Method for producing modified maleimide resin solution

Abstract

Provided are a method for producing a modified maleimide resin solution, the method comprising reacting, in an organic solvent, (A) a maleimide resin having an acid value of 3.50 mgKOH / g or more and having two or more N-substituted maleimide groups, (B) an amine compound having two or more primary amino groups and (C) a monoamine compound having an acidic substituent; a method for producing a resin composition, comprising using the modified maleimide resin solution produced by said production method; a method for producing a prepreg; a method for producing a laminate; a method for producing a resin film; a method for producing a printed wiring board; and a method for producing a semiconductor package.

Description

Method for producing modified maleimide resin solution

[0001] The present embodiment relates to a method for producing a modified maleimide resin solution, a method for producing a resin composition, a method for producing a prepreg, a method for producing a laminate, a method for producing a resin film, a method for producing a printed wiring board, and a method for producing a semiconductor package.

[0002] 2. Description of the Related Art In mobile communication devices such as mobile phones, their base station equipment, servers, routers and other network infrastructure devices, and electronic devices such as mainframe computers, the speed and capacity of the signals used are increasing year by year.

[0003] Resin compositions containing a thermosetting resin as a main component are commonly used as substrate materials for printed wiring boards. Among thermosetting resins, maleimide resins are known to have excellent heat resistance and low thermal expansion. Patent Document 1 describes a thermosetting resin composition containing (A) a copolymer resin having structural units derived from an aromatic vinyl compound and structural units derived from maleic anhydride, (B) an epoxy-modified polybutadiene having hydroxyl groups, and (C) a maleimide compound.

[0004] Japanese Patent Application Laid-Open No. 2017-115020

[0005] Patent Document 1 describes, as preferred examples of the (C) maleimide compound, maleimide compounds modified with monoamine compounds and diamine compounds having acidic substituents. A specific example is a modified maleimide resin solution obtained by pre-reacting 4,4'-diphenylmethane bismaleimide with p-aminophenol and 4,4'-diaminodiphenylmethane in an organic solvent. As described above, modifying the maleimide compound introduces an acidic substituent into the maleimide compound, which is expected to improve the mechanical strength of the cured resin composition and the solubility of the maleimide compound in solvents. However, according to studies by the present inventors, it has been found that the modified maleimide resin solution generates precipitates depending on the storage period. As a result, it is difficult to extend the storage period and there are problems with poor handleability.

[0006] In view of the current situation, the present embodiment relates to a method for producing a modified maleimide resin solution that is less likely to produce precipitates during storage, a method for producing a resin composition that uses the modified maleimide resin solution produced by the production method, a method for producing a prepreg, a method for producing a laminate, a method for producing a resin film, a method for producing a printed wiring board, and a method for producing a semiconductor package.

[0007] As a result of extensive research aimed at solving the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by the following embodiment. [1] A method for producing a modified maleimide resin solution, comprising reacting (A) a maleimide resin having an acid value of 3.50 mg KOH / g or more and having two or more N-substituted maleimide groups, (B) an amine compound having two or more primary amino groups, and (C) a monoamine compound having an acidic substituent in an organic solvent. [2] A method for producing a modified maleimide resin solution according to the above item [1], wherein the component (A) is an aromatic bismaleimide resin. [3] A method for producing a modified maleimide resin solution according to the above item [1] or [2], wherein the component (B) is an aromatic diamine compound. [4] A method for producing a modified maleimide resin solution according to any one of the above items [1] to [3], wherein the reaction is carried out at 50 to 160°C. [5] A method for producing a resin composition, using a modified maleimide resin solution produced by the method for producing a modified maleimide resin solution described in any one of [1] to [4] above. [6] A method for producing a prepreg, using a resin composition produced by the method for producing a resin composition described in [5] above. [7] A method for producing a resin film, using a resin composition produced by the method for producing a resin composition described in [5] above. [8] A method for producing a laminate, using a resin composition produced by the method for producing a resin composition described in [5] above. [9] A method for producing a printed wiring board, using a resin composition produced by the method for producing a resin composition described in [5] above.

[10] A method for producing a semiconductor package, using a printed wiring board produced by the method for producing a printed wiring board described in [9] above.

[0008] According to the present embodiment, it is possible to provide a method for producing a modified maleimide resin solution that is less likely to produce precipitates during storage, a method for producing a resin composition that uses the modified maleimide resin solution produced by the production method, a method for producing a prepreg, a method for producing a laminate, a method for producing a resin film, a method for producing a printed wiring board, and a method for producing a semiconductor package.

