Curable resin composition, cured material, and related products

Abstract

To provide a curable resin composition that yields a cured product with high adhesion and low elasticity.SOLUTION: A curable resin composition comprises: a resin (R1) with a first polymerizable unsaturated group, derived from reactive raw materials, consisting of a glycidyl ether product (E1) of a biphenol compound (P1) and an unsaturated monobasic acid (F1); and a resin (R2) with a second polymerizable unsaturated group, derived from reactive raw materials, consisting of a glycidyl ether product (E2) of a polyhydric hydroxy resin (P2) and an unsaturated monobasic acid (F2). The polyhydric hydroxy resin (P2) is a polymer derived from reactive raw materials, consisting of an aromatic compound (A) with an aromatic ring containing a phenolic hydroxy group and two or more hydrocarbon groups and an aromatic divinyl compound (B1).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a curable resin composition, a cured product, and an article.

Background Art

[0002] In recent years, curable resin compositions such as active energy ray-curable compositions curable by active energy rays such as ultraviolet rays and thermosetting compositions curable by heat have been widely used in fields such as inks, paints, coating agents, adhesives, and optical members. Among these, in the use of the above coating agents, in general, it is required that they can impart designability to the surfaces of various substrates, have excellent curability, and can form a coating film capable of preventing deterioration of the substrate surface. Furthermore, in recent years, it has also been required that the obtained cured product be excellent in adhesion to adjacent members (such as copper foil) and low elastic modulus (internal stress relaxation property).

[0003] As a conventional active energy ray-curable composition, a photosensitive resin composition containing an epoxy acrylate resin obtained by reacting an intermediate obtained by reacting a cresol novolak type epoxy resin, acrylic acid, and phthalic anhydride with tetrahydrophthalic anhydride is known (for example, see Patent Document Ⅰ).

Prior Art Documents

Patent Documents

[0007] The inventors of the present invention conducted extensive research to solve the above problems and, as a result, discovered that by incorporating two polymerizable unsaturated resins, obtained by reacting two specific glycidyl ethers with unsaturated monobasic acids, into a curable resin composition, the adhesion and low modulus of elasticity of the cured product obtained by curing such a curable resin composition are improved, thus completing the present invention. In other words, the gist of the present invention that solves the above problems is as follows.

[0008] [1] A resin (R1) having a first polymerizable unsaturated group, obtained by reacting a glycidyl ether (E1) of a biphenol compound (P1) with an unsaturated monobasic acid (F1) as reaction materials, It contains a resin (R2) having a second polymerizable unsaturated group, which is reacted with a glycidyl ether (E2) of a polyvalent hydroxy resin (P2) and an unsaturated monobasic acid (F2) as reaction materials. A curable resin composition characterized in that the polyvalent hydroxy resin (P2) is a polymer reacted with an aromatic compound (A) containing a phenolic hydroxyl group and an aromatic ring having two or more hydrocarbon groups, and an aromatic divinyl compound (B1).

[0009] [2] The polyvalent hydroxy resin (P2) is a polymer reacted with the aromatic compound (A), the aromatic divinyl compound (B1), and the aromatic monovinyl compound (B2) as raw materials. The curable resin composition according to [1], wherein the mass ratio (B1 / B2) of the aromatic divinyl compound (B1) to the aromatic monovinyl compound (B2) is in the range of 50 / 50 to 99 / 1.

[0010] [3] The curable resin composition according to [1] or [2], wherein the aromatic divinyl compound (B1) comprises divinylbenzene.

[0011] [4] A curable resin composition according to any one of [1] to [3], further comprising a photopolymerization initiator.

[0012] [5] A cured product of any of the curable resin compositions described in [1] to [4] above.

[0013] [6] An article characterized by having a coating film made of the cured product described in [5] above. [Effects of the Invention]

[0014] According to the present invention, it is possible to provide a curable resin composition that can produce a cured product with high adhesion and excellent low modulus of elasticity. Furthermore, according to the present invention, it is possible to provide a cured product with high adhesion and excellent low modulus of elasticity, and an article having a coating film made of such a cured product. [Modes for carrying out the invention]

[0015] (Explanation of terms) Unless otherwise specified in this specification, the following definitions of terms apply. Please note that some terms used in the following explanation may not appear in this specification.

[0016] In this specification, examples of "aryl group" include phenyl group, naphthyl group, phenalenyl group, phenantrenyl group, anthryl group, azlenyl group, indenyl group, indanyl group, tetralinyl group, and the like. Furthermore, the hydrogen atoms of the aromatic ring in the "aryl group" may be substituted with, for example, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom.

[0017] In this specification, "aralkyl group" refers to, for example, a benzyl group, a diphenylmethyl group, a biphenyl group, a naphthylmethyl group, and the like.

[0018] In this specification, "alkyl group" refers to, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a tert-pentyl group, a neopentyl group, a 1,2-dimethylpropyl group, an n-hexyl group, an isohexyl group, an (n-)heptyl group, an (n-)octyl group, an (n-)nonyl group, an (n-)decyl group, an (n-)undecyl group, an (n-)dodecyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, or a cyclononyl group.

[0019] In this specification, examples of "alkoxy group (alkyloxy group)" include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyloxy group, octyloxy group, nonyloxy group, and the like.

[0020] In this specification, "halogen atoms" include, for example, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, and the like.

[0021] In this specification, examples of "alkylene group" include methylene group, ethylene group, propylene group, 1-methylmethylene group, 1,1-dimethylmethylene group, 1-methylethylene group, 1,1-dimethylethylene group, 1,2-dimethylethylene group, propylene group, butylene group, 1-methylpropylene group, 2-methylpropylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, and the like.

[0022] In this specification, "monovalent hydrocarbon group" refers, for example, to the alkyl group described above, and one or more -CH2- in the alkyl group may be substituted with -O- or -S- so as not to be adjacent to each other, or one or more -CH2-CH2- in the alkyl group may be substituted with -CH=CH- so as not to be adjacent to each other.

[0023] In this specification, "divalent hydrocarbon group" refers, for example, to the alkylene group described above. In the alkylene group, one or more -CH2- groups may be replaced with -O- or -S- groups such that they are not adjacent to each other, or one or more -CH2-CH2- groups may be replaced with -CH=CH2- groups such that they are not adjacent to each other.

[0024] In this specification, the "aliphatic hydrocarbon group" may be linear or branched, and may have unsaturated bonds in its structure. That is, if the aliphatic hydrocarbon group has two or more carbon atoms, one or more -CH2-CH2- atoms in the aliphatic hydrocarbon group may be independently substituted with -CH=CH- or -C≡C-.

[0025] In this specification, "(meth)acrylate" means acrylate and / or methacrylate. In this specification, "(meth)acryloyl" means acryloyl and / or methacryloyl. Furthermore, in this specification, "(meth)acrylic" means acrylic and / or methacrylic.

[0026] In this specification, "reaction raw materials" means compounds used to obtain a target compound (including intermediate compounds) through chemical reactions such as combination or decomposition, and which partially constitute the chemical structure of the target compound. Substances that act as aids to chemical reactions, such as solvents and catalysts, are excluded from the definition of "reaction raw materials." The term "reaction material" is used in this specification because it is generally impractical to directly identify the target compound by its structure.

[0027] The embodiments of the present invention (which may be referred to as "these embodiments") will be described in detail below, but the present invention is not limited to the following description and can be implemented in various ways within the scope of its gist.

[0028] (Curable resin composition) The curable resin composition of this embodiment contains two polymerizable unsaturated resins obtained by reacting two specific glycidyl ethers with an unsaturated monobasic acid as a reaction material. More specifically, the curable resin composition of this embodiment contains a first polymerizable unsaturated resin (R1) (hereinafter sometimes simply referred to as "the first resin (R1)") obtained by reacting a glycidyl ether of a biphenol compound (P1) (E1) with an unsaturated monobasic acid (F1) as a reaction material, and It contains a resin (R2) having a second polymerizable unsaturated group (hereinafter sometimes simply referred to as "the second resin (R2)"), which is reacted with a glycidyl ether (E2) of a polyvalent hydroxy resin (P2) and an unsaturated monobasic acid (F2) as reaction raw materials. The polyvalent hydroxy resin (P2) is characterized in that it is a polymer reacted with an aromatic compound (A) containing a phenolic hydroxyl group and an aromatic ring having two or more hydrocarbon groups, and an aromatic divinyl compound (B1) as reaction raw materials. Such a curable resin composition makes it possible to obtain a cured product with high adhesion and excellent low modulus of elasticity.

[0029] The curable resin composition of this embodiment may optionally contain other components (described later) other than the first resin (R1) and the second resin (R2).

[0030] <Resin having a first polymerizable unsaturated group (R1)> The first polymerizable unsaturated resin (R1) is a resin reacted with a glycidyl ether of a biphenol compound (P1) (E1) and an unsaturated monobasic acid (F1). In other words, the first resin (R1) is the reaction product of a glycidyl ether of a biphenol compound (P1) (E1) and an unsaturated monobasic acid (F1). Furthermore, other compounds besides those mentioned above may or may not be used as reaction materials for the first resin (R1) as needed.

[0031] Examples of polymerizable unsaturated groups in the first resin (R1) include (meth)acryloyl groups, allyl groups, isopropenyl groups, 1-propenyl groups, styryl groups, styrylmethyl groups, maleimide groups, vinyl ether groups, and the like.

[0032] [Biphenol compound (P1)] Biphenol compounds (P1) are compounds having a structure in which two hydroxyphenyl groups are linked. Biphenol compounds (P1) are not particularly limited, but examples include 2,2'-biphenol, 2,4'-biphenol, 3,3'-biphenol, 4,4'-biphenol, and biphenol derivatives in which one or more hydrogen atoms in the aromatic ring are substituted with one or more monovalent substituents. These biphenol compounds (P1) may be used individually or in combination of two or more.

[0033] Examples of the substituents include aliphatic hydrocarbon groups, alkoxy groups, or halogen atoms. The aliphatic hydrocarbon group is preferably an alkyl group or alkenyl group having 1 to 4 carbon atoms. Specific examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, isobutyl group, vinyl group, allyl group, and the like. The alkoxy group is preferably one having 1 to 4 carbon atoms, and specific examples include a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, and the like. The halogen atom is preferably a fluorine atom, a chlorine atom, or a bromine atom.

[0034] In particular, 4,4'-biphenol and its derivatives having substituents on the aromatic ring are preferred as the biphenol compound (P1), with 4,4'-biphenol being more preferred.

