JP5339146B2 - Epoxy resin composition, cured product thereof, circuit board, build-up material, and semiconductor sealing material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide: an epoxy resin composition having flame-retardance of UL 94V-0 rating, moisture-resistant reliability and heat-resistant reliability; its cured product; a circuit board using the composition; a build-up material; a semiconductor sealing material; and a new epoxy resin giving those characteristics. <P>SOLUTION: This epoxy resin composition includes an epoxy resin, as a base resin, having a molecular structure obtained by reacting an epoxy resin (a1) with an active hydrogen atom-containing aromatic phosphine compound (a2). In the composition, the epoxy resin (a1) has each structural site of: a glycidyloxy group-containing aromatic hydrocarbon group (E); an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (X); and a divalent hydrocarbon group (Y) selected from among a methylene group, alkylidene group and aromatic hydrocarbon structure-containing methylene group. In addition, the epoxy resin (a1) has a structure in which the (E) and the (X) is bonded through the (Y) in its molecular structure. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

The cured product obtained in the present invention is excellent in flame retardancy and heat resistance reliability, circuit board (laminated board, printed wiring board, build-up substrate, flexible wiring board), semiconductor sealing material, resist ink material, underfill It can be suitably used for liquid sealing materials such as adhesives, adhesives such as conductive paste, liquid crystal sealing materials, flexible substrate coverlays, composite materials (carbon fiber reinforced plastics), optical materials, paints, casting applications, etc. The present invention relates to an epoxy resin composition and a novel epoxy resin.

Epoxy resin compositions containing an epoxy resin and its curing agent as essential components are excellent in various properties such as electrical insulation, high heat resistance, moisture resistance, and dimensional stability. Substrates, electronic components such as resist ink, conductive adhesives such as conductive paste and other adhesives, liquid sealing materials such as underfill, liquid crystal sealing materials, flexible substrate coverlays, matrix for composite materials, paints, photoresists Widely used in materials and color developing materials. Among these, in the field of electronic materials such as semiconductors and printed wiring boards, they are used as sealing materials and substrate materials, and the demand for higher performance is increasing with technological innovation in these fields.

  For example, from the viewpoint of preventing fire and fire and maintaining safety, such as semiconductor sealing materials used in electrical and electronic equipment, circuit boards (laminates, printed wiring boards, build-up substrates, flexible wiring boards) Flame resistance is required for electronic and electrical fields. In order to ensure this flame retardancy, generally, a flame retardant containing a halogen element, particularly a brominated flame retardant has been used. However, from the viewpoint of the recent conservation and prevention of deterioration of the global environment, a technology for making flame retardant without containing halogen elements that may generate highly toxic dioxins, benzofuran, etc. is essential.

  Epoxy resins are often used for the above-mentioned electronic and electrical materials. However, since epoxy resins are generally flammable, it is difficult to achieve UL94V-0 class flame retardancy. And phosphate esters such as cresyl diphenyl phosphate have been used as flame retardants.

  However, when these phosphoric acid esters are added to an epoxy resin or the like, there has been a drawback that the glass transition point of the resin is significantly lowered due to the plasticity of these compounds. In addition, since the phosphate esters do not form a covalent bond with the skeleton of the epoxy resin, and the interaction between the phosphorus compounds is larger than the interaction between the phosphorus compound and the resin skeleton, these phosphate esters are used as resins. When a prepreg was prepared by adding to the prepreg, the phosphoric acid esters easily crystallized after a certain period of time and deposited on the surface of the prepreg, so that there was a problem that they could not be used. Furthermore, since phosphorus compounds are easily hydrolyzed, when compounded in a large amount, they easily dissolve in chemicals used in the printed wiring board manufacturing process (mainly alkaline solutions), and those that cause a decrease in moisture resistance and heat resistance. There was also a problem that there were many.

  Therefore, a technique using a phosphorus-containing epoxy resin obtained by reacting a novolac-type epoxy resin and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide as a main component of an epoxy resin composition has been known. (See Patent Document 1 below).

  However, although this phosphorus-containing epoxy resin exhibits UL94V-0 class flame retardancy, the improvement effect of moisture resistance reliability and heat resistance reliability is not sufficient, and it has not been particularly applicable to recent lead-free solder.

Japanese Patent No. 3613724

  Therefore, the problem to be solved by the present invention is that an epoxy resin composition, cured product, circuit board using the composition, and build-up having UL94V-0 class flame retardancy, moisture resistance reliability and heat resistance reliability. It is an object of the present invention to provide a material, a semiconductor sealing material, and a novel epoxy resin that provides these performances.

  As a result of intensive investigations to solve the above problems, the inventors of the present invention are based on an epoxy resin obtained by reacting an epoxy resin having a specific structure having an alkoxy group-containing condensed polycyclic structure with an active hydrogen atom-containing aromatic phosphine compound. As a result, it was found that a cured product having flame retardancy, moisture resistance reliability and heat resistance reliability was obtained, and the present invention was completed.

