be the same group as the divalent group of L 1 already described. Among the plurality of Ts 3 at least one is a divalent group having a dynamic covalent bond, and all may be groups having a dynamic covalent bond. When T 3 has a dynamic covalent bond, T 3 may be the dynamic covalent bond itself (such as a disulfide group), or a combination with another divalent group. In that case, a combination with an alkylene group having 1 to 5 carbon atoms which may have a substituent is preferred. When T 3 is a group having no dynamic covalent bond, T 3 is preferably an alkylene group having 1 to 5 carbon atoms which may have a substituent.

[0039] In formula (3b), Q 4 represents a tetravalent group. T 4 represents a single bond or a divalent group, and the four Ts 4 may be the same as or different from each other. Note that at least one or more of the Ts 4 are divalent groups. Note that as Q 4 , there may be mentioned a tetravalent hydrocarbon group (preferably having 1 to 10 carbon atoms. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group.), a tetravalent heterocyclic group (preferably a 5- to 7-membered heterocyclic group), and the hydrocarbon group may contain a hetero atom (for example, -O-). Q 4 Specific examples of Q

[0040] Note that the divalent group of T 4 may be the same group as the divalent group of L 1 already described, and the preferred forms are also the same. However, among the plurality of Ts 4 , at least one is a divalent group having a dynamic covalent bond, and all may be groups having a dynamic covalent bond. When T 4 has a dynamic covalent bond, T 4 may be the dynamic covalent bond (such as a disulfide group) itself, or a combination with another divalent group. In that case, a combination with an alkylene group having 1 to 5 carbon atoms which may have a substituent is preferred. T 4 When T is a group having no dynamic covalent bond, T 4 is preferably an alkylene group having 1 to 5 carbon atoms which may have a substituent.

[0041] In formula (3c), Q 5 represents a pentavalent group. T 5 represents a single bond or a divalent group, and the five Ts 5 may be the same as or different from each other. Note that at least one or more of the Ts 5 are divalent groups. Note that as Q5 Examples thereof include a pentavalent hydrocarbon group (preferably having 2 to 10 carbon atoms. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group), or a pentavalent heterocyclic group (preferably a 5- to 7-membered heterocyclic group). The hydrocarbon group may contain a heteroatom (e.g., -O-). Q 5 Specific examples of Q include an arabinitol residue, a phloroglucinol residue, and a cyclohexanepentol residue.

[0042] Note that T 5 The divalent group of may be the same as the divalent group of L described above, and the preferred forms are also the same. However, among the plurality of T 1 at least one of them is a divalent group having a dynamic covalent bond, and all of them may be groups having a dynamic covalent bond. T 5 When has a dynamic covalent bond, T 5 may be the dynamic covalent bond (such as a disulfide group) itself, or a combination with other divalent groups. In that case, a combination with an alkylene group having 1 to 5 carbon atoms which may have a substituent is preferred. 5 When T does not have a dynamic covalent bond, T T 5 is preferably an alkylene group having 1 to 5 carbon atoms which may have a substituent. 5

[0043] In formula (3d), Q 6 represents a hexavalent group. T 6 represents a single bond or a divalent group, and the six Ts 6 may be the same as or different from each other. Note that at least one or more of T 6 are divalent groups. Note that Q 6 Examples thereof include a hexavalent hydrocarbon group (preferably having 2 to 10 carbon atoms. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group), or a hexavalent heterocyclic group (preferably a 6- to 7-membered heterocyclic group). The hydrocarbon group may contain a heteroatom (e.g., -O-). Q 6 ​Specific examples thereof include a mannitol residue, a sorbitol residue, a dipentaerythritol residue, hexahydroxybenzene, and a hexahydroxycyclohexane residue.

[0044] Note that the divalent group of T 6 may be the same as the divalent group of L 1 already described, and the preferred forms are also the same. However, among the plurality of Ts 6 at least one is a divalent group having a dynamic covalent bond, and all of them may be groups having a dynamic covalent bond. When T 6 has a dynamic covalent bond, T 6 may be the dynamic covalent bond (such as a disulfide group) itself, or a combination with another divalent group. In that case, a combination with an alkylene group having 1 to 5 carbon atoms which may have a substituent is preferred. T 6 is a group having no dynamic covalent bond, T 6 is preferably an alkylene group having 1 to 5 carbon atoms which may have a substituent.

[0045] Note that when L 1 is a group having 7 or more valences, a group obtained by combining the groups represented by formulas (3a) to (3d) can be used.

[0046] In formula (1), the group having a curable group of Z 1 is not particularly limited, but a group represented by the following formula (11) is preferred.

[0047]

Chemical formula

[0048] In formula (11), L 11 represents a single bond or a divalent group, and X 3 represents a curable group. L 11 The divalent group of is not particularly limited, but examples thereof include the same groups as the divalent group of L 1 already described. Note that L 1It may have dynamic covalent bonds, but it is preferably not. Among them, in terms of obtaining more excellent effects of the present invention, 11 As the divalent group of L, -O-, -C(=O)-, an alkylene group having 1 to 5 carbon atoms, a poly(oxyalkylene) group, and a group combining these are preferable.

[0049] X 3 The curable group of X is a group selected from the combinations of (a) to (d) in Table 1, 1 or X 2 Among them, in terms of obtaining more excellent effects of the present invention, a group selected from the group consisting of a glycidyl group, a hydroxy group, a carboxy group, an acid anhydride group, and an isocyanate group is preferable, and a group selected from the group consisting of a glycidyl group, a hydroxy group, a carboxy group, and an acid anhydride group is more preferable. In addition, as the acid anhydride group, a carboxylic acid anhydride group is preferable. The carboxylic acid anhydride group is a group obtained by removing one arbitrary hydrogen atom possessed by the carboxylic acid anhydride group, and a group obtained by removing one arbitrary hydrogen atom from at least one selected from the group consisting of an acetic anhydride group, a succinic anhydride group, a phthalic anhydride group, and a maleic anhydride group is more preferable.

[0050] Monomer A can be synthesized by a known method or a commercially available product can be used. Specifically, 4,4′-dihydroxydiphenyl disulfide, 6,6′-dihydroxy-2,2′-dinaphthyl disulfide, bis(2-hydroxyethyl) disulfide, bis(2-hydroxyethyl) disulfide, bis(3-carboxypropyl) disulfide (all manufactured by Tokyo Chemical Industry Co., Ltd.); 2,2′-dithiobisbenzoic acid, 4,4′-dithiobisbenzoic acid, and 3,3′-dihydroxydiphenyl disulfide (all manufactured by Fujifilm Wako Chemicals); Trans-4,5-dihydroxy-1,2-dithiane, Dithiodiglycolic acid, 2,2′-Dithiodipropionic acid, 3,3′-Dithiobisbenzoic acid, and "HG-4045" (all manufactured by Combi-Blocks); "ACID-PEG2-SS-PEG2-ACID", "ACID-PEG3-SS-PEG3-ACID", "ACID-PEG4-SS-PEG4-ACID", and "ACID-PEG6-SS-PEG6-ACID" (all manufactured by Apollo Scientific); Hydroxy-PEG3-SS-PEG3-alcohol (manufactured by BROAD PHARM); etc. can be used. Moreover, commercially available products represented by the following formula can also be used.

