Method for producing resin having polymerizable unsaturated group, resin having polymerizable unsaturated group, curable resin composition, and cured product

Abstract

To provide a method for producing a resin having a polymerizable unsaturated group which can enhance heat resistance and adhesion of a cured product of a resin having a polymerizable unsaturated group as the final product, and also to provide the resin and a curable resin composition.SOLUTION: There is provided a method for producing a resin having a polymerizable unsaturated group, using a solvent represented by formula (1) having a biomass carbon content (pMC%) of 50% or more and containing an amide bond, wherein the method comprises mixing, in the presence of the solvent, an epoxy resin (A) with an unsaturated monocarboxylic acid (B). (In general formula (1), R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R3 represents a monovalent organic group having 4 to 10 carbon atoms.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a resin having a polymerizable unsaturated group, a resin having a polymerizable unsaturated group, a curable resin composition, and a cured product. [Background technology]

[0002] When mounting and soldering electronic components on a printed wiring board, solder resists are widely used as insulating materials to prevent solder from adhering to areas other than the mounted area and to form a coating that semi-permanently prevents oxidation or corrosion of wiring. Techniques for forming such solder resist patterns include photoresist methods, which can accurately form fine patterns, and among these, alkali-developable liquid photoresist methods are the mainstream, due to environmental considerations and other factors.

[0003] For example, Patent Document 1 discloses a photosensitive resin composition containing an active ester curing agent and a carboxyl group-containing radical polymerizable compound as a material used in an alkali development type photoresist method. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-214057 Summary of the Invention [Problem to be solved by the invention]

[0005] Recently, a new method for forming solder resist using an inkjet method has been proposed. This method does not require development, as is required with the alkaline development method, and therefore can reduce the number of steps, time, and consumables. However, when the viscosity of the ink used in the inkjet method decreases, the physical properties required for a solder resist film, such as heat resistance and chemical resistance, tend to deteriorate significantly. Furthermore, there is room for improvement in terms of excellent adhesion to wiring or substrates, in order to prevent defects such as cracking and peeling.

[0006] Therefore, an object of the present invention is to provide a resin and a curable resin composition that exhibit high heat resistance and adhesion. Another object of the present invention is to provide a cured product that has excellent heat resistance and adhesion. [Means for solving the problem]

[0007] The present inventors conducted extensive research to solve the above-mentioned problems, and as a result, they focused on solvents used in the production of resins and their cured products. They discovered that using a solvent with a specific structure can improve the heat resistance and adhesion of the resulting cured resin. They also discovered that because this solvent with a specific structure is naturally derived, it can reduce the environmental impact of resin production. Based on this knowledge, they discovered that the above-mentioned problems can be solved by using a solvent with a specific structure, and have completed the present invention. That is, the gist of the present invention that solves the above-mentioned problems is as follows.

[0008] [1] A method for producing a resin having a polymerizable unsaturated group, which has a biomass carbon content (%) (pMC%) of 50% or more and contains a solvent represented by the following general formula (1) having an amide bond: [ka] (In the above general formula (1), R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; R 3represents a monovalent organic group having 4 to 10 carbon atoms.

[0009] [2] The method for producing a resin having a polymerizable unsaturated group according to [1], wherein the epoxy resin (A) and the unsaturated monobasic acid (B) are mixed in the presence of the solvent.

[0010] [3] The method for producing a resin having a polymerizable unsaturated group according to [2], wherein the mixing ratio of the epoxy resin (A) and the unsaturated monobasic acid (B) is within a range of 0.20 to 1.05 mol of the unsaturated monobasic acid (B) per 1 mol of the epoxy group of the epoxy resin (A).

[0011] [4] The method for producing a resin having a polymerizable unsaturated group according to [1], comprising mixing an amide-imide resin (C) having an acid group and / or an acid anhydride group with a hydroxy(meth)acrylate compound (D) in the presence of the solvent.

[0012] [5] The method for producing a resin having a polymerizable unsaturated group according to [4], further comprising mixing a (meth)acrylate compound (E) having an epoxy group in the presence of the solvent.

[0013] [6] The method for producing a resin having a polymerizable unsaturated group according to [4] or [5], wherein the amide-imide resin (C) having an acid group and / or an acid anhydride group is prepared by reacting a polyisocyanate compound (c1) with a polycarboxylic acid (c2) or a polycarboxylic anhydride (c3) as reaction raw materials.

[0014] [7] The method for producing a resin having a polymerizable unsaturated group according to [6], wherein the polyisocyanate compound (c1) comprises an aliphatic diisocyanate compound, an alicyclic diisocyanate compound, or a modified product thereof.

[0015] [8] The method for producing a resin having a polymerizable unsaturated group according to [6] or [7], wherein the polycarboxylic acid (c2) or the polycarboxylic acid anhydride (c3) contains a tricarboxylic acid or a tricarboxylic acid anhydride.

[0016] [9] A resin having a polymerizable unsaturated group, which uses a solvent having an amide bond and represented by the following general formula (1) as an essential synthetic raw material, and has a biomass carbon content (%) (pMC%) of 15% or more in the entire resin having a polymerizable unsaturated group. [ka] (In the above general formula (1), R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; R 3 represents a monovalent organic group having 4 to 10 carbon atoms.

[0017]

[10] The resin having a polymerizable unsaturated group according to [9], which contains the solvent, an epoxy resin (A), and an unsaturated monobasic acid (B).

[0018]

[11] The resin having a polymerizable unsaturated group according to [9], which contains the solvent, an amide-imide resin (C) having an acid group and / or an acid anhydride group, and a hydroxy(meth)acrylate compound (D).

[0019]

[12] The resin having a polymerizable unsaturated group according to

[11] , further comprising a (meth)acrylate compound (E) having an epoxy group as the synthesis raw material.

[0020]

[13] The resin having a polymerizable unsaturated group according to

[11] or

[12] , wherein the amide-imide resin (C) having an acid group and / or an acid anhydride group is prepared by reacting a polyisocyanate compound (c1) with a polycarboxylic acid (c2) or a polycarboxylic anhydride (c3) as reaction raw materials.

[0021]

[14] A curable resin composition comprising the resin having a polymerizable unsaturated group according to any one of [9] to

[13] and a photopolymerization initiator.

[0022]

[15] The curable resin composition according to

[14] , further comprising a resin (X) having a polymerizable unsaturated group other than the resin having a polymerizable unsaturated group.

[0023]

[16] A cured product of the curable resin composition according to

[14] or

[15] .

[0024]

[17] An article having a coating film made of the cured product according to

[16] . [Effects of the Invention]

[0025] According to the present invention, it is possible to provide a method for producing a resin having a polymerizable unsaturated group, which can provide a cured product of the resin having excellent heat resistance and adhesion, as well as the resin and a curable resin composition. Furthermore, according to the present invention, a cured product having excellent heat resistance can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0026] (Terminology explanation) Unless otherwise specified in this specification, the following explanations of terms apply.

[0027] In this specification, examples of the "alkyl group" include a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, (n-)heptyl group, (n-)octyl group, (n-)nonyl group, (n-)decyl group, (n-)undecyl group, (n-)dodecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and cyclononyl group.

[0028] In this specification, examples of the "alkoxy group" include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a 2-ethylhexyloxy group, an octyloxy group, and a nonyloxy group.

[0029] In this specification, examples of the "alkylene group" include a methylene group, an ethylene group, a propylene group, a 1-methylmethylene group, a 1,1-dimethylmethylene group, a 1-methylethylene group, a 1,1-dimethylethylene group, a 1,2-dimethylethylene group, a propylene group, a butylene group, a 1-methylpropylene group, a 2-methylpropylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, and a dodecylene group.

[0030] In this specification, the "monovalent organic group" includes an alkyl group, an alkenyl group, an alkoxy group, and an aryl group. In addition, one or two or more non-adjacent -CH- groups in the alkyl group, alkenyl group, or alkoxy group may be substituted with -O-, -C(=O)-, -COO-, or -OCO-.

[0031] As used herein, "(meth)acrylate" means acrylate and / or methacrylate. Also, as used herein, "(meth)acryloyl" means acryloyl and / or methacryloyl. Furthermore, as used herein, "(meth)acrylic" means acrylic and / or methacrylic.

[0032] In this specification, the term "synthesis raw materials" broadly includes substances that play the role of chemical reaction auxiliaries, such as solvents and catalysts. These also include compounds that are used as reaction raw materials to obtain a target compound (including intermediate compounds) through a chemical reaction such as synthesis or decomposition, and that partially constitute the chemical structure of the target compound. The term "synthetic raw materials" is used in this specification because it is practically impossible to directly identify a target compound by its structure. On the other hand, the term "reaction raw materials" in this specification refers to compounds that are used to obtain a target compound by a chemical reaction such as synthesis or decomposition and that partially constitute the chemical structure of the target compound, and excludes substances that act as auxiliary agents in chemical reactions, such as solvents and catalysts.

[0033] In this specification, the term "resin" includes not only solid content but also a mixture of solid content and solvent.

[0034] In this specification, it is preferable that the "resin having a polymerizable unsaturated group" does not substantially contain an acid group.

[0035] The following describes in detail an embodiment of the present invention (hereinafter sometimes referred to as the "present embodiment"); however, the present invention is not limited to the following description and can be implemented in various modifications within the scope of its gist.

[0036] (Resin having polymerizable unsaturated groups) The resin having a polymerizable unsaturated group of this embodiment (hereinafter sometimes simply referred to as "the resin of this embodiment") is a resin having a polymerizable unsaturated group, which uses a solvent having an amide bond and represented by the following general formula (1) as an essential synthetic raw material, has a polymerizable unsaturated group, and has a biomass carbon content (%) (pMC%) of 15% or more in the entire resin. [ka] (In the above general formula (1), R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; R 3 represents a monovalent organic group having 4 to 10 carbon atoms.

[0037] In this embodiment, in the general formula (1), R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, and R 1 and R 2 Preferably, at least one of R is an alkyl group having 1 or 2 carbon atoms, 1 and R 2 and R are more preferably alkyl groups having 1 or 2 carbon atoms. 1 and R 2 It is more preferable that both of R have 1 carbon atom. 3is preferably an alkyl group, alkenyl group, alkoxy group or aryl group having 7 to 9 carbon atoms, and one or two or more non-adjacent -CH2- groups in the alkyl group, alkenyl group or alkoxy group may be substituted with -O-, -C(=O)-, -COO- or -OCO-. And R 1 and R 2 Both of these have one carbon atom, and R 3 is preferably an alkyl group, alkenyl group, alkoxy group or aryl group having 7 to 9 carbon atoms, and one or two or more non-adjacent -CH2- groups in the alkyl group, alkenyl group or alkoxy group may be substituted with -O-, -C(=O)-, -COO- or -OCO-. 3 The monovalent organic group may be linear, branched, or cyclic. The solvent represented by the general formula (1) may be a single compound or a mixed solvent in which a plurality of solvents represented by the general formula (1) are mixed.

[0038] Examples of the acid group contained in the resin of this embodiment include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Examples of the polymerizable unsaturated group contained in the resin of this embodiment include a (meth)acryloyl group, an allyl group, an isopropenyl group, a 1-propenyl group, a styryl group, a styrylmethyl group, a maleimide group, a vinyl ether group, etc. Among these, from the viewpoint of improving the insulation reliability, heat resistance, and adhesion of the finally obtained cured product of the resin having a polymerizable unsaturated group, it is preferable to use a carboxyl group as the acid group, and it is preferable to use a (meth)acryloyl group, an allyl group, an isopropenyl group, or a 1-propenyl group as the polymerizable unsaturated group.

[0039] The resin having a polymerizable unsaturated group of this embodiment is characterized by containing a solvent represented by the above formula (1) having an amide bond. In this embodiment, by using the solvent represented by the above formula (1), the heat resistance and adhesion of the cured product of the resin having a polymerizable unsaturated group obtained as a final product can be improved. Furthermore, since the solvent is derived from biomass raw materials, the environmental impact can be reduced by setting the biomass carbon content (%) (pMC%) to 50% or more. Therefore, the resin of this embodiment can be suitably used for insulating materials and resist materials such as solder resists.

[0040] In general, organic solvents are used as reaction raw materials in the manufacturing process of resins containing polymerizable unsaturated groups. When the resin is cured, the organic solvents are almost always released into the atmosphere (volatilized) without being recovered, which causes environmental impact. Furthermore, the release of volatile organic solvents (VOCs) contributes to worsening air pollution and global warming. However, in the resin having a polymerizable unsaturated group of this embodiment, the biomass carbon content (%) (pMC%) in the resin is 15% or more, and it is believed that such environmental burden can be reduced. From this perspective, the biomass carbon content (%) (pMC%) in the resin having a polymerizable unsaturated group is preferably 20% or more, and more preferably 30% or more. The upper limit of the biomass carbon content in the entire resin having a polymerizable unsaturated group is not particularly limited, but may be 90% or less or 80% or less.

[0041] When a compound having an epoxy group (including an epoxy resin (A) and a (meth)acrylate compound (E) having an epoxy group) is used as a component of the resin or curable resin composition of this embodiment, the epoxy group is generally introduced into the compound having an epoxy group industrially using a chlorine atom-containing compound such as epichlorohydrin. However, in this case, the amount of remaining chlorine atoms cannot be ignored, and there is a concern that at least one of insulation reliability, heat resistance, and adhesion may be reduced. Furthermore, if the resin contains chlorine, environmental hormones such as dioxins will be released when the resin is incinerated, which also causes an environmental load. Therefore, in this embodiment, it is also important to pay attention to the chlorine atom content of each material used.

[0042] The biomass carbon content (%) (pMC%) of the entire resin having a polymerizable unsaturated group of this embodiment is 15% or more, preferably 20% or more, and more preferably 30% or more. The upper limit of the biomass carbon content of the entire resin having a polymerizable unsaturated group is not particularly limited, but may be 90% or less or 80% or less.

[0043] The chlorine atom content can be measured by combusting and decomposing a sample to be measured (e.g., epoxy resin (A), (meth)acrylate compound (E) having an epoxy group, resin having a polymerizable unsaturated group, curable resin composition, etc.) at high temperature using a combustion tube combustion method, absorbing the decomposition gas into an absorption liquid, and quantifying the content by ion chromatography. More specifically, the chlorine atom content can be measured by the procedure described in the Examples.

[0044] In this embodiment, the means for reducing the chlorine atom content in the resin having a polymerizable unsaturated group include: (1) using at least one of the synthesis raw materials, catalysts, solvents, and additives used to obtain the resin having a polymerizable unsaturated group, and the further reaction materials, catalysts, solvents, and additives used to obtain the reaction materials, which do not contain chlorine atoms or contain a sufficiently small amount of chlorine atoms; (2) performing purification to remove chlorine atoms from at least one of the reaction materials, catalysts, solvents, and additives used to obtain the resin having a polymerizable unsaturated group, and the further reaction materials, catalysts, solvents, and additives used to obtain the reaction materials; etc. In addition, the above-mentioned purification can be, for example, purification under known conditions using preparative HPLC.

[0045] Although the specific chlorine atom content is not particularly limited, in order to make the chlorine atom content in the resin having a polymerizable unsaturated group 700 ppm by mass or less, it is useful to use epoxy resin (A) and (meth)acrylate compound (E) having an epoxy group that do not contain chlorine atoms or that contain a sufficiently small amount of chlorine atoms. More specifically, the chlorine atom content of the epoxy resin (A) and (meth)acrylate compound (E) having an epoxy group used in this embodiment is preferably 10 ppm by mass or less, particularly below the detection limit, as described below, in order to obtain the desired resin.

[0046] From the viewpoint of reducing the environmental impact, the resin having a polymerizable unsaturated group of this embodiment preferably has a biomass carbon content of 2% or more, 4% or more, 10% or more, 13% or more, 15% or more, 17% or more, 20% or more, 22% or more, 25% or more, or 35% or more in the solid content. Meanwhile, the biomass carbon content can be 100% or less, 90% or less, 80% or less, 73% or less, or 68% or less. Furthermore, a high biomass carbon content in the solid content can also contribute to improved heat resistance.

