Carboxyl-modified amide resins, resin compositions, laminates and flexible printed wiring boards

Abstract

This invention provides a carboxyl-containing modified amide resin, which can be used as an adhesive for electronic components, or as a coating material for surface protective layers and insulating protective films, exhibiting superior solution stability, elastic modulus, heat resistance, and low warpage. This invention is a carboxyl-containing modified amide resin comprising: units derived from polyol (a), units derived from polyamine (b), and units derived from tetracarboxylic dianhydride (c), and having the structure shown in the following general formula (X) (in general formula (X), n represents a number from 0 to 20, R1 represents an organic group from tetracarboxylic dianhydride with the anhydride group removed, R2 represents an organic group from polyamine (b) with the amine group removed, and R3 represents an organic group from polyol (a) with the hydroxyl group removed); the polyamine (b) contains an aromatic diamine (b1) and a dimerized diamine (b2), and the amide bond concentration is 0.5 to 2.0 mmol / g.

Description

Technical Field

[0001] This invention relates to carboxyl-modified amide resin, resin composition, laminate, and flexible printed wiring board. Prior Technology

[0002] Generally speaking, polyimide resins are widely used as adhesive layers, surface protective layers, and insulating protective layers for electronic components due to their high elasticity, excellent heat resistance, flexibility, and insulation properties. However, although polyimide resins have excellent heat resistance, their rigid structure leads to the problem of significant warping of the substrate when coated onto it.

[0003] Furthermore, polyimide resins are not easily soluble in solvents, and high-boiling-point solvents are often required for their dissolution. Moreover, there are cases where high-temperature treatments above 200°C are necessary to form a coating film, posing challenges in processability. When coating and drying resin solutions to form insulating protective layers for electronic components, it is preferable to dry and harden at lower temperatures and for shorter periods. For polyimide resins, improved solubility in solvents with boiling points below 200°C and improved solution stability are required.

[0004] To address the aforementioned issues, attempts have been made to improve warpage or solution stability by incorporating a highly flexible backbone into polyimide resins. For example, a carboxyl-containing ethyl carbamate propylene resin has been proposed, obtained by reacting isocyanate-terminated polyurethane obtained from polycarbonate polyols and isocyanates with an anhydride and a chain extender (Patent Document 1). Another proposal is for a polyimide resin with carboxyl groups on its side chains, obtained by reacting an anhydride-terminated propylene oligomer obtained from the reaction of tetracarboxylic dianhydride and isocyanate with a polyol (Patent Documents 2 and 3). Furthermore, a propylene resin synthesized from a polyol, dimericane, and tetracarboxylic dianhydride has been proposed (Patent Document 4). Additionally, an adhesive composition has been proposed containing: a polyimide resin obtained using dimericane, monoamine, and tetracarboxylic dianhydride; and a curing agent (Patent Document 5). [Previous Technical Documents] [Patent Literature]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2011-094037 [Patent Document 2] Japanese Patent No. 6882263 [Patent Document 3] Japanese Patent No. 5304954 [Patent Document 4] Japanese Patent No. 7436352 [Patent Document 5] Japanese Patent Application Publication No. 2023-097359 Summary of the Invention

[0006] (The problem the invention aims to solve) However, while the ethyl carbamate amide resin proposed in Patent Document 1 exhibits good low warpage and flexibility, its high proportion of polyol-derived units and low amide bond concentration may not necessarily indicate good heat resistance. Furthermore, while the polyamide resins proposed in Patent Documents 2 and 3 also exhibit good low warpage and flexibility, their shorter distances between amide bonds and stronger aggregation due to the presence of isocyanate-derived units with smaller molecular weights result in lower amide bond distances. Therefore, there is room for improvement in solution stability.

[0007] The polyimide resins proposed in Patent Documents 4 and 5, due to their high content of highly flexible constituent units derived from dimeric diamine, exhibit good solution stability, flexibility, and low warpage. However, their modulus of elasticity may not be considered optimal. Furthermore, dimeric diamines, due to their numerous branched structures, are prone to oxidative degradation, leaving room for improvement in long-term heat resistance. Moreover, the polyimide resin proposed in Patent Document 5, with its crosslinking points concentrated at the resin ends, struggles to sufficiently increase the crosslinking density of the cured material, thus requiring further improvement in thermal dimensional stability.

[0008] This invention was made in view of the problems of the prior art. Its objective is to provide a carboxyl-modified amide resin that can be used as an adhesive for electronic components, or as a material for forming surface protective layers and insulating protective films, exhibiting excellent solution stability, elastic modulus, heat resistance, and low warpage. Furthermore, this invention aims to provide a resin composition that can form a cured material with excellent elastic modulus, thermal dimensional stability, long-term heat resistance, flexibility, and low warpage. Moreover, this invention aims to provide a multilayer having a cured layer formed using the above-mentioned resin composition that exhibits excellent solder heat resistance, and a flexible printed circuit board containing this multilayer as a constituent element. (Technical means to solve the problem)

[0009] That is, according to the present invention, a carboxyl-containing modified amide resin is provided as shown below. [1] A modified amide resin containing carboxyl groups comprises: a constituent unit derived from a polyol (a), a constituent unit derived from a polyamine (b), and a constituent unit derived from a tetracarboxylic dianhydride (c), and has the structure shown in the following general formula (X); wherein the polyamine (b) contains an aromatic diamine (b1) and a dimeric diamine (b2), and the amide bond concentration is 0.5~2.0 mmol / g.

[0010] (In the general formula (X) above, n represents a number from 0 to 20, R1 represents an organic group from tetracarboxylic acid dianhydride with the anhydride group removed, R2 represents an organic group from polyamine (b) with the amine group removed, and R3 represents an organic group from polyol (a) with the hydroxyl group removed).

[0011] [2] The carboxyl-containing modified amide resin described in [1] above, wherein the polyol (a) contains at least one selected from the group consisting of polycarbonate diol and polyester diol. [3] The modified amide resin containing carboxyl groups as described in [2] above, wherein the polyol (a) further contains a polyol (a1) that is liquid at 25°C, and the content of the constituent units derived from the polyol (a1) is 20 to 60% by mass. [4] The modified amide resin containing carboxyl groups described in any of [1] to [3] above, wherein the molar ratio (b2) / (b) of the dimeric diamine (b2) in the above polyamine (b) is 0.1 to 0.7. [5] The modified amide resin containing carboxyl groups described in any of [1] to [4] above, wherein the aromatic diamine (b1) is a compound having an aromatic ether bond, and the molecular weight of the part of the aromatic diamine (b1) other than the amino group is 240 to 500. [6] The carboxyl-containing modified amide resin described in any of [1] to [5] above, wherein the number average molecular weight is 10,000 to 50,000 and the acid value is 5 to 40 mgKOH / g.

[0012] Furthermore, according to the present invention, the following resin composition is provided. [7] A resin composition comprising a carboxyl-containing modified amide resin as described in any one of [1] to [6] above, and an epoxy resin having two or more epoxy groups in one molecule. [8] The resin composition described in [7] above further contains an organic solvent that dissolves the above-mentioned modified amide resin containing carboxyl groups and has a boiling point of 200°C or less.

[0013] Furthermore, according to the present invention, a multilayer and a flexible printed wiring board are provided as shown below. [9] A laminate is a hardened layer having the resin composition described in [7] or [8] above and hardened.

[10] A flexible printed wiring board contains the laminate described above [9] as a constituent element. (Compared to the effectiveness of previous technologies)

[0014] According to the present invention, a carboxyl-modified amide resin can be provided, which can be used as an adhesive for electronic components, or as a material for forming coatings such as surface protective layers and insulating protective films, exhibiting excellent solution stability, elastic modulus, heat resistance, and low warpage. Furthermore, according to the present invention, a resin composition can be provided that can form a cured material with excellent elastic modulus, thermal dimensional stability, long-term heat resistance, flexibility, and low warpage. Moreover, according to the present invention, a multilayer having a cured layer formed using the above-described resin composition and exhibiting excellent solder heat resistance can be provided, and a flexible printed wiring board containing this multilayer as a constituent element can be provided. Implementation

[0015] <Carboxyl-modified amide resin> The following describes embodiments of the present invention, but the present invention is not limited to these embodiments. One embodiment of the carboxyl-containing modified amide resin of the present invention (hereinafter also simply referred to as "modified amide resin") comprises: a resin having a constituent unit derived from a polyol (a), a constituent unit derived from a polyamine (b), and a constituent unit derived from a tetracarboxylic dianhydride (c), and having the structure shown in the following general formula (X); The polyamine (b) comprises an aromatic diamine (b1) and a dimerized diamine (b2). Furthermore, the amide bond concentration of the carboxyl-containing modified amide resin of this embodiment is 0.5~2.0 mmol / g. Moreover, the modified amide resin of this embodiment may be a resin substantially composed only of the structure shown in the following general formula (X), or it may be a resin further comprising a structure other than that shown in the following general formula (X). The following describes the details of the carboxyl-containing modified amide resin (modified amide resin) of this embodiment.