[0051] [Chemical formula]

[0052] The molecular weight of monomer A is not particularly limited. As one form, it is preferably 100 or more, more preferably 120 or more, still more preferably 130 or more, preferably 3000 or less, and more preferably 2000 or less.

[0053] The content of monomer A in the composition is not particularly limited. However, in terms of obtaining a more excellent effect of the present invention, it is preferably prepared so that the dynamic covalent bond is 0.1 to 3.0 moles, more preferably 0.5 to 2.5 moles, and still more preferably 1.1 to 2.5 moles, per 1 mole of the ethylenically unsaturated group possessed by monomer B described later. Note that monomer A may be used alone or in combination of two or more. When two or more monomers A are used in combination, it is preferable that the total content is within the above range.

[0054] · Monomer B Monomer B is a compound contained in the composition and reacts with radicals generated by cleavage of the dynamic covalent bond of monomer A by light irradiation. Typically, it is a compound that reacts with a thiyl radical generated by cleavage of the disulfide bond of monomer A. Monomer B has at least two or more ethylenically unsaturated groups in the molecule. Among them, it is preferable that it does not have any of the above-mentioned pair of curable groups. Further, it may have a dynamic covalent bond, but it is preferably not present.

[0055] Examples of the ethylenically unsaturated group include a vinyl group, a vinyl ether group, a vinyl ester group, and a (meth)acryloyl group, and a (meth)acryloyl group is preferable.

[0056] In terms of obtaining more excellent effects of the present invention, monomer B is preferably a compound represented by the following formula (2).

[0057]

Chemical formula

[0058] In formula (2), R 2 represents a hydrogen atom or a monovalent organic group, Y 2 represents a group having an ethylenically unsaturated group, L 2 represents a single bond or a u + t-valent group, t represents an integer of 2 or more, and u represents an integer of 0 or more.

[0059] t is preferably 10 or less, more preferably 8 or less, and still more preferably 6 or less. In terms of obtaining a composition having more excellent effects of the present invention, t is preferably 2 to 4. u is preferably 8 or less, more preferably 6 or less, still more preferably 4 or less, and particularly preferably 2 or less. In terms of obtaining a composition having more excellent effects of the present invention, u is preferably 0 to 2.

[0060] L 2 When is a divalent group, -S-, -C(O)-, -C(O)O-, -OC(O)-, -O-, -NR 20 -(R 20 (wherein R represents a hydrogen atom or a monovalent organic group), -N=, an alkylene group (preferably having 1 to 20 carbon atoms, including cyclic and chain-like), an alkenylene group (preferably having 2 to 20 carbon atoms, including cyclic and chain-like), an arylene group, a heteroarylene group, a poly(oxyalkylene) group, and combinations thereof, etc. may be mentioned. L 2 The divalent group of is preferably free of dynamic covalent bonds. In addition, the rings of the cyclic alkylene group, the cyclic alkenylene group, the arylene group, and the heteroarylene group may each form a condensed ring.

[0061] Among these, examples of the arylene group include a 1,2-phenylene group, a 1,2-naphthylene group, a 2,3-naphthylene group, a 1,8-naphthylene group, a 1,2-anthrylene group, a 2,3-anthrylene group, a 1,2-phenanthrylene group, a 3,4-phenanthrylene group, and a 9,10-phenanthrylene group, etc., and any of them may have a substituent.

[0062] Examples of the heteroarylene group include a group obtained by removing any two hydrogen atoms from thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, and quinoxaline, etc.

[0063] Among them, in terms of obtaining a composition having a more excellent effect of the present invention, L 2 As the divalent group of, -O-, a chain or cyclic alkylene group, an arylene group, a poly(oxyalkylene) group, and combinations thereof are preferable.

[0064] Also, when L 2 is a trivalent or higher-valent group, there is no particular limitation, and examples thereof include groups represented by (4a) to (4d). In the following formulas, "*" represents the bonding position.

[0065]

Chemical formula

[0066] In formula (4a), Q 31 represents a trivalent group. T 31 represents a single bond or a divalent group, and the three Ts 31 may be the same as or different from each other. As Q 31 , a tertiary amino group, a trivalent hydrocarbon group (preferably having 1 to 10 carbon atoms. Note that the hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group.), or a trivalent heterocyclic group (preferably a 5-membered to 7-membered heterocyclic group) can be mentioned, and the hydrocarbon group may contain a heteroatom (for example, -O-). Specific examples of Q 31 include a glycerin residue, a trimethylolpropane residue, a phloroglucinol residue, a cyanuric acid residue, a xanthine residue, and a cyclohexanetriol residue, etc. Also, as the divalent group of T 31 , the same groups as the divalent groups of L 2 can be mentioned, and the preferred forms are the same.

[0067] In formula (4b), Q 41 represents a tetravalent group. T 41 represents a single bond or a divalent group, and the four Ts 41 may be the same as or different from each other. Note that Q 41Examples thereof include a tetravalent hydrocarbon group (preferably having 1 to 10 carbon atoms. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group.), and a tetravalent heterocyclic group (preferably a 5- to 7-membered heterocyclic group). The hydrocarbon group may contain a heteroatom (e.g., -O-). Q 41 Specific examples of 41 include a pentaerythritol residue, a glycoluril residue, a ditrimethylolpropane residue, and the like. Also, T 41 Examples of the divalent group of 41 include the same groups as the divalent group of L 2 and preferred embodiments are also the same.

[0068] In formula (4c), Q 51 represents a pentavalent group. T 51 represents a single bond or a divalent group, and the five Ts 51 may be the same as or different from each other. Note that examples of Q 51 include a pentavalent hydrocarbon group (preferably having 2 to 10 carbon atoms. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group.), or a pentavalent heterocyclic group (preferably a 5- to 7-membered heterocyclic group). The hydrocarbon group may contain a heteroatom (e.g., -O-). Q 51 Specific examples of 51 include an arabinitol residue, a phloroglucinol residue, and a cyclohexanepentaol residue, and the like. Also, T 51 Examples of the divalent group of 51 include the same groups as the divalent group of L 2 and preferred embodiments are also the same.

[0069] In formula (4d), Q 61 represents a hexavalent group. T 61 represents a single bond or a divalent group, and the six Ts 61 may be the same as or different from each other. Note that Q 61Examples include a hexavalent hydrocarbon group (preferably having 2 to 10 carbon atoms. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group), or a hexavalent heterocyclic group (preferably a 6- to 7-membered heterocyclic group). The hydrocarbon group may contain a heteroatom (e.g., -O-). Q 61 Specific examples of 61 include a mannitol residue, a sorbitol residue, a dipentaerythritol residue, hexahydroxybenzene, and a hexahydroxycyclohexane residue, etc. Also, T 61 Examples of the divalent group of 61 include the same groups as the divalent group of L 2 and the preferred forms are also the same.

[0070] Note that when L 2 is a group with 7 or more valences, a group formed by combining the groups represented by formulas (4a) to (4d) can be used.

