TWI815938B - Aromatic amine resin having N-alkyl group, curable resin composition and cured product thereof - Google Patents

Abstract

The present invention provides an aromatic amine resin compound having an N-alkyl group and a curable resin composition thereof that exhibits excellent heat resistance and electrical characteristics. An aromatic amine resin having an N-alkyl group represented by the following formula (1). (In formula (1), the presence of multiple R's each independently represents hydrogen or a hydrocarbon group having 1 to 15 carbon atoms; the case where all R's are hydrogen is excluded. The presence of multiple X's each independently represents a hydrogen atom, a carbon number Hydrocarbon group of 1 to 15. l ₁ , l ₂ and m represent integers above 1, and satisfy l ₁ +m≦5 and l ₂ +m≦4. n represents 1≦n≦15)

Description

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

The present invention relates to an aromatic amine resin having an N-alkyl group, a curable resin composition and its cured product, which can be preferably used as a sealing material for semiconductor elements, a sealing material for liquid crystal display elements, and an organic EL element. In composite materials for electrical and electronic parts such as sealing materials, printed wiring boards, and build-up laminates, and lightweight and high-strength structural materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics.

In recent years, laminate boards equipped with electrical and electronic components have been required to have a wide range of characteristics and become more advanced due to the expansion of their application fields. In particular, as semiconductor packages (hereinafter referred to as PKG) used in smartphones and the like become smaller, thinner, and higher in density, the PKG substrate is required to be thinner. However, if the PKG substrate becomes thinner, Rigidity is reduced, so heating when soldering PKG to a motherboard (printed circuit board (PCB)) may cause problems such as large warping. To reduce this aspect, a PKG substrate material with a high Tg above the soldering mounting temperature is required.

In addition, with the development of large-capacity and high-speed communications in recent years, the frequency of electrical signals processed by information communication equipment tends to become higher every year. The higher the frequency of the signal, the electrical signal is converted into heat in the circuit, resulting in transmission loss. Increase, it is difficult to transmit signals efficiently. In order to reduce this aspect, substrate materials with low dielectric loss tangent are also required.

In particular, in the fifth-generation communication system "5G", which is currently being developed at an accelerated pace, data communication with various devices represented by smartphones is expected to further promote large-capacity and high-speed communication. The demand for low dielectric loss tangent materials is increasing. At least a dielectric loss tangent of 0.005 or less at 1 GHz is required, and materials that can achieve the above-mentioned heat resistance and dielectric properties (dielectric loss tangent) are required.

Furthermore, as electronics advances in the automotive field, precision electronic equipment is sometimes installed near the engine drive unit, so higher levels of heat resistance and moisture resistance are required. In addition, SiC semiconductors have begun to be used in trains, air conditioners, etc., and sealing materials for semiconductor elements are required to have extremely high heat resistance, so existing epoxy resin sealing materials have become unable to cope.

Against the background of such technological changes, various functional groups are being studied. For example, Patent Document 1 all uses acryl-substituted phenol resins, but their hygroscopicity and electrical properties are insufficient. In addition, Patent Document 2 all uses allyl-substituted phenol resins, but the reactivity is insufficient. Claisen rearrangement occurs simultaneously during the curing process and hydroxyl groups are generated, so the electrical properties are also unsatisfactory.

As mentioned above, it is not easy to develop materials or hardening systems that have both high heat resistance and electrical properties, and it is one of the issues that still needs to be solved. [Prior art documents] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 04-359911 [Patent Document 2] International Publication No. 2016/002704

[Problem to be solved by the invention]

The present invention was 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. [Means to solve the problem]

The present inventors conducted intensive research to solve the above-mentioned problems, and as a result found that the cured product of an aromatic amine resin having an N-alkyl group and its curable resin composition has excellent electrical characteristics, and completed the present invention.

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).

[Chemical 1] (In formula (1), the presence of multiple R's each independently represents hydrogen or a hydrocarbon group having 1 to 15 carbon atoms; the case where all R's are hydrogen is excluded. The presence of multiple X's each independently represents a hydrogen atom, a carbon number A hydrocarbon group of 1 to 15; Y represents a hydrocarbon group with a carbon number of 2 to 30. l ₁ , l ₂ and m represent integers above 1, and satisfy l ₁ +m≦5 and l ₂ +m≦4. n represents 1≦n ≦15).

[2] The aromatic amine resin having an N-alkyl group as described in the previous item [1], wherein in the formula (1), Y is any one of (a) to (d) described in the following formula (2). One.

[Chemicalization 2]

[3] The aromatic amine resin having an N-alkyl group as described in the previous item [2] is represented by the following formula (3).

[Chemical 3] (n is the average value, indicating 1≦n≦15).

[4] The aromatic amine resin having an N-alkyl group as described in the previous item [1], wherein in the formula (1), Y is a methylene bond, and the component represented by n=1 in gel permeation analysis It is more than 5 area% and less than 50 area%. [5] The aromatic amine resin having an N-alkyl group as described in the preceding item [4], wherein in the formula (1), the component represented by n=4 or more accounts for 5 area % or more and less than 80 area %. [6] The aromatic amine resin having an N-alkyl group as described in the preceding item [4] or [5] is represented by the following formula (4).

[Chemical 4] (n is the average value, indicating 1≦n≦15).

[7] The aromatic amine resin having an N-alkyl group as described in any one of the preceding items [4] to [6], wherein in the formula (1) or formula (4), when n in the gel permeation analysis is When the component represented by =1 is taken as A area% and the component represented by n=4 or more is taken as B area%, B/A is 0.1 or more and less than 20. [8] The aromatic amine resin having an N-alkyl group as described in any one of the preceding items [4] to [7], wherein the amine equivalent is 116 g/eq. or more and less than 120 g/eq. [9] A curable resin composition containing an aromatic amine resin having an N-alkyl group and a maleimine resin as described in any one of [1] to [8] above. [10] The curable resin composition as described in the preceding item [9], wherein the blending equivalent ratio of the blending equivalent α of the aromatic amine resin having an N-alkyl group to the blending equivalent β of the maleimine resin is 0.9≦α/β ≦2.5. [11] A hardened product obtained by hardening the curable resin composition described in the preceding item [9] or [10]. [Effects of the invention]

The curable resin composition of the present invention has excellent curability, and its cured product has excellent electrical properties and heat resistance. Therefore, it can be used in insulating materials for electrical and electronic parts (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, In various composite materials, coatings and other applications including organic EL sealing materials, adhesives (conductive adhesives, etc.) and carbon fiber reinforced plastic (CFRP).

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).