[0016] (In the general formula (X) above, n represents a number from 0 to 20, R1 represents an organic group from tetracarboxylic acid dianhydride with the anhydride group removed, R2 represents an organic group from polyamine (b) with the amine group removed, and R3 represents an organic group from polyol (a) with the hydroxyl group removed).

[0017] (Polyol(a)) Polyol (a) is a compound (diol) having two hydroxyl groups in its molecule. Polycarbonate diol and polyester diol are preferred as polyol (a). By using polycarbonate diol as polyol (a), cured layers and other cured products with superior heat resistance can be formed. Furthermore, by using polyester diol as polyol (a), cured layers and other cured products with superior low warpage and flexibility can be formed.

[0018] The polyol (a) preferably contains at least one selected from the group consisting of polycarbonate diol and polyester diol. Furthermore, the polyol (a) preferably further contains a polyol (a1) that is liquid at 25°C. By using a polyol (a1) that is liquid at 25°C, the viscosity of the resin solution can be reduced, and the solution stability of the modified amide resin can be further improved. Also, the polyol (a) preferably contains 30% by mass or more of the polyol (a1) that is liquid at 25°C. On the other hand, if the polyol (a) contains more than 70% by mass of the polyol that is solid at 25°C, compared to the case containing a polyol that is liquid at 25°C, the heat resistance or modulus of elasticity is improved, and the stickiness (clumping) during film formation is reduced, tending to improve processability.

[0019] In modified amide resins, the content of polyol (a1)-derived constituent units that are liquid at 25°C is preferably 20-60% by mass, more preferably 25-55% by mass, and especially preferably 30-50% by mass. If the content of polyol (a1)-derived constituent units that are liquid at 25°C is less than 20% by mass, the improvement effect on low warpage and bending performance is insufficient. On the other hand, if the content of polyol (a1)-derived constituent units that are liquid at 25°C exceeds 60% by mass, the heat resistance or modulus of elasticity is slightly reduced.

[0020] As a polycarbonate diol, a reaction product of a dialkyl carbonate such as dimethyl carbonate and a diol compound having two hydroxyl groups in its molecule can be used. Alternatively, commercially available polycarbonate diols can also be used. Examples of diol compounds include linear diols with 2 to 10 carbon atoms or those having side chains.

[0021] Examples of diol compounds include aliphatic and alicyclic diols. Examples of aliphatic diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, and 2-methyl-1,8-octanediol. Examples of alicyclic diols include 1,4-cyclohexanediol. From the viewpoint of improving the flexibility of modified amide resin, aliphatic diols are preferred, and more preferably 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentanediol, and 3-methyl-1,5-pentanediol.

[0022] Examples of polyester diols include at least one aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, polymerized with low molecular weight diols. Examples of aliphatic dicarboxylic acids include succinic acid, adipic acid, sebacic acid, glutaric acid, and azelaic acid. Examples of aromatic dicarboxylic acids include isophthalic acid and p-phthalic acid. Examples of low molecular weight diols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 3-methylpentanediol, 1,6-hexanediol, neopentanediol, and 1,4-dihydroxymethylcyclohexane.

[0023] As the polyol (a), other polymeric polyols besides the aforementioned polycarbonate diol or polyester diol can also be used. Examples of other polymeric polyols include polyether polyols, polylactone polyols, and dimerized diols. Furthermore, short-chain polyols with a molecular weight of 300 or less can also be used. Moreover, by appropriately using short-chain polyols, the acid value of the modified amide resin can be adjusted.

[0024] The number average molecular weight (Mn) of the polyol (a) is preferably 350-3,500, and more preferably 400-3,000. If the number average molecular weight (Mn) of the polyol (a) is less than 300, the acid value of the modified amide resin will increase, and the warpage of the modified amide resin or the cured product will easily decrease (become prone to warping). On the other hand, if the number average molecular weight (Mn) of the polyol (a) exceeds 3,500, it will be difficult to increase the acid value of the modified amide resin, and the heat resistance of the cured product will decrease.

[0025] (Polyamine(b)) The polyamine (b) comprises an aromatic diamine (b1) and a dimeric diamine (b2). Preferably, the polyamine (b) is substantially composed only of an aromatic diamine (b1) and a dimeric diamine (b2). By using the polyamine (b), amide bonds can be introduced into the resin.

[0026] By introducing amide bonds derived from aromatic diamine (b1), the tensile elastic modulus, thermal dimensional stability, and long-term heat resistance of the resulting modified amide resin or its composition can be improved. However, if only amide bonds derived from aromatic diamine (b1) are introduced, or if an excessive amount of amide bonds derived from aromatic diamine (b1) are introduced, the warpage and flexural properties of the modified amide resin are easily reduced.

[0027] In contrast, the modified amide resin of this embodiment not only incorporates amide bonds derived from aromatic diamine (b1), but also amide bonds derived from dimeric diamine (b2), thereby improving warpage, flexibility, and solution stability. Furthermore, depending on the type of solvent used, insufficient introduction of amide bonds derived from dimeric diamine (b2) can result in a cloudy amide resin solution. Moreover, if only amide bonds derived from dimeric diamine (b2) are introduced, or if an excessive amount of amide bonds derived from dimeric diamine (b2) are introduced, the long-term heat resistance may easily decrease due to the oxidative degradation of the dimeric diamine containing more divergent structures.

[0028] The molar ratio (b2) / (b) of the dimeramine (b2) in the polyamine (b) is 0.1~0.7, preferably 0.15~0.6, and particularly preferably 0.3~0.5. If the molar ratio (=(b2) / (b)) of the dimeramine (b2) in the polyamine (b) exceeds 0.7, the elastic modulus or the long-term heat resistance of the hardened material may easily decrease. On the other hand, if the above molar ratio (=(b2) / (b)) is less than 0.1, the warpage or flexibility may easily decrease.

[0029] Examples of aromatic diamines (b1) include 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,3'-diaminodiphenyl sulfone, 1,5-diaminonaphthalene, m-phenylenediamine, p-phenylenediamine, 3,3'-dimethyl-4,4'-biphenyldiamine, benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenylpropane, 2,4-diaminotoluene, bis(4-amino- 3-Carboxyphenyl)methane, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]phenyl, bis-p-(1,1-dimethyl-5-amino-pentyl)benzene, 1-isopropyl-2,4-m-phenylenediamine, m-toluenediamine, p-toluenediamine, 4,4'-methylenebis(2,6-dimethylamine), and α,α'-bis(4-aminophenyl)-1,4-diisopropylbenzene, etc.

[0030] Aromatic diamines (b1) are preferably compounds containing aromatic ether bonds. Furthermore, the molecular weight of the portion of the aromatic diamine (b1) excluding the amino group is 240-500. If an aromatic diamine without aromatic ether bonds and whose molecular weight of the portion excluding the amino group is less than 240 is used, the distance between the amide bonds in the resulting modified amide resin becomes shorter, and the solution stability tends to decrease due to the cohesive force between the amide bonds. Also, the heat resistance tends to decrease due to the increased proportion of polyols. On the other hand, if an aromatic diamine with a molecular weight of more than 500 in the portion excluding the amino group is used, the proportion of aromatic diamines in the resulting modified amide resin tends to decrease, resulting in reduced warpage or bendability.

[0031] Examples of aromatic diamines (b1) having an aromatic ether bond and a molecular weight of 240-500 in the portion other than the amino group include 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, and bis[4-(4-aminophenoxy)phenyl]phenoxide. Using these aromatic diamines (b1) with appropriately separated aniline structures at both ends can effectively suppress the occurrence of turbidity or precipitation during synthesis.

[0032] The modified amide resin may, as needed, further contain constituent units derived from polyamines (other polyamines (diamines)) other than aromatic diamines (b1) and dimerized diamines (b2). Examples of other polyamines include cyclic aliphatic diamines and chain aliphatic diamines.