That is, the present invention is an epoxy resin composition comprising an epoxy resin (A) and a curing agent (B) as essential components,
The epoxy resin (A) is
Glycidyloxy group-containing aromatic hydrocarbon group (E),
An alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (X), and
Each structural site of a divalent hydrocarbon group (Y) selected from a methylene group, an alkylidene group, and an aromatic hydrocarbon structure-containing methylene group, and
The glycidyloxy group-containing aromatic hydrocarbon group (E) and the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (X) are selected from the methylene group, the alkylidene group, and the aromatic hydrocarbon structure-containing methylene group. An epoxy resin (a1) having a structure bonded through a divalent hydrocarbon group (Y) in the molecular structure;
The present invention relates to an epoxy resin composition characterized by being an epoxy resin having a molecular structure obtained by reacting an active hydrogen atom-containing aromatic phosphine compound (a2).

  The present invention further relates to a cured product obtained by curing the epoxy resin composition.

  The present invention further relates to a circuit board characterized by using the epoxy resin composition.

  The present invention further relates to a build-up material characterized by using the epoxy resin composition.

  The present invention further relates to a semiconductor sealing material using the epoxy resin composition.

The present invention further includes a glycidyloxy group-containing aromatic hydrocarbon group (E),
An alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (X), and
Each structural site of a divalent hydrocarbon group (Y) selected from a methylene group, an alkylidene group, and an aromatic hydrocarbon structure-containing methylene group, and
The glycidyloxy group-containing aromatic hydrocarbon group (E) and the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (X) are selected from the methylene group, the alkylidene group, and the aromatic hydrocarbon structure-containing methylene group. Structure obtained by reacting an epoxy resin (a1) having a structure bonded through a divalent hydrocarbon group (Y) in the molecular structure with an active hydrogen atom-containing aromatic phosphine compound (a2) It is related with the epoxy resin characterized by having.

  According to the present invention, an epoxy resin composition that combines UL94V-0 class flame retardancy, moisture resistance reliability, and heat resistance reliability, a cured product, a circuit board using the composition, a build-up material, and a semiconductor encapsulation Materials and new epoxy resins that provide these performances can be provided.

FIG. 1 is a GPC chart of the epoxy resin (A-1) obtained in Example 1.

Hereinafter, the present invention will be described in detail.
The epoxy resin used in the present invention is as described above.
The epoxy resin (A) is
Glycidyloxy group-containing aromatic hydrocarbon group (E),
An alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (X), and
Each structural site of a divalent hydrocarbon group (Y) selected from a methylene group, an alkylidene group, and an aromatic hydrocarbon structure-containing methylene group, and
The glycidyloxy group-containing aromatic hydrocarbon group (E) and the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (X) are selected from the methylene group, the alkylidene group, and the aromatic hydrocarbon structure-containing methylene group. Structure obtained by reacting an epoxy resin (a1) having a structure bonded through a divalent hydrocarbon group (Y) in the molecular structure with an active hydrogen atom-containing aromatic phosphine compound (a2) It is what has.

  Here, the epoxy resin (a1) to be used is specifically a glycidyloxy group-containing aromatic hydrocarbon group (E), an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (X), a methylene group or the like ( When each structural unit of Y) is represented by “E”, “X”, “Y”, the following structural site A1

であらわされる構造部位を必須として分子構造内に含むものであるが、更に具体的には、下記構造式Ａ２及びＡ３で表される構造、

The structure represented by the formula is essentially included in the molecular structure, more specifically, structures represented by the following structural formulas A2 and A3,

で表される構造を繰り返し単位とするノボラック構造の分子末端に、下記構造式Ａ６ Structural formula A4 or A5

At the molecular end of the novolak structure having the structure represented by

で表される構造を有する構造、その他下記構造式Ａ７〜Ａ８

Other structures having the structure represented by the following structural formulas A7 to A8

で表される構造を繰り返し単位とする交互共重合体構造が挙げられる。

The alternating copolymer structure which makes the structure represented by repeating unit a repeating unit is mentioned.

  In the present invention, the epoxy resin (A) can have various structures as described above. By having the structure represented by the structural formula A6 at the molecular end, the dielectric loss tangent of the cured epoxy resin is obtained. Can be significantly reduced. Accordingly, an epoxy resin having the structure of the structural formula A3 or an epoxy resin having the structure represented by the structural formula A6 at the molecular end thereof and having the repeating unit of A4 or A7 is particularly preferable. From the standpoint of the effect of the above, an epoxy resin having the structure of the structural formula A3 or an epoxy resin having the structure represented by the structural formula A6 at the molecular end of the A4 as a repeating unit is preferable. .

  Here, the glycidyloxy group-containing aromatic hydrocarbon group (E) specifically includes glycidyloxybenzenes, glycidyloxynaphthalenes, and aromatic nuclei represented by the following structural formulas E1 to E16. A compound having an alkyl group as a substituent is preferable in that it has excellent flame retardancy.

