Photothermally reactive diluent

Abstract

The present invention addresses the problem of providing a diluent with which the elastic modulus of a cured product after photocuring can be adjusted in a curing system in which photocuring and thermal curing can be performed in combination.　The present invention contains a mixture that: contains a compound (A) containing one or more isocyanate groups and one or more ethylenically unsaturated groups, and a carboxylic acid anhydride (B) containing an ethylenically unsaturated group; and contains 0.001 to 10 mass% of the carboxylic acid anhydride (B) with respect to the total 100 mass% of the compound (A) and the carboxylic acid anhydride (B).

Description

Photothermally reactive diluent

[0001] This invention relates to a photothermal reactive diluent.

[0002] Crosslinking in resins is an important means of improving various properties of resins. Processes for this crosslinking include photocuring by UV irradiation in the presence of ethylenically unsaturated groups and photoradical generators, and thermocuring by heating of heat-reactive functional groups. Systems that combine both photocuring and thermocuring also exist. For example, dual-curing adhesives allow for quick temporary fixing of the adherend by placing it on an ink-coated surface and irradiating it with UV light, followed by complete curing and bonding through thermocuring.

[0003] For example, Patent Document 1 discloses a coating composition comprising the following components: (a) at least one first substance comprising at least one irradiation-curable reactive functional group; (b) at least one second substance comprising at least one thermosetting reactive functional group; (c) at least one curing agent reactive with the at least one thermosetting reactive functional group, wherein the at least one curing agent is selected from aminoplast resins, polyisocyanates, blocked polyisocyanates, triazine-derived isocyanates, polyepoxides, polyacids, polyols and mixtures thereof; and (d) a plurality of particles selected from inorganic particles, composite particles and mixtures thereof, wherein each component is different.

[0004] Special table number 2004-505159

[0005] In dual curing, having reactive groups that can be photocured and thermocured is an absolute requirement. However, in the technology disclosed in Patent Document 1, it was not possible to adjust the hardness after photocuring during the photoreaction, leaving room for improvement.

[0006] The object of this invention is to provide a diluent that can adjust the elastic modulus of a cured product after photocuring in a curing system that can use both photocuring and thermal curing.

[0007] The inventors diligently studied to solve the above problems. As a result, they found that the above problems can be solved by having the following configuration, and thus completed the present invention. The aspects of the present invention relate, for example, to the following [1] to [9].

[0008] [1] A mixture comprising a compound (A) containing one or more isocyanate groups and ethylenically unsaturated groups, and a carboxylic acid anhydride (B) containing ethylenically unsaturated groups, wherein the carboxylic acid anhydride (B) is present in an amount of 0.001 to 10% by mass relative to 100% by mass of the total of compound (A) and the carboxylic acid anhydride (B).

[0009] [2] The mixture according to [1], wherein the compound (A) is represented by the following general formula (1) or (2).

[0010]

[0011]

[0012] In general formula (1) or (2), R １ R is a hydrogen atom or a methyl group, ２ R is a hydrogen atom, a methyl group, or an isocyanate group. ３ This is an alkylene group having 1 to 10 carbon atoms, which may have substituents, or a group obtained by substituting the single bonds between carbon atoms of the alkylene group with ether bonds. The two R in general formula (2) １ The two Rs can be the same or different. ３ They can be the same or different.

[0013] [3] A mixture according to any one of [1] to [3], wherein compound (A) is selected from the group consisting of 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, 2-(2-methacryloyloxy)ethoxyethyl isocyanate, and 1,1-(bisacryloyloxymethyl)ethyl isocyanate. [4] A mixture according to any one of [1] to [3], wherein compound (A) is 2-methacryloyloxyethyl isocyanate. [5] A mixture according to any one of [1] to [4], wherein the carboxylic acid anhydride (B) is acrylic anhydride or methacrylic anhydride. [6] A curable composition comprising a mixture according to any one of [1] to [5] and a polymerizable compound (C). [7] A curable composition according to [6], comprising a compound (D) containing an active hydrogen group. [8] A cured product obtained by photocuring the curable composition according to [6] or [7]. [9] A cured product obtained by photocuring and then thermally curing the curable composition described in [6] or [7].

[0014] According to the present invention, a diluent can be provided that can adjust the elastic modulus of a cured product after photocuring in a curing system that can use both photocuring and thermal curing.