[0047] <Biomass carbon content (%)> In this specification, "biomass carbon content (%)" refers to the amount of radiocarbon ( 14This is a corrected value obtained by multiplying the content ratio (pMC%) of C) by 0.93, which is a correction ratio, and when the corrected value is 100% or more, it is considered to be 100%. In this specification, radiocarbon ( 14 The content ratio (pMC%) of radioactive carbon (C) in the biomass-derived components indicates the carbon concentration (mass ratio) of the biomass-derived components, and is related to the so-called biomass blending ratio. More specifically, the radioactive carbon (C) content ratio (pMC%) in accordance with ASTM-D6866 (especially ASTM D6866 Method B) is 14 C) Radiocarbon ( 14 C) content ratio. 14 C) has a half-life of 5730 years, and nitrogen ( 14 It is known that radioactive carbon ( 14 C) is carbon dioxide 14 After being oxidized to CO2 and dispersed into the atmosphere, it is taken up by animals and plants in the food chain, and disappears according to its half-life as it circulates through the environment via the food chain. 14 C) The measurement method is that fossil fuels are radiocarbon ( 14 C), and biomass (or biological carbon) is essentially free of radioactive carbon ( 14 C) in the carbon contained in biomass materials (or living organisms), 14 C) ratio to radiocarbon ( 14 This is a method to estimate the radiocarbon content (pMC%). 14 The higher the content ratio (pMC%) of radioactive carbon (C), the less fossil fuels are used, which can have an effect on reducing the environmental load. 14 The value of the carbon content ratio (pMC%) of carbon dioxide (C) is related to the index (=biomass carbon content (%)) that indicates the blend ratio of biomass, which is a renewable, biologically derived organic resource.

[0048] The radiocarbon ( 14By measuring the ratio of radioactive carbon (C), the ratio of carbon derived from biomass can be calculated. Specifically, the ratio of radioactive carbon (C) in the sample to be measured can be calculated using the following formula (A). 14 The content ratio (pMC%) of C) can be calculated. Formula (A): Radiocarbon ( 14 C) content ratio (pMC%) = [{radioactive carbon in the sample ( 14 C) ÷ carbon in the sample to be measured ( 12 C)} / {Radiocarbon of standard material ( 14 C) / carbon of standard material ( 12 C)}×100 (In the above formula, the standard material is oxalic acid (SRM4990C), supplied by the National Institute of Standards and Technology as a standard material for dating, converted into graphite using the same pretreatment method (described below) as for the graphite used for measurements.)

[0049] Next, the radiocarbon ( 14 The biomass carbon content (%) can be calculated by multiplying the biomass carbon content (pMC%) by 0.93, taking into account the effects of atmospheric nuclear testing from 1950 to the present day. Formula (B): Biomass carbon content (%) = radiocarbon ( 14 C) content ratio (pMC%) x 0.93

[0050] As a supplement, radioactive carbon ( 14 C), which produces about 1.5 times the amount of radiocarbon ( 14 However, this has gradually decreased over time, and the current value is around 107.5 (pMC%). Therefore, in this embodiment, radiocarbon ( 14The biomass carbon content (%) is defined as the value obtained by multiplying the content ratio (pMC%) of carbon (C) (pMC%) by 0.93 (=100 / 107.5). However, even when the method using the above formula (B) is adopted, there are cases where a value of 100% or more is calculated. Therefore, in this embodiment, as in the ASTM standard, when the value calculated using the above formula (B) is 100% or more, the biomass carbon content (%) is considered to be 100%.

[0051] Radiocarbon ( 14 The concentration of C is measured by accelerator mass spectrometry (AMS), which combines a tandem accelerator and a mass spectrometer, to measure the carbon isotopes (specifically, 12 C, 13 C, 14 C is an example.) can be physically separated using an accelerator by utilizing the difference in atomic weight, and the abundance of each atom of the isotope can be measured. The sample to be measured requires pretreatment. Specifically, as described in the Examples section below, the carbon contained in the sample to be measured is oxidized and converted into carbon dioxide. The resulting carbon dioxide is then separated from water and nitrogen, reduced, and converted into measurement graphite, which is solid carbon. Then, Cs is added to this measurement graphite. + The carbon ions are accelerated using a 3MV tandem accelerator, and the negative ions are converted to positive ions. 12 C 3+ , 13 C 3+ , 14 C 3+ Separating the traveling orbit of 14 C 3+ is measured using an electrostatic analyzer. The carbon isotopes contained in the measurement graphite obtained in the pretreatment 12 C. 13 C and 14 C is accelerated at the same speed, and its flight path is bent by the magnetic field of the mass analysis electromagnet. 12 C. 13C is on the inside, the heaviest 14 C flies on the outermost side of the bend. 12 C. 13 Since the amount of C is large, it is detected as a current by a Faraday cup detector. 14 C is counted one by one by an ionization chamber type ion detector.

[0052] In this embodiment, examples of the measurement sample (the object for measuring the biomass carbon content) include resins having polymerizable unsaturated groups, as well as various reactive raw materials such as epoxy resins (A), unsaturated monobasic acids (B), amide-imide resins (C), hydroxy(meth)acrylate compounds (D), and (meth)acrylate compounds having epoxy groups (E), curable resin compositions, etc.

[0053] The acid value of the resin having a polymerizable unsaturated group in this embodiment is preferably 2 mgKOH / g or less, more preferably 1 mgKOH / g or less, from the viewpoint of improving the insulating reliability, heat resistance, and adhesion of the cured resin. Furthermore, in this specification, "substantially free of acid groups" refers to an acid value of 2 mgKOH / g or less, more preferably 1 mgKOH / g or less, or may be completely free of acid groups. The acid value is a value measured by the acid value measurement method described in the Examples section below.

[0054] In addition, the double bond equivalent (g / eq) of the resin having a polymerizable unsaturated group of this embodiment is preferably 500 (g / eq) or less, more preferably 400 (g / eq) or less, and even more preferably 300 (g / eq) or less, from the viewpoint of improving the insulation reliability, heat resistance, and adhesion of the cured resin. From the same viewpoint, the double bond equivalent of the resin having a polymerizable unsaturated group of this embodiment is preferably 150 (g / eq) or more, more preferably 200 (g / eq) or more. In this specification, the "double bond equivalent" is an index of the amount of double bonds contained in a molecule. For compounds of the same molecular weight, the smaller the double bond equivalent value, the greater the amount of double bonds introduced. In this specification, the "double bond equivalent" may be essentially the equivalent of a (meth)acryloyl group (CH═CR-C(═O)-O (R represents a hydrogen atom or a methyl group)). The "double bond equivalent" is a calculated value calculated from the amounts of raw materials charged, as described in the Examples section. Here, a first embodiment and a second embodiment will be described below as examples of the resin of this embodiment.

[0055] First Embodiment First, the resin having a polymerizable unsaturated group according to the first embodiment (hereinafter sometimes simply referred to as "first embodiment") contains an epoxy resin (A) and an unsaturated monobasic acid (B) as residues. In this specification, the term "residue" refers to a partial structure of each raw material compound that remains in the molecule of the resin having a polymerizable unsaturated group of the present embodiment produced by reaction or polymerization, and is composed of a chemical bond formed by the reaction or polymerization and a group derived from each raw material compound that is other than the chemical bond.

[0056] <Epoxy resin (A)> The epoxy resin (A) is one of the essential reaction raw materials for obtaining the resin having a polymerizable unsaturated group of the first embodiment.

[0057] The total amount of chlorine contained as an impurity in the epoxy resin (A) is preferably 2400 ppm or less, more preferably 2200 ppm or less, even more preferably 2000 ppm or less, and even more preferably 1800 ppm or less. Using an epoxy resin (A) with such a reduced total chlorine content as a reaction raw material can contribute to reducing the chlorine atom content in the resin having polymerizable unsaturated groups of the first embodiment, thereby improving the insulation reliability, heat resistance, and adhesion of the cured product of the resin. Examples of chlorine content in an epoxy resin include inorganic chlorine and hydrolyzable chlorine, and the total amount of these chlorine content is referred to as the total chlorine content. The total chlorine content in the epoxy resin (A) can be calculated according to JIS K7246. Methods for removing or reducing chlorine content from the epoxy resin (A) include adding the epoxy resin (A) to purified water and dissolving the chlorine content in the aqueous solution as chlorine ions for removal.

[0058] The amount of α-glycol in the epoxy resin (A) is preferably 0.20 meq / g or less. This allows the final cured product of the resin having a polymerizable unsaturated group to have better insulation reliability, heat resistance, and adhesion. From the same viewpoint, the amount of α-glycol in the epoxy resin (A) is more preferably 0.15 meq / g or less. Furthermore, the amount of α-glycol in the epoxy resin (A) is preferably 0.01 meq / g or more. This allows the final cured product of the resin having a polymerizable unsaturated group to be prevented from decreasing in heat resistance. From the same viewpoint, the amount of α-glycol in the epoxy resin (A) is more preferably 0.02 meq / g or more. The amount of α-glycol in epoxy resin (A) can be calculated in accordance with JIS K7146. Specifically, the amount can be measured in accordance with the method described in the analytical report "Quantitative Determination of α-glycol Content in Epoxy Resins by Potentiometric Titration and Its Reliability" by Saito et al., BUNSEKI KAGAKU, Vol. 57, No. 6, pp. 499-503 (2008), which has been improved to a method using a commercially available autotitrator based on the rules of JIS K7146. Utilizing the fact that α-glycol quantitatively reacts with periodic acid, is cleaved, and oxidized to a carbonyl compound, the amount of α-glycol can be calculated by adding potassium iodide to excess periodic acid and titrating the generated iodine with a sodium thiosulfate solution. Furthermore, examples of a method for removing or reducing the α-glycol content from the epoxy resin (A) include a method in which the reaction is carried out while reducing and controlling the amount of water in the reaction system when synthesizing the epoxy resin (A), thereby adjusting the amount of α-glycol by preventing hydrolysis of the generated epoxy groups.

[0059] The softening point of the epoxy resin (A) is preferably 60°C or higher. In this case, the final cured product of the resin having a polymerizable unsaturated group can be made to have better insulation reliability, heat resistance, and adhesion. From the same viewpoint, the softening point of the epoxy resin (A) is more preferably 65°C or higher, even more preferably 70°C or higher, and even more preferably 72°C or higher, and is preferably 115°C or lower, more preferably 110°C or lower, and even more preferably 105°C or lower.

[0060] The epoxy equivalent of the epoxy resin (A) is preferably less than 240 g / equivalent. In this case, the final cured product of the resin having a polymerizable unsaturated group can be made to have better insulation reliability, heat resistance, and adhesion. From the same viewpoint, the epoxy equivalent of the epoxy resin (A) is more preferably less than 225 g / equivalent, and even more preferably less than 222 g / equivalent. From the same viewpoint, the epoxy equivalent of the epoxy resin (A) is preferably 150 g / equivalent or more, more preferably 160 g / equivalent or more, and even more preferably 170 g / equivalent or more.

[0061] The epoxy resin (A) may be synthesized from a biomass-derived raw material. More specifically, the biomass carbon content of the epoxy resin (A) used in the first embodiment is preferably 6% or more, and more preferably 10% or more. This can contribute to reducing the environmental load. The biomass carbon content of the epoxy resin (A) used in the first embodiment is not particularly limited, but can be 90% or less, or 80% or less.

[0062] The epoxy resin (A) may be a commonly used epoxy resin, and specific examples thereof include bisphenol-type epoxy resins, hydrogenated bisphenol-type epoxy resins, biphenol-type epoxy resins, hydrogenated biphenol-type epoxy resins, phenylene ether-type epoxy resins, naphthalene-type epoxy resins, naphthylene ether-type epoxy resins, biphenyl-type epoxy resins, triphenylmethane-type epoxy resins, phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, bisphenol novolac-type epoxy resins, naphthol novolac-type epoxy resins, naphthol-phenol co-condensed novolac-type epoxy resins, naphthol-cresol co-condensed novolac-type epoxy resins, phenol aralkyl-type epoxy resins, naphthol aralkyl-type epoxy resins, dicyclopentadiene-phenol addition reaction-type epoxy resins, biphenyl aralkyl-type epoxy resins, fluorene-type epoxy resins, xanthene-type epoxy resins, dihydroxybenzene-type epoxy resins, and trihydroxybenzene-type epoxy resins. These epoxy resins (A) may be used singly or in combination of two or more. Among these, bisphenol-type epoxy resins, novolac-type epoxy resins, and naphthalene-type epoxy resins are preferred from the viewpoint of improving the insulating reliability, heat resistance, and adhesion of the final cured product of the resin having a polymerizable unsaturated group.

[0063] The epoxy resin (A) can be synthesized from a phenolic resin by reacting the phenolic hydroxyl groups of the phenolic resin with epihalohydrin to form a reaction product having a glycidyl ether group. That is, the epoxy resin (A) can be an epoxy resin into which a glycidyl ether group has been introduced by reacting the phenolic hydroxyl groups of the phenolic resin with epihalohydrin (epoxidation reaction). In this case, the epoxidation reaction is preferably carried out at a temperature of 40°C to 150°C.

[0064] In addition, the reaction rate in the synthesis of the epoxy resin (A) can be increased by using an organic solvent during the epoxidation reaction. Examples of such organic solvents include hydrocarbon solvents such as toluene, xylene, heptane, hexane, and mineral spirits; ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, cyclohexanone, and dimethylacetamide; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, and solvent naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; and carbitol, cellosolve, methanol, ethanol, propanol, isopropanol, butanol, cyclohexanol, and propylene glycol monomethyl ether. Examples of suitable organic solvents include alcohol solvents; ether solvents such as propyl ether, methyl cellosolve, cellosolve, butyl cellosolve, and methyl carbitol; glycol ether solvents such as alkylene glycol monoalkyl ethers, dialkylene glycol monoalkyl ethers, and dialkylene glycol monoalkyl ether acetates; vegetable oils and fats such as soybean oil, linseed oil, rapeseed oil, and safflower oil; and methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate. These organic solvents may be biomass solvents or may be solvents represented by the general formula (1) above. These organic solvents may be used alone or in combination. From the viewpoint of reaction efficiency, the amount of the organic solvent used is preferably about 0.1 to 5 times the total mass of the reaction raw materials.

[0065] In the epoxidation reaction, a mixed solvent containing the organic solvent and water may be used instead of the organic solvent. In this case, the proportion of water per 100 parts by mass of the mixed solvent is preferably in the range of 5 to 60 parts by mass, more preferably 10 to 50 parts by mass.

[0066] The epoxidation reaction can be carried out using a basic catalyst. Examples of the basic catalyst include alkali metal hydroxides such as sodium hydroxide, lithium hydroxide, and potassium hydroxide; oxides and hydroxides of alkaline earth metals such as calcium, magnesium, and barium; primary amines such as ammonia and monoethanolamine; secondary amines such as diethanolamine; tertiary amines such as trimethylamine, triethylamine, triethanolamine, and diazabicycloundecene; and basic substances such as sodium carbonate and hexamethylenetetramine. These basic catalysts may be used alone or in combination of two or more. Among these basic catalysts, sodium hydroxide, potassium hydroxide, barium hydroxide, and calcium hydroxide are preferred because of their excellent catalytic activity.

[0067] [Epihalohydrin] Examples of the epihalohydrin include epichlorohydrin, epibromohydrin, and β-methylepichlorohydrin. One type of epihalohydrin may be used alone, or two or more types may be used in combination. Among these, epichlorohydrin is preferably used as the epihalohydrin because it is easily available industrially.

[0068] The ratio of epihalohydrin used is preferably in the range of 1 to 10 moles per mole of phenolic hydroxyl groups in the phenolic resin. This allows the final cured product of the resin having polymerizable unsaturated groups to have better insulation reliability, heat resistance, and adhesion. From the same viewpoint, the amount of epihalohydrin per mole of phenolic hydroxyl groups in the phenolic resin is more preferably 1.5 moles or more, even more preferably 2 moles or more, and more preferably 8 moles or less, even more preferably 6 moles or less. When epichlorohydrin is used as the epihalohydrin, it is preferable to keep the amount used to a minimum in order to reduce the chlorine atom content in the final resin having a polymerizable unsaturated group.

[0069] As the epihalohydrin, an epihalohydrin synthesized from a raw material derived from biomass may be used.

