JPWO2020027179A1 - Aromatic amine resin having N-alkyl group, curable resin composition and cured product thereof - Google Patents

Abstract

（式（１）中、複数存在するＲはそれぞれ独立して水素、炭素数１〜１５の炭化水素基を表す。但し、Ｒが全て水素となる場合を除くものとする。複数存在するＸはそれぞれ独立して水素原子、炭素数１〜１５の炭化水素基を表す。ｌ_１、ｌ_２およびｍは１以上の整数を表し、ｌ_１＋ｍ≦５、ｌ_２＋ｍ≦４を満たす。ｎは１≦ｎ≦１５を表す。）
Provided is an aromatic amine resin compound having an N-alkyl group that exhibits excellent heat resistance and electrical characteristics, and a curable resin composition thereof. An aromatic amine resin having an N-alkyl group represented by the following formula (1).
[Chemical 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 the R's are hydrogen. Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms, l ₁ , l ₂ and m represent an integer of 1 or more and satisfy l ₁ +m≦5 and l ₂ +m≦4, and n is Represents 1≦n≦15.)

Description

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, and a semiconductor element sealing material, a liquid crystal display element sealing material, an organic EL element sealing material. It is preferably used for electric/electronic parts such as materials, printed wiring boards, and build-up laminated boards, and composite materials for lightweight and high strength structural materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics.

2. Description of the Related Art In recent years, laminated boards on which electric/electronic components are mounted have been required to have a wide range of required characteristics due to the expansion of their fields of use. In particular, as semiconductor packages (hereinafter referred to as PKGs) used in smartphones and the like have become smaller, thinner, and higher in density, PKG substrates have been required to be thinner, but when PKG substrates become thinner, Since the rigidity is reduced, a problem such as a large warpage occurs due to heating when the PKG is solder-mounted on the 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 devices tends to increase year by year, but the higher the signal frequency, the more electric signals are converted into heat in the circuit. Transmission loss increases, making it difficult to transmit signals efficiently. In order to reduce this, a substrate material having a low dielectric loss tangent is also required.

In particular, in the fifth-generation communication system “5G”, which is currently under development, it is expected that the data communication of various devices such as smartphones will have a larger capacity and higher speed. The need for low dielectric loss tangent materials is increasing, 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. ..

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

Against the background of such technological changes, various functional groups have been investigated. For example, Patent Document 1 uses a phenol resin substituted with a propenyl group, but has insufficient hygroscopicity and electrical characteristics. Further, in Patent Document 2, all of the phenol resin substituted with an allyl group is used, but the reactivity is poor, and Claisen rearrangement occurs concurrently during the curing process, and hydroxyl groups are generated, so that the electrical characteristics are not satisfactory.

Thus, it is not easy to develop a material and a curing system that can achieve both high heat resistance and electrical characteristics, and it is one of the problems still to be solved.

JP-A-04-359911 International publication 2016/002704

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

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

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 the R's are hydrogen. Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms, Y represents a hydrocarbon group having 2 to 30 carbon atoms, l ₁ , l ₂ and m each represent an integer of 1 or more, and l ₁ +m≦5 and l ₂ +m≦4 are satisfied, and n represents 1≦n≦15.)
[2]
In the above 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) shown in the following formula (2).

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

(N is an average value and represents 1≦n≦15.)
[4]
In the formula (1), Y is a methylene bond, and the component represented by n=1 by gel permeation analysis is 5 area% or more and less than 50 area%, and the N-alkyl group according to the above item [1] is used. Aromatic amine resin having.
[5]
In the above formula (1), the aromatic amine resin having an N-alkyl group according to the above item [4], wherein the component represented by n=4 or more is 5 area% or more and less than 80 area %.
[6]
An aromatic amine resin having an N-alkyl group according to the above item [4] or [5], which is 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 items [4] to [6], which is 0.1 or more and less than 20.
[8]
The amine equivalent is 116 g/eq. Above 120 g/eq. The aromatic amine resin having an N-alkyl group according to any one of the above items [4] to [7], which is less than.
[9]
A curable resin composition containing the N-alkyl group-containing aromatic amine resin 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 and the compounding equivalent β of the maleimide resin is 0.9≦α/β≦2.5. Stuff.
[11]
A cured product obtained by curing the curable resin composition according to the above [9] or [10].