  Here, each structure becomes a monovalent aromatic hydrocarbon group when the structure is located at the molecular end as in the structural formula A2. In addition, among the structures listed above, those having two or more bonding positions with other structural sites on the naphthalene skeleton may be on the same nucleus or on different nuclei. There may be.

  Next, the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (X) contained in the epoxy resin (A) structure is a monovalent aromatic having an alkoxy group as a substituent on the condensed polycyclic aromatic nucleus. A hydrocarbon group, specifically, an alkoxynaphthalene structure represented by the following structural formulas X1 to X11 or an alkoxyanthracene structure represented by the following structural formula X12.

  Here, each structure becomes a monovalent aromatic hydrocarbon group when the structure is located at the molecular end. In addition, among the structures listed above, those having two or more bonding positions with other structural sites on the naphthalene skeleton may be on the same nucleus or on different nuclei. There may be.

  Among the alkoxy group-containing condensed polycyclic aromatic hydrocarbon groups (X) described in detail above, those having an alkoxynaphthalene type structure from the viewpoint that the flame retardancy of the cured epoxy resin is particularly good. Preferably, a naphthalene structure having a methoxy group or an ethoxy group as a substituent, represented by the structural formulas X1 to X10, and the like, in view of the fact that in recent years it is possible to design a halogen-free material that is highly required in the field of electronic components Furthermore, it is preferably an aromatic hydrocarbon group formed from a structure having a methyl group as a substituent.

  Next, each structural site of the divalent hydrocarbon group (Y) selected from the above-mentioned methylene group, alkylidene group, and aromatic hydrocarbon structure-containing methylene group includes methylene group and alkylidene group as ethylidene group. Group, 1,1-propylidene group, 2,2-propylidene group, dimethylene group, propane-1,1,3,3-tetrayl group, n-butane-1,1,4,4-tetrayl group, n-pentane A -1,1,5,5-tetrayl group is mentioned. In addition, examples of the aromatic hydrocarbon structure-containing methylene group include the following Y1 to Y4 structures.

これらの中でも誘電効果に優れる点、更に有機溶剤へ溶解させた際の粘度が低い点から、とりわけメチレン基であることが好ましい。
従って、エポキシ樹脂（Ａ）は、特に下記構造式（１）

Among these, a methylene group is particularly preferable because of its excellent dielectric effect and its low viscosity when dissolved in an organic solvent.
Accordingly, the epoxy resin (A) particularly has the following structural formula (1)

（式中、Ｅはグリシジルオキシ基含有芳香族炭化水素基を、Ｘはアルコキシ基含有縮合多環式芳香族炭化水素基、Ｘ’はアルコキシ基含有縮合多環式芳香族炭化水素基又はグリシジルオキシ基含有芳香族炭化水素基を表し、ｎは繰り返し単位で１〜１００の整数である。）で表される構造を有するものがとりわけ好ましい。
ここで、Ｘ’のアルコキシ基含有縮合多環式芳香族炭化水素基又はグリシジルオキシ基含有芳香族炭化水素基とは、Ｘ’が任意にアルコキシ基含有縮合多環式芳香族炭化水素基（Ｘ）又はグリシジルオキシ基含有芳香族炭化水素基（Ｅ）であることを示すものである。

(In the formula, E represents a glycidyloxy group-containing aromatic hydrocarbon group, X represents an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group, and X ′ represents an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group or glycidyloxy. A group-containing aromatic hydrocarbon group is preferred, and n is a repeating unit and is preferably an integer of 1 to 100).
Here, the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group or the glycidyloxy group-containing aromatic hydrocarbon group represented by X ′ is an X ′ is optionally an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (X Or a glycidyloxy group-containing aromatic hydrocarbon group (E).

  In addition, when the epoxy resin (a1) has a structure represented by the structural formula (1), the resin usually contains the following structural formula (1 ′).

（式中、Ｅはグリシジルオキシ基含有芳香族炭化水素基（Ｅ）を表す。）
で表される化合物が含まれることになるが、その含有率はエポキシ樹脂（ａ１）中、５質量％以下となる割合、特に１．０〜３．５質量％なる範囲であることが難燃性の点から好ましい。

(In the formula, E represents a glycidyloxy group-containing aromatic hydrocarbon group (E).)
In the epoxy resin (a1), the content ratio is 5% by mass or less, particularly 1.0 to 3.5% by mass flame retardant. From the viewpoint of sex.

  In the present invention, as the main component of the epoxy resin (a1), the following structural formula

（式中、Ｅはグリシジルオキシ基含有芳香族炭化水素基を表す。）
で表される構造単位を繰り返し単位とする主骨格の末端にＸはアルコキシ基含有縮合多環式芳香族炭化水素基を導入すること該エポキシ樹脂（Ａ）の硬化物の難燃性を飛躍的に改善できる。

(In the formula, E represents a glycidyloxy group-containing aromatic hydrocarbon group.)
Introducing an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group to the terminal of the main skeleton having the structural unit represented by the formula as a repeating unit, the flame retardancy of the cured product of the epoxy resin (A) is dramatically improved Can be improved.

