Polymerizable composition

Abstract

To provide: a polymerizable composition that can cure an epoxy resin in a short time upon light irradiation while preventing corrosion of a metal substrate; a cured product based on the composition; and a method for producing the same.SOLUTION: A polymerizable composition comprises an epoxy resin (A), a curing agent (B), and a photothermal conversion material (C), where the photothermal conversion material (C) is one or more compounds selected from the group consisting of compounds represented by general formulas (1), (2), (3) and (4).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polymerizable composition, a cured product, and a method for producing the cured product. [Background technology]

[0002] Light-curing technology is solvent-free and can cure in a short time, which gives it advantages over heat-curing technology, such as environmental friendliness and improved productivity. In particular, cationic curing systems using materials such as epoxy resins and oxetane resins are less susceptible to curing inhibition by oxygen and suppress curing shrinkage compared to radical curing systems, which are the mainstream of light-curing, and are therefore widely used in fields such as paints, adhesives, display sealants, printing inks, three-dimensional modeling, photoresists, and sealants for electronic components.

[0003] However, one issue with cationic curing systems is that they generally use a photoacid generator as a catalyst, which generates acid upon exposure to light, potentially leaving residual acid in the cured product after curing. Possible reasons for this residual acid include the acid generated by light not being used entirely for curing, or the polymer's growing end (oxonium ion) being deactivated by trace amounts of water in the system, resulting in acid generation. These residual acids can cause corrosion of the metal substrate surface or denaturation of the resin. In particular, in electronic materials applications, these acids can cause problems such as device degradation. Therefore, while the application of thermal curing technology, which allows for curing without generating acid, is considered, there are limitations, such as the requirement for heat resistance in the substrate.

[0004] As a solution to the above problems, a photosensitive resin composition using an anion-curing photobase generator instead of a cation-curing photobase generator (e.g., Patent Document 1) and a method using an acid scavenger (e.g., Patent Document 2) have been proposed. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2019 / 168113 [Patent Document 2] Patent Publication No. 2021-165385 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the anionic curing photobase generator used in Patent Document 1 has a drawback in that it is less sensitive to light than the photopolymerization initiators used in radical curing systems and the photoacid generators used in cationic curing systems, and therefore requires stronger light irradiation. Also, the acid scavenger used in Patent Document 2 traps the acid generated by light irradiation before it can cause cationic polymerization, which could result in inefficient curing.

[0007] The present invention has been made in view of the above circumstances. That is, an object of the present invention is to provide a polymerizable composition that can cure an epoxy resin in a short time by irradiation with light and that can prevent corrosion of a metal substrate, a cured product using the composition, and a method for producing the same. [Means for solving the problem]

[0008] That is, the present invention relates to a polymerizable composition containing an epoxy resin (A), a curing agent (B), and a photothermal conversion material (C), wherein the photothermal conversion material (C) is one or more compounds selected from the group consisting of the following general formulas (1), (2), (3), and (4): General formula (1): [ka] (In general formula (1), R 1 , R 2 , R 3 and R 4 independently represent a methyl group or an ethyl group, and R 5 represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R 6are independent substituents each representing an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a chlorine atom, and n represents an integer of 0 to 2. General formula (2): [ka] (In general formula (2), R 7 and R 8 R independently represents a methyl group or an ethyl group. 9 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group. X represents a group represented by the following general formula (2-a): Ar 1 , Ar 2 , Ar 3 or Ar 4 n is an integer of 0 to 2. A triazine derivative having a peroxide bond represented by the formula: [ka] (In the general formula (2-a), m represents an integer of 0 to 3. R 10 are independent substituents, and are alkyl groups having 1 to 18 carbon atoms, and are represented by the general formula (2-b): R 11 represents a substituent represented by -Y-, a nitro group, or a cyano group. The Y represents an oxygen atom or a sulfur atom. The R 11 represents a hydrocarbon group having 1 to 18 carbon atoms which may have one or more of an ether bond, a thioether bond, and a terminal hydroxyl group in the carbon skeleton, an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group, or an acyl group having 1 to 8 carbon atoms. 10 is two adjacent groups of the general formula (2-b): R 11 -Y- may form a 5- or 6-membered ring.) General formula (3): [ka] (In general formula (3), R 12 and R 13 are independently a methyl group or an ethyl group, R 14represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group, and R 15 represents an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, an optionally substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, an optionally substituted acyl group having 1 to 20 carbon atoms, -YR, or -N-RR', where Y represents an oxygen atom or a sulfur atom, and R and R' independently represent a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or an optionally substituted heterocyclic ring-containing group having 2 to 20 carbon atoms. Ar represents a group represented by the following general formula (3-a): Ar 5 , Ar 6 , Ar 7 or Ar 8 The triazine derivative having a peroxide bond represented by the formula (I) is an aryl group represented by the formula (I). [ka] (In general formula (3-a), m represents an integer of 0 to 3. R 16 are independent substituents, and are alkyl groups having 1 to 18 carbon atoms, and are represented by the general formula (3-b): R 17 represents a substituent represented by -Y-, a nitro group, or a cyano group. The Y represents an oxygen atom or a sulfur atom. The R 17 represents a hydrocarbon group having 1 to 18 carbon atoms which may have one or more of an ether bond, a thioether bond, and a terminal hydroxyl group in the carbon skeleton, an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group, or an acyl group having 1 to 8 carbon atoms. 16 is two adjacent groups of the general formula (3-b): R 17 -Y- may form a 5- or 6-membered ring.) General formula (4): [ka] (In general formula (4), R 18 and R 19 are independently an alkyl group having 4 to 8 carbon atoms or an aralkyl group having 9 to 12 carbon atoms, and R20 and R 21 are independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 4 to 8 carbon atoms, or an aralkyloxy group having 9 to 12 carbon atoms.