The curable resin composition of the present invention has excellent curability, and the cured product has excellent electrical characteristics and heat resistance. Therefore, insulating materials for electric and electronic parts (high reliability semiconductor encapsulation materials, etc.) and laminated boards (printed wiring boards, ball grid array (BGA) substrates, build-up boards, etc.), liquid crystal encapsulation materials, organic EL encapsulation materials. , Various composite materials including adhesives (conductive adhesives) and carbon fiber reinforced plastics (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 the R's are hydrogen. Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms, Y represents a hydrocarbon group having 2 to 30 carbon atoms, l ₁ , l ₂ and m each represent an integer of 1 or more, and l ₁ +m≦5 and l ₂ +m≦4 are satisfied, and n represents 1≦n≦15.)

Hereinafter, in the above formula (1), preferable embodiments will be described respectively when Y is a hydrocarbon group having 2 to 30 carbon atoms (A) and when 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, it is more preferable that Y 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 the N-alkyl group of the formula (1).)

Among the above formulas (2), the structures (b) and (d) are preferable, and the structure (b) is more preferable.

When Y in the formula (1) is represented by the formula (2), the lower limit of the component represented by n=1 in the formula (1) by gel permeation (GPC) analysis is 5 area% or more. It is preferable that the amount is 10% by area or more, further preferably 20% by area or more. The 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 is not extremely high and the handling property is good, and when it is less than 50 area%, the 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 (two), 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 formula (1) is represented by the formula (2), the amine equivalent is 115 g/eq. 400 g/eq. Less than 120 g/eq. 250 g/eq. It is more preferable that it is less than. The amine equivalent is 115 g/eq. If it is above, since the polar group concentration in a molecule will be reduced, electric characteristics will improve. If it is 400 or less, the curability will be good.

When Y in the formula (1) is represented by the formula (2), the softening point is preferably 30°C or higher and lower than 120°C, more preferably 40°C or higher and lower 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 rig property during mixing is good.

When 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 handling property during mixing will be 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 %. The preferred upper limit is less than 50 area %, and more preferably less than 40 area %. When the component represented by n=1 is 5% by area or more, the viscosity is not extremely high and the handling property is improved, and when it is less than 50% by area, deterioration of heat resistance can be suppressed.
Further, the lower limit value 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. The 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, the solvent solubility is improved. In addition, the cured product has a more rigid cross-linking structure, which suppresses molecular motion, thereby improving heat resistance and electrical properties, and increasing the number of cross-linking points also improves chemical resistance. If it is less than 80% by area, the handling property does not deteriorate.

When Y in the formula (1) is a methylene bond, both the low molecular weight component and the high molecular weight component have a distribution as described above, and have a wide molecular weight distribution. Therefore, it has an effect of being excellent in handleability, solvent solubility, heat resistance, electrical characteristics, chemical resistance, and a balance of those characteristics.
Therefore, in the above 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 preferable that it is not less than 118 g/eq. It is more preferable when it is above. The upper limit of the amine equivalent is 125 g/eq. It is preferably less than 120 g/eq. Is less than. Within the above range, a certain degree of reactivity is exhibited, and desired characteristics such as high heat resistance and good electrical characteristics can be obtained at the same time.

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

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

In the aromatic amine resin having an N-alkyl group of the present invention, no polar group remains after the reaction with the maleimide resin. In addition, since the three-dimensional crosslinked structure formed by the reaction of the maleimide group and the amino group is rigid, it exhibits excellent heat resistance and electrical characteristics.

Next, a method for producing the N-alkyl group-containing aromatic amine resin 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 reactive hydroxyl group is used as a raw material.

(In the formula (5), R, X, l ₂ , and m are the same as those 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 thereof include p-toluidine, N-methyl-o-anisidine, N-methyl-m-anisidine, N-methyl-p-anisidine, etc., but are not limited thereto. These may be used alone or in combination of two or more. From the viewpoint of heat resistance and electric characteristics, N-methylaniline, N-ethylaniline, N-propylaniline, N-isopropylaniline, N-butylaniline and Nt-butylaniline are preferable, and more preferably N-methylaniline. , N-ethylaniline, N-propylaniline, N-isopropylaniline, and more preferably N-methylaniline and N-ethylaniline.

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

(In formula (6), a plurality of R ^2's each independently represent 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, or a carbon number. It 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. Indicates 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, brombenzaldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde and adipine. Aldehydes, pimelinaldehyde, sebacinaldehyde, acrolein, crotonaldehyde, salicylaldehyde, phthalaldehyde, hydroxybenzaldehyde, furfural, tolualdehyde, α-naphthaldehyde, β-naphthaldehyde and other aldehydes, acetone, methyl ethyl ketone, diethyl ketone, benzyl , Acetylacetone, methylisopropylketone, methylisobutylketone, acetophenone, ethylphenylketone, cyclohexanone, cyclopentanone, benzophenone, fluorenone, indanone, 3,3,5-trimethylcyclohexanone, anthraquinone, 4-hydroxyacetophenone, acenaphthenequinone, Examples thereof include quinone, benzoylacetone, adamantane, and diacetyl. The carbonyl compound may be used alone or in combination of two or more kinds.