[0070] [Phenol resin] Examples of the phenolic resin include phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin-modified phenolic resin, dicyclopentadiene phenol adduct resin, phenol aralkyl resin, α-naphthol aralkyl resin, β-naphthol aralkyl resin, biphenyl aralkyl resin, trimethylolmethane resin, tetraphenylolethane resin, naphthol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, aminotriazine-modified phenolic resin, etc. Specific examples of the aminotriazine-modified phenolic resin include copolymers of an amino group-containing triazine compound such as melamine or benzoguanamine, a phenol such as phenol or cresol, and formaldehyde.

[0071] The phenolic resin may be synthesized from a raw material derived from biomass.

[0072] The phenolic resin is obtained by reacting a phenolic hydroxyl group-containing compound with a ketone group-containing compound. By introducing a skeleton based on the reaction between the phenolic hydroxyl group-containing compound and the ketone group-containing compound, the intermolecular interaction is appropriately weakened, resulting in a phenolic resin with low melt viscosity and excellent handleability, which is preferable. Furthermore, the resulting cured product is also preferable because it has excellent heat resistance, etc.

[0073] Specific examples of the phenolic hydroxyl group-containing compound include phenol, orthocresol, meta-cresol, para-cresol, 2,6-dimethylphenol, 2,5-dimethylphenol, 2,4-dimethylphenol, 3,5-dimethylphenol, 4-isopropylphenol, 4-tert-butylphenol, 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 2-methoxy-4-methylphenol, 2-tert-butyl-4-methoxyphenol, 2,6-dimethoxyphenol, 3,5-dimethoxyphenol, 2-ethoxyphenol, 3-ethoxyphenol, 4-ethoxyphenol, 2-furan, Examples of the phenolic hydroxyl group-containing compound include phenylphenol, 3-phenylphenol, 4-phenylphenol, 4-benzylphenol, 1,2-dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-dihydroxybenzene, 3-methylcatechol, 4-methylcatechol, 4-allylpyrocatechol, 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene, 1-naphthol, 2-naphthol, 1,3-naphthalenediol, 1,5-naphthalenediol, 1,6-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, polyphenylene ether diol, and polynaphthylene ether diol. These phenolic hydroxyl group-containing compounds may be used alone or in combination of two or more. Among these, it is preferable to use, as the phenolic hydroxyl group-containing compound, phenol or a derivative in which the hydrogen atoms on the aromatic nucleus are substituted with an alkyl group, an alkoxy group, a halogen atom, etc., because the heat resistance of the cured product of the finally obtained resin having a polymerizable unsaturated group is high. Furthermore, it is also preferable to use, as the phenolic hydroxyl group-containing compound, one having a naphthalene skeleton (1-naphthol, 2-naphthol, 1,3-naphthalenediol, 1,5-naphthalenediol, 1,6-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, etc., from among the above-listed compounds).

[0074] On the other hand, examples of the ketone group-containing compound include aromatic ketones, aliphatic ketones, formyl group-containing compounds, etc. These ketone group-containing compounds may be used alone or in combination of two or more.

[0075] Examples of aromatic ketones include benzophenone, fluorenone, indanone, etc. The aromatic ketones may be used alone or in combination of two or more.

[0076] Examples of aliphatic ketones include acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, methyl amyl ketone (2-heptanone), cyclopentanone, cyclohexanone, isophorone, cycloheptanone, and cyclooctanone. Among these, from the viewpoints of reactivity during synthesis of the phenolic resin and the epoxy resin (A) and ease of availability, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are preferred as aliphatic ketones. One of the aliphatic ketones may be used alone, or two or more may be used in combination.

[0077] Examples of formyl group-containing compounds include formaldehyde, acetaldehyde, propionaldehyde, glyoxal, succinaldehyde, benzaldehyde, 4-methylbenzaldehyde, 3,4-dimethylbenzaldehyde, 4-biphenylaldehyde, naphthylaldehyde, and 4-methoxybenzaldehyde. Among these, formaldehyde is preferred as the formyl group-containing compound from the viewpoints of reactivity during synthesis of the epoxy resin (A) and ease of handling. The formyl group-containing compounds may be used alone or in combination of two or more.

[0078] As the ketone group-containing compound, it is preferable to use a formyl group-containing compound, and among them, as described above, it is preferable to use formaldehyde. The formaldehyde may be used in the form of formalin or paraformaldehyde.

[0079] When a phenolic resin is obtained by reacting a phenolic hydroxyl group-containing compound with a ketone group-containing compound, the reaction ratio of the ketone group-containing compound, more specifically, formaldehyde, is preferably in the range of 0.5 to 1.0 moles per mole of the phenolic hydroxyl group-containing compound. By using formaldehyde as the ketone group-containing compound and using the phenolic hydroxyl group-containing compound and formaldehyde in the above ratio, the resulting cured resin having polymerizable unsaturated groups can be made to have better insulation reliability, heat resistance, and adhesion. From the same perspective, the amount of formaldehyde per mole of the phenolic hydroxyl group-containing compound is preferably 0.6 moles or more, more preferably 0.65 moles or more, and more preferably 1.0 moles or less, even more preferably 0.98 moles or less.

[0080] The reaction between the phenolic hydroxyl group-containing compound and the ketone group-containing compound proceeds even in the absence of a catalyst due to their high reactivity, but may be carried out using an acidic catalyst as appropriate. Examples of acidic catalysts include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid; and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. When using these acidic catalysts, it is preferable to use them in an amount of 10% by mass or less based on the total mass of the phenolic hydroxyl group-containing compound and the ketone group-containing compound.

[0081] The reaction is preferably carried out under solvent-free conditions, but may be carried out in an organic solvent if necessary. The organic solvent may be the same as that used in the above-mentioned epoxidation reaction. When an organic solvent is used, it is preferable to use the organic solvent in a proportion of 50 to 200 parts by mass per 100 parts by mass of the total of the phenolic hydroxyl group-containing compound and the ketone group-containing compound, since this improves the reaction efficiency.

[0082] After the reaction between the phenolic hydroxyl group-containing compound and the ketone group-containing compound is completed, the target phenolic resin can be obtained by drying under reduced pressure or the like.

[0083] The phenolic hydroxyl group equivalent of the phenolic resin is preferably in the range of 50 to 150 g / equivalent from the viewpoint of improving the insulating reliability, heat resistance, and adhesion of the final cured product of the resin having a polymerizable unsaturated group. From the same viewpoint, the phenolic hydroxyl group equivalent of the phenolic resin is more preferably 55 g / equivalent or more, even more preferably 60 g / equivalent or more, and is more preferably 140 g / equivalent or less, and even more preferably 130 g / equivalent or less.

[0084] From the viewpoint of improving the insulating reliability, heat resistance, and adhesion of the final cured product of the resin having a polymerizable unsaturated group, the softening point of the phenolic resin is preferably in the range of 60 to 150° C. From the same viewpoint, the softening point of the phenolic resin is more preferably 65° C. or higher, and even more preferably 70° C. or higher, and is more preferably 145° C. or lower, and even more preferably 140° C. or lower.

[0085] <Unsaturated monobasic acid (B)> The unsaturated monobasic acid (B) is one of the essential reaction raw materials for obtaining the resin having a polymerizable unsaturated group of the first embodiment. The unsaturated monobasic acid (B) is a compound having a polymerizable unsaturated bond in one molecule. In the present invention, the term "polymerizable unsaturated bond" refers to an unsaturated bond that can be radically polymerized.

[0086] Examples of the polymerizable unsaturated group include a (meth)acryloyl group, an allyl group, an isopropenyl group, and a 1-propenyl group.

[0087] Examples of the unsaturated monobasic acid (B) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, and β-furfurylacrylic acid. Esters, acid halides, and acid anhydrides of the unsaturated monobasic acids can also be used. These unsaturated monobasic acids (B) may be used singly or in combination of two or more.

[0088] Furthermore, the unsaturated monobasic acid (B) may be a compound represented by the following general formula (2):

[0089] [ka] [In the above general formula (2), X represents an alkylene chain having 1 to 10 carbon atoms, a polyoxyalkylene chain, a (poly)ester chain, an aromatic hydrocarbon chain, or a (poly)carbonate chain, and a hydrogen atom in the structure of X may be substituted with a halogen atom or an alkoxy group, and Y represents a hydrogen atom or a methyl group.] can be used.

[0090] Examples of the polyoxyalkylene chain include a polyoxyethylene chain and a polyoxypropylene chain.

[0091] The (poly)ester chain is, for example, a chain represented by the following general formula (9-1):

[0092] [ka] [In the above general formula (9-1), R 4 and R 5 each independently represents an alkylene group having 1 to 10 carbon atoms, and n1 represents an integer of 1 to 5. Examples of suitable (poly)ester chains include those represented by the following formula:

[0093] Examples of the aromatic hydrocarbon chain include a phenylene chain, a naphthylene chain, a biphenylene chain, a phenylnaphthylene chain, a binaphthylene chain, etc. Furthermore, a hydrocarbon chain having an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring as a partial structure can also be used.

[0094] The (poly)carbonate chain may be, for example, a chain represented by the following general formula (9-2):

[0095] [ka] [In the above general formula (9-2), R 6 each independently represents an alkylene group having 1 to 10 carbon atoms, and n2 represents an integer of 1 to 5. Examples of suitable (poly)carbonate chains include those represented by the following formula:

[0096] The molecular weight of the compound represented by the above formula (2) is preferably in the range of 100 to 500, more preferably in the range of 150 to 400.

[0097] Further examples of the compound having a carboxyl group and a (meth)acryloyl group as the first polymerizable unsaturated group include compounds represented by the following general formula (3): [ka] [In the above general formula (3), R 8 R each independently represents an alkylene chain having 1 to 10 carbon atoms, and may contain a halogen atom or the like in the structure. 7 is a hydrogen atom or a methyl group, and n3 is an integer of 1 to 5. Compounds represented by the following formula may also be used.

[0098] These compounds having a carboxyl group and a first polymerizable unsaturated group can be used alone or in combination of two or more. Among these, acrylic acid, methacrylic acid, and ω-carboxy-polycaprolactone mono(meth)acrylate are preferred because they tend to produce a resin having a polymerizable unsaturated group that can form a cured product excellent in elongation, heat yellowing resistance, and adhesion.

[0099] The unsaturated monobasic acid (B) may be synthesized from a biomass-derived raw material. More specifically, the biomass carbon content of the unsaturated monobasic acid (B) used in the first embodiment is preferably 6% or more, more preferably 10% or more. In this case, it is possible to contribute to reducing the environmental load. Furthermore, the biomass carbon content of the unsaturated monobasic acid (B) used in the first embodiment is not particularly limited, but can be 90% or less, or 80% or less.

[0100] When obtaining the resin having a polymerizable unsaturated group according to the first embodiment, the blending ratio (reaction ratio) of the epoxy resin (A) and the unsaturated monobasic acid (B) is preferably within a range of 0.20 to 1.05 mol of the unsaturated monobasic acid (B) per mol of epoxy groups in the epoxy resin (A). By using this blending ratio, the cured product of the resin having a polymerizable unsaturated group finally obtained can have better insulation reliability, heat resistance, and adhesion. From the same viewpoint, the amount of the unsaturated monobasic acid (B) per mol of epoxy groups in the epoxy resin (A) is more preferably 0.25 mol or more, even more preferably 0.30 mol or more, and even more preferably 0.40 mol or more. Furthermore, the amount of the unsaturated monobasic acid (B) per mol of epoxy groups in the epoxy resin (A) is more preferably 1.04 mol or less, even more preferably 1.03 mol or less, and even more preferably 1.00 mol or less. The above upper and lower limits can be combined in any desired manner.

[0101] The reaction between the epoxy resin (A), the unsaturated monobasic acid (B), and other reaction raw materials, if necessary, is preferably carried out in a solvent represented by the above general formula (1). If necessary, an organic solvent other than the solvent represented by the above general formula (1) may also be used. The organic solvent to be used is appropriately selected depending on the solubility of the reaction raw materials and the product, the reaction temperature conditions, etc., but the same organic solvents as those used in the above-mentioned epoxidation reaction can be used. These organic solvents may be used alone or in combination of two or more. The amount of the organic solvent used is preferably in the range of about 0.1 to 5 times the total mass of the reaction raw materials, as this improves the reaction efficiency.

[0102] The reaction between the epoxy resin (A) and the unsaturated monobasic acid (B) may be carried out using a basic catalyst, if necessary. Examples of the basic catalyst include N-methylmorpholine, pyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), tri-n-butylamine, dimethylbenzylamine, trimethylamine, dimethylethylamine, diethylmethylamine, triethylamine, dimethylpropylamine, diethylpropylamine, and dipropylmethylamine. amine, dipropylethylamine, tripropylamine, dimethylbutylamine, diethylbutylamine, dibutylmethylamine, dibutylethylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2,4-dimethylimidazole, 1,4-diethanolamine Amine compounds such as ethylimidazole, 2-ethyl-4-methylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, and tetramethylammonium hydroxide; quaternary ammonium salts such as trioctylmethylammonium chloride and trioctylmethylammonium acetate; phosphine compounds such as trimethylphosphine, tributylphosphine, and triphenylphosphine; phosphonium salts such as tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl(2-hydroxypropyl)phosphonium chloride, triphenylphosphonium chloride, and benzylphosphonium chloride;Examples of suitable basic catalysts include organic tin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octoate, and 1,1,3,3-tetrabutyl-1,3-dodecanoyldistannoxane; organic metal compounds such as zinc octoate and bismuth octoate; inorganic tin compounds such as tin octoate; and inorganic metal compounds. Alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides can also be used. These basic catalysts may be used alone or in combination of two or more. The amount of the basic catalyst added is preferably in the range of 0.001 to 5 parts by mass per 100 parts by mass of the total of the reaction raw materials.

[0103] <Other reaction raw materials> The reaction raw materials for obtaining the resin having a polymerizable unsaturated group of the first embodiment may contain the above-mentioned epoxy resin (A) and unsaturated monobasic acid (B) as needed, and may further contain a polybasic acid anhydride, a polyisocyanate compound (c1), a hydroxy(meth)acrylate compound (D), etc., as described below, and may further contain other compounds.

[0104] However, from the viewpoint of fully exerting the desired effects, the total proportion of the epoxy resin (A) and the unsaturated monobasic acid (B) in the reaction raw materials (solid content) of the resin having a polymerizable unsaturated group of the first embodiment is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 85% by mass or more.

[0105] Second Embodiment Next, a resin having a polymerizable unsaturated group according to a second embodiment (hereinafter sometimes simply referred to as "second embodiment") contains an amide-imide resin (C) having an acid group and / or an acid anhydride group and a hydroxy(meth)acrylate compound (D) as residues. It is also preferable that the resin further contains a (meth)acrylate compound (E) having an epoxy group as a synthesis raw material.

[0106] <Amide-imide resin (C) having an acid group and / or an acid anhydride group> An amide-imide resin (C) having an acid group and / or an acid anhydride group (hereinafter sometimes simply referred to as "amide-imide resin (C)") is one of the essential reaction raw materials for obtaining the resin having a polymerizable unsaturated group of this embodiment. This amide-imide resin (C) has both an amide group and an imide group in the molecule.

[0107] The amide-imide resin (C) having an acid group and / or an acid anhydride group may have either an acid group or an acid anhydride group, or may have both. In particular, from the viewpoint of reactivity with the hydroxy(meth)acrylate compound (D) and the (meth)acrylate compound (E) having an epoxy group and reaction control, the amide-imide resin (C) preferably has an acid anhydride group, and more preferably has both an acid group and an acid anhydride group.

[0108] Furthermore, the amide-imide resin (C) used in this embodiment is more preferably prepared by reacting a polyisocyanate compound (c1) with a polycarboxylic acid (c2) or a polycarboxylic anhydride (c3) as reaction raw materials.

[0109] [Polyisocyanate compound (c1)] The polyisocyanate compound (c1) is a compound having two or more isocyanate groups (—NCO). The number of isocyanate groups that the polyisocyanate compound (c1) has is, for example, 2 to 10.

[0110] As the polyisocyanate compound (c1), known isocyanate compounds can be used. Examples of the polyisocyanate compound (c1) include aliphatic diisocyanate compounds, alicyclic diisocyanate compounds, aromatic diisocyanate compounds, and modified products thereof. These polyisocyanate compounds (c1) may be used alone or in combination of two or more.