[Chemistry 5]

(In formula (1), the presence of multiple R's each independently represents hydrogen or a hydrocarbon group having 1 to 15 carbon atoms; the case where all R's are hydrogen is excluded. The presence of multiple X's each independently represents a hydrogen atom, a carbon number A hydrocarbon group of 1 to 15; Y represents a hydrocarbon group with a carbon number of 2 to 30. l ₁ , l ₂ and m represent integers above 1, and satisfy l ₁ +m≦5 and l ₂ +m≦4. n represents 1≦n ≦15).

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

[A: When Y is a hydrocarbon group having 2 to 30 carbon atoms] In the formula (1), Y represents a hydrocarbon group having 2 to 30 carbon atoms, preferably a hydrocarbon group having 6 to 18 carbon atoms. In addition, from the viewpoint of improving flame retardancy, electrical characteristics, and water absorption characteristics, it is more preferable that Y has one or more aromatic groups. In this case, Y is exemplified by the following formula (2), but is not limited to this.

[Chemical 6]

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

In the formula (2), structures (b) and (d) are preferred, and structure (b) is more preferred.

When Y in the formula (1) is represented by the formula (2), in gel permeation (gel permeation chromatography (GPC)) analysis, n in the formula (1) The lower limit value of the component represented by =1 is preferably 5 area % or more, more preferably 10 area % or more, and particularly preferably 20 area % or more. A preferable upper limit is less than 50 area %, more preferably less than 45 area %, and particularly preferably less than 40 area %. If the component represented by n=1 is 5 area % or more, the viscosity will not be extremely high and the workability will be good. If 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: Protection column, SHODEX GPC KF-601 (two), KF-602, KF-602.5, KF-603 Flow rate: 1.23 ml/min. Column temperature: 25℃ Solvent used: THF (tetrahydrofuran) Detector: RI (refractive index) (differential refraction detector)

When Y in the formula (1) is represented by the formula (2), the amine equivalent is preferably 115 g/eq. or more and less than 400 g/eq., more preferably 120 g/eq. or more and less than 400 g/eq. 250 g/eq. When the amine equivalent is 115 g/eq. or more, the polar group concentration in the molecule decreases, thereby improving the electrical characteristics. In addition, if it is 400 g/eq. or less, the hardenability becomes good.

When 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, 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 workability during mixing and the like becomes 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 workability during mixing etc. will be good.

[B: When Y is a hydrocarbon group with 1 carbon atoms] 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 areas % or more is preferred, more preferably 10 area % or more, particularly preferably 20 area % or more, and most preferably 30 area % or more. A preferable upper limit value is less than 50 area %, and more preferably less than 40 area %. If the component represented by n=1 is 5 area % or more, the viscosity will not be extremely high and the workability will be improved. If it is less than 50 area %, the decrease in heat resistance can be suppressed. In addition, 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. A preferable upper limit value is less than 80 area %, more preferably less than 60 area %, and particularly preferably less than 50 area %. If the component represented by n=4 or more accounts for 5 area % or more, the solvent solubility improves. In addition, when the cured product is made, the cross-linked structure becomes stiffer and molecular motion is suppressed, so the heat resistance and electrical properties are improved, and the chemical resistance is also improved due to the increase in cross-linking points. If it is less than 80 area %, operability will not be reduced.

When Y in the formula (1) is a methylene bond, as described above, both low molecular weight components and high molecular weight components are distributed, and the molecular weight distribution is broad. Therefore, it has excellent effects in terms of operability, solvent solubility, heat resistance, electrical properties, chemical resistance, and the balance of these properties. Therefore, in the above formula (1), when the component represented by n=1 in the GPC analysis is taken as A area%, and the total value of the GPC area% of the components represented by n=4 or more is taken as B area% When , B/A is usually above 0.1 and less than 20. The lower limit value 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 preferably 116 g/eq. or more, more preferably 118 g/eq. or more. The upper limit of the amine equivalent is preferably less than 125 g/eq., more preferably less than 120 g/eq. If it is within the above range, a certain reactivity is shown, and desired characteristics such as high heat resistance and good electrical characteristics can be obtained.

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

[Chemical 7]

(n is the average value, indicating 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 maleimine resin. In addition, the three-dimensional cross-linked structure produced by the reaction of maleimide groups and amine groups is rigid, and therefore exhibits excellent heat resistance and electrical characteristics.

Next, a method for producing the 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 uses an aniline compound represented by the following formula (5); and any carbonyl compound, any halogen compound, any olefin compound, or any having Alcoholic hydroxyl compounds are used as raw materials.

[Chemical 8]

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

Examples of the aniline compound represented by formula (5) include aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N-isopropylaniline, and N-butylaniline. N-tert-butylaniline, N-pentylaniline, N-hexylaniline, N-heptylaniline, N-octylaniline, N-nonylaniline, N-decylaniline, N-methyl-o-methyl Aniline, N-methyl-m-toluidine, N-methyl-p-toluidine, N-methyl-o-methoxyaniline, N-methyl-m-methoxyaniline, N-methyl-p-methoxyaniline, etc. , but is not limited to this. These may be used individually or in combination of 2 or more types. From the viewpoint of heat resistance and electrical characteristics, N-methylaniline, N-ethylaniline, N-propylaniline, N-isopropylaniline, N-butylaniline, and N-tert-butylaniline are preferred. Examples of the base aniline include N-methylaniline, N-ethylaniline, N-propylaniline, and N-isopropylaniline, and more preferably N-methylaniline and N-ethylaniline.

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

[Chemical 9]

(In formula (6), the presence of a plurality of R ² each independently represents 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 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. The dotted line indicates that it can bond to form a ring structure).

Examples of the carbonyl compound represented by formula (6) include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, hexanal, benzaldehyde, chlorobenzaldehyde, bromobenzaldehyde, glyoxal, and malondialdehyde. , butyraldehyde, glutaraldehyde, adipic aldehyde, peptaldehyde, sebacraldehyde, acrolein, crotonaldehyde, salicylaldehyde, o-phthalaldehyde, hydroxybenzaldehyde, furfuraldehyde, tolualdehyde, α- Naphthalaldehyde, β-naphtaldehyde and other aldehydes; acetone, methyl ethyl ketone, diethyl ketone, benzoyl ketone, acetyl acetone, methyl isopropyl ketone, methyl isobutyl ketone, acetophenone, Ethyl phenyl ketone, cyclohexanone, cyclopentanone, benzophenone, fluorenone, indanone, 3,3,5-trimethylcyclohexanone, anthraquinone, 4-hydroxybenzene Ethyl ketone, acenaphthyroquinone, quinone, benzoyl acetone, adamantanone, diacetyl, etc. Only one type of carbonyl compound may be used, or two or more types of carbonyl compounds may be used in combination.