[0015] Figure 1 is a graph showing the complex modulus of a curable composition containing a mixture, which is one embodiment of the present invention, after being irradiated with light for a predetermined time.

[0016] The following describes preferred embodiments for carrying out the present invention. The embodiments described below are examples of typical embodiments of the present invention and should not be interpreted as narrowing the scope of the present invention. In this specification, unless otherwise specified, the notation "A to B" in relation to numerical ranges means A or more and B or less. For example, the notation "1 to 5%" means 1% or more and 5% or less. Also, "(meth)acryloyl" refers to methacryloyl or acryloyl. For example, (meth)acryloyl group refers to a methacryloyl group or an acryloyl group.

[0017] <Mixture> One embodiment of the present invention is a mixture containing a compound (A) containing one or more isocyanato groups and one or more ethylenically unsaturated groups, and a carboxylic anhydride (B) containing an ethylenically unsaturated group, and containing 0.001 to 10% by mass of the carboxylic anhydride with respect to a total of 100% by mass of the compound (A) and the carboxylic anhydride (B).

[0018] The mixture includes not only the mode in which the carboxylic anhydride (B) is added to the compound (A) containing one or more isocyanato groups and one or more ethylenically unsaturated groups, but also the mode in which the carboxylic anhydride (B) is contained in the compound (A) containing one or more isocyanato groups and one or more ethylenically unsaturated groups in advance.

[0019] [Compound (A) containing one or more isocyanato groups and one or more ethylenically unsaturated groups] The compound (A) containing one or more isocyanato groups and one or more ethylenically unsaturated groups used in the present invention (hereinafter referred to as "compound (A)") is a compound containing one or more isocyanato groups and one or more ethylenically unsaturated groups in the molecule, preferably two or more. There is no limitation on the combination of the number of isocyanato groups and ethylenically unsaturated groups, but it is more preferable that there is one isocyanato group and one or two ethylenically unsaturated groups.

[0020] From the viewpoints of availability and reactivity, the compound (A) is preferably a compound represented by the following general formula (1) or (2).

[0021]

[0022]

[0023] In formula (1) or (2), R １ is a hydrogen atom or a methyl group, and R ２ is a hydrogen atom, a methyl group, or an isocyanato group, and R ３ is an alkylene group having 1 to 10 carbon atoms which may have a substituent, or a group obtained by substituting a single bond between carbon atoms of the alkylene group with an ether bond. The two Rs １ in the general formula (2) may be the same or different, and the two Rs ３ may be the same or different.

[0024] In formula (1) or (2), R ３ The alkylene group having 1 to 10 carbon atoms is preferably an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and still more preferably an alkylene group having 1 to 4 carbon atoms. In the present specification, the alkylene group refers to a group formed by removing any two hydrogen atoms bonded to carbon atoms in an aliphatic saturated hydrocarbon.

[0025] R ３ The alkylene group in is preferably a linear or branched alkylene group, more preferably a linear alkylene group.

[0026] In the group formed by substituting the single bond between carbon atoms of the above alkylene group with an ether bond, the single bond substituted by the bond may be one or two or more, but one is preferable.

[0027] R ３ In, examples of the substituent include a hydrocarbon group, a nitro group, a cyano group, -OR', -COR', -COOR'. R' represents an alkyl group.

[0028] Examples of the above hydrocarbon group include a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrocarbon group having 1 to 6 carbon atoms. Specifically, a methyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a vinyl group, etc. can be mentioned.

[0029] Examples of the above R' include a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrocarbon group having 1 to 6 carbon atoms. Specifically, a methyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a vinyl group, etc. can be mentioned.

[0030] R ３Preferably, among the above, is an alkylene group having 1 to 8 carbon atoms, or a group obtained by substituting the single bonds between carbon atoms of the alkylene group with at least one ether bond; more preferably, is an alkylene group having 1 to 6 carbon atoms, or a group obtained by substituting the single bonds between carbon atoms of the alkylene group with at least one ether bond; even more preferably, is an alkylene group having 1 to 4 carbon atoms, or a group obtained by substituting the single bonds between carbon atoms of the alkylene group with at least one ether bond; and particularly preferably, is -CH ２ -ien-CH ２ -CH ２ -ien-CH ２ -O-CH ２ -CH ２ -, or -CH ２ -CH ２ -O-CH ２ -CH ２ - is the case.

