JP2014129520A - Amino-modified siloxane compound, modified imide resin, thermosetting resin composition, prepreg, resin-clad film, laminate sheet, multilayer printed wiring board, and semiconductor package - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an amino-modified siloxane compound capable of providing a modified imide resin or thermosetting resin composition exhibiting, when used for various applications, an excellent low curing shrinkage, a low thermal expansion, favorable dielectric characteristics, and a high modulus of elasticity.SOLUTION: The provided amino-modified siloxane compound possessing, within the molecule structure thereof, an aromatic azomethine is obtained by reacting (A) a modified siloxane compound possessing at least one intramolecular aldehyde group and obtained by reacting (i) a siloxane compound whose molecule terminal possesses at least two primary amino groups and (ii) an aromatic aldehyde compound possessing at least two intramolecular aldehyde groups with (B) an aromatic amine compound possessing at least two intramolecular primary amino groups; a modified imide resin and a thermosetting resin composition each using the same, etc. are also provided.

Description

  The present invention relates to an amino-modified siloxane compound having an aromatic azomethine suitable for semiconductor packages and printed wiring boards, a modified imide resin using the same, a thermosetting resin composition, a prepreg, a film with a resin, a laminate, and a multilayer print The present invention relates to a wiring board and a semiconductor package.

  With the trend toward smaller and higher performance electronic devices in recent years, printed wiring boards have become increasingly dense and highly integrated, and with this, reliability has been improved by improving the heat resistance of laminated boards for wiring. There is an increasing demand for improvement. In such applications, particularly semiconductor packages, it is required to have both excellent heat resistance and low thermal expansion. In addition, dielectric characteristics corresponding to higher frequency of electric signals have been required.

  In this regard, known liquid crystalline polymers such as polyesters, polyamides, polycarbonates, polythiols, polyethers, and polyazomethines are thermosetting resins that are excellent in low thermal expansion, dielectric properties, and heat resistance. However, there is a problem that workability and moldability are insufficient, and a problem that solubility in an organic solvent is insufficient and handling is difficult.

  Among these liquid crystalline polymers, G.I. F. Since D'Aleio found polyazomethine (see Non-Patent Document 1), which is a liquid crystalline oligomer, there have been reports on cases involving resins using many polyazomethines (see, for example, Patent Documents 1 to 7).

  Patent Document 1 discloses various polyazomethines, and Patent Documents 2 to 7 disclose polyazomethines having specific structures. Patent Document 8 discloses thermosetting polyazomethine resins containing unsaturated groups, and describes that these resins exhibit high heat resistance.

JP 51-138800 A JP-A-60-181127 JP-A-60-101123 JP 2003-073470 A JP-A-63-193925 Japanese Patent Laid-Open No. 01-069631 Japanese Patent Laid-Open No. 01-079233 Japanese Patent Laid-Open No. 05-140067

Polymer Sci. Tech., Wiley-Interscience, NewYork, 1969, Vol.10, pp.659-670

However, when the polyazomethine described in Patent Documents 1 to 7 is applied as a copper clad laminate or an interlayer insulating material, heat resistance and formability may be insufficient. Further, the thermosetting polyazomethine resin described in Patent Document 8 still lacks improvement in heat resistance and toughness, and even when these are applied as a copper clad laminate or an interlayer insulating material, the heat resistance and reliability are also improved. , Workability and the like may be insufficient.
In view of the current situation, the object of the present invention is a modified imide resin or thermosetting which exhibits excellent low curing shrinkage, low thermal expansion, good dielectric properties, and high elastic modulus when applied to various applications. Amino-modified siloxane compound having an aromatic azomethine capable of realizing a functional resin composition, the modified imide resin and a thermosetting resin composition, a prepreg using the same, a film with a resin, a laminate, a multilayer printed wiring board, and It is to provide a semiconductor package.

  As a result of intensive studies to achieve the above object, the present inventors have found that the above object can be achieved by using an amino-modified siloxane compound having an aromatic azomethine, and have reached the present invention. The present invention is based on such knowledge.

  That is, the present invention provides an amino-modified siloxane compound having the following aromatic azomethine, a modified imide resin using the amino-modified siloxane compound, a thermosetting resin composition containing the amino-modified siloxane compound, a prepreg, and a film with a resin The present invention provides a laminated board, a multilayer printed wiring board, and a semiconductor package.

[1] In one molecule obtained by reacting a siloxane compound (i) having at least two primary amino groups at the molecular terminals and an aromatic aldehyde compound (ii) having at least two aldehyde groups in one molecule The aromatic azomethine in the molecular structure can be obtained by reacting the modified siloxane compound (A) having at least one aldehyde group with the aromatic amine compound (B) having at least two primary amino groups in one molecule. An amino-modified siloxane compound having:

（式（１）中、Ｒ₁は各々独立に、酸性置換基である水酸基、カルボキシル基又はスルホン酸基を、Ｒ₂は各々独立に、水素原子、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子を示し、ｘは１〜５の整数、ｙは０〜４の整数で、且つｘとｙの和は５である。） [2] A modified imide having an aromatic azomethine obtained by reacting the amino-modified siloxane compound according to [1] with a maleimide compound (C) having at least two N-substituted maleimide groups in one molecule. resin.
[3] The modified imide resin according to [2], further having an acidic substituent, wherein the acidic substituent is derived from the acidic substituent of the amine compound (D) represented by the following general formula (1).

(In formula (1), each R ₁ independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group which is an acidic substituent, and each R ₂ independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. Or a halogen atom, x is an integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5.)

（式（１）中、Ｒ₁は各々独立に、酸性置換基である水酸基、カルボキシル基又はスルホン酸基を、Ｒ₂は各々独立に、水素原子、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子を示し、ｘは１〜５の整数、ｙは０〜４の整数で、且つｘとｙの和は５である。）
［６］ さらに、熱可塑性エラストマー（Ｅ）を含有する［４］又は［５］に記載の熱硬化性樹脂組成物。
［７］ さらに、エポキシ樹脂及びシアネート樹脂から選ばれた少なくとも一種の熱硬化性樹脂（Ｆ）を含有する［４］〜［６］のいずれかに記載の熱硬化性樹脂組成物。
［８］ さらに、無機充填材（Ｇ）を含有する［４］〜［７］のいずれかに記載の熱硬化性樹脂組成物。
［９］ さらに、硬化促進剤（Ｈ）を含有する［４］〜［８］のいずれかに記載の熱硬化性樹脂組成物。 [4] A thermosetting resin composition comprising the amino-modified siloxane compound having an aromatic azomethine according to [1] and a maleimide compound (C) having at least two N-substituted maleimide groups in one molecule. .
[5] The thermosetting resin composition according to [4], further comprising an amine compound (D) having an acidic substituent represented by the following general formula (1).

(In formula (1), each R ₁ independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group which is an acidic substituent, and each R ₂ independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. Or a halogen atom, x is an integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5.)
[6] The thermosetting resin composition according to [4] or [5], further containing a thermoplastic elastomer (E).
[7] The thermosetting resin composition according to any one of [4] to [6], further containing at least one thermosetting resin (F) selected from an epoxy resin and a cyanate resin.
[8] The thermosetting resin composition according to any one of [4] to [7], further containing an inorganic filler (G).
[9] The thermosetting resin composition according to any one of [4] to [8], further containing a curing accelerator (H).

[10] A prepreg obtained by impregnating a base material with the thermosetting resin composition according to any one of [4] to [9].
[11] A film with a resin formed by layering the thermosetting resin composition according to any one of [4] to [9] on a support.
[12] A laminate obtained by laminate-molding the prepreg according to [10].
[13] A laminate obtained by laminating the film with resin according to [11].
[14] A multilayer printed wiring board produced using the laminated board according to [12] or [13].
[15] A semiconductor package comprising a semiconductor element mounted on the multilayer printed wiring board according to [14].

  According to the present invention, a modified imide resin or thermosetting resin composition that exhibits excellent low curing shrinkage and low thermal expansion, good dielectric properties, and high elastic modulus when applied to various applications. An amino-modified siloxane compound having an aromatic azomethine that can be realized, the modified imide resin and a thermosetting resin composition, a prepreg using the same, a film with a resin, a laminate, a multilayer printed wiring board, and a semiconductor package can be provided. .

  In particular, a prepreg obtained by impregnating a base material with a modified imide resin or thermosetting resin composition using an amino-modified siloxane compound having an aromatic azomethine of the present invention, and a resin-coated film formed on a support. The laminate produced by laminating the prepreg has particularly low curing shrinkage, low thermal expansion, excellent dielectric properties, and high elastic modulus, and is useful as a multilayer printed wiring board and a semiconductor package.

Hereinafter, the present invention will be described in detail.
(Amino-modified siloxane compound)
The amino-modified siloxane compound having an aromatic azomethine of the present invention includes a siloxane compound (i) having at least two primary amino groups at a molecular end and an aromatic aldehyde compound (ii) having at least two aldehyde groups in one molecule. ) And a modified siloxane compound (A) having at least one aldehyde group in one molecule and an aromatic amine compound (B) having at least two primary amino groups in one molecule. Can be obtained.
Here, the aromatic azomethine refers to a compound in which at least one aromatic is bonded to a Schiff base (—N═CH—).