[0009] The present invention also relates to the polymerizable composition, wherein the curing agent (B) is preferably one or more compounds selected from the group consisting of amine compounds, acid anhydrides, polyamide compounds, imidazole compounds, phenolic resins, hydrazide compounds, and mercaptan compounds.

[0010] The present invention also relates to the polymerizable composition, which preferably further contains a filler (D).

[0011] The present invention also relates to a cured product formed from the polymerizable composition.

[0012] The present invention also relates to a method for producing a cured product, comprising the steps of applying the polymerizable composition to a substrate to form a film, and irradiating the film with active energy rays to cure the film. [Effects of the Invention]

[0013] According to the present invention, one or more compounds selected from the group consisting of the above general formulas (1), (2), (3), and (4) can convert light energy into thermal energy and use the generated heat to promote curing of the polymerizable composition. Therefore, it is possible to provide a polymerizable composition that can cure an epoxy resin in a short time by irradiation with light and can prevent corrosion of metal substrates, as well as a cured product using the composition and a method for producing the same. DETAILED DESCRIPTION OF THE INVENTION

[0014] The present invention will be described in detail below.

[0015] The polymerizable composition of the present invention contains an epoxy resin (A), a curing agent (B), and a photothermal conversion material (C).

[0016] <Epoxy resin (A)> The epoxy resin (A) of the present invention is not particularly limited as long as it has one or more epoxy groups in the molecule, and conventionally known compounds can be used. Examples of compounds having one or more epoxy groups in the molecule include bisphenol A epoxy resins derived from bisphenol A and epichlorohydrin, bisphenol F epoxy resins derived from bisphenol F and epichlorohydrin, bisphenol S epoxy resins, phenol novolac epoxy resins, cresol novolac epoxy resins, bisphenol A novolac epoxy resins, bisphenol F novolac epoxy resins, alicyclic epoxy resins, diphenyl ether epoxy resins, hydroquinone epoxy resins, naphthalene epoxy resins, biphenyl epoxy resins, fluorene epoxy resins, multifunctional epoxy resins such as trifunctional epoxy resins and tetrafunctional epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, hydantoin epoxy resins, isocyanurate epoxy resins, and aliphatic linear epoxy resins. These epoxy resins may be halogenated or hydrogenated. Among these, bisphenol-type epoxy resins are preferred because grades with different molecular weights are widely available and the reactivity and other properties can be set as desired.

[0017] The epoxy resin (A) may also be a modified product. Blending or adding other resin components to the epoxy resin can increase the flexibility and improve the mechanical properties of the cured product. Examples of such modified products include CTN (carboxyl-terminated butadiene-acrylonitrile rubber)-modified epoxy resins; epoxy resins in which various rubbers such as acrylic rubber, NBR, SBR, butyl rubber, or isoprene rubber are dispersed in the resin; epoxy resins modified with the above-mentioned liquid rubbers; epoxy resins to which various resins such as acrylic, urethane, urea, polyester, and styrene are added; chelate-modified epoxy resins; and polyol-modified epoxy resins. The epoxy resins (A) may be used alone or in combination of two or more.

[0018] The epoxy resin (A) may be either liquid or solid, and a liquid epoxy resin and a solid epoxy resin may be used in combination. Here, "liquid" and "solid" refer to the state of the epoxy resin at room temperature (25°C) and normal pressure (1 atm). From the viewpoints of coatability, processability, and adhesiveness, it is preferable that 10 mass% or more of the total epoxy resin (A) used be liquid epoxy resin.

[0019] <Curing agent (B)> The curing agent (B) of the present invention refers to a substance that contributes to the crosslinking reaction between the epoxy groups of the epoxy resin (A) and groups reactive with the epoxy groups. There are no particular limitations on the curing agent (B), and any commonly known curing agent for epoxy resins can be used. Examples of the curing agent (B) include amine-based curing agents such as aliphatic amines, polyether amines, alicyclic amines, and aromatic amines, acid anhydride-based curing agents, amide-based curing agents, phenolic resins, organic acid dihydrazides, polymercaptan-based curing agents, isocyanate-based curing agents, and blocked isocyanate-based curing agents. The curing agent (B) may be used alone or in any combination and ratio of two or more.

[0020] The content of the curing agent (B) in the polymerizable composition is not particularly limited, but is preferably 1% by mass or more and 60% by mass or less, and more preferably 3% by mass or more and 55% by mass or less, based on the total mass of the polymerizable composition. By making the content of the curing agent (B) equal to or more than the above lower limit, the polymerizable composition also tends to be appropriately cured without impairing storage stability.

[0021] The polymerizable composition of the present invention may contain a curing accelerator to improve curability. Examples of the curing accelerator include tertiary amines, imidazole and its derivatives, organic phosphines, phosphonium salts, tetraphenylboron salts, and boron halide amine complexes. These may be used alone or in any combination and ratio of two or more.

[0022] The amount of the curing accelerator in the polymerizable composition is not particularly limited, but is preferably 0.01% by mass or more and 10% by mass or less, and more preferably 0.05% by mass or more and 5% by mass or less, based on the total amount of the polymerizable composition. By making the content of the curing accelerator equal to or more than the lower limit, the polymerizable composition can be easily cured appropriately without impairing its storage stability.

