Curable Composition, Cured Product Obtained Using the Same, and Method for Producing Cured Product

Abstract

The present invention provides a curable composition having excellent storage stability and excellent reactivity after storage, a cured product obtained by using the same, and a method for producing the cured product. A curable composition contains 0.1 part by mass to 10.0 parts by mass of a compound (A) having a structure represented by the following general formula (I) and 0.01 part by mass to 10.0 parts by mass of a base (B) with respect to 100 parts by mass of a curable compound. (In the general formula (I), X represents a chalcogen atom, and R 1 and R 2 each independently represents any one of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group. R 3 and R 4 each independently represents a hydrogen atom, any one of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group.)#imgabs0#

Description

Technical Field

[0001] The present invention relates to a curable composition containing a specific compound having an unsaturated double bond, a cured product obtained by using the same, and a method for producing the cured product. Background Art

[0002] Free-radical polymerizable monomers such as (meth)acrylates for coating agents, paints, and three-dimensional shaping materials can be polymerized and cured by generating free radicals from a polymerization initiator by heating, irradiation with active energy rays, etc. When these free-radical polymerizable monomers are used for coating applications, etc., since curing is usually carried out in an air atmosphere, there are problems such as the polymerization reaction being easily hindered by oxygen in the air, the curing being slowed down, or the surface of the cured product being sticky.

[0003] As a method for solving these problems, techniques for adding an oxygen absorber to a resin have been proposed in Patent Documents 1 and 2. In addition, techniques for using allyl glycidyl ether, etc. as the oxygen absorber are described in Patent Documents 3 and 4. Furthermore, Patent Document 5 proposes a curable composition containing a polymer, a polyfunctional monomer, and a free-radical polymerizable resin, the polymer containing a structural unit derived from a specific compound having an unsaturated double bond that exhibits oxygen absorption performance.

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: Japanese Patent Laid-Open No. 63-130610

[0007] Patent Document 2: Japanese Patent Laid-Open No. 5-78459

[0008] Patent Document 3: Japanese Patent Laid-Open No. 61-101518

[0009] Patent Document 4: US Patent No. 3644568 Specification

[0010] Patent Document 5: International Publication No. 2019 / 208259 Summary of the Invention

[0011] Problems to be Solved by the Invention

[0012] When using a compound having an unsaturated double bond that exhibits oxygen absorption performance as described in Patent Document 5, although the oxygen concentration in the composition can be reduced and the reactivity can be improved, on the other hand, there is a problem of reduced storage stability.

[0013] Accordingly, an object of the present invention is to provide a curable composition having excellent storage stability and excellent reactivity after storage, a cured product obtained using the same, and a method for producing the cured product.

[0014] Means for Solving the Problems

[0015] The present inventors conducted intensive studies to achieve the above object, and as a result, found that by using a compound having a specific structure containing an unsaturated double bond and a base in a specific blending amount in combination, a curable composition having improved storage stability and excellent reactivity even after storage for a certain period of time can be obtained, thereby completing the present invention.

[0016] That is, the present invention provides the following [1] to [9].

[0017] [1] A curable composition containing 0.1 to 10.0 parts by mass of a compound (A) having a structure represented by the following general formula (I) and 0.01 to 10.0 parts by mass of a base (B) with respect to 100 parts by mass of a curable compound,

[0018] [Chemical Formula 1]

[0019]

[0020] (In the general formula (I), X represents a chalcogen atom, and R 1 and R 2 each independently represent any one of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group, and R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group.)

[0021] [2] The curable composition according to [1] above, wherein R 1 and R 2 in the general formula (I) each independently are an alkyl group having 1 to 4 carbon atoms.

[0022] [3] The curable composition according to [1] or [2] above, wherein X in the general formula (I) is an oxygen atom.

[0023] [4] The curable composition according to [1] above, wherein the compound (A) having a structure represented by the general formula (I) is a compound represented by the following general formula (II).

[0024] [Chemical Formula 2]

[0025]

[0026] (In general formula (II), R 5 and R 6 are each independently and represent any one of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group. R 7 and R 8 are each independently and represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group. R 9 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group. R 10 represents a hydrogen atom, a (meth)acryloyl group, a 4-vinylphenyl group, and an alkenyl group having 2 to 6 carbon atoms. n is an arbitrary integer.)