[0031] Examples of specific compounds represented by formula (1) include (meth)acryloyloxymethyl isocyanate, (meth)acryloyloxyethoxyethyl isocyanate, (meth)acryloyloxyethyl isocyanate, (meth)acryloyloxypropyl isocyanate, (meth)acryloyloxybutyl isocyanate, (meth)acryloyloxypentyl isocyanate, (meth)acryloyloxyhexyl isocyanate, (meth)acryloyloxyheptyl isocyanate, (meth)acryloyloxyoctyl isocyanate, (meth)acryloyloxynonyl isocyanate, and (meth)acryloyloxydecyl isocyanate. Of these, (meth)acryloyloxymethyl isocyanate and (meth)acryloyloxyethoxyethyl isocyanate are preferred in terms of availability and reactivity.

[0032] A specific compound represented by formula (2) is, for example, 1,1-(bisacryloyloxymethyl)ethyl isocyanate.

[0033] Compound (A) can be produced, for example, by the method described in US Patent No. 2,821,544. Alternatively, a commercially available compound (A) may be used. Examples of commercially available compound (A) include Karenz (registered trademark) MOI (manufactured by Resonac Co., Ltd.; 2-methacryloyloxyethyl isocyanate), Karenz (registered trademark) AOI (manufactured by Resonac Co., Ltd.; 2-acryloyloxyethyl isocyanate), Karenz (registered trademark) MOI-EG (manufactured by Resonac Co., Ltd.; methacryloyloxyethoxyethyl isocyanate), and Karenz (registered trademark) BEI (manufactured by Resonac Co., Ltd.; 1,1-(bisacryloyloxymethyl)ethyl isocyanate).

[0034] [Carboxylic Anhydride (B) Containing an Ethylenically Unsaturated Group] The carboxylic anhydride (B) containing an ethylenically unsaturated group (hereinafter referred to as "carboxylic anhydride (B)") used in the present invention is a compound having a skeleton formed by dehydration condensation of two carboxy groups represented by an ethylenically unsaturated group and -C(=O)-O-C(=O)-.

[0035] Examples of the ethylenically unsaturated group include (meth)acryloyl group, vinyl group, and allyl group. Carboxylic anhydride (B) preferably has at least one of these groups.

[0036] Examples of carboxylic anhydride (B) include acrylic anhydride, methacrylic anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, and fumaric anhydride. Among these, from the viewpoint of reactivity, carboxylic anhydride (B) is preferably acrylic anhydride or methacrylic anhydride.

[0037] [Amount ratio of compound (A) to carboxylic acid anhydride (B)] The content of carboxylic acid anhydride (B) in the above mixture is 0.001 to 10% by mass, preferably 0.005 to 8% by mass, and more preferably 0.01 to 3% by mass, relative to 100% by mass of the total of compound (A) and carboxylic acid anhydride (B). If the content of carboxylic acid anhydride (B) is less than 0.001% by mass relative to 100% by mass of the total of compound (A) and carboxylic acid anhydride (B), the effect when cured may be insufficient, and if it is more than 10% by mass, the curing shrinkage when cured may be large.

[0038] [Optional Components] In addition to compound (A) and carboxylic acid anhydride (B), the above mixture may also contain optional components. Examples of optional components include polymerization inhibitors.

[0039] The amount of any component in the mixture is usually 0 to 5% by mass, preferably 0.001 to 3% by mass, and more preferably 0.01 to 1% by mass, based on 100% by mass of the total of compound (A) and carboxylic acid anhydride (B).

[0040] [Manufacturing Method] Examples of methods for manufacturing the above mixture include adding carboxylic acid anhydride (B) to compound (A) and stirring and mixing, or adding compound (A) to carboxylic acid anhydride (B) and stirring and mixing. If the above mixture contains the above optional component, the optional component may be added when adding carboxylic acid anhydride (B) to compound (A) or when adding compound (A) to carboxylic acid anhydride (B), or the optional component may be added after stirring and mixing compound (A) and carboxylic acid anhydride. Stirring and mixing can be carried out, for example, using a mixer, bubbling, etc., and conditions such as temperature and stirring speed can be set as appropriate.

[0041] [Applications] The above mixture can be used as a diluent for the curable composition described later, and can be used to adjust the elastic modulus of the cured product obtained by photocuring, or by photocuring and thermal curing of the curable composition.