[0033] Examples of cyclic aliphatic diamines include di(p-aminocyclohexyl)methane, 1,4-diaminocyclohexane, 1,3-diaminomethylcyclohexane, isophorone diamine, and norethane diamine. Furthermore, examples of chain-like aliphatic diamines include hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, diaminopropyltetramethylene, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 2,11-diaminododecane, 1,2-bis-3-aminopropoxyethane, 2,2-dimethylpropanediamine, 3-methoxyhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 3-methylheptamethylenediamine, 5-methylnonamethylenediamine, 2,17-diaminoeicosane, 1,10-diamino-1,10-dimethyldecane, and 1,12-diaminooctadecane.

[0034] (Tetracarboxylic dianhydride (c)) Examples of tetracarboxylic dianhydrides (C) (hereinafter also simply referred to as "anhydride (C)") include esters of benzotriglycerides and ethylene glycol, 4,4'-(4,4'-isopropylidenedidiphenoxy)phthalic anhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, pyrocalcite dianhydride, 3,3',4,4'-diphenylketone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl tannic acid tetracarboxylic dianhydride, 3,4' 4,4'-Oxydiphthalic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, ethylene glycol bis(benzotriptamine), p-phenyl bis(benzotriptamine), cyclobutanetetracarboxylic anhydride, methylcyclobutanetetracarboxylic anhydride, cyclopentanetetracarboxylic anhydride, 1,2,4,5-cyclohexanetetracarboxylic anhydride, ethanetetracarboxylic anhydride, and 3,3',4,4'-bicyclohexyltetracarboxylic anhydride, etc.

[0035] From the perspective of heat resistance, the preferred acid anhydride (c) is an ester of benzotriglyceride and ethylene glycol, 4,4'-(4,4'-isopropylidene diphenoxy) phthalic anhydride, 3,3',4,4'-biphenyltetracarboxylic anhydride, 3,3',4,4'-diphenoxyketone tetracarboxylic anhydride, 3,3',4,4'-diphenyltrimethyltetracarboxylic anhydride, and 4,4'-oxophthalic anhydride.

[0036] (Polyisocyanate) The modified amide resin of this embodiment may further have constituent units containing urethane bonds derived from polyisocyanate. That is, the modified amide resin of this embodiment preferably has the structure shown in the following general formula (Y), or may be substantially composed only of the structure shown in the following general formula (Y). By having constituent units with urethane bonds (urethane modification), the compatibility with epoxy resin can be improved. Furthermore, by extending the polyisocyanate into urethane, the molecular weight can be easily adjusted to any value. The polyisocyanate is preferably a diisocyanate having two isocyanate groups in its molecule. Examples of diisocyanates include aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates.

[0037] (In the general formula (Y) above, n represents a number from 0 to 20, m represents a number from 1 to 5, R1 represents an organic group from tetracarboxylic dianhydride with the anhydride group removed, R2 represents an organic group from polyamine (b) with the amine group removed, R3 represents an organic group from polyol (a) with the hydroxyl group removed, and R4 represents an organic group from polyisocyanate with the isocyanate group removed).

[0038] Examples of aromatic diisocyanates include toluene diisocyanate, 4-methoxy-1,3-phenyl diisocyanate, 4-isopropyl-1,3-phenyl diisocyanate, 4-chloro-1,3-phenyl diisocyanate, 4-butoxy-1,3-phenyl diisocyanate, 2,4-diisocyanate diphenyl ether, diphenylmethane diisocyanate, tetramethyl diisocyanate, xylene diisocyanate, 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, and 4,4'-diisocyanate dibenzyl, etc.

[0039] Examples of aliphatic diisocyanates include methylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, and 1,10-decamethylene diisocyanate.

[0040] Examples of alicyclic diisocyanates include 1,4-cyclohexyl diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), 1,5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated xylene diisocyanate.

[0041] From the perspective of reactivity, preferred polyisocyanates are diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), 1,6-hexamethylene diisocyanate (HDI), 1,5-pentamethylene diisocyanate (PDI), and hydrogenated diphenylmethane diisocyanate (HMDI).

[0042] (Carboxyl-modified amide resin) The modified amide resin of this embodiment, having constituent units derived from polyamines (b) including aromatic diamines (b1) and dimerized diamines (b2), exhibits superior elastic modulus, low warpage, and solution stability, and can form cured products with excellent elastic modulus, flexibility, and long-term heat resistance. Furthermore, because the modified amide resin of this embodiment has carboxyl groups on the side chains of its polymer chains that serve as epoxy reaction sites, compared to amide resins with crosslinking sites such as carboxyl groups or anhydride groups at the ends of the polymer chains, the cured product obtained by curing with epoxy resin has a higher crosslinking density, resulting in cured layers and other cured products with superior thermal dimensional stability.

[0043] In modified amide resins, the concentration of amide bonds (constituent units derived from polyamine(b)) is 0.5–2.0 mmol / g, preferably 0.7–1.8 mmol / g, and more preferably 0.8–1.7 mmol / g. If the amide bond concentration is less than 0.5 mmol / g, heat resistance and elastic modulus decrease. Conversely, if the amide bond concentration exceeds 2.0 mmol / g, solution stability or low warpage decreases.

[0044] The "acetylinium bond concentration" in this specification refers to the amount of acetylinium bonds per 1g of modified acetylinium resin (mmol). Furthermore, the "acetylinium bond" in this specification does not include bonds derived from the reaction between the acid anhydride and the polyamine (b). The acetylinium bond concentration of the modified acetylinium resin can be controlled, for example, by adjusting the amount (mol) of the polyamine (b) and the amount (g) of the packed solids containing the polyol (a) and tetracarboxylic dianhydride (c). The theoretical value of the acetylinium bond concentration of the modified acetylinium resin can be calculated using the following formula (A). The theoretical concentration of amide bonds in modified amide resin = A1 × N1 × 1,000 / C1 ･･･(A) A1: Amount of polyamine (b) (mol) N1: The number of amine groups in polyamine (b) C1: Filling solids content (g)

[0045] When the modified amide resin contains the structure shown in general formula (Y), the concentration of amide bonds in the modified amide resin is preferably 1.0 mmol / g or less, and more preferably 0.5 mmol / g or less. If the concentration of amide bonds in the modified amide resin exceeds 1.0 mmol / g, the heat resistance may easily decrease.

[0046] The term "amide bond concentration" refers to the amount (mmol) of urethane bonds per 1g of modified amide resin. The amide bond concentration of the modified amide resin can be controlled by adjusting, for example, the amount (mol) of polyisocyanate and the filler solids (g) containing polyol (a) and tetracarboxylic dianhydride (c). Furthermore, the theoretical value of the amide bond concentration of the modified amide resin can be calculated using the following formula (B). Theoretical concentration of urethane bonds in modified amide resin = A² × N² × 1,000 / C² ･･･(B) A2: Amount of polyisocyanate (mol) N2: The number of isocyanate groups in polyisocyanate. C2: Enter the solid content (g)

[0047] The number average molecular weight (Mn) of the modified amide resin is preferably 10,000 to 50,000, and more preferably 12,000 to 45,000. If the number average molecular weight of the modified amide resin is less than 10,000, the film-forming properties are slightly reduced, and the heat resistance of the hardened layer and other cured products is reduced. On the other hand, if the number average molecular weight of the modified amide resin exceeds 50,000, the solubility in organic solvents is reduced.

[0048] In this specification, the "number average molecular weight (Mn)" of the resin refers to the polystyrene equivalent value determined by gel permeation chromatography (GPC). GPC is performed, for example, using the following apparatus and conditions.

[0049] (1) Machine device: Trade name "HLC-8020" (manufactured by Tosoh Corporation) (2) Tube Columns: Trade names "TSKgel G2000HXL", "G3000HXL", "G4000GXL" (manufactured by Tosoh Corporation) (3) Solvent:THF (4) Flow rate: 1.0 mL / min (5) Sample concentration: 2 g / L (6) Injection volume: 100 μL (7) Temperature: 40℃ (8) Detector: Model "RI-8020" (manufactured by Tosoh Corporation) (9) Standard material: TSK standard polystyrene (manufactured by Tosoh Corporation)

[0050] The preferred acid value of modified amide resin is 5-40 mgKOH / g. If the acid value of the modified amide resin is above 5 mgKOH / g, the crosslinking density of the hardened product (crosslinked product) formed by reacting with hardeners such as epoxy resin increases, further improving the heat resistance or thermo-dimensional stability of the hardened product. Conversely, if the acid value of the modified amide resin is below 40 mgKOH / g, excessively high crosslinking density in the hardened product (crosslinked product) formed by reacting with hardeners such as epoxy resin can be prevented. This suppresses strain and further improves the low warpage or bending resistance of the hardened product. Furthermore, an acid value of 10-35 mgKOH / g is preferred because it is easier to adjust the crosslinking density of the hardened product (crosslinked product) to an appropriate range. An acid value of 15-25 mgKOH / g is particularly preferred because it easily achieves the optimal crosslinking density.

