TWI614262B - A siloxane compound, a modified quinone imine resin, a thermosetting resin composition, a prepreg, a resin-attached film, a laminate, a multilayer printed wiring board, and a semiconductor package - Google Patents

Description

A siloxane compound, a modified quinone imine resin, a thermosetting resin composition, a prepreg, a resin-attached film, a laminate, a multilayer printed wiring board, and a semiconductor package

The present invention relates to a siloxane compound suitable for use in a semiconductor package and a printed wiring board, and a modified yttrium imide resin, a thermosetting resin composition, a prepreg, and a resin-attached film using the siloxane compound , laminated boards, multilayer printed wiring boards and semiconductor packages.

In recent years, with the trend of miniaturization and high performance of electronic equipment, multilayer printed wiring boards have continued to develop in height and high integration of line density, and accordingly, heat resistance of laminate boards for multilayer printed wiring has been improved. Sexuality increases the need for increased reliability. In such a use, particularly in a semiconductor package, it is required to have both excellent heat resistance and low thermal expansion. In addition, dielectric characteristics are also required in response to high frequency of electronic signals.

In this case, a well-known liquid crystalline polymer such as a polyester-based or polyamidiamine-based, polycarbonate-based, polythiol-based, polyether-based, or polymethylenimine-based polymer has low thermal expansion properties. A thermosetting resin excellent in electrical properties and heat resistance has a problem of workability and moldability, or has a problem that solubility in an organic solvent is low and it is difficult to handle.

Among these liquid crystalline polymers, polymethyl was found from G.F.D’Alelio. A liquid crystal oligomer (i.e., Non-Patent Document 1) has been reported as a case of a resin using a polymethylenimine (see Patent Documents 1 to 7).

Patent Document 1 discloses various types of polyimine, and Patent Documents 2 to 7 disclose polymethylenimine having a specific structure. Further, Patent Documents 8 and 9 disclose thermosetting polyimine resins containing an unsaturated group, and it is described that these resins exhibit higher heat resistance.

[Previous Technical Literature] (Patent Literature)

Patent Document 1: Japanese Laid-Open Patent Publication No. 51-138800

Patent Document 2: Japanese Laid-Open Patent Publication No. 60-181127

Patent Document 3: Japanese Laid-Open Patent Publication No. 60-101123

Patent Document 4: Japanese Laid-Open Patent Publication No. 2003-073470

Patent Document 5: Japanese Laid-Open Patent Publication No. SHO63-193925

Patent Document 6: Japanese Laid-Open Patent Publication No. 01-069631

Patent Document 7: Japanese Laid-Open Patent Publication No. 01-079233

Patent Document 8: Japanese Laid-Open Patent Publication No. 05-140067

Patent Document 9: Japanese Laid-Open Patent Publication No. 2011-195476

(Non-patent literature)

Non-Patent Document 1: Polymer Sci. Tech., Wiley-Interscience, New York, 1969, Vol. 10, pp. 659-670

However, the polymethylenimine described in Patent Documents 1 to 7 is applied. When it is used as a copper clad laminate or an interlayer insulating material, heat resistance or formability may be insufficient.

Moreover, the thermosetting polyimine resin described in Patent Document 8 is still insufficient in improvement in heat resistance and toughness, and when such a polyimide resin is used as a copper clad laminate or an interlayer insulating material, There are still cases of insufficient heat resistance, reliability, and processability.

Further, the thermosetting polyimine resin described in Patent Document 9 cannot satisfy the portion having low curing shrinkage and low thermal expansion coefficient.

In view of the above circumstances, an object of the present invention is to provide a siloxane compound which can realize a thermosetting resin composition which is excellent when applied to various applications. Low hardening shrinkage, low thermal expansion, good dielectric properties, high modulus of elasticity, and a modified quinone imine resin, thermosetting resin composition, and the use of the siloxane compound, modified 醯A prepreg composed of an amine resin or a thermosetting resin composition, a resin-attached film, a laminate, a multilayer printed wiring board, and a semiconductor package.

The inventors of the present invention have conducted extensive studies in order to achieve the above-described objects, and as a result, have found that the above object can be attained by using a modified methoxyalkylene compound having an aromatic carbamide, and the present invention has been completed. The present invention is based on this knowledge.

That is, the present invention provides the following oxoxane compound, modified quinone imine resin, thermosetting resin composition, prepreg, resin-attached film, laminated board, multilayer printed wiring board, and semiconductor package. .

[1] A oxoxane compound comprising a structure represented by the following formula (1) and the following formula (2):

(wherein R ₁ and R ₂ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, a halogenated alkyl group, a thiol group, an ethyl fluorenyl group, a hydroxyl group, a sulfonic acid group, or a carbon number of 1~ 3 sulfoalkoxyl, or alkoxy having 1 to 3 carbon atoms; x, y are each independently an integer of 0 to 4; A is a single bond or a methylenimine group, an ester group, a guanamine group , oxyazo, azo, vinyl or ethynyl).

(式中，R₃和R₄分別獨立地表示烷基、苯基或取代苯基，n表示1~100的整數)。

(wherein R ₃ and R ₄ each independently represent an alkyl group, a phenyl group or a substituted phenyl group, and n represents an integer of from 1 to 100).

[2] The oxirane compound according to [1], which further contains an aromatic carbimimine.

[3] The alkane compound according to [2], which is an aromatic amine compound (A) having at least two primary amine groups in one molecule, and having at least two aldehyde groups in one molecule. The aldehyde compound (B) is obtained by reacting a oxoxane compound (C) having at least two amine groups at the molecular terminal.

[4] The alkoxyalkyl compound according to [2], which is an aromatic amine compound (A) having at least two primary amine groups in one molecule and having at least one molecule The two aldehyde group aromatic aldehyde compound (B) is reacted, and then reacted with a oxoxane compound (C) having at least two amine groups at the molecular terminal.

[5] The alkoxylate compound according to [2], which is an aromatic aldehyde compound (B) having at least two aldehyde groups in one molecule and an oxygen group having at least two amine groups at a molecular terminal. After the reaction of the alkyl compound (C), it is further reacted with an aromatic amine compound (A) having at least two primary amino groups in one molecule.

[6] A modified quinone imine resin having an aromatic carbamide, which is a oxoxane compound according to any one of [1] to [5], and It is obtained by reacting a maleimine compound (D) having at least two N-substituted maleimine groups in one molecule.

(式中，R₅各自獨立地表示作為酸性取代基的羥基、羧基或磺酸基；R₆各自獨立地表示氫原子、碳數1~5的脂肪族烴基或鹵素原子；x為1~5的整數，y為0~4的整數，且x與y的和為5)。 [7] The modified quinone imine resin according to [6], which further has an acidic substituent derived from an acidic substituent of the amine compound (E) represented by the following formula (3),

(wherein R ₅ each independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group as an acidic substituent; and R ₆ each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom; and x is 1 to 5 The integer, y is an integer from 0 to 4, and the sum of x and y is 5).

[8] A thermosetting resin composition, comprising: the oxoxane compound according to any one of [1] to [5], and having at least two N-substituted maleates in one molecule; An imido group of maleimide compound (D).

(式中，R₅各自獨立地表示為酸性取代基的羥基、羧基或磺酸基；R₆各自獨立地表示氫原子、碳數1~5的脂肪族烴基或鹵素原子；x為1~5的整數，y為0~4的整數，且x與y的和為5)。 [9] The thermosetting resin composition according to [8], further comprising an amine compound (E) having an acidic substituent represented by the following formula (3),

(wherein R _{5 is} each independently represented by a hydroxyl group, a carboxyl group or a sulfonic acid group of an acidic substituent; and R ₆ each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom; and x is 1 to 5 The integer, y is an integer from 0 to 4, and the sum of x and y is 5).

[10] The thermosetting resin composition according to [8], which further comprises a thermoplastic elastomer (F).

The thermosetting resin composition according to any one of the above aspects, wherein the thermosetting resin composition further contains at least one selected from the group consisting of an epoxy resin and a cyanate resin (G). ).

[12] The thermosetting resin composition according to any one of [8] to [11] further comprising an inorganic filler (H).

[13] The thermosetting resin composition according to any one of [8] to [12] further comprising a curing accelerator (I).

[14] A prepreg obtained by impregnating a thermosetting resin composition according to any one of [8] to [13] into a substrate.

[15] A resin-coated film obtained by forming a layer of a thermosetting resin composition according to any one of [8] to [13] on a support.

[16] A laminated board obtained by laminating a prepreg according to [14].

[17] A laminate which is obtained by laminating a resin-attached film as described in [15] The layer is formed.

[18] A multilayer printed wiring board manufactured by using the laminated board according to [16] or [17].

[19] A semiconductor package obtained by carrying a semiconductor element on a multilayer printed wiring board as described in [18].

According to the present invention, it is possible to provide a siloxane compound which can realize a thermosetting resin composition which exhibits excellent low hardening shrinkage when applied to various applications. , low thermal expansion, good dielectric properties, high modulus of elasticity, and can provide modified quinone imine resin, thermosetting resin composition, and use of the decane compound, modified quinone imide resin, thermosetting A prepreg composed of a resin composition, a resin-attached film, a laminate, a multilayer printed wiring board, and a semiconductor package.

In particular, the thermosetting resin composition (containing the modified methoxyalkylene compound having an aromatic carbamide of the present invention) is impregnated with a prepreg obtained by coating the substrate, and attached to the support. The resin-coated film and the laminate produced by laminating the prepreg have particularly low heat shrinkage, low thermal expansion, excellent dielectric properties, and high modulus of elasticity, and are therefore suitable for multilayer printing. Circuit board and semiconductor package.

The invention is described in detail below.

(矽 oxane compound)

The oxirane compound of the present invention contains a structure represented by the following formula (1) and the following formula (2). This structure is, for example, a structure represented by the following formula (1) The compound is obtained by reacting a compound having a structure represented by the following formula (2).

(式中，R₁和R₂各自獨立地表示氫原子、鹵素原子、碳數1~3的烷基、鹵化烷基、硫醇基、乙醯基、羥基、磺酸基、碳數1~3的磺烷氧基、或碳數1~3的烷氧基；x、y各自獨立為0~4的整數；A為單鍵或是甲亞胺基、酯基、醯胺基、氧偶氮基、偶氮基、乙烯基或乙炔基)。

(Wherein, R ₁ and R ₂ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a halogenated alkyl group, a thiol group, an acetyl group, a hydroxyl group, a sulfonic acid group, C 1 - a sulfoalkoxy group of 3 or an alkoxy group having 1 to 3 carbon atoms; x and y are each independently an integer of 0 to 4; A is a single bond or a methylimine group, an ester group, a decyl group, an oxirane Nitro, azo, vinyl or ethynyl).

(式中，R₃和R₄分別獨立地表示烷基、苯基或取代苯基，n表示1~100的整數)。

(wherein R ₃ and R ₄ each independently represent an alkyl group, a phenyl group or a substituted phenyl group, and n represents an integer of from 1 to 100).

Further, the oxirane compound of the present invention preferably contains an aromatic carbimimine.

Here, the aromatic methylimine means a substance in which at least one aromatic group is bonded to a Schiff base (-N=CH-).

Hereinafter, the oxirane compound of the present invention will be described in detail.

The oxirane compound of the present invention is an aromatic amine compound (A) having at least two primary amine groups in one molecule (hereinafter also referred to as an aromatic amine compound (A)), and has at least 2 in one molecule. Aldehyde-based aromatic aldehyde compound (B) The base oxane compound (C) (hereinafter also referred to as a oxoxane compound (C)) is obtained by a reaction.

As the present invention, at least two primary amino groups are present in one molecule Examples of the aromatic amine compound (A) include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3-methyl-1,4-diamine benzene, and 2,5-di. Methyl-1,4-diamine benzene, 4,4'-diamine diphenylmethane, 4,4'-diamine-3,3'-dimethyl-diphenylmethane, 4,4'-di Amine-3,3'-diethyl-diphenylmethane, 4,4'-diamine diphenyl ether, 4,4'-diamine diphenyl hydrazine, 3,3'-diamine diphenyl hydrazine , 4,4'-diamine diphenyl ketone, benzidine, 3,3'-dimethyl-4,4'-diamine biphenyl, 2,2'-dimethyl-4,4'-di Amine biphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4 , 4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3 - bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'- Bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)anthracene, bis(4-(3-aminophenoxy)phenyl)anthracene, 9 , 9-bis(4-aminophenyl)anthracene, 4,4'-diaminobenzimidamide, bis(4-aminophenyl)-p-nonylamine, 4-aminophenyl-4' -amine Benzoate, 3,5-diaminobenzyl benzoate, 4,4'-diaminoazobenzene, 3,3'-diamine-2,2'-dimethyloxy Nitrobenzene, (E)-4,4'-diaminostilbene, (Z)-4,4'-diaminostilbene, 4,4'-diaminostilbene-2,2 '-Disulfonic acid, 1,3-bis(4-aminophenoxy)-5-(2-phenylethynyl)benzene, and the like. These compounds may be used singly or in combination of two or more.

Among them, for example, the reactivity at the time of reaction is high, and heat resistance can be improved. Further, further preferred are: 4,4'-diamine diphenylmethane, 3,3'-dimethyl-4,4'-diamine biphenyl, 4,4'-diamine- 3,3'-dimethyl-diphenylmethane, 4,4'- Methyl-4,4'-diamine biphenyl, 4,4'-diamine-3,3'-dimethyl-diphenylmethane, 4,4'-diamine-3,3'-diethyl - Diphenylmethane, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)propane, and the like. Further, from the viewpoints of low cost and solubility in a solvent, preferred are: 4,4'-diamine diphenylmethane, 3,3'-dimethyl-4,4'-diamine. Benzene, 4,4'-diamine-3,3'-diethyl-diphenylmethane, bis(4-(4-aminophenoxy)phenyl)propane. Further, from the viewpoint of low thermal expansion property and dielectric properties, particularly preferred are: 4,4'-diamine-3,3'-diethyl-diphenylmethane, bis(4-(4-amino group) Phenoxy)phenyl)propane. Further, it is also preferably p-phenylenediamine, m-phenylenediamine, 3-methyl-1,4-diamine benzene, 2,5-dimethyl-1,4- which can increase the elastic modulus. Diamine benzene.