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

As any halogen compound, any compound can be used as long as it is a known compound. Preferable examples include compounds having a structure represented by the following formula (7) in the molecule.

[Chemical 10]

(In formula (7), N represents a natural number above 1).

Examples of the halogen compound that can form the structure of the formula (7) include o-xylene difluoride, m-xylene difluoride, p-xylene difluoride, o-xylene dichloride, and m-xylene Dichloride, p-xylene dichloride, o-xylene dibromide, m-xylene dibromide, p-xylene dibromide, o-xylene diiodide, m-xylene diiodide, p-xylene di Iodide, 4,4'-bisfluoromethylenebiphenyl, 4,4'-bischloromethylenebiphenyl, 4,4'-bisbromomethylenebiphenyl, 4,4'-bisiodophenylene Methylbiphenyl, 2,4-bisfluoromethylenebiphenyl, 2,4-bischloromethylenebiphenyl, 2,4-bisbromomethylenebiphenyl, 2,4-bisiodomethylenebiphenyl Biphenyl, 2,2'-bisfluoromethylenebiphenyl, 2,2'-bischloromethylenebiphenyl, 2,2'-bisbromomethylenebiphenyl, 2,2'-bisiodophenylene From the viewpoint of the reactivity of raw materials during synthesis, methylbiphenyl is preferably a chloride-based compound, a bromide-based compound, or an iodide-based compound, and more preferred examples include a chloride-based compound and a bromide-based compound. .

In 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 difficult to coexist heat resistance and dielectric properties, and the hardenability also decreases.

As any olefin compound, any compound can be used as long as it is a known compound. Preferable examples include compounds having a structure represented by the following formula (8) in the molecule.

[Chemical 11]

As any compound having an alcoholic hydroxyl group, any compound can be used as long as it is a known compound. Preferably, it can be enumerated: Nikanol Y-50, Nikanol Y-100, Nikanol Y-1000, Nikanol LLL, Nikanol LL, Nikanol ( xylene formalin resins such as Nikanol L, Nikanol H, Nikanol G, Nikanol H-80 (all manufactured by Fudow Co., Ltd.) or o-xylene glycol, m-xylene glycol, p-xylene glycol, and compounds having a structure represented by the following formula (9) in the molecule.

[Chemical 12]

The reaction between the aniline compound having an N-alkyl group represented by formula (5) and any carbonyl compound, any halogen compound, any olefin compound, or any compound having an alcoholic hydroxyl group can be achieved by Performed by known methods. The usage amount of any carbonyl compound, any halogen compound, any olefin compound, or any compound having an alcoholic hydroxyl group is usually 0.05 mole to 1.0 mole per 1 mole of the aniline compound used, and is preferably It is 0.1 mol ~ 1.0 mol. More preferably, it is 0.1 mol to 0.9 mol. If the added amount of any halogen compound, any olefin compound, or any compound having an alcoholic hydroxyl group is small, the molecular weight of the target condensate cannot be sufficiently increased.

During the reaction, acidic catalysts 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 as needed. These may be used individually or in combination of 2 or more types. The amount of catalyst used is usually 0.1 mole to 2.0 mole, preferably 0.2 mole to 1.5 mole, relative to 1 mole of aniline used. If it is too much, the amount of alkali required in the neutralization step will increase, and industrial waste may increase. If it is too little, the progress of the reaction may be slowed down. As the reaction solvent, in addition to water, organic solvents such as toluene and xylene may be used as needed, or the reaction may be carried out 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 temperature is 20°C to 200°C, preferably 30°C to 150°C. Next, add any carbonyl compound or any halogen compound for 0.1 to 10 hours, preferably 0.5 to 5 hours, and then heat it up at 40°C to 300°C, preferably 40°C to 250°C for 1 hour to The reaction time is 30 hours, preferably 2 hours to 20 hours. After the reaction is completed, an alkaline aqueous solution is used to neutralize the acid catalyst, and then a non-water-soluble organic solvent is added to the oil layer, and the water is washed repeatedly until the waste water becomes neutral.

The curable resin composition of the present invention contains 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, and m-phenylbismaleimide , 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'- Diphenylmethane bismaleimide, 4-methyl-1,3-phenylbismaleimide, 4,4'-diphenyl ether bismaleimide, 4,4' -Diphenylbismaleimide, 1,3-bis(3-maleimidephenoxy)benzene, 1,3-bis(4-maleimidephenoxy)benzene, etc. . From the viewpoint of solvent solubility, polyphenylmethanemaleimide or polyphenylmethanemaleimide or polyphenylmethane having maleimide as described in Japanese Patent Laid-Open No. 2009-001783 and Japanese Patent Laid-Open No. 01-294662 is preferred. Maleimide resin with molecular weight distribution similar to imine resin. These may be used individually or in combination of 2 or more types. The compounding amount of the maleimide resin is preferably 5 times or less in terms of mass ratio, more preferably 2 times or less. In addition, the maleimide resin described in Japanese Patent Application Laid-Open No. 2009-001783 or Japanese Patent Application Laid-Open No. 01-294662 is particularly preferred because of its low hygroscopicity, excellent flame retardancy and dielectric properties.

The lower limit of the blending equivalent ratio α/β of the blending equivalent α of the aromatic amine resin having an N-alkyl group and the blending equivalent β of the maleimine resin is preferably 0.9 or more, more preferably 1.1 or more, especially The best value is 1.2 or more, and the best value is 1.4 or more. In addition, the upper limit of the blending equivalent ratio α/β is preferably 2.5 or less, more preferably 2.2 or less, and particularly preferably 2.0 or less. If the blending equivalent ratio α/β is 0.5 or more, the effect of lowering the dielectric can be obtained. In addition, during the curing reaction between maleimine and the aromatic amine resin described in the present invention, anionic polymerization of maleimines also occurs simultaneously. Therefore, if the blending equivalent ratio α/β is 3.0 or less, it will not Remaining amine that cannot participate in polymerization remains, resulting in improved dielectric properties and heat resistance.