[0111] Examples of the aliphatic diisocyanate compound include compounds represented by the general formula: OCN-R-NCO. In the general formula, R is a linear or branched alkylene group having 1 to 10 carbon atoms. Specific examples of the aliphatic diisocyanate compound include butane diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate.

[0112] Examples of the alicyclic diisocyanate compound include norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate.

[0113] Examples of the aromatic diisocyanate compound include tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, and o-tolidine diisocyanate.

[0114] In addition to the above-mentioned compounds, the polyisocyanate compound (c1) may also be a compound represented by the following general formula (4):

[0115] [ka] [In the above general formula (4), R 41 and R 42 are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and R 43 are each independently an alkyl group having 1 to 4 carbon atoms or a bonding point connecting the structural portion represented by general formula (4) to the methylene group marked with an *, k41 is 0 or an integer of 1 to 3, and n4 is an integer of 1 or greater.

[0116] The polyisocyanate compound (c1) may be a compound having an isocyanurate structure, a biuret structure, or an allophanate structure as part of its structure.

[0117] Here, the isocyanurate structure refers to one or more selected from the group consisting of the following structures (I), (II), and (III) in the following general formula (5): In the structures, * each independently represents a linking moiety to another part of the polyisocyanate compound (c1) or hydrogen.

[0118] [ka]

[0119] The biuret structure refers to -N(CONH-)2, and the allophanate structure refers to -OC(O)NC(O)-NH-.

[0120] In one embodiment of the second embodiment, the polyisocyanate compound (c1) has an isocyanurate structure. In one embodiment, the polyisocyanate compound (c1) has an isocyanurate structure of Structure I or Structure II. In yet another embodiment, the polyisocyanate compound (c1) is an alicyclic diisocyanate having Structure (I), (II), or (III). In yet another embodiment, the polyisocyanate compound (c1) is isophorone diisocyanate having Structure (I), (II), or (III). In yet another embodiment, the polyisocyanate compound (c1) is one or more selected from the group consisting of Formula (6), Formula (7), and Formula (8) below.

[0121] [ka] [ka] [ka]

[0122] The above formulas (6), (7), and (8) each exemplify the case where the compound has three isocyanate groups. However, in another embodiment, the polyisocyanate compound (c1) may have a total of four or five isocyanate groups in the portion derived from isophorone diisocyanate, while the isocyanurate structure of formulas (6), (7), and (8) remains unchanged.

[0123] Commercially available polyisocyanate compounds (c1) include, for example, the VESTANAT series, such as VESTANAT (registered trademark) IPDI, TMDI, and H12MDI from EVONIK; VESTANAT (registered trademark) T 1890 E, T 1890 L, T 1890 M, and T 1890 / 100 from EVONIK; and the Takenate series, such as Takenate (registered trademark) D-127N from Mitsui Chemicals. Some of these commercially available products contain a relatively large amount of chlorine (a chlorine-containing compound is used for production). More specifically, methods for producing polyisocyanate compounds include a method using phosgene (the so-called phosgene method) and a urea method, and in the phosgene method, chlorine is used during the process (phosgene itself contains chlorine in the molecule). Therefore, in the second embodiment, it is important to appropriately select or prepare the polyisocyanate compound (c1) while also considering whether the chlorine atom content in the finally obtained resin having a polymerizable unsaturated group can be sufficiently reduced.

[0124] Among the above, from the viewpoint of improving the insulating reliability, heat resistance, and adhesion of the finally obtained cured product of the resin having a polymerizable unsaturated group, the polyisocyanate compound (c1) preferably contains an aliphatic diisocyanate compound, an alicyclic diisocyanate compound, or a modified product thereof, more preferably contains an aliphatic diisocyanate compound, an alicyclic diisocyanate compound, or an isocyanurate modified product thereof (a diisocyanate compound having the isocyanurate structure), and even more preferably contains an alicyclic diisocyanate compound or an isocyanurate modified product thereof.

[0125] The polyisocyanate compound (c1) may be synthesized from a raw material derived from biomass. More specifically, the biomass carbon content of the polyisocyanate compound (c1) used in the second embodiment is preferably 6% or more, more preferably 10% or more. This can contribute to reducing the environmental load. The biomass carbon content of the polyisocyanate compound (c1) used in the second embodiment is not particularly limited, but can be 90% or less, or 80% or less.

[0126] [Polycarboxylic acid (c2) or polycarboxylic anhydride (c3)] The polycarboxylic acid (c2) or polycarboxylic acid anhydride (c3) is a compound having multiple carboxy groups in the molecule or an acid anhydride thereof. The polycarboxylic acid (c2) or polycarboxylic acid anhydride (c3) may be used alone or in combination of two or more.

[0127] In order to obtain the amide-imide resin (C) (to form both an amide group and an imide group in the molecule), both a carboxy group and an acid anhydride group must be present in the system. In the second embodiment, however, a compound having both a carboxy group and an acid anhydride group in the molecule may be used as the polycarboxylic acid (c2) or the polycarboxylic acid anhydride (c3), or a compound having a carboxy group and a compound having an acid anhydride group may be used in combination.

[0128] Examples of the polycarboxylic acid (c2) or polycarboxylic acid anhydride (c3) include aliphatic polycarboxylic acid compounds, aliphatic polycarboxylic acid anhydrides, alicyclic polycarboxylic acid compounds, alicyclic polycarboxylic acid anhydrides, aromatic polycarboxylic acid compounds, and aromatic polycarboxylic acid anhydrides.

[0129] In the aliphatic polycarboxylic acid compound or aliphatic polycarboxylic acid anhydride, the aliphatic hydrocarbon group may be either linear or branched, and may have an unsaturated bond in the structure. Examples of the aliphatic polycarboxylic acid compound or aliphatic polycarboxylic acid anhydride include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, and acid anhydrides thereof.

[0130] In this specification, the alicyclic polycarboxylic acid compound or alicyclic polycarboxylic acid anhydride is defined as one in which a carboxy group or an acid anhydride group is bonded to an alicyclic structure, and the presence or absence of an aromatic ring in other structural portions is not important. Examples of the alicyclic polycarboxylic acid compound or alicyclic polycarboxylic acid anhydride include tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanecarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, and acid anhydrides thereof.

[0131] Examples of the aromatic polycarboxylic acid compound or aromatic polycarboxylic acid anhydride include phthalic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, benzophenone tetracarboxylic acid, and acid anhydrides thereof.

[0132] Among the above, from the viewpoint of further improving heat resistance, the polycarboxylic acid (c2) or polycarboxylic anhydride (c3) is preferably the alicyclic polycarboxylic acid compound or its acid anhydride, or the aromatic polycarboxylic acid compound or its acid anhydride. Furthermore, the polycarboxylic acid (c2) or polycarboxylic anhydride (c3) preferably contains a tricarboxylic acid or a tricarboxylic anhydride. In particular, from the viewpoint of improving the insulating reliability, heat resistance, and adhesion of the final cured product of the resin having a polymerizable unsaturated group, and from the viewpoint of efficiently producing the amide-imide resin (C), it is preferable that the polycarboxylic acid (c2) or polycarboxylic anhydride (c3) contains a tricarboxylic acid anhydride (i.e., a compound having both a carboxy group and an acid anhydride group in the molecule), and more preferably contains cyclohexanetricarboxylic anhydride or trimellitic anhydride (also called trimellitic anhydride).

[0133] The polycarboxylic acid (c2) or polycarboxylic anhydride (c3) may be synthesized from a biomass-derived raw material. More specifically, the biomass carbon content of the polycarboxylic acid (c2) or polycarboxylic anhydride (c3) used in the second embodiment is preferably 6% or more, more preferably 10% or more. In this case, it is possible to contribute to reducing the environmental load. Furthermore, the biomass carbon content of the polycarboxylic acid (c2) or polycarboxylic anhydride (c3) used in the second embodiment is not particularly limited, but may be 90% or less, or 80% or less.

[0134] As a reaction raw material for obtaining the amide-imide resin (C) having an acid group and / or an acid anhydride group, compounds other than the above-mentioned polyisocyanate compound (c1), polycarboxylic acid (c2) or polycarboxylic acid anhydride (c3) may be used, if necessary.

[0135] The method for obtaining the amide-imide resin (C) having an acid group and / or an acid anhydride group is not particularly limited as long as a polyisocyanate compound (c1) and a polycarboxylic acid (c2) or a polycarboxylic anhydride (c3) are used as reaction raw materials. For example, a method may be used in which 0.8 to 2.0 moles of the polycarboxylic acid (c2) or the polycarboxylic anhydride (c3) are used per mole of the isocyanate group of the polyisocyanate compound (c1), and the mixture is stirred and mixed at a temperature of about 120 to 180°C to react them. In the reaction of the polyisocyanate compound (c1) with the polycarboxylic acid (c2) or the polycarboxylic acid anhydride (c3), it is preferable to appropriately adjust conditions such as the compounding ratio (reaction ratio) so that the resulting amide-imide resin (C) has an acid group and / or an acid anhydride group (particularly an acid anhydride group).

[0136] The reaction of the polyisocyanate compound (c1) with the polycarboxylic acid (c2) or polycarboxylic anhydride (c3) is preferably carried out in a solvent represented by the above general formula (1), and an organic solvent other than the solvent represented by the above general formula (1) may be further used as needed. A basic catalyst may also be used as needed. The organic solvent and basic catalyst may be the same as those used in the reaction of the epoxy resin (A) with the unsaturated monobasic acid (B).

[0137] <Hydroxy(meth)acrylate compound (D)> The hydroxy(meth)acrylate compound (D) is one of the essential reaction raw materials for obtaining the resin having a polymerizable unsaturated group of the second embodiment. The hydroxy(meth)acrylate compound (D) is a compound having a hydroxyl group and a (meth)acryloyl group in the molecule.

[0138] Examples of the hydroxy(meth)acrylate compound (D) include hydroxy(meth)acrylate compounds such as hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylate; (poly)oxyalkylene-modified compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the above-mentioned various hydroxy(meth)acrylate compounds; and lactone-modified compounds in which a (poly)lactone structure has been introduced into the molecular structure of the above-mentioned various hydroxy(meth)acrylate compounds. These hydroxy(meth)acrylate compounds (D) may be used singly or in combination of two or more.

[0139] Incidentally, examples of commercially available hydroxy(meth)acrylate compounds (D) include the "Aronix" series (pentaerythritol polyacrylate mixtures) from Toagosei Co., Ltd. However, some of these commercially available products contain relatively large amounts of chlorine (chlorine-containing compounds are used for production). Therefore, in the second embodiment, it is important to appropriately select or prepare the hydroxy(meth)acrylate compound (D) in consideration of whether the chlorine atom content in the final resin having a polymerizable unsaturated group can be sufficiently reduced.

[0140] The hydroxy(meth)acrylate compound (D) may be synthesized from a raw material derived from biomass. More specifically, the biomass carbon content of the hydroxy(meth)acrylate compound (D) used in the second embodiment is preferably 6% or more, and more preferably 10% or more. This can contribute to reducing the environmental load. Furthermore, the biomass carbon content of the hydroxy(meth)acrylate compound (D) used in the second embodiment is not particularly limited, but can be 90% or less, or 80% or less.

[0141] <(Meth)acrylate Compound (E) Having Epoxy Group> The (meth)acrylate compound (E) having an epoxy group (hereinafter, sometimes simply referred to as "compound (E)") is one of the optional reaction raw materials for obtaining the resin having a polymerizable unsaturated group of the second embodiment.

[0142] The (meth)acrylate compound (E) having an epoxy group is not particularly limited as long as it has an epoxy group and a (meth)acryloyl group in its molecular structure. Specific examples of the (meth)acrylate compound (E) having an epoxy group include (meth)acrylate monomers having a glycidyl group, such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate; and mono(meth)acrylates of diglycidyl ether compounds, such as dihydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. These (meth)acrylate compounds (E) having an epoxy group may be used alone or in combination of two or more. Among these, glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate are preferred as the (meth)acrylate compound (E) having an epoxy group.

[0143] The chlorine atom content of the (meth)acrylate compound (E) having an epoxy group is preferably 500 ppm by mass or less, more preferably 100 ppm by mass or less, and even more preferably 10 ppm by mass or less, particularly preferably below the detection limit, which makes it easier to reduce the chlorine atom content in the final resin having a polymerizable unsaturated group to 100 ppm by mass or less.

[0144] Here, a common method for synthesizing a (meth)acrylate compound (E) having an epoxy group is to react a (meth)acrylate compound with epichlorohydrin to synthesize the compound by glycidylating it. However, because this method uses epichlorohydrin, a compound having chlorine atoms in its molecule, it is believed that the resulting compound (E) will contain chlorine atoms in an amount of from more than 700 ppm by mass to several percent. Furthermore, it is believed that a resin having a polymerizable unsaturated group obtained using the compound (E) as a reaction raw material will also contain chlorine atoms in an amount of from more than 700 ppm by mass to several percent. Therefore, when the compound (E) is synthesized using epichlorohydrin, it is preferable to purify the compound (E) before the subsequent synthesis of a resin having a polymerizable unsaturated group to reduce the chlorine atom content of the compound (E) to 700 ppm by mass or less.

[0145] Alternatively, the (meth)acrylate compound (E) having an epoxy group can also be obtained by a transesterification reaction between an epoxy group- and hydroxyl group-containing compound (e.g., glycidol) and a (meth)acrylate compound such as (meth)acrylic acid. If the epoxy group- and hydroxyl group-containing compound does not have a chlorine atom in the molecule, it is preferable to obtain the compound (E) by the above transesterification reaction, from the viewpoint of reducing the chlorine atom content of the obtained epoxy group-containing (meth)acrylate compound (E) and, ultimately, the resin having a polymerizable unsaturated group (note that glycidol does not have a chlorine atom in the molecule). That is, the (meth)acrylate compound (E) having an epoxy group is preferably a compound obtained by reacting an epoxy group- and hydroxyl group-containing compound (e.g., glycidol) with a (meth)acrylate compound such as (meth)acrylic acid as reaction raw materials. Furthermore, from the viewpoint of further reducing the chlorine atom content of the finally obtained resin having a polymerizable unsaturated group, the (meth)acrylate compound (E) having an epoxy group is more preferably a compound obtained by reacting an epoxy group- and hydroxyl group-containing compound (e.g., glycidol) produced using a biomass material with a (meth)acrylate compound as reaction raw materials.

[0146] The (meth)acrylate compound is not particularly limited as long as it has a (meth)acryloyl group, and examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, and the (meth)acrylate compounds described in the section below under <Compounds having a polymerizable unsaturated group>.

[0147] Examples of the epoxy group- and hydroxyl group-containing compound include hydroxyalkene oxides (epoxyalkanols), such as hydroxyalkene oxides having 3 to 10 carbon atoms, such as 2,3-epoxypropanol (glycidol) and 2,3-epoxybutanol; and hydroxycycloalkene oxides having 4 to 10 carbon atoms, such as 2,3-epoxycyclobutanol and 2,3-epoxycyclopentanol.

[0148] The epoxy group- and hydroxyl group-containing compound (e.g., glycidol) may be synthesized from a biomass-derived raw material. More specifically, the biomass carbon content of the epoxy group- and hydroxyl group-containing compound (e.g., glycidol) is preferably 20% or more, more preferably 22% or more, 34% or more, 46% or more, or 80% or more. This can contribute to reducing the environmental load. Furthermore, the biomass carbon content of the epoxy group- and hydroxyl group-containing compound (e.g., glycidol) is not particularly limited, but can be 100% or less, 95% or less, or 83% or less.

[0149] It is known that the epoxy group- and hydroxyl group-containing compound (e.g., glycidol) can be derived from glycerin, a plant-derived chemical product. Therefore, the epoxy group- and hydroxyl group-containing compound is preferably synthesized from a plant (e.g., a vegetable oil such as soybean oil) or biodiesel fuel (mainly composed of fatty acid methyl esters). In other words, the epoxy group- and hydroxyl group-containing compound is preferably a compound derived from a plant or biodiesel fuel. This can also contribute to reducing the environmental load. Furthermore, the epoxy group- and hydroxyl group-containing compound is preferably glycidol derived from plant-derived glycerin. Methods for synthesizing glycidol from plant-derived glycerin are described, for example, in "Quaternary Alkyl Ammonium Salt-Catalyzed Transformation of Glycidol to Glycidyl Esters by Transesterification of Methyl Esters, Shinji Tanaka et. al., ACS Catalysis, 2018, 8, 2, 1097-1103" and "Synthesis of glycidol from glycerol, LIU Xuemin et. al., Huagong Jinzhan, vol. 28, 1445-1448, 2009."

