WO2020027179A1

WO2020027179A1 - Aromatic amine resin having n-alkyl group, curable resin composition, and cured product thereof

Info

Publication number: WO2020027179A1
Application number: PCT/JP2019/029965
Authority: WO
Inventors: 隆行遠島; 政隆中西; 正人鎗田; 篤彦長谷川
Original assignee: 日本化薬株式会社
Priority date: 2018-08-01
Filing date: 2019-07-31
Publication date: 2020-02-06
Also published as: CN112105673B; JPWO2020027179A1; KR20210036863A; TW202007704A; CN112105673A; JP6755418B2; TWI815938B

Abstract

Provided is the provision of an aromatic amine resin compound having an N-alkyl group that presents exceptional heat resistance and electrical characteristics, and a curable resin composition thereof. An aromatic amine resin having an N-alkyl group represented by formula (1). (In formula (1), the plurality of R present each independently represent a hydrogen or a C1-15 hydrocarbon group; however, this excludes the instance in which all R are hydrogen. The plurality of X present each independently represent a hydrogen atom or a C1-15 hydrocarbon group. I₁, I₂, and m represent integers of 1 or higher and satisfy the relationships I₁ + m ≤ 5 and I₂ + m ≤ 4. n represents 1 ≤ n ≤ 15.)

Description

Aromatic amine resin having N-alkyl group, curable resin composition and cured product thereof

TECHNICAL FIELD The present invention relates to an aromatic amine resin having an N-alkyl group, a curable resin composition, and a cured product thereof. The present invention relates to a sealing material for a semiconductor device, a sealing material for a liquid crystal display device, and a sealing material for an organic EL device. It is suitably used for electric and electronic parts such as materials, printed wiring boards, build-up laminates, and composite materials for lightweight and high-strength structural materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics.

In recent years, the required characteristics of laminates on which electric and electronic components are mounted have been broadened and advanced due to the expansion of their application fields. In particular, with the miniaturization, thinning, and high density of semiconductor packages (hereinafter, referred to as PKG) used for smartphones and the like, thinning of the PKG substrate is required. Since the rigidity is reduced, a problem such as a large warpage occurs due to heating when the PKG is solder-mounted on a motherboard (PCB). In order to reduce this, a PKG substrate material having a high Tg higher than the solder mounting temperature is required.

In addition, with the recent increase in capacity and high-speed communication, the frequency of electric signals handled by information and communication equipment tends to increase year by year, but as the signal frequency increases, the electric signals are converted into heat in the circuit. Transmission loss increases, and it becomes difficult to transmit a signal efficiently. In order to reduce this, a substrate material having a low dielectric loss tangent is also required.

Especially, in the fifth generation communication system “5G” whose development is currently accelerating, it is expected that the data communication of various devices such as smartphones will have even larger capacity and higher speed communication. The need for a low dielectric loss tangent material is increasing more and more, and a dielectric loss tangent of 0.005 or less at least at 1 GHz is required, and a material that can achieve the above heat resistance and dielectric properties (dielectric loss tangent) is required. .

Furthermore, in the field of automobiles, computerization is progressing, and precision electronic devices may be arranged near the engine drive unit, so that a higher level of heat and moisture resistance is required. In addition, SiC semiconductors have begun to be used in electric trains, air conditioners, and the like, and extremely high heat resistance is required for sealing materials for semiconductor elements, so that conventional epoxy resin sealing materials cannot be used.

を Various functional groups are being studied against the background of this technological change. For example, Patent Document 1 uses a phenol resin substituted with a propenyl group, but has insufficient hygroscopicity and electrical properties. In addition, in Patent Document 2, a phenol resin substituted with an allyl group is used, but the reactivity is poor, Claisen rearrangement occurs simultaneously in the curing process, and a hydroxyl group is generated, so that electrical characteristics are not satisfactory.

材料 It is not easy to develop materials and hardening systems that can achieve both high heat resistance and electrical characteristics, and this is one of the issues that need to be solved.

JP-A-04-359911 WO 2016/002704

The present invention has been made in view of such circumstances, and has as its object to provide a compound exhibiting excellent heat resistance and electrical properties, and a curable resin composition thereof.

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that an aromatic amine resin having an N-alkyl group and a cured product of the curable resin composition have excellent electrical properties, and completed the present invention. It led to.

That is, the present invention relates to the following [1] to [11].
[1]
An aromatic amine resin having an N-alkyl group represented by the following formula (1).

(In the formula (1), a plurality of R's each independently represent hydrogen or a hydrocarbon group having 1 to 15 carbon atoms, provided that all R's are hydrogen. each independently represent a hydrogen atom, a hydrocarbon group of 1 to 15 carbon atoms, Y is _.l 1, _{l 2} and m representing a hydrocarbon group having 2 to 30 carbon atoms is an integer of 1 or more, _{l 1} + M ≦ 5, l ₂ + m ≦ 4, and n represents 1 ≦ n ≦ 15.)
[2]
In the formula (1), the aromatic amine resin having an N-alkyl group according to the above item [1], wherein Y is any one of (a) to (d) described in the following formula (2).

[3]
An aromatic amine resin having an N-alkyl group according to the above item [2] represented by the following formula (3).

(N is an average value and represents 1 ≦ n ≦ 15.)
[4]
In the above formula (1), the N-alkyl group according to the above [1], wherein Y is a methylene bond, and the component represented by n = 1 in gel permeation analysis is at least 5 area% and less than 50 area%. Aromatic amine resin having.
[5]
The aromatic amine resin having an N-alkyl group according to the above item [4], wherein in the formula (1), the component represented by n = 4 or more is 5 to less than 80 area%.
[6]
The aromatic amine resin having an N-alkyl group according to the above item [4] or [5], represented by the following formula (4):

(N is an average value and represents 1 ≦ n ≦ 15.)
[7]
In the above formula (1) or (4), when the component represented by n = 1 in the gel permeation analysis is A area% and the component represented by n = 4 or more is B area%, B / A is The aromatic amine resin having an N-alkyl group according to any one of the above items [4] to [6], which has a value of 0.1 or more and less than 20.
[8]
When the amine equivalent is 116 g / eq. 120 g / eq. The aromatic amine resin having an N-alkyl group according to any one of the above items [4] to [7], wherein
[9]
A curable resin composition comprising the aromatic amine resin having an N-alkyl group according to any one of the above items [1] to [8] and a maleimide resin.
[10]
The curable resin composition according to the above item [9], wherein the compounding equivalent ratio of the compounding equivalent α of the aromatic amine resin having an N-alkyl group to the compounding equivalent β of the maleimide resin is 0.9 ≦ α / β ≦ 2.5. object.
[11]
A cured product obtained by curing the curable resin composition according to [9] or [10].

硬化 The curable resin composition of the present invention has excellent curability, and the cured product has excellent electrical properties and heat resistance. Therefore, insulating materials for electric and electronic components (high-reliability semiconductor sealing materials, etc.) and laminated boards (printed wiring boards, ball grid array (BGA) substrates, build-up substrates, etc.), liquid crystal sealing materials, organic EL sealing materials It can be used for adhesives (conductive adhesives and the like) and various composite materials including carbon fiber reinforced plastic (CFRP), paints and the like.