（式中、Ｒ₃及びＲ₄はそれぞれ独立にアルキル基、フェニル基又は置換フェニル基を示し、ｎは１〜１００の整数である。）
一般式（２）の式中、ｎは１〜１００の整数であり、より好ましくは、２〜５０の整数である。
本発明の分子末端に少なくとも２個の一級アミノ基を有するシロキサン化合物（i）としては、市販品を用いることができる。市販品としては、例えば、「ＫＦ−８０１０」（アミノ基当量４３０）、「Ｘ−２２−１６１Ａ」（アミノ基当量８００）、「Ｘ−２２−１６１Ｂ」（アミノ基当量１５００）、「ＫＦ−８０１２」（アミノ基当量２２００）、「ＫＦ−８００８」（アミノ基当量５７００）、「Ｘ−２２−９４０９」（アミノ基当量７００）、「Ｘ−２２−１６６０Ｂ−３」（アミノ基当量２２００）（以上、信越化学工業株式会社製、商品名）、「ＢＹ−１６−８５３Ｕ」（アミノ基当量４６０）、「ＢＹ−１６−８５３」（アミノ基当量６５０）、「ＢＹ−１６−８５３Ｂ」（アミノ基当量２２００）（以上、東レダウコーニング株式会社製、商品名）等が挙げられる。 これらは単独で、あるいは２種類以上を混合して用いてもよい。
これらの中で、例えば、合成時の反応性が高く、低熱膨張性の点から、Ｘ−２２−１６１Ａ、Ｘ−２２−１６１Ｂ、ＫＦ−８０１２、Ｘ−２２−１６６０Ｂ−３、ＢＹ−１６−８５３Ｂが好ましく、相溶性に優れ、高弾性率化できる点から、Ｘ−２２−１６１Ａ、Ｘ−２２−１６１Ｂが特に好ましい。 The siloxane compound (i) having at least two primary amino groups at the molecular terminals of the present invention includes a structure represented by the following general formula (2).

(In the formula, R ₃ and R ₄ each independently represents an alkyl group, a phenyl group or a substituted phenyl group, and n is an integer of 1 to 100.)
In the formula of the general formula (2), n is an integer of 1 to 100, more preferably an integer of 2 to 50.
A commercially available product can be used as the siloxane compound (i) having at least two primary amino groups at the molecular ends of the present invention. Examples of commercially available products include “KF-8010” (amino group equivalent 430), “X-22-161A” (amino group equivalent 800), “X-22-161B” (amino group equivalent 1500), “KF— 8012 "(amino group equivalent 2200)," KF-8008 "(amino group equivalent 5700)," X-22-9409 "(amino group equivalent 700)," X-22-1660B-3 "(amino group equivalent 2200) (Brand name manufactured by Shin-Etsu Chemical Co., Ltd.), “BY-16-853U” (amino group equivalent 460), “BY-16-853” (amino group equivalent 650), “BY-16-853B” ( Amino group equivalent 2200) (above, trade name, manufactured by Toray Dow Corning Co., Ltd.) and the like. These may be used alone or in admixture of two or more.
Among these, for example, X-22-161A, X-22-161B, KF-8012, X-22-1660B-3, BY-16 are highly reactive at the time of synthesis and have low thermal expansion. 853B is preferable, and X-22-161A and X-22-161B are particularly preferable in terms of excellent compatibility and high elastic modulus.

  Examples of the aromatic aldehyde compound (ii) having at least two aldehyde groups in one molecule of the present invention include terephthalaldehyde, isophthalaldehyde, o-phthalaldehyde, 2,2′-bipyridine-4,4′-. Dicarboxaldehyde etc. are mentioned. Among these, for example, terephthalaldehyde, which can be further reduced in thermal expansion, has high reactivity during reaction, is excellent in solvent solubility, and is easily available commercially, is preferable.

  Examples of the aromatic amine compound (B) having at least two primary amino groups in one molecule of the present invention include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, and 3-methyl-1,4. -Diaminobenzene, 2,5-dimethyl-1,4-diaminobenzene, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyl-diphenylmethane, 4,4'-diamino-3, 3'-diethyl-diphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ketone, benzidine, 3,3'-dimethyl -4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxy Benzidine, 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) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, 9,9-bis (4-aminophenyl) fluorene and the like can be mentioned. These may be used alone or in admixture of two or more.

  Among these, for example, 4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminobiphenyl, 4,4 has high reactivity during the reaction and can have higher heat resistance. '-Diamino-3,3'-dimethyl-diphenylmethane, 4,4'-diamino-3,3'-diethyl-diphenylmethane, 4,4'-bis (4-aminophenoxy) biphenyl, bis (4- (4- Aminophenoxy) phenyl) propane and the like are preferred. Furthermore, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-3,3 'from the point of being inexpensive and soluble in a solvent. -Diethyl-diphenylmethane and bis (4- (4-aminophenoxy) phenyl) propane are more preferred. Furthermore, 4,4′-diamino-3,3′-diethyl-diphenylmethane and bis (4- (4-aminophenoxy) phenyl) propane are particularly preferable from the viewpoint of low thermal expansion and dielectric properties. Further, for example, p-phenylenediamine, m-phenylenediamine, 3-methyl-1,4-diaminobenzene, and 2,5-dimethyl-1,4-diaminobenzene are also preferable from the viewpoint of increasing the elastic modulus.

In the present invention, as a reaction for obtaining an amino-modified siloxane compound having an aromatic azomethine in the molecular structure, for example, first, a siloxane compound (i) having at least two primary amino groups at the molecular end, one molecule The modified siloxane compound (A) having at least one aldehyde group in one molecule is obtained by subjecting the aromatic aldehyde compound (ii) having at least two aldehyde groups therein to a dehydration condensation reaction in an organic solvent. Next, an amino-modified siloxane having an aromatic azomethine in the molecular structure is obtained by subjecting the compound and an aromatic amine compound (B) having at least two primary amino groups in one molecule to a dehydration condensation reaction in an organic solvent. A compound can be obtained.
In addition, this reaction is characterized in that the molecular weight of the siloxane in the molecule of the amino-modified siloxane compound having the aromatic azomethine of the present invention can be easily controlled, and is effective for lowering the thermal expansion coefficient of the resin composition containing this. It is.

Siloxane compound (i) having at least two primary amino groups at the molecular terminals (hereinafter sometimes referred to as component (i)) and aromatic aldehyde compound (ii) having at least two aldehyde groups in one molecule Examples of the organic solvent used in the dehydration condensation reaction (hereinafter sometimes referred to as component (ii)) include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, acetone, Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene and mesitylene, nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, dimethyl Sulfo Sulfur-containing solvents Sid like, and ester solvents such as γ- butyrolactone. These can be used alone or in combination of two or more. Among these, from the viewpoint of solubility, propylene glycol monomethyl ether, cyclohexanone, toluene, dimethylformamide, dimethylacetamide, γ-butyrolactone, and the like are preferable. Furthermore, propylene glycol monomethyl ether and toluene are more preferable because they are highly volatile and hardly remain as residual solvents during the production of prepreg.
Moreover, since this reaction is a dehydration condensation reaction, water is produced as a by-product. For the purpose of removing water as a by-product, it is preferable to react while removing water as a by-product by azeotropy with an aromatic solvent, for example.

  In the dehydration condensation reaction of component (i) and component (ii), a reaction catalyst can be optionally used as necessary. Examples of the reaction catalyst include acidic catalysts such as p-toluenesulfonic acid, amines such as triethylamine, pyridine and tributylamine, imidazoles such as methylimidazole and phenylimidazole, and phosphorus catalysts such as triphenylphosphine. . These can be used alone or in combination of two or more. In order to advance the dehydration condensation reaction efficiently, for example, an acidic catalyst such as p-toluenesulfonic acid is preferable.

  As a method for synthesizing an amino-modified siloxane compound having an aromatic azomethine in the molecular structure of the present invention, for example, first, the component (i) and the component (ii) are subjected to a dehydration condensation reaction in an organic solvent, A modified siloxane compound (A) having at least one aldehyde group in the molecule (hereinafter sometimes referred to as component (A)) is obtained.

  Here, the amount of component (i) and component (ii) used is, for example, the number of primary amino groups of component (i) [the amount of component (i) used / the amount of primary amino group equivalent of component (i)] It is preferably used in a range of 0.1 to 5.0 times the number of aldehyde groups of ii) [amount of component (ii) used / aldehyde equivalent of component (ii)] It is more preferable to use it so as to be in the range of 1.0 times. By setting it to 0.1 times or more, a decrease in solubility in a solvent tends to be suppressed. Moreover, it is in the tendency for the fall of the molecular weight of the component (A) obtained by this reaction to be suppressed by setting it as 5.0 times or less.