[0150] Furthermore, whether or not the epoxy group- and hydroxyl group-containing compound (e.g., glycidol) is a derivative derived from plant-derived glycerin can be determined by analyzing the epoxy group- and hydroxyl group-containing compound using the radiocarbon ( 14 This can be confirmed by the method for measuring the content ratio (pMC%) of biomass carbon and the method for calculating the biomass carbon content (%).

[0151] As described above, the (meth)acrylate compound (E) having an epoxy group is preferably synthesized from a raw material derived from biomass. More specifically, the biomass carbon content of the (meth)acrylate compound (E) having an epoxy group used in the first embodiment is preferably 6% or more, more preferably 10% or more, and even more preferably 20% or more. In this case, it is possible to contribute to reducing the environmental load. Furthermore, the biomass carbon content of the (meth)acrylate compound (E) having an epoxy group used in the first embodiment is not particularly limited, but can be 90% or less, or 80% or less.

[0152] In the second embodiment, the polymerizable unsaturated group-containing resin is prepared by mixing the amide-imide resin (C) having an acid group and / or anhydride group with the hydroxy(meth)acrylate compound (D) in a ratio (reaction ratio) of 0.5 to 10 moles of hydroxyl groups in the hydroxy(meth)acrylate compound (D) per mole of acid groups and / or anhydride groups in the amide-imide resin (C), and more preferably 0.5 to 2 moles of hydroxyl groups in the hydroxy(meth)acrylate compound (D) per mole of acid anhydride groups in the amide-imide resin (C). This ratio allows the resulting cured product of the polymerizable unsaturated group-containing resin to have superior insulating reliability, heat resistance, and adhesion.

[0153] The reaction between the amide-imide resin (C) having an acid group and / or an acid anhydride group, the hydroxy(meth)acrylate compound (D), and other reaction raw materials used as needed is preferably carried out in a solvent represented by the above general formula (1). If necessary, an organic solvent other than the solvent represented by the above general formula (1) may also be used. Furthermore, the reaction may be carried out in the presence of a basic catalyst, if necessary. The organic solvent and the basic catalyst may be the same as those used in the reaction between the epoxy resin (A) and the unsaturated monobasic acid (B).

[0154] <Other reaction raw materials> Examples of the other reaction raw materials include compounds other than the amide-imide resin (C), the hydroxy(meth)acrylate compound (D), and the (meth)acrylate compound having an epoxy group (E), and which have one or more reactive functional groups selected from the group consisting of a hydroxyl group, a carboxyl group, an isocyanate group, and a glycidyl group. In other words, the reaction raw materials for obtaining the resin having a polymerizable unsaturated group of the second embodiment include the above-mentioned amide-imide resin (C) having an acid group and / or an acid anhydride group and hydroxy(meth)acrylate compound (D), and preferably further include a (meth)acrylate compound (E) having an epoxy group. In addition to the amide-imide resin (C), the hydroxy(meth)acrylate compound (D), and the (meth)acrylate compound (E) having an epoxy group, the reaction raw materials may also include, as necessary, a compound having one or more reactive functional groups selected from the group consisting of a hydroxyl group, a carboxyl group, an isocyanate group, and a glycidyl group.

[0155] However, from the viewpoint of fully exerting the desired effects, the total proportion of the amide-imide resin (C) having an acid group and / or an acid anhydride group and the hydroxy(meth)acrylate compound (D) in the reaction raw material (solid content) of the resin having a polymerizable unsaturated group of the second embodiment is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 85% by mass or more. Furthermore, the reaction raw material (solid content) of the resin having a polymerizable unsaturated group of the second embodiment preferably further contains a (meth)acrylate compound (E) having an epoxy group in addition to the amide-imide resin (C) having an acid group and / or an acid anhydride group and the hydroxy(meth)acrylate compound (D), and in that case, the total proportion is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 85% by mass or more.

[0156] (Method of producing a resin having a polymerizable unsaturated group) The method for producing a resin having a polymerizable unsaturated group described above is a method for producing a resin having a polymerizable unsaturated group, which contains a solvent having a biomass carbon content (%) (pMC%) of 50% or more and an amide bond, represented by the following general formula (1). The biomass carbon content (%) (pMC%) of the solvent is preferably 60% or more, more preferably 70% or more, and even more preferably 80% or more. The upper limit of the biomass carbon content (%) (pMC%) of the solvent is not particularly limited, but can be 100% or less or 90% or less. [ka] (In the above general formula (1), R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; R 3 represents a monovalent organic group having 4 to 10 carbon atoms.

[0157] As an example of a method for producing a resin having a polymerizable unsaturated group according to the present invention, the method for producing the resin of the first and second embodiments will be described.

[0158] <Method for producing resin according to the first embodiment> In the method for producing a resin having a polymerizable unsaturated group according to the first embodiment of the present invention, an epoxy resin (A) and an unsaturated monobasic acid (B) are mixed together.

[0159] The method for reacting the reactant materials including the epoxy resin (A), the unsaturated monobasic acid (B), and other reactant materials used as needed is not particularly limited. For example, a resin having a polymerizable unsaturated group may be produced by reacting all of the reactant materials at once, or the resin may be produced by reacting the reactant materials sequentially. In this case, the biomass carbon content (%) (pMC%) of the mixture of the epoxy resin (A), the unsaturated monobasic acid (B), and other reactant materials used as needed with the compound represented by general formula (1) is preferably 10% or more, more preferably 20% or more, and even more preferably 30% or more.

[0160] When the above-described sequential reaction is employed, the reaction between the epoxy resin (A) and the unsaturated monobasic acid (B) can be carried out by heating and stirring at a temperature ranging from 70 to 160°C for a reaction time of 1 to 20 hours. The amount of unsaturated monobasic acid (B) is preferably in the range of 0.20 to 1.05 moles per mole of epoxy groups in the epoxy resin (A). The amount of unsaturated monobasic acid (B) is preferably 0.25 moles or more, more preferably 0.30 moles or more, and even more preferably 0.40 moles or more per mole of epoxy groups in the epoxy resin (A). The amount of unsaturated monobasic acid (B) is preferably 1.04 moles or less, more preferably 1.03 moles or less, and even more preferably 1.00 moles or less per mole of epoxy groups in the epoxy resin (A).

[0161] Each reaction in the production of the resin having a polymerizable unsaturated group is preferably carried out in a solvent represented by the above general formula (1), and an organic solvent other than the solvent represented by the above general formula (1) may be further used as needed. In this case, a basic catalyst may also be used as needed. The organic solvent and basic catalyst may be the same as those used in the reaction between the epoxy resin (A) and the unsaturated monobasic acid (B) described above. Furthermore, each reaction may also use a polymerization inhibitor or an antioxidant as needed.

[0162] The amount of the organic solvent used is preferably in the range of about 0.1 to 5 times the total mass of the reaction raw materials, as this improves the reaction efficiency.

[0163] Alternatively, a mixed solvent containing the organic solvent and water may be used instead of the organic solvent. In this case, the proportion of water per 100 parts by mass of the mixed solvent is preferably in the range of 5 to 60 parts by mass, more preferably 10 to 50 parts by mass.

[0164] Examples of the polymerization inhibitor include p-methoxyphenol (methoquinone), p-methoxycresol, 4-methoxy-1-naphthol, 4,4'-dialkoxy-2,2'-bi-1-naphthol, 3-(N-salicyloyl)amino-1,2,4-triazole, N'1,N'12-bis(2-hydroxybenzoyl)dodecane dihydrazide, styrenated phenol, N-isopropyl-N'-phenylbenzene-1,4-diamine, 6-ethoxy-2,2,4-trimethylolpropane, ... phenolic compounds such as 1,2-dihydroquinoline; quinone compounds such as hydroquinone, methylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone, anthraquinone, and diphenoquinone; melamine, p-phenylenediamine, 4-aminodiphenylamine, N,N'-diphenyl-p-phenylenediamine, Ni-propyl-N'-phenyl-p-phenylenediamine, N-(1,Amine compounds such as 3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, diphenylamine, 4,4'-dicumyl-diphenylamine, 4,4'-dioctyl-diphenylamine, poly(2,2,4-trimethyl-1,2-dihydroquinoline), styrenated diphenylamine, reaction products of styrenated diphenylamine with 2,4,4-trimethylpentene, and reaction products of diphenylamine with 2,4,4-trimethylpentene; phenothiazine, distearyl thiodipropionate, 2,2-bis({[3-(dodecyl) Thioether compounds such as (methylthio)propionyl]oxy}methyl)-1,3-propanediyl bis[3-(dodecylthio)propionate] and ditridecan-1-yl 3,3'-sulfanediyl dipropanoate; N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, etc.; N,N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrosodimethylamine, p-nitrosoaniline, -N,N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-Nn-butyl-4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitroso-N-phenylhydroxylamine ammonium salt, nitrosobenzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-Nn -Propyl urethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, sodium 1-nitroso-2-naphthol-3,6-sulfonate, sodium 2-nitroso-1-naphthol-4-sulfonate, 2-nitroso-5-methylaminophenol hydrochloride, 2-nitroso-5-methylaminophenol hydrochloride and other nitroso compounds; esters of phosphoric acid and octadecan-1-ol, triphenyl phosphite, 3,9-dioctadecan-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]Undecane, trisnonylphenyl phosphite, phosphorous acid-(1-methylethylidene)-di-4,1-phenylenetetra-C12-15-alkyl ester, 2-ethylhexyl diphenyl phosphite, diphenyl isodecyl phosphite, triisodecyl phosphite, phosphite compounds such as tris(2,4-di-tert-butylphenyl) phosphite; bis(dimethyldithiocarbamato-κ(2)S,S')zinc, zinc diethyldithiocarbamate Examples of the polymerization inhibitor include zinc compounds such as zinc dibutyl dithiocarbamate; nickel compounds such as bis(N,N-dibutylcarbamodithioato-S,S')nickel; and sulfur compounds such as 1,3-dihydro-2H-benzimidazole-2-thione, 4,6-bis(octylthiomethyl)-o-cresol, 2-methyl-4,6-bis[(octan-1-ylsulfanyl)methyl]phenol, dilauryl thiodipropionate, and distearyl 3,3'-thiodipropionate. The polymerization inhibitors may be used alone or in combination of two or more.

[0165] The antioxidant is not particularly limited, and the same compounds as those exemplified as the polymerization inhibitor can be used. The antioxidant may be used alone or in combination of two or more.

[0166] Commercially available polymerization inhibitors and antioxidants include, for example, "Q-1300" and "Q-1301" manufactured by Wako Pure Chemical Industries, Ltd., and "Sumilizer BBM-S" and "Sumilizer GA-80" manufactured by Sumitomo Chemical Co., Ltd.

[0167] Next, a method for producing a resin having a polymerizable unsaturated group according to a second embodiment will be described as another example of the method for producing a resin having a polymerizable unsaturated group according to the present invention.

[0168] <Method for producing resin according to the second embodiment> In the second embodiment of the method for producing a resin having a polymerizable unsaturated group according to the present invention, an amide-imide resin (C) having an acid group and / or an acid anhydride group is mixed with a hydroxy(meth)acrylate compound (D). Preferably, a (meth)acrylate compound (E) having an epoxy group is further mixed in the presence of a solvent.

[0169] The amide-imide resin (C) having an acid group and / or an acid anhydride group is preferably produced by reacting a polyisocyanate compound (c1) with a polycarboxylic acid (c2) or a polycarboxylic acid anhydride (c3) as reaction raw materials. The polyisocyanate compound (c1) preferably contains an aliphatic diisocyanate compound, an alicyclic diisocyanate compound, or a modified product thereof, and the polycarboxylic acid (c2) or the polycarboxylic acid anhydride (c3) preferably contains a tricarboxylic acid anhydride.

[0170] The method for reacting the reactants including the polyisocyanate compound (c1) and the polycarboxylic acid (c2) or the polycarboxylic acid anhydride (c3) is not particularly limited. For example, the amide-imide resin (C) having an acid group and / or an acid anhydride group may be produced by reacting all of the reactants at once, or the resin may be produced by reacting the reactants sequentially.

[0171] The method for reacting the reactants including the amide-imide resin (C) having an acid group and / or an acid anhydride group, the hydroxy(meth)acrylate compound (D), the (meth)acrylate compound (E) having an epoxy group, and other reactants used as needed is not particularly limited. For example, the resin having a polymerizable unsaturated group may be produced by a method in which all of the reactants are reacted at once, or the resin may be produced by a method in which the reactants are reacted sequentially. Among these, a method in which an amide-imide resin (C) having an acid group and / or an acid anhydride group is reacted with a hydroxy(meth)acrylate compound (D) to synthesize a product (1), and then a (meth)acrylate compound (E) having an epoxy group is reacted to obtain a resin having a polymerizable unsaturated group is preferred, because the reaction can be easily controlled. In other words, the resin having a polymerizable unsaturated group of this embodiment is preferably one obtained by reacting an amide-imide resin (C) with a hydroxy(meth)acrylate compound (D), and then a (meth)acrylate compound (E) having an epoxy group.

[0172] In the reaction between the amide-imide resin (C) and the hydroxy(meth)acrylate compound (D) (synthesis of product (1)), the acid group and / or acid anhydride group in the amide-imide resin (C) may react mainly with the hydroxy group in the hydroxy(meth)acrylate compound (D). Since the hydroxy(meth)acrylate compound (D) has excellent reactivity, particularly with acid anhydride groups, it is preferable that the amide-imide resin (C) has an acid anhydride group, as described above. The blending ratio (reaction ratio) of the amide-imide resin (C) and the hydroxy(meth)acrylate compound (D) is preferably within a range of 0.9 to 10 moles of the hydroxy(meth)acrylate compound (D) per mole of the total of acid groups and acid anhydride groups in the amide-imide resin (C). In particular, the amount of the hydroxy(meth)acrylate compound (D) is preferably within a range of 0.9 to 1.1 moles per mole of the total of acid anhydride groups in the amide-imide resin (C). The content of acid anhydride groups in the amide-imide resin (C) can be calculated from the difference between the acid value under neutral conditions, i.e., conditions under which the acid anhydride groups are not ring-opened, and the acid value under conditions under which the acid anhydride groups are ring-opened, such as in the presence of water.

[0173] The reaction between the amide-imide resin (C) and the hydroxy(meth)acrylate compound (D) (synthesis of product (1)) can be carried out, for example, by heating and stirring in the presence of a suitable basic catalyst at a temperature ranging from about 80 to 140°C for a reaction time of 0.5 to 20 hours. The basic catalyst may be the same as that used in the reaction between the epoxy resin (A) and the unsaturated monobasic acid (B). These basic catalysts may be used alone or in combination of two or more. The amount of the basic catalyst added is preferably in the range of 0.03 to 5% by mass based on the total mass of the reaction raw materials.

[0174] The reaction may be carried out in an organic solvent if necessary. When an organic solvent is used, it is preferably carried out in the solvent represented by the general formula (1), and other organic solvents may also be used if necessary. The organic solvent may be the same as that used in the reaction between the epoxy resin (A) and the unsaturated monobasic acid (B). These organic solvents may be used alone or in combination of two or more. When the production of the amide-imide resin (C) and the synthesis of the product (1) are carried out consecutively, the reaction may be continued in the organic solvent used in the production of the amide-imide resin (C).

[0175] In the reaction between the product (1) and the (meth)acrylate compound (E) having an epoxy group, the (meth)acrylate compound (E) having an epoxy group can react mainly with the carboxy group in the product (1). The compounding ratio (reaction ratio) of the product (1) and the (meth)acrylate compound (E) having an epoxy group is preferably 0.1 to 1.1 moles, more preferably 0.5 to 1.05 moles, of the (meth)acrylate compound (E) having an epoxy group per mole of carboxyl groups in the product (1). The reaction of the product (1) with the (meth)acrylate compound (E) having an epoxy group can be carried out, for example, by heating and stirring in the presence of a suitable basic catalyst at a temperature of about 90 to 140°C for a reaction time of 0.5 to 20 hours. When the synthesis of the product (1) and the reaction with the (meth)acrylate compound (E) having an epoxy group are carried out consecutively, a basic catalyst may or may not be added as appropriate. The reaction may also be carried out in an organic solvent, if necessary.