Hereinafter, the present invention will be described in detail.
The present invention relates to an aromatic amine resin having an N-alkyl group represented by the following formula (1).

(In the formula (1), a plurality of R's each independently represent hydrogen or a hydrocarbon group having 1 to 15 carbon atoms, provided that all R's are hydrogen. each independently represent a hydrogen atom, a hydrocarbon group of 1 to 15 carbon atoms, Y is _.l 1, _{l 2} and m representing a hydrocarbon group having 2 to 30 carbon atoms is an integer of 1 or more, _{l 1} + M ≦ 5, l ₂ + m ≦ 4, and n represents 1 ≦ n ≦ 15.)

Hereinafter, in the above formula (1), preferred embodiments will be described for each of a case where Y is a hydrocarbon group having 2 to 30 carbon atoms (A) and a case where Y is a hydrocarbon group having 1 carbon atom (B). .

[A: when Y is a hydrocarbon group having 2 to 30 carbon atoms]
In the above formula (1), Y is preferably a hydrocarbon group having 2 to 30 carbon atoms, and more preferably a hydrocarbon group having 6 to 18 carbon atoms. Further, Y preferably further has one or more aromatic groups from the viewpoint of improving flame retardancy, electric characteristics, and water absorption characteristics.
In the above case, Y is exemplified by the following formula (2), but is not limited thereto.

(In the formula (2), * represents a bond to the aromatic amine segment having an N-alkyl group in the formula (1).)

中でも Of the formula (2), the structures of (b) and (d) are preferable, and the structure of (b) is more preferable.

When Y in the above formula (1) is represented by the above formula (2), the lower limit of the component represented by n = 1 in the above formula (1) by gel permeation (GPC) analysis is 5% by area or more. Preferably, it is at least 10 area%, particularly preferably at least 20 area%. A preferred upper limit is less than 50 area%, more preferably less than 45 area%, and particularly preferably less than 40 area%. When the component represented by n = 1 is 5 area% or more, the viscosity does not become extremely high and the handleability is good, and when it is less than 50 area%, a decrease in heat resistance can be suppressed.

In the present invention, GPC analysis is measured under the following conditions.
[Various conditions of GPC]
Manufacturer: Waters
Column: Guard column SHOdex GPC KF-601 (2), KF-602, KF-602.5, KF-603
Flow rate: 1.23 ml / min.
Column temperature: 25 ° C
Solvent used: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)

{When Y in the above formula (1) is represented by the above formula (2), the amine equivalent is 115 g / eq. 400 g / eq. Less than 120 g / eq. 250 g / eq. More preferably, it is less than. When the amine equivalent is 115 g / eq. With the above, the concentration of the polar group in the molecule is reduced, so that the electric characteristics are improved. In addition, if it is 400 or less, the curability becomes good.

ＹWhen Y in the formula (1) is represented by the formula (2), the softening point is preferably 30 ° C. or more and less than 120 ° C., and more preferably 40 ° C. or more and less than 100 ° C. When the softening point is 30 ° C. or higher, the heat resistance is good, and when the softening point is 120 ° C. or lower, the hand rigging property during mixing and the like is good.

ＹWhen Y in the formula (1) is represented by the formula (2), the ICI viscosity (150 ° C.) is preferably less than 4 Pa · s, more preferably less than 3 Pa · s. If the ICI viscosity (150 ° C.) is less than 4 Pa · s, the handleability during mixing and the like is good.

[B: when Y is a hydrocarbon group having 1 carbon atom]
In the aromatic amine resin having an N-alkyl group of the present invention, in the formula (1), Y is a methylene bond, and the lower limit of the component represented by n = 1 in GPC analysis is 5 area% or more. It is preferably at least 10 area%, more preferably at least 20 area%, most preferably at least 30 area%. A preferred upper limit is less than 50 area%, and more preferably less than 40 area%. When the component represented by n = 1 is 5 area% or more, the viscosity does not become extremely high and the handling property is improved, and when it is less than 50 area%, a decrease in heat resistance can be suppressed.
Further, the lower limit of the component represented by n = 4 or more is preferably 5 area% or more, more preferably 10 area% or more, and particularly preferably 30 area% or more. A preferred upper limit is less than 80 area%, more preferably less than 60 area%, and particularly preferably less than 50 area%. When the component represented by n = 4 or more is 5 area% or more, solvent solubility is improved. In addition, the crosslinked structure of the cured product becomes more rigid, and molecular motion is suppressed, so that heat resistance and electrical properties are improved, and chemical resistance is improved by increasing the number of crosslink points. If it is less than 80% by area, the handling property does not decrease.

When Y in the above formula (1) is a methylene bond, as described above, both the low molecular weight component and the high molecular weight component have a distribution, and have a wide molecular weight distribution. Therefore, it has an effect of being excellent in handling properties, solvent solubility, heat resistance, electrical properties, chemical resistance and a balance of these properties.
Therefore, in the formula (1), when the component represented by n = 1 in the GPC analysis is A area%, and the total value of the GPC area% of the components represented by n = 4 or more is B area%, / A is usually 0.1 or more and less than 20. The lower limit of B / A is preferably 0.3 or more, more preferably 0.5 or more, and particularly preferably 1 or more. The upper limit of B / A is preferably less than 10, more preferably less than 5, and particularly preferably less than 3.

{When Y in the formula (1) is a methylene bond, the lower limit of the amine equivalent is 116 g / eq. It is preferably at least 118 g / eq. More preferably, the above is true. The upper limit of the amine equivalent is 125 g / eq. Is preferably less than 120 g / eq. Is less than. When it is in the above range, a certain reactivity is exhibited, and desired characteristics such as high heat resistance and good electrical characteristics can be obtained.

最も The most preferred structure when Y in the above formula (1) is a methylene bond is represented by the following formula (4).

(N is an average value and represents 1 ≦ n ≦ 15.)

極性 The aromatic amine resin having an N-alkyl group of the present invention has no polar group remaining after the reaction with the maleimide resin. In addition, since the three-dimensional crosslinked structure generated by the reaction between the maleimide group and the amino group is rigid, it exhibits excellent heat resistance and electrical properties.

Next, a method for producing an aromatic amine resin having an N-alkyl group of the present invention will be described.
First, the aromatic amine compound having an N-alkyl group of the present invention is an aniline compound represented by the following formula (5), and any carbonyl compound, any halogen compound, any olefin compound, or any alcohol. A compound having a hydrophilic hydroxyl group is used as a raw material.

(In the formula (5), R, X, l ₂ , and m are the same as in the formula (1).)

Examples of the aniline-based compound represented by the formula (5) include aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N-isopropylaniline, N-butylaniline, Nt-butylaniline, N-pentylaniline, N-hexylaniline, N-heptylaniline, N-octylaniline, N-nonylaniline, N-decylaniline, N-methyl-o-toluidine, N-methyl-m-toluidine, N-methyl- Examples include, but are not limited to, p-toluidine, N-methyl-o-anisidine, N-methyl-m-anisidine, N-methyl-p-anisidine. These may be used alone or in combination of two or more. From the viewpoint of heat resistance and electrical properties, N-methylaniline, N-ethylaniline, N-propylaniline, N-isopropylaniline, N-butylaniline, and Nt-butylaniline are preferable, and N-methylaniline is more preferable. , N-ethylaniline, N-propylaniline and N-isopropylaniline, more preferably N-methylaniline and N-ethylaniline.