The aromatic aldehyde compound (B) having at least two aldehyde groups in one molecule in the present invention may, for example, be terephthalaldehyde, isophthalaldehyde, o-benzenedialdehyde, 2,2'- Bipyridyl-4,4'-diformaldehyde and the like. Among these compounds, terephthalaldehyde is particularly preferable, for example, the thermal expansion is lowered, the reactivity at the time of the reaction is high, the solvent solubility is also excellent, and it is commercially easy to obtain.

The oxirane compound (C) having at least two amine groups at the molecular terminal of the present invention contains a structure represented by the following formula (2).

(式中，R₃和R₄分別獨立地表示烷基、苯基或取代苯基，n表示1~100的整數)。

(wherein R ₃ and R ₄ each independently represent an alkyl group, a phenyl group or a substituted phenyl group, and n represents an integer of from 1 to 100).

In the formula (2), n is an integer of from 1 to 100, and more preferably from 2 to 50. Integer.

Further, as an oxoalkylation having at least two amine groups at the terminal of the molecule For the compound (C), a commercially available product can be used. Examples of the commercially available product include "KF-8010" (amine equivalent 430), "X-22-161A" (amine equivalent: 800), and "X-22-161B" (amine equivalent 1500), " KF-8012" (amine equivalent: 2200), "KF-8008" (amine equivalent: 5700), "X-22-9409" (amine equivalent: 700), "X-22-1660B-3" (amine equivalent) 2200) (The above is manufactured by Shin-Etsu Chemical Co., Ltd.), "BY-16-853U" (amine equivalent 460), "BY-16-853" (amine equivalent 650), "BY-16-853B" ( The amine group equivalent is 2,200) (the above is manufactured by Dow Corning Toray Co., Ltd.) and the like. These compounds may be used singly or in combination of two or more.

Among these compounds, from the viewpoint of high reactivity at the time of synthesis and low thermal expansion property, for example, X-22-161A, X-22-161B, KF-8012, X-22-1660B-3, and the like are preferable. BY-16-853B, X-22-161A and X-22-161B are particularly preferable from the viewpoint of excellent compatibility and an increase in elastic modulus.

In the present invention, as a reaction for obtaining a oxoxane compound, For example, the following methods are mentioned.

Reaction method a: by having at least 2 stages in 1 molecule An amine-based aromatic amine compound (A), an aromatic aldehyde compound (B) having at least two aldehyde groups in one molecule, and a oxoxane compound (C) having at least two amine groups at a molecular terminal, The naphthenic compound (i) is obtained.

Reaction method b: First, by having at least 2 in 1 molecule The primary amine group-containing aromatic amine compound (A) is reacted with an aromatic aldehyde compound (B) having at least two aldehyde groups in one molecule to obtain an aromatic carbamide having at least one aldehyde group in one molecule. Amine compound. Next, by making the aforementioned aromatic The methylimine compound and the decane compound (C) having at least two amine groups at the molecular terminal are subjected to a dehydration condensation reaction in an organic solvent to obtain a modified methoxyalkylene compound (ii) having an aromatic methylimine.

Reaction method c: first, by having at least 2 in 1 molecule The aldehyde group-containing aromatic aldehyde compound (B) is reacted with a oxoxane compound (C) having at least two amine groups at the molecular terminal to obtain at least one aldehyde group and a methylenimine group in one molecule (- A modified oxoxane compound of N=CH-). Next, a modified methoxy oxyalkylene compound having an aromatic methylimine can be obtained by reacting the modified methoxy oxane compound with an aromatic amine compound (A) having at least two primary amine groups in one molecule. (iii).

As the oxoxane compound of the present invention, any of the above a, b, and c can be used. A reaction method, for example, the reaction method a is particularly simple in operation, and is particularly effective when the solvent solubility of the modified oxirane compound of the present invention is insufficient. Further, the reaction method b is characterized in that the molecular weight of the aromatic methylimine in the molecule of the siloxane compound of the present invention can be easily controlled, and the elastic modulus of the resin composition containing the siloxane compound is particularly improved. effective. Further, the reaction method c is characterized in that the molecular weight of the oxoxane in the molecule of the siloxane compound of the present invention can be easily controlled, and the coefficient of thermal expansion of the resin composition containing the siloxane compound can be effectively reduced.

First, the reaction method a will be described in detail. In reaction method a, An aromatic aldehyde compound (B) having at least two primary amine groups in one molecule, an aromatic aldehyde compound (B) having at least two aldehyde groups in one molecule, and at least 2 at the molecular terminal The oxime compound (C) of the present invention can be obtained by reacting an amine group-containing oxane compound (C).

Here, an aromatic having at least two primary amine groups in one molecule The amount of the amine compound (A), the aromatic aldehyde compound (B) having at least two aldehyde groups in one molecule, and the oxane compound (C) having at least two amine groups at the molecular terminal are preferably used. It is used in the following manner: the number of primary amine groups of the aromatic amine compound (A) and the siloxane compound (C) [the amount of the aromatic amine compound (A) used / the primary amine equivalent of the aromatic amine compound (A) The amount of the oxo group (C) used in the aromatic aldehyde compound (B) The aldehyde group equivalent of the aldehyde compound (B) is in the range of 1.0 to 10.0 times. When the number of primary amine groups of the aromatic amine compound (A) and the siloxane compound (C) is 1.0 times or more the number of aldehyde groups of the aromatic aldehyde compound (B), the solubility in the solvent is lowered. Propensity. In addition, when the number of primary amine groups of the aromatic amine compound (A) and the siloxane compound (C) is 10.0 times or less the number of aldehyde groups of the aromatic aldehyde compound (B), the modified siloxane compound is contained ( i) The thermosetting resin of the modified siloxane compound (i) having an aromatic carbamide has a tendency to be lowered in heat resistance.

An organic solvent can be used in this reaction. As the organic solvent used The agent is not particularly limited, and examples thereof include alcohol solvents such as ethanol, propanol, butanol, acesulfame, dexamethasone, and propylene glycol monomethyl ether; acetone, methyl ethyl ketone, and methyl isobutylene. Ketone solvent such as ketone or cyclohexanone; ether solvent such as tetrahydrofuran; aromatic solvent such as toluene, xylene or trimethylbenzene; dimethylformamide, dimethylacetamide, N-methyl A nitrogen-containing solvent such as a pyrrolidone; a sulfur-containing solvent such as dimethyl hydrazine; an ester solvent such as γ-butyrolactone; These solvents may be used alone or in combination of two or more. Among them, for example, From the viewpoint of solubility, preferred are: propylene glycol monomethyl ether, cyclohexanone, toluene, dimethylformamide, dimethylacetamide, γ-butyrolactone. Further, from the viewpoint of high volatility and difficulty in producing a pre-impregnated body, it is more preferably propylene glycol monomethyl ether or toluene. Further, since the reaction is a dehydration condensation reaction, water is produced as a by-product. For the purpose of removing water, which is a by-product, for example, it is preferred to carry out the reaction while removing a by-product, that is, water, by azeotroping with an aromatic solvent.

The amount of organic solvent used, for example, relative to an aromatic amine compound The total of 100 parts by mass of the solid content of the aromatic aldehyde compound (B) and the oxirane compound (C) is preferably 25 to 2000 parts by mass, more preferably 40 to 1000. The mass fraction is particularly preferably set to 40 to 500 parts by mass. When the amount of the organic solvent used is 25 parts by mass or more, the problem of insufficient solubility tends to be suppressed. In addition, when the amount of the organic solvent used is 2,000 parts by mass or less, the reaction time becomes more appropriate.

For this reaction, the reaction catalyst can be used as needed. Reaction used The catalyst is not particularly limited. Examples of the reaction catalyst include an acidic catalyst such as p-toluenesulfonic acid; an amine such as triethylamine, pyridine or tributylamine; and an imidazole such as methylimidazole or phenylimidazole; A phosphorus-based catalyst such as phenylphosphine. These catalysts may be used alone or in combination of two or more. In order to carry out the dehydration condensation reaction efficiently, it is preferred to use an acidic catalyst such as p-toluenesulfonic acid.

The raw material, the organic solvent, and the desired reaction catalyst are introduced into the reaction vessel, and the mixture is heated and kept as needed, and stirred for 0.1 to 10 hours to carry out a dehydration condensation reaction to obtain a deuterium oxide. Compound (i).

The reaction temperature is, for example, preferably 70 to 150 ° C. It is preferred to carry out the reaction while removing by-product, i.e., water, and the preferred reaction temperature is 100 to 130 ° C. When the reaction temperature is lower than 70 ° C, the reaction rate is slow. When the reaction temperature is 150 ° C or lower, the reaction solvent does not need to be a solvent having a high boiling point, and when the prepreg is produced, it is difficult to leave residual solvent. It is possible to suppress a decrease in heat resistance.

Next, the reaction method b will be described in detail. In reaction method b, one The reaction is carried out by reacting an aromatic amine compound (A) having at least two primary amine groups in one molecule with an aromatic aldehyde compound (B) having at least two aldehyde groups in one molecule. An aromatic methylimine compound having at least one aldehyde group. Next, by reacting the above-mentioned aromatic methylimine compound with a oxoxane compound (C) having at least two amine groups at the terminal of the molecule, a modified siloxane compound having an aromatic carbamide can be obtained (ii) ).

In the reaction method b, the organic solvent used for the reaction and the reaction catalyst used as needed can be arbitrarily used in the same manner as in the reaction method a.

In the beginning, by having at least 2 primary amines in one molecule The aromatic amine compound (A) and the aromatic aldehyde compound (B) having at least two aldehyde groups in one molecule are subjected to a dehydration condensation reaction in an organic solvent to obtain at least one aldehyde group in one molecule. An aromatic methylimine compound.

Here, the amount of the aromatic aldehyde compound (A) having at least two primary amino groups in one molecule and the aromatic aldehyde compound (B) having at least two aldehyde groups in one molecule is preferably, for example, It is used in such a manner that the primary amine group of the aromatic amine compound (A) [the amount of the aromatic amine compound (A) used / the primary amine equivalent of the aromatic amine compound (A)] becomes an aromatic aldehyde compound. (B) The number of aldehyde groups [the amount of the aromatic aldehyde compound (B) used / the aldehyde group equivalent of the aromatic aldehyde compound (B)] is in the range of 0.1 to 5.0 times. When the number of primary amine groups of the aromatic amine compound (A) is 0.1 times or more the number of aldehyde groups of the aromatic aldehyde compound (B), the molecular weight of the aromatic methylimine compound obtained by the reaction is lowered. Propensity. In addition, when the number of primary amine groups of the aromatic amine compound (A) is 5.0 times or less the number of aldehyde groups of the aromatic aldehyde compound (B), the solubility in a solvent tends to be lowered.

Further, the amount of the organic solvent used, for example, relative to aromatic amination The total amount of the resin component of the compound (A) and the aromatic aldehyde compound (B) is preferably from 25 to 2,000 parts by mass, more preferably from 40 to 1,000 parts by mass, even more preferably from 100 to 1000 parts by mass. 40 to 500 parts by mass. When the amount of the organic solvent used is 25 parts by mass or more, the problem of insufficient solubility tends to be suppressed. In addition, when the amount of the organic solvent used is 2,000 parts by mass or less, the reaction time becomes more appropriate.

By using the above raw materials, organic solvents, and the desired reaction catalyst, Into the reaction vessel, the mixture is heated and kept as needed, and stirred for 0.1 to 10 hours to carry out a dehydration condensation reaction, thereby obtaining an aromatic carbimimine compound having at least one aldehyde group in one molecule.

The reaction temperature is, for example, preferably 70 to 150 ° C, more preferably 100 to 130 ° C. Further, it is preferred to carry out the reaction while removing water, which is a by-product. When the reaction temperature is 70 ° C or more, the reaction rate tends not to be too slow. In addition, when the reaction temperature is 150° C. or lower, the reaction solvent does not need to be a solvent having a high boiling point, and when the prepreg is produced, the residual solvent is less likely to remain, and the heat resistance can be suppressed from being lowered.

Next, at least one molecule obtained by the above reaction has An aldehyde group-containing aromatic methylimine compound and a decane compound (C) having at least two amine groups at a molecular terminal are subjected to a dehydration condensation reaction in an organic solvent, whereby an aromatic methylimine can be obtained. Modification of the oxoxane compound (ii).

Here, the amount of the aromatic carbamide compound and the siloxane compound (C) to be used, for example, is preferably used in the following manner: the primary amine number of the siloxane compound (C) [the oxirane compound] The amount of (C) used / the primary amine equivalent of the oxirane compound (C)], the number of aldehyde groups of the aromatic methylimine compound [Amount of aromatic methylimine compound used / aldehyde of aromatic methylimine compound The range of 1.0 to 10.0 times the base equivalent. When the number of primary amine groups of the siloxane compound (C) is 1.0 times or more the number of aldehyde groups of the aromatic carbamide compound, the solubility in a solvent tends to be lowered. In addition, when the number of primary amine groups of the siloxane compound (C) is 10.0 times or less the number of aldehyde groups of the aromatic carbamide compound, the modified oxirane compound (ii) is contained (the modified oxirane) The thermosetting resin of the compound (ii) having an aromatic methylimine) tends to have a reduced modulus of elasticity.