[0042] <Curable Composition> One embodiment of the present invention is a curable composition comprising the above mixture and a polymerizable compound (C).

[0043] [Polymerizable compound (C)] Polymerizable compound (C) is not particularly limited as long as it is a polymerizable compound that can be photocured by light irradiation or thermocured by heating, but for example, compounds having a double bond are mentioned, and compounds having an ethylenically unsaturated group are more preferred. Polymerizable compound (C) preferably has a urethane bond in addition to a double bond.

[0044] The content of polymerizable compound (C) in the above curable composition is usually 10 to 500 parts by mass, preferably 50 to 300 parts by mass, and more preferably 70 to 200 parts by mass, based on 100 parts by mass of the total of compound (A) and carboxylic acid anhydride (B).

[0045] When polymerizable compound (C) has a urethane bond, polymerizable compound (C) can be synthesized using isocyanate monomers and diol compounds as raw materials in the presence of a catalyst.

[0046] The isocyanate monomer can be one of those compounds (A) containing one or more isocyanate groups and ethylenically unsaturated groups.

[0047] The diol compounds are not particularly limited, but examples include polybutadiene diol, polyisoprendiol, polycarbonate diol containing aliphatic diol-derived structural units, polyether diol, polyester diol, polycaprolactone diol, silicone diol, and dihydroxy compounds having a carboxyl group.

[0048] The molar ratio of isocyanate monomer to diol is preferably 10:1 to 1:5, more preferably 5:1 to 1:3, and even more preferably 3:1 to 1:1.

[0049] The catalyst is not particularly limited, but examples include metal catalysts and amine-based catalysts. Examples of metal catalysts are not particularly limited, but examples include tin catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, and dibutyltin dioctate; lead catalysts such as lead octoate, lead octate, and lead naphthenate; and bismuth catalysts such as bismuth octoate and bismuth neodecanoate. Examples of amine-based catalysts are not particularly limited, but examples include tertiary amine compounds such as triethylenediamine.

[0050] [Compound (D) containing an active hydrogen group] The above curable composition is preferable in that it contains a compound (D) containing an active hydrogen group (hereinafter referred to as "compound (D)"), as this allows the cured product to form a network structure and improve the gel fraction when thermal curing is performed after photocuring. Active hydrogen is, for example, a hydrogen atom bonded to a nitrogen atom, oxygen atom, or sulfur atom. An active hydrogen group is a group containing active hydrogen, and examples include a hydroxyl group, a mercapto group, a carboxyl group, and an amino group.

[0051] Compounds (D) containing hydroxyl groups as active hydrogen groups include, for example, polyhydric alcohols such as 1,6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, glycerin, diglycerin, D-glucose, D-glucitol, isoprene glycol, butanediol, 1,5-pentanediol, 1,9-nonanediol, neopentyl glycol, etc.; 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2,3-dihydroxybutyl (meth)acrylate, 4-hydroxypropyl Hydroxyalkyl (meth)acrylates such as hydroxyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 8-hydroxyoctyl (meth)acrylate; vinyl ethers such as 2-hydroxyethyl vinyl ether and 4-hydroxybutyl vinyl ether; monoesters of polyhydric alcohols and (meth)acrylic acid, such as 4-hydroxymethylcyclohexyl (meth)acrylate and polyalkylene glycol mono(meth)acrylate; compounds obtained by ring-opening polymerization of the above monoesters of polyhydric alcohols and (meth)acrylic acid with ε-caprolactone, or hydroxyl group-containing compounds obtained by ring-opening polymerization of ethylene oxide or propylene oxide; R ４ OH(R ４ Examples include monoalcohols such as (where is an alkyl group having 1 to 10 carbon atoms); polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol, and polytetramethylene glycol; and polymer polyols such as polycaprolactone diol, polycaprolactone triol, and polycarbonate diol.

