Resin composition, cured product, insulating material, and resist member

Abstract

To provide a resin composition which shows high photosensitivity and developability and allows a cured product (cured coating film) obtained therefrom to exhibit excellent heat resistance and coating film appearance.SOLUTION: A resin composition contains a maleimide resin (A) and a resin (B) having an acid group and a polymerizable unsaturated group. The maleimide resin (A) contains a maleimide compound (a) having a first aromatic ring-maleimide skeleton and a second aromatic ring-maleimide skeleton in one molecule. The maleimide compound (a) is an asymmetric bismaleimide compound in which the first aromatic ring-maleimide skeleton and the second aromatic ring-maleimide skeleton are bonded via an organic group having 1-200 carbon atoms.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to resin compositions, cured products, insulating materials, and resist members. [Background technology]

[0002] Solder resist is widely used as an insulating material to prevent solder from adhering to areas other than the mounting area when soldering electronic components onto printed circuit boards, and to form a coating that semi-permanently prevents oxidation or corrosion of the wiring. One technique for forming patterns on such solder resist is the photoresist method, which can accurately form fine patterns. Among these, the alkali-developable liquid photoresist method has become the mainstream due to environmental considerations.

[0003] Furthermore, in recent years, printed circuit boards have been progressively miniaturized, multilayered, and integrated into a single board to achieve higher density of electronic components, and mounting methods have also shifted towards surface mount technology (SMT). As a result, there is a growing demand for solder resist films that are finer, have high Tg, high resolution, high precision, and high reliability.

[0004] Here, since the resist film requires various properties, including heat resistance, it is crucial to manufacture it using appropriate materials that meet these properties. In this regard, maleimide resin is one resin that tends to have excellent heat resistance in its cured product, and there is room for consideration regarding the application of maleimide resin to the liquid photoresist method.

[0005] Conventionally, 4,4'-diphenylmethanebismaleimide type compounds are widely known as maleimide resins (see, for example, Patent Document 1). Furthermore, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane-type compounds are also known as maleimide resins that are relatively easy to handle (see, for example, Patent Document 2). [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2-269716 [Patent Document 2] Japanese Patent Application Publication No. 6-128225 [Overview of the project] [Problems that the invention aims to solve]

[0007] However, when the aforementioned 4,4'-diphenylmethanebismaleimide-type maleimide resin is used in the photoresist method, problems arise such as insufficient light sensitivity and developability, as well as turbidity during compounding, resulting in poor appearance of the resulting cured coating film. In addition, further improvement in heat resistance is required. Furthermore, the aforementioned 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane-type maleimide resin did not meet current market demands in terms of various properties of the cured product, including heat resistance.

[0008] Therefore, the object of the present invention is to provide a resin composition that exhibits high photosensitivity and developability, and that can produce excellent heat resistance and coating appearance in the resulting cured product (cured coating film). Furthermore, the object of the present invention is to provide a cured product, an insulating material, and a resist member that can be obtained using the resin composition. [Means for solving the problem]

[0009] In order to solve the above problems, the present inventors conducted extensive research and found that a resin composition containing a specific maleimide resin and a resin having acidic groups and polymerizable unsaturated groups exhibits high photosensitivity and developability, and that the resulting cured product (cured coating film) exhibits excellent heat resistance and coating film appearance, thus completing the present invention.

[0010] The present invention provides a resin composition comprising a maleimide resin (A) and a resin (B) having acidic groups and polymerizable unsaturated groups, The maleimide resin (A) contains the following general formula (1) in one molecule: [ka] The first aromatic ring-maleimide skeleton shown by and the following general formula (2): [ka] The maleimide compound (a) comprises a second aromatic ring-maleimide skeleton represented by [wherein formulas (1) and (2), R 1 ~R 4 Each of these independently represents hydrogen, a methyl group, or an ethyl group, and Ar 1 and Ar 2 Each of these independently represents an aromatic ring which may have one or more substituents, and * represents a bond from the aromatic ring to another site, where Ar 1 and Ar 2 The resin composition is characterized in that at least one of the types of substituents, the number of substituents, and the positions of the substituents are different from each other. [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a resin composition that exhibits high photosensitivity and developability, and that can produce excellent heat resistance and coating appearance in the resulting cured product (cured coating film). Furthermore, according to the present invention, it is possible to provide a cured product, an insulating material, and a resist member obtained using the resin composition. [Brief explanation of the drawing]

[0012] [Figure 1] This is a GPC chart of the maleimide resin (A-1) obtained in Synthesis Example 1. [Figure 2] This is a GPC chart of the maleimide resin (A-2) obtained in Synthesis Example 2. [Figure 3]This is a GPC chart of the maleimide resin (A-3) obtained in Synthesis Example 3. [Figure 4] This is a GPC chart of the maleimide resin (A-4) obtained in Synthesis Example 4. [Figure 5] This is a GPC chart of the maleimide resin (A-5) obtained in Synthesis Example 5. [Figure 6] This is a GPC chart of the maleimide resin (A-6) obtained in synthesis example 6. [Modes for carrying out the invention]

[0013] (Explanation of terms) Unless otherwise specified in this specification, the following definitions of terms apply.

[0014] In this specification, examples of "aryl group" include phenyl group, naphthyl group, phenalenyl group, phenantrenyl group, anthryl group, azulenyl 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.

[0015] In this specification, "aralkyl group" refers to, for example, a benzyl group, a diphenylmethyl group, a biphenyl group, a naphthylmethyl group, and the like.

[0016] 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.

[0017] 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.

[0018] In this specification, "halogen atoms" include, for example, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, and the like.

[0019] 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.

[0020] 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.

[0021] 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.

[0022] In this specification, "maleimide resin" means a resin having a maleimide group. Furthermore, in this specification, "maleimide compound" means a compound having a maleimide group.

[0023] 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.

[0024] 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.

[0025] [Resin composition] The resin composition of this embodiment is a resin composition containing a maleimide resin (A) and a resin (B) having an acid group and a polymerizable unsaturated group (hereinafter also simply referred to as "resin (B)"). The maleimide resin (A) contains the following general formula (1) in one molecule: [ka] The first aromatic ring-maleimide skeleton shown by and the following general formula (2): [ka] The compound comprises a maleimide compound (a) having a second aromatic ring-maleimide skeleton represented by . Here, in formulas (1) and (2), R 1~R 4 each independently represents a hydrogen, methyl group or ethyl group, and Ar 1 and Ar 2 each independently represents an aromatic ring which may have one or more substituents, and * represents a bond from the aromatic ring to another site, provided that Ar 1 and Ar 2 differ from each other in at least one of the type of substituent, the number of substituents, and the position of the substituent. Such a resin composition exhibits high photosensitivity and developability, and can exhibit excellent heat resistance and coating film appearance properties in the obtained cured product (cured coating film).

[0026] Note that developability relates to the contrast between the exposed part and the unexposed part, and "low developability" means that the above contrast is not sufficient. One of the causes of low developability is that when the curable resin composition applied to the substrate is dried and then exposed, the unexposed part remains after (alkali) development due to heating during drying, etc., thereby reducing the contrast. Therefore, in the present invention, as described in the examples below, the developability is evaluated by the drying control width (minutes). In this drying control width, the range of drying conditions (drying time) in which development defects are unlikely to occur due to coating film drying, etc., is defined. Therefore, if development residues are unlikely to occur even when the drying time is lengthened (that is, when the drying control width is large), it is considered that high developability is exhibited.

[0027] From the viewpoint of improving photosensitivity, developability, heat resistance and coating film appearance properties in a balanced manner, the content of the maleimide resin (A) in the total amount (100% by mass) of the resin composition of the present embodiment is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and preferably 80% by mass or less, more preferably 50% by mass or less, still more preferably 30% by mass or less.

[0028] Furthermore, the content of resin (B) having acidic groups and polymerizable unsaturated groups in the total amount (100% by mass) of the resin composition of this embodiment is preferably 20% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, and preferably 99% by mass or less, more preferably 90% by mass or less, and even more preferably 80% by mass or less, from the viewpoint of improving light sensitivity, developability, heat resistance and coating film appearance in a balanced manner.

[0029] In the resin composition of this embodiment, the mass ratio of solids [(A) / (B)] between the maleimide resin (A) and the resin having acidic groups and polymerizable unsaturated groups (B) is preferably in the range of 1 / 100 to 100 / 100, from the viewpoint of improving light sensitivity, developability, heat resistance, and coating film appearance in a well-balanced manner. From the same viewpoint, the above mass ratio [(A) / (B)] is more preferably 10 / 90 or more, and more preferably 40 / 60 or less.

[0030] The resin composition of this embodiment may consist substantially of maleimide resin (A) and resin (B) alone. Alternatively, the resin composition of this embodiment may further contain a compound having polymerizable unsaturated groups in addition to maleimide resin (A) and resin (B). Furthermore, the resin composition of this embodiment may further contain a photopolymerization initiator in addition to maleimide resin (A) and resin (B). Furthermore, the resin composition of this embodiment may further contain optional additives as optional components. Moreover, the resin composition of this embodiment may contain unavoidable impurities in addition to maleimide resin (A), resin (B), a compound having polymerizable unsaturated groups, a photopolymerization initiator, and optional additives, as long as the effects of this disclosure are not impaired. The total content of maleimide resin (A) and resin (B) in the total amount (100% by mass) of the resin composition of this embodiment is preferably 40% by mass or more, more preferably 50% by mass or more, preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less, from the viewpoint of improving light sensitivity, developability, heat resistance and coating film appearance in a balanced manner.

[0031] The following will describe, in order, maleimide resin (A), resin having acidic groups and polymerizable unsaturated groups (B), compounds having polymerizable unsaturated groups, photopolymerization initiators, and optional additives.

[0032] (Maleimide resin (A)) Maleimide resin (A) is one of the essential components in the resin composition of this embodiment. As described above, maleimide resin (A) is a resin containing at least maleimide compound (a). Maleimide compound (a) contains the following general formula (1) in one molecule: [ka] The first aromatic ring-maleimide skeleton shown by and the following general formula (2): [ka] It is a maleimide compound having a second aromatic ring-maleimide skeleton represented by . Here, in formulas (1) and (2), R 1 ~R 4 Each of these independently represents hydrogen, a methyl group, or an ethyl group, and Ar 1 and Ar 2 (Hereafter, these may be collectively referred to as "Ar") Each independently represents an aromatic ring which may have one or more substituents, and * represents a bond from the aromatic ring to another site, however, Ar 1 and Ar 2 The compounds differ from each other in at least one of the following ways: the type of substituent, the number of substituents, and the position of the substituents (hereinafter, these may be collectively referred to as "substituent form"). Maleimide compound (a) may be a single compound or a combination of two or more compounds. By using a maleimide compound (a) having two or more aromatic ring-maleimide skeletons with different substituent configurations, the crystallinity of the maleimide alone is reduced, and the compatibility of each component in the resin composition is improved. As a result, the photosensitivity, developability, heat resistance, and coating film appearance can be improved.

[0033] Furthermore, the maleimide resin (A) may contain, in addition to the maleimide compound (a), other maleimide compounds (for example, maleimide compounds having two or more aromatic ring-maleimide skeletons in which all substituents are identical). Furthermore, while formulas (1) and (2) show only one * (bond from the aromatic ring to another site) for convenience, the number of such bonds* may be two or three.

[0034] R in equations (1) and (2) 1 ~R 4 Each of these is independently a hydrogen, a methyl group, or an ethyl group, but from the viewpoint of the reactivity of maleimide, it is preferable that they be hydrogen or a methyl group, and more preferably all are hydrogen. Also, from the viewpoint of ease of manufacture, R 1 and R 2 The combination and R 3 and R 4 It is preferable that the combination is the same as the other combination.

[0035] Ar in equations (1) and (2) 1 and Ar 2 Examples of aromatic rings include benzene, naphthalene, and anthracene. 1 and Ar 2 The aromatic rings may be the same or different.

[0036] Ar 1 and Ar 2 Examples of substituents that the aromatic ring may have include aliphatic hydrocarbon groups, alkyloxy groups, alkenyloxy groups, alkynyloxy groups, halogen atoms, aryl groups, aralkyl groups, and hydroxyl groups.

[0037] The above aliphatic hydrocarbon group may be linear, branched, or cyclic, and may have unsaturated bonds in its structure. Specific examples of the above aliphatic hydrocarbon group include methyl, ethyl, vinyl, propyl, allyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, and nonyl groups. Examples of the alkyloxy groups mentioned above include methoxy groups, ethoxy groups, propyloxy groups, and butoxy groups. Examples of the above-mentioned alkenyloxy group include allyloxy groups. Examples of the halogen atoms mentioned above include fluorine atoms, chlorine atoms, and bromine atoms. Examples of the aryl groups mentioned above include phenyl groups, naphthyl groups, anthryl groups, and groups in which the above aliphatic hydrocarbon groups, alkyloxy groups, or halogen atoms are substituted on the aromatic core of these groups. Examples of the above-mentioned aralkyl groups include benzyl groups, phenylethyl groups, naphthylmethyl groups, naphthylethyl groups, and groups in which an alkyl group, or the alkyloxy group or halogen atom mentioned above, is substituted on the aromatic core of these groups. In particular, Ar 1 and Ar 2 The aromatic rings preferably have an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and more preferably have an alkyl group having 1 to 4 carbon atoms (methyl group, ethyl group, propyl group, butyl group, etc.).

[0038] Also, Ar 1 and Ar 2 The number of substituents that the aromatic ring may have is 0, 1, 2, 3, or 4, and if the aromatic ring is not benzene, it may have 5 or more substituents. If there are two or more substituents, they may be the same or different. In particular, Ar 1 and Ar 2 Each aromatic ring preferably has at least one substituent.

[0039] Also, Ar 1 and Ar 2 Possible positions of substituents on the aromatic ring include the carbon adjacent to the carbon to which the maleimide group is bonded (i.e., the ortho position in the case of benzene), the carbon two positions away from the carbon to which the maleimide group is bonded (i.e., the meta position in the above case), and the carbon three positions away from the carbon atom to which the maleimide group is bonded (i.e., the para position in the above case). In particular, Ar1 and Ar 2 It is preferable that each aromatic ring has at least one substituent at the ortho position of one or both carbons adjacent to the carbon to which the maleimide group is attached.