Further, the amount of the organic solvent used is, for example, relative to one molecule to The total amount of the resin component of the aromatic carbamide compound having one aldehyde group and the oxyalkylene compound (C) is preferably from 25 to 2,000 parts by mass, more preferably from 40 to 1,000. The mass fraction is particularly preferably set to 40 to 500 parts by mass. When the amount of the organic solvent used is 25 parts by mass or more, the problem of insufficient solubility tends to be suppressed. In addition, when the amount of the organic solvent used is 2,000 parts by mass or less, the reaction time becomes more appropriate.

By using the above raw materials, organic solvents, and the desired reaction catalyst, The reactor is charged and heated and kept as needed, and stirred for 0.1 to 10 hours to carry out a dehydration condensation reaction to obtain a modified methoxyalkylene compound (ii) having an aromatic methylenimine.

The reaction temperature is, for example, preferably 70 to 150 ° C, more preferably 100 to 130 ° C. Further, it is preferred to carry out the reaction while removing water, which is a by-product. When the reaction temperature is 70 ° C or more, the reaction rate tends not to be too slow. In addition, when the reaction temperature is 150° C. or lower, the reaction solvent does not need to be a solvent having a high boiling point, and when the prepreg is produced, the residual solvent is less likely to remain, and the heat resistance can be suppressed from being lowered.

Next, the reaction method c will be described in detail. In reaction method c, Initially, an aromatic aldehyde compound (B) having at least two aldehyde groups in one molecule is reacted with a oxoxane compound (C) having at least two amine groups at the molecular terminal to obtain one molecule. A modified oxoxane compound having at least one aldehyde group and a methylenimine group (-N=CH-). Next, a modified methoxy oxyalkylene compound having an aromatic methylimine can be obtained by reacting the modified methoxy oxane compound with an aromatic amine compound (A) having at least two primary amine groups in one molecule. (iii).

In the reaction method c, the organic solvent used for the reaction and the reaction catalyst used as required can be arbitrarily used in the same manner as in the reaction methods a and b.

By aromatic hydroformylation of at least two aldehyde groups in one molecule The compound (B) is dehydrated and condensed in an organic solvent with a oxoxane compound (C) having at least two amine groups at the terminal of the molecule, and is obtained by having at least one aldehyde group and a methylenimine group in one molecule. (-N=CH-) modified hafnoxy compound.

Here, an aromatic aldehyde compound having at least two aldehyde groups in one molecule (B) The amount of the oxoxane compound (C) to be used with at least two amine groups at the terminal of the molecule is preferably used, for example, in the following manner: the number of primary amine groups of the oxoxane compound (C) The amount of the compound (C) used / the primary amine group equivalent of the oxirane compound (C)], the number of aldehyde groups of the aromatic aldehyde compound (B) [the amount of the aromatic aldehyde compound (B) used / the aromatic aldehyde compound ( The range of 0.1 to 5.0 times the aldehyde group equivalent of B). When the number of primary amine groups of the siloxane compound (C) is 0.1 times or more the number of aldehyde groups of the aromatic aldehyde compound (B), the solubility in a solvent is lowered. In addition, when the number of primary amine groups of the siloxane compound (C) is 5.0 times or less the number of aldehyde groups of the aromatic aldehyde compound (B), at least one aldehyde group in one molecule obtained by the present reaction is The molecular weight reduction of the modified methoxy oxane compound of the methylimine group (-N=CH-) is suppressed.

Further, the amount of the organic solvent used, for example, relative to aromatic hydroformylation The total amount of the resin component of the compound (B) and the siloxane compound (C) is preferably from 25 to 2,000 parts by mass, more preferably from 40 to 1,000 parts by mass, even more preferably from 100 to 1000 parts by mass. 40 to 500 parts by mass. When the amount of the organic solvent used is 25 parts by mass or more, insufficient solubility may occur. In addition, when the amount of the organic solvent used is 2,000 parts by mass or less, the reaction time becomes more appropriate.

By using the above raw materials, organic solvents, and the desired reaction catalyst, The reaction vessel is put into a reaction vessel and heated and kept as needed, and stirred for 0.1 to 10 hours to carry out a dehydration condensation reaction, and at least one aldehyde group and a methylenimine group (-N=CH-) can be obtained in one molecule. a modified oxirane compound.

The reaction temperature is, for example, preferably 70 to 150 ° C, more preferably 100 to 130 ° C. Further, it is preferred to carry out the reaction while removing water, which is a by-product. When the reaction temperature is 70 ° C or more, the reaction rate does not become too slow. to. In addition, when the reaction temperature is 150° C. or lower, the reaction solvent does not need to be a solvent having a high boiling point, and when the prepreg is produced, the residual solvent is less likely to remain, and the heat resistance can be suppressed from being lowered.

Next, at least one molecule obtained by the above reaction has a modified oxoxane compound having an aldehyde group and a methylimido group (-N=CH-) and an aromatic amine compound (A) having at least two primary amino groups in one molecule, dehydrated in an organic solvent The condensation reaction, whereby a modified methoxyalkylene compound (iii) having an aromatic methylimine can be obtained.

Here, the amount of the modified oxoxane compound and the aromatic amine compound (A) used is, for example, preferably used in the following manner: the primary amine group of the aromatic amine compound (A) [aromatic amine compound] The amount of (A) used / the primary amine equivalent of the aromatic amine compound (A)], the number of aldehyde groups of the modified oxoxane compound [the amount of the modified oxoxane compound / the aldehyde of the modified oxoxane compound The range of 1.0 to 10.0 times the base equivalent. When the number of primary amine groups of the aromatic amine compound (A) is 1.0 times or more the number of aldehyde groups of the modified oxoxane compound, the modified oxirane compound (iii) is contained (the modified oxirane compound ( Iii) The case where the low thermal expansion property of the thermosetting resin having an aromatic carbamide has a tendency to be suppressed is suppressed. In addition, when the number of primary amine groups of the aromatic amine compound (A) is 10.0 times or less of the number of aldehyde groups of the modified siloxane oxide compound, the solubility in a solvent tends to be lowered.

Further, the amount of the organic solvent used is, for example, relative to one molecule to The total amount of the modified oxime compound having one aldehyde group and the methylenimine group (-N=CH-) and the resin component of the aromatic amine compound (A) is preferably 100 parts by mass. 2000 parts by mass, and more preferably 40 to 1000 parts by mass, It is preferably set to 40 to 500 parts by mass. When the amount of the organic solvent used is 25 parts by mass or more, the problem of insufficient solubility tends to be suppressed. In addition, when the amount of the organic solvent used is 2,000 parts by mass or less, the reaction time becomes more appropriate.

By using the above raw materials, organic solvents, and the desired reaction catalyst, The reactor is charged and heated and kept as needed, and stirred for 0.1 to 10 hours to carry out a dehydration condensation reaction to obtain a modified methoxyalkylene compound (iii) having an aromatic methylimine.

The reaction temperature is, for example, preferably 70 to 150 ° C, more preferably 100 to 130 ° C. Further, it is preferred to carry out the reaction while removing water, which is a by-product. When the reaction temperature is 70 ° C or more, the reaction rate tends not to be too slow. In addition, when the reaction temperature is 150° C. or lower, the reaction solvent does not need to be a solvent having a high boiling point, and when the prepreg is produced, the residual solvent is less likely to remain, and the heat resistance can be suppressed from being lowered.

The modified oxirane compound of the present invention obtained by the above reaction methods a, b, and c can be confirmed by infrared spectrum measurement (IR measurement). It was confirmed by infrared spectroscopy that the 1620 cm ^-1 peak due to the methylimine group (-N=CH-) was observed, and it was confirmed that there were peaks in the vicinity of 3440 cm ^-1 and 3370 cm ^-1 due to the primary amino group. It was confirmed that the reaction proceeded well, and the desired compound was obtained. Further, the weight average molecular weight (Mw) is not particularly limited, and is, for example, preferably from 1,000 to 300,000, particularly preferably from 6,000 to 150,000. When the weight average molecular weight is at least the above lower limit value, the low curing shrinkage property and the low thermal expansion property are improved. When the weight average molecular weight is at most the above upper limit value, the compatibility and the elastic modulus are improved. Further, the weight average molecular weight was measured by gel permeation chromatography (GPC) and converted from a standard curve prepared by standard polystyrene. For example, the measurement can be carried out under the following conditions. As a measuring device, an autosampler (Auto-sampler) (AS-8020, manufactured by TOSOH Co., Ltd.), a column oven (manufactured by JASCO Corporation, 860-C0), and a refractive index detector (Japan) were used. Seiko Co., Ltd., 830-RI), ultraviolet visible light detector (manufactured by JASCO Corporation, 870-UV), HPLC pump (manufactured by JASCO Corporation, 880-PU).

Further, as the column to be used, TSKgel SuperHZ 2000 and 2300, which are manufactured by TOSOH Co., Ltd., can be used as a measurement condition at a measurement temperature of 40 ° C, a flow rate of 0.5 ml/min, and a solvent of tetrahydrofuran.

(modified imimine resin)

The modified quinone imine resin of the present invention is such that the amine-modified methoxy oxane compound of the present invention described above and the maleimide having at least two N-substituted maleimine groups in one molecule The compound (C) is obtained by a reaction.

Further, the modified quinone imine resin preferably has an acidic substituent which is an acidic substituent derived from the amine compound (D) represented by the following formula (3). The acidic substituent can be introduced by reacting with the amine compound (D). By having this acidic substituent, good low thermal expansion properties can be obtained.

(式(3)中，R₅各自獨立地表示作為酸性取代基的羥基、羧基或磺酸基；R₆各自獨立地表示氫原子、碳數1~5的脂肪族烴基或鹵素原子；x為1~5的整數，y為0~4的整數，且x與y 的和為5)。

(In the formula (3), R ₅ each independently represent a hydroxyl, carboxyl or sulfonic acid group as a substituent; R ₆ each independently represent a hydrogen atom, or an aliphatic hydrocarbon group having a carbon number of 1 to 5 halogen atoms; x is An integer from 1 to 5, y is an integer from 0 to 4, and the sum of x and y is 5).

Further, further details regarding the amine compound (D) will be described later.

Moreover, "the substance derived from the acidic substituent of the amine compound (D)" means the acidic substitution of the amine compound (D) and the substance containing the acidic substituent.

The modified quinone imine resin can be produced by "pre-reaction" in the production of a thermosetting resin composition to be described later.

(thermosetting resin composition)

The thermosetting resin composition of the present invention is a modified maleoxane compound of the present invention, and a maleic imine compound (D) having at least two N-substituted maleimine groups in one molecule. Made into.

The maleidinide compound (D) having at least two N-substituted maleimine groups in one molecule (hereinafter also referred to as a maleimide compound (D)) may, for example, be: Bis(4-maleimidophenyl)methane, polyphenylmethane maleimide, bis(4-maleimidophenyl)ether, bis(4-maleimido) Phenyl) guanidine, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene double horse Yttrium imine, m-phenylene bismaleimide, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, and the like. These maleimide compounds may be used singly or in combination of two or more.

Among them, for example, from the viewpoint of high reactivity and further improvement in heat resistance, bis(4-maleimidophenyl)methane and bis(4-maleimido) are preferred. Phenyl) fluorene, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, from the viewpoint of solubility in a solvent, further preferably: double ( 4-maleimide phenyl)methane, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, from the standpoint of low cost, particularly good Is a double (4-Malaysia Aminophenyl)methane.

In the thermosetting resin composition of the present invention, the oxime of the present invention The amount of the compound (the amount of the compound) is preferably from 1 to 30 parts by mass, based on 100 parts by mass of the total of the resin components, and is further preferably from the viewpoint of copper foil adhesion and chemical resistance. It is set to 5 to 20 parts by mass.

The amount of the maleimide compound (D) to be used is, for example, 30 to 99 parts by mass based on 100 parts by mass of the total of the resin components, from the viewpoint of low thermal expansion property and high elastic modulus. Further, it is preferably 40 to 95 parts by mass.

The thermosetting resin composition of the present invention contains the hydrazine of the present invention. The oxane compound and the maleidinide compound (D) having at least two N-substituted maleimine groups in one molecule, the compound can be pre-reacted as having an aromatic carbamide The modified quinone imine resin is used. By performing such a pre-reaction, the molecular weight can be controlled, and the low-hardening shrinkage property and the low thermal expansion property can be further improved.

Such a pre-reaction is preferably carried out in the following manner: in organic dissolution In the agent, the oxime compound of the present invention is reacted with the maleimide compound (D) having at least two N-substituted maleimine groups in one molecule while being heated and kept, and the synthesis is changed. Yttrium imine resin.

The reaction temperature at the time of reacting the modified siloxane compound with the maleimide compound (D) in an organic solvent is, for example, preferably 70 to 150 ° C, more preferably 100 to 130 ° C. The reaction time is, for example, preferably 0.1 to 10 hours, more preferably 1 to 6 hours.

In this pre-reaction, the amount of the maleimide compound (D) and the oxoxane compound of the present invention is preferably used in the following manner: The maleimide group number of the imine compound (D) [the amount of the maleimide compound (D) used / the maleimide equivalent of the maleimide compound (D)] becomes the present invention. The primary amine group number of the siloxane compound [the amount of the oxoxane compound of the present invention / the primary amine equivalent of the oxirane compound of the present invention] is in the range of 2.0 times to 10.0 times. When the number of maleimide groups of the maleimide compound (D) is 2.0 times or more the number of primary amine groups of the oxirane compound of the present invention, the gelation and heat resistance are lowered. . In addition, the number of maleimide groups of the maleimide compound (D) is 10.0 times or less of the number of primary amine groups of the oxirane compound of the present invention, and the solubility in an organic solvent and heat resistance are lowered. The situation has a tendency to be suppressed.