[0052] Compounds (D) containing a mercapto group as an active hydrogen group include, for example, monothiols such as 1-butanethiol, 1-pentanethiol, 1-octanthiol, 1-dodecanethiol, n-octandecanethiol, α-toluenethiol, 2-benzimidazolethiol, 2-thiazoline-2-thiol, 2-methyl-2-propanethiol, and O-aminothiophenol; hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, and pentaerythritol tetrakisthiopropionate. Tris(2-hydroxyethyl) isocyanurate, trimercaptopropionate tris(2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, tetraethylene glycol bis-3-mercaptopropionate, trimethylolpropane tris-3-mercaptopropionate, tris(3-mercaptopropynyloxyethyl) isocyanurate Examples include polyhydric thiols such as anulates, pentaerythritol tetrakiss 3-mercaptopropionate, dipentaerythritol tetrakiss 3-mercaptopropionate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and pentaerythritol tetrakiss(3-mercaptobutyrate).

[0053] Examples of compounds (D) containing a mecarboxyl group as an active hydrogen group include monocarboxylic acids such as acetic acid and propionic acid; aliphatic and aromatic polycarboxylic acids such as succinic acid, adipic acid, dimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid; and polymeric polycarboxylic acids such as polyamic acid and (co)polymers of acrylic acid.

[0054] Examples of compounds (D) containing an amino group as an active hydrogen group include monoamines such as butylamine, hexylamine, and aniline; aliphatic polyamines such as diethylenetriamine, triethylenetetramine, 1,3- or 1,4-bisaminomethylcyclohexane, isophoronediamine, hexamethylenediamine, and bis(4-aminocyclohexyl)methane; aromatic polyamines such as m- or p-xylylenediamine, bis(4-aminophenyl)methane, and 2,4- or 2,6-tolylenediamine; glycosamines such as chitosan; and silicone compounds such as bis(3-aminopropyl)polydimethylsiloxane and bis(3-aminopropyl)polydiphenylsiloxane.

[0055] The amount of compound (D) in the above curable composition divided by the number of moles of the portion that reacts with the isocyanate group is usually 0.1 to 10 moles, preferably 0.3 to 8 moles, and more preferably 0.5 to 5 moles, per 100 moles of compound (A).

[0056] The above curable composition preferably further contains a polymerization initiator (E). A photopolymerization initiator is preferred as the polymerization initiator (E) according to one embodiment of the present invention. While not particularly limited, the photopolymerization initiator may include benzophenone, benzyl, benzoin, ω-bromoacetophenone, chloroacetone, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, 2-chlorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, Michler ketone, benzoin methyl ether, benzoin isobutyl ether, benzoin-n-butyl ether, benzyl methyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, methylbenzo Examples of photopolymerization initiators include carbonyl-based photopolymerization initiators such as methylformate, 2,2-diethoxyacetophenone, 4-N,N'-dimethylacetophenone, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one; sulfide-based photopolymerization initiators such as diphenyl disulfide, dibenzyl disulfide, tetraethylthiuram disulfide, and tetramethylammonium monosulfide; acylphosphine oxide-based photopolymerization initiators such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide; quinone-based photopolymerization initiators such as benzoquinone and anthraquinone; sulfochloride-based photopolymerization initiators; and thioxanthone-based photopolymerization initiators such as thioxanthone, 2-chlorothioxanthone, and 2-methylthioxanthone.

[0057] These may be used individually or in combination of two or more. Among them, 1-hydroxycyclohexylphenyl ketone is preferred from the viewpoint of solubility in curable compositions.

[0058] The content of the photopolymerization initiator is preferably 0.2 to 5 parts by mass, and more preferably 0.5 to 3 parts by mass, per 100 parts by mass of the total amount of compound (A), carboxylic acid anhydride (B), and polymerizable compound (C). A content of 0.2 to 5 parts by mass per 100 parts by mass of the total amount of compound (A), carboxylic acid anhydride (B), and polymerizable compound (C) is preferable because it provides a good balance between photocurability and the strength and tackiness of the resulting adhesive sheet.

[0059] [Manufacturing Method] Examples of methods for manufacturing the curable composition include adding compound (C) to the mixture and stirring, or adding the mixture to compound (C) and stirring. If the curable composition contains compound (D), compound (D) may be added when adding compound (C) to the mixture, or when adding the mixture to compound (C), or compound (D) may be added after stirring the mixture and compound (C). If the curable composition contains polymerization initiator (E), polymerization initiator (E) may be added when adding compound (C) to the mixture, or when adding the mixture to compound (C), or polymerization initiator (E) may be added after stirring the mixture and compound (C). Stirring can be performed, for example, using a mixer, with appropriate settings for temperature, stirring speed, and other conditions.