[0027] [5] According to the curable composition described in [1] above, the compound (A) containing the structure represented by the general formula (I) is a compound represented by the following general formula (III).

[0028] [Chemical formula 3]

[0029]

[0030] (In general formula (III), R 11 , R 12 , R 17 and R 18 are each independently and represent any one of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group. R 13 and R 14 are each independently and represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group. R 15 represents a hydrogen atom or a methyl group. R 16 represents any one of a hydroxyl group, a (meth)acryloyloxy group, a 4-vinylphenoxy group, and an alkenyloxy group having 2 to 6 carbon atoms.)

[0031] [6] According to the curable composition described in any one of [1] to [5] above, the base (B) is one or more selected from sodium hydroxide, sodium methoxide, triethylamine, and trioctylamine.

[0032] [7] A cured product obtained by curing the curable composition described in any one of [1] to [6] above.

[0033] [8] A method for producing a cured product, which cures the curable composition described in any one of [1] to [6] above.

[0034] [9]According to the method for producing a cured product described in [8], it has the following steps: a step of neutralizing the base (B) contained in the curable composition to obtain a neutralized product; and a step of curing the neutralized product.

[0035] Advantages of the Invention

[0036] According to the present invention, it is possible to provide a curable composition having excellent storage stability and excellent reactivity after storage, a cured product obtained by using the same, and a method for producing a cured product. Detailed Description of Embodiments

[0037] [Curable Composition]

[0038] The curable composition of the present invention contains 0.1 to 10.0 parts by mass of a compound (A) having a structure represented by the following general formula (I) and 0.01 to 10.0 parts by mass of a base (B) with respect to 100 parts by mass of a curable compound.

[0039] [Chemical Formula 4]

[0040]

[0041] (In the general formula (I), X represents a chalcogen atom, and R 1 and R 2 are each independently any of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group, and R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, or an aralkyl group.)

[0042] In the curable composition of the present invention, since a specific compound having an unsaturated double bond is used in combination with a base, the storage stability of the curable composition is improved, and excellent reactivity is exhibited even after storage for a certain period of time. The reason is considered as follows.

[0043] In a curable composition containing a radical polymerizable monomer such as (meth)acrylate, oxygen contained in the composition becomes a factor hindering radical polymerization, and thus it is difficult to obtain a desired cured product. In contrast, if a compound having a structure represented by the general formula (I) (for example, a compound in which X is an oxygen atom) is blended in a curable compound, a part derived from the allyl ether skeleton captures oxygen by a reaction with a radical, and thus the polymerization reaction proceeds easily and a desired cured product is easily obtained. On the other hand, there is a problem that since the oxygen concentration in the composition decreases, the radical polymerization reaction proceeds during storage, and thus the storage stability decreases.

[0044] In view of this, when a compound having the structure represented by the general formula (I) is used in combination with a base, since the base removes the hydrogen at the allyl position, the ionic reaction preferentially proceeds, and the oxygen capture reaction by radicals is less likely to occur. As a result, it is considered that the oxygen absorption performance of the compound represented by the general formula (I) is reduced, and the oxygen concentration in the curable composition is not easily reduced, so the storage stability is improved.

[0045] On the other hand, it is speculated that: when the curable composition is cured, by neutralizing the base, the dehydrogenation reaction at the allyl position is inhibited, and the oxygen absorption of the compound having the structure represented by the general formula (I) is improved. As a result, the oxygen concentration in the curable composition is reduced, and thus the reactivity is improved.

[0046] <Curable compound>

[0047] The curable composition of the present invention contains a curable compound. The curable compound is not particularly limited as long as it is a monomer capable of copolymerizing with the compound (A) described later. Specifically, at least one selected from monofunctional monomers (M1) and polyfunctional monomers (M2) can be used. Among these, the monofunctional monomer (M1) which is likely to obtain the effects of the present invention is preferred.

