Compound, thermal base generator, reactive composition, and reaction product

Abstract

To provide a compound capable of preparing a reactive composition excellent in reactivity of a base-reactive compound when heated.SOLUTION: The compound is represented by general formula (1), wherein X is O or S, R1, R2 and R3 are each a monovalent organic group, at least one of R1, R2 and R3 has an aminopyridine skeleton, and the N atom in the amino group is bonded to the P atom in general formula (1). [Chemical Formula 1] SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to compounds, thermal base generators, reactive compositions and reaction products. [Background technology]

[0002] Thermopolymerizable materials, which are polymerized by heating, and photopolymerizable materials, which are polymerized by irradiation with light, are widely used in practice because the polymerization reaction can be precisely controlled with relatively simple operations, and they occupy an important position in, for example, the fields of electronic materials and printing materials.

[0003] Known thermally polymerizable materials and photopolymerizable materials include those based on a base catalyst system that contains a base generator that generates a base upon heating or irradiation with light, and a monomer or oligomer that polymerizes under the action of a base. For example, known thermal base generators and photobase generators include ionic types that correspond to salts of carboxylic acids with strong bases such as guanidine (see, for example, Patent Document 1 and Non-Patent Document 1). In such ionic base generators, a decarboxylation reaction occurs at the carboxy group upon heating or exposure to light, and the strong base that formed a salt with the carboxy group is liberated, thereby generating a base.

[0004] However, although such ionic base generators have high reactivity, they have problems such as low storage stability and low solubility, and further, resin compositions using such ionic photobase generators also have problems such as low stability.

[0005] In response to this, non-ionic base generators have also been investigated. Known examples of non-ionic photobase generators include carbamates with a nitrobenzyl skeleton, which undergo a decarboxylation reaction upon exposure to light, liberating a primary amine or a secondary amine to generate a base (see, for example, Non-Patent Document 2). Such non-ionic photobase generators solve the problems associated with ionic base generators. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2019 / 162981 [Non-patent literature]

[0007] [Non-Patent Document 1] K.Arimitsu,R.Endo,Chem.Mater.2013,25,4461-4463. [Non-patent document 2] JFCameron,JMJFrechet,J.Am.Chem.Soc.1991,113,4303. Summary of the Invention [Problem to be solved by the invention]

[0008] In addition to the base generators described in the above-mentioned patent documents and non-patent documents, there is a demand for a thermal base generator that can prepare a reactive composition that exhibits excellent reactivity of a base-reactive compound (e.g., an epoxy compound) when heated.

[0009] An object of the present disclosure is to provide a base generator and compound capable of preparing a reactive composition that exhibits excellent reactivity of a base-reactive compound when heated, a reactive composition that exhibits excellent reactivity of a base-reactive compound when heated, and a reaction product obtained by reacting this reactive composition. [Means for solving the problem]

[0010] Specific means for solving the above problems are as follows. <1> A compound represented by the following general formula (1):

[0011] [ka]

[0012] In general formula (1), X is an oxygen atom or a sulfur atom, R1, R2, and R3 are monovalent organic groups, at least one of R1, R2, and R3 has an aminopyridine skeleton, and the nitrogen atom in the amino group is bonded to the phosphorus atom in general formula (1). <2> In the general formula (1), one or two of R1, R2, and R3 have an aminopyridine skeleton, and the nitrogen atom in the amino group is bonded to the phosphorus atom in the general formula (1). <1> The compound described in <3> At least one of R1, R2, and R3 is an aryl group which may have a substituent. <1> or <2> The compound described in <4> At least one of R1, R2, and R3 is a group represented by R4-Y-*, where R4 is a monovalent organic group having 1 to 10 carbon atoms, and Y is an oxygen atom, a sulfur atom, or -N(R X )-(R x is a monovalent organic group) or a methylene group, and * is the bonding position to the phosphorus atom <1> The compound described in <5> A compound represented by the following general formula (2) or (3): <1> ~ <3> Any one of the compounds.

[0013] [ka]

[0014] In general formula (2) and general formula (3), each X is independently an oxygen atom or a sulfur atom; each R is independently a monovalent organic group; and n is an integer of 0-5. <6> It is a compound represented by the following general formula (4): <1> ~ <3> Any one of the compounds.

[0015] [ka] In the general formula (4), X is an oxygen atom or a sulfur atom, R4 is a monovalent organic group having 1 to 10 carbon atoms, and Y is an oxygen atom, a sulfur atom, or —N(R X )-(R xis a monovalent organic group) or a methylene group; each R is independently a monovalent organic group; and n is an integer of 0 to 5. <7> The compound represented by the general formula (4) is a compound represented by the following general formula (4-1), (4-2), (4-3) or (4-4): <6> Compound.