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

Any halogen compound may be used as long as it is publicly known. Preferred are those containing a structure represented by the following formula (7) in the molecule.

(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 formula (7) include о-xylylene difluoride, m-xylylene difluoride, p-xylylene difluoride, о-xylylene dichloride and 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 Chloromethylene biphenyl, 2,4-bisbromomethylene biphenyl, 2,4-bisiodomethylene biphenyl, 2,2'-bisfluoromethylene biphenyl, 2,2'-bischloromethylene biphenyl, 2,2'-bisbromomethylene Examples thereof include biphenyl and 2,2′-bisiodomethylene biphenyl, and from the viewpoint of reactivity of raw materials during synthesis, chloride compounds, bromide compounds and iodide compounds are preferable, and chloride compounds and bromide compounds are more preferable. Are listed.

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

Any known olefin compound may be used as long as it is known. Preferred are those containing a structure represented by the following formula (8) in the molecule.

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

The reaction between the aniline-based compound having the N-alkyl group represented by the 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 any way. The amount of any carbonyl compound or any halogen compound or any olefin compound, or any compound having an alcoholic hydroxyl group used is usually 0.05 to 1.0 mol with respect to 1 mol of the aniline compound used. , And preferably 0.1 to 1.0 mol. It is more preferably 0.1 to 0.9 mol. If the charged amount of any halogen compound or any olefin compound or any compound having an alcoholic hydroxyl group is small, the molecular weight of the desired condensate will not be sufficiently extended.

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

For example, after adding an acid catalyst to a mixed solution of an aniline compound having an N-alkyl group represented by the formula (5) and water, the carbonyl compound at 20 to 200° C., preferably 30 to 150° C., or Any 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 Allow to react for ~20 hours. After the reaction is completed, the acid catalyst is neutralized with an alkaline aqueous solution, 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.
A conventionally known maleimide resin can be used as the maleimide resin. Specific examples of the maleimide resin include 4,4′-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, 2,2′-bis[4-(4-maleimidophenoxy)phenyl]propane, 3,3. '-Dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenyl sulfone bismaleimide , 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene and the like. From the viewpoint of solvent solubility, polyphenylmethane maleimide and maleimide resins having a molecular weight distribution such as the maleimide resins 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.
Further, maleimide resins described in JP-A-2009-001783 and JP-A-01-294662 are particularly preferable because they have low hygroscopicity, flame retardancy and dielectric properties.

The lower limit of the compounding equivalent ratio α/β of 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 compounding equivalent ratio α/β is 0.5 or more, the effect of lowering the dielectric constant can be obtained. Further, in the curing reaction of the maleimide and the aromatic amine resin according to the present invention, anionic polymerization of maleimides also occurs, so if the compounding equivalent ratio α/β is 3.0 or less, excess amine that cannot participate in the polymerization remains. The dielectric properties, heat resistance, etc. are improved.

In the curable resin composition of the present invention, a radical polymerization initiator can be used to react the 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, t-butylperoxybenzoate, peroxyketals such as 1,1-di-t-butylperoxycyclohexane, α-cumylperoxyneodecanoate, t-butyl Peroxyneodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t- Butylperoxy-2-ethylhexanoate, t-amylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, t-amylperoxy Alkyl peresters such as benzoate, di-2-ethylhexyl peroxydicarbonate, bis(4-t-butylcyclohexyl) peroxydicarbonate, t-butyl peroxyisopropyl carbonate, 1,6-bis(t-butyl percarbonate) Peroxycarbonates such as (oxycarbonyloxy)hexane, organic peroxides such as t-butylhydroperoxide, cumene hydroperoxide, t-butylperoxyoctoate and lauroyl peroxide, and azobisisobutyronitrile, 4 , 4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2,4-dimethylvaleronitrile), and other known radical polymerization initiators such as azo compounds, but are not particularly limited thereto. It is not something that will be done. Ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkylperesters, peroxycarbonates and the like are preferable, and dialkyl peroxides are more preferable. The addition amount of the radical polymerization initiator is preferably 0.01 to 5 parts by mass, and particularly preferably 0.01 to 3 parts by mass with respect to 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 extend sufficiently during the polymerization reaction.