The amount of maleimide compound (D) used in the pre-reaction is maintained In the above-described relationship, for example, the amount of the maleimide compound (D) to be used is preferably from 50 to 3,000 parts by mass, more preferably from 100 parts by mass to the resin component of the siloxane compound of the present invention. 100 to 1500 parts by mass. When the amount of the maleic imine compound (D) used is 50 parts by mass or more, the heat resistance is likely to be lowered. In addition, when the amount of the maleic imine compound (D) used is 3,000 parts by mass or less, the low thermal expansion property can be favorably maintained.

The organic solvent used in this pre-reaction may, for example, be ethanol. An alcohol solvent such as propanol, butanol, acesulfame, butyl sulfonium, propylene glycol monomethyl ether; a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; An ester solvent such as an ester or γ-butyrolactone; an ether solvent such as tetrahydrofuran; an aromatic solvent such as toluene, xylene or trimethylbenzene; dimethylformamide, dimethylacetamide, and N- A nitrogen-containing solvent such as methylpyrrolidone; a sulfur-containing solvent such as dimethyl hydrazine or the like. These organic solvents can be used in one type or can be mixed. Use in combination of two or more.

Among these organic solvents, for example, from the viewpoint of solubility, Preferred are cyclohexanone, propylene glycol monomethyl ether, acesulfame, γ-butyrolactone; from the viewpoint of low toxicity or high volatility and not easily remaining as a residual solvent, it is particularly preferred to be cyclohexanone or propylene glycol. Methyl ether, dimethylformamide.

The amount of the organic solvent used, for example, relative to the oxime of the present invention The total amount of the resin component of the compound and the maleimide compound (D) is preferably from 25 to 2,000 parts by mass, more preferably from 40 to 1,000 parts by mass, even more preferably from 40 to 2,000 parts by mass. 500 parts by mass. When the amount of the organic solvent used is 25 parts by mass or more, insufficient solubility may occur. In addition, when the amount of the organic solvent used is 2,000 parts by mass or less, the reaction time becomes more appropriate.

Further, in this pre-reaction, the reaction catalyst can be used arbitrarily. Reaction touch The medium is not particularly limited, and examples thereof include amines such as triethylamine, pyridine, and tributylamine; imidazoles such as methylimidazole and phenylimidazole; and phosphorus-based catalysts such as triphenylphosphine; An alkali metal amine such as lithium amide, sodium amine or potassium amine. These reaction catalysts may be used alone or in combination of two or more.

The modified imidamine obtained by the above pre-reaction The amount of the imine resin used is, for example, 50 to 100 parts by mass, and more preferably 60 to 100 parts by mass, based on 100 parts by mass of the total of the resin components. By setting the amount of the modified quinone imine resin having an aromatic carbamide to 50 parts by mass or more, low thermal expansion property and high elastic modulus can be obtained.

Composition of thermosetting resin of the present invention containing the following compound And a maleidin compound (D) having at least two N-substituted maleimine groups in one molecule, and the present invention a modified quinone imine resin having an aromatic methylimine obtained by pre-reacting a compound, and the resin composition or resin may have good thermosetting reactivity when used alone, but may be hardened according to requirements. The agent and the radical initiator are used in combination. Heat resistance, adhesion, and mechanical strength can be improved by using a hardener and a radical initiator.

Examples of the curing agent to be used together include dicyandiamide or 4,4'-diaminodiphenylmethane, and 4,4'-diamine-3,3'diethyl-diphenylmethane. An aromatic amine such as 4,4'-diaminodiphenyl hydrazine, phenylenediamine or xylene diamine; an aliphatic amine such as hexamethylenediamine or 2,5-dimethylhexanediamine; melamine A guanamine compound such as benzoguanamine or the like.

Further, the radical initiator is not particularly limited, and for example, a mercapto peroxide, a hydroperoxide, a ketone peroxide, an organic peroxide having a t-butyl group, and a cumyl group can be used. An organic peroxide such as a peroxide of (cumyl). These hardeners and radical initiators may be used singly or in combination of two or more. Among these curing agents and radical initiators, for example, aromatic amines are preferred from the viewpoint of good reactivity and heat resistance.

Furthermore, the thermosetting resin composition of the present invention may contain an amine compound (E) having an acidic substituent represented by the following formula (3).

(式(3)中，R₅各自獨立地表示作為酸性取代基的羥基、羧基或磺酸基；R₆各自獨立地表示氫原子、碳數1~5的脂肪族烴基 或鹵素原子；x為1~5的整數，y為0~4的整數，且x與y的和為5)。

(In the formula (3), R ₅ each independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group as an acidic substituent; and R ₆ each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom; An integer from 1 to 5, y is an integer from 0 to 4, and the sum of x and y is 5).

As the amine compound (E) having an acidic substituent, for example, M-aminophenol, p-aminophenol, o-aminophenol, p-amine benzoic acid, m-amine benzoic acid, o-amine benzoic acid, o-aminobenzenesulfonic acid, m-amine benzenesulfonic acid, P-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline, and the like. Among them, for example, from the viewpoint of solubility or synthetic yield, m-aminophenol, p-aminophenol, o-aminophenol, p-amine benzoic acid, m-amine benzoic acid, 3,5-dihydroxyaniline is more preferably m-aminophenol or p-aminophenol from the viewpoint of heat resistance.

The amount of the amine compound (E) having an acidic substituent, for example, phase The total amount of the resin components is preferably 0.5 to 30 parts by mass, and more preferably 1 to 20 parts by mass from the viewpoint of low thermal expansion.

The thermosetting resin composition of the present invention may further comprise: the present invention The modified oxoxane compound, the maleic imine compound (D) having at least two N-substituted maleimine groups in one molecule, and the amine compound (E) having an acidic substituent may also be used. The above compound is pre-reacted and used as a modified quinone imine resin having an acidic substituent and an aromatic methylimine. By performing such a pre-reaction, the molecular weight can be controlled, and the low-hardening shrinkage property and the low thermal expansion property can be further improved.

This pre-reaction is preferably carried out in the following manner: in an organic solvent, The oxime imine resin having an acidic substituent is synthesized by reacting the oxime compound of the present invention, the maleimide compound (D), and the amine compound (E) having an acidic substituent while heating and keeping warm. .

The reaction temperature at the time of reacting the oxime compound of the present invention, the maleimide compound (D), and the amine compound (E) having an acidic substituent in an organic solvent is, for example, preferably 70 to 150 ° C. Further preferably, it is 100 to 130 °C. The reaction time is, for example, preferably 0.1 to 10 hours, more preferably 1 to 6 hours.

In this pre-reaction, the maleic imine compound (D), and the present invention The amount of the oxoxane compound and the amine compound (E) having an acidic substituent is preferably used, for example, in the following manner: the maleic imine group of the maleimide compound (D) [MA] The amount of the quinone imine compound (D) used / the maleimide equivalent of the maleimide compound (D)], which becomes the oxirane compound of the present invention and the amine compound (E) having an acidic substituent Primary amine group number [Use amount of the oxoxane compound of the present invention / Primary amine equivalent of the oxirane compound of the present invention + Use of the amine compound (E) having an acidic substituent / Amine compound having an acidic substituent The range of 2.0 times to 10.0 times the primary amine equivalent of (E). The gelatinization is carried out by setting the maleimide group of the maleimide compound (D) to 2.0 times or more the primary amine group of the azide compound of the present invention and the amine compound (E) having an acidic substituent. There is a tendency that the heat resistance is lowered. In addition, the number of maleimide groups of the maleimide compound (D) is 10.0 times or less of the number of primary amine groups of the oxirane compound of the present invention and the amine compound (E) having an acidic substituent. The case where the solubility in an organic solvent and heat resistance are lowered tend to be suppressed.

The amount of maleimide compound (D) used in the pre-reaction is maintained In the above-described relationship, for example, the amount of the maleimide compound (D) used is preferably 100 parts by mass based on 100 parts by mass of the resin component of the siloxane compound of the present invention. 50 to 3000 parts by mass, and more preferably 100 to 1500 parts by mass. When the amount of the maleimide compound (D) used is 50 parts by mass or more, the heat resistance can be suppressed from being lowered. In addition, when the amount of the maleic imine compound (D) used is 3,000 parts by mass or less, the low thermal expansion property can be favorably maintained.

In the pre-reaction, the amount of the amine compound (E) having an acidic substituent, for example, the use of the amine compound (E) having an acidic substituent with respect to 100 parts by mass of the resin component of the siloxane compound of the present invention The amount is preferably from 1 to 1,000 parts by mass, more preferably from 5 to 500 parts by mass. When the amount of the amine compound (E) having an acidic substituent is 1 part by mass or more, the deterioration of heat resistance can be suppressed. In addition, when the amount of the amine compound (E) having an acidic substituent is used in an amount of 1000 parts by mass or less, the low thermal expansion property can be favorably maintained.

The organic solvent used in the pre-reaction is not particularly limited and may be For example, alcoholic solvents such as ethanol, propanol, butanol, acesulfame, dexamethasone, propylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. a ketone solvent; an ester solvent such as ethyl acetate or γ-butyrolactone; an ether solvent such as tetrahydrofuran; an aromatic solvent such as toluene, xylene or trimethylbenzene; dimethylformamide or dimethyl group; A nitrogen-containing solvent such as acetamide or N-methylpyrrolidone; a sulfur-containing solvent such as dimethyl hydrazine or the like. These organic solvents may be used alone or in combination of two or more.

Among these organic solvents, for example, from the viewpoint of solubility, Preferably, cyclohexanone, propylene glycol monomethyl ether, acesulfame, γ-butyrolactone; from the viewpoint of low toxicity or high volatility and not easily remaining as a residual solvent, particularly preferred is cyclohexanone, propylene glycol monomethyl Ether, dimethylformamide.

The amount of the organic solvent used, for example, relative to the oxime of the present invention The total amount of the resin component of the compound, the maleimide compound (D), and the amine compound (E) having an acidic substituent is preferably from 25 to 2,000 parts by mass, more preferably from 40 to 2,000 parts by mass. 1000 parts by mass, particularly preferably 40 to 500 parts by mass. When the amount of the organic solvent used is 25 parts by mass or more, the problem of insufficient solubility tends to be suppressed. In addition, when the amount of the organic solvent used is 2,000 parts by mass or less, the reaction time becomes more appropriate.

Further, in this pre-reaction, the reaction catalyst can be used arbitrarily. Reaction touch The medium is not particularly limited, and examples thereof include amines such as triethylamine, pyridine, and tributylamine; imidazoles such as methylimidazole and phenylimidazole; and phosphorus-based catalysts such as triphenylphosphine; An alkali metal amine such as a lithium amine, a sodium amine or a potassium amine. These catalysts may be used alone or in combination of two or more.

Moreover, the acidic substituent and the aromatic obtained by the above pre-reaction The amount of the modified ether imine resin to be used is, for example, 50 to 100 parts by mass, and more preferably 60 to 100 parts by mass, based on 100 parts by mass of the total of the resin components. By setting the amount of the modified quinone imine resin having an acidic substituent and an aromatic carbamide to 50 parts by mass or more, low thermal expansion property and high elastic modulus can be obtained.

Composition of thermosetting resin of the present invention containing the following compound And a modified hafnoxy compound having an aromatic methylimine, a maleimide compound (D) having at least two N-substituted maleimine groups in one molecule, and an acidic substituent The amine compound (E), and the modified quinone imine resin having an acidic substituent and an aromatic methylimine obtained by pre-reacting the above compound of the present invention, the resin composition or resin, although used alone Has good thermal hardening reactivity, but can be combined with hardeners and free radicals according to demand The starting agent is used in combination. Heat resistance, adhesion, and mechanical strength can be improved by using a hardener and a radical initiator.

As a hardening agent to be used together, for example, dicyandiamide or 4,4'- may be mentioned. Diaminodiphenylmethane, 4,4'-diamine-3,3'diethyl-diphenylmethane, 4,4'-diaminodiphenylanthracene, phenylenediamine, xylylenediamine An aromatic amine such as an aliphatic amine such as hexamethylenediamine or 2,5-dimethylhexamethylenediamine; or a guanamine compound such as melamine or benzoguanamine.

Further, as the radical initiator, for example, a mercapto peroxide, a hydroperoxide, a ketone peroxide, an organic peroxide having a t-butyl group, a peroxide having a cumyl group, or the like can be used. Organic peroxides, etc. These hardeners and radical initiators may be used singly or in combination of two or more. Among these curing agents and radical initiators, for example, aromatic amines are preferred from the viewpoint of good reactivity and heat resistance.

Further, the thermosetting resin composition of the present invention may contain heat Plastic elastomer (F).

Examples of the thermoplastic elastomer (F) include a styrene-based elastomer, an olefin-based elastomer, an urethane-based elastomer, a polyester-based elastomer, a polyamide-based elastomer, and an acrylic elastomer. A silicone elastomer or a derivative of such an elastomer. These elastomers include a hard segment component and a soft segment component. Generally, the former imparts heat resistance and strength to the elastomer, and the latter imparts flexibility and toughness to the elastomer. These elastomers may be used alone or in combination of two or more.

Further, as these elastomers, those having a reactive functional group at a molecular terminal or a molecular chain can be used. Examples of the reactive functional group include a reactive functional group. For example: epoxy group, hydroxyl group, carboxyl group, amine group, decylamino group, isocyanate group, propenyl group, methacryl group, vinyl group and the like. By having these reactive functional groups at the molecular terminal or in the molecular chain, the compatibility with the resin is improved, and the internal stress generated in the hardening resin composition of the present invention at the time of hardening can be more effectively reduced. Therefore, as a result, the warpage of the substrate can be remarkably lowered.

Among these elastomers, for example, the viewpoint of heat resistance and insulation reliability In particular, a styrene-based elastomer, an olefin-based elastomer, a polyamine-based elastomer, and a fluorene-based elastomer are preferable, and a styrene-based system is particularly preferable from the viewpoint of dielectric properties. Elastomer, olefin elastomer.