[0035] In this embodiment, the biphenol compound (P1) is, for example, the following general formula (P1): [ka] [In the formula, R p1 and R p2 Each of these independently represents an aliphatic hydrocarbon group, an alkoxy group, or a halogen atom, and n p1 and n p2 Each of these independently represents an integer from 0 to 4. They can be represented as ].

[0036] In the above general formula (P1), R p1 and R p2 Each of these is preferably an alkyl group, alkenyl group, or alkoxy group having 1 to 4 carbon atoms. n in the above general formula (P1) p1 and n p2 Preferably, each of these is an independent integer between 0 and 2.

[0037] [Glycidyl ether (E1)] Glycidyl ether (E1) is a compound obtained by glycidyl etherification of the above biphenol compound (P1), and more specifically, a compound in which one or more hydroxyl groups in the biphenol compound (P1) are replaced with glycidyl groups. Glycidyl ether (E1) is one of the essential reaction raw materials for obtaining the first resin (R1). Glycidyl ether (E1) is obtained by reacting the biphenol compound (P1) with an epihalohydrin (glycidyl etherification).

[0038] In this embodiment, the glycidyl ether (E1) is, for example, the following general formula (E1): [ka] [In the formula, G e1 represents a glycidyl group, and R p1 , R p2 , n p1 and n p2 respectively correspond to those in the general formula (P1). It can be represented by.]

[0039] 〔Unsaturated monobasic acid (F1)〕<00​​​​​​​​​​​​​​​​​​​​represents a hydrogen atom or a methyl group. Compounds represented by ] can be used.

[0042] Examples of the polyoxyalkylene chains include polyoxyethylene chains and polyoxypropylene chains.

[0043] Examples of the (poly)ester chain include the following general formula (3-1): [ka] [In the formula, R 311 and R 312 This represents an alkylene group with 1 to 10 carbon atoms, n 311 represents an integer from 1 to 5. Examples include (poly)ester chains represented by ].

[0044] Examples of the aromatic hydrocarbon chains include phenylene chains, naphthylene chains, biphenylene chains, phenylnaphthylene chains, or binaphthylene chains. Hydrocarbon chains having aromatic rings such as benzene rings, naphthalene rings, anthracene rings, and phenanthrene rings as partial structures can also be used.

[0045] The (poly)carbonate chain mentioned above is, for example, the following general formula (3-2): [ka] [In the formula, R 321 This represents an alkylene group with 1 to 10 carbon atoms, n 321 represents an integer from 1 to 5. An example is a (poly)carbonate chain represented by ].

[0046] The molecular weight of the compound represented by the above general formula (3) is preferably in the range of 100 to 500, and more preferably in the range of 150 to 400.

[0047] <Resin having a second polymerizable unsaturated group (R2)> The second polymerizable unsaturated resin (R2) is a resin reacted with a glycidyl ether (E2) of a polyvalent hydroxy resin (P2) and an unsaturated monobasic acid (F2). In other words, the second resin (R2) is the reaction product of a glycidyl ether (E2) of a polyvalent hydroxy resin (P2) and an unsaturated monobasic acid (F2). Furthermore, other compounds besides those mentioned above may or may not be used as reaction materials for the second resin (R2) as needed. Furthermore, the polyvalent hydroxy resin (P2) is a polymer reacted with an aromatic compound (A) containing a phenolic hydroxyl group and an aromatic ring having two or more hydrocarbon groups, and an aromatic divinyl compound (B1). If necessary, other compounds besides those mentioned above may or may not be used as reaction materials for the polyvalent hydroxy resin (P2).

[0048] Examples of polymerizable unsaturated groups in the second resin (R2) include (meth)acryloyl groups, allyl groups, isopropenyl groups, 1-propenyl groups, styryl groups, styrylmethyl groups, maleimide groups, vinyl ether groups, and the like. In this embodiment, the polymerizable unsaturated groups of the second resin (R2) may be the same as or different from the polymerizable unsaturated groups of the first resin (R1). However, from the viewpoint of efficiently obtaining the curable resin composition of this embodiment, it is preferable that these polymerizable unsaturated groups are the same.

[0049] [Polyvalent hydroxy resin (P2)] As described above, the polyvalent hydroxy resin (P2) is a polymer reacted with an aromatic compound (A) containing a phenolic hydroxyl group and an aromatic ring having two or more hydrocarbon groups, and an aromatic divinyl compound (B1). In other words, the polyvalent hydroxy resin (P2) has a structure in which aromatic compound (A) units containing a phenolic hydroxyl group and an aromatic ring having two or more hydrocarbon groups are chemically bonded to aromatic divinyl compound (B1) units.

[0050] In this embodiment, a phenolic compound having two or more hydrocarbon groups in its aromatic ring (i.e., aromatic compound (A)) is used as the reaction raw material. Since this aromatic compound (A) unit is used as a repeating unit, it is easy to control the reaction site with the aromatic divinyl compound (B1). As a result, a polyvalent hydroxy resin (P2) with a uniform chemical structure or molecular chain length is easily obtained. Consequently, high adhesion can be achieved, and it is believed that the elastic modulus can be reduced by optimizing the distance between the crosslinking points between the so-called linking group and the aromatic divinyl compound (B1) that acts upon it.

[0051] On the other hand, in conventional phenolic resins, which use phenolic compounds having one or fewer hydrocarbon groups in the aromatic ring as repeating units, there are numerous bonding sites between the phenolic compound and the aromatic divinyl compound unit. As a result, the resulting phenolic resin has a large number of chemical structures and molecular chain lengths, and consequently, tends to have a broader molecular weight distribution compared to this embodiment.

[0052] Furthermore, other compounds besides those mentioned above (for example, aromatic monovinyl compounds (B2) described later) may be used as reaction raw materials to obtain the polyvalent hydroxy resin (P2).

[0053] Furthermore, in the polyvalent hydroxy resin (P2), the total proportion of aromatic compound (A) units, aromatic divinyl compound (B1) units, and optionally aromatic monovinyl compound (B2) units derived from the reaction raw materials is preferably 80% by mass or more, and more preferably 90% by mass or more, relative to the total amount (100% by mass) of the polyvalent hydroxy resin (P2).

[0054] The hydroxyl group equivalent of the polyvalent hydroxy resin (P2) is preferably 200 to 500 g / eq, and more preferably 200 to 400 g / eq. In this specification, the hydroxyl group equivalent of polyvalent hydroxy resin (P2) shall be measured using a method compliant with the neutralization titration method specified in JIS K 0070 (1992).

[0055] The polyvalent hydroxy resin (P2) preferably has a melt viscosity at 150°C measured with an ICI viscometer of 0.01 to 5 dPa·s, more preferably 0.01 to 2 dPa·s, and even more preferably 0.01 to 1 dPa·s. When the melt viscosity of the polyvalent hydroxy resin (P2) is within the above range, it has low viscosity and excellent fluidity, which improves the moldability of the cured product obtained by curing the curable resin composition.

[0056] The number-average molecular weight (Mn) of the polyvalent hydroxy resin (P2) is preferably in the range of 200 to 1500, and more preferably in the range of 220 to 1000, in order to achieve low viscosity and excellent fluidity. The weight-average molecular weight (Mw) of the polyvalent hydroxy resin (P) is preferably in the range of 250 to 2000, more preferably in the range of 300 to 1500, and even more preferably in the range of 400 to 1200. The molecular weight distribution (Mw / Mn) of the polyvalent hydroxy resin (P) is preferably in the range of 1.1 to 3, and more preferably in the range of 1.5 to 1.8.

[0057] -Aromatic compound (A)- In this embodiment, the aromatic compound (A) has an aromatic ring comprising a phenolic hydroxyl group and two or more hydrocarbon groups (R a ) is present. Therefore, aromatic compound (A) may be a phenolic compound. Furthermore, the aromatic ring that forms the central structure of aromatic compound (A) may include an aromatic hydrocarbon ring. The aromatic ring may be monocyclic or polycyclic. Examples of aromatic hydrocarbon rings include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, and phenalene rings. However, it is preferable that the aromatic ring is monocyclic.

[0058] The above 2 or more hydrocarbon groups (R a Examples of hydrocarbon groups include those having 1 to 6 carbon atoms. aExamples of the aliphatic hydrocarbon group (R) include monovalent aliphatic hydrocarbon groups having 1 to 6 carbon atoms. The aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group in order to prevent addition reactions with other compounds. Examples of saturated aliphatic hydrocarbon groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, and hexyl groups. a The lower the molecular weight of the compound, the greater the potential for improved adhesion when the material is cured.

[0059] A hydrocarbon group (R) in the aromatic ring of aromatic compound (A) a The number of (i.e., substitutions) is 2 or more. The hydrocarbon group (R a The number of hydrocarbon groups (R) is 2 or more, which can result in excellent adhesion and a low modulus of elasticity. On the other hand, the hydrocarbon group (R) a The upper limit of the number of hydrocarbon groups (R) is, from the viewpoint that the aromatic ring has a phenolic hydroxyl group and two bonds are used in polymerization, the number of substituted ring constituent atoms in the unsubstituted aromatic ring minus 3. For example, if the aromatic ring is a benzene ring, the hydrocarbon group (R) a The number of ) is 3 or less.

[0060] The preferred form of aromatic compound (A) will be described below, using the case where aromatic compound (A) contains an aromatic hydrocarbon ring (e.g., a benzene ring, a naphthalene ring) as an example.

[0061] In this embodiment, it is preferable that the carbon atom in the aromatic hydrocarbon ring constituting the aromatic compound (A) that has the highest HOMO electron density (Hückel coefficient) is unsubstituted (or substituted with a hydrogen atom). This allows for the formation of ArS by the cationoid reagent from the aromatic divinyl compound (B1) described later. EThis makes it easier to control the reaction and molecular design. More specifically, if the carbon atom with the highest HOMO electron density (Hückel coefficient) among the carbon atoms in the aromatic hydrocarbon ring constituting aromatic compound (A) is unsubstituted (or bonded to a hydrogen atom), then the carbocation of the cationoid reagent aromatic divinyl compound (B1) readily reacts with the carbon atom with the highest HOMO electron density. Therefore, the hydrocarbon group (R a By controlling the number and position of the phenolic hydroxyl groups, or the number and position of the phenolic hydroxyl groups, the bonding sites or number of bonds with the aromatic divinyl compound (B1) can be adjusted. Therefore, it is presumed that the chemical structure or molecular chain length of the resulting polyvalent hydroxy resin (P2) will be easier to control.