[0051] The acid value (measured value) of modified amide resin can be determined by using a solution prepared by dissolving the modified amide resin in an organic solvent such as methyl ethyl ketone (MEK) as a sample, according to the method in JIS K1557-5:2007.

[0052] (Method for manufacturing carboxyl-modified amide resin) Modified amide resins can be manufactured, for example, by a manufacturing method comprising steps (1) and (2) shown below. Steps (1) and (2) can be performed simultaneously. Furthermore, step (2) may further comprise: reacting polyisocyanate with the hydroxyl groups present at the ends of the obtained modified amide resin to introduce amide bonds. Step (1): Reaction of tetracarboxylic acid dianhydride (c) with polyamine (b) to obtain amide oligomers with anhydride terminals. Step (2): React the anhydride-terminated amide oligomer obtained in step (1) with polyol (a) to obtain a carboxyl-modified amide resin.

[0053] The specific procedure for manufacturing the modified amide resin according to this embodiment is illustrated below. First, a polyamine (b), a tetracarboxylic acid dianhydride (c), and an organic solvent are mixed and reacted at 130-160°C for approximately 1-7 hours with stirring to obtain an amide oligomer with an anhydride group at its end. Next, a polyol (a) is added with a molar ratio of anhydride group to hydroxyl group (= anhydride group / hydroxyl group) of approximately 0.5-1.0 (preferably 0.7-1.0 when no carbamate modification is performed, and preferably 0.5-0.7 when carbamate modification is performed), and the reaction is carried out at 50-150°C for approximately 1-12 hours. Subsequently, the mixture is diluted with an organic solvent as needed and cooled to obtain the target carboxyl-containing modified amide resin in the form of a resin solution. Furthermore, the molar ratio of anhydride groups to hydroxyl groups (= anhydride group / hydroxyl group) determines the acid value of the modified amide resin containing carboxyl groups. For example, if the molar ratio of anhydride group to hydroxyl group is less than 0.5 or more than 1.0, the molecular weight of the modified amide resin containing carboxyl groups cannot be sufficiently extended, resulting in reduced flexibility.

[0054] As the organic solvent, it is preferable to use an organic solvent that does not substantially react with any of the polyols (a), polyamines (b), and tetracarboxylic dianhydrides (c). Preferably, an organic solvent with a boiling point below 200°C is used. By using an organic solvent with a boiling point below 200°C for reaction and dilution, the resulting resin solution can be directly used as a coating or composition, and can be dried or hardened at low temperature and in a short time.

[0055] Examples of organic solvents with a boiling point below 200°C include toluene, cyclohexane, methylcyclohexane, ethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl acetate, n-butyl acetate, isoamyl acetate, acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, dimethyl carbonate, tetrahydrofuran, and dimethyl ether. Among these, toluene, methyl ethyl ketone, dimethyl carbonate, cyclopentanone, and cyclohexanone are preferred from the viewpoint of the solubility and ease of drying of the modified amide resin; toluene, methyl ethyl ketone, cyclohexanone, and dimethyl carbonate are even more preferred.

[0056] <Resin Composition> One embodiment of the resin composition of the present invention comprises the above-mentioned modified amide resin containing carboxyl groups and an epoxy resin having two or more epoxy groups per molecule. That is, by reacting and curing the above-mentioned modified amide resin with the epoxy resin, which is a curing agent, a cured product with excellent elastic modulus, thermal dimensional stability, long-term heat resistance, flexibility, and low warpage can be formed.

[0057] Epoxy resins used as curing agents have two or more epoxy groups per molecule. Examples of such epoxy resins include bisphenol A type epoxy resins, hydrogenated bisphenol A type epoxy resins, bisphenol F type epoxy resins, brominated bisphenol A type epoxy resins, phenolic varnish type epoxy resins, o-cresol phenolic varnish type epoxy resins, flexible epoxy resins, epoxidized polybutadiene, amino epoxy resins, heterocyclic epoxy resins, alicyclic epoxy resins, bisphenol S type epoxy resins, dicyclopentadiene type epoxy resins, triglycidyl triisocyanate, bixylenol type epoxy resins, and compounds containing glycidyl groups.

[0058] The epoxy equivalent of epoxy resin is determined from the perspective of the mechanical strength, flexibility and heat resistance of the hardened product formed, and is preferably 100~10,000 g / eq, more preferably 100~600 g / eq.

[0059] The number average molecular weight (Mn) of the epoxy resin is preferably 100 to 100,000, and more preferably 300 to 70,000, from the perspective of compatibility with the modified amide resin to which it is reacted.

[0060] By adjusting the molar ratio of epoxy groups in the epoxy resin to carboxyl groups in the modified amide resin, a cured product with desired properties can be prepared. For example, it is preferable to react the epoxy resin and the modified amide resin with an epoxy group / carboxyl group (molar ratio) of 10 / 1 to 1 / 2. If the molar ratio is outside the above range, the crosslinking property may be reduced, and the thermal dimensional stability of the resulting cured product may be slightly reduced.

[0061] In the resin composition, the epoxy resin content is preferably 5 to 200 parts by weight, and more preferably 10 to 100 parts by weight, relative to 100 parts by weight of modified amide resin (solids). By setting the epoxy resin content to 5 parts by weight or more relative to 100 parts by weight of modified amide resin, the crosslinking property becomes better. Furthermore, by setting the epoxy resin content to 200 parts by weight or less relative to 100 parts by weight of modified amide resin, the crosslinking property is less likely to decrease, and the heat resistance of the resulting cured product can be further improved.

[0062] The resin composition can be prepared by mixing epoxy resin and the modified amide resin in the required proportions. During preparation, mixing can be performed in the presence of the aforementioned organic solvent, or by adding epoxy resin to a solution of the modified amide resin. That is, the resin composition of this embodiment may further contain an organic solvent. By using an organic solvent, it can be used as a coating composition. As a coating composition, it can be dried and cured at low temperatures, and can be used as an adhesive with excellent heat resistance and adhesion properties. Such a coating composition can be used, for example, as an adhesive for electronic components, or as a coating composition for forming insulating protective films. Furthermore, the coating composition can be used in applications such as solder resists, electromagnetic wave shielding films, and coatings, or as an adhesive for flexible printed wiring boards (substrates), conductive adhesives, and adhesives for structural materials.

[0063] The organic solvent is preferably one that can dissolve either epoxy resin or modified amide resin. If it is intended for use as a coating component, it is preferable to use an organic solvent with a boiling point below 200°C, and more preferably a non-nitrogen-based organic solvent with a boiling point below 200°C. By using an organic solvent with a boiling point below 200°C, drying and curing can be carried out at lower temperatures.

[0064] As organic solvents, the same organic solvents used in the manufacture of modified amide resins can be used. Specifically, toluene, cyclohexane, methylcyclohexane, ethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl acetate, n-butyl acetate, isoamyl acetate, acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, and dimethyl carbonate can be used. Among these, from the viewpoint of the solubility of epoxy resins or modified amide resins and the drying efficiency when used as a coating component, toluene, methyl ethyl ketone, cyclohexanone, and dimethyl carbonate are preferred.

[0065] The resin composition may further contain other components besides the aforementioned modified amide resin, epoxy resin, and organic solvent, as needed. Examples of such other components include curing accelerators, isocyanate crosslinking agents, thermoplastic polymers, adhesive-improving resins, pigments, antioxidants, UV absorbers, surfactants, and fillers.

[0066] The resin composition of this embodiment is preferably coated onto a desired substrate and then cured by holding it at a temperature of 40-200°C, more preferably 130-180°C.