Moreover, these elastomers have a molecular end or a molecular chain. The reactive functional group is preferably an epoxy group, a hydroxyl group, a carboxyl group, an amine group or a guanamine group from the viewpoint of adhesion to the metal foil, and is heat-resistant and insulating. Particularly preferred are: epoxy groups, hydroxyl groups, and amine groups.

The amount of thermoplastic elastomer (F) used, for example, relative to the resin 100 parts by mass, preferably 0.1 to 50 parts by mass, and further, from the viewpoints of good resin compatibility, low hardenability and shrinkage of a cured product, low thermal expansion property, and more excellent display of excellent dielectric properties, It is preferably 2 to 30 parts by mass.

Furthermore, the thermosetting resin composition of the present invention may contain a thermosetting resin (G) selected from at least one of an epoxy resin and a cyanate resin.

(triazine)骨架之環氧樹脂、含茀骨架之環氧樹脂、三酚基酚 基甲烷型環氧樹脂、聯苯型環氧樹脂、伸苯二甲基型環氧樹脂、聯苯芳烷型環氧樹脂、萘型環氧樹脂、二環戊二烯型環氧樹脂、脂環式環氧樹脂、多官能酚類及蒽等多環芳香族類的二縮水甘油醚化合物、以及將磷化合物導入該等環氧樹脂中而成的含磷環氧樹脂等。這些環氧樹脂可單獨使用，或是可混合2種以上使用。其中，例如，由耐熱性、難燃性的觀點而言，較佳的是聯苯芳烷型環氧樹脂及萘型環氧樹脂。 Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolak epoxy resin, and cresol novolac epoxy resin. , bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, styrene type epoxy resin, containing three

(triazine) epoxy resin of skeleton, epoxy resin containing ruthenium skeleton, trisphenol phenol methane type epoxy resin, biphenyl type epoxy resin, benzoyl type epoxy resin, biphenyl aralkyl type Epoxy resin, naphthalene epoxy resin, dicyclopentadiene type epoxy resin, alicyclic epoxy resin, polyfunctional phenols, polycyclic aromatic diglycidyl ether compounds such as hydrazine, and phosphorus compounds A phosphorus-containing epoxy resin or the like obtained by introducing the epoxy resin. These epoxy resins may be used singly or in combination of two or more. Among them, for example, from the viewpoint of heat resistance and flame retardancy, a biphenyl aralkyl type epoxy resin and a naphthalene type epoxy resin are preferable.

而成的預聚合物等。這些樹脂可單獨使用，或是可混合2種以上使用。這些樹脂中，例如，由耐熱性、難燃性的觀點而言，較佳是酚醛清漆型氰酸酯樹脂。 Further, examples of the cyanate resin include a novolac type cyanate resin, a bisphenol A type cyanate resin, a bisphenol E type cyanate resin, and a tetramethylbisphenol F type cyanate resin. a bisphenol type cyanate resin, and a part of these resins form three

Prepolymers and the like. These resins may be used singly or in combination of two or more. Among these resins, for example, a novolac type cyanate resin is preferred from the viewpoint of heat resistance and flame retardancy.

酚醛清漆樹脂等的多官能酚化合物；二氰二胺、二胺基二苯基甲烷、二胺基二苯基碸等的胺化合物；鄰苯二甲酸酐、苯均四酸二酐、馬來酸酐、馬來酸酐共聚物等的酸酐等。這些硬化劑，可單獨使用1種，或是可混合2種以上使用。 These thermosetting resins (G) can be used as needed. Examples of the curing agent include phenol novolac, cresol novolac, and amine tri

a polyfunctional phenol compound such as a novolak resin; an amine compound such as dicyandiamide, diaminodiphenylmethane or diaminodiphenylphosphonium; phthalic anhydride, pyromellitic dianhydride, and Malay An acid anhydride such as an acid anhydride or a maleic anhydride copolymer. These hardeners may be used alone or in combination of two or more.

The amount of the thermosetting resin (G) to be used is, for example, preferably from 1 to 50 parts by mass based on 100 parts by mass of the total of the resin components, and further preferably from the viewpoint of heat resistance and chemical resistance. It is 3 to 30 parts by mass.

The thermosetting resin composition of the present invention may contain an inorganic filler (H). Examples of the inorganic filler include cerium oxide, aluminum oxide, and slip. Stone, mica, kaolin, aluminum hydroxide, bauxite, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide, titanium oxide, boron nitride, calcium carbonate, barium sulfate, aluminum borate, potassium titanate, E glass Glass powder such as fiber or T glass fiber, D glass fiber, or hollow glass beads. These inorganic fillers may be used singly or in combination of two or more.

Among these inorganic fillers, for example, dielectric properties, heat resistance, Particularly preferred from the viewpoint of low thermal expansion is cerium oxide. Examples of the cerium oxide include precipitated cerium oxide which is produced by a wet method and has a high water content, and dry cerium oxide which is produced by a dry method and contains almost no bound water. Further, examples of the dry method of cerium oxide include crushing of cerium oxide, fumed silica, and melting spherical cerium oxide by a difference in a production method. Among these cerium oxides, in terms of low thermal expansion property and high fluidity when filled in a resin, it is preferred to melt spherical cerium oxide.

The case of using molten spherical ceria as an inorganic filler Next, for example, it is preferred that the average particle diameter is from 0.1 to 10 μm, and more preferably from 0.3 to 8 μm. By setting the average particle diameter of the molten spherical cerium oxide to 0.1 μm or more, the fluidity when the inorganic filler is highly filled in the resin can be favorably maintained, and the particle diameter can be reduced to 10 μm or less. The probability of mixing coarse particles suppresses the occurrence of defects caused by coarse particles. Here, the average particle diameter refers to a particle diameter when the total volume of the particles is set to 100% to obtain a cumulative frequency distribution curve of the particle diameter, which corresponds to a particle diameter of 50%, which can be obtained by using laser diffraction scattering. The particle size distribution measuring apparatus of the method is measured.

The content of the inorganic filler, for example, the sum of the resin components 100 parts by mass, preferably 20 to 500 parts by mass, and more preferably 50 to 350 Parts by mass. By setting the content of the inorganic filler to 20 to 500 parts by mass or more with respect to 100 parts by mass of the total of the resin components, the moldability and low thermal expansion property of the resin composition can be favorably maintained.

In addition, when the inorganic filler is blended in the resin composition, for example, the inorganic filler is preferably subjected to a surface treatment agent such as a coupling agent such as a decane-based or titanate-based or a siloxane oligomer. Treatment, or integral blend processing.

The thermosetting resin composition of the present invention may contain a hardening accelerator (I). Examples of the curing accelerator include an organic metal salt such as zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octoate, cobalt(II) diacetate, cobalt (III) triacetate, or the like; Classes and derivatives thereof; organophosphorus compounds such as phosphines and phosphonium salts; secondary amines, tertiary amines, and quaternary ammonium salts. These hardening accelerators may be used alone or in combination of two or more.

Among them, for example, zinc naphthenate, an imidazole derivative, and a phosphonium salt are preferred from the viewpoint of promoting effect and preservation stability.

The content of the hardening accelerator, for example, the sum of the resin components 100 parts by mass, preferably 0.01 to 3.0 parts by mass, more preferably 0.05 to 1.5 parts by mass. By setting the content of the curing accelerator to 0.01 to 3.0 parts by mass based on 100 parts by mass of the total of the resin components, the promotion effect and the storage stability can be favorably maintained.

In the present invention, it is optional without departing from the object of the present invention. Well-known thermoplastic resins, organic fillers, flame retardants, ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent whitening agents, and adhesion promoters are used. These components may be used alone or in combination of two or more. use.

Examples of the thermoplastic resin include polyphenylene ether resin and benzene. An oxy resin, a polycarbonate resin, a polyester resin, a polyamide resin, a polyimide resin, a xylene resin, a petroleum resin, a silicone resin, or the like.

Examples of the organic filler include polyethylene, polypropylene, and a resin filler composed of polystyrene, a polyphenylene ether resin, a fluorinated resin, a tetrafluoroethylene resin, or the like; a core-shell resin filler, etc., the core-shell resin filler having an acrylate resin or a methacrylate resin a rubber-like core layer composed of a conjugated diene resin or the like, and a glassy shell composed of an acrylate resin, a methacrylate resin, an aromatic vinyl resin, a vinyl cyanide resin, or the like. Quality layer.

Examples of the flame retardant include halogen-containing compounds containing bromine or chlorine. Flame retardant; phosphorus-based flame retardant such as triphenyl phosphate, tricresyl phosphate, tris(dichloropropyl) phosphate, phosphate ester compound, red phosphorus, etc.; amide sulfonate, melamine sulfate, polyphosphoric acid A nitrogen-based flame retardant such as melamine or melamine cyanurate; a phosphazene-based flame retardant such as cyclophosphazene or polyphosphazene; and an inorganic flame retardant such as antimony trioxide.

Further, as an example of the ultraviolet absorber, benzotriazole may be mentioned. Examples of the antioxidant include a hindered phenol-based or hindered amine-based antioxidant; and examples of the photopolymerization initiator include benzophenones, benzyl ketals, and thiophenes. A tonoketone-based photopolymerization initiator; a fluorescent whitening agent; a fluorescent whitening agent of a stilbene derivative; and an example of the adhesion improving agent: urea such as urea decane A compound or a coupling agent such as a decane system, a titanate system or an aluminate system.

Composition of thermosetting resin containing oxirane compound of the present invention Since it is used for a prepreg, it is preferred that the last components are in a varnish state dissolved or dispersed in an organic solvent.

The organic solvent to be used at this time may, for example, be methanol or ethanol. An alcohol solvent such as propanol, butanol, acesulfame, acesulfame, propylene glycol monomethyl ether; a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; An ester solvent such as an ester or propylene glycol monomethyl ether acetate; an ether solvent such as tetrahydrofuran; an aromatic solvent such as toluene, xylene or trimethylbenzene; dimethylformamide or dimethylacetamide; A nitrogen-containing solvent such as N-methylpyrrolidone; a sulfur-containing solvent such as dimethyl hydrazine or the like. These organic solvents may be used alone or in combination of two or more.

Among these organic solvents, for example, from the viewpoint of solubility, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acesulfame, propylene glycol monomethyl ether; Further preferred are methyl isobutyl ketone, cyclohexanone, and propylene glycol monomethyl ether.

The resin component in the finally obtained varnish is, for example, preferably clear. The total amount of the paint is 40 to 90% by mass, and more preferably 50 to 80% by mass. By setting the content of the resin component in the varnish to 40 to 90% by mass, it is possible to maintain good paintability and obtain a prepreg having a suitable amount of resin composition adhesion.

Here, the "resin component" in the present specification means: a siloxane compound And modified yttrium imide resin (including the modified quinone imine resin described above, the modified quinone imine resin having an acidic substituent derived from the amine compound represented by the general formula (3) E) acidic substituent), maleic imine compound (D), amine compound (E) having acidic substituent, thermoplastic elastomer (F), thermosetting Resin (G) and a reaction product of these substances. In addition, the "thermosetting resin composition" means an inorganic filler, a curing accelerator, or the like in the resin component.

(prepreg)

The prepreg of the present invention is obtained by impregnating the thermosetting resin composition of the present invention into a substrate. The prepreg relating to the present invention will be described in detail below. The prepreg of the present invention can be produced by impregnating the thermosetting resin composition of the present invention with a substrate and performing semi-curing (B-stage) by heating or the like. The method of impregnating the thermosetting resin composition of the present invention with a substrate is not particularly limited, and examples thereof include a method of immersing a substrate in a resin varnish, and coating by various coaters. Method, method of spraying by a spray machine, and the like. Among them, a method of immersing the substrate in a resin varnish is preferred. Thereby, the impregnation property of a resin composition with respect to a base material can be improved.

As the substrate of the present invention, for example, various conventional materials for laminated sheets for electrical insulating materials can be used. Examples of the material of the substrate include inorganic fibers such as E glass fiber, D glass fiber, S glass fiber, and Q glass fiber; organic fibers such as polyimine, polyester, and tetrafluoroethylene; and these a mixture of substances, etc. For other uses, for example, carbon fiber or the like may be used as the fiber-reinforced substrate.

These substrates, for example, have woven, non-woven, and roving (roving), the shape of the stranded felt and the surface felt, but the material and shape are selected according to the purpose and performance of the intended molded product, and may be used alone or in combination of two or more materials and shapes as needed. The thickness of the substrate, for example, can be used in a thickness of about 0.03 to 0.5 mm, and is processed by heat resistance or moisture resistance. On the sexual level, it is preferable to use a surface treated with a decane coupling agent or the like, or a mechanical open fiber treatment.

The prepreg of the present invention can be obtained, for example, in the following manner: The amount of the thermosetting resin composition to be adhered to the substrate is such that the content of the thermosetting resin composition in the prepreg after drying is 20 to 90% by mass, and is impregnated or coated on the substrate. Then, it is usually dried at a temperature of 100 to 200 ° C for 1 to 30 minutes to be semi-cured (B-staged).

(film with resin)

The resin-attached film of the present invention is obtained by forming a layer of the thermosetting resin composition of the present invention on a support. The method of forming the layer of the thermosetting resin composition obtained by the present invention on the support is not particularly limited, and the thermosetting resin composition obtained by the present invention can be made into a varnish by, for example, the following method. The resin composition layer is formed by applying it to the support by using various coaters, and drying it by heating or hot air blowing. The resin-attached film of the present invention can be produced by performing semi-hardening (B-stage) by heating or the like. In such a semi-hardened state, it is preferable to maintain the adhesion between the resin composition layer of the resin-attached film and the circuit board when the resin-attached film and the circuit board are laminated and cured. State; or a state in which the embedding property (fluidity) of the circuit board can be maintained.

When the thermosetting resin composition of the present invention is applied onto a support The coater to be used is not particularly limited, and examples thereof include a die coater, a notch wheel coater, a bar coater, a kiss coater, a roller coater, and the like. . These coaters can be suitably selected according to the thickness of the resin composition layer. Also, as a drying method, heating or hot air blowing can be used. The method of waiting.