[0009] In this specification, a numerical range indicated using "to" indicates a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. For example, a numerical range "X to Y" (X and Y are real numbers) means a numerical range that is equal to or greater than X and equal to or less than Y. In this specification, the term "X or greater" means X and a numerical value that exceeds X. In addition, the term "Y or less" in this specification means Y and a numerical value that is less than Y. The lower limit and upper limit of a numerical range described in this specification can be arbitrarily combined with the lower limit or upper limit of another numerical range. In the numerical ranges described in this specification, the lower limit or upper limit of that numerical range may be replaced with a value shown in the examples.

[0010] Unless otherwise specified, each of the components and materials exemplified in this specification may be used alone or in combination of two or more. In this specification, when a resin composition contains a plurality of substances corresponding to each component, the content of each component in the resin composition means the total amount of the plurality of substances present in the resin composition, unless otherwise specified.

[0011] The expression "containing XX" as used herein means both containing XX in a reacted state if XX is capable of reacting, and simply containing XX.

[0012] In this specification, the term "solid content" refers to components other than the solvent, and components that are liquid at 25°C are also considered to be solid content.

[0013] In this specification, the term "semi-cured product" is synonymous with a resin composition in a B-stage state according to JIS K 6800 (2006), and the term "cured product" is synonymous with a resin composition in a C-stage state according to JIS K 6800 (2006).

[0014] The mechanism of action described in this specification is speculation and does not limit the mechanism by which the effects of this embodiment are achieved.

[0015] Any combination of the features described in this specification is also included in this embodiment.

[0016] [Method for Producing Modified Maleimide Resin Solution] The method for producing a modified maleimide resin solution of the present embodiment comprises reacting, in an organic solvent, (A) a maleimide resin having an acid value of 3.50 mgKOH / g or more and having two or more N-substituted maleimide groups, (B) an amine compound having two or more primary amino groups, and (C) a monoamine compound having an acidic substituent.

[0017] In this specification, each component may be abbreviated as component (A), component (B), etc., and the same abbreviation may be used for other components. The reaction of components (A) to (C) may be referred to as a "pre-reaction."

[0018] <Component (A)> The component (A) is a maleimide resin having an acid value of 3.50 mgKOH / g or more and having two or more N-substituted maleimide groups. As the component (A), one type may be used alone, or two or more types may be used in combination.

[0019] When the acid value of component (A) is 3.50 mgKOH / g or more, the modified maleimide resin solution obtained by the production method of the present embodiment is less likely to produce precipitates during storage. Although the details of the reason for this are unknown, it is presumed that one of the reasons is that, when component (A) having an acid value within the above range is used, the reaction of unreacted maleimide resin gradually progresses during storage after the pre-reaction of component (A) with components (B) and (C) is carried out.

[0020] From the viewpoint of further suppressing the formation of precipitates during storage, the acid value of component (A) is preferably 3.60 mgKOH / g or more, more preferably 3.70 mgKOH / g or more, even more preferably 3.80 mgKOH / g or more, still more preferably 3.90 mgKOH / g or more, and particularly preferably 4.00 mgKOH / g or more. Furthermore, the acid value of component (A) may be 5.00 mgKOH / g or more, or even 6.00 mgKOH / g or more. From the viewpoint of easily controlling the reaction rate of the pre-reaction, the acid value of component (A) is preferably 10.0 mgKOH / g or less, more preferably 9.00 mgKOH / g or less, even more preferably 8.00 mgKOH / g or less, still more preferably 7.50 mgKOH / g or less, and particularly preferably 7.00 mgKOH / g or less. Furthermore, the acid value of component (A) may be 6.80 mgKOH / g or less, or may be 6.60 mgKOH / g or less. The acid value of component (A) can be measured by the method described in the Examples. The acid value of component (A) can be controlled, for example, by the synthesis and purification conditions of component (A). As disclosed in JP-A-6-100536, maleimide compounds are synthesized, for example, by the reaction of a diamine compound with maleic anhydride, and acidic substituents derived from maleic anhydride may remain. By adjusting the amount of such remaining acidic substituents by the synthesis and purification conditions, the acid value of component (A) can be adjusted to fall within the above range.