[0071] Y 2 The group having an ethylenically unsaturated group of 2 is preferably a group represented by *-L 21 -Y 21 where Y 21 represents an ethylenically unsaturated group, examples of which include a vinyl group, a vinyl ether group, a vinyl ester group, and a (meth)acryloyl group, etc., and a (meth)acryloyl group is preferred. L 21 is a single bond or a divalent group. As the divalent group, it is the same as the divalent group of L 21 and the preferred forms are also the same. Note that * represents the bonding position. 2 Monomer B can be synthesized by a known method or a commercially available product can be used.

[0072] Examples of Monomer B include, for example, those having two (meth)acryloyl groups such as bisphenol A di(meth)acrylate, nonamethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and polyethylene glycol di(meth)acrylate, etc. ​In addition, examples of those having three (meth)acryloyl groups include tris(2-acryloyloxyethyl) isocyanurate, trimethylolpropane tri(meth)acrylate, and glycerol tri(meth)acrylate. In addition, examples of those having four (meth)acryloyl groups include pentaerythritol tetra(meth)acrylate and ditrimethylolpropane tetraacrylate. In addition, examples of those having six (meth)acryloyl groups include dipentaerythritol hexa(meth)acrylate.

[0073] In addition, a compound represented by the following formula can also be used as monomer B.

Chemical formula

[0074] The molecular weight of monomer B is not particularly limited, but in one form, it is preferably 100 or more, more preferably 150 or more, still more preferably 180 or more, preferably 1500 or less, and more preferably 1000 or less.

[0075] The content of monomer B in the composition is not particularly limited, but in terms of obtaining a more excellent effect of the present invention, it is preferably prepared so that the amount of ethylenically unsaturated groups is 0.3 to 10.0 moles, more preferably 0.4 to 2.0 moles, and still more preferably 0.4 to 0.9 moles, per 1 mole of the dynamic covalent bond of monomer A. Note that monomer B may be used alone or in combination of two or more. When two or more kinds of monomer B are used in combination, it is preferable that the total content is within the above range.

[0076] ·Curing agent The curing agent is a compound contained in the composition and having at least two or more of one of a pair of curable groups capable of reacting with the curable group of monomer A in the molecule. The curing agent is a compound that contributes to the formation of the network of the cured product by reacting with monomer A.

[0077] The curable group of the curing agent is specified by the combination with the curable group of monomer A. That is, when the curable group of monomer A is selected from the combinations of (X 1 , X 2 ) described in Table 1 above, the curable group of the curing agent is correspondingly selected.

[0078] The curing agent has two or more specific groups capable of reacting with the curable group of monomer A. This pair of curable groups is a combination of curable groups that are less active, typically inactive, against light irradiation. Therefore, even when the composition is irradiated with light, the reaction of the pair of curable groups hardly proceeds. On the other hand, the dynamic covalent bond of monomer A is cleaved by light irradiation, and the reaction with the ethylenically unsaturated group of monomer B proceeds.

[0079] It is presumed that the above leads to the difference in the molecular structure of the cured product due to exposure / non-exposure and / or the change in the exposure amount for each site, and contributes to the expression of the contrast of the positional mechanical properties (typically viscoelasticity) of the obtained cured product.

[0080] The structure of the curing agent is not particularly limited, but typically, the compound represented by the following formula (3) is preferred.

[0081]

Chemical formula

[0082] In formula (3), R 3 represents a hydrogen atom or a monovalent organic group, Z 3 represents a group having a curable group, and L 3represents a single bond or an r + s-valent group, where r represents an integer of 0 or more and s represents an integer of 2 or more.

[0083] R 3 The monovalent organic group of is not particularly limited, but the same groups as the monovalent organic group of R in formula (1) are exemplified, and the preferred forms are also the same. 1 The monovalent organic group of is not particularly limited, but the same groups as the monovalent organic group of R in formula (1) are exemplified, and the preferred forms are also the same.

[0084] Z 3 As the group having a curable group of, the same groups as the group having a curable group of Z in formula (1) are exemplified, and the preferred forms are also the same. However, the curable group that has and the curable group that has are a pair of groups that can react with each other and are selected from each other from the combinations in Table 1 already described. 1 As the group having a curable group of, the same groups as the group having a curable group of Z in formula (1) are exemplified, and the preferred forms are also the same. However, the curable group that has and the curable group that has are a pair of groups that can react with each other and are selected from each other from the combinations in Table 1 already described. 1 The curable group that has and the curable group that has are a pair of groups that can react with each other and are selected from each other from the combinations in Table 1 already described. 3 The curable group that has and the curable group that has are a pair of groups that can react with each other and are selected from each other from the combinations in Table 1 already described.

[0085] In formula (3), the r + s-valent group of L is not particularly limited, but the same groups as L in formula (2) are exemplified, and the preferred forms are also the same. If the group represented by L in formula (2) and the group represented by L in formula (3) have the same part or are the same, it is preferable in terms of enhancing the compatibility of each component in the composition and being able to prepare a more uniform cured product. 3 In formula (3), the r + s-valent group of L is not particularly limited, but the same groups as L in formula (2) are exemplified, and the preferred forms are also the same. 2 In formula (2), the same groups as L are exemplified, and the preferred forms are also the same. If the group represented by L in formula (2) and the group represented by L in formula (3) have the same part or are the same, it is preferable in terms of enhancing the compatibility of each component in the composition and being able to prepare a more uniform cured product. 2 The group represented by L in formula (2) and the group represented by L in formula (3) have the same part or are the same, it is preferable in terms of enhancing the compatibility of each component in the composition and being able to prepare a more uniform cured product. 3 If the group represented by L in formula (2) and the group represented by L in formula (3) have the same part or are the same, it is preferable in terms of enhancing the compatibility of each component in the composition and being able to prepare a more uniform cured product.

[0086] In formula (3), r is an integer of 0 or more, preferably an integer of 10 or less, more preferably an integer of 8 or less, still more preferably an integer of 6 or less, particularly preferably an integer of 4 or less, and most preferably an integer of 2 or less.

[0087] In formula (3), s is an integer of 2 or more, preferably an integer of 10 or less, more preferably an integer of 8 or less, still more preferably an integer of 6 or less, and particularly preferably an integer of 4 or less. <�

[0088] The compound represented by formula (3) may be synthesized by a known method or a commercially available product may be used. Examples of commercially available products include "Epolite" from Kyoeisha Chemical, "Epogosec" from Yokkaichi Synthesis, "Denacol" from Nagase ChemteX, "jER" from Mitsubishi Chemical, "Glycier PP" from Sanyo Chemical Industries, "Sho Free" from Showa Denko, "Ricarezine" from Shin Nippon Rika, and "Nonhalite" from National Institute for Materials Science, etc.

[0089] [Chemical formula]

[0090] The molecular weight of the curing agent is not particularly limited, but in one form, 100 to 3000 is preferable, and 140 to 2000 is more preferable.

[0091] The content of the curing agent in the composition is not particularly limited, but in terms of obtaining a more excellent effect of the present invention, it is preferably prepared so that the dynamic covalent bond is 0.1 to 2.5 moles, more preferably 0.5 to 2.0 moles, and still more preferably 0.7 to 1.3 moles, per 1 mole of the curable group of monomer A described later. Note that the curing agent may be used alone or in combination of two or more. When two or more curing agents are used in combination, it is preferable that the total content is within the above range.