  The value of n in the structural formula (1) is the number of repeating units derived from GPC measurement. Here, the conditions for the GPC measurement are specifically as follows.

  The epoxy resin (a1) has good curability of the composition when the epoxy equivalent is small, and the flame retardancy of the cured product is good when the epoxy equivalent is large. Accordingly, the epoxy equivalent is 200 to 600 g / eq. In the range of 250 to 550 g / eq. It is preferable that it is the range of these.

  Furthermore, in the epoxy resin (a1), the abundance ratio of the glycidyloxy group-containing aromatic hydrocarbon group (E) and the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (X) is the former in terms of molar ratio. / The latter is preferably in the range of 30/70 to 98/2 from the viewpoint of flame retardancy.

  The epoxy resin (a1) described in detail above includes a phenolic hydroxyl group-containing aromatic hydrocarbon group (P), an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (X), a methylene group, an alkylidene group, and Each of the divalent hydrocarbon groups (Y) selected from the aromatic hydrocarbon structure-containing methylene group, and the phenolic hydroxyl group-containing aromatic hydrocarbon group (P) and the alkoxy group A structure in which the contained condensed polycyclic aromatic hydrocarbon group (B) is bonded via a divalent hydrocarbon group (X) selected from the methylene group, alkylidene group, and aromatic hydrocarbon structure-containing methylene group Can be obtained by reacting a phenolic resin (ph1) having a quinone in the molecular structure with epihalohydrin.

  Moreover, the said phenol resin (ph1) can be manufactured by making a hydroxyl group containing aromatic compound (p), an alkoxy group containing aromatic compound (x), and a carbonyl group containing compound (y) react. .

  Specific examples of the hydroxy group-containing aromatic compound (p) used in the above production method include unsubstituted phenols such as phenol, resorcinol and hydroquinone, cresol, phenylphenol, ethylphenol, n-propylphenol and iso-propyl. Monosubstituted phenols such as phenol and t-butylphenol, disubstituted phenols such as xylenol, methylpropylphenol, methylbutylphenol, methylhexylphenol, dipropylphenol and dibutylphenol, mesitol, 2,3,5-trimethylphenol, 2 , 3,6-trimethylphenol and the like, and naphthols such as 1-naphthol, 2-naphthol and methylnaphthol. When manufacturing the said phenol resin (ph1), the said compound may be used independently and may use 2 or more types together.

  Among these, 1-naphthol, 2-naphthol, cresol, and phenol are particularly preferable because the cured product has excellent flame retardancy.

Next, the alkoxy group-containing aromatic compound (x) specifically includes 1-methoxynaphthalene, 2-methoxynaphthalene, 1-methyl-2-methoxynaphthalene, 1-methoxy-2-methylnaphthalene, 1,3. , 5-trimethyl-2-methoxynaphthalene, 2,6-dimethoxynaphthalene, 2,7-dimethoxynaphthalene, 1-ethoxynaphthalene,
1,4-dimethoxynaphthalene, 1-t-butoxynaphthalene, 1-methoxyanthracene, and the like can be given.

  Among these, 1-methoxynaphthalene, 2-methoxynaphthalene, and 2,7-dimethoxynaphthalene are preferable from the viewpoint of flame retardancy and dielectric properties.

  Next, the carbonyl group-containing compound (y) is specifically an aliphatic aldehyde such as formaldehyde, acetaldehyde or propionaldehyde, a dialdehyde such as glyoxal, benzaldehyde, 4-methylbenzaldehyde, 3,4-dimethylbenzaldehyde, Examples thereof include aromatic aldehydes such as 4-biphenylaldehyde and naphthylaldehyde, and ketone compounds such as benzophenone, fluorenone and indanone.

  Among these, formaldehyde, benzaldehyde, 4-biphenylaldehyde, and naphthylaldehyde are preferable from the viewpoint that the obtained cured product has excellent flame retardancy, and formaldehyde is preferable from the viewpoint that the obtained resin has low viscosity.

  The following methods 1) to 3) are the methods for reacting the hydroxy group-containing aromatic compound (p), the alkoxy group-containing condensed polycyclic aromatic compound (x) and the carbonyl group-containing compound (y). Can be mentioned.

Method 1): A hydroxy group-containing aromatic compound (p), an alkoxy group-containing condensed polycyclic aromatic compound (x), and a carbonyl group-containing compound (y) are charged substantially simultaneously, and an appropriate polymerization catalyst is present. A method in which the reaction is carried out with stirring under heating.
Method 2): After reacting 0.05 to 30 mol, preferably 2 to 30 mol, of the carbonyl group-containing compound (y) with respect to 1 mol of the alkoxy group-containing condensed polycyclic aromatic compound (x), A method in which a hydroxy group-containing aromatic compound (p) is charged and reacted.
Method 3): Hydroxy group-containing aromatic compound (p) and alkoxy group-containing condensed polycyclic aromatic compound (x) are mixed in advance, and carbonyl group-containing compound (y) is continuously or intermittently added thereto. A method in which a reaction is carried out by adding it to the system.