Any carbonyl compound is represented by the following formula (6).

(In the formula (6), a plurality of R ² are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, Represents a fluoroaryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, or an arylalkenyl group having 8 to 40 carbon atoms. Indicate that they may combine to form a ring structure.)

Examples of the carbonyl compound represented by the formula (6) include formaldehyde, acetaldehyde, propylaldehyde, butyraldehyde, valeraldehyde, capronaldehyde, benzaldehyde, chlorbenzaldehyde, bromobenzaldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, adipine Aldehydes such as aldehyde, pimeraldehyde, sebacinaldehyde, acrolein, crotonaldehyde, salicylaldehyde, phthalaldehyde, hydroxybenzaldehyde, furfural, tolualdehyde, α-naphthaldehyde, β-naphthaldehyde, acetone, methyl ethyl ketone, diethyl ketone, benzyl , Acetylacetone, methyl isopropyl ketone, methyl isobutyl keto , Acetophenone, ethylphenylketone, cyclohexanone, cyclopentanone, benzophenone, fluorenone, indanone, 3,3,5-trimethylcyclohexanone, anthraquinone, 4-hydroxyacetophenone, acenaphthenequinone, quinone, benzoylacetone, adamantanone, diacetyl And the like. One type of carbonyl compound may be used alone, or two or more types may be used in combination.

Of the carbonyl compounds, formaldehyde, acetaldehyde, benzaldehyde, acetone, methyl ethyl ketone, acetophenone, cyclohexanone, cyclopentanone, and benzophenone are preferable in terms of heat resistance, and glutaraldehyde, glyoxal, and formaldehyde are more preferable, and formaldehyde is more preferable.

As the arbitrary halogen compound, any known compounds may be used. Preferably, a compound containing a structure represented by the following formula (7) in a molecule is exemplified.

(In the formula (7), N represents a natural number of 1 or more.)

Examples of the halogen compound capable of forming the structure of the above formula (7) include о-xylylene difluoride, m-xylylene difluoride, p-xylylene difluoride, о-xylylene dichloride, m-xylylene dichloride , P-xylylene dichloride, о-xylylene dibromide, m-xylylene dibromide, p-xylylene dibromide, о-xylylene diiodide, m-xylylene diiodide, p-xylylene diiodide, 4,4 ' -Bisfluoromethylenebiphenyl, 4,4'-bischloromethylenebiphenyl, 4,4'-bisbromomethylenebiphenyl, 4,4'-bisiodomethylenebiphenyl, 2,4-bisfluoromethylenebiphenyl, 2,4-bis Chloromethylenebiphenyl, 2,4-bisbromomethylenebi Phenyl, 2,4-bisiodomethylenebiphenyl, 2,2′-bisfluoromethylenebiphenyl, 2,2′-bischloromethylenebiphenyl, 2,2′-bisbromomethylenebiphenyl, 2,2′-bisiodomethylenebiphenyl From the viewpoint of the reactivity of the raw materials during synthesis, chloride compounds, bromide compounds, and iodide compounds are preferable, and chloride compounds and bromide compounds are more preferable.

中 In the formula (7), N is preferably 1 to 8, more preferably 1 to 5. More preferably, it is 1 to 3. As the number of N increases, it becomes more difficult to achieve both heat resistance and dielectric properties, and curability also decreases.

As the arbitrary olefin compound, any known olefin compound may be used. Preferably, a compound containing a structure represented by the following formula (8) in a molecule is exemplified.

化合物 As the compound having an arbitrary alcoholic hydroxyl group, any known compound may be used. Preferably, a xylene formalin resin such as Nicanol Y-50, Nikanol Y-100, Nikanol Y-1000, Nikanol LLL, Nikanol LL, Nikanol L, Nikanol H, Nikanol G, Nikanol H-80 (all manufactured by Fudoh Co., Ltd.) Besides o-xylylene glycol, m-xylylene glycol and p-xylene glycol, those containing a structure represented by the following formula (9) in the molecule can be mentioned.

The reaction with an aniline compound having an N-alkyl group represented by the above formula (5) and any carbonyl compound or any halogen compound or any olefin compound, or any compound having an alcoholic hydroxyl group is known. Can be done in a way. The amount of any carbonyl compound, any halogen compound, any olefin compound, or any compound having an alcoholic hydroxyl group to be used is generally 0.05 to 1.0 mol per 1 mol of the aniline compound used. , Preferably 0.1 to 1.0 mol. More preferably, it is 0.1 to 0.9 mol. If the charged amount of an arbitrary halogen compound, an arbitrary olefin compound, or an arbitrary compound having an alcoholic hydroxyl group is small, the molecular weight of a target condensate is not sufficiently increased.

During the reaction, an acidic catalyst such as hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, zinc chloride, ferric chloride, aluminum chloride, p-toluenesulfonic acid, methanesulfonic acid, and activated clay may be used, if necessary. These may be used alone or in combination of two or more. The amount of the catalyst to be used is generally 0.1 to 2.0 mol, preferably 0.2 to 1.5 mol, per 1 mol of aniline used. If the amount is too large, the amount of the base necessary for the neutralization step increases, and industrial waste may increase. If the amount is too small, the progress of the reaction may slow down. As a reaction solvent, an organic solvent such as toluene or xylene may be used as necessary, in addition to water, or may be used without a solvent.

For example, after adding an acid catalyst to a mixed solution of an aniline-based compound having an N-alkyl group represented by the formula (5) and water, the carbonyl compound or an arbitrary carbonyl compound is added at 20 to 200 ° C., preferably 30 to 150 ° C. An optional halogen compound is added over 0.1 to 10 hours, preferably 0.5 to 5 hours, and the temperature is raised to 40 to 300 ° C., preferably 40 to 250 ° C. for 1 to 30 hours, preferably 2 to 30 hours. Perform the reaction for ２０20 hours. After completion of the reaction, the acid catalyst is neutralized with an aqueous alkali solution, and a water-insoluble organic solvent is added to the oil layer, and washing with water is repeated until the wastewater becomes neutral.

The curable resin composition of the present invention contains a maleimide resin.
As the maleimide resin, a conventionally known maleimide resin can be used. Specific examples of the maleimide resin include 4,4'-diphenylmethanebismaleimide, polyphenylmethanemaleimide, m-phenylenebismaleimide, 2,2'-bis [4- (4-maleimidophenoxy) phenyl] propane, 3,3 '-Dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 4,4'-diphenylether bismaleimide, 4,4'-diphenylsulfonebismaleimide , 1,3-bis (3-maleimidophenoxy) benzene, 1,3-bis (4-maleimidophenoxy) benzene and the like. From the viewpoint of solvent solubility, polyphenylmethane maleimide and a maleimide resin having a molecular weight distribution such as a maleimide resin described in JP-A-2009-001783 and JP-A-01-294662 are preferable. These may be used alone or in combination of two or more. The blending amount of the maleimide resin is preferably 5 times or less, more preferably 2 times or less in terms of mass ratio.
Maleimide resins described in JP-A-2009-001783 and JP-A-01-294662 are particularly preferable because of their excellent low moisture absorption, flame retardancy and dielectric properties.