[0092] ·Other components The composition may contain other components as long as it contains the above components. Examples of other components include coloring pigments, extender pigments, dyes, ultraviolet absorbers, various fillers, and solvents.

[0093] The solvent is not particularly limited, and known organic solvents and the like can be used. Specifically, it is preferable to use an alcohol having 1 to 6 carbon atoms and an aprotic polar solvent such as tetrahydrofuran. When the composition contains a solvent, the content of the solvent in the composition is not particularly limited, but in one embodiment, it may be adjusted so that the solid content of the composition is 1 to 99%. In addition, one kind of solvent may be used alone, or two or more kinds may be used in combination. When two or more kinds of solvents are used in combination, it is preferable that the total content is within the above range.

[0094] (Other embodiments of the composition) Another embodiment of the composition is a composition containing monomer C having a dynamic covalent bond, which will be described later, and the above-mentioned monomer B. The difference between this composition and the composition already described is that this composition does not require a curing agent.

[0095] Monomer C contained in this composition has two or more benzoxazine rings or alkoxysilyl groups in the molecule. Therefore, by heating or the like, a ring-opening polymerization reaction of the benzoxazine ring or a hydrolysis-condensation reaction of the alkoxysilyl group occurs, and monomers C react with each other to cure. Therefore, it has the characteristic that it does not need to contain the curing agent contained in the composition already described (which requires a curing agent).

[0096] Hereinafter, the differences between the composition already described and the composition according to this embodiment will be described, and the description of the same parts will be omitted. The parts for which the description is omitted are the same as the description of the corresponding parts of the composition already described, and the preferred forms are also the same.

[0097] ·Monomer C Monomer C is a compound contained in the composition and contributes to the formation of a network in the cured product by light irradiation and heating. Monomer C has at least one dynamic covalent bond selected from the group consisting of disulfide bonds (-S-S-), diselenide bonds (-Se-Se-), and ditelluride bonds (-Te-Te-) in the molecule.

[0098] Monomer C has two or more benzoxazine rings or alkoxysilyl groups in the molecule. As Monomer C, for example, compounds represented by the following formula (4) or (5) are preferable.

[0099] [Chemical formula]

[0100] In formula (4), R 4 represents a hydrogen atom or a monovalent organic group, Z 4 represents a group obtained by removing one arbitrary hydrogen atom from a benzoxazine ring, and L 4 represents a (j + k)-valent group containing a dynamic covalent bond, k represents an integer of 2 or more, and j represents an integer of 0 or more.

[0101] In formula (4), k is an integer of 2 or more, preferably 10 or less, more preferably 8 or less, still more preferably 6 or less, and particularly preferably 4 or less.

[0102] In formula (4), j is an integer of 0 or more, preferably 10 or less, more preferably 8 or less, still more preferably 6 or less, particularly preferably 4 or less, and most preferably 2 or less. Among them, j is preferably 0.

[0103] In formula (4), the monovalent organic group of R 4 is not particularly limited, and examples include the same groups as R 1 in formula (1), and the preferred forms are also the same.

[0104] In formula (4), the divalent group of L 4 is not particularly limited, but has at least one dynamic covalent bond (-S-S-, -Se-Se-, and -Te-Te-) selected from the group consisting of a sulfide bond, a diselenide bond, and a ditelluride bond, and its form is the same as the group of L 1 in formula (1), and the preferred forms are also the same. Further, as the trivalent or higher-valent group of L 4 , examples include the same groups as the trivalent or higher-valent groups of L 1 , and the preferred forms are also the same.

[0105] The compound represented by formula (4) can be synthesized by a known method. As one form, it can be synthesized by reacting a phenol compound, an amine compound, and formaldehyde. In addition, a method for synthesizing a benzoxazine compound having a disulfide bond is also described in JP-A-2011-231027, and reference can be made thereto.

[0106]

Chemical formula

[0107] In formula (5), R 5 represents a hydrogen atom or a monovalent organic group, and R 51 , and R 52 represent an alkyl group having 1 to 10 carbon atoms (preferably 1 to 4 carbon atoms), L 5 represents a g + i-valent group containing a dynamic covalent bond, h represents an integer of 0 to 3, g represents an integer of 0 or more, and i represents an integer of 2 or more.

[0108] In formula (5), i is an integer of 2 or more, preferably 10 or less, more preferably 8 or less, still more preferably 6 or less, and particularly preferably 4 or less.

[0109] In formula (5), g is an integer of 0 or more, preferably 10 or less, more preferably 8 or less, still more preferably 6 or less, particularly preferably 4 or less, and most preferably 2 or less. Among them, g is preferably 0.

[0110] In formula (5), the monovalent organic group of R 5 is not particularly limited, and examples thereof include the same groups as R 1 in formula (1), and the preferred forms are the same.

[0111] In formula (5), L 5The divalent group is not particularly limited, but has at least one dynamic covalent bond (-S-S-, -Se-Se-, and -Te-Te-) selected from the group consisting of a sulfide bond, a diselenide bond, and a ditelluride bond, and its form is L in formula (1). 1 Groups similar to those of 1 can be mentioned, and preferred forms are also the same. Also, L 5 As the trivalent or higher-valent group of, groups similar to the trivalent or higher-valent group of L 1 can be mentioned, and preferred forms are also the same.

[0112] The compound represented by formula (5) may be synthesized by a known method or a commercially available product may be used. Examples of commercially available products include bis(3-triethoxysilylpropyl)disulfide, bis(2-triethoxysilylethyl)disulfide, bis(4-triethoxysilylbutyl)disulfide, bis(3-trimethoxysilylpropyl)disulfide, bis(2-trimethoxysilylethyl)disulfide, and bis(4-trimethoxysilylbutyl)disulfide, etc., and products of companies such as Degussa, USI Chemical, and Momentive can be used.

[0113] The content of monomer C in the composition is not particularly limited, but in terms of obtaining more excellent effects of the present invention, it is preferably prepared so that the dynamic covalent bond is 0.1 to 3.0 moles with respect to 1 mole of the ethylenically unsaturated group of monomer B described later, more preferably prepared so that it is 0.5 to 2.5 moles, and still more preferably prepared so that it is 1.1 to 2.5 moles. Note that monomer C may be used alone or in combination of two or more. When two or more kinds of monomer C are used in combination, it is preferable that the total content is within the above range.

[0114] ·Monomer B The composition contains monomer B. As monomer B, the same compounds as those contained in the composition used in the method for producing a cured product according to the first embodiment can be used, and preferred forms are also the same.

[0115] The content of monomer B in the composition is not particularly limited, but in terms of obtaining better effects of the present invention, it is preferably prepared such that the amount of ethylenically unsaturated groups is 0.3 to 10.0 moles, more preferably 0.4 to 2.0 moles, and even more preferably 0.4 to 0.9 moles, per 1 mole of the dynamic covalent bond possessed by monomer C. Note that monomer B may be used alone or in combination of two or more. When two or more monomers B are used in combination, it is preferable that the total content is within the above range.