  Moreover, it is preferable that the usage-amount of an organic solvent shall be 25-2000 mass parts with respect to 100 mass parts of sum total of the resin component of a component (i) and a component (ii), and shall be 40-1000 mass parts, for example. It is more preferable to set it as 40-500 mass parts. When the amount of the organic solvent used is 25 parts by mass or more, insufficient solubility tends to be suppressed. Moreover, by setting it as 2000 mass parts or less, reaction does not require a long time.

Component (A) is obtained by charging the above raw materials, an organic solvent and, if necessary, a reaction catalyst in a reaction kettle and stirring for 0.1 to 10 hours while heating and keeping heat as necessary to cause a dehydration condensation reaction.
The reaction temperature at this time is preferably, for example, 70 to 150 ° C., and the reaction temperature is more preferably 100 to 130. Moreover, it is preferable to react, removing the water which is a by-product. By making the reaction temperature 70 ° C. or higher, the reaction rate does not become too slow, and by making the reaction temperature 150 ° C. or lower, the reaction solvent does not require a high boiling point solvent, and when producing a prepreg, Residual solvent hardly remains, and the heat resistance tends to be suppressed.

  Next, the component (A) obtained by the reaction and the aromatic amine compound (B) having at least two primary amino groups in one molecule (hereinafter sometimes referred to as component (B)) are mixed with an organic solvent. An amino-modified siloxane compound having an aromatic azomethine in the molecular structure can be obtained by performing a dehydration condensation reaction therein.

  Here, the amount of component (A) and component (B) used is, for example, the number of primary amino groups in component (B) [the amount of component (B) used / the primary amino group equivalent of component (B)] It is preferably used in a range of 1.0 to 10.0 times the number of aldehyde groups of A) [amount of component (A) used / aldehyde equivalent of component (A)]. By setting it to 1.0 times or more, there is a tendency that a decrease in low thermal expansion of the thermosetting resin containing an amino-modified siloxane compound having an aromatic azomethine in the molecular structure is suppressed. Moreover, it exists in the tendency for the fall of the solubility to a solvent to be suppressed by setting it as 10.0 times or less.

  The amount of the organic solvent used when the component (A) and the component (B) are subjected to a dehydration condensation reaction is, for example, relative to 100 parts by mass of the sum of the resin components of the component (A) and the component (B). It is preferable to set it as 25-2000 mass parts, It is more preferable to set it as 40-1000 mass parts, It is especially preferable to set it as 40-500 mass parts. When the amount of the organic solvent used is 25 parts by mass or more, insufficient solubility tends to be suppressed. Moreover, by setting it as 2000 mass parts or less, reaction does not require a long time. Although it does not specifically limit as an organic solvent to be used, For example, the organic solvent used for the dehydration condensation reaction of component (i) and component (ii) can be used.

Amino acids having an aromatic azomethine in the molecular structure are prepared by charging the above raw materials, organic solvent and, if necessary, a reaction catalyst in a reaction kettle and stirring for 0.1 to 10 hours while heating and holding as necessary to cause a dehydration condensation reaction. A modified siloxane compound is obtained.
For example, the reaction temperature is preferably 70 to 150 ° C., more preferably 100 to 130. Moreover, it is preferable to react, removing the water which is a by-product. By setting the reaction temperature to 70 ° C. or higher, the reaction rate does not become too slow. Moreover, by making reaction temperature 150 degrees C or less, when a prepreg is manufactured, a high boiling point solvent is not required for a reaction solvent, and a residual solvent hardly remains and it exists in the tendency for a heat resistant fall to be suppressed. Although it does not specifically limit as a reaction catalyst to be used, For example, the reaction catalyst used for the dehydration condensation reaction of component (i) and component (ii) can be used.

The amino-modified siloxane compound having aromatic azomethine in the molecular structure obtained by the above reaction can be confirmed by performing IR measurement. The IR measurement, to confirm that the peak of 1620 cm ^-1 attributable to the azomethine group (-N = CH-) appears, also, at 3,440 cm ^-1 due to the primary amino group, and there is a peak of 3370cm around ^-1 By confirming that the reaction is carried out, it can be confirmed that the reaction proceeds well and the desired compound is obtained. Moreover, although a weight average molecular weight (Mw) is not specifically limited, For example, 1000-300000 are preferable and 6000-150000 are especially preferable. When the weight average molecular weight (Mw) is equal to or more than the lower limit value, lower curing shrinkage and lower thermal expansibility tend to be suppressed. Moreover, it exists in the tendency for the fall of compatibility and an elasticity modulus to be suppressed as a weight average molecular weight (Mw) is below the said upper limit. The weight average molecular weight (Mw) is measured by gel permeation chromatography (GPC) and converted by a calibration curve produced using standard polystyrene.

For example, it can be performed under the following conditions.
As a measuring device, an auto sampler (AS-8020 manufactured by Tosoh Corporation), a column oven (860-C0 manufactured by JASCO Corporation), an RI detector (830-RI manufactured by JASCO Corporation), a UV / VIS detector ( JASCO Corporation 870-UV) and HPLC pump (JASCO Corporation 880-PU) are used.
Further, TSKgel SuperHZ2000, 2300 manufactured by Tosoh Corporation can be used as the column used, and measurement can be performed by using a measurement temperature of 40 ° C., a flow rate of 0.5 ml / min, and a solvent tetrahydrofuran.

(Modified imide resin)
The modified imide resin of the present invention is obtained by reacting the aforementioned amino-modified siloxane compound of the present invention with a maleimide compound (C) having at least two N-substituted maleimide groups in one molecule.

（式（１）中、Ｒ₁は各々独立に、酸性置換基である水酸基、カルボキシル基又はスルホン酸基を、Ｒ₂は各々独立に、水素原子、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子を示し、ｘは１〜５の整数、ｙは０〜４の整数で、且つｘとｙの和は５である。）
なお、アミン化合物（Ｄ）のさらなる詳細については後述する。また、「アミン化合物（Ｄ）の酸性置換基に由来するもの」とは、アミン化合物（Ｄ）の酸性置換基そのもの、及び、当該酸性置換基を含むものをいう。 Furthermore, such a modified imide resin preferably has an acidic substituent, and the acidic substituent is derived from the acidic substituent of the amine compound (D) represented by the following general formula (1). The acidic substituent can be introduced by reacting the amine compound (D).
By having such an acidic substituent, good low thermal expansibility can be obtained.

(In formula (1), each R ₁ independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group which is an acidic substituent, and each R ₂ independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. Or a halogen atom, x is an integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5.)
Further details of the amine compound (D) will be described later. The term “derived from the acidic substituent of the amine compound (D)” refers to the acidic substituent itself of the amine compound (D) and the one containing the acidic substituent.

  The modified imide resin can be produced by a “pre-reaction” when producing a thermosetting resin composition described later.

(Thermosetting resin composition)
The thermosetting resin composition of the present invention comprises an amino-modified siloxane compound having an aromatic azomethine and a maleimide compound (C) having at least two N-substituted maleimide groups in one molecule. .

  Examples of maleimide compounds (C) having at least two N-substituted maleimide groups in one molecule (hereinafter sometimes referred to as component (C)) include bis (4-maleimidophenyl) methane and polyphenylmethane. Maleimide, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebis Maleimide, m-phenylene bismaleimide, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane and the like can be mentioned. These may be used alone or in combination of two or more.

  Among these, for example, bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) sulfone, 2,2-bis (4- (4- (4- (4-m Maleimidophenoxy) phenyl) propane is preferred. Furthermore, from the viewpoint of solubility in a solvent, bis (4-maleimidophenyl) methane and 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane are more preferable. Furthermore, bis (4-maleimidophenyl) methane is particularly preferred because of its low cost.

In the thermosetting resin composition of the present invention, the amount of the amino-modified siloxane compound having an aromatic azomethine in the molecular structure is preferably, for example, 1 to 30 parts by mass per 100 parts by mass of the total resin components. 5 to 20 parts by mass is more preferable from the viewpoint of copper foil adhesion and chemical resistance.
The amount of component (C) used is, for example, preferably 30 to 99 parts by mass, and 40 to 80 parts by mass per 100 parts by mass of the total resin components, in terms of low thermal expansion and high elastic modulus. More preferred

  The thermosetting resin composition of the present invention comprises an amino-modified siloxane compound having an aromatic azomethine in the molecular structure and a component (C). The compound is pre-reacted to give an aromatic azomethine. It can also be used as a modified imide resin having By performing such a pre-reaction, the molecular weight can be controlled, and further low curing shrinkage and low thermal expansion can be improved.

In this pre-reaction, an amino-modified siloxane compound having an aromatic azomethine in the molecular structure and a component (C) are reacted while being heated and kept in an organic solvent to synthesize a modified imide resin having an aromatic azomethine. preferable.
Examples of the organic solvent used in this pre-reaction include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and acetic acid. Ester solvents such as ethyl ester and γ-butyrolactone, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene and mesitylene, nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, dimethyl sulfoxide And sulfur atom-containing solvents such as These can be used alone or in combination of two or more.