[0016] [ka] [ka] In the general formula (4-1), (4-2), (4-3) or (4-4), X is independently an oxygen atom or a sulfur atom, and R x is a monovalent organic group, each R is independently a monovalent organic group, and n is an integer of 0 to 5. <8> A thermal base generator comprising a compound represented by the following general formula (1):

[0017] [ka]

[0018] In general formula (1), X is an oxygen atom or a sulfur atom, R1, R2, and R3 are monovalent organic groups, at least one of R1, R2, and R3 has an aminopyridine skeleton, and the nitrogen atom in the amino group is bonded to the phosphorus atom in general formula (1). <9> In the general formula (1), one or two of R1, R2, and R3 have an aminopyridine skeleton, and the nitrogen atom in the amino group is bonded to the phosphorus atom in the general formula (1). <8> The thermal base generator according to claim 1. <10> At least one of R1, R2, and R3 is an aryl group which may have a substituent. <8> or <9> The thermal base generator according to claim 1. <11> At least one of R1, R2, and R3 is a group represented by R4-Y-*, where R4 is a monovalent organic group having 1 to 10 carbon atoms, and Y is an oxygen atom, a sulfur atom, or -N(R X )-(Rx is a monovalent organic group) or a methylene group, and * is the bonding position to the phosphorus atom <8> ~ <10> 1. The thermal base generator according to claim 1 . <12> The compound represented by the general formula (1) is a compound represented by the following general formula (2) or (3): <8> ~ <10> 1. The thermal base generator according to claim 1 .

[0019] [ka]

[0020] In general formula (2) and general formula (3), each X is independently an oxygen atom or a sulfur atom; each R is independently a monovalent organic group; and n is an integer of 0-5. <13> It is a compound represented by the following general formula (4): <8> ~ <10> Any one of the thermal base generators. [ka]

[0021] In the general formula (4), X is an oxygen atom or a sulfur atom, R4 is a monovalent organic group having 1 to 10 carbon atoms, and Y is an oxygen atom, a sulfur atom, or —N(R X )-(R x is a monovalent organic group) or a methylene group; each R is independently a monovalent organic group; and n is an integer of 0 to 5. <14> The compound represented by the general formula (4) is a compound represented by the following general formula (4-1), (4-2), (4-3) or (4-4): <8> ~ <10> Any one of the thermal base generators. [ka] [ka] In the general formula (4-1), (4-2), (4-3) or (4-4), X is independently an oxygen atom or a sulfur atom, and R xis a monovalent organic group, each R is independently a monovalent organic group, and n is an integer of 0 to 5. <15> <8> ~ <14> a thermal base generator according to any one of the above items; a base-reactive compound; Including, The base-reactive compound is a reactive composition which is a compound having a functional group that is converted into a group that exhibits reactivity by the action of a base, or a compound having a group that reacts by the action of a base. <16> <15> A reaction product obtained by reacting the reactive composition described in 1. [Effects of the Invention]

[0022] According to one embodiment of the present invention, it is possible to provide a base generator and a compound capable of preparing a reactive composition that exhibits excellent reactivity of a base-reactive compound when heated, a reactive composition that exhibits excellent reactivity of a base-reactive compound when heated, and a reaction product obtained by reacting this reactive composition. DETAILED DESCRIPTION OF THE INVENTION

[0023] In the present disclosure, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In the numerical ranges described in stages in this disclosure, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. In addition, in the numerical ranges described in this disclosure, the upper or lower limit value of that numerical range may be replaced with a value shown in the examples. In the present disclosure, each component may contain multiple substances corresponding to the component. When multiple substances corresponding to each component are present in the composition, the content of each component means the total content of the multiple substances present in the composition, unless otherwise specified.

[0024] [Thermal base generator] The thermal base generator of the present disclosure includes a compound represented by the following general formula (1):

[0025] [ka]

[0026] In general formula (1), X is an oxygen atom or a sulfur atom, R1, R2, and R3 are monovalent organic groups, at least one of R1, R2, and R3 has an aminopyridine skeleton, and the nitrogen atom in the amino group is bonded to the phosphorus atom in general formula (1).

[0027] The thermal base generator of the present disclosure generates a base, specifically a base having an aminopyridine skeleton, upon heating. The generated base converts functional groups contained in the base-reactive compound in the reactive composition, making them reactive, or the generated base causes functional groups contained in the base-reactive compound to react. Therefore, by heating the reactive composition to generate a base, the base-reactive compound contained in the reactive composition reacts to give a reaction product.

[0028] Furthermore, the compound represented by general formula (1) is a non-ionic thermal base generator, and unlike conventional ionic thermal base generators, it has relatively high storage stability and solubility, and reactive compositions using it are highly stable. Furthermore, when the base-reactive compound is an epoxy compound, the reactivity of the base-reactive compound is good when heated, and for example, the reaction of the base-reactive compound can proceed at a relatively low temperature. Furthermore, the compound represented by general formula (1) contained in the thermal base generator of the present disclosure does not undergo decarboxylation upon heating. This makes it possible to suppress the generation of bubbles due to carbon dioxide generation and the reduction in strength of the reaction product when it is cured.

[0029] X is an oxygen atom or a sulfur atom, and from the viewpoint of excellent reactivity of the base-reactive compound when heated, X is preferably an oxygen atom.

[0030] It is preferred that at least one of R1, R2, and R3 has an aminopyridine skeleton, and that the nitrogen atom in the amino group is bonded to the phosphorus atom in general formula (1), and that one or two of R1, R2, and R3 have an aminopyridine skeleton, and that the nitrogen atom in the amino group is bonded to the phosphorus atom in general formula (1).From the viewpoint of easily obtaining a reaction product that has excellent reactivity of the base-reactive compound when heated and, for example, excellent hardness, it is more preferred that two of R1, R2, and R3 have an aminopyridine skeleton, and that the nitrogen atom in the amino group is bonded to the phosphorus atom in general formula (1).

[0031] Examples of the aminopyridine skeleton include a 4-aminopyridine skeleton and a 4-alkylaminopyridine skeleton such as a 4-methylaminopyridine skeleton.