[0023] <Photothermal conversion materials (C)> The photothermal conversion material (C) of the present invention is capable of converting light energy into thermal energy upon irradiation with active energy rays, and promoting the curing of a polymerizable composition by the generated heat, and is one or more compounds selected from the group consisting of the following general formulas (1), (2), (3), and (4):

[0024] General formula (1): [ka] (In general formula (1), R 1 , R 2 , R 3 and R 4 independently represent a methyl group or an ethyl group, and R 5 represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R 6 are independent substituents each representing an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a chlorine atom, and n represents an integer of 0 to 2.

[0025] In general formula (1), R 1 , R 2 , R 3 and R 4 In the present invention, from the viewpoint of improving the stability of the thioxanthone derivative having a peroxide bond represented by general formula (1), R 1 , R 2 , R 3 and R 4 are preferably all methyl groups.

[0026] In general formula (1), R 5 is an alkyl group having 1 to 6 carbon atoms or a phenyl group. The alkyl group may be a straight chain or a branched chain. 5 Specific examples of R include a methyl group, an ethyl group, a propyl group, a 2,2-dimethylpropyl group, and a phenyl group. Among these, from the viewpoint of ease of synthesis of a thioxanthone derivative having a peroxide bond, R 5 is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably one selected from a methyl group, an ethyl group, and a propyl group. From the viewpoint of efficiently converting light energy into thermal energy, R 5 is more preferably a methyl group or an ethyl group.

[0027] In general formula (1), the substitution position of the dialkyl peroxide on the thioxanthone is not particularly limited. From the viewpoint of efficiently converting light energy into thermal energy, the substitution is preferably at the 2nd, 3rd, or 4th position of the thioxanthone skeleton, and from the viewpoint of ease of synthesis, the substitution is more preferably at the 2nd or 3rd position of the thioxanthone skeleton.

[0028] In general formula (1), R 6 are independent substituents and represent an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a chlorine atom. These substituents improve the light absorption characteristics of the thioxanthone derivative having a peroxide bond due to the push-pull effect of these substituents at the emission wavelength of the light source used, enabling efficient conversion of light energy into thermal energy.

[0029] In the general formula (1), n ​​represents an integer of 0 to 2. Among these, n is preferably an integer of 0 to 1, and more preferably 0, from the viewpoint of easily synthesizing a thioxanthone derivative having a peroxide bond.

[0030] In general formula (1), when n is an integer of 1 to 2, R 6The substitution position of is not particularly limited, but from the viewpoint of efficiently converting light energy into thermal energy, it is preferably the 6th or 7th position of the thioxanthone skeleton, and from the viewpoint of easily synthesizing a thioxanthone derivative having a peroxide bond, it is more preferably the 7th position of the thioxanthone skeleton.

[0031] R 6 Specific examples of R include alkyl groups such as methyl, ethyl, isopropyl, and n-butyl; alkoxy groups such as methoxy, ethoxy, n-propyloxy, sec-butyloxy, and tert-butyloxy; and chlorine atoms. Among these, from the viewpoint of efficiently converting light energy into thermal energy, R 6 is more preferably a methoxy group or an ethoxy group.

[0032] General formula (2): [ka] (In general formula (2), R 7 and R 8 R independently represents a methyl group or an ethyl group. 9 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group. X represents a group represented by the following general formula (2-a): Ar 1 , Ar 2 , Ar 3 or Ar 4 n is an integer of 0 to 2. A triazine derivative having a peroxide bond represented by the formula: [ka] (In the general formula (2-a), m represents an integer of 0 to 3. R 10 are independent substituents, and are alkyl groups having 1 to 18 carbon atoms, and are represented by the general formula (2-b): R 11 represents a substituent represented by -Y-, a nitro group, or a cyano group. The Y represents an oxygen atom or a sulfur atom. The R 11represents a hydrocarbon group having 1 to 18 carbon atoms which may have one or more of an ether bond, a thioether bond, and a terminal hydroxyl group in the carbon skeleton, an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group, or an acyl group having 1 to 8 carbon atoms. 10 is two adjacent groups of the general formula (2-b): R 11 -Y- may form a 5- or 6-membered ring.)

[0033] In general formula (2), R 7 and R 8 R independently represents a methyl group or an ethyl group. 7 and R 8 is preferably a methyl group, from the viewpoint of increasing the stability of the triazine derivative having a peroxide bond.

[0034] In general formula (2), R 9 R is an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group. The alkyl group may be either a straight chain or a branched chain. 9 Specific examples of the group include a methyl group, an ethyl group, a propyl group, a 2,2-dimethylpropyl group, a phenyl group, and an isopropylphenyl group. Among these, from the viewpoint of facilitating synthesis of a triazine derivative having a peroxide bond, a methyl group, an ethyl group, a propyl group, a 2,2-dimethylpropyl group, and a phenyl group are preferred. From the viewpoint of efficiently converting light energy into thermal energy, a methyl group and an ethyl group are more preferred.

[0035] In the general formula (2), n represents an integer of 0 to 2. From the viewpoint of easiness in synthesis of a triazine derivative having a peroxide bond, n is preferably 0 or 1. When n is 0, X is preferably Ar 2 , Ar 3 , or Ar 4 and when n is 1, X is Ar 1 is more preferable from the viewpoint of efficiently converting light energy into heat energy.

[0036] In general formula (2-a), m represents an integer of 0 to 3. From the viewpoint of easiness in synthesis of a triazine derivative having a peroxide bond, m is preferably 0 to 2, and from the viewpoint of efficient conversion of light energy into thermal energy, m is more preferably 1.