  In the above method 1), “substantially simultaneously” means that all raw materials are charged until the reaction is accelerated by heating.

  The desired epoxy resin (a1) can be obtained by reacting the phenol resin (ph1) thus obtained with epihalohydrin. Specifically, 2 to 10 mol of epihalohydrin is added to 1 mol of phenolic hydroxyl group in the phenol resin (ph1), and further 0.9 to 2.0 mol of basicity to 1 mol of phenolic hydroxyl group. The method of making it react at the temperature of 20-120 degreeC for 0.5 to 10 hours, adding a catalyst collectively or gradually is mentioned. The basic catalyst may be solid or an aqueous solution thereof. When an aqueous solution is used, it is continuously added and water and epihalohydrins are continuously distilled from the reaction mixture under reduced pressure or normal pressure. It is preferable that the solution is further separated to remove water and the epihalohydrin is continuously returned to the reaction mixture.

  In the first batch of epoxy resin production, all of the epihalohydrins used for preparation are new in industrial production, but the subsequent batches are consumed by the reaction with epihalohydrins recovered from the crude reaction product. It is preferable to use in combination with new epihalohydrins corresponding to the amount disappeared. At this time, the epihalohydrin used is not particularly limited, and examples thereof include epichlorohydrin, epibromohydrin, β-methylepichlorohydrin, and the like. Of these, epichlorohydrin is preferred because it is easily available industrially.

  Specific examples of the basic catalyst include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. In particular, alkali metal hydroxides are preferable from the viewpoint of excellent catalytic activity of the epoxy resin synthesis reaction, and examples thereof include sodium hydroxide and potassium hydroxide. In use, these basic catalysts may be used in the form of an aqueous solution of about 10 to 55% by mass, or in the form of a solid. Moreover, the reaction rate in the synthesis | combination of an epoxy resin can be raised by using an organic solvent together. Examples of such organic solvents include, but are not limited to, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary butanol, and tertiary butanol, methyl Examples include cellosolves such as cellosolve and ethyl cellosolve, ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane and diethoxyethane, and aprotic polar solvents such as acetonitrile, dimethyl sulfoxide and dimethylformamide. These organic solvents may be used alone or in combination of two or more as appropriate in order to adjust the polarity.

  After the reaction product of the epoxidation reaction is washed with water, unreacted epihalohydrin and the organic solvent to be used in combination are distilled off by distillation under heating and reduced pressure. Further, in order to obtain an epoxy resin with less hydrolyzable halogen, the obtained epoxy resin is again dissolved in an organic solvent such as toluene, methyl isobutyl ketone, methyl ethyl ketone, and alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. Further reaction can be carried out by adding an aqueous solution of the product. At this time, a phase transfer catalyst such as a quaternary ammonium salt or crown ether may be present for the purpose of improving the reaction rate. When the phase transfer catalyst is used, the amount used is preferably in the range of 0.1 to 3.0% by mass relative to the epoxy resin used. After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and a solvent such as toluene and methyl isobutyl ketone is distilled off under heating and reduced pressure to obtain a high purity epoxy resin (a1).

  Next, the active hydrogen atom-containing aromatic phosphine compound (a2) to be reacted with the epoxy resin (a1) specifically has the following structural formula a2-1.

（式中、Ｒ¹、Ｒ²はそれぞれ独立に水素原子又は炭素原子数１〜６のアルキル基を表す。）又は、下記構造式ａ２−２

(Wherein R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) or the following structural formula a2-2

（式中、Ｒ^３、Ｒ^４はそれぞれ独立に水素原子又は炭素原子数１〜６のアルキル基を表す。）
で表される分子構造を有するものが挙げられる。

(In formula, R < ³ >, R < ⁴ > represents a hydrogen atom or a C1-C6 alkyl group each independently.)
The thing which has the molecular structure represented by these is mentioned.

R ¹ and R ² in the structural formula a2-1 are each independently a hydrogen atom, or a methyl group, ethyl group, propyl group, i-butyl group, t-butyl group, pentyl group, n-hexyl group, Or it is C1-C6 alkyl groups, such as a cyclohexyl group, but it is preferable that both R < ¹ > and R < ² > are hydrogen atoms from the point which is especially excellent in a flame retardance.
On the other hand, R ³ and R ⁴ in the structural formula a2-2 are each independently a hydrogen atom, or a methyl group, an ethyl group, a propyl group, an i-butyl group, a t-butyl group, a pentyl group, and an n-hexyl group. Group, or an alkyl group having 1 to 6 carbon atoms such as a cyclohexyl group. Among these, R ¹ and R ² are preferably hydrogen atoms because they are particularly excellent in flame retardancy.