[0067] <Laminated Fabrics and Flexible Printed Wiring Boards> One embodiment of the laminate of the present invention includes a hardening layer for curing the aforementioned resin composition. Furthermore, one embodiment of the flexible printed wiring board of the present invention includes this laminate as a constituent element.

[0068] The aforementioned resin composition containing organic solvents can be used as a coating composition. For example, the coating composition can be applied to a release film by methods such as screen printing, spraying, roller coating, electrostatic coating, and curtain coating to form a coating film with a thickness of 5-80 μm. Then, the organic solvent is removed by maintaining a temperature of 0-180°C for 3-10 minutes, allowing the coating film to dry. This yields an adhesive film that is a dried film. The coating film can be dried in air or in an inert gas environment. Furthermore, to adjust the flowability during hot pressing, a heat treatment can be performed after drying to partially react the modified amide resin with the hardener. This state before hot pressing is generally referred to as Stage B.

[0069] The multilayer structure of this embodiment is suitable as a component of flexible printed circuit boards (FPCs). Among the constituent layers of the FPC, those formed by the aforementioned resin composition (coating composition (adhesive)) or multilayer structure can be, for example, CL (protective layer) film, adhesive film, and three-layer copper foil multilayer board.

[0070] Since CL films and adhesive films are generally processed by winding, storing, cutting, and punching in the B-stage state, they must be flexible in the B-stage state. Furthermore, after the film in the B-stage state is heat-pressed with the substrate, a hardened layer is formed by heat curing.

[0071] CL films are, for example, composed of "insulating plastic film / adhesive layer" or "insulating plastic film / adhesive layer / protective film". The insulating plastic film is a film with a thickness of 1 to 200 μm formed from plastics such as polyimide, polyimide urethane, polyester, polyphenylene sulfide, polyether ether, polyether ether ketone, arylamine, polycarbonate, and polyarylate. Furthermore, these films can also be laminated in multiple layers.

[0072] The protective film is preferably a film that can be peeled off without impairing the adhesive properties. Examples of protective films include films made of plastics such as polyethylene, polypropylene, polyolefins, polyester, polymethylpentene, polyvinyl chloride, polyvinylidene fluoride, and polyphenylene sulfide; films coated with polysiloxane, fluorides, and other release agents; paper laminated with such films; and paper impregnated or coated with a release-resistant resin.

[0073] The adhesive film has a structure in which a protective film is provided on at least one side of the adhesive layer formed of a resin composition (coating composition), for example, it is composed of "protective film / adhesive layer" or "protective film / adhesive layer / protective film". There are also cases where an insulating plastic film layer is provided in the adhesive layer. Furthermore, the adhesive film can be used in multilayer printed circuit boards.

[0074] Three-layer copper foil laminate has a structure in which copper foil is bonded to at least one side of an insulating plastic film via an adhesive layer formed by a resin composition (coating composition). The copper foil used is, for example, rolled copper foil or electrolytic copper foil conventionally used in flexible printed wiring boards. The resin composition (coating composition) serves as a solder resist layer, surface protective layer, interlayer insulating layer, or adhesive layer of the FPC.

[0075] The resin composition (coating composition) of this embodiment can be used as a material for constructing protective coating inks, solder resist inks, and interlayer insulating films for semiconductor components and various electronic components. It can also be used as a coating, coating agent, and adhesive. Solder resist ink is an ink used with a solder resist layer. The solder resist layer is a film formed on the entire circuit conductor after the solder portion has been removed. When wiring electronic components on a printed circuit board, it can prevent solder from adhering to unnecessary parts and functions as a protective film to prevent the circuit from being directly exposed to the air.

[0076] Surface protective layers are layers used to mechanically and chemically protect electronic components during bonding processes or in the environment of use. Interlayer insulating layers (films) are layers (films) used to prevent electrical conduction between layers with fine wiring formed in the packaging substrate. Adhesive layers mainly bond metal layers to thin film layers and are used during bonding processes. [Example]

[0077] The present invention will be described in detail below with reference to the embodiments, but the present invention is not limited to these embodiments. Furthermore, unless otherwise specified, "parts" and "%" in the embodiments and comparative examples are mass measurements.

[0078] <Materials Preparation> Prepare the materials shown below.

[0079] (Polyol(a)) • PH-50: Trade name "ETHANACOL PH-50", manufactured by UBE Corporation, polyhexamethylene / pentamethylene copolymer carbonate diol, quantity average molecular weight 508, liquid at 25°C • PH-100: Trade name "ETHANACOL PH-100", manufactured by UBE Corporation, polyhexamethylene / pentamethylene copolymer carbonate diol, quantity average molecular weight 984, liquid at 25°C • PH-200: Trade name "ETHANACOL PH-200", manufactured by UBE Corporation, polyhexamethylene / pentamethylene copolymer carbonate diol, quantity average molecular weight 1,968, liquid at 25°C • PH-300: Trade name "ETHANACOL PH-300", manufactured by UBE Corporation, polyhexamethylene / pentamethylene copolymer carbonate diol, quantity average molecular weight 2,914, liquid at 25°C • UH-100: Trade name "ETHANACOL UH-100", manufactured by UBE Corporation, polyhexamethylene carbonate diol, quantity average molecular weight 1,000, solid at 25°C • UH-200: Trade name "ETHANACOLUH-200", manufactured by UBE Corporation, polyhexamethylene carbonate diol, quantity average molecular weight 1,958, solid at 25°C • P-1050: Trade name "Kuraray Polyol P1050", manufactured by Kuraray Corporation, 3-methyl-1,5-pentanediol / sebacic acid polyester diol, quantity average molecular weight 989, liquid at 25°C • P-2050: Trade name "Kuraray Polyol P2050", manufactured by Kuraray Corporation, 3-methyl-1,5-pentanediol / sebacic acid based polyester diol, quantity average molecular weight 1,941, liquid at 25°C • 1,6-HD: 1,6-hexanediol, solid at 25°C

[0080] (Aromatic diamine (b1)) • BAPP: 2,2-bis[4-(4-aminophenoxy)phenyl]propane, molecular weight 410 (378 for the portion excluding the amino group) • TPE-R: 1,3-bis(4-aminophenoxy)benzene, molecular weight 292 (260 for the portion excluding the amino group) • ODA: 4,4'-Diaminodiphenyl ether, molecular weight 200 (molecular weight of the portion excluding the amino group is 168)

[0081] (dimeric diamine (b2)) • P1074: Trade name "PRIAMINE 1074", manufactured by CRODA, dimeric diamine, quantity average molecular weight 529

[0082] (Aliphatic diamine) • 1,3-BAC: 1,3-Diaminomethylcyclohexane, quantity average molecular weight 142.25

[0083] (acid anhydride(c)) ‧BPADA: 4,4'-(4,4'-isopropylidene diphenoxy)phthalic anhydride ‧BPDA: 3,3',4,4'-Biphenyltetracarboxylic acid dianhydride

[0084] (Polyisocyanate) • TDI: Toluene-2,4-diisocyanate • MDI: Diphenylmethane diisocyanate

[0085] (hardener) • Epoxy Resin A: Trade name "jER828", manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin, epoxy equivalent 184 g / eq, quantity average molecular weight 368

[0086] <Manufacturing of Modified Imino Resin> (Example 1) In a separating flask equipped with a stirrer, 26.0 parts (0.06 mol) of BAPP, 26.0 parts (0.05 mol) of P1074, 85.6 parts (0.16 mol) of BPADA, and 58.5 parts of cyclohexanone were added. The mixture was reacted at 150°C for 3 hours to obtain a nitriloimide oligomer with anhydride groups at the ends. After dilution with 97.5 parts of cyclohexanone, 100.0 parts (0.05 mol) of PH-200 and 0.5 parts (0.004 mol) of 1,6-HD were added, and the mixture was reacted at 120°C for 5 hours. After the absorption at 1,850 cm⁻¹ from the free anhydride groups disappeared by infrared absorption spectroscopy, 195.1 parts of cyclohexanone were added for further dilution, and the mixture was cooled to room temperature to obtain a solution of modified nitriloimide resin A with a solids concentration of 40%. The number average molecular weight (Mn) of the modified amide resin A is 15,000, and the acid value (measured value) is 25 mgKOH / g.