  Among these organic solvents, for example, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, and γ-butyrolactone are preferable from the viewpoint of solubility, and cyclohexanone has low toxicity and is highly volatile and hardly remains as a residual solvent. , Propylene glycol monomethyl ether, and dimethylacetamide are particularly preferable.

The amount of the organic solvent used is preferably, for example, 25 to 2000 parts by mass with respect to 100 parts by mass of the total of the resin component of the modified siloxane compound having aromatic azomethine in the molecular structure and compound (C), It is more preferable to set it as 40-1000 mass parts, and it is especially preferable to set it as 40-500 mass parts. When the amount of the organic solvent used is 25 parts by mass or more, the solubility does not become insufficient, and when it is 2000 parts by mass or less, the reaction does not take a long time.
The reaction temperature for this pre-reaction is, for example, preferably 70 to 150 ° C, and more preferably 100 to 130 ° C. For example, the reaction time is preferably 0.1 to 10 hours, and more preferably 1 to 6 hours.

  In this pre-reaction, the amount of the component (C) and the amino-modified siloxane compound having an aromatic azomethine in the molecular structure is, for example, the number of maleimide groups in the component (C) [the amount of component (C) used / component (C) The number of primary amino groups in the amino-modified siloxane compound having an aromatic azomethine in the molecular structure [Amount of amino-modified siloxane compound having an aromatic azomethine in the molecular structure / Aromatic azomethine in the molecular structure] The primary amino group equivalent of the amino-modified siloxane compound is preferably in the range of 2.0 to 10.0 times. By setting it to 2.0 times or more, gelation and a decrease in heat resistance tend to be suppressed. Moreover, it exists in the tendency for the solubility to an organic solvent and the fall of heat resistance to be suppressed by setting it as 10.0 times or less.

  The amount of the component (C) used in the pre-reaction is, for example, 50 to 3000 masses with respect to 100 mass parts of the resin component of the amino-modified siloxane compound having an aromatic azomethine in the molecular structure while maintaining the above relationship. Part is preferable, and 100-1500 mass parts is more preferable. When the amount is 50 parts by mass or more, a decrease in heat resistance tends to be suppressed. Moreover, low thermal expansibility can be kept favorable by setting it as 3000 mass parts or less.

  In addition, a reaction catalyst can be optionally used for this pre-reaction. Examples thereof include amines such as triethylamine, pyridine, and tributylamine, imidazoles such as methylimidazole and phenylimidazole, phosphorus-based catalysts such as triphenylphosphine, and alkali metal amides such as lithium amide, sodium amide, and potassium amide. These can be used alone or in combination of two or more.

  Moreover, it is preferable that the usage-amount of the modified imide resin which has the aromatic azomethine obtained from the said pre-reaction is 50-100 mass parts per 100 mass parts of sum total of a resin component, for example, and 60-100 mass parts More preferably. By setting the blending amount of the modified imide resin having aromatic azomethine to 50 parts by mass or more, good low thermal expansibility and high elastic modulus can be obtained.

A thermosetting resin composition comprising the amino-modified siloxane compound having an aromatic azomethine of the present invention and a maleimide compound (C) having at least two N-substituted maleimide groups in one molecule, and The modified imide resin having an aromatic azomethine obtained by the reaction alone has good thermosetting reactivity, but if necessary, a curing agent and a radical initiator can be used in combination. By using a curing agent and a radical initiator, heat resistance, adhesiveness, and mechanical strength can be improved.
Examples of the curing agent used in combination include dicyandiamide, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-diethyl-diphenylmethane, 4,4′-diaminodiphenylsulfone, phenylenediamine, and xylenediamine. Aromatic amines such as hexamethylene diamine, and aliphatic amines such as 2,5-dimethylhexamethylene diamine, and guanamine compounds such as melamine and benzoguanamine. These may be used alone or in admixture of two or more.

  Examples of the radical initiator include organic peroxides such as acyl peroxides, hydroperoxides, ketone peroxides, organic peroxides having a t-butyl group, and peroxides having a cumyl group. Can be used. These may be used alone or in admixture of two or more. Among these, for example, aromatic amines are preferable from the viewpoint of good reactivity and heat resistance.

（式（１）中、Ｒ₁は各々独立に、酸性置換基である水酸基、カルボキシル基又はスルホン酸基を、Ｒ₂は各々独立に、水素原子、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子を示し、ｘは１〜５の整数、ｙは０〜４の整数で、且つｘとｙの和は５である。） Furthermore, the thermosetting resin composition of the present invention can contain an amine compound (D) having an acidic substituent represented by the following general formula (1).

(In formula (1), each R ₁ independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group which is an acidic substituent, and each R ₂ independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. Or a halogen atom, x is an integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5.)

  Examples of the amine compound (D) having an acidic substituent (hereinafter sometimes referred to as component (D)) include m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m -Aminobenzoic acid, o-aminobenzoic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline, etc. . Among these, for example, in terms of solubility and synthesis yield, m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, and 3,5- Dihydroxyaniline is preferred. Moreover, m-aminophenol and p-aminophenol are more preferable from the viewpoint of heat resistance.

  The amount of the component (D) used is, for example, preferably 0.5 to 30 parts by mass, and more preferably 1 to 20 parts by mass per 100 parts by mass of the total resin components, from the viewpoint of low thermal expansion. preferable

  The thermosetting resin composition of the present invention comprises an amino-modified siloxane compound having an aromatic azomethine in the molecular structure, component (C), and component (D). The compound is pre-reacted. It can also be used as a modified imide resin having an acidic substituent and an aromatic azomethine. By performing such a pre-reaction, the molecular weight can be controlled, and further low curing shrinkage and low thermal expansion can be improved.

In this pre-reaction, an amino-modified siloxane compound having aromatic azomethine in the molecular structure, component (C), and component (D) are reacted while being heated and kept in an organic solvent, thereby modifying a modified imide resin having an acidic substituent. It is preferable to synthesize.
The reaction temperature at the time of reacting the amino-modified siloxane compound having an aromatic azomethine in the molecular structure in the organic solvent, the component (C), and the component (D) is preferably 70 to 150 ° C., for example. More preferably, it is -130 degreeC. For example, the reaction time is preferably 0.1 to 10 hours, and more preferably 1 to 6 hours.

  In this pre-reaction, the amount of the component (C), the amino-modified siloxane compound having an aromatic azomethine in the molecular structure, and the amount of the component (D) is, for example, the number of maleimide groups in the component (C) [use of the component (C) Amino modified siloxane compound having aromatic azomethine in the molecular structure] and the number of primary amino groups in component (D) [amino modified siloxane compound having aromatic azomethine in the molecular structure] Used / primary amino group equivalent of amino-modified siloxane compound having aromatic azomethine in the molecular structure + used amount of component (D) / primary amino group equivalent of component (D)] to 2.0 to 10.0 times It is preferable to be in the range. By setting it to 2.0 times or more, gelation and a decrease in heat resistance tend to be suppressed. Moreover, it exists in the tendency for the solubility to an organic solvent and the fall of heat resistance to be suppressed by setting it as 10.0 times or less.

The amount of the component (C) used in the pre-reaction is, for example, 50 to 3000 masses with respect to 100 mass parts of the resin component of the amino-modified siloxane compound having an aromatic azomethine in the molecular structure while maintaining the above relationship. Part is preferable, and 100-1500 mass parts is more preferable. When the amount is 50 parts by mass or more, a decrease in heat resistance tends to be suppressed. Moreover, low thermal expansibility can be kept favorable by setting it as 3000 mass parts or less.
The amount of the component (D) used in the pre-reaction is, for example, preferably 1 to 1000 parts by weight, and 5 to 500 parts by weight with respect to 100 parts by weight of the resin component of the amino-modified siloxane compound having an aromatic azomethine in the molecular structure. Part is more preferred. When the content is 1 part by mass or more, a decrease in heat resistance tends to be suppressed. Moreover, low thermal expansibility can be kept favorable by setting it as 1000 mass parts or less.

  Examples of the organic solvent used in this pre-reaction include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and acetic acid. Ester solvents such as ethyl ester and γ-butyrolactone, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene and mesitylene, nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, dimethyl sulfoxide And sulfur atom-containing solvents such as These can be used alone or in combination of two or more.

  Among these organic solvents, for example, from the viewpoint of solubility, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, and γ-butyrolactone are preferable, because they are low in toxicity and highly volatile and hardly remain as residual solvents. Cyclohexanone, propylene glycol monomethyl ether, and dimethylacetamide are particularly preferable.

  The amount of the organic solvent used is, for example, 25 to 2000 with respect to 100 parts by mass of the total of the resin component of the amino-modified siloxane compound having an aromatic azomethine in the molecular structure, the component (C), and the component (D). It is preferable to set it as a mass part, It is more preferable to set it as 40-1000 mass parts, It is especially preferable to set it as 40-500 mass parts. When the amount of the organic solvent used is 25 parts by mass or more, insufficient solubility tends to be suppressed. In addition, when the amount is 2000 parts by mass or less, the reaction does not take a long time.