In the curable resin composition of the present invention, a radical polymerization initiator can be used in order to react maleimide groups. Examples of usable radical polymerization initiators include ketone peroxides such as methyl ethyl ketone peroxide and acetyl acetone peroxide; diyl peroxides such as benzoyl peroxide; dialkyl peroxides such as 1,3-bis(tert-butylperoxyisopropyl)benzene; tert-butyl peroxybenzoate, 1,1-di-tert-butyl peroxybenzoate Peroxyketals such as cyclohexane peroxide; α-cumyl peroxyneodecanate, tert-butylperoxyneodecanate, tert-butylperoxytrimethylacetate, 1,1 ,3,3-Tetramethylbutylperoxy-2-ethylhexanoate, tert-pentylperoxy-2-ethylhexanoate, tert-butylperoxy-2-ethylhexanoate , tertiary amylperoxy-3,5,5-trimethylhexanoate, tertiary butylperoxy-3,5,5-trimethylhexanoate, tertiary amylperoxybenzoic acid Alkyl peroxyesters such as esters; di-2-ethylhexylperoxydicarbonate, bis(4-tert-butylcyclohexyl)peroxydicarbonate, tert-butylperoxyisopropylcarbonate ester, 1,6-bis(tert-butylperoxycarbonyloxy)hexane and other peroxycarbonates; tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxyoctanoate , lauryl peroxide and other organic peroxides or azobisisobutyronitrile, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2,4-dimethyl Well-known radical polymerization initiators such as azo compounds such as valeronitrile) are not particularly limited to these. Preferred are ketone peroxides, diyl peroxides, hydroperoxides, dialkyl peroxides, peroxy ketals, alkyl peroxyacid esters, and peroxycarbonates. etc., more preferably dialkyl peroxides. The amount of the radical polymerization initiator added is preferably 0.01 to 5 parts by mass, and particularly preferably 0.01 to 3 parts by mass relative to 100 parts by mass of the curable resin composition. If a large amount of radical polymerization initiator is used, the molecular weight cannot be sufficiently increased 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. Specific examples include bisphenols (bisphenol A, bisphenol F, bisphenol S, bisphenol, 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, alkanes Condensation polymers of base aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphtaldehyde, glutaraldehyde, o-phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.); the phenols and various diene compounds (diene compounds Cyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butanediene olefin, isoprene, etc.); the condensation polymer of the phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.); the The condensation polymer of the above-mentioned phenols and aromatic dimethyl alcohols (phenylene glycol, biphenyl dimethanol, etc.); the above-mentioned phenols and aromatic dichloromethyls (α,α'-dichloroxylene, dichloromethylbenzene, etc.) biphenyl, etc.); the phenols and aromatic dialkoxymethyls (bismethoxymethylbiphenyl, bismethoxymethylbiphenyl, bisphenoxymethylbiphenyl, etc.) ); condensation polymers of the bisphenols and various aldehydes or glycidyl ether epoxy resins, alicyclic epoxy resins, glycidyl amine epoxy resins obtained by glycidylizing alcohols, etc. The resin, glycidyl ester type epoxy resin, etc. are not limited to these as long as they are commonly used epoxy resins. These may be used individually, or two or more types may be used. Epoxy obtained by dehydrochlorination reaction with epichlorohydrin using phenol aralkyl resin obtained by the condensation reaction of phenols and bishalomethyl aralkyl derivatives or aralkyl alcohol derivatives as raw materials The resin has low hygroscopicity, flame retardancy, and excellent dielectric properties, so it is particularly suitable as an epoxy resin.

The curable resin composition of the present invention may use a curing agent other than an aromatic amine compound having an N-alkyl group in combination. Examples include acid anhydride compounds, amide compounds, phenol compounds, active ester compounds, and the like. Specific examples of hardeners that can be used in combination include amide-based compounds such as dicyandiamine and polyamide resins synthesized from dimers of linolenic acid and ethylenediamine; phthalic anhydride, metaphase Mellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydro Acid anhydride compounds such as phthalic anhydride; bisphenols (bisphenol A, bisphenol F, bisphenol S, bisphenol, 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, alkyl aldehydes, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde , naphtaldehyde, glutaraldehyde, o-phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), or the phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene , norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.) polymers, or all Condensation polymers of the above-mentioned phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), or the above-mentioned phenols and aromatic dimethyl alcohols (phenylene dimethyl alcohols) methanol, biphenyl dimethanol, etc.), or the condensation polymer of the phenols and aromatic dichloromethyls (α, α'-dichloroxylene, dichloromethylbiphenyl, etc.), or the Condensation polymers of the above-mentioned phenols and aromatic dialkoxymethyls (bismethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenoxymethylbiphenyl, etc.), or the bisphenol Phenolic compounds such as condensation polymers with various aldehydes and modified products of these; imidazole, trifluoroborane-amine complex, guanidine derivatives; phenol esters, thiophene esters, N-hydroxyamine esters, Active ester compounds such as esters of heterocyclic hydroxy compounds, etc., but are not limited to these.

When using a hardener in the curable resin composition of the present invention, the usage amount is preferably 0.6 to 1.1 equivalents relative to 1 equivalent of the epoxy group of the epoxy resin. When the amount exceeds 1.1 equivalents of the epoxy group, and when the amount is less than 0.6 equivalents, the hardening agent remains and the curing is incomplete, and good cured physical properties may not be obtained. Among them, when a special resin that can be hardened with an epoxy resin is contained, it is not limited to this, because the amount of the hardener is relative to the remaining epoxy group obtained by subtracting the amount of epoxy consumed by the special resin. , so it needs to be adjusted appropriately according to the deployment.

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

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

The fillers that can be blended are not particularly limited. Examples of inorganic fillers include: fused silica, crystalline silica, alumina, calcium carbonate, calcium silicate, barium sulfate, talc, clay, magnesium oxide, oxide Aluminum, beryllium oxide, iron oxide, titanium oxide, aluminum nitride, silicon nitride, boron nitride, mica (mica), glass, quartz, etc. Furthermore, in order to provide a flame retardant effect, it is also preferable to use metal hydroxides such as magnesium hydroxide and aluminum hydroxide. In addition, two or more types may be mixed and used. Among these inorganic fillers, silicas such as fused silica and crystalline silica are preferred because they are low in cost and have good electrical reliability.

In the curable resin composition used in the present invention, the usage amount of the inorganic filler is usually 10% to 95% by weight of the total amount, preferably 10% to 80% by weight, and more preferably 10% by weight. % to 75% by weight. If it is 10% by weight or more, the flame retardant effect is good and the elastic coefficient is also improved. On the other hand, if the content is 95% by weight or less, the filler will not settle in the varnish, and a homogeneous molded body can be obtained. Furthermore, the shape, particle size, etc. of the inorganic filler are not particularly limited. The particle size is usually 0.01 μm to 50 μm, preferably 0.1 μm to 20 μm.

