Photothermal reactive diluent

Abstract

Provided is a diluent that allows adjustment of the modulus of elasticity of a cured product after photocuring in a curing system that allows the use of both photocuring and thermocuring. The present invention includes a mixture containing a compound (A) containing one or more isocyanate groups and an olefinically unsaturated group, and a carboxylic anhydride (B) containing an olefinically unsaturated group, containing 0.001 to 10 mass% of the carboxylic anhydride (B) relative to 100 mass% of the compound (A) and the carboxylic anhydride (B).

Description

Technical Field

[0001] This invention relates to photothermal reactive diluents. Background Technology

[0002] Crosslinking in resins is an important means of improving various properties of resins. Processes for this crosslinking formation include photocuring using UV irradiation in the presence of olefinic unsaturated groups and photoradical generators, and thermocuring by heating functional groups capable of thermal reaction. Systems that combine photocuring and thermocuring also exist. Examples include dual-curing adhesives that rapidly and temporarily fix the adherends by placing them on a surface coated with ink and subjecting them to UV irradiation, followed by complete curing by thermocuring.

[0003] For example, Patent Document 1 discloses a coating composition formed from components comprising the following (a) to (d): (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) a curing agent, which is at least one curing agent reactive with the at least one thermosetting reactive functional group, the at least one curing agent being selected from amino plastic 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 the components are different.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent No. 2004-505159 Summary of the Invention

[0007] The problem that the invention aims to solve

[0008] Having reactive groups capable of both photocuring and thermal curing is an absolute requirement in dual-curing systems. However, in the technology disclosed in Patent Document 1, the hardness after photocuring during photoreaction cannot be adjusted, leaving room for improvement.

[0009] The present invention aims to provide a diluent that can adjust the elastic modulus of the cured product after photocuring in a curing system that can combine photocuring and thermal curing.

[0010] Methods for solving problems

[0011] The inventors conducted in-depth research to solve the aforementioned problems. As a result, they discovered that the above-mentioned problems can be solved by having the following configuration, thus completing the present invention.

[0012] The present invention relates to, for example, the following [1] to [9].

[0013] [1] A mixture comprising a compound (A) comprising one or more isocyanate groups and an olefinic unsaturated group and a carboxylic anhydride (B) comprising an olefinic unsaturated group, wherein the carboxylic anhydride (B) comprises 0.001 to 10% by mass of the carboxylic anhydride (B) relative to 100% by mass of the total of the compound (A) and the carboxylic anhydride (B).

[0014] [2] According to the mixture described in [1], the above compound (A) is represented by the following general formula (1) or general formula (2).

[0015]

[0016]

[0017] In general formula (1) or general formula (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 It is an alkylene group having 1 to 10 carbon atoms that may have substituents, or a group formed by replacing the single bonds between the carbon atoms of the alkylene group with ether bonds. The two Rs in general formula (2) 1 They can be the same or different, 2 Rs 3 They can be the same or different.

[0018] [3] The mixture according to any one of [1] to [3], wherein the compound (A) is selected from 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, 2-(2-methacryloyloxy)ethoxyethyl isocyanate and 1,1-(bisacryloyloxymethyl)ethyl isocyanate.

[0019] [4] The mixture according to any one of [1] to [3], wherein the above compound (A) is 2-methacryloyloxyethyl isocyanate.

[0020] [5] In any one of [1] to [4], the above-mentioned carboxylic anhydride (B) is acrylic anhydride or methacrylic anhydride.

[0021] [6] A curable composition comprising a mixture of any one of [1] to [5] and a polymeric compound (C).

[0022] [7] The curable composition according to [6] comprises a compound (D) containing an active hydrogen group.

[0023] [8] A cured product obtained by photocuring the curable composition described in [6] or [7].

[0024] [9] A cured product obtained by photocuring the curable composition described in [6] or [7] followed by thermocuring.