  In addition, a reaction catalyst can be optionally used for this pre-reaction. Examples of the reaction catalyst include amines such as triethylamine, pyridine, and tributylamine, imidazoles such as methylimidazole and phenylimidazole, phosphorus-based catalysts such as triphenylphosphine, and alkali metal amides such as lithium amide, sodium amide, and potassium amide. Etc. These can be used alone or in combination of two or more.

  Moreover, it is preferable that the usage-amount of the modified imide resin which has the acidic substituent obtained from the said pre reaction and aromatic azomethine is 50-100 mass parts per 100 mass parts of sum total of a resin component, for example. More preferably, it is 90 parts by mass. By setting the blending amount of the modified imide resin having an acidic substituent and aromatic azomethine to 50 parts by mass or more, low thermal expansibility and high elastic modulus can be obtained.

Obtained by pre-reacting an amino-modified siloxane compound having an aromatic azomethine in the molecular structure of the present invention, a thermosetting resin composition comprising component (C) and component (D), and the compound. A modified imide resin having an acidic substituent and an aromatic azomethine alone has good thermosetting reactivity, but if necessary, by using a curing agent and a radical initiator in combination, heat resistance, adhesiveness, and mechanical strength can be improved. Can be improved.
Examples of the curing agent used in combination include dicyandiamide, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-diethyl-diphenylmethane, 4,4′-diaminodiphenylsulfone, phenylenediamine, and xylenediamine. Aromatic amines such as hexamethylene diamine, and aliphatic amines such as 2,5-dimethylhexamethylene diamine, and guanamine compounds such as melamine and benzoguanamine.
Examples of the radical initiator include organic peroxides such as acyl peroxides, hydroperoxides, ketone peroxides, organic peroxides having a t-butyl group, and peroxides having a cumyl group. Can be used. These may be used alone or in admixture of two or more. Among these, for example, aromatic amines are preferable from the viewpoint of good reactivity and heat resistance.

Furthermore, the thermosetting resin composition of the present invention can contain a thermoplastic elastomer (E).
Examples of the thermoplastic elastomer (E) (hereinafter sometimes referred to as the component (E)) include, for example, a styrene elastomer, an olefin elastomer, a urethane elastomer, a polyester elastomer, a polyamide elastomer, an acrylic elastomer, and a silicone elastomer. Examples thereof include elastomers and derivatives thereof. These include a hard segment component and a soft segment component. In general, the former contributes to heat resistance and strength, and the latter contributes to flexibility and toughness. These can be used individually by 1 type or in mixture of 2 or more types.

  Moreover, what has a reactive functional group in a molecular terminal or a molecular chain can be used as these components (E). Examples of the reactive functional group include an epoxy group, a hydroxyl group, a carboxyl group, an amino group, an amide group, an isocyanato group, an acryl group, a methacryl group, and a vinyl group. By having these reactive functional groups in the molecular terminal or molecular chain, compatibility with the resin is improved, and internal stress generated during curing of the thermosetting resin composition of the present invention is more effectively reduced. As a result, it is possible to significantly reduce the warpage of the substrate.

  Among these components (E), for example, styrene elastomers, olefin elastomers, polyamide elastomers, and silicone elastomers are preferable from the viewpoint of heat resistance and insulation reliability, and styrene elastomers from the viewpoint of dielectric properties. And olefin-based elastomers are particularly preferred.

  Further, the reactive functional group possessed in the molecular terminal or molecular chain of these components (E) is preferably, for example, an epoxy group, a hydroxyl group, a carboxyl group, an amino group, and an amide group in terms of adhesion to the metal foil. In view of heat resistance and insulation reliability, an epoxy group, a hydroxyl group, and an amino group are particularly preferable.

  The amount of the component (E) used is, for example, preferably 0.1 to 50 parts by mass, and 2 to 30 parts by mass with respect to 100 parts by mass of the total resin components. It is more preferable because it can effectively exhibit low curing shrinkage, low thermal expansion, and excellent dielectric properties of the cured product.

Furthermore, the thermosetting resin composition of the present invention may contain at least one thermosetting resin (F) (hereinafter sometimes referred to as component (F)) selected from epoxy resins and cyanate resins. it can.
Examples of the component (F) epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, and bisphenol. F novolac type epoxy resin, stilbene type epoxy resin, triazine skeleton containing epoxy resin, fluorene skeleton containing epoxy resin, triphenolphenol methane type epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy Resin, dicyclopentadiene type epoxy resin, alicyclic epoxy resin, polyfunctional phenols and diglycidyl esters of polycyclic aromatics such as anthracene And phosphorus-containing epoxy resin obtained by introducing a phosphorus compounds ether compounds and to these. These may be used alone or in admixture of two or more. Among these, for example, biphenyl aralkyl type epoxy resins and naphthalene type epoxy resins are preferable from the viewpoint of heat resistance and flame retardancy.

  Examples of the cyanate resin of component (F) include bisphenol type cyanate resins such as novolak type cyanate resin, bisphenol A type cyanate resin, bisphenol E type cyanate resin, tetramethylbisphenol F type cyanate resin, and some of these are triazines. The prepolymer etc. which were formed can be mentioned, These may be used individually or in mixture of 2 or more types. Among these, for example, a novolac type cyanate resin is preferable from the viewpoint of heat resistance and flame retardancy.

  A curing agent can be used for these components (F) as needed. Examples of the curing agent include polyfunctional phenol compounds such as phenol novolak, cresol novolak, and aminotriazine novolak resin; amine compounds such as dicyandiamide, diaminodiphenylmethane, and diaminodiphenylsulfone; phthalic anhydride, pyromellitic anhydride, maleic anhydride, Examples thereof include acid anhydrides such as maleic anhydride copolymers. These 1 type can be used individually or in mixture of 2 or more types.

  As a usage-amount of a component (F), it is preferable to set it as 0-50 mass parts per 100 mass parts of total of a resin component, for example, and it is 10-30 mass parts from the point of heat resistance and chemical resistance. Is more preferable.

  The thermosetting resin composition of the present invention can contain an inorganic filler (G) (hereinafter sometimes referred to as component (G)). Examples of the component (G) include silica, alumina, talc, mica, kaolin, aluminum hydroxide, boehmite, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide, titanium oxide, boron nitride, calcium carbonate, sulfuric acid. Examples thereof include glass powder such as barium, aluminum borate, potassium titanate, E glass, T glass, and D glass, and hollow glass beads. These may be used alone or in admixture of two or more.

  As the component (G), for example, silica is particularly preferable from the viewpoint of dielectric properties, heat resistance, and low thermal expansion. Examples of the silica include precipitated silica produced by a wet method and having a high water content, and dry method silica produced by a dry method and containing almost no bound water. Examples of the dry process silica include crushed silica, fumed silica, fused spherical silica and the like depending on the production method. Among these, fused spherical silica is preferable because of its low thermal expansion and high fluidity when filled in a resin.

  When using fused spherical silica as the component (G), for example, the average particle size is preferably 0.1 to 10 μm, and more preferably 0.3 to 8 μm. By setting the average particle diameter of the fused spherical silica to 0.1 μm or more, the fluidity when the resin is highly filled can be kept good, and by setting it to 10 μm or less, the mixing probability of coarse particles is reduced. Generation of defects due to coarse particles can be suppressed. Here, the average particle diameter is the particle diameter at a point corresponding to a volume of 50% when the cumulative frequency distribution curve by the particle diameter is obtained with the total volume of the particles as 100%, and the laser diffraction scattering method is used. It can be measured with a particle size distribution measuring device.

The content of the component (G) is, for example, preferably 20 to 500 parts by mass, and more preferably 50 to 350 parts by mass with respect to 100 parts by mass of the total resin components. By making content of a component (G) into 20-500 mass parts with respect to 100 mass parts of sum total of a resin component, the moldability and low thermal expansibility of a resin composition can be kept favorable.
In addition, when the component (G) is blended into the resin composition, for example, the component (G) is pretreated with a silane or titanate coupling agent, a surface treatment agent such as a silicone oligomer, or an integral blend treatment. You may do.

The thermosetting resin composition of the present invention can contain a curing accelerator (H). Examples of the curing accelerator (hereinafter sometimes referred to as component (H)) include zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, bisacetylacetonate cobalt (II), and trisacetylacetonate. And organometallic salts such as cobalt (III), imidazoles and derivatives thereof, organophosphorus compounds such as phosphines and phosphonium salts, secondary amines, tertiary amines, and quaternary ammonium salts. . These 1 type can be used individually or in mixture of 2 or more types.
Among these, for example, zinc naphthenate, imidazole derivatives, and phosphonium salts are preferable from the viewpoint of the promoting effect and storage stability.