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, and specific examples thereof include 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, dihydroxynaphthalene, etc. and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde) , Phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.); polyphenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, di) Polymerization products with isopropenyl biphenyl, butadiene, isoprene, etc.; Polycondensation products of the phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.); Phenols and aromatic dimethanols ( Polycondensate with benzenedimethanol, biphenyldimethanol, etc.; Polycondensate with the above phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.); Polycondensates with group bisalkoxymethyls (bismethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenoxymethylbiphenyl, etc.); polycondensates of the above bisphenols with various aldehydes, or glycidyl ether-based glycidyl ethers Examples thereof include resins, alicyclic epoxy resins, glycidyl amine-based epoxy resins, glycidyl ester-based epoxy resins, and the like, but the epoxy resins that are normally used are not limited to these. These may be used alone or in combination of two or more. Starting material is a phenol aralkyl resin obtained by subjecting a phenol and a bishalogenomethyl aralkyl derivative or an aralkyl alcohol derivative to a condensation reaction, and an epoxy resin obtained by subjecting epichlorohydrin to a dehydrochlorination reaction has low hygroscopicity, flame retardance, and It is particularly preferable as an epoxy resin because it has excellent dielectric properties.

The curable resin composition of the present invention may use a curing agent other than the aromatic amine compound having an N-alkyl group in combination. Examples thereof include acid anhydride compounds, amide compounds, phenol compounds and active ester compounds. Specific examples of the curing agent that can be used in combination include amide compounds such as dicyandiamide, a polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride. Acid anhydride compounds such as acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride; bisphenols (bisphenol A, bisphenol A) F, bisphenol S, biphenol, bisphenol AD, etc. or phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene) , Alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and polycondensation of various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) Or the above-mentioned phenols with various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.) Or a polycondensation product of the above-mentioned phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), or the above-mentioned phenols and aromatic dimethanols (benzenedimethanol) , Biphenyl dimethanol, etc.), or a polycondensation product of the above phenols with aromatic dichloromethyls (α,α′-dichloroxylene, bischloromethylbiphenyl, etc.), or the above phenol -Condensation product of an aromatic bisalkoxymethyl compound (bismethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenoxymethylbiphenyl, etc.), or a polycondensation product of the bisphenol compound and various aldehydes, and Modified compounds and other phenolic compounds; imidazoles, trifluoroborane-amine complexes, guanidine derivatives; phenolic esters, thiophenolic esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc. And the like, but are not limited thereto.

When using a hardening|curing agent in the curable resin composition of this invention, 0.6-1.1 equivalent is preferable with respect to 1 equivalent of epoxy groups of an epoxy resin. If the epoxy group exceeds 1.1 equivalents, or if less than 0.6 equivalents, the curing agent is left behind, and curing may be incomplete and good cured physical properties may not be obtained. However, this is not limited to the case where the epoxy resin and the curable special resin are contained, and the amount of the curing agent relative to the remaining epoxy groups after subtracting the amount of epoxy consumed by the special resin is adjusted, so it is adjusted appropriately depending on the formulation. 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 and 2-ethyl-4-methylimidazole, 2-(dimethylaminomethyl)phenol, 1,8-diaza-. Examples thereof include 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, if necessary.

If necessary, the curable resin composition used in the present invention may contain additives such as flame retardants and fillers within a range that does not deteriorate the dielectric properties and heat resistance of the cured product.

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, and oxide. Examples thereof include iron, titanium oxide, aluminum nitride, silicon nitride, boron nitride, mica, glass and quartz. Further, in order to impart a flame retardant effect, it is also preferable to use a metal hydroxide such as magnesium hydroxide or aluminum hydroxide. Further, two or more kinds may be mixed and used. Among these inorganic fillers, silicas such as fused silica and crystalline silica are preferable because they are low in cost and have 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. If it is 10% by weight or more, the flame retardant effect is improved and the elastic modulus is also improved. On the other hand, when the content is 95% by weight or less, a homogeneous molded body can be obtained without the sedimentation of the filler in the varnish.
The shape and particle size of the inorganic filler are not particularly limited, but the particle size is usually 0.01 to 50 μm, preferably 0.1 to 20 μm.

The curable resin composition used in the present invention may contain a coupling agent in order to enhance the adhesiveness between the glass cloth or the inorganic filler and the resin component. As the coupling agent, any conventionally known one can be used, for example, vinylalkoxysilane, epoxyalkoxysilane, styrylalkoxysilane, methacryloxyalkoxysilane, acryloxyalkoxysilane, aminoalkoxysilane, mercaptoalkoxysilane, isocyanatoalkoxy. 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 for adding the coupling agent may be such that the surface of the inorganic filler is treated with the coupling agent in advance and then mixed with the resin, or the resin may be mixed with the coupling agent and then the inorganic filler may be mixed. ..