[0116] Next, a method for producing a cured product using each of the above-described compositions will be described. As one embodiment of the method for producing a cured product, a method is provided in which a composition layer is formed on a temporary substrate using the composition obtained by mixing the above components, and the composition layer is irradiated with light in a pattern and heated to obtain a cured product. The order of the patterned light irradiation and heating is not particularly limited, and either may be performed first or they may be performed simultaneously. Among these, from the viewpoint that the reaction between the radicals generated by the cleavage of the dynamic covalent bond and the ethylenically unsaturated groups is more likely to occur by performing the light irradiation in a state where the composition has high fluidity, it is preferable to perform heating sequentially after the light irradiation.

[0117] The composition can be prepared by mixing the above components in a predetermined ratio. Examples of the method for forming a composition layer using the prepared composition include a method of coating on a temporary substrate by a known method. When the composition contains a solvent, it may be dried as necessary (in this case, reduced pressure may be applied). The material of the temporary substrate is not particularly limited, and examples include glass and resin.

[0118] The thickness of the composition layer is not particularly limited and may be appropriately selected according to the use of the cured product. As one form, when the obtained cured product is used for assembling a three-dimensional structure, the thickness of the composition layer is preferably 0.1 to 5000 μm in the cured state.

[0119] The method of applying the composition onto the temporary substrate is not particularly limited, and examples thereof include coating methods such as spin coating method, extrusion method, gravure coating method, die coating method, bar coating method, and applicator method; printing methods such as flexo method; and other known methods.

[0120] By irradiating light to the thus obtained composition layer, the dynamic covalent bond possessed by monomer A (or monomer C) is cleaved and reacts with the ethylenically unsaturated group possessed by monomer B.

[0121] The light to be irradiated may be appropriately selected depending on each component, particularly the content of monomer A in the composition, etc. Specific examples thereof include one or more kinds of light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, and γ-rays, and active energy rays such as active electron beams. Among them, ultraviolet light is preferable from the viewpoint that the effects of the present invention can be more easily obtained.

[0122] In addition, the temperature of the composition layer may be adjusted during light irradiation. For example, when the composition layer is formed on the temporary substrate, the composition layer may be cooled according to the heat resistance of the substrate. On the other hand, from the viewpoint of allowing the reaction between the radicals generated by the cleavage of the dynamic covalent bond and the ethylenically unsaturated group to proceed more uniformly, the composition layer may be heated. When heating the composition layer, the heating temperature is not particularly limited, but it is preferably a temperature lower than the temperature at which the curing reaction due to the reaction of the curable groups of each monomer easily occurs, specifically, 100 °C or lower, and more preferably 80 °C or lower.

[0123] The light irradiation is preferably performed in a pattern. By irradiating light in a pattern, the residual amount of the dynamic covalent bond in the cured product can be controlled. The method of performing light irradiation in a pattern is not particularly limited, and examples thereof include a method of irradiating light to the composition layer through a photomask, and a method using an electron beam lithography apparatus.

[0124] The light source is not particularly limited, and examples thereof include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a halogen lamp, a carbon arc lamp, a tungsten lamp, a gallium lamp, an excimer laser, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, and a metal halide lamp.

[0125] The light irradiation intensity may be appropriately selected depending on how to control the contrast of the viscoelastic properties between the exposed portion and the unexposed portion. In one embodiment, 10 to 3,000 mW / cm 2 is preferable. The time for irradiating light is preferably 0.1 second to 60 minutes, more preferably 1 second to 30 minutes, and even more preferably 10 seconds to 20 minutes in one embodiment. As the integrated light quantity, 10 to 9,000 mJ / cm 2 is preferable.

[0126] Next, by heating the composition layer, the curable group of monomer A and the curable group of the curing agent are reacted (or monomer C is cured). In other words, a curing reaction is caused. The heating time is preferably 140°C or higher and preferably 200°C or lower in one embodiment. The heating time is not particularly limited, but 0.5 to 24 hours is preferable, and 0.5 to 4 hours is more preferable. Note that after curing, the cured product may be peeled off from the temporary substrate.

[0127] The cured product thus obtained is cured by two different energy application methods, in which radicals generated by cleavage of dynamic covalent bonds by light irradiation react with ethylenically unsaturated groups, and a pair of curable groups react with each other by heating to cause a curing reaction.

[0128] When the composition is irradiated with light in a pattern through a photomask, depending on the irradiation amount, radicals generated by cleavage of dynamic covalent bonds in the exposed portion react with ethylenically unsaturated groups, and then, when the composition is heated, a pair of curable groups react with each other throughout the composition to cause a curing reaction. In the resulting cured product, a network structure is formed by at least monomer A and a curing agent (or monomer C) not only in the exposed portion but also in the unexposed portion, and the shape is fixed.

[0129] In the unexposed portion, the dynamic covalent bonds of monomer A (or monomer C) tend to remain. On the contrary, in the exposed portion, the dynamic covalent bonds are consumed in the reaction with the ethylenically unsaturated group and hardly remain in the molecule of the cured product.

[0130] The dynamic covalent bond causes an exchange reaction by heating. Therefore, when the cured product is heated, an exchange reaction occurs at the portion where the dynamic covalent bond remains. When the exchange reaction occurs, even if stress is applied to the cured product, it is gradually relaxed. Therefore, when viewed as a whole of the cured product, large deformation becomes possible. The cured product becomes a state as if it is "softened" by heating, like a thermoplastic resin.

[0131] When irradiating light in a pattern, more dynamic covalent bonds remain in the unexposed portion. Therefore, this portion can be deformed more by heating. On the other hand, in the exposed portion, since the remaining amount of the dynamic covalent bond is small, "softening" is less likely to occur compared to the unexposed portion. It behaves like a thermosetting resin.

[0132] The cured product obtained by irradiating the composition of the present invention with light in a pattern and heating can arbitrarily control the "softening" tendency by heating for each site according to the light irradiation amount. Therefore, for example, the unexposed portion of the sheet-like composition is used as a "crease", the exposed portion is used as a "surface", and this is heated to soften the unexposed portion and bent to assemble a three-dimensional structure like origami.

[0133] Conventionally, in order to industrially mold a three-dimensional structure, a molding method using a mold or the like has often been used. When using this composition, without using a mold, a three-dimensional structure can be easily obtained by simply heating a sheet-like cured product (in a state like a developed view) and bending and assembling it along a pre-designed unexposed portion.

[0134] Note that the heating temperature for forming the three-dimensional structure (for softening the cured product) is not particularly limited, but it is preferably in a temperature range that can more effectively suppress the reaction between the radicals generated by the cleavage of the dynamic covalent bond and the ethylenically unsaturated group of monomer B. By setting the heating temperature within the above range, repeated deformation becomes possible. That is, when the non-exposed part is softened by heating and then cooled after forming, the structure is fixed. When heated again, the non-exposed part is softened again and forming becomes possible.

[0135] From the above perspective, the heating temperature of the cured product for deformation (forming) is preferably 100 to 140 °C, more preferably 105 to 135 °C, and even more preferably 110 to 130 °C.

Examples

[0136] Hereinafter, the present invention will be described by way of examples, but the present invention is not limited thereto.