[0048] As the monofunctional monomer (M1), a monomer having one reactive double bond can be preferably used. Specifically, for example, vinyl monomers such as styrene, 2-methylstyrene, vinyl acetate, and vinyl chloride can be mentioned; (meth)acrylic acid alkyl esters such as (meth)acrylic acid methyl ester, (meth)acrylic acid propyl ester, (meth)acrylic acid butyl ester, (meth)acrylic acid pentyl ester, and (meth)acrylic acid hexyl ester; (meth)acrylic acid esters having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and caprolactone-modified 2-hydroxyethyl (meth)acrylate; (meth)acrylic acid esters having an alkylene glycol structure such as methoxydiethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, isooctoxydiethylene glycol (meth)acrylate, phenoxytriethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, and methoxypolyethylene glycol (meth)acrylate; silane or silyl-terminated (meth)acrylic acid esters such as 2-trimethylsilyloxyethyl (meth)acrylate; (meth)acrylic acid esters having an epoxy group at the end such as glycidyl (meth)acrylate and 3,4-epoxycyclohexylmethyl (meth)acrylate; unsaturated dicarboxylic acids such as maleic anhydride or its derivatives. The monofunctional monomer (M1) can be used alone or in combination of two or more.

[0049] It should be noted that in the present invention, “(meth)acrylate” means acrylate or methacrylate, and other similar expressions have the same meaning.

[0050] As the monofunctional monomer (M1), from the viewpoint of more significantly obtaining the effects of the present invention, (meth)acrylic acid alkyl esters are preferred, and methyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, and hexyl (meth)acrylate are more preferred, and methyl (meth)acrylate is further preferred.

[0051] The type of the polyfunctional monomer (M2) is not particularly limited, and a compound having two or more polymerizable groups in the molecule can be preferably used. As such a polymerizable group, for example, a radical polymerizable group such as a (meth)acryloyl group or a vinyl group can be mentioned. The polyfunctional monomer is preferably a compound having two or more radical polymerizable groups in the molecule. As the polyfunctional monomer (M2), for example, a poly(meth)acrylate having two or more (meth)acryloxy groups in the molecule can be mentioned. It should be noted that the poly(meth)acrylate may be a poly(meth)acrylate containing a hydroxyl group. In the curable composition of the present invention, the polyfunctional monomer may contain only one type or may contain two or more types.

[0052] As the poly(meth)acrylate, (meth)acrylates of polyhydric alcohols such as diols and triols can be used. More specifically, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate (Japanese: 1,6-hexamethylene di(meth)acrylate), neopentyl glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, glycerol di(meth)acrylate, di(meth)acrylate of hydrogenated bisphenol A or hydrogenated bisphenol F, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate, etc. can be mentioned.

[0053] In addition, as the poly(meth)acrylate containing a hydroxyl group, for example, glycerol di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol monohydroxy penta(meth)acrylate, etc. can be mentioned.

[0054] Among these polyfunctional monomers, from the viewpoint of water resistance of the obtained cured product, poly(meth)acrylate is preferred, and 1,6 - hexanediol di(meth)acrylate, 1,9 - nonanediol di(meth)acrylate, and pentaerythritol tri(meth)acrylate are more preferred.

[0055] The content of the curable compound in the curable composition of the present invention is preferably 70.0 to 99.0% by mass, more preferably 80.0 to 99.0% by mass, and still more preferably 90.0 to 99.0% by mass. When the content of the curable compound is at least the lower limit value, the strength of the cured product obtained by curing the curable compound is improved. In addition, when the content of the curable compound in the curable compound is at most the upper limit value, the contents of the compound (A) and the base (B) described later become relatively large, and thus the storage stability of the curable compound is improved.

[0056] <Compound (A) containing the structure represented by the general formula (I)>

[0057] In the general formula (I), X represents a chalcogen atom, and from the viewpoint of improving the storage stability of the curable composition, it is preferably an oxygen atom or a sulfur atom, and more preferably an oxygen atom.

[0058] In the general formula (I), R 1 and R 2 are each independently any of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group.

[0059] Examples of the alkyl group having 1 to 6 carbon atoms represented by R 1 and R 2 include methyl, ethyl, n - propyl, isopropyl, n - butyl, isobutyl, sec - butyl, tert - butyl, n - pentyl, isopentyl, neopentyl, n - hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.