[0040] Ar 1 and Ar 2 If the aromatic ring is benzene, it is preferable that the bond to other sites* extends from the para position relative to the maleimide group in the aromatic ring.

[0041] And in equations (1) and (2), Ar 1 and Ar 2 This requires that at least one of the types of substituents, the number of substituents, and the positions of the substituents are different from each other. Examples of "different from each other" as described above are not limited to the following: [1] Different types of substituents (Specific example: one Ar atom has a methyl group, the other Ar atom has an ethyl group) [2] The number of substituents is different (specific example: one Ar molecule has one substituent, and the other Ar molecule has two substituents) [3] Different substituent positions (Specific example: Ar 1 and Ar 2 (When the aromatic ring is benzene, one Ar is at the ortho position and the other Ar is at the meta position.) [4] Any combination of the above [1] to [3] (Specific example: Ar 1 and Ar 2 If the aromatic ring is benzene, one Ar group has one ethyl group at one of the ortho positions relative to the maleimide group, and the other Ar group has one methyl group at each of the ortho positions relative to the maleimide group, for a total of two groups.

[0042] The number of aromatic ring-maleimide skeletons in one molecule of maleimide compound (a) must be two or more, but it may be two (i.e., a dinuclear component (bismaleimide compound)), three (i.e., a trinuclear component (trismaleimide compound)), four (i.e., a tetranuclear component), or five or more. Herein, in this specification, "nuclear body number" refers to the number of aromatic ring-maleimide skeletons in one molecule. The above aromatic ring-maleimide skeleton is typically a skeleton derived from the aromatic monoamine compound that is the reaction raw material.

[0043] Specifically, the maleimide compound (a) is preferably a component with a relatively low molecular weight, such as a dinuclear component represented by the following formula (3-1), a trinuclear component represented by the following formula (3-2), a tetranuclear component represented by the following formula (3-3), or a tetranuclear component represented by the following formula (3-4).

[0044] [ka] [In the formula, A is the aromatic ring-maleimide skeleton, and B is an arbitrarily selected site. A and B in the formula may be the same or different.]

[0045] If a molecule contains three or more aromatic ring-maleimide skeletons, it is classified as maleimide compound (a) if the substituents on at least two of these aromatic rings are different in form.

[0046] In particular, the maleimide resin (A) preferably contains a dinuclear component (bismaleimide compound). Furthermore, the proportion of the dinuclear component (bismaleimide compound) in the maleimide resin (A) is preferably 30% or more, and more preferably 50% or more. The content of dinuclear components in maleimide resin (A) is calculated from the area ratio of the gel permeation chromatography (GPC) chart. The measurement conditions for gel permeation chromatography (GPC) are as shown in the examples below.

[0047] The maleimide compound (a) is preferably an asymmetric bismaleimide compound in which the first aromatic ring-maleimide skeleton and the second aromatic ring-maleimide skeleton are bonded via an organic group having 1 to 200 carbon atoms. More specifically, the following general formula (3-5): [ka] [Here in equation (3-5), R 1 ~R 4 Ar 1 and Ar 2 The definition of is the same as in formulas (1) and (2), and Z is an organic group having 1 to 200 carbon atoms. Preferably, it is an asymmetric bismaleimide compound (a dinuclear component) represented by ]. In this embodiment, the asymmetric bismaleimide compound may be isolated and purified before use.

[0048] Ar in equation (3-5) 1 and Ar 2 When the aromatic ring is benzene, the bond from the aromatic ring to Z is preferably in the para position relative to the maleimide group.

[0049] In the above formulas (3-5), Z is typically a site derived from the binder, which is the reaction raw material. Z is a divalent organic group having 1 to 200 carbon atoms, but it may also be a site containing other atoms such as oxygen atoms or halogen atoms, as long as the number of carbon atoms is in the range of 1 to 200. In particular, Z is more preferably a divalent organic group having 1 to 20 carbon atoms. Specific examples of Z include, for example, the sites represented by the following general formulas (Z-1) to (Z-8).

[0050] [ka]

[0051] R in the general formula (Z-1) 5 Each of these independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, or an aromatic ring which may have substituents. The above-mentioned aliphatic hydrocarbon group having 1 to 4 carbon atoms may be linear, branched, or cyclic, and may contain unsaturated bonds in its structure. Specific examples of the above-mentioned aliphatic hydrocarbon group having 1 to 4 carbon atoms include methyl, ethyl, vinyl, propyl, allyl, and butyl groups. Examples of aromatic rings that may have the above substituents include phenyl groups, naphthyl groups, and structural sites having one or more substituents on these aromatic rings. Examples of the above substituents include aliphatic hydrocarbon groups, alkyloxy groups, alkenyloxy groups, halogen atoms, aryl groups, aralkyl groups, hydroxyl groups, and the like. The above aliphatic hydrocarbon group may be linear, branched, or cyclic, and may have unsaturated bonds in its structure. Specific examples of the above aliphatic hydrocarbon group include methyl, ethyl, vinyl, propyl, allyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, and nonyl groups. Examples of the alkyloxy groups mentioned above include methoxy groups, ethoxy groups, propyloxy groups, and butoxy groups. Examples of the above-mentioned alkenyloxy group include allyloxy groups. Examples of the halogen atoms mentioned above include fluorine atoms, chlorine atoms, and bromine atoms. Examples of the aryl groups mentioned above include phenyl groups, naphthyl groups, anthryl groups, and groups in which the above aliphatic hydrocarbon groups, alkyloxy groups, or halogen atoms are substituted on the aromatic core of these groups. Examples of the above-mentioned aralkyl groups include benzyl groups, phenylethyl groups, naphthylmethyl groups, naphthylethyl groups, and groups in which an alkyl group, or the alkyloxy group or halogen atom mentioned above, is substituted on the aromatic core of these groups.

[0052] Ar in general formulas (Z-2), (Z-3), and (Z-8) 3 Each of these independently represents an aromatic ring that may have substituents. 3 Specifically, examples include phenylene groups, naphthylene groups, and those having one or more substituents on their aromatic rings. Examples of such substituents include aliphatic hydrocarbon groups, alkyloxy groups, alkenyloxy groups, halogen atoms, aryl groups, aralkyl groups, and hydroxyl groups. The above aliphatic hydrocarbon group may be linear, branched, or cyclic, and may have unsaturated bonds in its structure. Specific examples of the above aliphatic hydrocarbon group include methyl, ethyl, vinyl, propyl, allyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, and nonyl groups. Examples of the alkyloxy groups mentioned above include methoxy groups, ethoxy groups, propyloxy groups, and butoxy groups. Examples of the above-mentioned alkenyloxy group include the allyloxy group. Examples of the halogen atoms mentioned above include fluorine atoms, chlorine atoms, and bromine atoms. Examples of the aryl groups mentioned above include phenyl groups, naphthyl groups, anthryl groups, and groups in which the above aliphatic hydrocarbon groups, alkyloxy groups, or halogen atoms are substituted on the aromatic core of these groups. Examples of the above-mentioned aralkyl groups include benzyl groups, phenylethyl groups, naphthylmethyl groups, naphthylethyl groups, and groups in which an alkyl group, or the alkyloxy group or halogen atom mentioned above, is substituted on the aromatic core of these groups.

[0053] In the above general formulas (Z-2) and (Z-3), R 6 Each of these independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. The aliphatic hydrocarbon group having 1 to 4 carbon atoms may be linear, branched, or cyclic, and may have unsaturated bonds in its structure. Specific examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms include methyl, ethyl, vinyl, propyl, allyl, and butyl groups.

[0054] In the above general formula (Z-3), Y represents a single bond, a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, an oxygen atom, a sulfur atom, or a sulfonyl group. The above divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms may be linear, branched, or cyclic, and may contain unsaturated bonds in its structure.

[0055] In the above general formula (Z-4), R 8Each of these is independently an aliphatic hydrocarbon group, an alkyloxy group, an alkenyloxy group, an alkynyloxy group, a halogen atom, an aryl group, or an aralkyl group, where l is an integer from 0 to 3 and n is an integer of 1 or greater. The above aliphatic hydrocarbon group may be linear, branched, or cyclic, and may contain unsaturated bonds in its structure. Specific examples of the above aliphatic hydrocarbon group include methyl, ethyl, vinyl, propyl, allyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, and nonyl groups. Examples of the alkyloxy groups mentioned above include methoxy groups, ethoxy groups, propyloxy groups, and butoxy groups. Examples of the above-mentioned alkenyloxy group include the allyloxy group. Examples of the halogen atoms mentioned above include fluorine atoms, chlorine atoms, and bromine atoms. Examples of the aryl groups mentioned above include phenyl groups, naphthyl groups, anthryl groups, and groups in which the above aliphatic hydrocarbon groups, alkyloxy groups, or halogen atoms are substituted on the aromatic core of these groups. Examples of the above-mentioned aralkyl groups include benzyl groups, phenylethyl groups, naphthylmethyl groups, naphthylethyl groups, and groups in which an alkyl group, or the alkyloxy group or halogen atom mentioned above, is substituted on the aromatic core of these groups.

[0056] In the above general formula (Z-7), R 7 This represents a divalent aliphatic hydrocarbon group other than those represented by the general formula (Z-1), an aromatic group which may have substituents, or a combination thereof. The above divalent aliphatic hydrocarbon group may be linear, branched, or cyclic, and may have unsaturated bonds in its structure.

[0057] <Manufacturing of Maleimide Resin (A)> Maleimide resin (A) (i.e., a resin containing maleimide compound (a)) is obtained by reacting multiple types of aromatic monoamine compounds (i.e., compounds with different substituent configurations) with a binder to produce a polyamine compound, and then maleimidizing the polyamine compound. The structures of the multiple types of aromatic monoamine compounds contribute to the first aromatic ring-maleimide skeleton and the second aromatic ring-maleimide skeleton in the obtained maleimide compound (a).

[0058] As for the above-mentioned aromatic monoamine compound, as long as it has one NH2 group on the aromatic ring, there are no particular limitations on its other specific structure, and a wide variety of compounds can be used. Specifically, examples of the above-mentioned aromatic monoamine compound include a compound having one NH2 group on the aromatic ring, and a compound having one or more substituents in addition to the NH2 group on the aromatic ring.

[0059] Examples of the aromatic rings mentioned above include benzene, naphthalene, and anthracene.

[0060] Examples of the substituents mentioned above include aliphatic hydrocarbon groups, alkyloxy groups, alkenyloxy groups, alkynyloxy groups, halogen atoms, aryl groups, aralkyl groups, hydroxyl groups, etc. Note that the substituents are substantially the Ar in the resulting maleimide compound (a). 1 and Ar 2 This corresponds to the substituents on the aromatic ring. Therefore, specific examples of the substituents are as previously described.

[0061] Among aromatic monoamine compounds, it is preferable to use aniline, compounds having a substituent at the 2-position of aniline, and / or compounds having a substituent at the 2,6-position of aniline. Furthermore, in the case of compounds having a substituent at the 2-position of aniline and compounds having a substituent at the 2,6-position of aniline, the substituent is preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms (methyl group, ethyl group, propyl group, butyl group, etc.), as this results in a maleimide resin with excellent heat resistance in the cured product.

[0062] In this embodiment, as described above, multiple types of the above-mentioned aromatic monoamine compounds are used. This results in a maleimide resin that maintains the high heat resistance characteristic of maleimide resins while having low melting and softening points and excellent handling properties, thereby achieving the desired effect. The number of aromatic monoamine compounds used may be two or more, and there is no particular upper limit, but it is preferable to use two to five types, and more preferably two or three types, as it allows for relatively simple production.

[0063] Furthermore, the amount of each aromatic monoamine compound used is preferably at least 10% by mass, and more preferably 25% by mass, relative to the total amount of aromatic monoamine compounds, in order to fully exhibit the effects of improving photosensitivity, developability, heat resistance, and coating film appearance. In addition, the amount of each aromatic monoamine compound used is preferably 90% by mass or less, and more preferably 75% by mass or less, relative to the total amount of aromatic monoamine compounds. In particular, when two types of aromatic monoamine compounds are used, the mass ratio of the two is preferably in the range of 10 / 90 to 90 / 10, and more preferably in the range of 20 / 80 to 80 / 20.

[0064] As a binder, any compound that reacts with an aromatic monoamine compound and bonds the aromatic rings of the aromatic monoamine compound is acceptable, and its specific structure is not particularly limited; a variety of compounds can be used. The binder may be used alone or in combination of two or more. Specific examples of the above-mentioned binders include, for example, aldehyde compounds (B-1) and ketone compounds (B-2). Examples of aldehyde compounds (B-1) include aliphatic aldehyde compounds such as formaldehyde and acetaldehyde, and aromatic aldehyde compounds such as benzaldehyde and naphthaldehyde. Aldehyde compounds (B-1) may be used individually or in combination of two or more. Examples of ketone compounds (B-2) include aliphatic ketone compounds such as acetone, methyl ethyl ketone, and diethyl ketone, and aromatic ketone compounds such as acetophenone. Ketone compounds (B-2) may be used individually or in combination of two or more.

[0065] Furthermore, specific examples of the above-mentioned binders include aromatic compounds represented by the following general formula (B-3) (B-3), aromatic compounds represented by the following general formula (B-4) (B-4), aromatic compounds represented by the following general formula (B-5) (B-5), aromatic compounds represented by the following general formula (B-6) (B-6), aromatic compounds represented by the following general formula (B-7) (B-7), aromatic compounds represented by the following general formula (B-8) (B-8), and so on.

[0066] [ka]

[0067] Ar in the above general formulas (B-3) to (B-6) 3 Each of these independently represents an aromatic ring that may have substituents. 3 A concrete example of this is Ar in the general formulas (Z-2), (Z-3), and (Z-8) mentioned above. 3 Similar examples include the above.