[0062] For example, if the aromatic compound (A) is a phenol skeleton having one benzene ring and one hydroxyl group, it is preferable that at least one carbon atom among the 2nd, 4th, and 6th positions is substituted with a hydrogen atom. This makes it easier for the cationoid reagent formed from the aromatic divinyl compound (B1), described later, to attack at least one carbon atom among the 2nd, 4th, and 6th positions, which are the ortho and para positions of the phenol nucleus where the electron density is high. In particular, it is preferable that the cationoid reagent formed from the aromatic divinyl compound (B1) is added to the 4th position of the phenol nucleus. As a result, the benzene ring of the phenol nucleus becomes p-substituted, and due to its symmetrical structure, it is thought to form a cross-linked structure that is easily stress-relaxed, resulting in favorable adhesion and Charpy impact strength. This mechanism of action is thought to work similarly whether the polyvalent hydroxy resin (P2) is used as an epoxy resin or as a phenol resin (curing agent).

[0063] Similarly, in an unsubstituted naphthalene ring, the carbon atoms at positions 1, 4, 5, and 8 have the highest HOMO electron density. The position of the carbon atom with the highest HOMO electron density changes depending on the bond position of the phenolic hydroxyl group, but for example, in 2-naphthol, which has one naphthalene ring and one hydroxyl group, the carbocation generated from an aromatic divinyl compound (B1) readily reacts with positions 1 and 3. Therefore, for example, the hydrogen atom of the CH group at position 1 is converted to a hydrocarbon group (R a When substituted by ), ArS is added to the carbon atom at position 3. E Because it becomes more reactive, the chemical structure or molecular chain length of the resulting polyvalent hydroxy resin (P2) can be controlled.

[0064] Furthermore, for example, if the aromatic compound (A) has a 2,7-hydroxynaphthalene skeleton, the carbocation generated from the aromatic divinyl compound (B1) readily reacts with the 1st, 3rd, 6th, and 8th positions. Therefore, for example, a hydrocarbon group (R) is attached to the three carbon atoms at positions 1, 3, and 6. a When ) is bonded, ArS is attached to the carbon atom at position 8. E It becomes more responsive.

[0065] From the above, two or more hydrocarbon groups (R a It is thought that using an aromatic compound (A) having ) will make it easier to control the resin structure.

[0066] Specific examples of aromatic compounds (A) include, for example, xylenol (2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol), trimethylphenol (2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, 2,4,5-trimethylphenol, 2,4,6-trimethylphenol, 3,4,5-trimethylphenol) and dialkylphenols such as their derivatives. Nol compounds; and compounds selected from the group consisting of 1-naphthol, 2-naphthol, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene, in which two or more hydrogen atoms of CH groups are converted into the above hydrocarbon group (R a Examples include compounds substituted with ), so-called dialkylhydroxynaphthalene compounds. These aromatic compounds (A) may be used individually or in combination of two or more. However, from the viewpoint of low viscosity in melt, dialkylphenol compounds are preferred as aromatic compound (A).

[0067] In this embodiment, the aromatic compound (A) is, for example, the following general formula (A1): [ka] [In the formula, R a This represents a hydrocarbon group with 1 to 6 carbon atoms, p a This represents 2 or 3, and there are multiple R a These elements may be identical or different. They can be represented as [ ].

[0068] In the above general formula (A1), R a It is preferable that it is a hydrocarbon group having 1 to 3 carbon atoms. The hydrocarbon group having 1 to 6 carbon atoms in the above general formula (A1) is the hydrocarbon group (R) mentioned above. a ) is equivalent to [the above].

[0069] -Aromatic divinyl compound (B1)- In this embodiment, the aromatic divinyl compound (B1) is a compound in which two vinyl groups are added as substituents to an aromatic ring, and can be used without particular limitations as long as it can react with the aromatic compound (A). That is, the aromatic divinyl compound (B1) can form a linking group in the polyvalent hydroxy resin (P2) that links aromatic compounds (A) together via a predetermined site.

[0070] As mentioned above, ArS E The reaction can introduce an aromatic divinyl compound (B1) to a specific position on the aromatic ring of the aromatic compound (A). This makes it easier to obtain a polyvalent hydroxy resin (P2) with a uniform chemical structure or molecular chain length, resulting in excellent adhesion and a low modulus of elasticity.

[0071] Specific examples of aromatic divinyl compounds (B1) include, for example, 1,2-divinylbenzene, 1,3-divinylbenzene, 1,4-divinylbenzene, 2,5-dimethyl-1,4-divinylbenzene, 2,5-diethyl-1,4-divinylbenzene, cis,cis,β,β'-diethoxy-mm-divinylbenzene, 1,4-divinyl-2,5-dibutylbenzene, 1,4-divinyl-2,5-dihexylbenzene, 1,4-divinyl-2,5-dimethoxybenzene, and their derivatives. Examples include divinylbenzenes; divinylbiphenyls; and divinylnaphthalenes such as 1,3-divinylnaphthalene, 1,4-divinylnaphthalene, 1,5-divinylnaphthalene, 1,6-divinylnaphthalene, 1,7-divinylnaphthalene, 2,3-divinylnaphthalene, 2,6-divinylnaphthalene, 2,7-divinylnaphthalene, 3,4-divinylnaphthalene, 1,8-divinylnaphthalene, 1,5-dimethoxy-4,8-divinylnaphthalene and derivatives thereof. These aromatic divinyl compounds (B1) may be used individually or in combination of two or more.

[0072] The above derivatives are, for example, compounds having one or more substituents such as alkyl groups or alkoxy groups, or halogen atoms, on an aromatic ring. The alkyl group or alkoxy group may be linear or branched. In particular, the alkyl group or alkoxy group is preferably 1 to 4 carbon atoms, from the viewpoint of more effectively improving adhesion and low modulus of elasticity.

[0073] In particular, from the viewpoint of fluidity, divinylbenzene and compounds having substituents on its aromatic ring are preferred as the aromatic divinyl compound (B1), with divinylbenzene being more preferred. Furthermore, the substitution position of the vinyl group of divinylbenzene is not particularly limited, but it is preferable that the meta isomer be the main component. The content of the meta isomer in divinylbenzene is preferably 40% by mass or more, and more preferably 50% by mass or more, relative to the total amount of divinylbenzene.

[0074] In this embodiment, the aromatic divinyl compound (B1) is, for example, the following general formula (B1): [ka] [In the formula, R b1 represents a halogen atom or an alkyl or alkoxy group having 1 to 4 carbon atoms, p b1 represents an integer from 0 to 4, and p b1 If R is an integer greater than or equal to 2, there are multiple R's. b1 They may be identical or different. They can be represented as ].

[0075] In the above general formula (B1), R b1 It is preferable that it is an alkyl group having 1 to 3 carbon atoms. The alkyl or alkoxy group having 1 to 4 carbon atoms in the above general formula (B1) is equivalent to the alkyl or alkoxy group described above. In the above general formula (B1), p b1 It is preferable that the value is between 0 and 1.

[0076] -Aromatic monovinyl compound (B2)- In this embodiment, it is preferable to further use an aromatic monovinyl compound (B2) as a reaction raw material for obtaining the polyvalent hydroxy resin (P2). That is, it is preferable that the polyvalent hydroxy resin (P2) is a polymer obtained by reacting an aromatic compound (A), an aromatic divinyl compound (B1), and an aromatic monovinyl compound (B2) as reaction raw materials. In this case, the polyvalent hydroxy resin (P2) has a structure in which an aromatic compound (A) unit containing a phenolic hydroxyl group and an aromatic ring having two or more hydrocarbon groups is chemically bonded to an aromatic divinyl compound (B1) unit, and an aromatic monovinyl compound (B2) unit is chemically bonded to the aromatic ring in the aromatic compound (A) unit.

[0077] Aromatic monovinyl compounds (B2) are groups that can substitute for hydrogen atoms in the ring structure of aromatic compound (A) in polyvalent hydroxy resin (P2). When the glycidyl ether (E2) obtained by further using aromatic monovinyl compounds (B2) is used as a semiconductor encapsulation material, it exhibits excellent low hygroscopicity, thus providing good reliability. Furthermore, moisture resistance can be improved by further using aromatic monovinyl compounds (B2). In addition, aromatic monovinyl compounds (B2), like aromatic divinyl compounds (B1), generate carbocations, and therefore readily react with the carbon atom in the aromatic hydrocarbon ring constituting aromatic compound (A) that has the highest HOMO electron density (Hückel coefficient).

[0078] Specific examples of aromatic monovinyl compounds (B2) include vinylbenzenes such as styrene, fluorostyrene, vinyl benzyl chloride, alkyl vinylbenzenes (o-,m-,p-methylstyrene, o-,m-,p-ethyl vinylbenzene), o-,m-,p-(chloromethyl)styrene and their derivatives; biphenyl compounds such as 4-vinyl biphenyl, 4-vinyl-p-terphenyl and their derivatives; and vinyl naphthalenes such as 1-vinyl naphthalene, 2-vinyl naphthalene and their derivatives. These aromatic monovinyl compounds (B2) may be used individually or in combination of two or more.

[0079] The above derivatives are, for example, compounds having one or more substituents such as alkyl groups or alkoxy groups, or halogen atoms, on an aromatic ring. The alkyl group or alkoxy group may be linear or branched. In particular, the alkyl group or alkoxy group is preferably 1 to 4 carbon atoms, from the viewpoint of more effectively improving adhesion and low modulus of elasticity.

[0080] In particular, the aromatic monovinyl compound (B2) is preferably alkyl vinylbenzene and compounds having substituents on its aromatic ring, and more preferably ethyl vinylbenzene. Furthermore, the substitution positions of the vinyl group and ethyl group of ethyl vinylbenzene are not particularly limited, but it is preferable that the meta isomer is the main component. The content of the meta isomer in ethyl vinylbenzene is more preferably 40% by mass or more, and more preferably 50% by mass or more, relative to the total amount of ethyl vinylbenzene.

[0081] In this embodiment, the aromatic monovinyl compound (B2) is, for example, the following general formula (B2): [ka] [In the formula, R b2 represents a halogen atom or an alkyl or alkoxy group having 1 to 4 carbon atoms, p b2 represents an integer from 0 to 5, and p b2 If R is an integer greater than or equal to 2, there are multiple R's. b2 They may be identical or different. They can be represented as ].