The lower limit of the compounding equivalent ratio α / β between the compounding equivalent α of the aromatic amine resin having an N-alkyl group and the compounding equivalent β of the maleimide resin is preferably 0.9 or more, more preferably 1.1 or more. Yes, particularly preferably 1.2 or more, and most preferably 1.4 or more. The upper limit of the compounding equivalent ratio α / β is preferably 2.5 or less, more preferably 2.2 or less, and particularly preferably 2.0 or less.
When the blending equivalent ratio α / β is 0.5 or more, an effect of lowering the dielectric constant can be obtained. Further, in the curing reaction between the maleimide and the aromatic amine resin described in the present invention, anionic polymerization between the maleimides occurs simultaneously, so that if the blending equivalent ratio α / β is 3.0 or less, surplus amine that cannot participate in the polymerization remains. Without this, the dielectric properties, heat resistance and the like are improved.

ラジカル In the curable resin composition of the present invention, a radical polymerization initiator can be used for reacting a maleimide group. Examples of the radical polymerization initiator that can be used include ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, diacyl peroxides such as benzoyl peroxide, dicumyl peroxide, and 1,3-bis- (t-butylperoxy). Dialkyl peroxides such as isopropyl) -benzene, peroxyketals such as t-butylperoxybenzoate and 1,1-di-t-butylperoxycyclohexane, α-cumylperoxy neodecanoate, t-butyl Peroxyneodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t- Butyl peroxy-2-ethylhexanoe And alkyl peresters such as t-amyl peroxy-3,5,5-trimethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, t-amyl peroxybenzoate, Peroxy such as -2-ethylhexylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxyisopropylcarbonate, 1,6-bis (t-butylperoxycarbonyloxy) hexane Organic peroxides such as carbonates, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyoctoate, lauroyl peroxide, azobisisobutyronitrile, 4,4′-azobis (4-cyano Valeric acid), 2,2'-azobis (2,4- Known radical polymerization initiators such as azo compounds such as dimethylvaleronitrile) are exemplified, but not particularly limited thereto. Ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, peroxycarbonates, and the like are preferable, and dialkyl peroxides are more preferable. The amount of the radical polymerization initiator to be added is preferably from 0.01 to 5 parts by mass, particularly preferably from 0.01 to 3 parts by mass, per 100 parts by mass of the curable resin composition. If the amount of the radical polymerization initiator used is large, the molecular weight does not sufficiently elongate during the polymerization reaction.

エポキシ The curable resin composition of the present invention may contain an epoxy resin. As the epoxy resin, any of conventionally known epoxy resins can be used. Specific examples thereof include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.) and phenols (phenol, alkyl-substituted). Phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc. and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde) Phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.); And phenols with various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.); Polycondensates with ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.); polycondensates with the above phenols and aromatic dimethanols (benzene dimethanol, biphenyl dimethanol, etc.); Polycondensates of phenols with aromatic dichloromethyls (α, α′-dichloroxylene, bischloromethylbiphenyl and the like); and the phenols and aromatic bisalkoxymethyls (bismethoxymethylbenzene, Glycidyl ether-based epoxy resin, alicyclic epoxy resin, glycidylamine-based polycondensate with bismethoxymethyl biphenyl, bisphenoxymethyl biphenyl, etc .; Examples include an epoxy resin and a glycidyl ester-based epoxy resin, but are not limited thereto as long as it is a commonly used epoxy resin. These may be used alone or in combination of two or more. Starting from a phenol aralkyl resin obtained by a condensation reaction between a phenol and a bishalogenomethylaralkyl derivative or an aralkyl alcohol derivative, an epoxy resin obtained by dehydrochlorination with epichlorohydrin has low hygroscopicity, flame retardancy, It is particularly preferable as an epoxy resin because of its excellent dielectric properties.

(4) The curable resin composition of the present invention may contain a curing agent other than the aromatic amine compound having an N-alkyl group. For example, acid anhydride compounds, amide compounds, phenol compounds, active ester compounds and the like can be mentioned. Specific examples of the curing agent that can be used in combination are amide compounds such as polyamide resin synthesized from dicyandiamide, a dimer of linolenic acid and ethylenediamine; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and maleic anhydride. Acid anhydride compounds such as acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride; bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc. or phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene) , Alkyl-substituted dihydroxybenzene, dihydroxynaphthale Etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) or the above-mentioned phenols And polymers of various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), or the above-mentioned phenols Polycondensates of ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.) Or a polycondensate of the above phenols with aromatic dimethanols (benzene dimethanol, biphenyl dimethanol, etc.), or the above phenols and aromatic dichloromethyls (α, α Polycondensate with '-dichloroxylene, bischloromethylbiphenyl, etc.), or polycondensation of the above phenols with aromatic bisalkoxymethyls (bismethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenoxymethylbiphenyl, etc.) Phenol compounds such as condensates, polycondensates of the above bisphenols and various aldehydes, and modified products thereof; imidazole, trifluoroborane-amine complex, guanidine derivatives; phenol esters, thiophenol esters , N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc. Ester compounds; are may be mentioned is the it is not limited to such.

場合 When a curing agent is used in the curable resin composition of the present invention, the amount used is preferably 0.6 to 1.1 equivalents to 1 equivalent of the epoxy group of the epoxy resin. If the epoxy group exceeds 1.1 equivalents, or if the epoxy group is less than 0.6 equivalents, the curing agent will be left behind, and curing may be incomplete and good cured physical properties may not be obtained. However, this does not apply when the epoxy resin and the curable special resin are contained.The amount is the amount of the curing agent for the remaining epoxy groups after subtracting the amount of epoxy consumed by the special resin. Is required.

The curable resin composition used in the present invention may contain a curing accelerator. Specific examples of the curing accelerator that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, and 1,8-diaza- Tertiary amines such as bicyclo (5,4,0) undecene-7; phosphines such as triphenylphosphine; and metal compounds such as tin octylate. The curing accelerator is used in an amount of 0.1 to 10.0 parts by weight based on 100 parts by weight of the epoxy resin as required.

(4) The curable resin composition used in the present invention may contain additives such as a flame retardant and a filler, if necessary, as long as the properties such as dielectric properties and heat resistance of the cured product are not deteriorated.

The filler that can be blended is not particularly limited, but as the inorganic filler, fused silica, crystalline silica, alumina, calcium carbonate, calcium silicate, barium sulfate, talc, clay, magnesium oxide, aluminum oxide, beryllium oxide, oxide Examples include iron, titanium oxide, aluminum nitride, silicon nitride, boron nitride, mica, glass, and quartz. It is also preferable to use a metal hydroxide such as magnesium hydroxide or aluminum hydroxide to further impart a flame retardant effect. Also, two or more kinds may be used in combination. Among these inorganic fillers, silicas such as fused silica and crystalline silica are preferable because of their low cost and good electrical reliability.