[0087] (Example 9) In a separating flask equipped with a stirrer, 31.0 parts (0.08 mol) of BAPP, 31.0 parts (0.06 mol) of P1074, 115.0 parts (0.20 mol) of BPADA, and 69.6 parts (69.6 mol) of cyclohexanone were added. The mixture was reacted at 150 °C for 3 hours to obtain an amide oligomer with an anhydride group at the end. After dilution with 116.0 parts (69.6 mol) of cyclohexanone, 100.0 parts (0.1 mol) of PH-100 were added, and the mixture was reacted at 120 °C for 5 hours. After the absorption at 1,850 cm⁻¹ from the free anhydride group disappeared by infrared absorption spectroscopy, 6.3 parts (0.04 mol) of TDI were added, and the mixture was reacted at 90 °C for 2 hours. Infrared absorption spectroscopy analysis confirmed the disappearance of the absorption at 2,270 cm⁻¹ from the free isocyanate groups. After dilution with 232.0 parts of cyclohexanone and cooling to room temperature, a solution of modified amide resin I with a solid content of 40% and containing carbamate bonds was obtained. The number average molecular weight (Mn) of modified amide resin I was 25,000, and the measured acid value was 25 mg KOH / g.

[0088] (Comparative Example 1) In a separating flask equipped with a stirrer, 70.0 parts (0.13 mol) of P1074, 99.6 parts (0.19 mol) of BPADA, and 66.6 parts (66.6 mol) of cyclohexanone were added. The mixture was reacted at 150°C for 3 hours to obtain a nitriloimide oligomer with anhydride groups at the ends. After dilution with 110.9 parts (60.9 mol) of cyclohexanone, 100.0 parts (0.10 mol) of PH-200 and 1.4 parts (0.01 mol) of 1,6-HD were added, and the mixture was reacted at 120°C for 5 hours. After the absorption at 1,850 cm⁻¹ from the free anhydride groups disappeared by infrared absorption spectroscopy, 221.9 parts (60.9 mol) of cyclohexanone were added for further dilution, and the mixture was cooled to room temperature to obtain a solution of modified nitriloimide resin AA with a solids concentration of 40%. The modified acetilimide resin AA has a number average molecular weight (Mn) of 15,000 and an acid value (measured value) of 25 mgKOH / g.

[0089] (Comparative Example 7: Reaction of acid anhydrides with isocyanates) 85.7 parts (0.16 mol) of BPADA, 30.0 parts (0.12 mol) of MDI, and 50.4 parts of cyclohexanone were added to a dispersion flask equipped with a stirrer. 0.1 parts of diazabicycloundecene (DBU) was added as a catalyst, and the mixture was reacted at 150°C for 8 hours to obtain amide resin. After dilution with 84.1 parts of cyclohexanone, 92.0 parts (0.05 mol) of PH-200 were added, and the mixture was reacted at 120°C for 5 hours. However, the resin became insoluble and could not be obtained.

[0090] (Comparative Example 8: Imide resin with crosslinking points at the ends) In a dispersion flask equipped with a stirrer, 50 parts (0.09 mol) of P1074, 50 parts (0.12 mol) of BAPP, 139.2 parts (0.27 mol) of BPADA, and 154.3 parts of cyclohexanone were added, and the mixture was reacted at 150°C for 5 hours. After dilution with 189.2 parts of cyclohexanone, the mixture was cooled to room temperature to obtain a 40% solids concentration solution of modified amide resin HH. This modified amide resin HH is a modified amide resin with anhydride groups at its ends. The number average molecular weight (Mn) of the modified amide resin HH is 15,000, and the theoretical valence of the anhydride group is 12.5 mgKOH / g.

[0091] (Examples 2-8, 11-17) Except for the formulations shown in Tables 1-1 and 1-2 (unit: parts), the process was the same as in Example 1 above, to obtain solutions of modified amide resins B~H and K~Q (solid content concentration of 40%). The physical properties of the modified amide resins are shown in Tables 1-1 and 1-2.

[0092] (Example 10) Except for the formulation shown in Table 1-2 (unit: parts), the process was the same as in Example 9 above to obtain a solution of modified amide resin J. The physical properties of the modified amide resin are shown in Table 1-2.

[0093] (Comparative Examples 2-6) Except for the formulations shown in Table 1-3 (unit: parts), the process was the same as in Comparative Example 1 above, yielding solutions of modified amide resins BB~FF. The physical properties of the modified amide resins are shown in Table 1-3. Furthermore, regarding Comparative Example 3 (modified amide resin CC), insolubility occurred during the reaction. Regarding Comparative Examples 4 and 6 (modified amide resins DD and FF), turbidity or precipitation occurred during the reaction.

[0094] Evaluation of Modified Imino Resins The solution stability, elastic modulus, heat resistance, and low warpage of modified amide resins were evaluated below. The results are shown in Tables 1-1 to 1-3. Furthermore, regarding the elastic modulus, heat resistance, and low warpage, only modified amide resins other than CC and GG that became insoluble during synthesis, and modified amide resins other than DD and FF that exhibited turbidity or precipitation, were evaluated.

[0095] (Solution stability) The stability of the solution during and after synthesis was evaluated according to the following evaluation criteria. ○: After the obtained solution was stored at 25°C for 1 week, no turbidity or precipitation occurred. ×: Turbidity or precipitates may occur during synthesis.

[0096] (elasticity coefficient) A solution of modified amide resin was coated onto release paper to a thickness of 40 μm after drying, and then dried at 150°C for 10 minutes to form a coating film (dried film). The formed coating film was cut into pieces with dimensions of 60 mm long × 15 mm wide to obtain test pieces. Tensile tests according to JIS K-7127:1999 were performed on the obtained test pieces using a universal testing machine (trade name "AGS-J", manufactured by Shimadzu Corporation) at room temperature (25°C). The tensile elastic modulus of the test pieces was then measured, and the elastic modulus was evaluated according to the evaluation criteria shown below. ◎: The tensile elastic modulus is above 600 N / mm2. ○: Tensile elasticity coefficient is above 180 N / mm2 but less than 600 N / mm2. △: Tensile elasticity coefficient is above 100 N / mm2 but less than 180 N / mm2. ×: Tensile elasticity coefficient is less than 100 N / mm2.

[0097] (Heat resistance) A solution of modified amide resin was coated onto release paper to a thickness of 40 μm after drying, and then dried at 150°C for 10 minutes to form a coating film (dried film). Next, using TG-DTA (trade name "TG8120", manufactured by RIGAKU), the temperature was increased from room temperature at a rate of 10°C / min in dry air at a flow rate of 100 mL / min to obtain the TG-DTA curve. Then, the temperature at which 10% mass is lost (10% decomposition temperature) was monitored, and the heat resistance was evaluated according to the evaluation criteria shown below. ○: 10% decomposition temperature is above 335℃. △: 10% decomposition temperature is above 330℃ but below 335℃. ×: 10% decomposition temperature is less than 330℃.

[0098] (Low warpage) A solution of modified amide resin was coated onto a 50 μm thick polyamide film to a dry thickness of 20 μm, and then dried at 150°C for 10 minutes to form a coating (dried film). The formed coating was cut into 5 cm × 5 cm pieces, heated to 25°C, placed on a horizontal glass plate, and the average warpage height at the four corners was measured. Low warpage (resistance to warping) was evaluated according to the following criteria. ◎: The average height is less than 2mm. ○: The average height is 2mm or more but less than 4mm. △: The average height is 4mm or more but less than 10mm. ×: The average height is 10mm or more but less than 15mm.