[0068] In the above general formulas (B-3) and (B-5), R 9 Each of these is independently either a hydrogen atom or a methyl group.

[0069] In the above general formulas (B-4) and (B-6), R 10 Each of these independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. The aliphatic hydrocarbon group having 1 to 4 carbon atoms may be linear, branched, or cyclic, and may have unsaturated bonds in its structure. Specific examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms include methyl, ethyl, vinyl, propyl, allyl, and butyl groups.

[0070] In the above general formulas (B-7) and (B-8), R 8 Each of these independently represents an aliphatic hydrocarbon group, an alkyloxy group, an alkenyloxy group, an alkynyloxy group, a halogen atom, an aryl group, or an aralkyl group, and l is an integer from 0 to 3. 8 A concrete example of this is R in the general formula (Z-4) mentioned above. 8 Similar examples include the above.

[0071] In the above general formulas (B-4), (B-6), and (B-8), X represents a hydroxyl group, a halogen atom, or an alkyloxy group. Examples of the alkyloxy group include a methoxy group, an ethoxy group, a propyloxy group, and a butoxy group.

[0072] In the general formulas (B-5) and (B-6) above, Y represents a single bond, a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, an oxygen atom, a sulfur atom, or a sulfonyl group. The divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms may be linear, branched, or cyclic, and may contain unsaturated bonds in its structure.

[0073] One method for producing a polyamine compound by reacting multiple aromatic monoamine compounds with a binder is to react the multiple aromatic monoamine compounds with the binder under acidic catalytic conditions. In particular, it is preferable to add the binder in divided portions to the aromatic monoamine compounds because it facilitates reaction control. This reaction may be carried out in a solvent as appropriate. Furthermore, the reaction can be efficiently carried out by heating to about 50 to 200°C in the above step. After the reaction is complete, the intermediate polyamine compound can be obtained by washing with an alkaline aqueous solution or distilled water.

[0074] Examples of the above-mentioned acidic catalysts include p-toluenesulfonic acid, dimethyl sulfuric acid, diethyl sulfuric acid, sulfuric acid, hydrochloric acid, oxalic acid, and activated clay. The acidic catalyst may be used alone or in combination of two or more types. The amount of acidic catalyst added is preferably in the range of 0.01 to 0.5 moles, and more preferably in the range of 0.1 to 0.3 moles, per 2 moles of the above-mentioned aromatic monoamine compound. If the number of moles cannot be defined, it is preferable that the amount is in the range of 1% to 50% by mass of the total amount of the aromatic monoamine compound, binder, solvent, and acidic catalyst.

[0075] Examples of the solvents mentioned above include distilled water and organic solvents such as toluene and xylene. The solvent may be used alone or in combination of two or more. The amount of solvent used is preferably in the range of 5% to 100% by mass relative to the total amount of the aromatic monoamine compound and the binder.

[0076] Next, as a step to maleimide the intermediate polyamine compound (maleimide reaction), for example, a method of reacting the polyamine compound with an acid anhydride under acidic catalytic conditions can be used. In particular, since reaction control is easier, it is preferable to add the acid anhydride to the polyamine compound in divided portions or to dissolve the acid anhydride in a suitable solvent and add it dropwise. This reaction may also be carried out in a solvent as appropriate. As for the reaction procedure, it is preferable to first stir the polyamine compound and acid anhydride at room temperature to obtain an amic acid intermediate, then add an acid catalyst, and heat to 50 to 200°C, more preferably 70 to 150°C to allow the reaction to proceed. At this time, it is preferable to remove water from the system. After the reaction is complete, the desired maleimide resin (A) can be obtained by washing with an alkaline aqueous solution or distilled water, etc.

[0077] Examples of the above-mentioned acid anhydrides include maleic anhydride, citraconic anhydride, and 2,3-dimethylmaleic anhydride. The acid anhydrides may be used individually or in combination of two or more types.

[0078] Examples of the above-mentioned acidic catalysts include p-toluenesulfonic acid, hydroxy-p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, and phosphoric acid. The acidic catalyst may be used alone or in combination of two or more types. The amount of acidic catalyst added is usually 0.01 to 10 mol, preferably 0.03 to 3 mol, per 1 g / mol of amino group equivalent of the above-mentioned polyamine compound.

[0079] The solvent mentioned above is not particularly limited as long as it can dissolve the polyamine compound and the acid anhydride. In particular, it is preferable to use a mixed solvent of a nonpolar solvent such as toluene and an aprotic polar solvent such as dimethylformamide, as this provides high solubility for the polyamine compound and acid anhydride and allows the reaction to proceed efficiently. Examples of the nonpolar solvent include toluene, xylene, and chlorobenzene. Examples of the aprotic polar solvent include dimethylformaldehyde and methyl ethyl ketone. The mixing ratio of the two and the amount of solvent used can be appropriately adjusted depending on the solubility of the polyamine compound and the acid anhydride. For example, the mass ratio of the nonpolar solvent to the aprotic solvent can be in the range of 1 / 99 to 99 / 1, and the total amount of solvent can be in the range of 0.5 to 80% by mass relative to the total amount of the polyamine compound, acid anhydride, and total solvent.

[0080] (Resin (B) having acidic groups and polymerizable unsaturated groups) Resin (B), which has acidic groups and polymerizable unsaturated groups, is one of the essential components in the resin composition of this embodiment. Resin (B) only needs to have acidic groups and polymerizable unsaturated groups; other specific structures or molecular weights are not particularly limited, and a wide variety of resins can be used.

[0081] In this embodiment, examples of acidic groups in resin (B) include carboxyl groups, sulfonic acid groups, and phosphoric acid groups. Among these, carboxyl groups are preferred as acidic groups because they exhibit excellent alkali developability. Examples of polymerizable unsaturated groups in resin (B) include (meth)acryloyl groups, allyl groups, isopropenyl groups, 1-propenyl groups, styryl groups, styrylmethyl groups, maleimide groups, and vinyl ether groups.

[0082] Examples of the resin (B) having acidic groups and polymerizable unsaturated groups in this embodiment include the following [1] to [6]: [1] Epoxy resin having acid groups and polymerizable unsaturated groups (B1), [2] Urethane resin having acidic groups and polymerizable unsaturated groups (B2) [3] Acrylic resin having acidic groups and polymerizable unsaturated groups (B3), [4] Amidoimide resin having acid groups and polymerizable unsaturated groups (B4), [5] Acrylamide resin having acidic groups and polymerizable unsaturated groups (B5), [6] Ester resin having acidic groups and polymerizable unsaturated groups (B6), Examples include resins such as the above. The epoxy resin (B1) to ester resin (B6) will be explained below in order.

[0083] <Epoxy resin having acidic groups and polymerizable unsaturated groups (B1)> Examples of epoxy resins (B1) having acidic groups and polymerizable unsaturated groups include epoxy (meth)acrylate resins having acidic groups, which require epoxy resin (b1-1), unsaturated monobasic acid (b1-2), and polybasic acid anhydride (b1-3) as essential reaction raw materials, and epoxy (meth)acrylate resins having acidic groups and urethane bonds, which require epoxy resin (b1-1), unsaturated monobasic acid (b1-2), polybasic acid anhydride (b1-3), polyisocyanate compounds (b1-4), and (meth)acrylate compounds having hydroxyl groups (b1-5) as reaction raw materials.

[0084] The specific structure of the epoxy resin (b1-1) is not particularly limited, as long as it has multiple epoxy groups in the resin. Examples of the epoxy resin (b1-1) include bisphenol type epoxy resin, hydrogenated bisphenol type epoxy resin, biphenol type epoxy resin, hydrogenated biphenol type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol copolymer novolac type epoxy resin, naphthol-cresol copolymer novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, biphenyl aralkyl type epoxy resin, fluorene type epoxy resin, xanthene type epoxy resin, dihydroxybenzene type epoxy resin, trihydroxybenzene type epoxy resin, oxazolidone type epoxy resin, and the like. These epoxy resins may be used individually or in combination of two or more types.

[0085] Examples of the bisphenol-type epoxy resins mentioned above include bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin. Examples of the above-mentioned hydrogenated bisphenol type epoxy resins include hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol B type epoxy resin, hydrogenated bisphenol E type epoxy resin, hydrogenated bisphenol F type epoxy resin, and hydrogenated bisphenol S type epoxy resin. Examples of the above-mentioned biphenol-type epoxy resins include 4,4'-biphenol-type epoxy resin, 2,2'-biphenol-type epoxy resin, tetramethyl-4,4'-biphenol-type epoxy resin, and tetramethyl-2,2'-biphenol-type epoxy resin. Examples of the above-mentioned hydrogenated biphenol-type epoxy resins include hydrogenated 4,4'-biphenol-type epoxy resin, hydrogenated 2,2'-biphenol-type epoxy resin, hydrogenated tetramethyl-4,4'-biphenol-type epoxy resin, and hydrogenated tetramethyl-2,2'-biphenol-type epoxy resin. The epoxy resin (b1-1) may be used alone or in combination of two or more types.

[0086] Examples of unsaturated monobasic acids (b1-2) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, and β-furfurylacrylic acid. Acid halides and esters of the above unsaturated monobasic acids can also be used. Furthermore, the following general formula (4) applies to unsaturated monobasic acids (b1-2): [ka] [In the above general formula (4), X 41 X represents an alkylene chain, polyoxyalkylene chain, (poly)ester chain, aromatic hydrocarbon chain, or (poly)carbonate chain having 1 to 10 carbon atoms. 41 The hydrogen atoms in the structure may be substituted with halogen atoms or alkoxy groups, Y 41 This is a hydrogen atom or a methyl group. Compounds represented by [ ] can also be used.

[0087] Examples of the polyoxyalkylene chains mentioned above include polyoxyethylene chains and polyoxypropylene chains. Examples of the above (poly)ester chain include the following general formula (5): [ka] [In the above general formula (5), R 51 and R 52 This represents an alkylene group with 1 to 10 carbon atoms, n 51 represents an integer from 1 to 5. Examples include (poly)ester chains represented by ].

[0088] Examples of the above-mentioned aromatic hydrocarbon chains include phenylene chains, naphthylene chains, biphenylene chains, phenylnaphthylene chains, or binaphthylene chains. In addition, hydrocarbon chains having aromatic rings such as benzene rings, naphthalene rings, anthracene rings, and phenanthrene rings as partial structures can also be used. Examples of the above (poly)carbonate chains include the following general formula (6): [ka] [In the above general formula (6), R 61 This represents an alkylene group with 1 to 10 carbon atoms, n 61 represents an integer from 1 to 5. An example is a (poly)carbonate chain represented by ].

[0089] The molecular weight of the compound represented by general formula (4) is preferably in the range of 100 to 500, and more preferably in the range of 150 to 400.

[0090] Unsaturated monobasic acids (b1-2) may be used individually or in combination of two or more.

[0091] Examples of polybasic acid anhydrides (b1-3) include aliphatic polybasic acid anhydrides, alicyclic polybasic acid anhydrides, aromatic polybasic acid anhydrides, acid halides of aliphatic polybasic acid anhydrides, acid halides of alicyclic polybasic acid anhydrides, and acid halides of aromatic polybasic acid anhydrides.

[0092] Examples of the above-mentioned aliphatic polybasic acid anhydrides include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, and acid anhydrides of 1,2,3,4-butanetetracarboxylic acid. Furthermore, the aliphatic hydrocarbon group in the aliphatic polybasic acid anhydride may be either linear or branched, and may have unsaturated bonds in its structure.

[0093] In this invention, the above-mentioned alicyclic polybasic acid anhydride is defined as one in which the acid anhydride group is bonded to an alicyclic structure, and the presence or absence of aromatic rings in other structural parts is irrelevant. Examples of the alicyclic polybasic acid anhydride include tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, and the acid anhydride of 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid.

[0094] Examples of the above-mentioned aromatic polybasic acid anhydrides include phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalentricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, and benzophenonetetracarboxylic acid.

[0095] The polybasic acid anhydrides (b1-3) may be used individually or in combination of two or more. Among these, tetrahydrophthalic anhydride, succinic anhydride, and cyclohexanedicarboxylic acid anhydride are preferred from the viewpoint of more effectively improving photosensitivity, developability, heat resistance, and / or coating film appearance.

[0096] Examples of polyisocyanate compounds (b1-4) include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; and tolylene diisocyanate. Aromatic diisocyanate compounds such as xylylene diisocyanate, tetramethyl xylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, and o-tolidine diisocyanate; polymethylene polyphenyl polyisocyanates having a repeating structure represented by the following general formula (7); and isocyanurate modified versions, biuret modified versions, allophanate modified versions, etc. of these compounds. Polyisocyanate compounds (b1-4) may be used individually or in combination of two or more. [ka] [In the above general formula (7), R 72 and R 73 Each of these independently represents either a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and R 71 Each of these independently represents an alkyl group with 1 to 4 carbon atoms, and k 71 n is an integer between 0 and 3, and n 71 [ is an integer greater than or equal to 1.]

[0097] Examples of (meth)acrylate compounds having a hydroxyl group (b1-5) include 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, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane (meth)acrylate, ditrimethylolpropane di(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate. Furthermore, polyoxyalkylene modified compounds, in which polyoxyalkylene chains such as polyoxyethylene chains, polyoxypropylene chains, and polyoxytetramethylene chains are introduced into the molecular structure of the various hydroxyl group-containing (meth)acrylate compounds, and lactone modified compounds, in which a polylactone structure is introduced into the molecular structure of the various hydroxyl group-containing (meth)acrylate compounds, can also be used.

[0098] Among these, those with a molecular weight of 1,000 or less are preferred from the viewpoint of more effectively improving light sensitivity, developability, heat resistance and / or coating film appearance. Furthermore, if the (meth)acrylate compound (b1-5) having a hydroxyl group is an oxyalkylene modified or lactone modified, it is preferable that its weight-average molecular weight (Mw) is 1,000 or less. The (meth)acrylate compounds (b1-5) having a hydroxyl group may be used individually or in combination of two or more.