In the curable resin composition used in the present invention, in order to improve the adhesion between the glass cloth or the inorganic filler and the resin component, a matching mixture can be adjusted. As the coupling agent, any of conventionally known coupling agents can be used. Examples thereof include vinyl alkoxysilane, epoxyalkoxysilane, styrylalkoxysilane, and methacryloxysilane. Oxysilane, acryloxyalkoxysilane, aminoalkoxysilane, mercaptoalkoxysilane, isocyanatoalkoxysilane and other alkoxysilane compounds, alkoxytitanium compounds, aluminum chelates Compounds, etc. These may be used individually or in combination of 2 or more types. The coupling agent can be added by pre-treating the surface of the inorganic filler with the coupling agent and then mixing it with the resin, or by mixing the coupling agent into the resin and then mixing the inorganic filler.

The curable resin composition of the present invention may contain cyanate ester resin. As the cyanate ester compound that can be blended in the curable resin composition of the present invention, conventionally known cyanate ester compounds can be used. Specific examples of the cyanate ester compound include condensation polymers of phenols and various aldehydes, polymers of phenols and various diene compounds, condensation polymers of phenols and ketones, and polycondensates of bisphenols and various aldehydes. Condensation polymers, etc., and cyanate ester compounds obtained by reacting cyanogen halide, but are not limited to these. These may be used individually, or two or more types may be used.

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

Examples of the various aldehydes include formaldehyde, acetaldehyde, alkyl aldehydes, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, o-phthalaldehyde, crotonaldehyde, cinnamaldehyde, and the like. Examples of the various diene compounds include dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, and divinylbenzene. Benzene, diisopropenylbiphenyl, butadiene, isoprene, etc. Examples of the ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, and the like. Specific examples of the cyanate ester compound include dicyanoxybenzene, tricyanoxybenzene, dicyanoxynaphthalene, dicyanoxybiphenyl, and 2,2'-bis(4-cyanooxyphenyl). )propane, bis(4-cyanooxyphenyl)methane, bis(3,5-dimethyl-4-cyanooxyphenyl)methane, 2,2'-bis(3,5-dimethyl- 4-cyanooxyphenyl)propane, 2,2'-bis(4-cyanooxyphenyl)ethane, 2,2'-bis(4-cyanooxyphenyl)hexafluoropropane, bis(4 -Cyanoxyphenyl)sulfide, bis(4-cyanoxyphenyl)sulfide, phenol novolak cyanate, those in which the hydroxyl group of phenol·dicyclopentadiene co-condensate is converted into a cyanate ester group, etc. , but are not limited to these. In addition, the cyanate ester compound whose synthesis method is described in Japanese Patent Application Laid-Open No. 2005-264154 is particularly suitable as a 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 ester resin, in order to trimerize the cyanate ester group to form a sym-triazine ring as necessary, zinc naphthenate, Catalysts such as cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octoate, tin octoate, lead acetyl acetonate, and dibutyltin maleate. 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 mass of the thermosetting resin composition.

In the curable resin composition of the present invention, known additives can be blended as necessary. Specific examples of additives that can be used include polybutadiene and modified products thereof, modified products of acrylonitrile copolymer, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, and silicone gel. Surface treatment agents, release agents, carbon black, phthalocyanine blue, phthalocyanine green and other colorants for filling materials such as glue, silicone oil, and silane coupling agents. The compounding amount of these additives is preferably 1,000 parts by mass or less, more preferably 700 parts by mass or less relative to 100 parts by mass of the curable resin composition.

The curable resin composition of the present invention may further add an organic solvent. Examples of the solvent used include: γ-butyrolactone; N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N - Amide solvents such as dimethyl imidazolidinone; tetramethylene glycol and other solvents; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetic acid Ether solvents such as esters and propylene glycol monobutyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; and aromatic solvents such as toluene and xylene. The solvent is usually used in a range of 10% to 80% by weight, preferably 20% to 70% by weight, of the solid content excluding the solvent in the obtained varnish. In addition, the obtained varnish can be used to shape prepregs or resin sheets.

Here, the prepreg is explained. The prepreg is formed by impregnating the varnish into a fiber base material. As a result, a prepreg excellent in heat resistance, low expansion, and flame retardancy can be obtained. Examples of the fiber base material include glass fiber base materials such as glass woven fabric, glass nonwoven fabric, and cellophane; woven fabrics containing synthetic fibers such as paper, aramid, polyester, aromatic polyester, and fluororesin; or Non-woven fabrics; woven fabrics, non-woven fabrics, mats, etc. including metal fibers, carbon fibers, mineral fibers, etc. These base materials can be used alone or in combination. Among these, a glass fiber base material is preferred. This can improve the rigidity and dimensional stability of the prepreg. As the glass fiber base material, a base material containing at least one selected from the group consisting of T glass, S glass, E glass, NE glass and quartz glass is preferred.

Examples of methods for impregnating the fiber base material with the curable resin composition of the present invention include: a method of impregnating the base material in a resin varnish; a method of coating with various coaters; and a method of blowing with a sprayer. methods etc. Among these, a method of immersing the base material in a resin varnish is preferred. Thereby, the impregnation property of the resin composition into the base material can be improved. In addition, when the base material is immersed in the resin varnish, ordinary dip coating equipment can be used. For example, after the curable resin composition of the present invention is impregnated into a base material such as glass cloth directly or in the form of varnish dissolved or dispersed in a solvent, the curable resin composition is dried in a drying oven or the like, usually at 80°C to 200°C (where, When a solvent is used, the prepreg is obtained by drying at a temperature of preferably 150°C to 200°C for 1 minute to 30 minutes, preferably 1 minute to 15 minutes (a temperature above which the solvent can volatilize). In addition, a method of pressing a resin sheet to be 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 is made by applying the varnish itself to a predetermined thickness after drying by various coating methods such as gravure coating, screen printing, metal masking, and spin coating. For example, it is obtained by coating a planar support with a thickness of 5 μm to 100 μm and then drying it. However, the coating method used depends on the type, shape, size, coating film thickness, and heat resistance of the support. Sexual and other appropriate choices. Examples of the planar support include polyamide, polyamide imide, polyarylate, polyethylene terephthalate, polybutylene terephthalate, polyether ketone, and polyether imide. Films made of various polymers such as amine, polyetheretherketone, polyketone, polyethylene, polypropylene, Teflon (registered trademark), and/or their copolymers, or metal foils such as copper foil, etc. After coating, the composition can be dried to obtain a sheet-like composition (the sheet of the present invention), or the sheet can be further heated to obtain a sheet-like cured product. In addition, the solvent drying and hardening steps can also be performed in one heating step. The aromatic amine resin composition having an N-alkyl group of the present invention can be coated on both sides or one side of the support by using the method described above and heated, so that the aromatic amine resin composition of the present invention can be formed on both sides or one side of the support. layer of hardened matter. In addition, a laminated body can also be produced by bonding an adherend together and hardening it before hardening. In addition, the resin sheet of the present invention can also be peeled off from the support body and used as an adhesive sheet. It can also be contacted with the adherend and adhered while curing by applying pressure and heat as necessary.