  The content of the component (H) is, for example, preferably 0.01 to 3.0 parts by mass and more preferably 0.05 to 2.0 parts by mass with respect to 100 parts by mass of the total resin components. preferable. By setting the content of the component (H) to 0.01 to 3.0 parts by mass with respect to 100 parts by mass of the total of the resin components, the acceleration effect and the storage stability can be kept good.

  In the present invention, any known thermoplastic resin, organic filler, flame retardant, ultraviolet absorber, antioxidant, photopolymerization initiator, fluorescent whitening agent, and adhesion improver may be used without departing from the object. Etc. can be used.

  Examples of the thermoplastic resin include polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyimide resin, xylene resin, petroleum resin, and silicone resin.

  Examples of the organic filler include a resin filler made of polyethylene, polypropylene, polystyrene, polyphenylene ether resin, silicone resin, tetrafluoroethylene resin, acrylate ester resin, methacrylate ester resin, conjugated diene resin, and the like. Examples thereof include a resin filler having a core-shell structure having a rubbery core layer and a glassy shell layer made of an acrylic ester resin, a methacrylic ester resin, an aromatic vinyl resin, a vinyl cyanide resin, or the like.

  Examples of the flame retardant include halogen-containing flame retardants containing bromine and chlorine, triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphoric ester compounds, phosphorous flame retardants such as red phosphorus, sulfamic acid Nitrogen flame retardants such as guanidine, melamine sulfate, melamine polyphosphate and melamine cyanurate, phosphazene flame retardants such as cyclophosphazene and polyphosphazene, and inorganic flame retardants such as antimony trioxide.

  Other examples of UV absorbers include benzotriazole UV absorbers, examples of antioxidants include hindered phenols and hindered amines, and examples of photopolymerization initiators include benzophenones, benzyl ketals, and thioxanthone. Examples of photopolymerization initiators and fluorescent brighteners include stilbene derivative fluorescent brighteners, and adhesion improvers such as urea compounds such as urea silane and silane, titanate and aluminate cups. A ring agent is mentioned.

  Since the thermosetting resin composition containing an amino-modified siloxane compound having an aromatic azomethine in the molecular structure of the present invention is used for a prepreg, each component is finally dissolved or dispersed in an organic solvent. A varnish is preferred.

Examples of the organic solvent used here include alcohol solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and butyl acetate. , Ester solvents such as propylene glycol monomethyl ether acetate, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene and mesitylene, nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, dimethyl sulfoxide And a sulfur atom-containing solvent. These can be used individually by 1 type or in mixture of 2 or more types.
Among these, for example, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl cellosolve, and propylene glycol monomethyl ether are preferable from the viewpoint of solubility, and methyl isobutyl ketone, cyclohexanone, and propylene glycol monomethyl ether are more preferable from the viewpoint of low toxicity.

The resin composition in the varnish finally obtained is, for example, preferably 40 to 90% by mass and more preferably 50 to 80% by mass with respect to the entire varnish. By setting the content of the resin composition in the varnish to 40 to 90% by mass, it is possible to maintain good coatability and obtain a prepreg having an appropriate resin composition adhesion amount.
Here, in this specification, “resin component” means an amino-modified siloxane compound, a modified imide resin (having an acidic substituent derived from the acidic substituent of the amine compound (D) represented by the general formula (1) described above). Modified imide resin), component (A), component (B), maleimide compound (C), amine compound (D) having an acidic substituent, thermoplastic elastomer (E), thermosetting resin (F), and These reaction products are referred to. The “thermosetting resin composition” refers to a resin component containing an inorganic filler and a curing accelerator.

(Prepreg)
The prepreg of the present invention is obtained by impregnating a base material with the above-described thermosetting resin composition of the present invention. Hereinafter, the prepreg of the present invention will be described in detail.
The prepreg of the present invention can be produced by impregnating the thermosetting resin composition of the present invention into a substrate and semi-curing (B-stage) by heating or the like. Although it does not specifically limit as a method to make a base material impregnate the thermosetting resin composition of this invention, For example, the method of immersing a base material in a resin varnish, the method of apply | coating with various coaters, the method of spraying, etc. are mentioned. Among these, the method of immersing the base material in the resin varnish is preferable. Thereby, the impregnation property of the resin composition with respect to a base material can be improved.
As a base material of this invention, the well-known thing used for the laminated board for various electrical insulation materials can be used, for example. Examples of the material include inorganic fibers such as E glass, D glass, S glass and Q glass, organic fibers such as polyimide, polyester and tetrafluoroethylene, and mixtures thereof. In other applications, for example, carbon fiber or the like can be used in the case of a fiber reinforced base material.

  These base materials have, for example, the shapes of woven fabric, non-woven fabric, robink, chopped strand mat and surfacing mat, and the material and shape are selected depending on the intended use and performance of the molded product, and if necessary, can be used alone. Alternatively, two or more kinds of materials and shapes can be combined. The thickness of the substrate can be, for example, about 0.03 to 0.5 mm, and the surface treated with a silane coupling agent or the like or mechanically subjected to a fiber opening treatment has heat resistance and It is suitable in terms of moisture resistance and processability.

  For example, the prepreg of the present invention is impregnated into the base material so that the amount of the resin composition attached to the base material is 20 to 90% by mass in terms of the content of the thermosetting resin composition of the prepreg after drying. Or after application | coating, it can heat-dry normally for 1 to 30 minutes at the temperature of 100-200 degreeC, and can be obtained by making it semi-cure (B-stage).

(Film with resin)
The film with a resin of the present invention is obtained by forming a layer of the thermosetting resin composition of the present invention on a support. Although it does not specifically limit as a method of carrying out layer formation of the thermosetting resin composition obtained by this invention on a support body, For example, the thermosetting resin composition obtained by this invention is made into a varnish state, and various coaters are used. The resin composition layer can be formed by applying to a support and further drying by heating or blowing hot air. Thus, the film with a resin of the present invention can be produced by being semi-cured (B-stage) by heating or the like. This semi-cured state is a state in which the adhesive force between the resin composition layer of the resin-coated film and the circuit board is secured when the film with resin and the circuit board are laminated and cured, and embedded in the circuit board. It is preferable that the property (fluidity) is ensured.
The coater used when the thermosetting resin composition of the present invention is applied on a support is not particularly limited, and for example, a die coater, a comma coater, a bar coater, a kiss coater, a roll coater, etc. can be used. . These can be appropriately selected depending on the thickness of the resin composition layer. As a drying method, heating, hot air blowing, or the like can be used.

  The drying conditions after applying the thermosetting resin composition to the support are, for example, such that the content of the organic solvent in the resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. dry. Depending on the amount of organic solvent in the varnish and the boiling point of the organic solvent, for example, a resin composition layer is formed by drying a varnish containing 30 to 60% by mass of an organic solvent at 50 to 150 ° C. for about 3 to 10 minutes. Is done. It is preferable to set suitable drying conditions as appropriate by simple experiments in advance.

  The thickness of the resin composition layer formed in the resin-attached film is usually not less than the thickness of the conductor layer that the circuit board has. The thickness of the conductor layer is preferably, for example, 5 to 70 μm, more preferably 5 to 50 μm, and particularly preferably 5 to 30 μm for reducing the thickness of the multilayer printed wiring board.

  The support in the film with resin is made of, for example, polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyesters such as polyethylene naphthalate, polycarbonate, polyimide, and the like. Examples of the film include metal foil such as release paper, copper foil, and aluminum foil. In addition, you may give a mold release process etc. to a support body and the protective film mentioned later other than a mat | matte process and a corona treatment, for example.

  For example, the thickness of the support is preferably 10 to 150 μm, more preferably 25 to 50 μm. A protective film can be further laminated on the surface of the resin composition layer on which the support is not provided. The thickness of the protective film is, for example, 1 to 40 μm. By laminating the protective film, foreign matter can be prevented from being mixed, and the film with resin can be wound into a roll and stored.

(Laminated board)
The laminate of the present invention is obtained by laminating the above-mentioned film with resin. For example, it can be manufactured by laminating a film with a resin on one side or both sides of a circuit board, a prepreg, a base material and the like using a vacuum laminator and curing by heating as necessary. Examples of the substrate used for the circuit substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. In addition, a circuit board means here that the circuit pattern was formed in the one or both surfaces of the above boards. In addition, a printed wiring board in which a plurality of conductor layers and insulating layers are alternately laminated and having a circuit pattern formed on one side or both sides of the outermost layer of the printed wiring board is also included in the circuit board here. The surface of the conductor layer may be subjected to a roughening process in advance by a blackening process or the like.

  In the above laminate, if the film with resin has a protective film, after removing the protective film, preheat the film with resin and the circuit board as necessary, while pressing and heating the film with resin Crimp to circuit board. In the film with resin of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is suitably used. Lamination conditions are, for example, that the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C., the pressure bonding pressure is preferably 0.1 to 1.1 MPa, and the lamination is performed under a reduced pressure of 20 mmHg (26.7 hPa) or less. preferable. The laminating method may be a batch method or a continuous method using a roll.