[0032] At least one of R1, R2, and R3 may be an aryl group which may have a substituent, or one or two of R1, R2, and R3 may be an aryl group which may have a substituent. From the viewpoint of providing a reaction product which has excellent reactivity of the base-reactive compound when heated and which is excellent in, for example, hardness, it is preferred that one of R1, R2, and R3 is an aryl group which may have a substituent, and the remaining two have an aminopyridine skeleton, and the nitrogen atom in the amino group is bonded to the phosphorus atom in general formula (1).

[0033] When the aryl group has a substituent, the substituent may be an electron-donating group or an electron-withdrawing group.

[0034] Examples of the electron-donating group include an alkyl group, an alkoxy group, an aryloxy group, a dialkylamino group, a diarylamino group, an alkylarylamino group, an alkylthio group, an arylthio group, -NHCOR (wherein R is a hydrocarbon group which may have a substituent), and -OCOR (wherein R is a hydrocarbon group which may have a substituent). Among these, the electron donating group is preferably an alkoxy group such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, or an n-butoxy group.

[0035] Examples of the electron-withdrawing group include a carboxy group, a cyano group, an aldehyde group, an ester group, a nitro group, a halogen atom, a phenyl group, an acyl group, and a sulfone group. Of these, the electron-withdrawing group is preferably a nitro group.

[0036] The position of the substituent in the aryl group is not particularly limited, and may be the ortho-, meta- or para-position.

[0037] At least one of R1, R2, and R3 may be a group represented by R4-Y-*, and one or two of R1, R2, and R3 may be a group represented by R4-Y-*. R4 is a monovalent organic group having 1 to 10 carbon atoms, and Y is an oxygen atom, a sulfur atom, or -N(R X )-(R x is a monovalent organic group) or a methylene group, and * is the bonding position to the phosphorus atom. R4 is preferably an alkyl group having 1 to 10 carbon atoms which may have a substituent, more preferably an alkyl group having 2 to 6 carbon atoms which may have a substituent, and even more preferably an alkyl group having 4 to 6 carbon atoms which may have a substituent. R x is preferably an alkyl group having 1 to 10 carbon atoms which may have a substituent, more preferably an alkyl group having 1 to 6 carbon atoms which may have a substituent, and even more preferably an alkyl group having 1 or 2 carbon atoms which may have a substituent.

[0038] It is preferred that one of R1, R2, and R3 is an aryl group which may have a substituent, one of R1, R2, and R3 is a group represented by R4-Y-*, and the remaining one of R1, R2, and R3 has an aminopyridine skeleton, and the nitrogen atom in the amino group is bonded to the phosphorus atom in general formula (1).

[0039] The compound represented by general formula (1) is preferably a compound represented by the following general formula (2) or (3).

[0040] [ka]

[0041] In general formula (2) and general formula (3), each X is independently an oxygen atom or a sulfur atom; each R is independently a monovalent organic group; and n is an integer of 0-5.

[0042] R may be an electron-donating group or an electron-withdrawing group, and is preferably an alkoxy group such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, or an n-butoxy group. n may be an integer of 0 to 2, and may be 0 or 1. When n is 1, R is preferably located in the para position.

[0043] The compound represented by general formula (1) is preferably a compound represented by the following general formula (4).

[0044] [ka]

[0045] In the general formula (4), X is an oxygen atom or a sulfur atom, R4 is a monovalent organic group having 1 to 10 carbon atoms, and Y is an oxygen atom, a sulfur atom, or —N(R X )-(R x is a monovalent organic group) or a methylene group; each R is independently a monovalent organic group; and n is an integer of 0 to 5. R4 is preferably an alkyl group having 1 to 10 carbon atoms which may have a substituent, more preferably an alkyl group having 2 to 6 carbon atoms which may have a substituent, and even more preferably an alkyl group having 4 to 6 carbon atoms which may have a substituent. R x is preferably an alkyl group having 1 to 10 carbon atoms which may have a substituent, more preferably an alkyl group having 1 to 6 carbon atoms which may have a substituent, and even more preferably an alkyl group having 1 or 2 carbon atoms which may have a substituent. Preferred R and n in the general formula (4) are the same as preferred R and n in the general formulas (2) and (3).

[0046] The compound represented by general formula (4) is preferably a compound represented by the following general formula (4-1), (4-2), (4-3) or (4-4).

[0047] [ka]

[0048] [ka]

[0049] X and R in general formula (4-1), (4-2), (4-3) or (4-4) x , R and n are X, R in general formula (4). x , R and n.

[0050] [Reactive composition] The reactive composition of the present disclosure comprises the thermal base generator of the present disclosure and a base-reactive compound, wherein the base-reactive compound is a compound having a functional group that is converted into a group that exhibits reactivity by the action of a base, or a compound having a group that reacts by the action of a base. The compound having a functional group that is converted into a group that exhibits reactivity by the action of a base may be a compound having only one of the above-mentioned functional groups, or may be a compound having two or more of the above-mentioned functional groups, or may be a mixture thereof. The compound having a group that reacts by the action of a base may be a compound having only one group that reacts by the action of a base, or may be a compound having two or more groups that react by the action of a base, or may be a mixture thereof.

[0051] For example, by heating the reactive composition of the present disclosure, a base is generated from the thermal base generator, and the functional group contained in the base-reactive compound in the reactive composition is converted by the action of the generated base to become reactive, or the functional group contained in the base-reactive compound is reacted by the action of the generated base. Therefore, by heating the reactive composition to generate a base, the base-reactive compound contained in the reactive composition reacts to give a reaction product.