[0021] From the viewpoints of conductor adhesion and heat resistance, component (A) is preferably an aromatic maleimide resin having two or more N-substituted maleimide groups, and more preferably an aromatic bismaleimide resin. In this specification, "aromatic maleimide resin" refers to a compound having an N-substituted maleimide group directly bonded to an aromatic ring. In this specification, "aromatic bismaleimide resin" refers to a compound having two N-substituted maleimide groups directly bonded to an aromatic ring. In this specification, "aromatic polymaleimide resin" refers to a compound having three or more N-substituted maleimide groups directly bonded to an aromatic ring. In this specification, "aliphatic maleimide resin" refers to a compound having an N-substituted maleimide group directly bonded to an aliphatic hydrocarbon.

[0022] The component (A) is preferably a maleimide resin represented by the following general formula (A-1).

[0023] (In the formula, X Ａ１ is a divalent organic group.

[0024] X in the above general formula (A-1) Ａ１ is a divalent organic group. Ａ１ Examples of the divalent organic group represented by formula (A-2) below, a divalent group represented by formula (A-3) below, a divalent group represented by formula (A-4) below, a divalent group represented by formula (A-5) below, and a divalent group represented by formula (A-6) below.

[0025] (In the formula, R Ａ１ is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. Ａ１ is an integer from 0 to 4. * represents a binding site.)

[0026] R in the above general formula (A-2) Ａ１Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and n-pentyl; alkenyl groups having 2 to 5 carbon atoms; and alkynyl groups having 2 to 5 carbon atoms. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. Hereinafter, halogen atoms represented by the general formulae in this specification include fluorine, chlorine, bromine, and iodine atoms, and examples thereof will be omitted. n in the above general formula (A-2) Ａ１ is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0. Ａ１ is an integer of 2 or more, a plurality of R Ａ１ They may be the same or different.

[0027] (In the formula, R Ａ２ and R Ａ３ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. Ａ２ n is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, a single bond, or a divalent group represented by the following general formula (A-3-1): Ａ２ and n Ａ３ are each independently an integer of 0 to 4. * represents a binding site.

[0028] R in the above general formula (A-3) Ａ２ and R Ａ３ Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by include alkyl groups having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and n-pentyl; alkenyl groups having 2 to 5 carbon atoms; and alkynyl groups having 2 to 5 carbon atoms. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched.

[0029] X in the above general formula (A-3)Ａ２ Examples of the alkylene group having 1 to 5 carbon atoms represented by include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, and a 1,5-pentamethylene group.

[0030] X in the above general formula (A-3) Ａ２ Examples of the alkylidene group having 2 to 5 carbon atoms represented by include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, and an isopentylidene group.

[0031] n in the above general formula (A-3) Ａ２ and n Ａ３ are each independently an integer of 0 to 4. Ａ２ or n Ａ３ is an integer of 2 or more, a plurality of R Ａ２ R Ａ３ They may be the same or different from each other.

[0032] X in the above general formula (A-3) Ａ２ The divalent group represented by formula (A-3-1) is as follows:

[0033] (In the formula, R Ａ４ and R Ａ５ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. Ａ３ is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond. Ａ４ and n Ａ５ are each independently an integer of 0 to 4. * represents a binding site.

[0034] R in the above general formula (A-3-1) Ａ４ and R Ａ５Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by include alkyl groups having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and n-pentyl; alkenyl groups having 2 to 5 carbon atoms; and alkynyl groups having 2 to 5 carbon atoms. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched.

[0035] X in the above general formula (A-3-1) Ａ３ Examples of the alkylene group having 1 to 5 carbon atoms represented by include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, and a 1,5-pentamethylene group.

[0036] X in the above general formula (A-3-1) Ａ３ Examples of the alkylidene group having 2 to 5 carbon atoms represented by include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, and an isopentylidene group.

[0037] n in the above general formula (A-3-1) Ａ４ and n Ａ５ are each independently an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0. Ａ４ or n Ａ５ is an integer of 2 or more, a plurality of R Ａ４ R Ａ５ They may be the same or different from each other.

[0038] (In the formula, n Ａ６ is an integer from 0 to 10. * represents a binding site.)

[0039] n in the above general formula (A-4) Ａ６ is preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and even more preferably an integer of 0 to 3.

[0040] (In the formula, n Ａ７ is a number from 0 to 5. * represents a binding site.)

[0041] (In the formula, R Ａ６ and R Ａ７ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. Ａ８ is an integer from 1 to 8. * represents a binding site.)

[0042] R in the above general formula (A-6) Ａ６ and R Ａ７ Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and n-pentyl; alkenyl groups having 2 to 5 carbon atoms; and alkynyl groups having 2 to 5 carbon atoms. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched. Ａ８ is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and even more preferably 1. Ａ８ is an integer of 2 or more, a plurality of R Ａ６ R Ａ７ They may be the same or different from each other.