[0025] The effects of the invention

[0026] According to the present invention, a diluent that can adjust the elastic modulus of a cured product after photocuring can be provided in a curing system that can combine photocuring and thermal curing. Attached Figure Description

[0027] Figure 1 A graph showing the complex modulus of elasticity after irradiating a curable composition containing a mixture as an embodiment of the present invention with light for a specified time. Detailed Implementation

[0028] The following describes a suitable mode for carrying out the present invention. It should be noted that the embodiments described below show an example of a representative embodiment of the present invention, and the scope of the present invention should not be interpreted as narrow because of this. It should be noted that in this specification, unless otherwise specified, the references to numerical ranges "A to B" indicate A or more and B or less. For example, the reference to "1 to 5%" means 1% or more and 5% or less. Furthermore, "(meth)acryloyl" represents methacryloyl or acryloyl. For example, (meth)acryloyl represents methacryloyl or acryloyl.

[0029] <Mixture>

[0030] One embodiment of the present invention is a mixture comprising a compound (A) comprising one or more isocyanate groups and an olefinic unsaturated group, and a carboxylic anhydride (B) comprising an olefinic unsaturated group, wherein the carboxylic anhydride comprises 0.001 to 10% by mass of the carboxylic anhydride relative to 100% by mass of the total of the compound (A) and the carboxylic anhydride (B).

[0031] The mixture includes not only the option of adding the carboxylic anhydride (B) to the compound (A) which contains one or more of the above-mentioned isocyanate groups and olefinic unsaturated groups respectively, but also the option of pre-containing the above-mentioned carboxylic anhydride (B) in the compound (A) which contains one or more of the above-mentioned isocyanate groups and olefinic unsaturated groups respectively.

[0032] [Compound (A) containing one or more isocyanate groups and one olefinic unsaturated group respectively]

[0033] The compound (A) used in this invention, which contains one or more isocyanate groups and olefin unsaturated groups respectively (hereinafter referred to as "compound (A)"), is a compound that contains one or more, preferably two or more, isocyanate groups and olefin unsaturated groups respectively within its molecule. There is no limitation on the combination of the number of isocyanate groups and olefin unsaturated groups, but one or two olefin unsaturated groups are more preferred than one isocyanate group.

[0034] As for compound (A), from the perspective of ease of acquisition and reactivity, the compound shown in general formula (1) or general formula (2) below is preferred.

[0035]

[0036]

[0037] In equation (1) or equation (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 It is an alkylene group having 1 to 10 carbon atoms that may have substituents, or a group formed by replacing the single bonds between the carbon atoms of the alkylene group with ether bonds. The two Rs in the above general formula (2) 1 They can be the same or different, 2 Rs 3 They can be the same or different.

[0038] In equation (1) or equation (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 even more preferably an alkylene group having 1 to 4 carbon atoms. It should be noted that, in this specification, the term alkylene group refers to a group formed by removing any two hydrogen atoms bonded to a carbon atom from an aliphatic saturated hydrocarbon.

[0039] R 3 The alkylene groups in the form are preferably straight-chain or branched alkylene groups, and more preferably straight-chain alkylene groups.

[0040] In the groups formed by replacing the single bonds between the carbon atoms of the aforementioned alkylene groups with ether bonds, the single bonds replaced by the ether bonds can be one or more, but are preferably one.

[0041] In R 3 In this context, examples of substituents include alkyl, nitro, cyano, -OR', -COR', and -COOR'. R' represents an alkyl group.

[0042] The aforementioned hydrocarbon group is, for example, a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrocarbon group having 1 to 6 carbon atoms. Specifically, examples include methyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, vinyl, etc.

[0043] As described above, R' is, for example, a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrocarbon group having 1 to 6 carbon atoms. Specifically, examples include methyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, vinyl, etc.

[0044] In the above, R 3 Preferably, it is an alkylene group having 1 to 8 carbon atoms or a group formed by replacing the single bond between the carbon atoms of the alkylene group with at least one ether bond; more preferably, it is an alkylene group having 1 to 6 carbon atoms or a group formed by replacing the single bond between the carbon atoms of the alkylene group with at least one ether bond; even more preferably, it is an alkylene group having 1 to 4 carbon atoms or a group formed by replacing the single bond between the carbon atoms of the alkylene group with at least one ether bond; particularly preferably, it is -CH2-, -CH2-CH2-, -CH2-O-CH2-CH2-, or -CH2-CH2-O-CH2-CH2-.