[0052] The reactive composition is a curable composition that is cured by the reaction of the base-reactive compound upon heating. The reactive composition may be used to produce a cured product by heating.

[0053] The reactive composition of the present disclosure may contain only one type of thermal base generator, or two or more types, and when two or more types are contained, the combination and ratio thereof can be set arbitrarily.

[0054] In the reactive composition of the present disclosure, the content of the thermal base generator is preferably 1 mol % to 40 mol %, more preferably 2 mol % to 35 mol %, and even more preferably 3 mol % to 10 mol %, relative to the functional group contained in the base-reactive compound. When the content of the thermal base generator is 1 mol % or more, the reaction of the base-reactive compound proceeds more easily. Furthermore, when the content of the thermal base generator is 40 mol % or less, excessive use of the thermal base generator is suppressed.

[0055] (Base-reactive compounds) The reactive composition of the present disclosure contains a base-reactive compound. The base-reactive compound is a compound having a functional group that is converted into a reactive group by the action of a base (sometimes referred to as "base-reactive compound (9-2a)" in the present disclosure), or a compound having a group that reacts by the action of a base (sometimes referred to as "base-reactive compound (9-2b)" in the present disclosure). The base-reactive compound (9-2b) differs from the base-reactive compound (9-2a) in that the reactive group is not a functional group that is converted into a reactive group by the action of a base.

[0056] Examples of reactions that proceed in the base-reactive compound include addition polymerization and condensation polymerization (polycondensation polymerization).

[0057] The base-reactive compound may be, for example, any of a monomer, an oligomer, and a polymer, and may be any of a low molecular weight compound and a high molecular weight compound.

[0058] As the base-reactive compound, known compounds can be used, for example, the base-reactive compounds described in JP-A-2011-80032, although this is just one example.

[0059] Examples of the base-reactive compound (9-2a) include compounds that are decomposed by the action of a base and have a functional group converted into a reactive group. Examples of such base-reactive compounds (9-2a) include compounds having a carbonate skeleton (-OC(=O)-O-), photosensitive polyimides, etc.

[0060] Examples of the base-reactive compound (9-2b) include epoxy compounds, silicone resins, alkoxysilane compounds, (meth)acrylate compounds, and thiol compounds. In the present disclosure, the term "(meth)acrylate" is a concept that encompasses both "acrylate" and "methacrylate."

[0061] The reactive composition of the present disclosure may contain only one type of base-reactive compound, or two or more types, and when two or more types are contained, the combination and ratio thereof can be set arbitrarily.

[0062] The content of the base-reactive compound in the reactive composition of the present disclosure may be 40% by mass to 95% by mass, or may be 45% by mass to 90% by mass, based on the total amount of nonvolatile components in the reactive composition.

[0063] <Epoxy compounds> The reactive composition of the present disclosure preferably contains an epoxy compound as a base-reactive compound. The epoxy compound may contain an epoxy compound having one or more epoxy groups in one molecule, and preferably contains an epoxy compound having two or more epoxy groups. The epoxy compound can be selected arbitrarily depending on the purpose. The epoxy compound may be, for example, any of a monomer, an oligomer, and a polymer, and may be any of a low molecular weight compound and a high molecular weight compound.

[0064] Since the reactive composition of the present disclosure contains an epoxy compound, when the reactive composition is heated, the reactivity of the epoxy compound is good even at a relatively low heating temperature (for example, 140°C or lower).

[0065] The epoxy compound is not particularly limited, and examples thereof include diglycidyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, diethylene glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, alkylphenol glycidyl ether, polyethylene glycol diglycidyl ether, and tripropylene glycol diglycidyl ether. , neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin polyglycidyl ether, diglycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, cresyl glycidyl ether, aliphatic diglycidyl ethers, polyfunctional glycidyl ethers, tertiary fatty acid monoglycidyl ethers, spiroglycol diglycidyl ether, glycidylpropoxytrimethoxysilane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, etc. These epoxy compounds may be halogenated or hydrogenated.

[0066] (Other ingredients) The reactive composition of the present disclosure may further contain other components in addition to the base-reactive compound and the thermal base generator. The other components are not particularly limited as long as they do not impair the effects of the present invention, and can be selected arbitrarily depending on the purpose. The reactive composition may contain only one type of other component, or two or more types. When there are two or more types, the combination and ratio thereof can be set arbitrarily.

[0067] Examples of the other components include a filler, a pigment, and a solvent. When the reactive composition is irradiated with light, the other components may include a photobase generator and a sensitizer.

[0068] <Filling material> The reactive composition of the present disclosure may contain a filler, which can adjust properties such as the viscosity of the reactive composition itself and the strength of the reactive composition after reaction (the reaction product described below). The filler may be any known filler without any particular limitation. For example, the filler may be fibrous, plate-like, or granular, and the shape, size, and material thereof may all be appropriately selected depending on the purpose. The reactive composition may contain only one type of filler, or two or more types, and when two or more types are contained, the combination and ratio thereof can be set arbitrarily. The content of the filler in the reactive composition is not particularly limited and may be adjusted appropriately depending on the purpose.