[0060] Examples of the alkenyl group having 2 to 6 carbon atoms represented by R 1 and R 2 include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, isoprenyl, hexenyl (cis - 3 - hexenyl, etc.), cyclohexenyl, etc.

[0061] Examples of the aryl group represented by R 1 and R 2 are preferably an aryl group having 6 to

[0062] Examples of the aralkyl group represented by R 1 and R 2The aralkyl group represented is preferably an aralkyl group having 7 to 20 carbon atoms, and examples thereof include benzyl, 2-phenylethyl, 2-naphthylethyl, diphenylmethyl, and the like.

[0063] Among these, from the viewpoints of improving the storage stability of the curable composition and improving the reactivity after storage, R 1 and R 2 are each independently and preferably any one of an alkyl group having 1 to 6 carbon atoms and an alkenyl group having 2 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably a methyl group.

[0064] In the general formula (I), R 3 and R 4 are each independently and represent any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group. Examples of the alkyl group having 1 to 6 carbon atoms, the alkenyl group having 2 to 6 carbon atoms, the aryl group, and the aralkyl group represented by R 3 and R 4 are the same as those described above for R 1 and R 2 , and repeated descriptions are omitted here.

[0065] Among these, R 3 and R 4 are each independently and preferably any one of a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 or 3 carbon atoms, and an aryl group, more preferably any one of a hydrogen atom and a methyl group, and still more preferably a hydrogen atom. Among them, from the viewpoints of improving the oxygen absorption performance of the obtained polymer, etc., it is preferred that R 3 and R 4 are both hydrogen atoms.

[0066] As the compound (A) containing the structure represented by the general formula (I), from the viewpoints of improving the storage stability of the curable composition and improving the reactivity after storage for a certain period of time, etc., a compound represented by the following general formula (II) or the following general formula (III) is preferred, and a compound represented by the following general formula (II-a) or the following general formula (III) is more preferred.

[0067] [Chemical formula 5]

[0068]

[0069] (In the general formula (II), R 5 and R 6 are each independently and represent any one of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group. R 7 and R 8Each is independent and represents any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group. R 9 represents any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group. R 10 represents any one of a hydrogen atom, a (meth)acryloyl group, a 4-vinylphenyl group, and an alkenyl group having 2 to 6 carbon atoms. n is an arbitrary integer.)

[0070] [Chemical Formula 6]

[0071]

[0072] (In this case, the polystyrene-reduced weight-average molecular weight (Mw) of the compound represented by the general formula (II-a) is 200 to 50,000.)

[0073] [Chemical Formula 7]

[0074]

[0075] (In the general formula (III), R 11 , R 12 , R 17 and R 18 are each independent and represent any one of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group. R 13 and R 14 are each independent and represent any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group. R 15 represents a hydrogen atom or a methyl group, and R 16 represents any one of a hydroxyl group, a (meth)acryloyloxy group, a 4-vinylphenoxy group, and an alkenyloxy group having 2 to 6 carbon atoms.)

[0076] In the general formula (II), R 5 , R 6 , R 7 and R 8 are respectively the same as the descriptions of R 1 , R 2 , R 3 and R 4 in the general formula (I), and the repeated description is omitted here.)

[0077] In the general formula (II), R 9 represents any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group, preferably an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms, and more preferably a methyl group or an isoprenyl group.)

[0078] In general formula (II), R 10 represents any one of a hydrogen atom, a (meth)acryloyl group, a 4-vinylphenyl group, and an alkenyl group having 2 to 6 carbon atoms, and is preferably a hydrogen atom or a (meth)acryloyl group.

[0079] In general formula (III), R 11 , R 12 , R 13 and R 14 are respectively the same as the descriptions of R 1 , R 2 , R 3 and R 4 in the general formula (I), and the repeated description is omitted here.

[0080] In general formula (III), R 15 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom. R 16 represents any one of a hydroxyl group, a (meth)acryloyloxy group, a 4-vinylphenoxy group, and an alkenyloxy group having 2 to 6 carbon atoms, and is preferably a hydroxyl group or a (meth)acryloyloxy group. It should be noted that the alkenyloxy group having 2 to 6 carbon atoms may be a vinyloxy group having 2 to 6 carbon atoms.