The curable resin composition of the present invention may contain a cyanate ester resin. As a 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 the cyanate ester compound 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. Examples thereof include cyanate ester compounds obtained by reacting compounds with cyanogen halide, but are 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 above-mentioned ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, and benzophenone.
Specific examples of the cyanate ester compound include dicyanate benzene, tricyanate benzene, dicyanate naphthalene, dicyantobiphenyl, 2,2′-bis(4-cyanatophenyl)propane, 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 novolac cyanate, phenol dicyclopentadiene Examples thereof include those obtained by converting the hydroxyl group of the cocondensation product into a cyanate group, but are not limited thereto.
Further, the cyanate ester compound whose synthesis method is described in JP-A-2005-264154 is particularly preferable as the cyanate ester compound because it has low hygroscopicity, flame retardancy and dielectric properties.

When the curable resin composition of the present invention contains a cyanate resin, zinc naphthenate, cobalt naphthenate, copper naphthenate, in order to trimerize the cyanate group to form a sym-triazine ring, if necessary, A catalyst such as lead naphthenate, zinc octylate, tin octylate, lead acetylacetonate, dibutyltin maleate or the like may be contained. The catalyst is usually used in an amount of 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 amount of the thermosetting resin composition.

Known additives can be added to the curable resin composition of the present invention, if necessary. Specific examples of additives that can be used include polybutadiene and its modified products, modified products of acrylonitrile copolymer, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, silicone gel, silicone oil, and filling such as silane coupling agent. Examples include surface treatment agents for materials, release agents, coloring agents such as carbon black, phthalocyanine blue, and phthalocyanine green. The additive amount of these additives is preferably 1,000 parts by mass or less, and more preferably 700 parts by mass or less with respect to 100 parts by mass of the curable resin composition.

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

Here, the prepreg will be described. The prepreg is formed by impregnating the varnish into a fiber base material. This makes it possible to obtain a prepreg excellent in heat resistance, low expansion and flame retardancy. As the fiber base material, for example, glass woven cloth, glass non-woven cloth, glass fiber base material such as glass paper, paper, aramid, polyester, aromatic polyester, woven or nonwoven cloth made of synthetic fiber such as fluororesin, metal Examples thereof include woven fabrics, non-woven fabrics, mats and the like made of fibers, carbon fibers, mineral fibers and the like. You may use these base materials individually or in mixture. Of these, a glass fiber base material is preferable. This can improve the rigidity and dimensional stability of the prepreg. The glass fiber base material preferably contains at least one selected from the group consisting of T glass, S glass, E glass, NE glass, and quartz glass.

Examples of the method of impregnating the curable resin composition of the present invention into the fiber base material include a method of immersing the base material in a resin varnish, a method of coating with a coater, and a method of spraying. Among these, the method of immersing the substrate in the resin varnish is preferable. This can improve the impregnation property of the resin composition into the base material. When the base material is dipped 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 in a drying oven or the like, usually at 80 to 200°C ( However, when a solvent is used, 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. Further, a method of pressing a resin sheet described later on a glass cloth and transferring it to obtain a prepreg can also be applied.

Next, the resin sheet will be described. The resin sheet using the varnish has a varnish with a predetermined thickness after being dried on a planar support by various coating methods such as gravure coating method, screen printing, metal mask method and spin coating method known per se. It can be obtained by, for example, coating to a thickness of 5 to 100 μm and then drying. The coating method to be used depends on the type, shape, size of the support, coating thickness, heat resistance of the support, etc. It is selected appropriately. Examples of the planar support include various types of high-performance materials such as polyamide, polyamideimide, polyarylate, polyethylene terephthalate, polybutylene terephthalate, polyetherketone, polyetherimide, polyetheretherketone, polyketone, polyethylene, polypropylene and Teflon (registered trademark). Examples thereof include films made of molecules and/or copolymers thereof, and metal foils such as copper foil. After application, the composition can be dried to obtain a sheet-shaped composition (the sheet of the present invention), but the sheet can be further heated to obtain a sheet-shaped cured product. Further, the solvent drying and the curing step may be combined with one heating. The aromatic amine resin composition having an N-alkyl group of the present invention is coated on both sides or one side of the support by the above 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. It is also possible to bond the adherends and cure them before curing to form a laminate. Further, the resin sheet of the present invention can be used as an adhesive sheet by peeling it from a support, and it can also be brought into contact with an adherend and, if necessary, subjected to pressure and heat to be adhered together with curing.