[0069] <Pigments> The reactive composition of the present disclosure may contain a pigment. By including a pigment, for example, light transmittance and the like can be adjusted. The pigment contained in the reactive composition may be a known pigment, and may be, for example, any of white, blue, red, yellow, green, etc., without any particular limitation. The reactive composition may contain only one type of pigment, or two or more types, and when two or more types are contained, the combination and ratio thereof can be set arbitrarily. The content of the pigment in the reactive composition is not particularly limited and may be adjusted appropriately depending on the purpose.

[0070] <Solvent> The reactive composition of the present disclosure may contain a solvent, which improves handling properties. The solvent is not particularly limited and may be appropriately selected in consideration of the solubility, stability, etc. of the base-reactive compound and the base generator. The solvent is not particularly limited, and examples thereof include halogenated hydrocarbons such as dichloromethane and chloroform; aromatic hydrocarbons such as toluene, o-xylene, m-xylene, and p-xylene; aliphatic hydrocarbons such as hexane, heptane, and octane; carboxylic acid esters such as ethyl acetate and butyl acetate; ethers such as diethyl ether, tetrahydrofuran (THF), and 1,2-dimethoxyethane (dimethylcellosolve); ketones such as acetone, methyl ethyl ketone (MEK), cyclohexanone, and cyclopentanone; nitriles such as acetonitrile; and amides such as N,N-dimethylformamide (DMF) and N,N-dimethylacetamide.

[0071] The reactive composition may contain only one type of solvent, or two or more types of solvents. When two or more types of solvents are contained, the combination and ratio of the solvents can be set arbitrarily.

[0072] In the reactive composition, the content of the solvent is preferably 3 to 20 times by mass, more preferably 4 to 15 times by mass, and even more preferably 5 to 10 times by mass, relative to the content of the base-reactive compound. When the content of the solvent is within such a range, the handleability of the reactive composition is further improved.

[0073] <Sensitizer> The reactive compositions of the present disclosure may contain a sensitizer. The sensitizer is not particularly limited, and examples thereof include benzophenone, naphthoquinone, anthraquinone, xanthene, thioxanthene, xanthone, thioxanthone, anthracene, phenanthrene, phenanthroline, pyrene, pentacene, and derivatives thereof. The sensitizer may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof can be set arbitrarily. The content of the sensitizer in the reactive composition is not particularly limited and may be adjusted appropriately.

[0074] The reactive composition can be obtained by blending a base-reactive compound, a thermal base generator, and, if necessary, other components. After blending the components, the resulting mixture may be used as the reactive composition as is, or may be used as the reactive composition after, if necessary, performing a known purification procedure or the like.

[0075] When blending the components, all the components may be added and then mixed, or some of the components may be added sequentially while mixing, or all the components may be added sequentially while mixing. The mixing method is not particularly limited, and may be appropriately selected from known methods such as a method of mixing by rotating a stirrer or stirring blades, a method of mixing using a mixer, or a method of mixing by adding ultrasound.

[0076] The temperature during blending is not particularly limited as long as the blended components do not deteriorate, and can be, for example, 3°C to 30°C. The blending time is not particularly limited as long as the blended components do not deteriorate, and can be, for example, 30 seconds to 1 hour. However, these compounding conditions are merely examples.

[0077] <Reaction products> The reaction product of the present disclosure is obtained by reacting the above-described reactive composition. A method for producing the reaction product of the present disclosure will be described later in the method for producing the reaction product of the present disclosure. The shape of the reaction product of the present disclosure can be selected arbitrarily depending on the purpose, for example, in the form of a film or a line.

[0078] (Method for producing reaction product) The method for producing a reaction product of the present disclosure includes a step of heating the reactive composition to generate the base from the thermal base generator. The base-reactive compound contained in the reactive composition becomes reactive by converting a functional group contained in the base-reactive compound under the action of the generated base, or the functional group contained in the base-reactive compound reacts under the action of the generated base. Therefore, by heating the reactive composition to generate a base, the base-reactive compound contained in the reactive composition reacts to obtain a reaction product.

[0079] The reactive composition may be applied to an object by a known method, and then optionally pre-baked (e.g., dried) to form a reactive composition layer, followed by post-baking. A base is generated by post-baking, and the base-reactive compound reacts with the generated base to produce a reaction product.

[0080] For example, when producing a film-like reaction product, the reactive composition may be applied to a target object using a coating means such as a spin coater, air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater, Mayer bar coater, or kiss coater, or an applicator, or the reactive composition may be adhered to a target object by immersing the target object in the reactive composition. For example, when producing a film-like or linear reaction product, the reactive composition may be attached to the target object by using a printing method such as screen printing, flexographic printing, offset printing, inkjet printing, dispenser printing, jet dispenser printing, gravure printing, gravure offset printing, or pad printing.

[0081] The pre-baking may be carried out under conditions of, for example, 40° C. to 120° C. and 30 seconds to 10 minutes, and is not particularly limited.

[0082] The post-baking may be carried out, for example, at 50°C to 180°C for 20 minutes to 2 hours. When an epoxy compound is used as the base-reactive compound, the post-baking may be carried out preferably at 70°C to 140°C for 20 minutes to 2 hours, and more preferably at 90°C to 120°C for 20 minutes to 2 hours.

[0083] The reactive composition layer may be irradiated with light after pre-baking and before post-baking. By irradiating with light, a base generated from the photobase generator upon irradiation with light promotes decomposition of the thermal base generator and reaction of the base-reactive compound.