[0099] The method for producing the epoxy resin (B1) having acidic groups and polymerizable unsaturated groups is not particularly limited and can be any method. In producing the epoxy resin (B1) having acidic groups and polymerizable unsaturated groups, the process may be carried out in an organic solvent as needed, and a basic catalyst may also be used as needed.

[0100] The method for producing the epoxy resin (B1) having acidic groups and polymerizable unsaturated groups is not particularly limited, as long as epoxy resin (b1-1), unsaturated monobasic acid (b1-2), and polybasic acid anhydride (b1-3) are used as essential reaction raw materials, or epoxy resin (b1-1), unsaturated monobasic acid (b1-2), polybasic acid anhydride (b1-3), polyisocyanate compound (b1-4), and (meth)acrylate compound (b1-5) having hydroxyl groups are used as reaction raw materials. For example, the epoxy resin (B1) may be produced by reacting all the reaction raw materials together, or by reacting the reaction raw materials sequentially. Among these, the method of reacting the epoxy resin (b1-1) with the unsaturated monobasic acid (b1-2) first, and then with the polybasic acid anhydride (b1-3), is preferred because the reaction can be easily controlled. This reaction can be carried out, for example, by reacting an epoxy resin (b1-1) with an unsaturated monobasic acid (b1-2) in the presence of a basic catalyst at a temperature range of 100 to 150°C, then adding a polybasic acid anhydride (b1-3) to the reaction system and reacting at a temperature range of 80 to 140°C.

[0101] In this embodiment, the reaction ratio of the epoxy resin (b1-1) to the unsaturated monobasic acid (b1-2) is preferably in the range of 0.9 to 1.1 moles of unsaturated monobasic acid (b1-2) per mole of epoxy groups in the epoxy resin (b1-1). Furthermore, the reaction ratio of the polybasic acid anhydride (b1-3) is preferably in the range of 0.2 to 1.0 mole per mole of epoxy groups in the epoxy resin (b1-1).

[0102] Examples of the above 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.

[0103] Furthermore, commercially available organic solvents can also be used, such as 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.

[0104] Examples of 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; phosphines 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 dianeodecanoate, dibutyltin diacetate, tin octyolate, and 1,1,3,3-tetrabutyl-1,3-dodecanoyldistanoxane; organometallic compounds such as zinc octyolate and bismuth octyoate; 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. The basic catalyst may be used alone or in combination of two or more types. Furthermore, the amount of basic catalyst added is preferably in the range of 0.001 to 5 parts by mass per 100 parts by mass of the total reaction raw materials.

[0105] The acid value of the epoxy resin (B1) having acidic groups and polymerizable unsaturated groups is preferably in the range of 30 to 150 mg KOH / g, and more preferably in the range of 40 to 120 mg KOH / g, from the viewpoint of more effectively improving photosensitivity, developability, heat resistance and / or coating film appearance. In this disclosure, the acid value of the resin (B) having acidic groups and polymerizable unsaturated groups is the value measured by the neutralization titration method of JIS 0070 (1992).

[0106] <Urethane resin (B2) having acidic groups and polymerizable unsaturated groups> As a urethane resin (B2) having acid groups and polymerizable unsaturated groups, for example, a resin obtained by reacting a polyisocyanate compound (b1-4), a hydroxyl group-containing (meth)acrylate compound (b1-5), a carboxyl group-containing polyol compound (b2-1), and, if necessary, a polybasic acid anhydride (b1-3), a polyol compound other than the carboxyl group-containing polyol compound (b2-2); polyisocyanate compound (b1-4) and hydroxyl group-containing ( Examples include resins obtained by reacting a meth)acrylate compound (b1-5) with a polybasic acid anhydride (b1-3) and a polyol compound other than a carboxyl group-containing polyol compound (b2-1) (b2-2); or resins obtained by reacting an epoxy resin (b1-1) with an unsaturated monobasic acid (b1-2), a polybasic acid anhydride (b1-3), a polyisocyanate compound (b1-4), and a hydroxyl group-containing (meth)acrylate compound (b1-5).

[0107] Examples of carboxyl group-containing polyol compounds (b2-1) include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylolvaleric acid. These carboxyl group-containing polyol compounds can be used individually or in combination of two or more.

[0108] Examples of polyol compounds other than carboxyl group-containing polyol compounds (b2-1) (b2-2) include aliphatic polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; aromatic polyol compounds such as biphenol and bisphenol; (poly)oxyalkylene modified compounds obtained by introducing (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains into the molecular structure of the various polyol compounds; and lactone modified compounds obtained by introducing (poly)lactone structures into the molecular structure of the various polyol compounds. The polyol compounds other than carboxyl group-containing polyol compounds can be used alone or in combination of two or more.

[0109] The method for producing the urethane resin (B2) having acidic groups and polymerizable unsaturated groups is not particularly limited and can be produced by any method. In producing the urethane resin having acidic groups and polymerizable unsaturated groups, the process may be carried out in an organic solvent as needed, and a basic catalyst may also be used as needed.

[0110] The organic solvent described above can be the same as the organic solvent described in the section above for "Epoxy resin having acidic groups and polymerizable unsaturated groups (B1)," and the organic solvent can be used alone or in combination of two or more types. Furthermore, the basic catalyst described above can be the same as the basic catalyst described in the section above for "Epoxy resin having acidic groups and polymerizable unsaturated groups (B1)," and the basic catalyst can be used alone or in combination of two or more types.

[0111] <Acrylic resin (B3) having acidic groups and polymerizable unsaturated groups> Examples of the acrylic resin (B3) having acidic groups and polymerizable unsaturated groups in this embodiment include a reaction product obtained by introducing (meth)acryloyl groups by further reacting an acrylic resin intermediate obtained by polymerizing an acrylic resin intermediate having a reactive functional group such as a hydroxyl group or a carboxyl group, isocyanate group, or glycidyl group with an acrylic resin intermediate having a reactive functional group that can react with these functional groups, or a resin obtained by reacting a polybasic acid anhydride (b1-3) with the hydroxyl groups in the reaction product.

[0112] In this embodiment, the acrylic resin intermediate may be copolymerized with other polymerizable unsaturated group-containing compounds in addition to the (meth)acrylate compound (α) as needed. Examples of such other polymerizable unsaturated group-containing compounds include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; alicyclic structure-containing (meth)acrylates such as cyclohexyl (meth)acrylate, isobolonyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; aromatic ring-containing (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, and phenoxyethyl acrylate; silyl group-containing (meth)acrylates such as 3-methacryloxypropyltrimethoxysilane; and styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene. Other polymerizable unsaturated group-containing compounds can be used individually or in combination of two or more.

[0113] The above (meth)acrylate compound (β) is not particularly limited as long as it can react with the reactive functional group of the above (meth)acrylate compound (α), but from the viewpoint of reactivity, the following combinations are preferred. That is, when a hydroxyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use an isocyanate group-containing (meth)acrylate as the (meth)acrylate compound (β). When a carboxyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use a glycidyl group-containing (meth)acrylate as the (meth)acrylate compound (β). When an isocyanate group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use a hydroxyl group-containing (meth)acrylate as the (meth)acrylate compound (β). When a glycidyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use a carboxyl group-containing (meth)acrylate as the (meth)acrylate compound (β). (Meth)acrylate compounds (β) can be used alone or in combination of two or more.

[0114] The method for producing the acrylic resin (B3) having acidic groups and polymerizable unsaturated groups in this embodiment is not particularly limited and may be produced by any method. The production of the acrylic resin (B3) having acidic groups and polymerizable unsaturated groups may be carried out in an organic solvent as needed, and a basic catalyst may also be used as needed. The organic solvent can be the same as the organic solvent described in the section above for <Epoxy resin having acidic groups and polymerizable unsaturated groups (B1)>, and the organic solvent can be used alone or in combination of two or more types. As the basic catalyst, the same basic catalyst as described in the section above, "<Epoxy resin having acidic groups and polymerizable unsaturated groups (B1)>", can be used, and the basic catalyst can be used alone or in combination of two or more types.

[0115] In this embodiment, the acid value of the acrylic resin (B3) having acid groups and polymerizable unsaturated groups is preferably in the range of 30 to 150 mg KOH / g, and more preferably in the range of 40 to 120 mg KOH / g, from the viewpoint of more effectively improving photosensitivity, developability, heat resistance and / or coating film appearance.

[0116] <Amido-imide resin (B4) having acidic groups and polymerizable unsaturated groups> In this embodiment, the amide-imide resin (B4) having an acid group and a polymerizable unsaturated group can be, for example, obtained by reacting an amide-imide resin (b4-1) having an acid group and / or an acid anhydride group with a (meth)acrylate compound (b1-5) having a hydroxyl group and / or an epoxy group having a compound having one or more reactive functional groups selected from the group consisting of a hydroxyl group, a carboxyl group, an isocyanate group, a glycidyl group, and an acid anhydride group. The compound having the reactive functional group may or may not have a (meth)acryloyl group. The amide-imide resin (b4-1) having acid groups and / or acid anhydride groups may have only one of them, or both. From the viewpoint of reactivity and reaction control with (meth)acrylate compounds (1-5) having hydroxyl groups or epoxy compounds having (meth)acryloyl groups, it is preferable that the amide-imide resin (b4-1) has acid anhydride groups, and more preferably that it has both acid groups and acid anhydride groups. The solid content acid value of the amide-imide resin (b4-1) is preferably in the range of 60 to 350 mgKOH / g when measured under neutral conditions, i.e., conditions in which the acid anhydride groups are not ring-opened. On the other hand, it is preferable that the measured value is in the range of 61 to 360 mgKOH / g when measured under conditions in which the acid anhydride groups are ring-opened, such as in the presence of water.

[0117] Furthermore, the amide-imide resin (b4-1) can be used in combination with polybasic acids as reaction raw materials, in addition to polyisocyanate compounds (b1-4) and polybasic acid anhydrides (b1-3), if necessary.

[0118] Any compound having two or more carboxyl groups in one molecule can be used as the polybasic acid mentioned above. For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3 Examples of polybasic acids include dicarboxylic acids, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalentricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, and the like. In addition, as the polybasic acid, for example, a copolymer of a conjugated diene vinyl monomer and acrylonitrile having a carboxyl group in its molecule can also be used. The polybasic acids mentioned above can be used individually or in combination of two or more.

[0119] The above-mentioned (meth)acrylate compounds having an epoxy group are not particularly limited in their specific structure as long as they have a (meth)acryloyl group and an epoxy group in their molecular structure, and a wide variety of compounds can be used. For example, examples include glycidyl group-containing (meth)acrylate monomers such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate, as well as mono(meth)acrylates of diglycidyl ether compounds such as hydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. The (meth)acrylate compounds having the epoxy group described above can be used alone or in combination of two or more.

[0120] Furthermore, the specific structure or manufacturing method of the amide-imide resin (b4-1) having acid groups and / or acid anhydride groups is not particularly limited, and general amide-imide resins can be widely used. The amide-imide resin (b4-1) in this embodiment is preferably obtained using a polyisocyanate compound (b1-4) and a polybasic acid anhydride (b1-3) as reaction raw materials. Furthermore, in this embodiment, as the polyisocyanate compound (b1-4), a resin composition having acidic groups with high solvent solubility and polymerizable unsaturated groups is obtained, therefore, alicyclic diisocyanate compounds or modified thereof, aliphatic diisocyanate compounds or modified thereof are preferred, and alicyclic diisocyanate or its isocyanurate modified, aliphatic diisocyanate or its isocyanurate modified are more preferred. In this embodiment, the total mass ratio of alicyclic diisocyanate compounds or their modified counterparts to aliphatic diisocyanate compounds or their modified counterparts in the total mass of polyisocyanate compounds (b1-4) is preferably 70% by mass or more, and preferably 90% by mass or more. Furthermore, when using an alicyclic diisocyanate compound or a modified version thereof in combination with an aliphatic diisocyanate compound or a modified version thereof, it is preferable that the mass ratio of the two (alicyclic diisocyanate compound or modified version thereof / aliphatic diisocyanate compound or modified version thereof) is in the range of 30 / 70 to 70 / 30.

[0121] The method for producing the amide-imide resin (B4) having acidic groups and polymerizable unsaturated groups is not particularly limited and can be produced by any method. In producing the amide-imide resin (B4) having acidic groups and polymerizable unsaturated groups, the process may be carried out in an organic solvent as needed, and a basic catalyst may also be used as needed. As the basic catalyst, the same basic catalyst as described in the section above, "<Epoxy resin having acidic groups and polymerizable unsaturated groups (B1)>", can be used, and the basic catalyst can be used alone or in combination of two or more types. Furthermore, the organic solvent can be the same as the organic solvent described in the section above for <Epoxy resin having acidic groups and polymerizable unsaturated groups (B1)>, and the organic solvent can be used alone or in combination of two or more types.

[0122] The amide-imide resin (B4) having acid groups and polymerizable unsaturated groups may also be used in combination with other reaction materials in addition to the reaction materials of the amide-imide resin (b4-1) having acid groups and / or acid anhydride groups, the hydroxyl group-containing (meth)acrylate compound (b1-5), and / or epoxy group-containing (meth)acrylate compound (b4-2), depending on the desired resin performance. In this case, it is preferable that the total mass ratio of the components (b4-1) to (b4-2) in the total mass of the reaction materials for the resin (B4) having acid groups and polymerizable unsaturated groups be 80% by mass or more, and more preferably 90% by mass or more.

[0123] The method for producing the amide-imide resin (B4) having acidic groups and polymerizable unsaturated groups is not particularly limited and can be carried out by any method. For example, it may be produced by reacting all the reaction materials, including the amide-imide resin (b4-1) and the hydroxyl group-containing (meth)acrylate compound (b1-5) and / or the epoxy group-containing (meth)acrylate compound (b4-2), all at once, or by reacting the reaction materials sequentially. For example, the reaction between the amide-imide resin (b4-1) and the hydroxyl group-containing (meth)acrylate compound (b1-5) can be carried out by heating and stirring under temperature conditions of about 80 to 140°C in the presence of a suitable basic catalyst. In the production of the amide-imide resin (B4) having acidic groups and polymerizable unsaturated groups, it may be carried out in an organic solvent as needed, and a basic catalyst or an acidic catalyst may be used as needed.