[0082] In the above general formula (B2), R b2 It is preferably an alkyl group having 1 to 3 carbon atoms. The alkyl or alkoxy group having 1 to 4 carbon atoms in the above general formula (B2) is equivalent to the alkyl or alkoxy group described above. In the general formula (B2) above, p b2 It is preferable that it is between 0 and 1.

[0083] When an aromatic monovinyl compound (B2) is used as a reaction raw material for the polyvalent hydroxy resin (P2), the mass ratio (B1 / B2) of the aromatic divinyl compound (B1) to the aromatic monovinyl compound (B2) is preferably in the range of 30 / 70 to 99 / 1, more preferably in the range of 50 / 50 to 99 / 1, and even more preferably in the range of 50 / 50 to 98 / 2. By having the mass ratio of the aromatic divinyl compound (B1) to the aromatic monovinyl compound (B2) within the above range, the handling properties of the resulting polyvalent hydroxy resin (P2) and the balance of moldability and curability properties during the production of the glycidyl ether (E2) and / or the second resin (R2) can be improved.

[0084] -Structure of polyvalent hydroxy resin (P2)- The following describes specific embodiments of the polyvalent hydroxy resin (P2), using the case where each aromatic ring is a benzene ring as an example. The chemical structural formulas shown below are for illustrative purposes only, and the disclosure is not limited to these chemical structural formulas.

[0085] In this embodiment, the polyvalent hydroxy resin (P2) is the following general formula (I) and / or (II): [ka] [ka] [In the above general formulas (I) and (II), R 1 , R 2 and R 3 Each of these independently represents a hydrocarbon group with 1 to 6 carbon atoms. R 4 and R 5 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R 6 The following general formula (a): [ka] [In general formula (a), R 7represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. ] represents a substituent, R 8 This represents a hydrogen atom or an organic group. p is the average R per phenol ring in the entire molecule. 6 The substitution number represents a number between 0 and 1, and * represents a bond with another atom. It is preferable to have a substructure represented by ].

[0086] In the above general formulas (I) and (II), the hydrocarbon group having 1 to 6 carbon atoms is the hydrocarbon group (R) described above. a It is preferable that it be defined as ). In the above general formulas (I) and (II), R 1 , R 2 and R 3 Each of these is preferably an alkyl group having 1 to 4 carbon atoms. In the above general formulas (I) and (II), R 4 and R 5 Each of these is preferably a hydrogen atom or a methyl group, independently of the others. In the above general formula (a), R 7 It is preferable that it is an alkyl group having 1 to 4 carbon atoms. The organic group in the above general formulas (I) and (II) is a monovalent organic group, preferably an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Furthermore, one or more non-adjacent -CH2- in the alkyl group, alkenyl group, or alkoxy group may be substituted with -O-, -COO-, or -OCO-.

[0087] In this embodiment, the polyvalent hydroxy resin (P2) is the following general formula (III) and / or (IV): [ka] [ka] [R in the above general formulas (III) and (IV) 1 ~R 8It is preferable that the structure is represented by ] where p and n are as in the general formulas (I) and (II) above, n is an integer from 1 to 20, and m is an integer from 1 to 20.

[0088] - Manufacturing of polyvalent hydroxy resin (P2) - There are no particular limitations on the method for producing the polyvalent hydroxy resin (P2), but for example, the polyvalent hydroxy resin (P2) can be produced by reacting an aromatic compound (A), an aromatic divinyl compound (B1) (e.g., divinylbenzene), and, if necessary, other compounds such as an aromatic monovinyl compound (B2) (e.g., ethylvinylbenzene) in the presence of an acid catalyst.

[0089] In the method for producing polyvalent hydroxy resin (P2), the properties of the resulting polyvalent hydroxy resin (P2), such as the hydroxyl group equivalent, can be controlled depending on the blending ratio of aromatic divinyl compound (B1) and the aromatic monovinyl compound (B2) that can be used.

[0090] For example, the molar ratio of aromatic divinyl compound (B1) to 1 mole of aromatic compound (A) is preferably 0.1 to 1 mole, and more preferably 0.1 to 0.8 moles, from the viewpoint of balancing the physical properties of the cured product during manufacturing. When using aromatic monovinyl compound (B2), the total molar ratio of aromatic divinyl compound (B1) and aromatic monovinyl compound (B2) to 1 mole of aromatic compound (A) is preferably 0.1 to 1 mole, and more preferably 0.1 to 0.8 moles.

[0091] Furthermore, considering the balance of moldability and curability properties during the production of the resulting cured product, the number of moles of vinyl groups contained in aromatic divinyl compound (B1) and aromatic monovinyl compound (B2) per mole of aromatic compound (A) is preferably 0.1 to 1 mole, and more preferably 0.1 to 0.95 moles.

[0092] The reaction between the aromatic compound (A) and other compounds such as the aromatic divinyl compound (B1) and, if necessary, the aromatic monovinyl compound (B2) can be carried out in the presence of an acid catalyst. This acid catalyst can be appropriately selected from well-known inorganic acids and organic acids. Examples include mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, p-toluenesulfonic acid hydrate, dimethyl sulfuric acid, and diethyl sulfuric acid; Lewis acids such as zinc chloride, aluminum chloride, iron chloride, and boron trifluoride; or solid acids such as ion exchange resins, activated clay, silica-alumina, and zeolites. The amount of the acid catalyst is preferably 0.01 to 50 parts by mass, more preferably 0.01 to 10 parts by mass, and even more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the total reaction raw materials of the polyvalent hydroxy resin (P2). The above reaction is usually carried out at 10 to 250°C for 1 to 20 hours.

[0093] Examples of solvents that can be used in the above reaction include alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, and ethyl cellosolve; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethers such as dimethyl ether, diethyl ether, diisopropyl ether, tetrahydrofuran, and dioxane; and aromatic compounds such as benzene, toluene, chlorobenzene, and dichlorobenzene.

[0094] Specific methods for carrying out the above reaction include either charging all reaction materials together and reacting them at a predetermined temperature, or charging aromatic compound (A) and acid catalyst and reacting them dropwise while maintaining the predetermined temperature with aromatic divinyl compound (B1) or other compounds (e.g., aromatic monovinyl compound (B2)). In this case, the dropwise addition time is usually 1 to 10 hours, preferably 5 hours or less. If a solvent is used, the polyvalent hydroxy resin (P2) can be obtained by distilling off the solvent and unreacted products after the reaction. On the other hand, if no solvent is used, the polyvalent hydroxy resin (P2) can be obtained by distilling off the unreacted products after the reaction.

[0095] [Glycidyl ether (E2)] Glycidyl ether (E2) is a compound obtained by glycidyl etherification of the above-mentioned polyhydric hydroxy compound (P2), and more specifically, a compound in which one or more hydroxyl groups in the polyhydric hydroxy compound (P2) are replaced with glycidyl groups. Specifically, glycidyl ether (E2) can have a structure in which an aromatic compound (A) unit containing an aromatic ring having a phenolic hydroxyl group and two or more hydrocarbon groups is chemically bonded to an aromatic divinyl compound (B1) unit, and an aromatic monovinyl compound (B2) unit is optionally chemically bonded to the aromatic ring in the aromatic compound (A) unit, and the phenolic hydroxyl group of the aromatic compound (A) is replaced with a glycidyl ether group. Glycidyl ether (E2) is obtained by reacting a polyhydric hydroxyl compound (P2) with an epihalohydrin (glycidyl etherification).

[0096] The epoxy equivalent of the glycidyl ether (E2) is preferably 200 to 1500 g / eq, more preferably 220 to 1000 g / eq, and even more preferably 240 to 800 g / eq.

[0097] The glycidyl ether (E2) preferably has a melt viscosity at 150°C measured by an ICI viscometer of 0.01 to 10 dPa·s, more preferably 0.01 to 5 dPa·s, and even more preferably 0.01 to 1 dPa·s.

[0098] The number-average molecular weight (Mn) of the glycidyl ether (E2) is preferably in the range of 200 to 1800, more preferably in the range of 250 to 1500, and even more preferably in the range of 430 to 1500, as this results in low viscosity and excellent fluidity. The weight-average molecular weight (Mw) of the glycidyl ether (E2) is preferably in the range of 250 to 2000, and more preferably in the range of 300 to 1800. In another embodiment, the weight-average molecular weight (Mw) of the glycidyl ether (E2) is preferably in the range of 800 to 2000. The molecular weight distribution (Mw / Mn) of the glycidyl ether (E2) is preferably in the range of 1.1 to 3, and more preferably in the range of 1.1 to 1.8.

[0099] As mentioned above, since polyvalent hydroxy resins (P2) have a more uniform molecular weight than conventional phenolic resins, the glycidyl ether derivative (E2) of polyvalent hydroxy resins (P2) can similarly exhibit homogeneous properties with a uniform molecular weight.

[0100] In this embodiment, the glycidyl ether (E2) is the following general formula (V) and / or (VI): [ka] [ka] [In the above general formulas (V) and (VI), G represents a glycidyl group, and R 1 ~R 8 , p and * are equivalent to those in the above general formulas (I) and (II). It is preferable to have a substructure represented by ].

[0101] In this embodiment, the glycidyl ether (E2) is the following general formula (VII) and / or (VIII): [ka] [ka] [R in the above general formulas (VII) and (VIII) 1 ~R 8It is preferable to have a structure represented by [ ] where p and n are as in the general formulas (I) and (II) above, n is an integer from 1 to 20, m is an integer from 1 to 20, and G is a glycidyl group.

[0102] [Unsaturated monobasic acid (F2)] An unsaturated monobasic acid (F2) is one of the essential reaction raw materials for obtaining the second resin (R2). The unsaturated monobasic acid (F2) is preferably a compound having an acid group and a polymerizable unsaturated group in one molecule. Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Examples of the polymerizable unsaturated group include a (meth)acryloyl group, an allyl group, an isopropenyl group, and a 1-propenyl group.

[0103] The specific explanation of unsaturated monobasic acid (F2) is the same as that for unsaturated monobasic acid (F1) described above. In this embodiment, the unsaturated monobasic acid (F2) may be the same as or different from the unsaturated monobasic acid (F1) described above. However, from the viewpoint of efficiently obtaining the curable resin composition of this embodiment, it is preferable that these unsaturated monobasic acids are the same.

[0104] <Photopolymerization initiator> The curable resin composition of this embodiment preferably further contains a photopolymerization initiator in addition to the first resin (R1) and the second resin (R2). This facilitates the initiation of the photo-induced curing reaction (polymerization). The photopolymerization initiator may be used alone or in combination of two or more types.