[0099] [Table 1-1] Example 1 2 3 4 5 6 7 8 9 Modified amide resin A B C D E F G H I Polyols (a) (a1)PH-50 (a1)PH-100 65.0 100.0 (a1)PH-200 100.0 100.0 100.0 35.0 92.0 (a1)PH-300 8.0 UH-100 100.0 UH-200 100.0 (a1)P-1050 (a1)P-2050 100.0 1,6-HD 0.5 1.0 0.6 0.6 Hsieh Amine Chengcheng point Aromatic diamines (b1) BAPP 26.0 80.7 60.0 43.0 20.0 70.0 15.0 27.0 31.0 TPE-R ODA Dimeric diamine (b2) P1074 26.0 80.7 60.0 12.0 35.0 70.0 15.0 27.0 31.0 Aliphatic diamine 1,3-BAC Polyisocyanate MDI Acid anhydride (c) BPADA 85.6 231.4 158.9 98.0 87.5 111.3 54.9 88.4 115.0 BPDA Polyisocyanate TDI 6.3 Position of reactive functional groups side chain side chain side chain side chain side chain side chain side chain side chain side chain Number average molecular weight (Mn) (×10⁴) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 2.5 Acrylimide bond concentration (mmol / g) (Theoretical value) 1.0 1.4 1.4 1.0 1.0 1.8 0.7 1.0 1.0 Dimeric diamine (b2) / polyamine (b) (mol ratio) 0.4 0.4 0.4 0.2 0.6 0.4 0.4 0.4 0.4 Content (%) of constituent units derived from liquid polyols 43 0 0 40 42 29 55 42 36 Carbamate bond concentration (mmol / g) 0 0 0 0 0 0 0 0 0.3 Acid value (mgKOH / g) 25 25 15 25 25 25 25 25 25 Basic value of acid anhydride (mgKOH / g) - - - - - - - - - Solution stability ○ ○ ○ ○ ○ ○ ○ ○ ○ Elasticity coefficient ○ ◎ ◎ ○ △ ◎ △ ○ ○ Heat resistance ○ ○ ○ ○ ○ ○ △ ○ ○ Low warp ○ ○ ○ △ ◎ △ ◎ ○ ○

[0100] [Table 1-2] Example 10 11 12 13 14 15 16 17 Modified amide resin J K L M N O P Q Polyols (a) (a1)PH-50 11.0 (a1)PH-100 (a1)PH-200 100.0 20.0 100.0 100.0 80.0 50.0 100.0 (a1)PH-300 80.0 UH-100 UH-200 20.0 (a1)P-1050 100.0 (a1)P-2050 50.0 1,6-HD 4.5 1.6 0.8 0.8 Composition of acyl imine Aromatic diamines (b1) BAPP 31.0 30.0 24.0 27.0 27.0 27.0 34.0 TPE-R 30.0 ODA Dimeric diamine (b2) P1074 31.0 30.0 24.0 30.0 27.0 27.0 27.0 34.0 Aliphatic diamine 1,3-BAC Polyisocyanate MDI Acid anhydride (c) BPADA 100.3 111.5 68.8 114.1 88.4 88.4 109.3 BPDA 88.4 Polyisocyanate TDI 6.6 Position of reactive functional groups side chain side chain side chain side chain side chain side chain side chain side chain Number average molecular weight (Mn) (×10⁴) 2.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Acrylimide bond concentration (mmol / g) (Theoretical value) 1.0 1.0 1.0 1.2 1.0 1.0 1.0 1.0 Dimeric diamine (b2) / polyamine (b) (mol ratio) 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Derived from liquid polyols Content of constituent units (%) 38 39 47 37 42 33 42 39 Carbamate bond concentration (mmol / g) 0.3 0 0 0 0 0 0 0 Acid value (mgKOH / g) 25 35 15 25 25 25 25 25 Basic value of acid anhydride (mgKOH / g) - - - - - - - - Solution stability ○ ○ ○ ○ ○ ○ ○ ○ Elasticity coefficient ○ ○ ○ ○ ○ ○ ○ ○ Heat resistance ○ ○ ○ ○ ○ ○ ○ ○ low curvature ○ △ ◎ ○ ○ ○ ○ ○

[0101] [Table 1-3] Comparative Example 1 2 3 4 5 6 7 8 Modified cellulose resin AA BB CC DD EE FF GG HH Multidimensional sake (a) (a1) PH-50 (a1) PH-100 100.0 (a1) PH-200 100.0 100.0 92.0 100.0 43.0 92.0 (a1) PH-300 8.0 57.0 UH-100 UH-200 (a1) P-1050 (a1) P-2050 1.6-HD 1.4 0.2 0.3 13.1 Imine components Aromatic diamines (b1) BAPP 45.0 5.0 50.0 TPE-R 90.0 ODA 13.0 Dimeric diamine (b2) P1074 70.0 28.0 5.0 90.0 50.0 Aliphatic diamine 1,3-BAC 13.5 Polyisocyanate MDI 30.0 Acid anhydride (c) BPADA 99.6 83.0 70.7 87.6 30.7 85.7 139.2 BPDA 169.7 Polyisocyanate TDI Position of reactive functional groups side chain side chain side chain side chain side chain side chain side chain end Number average molecular weight (Mn) (×10⁴) 1.5 1.5 - - 1.5 - - 1.5 Imine bond concentration (mmol / g) (theoretical value) 1.0 1.0 1.0 1.0 0.3 2.1 1.2 1.9 Dimeric diamine (b2) / polyamine (b) (mol ratio) 1.0 0 0 0.4 0.4 0.4 0 0.4 Content (%) of constituent units derived from liquid polyols 38 45 54 44 71 twenty two 46 0 Carbamate bond concentration (mmol / g) 0 0 0 0 0 0 0 0 Acid value (mgKOH / g) 25 25 - - 25 - - 0 Basic value of acid anhydride (mgKOH / g) - - - - - - - 12.5 Solution stability ○ ○ × × ○ × × ○ Elasticity coefficient × ○ - - × - - ○ Heat resistance ○ ○ - - × - - ○ Low warp ◎ × - - ◎ - - ×

[0102] <Manufacturing of Resin Components> (Examples 18-34, Comparative Examples 9-12) The solutions (solids concentration 40%) of the main agent (modified amide resins A~Q, AA, BB, EE, HH) and the curing agent were mixed according to the composition shown in Table 2 to obtain resin compositions 1~21.

[0103] <Evaluation of Resin Composition> (elasticity coefficient) The resin composition was coated onto release paper to a thickness of 40 μm after drying, and then dried at 120°C for 10 minutes to form a coating film (dried film). The formed coating film was then heated at 150°C for 3 hours to thermally harden it into a hardened film. The hardened film was cut into pieces with dimensions of 60 mm long × 15 mm wide to obtain test pieces. The obtained test pieces were subjected to tensile tests according to JIS K-7127:1999 at room temperature (25°C) using a universal testing machine (trade name "AGS-J"). The tensile elastic modulus of the test pieces was then measured, and the elastic modulus of the hardened film was evaluated according to the evaluation criteria shown below. The results are shown in Table 2. ◎: The tensile elastic modulus is above 800 N / mm2. ○: Tensile elastic modulus is above 280 N / mm2 but less than 800 N / mm2. △: Tensile elasticity coefficient is above 100 N / mm2 but less than 280 N / mm2. ×: The tensile elasticity coefficient is less than 100 N / mm2.

[0104] (Thermal dimensional stability) The resin composition was coated onto release paper to a thickness of 40 μm after drying, and then dried at 120°C for 10 minutes to form a coating film (dried film). The formed coating film was then heated at 150°C for 3 hours to heat-cur it and form a hardened film. The coefficient of linear expansion (CTE, 25~300°C) of the obtained test pieces was measured under the conditions shown below, and the heat resistance of the hardened film was evaluated according to the evaluation criteria shown below. The results are shown in Table 2. (1) Equipment: Trade name "Thermomechanical Analysis Apparatus TMA-7100E" (manufactured by Hitachi High-Tech Science Co., Ltd.) (2) Probe: Metal tension probe (3)Load:10 mN (4) Heating rate: 5℃ / min (5) Measurement temperature range: 20~300℃ (6) Sample length: 10 mm ◎: CTE is less than 200ppm / ℃. ○: CTE is above 200ppm / ℃ but less than 350ppm / ℃. △: CTE is above 350ppm / ℃ but less than 400ppm / ℃. ×: CTE is above 400ppm / ℃.

[0105] (Long-term heat resistance) The resin composition was coated onto release paper to a thickness of 40 μm after drying, and then dried at 120°C for 10 minutes to form a coating film (dried film). The formed coating film was heated at 150°C for 3 hours to heat-harden it into a hardened film. The hardened film was cut into 10 cm long × 10 cm wide pieces to obtain a hardened film. The hardened film was subjected to a long-term heat resistance test for 500 hours in an air environment in a hot air furnace at 150°C. The hardened film before and after the test was cut into 60 mm long × 15 mm wide pieces to obtain test pieces. The test pieces were subjected to a tensile test according to JIS K-7127:1999 at room temperature (25°C) using a universal testing machine (trade name "AGS-J" manufactured by Shimadzu Corporation). Then, while measuring the breaking strength of the test pieces, the rate of change of breaking strength was calculated according to the following formula (C), and the long-term heat resistance of the hardened film was evaluated according to the evaluation criteria shown below. The results are shown in Table 2. Breaking strength change rate (%) = (S2 / S1) × 100 ･･･(C) S1: Breaking strength of the hardened film before long-term heat resistance test S2: Breaking strength of the hardened film after long-term heat resistance test ◎: The rate of change in breaking strength is 90% or more but less than 110%. ○: The rate of change in breaking strength is 110% or more but less than 135%. △: The rate of change in breaking strength is 135% or more but less than 150%. ×: The rate of change in breaking strength is over 150%.