[0124] The basic catalyst described above can be the same as the acidic catalyst and basic catalyst described in the section above, "Epoxy resin having acidic groups and polymerizable unsaturated groups (B1)," and these can be used individually or in combination of two or more. Examples of the above-mentioned 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 can be used individually or in combination of two or more types.

[0125] The acid value of the amide-imide resin (B4) having acid groups and polymerizable unsaturated groups is preferably in the range of 30 to 150 mg KOH / g, and more preferably in the range of 40 to 120 mg KOH / g, from the viewpoint of more effectively improving photosensitivity, developability, heat resistance and / or coating film appearance.

[0126] <Acrylamide resin (B5) having acidic groups and polymerizable unsaturated groups> Examples of the acrylamide resin (B5) having acidic groups and polymerizable unsaturated groups in this embodiment include a resin obtained by reacting a phenolic hydroxyl group-containing compound (b5-1), an alkylene carbonate (b5-2a) or alkylene oxide (b5-2b), an N-alkoxyalkyl (meth)acrylamide compound (b5-3), a polybasic acid anhydride (b1-3), and optionally an unsaturated monobasic acid (b1-2) as reaction raw materials.

[0127] In this embodiment, the phenolic hydroxyl group-containing compound (b5-1) refers to a compound having at least one phenolic hydroxyl group in the molecule. As the phenolic hydroxyl group-containing compound (b5-1), for example, a compound represented by any of the following general formulas (8.1) to (8.5), a reaction product having an aromatic polyhydroxy compound (b5-4) and a compound represented by any of the following general formulas (9.1) to (9.5) as essential reaction raw materials, or a novolak-type phenol resin using one or more of an aromatic polyhydroxy compound (b5-4) or other compounds (b5-5) having one phenolic hydroxyl group in the molecule as reaction raw materials can also be used. [Chemical formula] [In the above general formulas (8.1) to (8.5), R 81 ~R 84 , R 87 each independently represents any of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, or a halogen atom, R 85 and R 86 each independently represents a hydrogen atom or a methyl group, j 81 ~j 85 each independently represents 0 or an integer of 1 or more, preferably 0 or an integer of 1 to 3, more preferably 0 or 1. k 81 ~k 85 each independently represents an integer of 1 or more, preferably 2 or 3.] Note that the positions of the substituents on the aromatic ring in the above general formulas (8.1) to (8.5) are arbitrary. For example, in the naphthalene ring of the general formula (8.2), it may substitute with any hydrogen atom on either ring. In the general formula (8.3), it may substitute with any hydrogen atom on the benzene ring existing in one molecule of biphenyl. In the general formula (8.4), it may substitute with any hydrogen atom on the benzene ring existing in one molecule of aralkyl. In the general formula (8.5), it may substitute with any hydrogen atom on the benzene ring existing in one molecule, indicating that the number of substituents in one molecule is j 81 ~j 85 and k 81 ~k85 It shows that it is. [Chemical formula] [In the above general formulas (9.1) to (9.5), h 91 represents 0 or 1, and R 91 ~R 96 each independently represents any one of a monovalent aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group or an aralkyl group, and k 91 ~k 96 each independently represents 0 or an integer of 1 to 4, and Z 91 ~Z 96 each independently represents any one of a vinyl group, a halomethyl group, a hydroxymethyl group or an alkyloxymethyl group, and Y 91 represents any one of an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom or a carbonyl group, and n 91 represents an integer of 1 to 4.] The compounds represented by the above general formulas (9.1) to (9.5) can be used alone or in combination of two or more.

[0128] Examples of aromatic polyhydroxy compounds (b5-4) include dihydroxybenzene, trihydroxybenzene, tetrahydroxybenzene, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxyanthracene, trihydroxyanthracene, tetrahydroxyanthracene, biphenol, tetrahydroxybiphenyl, bisphenol, and compounds having one or more substituents on these aromatic nuclei. Furthermore, examples of substituents on the aromatic nucleus include monovalent aliphatic hydrocarbon groups such as methyl, ethyl, vinyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, and nonyl groups; alkoxy groups such as methoxy, ethoxy, propyloxy, and butoxy groups; halogen atoms such as fluorine, chlorine, and bromine atoms; phenyl, naphthyl, and anthryl groups, and aryl groups on which these aromatic nuclei are substituted with the aliphatic hydrocarbon groups, alkoxy groups, halogen atoms, etc.; phenyloxy and naphthyloxy groups, and aryloxy groups on which these aromatic nuclei are substituted with the aliphatic hydrocarbon groups, alkoxy groups, halogen atoms, etc.; phenylmethyl, phenylethyl, naphthylmethyl, naphthylethyl groups, and aralkyl groups on which these aromatic nuclei are substituted with the aliphatic hydrocarbon groups, alkoxy groups, halogen atoms, etc. These aromatic polyhydroxy compounds can be used individually or in combination of two or more. Among these, compounds that do not contain halogens are preferred because they yield resins having acidic groups and polymerizable unsaturated groups with high insulating reliability.

[0129] Examples of the novolac-type phenolic resin mentioned above include resins obtained by reacting one or more compounds having one phenolic hydroxyl group in their molecule with an aldehyde compound under acidic catalyst conditions.

[0130] The above-mentioned compounds having one phenolic hydroxyl group in the molecule (b5-5) can be any aromatic compound having one hydroxyl group on the aromatic nucleus. Examples include phenol or phenol compounds having one or more substituents on the aromatic nucleus of phenol, naphthol or naphthol compounds having one or more substituents on the aromatic nucleus of naphthol, anthracenol or anthracenol compounds having one or more substituents on the aromatic nucleus of anthracenol, etc. Examples of substituents on the aromatic nucleus include monovalent aliphatic hydrocarbon groups, alkoxy groups, halogen atoms, aryl groups, aryloxy groups, aralkyl groups, etc., with specific examples of each being as described above. These compounds having one phenolic hydroxyl group can be used individually or in combination of two or more.

[0131] Examples of the above aldehyde compounds include formaldehyde; alkyl aldehydes such as acetaldehyde, propylaldehyde, butyraldehyde, isobutyraldehyde, pentylaldehyde, and hexylaldehyde; hydroxybenzaldehydes such as salicylaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2-hydroxy-4-methylbenzaldehyde, 2,4-dihydroxybenzaldehyde, and 3,4-dihydroxybenzaldehyde; and 2-hydroxy-3-methoxybenzaldehyde and 3-hydroxy-4-methoxybenzaldehyde. Examples include aldehydes, benzaldehydes having both a hydroxyl group and an alkoxy group, such as 4-hydroxy-3-methoxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, and 4-hydroxy-3,5-dimethoxybenzaldehyde; alkoxybenzaldehydes such as methoxybenzaldehyde and ethoxybenzaldehyde; hydroxynaphthaldehydes such as 1-hydroxy-2-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, and 6-hydroxy-2-naphthaldehyde; and halogenated benzaldehydes such as bromobenzaldehyde.

[0132] Examples of alkylene carbonates (b5-2a) include ethylene carbonate, propylene carbonate, butylene carbonate, and pentylene carbonate. Among these, ethylene carbonate or propylene carbonate are preferred from the viewpoint of the resin composition exhibiting higher photosensitivity and developability, and the resulting cured product (cured coating film) exhibiting superior heat resistance and coating film appearance. The alkylene carbonate can be used alone or in combination of two or more types.

[0133] Examples of alkylene oxides (b5-2b) include ethylene oxide, propylene oxide, butylene oxide, and pentylene oxide. Among these, ethylene oxide or propylene oxide is preferred from the viewpoint of the resin composition exhibiting higher photosensitivity and developability, and the resulting cured product (cured coating) exhibiting superior heat resistance and coating appearance. The alkylene oxide can be used alone or in combination of two or more types.

[0134] Examples of N-alkoxyalkyl(meth)acrylamide compounds (b5-3) include N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-methoxyethyl(meth)acrylamide, N-ethoxyethyl(meth)acrylamide, and N-butoxyethyl(meth)acrylamide. Among these, N-methoxymethyl(meth)acrylamide is preferred from the viewpoint of the resin composition exhibiting higher photosensitivity and developability, and the resulting cured product (cured coating film) exhibiting better heat resistance and coating film appearance. N-alkoxyalkyl(meth)acrylamide compounds (b5-3) can be used alone or in combination of two or more.

[0135] In this embodiment, when the N-alkoxyalkyl(meth)acrylamide compound (b5-3) is used as a reaction raw material for the acrylamide resin (B5) having acidic groups and polymerizable unsaturated groups, the equivalent ratio of the N-alkoxyalkyl(meth)acrylamide compound (b5-3) to the polybasic acid anhydride (b1-3) [(b5-3) / (b1-3)] is preferably in the range of 0.2 to 7, and more preferably in the range of 0.25 to 6.7, from the viewpoint of the resin composition exhibiting higher photosensitivity and developability, and the resulting cured product (cured coating film) exhibiting better heat resistance and coating film appearance.

[0136] In this embodiment, the method for producing the acrylamide resin (B5) having acidic groups and polymerizable unsaturated groups is not particularly limited and can be produced by any method. For example, it may be produced by reacting all the reaction materials at once, or by reacting the reaction materials sequentially. In particular, a method is preferred in which the reaction is easily controlled, in which a phenolic hydroxyl group-containing compound (b5-1) is first reacted with an alkylene carbonate (b5-2a) or alkylene oxide (b5-2b) (for example, in the presence of a basic catalyst and at a temperature range of 100 to 200°C), then an unsaturated monobasic acid (b1-2) and / or an N-alkoxyalkyl (meth)acrylamide compound (b2-3b) is reacted (for example, in the presence of an acidic catalyst and at a temperature range of 80 to 140°C), and finally a polybasic acid anhydride (b1-3) is reacted (for example, at a temperature range of 80 to 140°C).

[0137] The acrylamide resin (B5) having acidic groups and polymerizable unsaturated groups in this embodiment is a resin obtained from the above-mentioned reaction raw materials. For example, the acrylamide resin (B5) may be a resin having a resin structure in which structural units are repeatedly composed of structural units (I) represented by the following general formula (10.1) and structural units (II) represented by the following general formula (10.2), or a resin having a resin structure in which structural units are repeatedly composed of structural units (III) represented by the following formula (10.3) and structural units (IV) represented by the following formula (10.4). [ka] [In the above formula (10.1) or (10.2), R b2 and R b8 Each of these independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, and R b3 and R b9 Each of these independently represents one of the following: a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom. 1 and n 2 Each of them independently represents either 1 or 2, R b4 and R b10 Each of these independently represents a methylene group or a structural part represented by one of the following general formulas (11.1) to (11.5), and R b5 and R b6 Each of these independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, however, R b5 and R b6 These may be linked together to form a saturated or unsaturated ring, R b11 R represents a divalent hydrocarbon group with 1 to 12 carbon atoms. b12 R represents a hydrogen atom or a methyl group. b1 and R b7 Each of them independently, R b3 and R b9 The group represented by, or the structural part (I) represented by formula (10.1) or the structural part (II) represented by formula (10.2), is marked with an asterisk (*) in R b4 or R b10 It is a connection point that is linked via [a certain mechanism]. [ka] [In the above general formula (10.3) or (10.4), R b2 and R b8 Each of these independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and R b3 and R b9 Each of these independently represents one of the following: a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom. 3 and n 4 Each of them independently represents either 1 or 2, Rb4 and R b10 Each of these independently represents a methylene group or a structural part represented by any of the following formulas (11.1) to (11.5), and R b5 and R b6 Each of these independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, however, R b5 and R b6 These may be linked together to form a saturated or unsaturated ring, R b11 R represents a divalent hydrocarbon group with 1 to 12 carbon atoms. b12 R represents a hydrogen atom or a methyl group. b1 and R b7 Each of them independently, R b3 and R b9 The group represented by, or the structural part (III) represented by general formula (10.3) or the structural part (IV) represented by general formula (10.4), is marked with an asterisk (*) in R b4 or R b10 It is a connection point that is linked via [a certain mechanism]. [ka] [In the above general formulas (11.1) to (11.5), h 91 represents 0 or 1, R 91 ~R 96 Each of these independently represents one of the following: a monovalent aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, or an aralkyl group, n 91 ~n 96 Each of these independently represents either 0 or an integer from 1 to 4, and Y 91 n represents one of the following: an alkylene group with 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, or a carbonyl group. 91 represents integers from 1 to 4, and R 111 ~R 116 Each of these independently represents either a hydrogen atom or a methyl group, and W represents the following formula (12.1) or (12.2). [ka] [In the above formula (12.1) or (12.2), R 121 and R 124Each of these independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and R 122 and R 123 Each of these independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, however, R 122 and R 123 These may be linked together to form a saturated or unsaturated ring, R 125 R represents a divalent hydrocarbon group with 1 to 12 carbon atoms. 126 [This represents a hydrogen atom or a methyl group.]

[0138] The acid value of the acrylamide resin (B5) having acid groups and polymerizable unsaturated groups is preferably in the range of 30 to 150 mg KOH / g, and more preferably in the range of 40 to 120 mg KOH / g, from the viewpoint of the resin composition exhibiting higher photosensitivity and developability, and the resulting cured product (cured coating film) exhibiting better heat resistance and coating film appearance.

[0139] <Ester resin (B6) having acidic groups and polymerizable unsaturated groups> Examples of ester resins (B6) having acidic groups and polymerizable unsaturated groups include resins obtained by reacting a phenolic hydroxyl group-containing compound (b5-1) with an alkylene oxide (b5-2b) or alkylene carbonate (b5-2a) with an unsaturated monobasic acid (b1-2) and a polybasic acid anhydride (b1-3).