[0105] Examples of the aforementioned photopolymerization initiators include photoradical polymerization initiators such as 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, thioxanthones and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethane-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.

[0106] Examples of 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", "Omnirad 81" (manufactured by IGM Resins); "KAYACURE DETX", "KAYACURE MBP", "KAYACURE DMBI", "KAYACURE EPA", "KAYACURE OA" (manufactured by Nippon Kayaku Co., Ltd.); "Vicure 10", "Vicure 55" (Stoffa Examples include: Chemical Corporation; "Trigonal P1" (Akzo Nobel Corporation); "SANDORAY 1000" (SANDOZ Corporation); "DEAP" (Upjohn Chemical Corporation); "Quantacure PDO", "Quantacure ITX", "Quantacure EPD" (Ward Blenkinsop Corporation); "Runtecure 1104" (Runtec Corporation).

[0107] When using the aforementioned photopolymerization initiator, the amount of the photopolymerization initiator in the curable resin composition of this embodiment is preferably 0.5 parts by mass or more and 20 parts by mass or less, based on 100 parts by mass of the total of the first resin (R1) and the second resin (R2).

[0108] <Other resins containing polymerizable unsaturated groups> The curable resin composition of this embodiment may further contain a resin having polymerizable unsaturated groups that does not fall under either the first resin (R1) or the second resin (R2). Examples of the resin component having polymerizable unsaturated groups include epoxy resins and resins having polymerizable unsaturated groups. It is preferable that the epoxy resin and the resin having polymerizable unsaturated groups have polymerizable unsaturated groups but do not have acidic groups. Examples of such resins having polymerizable unsaturated groups include the resins described in paragraphs

[0082] -

[0158] of the specification of Japanese Patent Application No. 2022-153553, and these resins can be used in the manner described in those paragraphs.

[0109] <Various (meth)acrylate monomers> The curable resin composition of this embodiment may further contain various (meth)acrylate monomers.

[0110] The various (meth)acrylate monomers mentioned above are not particularly limited as long as they have a (meth)acryloyl group, and include, for example, 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, octyl (meth)acrylate, etc.; cyclohexyl (meth)acrylate, Alicyclic mono(meth)acrylate compounds such as 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, phenoxyethoxyethyl (meth)acrylate, Mono(meth)acrylate compounds such as aromatic mono(meth)acrylate compounds including 2-hydroxy-3-phenoxypropyl(meth)acrylate, phenoxybenzyl(meth)acrylate, benzylbenzyl(meth)acrylate, and phenylphenoxyethyl(meth)acrylate; (poly)oxyalkylene-modified mono(meth)acrylate compounds obtained by introducing polyoxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains into the molecular structure of the various mono(meth)acrylate monomers; lactone-modified mono(meth)acrylate compounds obtained by introducing a (poly)lactone structure into the molecular structure of the 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; (poly)oxyen Polyoxyalkylene-modified di(meth)acrylate compounds into which (poly)oxyalkylene chains such as ethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains have been introduced; lactone-modified di(meth)acrylate compounds into which a (poly)lactone structure has been introduced into the molecular structure of the above various di(meth)acrylate compounds; aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerin tri(meth)acrylate; molecules of the above aliphatic tri(meth)acrylate compounds (Poly)oxyalkylene-modified tri(meth)acrylate compounds having (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains introduced into their structure; lactone-modified tri(meth)acrylate compounds having a (poly)lactone structure introduced into the molecular structure of the aliphatic tri(meth)acrylate compound; pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth) Aliphatic poly(meth)acrylate compounds with four or more functions, such as acrylates; aliphatic poly(meth)acrylate compounds with four or more functions, obtained by introducing (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains into the molecular structure of the aliphatic poly(meth)acrylate compounds; aliphatic poly(meth)acrylate compounds with four or more functions, obtained by introducing (poly)lactone structures into the molecular structure of the aliphatic poly(meth)acrylate compounds;Hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate (meth)acrylate compounds having hydroxyl groups, such as dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane(meth)acrylate, ditrimethylolpropanedi(meth)acrylate, and ditrimethylolpropanetri(meth)acrylate; (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetraacrylates in the molecular structure of the said hydroxyl group-containing (meth)acrylate compounds; Examples include (poly)oxyalkylene modified compounds into which (poly)oxyalkylene chains such as ethylene chains have been introduced; lactone modified compounds into which a (poly)lactone structure has been introduced into the molecular structure of the hydroxyl group-containing (meth)acrylate compound; (meth)acrylate compounds having an isocyanate group such as 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate; (meth)acrylate monomers having a glycidyl group such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate; and (meth)acrylate compounds having an epoxy group such as mono(meth)acrylates of diglycidyl ether compounds of droxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. The various (meth)acrylate monomers mentioned above may be used individually or in combination of two or more.

[0111] <Optional addition ingredients> The curable resin composition of this embodiment may further contain optional additives, as long as they do not deviate from the purpose. Examples of optional additives include curing accelerators, ultraviolet absorbers, polymerization inhibitors, antioxidants, organic solvents, inorganic fillers and polymer fine particles, pigments, defoamers, viscosity modifiers, leveling agents, flame retardants, and preservation stabilizers.

[0112] [Curing accelerator] The curing accelerator is not particularly limited as long as it promotes the curing reaction, and examples include phosphorus compounds, amine compounds, imidazole compounds, organic acid metal salts, Lewis acids, amine complex salts, etc. These curing accelerators may be used individually or in combination of two or more. Furthermore, the amount of curing accelerator added is preferably in the range of 0.01 to 10% by mass of the solid content of the curable resin composition.

[0113] [UV absorber] Examples of the aforementioned ultraviolet absorbers include triazine derivatives such as 2-[4-{(2-hydroxy-3-dodecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-{(2-hydroxy-3-tridecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2'-xanthenecarboxy-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl)benzotriazole, 2-xanthenecarboxy-4-dodecyloxybenzophenone, and 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone. These ultraviolet absorbers may be used individually or in combination of two or more.

[0114] [Polymerization inhibitors] Examples of polymerization inhibitors include p-methoxyphenol, p-methoxycresol, 4-methoxy-1-naphthol, 4,4'-dialkoxy-2,2'-bi-1-naphthol, 3-(N-salicyroyl)amino-1,2,4-triazole, N'1,N'12-bis(2-hydroxybenzoyl)dodecanedihydrazide, styrene-phenol, N-isopropyl-N'-phenylbenzene-1,4-diamine, 6-ethoxy-2,2,4-trimethyl- Phenolic compounds such as 1,2-dihydroquinoline, hydroquinone, methylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone, anthraquinone, diphenoquinone and other quinone compounds, 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), styrene-diphenylamine, reaction products of styrene-diphenylamine and 2,4,4-trimethylpentene, reaction products of diphenylamine and 2,4,4-trimethylpentene, phenothiazine, distearylthiodipropionate, 2,2-bis({[3-(dodecyl Thioether compounds such as ruthio)propionyl]oxy}methyl)-1,3-propanediyl=bis[3-(dodecylthio)propionate], ditridecane-1-yl=3,3'-sulfandiyldipropanoate, N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, N,N-dimethylp-nitrosoaniline, p-nitrosodiphenylamine, p-nitronedimethylamine, p-nitrone -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 Nitroso compounds such as propyl urethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 1-nitroso-2-naphthol-3,6-sulfonate sodium, 2-nitroso-1-naphthol-4-sulfonate sodium, 2-nitroso-5-methylaminophenol hydrochloride, 2-nitroso-5-methylaminophenol hydrochloride, esters of phosphoric acid and octadecane-1-ol, triphenyl phosphite, 3,9-dioctadecane-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5] Phosphate compounds such as undecane, trisnonylphenyl phosphite, (1-methylethylidene)-di-4,1-phenylenetetra-C12-15-alkyl ester, 2-ethylhexyl=diphenyl=phosphite, diphenylisodecyl phosphite, triisodecyl=phosphite, tris(2,4-di-tert-butylphenyl)phosphite, bis(dimethyldithiocarbamato-κ(2)S,S')zinc, and diethyldithiocarbamate zinc Examples include zinc compounds such as zinc dibutyldithiocarbamate, nickel compounds such as bis(N,N-dibutylcarbamodithioato-S,S')nickel, and sulfur compounds such as 1,3-dihydro-2H-benzimidazole-2-thion, 4,6-bis(octylthiomethyl)-o-cresol, 2-methyl-4,6-bis[(octan-1-ylsulfanyl)methyl]phenol, dilaurylthiodipropionate, and 3,3'-distearyl thiodipropionate. These polymerization inhibitors may be used individually or in combination of two or more.

[0115] [Antioxidant] The antioxidant is not particularly limited, but compounds similar to those exemplified as polymerization inhibitors can be used. The antioxidant may be used alone or in combination of two or more.

[0116] Examples of commercially available polymerization inhibitors and antioxidants include "Q-1300" and "Q-1301" manufactured by Wako Pure Chemical Industries, Ltd., and "Sumiriser BBM-S" and "Sumiriser GA-80" manufactured by Sumitomo Chemical Co., Ltd.

[0117] [Organic solvents] The organic solvents are not particularly limited, but examples include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as diethyl ether and tetrahydrofuran; ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene, xylene, ethylbenzene, mesitylene, 1,2,3-trimethylbenzene, and 1,2,4-trimethylbenzene; and amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. The organic solvents may be used individually or in combination of two or more.

[0118] [Inorganic filler] Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide.

[0119] [Pigments] As the aforementioned pigment, known and conventional inorganic pigments or organic pigments can be used. Examples of the inorganic pigments include white pigment, antimony red, red iron oxide, cadmium red, cadmium yellow, cobalt blue, Prussian blue, ultramarine, carbon black, and graphite. These inorganic pigments may be used individually or in combination of two or more. Examples of the white pigments include titanium dioxide, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow resin particles, and zinc sulfide. Examples of the aforementioned organic pigments include quinacridone pigment, quinacridone quinone pigment, dioxazine pigment, phthalocyanine pigment, anthrapyrimidine pigment, ancenthron pigment, indanthron pigment, flavanthron pigment, perylene pigment, diketopyrrolopyrrole pigment, perinone pigment, quinophthalone pigment, anthraquinone pigment, thioindigo pigment, benzimidazolone pigment, and azo pigment. These organic pigments may be used individually or in combination of two or more.