[0045] Examples of specific compounds represented by formula (1) include, for example, (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. Among these, (meth)acryloyloxymethyl isocyanate and (meth)acryloyloxyethoxyethyl isocyanate are preferred from the perspectives of availability and reactivity.

[0046] As a specific compound represented by formula (2), 1,1-(bisacryloyloxymethyl)ethyl isocyanate is preferred, for example.

[0047] Compound (A) can be manufactured, for example, by the method described in US Publication No. 2821544. Furthermore, commercially available products can be used for compound (A). Examples of commercially available products of compound (A) include, for instance... MOI Co., Ltd. (Registered Trademark) (Preparation; 2-methacryloyloxyethyl isocyanate) (Registered Trademark) AOI (Co., Ltd.) (Preparation; 2-Acryloyloxyethyl isocyanate) (Registered Trademark) MOI-EG (Co., Ltd.) Preparation; methacryloyloxyethoxyethyl isocyanate), (Registered Trademark) BEI Co., Ltd. Preparation; 1,1-(bisacryloyloxymethyl)ethyl isocyanate).

[0048] [Carboxylic anhydrides (B) containing olefinic unsaturated groups]

[0049] The carboxylic anhydride (B) containing an olefinic unsaturated group used in this invention (hereinafter referred to as "carboxylic anhydride (B)") is a compound having a skeleton of a carboxyl group and a carboxyl group represented by -C(=O)-OC(=O)- which has undergone dehydration condensation.

[0050] Examples of olefinic unsaturated groups include (meth)acryloyl, vinyl, and allyl. The carboxylic anhydride (B) is preferably a substance having at least one of these groups.

[0051] Examples of carboxylic anhydrides (B) include acrylic anhydride, methacrylic anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, and fumaric anhydride. Among these, acrylic anhydride and methacrylic anhydride are preferred from a reactivity perspective.

[0052] [The molar ratio of compound (A) to carboxylic anhydride (B)]

[0053] The content of carboxylic anhydride (B) in the above mixture is 0.001 to 10% by mass relative to 100% by mass of the total of compound (A) and carboxylic anhydride (B), preferably 0.005 to 8% by mass, and more preferably 0.01 to 3% by mass. If the content of carboxylic anhydride (B) is less than 0.001% by mass relative to 100% by mass of the total of compound (A) and carboxylic anhydride (B), the effect when forming a cured product may be insufficient; if it exceeds 10% by mass, the curing shrinkage when forming a cured product may be greater.

[0054] [Optional Ingredients]

[0055] In addition to compound (A) and carboxylic anhydride (B), the mixture may also contain optional components. Examples of optional components include, for instance, polymerization inhibitors.

[0056] The amount of optional components in the mixture is typically 0 to 5% by mass relative to 100% of the total mass of compound (A) and carboxylic anhydride (B), preferably 0.001 to 3% by mass, and more preferably 0.01 to 1% by mass.

[0057] [Manufacturing Method]

[0058] Examples of methods for producing the above mixture include, for instance, adding carboxylic anhydride (B) to compound (A) and stirring to mix, or adding compound (A) to carboxylic anhydride (B) and stirring to mix. When the mixture contains the optional component, the optional component can be added when adding carboxylic anhydride (B) to compound (A) or when adding compound (A) to carboxylic anhydride (B), or the optional component can be added after stirring and mixing compound (A) and carboxylic anhydride. Stirring and mixing can be performed using, for example, a mixer, a bubbling device, etc., with appropriate settings for temperature, stirring speed, etc.

[0059] 〔use〕

[0060] The above mixture can be used as a diluent in the curable composition described later, and can be used to adjust the elastic modulus of the cured product obtained by light curing, or light curing and heat curing of the curable composition.

[0061] <Curing Composition>

[0062] One embodiment of the present invention is a curable composition comprising the above-described mixture and a polymeric compound (C).