[0043] Examples of component (A) include aromatic bismaleimide resins, aromatic polymaleimide resins, and aliphatic maleimide resins. Examples of component (A) include bis(4-maleimidophenyl)methane, m-phenylene bismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 4-methyl-1,3-phenylene bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, biphenylaralkyl maleimide, and aromatic bismaleimide resins having an indane skeleton. Among these, bis(4-maleimidophenyl)methane is preferred.

[0044] <Component (B)> The component (B) is not particularly limited as long as it is an amine compound having two or more primary amino groups. The component (B) may be used alone or in combination of two or more. The component (B) is preferably a compound represented by the following general formula (B-1):

[0045] (In the formula, X Ｂ１ is a divalent organic group, and * represents a bonding site.

[0046] X in the above general formula (B-1) Ｂ１ is preferably a divalent group represented by the following general formula (B-2).

[0047] (In the formula, R Ｂ１ and R Ｂ２ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, or a halogen atom. Ｂ２ n is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, a fluorenylene group, a single bond, or a divalent group represented by the following general formula (B-2-1) or (B-2-2). Ｂ１ and n Ｂ２ are each independently an integer of 0 to 4. * represents a binding site.

[0048] (In the formula, R Ｂ３ and R Ｂ４ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. Ｂ３ represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an m-phenylenediisopropylidene group, a p-phenylenediisopropylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond. Ｂ３ and n Ｂ４ are each independently an integer of 0 to 4. * represents a binding site.

[0049] (In the formula, R Ｂ５ is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. Ｂ４and X Ｂ５ are each independently an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond. Ｂ５ is an integer from 0 to 4. * represents a binding site.)

[0050] R in the above general formula (B-2), the above general formula (B-2-1) and the above general formula (B-2-2) Ｂ１ , R Ｂ２ , R Ｂ３ , R Ｂ４ and R Ｂ５ Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and n-pentyl; alkenyl groups having 2 to 5 carbon atoms; and alkynyl groups having 2 to 5 carbon atoms. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched. As the aliphatic hydrocarbon group having 1 to 5 carbon atoms, an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferred, an alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group or an ethyl group is even more preferred.

[0051] X in the above general formula (B-2) Ｂ２ , X in the above general formula (B-2-1) Ｂ３ and X in the above general formula (B-2-2) Ｂ４ and X Ｂ５ Examples of the alkylene group having 1 to 5 carbon atoms represented by include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, a 1,5-pentamethylene group, etc. The alkylene group having 1 to 5 carbon atoms is preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms, and even more preferably a methylene group.

[0052] X in the above general formula (B-2) Ｂ２ , X in the above general formula (B-2-1) Ｂ３ and X in the general formula (B-2-2) Ｂ４ and X Ｂ５Examples of the alkylidene group having 2 to 5 carbon atoms represented by include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, an isopentylidene group, etc. The alkylidene group having 2 to 5 carbon atoms is preferably an alkylidene group having 2 to 4 carbon atoms, more preferably an alkylidene group having 2 or 3 carbon atoms, and even more preferably an isopropylidene group.

[0053] n in the above general formula (B-2) Ｂ１ and n Ｂ２ are each independently an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and even more preferably 0 or 2. Ｂ１ or n Ｂ２ is an integer of 2 or more, a plurality of R Ｂ１ R Ｂ２ They may be the same or different from each other.

[0054] n in the above general formula (B-2-1) Ｂ３ and n Ｂ４ are each independently an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0. Ｂ３ or n Ｂ４ is an integer of 2 or more, a plurality of R Ｂ３ R Ｂ４ They may be the same or different from each other.

[0055] n in the above general formula (B-2-2) Ｂ５ is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0. Ｂ５ is an integer of 2 or more, a plurality of R Ｂ５ They may be the same or different.

[0056] Examples of the diamine compound include 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ketone, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'- Diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,3-bis(3-aminophenoxy)benzene , 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 1,3-bis[1-[4-(4-aminophenoxy)phenyl]-1-methylethyl]benzene, 1,4-bis[1-[4-(4-aminophenoxy)phenyl]-1-methylethyl]benzene, 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisaniline Examples of suitable aromatic diamine compounds include 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline, 3,3'-[1,3-phenylenebis(1-methylethylidene)]bisaniline, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, and 9,9-bis(4-aminophenyl)fluorene; and silicone compounds having two primary amino groups. Among these, aromatic diamine compounds are preferred, and 3,3'-diethyl-4,4'-diaminodiphenylmethane is more preferred. In this specification, the term "aromatic diamine compound" refers to a compound having two primary amino groups directly bonded to an aromatic ring.