[0084] The wavelength of the light irradiated onto the reactive composition is not particularly limited and may be, for example, a wavelength in the ultraviolet to visible light range. The wavelength of the light irradiated onto the reactive composition may be 10 nm or more, 200 nm or more, or 300 nm or more. Furthermore, the wavelength of the light irradiated onto the reactive composition may be 600 nm or less, 500 nm or less, or 400 nm or less.

[0085] The illuminance of the light irradiated onto the reactive composition is, for example, 1 mW / cm 2 ~100mW / cm 2 and preferably 5 mW / cm 2 ~80mW / cm 2 More preferably, it is 10 mW / cm 2 ~60mW / cm 2 It is more preferable that: The amount of light irradiated onto the reactive composition is, for example, 100 mJ / cm 2 2 ~20,000mJ / cm 2 and preferably 200 mJ / cm 2 ~15000mJ / cm 2 More preferably, it is 300 mJ / cm 2 ~12000mJ / cm 2 It is more preferable that: However, the light irradiation conditions given here are merely examples and are not limited to these.

[0086] The thickness of the reaction product may be appropriately set depending on the purpose and is not particularly limited. The thickness of the reaction product is, for example, preferably 1 μm to 500 μm, more preferably 5 μm to 200 μm. To form a reaction product of such a thickness, for example, the thickness of the reactive composition layer may be set to be equal to or greater than the thickness of the desired reaction product. [Example]

[0087] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples.

[0088] <Production of Compound (a)-1> First, as shown below, chlorodiphenylphosphine oxide (compound (X-1)) was reacted with 4-(methylamino)pyridine to produce compound (a)-1. 1.1 g (10 mmol) of 4-(methylamino)pyridine was placed in a 100 mL three-neck flask and dissolved in 30 mL of ultra-dehydrated dichloromethane. Then, 1.0 g (10 mmol) of triethylamine was added, and the flask was purged with nitrogen. Compound (X-1) (2.7 g, 20 mmol) dissolved in 5.0 mL of ultra-dehydrated dichloromethane was slowly added dropwise with stirring, and the mixture was stirred at room temperature for 24 hours. After the reaction was complete, the organic layer was washed twice with aqueous NaHCO3 and twice with aqueous NaCl, and then dried over magnesium sulfate. The solvent was then removed by distillation, and the mixture was recrystallized (good solvent: methanol, poor solvent: ultra-pure water) and dried under reduced pressure to obtain the target compound (a)-1 as a pale yellow solid (yield: 1.9 g, 62%).

[0089] [ka]

[0090] The obtained compound (a)-1 1 H-NMR, 13 The analytical results by C-NMR, ESI-MS and FT-IR are shown in Table 1.

[0091] [Table 1]

[0092] <Production of Compound (a)-2> First, as shown below, dichlorophenylphosphine oxide (compound (X-2)) was reacted with 4-(methylamino)pyridine to produce compound (a)-2. 1.6 g (15 mmol) of 4-(methylamino)pyridine was placed in a 100 mL three-neck flask and dissolved in 40 mL of ultra-dehydrated dichloromethane. Then, 1.0 g (10 mmol) of triethylamine was added, and the flask was purged with nitrogen. Compound (X-2) (1.0 g, 20 mmol) dissolved in 5.0 mL of ultra-dehydrated dichloromethane was slowly added dropwise with stirring, and the mixture was stirred at room temperature for 24 hours. After the reaction was complete, the organic layer was washed twice with aqueous NaHCO3 and twice with aqueous NaCl, and then dried over magnesium sulfate. The solvent was evaporated, the residue was dissolved in chloroform, and then subjected to column chromatography (methanol:chloroform = 1:15) on silica gel washed with methanol. The product was then dried under reduced pressure to obtain the target compound (a)-2 as a white solid (yield: 0.57 g, 33%).

[0093] [ka]

[0094] The obtained compound (a)-2 1 H-NMR, 13 The analytical results by C-NMR, ESI-MS and FT-IR are shown in Table 2.

[0095] [Table 2]

[0096] <Production of Compound (a)-3> First, as shown below, 4-methoxyphenyldichlorophosphine oxide (compound (X-3)) was reacted with 4-(methylamino)pyridine to produce compound (a)-3. 2.3 g (22 mmol) of 4-(methylamino)pyridine was placed in a 100 mL three-neck flask and dissolved in 40 mL of ultra-dehydrated dichloromethane. 2.0 g (22 mmol) of triethylamine was then added, and the flask was purged with nitrogen. Compound (X-3) (1.5 g, 10 mmol) dissolved in 5.0 mL of ultra-dehydrated dichloromethane was slowly added dropwise with stirring, and the mixture was stirred at room temperature for 24 hours. After the reaction was complete, the organic layer was washed twice with aqueous NaHCO3 and aqueous NaCl, and then dried over magnesium sulfate. The solvent was evaporated, the residue was dissolved in chloroform, and then subjected to column chromatography (methanol:chloroform = 1:15) on silica gel washed with methanol. The product was then dried under reduced pressure to obtain the target compound (a)-3 as a white solid (yield: 1.9 g, 52%).

[0097] [ka]

[0098] The obtained compound (a)-3 1 H-NMR, 13 The analytical results by C-NMR, ESI-MS and FT-IR are shown in Table 3.