  After laminating the resin-coated film on the circuit board and cooling it to around room temperature, when peeling the support, the resin composition layer is heat-cured after peeling the support (hereinafter, after heat-curing) The resin composition layer may be referred to as an insulating layer). The conditions for thermosetting may be appropriately selected according to the type and content of the resin component in the resin composition, but are preferably 150 to 220 ° C. for 20 to 180 minutes, more preferably 160 to 200 ° C. It is selected in the range of 30 to 120 minutes at ° C. Moreover, you may peel a support body, after thermosetting a resin composition layer.

  Next, if necessary, holes are formed in the insulating layer formed on the circuit board to form via holes and through holes. Drilling can be performed, for example, by a known method such as drilling, laser, or plasma, or a combination of these methods as necessary. For example, drilling by a laser such as a carbon dioxide laser or a YAG laser is the most common. Is the method.

  Next, a conductor layer is formed on the insulating layer by dry plating or wet plating. 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, the surface of the hardened insulating layer is first oxidized with permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid, etc. Roughening treatment is performed with an agent to form uneven anchors. As the oxidizing agent, an aqueous sodium hydroxide solution (alkaline permanganate aqueous solution) such as potassium permanganate and sodium permanganate is particularly preferably used. Next, a conductor layer is formed by a method combining electroless plating and electrolytic plating. Alternatively, a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating. As a subsequent pattern formation method, for example, a known subtractive method or semi-additive method can be used.

The laminate of the present invention is obtained by laminating the above-described prepreg of the present invention. The prepreg of the present invention can be produced, for example, by laminating 1 to 20 sheets and laminating with a configuration in which a metal foil such as copper or aluminum is disposed on one or both sides thereof.
The molding conditions for laminating the laminate can be, for example, the method of a laminate for an electrical insulating material and a multilayer plate, for example, using a multistage press, a multistage vacuum press, continuous molding, an autoclave molding machine, etc. It can be molded in a range of ˜250 ° C., a pressure of 0.2 to 10 MPa, and a heating time of 0.1 to 5 hours. Further, the prepreg of the present invention and the inner layer wiring board can be combined and laminated to produce a laminated board.

(Multilayer printed wiring board)
The multilayer printed wiring board of this invention is manufactured using the said laminated board. For example, the circuit board can be obtained by wiring processing the conductor layer of the laminate of the present invention by an ordinary etching method. Then, a plurality of laminated boards processed by wiring through the above-described prepreg are laminated and subjected to hot press processing to be multi-layered at once. Thereafter, a multilayer printed wiring board can be manufactured through formation of through holes or blind via holes by drilling, laser processing, etc., and formation of interlayer wiring by plating or conductive paste.

(Semiconductor package)
The semiconductor package of the present invention is obtained by mounting a semiconductor element on the multilayer printed wiring board. The semiconductor package of the present invention is manufactured by mounting a semiconductor element such as a semiconductor chip or a memory at a predetermined position of the printed wiring board.

Next, the present invention will be described in more detail with reference to the following examples, but these examples do not limit the present invention.
In addition, it measured by the following method about the cure shrinkage rate using the resin plate obtained in each Example and Comparative Example, and further using a copper-clad laminate, the glass transition temperature, the thermal expansion coefficient, the copper foil adhesiveness, The solder heat resistance with copper, the flexural modulus, and the dielectric properties were measured and evaluated by the following methods.

(1) Measurement of curing shrinkage rate of resin plate A 5 mm square (thickness 1 mm) resin plate was produced, and thermomechanical analysis was performed by a compression method using a TMA test apparatus (TA Instruments, Q400). . After mounting the resin plate in the Z direction on the device, load 5g, temperature increase rate 45 ° C / min, temperature profile from 20 ° C (5 min hold) to 260 ° C (2 min hold) to 20 ° C (5 min hold) Measured at The cure shrinkage rate of the resin plate was evaluated from the initial dimension of the resin plate and the dimensional change at 20 ° C. before starting the temperature increase and 20 ° C. after the temperature increase.
Specifically, the curing shrinkage rate of the resin plate was calculated using the following formula.
Curing shrinkage rate (%) = [(20 ° C. before starting temperature rise (mm) −20 ° C. after temperature raising (mm)) / 20 ° C. before temperature rising (mm)] × 100

(2) Measurement of glass transition temperature (Tg) A 5-mm square evaluation board from which copper foil was removed by immersing a copper-clad laminate in a copper etching solution was prepared, and a TMA test apparatus (TA Instruments, Q400) was prepared. ) Was used for thermomechanical analysis by the compression method. After mounting the evaluation substrate on the apparatus in the Z direction, the measurement substrate was measured twice continuously under the measurement conditions of a load of 5 g and a heating rate of 10 ° C./min. The Tg indicated by the intersection of tangents with different thermal expansion curves in the second measurement was determined, and the heat resistance was evaluated.

(3) Measurement of coefficient of thermal expansion A 5-mm square evaluation board from which copper foil was removed by immersing a copper clad laminate in a copper etching solution was prepared, and a TMA test apparatus (TA Instruments, Q400) was used. The thermomechanical analysis was performed by the compression method. After mounting the evaluation substrate on the apparatus in the X direction, the measurement substrate was measured twice continuously under the measurement conditions of a load of 5 g and a heating rate of 10 ° C./min. The average coefficient of thermal expansion from 30 ° C. to 100 ° C. in the second measurement was calculated and used as the value of the coefficient of thermal expansion.

(4) Evaluation of copper foil adhesion (copper foil peel strength) A copper-clad laminate is immersed in a copper etching solution to form a copper foil having a width of 3 mm to produce an evaluation substrate, and copper is tested using a tensile tester. The adhesion (peel strength) of the foil was measured.

(5) Evaluation of solder heat resistance with copper Solder heat resistance with copper by preparing a 25 mm square evaluation board from a copper clad laminate, floating the evaluation board in a solder bath at a temperature of 288 ° C. for 120 minutes, and observing the appearance Sex was evaluated.

(6) A bending elastic modulus copper-clad laminate was immersed in a copper etching solution to prepare a 25 mm × 50 mm evaluation board from which the copper foil was removed, and a 5-ton tensilon manufactured by Orientec Co., Ltd. was used, and the crosshead speed was 1 mm / min. Measured at a span distance of 20 mm.

(7) Dielectric properties (dielectric constant and dielectric loss tangent)
A 100 mm × 2 mm evaluation board from which copper foil was removed by immersing a copper clad laminate in a copper etching solution was used, and a cavity resonator device (manufactured by Kanto Electronics Application Development Co., Ltd.) was used to obtain a ratio at a frequency of 1 GHz. The dielectric constant and dielectric loss tangent were measured.

Production Example 1: Production of amino-modified siloxane compound (I-1) having aromatic azomethine In a reaction vessel having a volume of 2 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. Terephthalaldehyde: 5.2 g, X-22-161A (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), a siloxane compound having at least two primary amino groups at the molecular terminals: 24.8 g, propylene glycol monomethyl ether: 45 0.0 g was added, reacted at 115 ° C. for 4 hours, then heated to 130 ° C., dehydrated by atmospheric concentration, and a modified siloxane compound-containing solution having at least one aldehyde group in one molecule (resin component: 60 Mass%).
Next, bis (4- (4-aminophenoxy) phenyl) propane: 13.0 g and propylene glycol monomethyl ether: 44.4 g were added to the reaction solution, reacted at 115 ° C. for 4 hours, and then raised to 130 ° C. It dehydrated by warming and concentrating at atmospheric pressure to obtain a modified siloxane compound (I-1) -containing solution having an aromatic azomethine in the molecular structure (Mw: 11000, resin component: 90% by mass).

Production Example 2: Production of amino-modified siloxane compound (I-2) having aromatic azomethine In a reaction vessel having a volume of 2 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. Terephthalaldehyde: 3.0 g, X-22-161B [manufactured by Shin-Etsu Chemical Co., Ltd., trade name]: 27.0 g, propylene glycol monomethyl ether: 45.0 g were added and reacted at 115 ° C. for 4 hours, then 130 ° C. The solution was heated up to atmospheric pressure and dehydrated by atmospheric concentration to obtain a modified siloxane compound-containing solution (resin component: 60% by mass) having at least one aldehyde group in one molecule.
Next, 4.6 g of 3,3′-diethyl-4,4′-diaminodiphenylmethane and 31.9 g of propylene glycol monomethyl ether are added to the reaction solution and reacted at 115 ° C. for 4 hours, and then to 130 ° C. The temperature was raised and dehydration was performed by concentration under normal pressure to obtain a modified siloxane compound (I-2) -containing solution (Mw: 18000, resin component: 90% by mass) having an aromatic azomethine in the molecular structure.