In the curable resin composition used in the present invention, the amount of the inorganic filler used in the total amount is usually 10% by weight to 95% by weight, preferably 10% by weight to 80% by weight, more preferably 10% by weight to 75% by weight. % Range. When the content is 10% by weight or more, the effect of flame retardancy becomes good, and the elastic modulus also improves. On the other hand, when the content is 95% by weight or less, a uniform molded body can be obtained without the filler settling in the varnish.
The shape, particle size and the like of the inorganic filler are not particularly limited, but are usually from 0.01 to 50 μm, preferably from 0.1 to 20 μm.

カップ The curable resin composition used in the present invention may contain a coupling agent for enhancing the adhesiveness between the glass cloth or the inorganic filler and the resin component. As the coupling agent, any of conventionally known coupling agents can be used.For example, vinyl alkoxy silane, epoxy alkoxy silane, styryl alkoxy silane, methacryloxy alkoxy silane, acryloxy alkoxy silane, amino alkoxy silane, mercapto alkoxy silane, isocyanate alkoxy Examples include various alkoxysilane compounds such as silane, alkoxytitanium compounds, and aluminum chelates. These may be used alone or in combination of two or more. The method of adding the coupling agent may be such that after treating the surface of the inorganic filler with the coupling agent in advance, the inorganic filler may be mixed with the resin, or the inorganic filler may be mixed with the resin after mixing the coupling agent. .

シア The curable resin composition of the present invention may contain a cyanate ester resin. As the cyanate ester compound that can be added to the curable resin composition of the present invention, a conventionally known cyanate ester compound can be used. Specific examples of cyanate ester compounds include polycondensates of phenols and various aldehydes, polymers of phenols and various diene compounds, polycondensates of phenols and ketones, and polycondensations of bisphenols and various aldehydes. Cyanate ester compounds obtained by reacting a product with a cyanogen halide are exemplified, but not limited thereto. These may be used alone or in combination of two or more.

{Examples of the phenols include phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, and dihydroxynaphthalene.

Examples of the various aldehydes include formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, and the like.
Examples of the various diene compounds include dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, and isoprene.
Examples of the ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, and benzophenone.
Specific examples of the cyanate ester compound include dicyanatobenzene, tricyanatobenzene, dicyanatonaphthalene, dicyanatobiphenyl, 2,2′-bis (4-cyanatophenyl) propane, and bis (4-cyanatophenyl) Methane, bis (3,5-dimethyl-4-cyanatophenyl) methane, 2,2′-bis (3,5-dimethyl-4-cyanatophenyl) propane, 2,2′-bis (4-cyanatophenyl) ) Ethane, 2,2'-bis (4-cyanatophenyl) hexafluoropropane, bis (4-cyanatophenyl) sulfone, bis (4-cyanatophenyl) thioether, phenol novolak cyanate, phenol dicyclopentadiene Examples include those obtained by converting a hydroxyl group of a co-condensate to a cyanate group. The present invention is not limited to.
Further, a cyanate ester compound whose synthesis method is described in JP-A-2005-264154 is particularly preferable as a cyanate ester compound because of its low hygroscopicity, flame retardancy and excellent dielectric properties.

When the curable resin composition of the present invention contains a cyanate resin, in order to form a sym-triazine ring by trimerizing a cyanate group as needed, zinc naphthenate, cobalt naphthenate, copper naphthenate, A catalyst such as lead naphthenate, zinc octylate, tin octylate, lead acetylacetonate, dibutyltin maleate and the like can be contained. The catalyst is used in an amount of usually 0.0001 to 0.10 parts by mass, preferably 0.00015 to 0.0015 parts by mass, based on 100 parts by mass of the total mass of the thermosetting resin composition.

公知 The curable resin composition of the present invention may contain known additives as necessary. Specific examples of additives that can be used include polybutadiene and modified products thereof, modified acrylonitrile copolymer, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, silicone gel, silicone oil, and silane coupling agents. Coloring agents such as a surface treatment agent for a material, a release agent, carbon black, phthalocyanine blue, and phthalocyanine green are exemplified. The amount of these additives is preferably 1,000 parts by mass or less, more preferably 700 parts by mass or less, based on 100 parts by mass of the curable resin composition.

有機 The curable resin composition of the present invention may further contain an organic solvent. Examples of the solvent used include amide solvents such as γ-butyrolactones, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolidinone, and tetramethylene sulfone. Sulfones, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate, ether solvents such as propylene glycol monobutyl ether, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone Solvents, and aromatic solvents such as toluene and xylene. The solvent is used in a range where the solid content of the obtained varnish excluding the solvent is usually 10 to 80% by weight, preferably 20 to 70% by weight. In addition, a prepreg or a resin sheet can be molded using the obtained varnish.

Here, the prepreg will be described. The prepreg is obtained by impregnating the varnish into a fiber base material. Thereby, a prepreg excellent in heat resistance, low expansion property and flame retardancy can be obtained. Examples of the fiber base include glass fiber base such as glass woven cloth, glass nonwoven cloth, and glass paper; woven cloth and nonwoven cloth made of synthetic fibers such as paper, aramid, polyester, aromatic polyester, and fluororesin; and metal. Woven fabrics, nonwoven fabrics, mats, and the like made of fibers, carbon fibers, mineral fibers, and the like are included. These substrates may be used alone or as a mixture. Of these, glass fiber substrates are preferred. Thereby, rigidity and dimensional stability of the prepreg can be improved. The glass fiber substrate preferably contains at least one selected from the group consisting of T glass, S glass, E glass, NE glass, and quartz glass.

The method of impregnating the curable resin composition of the present invention into the fiber base material includes, for example, a method of dipping the base material in a resin varnish, a method of applying with a variety of coaters, and a method of spraying with a spray. Among these, the method of immersing the base material in the resin varnish is preferable. Thereby, the impregnation property of the resin composition to the base material can be improved. When the substrate is immersed in the resin varnish, ordinary impregnation coating equipment can be used. For example, the curable resin composition of the present invention as it is, or in the form of a varnish dissolved or dispersed in a solvent, is impregnated into a substrate such as a glass cloth, and then usually dried at 80 to 200 ° C. in a drying furnace or the like. However, in the case of using a solvent, the temperature is not lower than the temperature at which the solvent can be volatilized), preferably at a temperature of 150 to 200 ° C. for 1 to 30 minutes, preferably 1 to 15 minutes to obtain a prepreg. In addition, a method of pressing a resin sheet described below against a glass cloth, transferring the resin sheet, and obtaining a prepreg is also applicable.