Next, the laminated plate will be described. The laminated plate is formed by hot pressing the prepreg and/or the resin sheet. This makes it possible to obtain a printed wiring board excellent in heat resistance, low expansion and flame retardancy. In the case of one prepreg and/or one resin sheet, metal foils are laminated on both upper and lower surfaces or one surface thereof. Also, two or more prepregs and/or resin sheets may be laminated. When two or more prepregs and/or resin sheets are laminated, a metal foil or a film and/or a resin sheet is laminated on the outermost upper and lower surfaces or one side of the laminated prepregs and/or resin sheets. Next, the prepreg and/or the resin sheet and the metal foil are stacked and heat-pressed to obtain a printed wiring board. The heating temperature is not particularly limited, but is preferably 120 to 220°C, and particularly preferably 150 to 200°C. The pressure to be applied is not particularly limited, but 1.5 to 5 MPa is preferable, and 2 to 4 MPa is particularly preferable. If necessary, post-curing may be performed in a high temperature bath or the like at a temperature of 150 to 300°C.

Next, the printed wiring board will be described. The printed wiring board uses the laminated board as an inner layer circuit board. A circuit is formed on one side or both sides of the laminated plate. Depending on the case, it is also possible to form a through hole by drilling or laser processing and to make electrical connection on both sides by plating or the like.

A multilayer printed wiring board can be obtained by superposing the resin sheet or the prepreg on the internal circuit board and heat-pressing. Specifically, the insulating layer side of the resin sheet and the inner layer circuit board are combined, and vacuum heat pressure molding is performed using a vacuum pressure 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. The conditions for heat-press molding are not particularly limited, but as an example, it can be carried out at a temperature of 60 to 160° C. and a pressure of 0.2 to 3 MPa. The conditions for heat curing are not particularly limited, but for example, the temperature may be 140 to 240° C. and the time may be 30 to 120 minutes. Alternatively, it can be obtained by stacking the prepreg on the inner layer circuit board and heat-pressing the prepreg using a flat plate press or the like. The conditions for heat-press molding are not particularly limited, but as an example, it can be carried out 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 device, the insulating layer is heated and cured simultaneously with the heat and pressure molding.

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

The curing of the resin sheet or the insulating layer formed of the prepreg may be left in a semi-cured state in order to facilitate subsequent laser irradiation and removal of resin residue and improve desmearability. In addition, the first insulating layer is partially cured (semi-cured) by heating at a temperature lower than the normal heating temperature, and one or more insulating layers are further formed on the insulating layer to form a semi-cured insulating layer. The adhesive strength between the insulating layers and between the insulating layer and the circuit can be improved by heating and curing again to an extent that causes no practical problem. In this case, the semi-curing temperature is preferably 80°C to 200°C, more preferably 100°C to 180°C. In the next step, laser irradiation is performed to form an opening in the insulating layer, but the base material must be peeled off before that. There is no particular problem in peeling the base material after forming the insulating layer, before heat curing, or after heat curing. The inner layer circuit board used for obtaining the multilayer printed wiring board is preferably, for example, a copper clad laminate having predetermined conductor circuits formed on both surfaces by etching or the like and the conductor circuit portion being blackened. Can be used for.

It is preferable to remove resin residues and the like after laser irradiation with an oxidizing agent such as permanganate or dichromate. Further, the surface of the smooth insulating layer can be simultaneously roughened, and the adhesion of the conductive wiring circuit formed by the subsequent metal plating can be improved.

Next, the 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 prepreg is used. When a resin sheet having a metal foil or a prepreg is used, the circuit may be formed by etching for use as a conductor circuit without peeling the metal foil. In that case, if an insulating resin sheet with a base material using a thick copper foil is used, it becomes difficult to form a fine pitch in the subsequent circuit pattern formation. Therefore, use an ultra-thin copper foil of 1 to 5 μm or 12 to 18 μm. In some cases, the copper foil of (1) is half-etched to a thickness of 1 to 5 μm by etching.