[0063] [Polymerizing compound (C)]

[0064] As for the polymerizable compound (C), there is no particular limitation as long as it is a polymerizable compound that can be photocured by light irradiation or thermocured by heating. Examples include compounds having double bonds, and more preferably compounds having olefinic unsaturated groups. The polymerizable compound (C) preferably has urethane bonds in addition to double bonds.

[0065] The content of the polymerizable compound (C) in the above-mentioned curable composition is typically 10 to 500 parts by mass relative to 100 parts by mass of the total of compound (A) and carboxylic anhydride (B), preferably 50 to 300 parts by mass, and more preferably 70 to 200 parts by mass.

[0066] When the polymeric compound (C) has urethane bonds, the polymeric compound (C) can be synthesized from isocyanate monomers and diol compounds in the presence of a catalyst.

[0067] The isocyanate monomer can be used in the substances described in compound (A) which contains one or more isocyanate groups and olefinic unsaturated groups respectively.

[0068] As a diol compound, there is no particular limitation, but examples include polybutadiene diol, polyisoprene diol, polycarbonate diol containing structural units derived from aliphatic diols, polyether diol, polyester diol, polycaprolactone diol, organosilicon diol, and dihydroxy compounds having carboxyl groups.

[0069] 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.

[0070] As a catalyst, there is no particular limitation; examples include metal catalysts and amine catalysts. As a metal catalyst, there is no particular limitation; examples include tin catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, and dibutyltin dioctanoate; lead catalysts such as lead octanoate, lead octenate, and lead naphthenate; and bismuth catalysts such as bismuth octanoate and bismuth neodecanoate. As an amine catalyst, there is no particular limitation; examples include tertiary amine compounds such as triethylenediamine.

[0071] [Compounds containing active hydrogen groups (D)]

[0072] The curable composition described above, comprising a compound (D) containing an active hydrogen group (hereinafter referred to as "compound (D)"), is preferred in that, when photocured first and then thermocured, the cured product can form a network structure, thereby increasing the gel fraction. The active hydrogen group is, for example, a hydrogen atom bonded to a nitrogen atom, oxygen atom, or sulfur atom. The active hydrogen group is a group containing active hydrogen, such as, hydroxyl, mercapto, carboxyl, or amino groups.

[0073] Examples of compounds (D) containing a hydroxyl group as an active hydrogen group include, for example, 1,6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, glycerol, diglycerol, D-glucose, D-glucol, isoprenediol, butanediol, 1,5-pentanediol, 1,9-nonanediol, neopentanediol, and other polyols; 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, 2,3-dihydroxybutyl methacrylate, and 4-hydroxybutyl methacrylate. Esters, hydroxyalkyl methacrylates such as 6-hydroxyhexyl methacrylate and 8-hydroxyoctyl methacrylate; vinyl ethers such as 2-hydroxyethyl vinyl ether and 4-hydroxybutyl vinyl ether; monoesterifications of polyols and (meth)acrylic acid such as 4-hydroxymethylcyclohexyl methacrylate and polyalkylene glycol mono(meth)acrylate; compounds containing hydroxyl groups formed by ring-opening polymerization of ε-caprolactone in the monoesterifications of the above polyols and (meth)acrylic acid; and compounds containing hydroxyl groups formed by ring-opening polymerization of ethylene oxide or propylene oxide; R 4 OH(R 4 Alkyl groups having 1 to 10 carbon atoms; monohydric alcohols such as polyethylene glycol, polypropylene glycol, polybutane glycol, and polytetramethylene glycol; and polymeric polyols such as polycaprolactone diol, polycaprolactone triol, and polycarbonate diol.