[0137] (Preparation of Composition) Trimethylolpropane triglycidyl ether (TMPGDE, manufactured by Sigma - aldrich), 3,3'-dihydroxydiphenyldisulfide (DHP - SS, manufactured by Fujifilm Wako Chemicals), and ethylene glycol dimethacrylate (EGDMA, manufactured by Tokyo Chemical Industry) were mixed at 60 °C for 0.5 hours to obtain a uniform composition. The content ratio of each component in the composition was TMPGDE:EGDMA:DHP - SS = 8.0 g:4.0 g:10.0 g (26.7 mmol:20.0 mmol:40.0 mmol).

[0138] The obtained composition was poured into a mold made of poly(tetrafluoroethylene) (PTFE). Next, the composition was irradiated with ultraviolet light. The ultraviolet light irradiation was carried out using an “Optical ModuleX” light source device including a “SX-UID 502H” ultra-high pressure UV lamp (500 w) light source manufactured byUSHIO, and was irradiated at a fixed distance of 15 cm through (or without) a photomask. The irradiation time of the ultraviolet light was set to 0 to 15 minutes. Also, the ultraviolet light irradiation was carried out at 75°C. The obtained precursor was further heated at 150°C for 2 hours to be cured.

[0139] Figure 1 is a schematic diagram for explaining the procedures of pattern-like light irradiation and heating according to the above procedures. First, the above composition was poured into a mold to form a composition layer (described as “Monomers” in Figure 1). Next, ultraviolet light was irradiated from a light source (UV light source) through a photomask. Under this ultraviolet light irradiation, the methacryloyl group of EGDMA contained in the composition reacts with the disulfide group (the thiyl radical generated by the cleavage thereof) contained in DHP-SS, and a permanent (non-dynamic; permanent) bond is formed.

[0140] Figure 2 is one form of the predicted reaction product of EGDMA and DHP-SS (hereinafter sometimes referred to as “precursor”) through the disulfide-ene reaction by the above ultraviolet light irradiation, and its 1 1H-NMR spectrum. This test was carried out using a mixture obtained by putting DHP-SS (1.00 g, 4.0 mmol) and EGDMA (0.4 g, 2.0 mmol) into a 10 mL three-necked flask and adding DMSO-d6 and mixing them. The structure of the precursor obtained by irradiating this mixture with ultraviolet light (ultraviolet rays) for 0, 5, and 10 minutes respectively was 1 confirmed by 1H-NMR, and the result is shown in Figure 2. Note that 1 the 1H-NMR spectrum was acquired by JEOL-ESC400 (400 MHz) using dimethyl sulfoxide-d6 (DMSO-d6) with tetramethylsilane as an internal standard.

[0141] From the results in Figure 2, it can be seen that as the UV irradiation time increases from 0 to 10 minutes, the disulfide-ene reaction proceeds, and a new peak derived from the C-S bond appears at 2.37 ppm.

[0142] Figure 3 is a diagram showing the change in the FTIR spectrum of the composition due to the change in the UV irradiation time. The peak near 1636 cm -1 corresponds to the C=C bond of the methacryloyl group of EGDMA, and it can be seen that this decreases as the UV irradiation time (described at the right end of each spectrum) increases.

[0143] Figure 4 is a diagram showing the quantitative change in the above-mentioned residual C=C bond. The peak intensity at 1636 cm -1 decreases as the UV irradiation time increases, and after 15 minutes, it reaches a plateau region of about 4%. From this, it can be seen that the conversion rate by the disulfide-ene reaction is about 96%.

[0144] Figures 5 and 6 are diagrams showing the change in the solid 13 C-NMR spectrum due to the change in the UV irradiation time. Among them, "UV0", "UV6", and "UV15" indicate that the UV irradiation times are 0 minutes, 6 minutes, and 15 minutes, respectively. 0 minutes corresponds to the non-exposed part, 15 minutes indicates the state where most of the disulfide bonds have been used in the reaction with the C=C unsaturated bond as shown in Figure 4, and 6 minutes indicates an intermediate state. Note that "STD-SS" represents a disulfide-based polymer network without EGDMA (a cured product obtained by curing the composition excluding EGDMA). Note that the solid 13 C-NMR spectroscopy was measured using an "Oxford NMR 300 spectrometer".

[0145] Figure 22 is the solid 13 C-NMR spectrum of the cured product obtained by curing the composition excluding EGDMA, and Figure 23 is the solid 1313C-NMR spectrum. Figure 24 shows the solid state 13C-NMR spectrum of the exposed area (UV15) in the cured material. 13 It is a 13C-NMR spectrum.

[0146] When compared with the UV0 sample, new resonances appear at 177.5, 56.2, and 45.4 ppm in the UV15 sample, which are attributed to the C-S bond and the carbonyl group of the adjacent permanent bond.

[0147] According to the above results, it can be seen that the disulfide bonds decrease due to ultraviolet irradiation, and the network topology changes. The remaining disulfide bonds are presumably contributing to the plasticity of the cured material through an exchange reaction via radicals.

[0148] Figure 7 shows the results of electron spin resonance spectroscopy (ESR). The calculated g tensor value ≈ 2.05 can be regarded as evidence of typical polysulphanyl radicals R-Sn· (n ≥ 2), suggesting that thiyl radicals are involved in both polymerization networks. However, the radical intensity of the UV15 polymer is significantly lower than that of UV0 (about 14 times decrease), suggesting a low proportion of disulfide bonds in the network. Due to the decrease in disulfide bonds, the bond exchange reaction and its corresponding dynamic characteristics will be suppressed in the static topology.

[0149] The electron spin resonance (ESR) spectra were measured with an X-band JES-FA100 ESR spectrometer equipped with a cylindrical TE011 cavity. All ESR spectra were recorded at room temperature with a frequency of 9.15 GHz, a time constant of 0.03 s, a sweep width of 30 mT, and a power of 1.0 mW. The g tensor was calculated by the following formula. (Formula) hν = gβB Here, h represents the Planck constant, ν represents the frequency (MHz), β represents the Bohr magneton, and B represents the magnetic field (gauss).

[0150] Figure 8 shows the results of the depolymerization test. In this experiment, STD-SS, UV0, and UV15 were each immersed in a mixed solution of 2-mercaptoethanol / dimethylformamide. After immersion at room temperature for 72 hours, the sample of UV0 completely dissolved, while the sample of UV15 hardly dissolved. From this result, it was shown that the topology of the cured product can be programmed into different states by ultraviolet irradiation.

[0151] Returning to Figure 1, in the non-exposed part, the above-mentioned disulfide-ene reaction does not proceed. It is the same as the state at 0 min in Figure 2. After that, when thermally cured, the main frame of the cured product is formed by the reaction of hydroxy groups and glycidyl groups. This reaction occurs regardless of whether it is an exposed part or a non-exposed part.

[0152] As can also be understood from the peak intensity derived from the C-S bond according to the ultraviolet irradiation time in Figure 2, the ratio of the above-mentioned permanent bonds can be controlled by the irradiation amount of ultraviolet rays (UV-assisted topologically patterning). In Figure 1, for simplicity, the part where the disulfide-ene reaction has completely proceeded (exposed part) is shown in black, and the part where the disulfide-ene reaction has hardly proceeded (non-exposed part) is shown in gray.