Next, the resin sheet will be described. The resin sheet using the varnish has a predetermined thickness after drying the varnish on a planar support by various coating methods such as a gravure coating method known per se, screen printing, a metal mask method, and a spin coating method. For example, it is obtained by applying the coating so as to have a thickness of 5 to 100 μm and then drying it. The method of applying the coating depends on the type, shape, size, thickness of the coating, heat resistance of the support and the like. It is appropriately selected. Examples of the planar support include various high-grade materials such as polyamide, polyamideimide, polyarylate, polyethylene terephthalate, polybutylene terephthalate, polyetherketone, polyetherimide, polyetheretherketone, polyketone, polyethylene, polypropylene, and Teflon (registered trademark). Examples include a film made of a molecule and / or a copolymer thereof, and a metal foil such as a copper foil. After application, the sheet is dried to obtain a sheet-shaped composition (the sheet of the present invention), but the sheet may be further heated to form a sheet-shaped cured product. Further, the solvent may be dried and cured by a single heating. The aromatic amine resin composition having an N-alkyl group of the present invention is applied to both sides or one side of the support by the above-mentioned method and heated to form a layer of the cured product of the present invention on both sides or one side of the support. Can be formed. In addition, it is also possible to create a laminate by bonding and curing the adherend before curing. Further, the resin sheet of the present invention can be used as an adhesive sheet by peeling it off from the support, and can be brought into contact with an adherend, applied with pressure and heat as needed, and then adhered together with curing.

Next, the laminate will be described. The laminate is formed by heating and pressing the prepreg and / or the resin sheet. Thereby, a printed wiring board excellent in heat resistance, low expansion property and flame retardancy can be obtained. In the case of one prepreg and / or resin sheet, a metal foil is laminated on both upper and lower surfaces or one surface. Also, two or more prepregs and / or resin sheets can be laminated. When two or more prepregs and / or resin sheets are laminated, a metal foil or a film and / or a resin sheet are laminated on the outermost upper and lower surfaces or one surface of the laminated prepreg and / or resin sheet. Next, a printed wiring board can be obtained by subjecting a prepreg and / or a resin sheet and a metal foil to be laminated to each other with heat and pressure. The heating temperature is not particularly limited, but is preferably from 120 to 220 ° C, particularly preferably from 150 to 200 ° C. The pressure for pressurizing is not particularly limited, but is preferably 1.5 to 5 MPa, particularly preferably 2 to 4 MPa. If necessary, post-curing may be performed at a temperature of 150 to 300 ° C. in a high-temperature tank or the like.

Next, the printed wiring board will be described. The printed wiring board uses the laminated board as an inner circuit board. Circuits are formed on one or both sides of the laminate. In some cases, through holes may be formed by drilling or laser processing, and electrical connection between both surfaces may be made by plating or the like.

多層 The resin sheet or the prepreg is superimposed on the interior circuit board and heated and pressed to obtain a multilayer printed wiring board. Specifically, the insulating layer side of the resin sheet and the inner layer circuit board are combined, and they are vacuum-heat-pressed using a vacuum-pressing type laminator device or the like, and then the insulating layer is heated and cured by a hot-air drying device or the like. Can be obtained. Here, the conditions for the heat-press molding are not particularly limited. For example, the molding can be performed at a temperature of 60 to 160 ° C. and a pressure of 0.2 to 3 MPa. The conditions for the heat curing are not particularly limited. For example, the heat curing can be performed at a temperature of 140 to 240 ° C. for a time of 30 to 120 minutes. Alternatively, the prepreg can be obtained by superimposing the prepreg on an inner layer circuit board and subjecting the prepreg to heat and pressure molding using a flat plate press or the like. The conditions for the heat-press molding are not particularly limited. For example, the molding can be performed at a temperature of 140 to 240 ° C. and a pressure of 1 to 4 MPa. In the heat and pressure molding using such a flat plate press or the like, the insulating layer is cured by heating at the same time as the heat and pressure molding.

Further, the method of manufacturing a multilayer printed wiring board includes a step of continuously laminating the resin sheet or the prepreg on the surface of the inner circuit board on which the inner circuit pattern is formed, and a method of semi-additively forming the conductor circuit layer. Forming step by the build-up method.

硬化 Curing the insulating layer formed from the resin sheet or the prepreg may be in a semi-cured state in order to facilitate subsequent laser irradiation and removal of resin residue and improve desmear property. In addition, the first insulating layer is partially cured (semi-cured) by heating at a temperature lower than a normal heating temperature, and one or more insulating layers are further formed on the insulating layer to form a semi-cured insulating layer. By heating and curing again to such an extent that there is no practical problem, the adhesion between the insulating layer and between the insulating layer and the circuit can be improved. In this case, the semi-curing temperature is preferably from 80 ° C to 200 ° C, more preferably from 100 ° C to 180 ° C. In the next step, an opening is formed in the insulating layer by irradiating a laser in the next step. Before that, the substrate needs to be peeled off. There is no particular problem whether the peeling of the base material is performed after the formation of the insulating layer, before the heat curing, or after the heat curing. The inner circuit board used for obtaining the multilayer printed wiring board is preferably formed by forming a predetermined conductor circuit on both surfaces of a copper-clad laminate by etching or the like and subjecting the conductor circuit portion to blackening. Can be used.

樹脂 Resin residues and the like after laser irradiation are preferably removed with an oxidizing agent such as permanganate and dichromate. Further, the surface of the smooth insulating layer can be roughened at the same time, and the adhesion of the conductive wiring circuit formed by the subsequent metal plating can be improved.

Next, an outer layer circuit is formed. The outer layer circuit is formed by connecting the insulating resin layers by metal plating and forming the outer layer circuit pattern by etching. A multilayer printed wiring board can be obtained in the same manner as when a resin sheet or a prepreg is used. When a resin sheet or a prepreg having a metal foil is used, a circuit may be formed by etching without peeling the metal foil to use it as a conductor circuit. In this case, if an insulating resin sheet with a base material using a thick copper foil is used, it is difficult to form a fine pitch in the subsequent formation of a circuit pattern. Therefore, use an ultra-thin copper foil of 1 to 5 μm or 12 to 18 μm In some cases, half-etching is performed to reduce the thickness of the copper foil to 1 to 5 μm by etching.

絶縁 Furthermore, an insulating layer may be laminated and a circuit may be formed in the same manner as described above. However, due to the design of the multilayer printed wiring board, a solder resist is formed on the outermost layer after the circuit is formed. The method of forming the solder resist is not particularly limited. For example, a method in which a dry film type solder resist is laminated (laminated) and formed by exposure and development, or a method in which a liquid resist is printed is formed by exposure and development. It is done by the method of doing. When the obtained multilayer printed wiring board is used for a semiconductor device, a connection electrode portion is provided for mounting a semiconductor element. The connection electrode portion can be appropriately covered with a metal film such as gold plating, nickel plating, and solder plating. A multilayer printed wiring board can be manufactured by such a method.