Although an insulating layer may be further laminated to form a circuit in the same manner as described above, a solder resist is formed on the outermost layer after the circuit is formed in the design of the multilayer printed wiring board. The method for forming the solder resist is not particularly limited. For example, a method of forming a dry film type solder resist by laminating, exposing and developing, or forming a liquid resist printed by exposing and developing. It is done by the method. When the obtained multilayer printed wiring board is used in a semiconductor device, a connecting electrode portion is provided for mounting a semiconductor element. The connecting 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 achieved through 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 composed 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 as follows. After aligning the connecting electrode portion on the substrate with the solder bump of the semiconductor element using a flip chip bonder or the like, an IR reflow device, a hot plate, etc. The solder bumps are heated to a temperature equal to or higher than the melting point using a heating device, and the multilayer printed wiring board and the solder bumps are fused and connected to each other. In order to improve the connection reliability, a metal layer having a relatively low melting point such as solder paste may be formed in advance on the connecting electrode portion on the multilayer printed wiring board. Prior to this joining step, the connection reliability can be improved by applying flux to the solder bumps and/or the surface layer of the connecting electrode portion on the multilayer printed wiring board.

The board is used as a motherboard, a network board, a package board, or the like, and is used as a board. In particular, as a package substrate, it is useful as a thin layer substrate for a single-sided sealing material. When used as a semiconductor encapsulant, the semiconductor device obtained from the compound is, for example, DIP (dual inline package), QFP (quad flat package), BGA (ball grid array), CSP (chip size package), SOP. (Small outline package), TSOP (thin small outline package), TQFP (think quad flat package), and the like.

Hereinafter, the present invention will be described in detail with reference to Examples. 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 by a method according to JIS K-7234, and the unit is °C.
Melt viscosity ICI melt viscosity (150° C.) was measured by the cone and plate method, and the unit is Pa·s.

・GPC (gel permeation chromatography) analysis maker: Waters
Column: Guard column SHODEX GPC KF-601 (two), 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′-bischloromethylene biphenyl was added over 1 hour, and the mixture was reacted at 65° C. for 2 hours. Then, 36.1 g of 35% hydrochloric acid was added dropwise at 80°C or lower. After completion of the dropping, the temperature was raised to 210° C. while azeotropically dehydrating, and the reaction was carried out at 210° C. for 15 hours. After completion of the reaction, 100 g of a 17% aqueous sodium hydroxide solution was added dropwise to make the reaction solution alkaline, 100 g of toluene and 150 g of N-methylaniline were added, and the mixture was stirred for 6 hours. After standing still and waste water, washing was performed until the waste water became neutral. The solvent, water and unreacted N-methylaniline were distilled off by concentration under reduced pressure to obtain biphenyl-N-methylaniline novolac (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 in GPC area% n=1 component: 9.1%, n=2 component: 31%, n=3 component: 29%, n= High molecular weight component of 4 or more: 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. Then, 50.2 g of 4,4′-bischloromethylenebiphenyl was added over 1 hour, and the mixture was reacted at 65° C. for 2 hours. Then, 41.7 g of 35% hydrochloric acid was added dropwise at 80°C or lower. After completion of the dropping, the temperature was raised to 210° C. while azeotropically dehydrating, and the reaction was carried out 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, 50 g of toluene was further added, and the mixture was stirred for 6 hours. After standing still and waste water, washing was performed until the waste water became neutral. The solvent, water and unreacted N-methylaniline were distilled off by concentration under reduced pressure to obtain biphenyl-N-methylaniline novolac (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= High molecular weight component of 4 or more: 1.3%).

(Example 3)
To a flask equipped with a thermometer, a condenser and a stirrer, 200 g of water and 214 g of N-methylaniline were added and stirred. Then, 209 g of 35% hydrochloric acid was added dropwise at 40°C or lower. Then, 108 g of 37% aqueous formaldehyde solution was added dropwise at 40° C. or lower. After completion of the dropping, the reaction was carried out at 75 to 80°C for 5 hours. After the reaction was completed, 168 g of a 48% aqueous sodium hydroxide solution was added dropwise to make the reaction solution alkaline, 300 g of toluene was further added, and the mixture was stirred for 6 hours. After standing still and waste water, washing was performed until the waste water became neutral. The solvent, water and unreacted N-methylaniline were distilled off by concentration under reduced pressure to obtain 200 g of N-methylaniline novolac (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%, and n=4 or higher polymer component: 30%).

(Example 4)
N-methylaniline novolac (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%, and n=4 or more high molecular weight component: 47%).

(Example 5)
To a flask equipped with a thermometer, a cooling tube, 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 added. Addition and stirring. While azeotropically dehydrating, the internal temperature was raised to 160°C, and the reaction was carried out at 160°C for 24 hours. After allowing to cool, 150 g of toluene was added, the activated clay was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain an aromatic amine resin (BNMACB) containing a bis-N-methylaminocumylbenzene structure as a main component as a brown liquid resin. (Amine equivalent: 191 g/eq.).