[0060] <Cured Product> One embodiment of the present invention is a cured product obtained by photocuring the above curable composition. The cured product can be obtained by subjecting the above curable composition to treatment such as light irradiation or ultraviolet irradiation (hereinafter referred to as "light irradiation treatment").

[0061] The conditions for the light irradiation treatment, such as illuminance, frequency, and exposure time, can be appropriately set according to the composition and quantity of the curable composition to be irradiated, or the desired elastic modulus of the resulting cured product. For example, the illuminance is 5 to 500 mJ, preferably 20 to 100 mJ, the exposure time is 5 to 600 seconds, preferably 30 to 120 seconds, and the wavelength is 300 to 400 nm.

[0062] One embodiment of the present invention is a cured product obtained by photocuring the above-mentioned curable composition and then thermally curing it. The cured product can be obtained by subjecting the above-mentioned curable composition to the above-mentioned photoirradiation treatment and then further thermally curing it.

[0063] The conditions for thermosetting, such as temperature and time, can be appropriately set according to the composition and quantity of the curable composition being heated, or the desired elastic modulus of the resulting cured product. For example, the temperature is 50 to 300°C, preferably 100 to 200°C, and the time is 0.3 to 6 hours, preferably 0.5 to 2 hours.

[0064] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples and can be implemented with appropriate modifications without changing its essence. In the following descriptions of examples, unless otherwise specified, "parts" refers to "parts by mass".

[0065] In the examples, the method for measuring the complex modulus of elasticity to confirm photoreactivity is as follows: Measuring instrument: Rheometer (Anton Paar: MCR-301) Measuring temperature: 25°C Measuring mode: Vibration mode Measuring fixture: 12 mm parallel plate Strain: 10% Frequency: 1 Hz Illuminance (365 nm): 70 mJ / s Exposure time: 100 seconds (80 seconds stabilization followed by 100 seconds of irradiation)

[0066] [Preparation Example 1] Polymerizable compound a was synthesized as follows: 185.96 g (45.2 mmol) of Teslac TA22-976C (manufactured by Resonac Co., Ltd., polyester diol), 14.04 g (90.5 mmol) of 2-methacryloyloxyethyl isocyanate (MOI), and 0.14 g (0.22 mmol) of dibutyltin dilaurate were placed in a 300 mL separable flask and reacted with stirring at an internal temperature of 60°C for 2 hours. The completion of the reaction was confirmed by the disappearance of the isocyanate peak using IR, and the target polymerizable compound a was obtained.

[0067] [Example 1] 19.998 g of 2-methacryloyloxyethyl isocyanate (MOI) and methacrylic anhydride (MAA) were placed in a container and set in a rotary mixer, and stirred and mixed at 2000 rpm for 7 minutes to obtain mixture 1 of Example 1.

[0068] [Examples 2-6, Comparative Example 1] Mixtures 2-6 of Examples 2-6 and comparative mixture 1 of Comparative Example 1 were obtained in the same manner as in Example 1, except that the compositions were changed as shown in Table 1 below.

[0069] [Correction based on Rule 91, March 27, 2026]

[0070] [Example 7] 15.00 g of polymerizable compound a prepared in Preparation Example 1, 15.00 g of mixture 1, and 0.60 g of 1-hydroxycyclohexyl-1-ylphenyl ketone (Irgacre® 184 (Irg184): manufactured by BASF) as a photopolymerization initiator were stirred and mixed in a rotary-rotating mixer at 2000 rpm for 7 minutes to obtain the curable composition of Example 7.

[0071] [Examples 8-12, Comparative Example 2] Curable compositions for Examples 8-12 and Comparative Example 2 were obtained in the same manner as in Example 7, except that mixture 1 was replaced with each of the mixtures in Table 2 below.

[0072]

[0073] The complex modulus of elasticity of the cured products (resins) obtained by curing each curable composition using the method described above was measured. The results are shown in Table 3 and Figure 1 below.

[0074]

[0075] The results showed that the elastic modulus of the cured product improved with increasing amounts of methacrylic anhydride added to the mixture.

[0076] [Example 13 and Comparative Example 3] Curable compositions with the compositions shown in Table 4 below were prepared. In the table, IBMA represents isobutyl methacrylic acid, 1,6-HD represents 1,6-hexanediol, and DBTDL represents dibutyltin dilaurate.