Production Example 3 Production of Modified Imide Resin (J-1) Having Aromatic Azomethine In a reaction vessel having a volume of 2 liters that can be heated and cooled with a thermometer, a stirrer, and a moisture meter with a reflux condenser, 1 Modified siloxane compound (I-2) -containing solution having at least one aromatic azomethine in the molecule (resin component: 90% by mass): 62.5 g, 2,2-bis (4- (4-maleimidophenoxy) phenyl ) Propane: 243.8 g and propylene glycol monomethyl ether: 443.8 g were added, reacted at 115 ° C. for 4 hours, then heated to 130 ° C. and concentrated at normal pressure, and modified imide resin having aromatic azomethine (J- 1) A containing solution (Mw: 6000, resin component: 60% by mass) was obtained.

Production Example 4: Production of Modified Imide Resin (K-1) Having Acidic Substituent and Aromatic Azomethine Reaction of 2 liters in volume capable of heating and cooling with thermometer, stirrer, moisture meter with reflux condenser In a container, a solution containing a modified siloxane compound (I-2) having at least one aromatic azomethine in one molecule (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: 443.8 g, reacted at 115 ° C. for 4 hours, then heated to 130 ° C. and concentrated at atmospheric pressure Then, a modified imide resin (K-1) -containing solution having an acidic substituent and an aromatic azomethine (Mw: 5000, resin component: 60% by mass) was obtained.

Examples 1-18 and Comparative Examples 1-6
Amino-modified siloxane compound-containing solution (I-1, I-2) having an aromatic azomethine obtained in Production Examples 1 and 2, and a modified imide resin-containing solution having an aromatic azomethine obtained in Production Example 3 ( Modified imide resin-containing solution (K-1) having an acidic substituent and an aromatic azomethine obtained in J-1) and Production Example 4, and the following siloxane compound (i) and aromatic aldehyde compound (ii) , Aromatic amine compound (B), maleimide compound (C), amine compound (D) having an acidic substituent, thermoplastic elastomer (E), thermosetting resin (F), inorganic filler (G), curing acceleration Using methyl ethyl ketone as the agent (H) and the diluting solvent, mixing was performed at the blending ratio (parts by mass) shown in Tables 1 to 4 to obtain a varnish having a resin content of 65% by mass.
Next, the varnish was applied to a 16 μm polyethylene terephthalate film using a film applicator (PI-1210, manufactured by Tester Sangyo Co., Ltd.) so that the resin thickness after drying was 35 μm, and then at 160 ° C. for 10 minutes. Heat drying was performed to obtain a semi-cured resin powder. In this case, the support is not particularly limited, and a general-purpose one can be used. Also, the application method is not particularly limited, and may be applied using an ordinary desktop coater.
This resin powder is put into a form of Teflon sheet, the glossy surface of 12 μm electrolytic copper foil is placed up and down, pressed at a pressure of 2.0 MPa and a temperature of 240 ° C. for 60 minutes, and then the electrolytic copper foil is removed. A resin plate was obtained.
The varnish was impregnated with 0.1 mm thick E glass cloth and dried by heating at 160 ° C. for 10 minutes to obtain a prepreg having a resin content of 48 mass%.
Four prepregs were stacked, 12 μm electrolytic copper foils were placed one above the other, and pressed at a pressure of 3.0 MPa and a temperature of 240 ° C. for 60 minutes to obtain a copper-clad laminate.
Tables 1 to 4 show the measurement and evaluation results of the obtained resin plates and copper clad laminates.

Siloxane compound (i)
X-22-161B: terminal amino-modified siloxane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name]

Aromatic aldehyde compounds (ii)
・ TPAL: terephthalaldehyde (trade name, manufactured by Toray Fine Chemical Co., Ltd.)

Aromatic amine compound (B)
KAYAHARD AA: 3,3′-diethyl-4,4′-diaminodiphenylmethane [manufactured by Nippon Kayaku Co., Ltd., trade name]

Maleimide compound (C)
-BMI: Bis (4-maleimidophenyl) methane (trade name, manufactured by Kay Kasei Co., Ltd.)
BMI-4000: 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane (trade name, manufactured by Daiwa Kasei Kogyo Co., Ltd.)

Amine compound having acidic substituent (D)
・ P-Aminophenol (trade name, manufactured by Kanto Chemical Co., Inc.)

Thermoplastic elastomer (E)
・ Tuftec H1043: Hydrogenated styrene-butadiene copolymer resin (trade name, manufactured by Asahi Kasei Chemicals Corporation)
・ Epofriend CT-310: Epoxy-modified styrene-butadiene copolymer resin (trade name, manufactured by Daicel Corporation)

Thermosetting resin (F)
PT-30: Novolac-type cyanate resin [Lonza Japan Co., Ltd., trade name]
NC-7000L: α-naphthol / cresol novolac type epoxy resin (product name, manufactured by Nippon Kayaku Co., Ltd.)

Inorganic filler (G)
SC2050-KNK: fused silica [manufactured by Admatechs, trade name]
・ Zinc molybdate [manufactured by Sherwin Williams, trade name: KEMGARD1100]

Curing accelerator (H)
・ Zinc (II) naphthenate 8% mineral spirit solution [Tokyo Chemical Industry Co., Ltd., trade name]
G-8809L: Isocyanate mask imidazole [Daiichi Kogyo Seiyaku Co., Ltd., trade name]
・ TPP-MK: Tetraphenylphosphonium tetra-p-tolylborate [made by Hokuko Chemical Co., Ltd., trade name]

Hereinafter, the modified siloxane compound-containing solutions (I-1) and (I-2) having aromatic azomethines in Tables 1 to 4, the modified imide resin-containing solution (J-1) having aromatic azomethines, and acidic substituents The compounding amount (part by mass) of the modified imide resin-containing solution (K-1) having an aromatic azomethine indicates a value in terms of solid content of the resin component.

As is apparent from Tables 1 to 4, in the examples of the present invention, the curing shrinkage rate of the resin plate is small and excellent in low cure shrinkage, and also in the characteristics of the laminated plate, the thermal expansion rate, the copper foil Excellent adhesion, elastic modulus and dielectric properties.
On the other hand, the comparative example has a large curing shrinkage rate of the resin plate, and also in the characteristics of the laminated plate, the thermal expansion coefficient, the copper foil adhesiveness, the elastic modulus, and the dielectric characteristics are any of the characteristics. Inferior.

  A prepreg obtained by impregnating or coating a substrate with a modified imide resin using an amino-modified siloxane compound having an aromatic azomethine of the present invention or a thermosetting resin composition containing an amino-modified siloxane compound Film with resin obtained by coating on the body, and laminate produced by laminating the prepreg, especially low cure shrinkage, low thermal expansion, copper foil adhesion, high elastic modulus, excellent dielectric properties And is useful as a highly integrated semiconductor package and multilayer printed wiring board for electronic devices.

Claims (15)

  Siloxane compound (i) having at least two primary amino groups at the molecular terminals (1), obtained by reacting aromatic aldehyde compound (ii) having at least two aldehyde groups in one molecule, at least one in one molecule Amino having aromatic azomethine in the molecular structure obtained by reacting modified siloxane compound (A) having one aldehyde group with aromatic amine compound (B) having at least two primary amino groups in one molecule Modified siloxane compound.   A modified imide resin having an aromatic azomethine obtained by reacting the amino-modified siloxane compound according to claim 1 with a maleimide compound (C) having at least two N-substituted maleimide groups in one molecule. The modified imide resin according to claim 2, further comprising an acidic substituent, wherein the acidic substituent is derived from the acidic substituent of the amine compound (D) represented by the following general formula (1).

(In formula (1), each R ₁ independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group which is an acidic substituent, and each R ₂ independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. Or a halogen atom, x is an integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5.)   A thermosetting resin composition comprising the amino-modified siloxane compound having an aromatic azomethine according to claim 1 and a maleimide compound (C) having at least two N-substituted maleimide groups in one molecule. Furthermore, the thermosetting resin composition of Claim 4 containing the amine compound (D) which has an acidic substituent shown to following General formula (1).

(In formula (1), each R ₁ independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group which is an acidic substituent, and each R ₂ independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. Or a halogen atom, x is an integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5.)   Furthermore, the thermosetting resin composition of Claim 4 or 5 containing a thermoplastic elastomer (E).   Furthermore, the thermosetting resin composition of any one of Claims 4-6 containing the at least 1 type of thermosetting resin (F) chosen from the epoxy resin and cyanate resin.   Furthermore, the thermosetting resin composition of any one of Claims 4-7 containing an inorganic filler (G).   Furthermore, the thermosetting resin composition of any one of Claims 4-8 containing a hardening accelerator (H).   A prepreg obtained by impregnating a base material with the thermosetting resin composition according to any one of claims 4 to 9.   The film with a resin formed by layer-forming the thermosetting resin composition of any one of Claims 4-9 on a support body.   A laminate obtained by laminating the prepreg according to claim 10.   A laminate obtained by laminating the film with resin according to claim 11.   The multilayer printed wiring board manufactured using the laminated board of Claim 12 or 13.   A semiconductor package comprising a semiconductor element mounted on the multilayer printed wiring board according to claim 14.