[0140] As the alkylene oxide (b5-2b), the same as those exemplified above as alkylene oxide (b5-2b) can be used. Among these, ethylene oxide or propylene oxide is preferred from the viewpoint of more effectively improving light sensitivity, developability, heat resistance and / or coating film appearance. Alkylene oxides (b5-2b) can be used alone or in combination of two or more types.

[0141] As the alkylene carbonate (b5-2a) mentioned above, the same type as the example alkylene carbonate (b5-2a) described above can be used. Among these, ethylene carbonate or propylene carbonate is preferred from the viewpoint of more effectively improving light sensitivity, developability, heat resistance and / or coating film appearance. Alkylene carbonate (b5-2a) can be used alone or in combination of two or more types.

[0142] The method for producing the ester resin (B6) having acidic groups and polymerizable unsaturated groups is not particularly limited and can be produced by any method. In producing the ester resin having acidic groups and polymerizable unsaturated groups, the process may be carried out in an organic solvent as needed, and basic catalysts and acidic catalysts may also be used as needed.

[0143] The above-mentioned organic solvent can be the same as those exemplified above, and the organic solvent can be used alone or in combination of two or more. The above-mentioned basic catalyst can be the same as those exemplified above, and the basic catalyst can be used alone or in combination of two or more. The above-mentioned acidic catalyst can be the same as those exemplified above, and the acidic catalyst can be used alone or in combination of two or more.

[0144] (Compounds having polymerizable unsaturated groups) The resin composition of this embodiment may further contain a compound having a polymerizable unsaturated group in addition to the maleimide resin (A) and resin (B). Such a compound having a polymerizable unsaturated group is typically a compound that does not have an acid group.

[0145] Examples of compounds having the polymerizable unsaturated group mentioned above include (meth)acrylate compounds, specifically aliphatic mono(meth)acrylate compounds such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate, pentyl(meth)acrylate, hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, and octyl(meth)acrylate; and alicyclic compounds such as cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, and adamantylmono(meth)acrylate. Mono(meth)acrylate compounds; 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, 2-hydroxy-3-phenoxypropyl(meth)acrylate, phenoxybenzyl(meth)acrylate, benzylbenzyl(meth)acrylate, phenoxy Mono(meth)acrylate compounds such as aromatic mono(meth)acrylate compounds like phenoxyethyl (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; ethylene glycol di( Aliphatic di(meth)acrylate compounds such as meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, 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, tricyclodecane dimethanol di(meth)acrylate;Aromatic di(meth)acrylate compounds such as biphenol di(meth)acrylate and bisphenol di(meth)acrylate; polyoxyalkylene-modified di(meth)acrylate compounds in which (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains are introduced into the molecular structure of the above di(meth)acrylate compounds; lactone-modified di(meth)acrylate compounds in which a (poly)lactone structure is introduced into the molecular structure of the above di(meth)acrylate compounds; aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerin tri(meth)acrylate; (poly)oxyalkylene-modified di(meth)acrylate compounds in which (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains are introduced into the molecular structure of the above aliphatic tri(meth)acrylate compounds )Oxyalkylene-modified tri(meth)acrylate compounds; lactone-modified tri(meth)acrylate compounds in which a (poly)lactone structure is introduced into the molecular structure of the aliphatic tri(meth)acrylate compound; tetrafunctional or more aliphatic poly(meth)acrylate compounds such as pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; tetrafunctional or more (poly)oxyalkylene-modified poly(meth)acrylate compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain is introduced into the molecular structure of the aliphatic poly(meth)acrylate compound; tetrafunctional or more lactone-modified poly(meth)acrylate compounds in which a (poly)lactone structure is introduced into the molecular structure of the aliphatic poly(meth)acrylate compound;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 with (poly)oxyalkylene chains such as ethylene chains; lactone modified compounds with a (poly)lactone structure 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. Compounds having polymerizable unsaturated groups may be used individually or in combination of two or more.

[0146] (Photopolymerization initiator) As described above, the resin composition of this embodiment may further contain a photopolymerization initiator in addition to the maleimide resin (A) and resin (B) (and any compound having a polymerizable unsaturated group). A resin composition containing a photopolymerization initiator is, in other words, a curable resin composition. The photopolymerization initiator may be used alone or in combination of two or more types.

[0147] The photopolymerization initiator can be selected and used appropriately depending on the type of active energy ray used for irradiation. It may also be used in combination with photosensitizers such as amine compounds, urea compounds, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, and nitrile compounds. Furthermore, the photopolymerization initiator is preferably a radical polymerization initiator. Specific examples of such photopolymerization initiators include alkylphenone-based photopolymerization initiators such as 1-hydroxycyclohexylphenyl-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, and 1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; acylphosphine oxide-based photopolymerization initiators such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide; and intramolecular hydrogen abstraction type photopolymerization initiators such as benzophenone compounds.

[0148] Furthermore, specific examples of photopolymerization initiators include 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, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one.

[0149] Examples of commercially available photopolymerization initiators include "Omnirad-1173", "Omnirad-184", "Omnirad-127", "Omnirad-2959", "Omnirad-369", "Omnirad-379", "Omnirad-907", "Omnirad-4265", "Omnirad-1000", "Omnirad-651", "Omnirad-TPO", "Omnirad-819", "Omnirad-2022", "Omnirad-2100", "Omnirad-754", "Omnirad-784", "Omnirad-500", and "Omn Examples include "irad-81" (manufactured by IGM), "KayaCure-DETX", "KayaCure-MBP", "KayaCure-DMBI", "KayaCure-EPA", "KayaCure-OA" (manufactured by Nippon Kayaku Co., Ltd.), "ByCure-10", "ByCure-55" (manufactured by Stauffa Chemical), "Trigonal P1" (manufactured by Akzo), "Sandoz 1000" (manufactured by Sandoz), "Deep" (manufactured by Apjohn), "Quantacure-PDO", "Quantacure-ITX", "Quantacure-EPD" (manufactured by Ward Blenkinsop), and "Runtecure-1104" (manufactured by Runtec).

[0150] When a photopolymerization initiator is used, the amount of the photopolymerization initiator in the resin composition of this embodiment is preferably 0.1 parts by mass or more and 10 parts by mass or less, based on 100 parts by mass of the total of the maleimide resin (A) and the resin having acidic groups and polymerizable unsaturated groups (B).

[0151] (Optional addition ingredient) As described above, the resin composition of this embodiment may further contain optional additives, as long as it does not deviate from its purpose. Examples of optional additives include curing agents, curing accelerators, other resins, organic solvents, polymerization inhibitors, antioxidants, flame retardants, fillers, pigments, defoamers, viscosity modifiers, leveling agents, UV stabilizers, and preservation stabilizers.

[0152] <Hardening agent> Examples of curing agents include epoxy resins and other curing agents (amine curing agents, acid anhydride curing agents, phenolic resin curing agents, etc.), but epoxy resins are preferred among these.

[0153] The epoxy resin is not particularly limited, but is preferably a curable resin that contains two or more epoxy groups in its molecule and can be cured by forming a crosslinked network with the epoxy groups. The epoxy resin is not particularly limited, but may include novolac-type epoxy resins such as phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, α-naphthol novolac-type epoxy resins, β-naphthol novolac-type epoxy resins, bisphenol A novolac-type epoxy resins, and biphenyl novolac-type epoxy resins. Aralkyl epoxy resins such as phenol aralkyl epoxy resins, naphthol aralkyl epoxy resins, and phenol biphenyl aralkyl epoxy resins; Bisphenol-type epoxy resins such as bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol AF type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol C type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and tetrabromobisphenol A type epoxy resin; Biphenyl-type epoxy resins, tetramethylbiphenyl-type epoxy resins, and epoxy resins having a biphenyl skeleton and a diglycidyloxybenzene skeleton, etc. Naphthalene-type epoxy resin; Binaphthol-type epoxy resin; Binaphthyl-type epoxy resin; Dicyclopentadiene-type epoxy resins, such as dicyclopentadienephenol-type epoxy resins; Glycidylamine-type epoxy resins such as tetraglycidyldiaminodiphenylmethane-type epoxy resins, triglycidyl-p-aminophenol-type epoxy resins, and diaminodiphenylsulfone-type glycidylamine-type epoxy resins; Diglycidyl ester type epoxy resins such as 2,6-naphthalenedicarboxylic acid diglycidyl ester type epoxy resins and hexahydrophthalic anhydride glycidyl ester type epoxy resins; Examples include benzopyran-type epoxy resins such as dibenzopyran, hexamethyldibenzopyran, and 7-phenylhexamethyldibenzopyran. Of these epoxy resins, so-called glycidyl ether type epoxy resins obtained by epoxidizing phenol compounds are preferred, and among these, novolac type epoxy resins, aralkyl type epoxy resins, and dicyclopentadiene type epoxy resins are more preferred from the viewpoint of dielectric properties. The above epoxy resins may be used individually or in combination of two or more types.

[0154] The epoxy equivalent of the epoxy resin is preferably 120 to 400 g / eq, and more preferably 150 to 300 g / eq. A epoxy equivalent of 120 g / eq or more is preferred because it results in superior dielectric properties of the resulting cured product, while a epoxy equivalent of 400 g / eq or less is preferred because it provides an excellent balance between heat resistance and dielectric loss tangent of the resulting cured product.

[0155] The softening point of epoxy resin is preferably 20 to 200°C, and more preferably 40 to 150°C, from the viewpoint of improving light sensitivity, developability, heat resistance, and coating film appearance in a balanced manner.

[0156] Examples of amine curing agents are not particularly limited, but include aliphatic amines such as diethylenetriamine (DTA), triethylenetetramine (TTA), tetraethylenepentamine (TEPA), diproprendiamine (DPDA), diethylaminopropylamine (DEAPA), N-aminoethylpiperazine, mensendiamine (MDA), isophoronediamine (IPDA), 1,3-bisaminomethylcyclohexane (1,3-BAC), piperidine, N,N,-dimethylpiperazine, and triethylenediamine; and aromatic amines such as m-xylenediamine (XDA), methanephenylenediamine (MPDA), diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), benzylmethylamine, 2-(dimethylaminomethyl)phenol, and 2,4,6-tris(dimethylaminomethyl)phenol.

[0157] Examples of acid anhydride curing agents include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol bistrimellitate, glycerol trimellitate, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, and methylcyclohexendicarboxylic anhydride.

[0158] Examples of phenol resin curing agents include phenol novolac resins, cresol novolac resins, naphthol novolac resins, bisphenol novolac resins, biphenyl novolac resins, dicyclopentadiene-phenol addition type resins, phenol aralkyl resins, naphthol aralkyl resins, triphenolmethane type resins, tetraphenolethane type resins, and aminotriazine-modified phenol resins. The other curing agents mentioned above may be used individually or in combination of two or more.

[0159] When a curing agent is used, the curing agent content in the resin composition of this embodiment is preferably 10 to 40 parts by mass per 100 parts by mass of the total amount of maleimide resin (A) and resin (B). If it is 10 parts by mass or more, the heat resistance and curability can be further improved, and if it is 40 parts by mass or less, a lower dielectric loss tangent and higher flexibility can be achieved.

[0160] <Curing accelerator> The curing accelerator is not particularly limited, but examples include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and urea-based curing accelerators. The curing accelerator may be used alone or in combination of two or more types.

[0161] Examples of the phosphorus-based curing accelerators mentioned above include organophosphine compounds such as triphenylphosphine, tributylphosphine, triparatlylphosphine, diphenylcyclohexylphosphine, and tricyclohexylphosphine; organophosphine compounds such as trimethylphosphine and triethylphosphine; and phosphonium salts such as ethyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylphosphinetriphenylborane, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium dicyanamide, butylphenylphosphonium dicyanamide, and tetrabutylphosphonium decanoate.

[0162] Examples of the above-mentioned amine-based curing accelerators include triethylamine, tributylamine, N,N-dimethyl-4-aminopyridine (DMAP), 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo[5,4,0]-undecene-7 (DBU), and 1,5-diazabicyclo[4,3,0]-nonene-5 (DBN).

[0163] Examples of the above imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and the like.

[0164] Examples of the above guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-butylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and the like.

[0165] Examples of the above urea-based curing accelerators include 3-phenyl-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, chlorophenylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, and the like.

[0166] Among the above-mentioned curing accelerators, it is preferable to use 2-ethyl-4-methylimidazole and N,N-dimethyl-4-aminopyridine (DMAP).

[0167] When using a curing accelerator, the content of the curing accelerator in the resin composition of the present embodiment is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the total amount of the above-mentioned maleimide resin (A) and resin (B). When the content of the curing accelerator is 0.01 part by mass or more, the curability can be more reliably enhanced. On the other hand, when the content of the curing accelerator is 5 parts by mass or less, the insulation reliability can be maintained in a sufficiently good state. From the same viewpoint, the content of the curing accelerator is more preferably 0.1 part by mass or more and more preferably 5 parts by mass or less with respect to 100 parts by mass of the total amount of the above-mentioned maleimide resin (A) and resin (B).

[0168] <Other resins>[ Other resins are not particularly limited, but include maleimide resins other than maleimide resin (A), polyphenylene ether resins, polyimide resins, cyanate ester resins, benzoxazine resins, triazine-containing cresol novolak resins, cyanate ester resins, styrene-maleic anhydride resins, allyl group-containing resins such as diallylbisphenol and triallyl isocyanurate, polyphosphate esters, phosphate ester-carbonate copolymers, and the like. These other resins may be used alone or in combination of two or more.

[0169] When using other resins, the content of other resins in the resin composition of the present embodiment is preferably 50% by mass or less of the whole.

[0170] <Organic solvent>[ Organic solvents can have the function of adjusting the viscosity of the resin composition. Specific examples of organic solvents are not particularly limited, but 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. Organic solvents may be used individually or in combination of two or more.

[0171] When using an organic solvent, the content of the organic solvent in the resin composition of this embodiment is preferably 90% by mass or less, more preferably 10 to 90% by mass, and even more preferably 20 to 80% by mass, based on the total amount (100% by mass) of the resin composition. An organic solvent content of 10% by mass or more is preferable because it provides excellent handling properties. On the other hand, an organic solvent content of 90% by mass or less is preferable from an economic standpoint.