[0077]

[0078] The obtained curable composition was bar-coated to a thickness of 250 μm onto a glass surface and photocured by exposure to an LED exposure unit at an illuminance of 50 mJ / s (365 nm) for 60 seconds. The resulting film was then heated in a 110°C oven for 1 hour. The weight of the cured film after heating was measured, and it was immersed in a screw-cap tube filled with acetone and stored at room temperature for 24 hours. After immersion, the remaining cured film in the screw-cap tube was collected on a 500-mesh stainless steel mesh and dried in a 110°C oven for 1 hour. The weight of the dried cured film was then measured. The gel fraction was calculated from the weight of the cured film after photocuring and heating, and after acetone immersion and drying. The gel fraction results are shown in Table 5. The gel fraction is expressed by the following formula.

[0079]

[0080] Gel fraction (%) = Weight of cured film after acetone immersion - drying (g) / Weight of cured film after photocuring - heating (g) × 100

[0081] The mixture of the present invention is characterized by containing a compound (A) having one or more isocyanate groups in its molecule. Therefore, by adding a molecule (1,6-HD) having an active hydrogen group that can react with an isocyanate group to the reaction system and heating it, the two hydroxyl groups of 1,6-HD react with the compound (A) to form a crosslink. As a result, compared to a comparative example using IBMA, which does not have an isocyanate group in its molecule, the gel fraction after heating was higher, and the reaction with 1,6-hexanediol due to heat was confirmed.

[0082] [Examples 14-17 and Comparative Example 4] Curable compositions with the compositions shown in Table 6 below were prepared. In the table, AA represents acrylic anhydride.

[0083]

[0084] The obtained curable composition was bar-coated to a thickness of 250 μm onto a glass surface and photocured by exposure to an LED exposure machine at an illuminance of 40 mJ / s (365 nm) for 50 seconds. After photocuring, it was heated on a hot plate at 150°C for 1 hour. The weight of the resin film after heating was measured, and it was immersed in a screw-top tube filled with acetone and stored at room temperature for 24 hours. After immersion, the remaining resin film in the screw-top tube was collected on a 500-mesh stainless steel mesh and dried by heating in a 100°C oven for 1 hour. The weight of the resin film after drying was measured. The gel fraction was calculated from the weight of the resin film after photocuring and heating and the weight of the resin film after acetone immersion and drying using the above formula. The gel fraction results are shown in Table 7.

[0085]

[0086] The above results indicate that Examples 14-17 had a higher gel fraction than Comparative Example 4, confirming a reaction with 1,6-hexanediol due to heat.

Claims

1. A mixture comprising a compound (A) containing one or more isocyanate groups and ethylenically unsaturated groups, and a carboxylic acid anhydride (B) containing ethylenically unsaturated groups, wherein the carboxylic acid anhydride (B) is present in an amount of 0.001 to 10% by mass relative to 100% by mass of the total of compound (A) and the carboxylic acid anhydride (B).

2. The mixture according to claim 1, wherein the compound (A) is represented by the following general formula (1) or (2). [In the general formula (1) or (2), R １ is a hydrogen atom or a methyl group, R ２ is a hydrogen atom, a methyl group, or an isocyanato group, and R ３ is an alkylene group having 1 to 10 carbon atoms which may have a substituent, or a group formed by substituting a single bond between carbon atoms of the alkylene group with an ether bond. Two R １ in the general formula (2) may be the same or different, and two R ３ may be the same or different. ] 3. The mixture according to claim 1 or 2, wherein the compound (A) is selected from the group consisting of 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, 2-(2-methacryloyloxy)ethoxyethyl isocyanate, and 1,1-(bisacryloyloxymethyl)ethyl isocyanate.

4. The mixture according to claim 1 or 2, wherein the compound (A) is 2-methacryloyloxyethyl isocyanate.

5. The mixture according to claim 1 or 2, wherein the carboxylic acid anhydride (B) is acrylic anhydride or methacrylic anhydride.

6. A curable composition comprising the mixture according to claim 1 or 2 and a polymerizable compound (C).

7. The curable composition according to claim 6, comprising a compound (D) containing an active hydrogen group.

8. A cured product obtained by photocuring the curable composition according to claim 6.

9. A cured product obtained by photocuring and then thermally curing the curable composition according to claim 6.

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