[0057] <Component (C)> The component (C) is not particularly limited as long as it is a monoamine compound having an acidic substituent. The component (C) may be used alone or in combination of two or more. The amino group in the component (C) is preferably a primary amino group. Examples of the acidic substituent in the component (C) include a hydroxyl group, a carboxyl group, and a sulfonic acid group. Among these, from the viewpoints of solubility and reactivity, a hydroxyl group and a carboxyl group are preferred, and a hydroxyl group is more preferred.

[0058] The component (C) is preferably a compound represented by the following general formula (C-1).

[0059] (In the formula, R Ｃ１ is an acidic substituent selected from the group consisting of a hydroxyl group, a carboxyl group, and a sulfonic acid group, and R Ｃ２ is an alkyl group having 1 to 5 carbon atoms or a halogen atom; t is an integer of 1 to 5, and u is an integer of 0 to 4, and 1≦t+u≦5 is satisfied.

[0060] R Ｃ１ From the viewpoints of solubility and reactivity, the acidic substituent represented by is preferably a hydroxyl group or a carboxyl group, more preferably a hydroxyl group. t is an integer of 1 to 5, and from the viewpoints of adhesion to copper foil, heat resistance, dielectric properties, glass transition temperature, thermal expansion coefficient, and moldability, it is preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1. When t is an integer of 2 or more, a plurality of R Ｃ１ may be the same or different. Ｃ２ Examples of the alkyl group having 1 to 5 carbon atoms represented by R include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl group. The number of carbon atoms in the alkyl group is preferably 1 to 3. Ｃ２Examples of the halogen atom represented by u include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. u is an integer of 0 to 4, and from the viewpoints of adhesion to copper foil, heat resistance, dielectric properties, glass transition temperature, thermal expansion coefficient, and moldability, it is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, even more preferably 0 or 1, and particularly preferably 0. When u is an integer of 2 or more, a plurality of R Ｃ２ and may be the same or different. From the viewpoints of adhesion to copper foil, heat resistance, dielectric properties, glass transition temperature, thermal expansion coefficient, and moldability, the component (C) is more preferably a monoamine compound represented by the following general formula (C-1') or (C-1''), and even more preferably a monoamine compound represented by the following general formula (C-1'). However, when R Ｃ１ , R Ｃ２ and u are the same as those in formula (C-1), and the preferred values ​​are also the same.

[0061]

[0062] Examples of component (C) include o-aminophenol, m-aminophenol, p-aminophenol, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline, etc. Among these, from the viewpoints of solubility and reactivity, aminophenols such as o-aminophenol, m-aminophenol, and p-aminophenol are preferred, and p-aminophenol is more preferred.

[0063] <Organic Solvent> In the production method of this embodiment, the components (A) to (C) are reacted in an organic solvent. One type of organic solvent may be used alone, or two or more types may be used in combination. Examples of organic solvents include alcohol-based solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether-based solvents such as tetrahydrofuran; aromatic hydrocarbon-based solvents such as toluene, xylene, and mesitylene; nitrogen-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; sulfur-containing solvents such as dimethyl sulfoxide; and ester-based solvents such as γ-butyrolactone. Among these, alcohol-based solvents are preferred, and propylene glycol monomethyl ether is more preferred, from the viewpoint of the solubility of each component.

[0064] <Reaction Conditions> When carrying out the pre-reaction, the above-mentioned components (A), (B), and (C) are mixed with an organic solvent. The amount of component (B) used when carrying out the pre-reaction is preferably 2 to 60 parts by mass, more preferably 5 to 40 parts by mass, and even more preferably 10 to 20 parts by mass per 100 parts by mass of component (A), from the viewpoints of the solubility of the modified maleimide resin in the solvent and the heat resistance of the cured product. The amount of component (C) used when carrying out the pre-reaction is preferably 1 to 20 parts by mass, more preferably 2 to 10 parts by mass, and even more preferably 3 to 5 parts by mass per 100 parts by mass of component (A), from the viewpoints of the heat resistance and mechanical strength of the cured product.

[0065] -NH of component (B) and component (C) ２ The equivalent ratio (N-substituted maleimide group / -NH ２ The number of carbon atoms in the carbonyl group is preferably 0.05 to 10, more preferably 0.5 to 8, even more preferably 1 to 7, and particularly preferably 3 to 6, from the viewpoints of dielectric properties, heat resistance, flame retardancy, and glass transition temperature.