[0081] In general formula (III), R 17 and R 18 are each independent and represent any one of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group, and the exemplified or preferred groups thereof are the same as those described for R 1 and R 2 in the general formula (I).

[0082] Among these, R 17 and R 18 are each independent and are preferably any one of an alkyl group having 1 to 6 carbon atoms and an alkenyl group having 2 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably a methyl group.

[0083] The method for producing the compound having the structure represented by the general formula (I), the compounds represented by the general formula (II) and the general formula (II-a), and the compound represented by the general formula (III) is not particularly limited, and can be produced by applying known methods alone or in combination.

[0084] The curable composition of the present invention contains 0.1 to 10.0 parts by mass of the compound (A) having the structure represented by the general formula (I) with respect to 100 parts by mass of the curable compound. If the content of the compound (A) is less than 0.1 part by mass, the reactivity of the curable composition after being stored for a certain period of time decreases. On the other hand, if the content of the compound (A) exceeds 10.0 parts by mass, the amount of the curable compound relatively decreases, so that a desired cured product cannot be obtained. In addition, the balance between the manufacturing cost and the obtained effect deteriorates. From this viewpoint, the content of the compound (A) is preferably 0.3 to 5.0 parts by mass, more preferably 0.5 to 3.0 parts by mass, and still more preferably 0.7 to 2.5 parts by mass.

[0085] <Alkali (B)>

[0086] The curable composition of the present invention contains 0.01 to 10.0 parts by mass of an alkali (B) with respect to 100 parts by mass of the curable compound. In the present invention, the hydrogen at the allyl position of the compound (A) is removed by the alkali (B), so that the ionic reaction preferentially proceeds and the oxygen capture reaction by radicals is not likely to proceed. As a result, the oxygen concentration in the curable composition remains constant, and the storage stability of the curable composition is improved. It should be noted that when the curable composition is cured, the oxygen capture reaction becomes easy to proceed by neutralizing the alkali, so that the oxygen concentration in the curable composition decreases and the reactivity increases.

[0087] The alkali (B) that can be used in the curable composition of the present invention is not particularly limited, and examples thereof include inorganic bases and organic amines such as sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium methoxide, potassium tert-butoxide, triethylamine, tributylamine, trioctylamine, DBN (1,5-diazabicyclo[4,3,0]non-5-ene), DBU (1,8-diazabicyclo[5,4,0]undec-7-ene), methyldiethanolamine, and triethanolamine.

[0088] Among these, as the alkali (B), from the viewpoint of improving the storage stability of the curable composition, one or more selected from sodium hydroxide, sodium methoxide, triethylamine, and trioctylamine are preferred.

[0089] The curable composition of the present invention contains 0.01 to 10.0 parts by mass of the base (B) relative to 100 parts by mass of the curable compound described below. If the content of the base (B) is less than 0.01 part by mass, the dehydrogenation reaction at the allyl position of the compound (A) cannot proceed sufficiently, and thus the storage stability of the curable composition decreases. On the other hand, if the content of the base (B) exceeds 10.0 parts by mass, the balance between the manufacturing cost and the obtained effect deteriorates. From this viewpoint, the content of the base (B) is preferably 0.05 to 3.0 parts by mass, more preferably 0.07 to 1.0 part by mass.

[0090] <Polymerization initiator>

[0091] From the viewpoint of further improving curability and the like, the curable composition of the present invention may further contain a polymerization initiator. The type of this polymerization initiator is not particularly limited, and it can be appropriately selected according to the type of the curable compound used and the like. Specifically, a radical polymerization initiator is preferred. As the radical polymerization initiator, for example, there can be mentioned: thermal radical polymerization initiators that generate radicals by heat, photo radical polymerization initiators that generate radicals by light, and the like.

[0092] As the thermal radical polymerization initiator, for example, there can be mentioned: diacyl peroxide systems such as benzoyl peroxide; peroxide ester systems such as tert-butyl perbenzoate; hydroperoxide systems such as cumene hydroperoxide; dialkyl peroxide systems such as dicumyl peroxide; ketone peroxide systems such as methyl ethyl ketone peroxide and acetylacetone peroxide; perketal systems; alkyl perester systems; percarbonate systems and other organic peroxides.