[0037] In general formula (2-a), R 10 are independent substituents, and are alkyl groups having 1 to 18 carbon atoms, and are represented by the general formula (2-b): R 11 represents a substituent represented by -Y-, a nitro group, or a cyano group. Y represents an oxygen atom or a sulfur atom. R 11 represents a hydrocarbon group having 1 to 18 carbon atoms which may have one or more of an ether bond, a thioether bond, and a terminal hydroxyl group in the carbon skeleton, an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group, or an acyl group having 1 to 8 carbon atoms. 10 is two adjacent general formula (2-b): R 11 -Y- may form a 5- or 6-membered ring.

[0038] R 10 is an independent substituent, from the viewpoint of efficiently absorbing active energy rays, an alkyl group having 1 to 6 carbon atoms, or a group represented by the general formula (2-c): R 11´ represents a substituent represented by -Y-, where Y represents an oxygen atom, and R 11´ is preferably a hydrocarbon group having 1 to 6 carbon atoms which may have one or more of an ether bond and a hydroxyl group at a terminal in the carbon skeleton, or an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group. 10 is two adjacent general formula (2-c)R 11´ It is preferred that —Y— forms a 5- or 6-membered ring.

[0039] R 10Specific examples of the alkyl group include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, and n-hexyl; methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, sec-butyloxy, tert-butyloxy, n-pentyloxy, cyclopentyloxy, n-hexyloxy, cyclohexyloxy, 2-hydroxyethoxy, 2-methoxyethoxy, 2-ethoxyethoxy, 2-butoxyethoxy, 2-(2-hydroxyethoxy)ethoxy, 2-(2-ethoxyethoxy)ethoxy, 1,2-dihydroxypropoxy, and methylenedioxy. Examples of such functional groups include alkoxy groups such as oxy, dimethylmethylenedioxy, and ethylenedioxy; aryloxy groups such as phenyloxy and 4-isopropylphenyloxy; alkylsulfanyl groups such as methylsulfanyl, ethylsulfanyl, hexylsulfanyl, 2-methoxyethylsulfanyl, and 2-(2-methoxyethoxy)ethylsulfanyl; arylsulfanyl groups such as phenylsulfanyl, 2-methylphenylsulfanyl, and 4-methylphenylsulfanyl; and acyl groups such as acetyl, n-butanoyl, 2-ethylhexanoyl, benzoyl, and 2-methylbenzoyl. Compounds having these functional groups and represented by general formula (2) are preferred because they efficiently convert light energy into thermal energy.

[0040] Furthermore, among these, triazine derivatives having a peroxide bond are easy to synthesize and are suitable for efficiently converting light energy into heat energy. 10 is more preferably a methoxy group, an ethoxy group, or a 2-hydroxyethoxy group.

[0041] R 10 The substitution position of X is not particularly limited, but 1 In the case of R 10 Preferably, at least one of the following is substituted at the 4-position of the benzene ring substituted with the triazine group. 2 In the case of R 10Preferably, at least one of the following is substituted at the 4-position of a benzene ring other than the benzene ring substituted with the triazine group. 3 In the case of R 10 Preferably, at least one of the following is substituted at the 4-position of the triazine group substituted at the 1-position. 4 In the case of R 10 In terms of efficient conversion of light energy into heat energy, it is preferable that at least one of the above is substituted at the 4-position of a benzene ring other than the benzene ring substituted with the triazine group.

[0042] General formula (3): [ka] (In general formula (3), R 12 and R 13 are independently a methyl group or an ethyl group, R 14 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group, and R 15 represents an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, an optionally substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, an optionally substituted acyl group having 1 to 20 carbon atoms, -YR, or -N-RR', where Y represents an oxygen atom or a sulfur atom, and R and R' independently represent a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or an optionally substituted heterocyclic ring-containing group having 2 to 20 carbon atoms. Ar represents a group represented by the following general formula (3-a): Ar 5 , Ar 6 , Ar 7 or Ar 8 The triazine derivative having a peroxide bond represented by the formula (I) is an aryl group represented by the formula (I). [ka] (In general formula (3-a), m represents an integer of 0 to 3. R 16are independent substituents, and are alkyl groups having 1 to 18 carbon atoms, and are represented by the general formula (3-b): R 17 represents a substituent represented by -Y-, a nitro group, or a cyano group. The Y represents an oxygen atom or a sulfur atom. The R 17 represents a hydrocarbon group having 1 to 18 carbon atoms which may have one or more of an ether bond, a thioether bond, and a terminal hydroxyl group in the carbon skeleton, an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group, or an acyl group having 1 to 8 carbon atoms. 16 is two adjacent groups of the general formula (3-b): R 17 -Y- may form a 5- or 6-membered ring.)

[0043] In general formula (3), R 12 and R 13 are independently a methyl group or an ethyl group, and a methyl group is preferred from the viewpoint of increasing the stability of the triazine derivative having a peroxide bond.

[0044] In general formula (3), R 14 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group. The alkyl group may be either a straight chain or a branched chain. R 14 Specific examples of the group include a methyl group, an ethyl group, a propyl group, a 2,2-dimethylpropyl group, a phenyl group, and an isopropylphenyl group. Among these, from the viewpoint of facilitating the synthesis of a triazine derivative having a peroxide bond, a methyl group, an ethyl group, a propyl group, a 2,2-dimethylpropyl group, and a phenyl group are preferred. From the viewpoint of increasing the stability of a triazine derivative having a peroxide bond and efficiently converting light energy into thermal energy, a methyl group and an ethyl group are more preferred.