[0176] In each reaction in the production of a resin having a polymerizable unsaturated group, a polymerization inhibitor or an antioxidant can be used as needed, and the polymerization inhibitor and antioxidant can be the same as those described in the first embodiment.

[0177] (Curable resin composition) The curable resin composition of the present embodiment contains at least the resin having a polymerizable unsaturated group described above and a photopolymerization initiator, and can give a cured product having excellent heat resistance and adhesion.

[0178] The biomass carbon content (%) of the curable resin composition of this embodiment is preferably 2% or more, and more preferably 4% or more. This can contribute to reducing the environmental impact. The biomass carbon content of the curable resin composition used in this embodiment is not particularly limited, but can be 95% or less, or 90% or less. The ratio of each component in the curable resin composition can be changed as appropriate depending on the intended use, etc. Therefore, the biomass carbon content (%) of the curable resin composition can be roughly calculated from the weight ratio of the known biomass carbon contents (%) of each component in the composition.

[0179] <Photopolymerization initiator> Examples of the photopolymerization initiator include photoradical polymerization initiators such as 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethan-1-one, diphenyl(2,4,6-trimethoxybenzoyl)phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone. One type of photopolymerization initiator may be used alone, or two or more types may be used in combination.

[0180] Commercially available photopolymerization initiators include, for example, "Omnirad-1173", "Omnirad-184", "Omnirad-127", "Omnirad-2959", "Omnirad-369", "Omnirad-379", "Omnirad-907", "Omnirad-4265", "Omnirad-1000", "Omnirad-651", "Omnirad-TPO", "Omnirad-819", "Omnirad-2022", "Omnirad-2100", "Omnirad-754", "Omnirad-784", "Omnirad-500", and "Om Examples of suitable anti-inflammatory agents include "nirad-81" (manufactured by IGM), "Kayacure-DETX", "Kayacure-MBP", "Kayacure-DMBI", "Kayacure-EPA", and "Kayacure-OA" (manufactured by Nippon Kayaku Co., Ltd.), "Baicure-10", "Baicure-55" (manufactured by Stauffer Chemical Co., Ltd.), "Trigonal P1" (manufactured by Akzo), "Sandray 1000" (manufactured by Sandoz), "Deep" (manufactured by Upjohn), "Quantacure-PDO", "Quantacure-ITX", and "Quantacure-EPD" (manufactured by Ward-Blenkinsop), and "Runtecure-1104" (manufactured by Runtec).

[0181] The content of the photopolymerization initiator in the curable resin composition of this embodiment is preferably 0.1 parts by mass or more and 10 parts by mass or less relative to 100 parts by mass of the resin having a polymerizable unsaturated group (a mixture of solids and a solvent).

[0182] <Curing agent> The curable resin composition of the present embodiment may further contain a curing agent, which improves the curability of the curable resin composition.

[0183] Examples of the curing agent include epoxy resins and other curing agents (amine curing agents, acid anhydride curing agents, phenolic resin curing agents, etc.). The curing agents may be used alone or in combination of two or more. Among these, epoxy resins are preferred as the curing agent.

[0184] The epoxy resin used as a curing agent is not particularly limited, but is preferably a curable resin that contains two or more epoxy groups in the molecule and can be cured by forming a crosslinked network with the epoxy groups. The epoxy resin is not particularly limited, but may be a novolac epoxy resin such as a phenol novolac epoxy resin, a cresol novolac epoxy resin, an α-naphthol novolac epoxy resin, a β-naphthol novolac epoxy resin, a bisphenol A novolac epoxy resin, or a biphenyl novolac epoxy resin; aralkyl-type epoxy resins such as phenol aralkyl-type epoxy resins, naphthol aralkyl-type epoxy resins, and phenol biphenyl aralkyl-type epoxy resins; Bisphenol-type epoxy resins such as bisphenol A-type epoxy resin, bisphenol AP-type epoxy resin, bisphenol AF-type epoxy resin, bisphenol B-type epoxy resin, bisphenol BP-type epoxy resin, bisphenol C-type epoxy resin, bisphenol E-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, and tetrabromobisphenol A-type epoxy resin; biphenyl-type epoxy resins such as biphenyl-type epoxy resins, tetramethylbiphenyl-type epoxy resins, and epoxy resins having a biphenyl skeleton and a diglycidyloxybenzene skeleton; Naphthalene-type epoxy resin; Binaphthol-type epoxy resin; Binaphthyl-type epoxy resin; Dicyclopentadiene-type epoxy resins such as dicyclopentadiene phenol-type epoxy resins; glycidylamine-type epoxy resins such as tetraglycidyldiaminodiphenylmethane-type epoxy resins, triglycidyl-p-aminophenol-type epoxy resins, and diaminodiphenylsulfone-type glycidylamine-type epoxy resins; diglycidyl ester type epoxy resins such as 2,6-naphthalenedicarboxylic acid diglycidyl ester type epoxy resins and hexahydrophthalic anhydride glycidyl ester type epoxy resins; Examples thereof include benzopyran-type epoxy resins such as dibenzopyran, hexamethyldibenzopyran, and 7-phenylhexamethyldibenzopyran. Among these epoxy resins, so-called glycidyl ether epoxy resins obtained by epoxidizing a phenol compound are preferred, and among them, novolac epoxy resins, aralkyl epoxy resins, and dicyclopentadiene epoxy resins are more preferred from the viewpoint of various performances. The above-mentioned epoxy resins may be used alone or in combination of two or more.

[0185] The epoxy equivalent of the epoxy resin as a curing agent is preferably 120 to 400 g / eq, more preferably 150 to 300 g / eq, from the viewpoint of more effectively improving adhesion and low elastic modulus.

[0186] The softening point of the epoxy resin used as a curing agent is preferably 20 to 200°C, more preferably 40 to 150°C, from the viewpoint of more effectively improving adhesion and low modulus of elasticity.

[0187] The amine curing agent is not particularly limited, but examples thereof include aliphatic amines such as diethylenetriamine (DTA), triethylenetetramine (TTA), tetraethylenepentamine (TEPA), dipropylenediamine (DPDA), diethylaminopropylamine (DEAPA), N-aminoethylpiperazine, menthenediamine (MDA), isophoronediamine (IPDA), 1,3-bisaminomethylcyclohexane (1,3-BAC), piperidine, N,N-dimethylpiperazine, and triethylenediamine; and aromatic amines such as m-xylenediamine (XDA), methanephenylenediamine (MPDA), diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), benzylmethylamine, 2-(dimethylaminomethyl)phenol, and 2,4,6-tris(dimethylaminomethyl)phenol.

[0188] Examples of the acid anhydride curing agent include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitate, glycerol tristrimellitate, maleic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, endomethylene tetrahydrophthalic anhydride, methyl endomethylene tetrahydrophthalic anhydride, methylbutenyl tetrahydrophthalic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, and methylcyclohexene dicarboxylic anhydride.

[0189] Examples of the phenol resin curing agent include phenol novolac resin, cresol novolac resin, naphthol novolac resin, bisphenol novolac resin, biphenyl novolac resin, dicyclopentadiene-phenol adduct resin, phenol aralkyl resin, naphthol aralkyl resin, triphenolmethane type resin, tetraphenolethane type resin, and aminotriazine-modified phenol resin. Any of the other curing agents described above may be used alone or in combination of two or more.

[0190] When the curing agent is used, the content of the curing agent in the curable resin composition of this embodiment is preferably 5 to 40 parts by mass relative to 100 parts by mass of the resin having a polymerizable unsaturated group (a mixture of solids and a solvent). When the content is 5 parts by mass or more, the curability can be further improved, and when the content is 40 parts by mass or less, the flexibility can be improved.

[0191] <Organic solvents> The curable resin composition of the present embodiment may further contain an organic solvent in addition to the organic solvents used in the above-described reactions. By appropriately using the organic solvent, the viscosity of the curable resin composition can be adjusted. Specific examples of the organic solvent are not particularly limited, but the same organic solvents as those used in the above-mentioned epoxidation reaction can be used. The organic solvents can be used alone or in combination of two or more.

[0192] When the organic solvent is used, the content of the organic solvent in the curable resin composition of this embodiment is more preferably 5 to 90 mass %, and even more preferably 8 to 80 mass %, of the total amount (100 mass %) of the curable resin composition. An organic solvent content of 5 mass % or more is preferable because it provides excellent handleability. On the other hand, an organic solvent content of 90 mass % or less is preferable from the viewpoint of economy.

[0193] <Other Resins Having Polymerizable Unsaturated Groups (X)> The curable resin composition of this embodiment may further contain a resin (X) having a polymerizable unsaturated group other than the resin having a polymerizable unsaturated group of this embodiment described above. Such a resin (X) having a polymerizable unsaturated group may be any polymer material having a polymerizable unsaturated group in the resin, and examples thereof include the following [1] to [4]: [1] Urethane resin (X-1) having a polymerizable unsaturated group, [2] Acrylic resin (X-2) having a polymerizable unsaturated group, [3] Acrylamide resin (X-3) having a polymerizable unsaturated group, [4] Ester resin (X-4) having a polymerizable unsaturated group, and the like. Preferably, the resins [1] to [4] above have a polymerizable unsaturated group but do not have an acid group. The resin having a polymerizable unsaturated group of this embodiment differs from the resins [1] to [4] above in that they have different groups.

[0194] <Urethane resin (X-1) having polymerizable unsaturated groups> Examples of the urethane resin (X-1) having a polymerizable unsaturated group (hereinafter also referred to as resin (X-1)) of this embodiment include those obtained by reacting a polyisocyanate compound, a hydroxy(meth)acrylate compound, and, if necessary, a polyol compound and / or a polybasic acid anhydride. As mentioned above, polybasic acid anhydrides can be used as reaction raw materials for resin (X-1), but it is preferable not to use them.

[0195] The polyisocyanate compound used in the resin (X-1) may be the same as the polyisocyanate compound (c1) described above, and the polyisocyanate compound may be used alone or in combination of two or more kinds.

[0196] The hydroxy(meth)acrylate compound used in the resin (X-1) may be the same as the hydroxy(meth)acrylate compound (D) described above, and the hydroxy(meth)acrylate compound (D) may be used alone or in combination of two or more kinds.

[0197] The polybasic acid anhydride used in the resin (X-1) can be the same as the aliphatic polybasic acid anhydrides, alicyclic polybasic acid anhydrides, aromatic polybasic acid anhydrides, etc. exemplified in the above-mentioned polycarboxylic acid (c2) or polycarboxylic acid anhydride (c3). These polybasic acid anhydrides may be used alone or in combination of two or more.

[0198] Examples of the polyol compounds include aliphatic polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; aromatic polyol compounds such as biphenol and bisphenol; (poly)oxyalkylene-modified compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the above-mentioned various polyol compounds; lactone-modified compounds in which a (poly)lactone structure has been introduced into the molecular structure of the above-mentioned various polyol compounds, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylolvaleric acid. The above-mentioned polyol compounds may be used alone or in combination of two or more.

[0199] The method for producing the urethane resin (X-1) having a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the urethane resin (X-1) having a polymerizable unsaturated group may be carried out in an organic solvent, if necessary, and may also use a basic catalyst, if necessary.

[0200] Specific examples of the organic solvent are not particularly limited, but the same organic solvents as those used in the epoxidation reaction described above can be used. These organic solvents can be used alone or in combination of two or more.

[0201] As the basic catalyst, the same catalyst as that used in the reaction between the epoxy resin (A) and the unsaturated monobasic acid (B) can be used. The basic catalysts may be used alone or in combination of two or more.

[0202] <Acrylic resin having polymerizable unsaturated group (X-2)> Examples of the acrylic resin (X-2) having a polymerizable unsaturated group of this embodiment (hereinafter also referred to as resin (X-2)) include a reaction product obtained by polymerizing an acrylic resin intermediate obtained by polymerizing, as an essential component, a (meth)acrylate compound (α) having a reactive functional group such as a hydroxyl group, a carboxyl group, an isocyanate group, or a glycidyl group, and then further reacting this with a (meth)acrylate compound (β) having a reactive functional group capable of reacting with these functional groups to introduce a (meth)acryloyl group, and, if necessary, a product obtained by reacting a polybasic acid anhydride with the hydroxyl group in the reaction product. As mentioned above, polybasic acid anhydrides can be used as a reaction raw material for resin (X-2), but it is preferable not to use them. The acrylic resin intermediate may be copolymerized with the (meth)acrylate compound (α) and, if necessary, other compounds having polymerizable unsaturated groups. Examples of the compounds having polymerizable unsaturated groups include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; alicyclic structure-containing (meth)acrylates such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; aromatic ring-containing (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, and phenoxyethyl acrylate; silyl group-containing (meth)acrylates such as 3-methacryloxypropyltrimethoxysilane; and styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene. The compounds having other polymerizable unsaturated groups may be used singly or in combination of two or more.

[0203] The (meth)acrylate compound (β) is not particularly limited as long as it can react with the reactive functional group of the (meth)acrylate compound (α), but the following combinations are preferred from the viewpoint of reactivity. That is, when water (meth)acrylate is used as the (meth)acrylate compound (α), it is preferred to use a (meth)acrylate having an isocyanate group as the (meth)acrylate compound (β). When a (meth)acrylate having a carboxyl group is used as the (meth)acrylate compound (α), it is preferred to use a (meth)acrylate having a glycidyl group as the (meth)acrylate compound (β). When a (meth)acrylate having an isocyanate group is used as the (meth)acrylate compound (α), it is preferred to use water (meth)acrylate as the (meth)acrylate compound (β). When a (meth)acrylate having a glycidyl group is used as the (meth)acrylate compound (α), it is preferred to use a (meth)acrylate having a carboxyl group as the (meth)acrylate compound (β). The (meth)acrylate compound (β) may be used alone or in combination of two or more. The polybasic acid anhydride is the same as that described above for the resin (X-1) and the like. The method for producing the acrylic resin (X-2) having a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the acrylic resin (X-2) having a polymerizable unsaturated group may be carried out in an organic solvent as needed, and a basic catalyst may be used as needed. In this case, the organic solvent and the basic catalyst are the same as those described above for the resin (X-1) and the like.

[0204] <Acrylamide resin having polymerizable unsaturated group (X-3)> Examples of the acrylamide resin (X-3) having a polymerizable unsaturated group of this embodiment (hereinafter also referred to as resin (X-3)) include those obtained by reacting a compound having a phenolic hydroxyl group, an alkylene oxide or alkylene carbonate, an N-alkoxyalkyl (meth)acrylamide compound, and, if necessary, a polybasic acid anhydride and an unsaturated monobasic acid. As mentioned above, polybasic acid anhydrides can be used as reaction raw materials for resin (X-3), but it is preferable not to use them. The compound having a phenolic hydroxyl group refers to a compound having at least one phenolic hydroxyl group in the molecule. Examples of the compound having at least one phenolic hydroxyl group in the molecule include compounds represented by the following general formulas (10.1) to (10.5). [ka] (In the above general formulas (10.1) to (10.5), R 101 ~R 104 and R 107 each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, or a halogen atom; R 105 and R 106 each independently represents a hydrogen atom or a methyl group; j 101 ~j 105 Each independently represents an integer of 0 or 1 or more, preferably 0 or an integer of 1 to 3, and more preferably 0 or 1. 101 ~k 105 each independently represents an integer of 1 or more, preferably 2 or 3.