[0099] [Table 3]

[0100] <Production of Compound (a)-4> First, as shown below, dichlorophenylphosphine sulfide (compound (X-4)) was reacted with 4-(methylamino)pyridine to produce compound (a)-4. 2.3 g (22 mmol) of 4-(methylamino)pyridine was placed in a 100 mL three-neck flask and dissolved in 40 mL of ultra-dehydrated dichloromethane. 2.0 g (22 mmol) of triethylamine was then added, and the flask was purged with nitrogen. Compound (X-4) (1.5 g, 10 mmol) dissolved in 5.0 mL of ultra-dehydrated dichloromethane was slowly added dropwise with stirring, and the mixture was stirred at room temperature for 24 hours. After the reaction was complete, the organic layer was washed twice with aqueous NaHCO3 and aqueous NaCl, and then dried over magnesium sulfate. The solvent was removed, the residue was dissolved in chloroform, and then subjected to column chromatography (methanol:chloroform = 1:15) on silica gel washed with methanol. The product was then dried under reduced pressure to obtain the target compound (a)-4 as a white solid (yield: 1.9 g, 52%).

[0101] [ka]

[0102] The obtained compound (a)-4 1 H-NMR, 13 The analytical results by C-NMR, ESI-MS and FT-IR are shown in Table 4.

[0103] [Table 4]

[0104] <Production of Compound (a)-5> First, as shown below, dichlorophenylphosphine sulfide (compound (X-4)) was reacted with 4-(methylamino)pyridine and 1-pentanol to produce compound (a)-5. 1.6 g (15 mmol) of 4-(methylamino)pyridine was placed in a two-neck flask and dissolved in 40 mL of ultra-dehydrated dichloromethane. The flask was then conditioned under a nitrogen atmosphere. Compound (X-4) (2.9 g, 15 mmol) was placed in a vial and dissolved in 10 mL of ultra-dehydrated dichloromethane. Next, 3.9 g (38 mmol) of triethylamine and the solution of compound (X-4) in the vial were placed in a nitrogen atmosphere two-neck flask and stirred at room temperature for 24 hours. Next, 1.8 g (20 mmol) of 1-pentanol was added, and the mixture was stirred at room temperature for 24 hours. After the reaction was completed, the organic layer was washed twice with aqueous NaHCO3 and aqueous NaCl. The target compound (a)-5 was obtained as a yellow liquid (yield: 3.3 g, 69%).

[0105] [ka]

[0106] The obtained compound (a)-5 1 The results of the H-NMR analysis are shown in Table 5.

[0107] [Table 5]

[0108] [Example 1] (Thermal curing of epoxy compounds using compound (a)-1) First, a bisphenol A type epoxy resin (jER-828, 0.72 g), which is an epoxy compound having the structure shown below, compound (a)-1 (0.055 g, 5 mol % relative to the epoxy groups contained in jER-828), and 0.2 mL of chloroform were mixed to obtain reactive composition 1.

[0109] [ka]

[0110] The reactive composition 1 obtained above was applied to a silicon wafer by spin coating at 2000 rpm for 30 seconds. The coating film (reactive composition layer) was then pre-baked at 60°C for 3 minutes, and then post-baked at 100°C, 120°C, or 140°C for 60 minutes. In this manner, each coating film was finally converted into a reaction product (thickness: 11 μm to 16 μm) by polymerizing the epoxy compound jER-828.

[0111] [Example 2] (Thermal curing of epoxy compounds using compound (a)-2) Bisphenol A epoxy resin (jER-828, 0.72 g), compound (a)-2 (0.042 g, 5 mol % relative to the epoxy groups contained in jER-828), and 0.2 mL of chloroform were mixed to obtain reactive composition 2. An attempt was made to produce a reaction product (thickness 11 μm to 16 μm) in the same manner as in Example 1, except that reactive composition 2 was used.

[0112] [Example 3] (Thermal curing of epoxy compounds using compound (a)-3) Bisphenol A epoxy resin (jER-828, 0.72 g), compound (a)-3 (0.044 g, 5 mol % relative to the epoxy groups contained in jER-828), and 0.2 mL of chloroform were mixed to obtain reactive composition 3. An attempt was made to produce a reaction product (thickness 11 μm to 16 μm) in the same manner as in Example 1, except that reactive composition 3 was used.

[0113] [Example 4] (Thermal curing of epoxy compounds using compound (a)-4) Bisphenol A epoxy resin (jER-828, 0.72 g), compound (a)-4 (0.044 g, 5 mol % relative to the epoxy groups contained in jER-828), and 0.2 mL of chloroform were mixed to obtain reactive composition 4. An attempt was made to produce a reaction product (thickness 11 μm to 16 μm) in the same manner as in Example 1, except that reactive composition 4 was used.

[0114] (Pencil hardness test) The pencil hardness of the reaction products obtained in Examples 1 to 4 was measured. The results are shown in Table 6. It was confirmed that the pencil hardness could be changed by adjusting the types of compounds (a)-1 to (a)-4 used and the post-bake temperature.

[0115] [Table 6]

[0116] The conversion rates of epoxy groups in the reaction products obtained in Examples 1 to 4 were measured with a Fourier transform infrared spectrophotometer (FT-IR). The results are shown in Table 7.