[0045] In general formula (3), R 15represents an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, an optionally substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, an optionally substituted acyl group having 1 to 20 carbon atoms, -YR, or -N-RR', where Y represents an oxygen atom or a sulfur atom, and R and R' independently represent a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or an optionally substituted heterocyclic ring-containing group having 2 to 20 carbon atoms. The "substituent" in the above "optionally substituted" includes a halogen atom, an aliphatic hydrocarbon group which may have an ether bond or a thioether bond in the carbon skeleton, an aromatic hydrocarbon group, a heterocyclic ring-containing group, an acyl group, a cyano group, a nitro group, a carboxyl group, an epoxy group, a hydroxyl group, and the like. The above R 15 is preferably an optionally substituted aliphatic hydrocarbon group of 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group of 6 to 20 carbon atoms, an optionally substituted heterocyclic ring-containing group of 2 to 20 carbon atoms, an optionally substituted acyl group of 1 to 20 carbon atoms, or -YR, from the viewpoint of high stability, and is more preferably -OR, in which R is an optionally substituted aliphatic hydrocarbon group of 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group of 6 to 20 carbon atoms, or an optionally substituted heterocyclic ring-containing group of 2 to 20 carbon atoms, from the viewpoint of ease of synthesis.

[0046] In general formula (3-a), m represents an integer of 0 to 3. From the viewpoint of easiness in synthesis of a triazine derivative having a peroxide bond, m is preferably 0 to 2, and from the viewpoint of efficient conversion of light energy into thermal energy, m is more preferably 1.

[0047] In general formula (3-a), R 16 are independent substituents, and are alkyl groups having 1 to 18 carbon atoms, and are represented by the general formula (3-b): R 17 R represents a substituent represented by -Y-, a nitro group, or a cyano group. Y represents an oxygen atom or a sulfur atom. 17represents a hydrocarbon group having 1 to 18 carbon atoms which may have one or more of an ether bond, a thioether bond, and a terminal hydroxyl group in the carbon skeleton, an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group, or an acyl group having 1 to 8 carbon atoms. 16 is two adjacent general formula (2-b): R 17 -Y- may form a 5- or 6-membered ring.

[0048] R 16 is an independent substituent, from the viewpoint of efficiently absorbing active energy rays, an alkyl group having 1 to 6 carbon atoms, or a group represented by the general formula (2-c): R 17´ represents a substituent represented by -Y-, where Y represents an oxygen atom, and R 17´ is preferably a hydrocarbon group having 1 to 6 carbon atoms which may have one or more of an ether bond and a hydroxyl group at a terminal in the carbon skeleton, or an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group. 16 is two adjacent general formula (2-c)R 17´ It is preferred that —Y— forms a 5- or 6-membered ring.

[0049] R 16Specific examples of the alkyl group include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, and n-hexyl; methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, sec-butyloxy, tert-butyloxy, n-pentyloxy, cyclopentyloxy, n-hexyloxy, cyclohexyloxy, 2-hydroxyethoxy, 2-methoxyethoxy, 2-ethoxyethoxy, 2-butoxyethoxy, 2-(2-hydroxyethoxy)ethoxy, 2-(2-ethoxyethoxy)ethoxy, 1,2-dihydroxypropoxy, and methylenedioxy. Examples of such functional groups include alkoxy groups such as oxy, dimethylmethylenedioxy, and ethylenedioxy; aryloxy groups such as phenyloxy and 4-isopropylphenyloxy; alkylsulfanyl groups such as methylsulfanyl, ethylsulfanyl, hexylsulfanyl, 2-methoxyethylsulfanyl, and 2-(2-methoxyethoxy)ethylsulfanyl; arylsulfanyl groups such as phenylsulfanyl, 2-methylphenylsulfanyl, and 4-methylphenylsulfanyl; and acyl groups such as acetyl, n-butanoyl, 2-ethylhexanoyl, benzoyl, and 2-methylbenzoyl. Compounds having these functional groups and represented by general formula (3) are preferred because they efficiently convert light energy into thermal energy.

[0050] Furthermore, among these, triazine derivatives having a peroxide bond are easy to synthesize and are suitable for efficiently converting light energy into heat energy. 16 is more preferably a methoxy group, an ethoxy group, or a 2-hydroxyethoxy group.

[0051] R 16 The substitution position of X is not particularly limited, but 1 In the case of R 16 Preferably, at least one of the following is substituted at the 4-position of the benzene ring substituted with the triazine group. 2 In the case of R 16Preferably, at least one of the following is substituted at the 4-position of a benzene ring other than the benzene ring substituted with the triazine group. 3 In the case of R 16 is preferably substituted at the 4-position of the triazine group substituted at the 1-position. 4 In the case of R 16 In terms of efficient conversion of light energy into heat energy, it is preferable that at least one of the above is substituted at the 4-position of a benzene ring other than the benzene ring substituted with the triazine group.

[0052] General formula (4): [ka] (In general formula (4), R 18 and R 19 are independently an alkyl group having 4 to 8 carbon atoms or an aralkyl group having 9 to 12 carbon atoms, and R 20 and R 21 are independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 4 to 8 carbon atoms, or an aralkyloxy group having 9 to 12 carbon atoms.

[0053] In general formula (4), R 18 and R 19 are independently an alkyl group having 4 to 8 carbon atoms or an aralkyl group having 9 to 12 carbon atoms, and among these, a tertiary alkyl group having 4 to 8 carbon atoms is preferred from the viewpoint of efficiently converting light energy into thermal energy.