[0093] As the photo radical polymerization initiator, commercially available products can be used. For example, there can be mentioned: Irgacure (registered trademark, the same below) 651, Irgacure 184, Irgacure 2959, Irgacure 127, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 819, Irgacure 784, Irgacure OXE01, Irgacure OXE02, Irgacure754 (the above, manufactured by BASF Corporation), etc. These initiators can be used alone or in combination of two or more.

[0094] The content of the polymerization initiator in the curable composition of the present invention is not particularly limited. From the aspect of more significantly exerting the effects of the present invention, etc., it is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, further preferably 0.1 part by mass or more, and preferably 10.0 parts by mass or less, more preferably 5.0 parts by mass or less, relative to 100 parts by mass of the curable compound.

[0095] <Other Components>

[0096] The curable composition of the present invention may further contain other components other than the above components, such as diluents, pigments, dyes, fillers, ultraviolet absorbers, thickeners, low shrinkage agents, anti-aging agents, plasticizers, aggregates, flame retardants, stabilizers, fiber reinforcing materials, antioxidants, leveling agents, anti-sagging agents, etc.

[0097] <Method for Producing Curable Composition>

[0098] The method for producing the curable composition of the present invention is not particularly limited. For example, it can be obtained by mixing the curable compound, the compound (A), the base (B), the polymerization initiator as required, and other components by a known method.

[0099] [Method for Producing Curable Product]

[0100] The method for producing the curable product of the present invention is a method for curing the curable composition. Specifically, it is a production method having the following steps: a step of neutralizing the base (B) contained in the curable composition of the present invention to obtain a neutralized product; and a step of curing the neutralized product.

[0101] <Step of Obtaining Neutralized Product>

[0102] The step of obtaining the neutralized product in the production method of the present invention is a step of neutralizing the base (B) contained in the curable composition of the present invention. As long as the base can be neutralized, there is no particular limitation. It is preferable to add an acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, formic acid, propionic acid, oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, citric acid, etc. to the curable composition for neutralization. In particular, hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, which are strong acids, are more preferable.

[0103] <Step of Curing Neutralized Product>

[0104] In the step of curing the neutralized product in the present invention, as long as the neutralized product can be cured, the method is not particularly limited and can be appropriately selected according to the curable composition, the type of polymerization initiator, etc. For example, when the curable composition of the present invention contains a thermal free radical polymerization initiator, a method of curing by heating can be cited, and when it contains a photo free radical polymerization initiator, a method of curing by irradiating active energy such as UV can be cited.

[0105] In addition, when both are contained, heating can be performed after irradiating active energy rays. Although it also depends on uses, etc., from the aspect of more significantly exerting the effects of the present invention, etc., a method of curing by irradiating active energy is preferred.

[0106] [Cured product]

[0107] The cured product of the present invention is obtained by curing the curable composition of the present invention. As described above, the storage stability of the curable composition of the present invention is excellent, and excellent reactivity is exhibited even after storage for a certain period of time. Therefore, a cured product with excellent appearance can be formed. The physical properties and appearance of the cured product of the present invention are excellent, and thus it is suitable for use as, for example, a coating film, an adhesive layer, a coating layer, etc.

[0108] Examples

[0109] Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to these examples.

[0110] The evaluation methods used in the synthesis examples and examples are described below.

[0111] ·Quantification of the curable compound (MMA) based on GC / FID was carried out under the following conditions.

[0112] Apparatus: GC-2014 manufactured by Shimadzu Corporation,

[0113] Column: DB-1 (manufactured by Agilent J&W Corporation)

[0114] Inlet temperature: 280 °C

[0115] Detector temperature: 320 °C

[0116] Oven: 50 °C (2 minutes) → 20 °C / minute → 300 °C (15 minutes)

[0117] Split ratio: The measurement was carried out under the condition of 1:50.

[0118] ·Quantification of the curable compound (PETA) based on HPLC / UV was carried out under the following conditions.