Next, the laminated board will be described. The laminated board is formed by heating and pressing the prepreg and/or resin sheet. Thereby, a printed wiring board excellent in heat resistance, low expansion, and flame retardancy can be obtained. When the prepreg and/or the resin sheet are one piece, metal foil is laminated on both upper and lower sides or on one side. In addition, two or more prepregs and/or resin sheets may be laminated. When two or more prepregs and/or resin sheets are laminated, metal foils or films and/or resin sheets are laminated on both upper and lower surfaces or one side of the outermost outermost surfaces of the laminated prepregs and/or resin sheets. Next, a printed wiring board can be obtained by heating and press-molding a laminate of a prepreg and/or a resin sheet and a metal foil. The temperature at which the heating is performed is not particularly limited, but is preferably 120°C to 220°C, particularly preferably 150°C to 200°C. The pressure for performing the pressurization is not particularly limited, but is preferably 1.5 MPa to 5 MPa, particularly preferably 2 MPa to 4 MPa. In addition, if necessary, post-hardening may be performed in a high-temperature tank or the like at a temperature of 150°C 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. Form circuits on one or both sides of the laminate. Depending on the situation, through holes can also be formed by drilling or laser processing, and electrical connections on both sides can be obtained by plating.

By stacking the resin sheet or the prepreg on the built-in circuit board and performing heat and pressure molding, a multilayer printed wiring board can be obtained. Specifically, it can be obtained by combining the insulating layer side of the resin sheet with the inner circuit board, vacuum heating and pressure molding using a vacuum pressure laminator device, and then drying with hot air. The device, etc. heats and hardens the insulation layer. The conditions for heat and pressure molding here are not particularly limited. As an example, it can be carried out at a temperature of 60°C to 160°C and a pressure of 0.2 MPa to 3 MPa. In addition, the conditions for heat hardening are not particularly limited. As an example, it can be carried out at a temperature of 140° C. to 240° C. and a time of 30 minutes to 120 minutes. Alternatively, it can be obtained by laminating the prepreg on an inner circuit board and subjecting it to heat and pressure molding using a flat plate pressing device or the like. The conditions for heat and pressure molding here are not particularly limited. As an example, it can be carried out at a temperature of 140°C to 240°C and a pressure of 1 MPa to 4 MPa. In such heat-pressure molding using a flat plate press or the like, the insulating layer is heat-hardened simultaneously with the heat-pressure molding.

In addition, the manufacturing method of a multilayer printed wiring board includes the steps of continuously stacking the resin sheet or the prepreg on the surface of the inner layer circuit board on which the inner layer circuit pattern is formed; and using a semi-additive method or the like. The step of forming layers of conductor circuits using a build-up method.

Regarding the curing of the insulating layer formed of the resin sheet or the prepreg, in order to facilitate subsequent laser irradiation and removal of resin residues and improve desmearability, the insulation layer may be brought into a semi-cured state in advance. . In addition, by heating the first layer of insulating layer at a lower temperature than the usual heating temperature to partially harden it (semi-hardening), and further forming one or more insulating layers on the insulating layer, the semi-hardened insulation layer is The layers are heated and hardened again to a level that is no problem in practice, thereby improving the adhesion between the insulating layers and between the insulating layers and the circuit. The semi-hardening temperature at this time is preferably 80°C to 200°C, more preferably 100°C to 180°C. Furthermore, in the next step, laser is irradiated to form an opening in the insulating layer, but before that, the base material needs to be peeled off. There is no particular problem whether the base material peeling is performed after the insulating layer is formed, before heat hardening, or after heat hardening. Furthermore, as the inner circuit board used when obtaining the multilayer printed wiring board, for example, it is preferable to use a circuit board in which a predetermined conductor circuit is formed on both sides of a copper laminate by etching, etc., and the conductor is The circuit part has been blackened.

Resin residues after laser irradiation are preferably removed by oxidizing agents such as permanganate and dichromate. In addition, the surface of the smooth insulating layer can be roughened at the same time, and the adhesion of the formed conductive wiring circuit can be improved through subsequent metal plating.

Next, the outer circuit is formed. The formation method of the outer layer circuit is to realize the connection between the insulating resin layers through metal plating, and to form the outer layer circuit pattern through etching. In the same manner as when a resin sheet or prepreg is used, a multilayer printed wiring board can be obtained. Furthermore, when using a resin sheet or prepreg with metal foil, the circuit may be formed by etching in order to use it as a conductor circuit without peeling off the metal foil. In this case, if an insulating resin sheet with a base material using a thick copper foil is used, it will be difficult to achieve fine pitch in subsequent circuit pattern formation, so an extremely thin copper foil of 1 μm to 5 μm may be used. Alternatively, half-etching is performed to thin the copper foil of 12 μm to 18 μm to 1 μm to 5 μm by etching.

An insulating layer may be further laminated and a circuit may be formed in the same manner as described above. In the design of a multilayer printed wiring board, a solder resist may be formed on the outermost layer after the circuit is formed. The formation method of the solder resist is not particularly limited. For example, it can be implemented by the following methods: stacking (laminating) dry film type solder resist, forming the solder resist by exposure and development; or by printing liquid A method of forming a solder mask by exposing and developing a resist in the form of a resist. Furthermore, when the obtained multilayer printed wiring board is used for a semiconductor device, a connection electrode part is provided in order to mount a semiconductor element. The connection electrode portion can be appropriately covered with a metal film such as gold plating, nickel plating, or solder plating. By this method, a multilayer printed wiring board can be manufactured.

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 to 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 made of an alloy containing tin, lead, silver, copper, bismuth, etc. The method of connecting a semiconductor element to a multilayer printed wiring board is to use a flip chip bonder or the like to align the positions of the connection electrode portions on the substrate and the solder bumps of the semiconductor element. After it is accurate, use an infrared (IR) reflow device, a hot plate, or other heating devices to heat the solder bumps above the melting point, and fuse the multilayer printed wiring board and the solder bumps. Furthermore, in order to improve connection reliability, a layer of metal with a low melting point such as solder paste may be formed in advance on the connection electrode portion of the multilayer printed wiring board. Before the bonding step, connection reliability can be improved by applying flux to the surface layer of the solder bumps and/or the connection electrode portions on the multilayer printed wiring board.