[0120] [Flame retardant] Examples of the aforementioned flame retardants include inorganic phosphorus compounds such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, polyammonium phosphate, and other ammonium phosphates; phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phospholane compounds, organic nitrogen-containing phosphorus compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-(2,5-dihydrooxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxy Examples of flame retardants include cyclic organophosphorus compounds such as 10-(2,7-dihydrooxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and derivatives obtained by reacting them with compounds such as epoxy resins and phenolic resins; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, and phenothiazines; silicone-based flame retardants such as silicone oil, silicone rubber, and silicone resins; and inorganic flame retardants such as metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting-point glass. These flame retardants may be used individually or in combination of two or more. When these flame retardants are used, it is preferable that their concentration be in the range of 0.1 to 20% by mass of the total resin composition.

[0121] (Method for producing curable resin compositions) The method for producing the curable resin composition of this embodiment is not particularly limited, as long as a composition containing at least a first resin (R1) and a second resin (R2) is obtained. Furthermore, there are no particular limitations on the method used to produce the curable resin composition; kneading can be performed using a kneader such as a roller.

[0122] As an example of such a manufacturing method, Step (1-1): Reacting a biphenol compound (P1) with an epihalohydrin to synthesize a glycidyl ether (E1), Steps (1-2) involve reacting a reaction material containing a synthesized glycidyl ether (E1) and an unsaturated monobasic acid (F1) to obtain a first resin (R1). Step (2-1): Reacting a polyvalent hydroxy resin (P2) with an epihalohydrin to synthesize a glycidyl ether (E2), The process (2-2) involves reacting the synthesized glycidyl ether (E2) with a reaction material containing an unsaturated monobasic acid (F2) to obtain a second resin (R2), and, Step (3) involves mixing the first resin (R1) obtained in step (1-2) with the second resin (R2) obtained in step (2-2) to obtain a curable resin composition. Examples of manufacturing methods include those that include the following.

[0123] Here, both the first resin (R1) and the second resin (R2) share the commonality of using an unsaturated monobasic acid as a reaction raw material. Therefore, by mixing the glycidyl ether (E1) synthesized in step (1-1) with the glycidyl ether (E2) synthesized in step (2-1), steps (1-2) and (2-2) can be carried out simultaneously, and furthermore, step (3) can be omitted to obtain a curable resin composition. This method is preferred because of its simplicity and ease of use.

[0124] Furthermore, both glycidyl ether (E1) and glycidyl ether (E2) are similar in that they are obtained using epihalohydrin. Therefore, by mixing the biphenol compound (P1) and the polyhydric hydroxy resin (P2) in advance, steps (1-1) and (2-1) can be carried out in one step, and the subsequent steps (1-2) and (2-2) can be carried out in one step, and furthermore, step (3) can be omitted to obtain a curable resin composition. This method is preferred because it is simple and easy to work with.

[0125] Furthermore, components other than the first resin (R1) and the second resin (R2) or their reaction materials (such as the aforementioned components including photopolymerization initiators) can be added at appropriate timings if they are to be incorporated into the mixture.

[0126] <Glycidyl etherification> Examples of methods for the reaction between a biphenol compound (P1) and an epihalohydrin (glycidyl etherification), and the reaction between a polyvalent hydroxy resin (P2) and an epihalohydrin (glycidyl etherification), include reacting them for 0.5 to 10 hours at a temperature of typically 20 to 150°C, preferably 30 to 80°C, in the presence of a basic catalyst.

[0127] Examples of epihalohydrins include epichlorohydrin, epibromohydrin, and β-methylepichlorohydrin. The amount of epihalohydrin added is in excess of 1 mole of the total hydroxyl groups of the glycidyl ether target (biphenol compound (P1), polyvalent hydroxy resin (P2)), but is usually in the range of 1.5 to 30 moles, preferably 2 to 15 moles.

[0128] Examples of the basic catalyst include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. Among these, alkali metal hydroxides are preferred due to their excellent catalytic activity, and specifically, sodium hydroxide and potassium hydroxide are more preferred. These basic catalysts may be used in solid form or in aqueous solution form. The amount of basic catalyst added is preferably in the range of 0.9 to 2 moles per mole of total hydroxyl groups in the glycidyl ether target (biphenol compound (P1), polyvalent hydroxy resin (P2)).

[0129] The reaction between the glycidyl ether target (biphenol compound (P1), polyvalent hydroxy resin (P2)) and epihalohydrin may be carried out in an organic solvent. Examples of such organic solvents include ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary butanol, and tertiary butanol, cellosolves such as methyl cellosolve and ethyl cellosolve, ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, and diethoxyethane, and aprotic polar solvents such as acetonitrile, dimethyl sulfoxide, and dimethylformamide. These organic solvents may be used individually, or two or more may be used in appropriate combinations to adjust the polarity.

[0130] After the reaction with epihalohydrin is complete, the crude product can be obtained by distilling off the excess epihalohydrin. If necessary, the obtained crude product may be dissolved again in an organic solvent, and the reaction may be repeated with a basic catalyst to reduce the hydrolyzable halogen. The salts produced in the reaction can be removed by filtration or washing with water. If an organic solvent is used, the organic solvent may be distilled off to isolate only the resin solids, or the solution may be used as is.

[0131] The mass ratio of glycidyl ether (E1) to glycidyl ether (E2) is not particularly limited, but from the viewpoint of more effectively improving adhesion and low modulus of elasticity, the ratio calculated by (E1) / {(E1)+(E2)}×100 is preferably 0.5% by mass or more, preferably 1% by mass or more, more preferably 5% by mass or more, preferably 40% by mass or less, and more preferably 25% by mass or less.

[0132] Furthermore, while there are no particular limitations on the mass ratio of the biphenol compound (P1) to the polyvalent hydroxy resin (P2), from the viewpoint of more effectively improving adhesion and low modulus of elasticity, the ratio calculated by (P1) / {(P1)+(P2)}×100 is preferably 0.5% by mass or more, preferably 1% by mass or more, more preferably 5% by mass or more, preferably 40% by mass or less, and more preferably 25% by mass or less.

[0133] <Reactions of glycidyl ethers and unsaturated monobasic acids> The method for reacting the reaction materials, which include glycidyl ethers (E1, E2) and unsaturated monobasic acids (F1, F2), is not particularly limited. For example, a polymerizable unsaturated resin (first resin (R1), second resin (R2)) may be produced by reacting all of the reaction materials together in the presence of an acidic catalyst or a basic catalyst at a temperature range of 70 to 140°C. The reaction between the glycidyl ethers (E1, E2) and the unsaturated monobasic acids (F1, F2) may be carried out in an organic solvent if necessary.

[0134] The mass ratio of glycidyl ethers (E1, E2) to unsaturated monobasic acids (F1, F2) is not particularly limited, but the unsaturated monobasic acids (F1, F2) can be used in a range where the acid groups of the unsaturated monobasic acids (F1, F2) are preferably in the range of 0.2 to 1.1 moles, more preferably in the range of 0.2 to 1.05 moles, even more preferably in the range of 0.3 to 1.0 moles, and even more preferably in the range of 0.3 to 1.0 moles, per mole of epoxy groups in the glycidyl ethers (E1, E2).

[0135] Examples of the 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. Solid acid catalysts having strong acids such as sulfonyl groups can also be used. These acidic catalysts may be used individually or in combination of two or more types.

[0136] Examples of the basic catalysts include amine compounds such as 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 or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, tetramethylammonium hydroxide, etc.; trioctylmethylammonium chloride, trio Examples include quaternary ammonium salts such as ctylmethylammonium 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-hydroxylpropyl)phosphonium chloride, triphenylphosphonium chloride, and benzylphosphonium chloride; organotin 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-dodecanoyldistanoxane; organometallic compounds such as zinc octoate and bismuth octoate; inorganic tin compounds such as tin octanoate; 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 individually or in combination of two or more. Furthermore, they may be used in the form of an aqueous solution of approximately 10-55% by mass, or in solid form.

[0137] The amount of the basic catalyst used is preferably in the range of 0.01 to 1 part by mass, and more preferably in the range of 0.05 to 0.8 parts by mass, per 100 parts by mass of the total reaction raw materials, in order to obtain a resin composition having polymerizable unsaturated groups that can form a cured product with excellent adhesion and low modulus of elasticity.

[0138] Examples of the aforementioned 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, and cyclohexanone. Examples of organic solvents include alcohol solvents such as propylene glycol monomethyl ether; ether solvents such as propyl ether, methyl cellosolve, cellosolve, butyl cellosolve, and methyl carbitol; glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, and dialkylene glycol monoalkyl ether acetate; vegetable oils 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 used individually or in combination of two or more.

[0139] Furthermore, commercially available organic solvents can also be used, and examples of such commercially available products include: ENEOS Corporation's "Spindle Oil No. 1", "Solvent No. 3", "Solvent No. 4", "Solvent No. 5", "Solvent No. 6", "Naphthezol H", "Alken 56NT", "AF Solvent No. 4", "AF Solvent No. 5", "AF Solvent No. 6", "AF Solvent No. 7"; Mitsubishi Chemical Corporation's "Diadol 13", "Dialen 168"; Nissan Chemical Corporation's "F Oxocol", "F Oxocol 180"; Idemitsu Kosan Co., Ltd.'s "Supersol LA35", "Supersol LA38"; ExxonMobil Examples include Chemical's "Exsol D80," "Exsol D110," "Exsol D120," "Exsol D130," "Exsol D160," "Exsol D100K," "Exsol D120K," "Exsol D130K," "Exsol D280," "Exsol D300," and "Exsol D320." In this embodiment, the amount of organic solvent used is preferably in the range of 0.1 to 5 times the total mass of the reaction raw materials, as this results in good reaction efficiency.

[0140] (cured product) The cured product of this embodiment is a cured product of the curable resin composition described above. That is, the cured product of this embodiment is obtained by curing the curable resin composition described above. Because the cured product of this embodiment has high adhesion and excellent low modulus of elasticity, it can be suitably used, for example, as a package adhesive layer for solder resists, interlayer insulating materials, package materials, underfill materials, and circuit elements in semiconductor device applications, or as an adhesive layer between integrated circuit elements and circuit boards. It can also be suitably used as a thin-film transistor protective film, a liquid crystal color filter protective film, a pigment resist for color filters, a resist for black matrices, a spacer, etc., in thin-film display applications such as LCDs and OLEDs. Among these, it can be particularly suitably used for solder resist applications.