The drying condition after the thermosetting resin composition is applied to the support, for example, is dried until the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass. the following. The amount of the organic solvent in the varnish varies depending on the boiling point of the organic solvent. For example, a varnish containing 30 to 60% by mass of an organic solvent may be dried at 50 to 150 ° C for 3 to 10 minutes. Thereby, a resin composition layer is formed. For the drying conditions, it is preferred to set suitable and ideal drying conditions in advance by a simple experiment.

The thickness of the resin composition layer formed on the support is usually equal to or greater than the thickness of the conductor layer of the circuit board. The thickness of the conductor layer is, for example, preferably 5 to 70 μm. Since the multilayer printed wiring board becomes lighter, thinner and shorter, the thickness of the conductor layer is more preferably 5 to 50 μm, more preferably 5 to 30 μm.

The support in the resin-attached film may, for example, be a film made of a polyethylene such as polyethylene, polypropylene or polyvinyl chloride; or polyethylene terephthalate (hereinafter also referred to simply as "PET"), polyester such as polyethylene naphthalate; polycarbonate, polyimine, etc., and further, a metal foil such as a release paper, a copper foil, or an aluminum foil. Further, the support and the protective film described below may be subjected to a release treatment or the like in addition to mat processing or corona treatment.

The thickness of the support is, for example, preferably 10 to 150 μm, and more preferably 25 to 50 μm. On the surface of the resin composition layer on which the support is not provided, a protective film equivalent to the support may be laminated. The thickness of the protective film may be, for example, 1 to 40 μm. By laminating the protective film, foreign matter can be prevented from entering.

The film with the resin can also be rolled into a roll to be stored.

(Laminated board)

The laminated board of the present invention is obtained by laminating the resin-attached film. For example, a resin laminating film can be laminated on one surface or both surfaces of a circuit board, a prepreg, a substrate, or the like using a vacuum laminator, and can be produced by hardening by heating as needed. Examples of the substrate used for the circuit board include a glass epoxy resin substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin (Bismaleimide Triazine resin) substrate, and a thermosetting polyphenyl ether substrate. . Further, the circuit substrate herein refers to a material in which a circuit pattern is formed on one or both sides of the substrate. Further, in a printed wiring board formed by laminating a plurality of conductor layers and an insulating layer, a circuit pattern is formed on one or both sides of the outermost layer of the printed wiring board, and is also included in the circuit referred to herein. Inside the substrate. Further, the surface of the conductor layer may be subjected to a roughening treatment in advance by a blackening treatment or the like.

When laminating as described above, the film with resin is guaranteed In the case of the protective film, after removing the protective film, the resin-attached film and the circuit substrate are preheated as needed, and the film with the resin is pressed and heated, and the film is crimped to the circuit. On the substrate. The resin-attached film of the present invention is preferably a method of laminating on a circuit board under reduced pressure by a vacuum lamination method. The lamination conditions are preferably, for example, a crimping temperature (lamination temperature) of 70 to 140 ° C, a pressure of 0.1 to 1.1 MPa, and an atmospheric pressure of 20 mmHg (26.7 hPa) or less. Lamination is carried out under reduced pressure. Further, the lamination method can be carried out by a batch type or by a continuous type using a drum.

Laminating the film with the resin on the circuit board and cooling to room temperature The right and left sides are then peeled off when the support is to be peeled off, and thermally cured, whereby an insulating resin layer can be formed on the circuit board. The conditions of the heat curing can be appropriately selected depending on the kind and content of the resin component in the resin composition, and are preferably 150 to 220 ° C, 20 to 180 minutes, and more preferably 160 to 200 ° C, 30 °. Choose from a range of 120 minutes.

After the insulating resin layer is formed, the support is not peeled off before the hardening Next, peeling is performed at this time. Next, perforation is performed on the insulating layer formed on the circuit board as needed to form a via hole and a through hole. The perforation can be performed, for example, by a well-known method such as a drill, a laser, or a plasma, or by combining these methods as required, by a carbon dioxide laser, a YAG (yttrium-aluminum garnet laser), or the like. Laser penetration is the most common method.

Next, by dry plating or wet plating, on the insulating resin layer A conductor layer is formed thereon. As the dry plating, for example, a known method such as vapor deposition, sputtering, or ion plating can be used. In the case of wet plating, first, the surface of the hardened insulating resin composition layer is made of permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide. The oxidizing agent such as sulfuric acid or nitric acid is roughened to form an uneven anchor. As the oxidizing agent, an aqueous sodium hydroxide solution (alkaline permanganic acid aqueous solution) such as potassium permanganate or sodium permanganate is preferably used. Next, a conductor layer is formed by a combination of electroless plating and electrolytic plating. Further, a plating resist having a pattern opposite to that of the conductor layer may be formed, and the conductor layer may be formed only by electroless plating. As a method of forming a pattern later, for example, week can be used Known subtractive method, semi-additive method, etc.

The laminated board of the present invention is obtained by accumulating the aforementioned prepreg of the present invention. The layer is formed. For example, 1 to 20 sheets of the prepreg of the present invention are stacked, and a metal foil such as copper or aluminum is placed on one or both sides, and the laminated sheet of the present invention can be produced by laminating such a structure.

The molding conditions at the time of producing a laminated board, for example, a method of applying a laminated board and a multilayer board for an electrical insulating material, for example, can be formed by using a multi-stage pressing, a multi-stage vacuum pressing, a continuous forming, a autoclave forming machine, or the like. It is formed in a temperature range of 100 to 250 ° C, a pressure of 0.2 to 10 MPa, and a heating time of 0.1 to 5 hours. Further, the prepreg and the inner layer wiring board of the present invention may be combined and laminated to form a laminated board.

(multilayer printed circuit board)

The multilayer printed wiring board of the present invention is produced by using the above laminated board. For example, the conductor layer of the laminated board of the present invention can be subjected to line processing by a general etching method to obtain a circuit board. Then, the laminated board processed by the line is laminated in a plurality of layers through the prepreg described above, and multilayered by heat pressing. Thereafter, a through hole or a blind via hole is formed by drilling, laser processing, or the like, and an interlayer wiring is formed by plating or a conductive paste, whereby a multilayer printed wiring board can be manufactured.

(semiconductor package)

The semiconductor package of the present invention is obtained by carrying a semiconductor element on the multilayer printed wiring board. The semiconductor package of the present invention is manufactured by carrying a semiconductor element such as a semiconductor wafer or a memory at a specific position of the printed wiring board.

[Examples]

Next, the present invention will be described in more detail by way of the following examples, but the invention is not limited to the examples.

In addition, the resin plate obtained by each of the examples and the comparative examples was subjected to measurement and evaluation of the curing shrinkage ratio by the following method, and a copper-clad laminate was used, and the glass transition temperature and thermal expansion were performed by the following methods. The rate, copper foil adhesion, copper solder heat resistance, flexural modulus, and dielectric properties were measured and evaluated.

(1) Determination of hardening shrinkage rate of resin sheet

A resin plate (thickness: 1 mm) of 5 mm square was produced, and thermomechanical analysis was performed by a compression method using a TMA test apparatus (Q400 manufactured by TA Instruments Co., Ltd.). After installing the resin plate on the device in the Z direction, the load is 5g, the temperature rise rate is 45°C/min, and the temperature is 20°C (for 5 minutes) to 260°C (for 2 minutes) to 20°C (for 5 minutes). The temperature profile is used for the determination. The curing shrinkage ratio of the resin sheet was evaluated from the amount of dimensional change between 20 ° C before the start of the temperature rise and 20 ° C after the temperature rise.

Specifically, the curing shrinkage ratio of the resin sheet was calculated using the following formula. Hardening shrinkage ratio (%) = [(20 °C dimension before temperature rise (mm) - 20 °C dimension (mm) after temperature rise) / 20 °C dimension (mm) before temperature rise start] × 100

(2) Determination of glass transition temperature (Tg)

The copper-clad laminate was immersed in a copper etching solution to remove the copper foil, and a 5 mm square evaluation substrate was prepared, and a thermomechanical analysis was performed by a compression method using a TMA tester (Q400 manufactured by TA Instruments Co., Ltd.). After the evaluation substrate is mounted on the device in the Z direction, the load is 5 g, and the temperature increase rate is 10 ° C / min. The measurement conditions were measured twice in succession. The heat resistance was evaluated by the Tg indicated by the intersection of the distinct tangent lines of the thermal expansion curve in the second measurement.

(3) Determination of thermal expansion rate

The copper-clad laminate was immersed in a copper etching solution to remove the copper foil, and a 5 mm square evaluation substrate was prepared, and a thermomechanical analysis was performed by a compression method using a TMA tester (Q400 manufactured by TA Instruments Co., Ltd.). After the evaluation substrate was mounted on the apparatus in the X direction, the measurement was carried out twice under the measurement conditions of a load of 5 g and a temperature increase rate of 10 ° C/min. The average thermal expansion coefficient at 30 ° C to 100 ° C in the second measurement was calculated and used as a numerical value of the thermal expansion coefficient.

(4) Evaluation of copper foil adhesion (copper foil peel strength)

The copper clad laminate was immersed in a copper etching solution to adjust a copper foil having a width of 3 mm to prepare an evaluation substrate, and the adhesion (peeling strength) of the copper foil was measured using a tensile tester.

(5) Evaluation of heat resistance of copper solder

A 25 mm square evaluation substrate was prepared from a copper clad laminate, and the evaluation substrate was floated for 120 minutes in a solder bath having a temperature of 288 ° C, and the heat resistance of the copper solder was evaluated by observing the appearance.

(6) Bending elastic modulus

A 25 mm × 50 mm evaluation substrate from which copper foil was removed was prepared by immersing a copper clad laminate in a copper etching solution, and a crosshead speed of 1 mm/min was used using a 5 ton Tensilon tester manufactured by Orientec. The measurement was carried out under the condition that the distance was 20 mm.

(7) Dielectric properties (relative dielectric constant and dielectric loss tangent)

The copper clad laminate is immersed in a copper etching solution to form a copper foil. The 100 mm × 2 mm evaluation substrate was measured for relative dielectric constant and dielectric loss tangent at a frequency of 1 GHz using a cavity resonator device (manufactured by Kanto Electronics Development Co., Ltd.).

Production Example 1: Production of a oxoxane compound (i-1)

Add 3,3'-dimethyl-4,4'-diamine biphenyl to a heated and cooled reaction vessel with a thermometer, agitation device, and a reflux condenser with a volume of 2 liters. : 0.27 g, terephthalaldehyde: 0.33 g, X-22-161B: 199.4 g, propylene glycol monomethyl ether: 300.0 g, and reacted at 115 ° C for 4 hours, and then heated to 130 ° C, and dehydrated by atmospheric pressure concentration. A solution (Mw: 30000, resin component: 90% by mass) was obtained, and this solution contained a modified methoxyalkylene compound (i-1) having an aromatic methylimine.

Production Example 2: Production of a oxoxane compound (i-2)

Add 4,4'-diaminobenzimidamide: 0.27 g, p-benzene in a reaction vessel with a thermometer, a stirring device, a moisture analyzer with a reflux cooling tube and a heating and cooling volume of 2 liters. Diformaldehyde: 0.31 g, X-22-161B: 199.4 g, propylene glycol monomethyl ether: 300.0 g, and reacted at 115 ° C for 4 hours, heated to 130 ° C, and dehydrated by atmospheric pressure concentration to obtain a solution (Mw : 31000, resin component: 90% by mass), the solution contains a modified methoxyalkylene compound (i-2) having an aromatic methylimine.

Production Example 3: Production of a oxoxane compound (i-3)

Add 4-aminophenyl-4'-aminobenzoate to a heated vessel cooled to 2 liters with a thermometer, agitation device, and a moisture analyzer with a reflux cooling tube. 0.27 g, terephthalaldehyde: 0.31g, X-22-161B: 199.4g, propylene glycol monomethyl ether: 300.0g, and reversed at 115 ° C After 4 hours, the temperature was raised to 130 ° C, and dehydration was carried out by atmospheric pressure concentration to obtain a solution (Mw: 31000, resin component: 90% by mass) containing a modified siloxane compound having an aromatic methylimine. (i-3).

Production Example 4: Production of a oxoxane compound (i-4)

4,4'-diaminoazobenzene: 0.27 g, p-phenylene in a reaction vessel with a thermometer, a stirring device, a moisture meter with a reflux cooling tube and a heat and cooling volume of 2 liters Formaldehyde: 0.31 g, X-22-161B: 199.4 g, propylene glycol monomethyl ether: 300.0 g, and after reacting at 115 ° C for 4 hours, the temperature was raised to 130 ° C, and dehydration was carried out by atmospheric pressure concentration to obtain a solution (Mw: 30000, resin component: 90% by mass), the solution contains a modified methoxyalkylene compound (i-4) having an aromatic methylenimine.

Production Example 5: Production of a oxoxane compound (i-5)

Add 3,3'-diethyl-4,4'-diamino 2 to a heated and cooled reaction vessel with a thermometer, a stirring device, and a reflux condenser with a volume of 2 liters. Phenylmethane: 0.18 g, terephthalaldehyde: 0.19 g, KF-8012: 199.6 g, propylene glycol monomethyl ether: 300.0 g, and reacted at 115 ° C for 4 hours, then heated to 130 ° C, and concentrated by atmospheric pressure. The mixture was dehydrated to obtain a solution (Mw: 50,000, resin component: 90% by mass) containing a modified methoxyalkylene compound (i-5) having an aromatic methylimine.