[0172] <Polymerization inhibitor> Polymerization inhibitors are not particularly limited, but include p-methoxyphenol (methoquinone), 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-to Phenolic compounds such as methyl-1,2-dihydroquinoline; quinone compounds such as hydroquinone, methylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone, anthraquinone, and diphenoquinone; melamine, p-phenylenediamine, 4-aminodiphenylamine, N,N'-diphenyl-p-phenylenediamine, Ni-propyl-N'-phenyl-p-phenylenediamine, N-(1.Amine compounds such as 3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, diphenylamine, 4,4'-dicumyl-diphenylamine, 4,4'-dioctyl-diphenylamine, poly(2,2,4-trimethyl-1,2-dihydroquinoline), 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, phosphite-(1-methylethylidene)-di-4,1-phenylenetetra-C12-15-alkyl ester, 2-ethylhexyl=diphenyl=phosphite, diphenylisodecyl phosphite, triisodecyl=phosphite, and 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-thione, 4,6-bis(octylthiomethyl)-o-cresol, 2-methyl-4,6-bis[(octan-1-ylsulfanyl)methyl]phenol, dilaurylthiodipropionate, and 3,3'-distearyl thiodipropionate. Polymerization inhibitors may be used individually or in combination of two or more.

[0173] <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.

[0174] 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.

[0175] <Flame retardant> There are no particular restrictions on the flame retardants used, but examples include inorganic phosphorus-based flame retardants, organophosphorus-based flame retardants, and halogen-based flame retardants. Flame retardants may be used individually or in combination of two or more types.

[0176] The inorganic phosphorus-based flame retardants mentioned above are not particularly limited, but include red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and polyammonium phosphate; and phosphate amides.

[0177] The above organophosphorus flame retardants are not particularly limited, but include methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, dibutyl phosphate, monobutyl phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, bis(2-ethylhexyl) phosphate, monoisodecyl acid phosphate, lauryl acid phosphate, tridecyl acid phosphate, and stearyl acid phosphate. Phosphate esters such as isostearyl acid phosphate, oleyl acid phosphate, butyl pyrophosphate, tetracosyl acid phosphate, ethylene glycol acid phosphate, and (2-hydroxyethyl) methacrylate acid phosphate; diphenylphosphine such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and diphenylphosphine oxide; and 10-(2,5-dihydroxyphenyl)-10H-9-oxa Phosphorus-containing phenols such as -10-phosphaphenanthrene-10-oxide, 10-(1,4-dioxynaphthalene)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphinnylhydroquinone, diphenylphosphenyl-1,4-dioxynaphthalene, 1,4-cyclooctylenephosphinnyl-1,4-phenyldiol, and 1,5-cyclooctylenephosphinnyl-1,4-phenyldiol; 9,10-dihydro-9-oxa-10-phos Examples include cyclic phosphorus compounds such as phaphenanthrene-10-oxide, 10-(2,5-dihydrooxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-(2,7-dihydrooxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; and compounds obtained by reacting the aforementioned phosphate esters, diphenylphosphine, or phosphorus-containing phenols with epoxy resins, aldehyde compounds, or phenolic compounds.

[0178] The halogenated flame retardants mentioned above are not particularly limited, but examples include brominated polystyrene, bis(pentabromophenyl)ethane, tetrabromobisphenol A bis(dibromopropyl ether), 1,2-bis(tetrabromophthalimide), 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine, and tetrabromophthalic acid.

[0179] When a flame retardant is used, the amount of flame retardant used in the resin composition of this embodiment is preferably 0.1 to 50 parts by mass per 100 parts by mass of the total amount of maleimide resin (A) and resin (B). If the flame retardant content is 0.1 parts by mass or more, flame retardancy can be more reliably imparted. On the other hand, if the flame retardant content is 50 parts by mass or less, flame retardancy can be imparted while maintaining dielectric properties. From a similar viewpoint, the flame retardant content is more preferably 1 part by mass or more, and more preferably 30 parts by mass or less, per 100 parts by mass of the total amount of maleimide resin (A) and resin (B).

[0180] <Filler> Examples of fillers include organic fillers and inorganic fillers. Organic fillers have functions such as improving elongation and improving mechanical strength. Inorganic fillers have functions such as reducing the coefficient of thermal expansion and providing flame retardancy. The above-mentioned fillers may be used individually or in combination of two or more types.

[0181] The above-mentioned organic filler is not particularly limited, but examples include polyamide particles.

[0182] The inorganic fillers mentioned above are not particularly limited, but include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, carbon black, etc. Of these, silica is preferred. In this case, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. can be used as silica.

[0183] Furthermore, the above-mentioned fillers may be surface-treated as needed. In this case, there are no particular limitations on the surface treatment agents that can be used, but aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, titanate coupling agents, etc. Specific examples of surface treatment agents include 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, hexamethyldisilazane, etc. The above-mentioned fillers may be used individually or in combination of two or more types.

[0184] When using a filler, the amount of the filler used in the resin composition of the present embodiment is preferably 0.5 to 95 parts by mass with respect to 100 parts by mass of the total amount of the maleimide resin (A) and the resin (B). When the content of the filler is 0.5 parts by mass or more, the effect of the filler can be sufficiently imparted. On the other hand, when the content of the filler is 95 parts by mass or less, it is possible to suppress the deterioration of the moldability due to the increase in the viscosity of the blend. From the same viewpoint, the content of the filler is more preferably 5 parts by mass or more and more preferably 80 parts by mass or less with respect to 100 parts by mass of the total amount of the maleimide resin (A) and the resin (B).

[0185] The manufacturing method of the resin composition of the present embodiment is not particularly limited, and can be manufactured by kneading the above-described various components using a kneader such as a roll.

[0186] [Cured product] The cured product of the present embodiment is a cured product of the above-described resin composition (curable resin composition). In other words, the cured product of the present embodiment is obtained by irradiating the above-described resin composition (curable resin composition) with an active energy ray to cure it. Such a cured product of the present embodiment can function as an insulating material excellent in at least heat resistance and coating film appearance.

[0187] Examples of the active energy ray include ionizing radiations such as ultraviolet rays, electron beams, α-rays, β-rays, and γ-rays. When ultraviolet rays are used as the active energy ray, in order to efficiently perform the curing reaction by ultraviolet rays, it may be irradiated in an inert gas atmosphere such as nitrogen gas or in an air atmosphere.

[0188] Specific examples of the ultraviolet ray source include ultraviolet lamps such as low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, and metal halide lamps, sunlight, LEDs, etc. Among these, ultraviolet lamps are generally used from the viewpoints of practicality and economy.

[0189] The integrated light intensity of 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.

[0190] Another method for obtaining a cured product by curing a 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.

[0191] 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 heat resistance and coating appearance, 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.

[0192] [Insulating materials] The insulating material of this embodiment consists of the resin composition (curable resin composition) described above. Preferably, the insulating material of this embodiment is obtained by curing the resin composition (curable resin composition) described above by irradiation with active energy rays. The insulating material of this embodiment has excellent heat resistance and coating appearance, as well as excellent low dielectric properties and elongation.

[0193] Examples of insulating materials include the interlayer insulating material for build-up substrates, insulating materials for circuit boards such as build-up adhesive films, insulating materials for circuit boards, and insulating materials for substrates for embedding electronic components. For example, a method for manufacturing a build-up substrate from the above-mentioned curable resin composition is a method consisting of the following three steps. The first step is to apply the curable resin composition, which is appropriately blended with rubber, fillers, etc., to a circuit board with a circuit formed on it using a spray coating method, a curtain coating method, etc., and then cure it. The second step is to then drill holes such as predetermined through-holes as needed, treat the surface with a roughening agent, wash the surface with hot water to form irregularities, and then plate it with a metal such as copper. The third step is to repeat these operations sequentially as desired to alternately build up and form a resin insulating layer and a conductor layer of a predetermined circuit pattern. It is preferable to drill the through-holes after the formation of the outermost resin insulating layer. The first step can be carried out not only by the solution coating method described above, but also by laminating a build-up film that has been pre-coated to a desired thickness and dried. Furthermore, the build-up substrate of the present invention can also be manufactured by forming a roughened surface and omitting the plating process by heating and pressing a resin-coated copper foil, on which the resin composition has been semi-cured, onto a wiring board on which a circuit has been formed, at 170-250°C.

[0194] [Resist material] The resist member of this embodiment consists of the resin composition (curable resin composition) described above. The resist member can be obtained, for example, by applying the curable resin composition described above onto a substrate, drying it in a suitable temperature range of about 60 to 100°C, exposing it to active energy rays through a photomask on which a desired pattern has been formed, developing the unexposed areas with an alkaline aqueous solution, and further heating and curing it in a temperature range of about 140 to 180°C. The resist member (resist film) of this embodiment has excellent heat resistance and coating appearance, as well as excellent low dielectric properties and elongation. [Examples]

[0195] 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 examples described below. In the following, "parts" and "%" are based on mass unless otherwise specified.

[0196] The measurement conditions for gel permeation chromatography (GPC), high-performance liquid chromatography (HPLC), liquid chromatography-mass spectrometry (LC-MS), and amine equivalents are as follows:

[0197] <Measurement conditions for 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).

[0198] <Measurement conditions for high-performance liquid chromatography (HPLC) and liquid chromatography-mass spectrometry (LC-MS)> Controller: Agilent Technologies 1260 Infinity II Column: Agilent EC-C18 (4.6 x 50 mm, 2.7 μm) Column temperature: 40℃ Pump flow rate: 1.0 ml / min Elution conditions: K1-water, K2-acetonitrile K1 / K2 = 0 / 100 → 30 / 70 (linear concentration change of 0-1.67 minutes) K1 / K2 = 30 / 70 (1.67 - 5 minutes) K1 / K2 = 30 / 70 → 90 / 10 (5-8 minutes) (The ratio is by volume.) Detection wavelengths: UV254, 275, 300nm MS :Agilent Technologies InfinityLab LC / MSD

[0199] <Measurement of amine equivalents> Approximately 2.5 g of the polyamine compound sample was placed in a 500 mL stoppered Erlenmeyer flask, and 7.5 g of pyridine, 2.5 g of acetic anhydride, and 7.5 g of triphenylphosphine were accurately weighed. A condenser was then attached, and the mixture was heated under reflux in an oil bath set to 120°C for 150 minutes. After cooling, 5.0 mL of distilled water, 100 mL of propylene glycol monomethyl ether, and 75 mL of tetrahydrofuran were added, and the mixture was titrated with a 0.5 mol / L potassium hydroxide-ethanol solution by potentiometric titration. A blank test was performed in the same manner to correct for the result, and the amine equivalent was measured. Amine equivalent (g / eq.) = (S × 2,000) / (Blank - A) S: Amount of sample (g) A: Consumption volume (mL) of 0.5 mol / L potassium hydroxide-ethanol solution Blank: Amount of 0.5 mol / L potassium hydroxide-ethanol solution consumed in the blank test (mL)

[0200] Furthermore, the evaluation methods for light sensitivity, developability, heat resistance, and coating appearance are as follows.

[0201] <Evaluation of light sensitivity> The resin compositions obtained in each example and comparative example were applied to a glass substrate to a thickness of 50 μm using an applicator, and then dried at 80°C for 30 minutes. Subsequently, a metal halide lamp was used to heat the mixture to a density of 5 kJ / m³ via a Kodak Step Tablet No. 2. 2 The samples were irradiated with ultraviolet light. These were then developed in a 1% by mass sodium carbonate aqueous solution (alkaline aqueous solution) for 180 seconds, and evaluated by the number of remaining stages. A higher number of remaining stages indicates higher photosensitivity.

[0202] <Evaluation of developability> The resin compositions obtained in each example and comparative example were applied to a glass substrate to a thickness of 50 μm using an applicator, and then dried at 80°C for 50 minutes, 60 minutes, 70 minutes, 80 minutes, 90 minutes, 100 minutes, and 110 minutes to prepare samples with different drying times. These were developed in a 1% by mass sodium carbonate aqueous solution (alkaline aqueous solution) at 30°C for 180 seconds, and the drying time at 80°C for samples that left no residue on the substrate was evaluated as the drying control range (minutes). A longer drying control range (minutes) indicates higher developability.

[0203] <Heat resistance evaluation> The 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. A 6 mm x 35 mm test piece was cut from this cured material, and the temperature at which the change in elastic modulus was maximized was evaluated as the glass transition temperature (°C) using a viscoelasticity analyzer (DMA: Rheometric's RSAII solid viscoelasticity analyzer, tensile method: frequency 1 Hz, heating rate 3°C / min). A higher glass transition temperature (°C) indicates superior heat resistance.

[0204] <Evaluation of coating film appearance> The resin compositions obtained in each example and comparative example were applied to a 125 μm PET film (Cosmoshine A4300, manufactured by Toyobo Co., Ltd.) using a bar coater (#12) and dried at 80°C for 5 minutes. Then, a metal halide lamp was used to measure 5 kJ / m². 2 The film was irradiated with ultraviolet light to obtain a cured coating with a thickness of 10 μm. The appearance of this coating was evaluated visually according to the following criteria. ○: No cloudiness ×: Cloudy white

[0205] (Synthesis Example 1: Synthesis of Maleimide Resin (A-1)) In a 500 mL round-bottom flask attached to a rotary evaporator, 52.40 g (0.43 mol) of 2,6-xylidine, 64.52 g (0.43 mol) of 2,6-diethylaniline, 22.14 g of distilled water, and 22.73 g of p-toluenesulfonic acid were charged and heated to 70°C with stirring. After holding at 70°C for 30 minutes, 34.98 g (0.43 mol) of 37% formalin solution was added in four portions over 1 hour, and the mixture was reacted for 4 hours. After the reaction, the mixture was air-cooled to room temperature, and the reaction solution was transferred to a 2 L separable flask and diluted with 140 g of toluene. The diluted solution was washed once with 100 g of 10% sodium hydroxide aqueous solution and four times with 100 g of distilled water, and concentrated under reduced pressure to obtain 109.48 g of polyamine compound (1). The amine equivalent of polyamine compound (1) was 146 g / eq.