[0205] The positions of the substituents on the aromatic rings in the general formulas (10.1) to (10.5) are arbitrary. For example, in the naphthalene ring of the general formula (10.2), they may be substituted with any hydrogen atom on the ring. In the general formula (10.3), they may be substituted with any hydrogen atom on the benzene ring present in one biphenyl molecule. In the general formula (10.4), they may be substituted with any hydrogen atom on the benzene ring present in one aralkyl molecule. In the general formula (10.5), they may be substituted with any hydrogen atom on the benzene ring present in one molecule. When the number of substituents in one molecule is j, 101 ~j 105 and k 101 ~k 105 This indicates that Examples of the compound having a phenolic hydroxyl group include reaction products obtained by using, as essential reaction raw materials, a compound having at least one phenolic hydroxyl group in the molecule and a compound represented by any one of the following general formulas (11.1) to (11.5) and / or formaldehyde. Also usable are novolac-type phenolic resins obtained by using, as reaction raw materials, one or more compounds having at least one phenolic hydroxyl group in the molecule. [ka] (In the above general formulas (11.1) to (11.5), h 111 represents 0 or 1, R 111 ~R 116 each independently represents a monovalent aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, or an aralkyl group; k 111 ~k 116 each independently represents 0 or an integer of 1 to 4, and Z 111 ~Z 116 each independently represents a vinyl group, a halomethyl group, a hydroxymethyl group, or an alkyloxymethyl group; Y 111 represents an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, or a carbonyl group, and n 111 represents an integer from 1 to 4.)

[0206] Specific examples of the compound having a phenolic hydroxyl group include phenol, cresol, xylenol; dialkylphenols such as dimethylphenol and diethylphenol; trialkylphenols such as trimethylphenol and triethylphenol; diphenylphenol, triphenylphenol, catechol, resorcinol, hydroquinone, 3-methylcatechol, 4-methylcatechol, 4-allylpyrocatechol, tetramethylbisphenol A, 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene, 1-naphthol, 2-naphthol, 1,3-naphthalenediol, 1,5-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, polyphenylene ether type diol, polynaphthylene ether type diol, phenol novolac resin, cresol novolac resin, bisphenol novolac type resin, naphthol novolac type resin, phenol aralkyl type resin, naphthol aralkyl type resin, and phenol resins having a cyclo ring structure. The above compounds having a phenolic hydroxyl group may be used alone or in combination of two or more. Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and pentylene oxide. The alkylene oxides may be used alone or in combination of two or more. Among these, ethylene oxide or propylene oxide is preferred as the alkylene oxide. Examples of the alkylene carbonate include ethylene carbonate, propylene carbonate, butylene carbonate, and pentylene carbonate. The alkylene carbonate may be used alone or in combination of two or more. Among these, ethylene carbonate or propylene carbonate is preferred as the alkylene carbonate. Examples of the N-alkoxyalkyl(meth)acrylamide compound include N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-methoxyethyl(meth)acrylamide, N-ethoxyethyl(meth)acrylamide, N-butoxyethyl(meth)acrylamide, etc. The N-alkoxyalkyl(meth)acrylamide compounds may be used singly or in combination of two or more.

[0207] The unsaturated monobasic acid is the same as the unsaturated monobasic acid (B), and for example, a compound represented by the general formula (2) can also be used.

[0208] Examples of the polyoxyalkylene chain include a polyoxyethylene chain and a polyoxypropylene chain. The (poly)ester chain may be, for example, a (poly)ester chain represented by the general formula (9-1) above. These unsaturated monobasic acids may be used alone or in combination of two or more. The polybasic acid anhydride is the same as that described above for the resin (X-1) and the like. The method for producing the acrylamide resin (X-3) having a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the acrylamide resin (X-3) having a polymerizable unsaturated group may be carried out in an organic solvent, if necessary, and a basic catalyst and an acidic catalyst may be used, if necessary. In this case, the organic solvent and the basic catalyst are the same as those described above for the resin (X-1) and the like. The acidic catalyst may be any of the acidic catalysts used in the reaction of the phenolic hydroxyl group-containing compound with the ketone group-containing compound, and may be any of an organic acid, a Lewis acid, a solid acidic catalyst, etc. These acidic catalysts may be used alone or in combination of two or more.

[0209] <Ester resin (X-4) having polymerizable unsaturated groups> The ester resin (X-4) having a polymerizable unsaturated group of this embodiment (hereinafter also referred to as resin (X-4)) can be, for example, a compound having a phenolic hydroxyl group, an alkylene oxide or alkylene carbonate, an unsaturated monobasic acid, and, if necessary, a polybasic acid anhydride, which is obtained by reacting the compound. As mentioned above, the polybasic acid anhydride can be used as a reaction raw material for the resin (X-4), but it is preferable not to use the polybasic acid anhydride. The compounds having a phenolic hydroxyl group, alkylene oxides, alkylene carbonates, unsaturated monobasic acids, and polybasic acid anhydrides are the same as those described above for resin (X-1) and resin (X-3), etc. The method for producing the ester resin (X-4) having a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the ester resin (X-4) having a polymerizable unsaturated group may be carried out in an organic solvent as needed, and a basic catalyst and an acid catalyst may be used as needed. In this case, the organic solvent, basic catalyst, and acid catalyst are the same as those described above for the resin (X-1) and the resin (X-3).

[0210] When the resin (X) having the other polymerizable unsaturated group is used, the amount of the resin (X) used is preferably 10 parts by mass or more, and is preferably 900 parts by mass or less, more preferably 500 parts by mass or less, even more preferably 500 parts by mass or less, and still more preferably 100 parts by mass or less, relative to 100 parts by mass of the resin having the polymerizable unsaturated group of the present embodiment.

[0211] <Compound having a polymerizable unsaturated group> The curable resin composition of the present embodiment may further contain a compound having a polymerizable unsaturated group. Such a compound having a polymerizable unsaturated group is typically a compound having no acid group. Examples of the compound having a polymerizable unsaturated group include (meth)acrylate compounds, and specific examples thereof include aliphatic mono(meth)acrylate compounds such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and octyl (meth)acrylate; alicyclic mono(meth)acrylate compounds such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and adamantyl mono(meth)acrylate; heterocyclic mono(meth)acrylate compounds such as glycidyl (meth)acrylate and tetrahydrofurfuryl acrylate; benzyl (meth)acrylate, phenyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenoxy (meth)acrylate, phenoxyethyl (meth)acrylate, and phenoxyethoxyethyl (meth)acrylate. mono(meth)acrylate compounds such as aromatic mono(meth)acrylate compounds such as 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzyl (meth)acrylate, and phenylphenoxyethyl (meth)acrylate; (poly)oxyalkylene-modified mono(meth)acrylate compounds in which a polyoxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the above-mentioned various mono(meth)acrylate monomers; lactone-modified mono(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the above-mentioned various mono(meth)acrylate compounds; aliphatic di(meth)acrylate compounds such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate;Alicyclic di(meth)acrylate compounds such as 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate; aromatic di(meth)acrylate compounds such as biphenol di(meth)acrylate and bisphenol di(meth)acrylate; and (poly)oxyethylene compounds in the molecular structure of the above-mentioned various di(meth)acrylate compounds. Polyoxyalkylene-modified di(meth)acrylate compounds in which a (poly)oxyalkylene chain such as a propylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced; lactone-modified di(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the above-mentioned various di(meth)acrylate compounds; aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerin tri(meth)acrylate; (Poly)oxyalkylene-modified tri(meth)acrylate compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced; lactone-modified tri(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the aliphatic tri(meth)acrylate compounds; pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate and tetrafunctional or higher aliphatic poly(meth)acrylate compounds such as those mentioned above; tetrafunctional or higher (poly)oxyalkylene-modified poly(meth)acrylate compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the aliphatic poly(meth)acrylate compound; and tetrafunctional or higher lactone-modified poly(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the aliphatic poly(meth)acrylate compound. The compounds having a polymerizable unsaturated group may be used alone or in combination of two or more.

[0212] <Optional addition ingredients> The curable resin composition of the present embodiment may further contain optional additives within the scope of the purpose, such as a curing accelerator, other resins, a polymerization inhibitor, an antioxidant, a flame retardant, a filler, a pigment, an antifoaming agent, a viscosity modifier, a leveling agent, an ultraviolet stabilizer, and a storage stabilizer.

[0213] (cured product) The cured product of this embodiment is a cured product of the above-described curable resin composition. That is, the cured product of this embodiment is obtained by curing the above-described curable resin composition. The cured product of this embodiment has excellent insulation reliability, heat resistance, and adhesion.

[0214] The cured product of this embodiment is preferably obtained by irradiating the curable resin composition with active energy rays to cure it. Examples of the active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α-rays, β-rays, and γ-rays. When ultraviolet rays are used as the active energy rays, irradiation may be performed in an inert gas atmosphere such as nitrogen gas, or in an air atmosphere in order to efficiently carry out the ultraviolet curing reaction.

[0215] Specific examples of ultraviolet radiation sources include ultraviolet lamps such as low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, and metal halide lamps, as well as sunlight and LEDs. Of these, ultraviolet lamps are generally used from the viewpoints of practicality and economy.

[0216] The cumulative light amount of the active energy rays is not particularly limited, but is preferably 0.1 to 50 kJ / m 2 is preferably 0.5 to 10 kJ / m 2 It is more preferable that the integrated light amount is within the above range. When the integrated light amount is within the above range, the occurrence of uncured portions can be sufficiently prevented or suppressed. The irradiation of the active energy rays may be carried out in one step or in two or more steps.

[0217] Another method for curing the curable resin composition to obtain a cured product is, for example, heat curing. The heating temperature for heat curing is not particularly limited, but is preferably 100 to 300°C, and the heating time is preferably 1 to 24 hours.

[0218] The cured product of this embodiment can be suitably used in semiconductor device applications as solder resist, interlayer insulating material, packaging material, underfill material, package adhesive layer for circuit elements, etc., or adhesive layer between integrated circuit elements and circuit boards. It can also be suitably used in thin-film display applications such as LCDs and OELDs as thin-film transistor protective films, liquid crystal color filter protective films, pigment resists for color filters, black matrix resists, spacers, etc. [Example]

[0219] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples in any way.

[0220] The properties of each component in the examples were evaluated using the procedures shown below as appropriate.

[0221] <Epoxy equivalent (epoxy resin (A))> The epoxy equivalent was measured in accordance with JIS K 7236.

[0222] <Total chlorine content (epoxy resin (A))> The total amount of chlorine was calculated in accordance with JIS K 7246. Specifically, the epoxy resin was dissolved in diethylene glycol monobutyl ether, a 1N potassium hydroxide-propylene glycol solution was added, and the mixture was boiled for 20 minutes, after which potentiometric titration was performed with silver nitrate.

[0223] <α-glycol content (epoxy resin (A))> The amount of α-glycol was calculated in accordance with JIS K 7146. Specifically, taking advantage of the fact that α-glycol in the epoxy resin reacts quantitatively with periodic acid, is cleaved, and is oxidized to a carbonyl compound, the amount of α-glycol was calculated by adding potassium iodide to excess periodic acid and titrating the generated iodine with a sodium thiosulfate solution.

[0224] <Acid value (resin having polymerizable unsaturated groups)> The acid values ​​of the resins having a polymerizable unsaturated group obtained in the examples and comparative examples were measured in accordance with JIS K0070:1992 standard.

[0225] <Double bond equivalent (g / equivalent)> The double bond equivalent of the resin having a polymerizable unsaturated group prepared in the examples was calculated from the amount of each component in the reaction raw materials using the following formula. Double bond equivalent weight = (molecular weight of compound component in reactant having a double bond) / (molar equivalent weight per mole of functional group of compound having a double bond) That is, the double bond equivalent is the mass of the solid content of the resin solution per mole of double bonds in the resin having a polymerizable unsaturated group. The molecular weight of the compound component in the reaction raw material having a double bond is the weight of the solid content of the resin, calculated by adding up the masses of all the components of the reaction raw materials, under the assumption that all of the reaction raw materials constituting the resin having a polymerizable unsaturated group are reacted and bonded. In addition, the double bond equivalent (g / equivalent) can also be measured using various analyses such as titration and elemental analysis, NMR, IR, and differential scanning calorimetry. 1 Although it can be calculated from the area ratio of H-NMR, in the examples it was calculated from the amount charged as described above.

[0226] <Biomass carbon content (solvent, (meth)acrylate compound having an epoxy group, resin having a polymerizable unsaturated group, curable resin composition)> (1) Pretreatment of samples for accelerator mass spectrometry (AMS) 10 mg of the sample to be measured was placed in a quartz sample tube along with fine copper oxide, which was then degassed and sealed. The tube was then heated at 500°C for 30 minutes and then at 850°C for 2 hours to convert it to carbon dioxide. The sample tube was then connected to a vacuum line and purified to carbon dioxide using the cold trap method. The carbon dioxide was then transferred to a quartz tube containing iron powder, after which hydrogen gas was added and the tube was sealed. The tube was then heated at 650°C for 10 hours to carry out a reduction reaction, producing graphite for measurement.

[0227] (2) Radiocarbon ( 14 Calculation of the content ratio (pMC%) of C) Next, the obtained measurement graphite is filled into a sample holder and subjected to accelerator mass spectrometry (AMS), and the radioactive carbon ( 14 The content ratio (pMC%) of C) was calculated. Formula (A): Radiocarbon ( 14 C) content ratio (pMC%) = [{radioactive carbon in the sample ( 14 C) ÷ carbon in the sample to be measured ( 12 C)} / {Radiocarbon of standard material ( 14 C) / carbon of standard material ( 12 C)}×100 (In the above formula, the standard material used was oxalic acid (SRM4990C), supplied by the National Institute of Standards and Technology as a standard material for dating, which was converted to graphite using the same pretreatment method as the graphite used for measurement above.)

[0228] (3) Calculation of biomass carbon content (%) Next, the radiocarbon ( 14 The biomass carbon content (%) was calculated by multiplying the biomass carbon content (pMC%) by 0.93, taking into account the effects of atmospheric nuclear testing from 1950 to the present. Formula (B): Biomass carbon content (%) = radiocarbon ( 14 C) content ratio (pMC%) x 0.93 (Note that, since applying this method to a mixture (composition) may result in a large error, if the value calculated using the above formula (B) is 100% or more, the biomass carbon content (%) is considered to be 100%.)

[0229] (Preparation of phenolic resin (1)) A flask equipped with a thermometer, dropping funnel, condenser, fractionating column, and stirrer was charged with 1081 g (10 mol) of orthocresol and 22 g of oxalic acid, and the mixture was stirred while heating from room temperature to 100°C over 45 minutes. Subsequently, 679 g (9.5 mol) of a 42% by weight aqueous formalin solution was added dropwise over 3 hours. After the addition was complete, the mixture was stirred at 100°C for an additional hour, and then heated to 180°C over 3 hours. After the reaction was complete, the remaining water in the reaction system was removed under reduced pressure with heating, yielding 953 g of phenolic resin (3). The resulting phenolic resin (1) had a phenolic hydroxyl equivalent of 118 g / equivalent and a softening point of 131°C.

[0230] (Preparation of Epoxy Resin (A1)) A flask equipped with a thermometer, condenser, and stirrer was purged with nitrogen gas. 118 g (1.0 equivalent of hydroxyl groups) of the phenolic resin (1) obtained in the above reaction, 278 g (3.0 mol) of epichlorohydrin, and 53 g of n-butanol were charged and dissolved with stirring. After heating to 50°C, 220 g (1.10 mol) of 20% aqueous sodium hydroxide solution was added over 3 hours, and the mixture was then allowed to react at 50°C for an additional 1 hour. After the reaction was completed, stirring was stopped, the aqueous layer that had accumulated in the lower layer was removed, and stirring was resumed. Unreacted epichlorohydrin was distilled off under reduced pressure at 150°C. 300 g of methyl isobutyl ketone and 50 g of n-butanol were added to the crude epoxy resin and dissolved. 15 g of 10% aqueous sodium hydroxide solution was added to this solution and reacted at 80°C for 2 hours. The mixture was then washed three times with 100 g of water until the pH of the washings became neutral. The system was then dehydrated by azeotropy, and after microfiltration, the solvent was distilled off under reduced pressure to obtain the target epoxy resin (A1). The epoxy equivalent of the epoxy resin (A1) was 215 g / equivalent, the softening point was 96°C, the total chlorine content was 1140 ppm, and the α-glycol content was 0.06 meq / g.

[0231] (Preparation of (meth)acrylate compound having epoxy group) Glycidyl methacrylate was prepared as a (meth)acrylate compound having an epoxy group to be used later in the preparation of a resin having a polymerizable unsaturated group. The chlorine atom content of the glycidyl methacrylate was 10 mass ppm or less. More specifically, the numerical value could not be determined because it was below the detection limit (below the lower limit of quantification), but it is thought to be approximately several ppm. In addition, the biomass carbon content of the glycidyl methacrylate used in the examples was 43%.