[0153] As shown in Figure 1, in the non-exposed part, the disulfide bond derived from DHP-SS remains in the molecule even after heat curing. This disulfide bond is a "dynamic covalent bond" and, as will be described later, causes an exchange reaction by heating and contributes to the expression of the thermoplasticity of the cured product (Dynamic topology). On the other hand, in the exposed part, many disulfide bonds have changed to "permanent bonds" by light irradiation, and the exchange reaction of disulfide bonds by heating is less likely to occur, and softening by heating is less likely to occur (Static topoligy).

[0154] Figure 9 is a diagram schematically showing the relationship between "Dynamic topology" and "Static topology". In the figure, the horizontal axis represents temperature and the vertical axis represents plasticity. After irradiating with ultraviolet rays in a pattern, heating, and then cooling after obtaining a cured product, the plasticity of both the exposed part and the non-exposed part becomes low (Solid network). At this time, the molecular structure in the exposed part is in a state where the disulfide bond shown as a "key" shape fitting in Figure 9 remains in the molecule. On the other hand, in the exposed part, the disulfide bond is bonded to the C=C unsaturated group of the (meth)acryloyl group shown as an unfilled "convex" shape.

[0155] When this is heated to a certain extent, in the non-exposed part, an exchange reaction of the disulfide bond occurs and plasticity is expressed (Dynamic topology), in other words, the viscoelasticity changes greatly. On the other hand, in the exposed part, no exchange reaction occurs and almost no plasticity is expressed (Static topology).

[0156]

Table 2

[0157] Table 2 is a table showing the mechanical properties of UV0 and UV15. The elastic modulus at room temperature was sufficiently high for all samples, and all the cured products were robust at room temperature. The elastic modulus was measured at room temperature using a Shimadzu dynamic ultra-micro hardness tester "DUH-W201S". Also, the glass transition temperature was measured using a Shimadzu "DSC-60".

[0158] Figures 10 to 12 are diagrams showing the results of examining the change in the viscoelasticity of the cured product by isostrain stress relaxation. Figure 10 is a diagram showing the results of measurement for UV0 in the range of 110 to 150°C. Figure 11 is a diagram showing the results of measurement for UV15 in the range of 110 to 150°C. Figure 12 is a diagram showing the fitting by the Arrhenius equation for the UV0 sample. The UV0 sample showed Arrhenius-type stress relaxation (R 2 = 0.93). Note that the UV15 sample could only relax to 63% of the initial stress during the experiment.

[0159] The Arrhenius-type stress relaxation of the UV0 polymer reflects typical viscoelasticity due to rapid disulfide exchange in a dynamic topology. On the other hand, the slight relaxation of the UV15 polymer indicates that the exchange reaction is insufficient because there are few disulfide bonds in the static topology.

[0160] Figures 13 to 15 are diagrams showing the results of examining the change in the viscoelasticity of the cured product by isostress deformations. The temperature ranges are 60, 80, 100, 120, and 140°C, respectively, and the applied stress is 0.3 N.

[0161] Figures 13 and 14 show the results of UV0 and UV15. In the relatively low temperature range (≤100°C), both UV0 and UV15 showed typical elastic response deformations and maintained almost constant strain over time. However, when the temperature reaches 120°C or higher, for UV0, the strain continues even after the measurement time has elapsed while the force remains constant. For UV15, it maintains almost a constant strain value in the same temperature range. The strain rate was determined from the slope of strain vs. time.

[0162] Figure 15 is a diagram showing the unrecovered portion of the strain after the test at 140°C. For UV15, the strain has completely recovered, but for UV0, it has only recovered to about 50%.

[0163] FIG. 16 is a diagram showing the temperature dependence of strain rate. When comparing UV0 and UV15, in a relatively low temperature range (≦100° C.), no significant strain rate was observed in both the UV0 and UV15 samples, suggesting that it was a typical elastic response due to the movement of the polymer chains in the cured product.

[0164] In a relatively high temperature range (≧120° C.), it was found that the strain behaviors of the two samples were significantly different. The UV15 polymer maintained a strain rate of almost zero over the entire temperature range. On the other hand, for the UV0 polymer, the strain rate increased with increasing temperature. Specifically, it changed from 0.62% / hour at 120° C. to 2.73% / hour at 140° C. This thermoplasticity is considered to result in permanent plastic deformation. For example, the unrecovered degree of strain of the UV0 sample at 140° C. reached about 53%, while UV15 showed a recovery degree close to 100%.

[0165] FIG. 17 is a stress-strain curve obtained by changing the tensile speed at 120° C. For UV0 and UV15, significant differences were seen in the stress-strain curves. Taking a load stress of 0.06 MPa as an example, for UV0, the strain increased from 2.7% to 3.8% as the tensile speed decreased, while UV15 maintained a strain of almost constant 0.95% regardless of the tensile speed. This discrepancy is mainly considered to be due to the thermoplasticity effect. In a dynamic network topology, changing the tensile speed results in time-dependent plastic deformation leading to cumulative elongation, while in a static topology, there is no thermoplasticity, so the time-dependent deformation effect is limited.

[0166] FIG. 18 is a diagram showing the change in strain with respect to the periodic change in stress. The stress was periodically changed at 0 N and 0.3 N (vertical second axis). Also, during that time, the temperature was changed between 60° C. and 120° C. At 60° C., both UV0 and UV15 behaved like a standard elastic response without causing continuous plastic deformation while the force was applied.

[0167] On the one hand, when heated to 120 °C, in the UV0 sample, continuous elongation depending on time was observed in response to an external force, suggesting that the thermoplasticity of the crosslinked network was activated. However, the UV15 sample maintained almost constant strain even during stress loading. Subsequently, upon cooling, both samples returned to an elastic behavior again. Only slight differences were observed in the comparison between cycles, suggesting that there was no significant deterioration or repetition in the repeated performance of both.

[0168] Figure 19 shows one form of the three-dimensional structure formed using the above composition. First, the sheet-like composition was irradiated with light using the photomask shown in the figure so that the hinge (crease) part became the non-exposed part. Next, the whole was heated to obtain a cured product. Then, the whole of the cured product was heated (with a maximum temperature of 127 °C) to soften the non-exposed part to form a crease, assembled into a cube shape like origami, and then cooled to room temperature. As a result, the whole of the cured product was cured again, and a robust three-dimensional structure was obtained.

[0169] Figure 20 shows the experimental results of creating the three-dimensional structure. Figure 20(a) is a development view for creating a tent-shaped three-dimensional structure from a triangular sheet. In the figure, what is marked as Valley and Mountain are the parts that become the "creases" of the valley and the mountain, respectively, and the other parts are flat parts. Among these, the parts corresponding to the "creases" are non-exposed parts, and the parts corresponding to the flat surfaces are the exposed parts.

[0170] The sheet-like composition is irradiated with ultraviolet light through a photomask that shields the creases and heated to obtain a cured product. When this cured product is heated to about 120 °C, it can be folded into a tent shape.

[0171] Figure 20(b) shows the definition of the area of each part in a plan view for quantitatively analyzing the shape change. First, the area of the triangular sheet before folding is defined as A0 = 100%, and the area after deformation by the compressive stress from the three directions described as arrows is A deploy is defined, and the expansion ratio Adep is defined as A deploy / A0.