Of the compounds represented by the structural formula a2-1 and the compounds represented by the structural formula a2-2, the structural formula a2-1 is particularly preferable because of excellent reactivity with an epoxy resin and flame retardancy. Are preferred.

  Here, as a method of reacting the epoxy resin (a1) and the active hydrogen atom-containing aromatic phosphine compound (a2), for example, the epoxy resin (a1) is melted, and the active hydrogen atom-containing aromatic system is added thereto. The phosphine compound (a2) can be added or reacted in a batch or divided. The reaction temperature is preferably in the range of 100 ° C. to 200 ° C., particularly in the range of 120 ° C. to 180 ° C., and the reaction is preferably performed with stirring. At this time, a catalyst is used as necessary in consideration of the reaction rate. Specific examples of the catalyst include tertiary amines such as benzyldimethylamine, quaternary ammonium salts such as tetramethylammonium chloride, phosphines such as triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine, Examples include phosphonium salts such as ethyltriphenylphosphonium bromide, and imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole.

  As a method for confirming the end point of the reaction, a method for confirming that the value is 95% or more of the theoretical epoxy equivalent by tracing the epoxy equivalent, a phosphine represented by a general formula by instrumental analysis represented by liquid chromatography, etc. Although there is a method of tracking a compound and confirming that the residual substance has substantially disappeared, it is not limited thereto.

The epoxy resin (A) has an epoxy equivalent of 250 to 700 g / eq. Those in the above range are preferable from the viewpoint of further improving the flame retardancy, moisture resistance reliability and heat resistance reliability of the cured product.
Since the epoxy resin (A) has high flame retardancy of the epoxy resin itself before reacting with the phosphorus compound, the phosphorus atom content in the epoxy resin (A) does not need to be increased more than necessary. Since the moisture resistance reliability tends to decrease as the atomic content increases, the range is from 0.1% by mass to 5.0% by mass, especially from 0.3% by mass to 3.0% by mass, and particularly from 0.1% by mass. It is preferable that it is the range of% -1.5 mass%.

  In the epoxy resin composition of the present invention, the epoxy resin obtained by the production method of the present invention can be used alone or in combination with other epoxy resins as long as the effects of the present invention are not impaired. When used in combination, the proportion of the epoxy resin of the present invention in the entire epoxy resin is preferably 30% by mass or more, particularly preferably 40% by mass or more.

  As other epoxy resins that can be used in combination with the epoxy resin of the present invention, various epoxy resins can be used. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type Epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type Epoxy resin, naphthol novolac type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensate Type epoxy resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin type epoxy resin, a biphenyl novolak type epoxy resins. Among these, phenol aralkyl type epoxy resins, biphenyl novolak type epoxy resins, naphthol novolak type epoxy resins containing a naphthalene skeleton, naphthol aralkyl type epoxy resins, naphthol-phenol co-condensed novolac type epoxy resins, naphthol-cresol co-condensed novolacs. Type epoxy resins, crystalline biphenyl type epoxy resins, tetramethylbiphenyl type epoxy resins, and xanthene type epoxy resins are particularly preferable because a cured product having excellent flame retardancy and dielectric properties can be obtained.

As the curing agent used in the epoxy resin composition of the present invention, known curing agents for various epoxy resins, for example, curing agents such as amine compounds, amide compounds, acid anhydride compounds and phenol compounds can be used. . Specifically, examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complex, and guanidine derivative. Examples of the amide compound include dicyandiamide. And polyamide resins synthesized from dimer of linolenic acid and ethylenediamine. Examples of acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, and tetrahydrophthalic anhydride. Acid, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc., and phenolic compounds include phenol novolac resin, cresol novolac resin Aromatic hydrocarbon formaldehyde resin modified phenolic resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (commonly known as zylock resin), naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, naphthol novolac resin, naphthol-phenol Co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin (polyhydric phenol compound in which phenol nucleus is linked by bismethylene group), biphenyl-modified naphthol resin (polyvalent naphthol in which phenol nucleus is linked by bismethylene group) Compound), and polyphenol compounds such as aminotriazine-modified phenolic resins (polyphenol compounds in which phenol nuclei are linked with melamine, benzoguanamine, etc.) Can be mentioned.

  Among these, dicyandiamide, aminotriazine-modified phenol resin, phenol novolac resin, and cresol novolac resin are preferable because a cured product having excellent flame retardancy and heat resistance can be obtained.

  The blending amount of the epoxy resin and the curing agent in the epoxy resin composition of the present invention is not particularly limited, but from the point that the properties of the resulting cured product are good, in the epoxy resin containing the epoxy resin For a total of 1 equivalent of epoxy groups, the curing agent containing a nitrogen atom has an active group in the curing agent of 0.3 to 1.3 equivalent, and other curing agents have an active group in the curing agent of 0.7 to 0.7 equivalent. An amount of ~ 1.5 equivalents is preferred.