[0106] (Flexibility) The resin composition was coated onto release paper to a thickness of 40 μm after drying, and then dried at 120°C for 10 minutes to form a coating film (dried film). The formed coating film was heated at 150°C for 3 hours to thermally harden it into a hardened film. The hardened film was cut into pieces with dimensions of 1.5 cm long × 10 cm wide to obtain hardened thin films. For the obtained test pieces, a bending test was performed using an MIT testing machine under the conditions shown below, and the number of bends at which the hardened film broke was recorded. Then, the bending properties of the hardened film were evaluated according to the evaluation criteria shown below. The results are shown in Table 2. (1) Machine equipment: Trade name "MIT type flexural endurance tester" (manufactured by Yasuda Seiki Co., Ltd.) (2) Load: 0.98N (3) Angle: ±135° (4) Number of bends: 175 times / min (5) Radius of curvature: 0.38mm ○: The number of bends is more than 12,000. △: The number of bends is more than 5,000 but less than 12,000. ×: The number of bends is less than 5,000.

[0107] (Low warpage) The resin composition was coated onto a 50 μm thick polyimide film to a dry thickness of 20 μm, and then dried at 150°C for 10 minutes to form a coating (hardened film). The formed coating was cut into 5 cm × 5 cm pieces, heated to 25°C, placed on a horizontal glass plate, and the average warpage height at the four corners was measured. The low warpage (susceptibility to warping) of the hardened film was evaluated according to the following evaluation criteria. The results are shown in Table 2. ◎: The average height is less than 2mm. ○: The average height is 2mm or more but less than 4mm. △: The average height is 4mm or more but less than 10mm. ×: The average height is 10mm or more but less than 15mm.

[0108] [Table 2] Example Comparative example 18 19 20 twenty one twenty two twenty three twenty four 25 26 27 28 29 30 31 32 33 34 9 10 11 12 resin composition 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 twenty one main sword Modified cellulose resin A 90 Modified cellulose resin B 90 Modified cellulose resin C 90 Modified cellulose resin D 90 Modified cellulose resin E 90 Modified cellulose resin F 90 Modified cellulose resin G 90 Modified cellulose resin H 90 Modified cellulose resin I 90 Modified cellulose resin J 90 Modified cellulose resin K 90 Modified cellulose resin L 90 Modified cellulose resin M 90 Modified cellulose resin N 90 Modified cellulose resin O 90 Modified cellulose resin P 90 Modified cellulose resin Q 90 Modified cellulose resin AA 90 Modified amide resin BB 90 Modified ethylene imide resin EE 90 Modified amide resin HH 90 hardener Epoxy Resin A 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 evaluate Elasticity coefficient ○ ◎ ◎ ○ △ ◎ △ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ × ○ × ○ Thermal dimensional stability ○ ◎ ◎ ○ △ ◎ △ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ △ ○ × × Long-term heat resistance ○ ○ ○ ◎ △ ◎ △ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ × ◎ × ○ Bending ○ ○ ○ △ ○ △ ○ ○ ○ ○ △ 〇 ○ ○ ○ ○ ○ ○ × ○ × Low warp ○ △ △ △ ◎ △ ◎ ○ ○ ○ △ ◎ ○ ○ ○ ○ ○ ◎ × ◎ ×

[0109] <Manufacturing of Laminated Materials> Resin compositions 1-21 obtained in Examples 18-34 and Comparative Examples 9-12 were coated onto release films to a thickness of 20 μm after drying, and then dried at 150°C for 10 minutes to form coatings (dried films). The formed coatings were then heat-bonded at 100°C onto a polyimide (PI) film (trade name "Kapton 200H", manufactured by Toray-DuPont) using a laminator. A copper foil laminate (trade name "ESPANEX MC12-25-00HRM", manufactured by NIPPON STEEL Chemical & Material) was laminated with the copper side in contact with the coating, and then heat-bonded at 150°C and 3 MPa for 1 hour using a hot press. Subsequently, the laminate was heat-cured at 150°C for 2 hours to obtain a laminate (PI film / adhesive layer (cured resin composition) / copper foil laminate (copper side)).

[0110] <Evaluation of Laminations> (Solder heat resistance) The resulting multilayer was cut into 20 mm × 20 mm pieces to prepare test specimens. These test specimens were floated in a 288°C solder bath with the PI film side facing upwards for a predetermined time. The test specimens were observed after holding, and the solder heat resistance of the multilayer was evaluated according to the evaluation criteria shown below. The results are shown in Table 3. Generally, if no change occurs in the 288°C solder bath for 30 seconds, the solder heat resistance is considered acceptable. ○: No expansion occurred at 288℃ for 30 seconds. △: No expansion occurred at 288℃ for 20 seconds, but expansion occurred at 288℃ for 30 seconds. ×: Expansion occurs at 288℃ for 20 seconds.

[0111] [Table 3] Types of resin components Solder heat resistance Example 35 1 ○ 36 2 ○ 37 3 ○ 38 4 ○ 39 5 △ 40 6 ○ 41 7 △ 42 8 ○ 43 9 ○ 44 10 ○ 45 11 ○ 46 12 ○ 47 13 ○ 48 14 ○ 49 15 ○ 50 16 ○ 51 17 ○ Comparative example 13 18 △ 14 19 ○ 15 20 × 16 twenty one × (Industrial applicability)

[0112] The carboxyl-containing modified amide resin of this invention can be used as a material for, for example, flexible printed wiring substrates.

Claims

1. A carboxyl-containing modified amide resin, comprising: having constituent units derived from a polyol (a), a polyamine (b), and a tetracarboxylic dianhydride (c), and having the structure shown in the following general formula (X); or having constituent units derived from a polyol (a), a polyamine (b), a tetracarboxylic dianhydride (c), and a polyisocyanate, and having the structure shown in the following general formula (Y); wherein the polyamine (b) is composed of an aromatic diamine (b1) and a dimerized diamine (b2); wherein the aromatic diamine (b1) is a compound having an aromatic ether bond; wherein the molecular weight of the portion of the aromatic diamine (b1) other than the amino group is 240-500; and the amide bond concentration is 0.5-2.0 mmol / g; (In the above general formula (X), n represents a number from 0 to 20, R1 represents an organic group from tetracarboxylic dianhydride (c) with the anhydride group removed, R2 represents an organic group from polyamine (b) with the amine group removed, and R3 represents an organic group from polyol (a) with the hydroxyl group removed); (In the above general formula (Y), n represents a number from 0 to 20, m represents a number from 1 to 5, R1 represents an organic group from tetracarboxylic dianhydride (c) with the anhydride group removed, R2 represents an organic group from polyamine (b) with the amine group removed, R3 represents an organic group from polyol (a) with the hydroxyl group removed, and R4 represents an organic group from polyisocyanate with the isocyanate group removed).

2. The carboxyl-containing modified amide resin as described in claim 1, wherein, The aforementioned polyol (a) contains at least one selected from the group consisting of polycarbonate diol and polyester diol.

3. The carboxyl-containing modified amide resin as described in claim 2, wherein, The aforementioned polyol (a) further contains a polyol (a1) that is liquid at 25°C; the content of the constituent units derived from the aforementioned polyol (a1) is 20-60% by mass.

4. The carboxyl-containing modified amide resin as described in claim 1, wherein, The molar ratio (b2) / (b) of the aforementioned dimeric diamine (b2) in the above polyamine (b) is 0.1~0.

7.

5. The carboxyl-containing modified amide resin as described in claim 1, wherein, The number average molecular weight is 10,000~50,000, and the acid value is 5~40 mgKOH / g.

6. A resin composition comprising a carboxyl-containing modified amide resin according to any one of claims 1 to 5, and an epoxy resin having two or more epoxy groups in one molecule.

7. The resin composition as claimed in claim 6, wherein, It further contains an organic solvent, which is used to dissolve the above-mentioned modified amide resin containing carboxyl groups, and has a boiling point below 200°C.

8. A laminate, which is a hardened layer having the resin composition of claim 6.

9. A flexible printed wiring board comprising the laminate of claim 8 as a constituent element.