[0141] The cured product of this embodiment can be obtained by curing a curable resin composition by irradiating it with active energy rays. Examples of active energy rays include ionizing radiation such as ultraviolet rays, electron beams, alpha rays, beta rays, and gamma rays. When ultraviolet rays are used as the active energy rays, the irradiation may be carried out under an inert gas atmosphere such as nitrogen gas, or under an air atmosphere, in order to efficiently carry out the curing reaction by ultraviolet rays.

[0142] Specific sources of ultraviolet light include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, and other ultraviolet lamps, as well as sunlight and LEDs. Among these, ultraviolet lamps are generally used from the standpoint of practicality and economic efficiency.

[0143] The integrated light intensity of the aforementioned active energy rays is not particularly limited, but is between 0.1 and 50 kJ / m 2 Preferably, it is 0.5 to 10 kJ / m³. 2 It is more preferable that the cumulative light intensity is within the above range. If the cumulative light intensity is within the above range, the occurrence of uncured areas can be sufficiently prevented or suppressed. The irradiation of the active energy ray may be performed in one stage or in two or more stages.

[0144] Another method for obtaining a cured product by curing the curable resin composition is, for example, heat curing. The heating temperature during heat curing is not particularly limited, but is preferably 100 to 300°C, and the heating time is preferably 1 to 24 hours.

[0145] Applications of the curable resin composition or cured product of this embodiment include printed circuit board materials, resin compositions for flexible wiring boards, interlayer insulating materials for build-up substrates, insulating materials for circuit boards such as build-up adhesive films, resin casting materials, adhesives, semiconductor encapsulation materials, semiconductor devices, prepregs, conductive pastes, build-up films, build-up substrates, fiber-reinforced composite materials, and molded products obtained by curing the above composite materials. Among these various applications, in the applications of printed circuit board materials, insulating materials for circuit boards, and build-up adhesive films, it can be used as an insulating material for so-called electronic component-embedded substrates in which passive components such as capacitors and active components such as IC chips are embedded within the substrate. Furthermore, taking advantage of the characteristics of the cured product, such as its excellent adhesion and low modulus of elasticity, the curable resin composition or cured product of this embodiment can be suitably applied to semiconductor encapsulation materials, semiconductor devices, prepregs, flexible wiring boards, circuit boards, and build-up films, build-up substrates, multilayer printed circuit boards, fiber-reinforced composite materials, and molded products obtained by curing the above composite materials.

[0146] (Goods) The article of this embodiment is characterized by having a coating film made of the cured material described above. In the article of this embodiment, the coating film can function as a material with excellent adhesion and low modulus of elasticity. Examples of articles of this embodiment include plastic molded products such as mobile phones, home appliances, automotive interior and exterior materials, and office automation equipment, as well as semiconductor devices, display devices, and imaging devices. [Examples]

[0147] The present invention will be described in more detail below with reference to examples, but the present invention is not limited in any way to the following examples.

[0148] (Synthesis Example 1: Synthesis of polyvalent hydroxy resin (P2-1)) In a flask equipped with a thermometer, condenser, fractionation column, nitrogen gas inlet tube, and stirrer, 488.6 g (4.00 mol) of 2,6-xylenol and 244 g of toluene were charged, and 4.9 g of p-toluenesulfonic acid was added. The temperature was then raised to 115°C. After confirming that the raw materials were completely dissolved, 260.4 g of a mixture of divinylbenzene and ethylvinylbenzene (DVB-810, manufactured by Nippon Steel Chemical Co., Ltd.) was added dropwise over 2 hours, and the reaction was continued at 115°C for 1 hour. After the reaction was complete, the temperature was lowered to 80°C and neutralized with an aqueous sodium hydroxide solution. Unreacted 2,6-xylenol and toluene were removed under reduced pressure and heating to obtain polyvalent hydroxy resin (P2-1).

[0149] (Synthesis Example 2: Synthesis of polyvalent hydroxy resin (P2-2)) The reaction was carried out under the same conditions as in Synthesis Example 1, except that "2,6-xylenol 488.6 g (4.00 mol)" used in Synthesis Example 1 was replaced with "2,3,6-trimethylphenol 544.8 g (4.00 mol)" to obtain polyvalent hydroxy resin (P2-2).

[0150] (Synthesis Example 3: Synthesis of Phenolic Resin (1)) A phenolic resin (1) was obtained by synthesis using the method described in Synthesis Example 1 of Japanese Patent No. 5689230.

[0151] For each resin obtained in Synthesis Examples 1-3, the hydroxyl group equivalent was measured in accordance with the neutralization titration method specified in JIS K 0070 (1992). The results are shown in Table 1.

[0152] [Table 1]

[0153] (Synthesis Example 4: Synthesis of Precursor Composition (1)) In a flask equipped with a thermometer, dropping funnel, condenser, and stirrer, 224.0 g of polyvalent hydroxy resin (P2-1) obtained in Synthesis Example 1, 56.0 g of 4,4'-biphenol (P1-1), 1261 g of epichlorohydrin, 390 g of n-butanol, and 90 g of water were charged and dissolved to prepare a mixed solution. After raising the temperature of the mixed solution to 60°C, 392 g of 20% by mass aqueous sodium hydroxide solution was added dropwise over 5 hours. Stirring was then continued under the same conditions for 0.5 hours. Unreacted epichlorohydrin was then removed by vacuum distillation. Subsequently, 638 g of methyl isobutyl ketone was added to the obtained crude epoxy resin and dissolved to obtain a crude epoxy resin solution. Furthermore, 24 g of a 5% by mass aqueous sodium hydroxide solution was added to this crude epoxy resin solution and reacted at 80°C for 2 hours. Then, the mixture was washed three times with 180 g of water until the pH of the washing solution became neutral. Next, the system was dehydrated by azeotrope, and after microfiltration, the solvent was removed under reduced pressure to obtain precursor composition (1). In this operation, a glycidyl ether (E1-1) was produced by the reaction of 4,4'-biphenol (P1-1) with epihalohydrin, and a glycidyl ether (E2-1) was produced by the reaction of polyvalent hydroxy resin (P2-1) with epihalohydrin. In other words, the precursor composition (1) is an epoxy resin composition containing the glycidyl ether (E1-1) and the glycidyl ether (E2-1).

[0154] (Synthesis Example 5: Synthesis of Precursor Composition (2)) In Synthesis Example 4, the reaction was carried out under the same conditions as in Synthesis Example 4, except that "224.0 g of polyvalent hydroxy resin (P2-1)" was changed to "238.0 g of polyvalent hydroxy resin (P2-1)" and "56.0 g of 4,4'-biphenol (P1-1)" was changed to "42.0 g of 4,4'-biphenol (P1-1)" to obtain precursor composition (2). Precursor composition (2) is also an epoxy resin composition containing glycidyl ether (E1-1) and glycidyl ether (E2-1).

[0155] (Synthesis Example 6: Synthesis of Precursor Composition (3)) In Synthesis Example 4, the reaction was carried out under the same conditions as in Synthesis Example 4, except that "224.0 g of polyvalent hydroxy resin (P2-1)" was changed to "271.6 g of polyvalent hydroxy resin (P2-1)" and "56.0 g of 4,4'-biphenol (P1-1)" was changed to "8.4 g of 4,4'-biphenol (P1-1)" to obtain precursor composition (3). Precursor composition (3) is also an epoxy resin composition containing glycidyl ether (E1-1) and glycidyl ether (E2-1).

[0156] (Synthesis Example 7: Synthesis of Precursor Composition (4)) In Synthesis Example 4, the reaction was carried out under the same conditions as in Synthesis Example 4, except that "224.0 g of polyvalent hydroxy resin (P2-1)" was changed to "238.0 g of polyvalent hydroxy resin (P2-2)" and "56.0 g of 4,4'-biphenol (P1-1)" was changed to "42.0 g of 4,4'-biphenol (P1-1)" to obtain precursor composition (4). Precursor composition (4) is an epoxy resin composition containing glycidyl ether (E1-1) and glycidyl ether (E2-2).

[0157] (Synthesis Example 8: Synthesis of Precursor Composition (5)) In Synthesis Example 4, the reaction was carried out under the same conditions as in Synthesis Example 4, except that "224.0 g of polyvalent hydroxy resin (P2-1)" was replaced with "280.0 g of phenolic resin (1)" and 4,4'-biphenol (P1-1) was not used, to obtain precursor composition (5). Precursor composition (5) is an epoxy resin composition that does not contain at least a glycidyl ether of 4,4'-biphenol.

[0158] Each precursor composition obtained in Synthesis Example 4-8 was evaluated according to the following procedure. The results are shown in Table 2.

[0159] <Epoxy equivalent> The epoxy equivalent was measured according to JIS K 7236.

[0160] <Melting viscosity> The melt viscosity at 150°C was measured using an ICI viscometer in accordance with ASTM D4287.

[0161] <Gel Permeation Chromatography (GPC)> Measurement device: Tosoh Corporation "HLC-8320 GPC" Column: Guard column "HXL-L" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation + "TSK-GEL G3000HXL" manufactured by Tosoh Corporation + "TSK-GEL G4000HXL" manufactured by Tosoh Corporation Detector: RI (Differential Refractometer) Data processing: Tosoh Corporation's "GPC Workstation EcoSEC-WorkStation" Measurement conditions: Column temperature 40℃ Developing solvent: tetrahydrofuran Flow rate 1.0ml / min Standard: In accordance with the measurement manual for the aforementioned "GPC Workstation EcoSEC-WorkStation," the following monodisperse polystyrenes with known molecular weights were used. (Uses polystyrene) "A-500" manufactured by Tosoh Corporation "A-1000" manufactured by Tosoh Corporation "A-2500" manufactured by Tosoh Corporation "A-5000" manufactured by Tosoh Corporation "F-1" manufactured by Tosoh Corporation "F-2" manufactured by Tosoh Corporation "F-4" manufactured by Tosoh Corporation Tosoh Corporation's "F-10" F-20 manufactured by Tosoh Corporation Tosoh Corporation's "F-40" Tosoh Corporation's "F-80" Tosoh Corporation's "F-128" Sample: A tetrahydrofuran solution containing 1.0% by mass (based on the solid content of the resin) was filtered through a microfilter (50 μl). Based on the GPC measurement results mentioned above, the number-average molecular weight (Mn) and weight-average molecular weight (Mw) were calculated.