[0066] The solids concentration of the reaction solution is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, even more preferably 40 to 65% by mass, and particularly preferably 45 to 60% by mass. When the solids concentration of the reaction solution is equal to or greater than the lower limit, a good reaction rate is obtained, and productivity tends to be improved. On the other hand, when the solids concentration of the reaction solution is equal to or less than the upper limit, better solubility is obtained, stirring efficiency is improved, and gelation of the product during the reaction tends to be more effectively suppressed.

[0067] The reaction temperature of the pre-reaction is preferably 50 to 160°C, more preferably 60 to 150°C, and even more preferably 70 to 140°C, from the viewpoints of workability such as reaction rate, and suppression of gelation of the product during the reaction. The reaction time of the pre-reaction is preferably 0.5 to 10 hours, more preferably 1 to 8 hours, and even more preferably 2 to 6 hours, from the viewpoints of productivity and allowing the reaction to proceed sufficiently. However, these reaction conditions can be appropriately adjusted depending on the types of raw materials used, and are not particularly limited.

[0068] The production method of this embodiment provides a modified maleimide resin having a structure derived from component (A), a structure derived from component (B), and a structure derived from component (C). Here, the structure derived from component (A), the structure derived from component (B), and the structure derived from component (C) are structures formed by a Michael addition reaction between an N-substituted maleimide group in component (A) and a primary amino group in component (B) or component (C), respectively.

[0069] In the method for producing a modified maleimide resin solution of this embodiment, the GPC peak reduction rate evaluated by the [Method for Measuring GPC Peak Reduction Rate] described in the Examples below is preferably 17% or more, more preferably 18% or more, even more preferably 19% or more, and even more preferably 20% or more. When the GPC peak reduction rate is equal to or greater than the lower limit, the occurrence of precipitates during storage tends to be further suppressed. There is no particular restriction on the upper limit of the GPC peak reduction rate, and it may be 100% or less, 80% or less, 60% or less, or 40% or less.

[0070] [Method for Producing Resin Composition] The method for producing a resin composition according to this embodiment uses a modified maleimide resin solution produced by the method for producing a modified maleimide resin solution according to this embodiment. Components other than the modified maleimide resin solution used in the method for producing a resin composition according to this embodiment include, for example, thermosetting resins other than the modified maleimide resin, curing agents, thermoplastic resins, curing accelerators, inorganic fillers, flame retardants, antioxidants, heat stabilizers, antistatic agents, UV absorbers, pigments, colorants, lubricants, silane coupling agents, and other optional components such as additives. Each of these may be used alone, or two or more may be used in combination. The content of each of these components may be appropriately determined within a range that does not impair the effects of this embodiment. The resin composition can be produced by mixing the modified maleimide resin solution and other components used as needed. During this process, each component may be dissolved or dispersed while stirring. Mixing conditions such as the order of mixing, temperature, and time are not particularly limited and may be set as desired depending on the type of raw materials, etc.

[0071] [Method for Producing Prepreg] The method for producing a prepreg of this embodiment is a method for producing a prepreg using a resin composition produced by the method for producing a resin composition of this embodiment. Examples of the method for producing a prepreg of this embodiment include a method in which the resin composition produced by the method for producing a prepreg of this embodiment is impregnated into or applied to a sheet-like fiber base material, and then heated and dried to B-stage it.

[0072] As the sheet-like fiber substrate, for example, a known sheet-like fiber substrate used in various laminates for electrical insulating materials can be used. Examples of the material of the sheet-like fiber substrate include inorganic fibers such as E-glass, D-glass, S-glass, and Q-glass; organic fibers such as polyimide, polyester, and tetrafluoroethylene; and mixtures thereof. These sheet-like fiber substrates have shapes such as woven fabric, nonwoven fabric, roving, chopped strand mat, and surfacing mat.

[0073] The temperature and time for heat drying after impregnating the resin composition into the sheet-like fiber substrate are not particularly limited, but from the viewpoint of productivity and appropriately B-staging the resin composition, it can be, for example, 50 to 200°C and 1 to 30 minutes.

[0074] The content of the resin composition in the prepreg obtained by the prepreg manufacturing method of the present embodiment is not particularly limited, but from the viewpoint of easily obtaining better moldability when made into a laminate, it is preferably 20 to 90 mass%, more preferably 40 to 85 mass%, and even more preferably 50 to 80 mass%.