Production Example 6: Production of a oxoxane compound (ii-1)

Add 3,3'-diethyl-4,4'-diamino 2 to a heated and cooled reaction vessel with a thermometer, a stirring device, and a reflux condenser with a volume of 2 liters. Phenylmethane: 12.9 g, terephthalaldehyde: 17.1 g, propylene glycol monomethyl ether: 45.0 g, and reacted at 115 ° C for 4 hours, then raised to 130 At ° C, dehydration was carried out by atmospheric pressure concentration to obtain a solution (resin component: 60% by mass) containing an aromatic methylimine compound.

Next, X-22-161B: 325.5 g and propylene glycol monomethyl ether: 513.3 g were added to the above reaction solution, and after reacting at 115 ° C for 4 hours, the temperature was raised to 130 ° C, and dehydration was carried out by concentration under normal pressure. A solution (Mw: 30,000, resin component: 90% by mass) containing a modified methoxy oxane compound (ii-1) having an aromatic methylimine.

Production Example 7: Production of a oxoxane compound (ii-2)

2,5-Dimethyl-1,4-diamine benzene: 8.7 g in a reaction vessel with a thermometer, a stirring device, a moisture analyzer with a reflux cooling tube and a heat and cooling volume of 2 liters , terephthalaldehyde: 21.3 g, propylene glycol monomethyl ether: 45.0 g, and reacted at 115 ° C for 4 hours, and then heated to 130 ° C, and dehydrated by atmospheric pressure concentration to obtain a solution (resin component: 60% by mass) This solution contains an aromatic methylimine compound.

Next, X-22-161B: 413.8 g, propylene glycol monomethyl ether: 645.7 g was added to the above reaction solution, and after reacting at 115 ° C for 4 hours, the temperature was raised to 130 ° C, and dehydration was carried out by concentration under normal pressure. A solution (Mw: 25,000, resin component: 90% by mass) containing a modified methoxyalkylene compound (ii-2) having an aromatic methylimine.

Production Example 8: Production of a oxoxane compound (ii-3)

Add 4,4'-diaminobenzilide: 12.1 g, p-benzene in a reaction vessel with a thermometer, a stirring device, a moisture analyzer with a reflux cooling tube and a heating and cooling volume of 2 liters. Diformaldehyde: 17.9g, propylene glycol monomethyl ether: 45.0g, and after reacting at 115 ° C for 4 hours, the temperature is raised to 130 ° C, by atmospheric pressure The mixture was dehydrated to obtain a solution (resin component: 60% by mass) containing an aromatic methylimine compound.

Next, X-22-161B: 342.1 g, propylene glycol monomethyl ether: 538.1 g was added to the above reaction solution, and after reacting at 115 ° C for 4 hours, the temperature was raised to 130 ° C, and dehydration was carried out by atmospheric pressure concentration to obtain A solution (Mw: 31000, resin component: 90% by mass) containing a modified methoxyalkylene compound (ii-3) having an aromatic methylimine.

Production Example 9: Production of a oxoxane compound (ii-4)

Add 4-aminophenyl-4'-aminobenzoate in a reaction vessel with a thermometer, agitation device, and a moisture analyzer with a reflux cooling tube and a volume of 2 liters: 12.2 g, terephthalaldehyde: 17.9 g, propylene glycol monomethyl ether: 45.0 g, and reacted at 115 ° C for 4 hours, the temperature was raised to 130 ° C, and dehydrated by atmospheric pressure concentration to obtain a solution (resin component: 60% by mass) The solution contains an aromatic methylimine compound.

Next, X-22-161B: 341.6 g, propylene glycol monomethyl ether: 537.3 g was added to the above reaction solution, and after reacting at 115 ° C for 4 hours, the temperature was raised to 130 ° C, and dehydration was carried out by concentration under normal pressure. A solution (Mw: 31000, resin component: 90% by mass) containing a modified methoxyalkylene compound (ii-4) having an aromatic methylimine.

Production Example 10: Production of a oxoxane compound (ii-5)

4,4'-diaminoazobenzene: 11.6 g, p-phenylene in a reaction vessel with a thermometer, a stirring device, a moisture meter with a reflux cooling tube and a heat and cooling volume of 2 liters Formaldehyde: 18.4g, propylene glycol monomethyl ether: 45.0g, and reacted at 115 ° C for 4 hours, then heated to 130 ° C, by atmospheric pressure The mixture was dehydrated to obtain a solution (resin component: 60% by mass) containing an aromatic methylimine compound.

Next, X-22-161B: 352.1 g, propylene glycol monomethyl ether: 553.1 g was added to the above reaction solution, and after reacting at 115 ° C for 4 hours, the temperature was raised to 130 ° C, and dehydration was carried out by concentration under normal pressure. A solution (Mw: 30000, resin component: 90% by mass) containing a modified methoxyalkylene compound (ii-5) having an aromatic methylimine.

Production Example 11: Production of a oxoxane compound (iii-1)

Adding terephthalic acid: 5.2g, X-22-161A: 24.8g, propylene glycol in a reaction vessel with a thermometer, a stirring device, a moisture measuring device with a reflux cooling tube and a volume of 2 liters Monomethyl ether: 45.0 g, and after reacting at 115 ° C for 4 hours, the temperature was raised to 130 ° C, and dehydration was carried out by concentration under normal pressure to obtain a solution (resin component: 60% by mass) containing the aldehyde group and the acetyl group. Amine based modified oxirane compound.

Next, bis(4-(4-aminophenoxy)phenyl)propane: 13.0 g and propylene glycol monomethyl ether: 44.4 g were added to the above reaction solution, and after reacting at 115 ° C for 4 hours, the temperature was raised to Dehydration was carried out by atmospheric pressure concentration at 130 ° C to obtain a solution (Mw: 40000, resin component: 90% by mass) containing a modified methoxyalkylene compound (iii-1) having an aromatic methylimine.

Production Example 12: Production of a oxoxane compound (iii-2)

Adding terephthalaldehyde: 3.0 g, X-22-161B: 27.0 g, propylene glycol in a reaction vessel with a thermometer, a stirring device, a moisture analyzer with a reflux cooling tube and a volume of 2 liters. Monomethyl ether: 45.0 g, and reacted at 115 ° C for 4 hours, then warmed to 130 ° C, and concentrated by atmospheric pressure. Water, a solution (resin component: 60% by mass) was obtained, and this solution contained a modified siloxane compound having an aldehyde group and a methylimine group.

Next, 3,3'-diethyl-4,4'-diaminodiphenylmethane: 4.6 g, propylene glycol monomethyl ether: 31.9 g, and reacted at 115 ° C for 4 hours were added to the above reaction solution. Thereafter, the temperature was raised to 130 ° C, and dehydration was carried out by atmospheric pressure concentration to obtain a solution (Mw: 70,000, resin component: 90% by mass) containing a modified methoxyxane compound having an aromatic methylimine (iii- 2).

Production Example 13: Production of a oxoxane compound (iii-3)

Adding terephthalaldehyde: 3.0 g, X-22-161B: 27.0 g, propylene glycol in a reaction vessel with a thermometer, a stirring device, a moisture analyzer with a reflux cooling tube and a volume of 2 liters. Monomethyl ether: 45.0 g, and after reacting at 115 ° C for 4 hours, the temperature was raised to 130 ° C, and dehydration was carried out by concentration under normal pressure to obtain a solution (resin component: 60% by mass) containing the aldehyde group and the acetyl group. Amine based modified oxirane compound.

Next, 4,4'-diaminobenzimidamide: 4.1 g, propylene glycol monomethyl ether: 31.2 g was added to the above reaction solution, and after reacting at 115 ° C for 4 hours, the temperature was raised to 130 ° C by The mixture was concentrated under normal pressure to obtain a solution (Mw: 69000, resin component: 90% by mass) containing a modified methoxyalkylene compound (iii-3) having an aromatic methylimine.

Production Example 14: Production of a oxoxane compound (iii-4)

Adding terephthalaldehyde: 3.0 g, X-22-161B: 27.0 g, propylene glycol in a reaction vessel with a thermometer, a stirring device, a moisture analyzer with a reflux cooling tube and a volume of 2 liters. Monomethyl ether: 45.0 g, and reacted at 115 ° C for 4 hours, then warmed to 130 ° C, and concentrated by atmospheric pressure. Water, a solution (resin component: 60% by mass) was obtained, and this solution contained a modified siloxane compound having an aldehyde group and a methylimine group.

Next, 4-aminophenyl-4'-aminobenzoic acid ester: 4.5 g, propylene glycol monomethyl ether: 31.2 g was added to the above reaction solution, and after reacting at 115 ° C for 4 hours, the temperature was raised to 130. At ° C, dehydration was carried out by atmospheric pressure concentration to obtain a solution (Mw: 69000, resin component: 90% by mass) containing a modified methoxyxane compound (iii-4) having an aromatic methylimine.

Production Example 15: Production of a oxoxane compound (iii-5)

Adding terephthalaldehyde: 3.0 g, X-22-161B: 27.0 g, propylene glycol in a reaction vessel with a thermometer, a stirring device, a moisture analyzer with a reflux cooling tube and a volume of 2 liters. Monomethyl ether: 45.0 g, and after reacting at 115 ° C for 4 hours, the temperature was raised to 130 ° C, and dehydration was carried out by atmospheric pressure concentration to obtain a solution containing a modified oxirane having an aldehyde group and a methylimine group. Compound (resin component: 60% by mass).

Next, 4,4'-diaminoazobenzene: 3.9 g, propylene glycol monomethyl ether: 30.8 g was added to the above reaction solution, and after reacting at 115 ° C for 4 hours, the temperature was raised to 130 ° C, by usual The mixture was concentrated by pressure to carry out dehydration to obtain a solution (Mw: 68000, resin component: 90% by mass) containing a modified methoxyalkylene compound (iii-5) having an aromatic methylimine.

Production Example 16: Production of modified quinone imine resin (j-1) having aromatic methylimine

Adding a modified siloxane compound having an aromatic methylimine (i-1) to a reaction vessel having a thermometer, a stirring device, and a moisture analyzer having a reflux cooling tube and capable of heating and cooling and having a volume of 2 liters Solution (resin composition: 90% by mass): 62.4 g, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane: 243.9 g, propylene glycol monomethyl ether: 443.8 g, and reacted at 115 ° C After 4 hours, the temperature was raised to 130 ° C, and concentration was carried out under normal pressure to obtain a solution containing a modified quinone imine resin (j-1) having an aromatic methylimine (resin component: 60% by mass).

Production Example 17: Production of modified quinone imine resin (j-2) having aromatic methylimine

Adding a modified siloxane compound having an aromatic methylenimine (i-2) to a reaction vessel having a temperature, a volume of 2 liters, which can be heated and cooled with a thermometer, a stirring device, and a moisture measuring device having a reflux cooling tube Solution (resin component: 90% by mass): 62.5 g, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane: 243.8 g, propylene glycol monomethyl ether: 443.8 g, and after reacting at 115 ° C for 4 hours, the temperature was raised to 130 ° C, and concentrated under normal pressure to obtain a solution (resin component: 60% by mass) containing a modified quinone imine resin having an aromatic methylimine ( J-2).

Production Example 18: Production of modified quinone imine resin (j-3) having aromatic methylimine

Adding a modified siloxane compound having an aromatic carbamide (ii-1) to a reaction vessel having a temperature, a volume of 2 liters, which can be heated and cooled with a thermometer, a stirring device, and a moisture measuring device having a reflux cooling tube. Solution (resin component: 90% by mass): 62.5 g, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane: 243.7 g, propylene glycol monomethyl ether: 443.8 g, and after reacting at 115 ° C for 4 hours, the temperature was raised to 130 ° C, and concentrated under normal pressure to obtain a solution (resin component: 60% by mass) containing a modified quinone imine having an aromatic methylimine. Resin (j-3).

Production Example 19: Production of modified quinone imine resin (j-4) having aromatic methylimine

Adding a modified siloxane compound having an aromatic methylenimine (ii-3) to a reaction vessel having a temperature and a cooling capacity of 2 liters, which is equipped with a thermometer, a stirring device, and a moisture measuring device having a reflux cooling tube. Solution (resin component: 90% by mass): 62.3 g, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane: 243.9 g, propylene glycol monomethyl ether: 443.8 g, and after reacting at 115 ° C for 4 hours, the temperature was raised to 130 ° C, and concentrated under normal pressure to obtain a solution (resin component: 60% by mass) containing a modified quinone imine resin having an aromatic methylimine ( J-4).

Production Example 20: Production of modified quinone imine resin (j-5) having aromatic methylimine

Adding a modified siloxane compound having an aromatic carbamide (iii-2) to a reaction vessel having a temperature, a volume of 2 liters, which can be heated and cooled with a thermometer, a stirring device, and a moisture measuring device having a reflux cooling tube. Solution (resin component: 90% by mass): 62.5 g, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane: 243.8 g, propylene glycol monomethyl ether: 443.8 g, and after reacting at 115 ° C for 4 hours, the temperature is raised to 130 ° C, and concentrated under normal pressure to obtain a solution containing a modified quinone imine resin (j-5) having an aromatic methylimine (resin component: 60% by mass).

Production Example 21: Production of modified quinone imine resin (j-6) having aromatic methylimine

Moisture analyzer with thermometer, stirring device and reflux cooling tube A solution containing a modified methoxyalkane compound (iii-3) having an aromatic meridine (resin component: 90% by mass): 61.7 g, 2 was added to a reaction vessel which was heated and cooled and had a volume of 2 liters. , 2-bis(4-(4-maleimidophenoxy)phenyl)propane: 244.4 g, propylene glycol monomethyl ether: 443.8 g, and after reacting at 115 ° C for 4 hours, the temperature was raised to 130 ° C. The solution was concentrated under normal pressure to obtain a solution containing a modified quinone imine resin (j-6) having an aromatic carbamide (resin component: 60% by mass).