(Synthesis example 1)
217 g of N-methylaniline novolac (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: GPC area). %, n=1 component: 65%, n=2 component: 22%, n=3 component: 8.2%, and n=4 or higher high molecular weight component: 4.8%).

(Synthesis example 2)
A flask equipped with a thermometer, a condenser, 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 dropping, the mixture was heated to azeotropically cool water and toluene, and after liquid separation, only toluene as an organic layer was returned to the system for 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 of the system 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 added dropwise so that the inside of the system would not be vigorously refluxed. I put it. The separated lower aqueous layer was removed, and the washing of the reaction solution with water was repeated until the washing solution became neutral. Then, 173 parts of an aromatic amine resin (a1) was obtained by distilling off excess aniline and toluene from the oil layer under reduced pressure with 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 added with a rotary evaporator under heating and reduced pressure (200° C., 4 KPa), and water was added dropwise little by little 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 a diphenylamine content of 0.1% or less. Based on JIS K-7236 Annex A (correction method for glycidyl amine) and assuming the obtained value as the amine equivalent, the amine equivalent of A1 is 195 g/eq. Met.

(Synthesis example 3)
A flask equipped with a thermometer, a cooling tube, a Dean Stark azeotropic distillation trap, and a stirrer was charged with 147 parts of maleic anhydride and 300 parts of toluene, and after heating and azeotropically cooling and separating the water and toluene. Then, only toluene, which is an organic layer, was returned to the system for dehydration. Next, a resin solution prepared by dissolving 195 parts of the aromatic amine resin (A1) obtained in Synthesis Example 2 in 195 parts of N-methyl-2-pyrrolidone was added over 1 hour while maintaining the system temperature at 80 to 85°C. Dropped. After completion of the dropping, the reaction is carried out at the same temperature for 2 hours, 3 parts of p-toluenesulfonic acid is added, and condensed water and toluene which are azeotroped under the reflux condition are cooled and separated. Was returned to the system to carry out a reaction for 20 hours while dehydrating. After completion of the reaction, 120 parts of toluene was added, and washing with water 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. Then, the reaction solution was concentrated under reduced pressure to obtain a resin solution containing 70% of maleimide resin (M1). The diphenylamine content in the maleimide resin (M1) was 0.1% or less. The solvent of M1 was distilled off under heating and reduced pressure, 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 was 275 g/eq. Met.

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

The results of measuring the physical properties of the cured product thus obtained for the following items are shown in Table 1.
<Heat resistance test>
-Glass transition temperature: The temperature at which tan δ has the maximum value, measured by a dynamic viscoelasticity tester.
<Dielectric constant test/Dielectric loss tangent test>
-A test was performed by the cavity resonator perturbation method using a 1 GHz cavity resonator manufactured by Kanto Electronics Co., Ltd. However, the test was conducted with a sample size of 1.7 mm width×100 mm 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 have electric characteristics superior to Comparative Examples 1 and 2 and high heat resistance.

Therefore, the condensate of the N-alkyl group-containing aniline-based compound and formaldehyde of the present invention can be used as an insulating material for electric and electronic parts (such as a highly reliable semiconductor encapsulating material) and a laminated board (printed wiring board, BGA board, build It is useful for various kinds of composite materials such as an up board, an adhesive (a conductive adhesive, etc.) and CFRP, and a paint.

Claims (11)

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 the R's are hydrogen. Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms, Y represents a hydrocarbon group having 2 to 30 carbon atoms, l ₁ , l ₂ and m each represent an integer of 1 or more, and l ₁ +m≦5 and l ₂ +m≦4 are satisfied, and n represents 1≦n≦15.) 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).

The aromatic amine resin having an N-alkyl group according to claim 2, which is represented by the following formula (3).

(N is an average value and represents 1≦n≦15.) In the formula (1), Y is a methylene bond, and the component represented by n=1 by gel permeation analysis is 5 area% or more and less than 50 area%, and has an N-alkyl group. Aromatic amine resin. The aromatic amine resin having an N-alkyl group according to claim 4, wherein the component represented by n=4 or more in the formula (1) is 5 area% or more and less than 80 area %. The aromatic amine resin having an N-alkyl group according to claim 4 or 5, which is 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. Above 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 10. A curable resin composition containing the aromatic amine resin having an N-alkyl group according to claim 1 and a maleimide resin. The curable resin composition according to claim 9, wherein the compounding equivalent ratio of the compounding equivalent α of the N-alkyl group-containing aromatic amine resin and 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.