[0074] Examples of compounds (D) containing a thiol group as an active hydrogen group include, for example, monothiols such as 1-butanethiol, 1-pentanethiol, 1-octanethiol, 1-dodecanethiol, n-octanedecanethiol, α-toluenethiol, 2-benzimidazolethiol, 2-thiazolin-2-thiol, 2-methyl-2-propanethiol, and O-aminobenzylthiophenol; and hexanedithiol, decanedithiol, 1,4-butanediol dithiopropionate, 1,4-butanediol dithioglycolate, ethylene glycol dithioglycolate, ethylene glycol dithiopropionate, trimethylolpropane trithioglycolate, trimethylolpropane trithiopropionate, trimethylolpropane tri(3-mercaptobutyrate), pentaerythritol tetrathioglycolate, and pentaerythritol tetrathioglycolate. Propionates, tri(2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercaptotriazine, 2-(N,N-dibutylamino)-4,6-dimercaptotriazine, tetraethylene glycol bis-3-mercaptopropionate, trimethylolpropane tri-3-mercaptopropionate, tris(3-mercaptopropynoxyethyl) isocyanurate, pentaerythritol tetra-3-mercaptopropionate, dipentaerythritol tetra-3-mercaptopropionate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, pentaerythritol tetra(3-mercaptobutyrate), and other polythiols.

[0075] Examples of compounds (D) containing a carboxyl group as an active hydrogen group include monocarboxylic acids such as acetic acid and propionic acid; aliphatic / aromatic polycarboxylic acids such as succinic acid, adipic acid, dimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid; and high molecular weight polycarboxylic acids such as polyamic acid and (co)polymers of acrylic acid.

[0076] 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-diaminomethylcyclohexane, isophorone diamine, 1,6-hexanediamine, and bis(4-aminocyclohexyl)methane; aromatic polyamines such as m-phenylenediamine or p-phenylenediamine, bis(4-aminophenyl)methane, and 2,4- or 2,6-toluenediamine; glucosamines such as deacetylated chitosan; and organosilicon compounds such as bis(3-aminopropyl)polydimethylsiloxane and bis(3-aminopropyl)polydiphenylsiloxane.

[0077] The content of compound (D) in the above-mentioned curable composition divided by the number of moles of the portion that reacts with the isocyanate group is typically 0.1 to 10 moles of compound (A) per 100 moles, preferably 0.3 to 8 moles, and more preferably 0.5 to 5 moles.

[0078] The curable composition described above preferably further comprises a polymerization initiator (E).

[0079] As one embodiment of the polymerization initiator (E) according to the present invention, a photopolymerization initiator is preferred. There are no particular limitations on the photopolymerization initiator, and examples include benzophenone, benzoyl, benzoin, ω-bromoacetophenone, chloroacetone, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, p-dimethylaminoacetophenone, p-dimethylaminoacetophenone, 2-chlorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis(diethylamino)benzophenone, michalcone, benzoin methyl ether, benzoin isobutyl ether, benzoin-n-butyl ether, benzoyl dimethyl ketal, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, etc. Carbonyl photopolymerization initiators such as ketones, methyl benzoyl carboxylate, 2,2-diethoxyacetophenone, 4-N,N'-dimethylacetophenone, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one; sulfide photopolymerization initiators such as diphenyl disulfide, dibenzyl disulfide, tetraethylthiuram disulfide, and tetramethylammonium monosulfide; acylphosphine oxide photopolymerization initiators such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide; quinone photopolymerization initiators such as benzoquinone and anthraquinone; sulfonyl chloride photopolymerization initiators; and thioxanthone photopolymerization initiators such as thioxanthone, 2-chlorothioxanthone, and 2-methylthioxanthone.

[0080] They can be used individually, or in combination of two or more. Among them, 1-hydroxycyclohexylphenyl ketone is preferred in terms of solubility in curable compositions.

[0081] The content of the photopolymerization initiator is preferably 0.2 to 5 parts by mass relative to 100 parts by mass of the total amount of compound (A), carboxylic anhydride (B), and polymerizable compound (C), more preferably 0.5 to 3 parts by mass. If the content is 0.2 to 5 parts by mass relative to 100 parts by mass of the total amount of compound (A), carboxylic anhydride (B), and polymerizable compound (C), a good balance between photocurability and the strength and adhesion of the resulting adhesive sheet is achieved, which is preferred.