Production Example 22: Production of modified quinone imine resin (k-1) having an acidic substituent and an aromatic methylimine

Adding a modified siloxane compound having an aromatic methylimine (i-1) to a reaction vessel having a thermometer, a stirring device, and a moisture analyzer having a reflux cooling tube and capable of heating and cooling and having a volume of 2 liters Solution (resin component: 90% by mass): 62.5 g, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane: 238.1 g, p-aminophenol: 5.7 g, propylene glycol monomethyl ether: 443.8 g, and after reacting at 115 ° C for 4 hours, the temperature was raised to 130 ° C, and concentrated under normal pressure to obtain a solution (resin component: 60% by mass) containing an acidic substituent and A modified iminemine imine resin (k-1).

Production Example 23: Production of modified quinone imine resin (k-2) having an acidic substituent and an aromatic methylimine

Adding a modified siloxane compound having an aromatic methylenimine (i-2) to a reaction vessel having a temperature, a volume of 2 liters, which can be heated and cooled with a thermometer, a stirring device, and a moisture measuring device having a reflux cooling tube Solution (resin component: 90% by mass): 62.6 g, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane: 238.0 g, p-aminophenol: 5.7g, propylene glycol monomethyl ether: 443.7g, and After reacting at 115 ° C for 4 hours, the temperature was raised to 130 ° C, and concentration was carried out under normal pressure to obtain a solution (resin component: 60% by mass) containing a modified quinone imine resin having an acidic substituent and an aromatic methylimine ( K-2).

Production Example 24: Production of a modified quinone imine resin (k-3) having an acidic substituent and an aromatic methylimine

Adding a modified siloxane compound having an aromatic carbamide (ii-1) to a reaction vessel having a temperature, a volume of 2 liters, which can be heated and cooled with a thermometer, a stirring device, and a moisture measuring device having a reflux cooling tube. Solution (resin component: 90% by mass): 62.5 g, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane: 238.0 g, p-aminophenol: 5.7 g, propylene glycol monomethyl ether: 443.8 g, and after reacting at 115 ° C for 4 hours, the temperature was raised to 130 ° C, and concentrated under normal pressure to obtain a solution (resin component: 60% by mass) containing an acidic substituent and A modified iminemine imine resin (k-3).

Production Example 25: Production of a modified quinone imine resin (k-4) having an acidic substituent and an aromatic methylimine

Adding a modified siloxane compound having an aromatic methylenimine (ii-3) to a reaction vessel having a temperature and a cooling capacity of 2 liters, which is equipped with a thermometer, a stirring device, and a moisture measuring device having a reflux cooling tube. Solution (resin component: 90% by mass): 62.3 g, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane: 238.2 g, p-aminophenol: 5.7 g, propylene glycol monomethyl ether: 443.8 g, and after reacting at 115 ° C for 4 hours, the temperature was raised to 130 ° C, and concentrated under normal pressure to obtain a solution (resin component: 60% by mass) containing an acidic substituent and A modified iminemine imine resin (k-4).

Production Example 26: having an acidic substituent and an aromatic methylimine Manufacture of modified quinone imine resin (k-5)

Adding a modified siloxane compound having an aromatic carbamide (iii-2) to a reaction vessel having a temperature, a volume of 2 liters, which can be heated and cooled with a thermometer, a stirring device, and a moisture measuring device having a reflux cooling tube. Solution (resin component: 90% by mass): 62.6 g, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane: 238.0 g, p-aminophenol: 5.7 g, propylene glycol monomethyl ether: 443.7 g, and reacted at 115 ° C for 4 hours, heated to 130 ° C, and concentrated under normal pressure to obtain a solution (resin component: 60% by mass) containing an acidic substituent and A modified iminemine imine resin (k-5).

Production Example 27: Production of modified quinone imine resin (k-6) having an acidic substituent and an aromatic methylimine

Adding a modified siloxane compound having an aromatic carbamide to a reaction vessel having a thermometer, a stirring device, a moisture analyzer having a reflux cooling tube and being heated and cooled and having a volume of 2 liters (iii-3) Solution (resin component: 90% by mass): 61.8 g, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane: 238.6 g, p-aminophenol: 5.7 g, propylene glycol monomethyl ether: 443.8 g, and after reacting at 115 ° C for 4 hours, the temperature was raised to 130 ° C, and concentrated under normal pressure to obtain a solution (resin component: 60% by mass) containing an acidic substituent and A modified imine imine resin (k-6).

Examples 1 to 39 and Comparative Examples 1 to 12

The solution containing the modified methoxy oxane compound having an aromatic carbamide obtained in Production Examples 1 to 15 (i-1 to i-5, ii-1 to ii-5, iii-1 to iii-5) And the solutions (j-1 to j-6) containing the modified quinone imine resin having an aromatic carbamide obtained in Examples 16 to 21, and the production examples 22 to 27 A solution containing a modified quinone imine resin having an acidic substituent and an aromatic methylimine, and an aromatic amine compound (A), an aromatic aldehyde compound (B), and a siloxane compound (C) shown below ), a maleic imine compound (D), an amine compound (E) having an acidic substituent, a thermoplastic elastomer (F), a thermosetting resin (G), an inorganic filler (H), and a hardening accelerator ( I) and methyl ethyl ketone as a diluent solvent were mixed at a mixing ratio (parts by mass) shown in Tables 1 to 9 to obtain a varnish having a resin component of 65% by mass.

Next, it is made of polyethylene terephthalate having a thickness of 16 μm. The varnish was applied to the film by a film applicator (PI-1210, manufactured by Tester Industries Co., Ltd.) so that the thickness of the resin after drying was 35 μm, and dried by heating at 160 ° C for 10 minutes. And a semi-hardened resin powder is obtained. The support is not particularly limited, and a commonly used one can be used. Further, the method of application is not particularly limited, and it can be applied by a general table coater.

The resin powder is placed in a mold frame of a Teflon (registered trademark) sheet, and The shiny surface of the 12 μm-thick electrolytic copper foil was placed on the upper and lower sides, and after pressing at a pressure of 2.0 MPa and a temperature of 240 ° C for 60 minutes, the electrolytic copper foil was removed to obtain a resin plate.

Further, the varnish was impregnated and coated on a 0.1 mm E glass cloth, and dried by heating at 160 ° C for 10 minutes to obtain a prepreg having a resin content of 48% by mass.

Four sheets of the prepreg were placed, and a 12 μm-thick electrolytic copper foil was placed on the upper and lower sides, and pressed at a pressure of 3.0 MPa and a temperature of 240 ° C for 60 minutes to obtain a copper clad laminate.

The measurement and evaluation results of the obtained resin sheet and copper-clad laminate were shown in Tables 1 to 9.

Aromatic amine compound (A)

‧KAYAHARD A-A: 3,3'-diethyl-4,4'-diaminodiphenylmethane [manufactured by Nippon Kayaku Co., Ltd., trade name]

‧4,4'-Diaminobenzimidil [made by Tokyo Chemical Industry Co., Ltd., trade name]

‧4-Aminophenyl-4'-aminobenzoic acid ester [Changzhou Sunshine Pharmaceutical Co., Ltd., trade name]

Aromatic aldehyde compound (B)

‧TPAL: terephthalaldehyde [made by Toray Fine Chemical Co., Ltd., trade name]

Oxane compound (C)

‧X-22-161B: Two-terminal amine-based modified oxirane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name]

Maleic imine compound (D)

‧BMI: bis(4-maleimidophenyl)methane [made by KI Chemical Co., Ltd., trade name]

‧BMI-4000: 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane [manufactured by Daiwa Chemical Co., Ltd., trade name]

Amine compound having an acidic substituent (E)

‧p-Aminophenol [made by Kanto Chemical Co., Ltd., trade name]

Thermoplastic elastomer (F)

‧Tuftec H 1043: hydrogenated styrene-butadiene copolymer resin [Asahi Kasei Chemicals Co., Ltd., trade name]

‧EPFD CT-310: Epoxy modified styrene-butadiene copolymer resin [Daicel Co., Ltd., trade name]

Thermosetting resin (G)

‧ PT-30: Novolac type cyanate resin [manufactured by Lonza Japan Co., Ltd., trade name]

‧NC-7000L: α-naphthol/cresol novolac type epoxy resin [manufactured by Nippon Kayaku Co., Ltd., trade name]

Inorganic filler (H)

‧SC2050-KNK: Fused cerium oxide [Admatechs Co., Ltd., trade name]

‧Zinc molybdate: [Sherwin-Williams, trade name: KEMGARD1100]

Hardening accelerator (I)

‧Zinc naphthenate (II) 8% mineral spirit solution [Tokyo Chemical Industry Co., Ltd., trade name]

‧G-8009L: Isocyanate masked imidazole [manufactured by Daiichi Pharmaceutical Co., Ltd., trade name]

‧TPP-MK: tetraphenylphosphonium tetra-p-tolylboride [Beixing Chemical Industry Co., Ltd., trade name]

Hereinafter, the solutions containing the modified oxoxane compounds (i-1) to (iii-5) in Tables 1 to 9 and the modified quinone imine resin (j-1) to (j) having aromatic methylenimine a solution of -6) and a solution (parts by mass) of a solution containing a modified quinone imine resin (k-1) to (k-6) having an acidic substituent and an aromatic methylimine, which is a resin component The value of the solid component is converted.

As is clear from Tables 1 to 9, the resin sheet of the embodiment of the present invention has a small curing shrinkage ratio and is excellent in low hardening shrinkage, and in the characteristics of the laminated sheet, the coefficient of thermal expansion, the adhesion of the copper foil, and the elastic mold. The number and dielectric properties are also excellent.

On the other hand, the resin sheet of the comparative example has a large curing shrinkage ratio, and in the characteristics of the laminated sheet, the thermal expansion coefficient, the copper foil adhesive property, the elastic modulus, and the dielectric property of the comparative example are different from those of the examples. Any feature is inferior to the embodiment.

[Industrial availability]

a thermosetting resin composition containing a siloxane compound of the present invention, a prepreg obtained by impregnating or coating a substrate, a resin-coated film obtained by coating the support, and The laminate produced by laminating the prepreg has particularly low heat shrinkage, low thermal expansion, copper foil adhesion, high modulus of elasticity, and excellent dielectric properties, and is suitable for use as a highly integrated product. A multilayer printed wiring board for a semiconductor package or an electronic device.

Claims (19)

A oxoxane compound containing a structure represented by the following formula (1) and the following formula (2): (In the formula (1), R ₁ and R ₂ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, a halogenated alkyl group, a thiol group, an ethyl group, a hydroxyl group, a sulfonic acid group, or a carbon. a sulfoalkoxy group having 1 to 3 or an alkoxy group having 1 to 3 carbon atoms; x and y each independently an integer of 0 to 4; and A is a single bond or a methylenimine group, an ester group, or a decylamino group. , oxyazo, azo, vinyl or ethynyl); (In the formula (2), R ₃ and R ₄ each independently represent an alkyl group, a phenyl group or a substituted phenyl group, and n represents an integer of from 1 to 100). The oxirane compound according to claim 1, which further contains an aromatic meemidine. The oxoxane compound according to claim 2, which is an aromatic aldehyde compound having at least two primary amine groups in one molecule, and an aromatic aldehyde compound having at least two aldehyde groups in one molecule. (B) and a reaction of a oxoxane compound (C) having at least two amine groups at the terminal of the molecule. The alkoxyalkyl compound according to claim 2, which is an aromatic amine compound (A) having at least two primary amine groups in one molecule and at least one molecule The aromatic aldehyde compound (B) having two aldehyde groups is reacted, and then reacted with a oxoxane compound (C) having at least two amine groups at the molecular terminal. The oxoxane compound according to claim 2, which is an aromatic aldehyde compound (B) having at least two aldehyde groups in one molecule and a oxoxane compound having at least two amine groups at the terminal of the molecule ( C) After the reaction is carried out, it is further reacted with an aromatic amine compound (A) having at least two primary amino groups in one molecule. A modified quinone imine resin having an aromatic carbamide, the modified quinone amide resin having at least one of the oxirane compounds according to any one of claims 1 to 5, and at least one molecule The reaction of two N-substituted maleimide-based maleic imine compounds (D). The modified quinone imine resin according to claim 6, which further has an acidic substituent derived from an acidic substituent of the amine compound (E) represented by the following formula (3), (In the formula (3), R ₅ each independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group as an acidic substituent; and R ₆ each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom; An integer from 1 to 5, y is an integer from 0 to 4, and the sum of x and y is 5). A thermosetting resin composition comprising: the oxoxane compound according to any one of claims 1 to 5, and the horse having at least 2 N-substituted maleimine groups in one molecule The imine compound (D). The thermosetting resin composition according to claim 8, which further contains an amine compound (E) having an acidic substituent represented by the following formula (3), (In the formula (3), R _{5 is} each independently represented by a hydroxyl group, a carboxyl group or a sulfonic acid group of an acidic substituent; and R ₆ each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom; An integer from 1 to 5, y is an integer from 0 to 4, and the sum of x and y is 5). The thermosetting resin composition according to claim 8 or 9, which further contains a thermoplastic elastomer (F). The thermosetting resin composition according to claim 8, further comprising a thermosetting resin (G) selected from at least one of an epoxy resin and a cyanate resin. The thermosetting resin composition according to claim 8, which further contains an inorganic filler (H). The thermosetting resin composition according to claim 8, which further contains a curing accelerator (I). A prepreg obtained by impregnating a thermosetting resin composition according to any one of claims 8 to 13 with a substrate. A resin-attached film obtained by forming a layer of a thermosetting resin composition according to any one of claims 8 to 13 on a support. A laminated board obtained by laminating a prepreg as described in claim 14. A laminate comprising a resin-attached film as described in claim 15 It is obtained by forming a laminate. A multilayer printed wiring board manufactured using the laminate according to claim 16 or 17. A semiconductor package obtained by carrying a semiconductor element on a multilayer printed wiring board as described in claim 18.