Next, the semiconductor device will be described. A semiconductor element having solder bumps is mounted on the multilayer printed wiring board obtained above, and connection with the multilayer printed wiring board is made via the solder bumps. Then, a liquid sealing resin is filled between the multilayer printed wiring board and the semiconductor element to form a semiconductor device. The solder bumps are preferably made of an alloy made of tin, lead, silver, copper, bismuth, or the like. The method of connecting the semiconductor element and the multilayer printed wiring board is to use a flip chip bonder or the like to align the connection electrode portion on the substrate with the solder bump of the semiconductor element, and then use an IR reflow device, a hot plate, or the like. The solder bumps are heated to a melting point or higher using a heating device, and the multilayer printed wiring board and the solder bumps are connected by fusion bonding. In order to improve connection reliability, a layer of a metal having a relatively low melting point, such as a solder paste, may be formed in advance on the connection electrode portion on the multilayer printed wiring board. Prior to this joining step, the connection reliability can be improved by applying a flux to the solder bumps and / or the surface layer of the connection electrode portion on the multilayer printed wiring board.

The board is used for motherboards, network boards, package boards, etc., and is used as a board. Particularly, it is useful as a package substrate as a thin-layer substrate for a single-sided sealing material. When used as a semiconductor encapsulant, semiconductor devices obtained from the composition include, for example, DIP (dual inline package), QFP (quad flat package), BGA (ball grid array), CSP (chip size package), and SOP. (Small outline package), TSOP (thin small outline package), TQFP (thin quad flat package) and the like.

Hereinafter, the present invention will be described in detail with reference to examples. Note that the present invention is not limited to these examples.

Various analysis methods used in the examples were performed under the following conditions.
-Softening point Measured according to JIS K-7234, and the unit is ° C.
Melt viscosity ICI melt viscosity (150 ° C.) Measured by a cone plate method, and the unit is Pa · s.

・ GPC (gel permeation chromatography) analysis manufacturer: Waters
Column: Guard column SHOdex GPC KF-601 (2), KF-602, KF-602.5, KF-603
Flow rate: 1.23 ml / min.
Column temperature: 25 ° C
Solvent used: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)

(Example 1)
To a flask equipped with a thermometer, a condenser, and a stirrer, 150 g of toluene and 56.0 g of N-methylaniline were added and stirred. Next, 43.5 g of 4,4'-bischloromethylenebiphenyl was added over 1 hour and reacted at 65 ° C. for 2 hours. Next, 36.1 g of 35% hydrochloric acid was added dropwise at 80 ° C. or lower. After completion of the dropwise addition, the temperature was raised to 210 ° C. while azeotropic dehydration, and the reaction was performed at 210 ° C. for 15 hours. After the completion of the reaction, 100 g of a 17% aqueous sodium hydroxide solution was added dropwise to make the reaction solution alkaline, and 100 g of toluene and 150 g of N-methylaniline were further added, followed by stirring for 6 hours. After standing and the wastewater, washing was performed until the wastewater became neutral. The solvent, water and unreacted N-methylaniline were distilled off by concentration under reduced pressure to obtain biphenyl-N-methylaniline novolak (BNMAN-1) as a black solid resin (amine equivalent: 208 g, softening point: 79.6). ° C, ICI viscosity (150 ° C): 0.048 Pa · s, composition ratio is GPC area%, n = 1 component: 9.1%, n = 2 component: 31%, n = 3 component: 29%, n = 4 or more high molecular weight components: 30.9%).

(Example 2)
To a flask equipped with a thermometer, a condenser and a stirrer, 50 g of toluene and 171.5 g of N-methylaniline were added and stirred. Next, 50.2 g of 4,4'-bischloromethylenebiphenyl was added over 1 hour and reacted at 65 ° C. for 2 hours. Next, 41.7 g of 35% hydrochloric acid was added dropwise at 80 ° C. or lower. After completion of the dropwise addition, the temperature was raised to 210 ° C. while azeotropic dehydration, and the reaction was performed at 210 ° C. for 15 hours. After completion of the reaction, 40 g of a 48% aqueous sodium hydroxide solution was added dropwise to make the reaction solution alkaline, and 50 g of toluene was further added thereto, followed by stirring for 6 hours. After standing and the wastewater, washing was performed until the wastewater became neutral. The solvent, water and unreacted N-methylaniline were distilled off by concentration under reduced pressure to obtain biphenyl-N-methylaniline novolak (BNMAN-2) as a black solid resin (amine equivalent: 198 g, softening point: 47.3). ° C, ICI viscosity (150 ° C): 0.02 Pa · s, composition ratio in GPC area%: n = 1 component: 71%, n = 2 component: 18%, n = 3 component: 4.6%, n = 4 or more high molecular weight components: 1.3%).

(Example 3)
200 g of water and 214 g of N-methylaniline were added to a flask equipped with a thermometer, a condenser, and a stirrer, followed by stirring. Then, 209 g of 35% hydrochloric acid was added dropwise at 40 ° C. or lower. Next, 108 g of a 37% aqueous formaldehyde solution was added dropwise at 40 ° C. or lower. After the completion of the dropwise addition, the reaction was carried out at 75 to 80 ° C. for 5 hours. After completion of the reaction, 168 g of a 48% aqueous sodium hydroxide solution was added dropwise to make the reaction solution alkaline, and 300 g of toluene was further added thereto, followed by stirring for 6 hours. After standing and the wastewater, washing was performed until the wastewater became neutral. The solvent, water and unreacted N-methylaniline were distilled off by concentration under reduced pressure to obtain 200 g of N-methylaniline novolak (NMAN-1) as a black liquid resin (amine equivalent: 116 g / eq, composition ratio was GPC area). %, N = 1 component: 37%, n = 2 component: 19%, n = 3 component: 14%, n = 4 or more high molecular weight components: 30%).

(Example 4)
N-methylaniline novolak (NMAN-2) was obtained as a black semi-solid resin in the same manner as in Example 3 except that the 37% aqueous formaldehyde solution was changed to 122 g (amine equivalent: 118.6 g / eq, composition ratio: In terms of GPC area%, n = 1 component: 25%, n = 2 component: 15%, n = 3 component: 13%, n = 4 or more high molecular weight component: 47%).

(Example 5)
In a flask equipped with a thermometer, a condenser and a stirrer, 50 g of toluene, 64.1 g of N-methylaniline, α, α, α ′, α′-tetramethyl-1,3-benzenedimethanol and 20 g of activated clay were placed. In addition, the mixture was stirred. The internal temperature was raised to 160 ° C. while performing azeotropic dehydration, and the reaction was carried out at 160 ° C. for 24 hours. After cooling, 150 g of toluene was added, the activated clay was removed by filtration, and the filtrate was concentrated under reduced pressure to convert the aromatic amine resin (BNMACB) having a bis-N-methylaminocumylbenzene structure as a main component into a brown liquid resin. (Amine equivalent: 191 g / eq.).

(Synthesis example 1)
217 g of N-methylaniline novolak (NMAN-3) was obtained as a black liquid resin in the same manner as in Example 3 except that the 37% aqueous formaldehyde solution was changed to 89 g (amine equivalent: 115 g / eq, composition ratio was GPC area). %, N = 1 component: 65%, n = 2 component: 22%, n = 3 component: 8.2%, n = 4 or higher high molecular weight component: 4.8%).