[0082] [Manufacturing Method]

[0083] Examples of methods for manufacturing the above-described curable composition include, for instance, adding compound (C) to the mixture and stirring to mix, or adding compound (C) to the mixture and stirring to mix. When the curable composition contains compound (D), compound (D) can be added when compound (C) is added to the mixture or when the mixture is added to compound (C), or compound (D) can be added after stirring the mixture and compound (C). When the curable composition contains a polymerization initiator (E), polymerization initiator (E) can be added when compound (C) is added to the mixture or when the mixture is added to compound (C), or polymerization initiator (E) can be added after stirring the mixture and compound (C). Stirring and mixing can be performed using, for example, a mixer, with appropriate settings for temperature, stirring speed, etc.

[0084] <Cured product>

[0085] One embodiment of the present invention is a cured product obtained by photocuring the above-described curable composition. This cured product can be obtained by subjecting the above-described curable composition to treatments such as light irradiation or ultraviolet irradiation (hereinafter referred to as "light irradiation treatment").

[0086] The illuminance, frequency, and exposure time of the light irradiation treatment can be appropriately set according to the composition, quantity, and other state 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.

[0087] One embodiment of the present invention is a cured product obtained by photocuring the above-described curable composition followed by thermal curing. This cured product can be obtained by subjecting the above-described curable composition to photoirradiation treatment, followed by further thermal curing.

[0088] The temperature and time of heat curing can be appropriately set according to the composition, amount and other state of the curable composition to be 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.

[0089] Example

[0090] The present invention will be further described in detail below based on embodiments, but the present invention is not limited to these embodiments and may be implemented by appropriate modifications without changing its spirit. In the following description of embodiments, etc., unless otherwise specifically mentioned, "parts" means "parts by mass".

[0091] In an embodiment, the method for determining the complex elastic modulus to confirm photoreactivity is as follows.

[0092] Measurement equipment: Rheometer (Anton Paar: MCR-301)

[0093] Measurement temperature: 25℃

[0094] Measurement mode: Vibration mode

[0095] Measuring fixture: 12mm parallel plate

[0096] Strain: 10%

[0097] Frequency: 1Hz

[0098] Illuminance (365nm): 70mJ / s

[0099] Exposure time: 100 seconds (80 seconds of stabilization followed by 100 seconds of irradiation).

[0100] [Modulation Example 1]

[0101] Polymer compound a was synthesized by operating as follows.

[0102] Add to a 300mL detachable flask TA22-976C (Co., Ltd.) The reaction mixture consisted of 185.96 g (45.2 mmol) of polyester diol, 14.04 g (90.5 mmol) of 2-methacryloyloxyethyl isocyanate (MOI), and 0.14 g (0.22 mmol) of dibutyltin dilaurate. The mixture was stirred at an internal temperature of 60 °C for 2 hours. The reaction was confirmed to be complete by the disappearance of the isocyanate peak using IR spectroscopy, yielding the target polymerizable compound a.

[0103] [Example 1]

[0104] 19.998 g of 2-methacryloyloxyethyl isocyanate (MOI) and methacrylic anhydride (MAA) were added to a container and placed in a rotary mixer. The mixture was stirred at 2000 rpm for 7 minutes to obtain mixture 1 of Example 1.

[0105] [Examples 2-6, Comparative Example 1]

[0106] The compositions were changed to those in Table 1 below. Otherwise, the same procedure as in Example 1 was followed to obtain mixtures 2 to 6 of Examples 2 to 6 and comparative mixture 1 of Comparative Example 1.

[0107] [Table 1]

[0108]

[0109] [Example 7]

[0110] 15.00 g of polymeric compound a prepared in Preparation Example 1, 15.00 g of mixture 1, and 0.60 g of 1-hydroxycyclohexyl-1-ylphenyl ketone (Irgacure (registered trademark) 184 (Irg184): manufactured by BASF) as a photopolymerization initiator were mixed using a rotary mixer at 2000 rpm for 7 minutes to obtain the curable composition of Example 7.

[0111] [Examples 8-12, Comparative Example 2]

[0112] Instead of mixture 1, the mixtures listed in Table 2 below were used. Otherwise, the same procedures were followed as in Example 7 to obtain the curable compositions of Examples 8 to 12 and Comparative Example 2.

[0113] [Table 2]

[0114]

[0115] The complex modulus of elasticity of the cured products (resins) after curing each curable composition was determined using the method described above. The results are shown in Table 3 below. Figure 1 middle.