[0232] (Example 1: Preparation of Resin (1) Having Polymerizable Unsaturated Group) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 191.3 g of a biomass solvent (manufactured by Solvay Nicca Co., Ltd., "DV16J0401") having a biomass carbon content (pMC%) of 82% and an amide bond, represented by the following general formula (1). 215 g of epoxy resin (A1) was dissolved in the solvent. 0.3 g of dibutylhydroxytoluene and 0.1 g of methoquinone were added. Then, 72 g of acrylic acid (unsaturated monobasic acid (B)) and 2.8 g of triphenylphosphine were added. The mixture was stirred at 120 °C for 30 hours to obtain polymerizable unsaturated group-containing resin (1). (Here, "resin" refers to a mixture of solids and solvent.) This polymerizable unsaturated group-containing resin (1) had a nonvolatile content of 60% by mass, a solid acid value of 0.6 mg KOH / g, and a solid chlorine atom content of 860 ppm by mass. Furthermore, the biomass carbon content (%) (pMC%) of the entire resin (1) was 33% or more, and the biomass carbon content (%) of the solid content was 0%. [ka] (In the above general formula (1), R 1 and R 2 are methyl groups, and R 3 represents a monovalent organic group having 7 to 9 carbon atoms.

[0233] (Example 2: Preparation of Resin (2) Having Polymerizable Unsaturated Group) In a flask equipped with a thermometer, stirrer, and reflux condenser, 107.6 g of biomass solvent (Solvay Nicca Co., Ltd., "DV16J0401") was placed, as in Example 1, and 215 g of epoxy resin (A1) was dissolved therein. 0.3 g of dibutylhydroxytoluene and 0.1 g of methoquinone were added, followed by 36 g of acrylic acid (unsaturated monobasic acid (B)) and 0.8 g of triphenylphosphine. The mixture was stirred at 100 ° C for 30 hours. Next, 0.8 g of oxalic acid was added, and the mixture was stirred at 70 ° C for 0.5 hours to obtain a polymerizable unsaturated group-containing resin (2). (Here, "resin" refers to a mixture of solids and solvent.) This polymerizable unsaturated group-containing resin (2) had a nonvolatile content of 70% by mass, a solid acid value of 0.5 mg KOH / g, and a solid chlorine atom content of 980 ppm by mass. Furthermore, the biomass carbon content (%) (pMC%) of the entire resin (2) was 25% or more, and the biomass carbon content (%) of the solid content was 0%.

[0234] (Example 3: Preparation of Resin (3) Having Polymerizable Unsaturated Group) In a flask equipped with a thermometer, stirrer, and reflux condenser, 61 g of biomass solvent (Solvay Nicca Co., Ltd., "DV16J0401") was placed, as in Example 1, and 215 g of epoxy resin (A1) was dissolved therein. 0.3 g of dibutylhydroxytoluene and 0.1 g of methoquinone were added, followed by 28.8 g of acrylic acid (unsaturated monobasic acid (B)) and 0.8 g of triphenylphosphine. The mixture was stirred at 100 ° C for 20 hours. Next, 0.8 g of oxalic acid was added, and the mixture was stirred at 70 ° C for 0.5 hours to obtain a polymerizable unsaturated group-containing resin (3). (Here, "resin" refers to a mixture of solids and solvent.) This polymerizable unsaturated group-containing resin (3) had a nonvolatile content of 80% by mass, a solid acid value of 0.4 mg KOH / g, and a solid chlorine atom content of 1010 ppm by mass. Furthermore, the biomass carbon content (%) (pMC%) of the entire resin (3) was 16% or more, and the biomass carbon content (%) of the solid content was 0%.

[0235] (Example 4: Preparation of Resin (4) Having Polymerizable Unsaturated Group) In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 499.7 g of biomass solvent (Solvay Nicca Co., Ltd., "DV16J0401") was placed, as in Example 1. 244.3 g of an isocyanurate-modified isophorone diisocyanate (EVONIC Co., Ltd., "VESTANAT T-1890 / 100", NCO% = 17.2%) (polyisocyanate compound (e1)) and 192.0 g of trimellitic anhydride (polycarboxylic acid (e2) or polycarboxylic anhydride (e3)) were dissolved, and 1.0 g of dibutylhydroxytoluene was added. The mixture was reacted at 160 ° C for 6 hours under a nitrogen atmosphere, and it was confirmed that the NCO% was 0.1 or less (synthesis of amide-imide resin (E) having acid groups and / or acid anhydride groups). Next, 0.4 g of methoquinone was added, followed by 147.6 g of a pentaerythritol polyacrylate mixture ("Aronix M-306" manufactured by Toa Gosei Co., Ltd., hydroxyl value: 159.7 mg KOH / g) (hydroxy(meth)acrylate compound (D)) and 3.5 g of triphenylphosphine. The mixture was then reacted at 110°C for 5 hours while blowing in air. Subsequently, 165.0 g of glycidyl methacrylate (G) and 77 g of a biomass solvent ("DV16J0401" manufactured by Solvay Nicca Co., Ltd.) were added, and the mixture was reacted at 110°C for 6 hours to obtain a resin (4) having polymerizable unsaturated groups. This resin (4) having acid groups and polymerizable unsaturated groups had a nonvolatile content of 55% by mass, an acid value of 2 mg KOH / g in solids, and a chlorine atom content of 140 ppm by mass in solids. The biomass carbon content (%) (pMC%) of the entire resin (4) was 37% or more, and the biomass carbon content (%) of the solid content was about 10%.

[0236] (Example 5: Preparation of Resin (5) Having Polymerizable Unsaturated Group) Similar to Example 1, 670 g of biomass solvent (Solvay Nicca Co., Ltd., "DV16J0401") was placed in a flask equipped with a thermometer, stirrer, and reflux condenser. 244.3 g of an isocyanurate-modified isophorone diisocyanate (EVONIK Co., Ltd., "VESTANAT T-1890 / 100", NCO%=17.2%) (polyisocyanate compound (e1)) and 207.9 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride (polycarboxylic acid (e2) or polycarboxylic acid anhydride (e3)) were dissolved in the flask. 0.4 g of dibutylhydroxytoluene was added. The mixture was allowed to react at 140°C for 7 hours under a nitrogen atmosphere, and the NCO% was confirmed to be 0.1 or less (synthesis of amide-imide resin (E) having acid and / or acid anhydride groups). Next, 0.2 g of methoquinone was added, followed by 140.5 g of a pentaerythritol polyacrylate mixture ("Aronix M-306" manufactured by Toa Gosei Co., Ltd., hydroxyl value: 159.7 mg KOH / g) (hydroxy(meth)acrylate compound (D)) and 1.6 g of triphenylphosphine. The mixture was then reacted at 110°C for 7 hours while blowing in air. Next, 172.7 g of glycidyl methacrylate (G), 2.0 g of triphenylphosphine, and 219 g of a biomass solvent ("DV16J0401" manufactured by Solvay Nicca Co., Ltd.) were added, and the mixture was reacted at 110°C for 15 hours to obtain a resin (5) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (5) having acid groups and polymerizable unsaturated groups was 45% by mass, the acid value of the solid content was 2 mg KOH / g, and the chlorine atom content of the solid content was 135 ppm by mass. The biomass carbon content (%) (pMC%) of the entire resin (5) was 49% or more, and the biomass carbon content (%) of the solid content was about 10%.

[0237] (Comparative Example 1: Preparation of Resin (C1) Having Polymerizable Unsaturated Group) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 123 g of diethylene glycol monoethyl ether acetate and dissolved 215 g of orthocresol novolac epoxy resin (DIC Corporation, "EPICLON N-680," epoxy equivalent: 215 g / eq). 0.3 g of dibutylhydroxytoluene and 0.1 g of methoquinone were added. Then, 72 g of acrylic acid (unsaturated monobasic acid (B)) and 1.4 g of triphenylphosphine were added. The mixture was stirred at 120°C for 11 hours to yield Resin (C1) with polymerizable unsaturated groups. This Resin (C1) had a nonvolatile content of 70% by mass, an acid value of 0.5 mg KOH / g, and a biomass carbon content (%) of 0%.

[0238] (Comparative Example 2: Preparation of Resin (C2) Having Polymerizable Unsaturated Groups) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 499.7 g of diethylene glycol monoethyl ether acetate, and 244.3 g of an isocyanurate-modified isophorone diisocyanate (EVONIC "VESTANAT T-1890 / 100", NCO%=17.2%) (polyisocyanate compound (e1)) and 192.0 g of trimellitic anhydride (polycarboxylic acid (e2) or polycarboxylic anhydride (e3)) were dissolved therein. 1.0 g of dibutylhydroxytoluene was added. The mixture was reacted at 160°C for 6 hours under a nitrogen atmosphere, and it was confirmed that the NCO% was 0.1 or less (synthesis of amide-imide resin (E) having acid groups and / or acid anhydride groups). Next, 0.4 g of methoquinone was added, followed by 147.6 g of a pentaerythritol polyacrylate mixture ("Aronix M-306" manufactured by Toagosei Co., Ltd., hydroxyl value: 159.7 mg KOH / g) (hydroxy(meth)acrylate compound (D)) and 3.5 g of triphenylphosphine. The mixture was then reacted at 110°C for 5 hours while blowing in air. Subsequently, 165.0 g of commercially available glycidyl methacrylate was added, and the mixture was reacted at 110°C for 6 hours to obtain a resin (C2) having polymerizable unsaturated groups. This resin (C2) having acid groups and polymerizable unsaturated groups had a nonvolatile content of 59% by mass, an acid value of 1 mg KOH / g in solids, a chlorine atom content of 400 ppm by mass in solids, and a biomass carbon content (%) of 0% in solids.

[0239] (Examples 6 to 10, Comparative Examples 3 and 4) A curable resin composition was obtained by mixing the components shown in Table 1. The following tests were carried out on the curable resin composition. The results are shown in Table 1.

[0240] <Heat resistance> The curable resin compositions obtained in each of the Examples and Comparative Examples were applied to a copper foil (electrolytic copper foil "F2-WS" 18 μm, manufactured by Furukawa Sangyo Kaisha) using an applicator to a thickness of 50 μm, and dried at 80° C. for 30 minutes. Then, a metal halide lamp was used to apply the applied curable resin compositions to a copper foil to a thickness of 50 μm. 2After irradiating the coating with ultraviolet light, the coating was heated at 160°C for 1 hour to obtain a cured coating film. The cured coating film was then peeled off from the copper foil to obtain a cured product. A 6 mm x 40 mm test piece was cut out from the cured product, and the temperature at which the change in elastic modulus was maximized was evaluated as the glass transition temperature using a viscoelasticity measuring device (DMA: Rheometrics Corp. solid viscoelasticity measuring device "SOLIDS ANALYZER RSAII", tensile method: frequency 1 Hz, heating rate 3°C / min). A higher glass transition temperature indicates better heat resistance.

[0241] <Adhesion> Adhesion was evaluated by measuring peel strength. Specifically, the curable resin compositions obtained in the Examples and Comparative Examples were applied to copper foil (electrolytic copper foil "F2-WS" 18 μm, manufactured by Furukawa Sangyo Kaisha) using a 50 μm applicator, irradiated with 10 kJ / m2 of ultraviolet light using a metal halide lamp, and then heated at 160°C for 1 hour. The cured product was peeled off from the copper foil to obtain test piece 1 (cured product). This test piece 1 was cut into a size of 1 cm wide and 12 cm long, and the 90° peel strength (N / cm) was measured using a peel tester ("A&D Tensilon" manufactured by A&D Co., Ltd., peel speed 50 mm / min). A higher value indicates better adhesion.

[0242] [Table 1]

[0243] The specifications of each component shown in Table 1 are as follows: Acrylate monomer: Bisphenol A EO modified diacrylate, manufactured by MIWON Co., Ltd. Miramer® M-240 Organic solvent: Diethylene glycol monoethyl ether acetate Photopolymerization initiator: IGM Resins, product name "Omnirad-907"

[0244] From Table 1, it can be seen that the cured products made from the curable resin compositions according to the examples can exhibit excellent heat resistance and adhesion.

[0245] Therefore, according to the present invention, it is possible to provide a resin and a curable resin composition that can provide the final cured product of the resin having a polymerizable unsaturated group with improved heat resistance and adhesion properties. Furthermore, according to the present invention, it is possible to provide a cured product having excellent heat resistance and adhesion.

[0246] [Contribution to the United Nations-led Sustainable Development Goals (SDGs)] The SDGs have been proposed to realize a sustainable society. One embodiment of the present invention is thought to be a technology that can contribute to the achievement of goals such as "No. 7 - Affordable and clean energy for all," "No. 12 - Responsible consumption and production," and "No. 13 - Take urgent action against climate change."

Claims

1. A method for producing a resin having a polymerizable unsaturated group, the resin having a biomass carbon content (%) (pMC%) of 50% or more and containing a solvent represented by the following general formula (1) having an amide bond: 【Chemical 1】 (In the above general formula (1), R １ and R ２ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; R ３ represents a monovalent organic group having 4 to 10 carbon atoms.

2. 2. The method for producing a resin having a polymerizable unsaturated group according to claim 1, wherein the epoxy resin (A) and the unsaturated monobasic acid (B) are mixed in the presence of the solvent.

3. 3. The method for producing a resin having a polymerizable unsaturated group according to claim 2, wherein a mixing ratio of the epoxy resin (A) and the unsaturated monobasic acid (B) is in a range of 0.20 to 1.05 mol of the unsaturated monobasic acid (B) per 1 mol of epoxy groups in the epoxy resin (A).

4. 2. The method for producing a resin having a polymerizable unsaturated group according to claim 1, comprising mixing an amide-imide resin (C) having an acid group and / or an acid anhydride group with a hydroxy(meth)acrylate compound (D) in the presence of the solvent.

5. The method for producing a resin having a polymerizable unsaturated group according to claim 4 , further comprising mixing a (meth)acrylate compound (E) having an epoxy group in the presence of the solvent.

6. 6. The method for producing a resin having a polymerizable unsaturated group according to claim 4 or 5, wherein the amide-imide resin (C) having an acid group and / or an acid anhydride group is prepared by reacting a polyisocyanate compound (c1) with a polycarboxylic acid (c2) or a polycarboxylic anhydride (c3) as reaction raw materials.

7. 7. The method for producing a resin having a polymerizable unsaturated group according to claim 6, wherein the polyisocyanate compound (c1) comprises an aliphatic diisocyanate compound, an alicyclic diisocyanate compound, or a modified product thereof.

8. The method for producing a resin having a polymerizable unsaturated group according to claim 6 , wherein the polycarboxylic acid (c2) or the polycarboxylic acid anhydride (c3) includes a tricarboxylic acid or a tricarboxylic acid anhydride.

9. A resin having a polymerizable unsaturated group, which uses a solvent having an amide bond and is represented by the following general formula (1) as an essential synthetic raw material, and has a biomass carbon content (%) (pMC%) of 15% or more in the entire resin having a polymerizable unsaturated group. 【Chemistry 2】 (In the above general formula (1), R １ and R ２ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; R ３ represents a monovalent organic group having 4 to 10 carbon atoms.

10. The resin having a polymerizable unsaturated group according to claim 9 , comprising the solvent, an epoxy resin (A), and an unsaturated monobasic acid (B).

11. The resin having a polymerizable unsaturated group according to claim 9 , comprising the solvent, an amide-imide resin (C) having an acid group and / or an acid anhydride group, and a hydroxy(meth)acrylate compound (D).

12. The resin having a polymerizable unsaturated group according to claim 11, further comprising a (meth)acrylate compound (E) having an epoxy group as the synthesis raw material.

13. 13. The resin having a polymerizable unsaturated group according to claim 11 or 12, wherein the amide-imide resin (C) having an acid group and / or an acid anhydride group is prepared by reacting a polyisocyanate compound (c1) with a polycarboxylic acid (c2) or a polycarboxylic anhydride (c3) as reaction raw materials.

14. A curable resin composition comprising the resin having a polymerizable unsaturated group according to any one of claims 9 to 12 and a photopolymerization initiator.

15. The curable resin composition according to claim 14, further comprising a resin (X) having a polymerizable unsaturated group other than the resin having a polymerizable unsaturated group.

16. A cured product of the curable resin composition according to claim 14.

17. An article having a coating film comprising the cured product according to claim 16.

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