[0054] In general formula (4), R 20 and R 21 are independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 4 to 8 carbon atoms, or an aralkyloxy group having 9 to 12 carbon atoms, and among these, a tertiary alkoxy group having 4 to 8 carbon atoms is preferred from the viewpoint of efficiently converting light energy into thermal energy.

[0055] Examples of the compound represented by general formula (4) include 3,3',4,4'-tetra-(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra-(tert-amylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra-(tert-hexylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra-(tert-octylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra-(cumylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra-(p-isopropylcumylperoxycarbonyl)benzophenone, 3,3'-di-(meth Examples of the peroxycarbonyl group include 3,4'-di-(tert-butylperoxycarbonyl)benzophenone, 3,4'-di-(methoxycarbonyl)-4,3'-di-(tert-butylperoxycarbonyl)benzophenone, and 4,4'-di-(methoxycarbonyl)-3,3'-di-(tert-butylperoxycarbonyl)benzophenone. Among these, from the viewpoint of efficiently converting light energy into thermal energy, 3,3',4,4'-tetra-(tert-butylperoxycarbonyl)benzophenone and 3,3',4,4'-tetra-(tert-amylperoxycarbonyl)benzophenone are preferred.

[0056] The compounds represented by the general formulas (1) to (4) may be used alone or in combination of two or more kinds.

[0057] The content of the photothermal conversion material (C) is preferably 0.01 to 50 parts by mass, more preferably 0.05 to 40 parts by mass, and even more preferably 0.1 to 35 parts by mass, per 100 parts by mass of the epoxy resin (A). If the content of the photothermal conversion material (C) is less than 0.01 parts by mass per 100 parts by mass of the epoxy resin (A), the generated heat energy is too small to sufficiently melt the polymerizable composition. Furthermore, if the content of the photothermal conversion material (C) is more than 50 parts by mass per 100 parts by mass of the epoxy resin (A), the solubility of the photothermal conversion material in the epoxy resin (A) reaches saturation, causing precipitation of the photothermal conversion material during film formation from the polymerizable composition, resulting in problematic roughness of the coating film surface, which is undesirable.

[0058] <Filler (D)> The polymerizable composition of the present invention converts light energy into thermal energy and cures using the generated heat. Therefore, a high heat storage capacity is preferable for efficient curing. A filler (D) may be included to enhance heat storage capacity or mechanical properties such as the strength and heat resistance of the cured product. The type of filler (D) is not particularly limited, but specific examples include silica, calcium carbonate, aluminum oxide, boron nitride, magnesium oxide, aluminum nitride, thermoplastic polymers such as polyvinyl acetate, polyolefins, nylon fibers, gold, silver, copper, iron, nickel, silicon carbide, titanium nitride, and titanium carbide. Among these, silica, calcium carbonate, and polyolefins are preferred from the viewpoint of heat storage capacity. These fillers may be surface-treated with a silane coupling agent or the like to improve heat resistance, adhesiveness, and the like. The filler (D) may be used alone or in combination of two or more types.

[0059] The shape of the filler (D) is not particularly limited, and examples thereof include polygonal, cubic, elliptical, spherical, needle-like, flat, or flake-like shapes, or a combination thereof. The shape of the filler (D) is selected from the viewpoints of dispersibility and filling ability in the polymerizable composition. The average particle size of the filler (D) is not particularly limited, but from the viewpoints of dispersibility and coatability, the average particle size of the filler (D) is preferably 0.1 μm to 4.5 μm. An average particle size of 4.5 μm or less is preferred from the viewpoint of the extensibility of the polymerizable composition.

[0060] <Solvent> A solvent may be further added to the polymerizable composition in order to improve the viscosity, coatability, and smoothness of the cured film, and is used to ensure the handleability and workability of the polymerizable composition when molding, and the amount of the solvent used is not particularly limited.

[0061] Examples of the solvent include acetone, methyl ethyl ketone, toluene, xylene, methyl isobutyl ketone, ethyl acetate, ethylene glycol monomethyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, methanol, and ethanol. The solvents may be used alone or in combination of two or more.

[0062] <Other additives, etc.> The polymerizable composition may contain, as appropriate, known additives such as crosslinking agents, crosslinking accelerators, silane coupling agents, tackifying resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.), antioxidants, fillers, colorants (pigments, dyes, etc.), ultraviolet absorbers, antioxidants, chain transfer agents, plasticizers, softeners, surfactants, antistatic agents, thickeners, flame retardants, inorganic compounds, and electromagnetic wave absorbing fillers, either alone or in combination, within the scope that does not impair the properties of the present embodiment.

[0063] The content of the additives is appropriately selected depending on the purpose of use and is not particularly limited, but is usually preferably 300 parts by mass or less, and more preferably 100 parts by mass or less, per 100 parts by mass of the epoxy resin (A).

[0064] <Method for preparing polymerizable composition> When preparing the polymerizable composition, the epoxy resin (A), the curing agent (B), the photothermal conversion material (C), and, if necessary, the filler (D) and other additives are placed in a container, and then dissolved or dispersed in accordance with a conventional method using a paint shaker, a bead mill, a sand grind mill, a ball mill, an attritor mill, a two-roll mill, a three-roll mill, or the like.

[0065] <Method of manufacturing the cured product> The cured product of the present invention is formed from the polymerizable composition. The method for producing the cured product includes the steps of applying the polymerizable composition to a substrate and then irradiating the polymerizable composition with active energy rays to cure it.

[0066] Examples of the coating method include spin coating, bar coating, spray coating, dip coating, flow coating, slit coating, doctor blade coating, gravure coating, screen printing, offset printing, inkjet printing, dispenser printing, etc. Examples of the substrate include films and sheets of glass, silicon wafers, metals, plastics, etc., and three-dimensional molded products, and the shape of the substrate is not limited.