[0116] [Table 3]

[0117]

[0118] The results confirmed that the elastic modulus of the cured product increased with increasing amounts of methacrylic anhydride added to the mixture.

[0119] [Example 13 and Comparative Example 3]

[0120] Curable compositions with the compositions shown in Table 4 below were prepared. In the table, IBMA represents isobutyl methacrylate, 1,6-HD represents 1,6-hexanediol, and DBTDL represents dibutyltin dilaurate.

[0121] [Table 4]

[0122]

[0123] The obtained curable composition was coated onto a glass surface with a 250 μm thickness rod. After photocuring using an LED exposure machine at an illuminance of 50 mJ / s (365 nm) for 60 seconds, it was heated in an oven at 110 °C for 1 hour. The weight of the cured film obtained after heating was measured. The film was then immersed in a screw-type tube filled with acetone and stored at room temperature for 24 hours. After immersion, the remaining cured film in the screw-type tube was collected in a 500-mesh stainless steel mesh and dried in an oven at 110 °C 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 the weight of the cured film after acetone immersion and drying. The results of the gel fraction are shown in Table 5. It should be noted that the gel fraction is expressed by the following formula.

[0124] [Table 5]

[0125]

[0126] Gel fraction (%) = Weight of cured film after acetone impregnation and drying (g) / Weight of cured film after light curing and heating (g) × 100

[0127] 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 capable of reacting with the isocyanate group to the reaction system and heating it, crosslinking is formed by reacting with the two hydroxyl groups present in 1,6-HD. Thus, compared to the case where IBMA, which does not have isocyanate groups in its molecule, was used as a comparative example, the gel fraction after heating is higher, confirming the heat-induced reaction with 1,6-hexanediol.

[0128] [Examples 14-17 and Comparative Example 4]

[0129] Prepare curable compositions with the compositions shown in Table 6 below. In the table, AA represents acrylic anhydride.

[0130] [Table 6]

[0131]

[0132] The obtained curable composition was coated onto a glass surface with a 250 μm thickness rod. After photocuring using an LED exposure machine at an illuminance of 40 mJ / s (365 nm) for 50 seconds, it was heated on a hot plate at 150°C for 1 hour. The weight of the heated resin film was measured. The film was then impregnated in a screw-type tube filled with acetone and stored at room temperature for 24 hours. After impregnation, the remaining resin film in the screw-type tube was collected in a 500-mesh stainless steel mesh and dried in an oven at 100°C for 1 hour. The weight of the dried resin film was then measured. The gel fraction was calculated from the weight of the photocured-heated resin film and the weight of the acetone-impregnated-dried resin film using the above formula. The results of the gel fraction are shown in Table 7.

[0133] [Table 7]

[0134]

[0135] Based on the above results, Examples 14-17 showed higher gel fractions compared to Comparative Example 4, confirming the heat-induced reaction with 1,6-hexanediol.

Claims

1. A mixture comprising a compound (A) comprising one or more isocyanate groups and an olefinic unsaturated group, and a carboxylic anhydride (B) comprising an olefinic unsaturated group, wherein the carboxylic anhydride (B) comprises 0.001 to 10% by mass of the carboxylic anhydride (B) relative to 100% by mass of the total of said compound (A) and said carboxylic anhydride (B).

2. The mixture according to claim 1, wherein the compound (A) is represented by the following general formula (1) or general formula (2), In general formula (1) or general formula (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 It can be an alkylene group having 1 to 10 carbon atoms that may have substituents, or a group formed by replacing the single bond between the carbon atoms of the alkylene group with an ether bond; the two Rs in general formula (2) 1 They can be the same or different, 2 Rs 3 They can be the same or different.

3. The mixture according to claim 1 or 2, wherein the compound (A) is selected from any one 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 compound (A) is 2-methacryloyloxyethyl isocyanate.

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

6. A curable composition comprising the mixture of claim 1 or 2 and a polymeric 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 of claim 6.

9. A cured product obtained by photocuring the curable composition of claim 6 followed by thermocuring.

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