[0075] [Resin Film] The resin film manufacturing method of this embodiment is a method for manufacturing a resin film using a resin composition manufactured by the resin composition manufacturing method of this embodiment. Examples of the resin film manufacturing method of this embodiment include a method in which a resin composition containing an organic solvent manufactured by the manufacturing method of this embodiment is applied to a support and then heated and dried. Examples of the support include plastic film, metal foil, and release paper. The temperature and time of the heat drying are not particularly limited, but can be set to 50 to 200°C and 1 to 30 minutes from the viewpoints of productivity and appropriately B-staging the resin composition. The resin film obtained by the resin film manufacturing method of this embodiment is preferably used to form an insulating layer when manufacturing a printed wiring board.

[0076] [Laminate] The method for producing a laminate according to the present embodiment is a method for producing a laminate using a resin composition produced by the method for producing a resin composition according to the present embodiment. Note that a laminate having a metal foil is sometimes called a metal-clad laminate.

[0077] A method for manufacturing the laminate of this embodiment includes, for example, placing metal foil on one or both sides of the prepreg manufactured by the manufacturing method of this embodiment, followed by hot-press molding. Typically, this hot-press molding process hardens the B-staged prepreg to obtain a laminate. When hot-press molding, only one prepreg may be used, or two or more prepregs may be laminated together. For hot-press molding, for example, a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, or the like can be used. The conditions for hot-press molding are not particularly limited, but may be, for example, a temperature of 100 to 300°C, a time of 10 to 300 minutes, and a pressure of 1.5 to 5 MPa.

[0078] Examples of metals for the metal foil include copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, and alloys containing one or more of these metal elements.

[0079] [Printed Wiring Board] The method for producing a printed wiring board of this embodiment is a method for producing a printed wiring board using a resin composition produced by the method for producing a resin composition of this embodiment. Examples of the method for producing a printed wiring board of this embodiment include a method for forming a conductor circuit by a known method on one or more selected from the group consisting of a cured product of a prepreg, a cured product of a resin film, and a laminate produced by the method for producing this embodiment. Furthermore, a multilayer printed wiring board can also be produced by further performing a multilayer adhesive process as necessary. The conductor circuit can be formed, for example, by appropriately performing drilling, metal plating, etching of a metal foil, etc.

[0080] [Semiconductor Package] The semiconductor package manufacturing method of this embodiment is a method for manufacturing a semiconductor package using a printed wiring board manufactured by the printed wiring board manufacturing method of this embodiment. Examples of the semiconductor package manufacturing method of this embodiment include a method of mounting a semiconductor chip, a memory, etc., by a known method on the printed wiring board manufactured by the manufacturing method of this embodiment.

[0081] The present embodiment will be specifically described below with reference to examples, although the present embodiment is not limited to the following examples.

[0082] [Method for Measuring Acid Value] The acid value of the maleimide resin used in each example was measured by potentiometric titration using an automatic titrator "COM-1750S" manufactured by Hiranuma Sangyo Co., Ltd. Specifically, 1.0 g of the maleimide resin to be measured was weighed into a mighty vial, and 20 mL of N,N-dimethylformamide was added and stirred to dissolve. Next, 25 mL of a mixed solution of ethanol and toluene in a 1:2 (volume ratio) mixture was added to prepare a solution to be titrated. This solution was subjected to potentiometric titration using a 0.05 mol / L ethanolic potassium hydroxide solution to determine the acid value.

[0083] [Method for Producing Modified Maleimide Resin Solution] Examples 1 to 4, Comparative Examples 1 to 4 358.0 g of a maleimide resin shown in Table 1, 47.7 g of 3,3'-diethyl-4,4'-diaminodiphenylmethane, 13.6 g of p-aminophenol, and 412.50 g of propylene glycol monomethyl ether were charged into a 2-liter reaction vessel equipped with a thermometer, a stirrer, and a water content meter with a reflux condenser, and the mixture was allowed to react for 5 hours under a nitrogen atmosphere while refluxing at 120°C, to obtain a modified maleimide resin solution.

[0084] [Storage evaluation of modified maleimide resin solution] The modified maleimide resin solution obtained in each example was placed in a glass bottle (volume 9 ml, outer diameter 2 cm) and stored at 5°C for 10 days. After storage, the appearance of the glass bottle containing the modified maleimide resin solution was visually observed and evaluated according to the following criteria. [Evaluation criteria] 0: No precipitate was observed. 1: A slight precipitate was observed only on the bottom of the glass bottle. 2: A slight precipitate was observed on the bottom and other surfaces of the glass bottle. 3: A large precipitate was observed on the bottom and other surfaces of the glass bottle.