[0162] [Table 2]

[0163] (Example 1: Curable resin composition (1)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 138 g of butyl acetate was placed, and 250 g of the precursor composition (1) obtained in Synthesis Example 4 was dissolved. After adding 0.3 g of dibutylhydroxytoluene and 0.2 g of methoquinone, 72 g of acrylic acid (F-1) and 1.6 g of triphenylphosphine were added, and the reaction was carried out at 120°C for 12 hours while blowing in air to obtain curable resin composition (1). In this operation, the glycidyl ether (E1-1) in the precursor composition (1) reacts with acrylic acid (F-1) to produce a resin having a first polymerizable unsaturated group, and the glycidyl ether (E2-1) in the precursor composition (1) reacts with acrylic acid (F-1) to produce a resin having a second polymerizable unsaturated group. In other words, the curable resin composition (1) contains the first resin (R1) and the second resin (R2). This curable resin composition (1) had a non-volatile content of 70% by mass and a solid content epoxy equivalent (based on JIS K 7236; the same applies to the following resin compositions) of 10800 g / eq.

[0164] (Example 2: Curable resin composition (2)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 71.5 g of butyl acetate was placed, and 250 g of the precursor composition (1) obtained in Synthesis Example 4 was dissolved. After adding 0.1 g of dibutylhydroxytoluene and 0.2 g of methoquinone, 36 g of acrylic acid (F-1) and 0.9 g of triphenylphosphine were added, and the reaction was carried out at 100°C for 18 hours while blowing in air. Next, 0.9 g of oxalic acid was added, and the mixture was stirred at 70°C for 1 hour to obtain curable resin composition (2). Curable resin composition (2) also contains the first resin (R1) and the second resin (R2). This curable resin composition (2) had a non-volatile content of 80% by mass and an epoxy equivalent of 583 g / eq of solids.

[0165] (Example 3: Curable resin composition (3)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 140.1 g of butyl acetate was placed, and 255 g of the precursor composition (2) obtained in Synthesis Example 5 was dissolved. After adding 0.3 g of dibutylhydroxytoluene and 0.2 g of methoquinone, 72 g of acrylic acid (F-1) and 1.6 g of triphenylphosphine were added, and the reaction was carried out at 120°C for 12 hours while blowing in air to obtain curable resin composition (3). Curable resin composition (3) also contains the first resin (R1) and the second resin (R2). This curable resin composition (3) had a non-volatile content of 70% by mass and an epoxy equivalent of 12,400 g / eq of solids.

[0166] (Example 4: Curable resin composition (4)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 72.8 g of butyl acetate was placed, and 255 g of the precursor composition (2) obtained in Synthesis Example 5 was dissolved. After adding 0.2 g of dibutylhydroxytoluene and 0.2 g of methoquinone, 36 g of acrylic acid (F-1) and 0.9 g of triphenylphosphine were added, and the reaction was carried out at 100°C for 15 hours while blowing in air. Next, 0.9 g of oxalic acid was added, and the mixture was stirred at 70°C for 1 hour to obtain curable resin composition (4). Curable resin composition (4) also contains the first resin (R1) and the second resin (R2). This curable resin composition (4) had a non-volatile content of 80% by mass and an epoxy equivalent of 595 g / eq of solids.

[0167] (Example 5: Curable resin composition (5)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 150 g of butyl acetate was placed, and 278 g of the precursor composition (3) obtained in Synthesis Example 6 was dissolved. After adding 0.4 g of dibutylhydroxytoluene and 0.2 g of methoquinone, 72 g of acrylic acid (F-1) and 1.8 g of triphenylphosphine were added, and the reaction was carried out at 120°C for 12 hours while blowing in air to obtain curable resin composition (5). Curable resin composition (5) also contains the first resin (R1) and the second resin (R2). This curable resin composition (5) had a non-volatile content of 70% by mass and an epoxy equivalent of 13,300 g / eq of solids.

[0168] (Example 6: Curable resin composition (6)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 78.5 g of butyl acetate was placed, and 278 g of the precursor composition (3) obtained in Synthesis Example 6 was dissolved. After adding 0.2 g of dibutylhydroxytoluene and 0.2 g of methoquinone, 36 g of acrylic acid (F-1) and 0.9 g of triphenylphosphine were added, and the reaction was carried out at 100°C for 15 hours while blowing in air. Next, 0.9 g of oxalic acid was added, and the mixture was stirred at 70°C for 1 hour to obtain curable resin composition (6). Curable resin composition (6) also contains the first resin (R1) and the second resin (R2). This curable resin composition (6) had a non-volatile content of 80% by mass and an epoxy equivalent of 640 g / eq of solids.

[0169] (Example 7: Curable resin composition (7)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 146.1 g of butyl acetate was placed, and 269 g of the precursor composition (4) obtained in Synthesis Example 7 was dissolved. After adding 0.3 g of dibutylhydroxytoluene and 0.2 g of methoquinone, 72 g of acrylic acid (F-1) and 1.7 g of triphenylphosphine were added, and the reaction was carried out at 120°C for 13 hours while blowing in air to obtain curable resin composition (7). Curable resin composition (7) also contains the first resin (R1) and the second resin (R2). This curable resin composition (7) had a non-volatile content of 70% by mass and an epoxy equivalent of 11,700 g / eq of solids.

[0170] (Example 8: Curable resin composition (8)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 76.3 g of butyl acetate was placed, and 269 g of the precursor composition (4) obtained in Synthesis Example 7 was dissolved. After adding 0.2 g of dibutylhydroxytoluene and 0.2 g of methoquinone, 36 g of acrylic acid (F-1) and 0.9 g of triphenylphosphine were added, and the reaction was carried out at 100°C for 16 hours while blowing in air. Next, 0.9 g of oxalic acid was added, and the mixture was stirred at 70°C for 1 hour to obtain curable resin composition (8). Curable resin composition (8) also contains the first resin (R1) and the second resin (R2). This curable resin composition (8) had a non-volatile content of 80% by mass and an epoxy equivalent of 629 g / eq of solids.

[0171] (Comparative Example 1: Curable resin composition (C1)) In a flask equipped with a thermometer, stirrer, and reflux condenser, 153 g of butyl acetate was placed, and 285 g of the precursor composition (5) obtained in Synthesis Example 8 was dissolved. After adding 0.4 g of dibutylhydroxytoluene and 0.2 g of methoquinone, 72 g of acrylic acid and 1.8 g of triphenylphosphine were added, and the reaction was carried out at 120°C for 13 hours while blowing in air to obtain curable resin composition (C1). As described above, the precursor composition (5) used in this example does not contain at least a glycidyl ether of 4,4'-biphenol, so curable resin composition (C1) does not contain at least the first resin (R1). This curable resin composition (C1) had a non-volatile content of 70% by mass and an epoxy equivalent of 1250 g / eq of solids.

[0172] (Examples 9-16, Comparative Example 2) A curable resin composition was obtained by mixing the components shown in Table 3. The following tests were performed on the curable resin composition.

[0173] <modulus of elasticity> The curable resin compositions obtained in each example and comparative example were applied to copper foil (Furukawa Sangyo Co., Ltd., electrolytic copper foil "F2-WS", 18 μm) 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 measure 10 kJ / m³. 2 After irradiation with ultraviolet light, the material was heated at 160°C for 1 hour to obtain a cured coating. Next, the cured coating was peeled off the copper foil to obtain a cured material (test piece 1). Test piece 1 was cut to a size of 10 mm x 80 mm, and a tensile test was performed on the test piece using a Shimadzu Corporation Autograph "AG-IS" precision universal testing machine under the following measurement conditions. The elastic modulus (MPa) until the test piece fractured was measured. The results are shown in Table 3. Measurement conditions: temperature 23℃, humidity 50%, distance between gauge lines 20mm, distance between fulcrums 20mm, tensile speed 10mm / min

[0174] <Adhesion> The curable resin compositions obtained in each example and comparative example were applied to copper foil (Furukawa Sangyo Co., Ltd., electrolytic copper foil "F2-WS", 18 μm) 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 measure 10 kJ / m³. 2 After irradiating with ultraviolet light, test piece 2 was heated at 160°C for 1 hour. Test piece 2 was cut to a size of 1 cm wide and 12 cm long, and the 90° peel strength was measured using a peel tester (A&D Tensilon, manufactured by A&D Corporation, peel speed 50 mm / min). The results are shown in Table 3. A higher peel strength value indicates better adhesion. The measurement conditions for peel strength are as follows: Measuring instrument: "A&D Tensilon" manufactured by A&D Corporation. Test specimen: 1 cm wide, 12 cm long. Peel test machine. Test speed: 50 mm / min Conditions: Temperature 23℃, humidity 50%

[0175] [Table 3]

[0176] The specifications of each component shown in Table 3 are as follows: Acrylate monomer: EO-modified diacrylate of bisphenol A (Miramaer M240, manufactured by Miwon Specialty Chemical) Photopolymerization initiator: Omnirad-907, manufactured by IGM Resins.

[0177] Table 3 shows that the curable resin composition of the example exhibits superior adhesion and a lower modulus of elasticity in the resulting cured product compared to the comparative example.

[0178] According to the present invention, it is possible to provide a curable resin composition that can produce a cured product with high adhesion and excellent low modulus of elasticity. Furthermore, according to the present invention, it is possible to provide a cured product with high adhesion and excellent low modulus of elasticity, and an article having a coating film made of such a cured product.

Claims

1. A resin (R1) having a first polymerizable unsaturated group, obtained by reacting a glycidyl ether (E1) of a biphenol compound (P1) with an unsaturated monobasic acid (F1) as reaction materials, and It contains a resin (R2) having a second polymerizable unsaturated group, which is reacted with a glycidyl ether (E2) of a polyvalent hydroxy resin (P2) and an unsaturated monobasic acid (F2) as reaction materials. A curable resin composition characterized in that the polyvalent hydroxy resin (P2) is a polymer reacted with an aromatic compound (A) containing a phenolic hydroxyl group and an aromatic ring having two or more hydrocarbon groups, and an aromatic divinyl compound (B1).

2. The polyvalent hydroxy resin (P2) is a polymer that reacts with the aromatic compound (A), the aromatic divinyl compound (B1), and the aromatic monovinyl compound (B2) as reaction materials. The curable resin composition according to claim 1, wherein the mass ratio (B1 / B2) of the aromatic divinyl compound (B1) to the aromatic monovinyl compound (B2) is in the range of 50 / 50 to 99 / 1.

3. The curable resin composition according to claim 1 or 2, wherein the aromatic divinyl compound (B1) comprises divinylbenzene.

4. The curable resin composition according to claim 1 or 2, further comprising a photopolymerization initiator.

5. A cured product of the curable resin composition according to claim 4.

6. An article characterized by having a coating film made of the cured product described in claim 5.

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