[0206] In a 2L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer, 78.35g of polyamine compound (1) (0.54 mol in amine equivalents), 231.5g of toluene, and 23.3g of dimethylformamide were charged and stirred at room temperature. 59.53g of maleic anhydride (0.61 mol) was added in four portions over 1 hour, and the reaction was continued at room temperature for another hour. 2.3g of p-toluenesulfonic acid monohydrate was added, the reaction mixture was heated, and the azeotropic water and toluene were cooled and separated under reflux. Only the toluene was returned to the system, and the dehydration reaction was carried out for 6 hours. The solution, cooled to 60°C, was washed twice with 100g of 5% sodium bicarbonate aqueous solution and seven times with 150g of distilled water. During the process, 200g of toluene was added to improve the liquid-liquid efficiency. The solution was concentrated under reduced pressure to obtain 105.7g of maleimide resin (A-1). LC-MS spectroscopy revealed peaks with M+=432, 460, and 488. Each peak corresponds to an ammonia adduct of the following compound (including maleimide compound (a)). Furthermore, the content of the dinuclear component (bismaleimide compound), calculated from the area ratio in the GPC chart, was 96%. The GPC chart for maleimide resin (A-1) is shown in Figure 1.

[0207] [ka]

[0208] (Synthesis Example 2: Synthesis of Maleimide Resin (A-2)) In a 500 mL round-bottom flask attached to a rotary evaporator, 52.11 g (0.43 mol) of 2-ethylaniline, 64.17 g (0.43 mol) of 2,6-diethylaniline, 22.14 g of distilled water, and 22.73 g of p-toluenesulfonic acid were charged and heated to 70°C with stirring. After holding at 70°C for 30 minutes, 34.98 g (0.43 mol) of 37% formalin solution was added in four portions over 1 hour, and the mixture was reacted for 4 hours. After the reaction, the mixture was air-cooled to room temperature, and the reaction solution was transferred to a 2 L separable flask and diluted with 140 g of toluene. The diluted solution was washed once with 100 g of 10% sodium hydroxide aqueous solution and four times with 100 g of distilled water, and concentrated under reduced pressure to obtain 119.02 g of polyamine compound (2). The amine equivalent of polyamine compound (2) was 165 g / eq.

[0209] In a 2L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer, 87.45g of polyamine compound (2) (0.53 mol in amine equivalents), 231.5g of toluene, and 23.3g of dimethylformamide were charged and stirred at room temperature. 59.53g of maleic anhydride (0.61 mol) was added in four portions over 1 hour, and the reaction was continued at room temperature for another hour. 2.3g of p-toluenesulfonic acid monohydrate was added, the reaction mixture was heated, and the azeotropic water and toluene were cooled and separated under reflux. Only the toluene was returned to the system, and the dehydration reaction was carried out for 6 hours. The solution, cooled to 60°C, was washed twice with 100g of 5% sodium bicarbonate aqueous solution and seven times with 150g of distilled water. During the process, 200g of toluene was added to improve the liquid-liquid efficiency. The solution was concentrated under reduced pressure to obtain 123.36g of maleimide resin (A-2). LC-MS spectroscopy revealed peaks with M+=432, 460, and 488. Each peak corresponds to an ammonia adduct of the compound described below (including maleimide compound (a)). Furthermore, the content of the dinuclear component (bismaleimide compound), calculated from the area ratio in the GPC chart, was 56%. The GPC chart for maleimide resin (A-2) is shown in Figure 2.

[0210] [ka]

[0211] (Synthesis Example 3: Synthesis of Maleimide Resin (A-3)) In a 500 mL round-bottom flask attached to a rotary evaporator, 52.11 g (0.43 mol) of 2-ethylaniline, 52.11 g (0.43 mol) of 2,6-xylidine, 22.14 g of distilled water, and 22.73 g of p-toluenesulfonic acid were charged and heated to 70°C with stirring. After holding at 70°C for 30 minutes, 34.98 g (0.43 mol) of 37% formalin solution was added in four portions over 1 hour, and the mixture was reacted for 4 hours. After the reaction, the mixture was air-cooled to room temperature, and the reaction solution was transferred to a 2 L separable flask and diluted with 140 g of toluene. The diluted solution was washed once with 100 g of 10% sodium hydroxide aqueous solution and four times with 100 g of distilled water, and concentrated under reduced pressure to obtain 106.11 g of polyamine compound (3). The amine equivalent of polyamine compound (3) was 147 g / eq.

[0212] In a 2L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer, 77.91g of polyamine compound (3) (0.53 mol in amine equivalents), 231.5g of toluene, and 23.3g of dimethylformamide were charged and stirred at room temperature. 59.53g of maleic anhydride (0.61 mol) was added in four portions over 1 hour, and the reaction was continued at room temperature for another hour. 2.3g of p-toluenesulfonic acid monohydrate was added, the reaction mixture was heated, and the azeotropic water and toluene were cooled and separated under reflux. Only the toluene was returned to the system, and the dehydration reaction was carried out for 6 hours. The solution, cooled to 60°C, was washed twice with 100g of 5% sodium bicarbonate aqueous solution and seven times with 150g of distilled water. During the process, 200g of toluene was added to improve the liquid-liquid efficiency. The solution was concentrated under reduced pressure to obtain 113.09g of maleimide resin (A-3). A peak with M+=432 was observed in the LC-MS spectrum. This peak corresponds to the ammonia adduct of the following compound (including maleimide compound (a)). Furthermore, the content of the dinuclear component (bismaleimide compound), calculated from the area ratio in the GPC chart, was 58%. The GPC chart for maleimide resin (A-3) is shown in Figure 3.

[0213] [ka]

[0214] (Synthesis Examples 4-6: Synthesis of maleimide resins (A-4)-(A-6)) Maleimide resins (A-4) to (A-6) were synthesized using the same procedure as in Example 1, except that the type and amount (moles) of aromatic monoamine compounds were changed as shown in Table 1. The GPC charts for maleimide resins (A-4) to (A-6) are shown in Figures 4 to 6, respectively. The MS spectra of each maleimide resin confirmed that they contained an asymmetric bismaleimide compound (maleimide compound (a)). The content of the dinuclear component (bismaleimide compound) of each maleimide resin, calculated from the area ratio of the GPC chart, is shown in Table 1. [Table 1]

[0215] (Synthesis Example 7: Synthesis of a resin (B-1) having acidic groups and polymerizable unsaturated groups) In a flask equipped with a thermometer, stirrer, and reflux condenser, 123 g of diethylene glycol monoethyl ether acetate was added, and 214 g of orthocresol novolac type epoxy resin "EPICLON N-680" (manufactured by DIC Corporation, softening point 86°C, epoxy equivalent: 214 g / eq) was dissolved. After adding 0.9 g of dibutylhydroxytoluene and 0.2 g of methoquinone, 72 g of acrylic acid and 1.4 g of triphenylphosphine were added, and the reaction was carried out at 120°C for 10 hours while blowing in air. Next, 72 g of diethylene glycol monoethyl ether acetate and 76 g of tetrahydrophthalic anhydride were added, and the reaction was carried out at 110°C for 3 hours to obtain resin (B-1) having acidic groups and polymerizable unsaturated groups. The nonvolatile content of this resin (B-1) having acidic groups and polymerizable unsaturated groups was 65% by mass, and the solid content acid value was 80 mg KOH / g. The acid value was measured based on the neutralization titration method specified in JIS K 0070 (1992).

[0216] (Synthesis Example 8: Synthesis of resin (B-2) having acidic groups and polymerizable unsaturated groups) In a flask equipped with a thermometer, stirrer, and reflux condenser, 499.7 g of diethylene glycol monoethyl ether acetate was placed, and 244.3 g of isocyanurate-modified isophorone diisocyanate (EVONIK "VESTANAT T-1890 / 100", NCO%=17.2%) and 192.0 g of trimellitic anhydride were dissolved. Then, 1.0 g of dibutylhydroxytoluene was added. The mixture was reacted at 160°C for 6 hours under a nitrogen atmosphere, and it was confirmed that the NCO% was 0.1 or less. Next, 0.4 g of methoquinone was added as a thermal polymerization inhibitor, followed by 147.6 g of pentaerythritol polyacrylate mixture (Toagosei Co., Ltd. "Aronics M-306", hydroxyl value: 159.7 mg KOH / g) and 3.5 g of triphenylphosphine. The mixture was reacted at 110°C for 5 hours while blowing air into the mixture. Subsequently, 165.0 g of glycidyl methacrylate was added and the mixture was reacted at 110°C for 6 hours. Next, 110.4 g of succinic anhydride was added and the mixture was reacted at 110°C for 5 hours to obtain resin (B-2) having acidic groups and polymerizable unsaturated groups. The non-volatile content of this resin (B-2) was 62% by mass, and the solid content acid value was 80 mgKOH / g.

[0217] (Examples 1-12: Preparation of resin compositions (1)-(12)) A maleimide resin (A) obtained in the above synthesis example and a resin (B) having acidic groups and polymerizable unsaturated groups obtained in the above synthesis example were mixed in the composition ratios shown in Table 2 to obtain resin compositions (1) to (12), respectively. To this resin composition, an orthocresol novolac type epoxy resin (DIC Corporation, "EPICLON N-680", epoxy equivalent: 214 g / eq) as a curing agent, diethylene glycol monoethyl ether acetate as an organic solvent, a photopolymerization initiator (IGM Resins, "Omnirad 907"), 2-ethyl-4-methylimidazole as a curing accelerator, dipentaerythritol hexaacrylate as a compound having polymerizable unsaturated groups, and phthalocyanine green as a pigment were mixed in the composition ratios shown in Table 2 to obtain resin compositions (1) to (12), respectively. The photosensitivity and developability of the obtained resin compositions (1) to (12) were evaluated. The results are shown in Table 2.

[0218] (Comparative Example 1: Preparation of resin composition (C1)) Resin composition (C1) was obtained by mixing the materials in the same manner as in Example 1, except that 4,4'-diphenylmethanebismaleimide (BMI-1000, manufactured by Yamato Chemical Industries, Ltd.) was used instead of the maleimide resin (A) obtained in the above synthesis example, in the composition ratio shown in Table 2. Note that 4,4'-diphenylmethanebismaleimide is a maleimide compound having two identical aromatic ring-maleimide skeletons. The photosensitivity and developability of the obtained resin composition (C1) were evaluated. The results are shown in Table 2.

[0219] [Table 2]

[0220] (Examples 13-24: Preparation of resin compositions (13)-(24)) The maleimide resin (A) obtained in the above synthesis example and the resin (B) having acidic groups and polymerizable unsaturated groups obtained in the above synthesis example were mixed in the composition ratios shown in Table 3 to obtain a resin composition. To this resin composition, an orthocresol novolac type epoxy resin (DIC Corporation's "EPICLON N-680", epoxy equivalent: 214 g / eq) as a curing agent, diethylene glycol monoethyl ether acetate as an organic solvent, and a photopolymerization initiator (IGM Resins' "Omnirad 907") were mixed in the composition ratios shown in Table 3 to obtain resin compositions (13) to (24), respectively. The heat resistance and coating film appearance of the obtained resin compositions (13) to (24) were evaluated. The results are shown in Table 3.

[0221] (Comparative Example 2: Preparation of resin composition (C2)) Except for using 4,4'-diphenylmethanebismaleimide (BMI-1000, manufactured by Yamato Chemical Industries, Ltd.) instead of the maleimide resin (A) obtained in the above synthesis example, resin composition (C2) was obtained by mixing in the composition ratio shown in Table 3 in the same manner as in Example 13 above. The heat resistance and coating film appearance of the obtained resin composition (C2) were evaluated. The results are shown in Table 3.

[0222] [Table 3]

[0223] Tables 2 and 3 show that the resin compositions of the examples exhibit higher photosensitivity and developability compared to the comparative examples, and that the resulting cured product (cured coating) exhibits excellent heat resistance and coating appearance.

[0224] According to the present invention, it is possible to provide a resin composition that exhibits high photosensitivity and developability, and that can produce excellent heat resistance and coating appearance in the resulting cured product (cured coating film). Furthermore, according to the present invention, it is possible to provide a cured product, an insulating material, and a resist member obtained using the resin composition.

Claims

1. A resin composition comprising a maleimide resin (A) and a resin (B) having acidic groups and polymerizable unsaturated groups, The maleimide resin (A) contains the following general formula (1) in one molecule: 【Chemistry 1】 The first aromatic ring-maleimide skeleton shown by and the following general formula (2): 【Chemistry 2】 The maleimide compound (a) comprises a second aromatic ring-maleimide skeleton represented by [wherein formulas (1) and (2), R １ ~R ４ Each of these independently represents hydrogen, a methyl group, or an ethyl group, and Ar １ and Ar ２ Each of these independently represents an aromatic ring having one or more substituents, wherein the substituents are aliphatic hydrocarbon groups having 1 to 4 carbon atoms, and * represents a bond from the aromatic ring to another site, except Ar １ and Ar ２ A resin composition characterized in that at least one of the types of substituents, the number of substituents, and the positions of the substituents are different from each other.

2. The resin composition according to claim 1, wherein the maleimide compound (a) is an asymmetric bismaleimide compound in which the first aromatic ring-maleimide skeleton and the second aromatic ring-maleimide skeleton are bonded via an organic group having 1 to 200 carbon atoms.

3. The resin composition according to claim 1 or 2, wherein the mass ratio of the solid content of the maleimide resin (A) to the resin having acidic groups and polymerizable unsaturated groups (B) [(A) / (B)] is in the range of 1 / 100 to 100 / 100.

4. The resin composition according to any one of claims 1 to 3, further comprising a photopolymerization initiator.

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

6. An insulating material characterized by comprising the resin composition described in claim 4.

7. A resist member characterized by comprising the resin composition described in claim 4.

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