[0119] Column: L-Column2 ODS

[0120] Eluent: Solution A = water (10 mM ammonium acetate)

[0121] Solution B = methanol (10 mM ammonium acetate)

[0122] Gradient: Solution B = 50% (5 minutes) → (30 minutes) → 100% (15 minutes)

[0123] Column temperature: 40 °C, Detection wavelength: 215 nm

[0124] The compounds used in the examples and comparative examples are as follows.

[0125] <Curable compound>

[0126] MMA: Methyl methacrylate

[0127] PETA: Pentaerythritol triacrylate

[0128] <Compound (A)>

[0129] [Production Example 1] (Production of 1,3-bis(3-methyl-2-butenyloxy)-2-hydroxypropane (A-1))

[0130] In a reactor equipped with a stirrer, a thermometer, and a dropping funnel, 61.8 g (0.717 mol) of 3-methyl-2-buten-1-ol and 36.84 g (0.657 mol) of potassium hydroxide were introduced under a nitrogen stream. While maintaining the internal temperature at 10 °C or lower, 19.34 g (0.209 mol) of epichlorohydrin was added dropwise with stirring, and after the addition was completed, the temperature was raised to 50 °C. The mixture was stirred at 50 °C for 6 hours and then cooled to 25 °C. The reaction solution was neutralized with a 4M hydrochloric acid aqueous solution, and the upper layer was washed with 310 mL of ion-exchanged water. The obtained organic layer was purified by distillation to obtain 28.77 g (0.126 mol; yield 60.3%) of 1,3-bis(3-methyl-2-butenyloxy)-2-hydroxypropane represented by the following formula (A-1).

[0131] [Chemical Formula 8]

[0132]

[0133] [Reference Example 1]

[0134] Synthesis of 1-(3-methyl-2-butenyloxy)-2,3-epoxypropane

[0135] In a reactor equipped with a stirrer, a thermometer, and a dropping funnel, under a nitrogen stream, 324 g (manufactured by Kuraray Co., Ltd., 3.77 mol) of 3-methyl-2-buten-1-ol, 2300 mL of cyclohexane, 226 g (manufactured by Fujifilm Wako Pure Chemical Corporation, 5.65 mol) of sodium hydroxide, 15.2 g (manufactured by Tokyo Chemical Industry Co., Ltd., 37.3 mmol) of trioctylmethylammonium chloride, and 226 mL of purified water were charged. While maintaining the internal temperature at 25°C or below, 698 g (manufactured by Fujifilm Wako Pure Chemical Corporation, 7.54 mol) of epichlorohydrin was added dropwise over 90 minutes with stirring. After the addition was completed, the temperature was raised to 40°C over 30 minutes. The mixture was stirred at an internal temperature of 40°C for 3 hours and then cooled to 25°C. The upper layer of the reaction solution was washed 5 times with 670 mL of saturated brine, and the organic layer was dried over sodium sulfate. The sodium sulfate was filtered off, and the filtrate was concentrated to obtain 536 g of a concentrate. The concentrate was purified by distillation to obtain 242 g (1.67 mol; yield 44%) of 1-(3-methyl-2-butenyloxy)-2,3-epoxypropane represented by the following formula.

[0136] [Chemical Formula 9]

[0137]

[0138] [Production Example 2]

[0139] Synthesis of α-methoxy-ω-hydroxy poly[oxy(3-methyl-2-butenyloxymethylethane-1,2-diyl)] (A-2)

[0140] In a reactor equipped with a stirrer, a thermometer, and a dropping funnel, under a nitrogen stream, 20 g (0.14 mol) of 1-(3-methyl-2-butenyloxy)-2,3-epoxypropane and 76 mg (manufactured by Fujifilm Wako Pure Chemical Corporation, 1.4 mmol) of sodium methoxide were charged. The internal temperature was raised to 110°C and stirred for 9 hours, and then cooled to 25°C. After adding 1 mL of acetic acid to the reaction solution, low-boiling components were removed by evaporation to obtain 18.8 g (yield 94%) of α-methoxy-ω-hydroxy poly[oxy(3-methyl-2-butenyloxymethylethane-1,2-diyl)] represented by the following formula (A-2). By GPC measurement, the number-average molecular weight of the obtained compound was 4800, and the weight-average molecular weight was 7600 (in terms of polystyrene).