[0067] The method for curing the polymerizable composition is not particularly limited, and it is preferable to cure the composition by irradiation with active energy rays such as electron beams, ultraviolet rays, visible light, and radiation.

[0068] Examples of light sources that can be used for the light irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, ultraviolet electrodeless lamps, light-emitting diodes (LEDs), xenon arc lamps, carbon arc lamps, sunlight, solid-state lasers such as YAG lasers, semiconductor lasers, and gas lasers such as argon lasers.

[0069] The exposure dose of the active energy ray should be appropriately set depending on the wavelength and intensity of the active energy ray and the composition of the polymerizable composition. For example, the exposure dose in the UV-A region is 10 to 500 J / cm. 2 is preferably 100 to 400 J / cm 2 By setting the exposure dose of the actinic energy ray within the above range, light energy can be efficiently converted into heat energy.

[0070] The irradiation time of the active energy rays is not particularly limited, but is preferably 0.01 seconds to 30 minutes, and more preferably 0.1 seconds to 10 minutes. By setting the irradiation time within the above range, productivity can be improved.

[0071] In the method for producing the cured product, a heating step may be performed before or after the step of irradiating with active energy rays. In the step of heating the polymerizable composition, examples of the heating method include heating and ventilation heating. The heating method is not particularly limited, and examples thereof include an oven, a hot plate, infrared irradiation, and electromagnetic wave irradiation. In addition, examples of the ventilation heating method include a fan-type drying oven.

[0072] Furthermore, when the polymerizable composition contains the solvent, the method for producing a cured product may include a drying step. In particular, when the step of irradiating with active energy rays is subsequently applied after the polymerizable composition is applied to a substrate, it is preferable to provide a drying step before the step of irradiating with active energy rays.

[0073] In the drying step, examples of the method for drying the solvent include heat drying, ventilation heating drying, reduced pressure drying, etc. The method for heating drying is not particularly limited, and examples thereof include an oven, a hot plate, infrared irradiation, electromagnetic wave irradiation, etc. Furthermore, examples of the method for ventilation heating drying include a blower drying oven, etc.

[0074] Furthermore, in the drying step, the temperature of the polymerizable composition is lower than the set drying temperature due to the latent heat of vaporization of the solvent, so that a longer time is ensured until the polymerizable composition gels. Since the time until gelation is affected by the drying method, film thickness, etc., the drying temperature and time should be appropriately set, including the selection of the solvent. For example, the drying temperature is preferably 20 to 120°C, more preferably 40 to 100°C. The drying time is preferably 1 to 60 minutes, more preferably 1 to 30 minutes.

[0075] The polymerizable composition of the present invention can be used in a wide variety of applications, including paints and coatings such as hard coating agents, coating agents for optical disks, coating agents for optical fibers, paints for mobile terminals, paints for home appliances, paints for cosmetic containers, paints for woodworking, internal anti-reflection coatings for optical elements, high and low refractive index coating agents, heat-shielding coating agents, heat-dissipating coating agents, and anti-fogging agents; printing inks such as offset printing inks, gravure printing inks, screen printing inks, inkjet printing inks, conductive inks, insulating inks, and inks for light guide plates; photosensitive printing plates; nanoimprint materials; resins for 3D printers; holographic recording materials; dental materials; waveguide materials; black stripes for lens sheets; and coatings for optical elements. These materials can be used for a variety of purposes, including green sheets and electrode materials for capacitors; adhesives and sealants such as adhesives for FPDs, adhesives for HDDs, adhesives for optical pickups, adhesives for image sensors, sealants for organic EL, OCA for touch panels, OCR for touch panels; resists for FPDs such as color resists, black resists, protective films for color filters, photospacers, black column spacers, frame resists, photoresists for TFT wiring, and interlayer insulating films; resists for printed circuit boards such as liquid solder resists and dry film resists; and semiconductor materials such as semiconductor resists and buffer coat films, with no particular restrictions on their uses. [Example]

[0076] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0077] <Preparation of Polymerizable Composition> The epoxy resin (A), curing agent (B), photothermal conversion material (C), and filler (D) were mixed in the proportions shown in Table 1 to obtain polymerizable compositions of Examples 1 to 13 and Comparative Examples 1 to 3. These polymerizable compositions were evaluated according to the following methods.

[0078] <Evaluation method> (Curing evaluation) The polymerizable composition obtained above was applied to a PET film (Cosmoshine A4300, manufactured by Toyobo Co., Ltd.) that had been subjected to an easy-adhesion treatment using a bar coater to form a uniform coating film with a thickness of approximately 40 μm. The coating was then irradiated with ultraviolet light (illuminance 2 W / cm ) using a 365 nm LED light source. 2 ) for 60 seconds to evaluate the curability. A rating of B or higher was considered to be acceptable. A: When you touch the light-exposed area with your finger, fingerprints do not remain on the coating. B: When the exposed area is touched with a finger, fingerprints are left on the coating film. C: When the exposed area is touched with a finger, the coating film (coating liquid) adheres to the finger.