  Moreover, a hardening accelerator can also be suitably used together with the epoxy resin composition of this invention as needed. Various curing accelerators can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts. In particular, when used as a semiconductor encapsulating material, it is excellent in curability, heat resistance, electrical characteristics, moisture resistance reliability, etc., so that triphenylphosphine is used for phosphorus compounds and 1,8-diazabicyclo is used for tertiary amines. -[5.4.0] -undecene (DBU) is preferred.

  The epoxy resin composition of the present invention described in detail above is used conventionally because the resin itself has an excellent flame retardancy-imparting effect depending on the selection of the molecular structure of the epoxy resin or its curing agent. Even if the flame retardant which is added is not blended, the flame retardancy of the cured product is good. However, in order to exert a higher degree of flame retardancy, for example, in the field of circuit boards, a non-halogen flame retardant containing substantially no halogen atom (as long as the through-hole processability and moisture resistance reliability are not lowered) C) may be blended.

The epoxy resin composition containing such a non-halogen flame retardant (C) is substantially free of halogen atoms. For example, halogen atoms due to trace amounts of impurities of about 5000 ppm or less derived from epihalohydrin contained in the epoxy resin. May be included.

Examples of the non-halogen flame retardant (C) include:
Phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, organometallic salt flame retardants, etc., are not limited in any way, and even if used alone A plurality of flame retardants of the same system may be used, and different types of flame retardants may be used in combination.

  As the phosphorus flame retardant, either inorganic or organic can be used. Examples of the inorganic compounds include red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphates such as ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphate amide. .

  The red phosphorus is preferably subjected to a surface treatment for the purpose of preventing hydrolysis and the like. Examples of the surface treatment method include (i) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, water A method of coating with an inorganic compound such as titanium oxide, bismuth oxide, bismuth hydroxide, bismuth nitrate or a mixture thereof; (ii) an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide; and A method of coating with a mixture of a thermosetting resin such as a phenol resin, (iii) thermosetting of a phenol resin or the like on a coating of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, or titanium hydroxide For example, a method of double coating with a resin may be used.

  Examples of the organic phosphorus compound include, for example, general-purpose organic phosphorus compounds such as phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, and 9,10- Dihydro-9-oxa 10-phosphaphenanthrene = 10-oxide, 10- (2,5-dihydrooxyphenyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,7- Examples thereof include cyclic organophosphorus compounds such as dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide, and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins.

  The blending amount thereof is appropriately selected depending on the type of the phosphorus-based flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy. For example, epoxy resin, curing agent, non-halogen In 100 parts by mass of the epoxy resin composition containing all of the flame retardant and other fillers and additives, when using red phosphorus as a non-halogen flame retardant, in the range of 0.1 to 2.0 parts by mass It is preferable to mix, and when using an organophosphorus compound, it is also preferable to mix in the range of 0.1 to 10.0 parts by mass, particularly in the range of 0.5 to 6.0 parts by mass. Is preferred.

  In addition, when using the phosphorous flame retardant, the phosphorous flame retardant may be used in combination with hydrotalcite, magnesium hydroxide, boric compound, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc. Good.

  Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazines, and the like, and triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferable.

  Examples of the triazine compound include melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylene dimelamine, melamine polyphosphate, triguanamine, and the like, for example, (i) guanylmelamine sulfate, melem sulfate, sulfate (Iii) co-condensates of phenols such as phenol, cresol, xylenol, butylphenol and nonylphenol with melamines such as melamine, benzoguanamine, acetoguanamine and formguanamine and formaldehyde, (iii) (Ii) a mixture of a co-condensate of (ii) and a phenolic resin such as a phenol formaldehyde condensate, (iv) those obtained by further modifying (ii) and (iii) with paulownia oil, isomerized linseed oil, etc. It is.

  Specific examples of the cyanuric acid compound include cyanuric acid and cyanuric acid melamine.

  The amount of the nitrogen-based flame retardant is appropriately selected depending on the type of the nitrogen-based flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy. It is preferable to mix in the range of 0.05 to 10 parts by mass, especially in the range of 0.05 to 10 parts by mass, in 100 parts by mass of the epoxy resin composition containing all of the agent, non-halogen flame retardant and other fillers and additives. It is preferable to mix in the range of 5 parts by mass.

  Moreover, when using the said nitrogen-type flame retardant, you may use together a metal hydroxide, a molybdenum compound, etc.

  The silicone flame retardant is not particularly limited as long as it is an organic compound containing a silicon atom, and examples thereof include silicone oil, silicone rubber, and silicone resin.