[0172] Figure 20(c) shows the strain distribution during folding in the cured product calculated by finite element analysis simulation. From the calculation results, it was found that the strain was concentrated at the "crease" part, and almost no strain occurred in the flat part. The above shows that the cured product can be deformed like "origami".

[0173] Figure 20(d) is a diagram showing variations in molding and shape fixation by heating and cooling. First, it was heated to a maximum temperature of 131°C to soften the non-exposed part, then the expansion ratio was set to 65.7%, and this was cooled (to a maximum temperature of 32°C) to fix the shape. Next, it was heated again (to a maximum temperature of 135°C) to soften the non-exposed part again, and the expansion ratio was set to 31.4%, and this was cooled (to a maximum temperature of 35°C) to fix the shape. Furthermore, it was heated again (to a maximum temperature of 131°C) to soften the non-exposed part again, and the expansion ratio was set to 11.4%, and this was cooled (to a maximum temperature of 27°C) to fix the shape.

[0174] From the above, it was shown that softening of the non-exposed part by heating and shape fixation by cooling can be repeated at an arbitrary expansion ratio.

[0175] Figure 21 shows an example of creating a more complex three-dimensional structure without using mold molding in the same way as in Figure 20. Figure 21(a) is a development view of the cured product for assembling the Miura-fold structure. The sheet-like composition was irradiated with ultraviolet light through a photomask that blocked the "creases" marked as Valley and Mountain, and then heated to obtain a cured product.

[0176] Figure 21(b) shows the definition of the dihedral angle (θ d ) for quantitatively evaluating the shape of the Miura fold. Figure 21(c) shows the dihedral angle (θ d) It is a plot of the theoretical volume change accompanying the change. The theoretical volume is calculated from the basic geometric parameters in the tessellation of a plurality of units and is normalized by the maximum volume.

[0177] Figure 21(d) is a diagram showing the process of forming a Miura-fold structure from a sheet-like cured product. The forming starts from θ d = 23° and is folded in the order of θ d = 42°, 74°, 86°. At this time, the theoretical volume changes by 40% or more. This deformation can be repeated, and the shape is fixed when cooled. Figure 20(e) is an image of the state where a 100 g weight is placed on the three-dimensional structure with the shape fixed.

[0178] Figure 20(f) is a developed view of the cured product for assembling a cylindrical origami structure. Ultraviolet rays were irradiated on the sheet-like composition through a photomask that shields the "crease lines" marked as Valley and Mountain, and then heated to obtain a cured product.

[0179] Figure 20(i) is a perspective view and a plan view of a cylindrical origami. This three-dimensional structure is a pentagon in plan view having a desired height (h0). When an external force is applied to this three-dimensional structure from the arrow direction (height direction), it can be twisted and rotated to change the shape.

[0180] Figure 20(h) is a diagram showing the relationship between the change in the theoretical height (h / h0) and the rotation angle (θ R ). Figure 20(i) is a diagram showing the repeated state of shape change and fixation by heating and compression. Starting from the desired height of 28.5 mm, the non-exposed part was softened by heating, compressed to a height of 18.5 mm, and the shape was fixed. Next, this was heated again, the non-exposed part was softened and compressed to a height of 9.9 mm. The shape was fixed. A maximum compression height of 35% was obtained, and it was also possible to return to the original shape. Figure 20(i) is an image of the state where a 100 g weight is placed on the cylindrical origami with the shape fixed.

[0181] As described above, in the cured product obtained by irradiating the composition of the present invention with light in a pattern and heating it to cure, its mechanical properties change according to the light irradiation pattern. In the exposed portion, it does not soften upon heating and behaves like a thermosetting resin, while in the non-exposed portion, it softens upon heating and behaves like a thermoplastic resin. This property can also be continuously changed within the cured product by adjusting the exposure amount. The cured product produced in this way can be used to assemble a three-dimensional structure like origami with the non-exposed portion as a hinge. Conventionally, the production of a three-dimensional structure that required a mold can be carried out more easily without the need for a mold.

Claims

1. A method for producing a cured product by curing a composition, comprising: monomer A having a disulfide bond as a dynamic covalent bond in the molecule; monomer B having at least two ethylenically unsaturated groups in the molecule; irradiating the composition containing a curing agent with light in a pattern, and heating the composition; wherein the monomer A and the curing agent each have at least two of one of a pair of curable groups capable of reacting with each other in their respective molecules; the pair of curable groups are as follows (a) to (d): (a) a glycidyl group and at least one group selected from the group consisting of a hydroxy group, a carboxy group, and an acid anhydride group for the glycidyl group; (b) a hydroxy group and at least one group selected from the group consisting of a carboxy group and an acid anhydride group for the hydroxy group; (c) an isocyanate group and a hydroxy group for the isocyanate group; (d) a phenol group or a furyl group and a formyl group for the phenol group or the furyl group; A method for producing a cured product, selected from the group consisting of.

2. The method for producing a cured product according to claim 1, wherein the pair of curable groups is a glycidyl group and at least one group selected from the group consisting of a hydroxy group, a carboxy group, and an acid anhydride group for the glycidyl group.

3. The method for producing a cured product according to claim 1 or 2, including the step of irradiating the light before the heating.

4. A composition comprising monomer A having a disulfide bond as a dynamic covalent bond in the molecule, monomer B having at least two ethylenically unsaturated groups in the molecule, and a curing agent, wherein the monomer A and the curing agent each have at least two of one of a pair of curable groups capable of reacting with each other in their respective molecules; the pair of curable groups are as follows (a) to (d): (a) a glycidyl group and at least one group selected from the group consisting of a hydroxy group, a carboxy group, and an acid anhydride group for the glycidyl group; (b) a hydroxy group and at least one group selected from the group consisting of a carboxy group and an acid anhydride group for the hydroxy group; (c) an isocyanate group and a hydroxy group for the isocyanate group; (d) a phenol group or a furyl group and a formyl group for the phenol group or the furyl group; selected from the group consisting of.

5. The composition according to claim 4, wherein the pair of curable groups is at least one group selected from the group consisting of a glycidyl group and at least one group selected from the group consisting of a hydroxy group, a carboxy group, and an acid anhydride group relative thereto.

6. The composition according to claim 4 or 5, which is for forming a sheet for assembling a three-dimensional structure by folding.

7. A monomer A having a disulfide bond as a dynamic covalent bond in the molecule, A monomer B having at least two or more ethylenically unsaturated groups in the molecule, A curing agent, and the monomer A and the curing agent each have at least two or more of one of a pair of curable groups capable of reacting with each other in their respective molecules, The pair of curable groups is the following (a) to (d): (a) A glycidyl group and at least one group selected from the group consisting of a hydroxy group, a carboxy group, and an acid anhydride group relative thereto, (b) A hydroxy group and at least one group selected from the group consisting of a carboxy group and an acid anhydride group relative thereto, (c) An isocyanate group and a hydroxy group relative thereto, (d) A phenol group or a furyl group and a formyl group relative thereto, A cured product obtained by curing the composition selected from the group consisting of.

8. The cured product according to claim 7, wherein the pair of curable groups is at least one group selected from the group consisting of a glycidyl group and at least one group selected from the group consisting of a hydroxy group, a carboxy group, and an acid anhydride group relative thereto.

9. A three-dimensional structure assembled with the cured product according to claim 7 or 8.

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