As a substrate, it can be used for motherboards, network substrates, packaging substrates, etc., and is used in the form of substrates. In particular, it is useful as a packaging substrate and a thin-layer substrate for single-sided sealing materials. When used as a semiconductor sealing material, examples of the semiconductor device obtained by the preparation include a dual-in-line package (DIP) and a quad flat package. , QFP), ball grid array (BGA), chip size package (CSP), small outline package (SOP), thin small outline package (TSOP), Thin quad flat package (TQFP). [Example]

Hereinafter, the present invention will be described in detail through examples. Furthermore, the present invention is not limited to these Examples.

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

·GPC (gel permeation chromatography) analysis Manufacturer: Waters Column: Protection column SHODEX GPC KF-601 (two pieces), KF-602, KF-602.5, KF-603 Flow rate: 1.23 ml/min. Column temperature: 25℃ Solvent used: THF (tetrahydrofuran) Detector: RI (differential refraction detector)

(Example 1) Add 150 g of toluene and 56.0 g of N-methylaniline to a flask equipped with a thermometer, cooling tube, and stirrer, and stir. Then, 43.5 g of 4,4'-bischloromethylenebiphenyl was added over 1 hour, and the reaction was carried out at 65°C for 2 hours. Next, 36.1 g of 35% hydrochloric acid was added dropwise below 80°C. After completion of the dropwise addition, the temperature was raised to 210°C while performing azeotropic dehydration, and the reaction was carried out at 210°C for 15 hours. After the reaction, 100 g of 17% caustic soda aqueous solution was added dropwise to make the reaction solution alkaline, then 100 g of toluene and 150 g of N-methylaniline were added, and stirred for 6 hours. After standing and draining, wash with water until the waste water becomes neutral. The solvent, water, and unreacted N-methylaniline were distilled off by concentration under reduced pressure, and biphenyl-N-methylaniline novolac (BNMAN-1) was obtained in the form of a black solid resin (amine equivalent: 208 g, Softening point: 79.6℃, ICI viscosity (150℃): 0.048 Pa·s, composition ratio based on GPC area %: n=1 component: 9.1%, n=2 component: 31%, n=3 component: 29% , high molecular weight components with n=4 or above: 30.9%).

(Example 2) Add 50 g of toluene and 171.5 g of N-methylaniline to a flask equipped with a thermometer, cooling tube, and stirrer, and stir. Then, 50.2 g of 4,4'-bischloromethylenebiphenyl was added over 1 hour, and the reaction was carried out at 65°C for 2 hours. Next, 41.7 g of 35% hydrochloric acid was added dropwise at a temperature below 80°C. After completion of the dropwise addition, the temperature was raised to 210°C while performing azeotropic dehydration, and the reaction was carried out at 210°C for 15 hours. After the reaction is completed, 40 g of 48% caustic soda aqueous solution is added dropwise to make the reaction solution alkaline, and then 50 g of toluene is added and stirred for 6 hours. After standing and draining, wash with water until the waste water becomes neutral. The solvent, water, and unreacted N-methylaniline were distilled off by concentration under reduced pressure to obtain biphenyl-N-methylaniline novolac (BNMAN-2) in the form of a black solid resin (amine equivalent: 198 g, Softening point: 47.3℃, ICI viscosity (150℃): 0.02 Pa·s, composition ratio based on GPC area %: n=1 component: 71%, n=2 component: 18%, n=3 component: 4.6% , High molecular weight components with n=4 or above: 1.3%).

(Example 3) Add 200 g of water and 214 g of N-methylaniline to a flask equipped with a thermometer, cooling tube, and stirrer, and stir. Then, 209 g of 35% hydrochloric acid was added dropwise below 40°C. Then, 108 g of 37% formaldehyde aqueous solution was added dropwise at 40°C or below. After the dropwise addition is completed, the reaction is carried out at 75°C to 80°C for 5 hours. After the reaction, 168 g of 48% caustic soda aqueous solution was added dropwise to make the reaction solution alkaline, and then 300 g of toluene was added and stirred for 6 hours. After standing and draining, wash with water until the waste water becomes neutral. The solvent, water, and unreacted N-methylaniline were distilled off by concentration under reduced pressure, and 200 g of N-methylaniline novolak (NMAN-1) was obtained as a black liquid resin (amine equivalent: 116 g/ eq., the composition ratio is based on GPC area %: n=1 component: 37%, n=2 component: 19%, n=3 component: 14%, n=4 or higher high molecular weight component: 30%).

(Example 4) Except changing the 37% formaldehyde aqueous solution to 122 g, proceed in the same manner as Example 3 to obtain N-methylaniline novolac (NMAN-2) in the form of a black semi-solid resin (amine equivalent: 118.6 g/eq ., the composition ratio is based on GPC area %: n=1 component: 25%, n=2 component: 15%, n=3 component: 13%, n=4 or higher high molecular weight component: 47%).

(Example 5) Add 50 g of toluene, 64.1 g of N-methylaniline, α,α,α',α'-tetramethyl-1,3-benzenedimethanol, and activated clay 20 to a flask equipped with a thermometer, cooling tube, and stirrer. g, stir. While azeotropically dehydrating, the internal temperature was raised to 160°C, and the reaction was carried out at 160°C for 24 hours. After cooling, add 150 g of toluene, remove the activated clay by filtration, and concentrate the filtrate under reduced pressure to obtain a brown liquid resin with the bis-N-methylaminocumylbenzene structure as the main component. of aromatic amine resin (BNMACB) (amine equivalent: 191 g/eq.).

(Synthesis example 1) The procedure was carried out in the same manner as in Example 3 except that the 37% formaldehyde aqueous solution was changed to 89 g, and 217 g of N-methylaniline novolak (NMAN-3) was obtained in the form of a black liquid resin (amine equivalent: 115 g /eq., the composition ratio is based on 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) Put 372 parts of aniline and 200 parts of toluene into a flask equipped with a thermometer, cooling tube, Dean-Stark azeotropic distillation trap, and stirrer, and add 35% dropwise over 1 hour at room temperature. 146 parts of hydrochloric acid. After the dropwise addition, the heated and azeotropic water and toluene were cooled and separated, and then only the toluene as the organic layer 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°C to 70°C, and the reaction was further performed at the same temperature for 2 hours. After the reaction was completed, toluene was distilled off while raising the temperature, so that the temperature inside the system was 195°C to 200°C, and the reaction was carried out at this temperature for 15 hours. Then, while cooling, 330 parts of 30% sodium hydroxide aqueous solution was slowly added dropwise without violent reflux in the system, and the toluene distilled off when the temperature was raised below 80°C was returned to the system, and left to stand at 70°C to 80°C. The separated lower aqueous layer was removed, and the reaction liquid was repeatedly washed with water until the washing liquid became neutral. Next, excess aniline and toluene were distilled off from the oil layer using a rotary evaporator under heating and reduced pressure (200° C., 0.6 KPa), thereby obtaining 173 parts of aromatic amine resin (a1). The amount of diphenylamine in the aromatic amine resin (a1) measured by gas chromatography was 2.0%. To the obtained resin, a rotary evaporator was again used, and water was added dropwise in small amounts at a time under heating and reduced pressure (200°C, 4 KPa) instead of blowing water vapor. As a result, 166 parts of aromatic amine resin (A1) were 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. According to JIS K-7236 Annex A (Glycidylamine Correction Method), the obtained value is measured as amine equivalent. The amine equivalent of A1 is 195 g/eq.