[0085] [Method for Measuring GPC Peak Reduction Rate] In each example, GPC measurement was performed on the modified maleimide resin solution immediately after production and the modified maleimide resin solution after storage at 5°C for 10 days. Elution peak 1 derived from unreacted maleimide resin, elution peak 2 derived from a reaction product of the maleimide resin appearing immediately before elution peak 1, and elution peak 3 derived from another reaction product of the maleimide resin appearing immediately before elution peak 2 were identified. The ratio of the peak top height of elution peak 1 to the total peak top heights of elution peaks 1 to 3 [height of elution peak 1 × 100 / (height of elution peak 1 + height of elution peak 2 + height of elution peak 3)] (%) was calculated for each. The difference [A - B] between the ratio A of the peak top height of elution peak 1 in the modified maleimide resin solution immediately after production and the ratio B of the peak top height of elution peak 1 in the modified maleimide resin solution after storage at 5°C for 10 days is shown in Table 1 as the GPC peak reduction rate. The GPC measurement was performed under the following conditions. Apparatus: High-speed GPC apparatus HLC-8420GPC Detector: Differential refractometer Column: Guard column: TSK Guard column Super HZ-L + Column: TSKgel Super HZ3000 + TSKgel Super HZ2000 (all manufactured by Tosoh Corporation, trade names) Column size: 4.6 x 20 mm (guard column), 4.6 x 150 mm (column), 4.6 x 150 mm (reference column) Eluent: Tetrahydrofuran Sample concentration: 10 mg / 1 mL Injection volume: 10 μL Flow rate: 0.35 mL / min Measurement temperature: 40°C

[0086]

[0087] Details of maleimide resins A-1 to A-8 listed in Table 1 are as follows: All of maleimide resins A-1 to A-8 are products sold as bis(4-maleimidophenyl)methane. A-1: Manufactured by Daiwa Chemical Industry Co., Ltd., trade name "BMI-1000" A-2: Manufactured by HOS-Technik GmbH, trade name "Homide 121G" A-3: Manufactured by Shaanxi Yangchen New Material Technology Co., Ltd., trade name "BMI-100" A-4: Manufactured by Shaanxi Yangchen New Material Technology Co., Ltd., trade name "BMI-100" (however, this is a different production lot from A-3 above) A-5: Manufactured by K.I. Chemical Co., Ltd., trade name "BMI" A-6: Manufactured by Shandong Shengquan New Materials Co., Ltd., trade name "PFB002" A-7: Manufactured by Hunan Huateng Pharmaceutical Co., Ltd., trade name "Bismaleimide" A-8: Manufactured by UFC Corporation

[0088] The results shown in Table 1 indicate that the generation of precipitates during storage was suppressed in the modified maleimide resin solutions produced in Examples 1 to 4 of this embodiment. Furthermore, the GPC reduction rates suggest that the reaction of unreacted bis(4-maleimidophenyl)methane gradually progresses during storage after production in the modified maleimide resin solutions produced in Examples 1 to 4 of this embodiment, thereby suppressing the generation of precipitates.

Claims

1. A method for producing a modified maleimide resin solution, comprising reacting, in an organic solvent, (A) a maleimide resin having an acid value of 3.50 mg KOH / g or more and having two or more N-substituted maleimide groups, (B) an amine compound having two or more primary amino groups, and (C) a monoamine compound having an acidic substituent.

2. The method for producing a modified maleimide resin solution according to claim 1, wherein the component (A) is an aromatic bismaleimide resin.

3. The method for producing a modified maleimide resin solution according to claim 1 or 2, wherein the component (B) is an aromatic diamine compound.

4. The method for producing a modified maleimide resin solution according to claim 1 or 2, wherein the reaction is carried out at 50 to 160°C.

5. A method for producing a resin composition, which uses a modified maleimide resin solution produced by the method for producing a modified maleimide resin solution according to claim 1 or 2.

6. A method for producing a prepreg using a resin composition produced by the method for producing a resin composition according to claim 5.

7. A method for producing a resin film, using a resin composition produced by the method for producing a resin composition according to claim 5.

8. A method for producing a laminate using a resin composition produced by the method for producing a resin composition according to claim 5.

9. A method for producing a printed wiring board using a resin composition produced by the method for producing a resin composition according to claim 5.

10. A method for manufacturing a semiconductor package using a printed wiring board manufactured by the method for manufacturing a printed wiring board according to claim 9.

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