[0079] (Corrosion resistance evaluation) 15 μl of the polymerizable composition obtained above was dropped onto an electrolytic copper foil, and ultraviolet light (illuminance 2 W / cm ) was applied using a 365 nm LED light source. 2 ) for 60 seconds to form a cured product, which was used as an evaluation sample. The evaluation sample was left in an environment of 60°C and 90% RH, and evaluated by observing the appearance of the electrodeposited copper foil. However, for Comparative Examples 2 and 3, the test was not performed because the evaluation of the curability was poor. A rating of B or higher was considered to be acceptable. A: No change in appearance was observed in the electrolytic copper foil after being left in an environment of 60°C and 90% RH for 100 hours. B: No change in appearance was observed in the electrodeposited copper foil after being left in an environment of 60°C and 90% RH for 50 hours, but a change in appearance (blackening) was observed in the electrodeposited copper foil after being left for 100 hours. C: A change in appearance (blackening) was observed in the electrodeposited copper foil in an environment of 60°C and 90% RH for less than 50 hours.

[0080] [Table 1]

[0081] Compound 1 of the photothermal conversion material (C) was synthesized according to the method described in International Publication No. 2020 / 067118, compounds 2 to 7 were synthesized according to the method described in International Publication No. 2023 / 054225, compound 8 was synthesized according to the method described in International Publication No. 2018 / 221177, and compound 9 was synthesized according to the method described in Showa 59-197401. The synthesized compounds were analyzed by EI-MS and 1 The compounds were identified by H-NMR. Details of compounds 1 to 9 are shown in Table 2.

[0082] [Table 2]

[0083] Details of the abbreviations and other information listed in Table 1 are as follows: jER 828: Bisphenol A epoxy resin (Mitsubishi Chemical) Baxxodur EC302: Poly(propylene glycol) bis(2-aminopropyl ether) (manufactured by BASF) Compound 10: Diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate (Tokyo Chemical Industry Co., Ltd.) Compound 11: Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (manufactured by IGM Resins BV) PPW-5J: Polypropylene powder (manufactured by Seishin Enterprises)

[0084] As shown in Table 1, the polymerizable compositions of each Example had excellent curability and good corrosion resistance. On the other hand, the compositions of each Comparative Example showed results of insufficient curability or poor corrosion resistance.

Claims

1. Contains an epoxy resin (A), a curing agent (B), and a photothermal conversion material (C), The photothermal conversion material (C) is one or more compounds selected from the group consisting of the following general formulas (1), (2), (3), and (4): General formula (1): 【Chemical 1】 (In general formula (1), R １ , R ２ , R ３ and R ４ independently represent a methyl group or an ethyl group, R ５ represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R ６ are independent substituents each representing an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a chlorine atom, and n represents an integer of 0 to 2. General formula (2): 【Chemistry 2】 (In general formula (2), R ７ and R ８ R independently represents a methyl group or an ethyl group. ９ represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group. X represents a group represented by the following general formula (2-a): Ar １ , Ar ２ , Ar ３ or Ar ４ and n is an integer of 0 to 2. A triazine derivative having a peroxide bond represented by the formula: 【Chemistry 3】 (In general formula (2-a), m represents an integer of 0 to 3. R １０ are independent substituents, and are alkyl groups having 1 to 18 carbon atoms; １１ represents a substituent represented by -Y-, a nitro group, or a cyano group. The Y represents an oxygen atom or a sulfur atom. １１ represents a hydrocarbon group having 1 to 18 carbon atoms which may have one or more of an ether bond, a thioether bond, and a hydroxyl group at a terminal in the carbon skeleton, an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group, or an acyl group having 1 to 8 carbon atoms. １０ is two adjacent groups of the general formula (2-b): R １１ -Y- may form a 5- or 6-membered ring. General formula (3): 【Chemistry 4】 (In general formula (3), R １２ and R １３ are independently a methyl group or an ethyl group, R １４ represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group; R １５ represents an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, an optionally substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, an optionally substituted acyl group having 1 to 20 carbon atoms, -Y-R, or -N-RR', where Y represents an oxygen atom or a sulfur atom, and R and R' independently represent a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or an optionally substituted heterocyclic ring-containing group having 2 to 20 carbon atoms. Ar represents the following general formula (3-a): Ar ５ , Ar ６ , Ar ７ or Ar ８ The triazine derivative having a peroxide bond represented by the formula: 【Chemistry 5】 (In general formula (3-a), m represents an integer of 0 to 3. R １６ are independent substituents, and are alkyl groups having 1 to 18 carbon atoms; １７ represents a substituent represented by -Y-, a nitro group, or a cyano group. The Y represents an oxygen atom or a sulfur atom. １７ represents a hydrocarbon group having 1 to 18 carbon atoms which may have one or more of an ether bond, a thioether bond, and a hydroxyl group at a terminal in the carbon skeleton, an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group, or an acyl group having 1 to 8 carbon atoms. １６ is two adjacent groups of the general formula (3-b): R １７ -Y- may form a 5- or 6-membered ring. General formula (4): 【Chemistry 6】 (In general formula (4), R １８ and R １９ are independently an alkyl group having 4 to 8 carbon atoms or an aralkyl group having 9 to 12 carbon atoms, and R ２０ and R ２１ are independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 4 to 8 carbon atoms, or an aralkyloxy group having 9 to 12 carbon atoms.

2. 2. The polymerizable composition according to claim 1, wherein the curing agent (B) is one or more compounds selected from the group consisting of amine compounds, acid anhydrides, polyamide compounds, imidazole compounds, phenolic resins, hydrazide compounds, and mercaptan compounds.

3. The polymerizable composition according to claim 1 or 2, further comprising a filler (D).

4. A cured product formed from the polymerizable composition according to claim 1 or 2.

5. A method for producing a cured product, comprising the steps of applying the polymerizable composition according to claim 1 or 2 to a substrate and then curing the polymerizable composition by irradiating it with active energy rays.

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