(Synthesis example 3) Put 147 parts of maleic anhydride and 300 parts of toluene into a flask equipped with a thermometer, a cooling tube, a Dean Stark azeotropic distillation trap, and a stirrer, and cool and separate the heated and azeotropic water and toluene. Afterwards, only the toluene as the organic layer is returned to the system for dehydration. Next, while maintaining the system at 80°C to 85°C, 195 parts of the aromatic amine resin (A1) obtained in Synthesis Example 2 was dissolved in 195 parts of N-methyl-2-pyrrolidone. The resulting resin solution. After the dropwise addition, react at the same temperature for 2 hours. Add 3 parts of p-toluenesulfonic acid. After cooling and separating the azeotropic condensation water and toluene under reflux conditions, only the toluene as the organic layer is returned to the system. Dehydration was carried out within 20 hours while reaction was carried out for 20 hours. After the reaction, 120 parts of toluene was added, and water was washed repeatedly to remove p-toluenesulfonic acid and excess maleic anhydride. After heating, water was removed from the system by azeotropy. Then, the reaction solution was concentrated under reduced pressure to obtain a resin solution containing 70% maleimide resin (M1). The diphenylamine content in maleimide resin (M1) is 0.1% or less. The solvent of M1 was distilled off under heating and reduced pressure, and the solid was extracted to obtain solid maleimide resin (MIR). The theoretical maleimine equivalent of MIR calculated from the amine equivalent of the amine resin (A1) used as a raw material is 275 g/eq.

(Example 6 to Example 13, Comparative Example 1, Comparative Example 2) The aromatic amine resins (BNMAN-1, NMAN-1 to NMAN-3) having an N-alkyl group obtained in Example 1, Example 3, Example 4 and Synthesis Example 1 were prepared in the proportions (parts by weight) in Table 1. ), 4,4'-diaminodiphenylmethane (manufactured by Tokyo Chemical Industry Co., Ltd.), and the maleimide resin (MIR) of Synthesis Example 3 were heated, melted, mixed, and directly poured into the mold at 220 C harden for 2 hours.

The following items were measured for the physical properties of the cured material obtained in this manner, and the results are shown in Table 1. ＜Heat resistance test＞ ·Glass transition temperature: measured by a dynamic viscoelastic testing machine, the temperature at which tan δ reaches the maximum value. ＜Dielectric constant test·Dielectric loss tangent test＞ ·A 1 GHz cavity resonator manufactured by Kanto Electronics Application Development Co., Ltd. was used and tested using the cavity resonator perturbation method. Among them, the test was conducted with the sample size as 1.7 mm wide × 100 mm long and 1.7 mm thick.

[Table 1]

It was confirmed from Table 1 that Examples 6 to 13 using the aromatic amine compound having an N-alkyl group of the present invention have better electrical characteristics and high heat resistance than Comparative Examples 1 and 2. [Industrial availability]

Therefore, the condensate of the aniline compound having an N-alkyl group of the present invention and formaldehyde can be used in insulating materials for electrical and electronic parts (high-reliability semiconductor sealing materials, etc.) and laminates (printed wiring boards, BGA substrates, build-up layers). Substrates, etc.), adhesives (conductive adhesives, etc.) or various composite materials including CFRP, and are useful in coatings and other applications.

without

without

Claims (11)

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

(In formula (1), the presence of multiple R independently represents hydrogen or a hydrocarbon group with a carbon number of 1 to 15; the case where all R is hydrogen is excluded; the presence of multiple X independently represents a hydrogen atom, a carbon number A hydrocarbon group of 1 to 15; Y is any one of (a) to (c) described in the following formula (2); l ₁ , l ₂ and m represent integers of 1 or more, and satisfy l ₁ +m≦ 5. l ₂ +m≦4; n means 1≦n≦15)

The aromatic amine resin having an N-alkyl group as described in item 1 of the patent application is represented by the following formula (3):

(n is the average value, indicating 1≦n≦15). An aromatic amine resin having an N-alkyl group, which is represented by the following formula (1a), and the component represented by n=1 in gel permeation analysis is 5 area % or more and less than 50 area %

(In formula (1a), the presence of multiple R independently represents hydrogen or a hydrocarbon group with a carbon number of 1 to 15; the case where all R is hydrogen is excluded; the presence of multiple X independently represents a hydrogen atom, a carbon number Hydrocarbon groups of 1 to 15; Y is a methylene bond; l ₁ , l ₂ and m represent integers above 1, and satisfy l ₁ +m≦5, l ₂ +m≦4; 1≦n≦15). The aromatic amine resin having an N-alkyl group as described in claim 3, wherein in the formula (1a), the component represented by n=4 or more accounts for 5 area % or more and less than 80 area %. The aromatic amine resin having an N-alkyl group as described in item 3 or 4 of the patent application is represented by the following formula (4):

(n is the average value, indicating 1≦n≦15). The aromatic amine resin having an N-alkyl group as described in item 3 or 4 of the patent application, wherein in the formula (1a), when the component represented by n=1 in gel permeation analysis is assumed When A is the area % and the component represented by n=4 or more is B area %, B/A is 0.1 or more and less than 20. The aromatic amine resin having an N-alkyl group as described in item 3 or 4 of the patent application, wherein the amine equivalent is 116g/eq. or more and less than 120g/eq. A curable resin composition containing: an aromatic amine resin having an N-alkyl group as described in any one of claims 1 to 7; and a maleimine resin. The curable resin composition as described in claim 8, wherein the blending equivalent ratio of the blending equivalent α of the aromatic amine resin having an N-alkyl group to the blending equivalent β of the maleimine resin is 0.9≦α /β≦2.5. The curable resin composition as described in claim 8, wherein the blending equivalent ratio of the blending equivalent α of the aromatic amine resin having an N-alkyl group to the blending equivalent β of the maleimine resin is 1.4≦α /β≦2.5. A hardened product, which is as specified in items 8 to 10 of the patent application The curable resin composition described in any one of the items above is cured.