[0117] [Table 7]

[0118] (Storage stability test) The difference in storage stability between a reactive composition containing a thermal base generator and a reactive composition containing a base was confirmed as follows. Reactive composition 2 prepared in Example 2 was stored under refrigerated conditions at 3°C, and after 5 days and 18 days of storage, the glass test tube was shaken or inverted to evaluate the storage stability of reactive composition 2. No increase in viscosity was observed in reactive composition 2 after 5 days of storage, but an increase in viscosity was observed after 18 days of storage. As a comparison with Reactive Composition 2, Reactive Composition 5 was obtained by mixing bisphenol A type epoxy resin (jER-828, 0.72 g), the base 4-(methylamino)pyridine (5 mol % relative to the epoxy groups contained in jER-828), and 0.2 mL of chloroform. Reactive Composition 5 was stored in a refrigerator at 3°C, and the storage stability of Reactive Composition 5 was evaluated. After storage for 5 days, Reactive Composition 5 lost its viscosity and had hardened. From the above results, it was confirmed that Reactive Composition 2 in which the base was made latent had good storage stability.

Claims

1. A compound represented by the following general formula (1): 【Chemistry 1】 In the general formula (1), X is an oxygen atom or a sulfur atom, and R １ , R ２ and R ３ is a monovalent organic group, and R １ , R ２ and R ３ At least one of the above has an aminopyridine skeleton, and the nitrogen atom in the amino group is bonded to the phosphorus atom in general formula (1).

2. In general formula (1), R １ , R ２ and R ３ The compound according to claim 1, wherein one or two of the following have an aminopyridine skeleton, and the nitrogen atom in the amino group is bonded to the phosphorus atom in general formula (1).

3. R １ , R ２ and R ３ The compound according to claim 1, wherein at least one of the groups is an aryl group which may have a substituent.

4. R １ , R ２ and R ３ At least one of ４ -Y-*, and R ４ is a monovalent organic group having 1 to 10 carbon atoms, and Y is an oxygen atom, a sulfur atom, or —N(R Ｘ )-(R ｘ The compound according to claim 1, wherein * is a bonding position to the phosphorus atom.

5. The compound according to claim 1, which is a compound represented by the following general formula (2) or (3): 【Chemistry 2】 In general formula (2) and general formula (3), each X is independently an oxygen atom or a sulfur atom, each R is independently a monovalent organic group, and n is an integer of 0 to 5.

6. The compound according to claim 1, which is a compound represented by the following general formula (4): 【Transformation 3】 In the general formula (4), X is an oxygen atom or a sulfur atom, and R ４ is a monovalent organic group having 1 to 10 carbon atoms, and Y is an oxygen atom, a sulfur atom, or —N(R Ｘ )-(R ｘ is a monovalent organic group) or a methylene group; each R is independently a monovalent organic group; and n is an integer of 0 to 5.

7. The compound according to claim 6, wherein the compound represented by the general formula (4) is a compound represented by the following general formula (4-1), (4-2), (4-3) or (4-4): 【Chemistry 4】 【Transformation 5】 In the general formula (4-1), (4-2), (4-3) or (4-4), each X is independently an oxygen atom or a sulfur atom, and R ｘ is a monovalent organic group, each R is independently a monovalent organic group, and n is an integer of 0 to 5.

8. A thermal base generator comprising a compound represented by the following general formula (1): 【Transformation 6】 In the general formula (1), X is an oxygen atom or a sulfur atom, and R １ , R ２ and R ３ is a monovalent organic group, and R １ , R ２ and R ３ At least one of the above has an aminopyridine skeleton, and the nitrogen atom in the amino group is bonded to the phosphorus atom in general formula (1).

9. In general formula (1), R １ , R ２ and R ３ The thermal base generator according to claim 8, wherein one or two of the following have an aminopyridine skeleton, and the nitrogen atom in the amino group is bonded to the phosphorus atom in general formula (1).

10. R １ , R ２ and R ３ The thermal base generator according to claim 8 , wherein at least one of the groups is an aryl group which may have a substituent.

11. R １ , R ２ and R ３ At least one of ４ -Y-*, and R ４ is a monovalent organic group having 1 to 10 carbon atoms, and Y is an oxygen atom, a sulfur atom, or —N(R Ｘ )-(R ｘ The thermal base generator according to claim 8, wherein * is a monovalent organic group or a methylene group, and * is the bonding position to the phosphorus atom.

12. 9. The thermal base generator according to claim 8, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2) or (3): 【Transformation 7】 In general formula (2) and general formula (3), each X is independently an oxygen atom or a sulfur atom, each R is independently a monovalent organic group, and n is an integer of 0 to 5.

13. 9. The thermal base generator according to claim 8, which is a compound represented by the following general formula (4): 【Transformation 8】 In the general formula (4), X is an oxygen atom or a sulfur atom, and R ４ is a monovalent organic group having 1 to 10 carbon atoms, and Y is an oxygen atom, a sulfur atom, or —N(R Ｘ )-(R ｘ is a monovalent organic group) or a methylene group; each R is independently a monovalent organic group; and n is an integer of 0 to 5.

14. The thermal base generator according to claim 8, wherein the compound represented by the general formula (4) is a compound represented by the following general formula (4-1), (4-2), (4-3) or (4-4): 【Chemistry 9】 【Chemistry 10】 In the general formula (4-1), (4-2), (4-3) or (4-4), each X is independently an oxygen atom or a sulfur atom, and R ｘ is a monovalent organic group, each R is independently a monovalent organic group, and n is an integer of 0 to 5.

15. The thermal base generator according to any one of claims 8 to 14, a base-reactive compound; Including, The base-reactive compound is a reactive composition which is a compound having a functional group that is converted into a group that exhibits reactivity by the action of a base, or a compound having a group that reacts by the action of a base.

16. A reaction product obtained by reacting the reactive composition of claim 15.

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