(Synthesis example 2)
A flask equipped with a thermometer, a cooling tube, a Dean-Stark azeotropic distillation trap, and a stirrer was charged with 372 parts of aniline and 200 parts of toluene, and 146 parts of 35% hydrochloric acid was added dropwise at room temperature over 1 hour. After the completion of the dropwise addition, the mixture was heated and cooled to separate water and toluene, which were azeotropic, and then only the organic layer, toluene, was returned to the system to perform dehydration. Next, 125 parts of 4,4′-bis (chloromethyl) biphenyl was added over 1 hour while maintaining the temperature at 60 to 70 ° C., and the reaction was further performed at the same temperature for 2 hours. After completion of the reaction, toluene was distilled off while raising the temperature to 195 to 200 ° C., and the reaction was carried out at this temperature for 15 hours. Then, while cooling, 330 parts of a 30% aqueous sodium hydroxide solution was slowly dropped into the system so that the inside of the system was not violently refluxed. Was placed. The separated lower aqueous layer was removed, and washing of the reaction solution with water was repeated until the washing solution became neutral. Next, 173 parts of an aromatic amine resin (a1) was obtained by distilling off excess aniline and toluene from the oil layer under reduced pressure by heating (200 ° C., 0.6 KPa) using a rotary evaporator. The amount of diphenylamine in the aromatic amine resin (a1) measured by gas chromatography was 2.0%. The obtained resin was again dropped by water in a rotary evaporator under heating and reduced pressure (200 ° C., 4 KPa) instead of blowing steam. As a result, 166 parts of an aromatic amine resin (A1) was obtained. The obtained aromatic amine resin (A1) had a softening point of 56 ° C., a melt viscosity of 0.035 Pa · s, and diphenylamine of 0.1% or less. Based on JIS K-7236 Annex A (correction method for glycidylamine), when the obtained value is defined as amine equivalent, the amine equivalent of A1 is 195 g / eq. Met.

(Synthesis example 3)
A flask equipped with a thermometer, a cooling pipe, a Dean-Stark azeotropic distillation trap, and a stirrer was charged with 147 parts of maleic anhydride and 300 parts of toluene, and then heated and cooled to separate water and toluene, which were azeotropic. Then, only toluene, which is an organic layer, was returned into the system to perform dehydration. Next, a resin solution obtained by dissolving 195 parts of the aromatic amine resin (A1) obtained in Synthesis Example 2 in 195 parts of N-methyl-2-pyrrolidone was taken for 1 hour while maintaining the inside of the system at 80 to 85 ° C. It was dropped. After completion of the dropwise addition, the reaction was carried out at the same temperature for 2 hours, 3 parts of p-toluenesulfonic acid was added, and condensed water and toluene, which azeotrope under reflux conditions, were cooled and separated. Was returned to the system, and a reaction was carried out for 20 hours while performing dehydration. After the completion of the reaction, 120 parts of toluene was added, and water washing was repeated to remove p-toluenesulfonic acid and excess maleic anhydride, and the mixture was heated to remove water from the system by azeotropic distillation. Next, the reaction solution was concentrated under reduced pressure to obtain a resin solution containing 70% of the maleimide resin (M1). The diphenylamine content in the maleimide resin (M1) was 0.1% or less. M1 was heated under reduced pressure to remove the solvent, and the solid was taken out to obtain a solid maleimide resin (MIR). The theoretical maleimide equivalent of MIR calculated from the amine equivalent of the amine resin (A1) used as a raw material is 275 g / eq. Met.

(Examples 6 to 13, Comparative Examples 1 and 2)
N-alkyl group-containing aromatic amine resins (BNMAN-1, NMAN-1 to 3) obtained in Examples 1, 3, and 4 and Synthesis Example 1, 4,4′-diaminodiphenylmethane (manufactured by Tokyo Chemical Industry Co., Ltd.) The maleimide resin (MIR) of Synthesis Example 3 was blended in the ratio (parts by weight) shown in Table 1, heated and melt-mixed in a metal container, poured into a mold as it was, and cured at 220 ° C. for 2 hours.

The physical properties of the cured product thus obtained were measured for the following items, and the results are shown in Table 1.
<Heat resistance test>
Glass transition temperature: a temperature measured by a dynamic viscoelasticity tester when tan δ is the maximum value.
<Dielectric constant test and dielectric loss tangent test>
-A test was performed by a cavity resonator perturbation method using a 1 GHz cavity resonator manufactured by Kanto Electronics Application Development Co., Ltd. However, the test was performed with a sample size of 1.7 mm in width × 100 mm in length and a thickness of 1.7 mm.

From Table 1, it was confirmed that Examples 6 to 13 using the aromatic amine compound having an N-alkyl group of the present invention had better electrical characteristics and higher heat resistance than Comparative Examples 1 and 2.

Therefore, the condensate of an aniline compound having an N-alkyl group and formaldehyde of the present invention can be used as an insulating material for electric and electronic parts (such as a highly reliable semiconductor sealing material) and a laminate (printed wiring board, BGA substrate, build It is useful for various composite materials including CFRP, adhesives (conductive adhesives and the like), paints and the like.

Claims

An aromatic amine resin having an N-alkyl group represented by the following formula (1).

(In the formula (1), a plurality of R's each independently represent hydrogen or a hydrocarbon group having 1 to 15 carbon atoms, provided that all R's are hydrogen. each independently represent a hydrogen atom, a hydrocarbon group of 1 to 15 carbon atoms, Y is .l 1, l 2 and m representing a hydrocarbon group having 2 to 30 carbon atoms is an integer of 1 or more, l 1 + M ≦ 5, l 2 + m ≦ 4, and n represents 1 ≦ n ≦ 15.)
2. The aromatic amine resin having an N-alkyl group according to claim 1, wherein in the formula (1), Y is any one of (a) to (d) described in the following formula (2).
3. The aromatic amine resin having an N-alkyl group according to claim 2, represented by the following formula (3).

(N is an average value and represents 1 ≦ n ≦ 15.)
2. The N-alkyl group according to claim 1, wherein in the formula (1), Y is a methylene bond, and a component represented by n = 1 in gel permeation analysis is 5 to less than 50 area%. Aromatic amine resin.
(5) The aromatic amine resin having an N-alkyl group according to (4), wherein in the formula (1), the component represented by n = 4 or more is at least 5 area% and less than 80 area%.
The aromatic amine resin having an N-alkyl group according to claim 4 or 5, represented by the following formula (4).

(N is an average value and represents 1 ≦ n ≦ 15.)
In the above formula (1) or (4), when the component represented by n = 1 in the gel permeation analysis is A area% and the component represented by n = 4 or more is B area%, B / A is The aromatic amine resin having an N-alkyl group according to any one of claims 4 to 6, which is 0.1 or more and less than 20.
{The amine equivalent is 116 g / eq. 120 g / eq. The aromatic amine resin having an N-alkyl group according to any one of claims 4 to 7, which is less than the above.
A curable resin composition containing the aromatic amine resin having an N-alkyl group according to any one of claims 1 to 8 and a maleimide resin.
10. The curable resin composition according to claim 9, wherein the compounding equivalent ratio of the compounding equivalent α of the aromatic amine resin having an N-alkyl group to the compounding equivalent β of the maleimide resin is 0.9 ≦ α / β ≦ 2.5. .
A cured product obtained by curing the curable resin composition according to claim 9.