[0141] [Chemical Formula 10]

[0142]

[0143] <Comparative Compound>

[0144] MDEA: Methyldiethanolamine

[0145] <Polymerization Initiator>

[0146] Photopolymerization initiator: Irgacure 184 (manufactured by BASF Corporation)

[0147] <Examples 1 to 9, Comparative Examples 1 and 2>

[0148] Prepare a curable composition according to the formulation described in Table 1. After preparation, allow it to stand at 80 °C for 7 hours. For the curable composition after standing, measure the residual amount of the curable compound, and consider that the storage stability is qualified when 98% by mass or more of that before standing remains.

[0149] <Examples 10 and 11>

[0150] After neutralizing the curable compositions of Examples 1 and 2 with hydrochloric acid, coat them on a polyethylene film to a thickness of 125 μm. Next, irradiate UV light (34 mW / cm 2 ) for 2 minutes on this coating film to produce a cured film. For this cured film, use acetone as a solvent to extract the unreacted curable compound, and use HPLC or GC to quantify the amount of the unreacted curable compound.

[0151] [Table 1]

[0152]

[0153] It is clearly understood from the results in Table 1 that the curable composition of the present invention that combines the compound (A) having the structure represented by the general formula (I) and the base (B) does not cause the curable compound to react during storage, and has excellent storage stability. In addition, it is clearly understood from the results of Examples 10 and 11 that if the base in the curable composition is neutralized after storage, the curable composition can then be cured rapidly.

[0154] In contrast, Comparative Example 1 is an example using methyl diethanolamine (MDEA) as a conventional curing accelerator, and as a result, the storage stability of Comparative Example 1 is low. Since MDEA also promotes curing during the storage of the curing liquid, the storage stability is reduced. It can be seen that the combination of the compound (A) and the base (B) is excellent in terms of balancing storage stability and curing promotion effect compared with conventional curing accelerators.

Claims

1. A curable composition containing, per 100 parts by mass of a curable compound, 0.1 to 10.0 parts by mass of a compound (A) having a structure represented by the following general formula (I) and 0.01 to 10.0 parts by mass of one or more bases (B) selected from inorganic bases and organic amines. In general formula (I), X represents a chalcogen atom, R 1 and R 2 are each independently and represent any one of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group, R 3 and R 4 are each independently and represent a hydrogen atom, any one of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group.

2. The curable composition according to claim 1, wherein, R in the general formula (I) 1 and R 2 are each independently an alkyl group having 1 to 4 carbon atoms.

3. The curable composition according to claim 1, wherein, X in the general formula (I) is an oxygen atom.

4. The curable composition according to claim 1, wherein, The compound (A) having a structure represented by the general formula (I) is a compound represented by the following general formula (II). In general formula (II), R 5 and R 6 each independently represent any one of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group, R 7 and R 8 each independently represent a hydrogen atom, any one of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group, R 9 represents a hydrogen atom, any one of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group, R 10 represents any one of a hydrogen atom, a (meth)acryloyl group, a 4-vinylphenyl group, and an alkenyl group having 2 to 6 carbon atoms, and n is an arbitrary integer.

5. The curable composition according to claim 1, wherein, The compound (A) having a structure represented by the general formula (I) is a compound represented by the following general formula (III). In general formula (III), R 11 , R 12 , R 17 and R 18 are each independently and represent any of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group, and R 13 and R 14 are each independently and represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group, and R 15 represents a hydrogen atom or a methyl group, and R 16 represents any of a hydroxyl group, a (meth)acryloyloxy group, a 4-vinylphenoxy group, and an alkenyloxy group having 2 to 6 carbon atoms.

6. The curable composition according to any one of claims 1 to 5, wherein, The base (B) is one or more selected from sodium hydroxide, sodium methoxide, triethylamine, and trioctylamine.

7. A cured product obtained by curing the curable composition according to any one of claims 1 to 6.

8. A method for producing a cured product, which comprises curing the curable composition according to any one of claims 1 to 6.

9. The method for producing a cured product according to claim 8, comprising the following steps: a step of neutralizing the base (B) contained in the curable composition to obtain a neutralized product; and a step of curing the neutralized product.

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