  The amount of the silicone flame retardant is appropriately selected according to the type of the silicone flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy. It is preferable to mix in the range of 0.05 to 20 parts by mass in 100 parts by mass of the epoxy resin composition containing all of the agent, non-halogen flame retardant and other fillers and additives. Moreover, when using the said silicone type flame retardant, you may use a molybdenum compound, an alumina, etc. together.

  Examples of the inorganic flame retardant include metal hydroxide, metal oxide, metal carbonate compound, metal powder, boron compound, and low melting point glass.

  Specific examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, zirconium hydroxide and the like.

  Specific examples of the metal oxide include, for example, zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, and cobalt oxide. Bismuth oxide, chromium oxide, nickel oxide, copper oxide, tungsten oxide and the like.

  Specific examples of the metal carbonate compound include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, and titanium carbonate.

  Specific examples of the metal powder include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, and tin.

  Specific examples of the boron compound include zinc borate, zinc metaborate, barium metaborate, boric acid, and borax.

Specific examples of the low-melting-point glass include, for example, Ceeley (Bokusui Brown), hydrated glass SiO ₂ —MgO—H ₂ O, PbO—B ₂ O ₃ system, ZnO—P ₂ O ₅ —MgO system, P ₂ O ₅ —B ₂ O ₃ —PbO—MgO, P—Sn—O—F, PbO—V ₂ O ₅ —TeO ₂ , Al ₂ O ₃ —H ₂ O, lead borosilicate, etc. The glassy compound can be mentioned.

  The blending amount of the inorganic flame retardant is appropriately selected according to the type of the inorganic flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy. For example, epoxy resin, cured It is preferable to mix in the range of 0.05 to 100 parts by mass in 100 parts by mass of the epoxy resin composition containing all of the agent, non-halogen flame retardant and other fillers and additives, and particularly 0.5 to 100 parts by mass. It is preferable to mix in the range of 15 parts by mass.

  Examples of the organic metal salt flame retardant include ferrocene, acetylacetonate metal complex, organic metal carbonyl compound, organic cobalt salt compound, organic sulfonic acid metal salt, metal atom and aromatic compound or heterocyclic compound or an ionic bond or Examples thereof include a coordinated compound.

  The amount of the organometallic salt-based flame retardant is appropriately selected depending on the type of the organometallic salt-based flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy. It is preferable to mix in the range of 0.005 to 10 parts by mass in 100 parts by mass of the epoxy resin composition containing all of the epoxy resin, the curing agent, the non-halogen flame retardant, and other fillers and additives.

  An inorganic filler can be blended in the epoxy resin composition of the present invention as necessary. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. When particularly increasing the blending amount of the inorganic filler, it is preferable to use fused silica. The fused silica can be used in either a crushed shape or a spherical shape. However, in order to increase the blending amount of the fused silica and suppress an increase in the melt viscosity of the molding material, it is preferable to mainly use a spherical shape. In order to further increase the blending amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The filling rate is preferably higher in consideration of flame retardancy. For example, in the case of semiconductor sealing material use, it is particularly preferably in a range of 65% by mass or more with respect to the total amount of the epoxy resin composition. Moreover, when using for uses, such as an electrically conductive paste, electroconductive fillers, such as silver powder and copper powder, can be used.

  Various compounding agents, such as a silane coupling agent, a mold release agent, a pigment, an emulsifier, can be added to the epoxy resin composition of this invention as needed.

  The epoxy resin composition of the present invention can be obtained by uniformly mixing the above-described components. The epoxy resin composition of the present invention, in which the epoxy resin of the present invention, a curing agent and, if necessary, a curing accelerator are blended, can be easily made into a cured product by a method similar to a conventionally known method. Examples of the cured product include molded cured products such as laminates, cast products, adhesive layers, coating films, and films.

  Applications of the epoxy resin composition of the present invention include semiconductor sealing materials, resin compositions used for laminates and electronic circuit boards, resin casting materials, adhesives, interlayer insulation materials for build-up substrates, insulation Examples thereof include coating materials such as paints, and among these, they can be suitably used for semiconductor sealing materials.

  In order to process the epoxy resin composition of the present invention into a printed circuit board composition, for example, a resin composition for a prepreg can be used. Although it can be used without a solvent depending on the viscosity of the epoxy resin composition, it is preferable to obtain a resin composition for prepreg by varnishing using an organic solvent. As the organic solvent, it is preferable to use a polar solvent having a boiling point of 160 ° C. or lower such as methyl ethyl ketone, acetone, dimethylformamide, etc., and it can be used alone or as a mixed solvent of two or more kinds. The obtained varnish is impregnated into various reinforcing substrates such as paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth, and the heating temperature according to the solvent type used, preferably 50 By heating at ˜170 ° C., a prepreg that is a cured product can be obtained. The mass ratio of the resin composition and the reinforcing substrate used at this time is not particularly limited, but it is usually preferable that the resin content in the prepreg is 20 to 60% by mass. Moreover, when manufacturing a copper clad laminated board using this epoxy resin composition, the prepreg obtained as mentioned above is laminated | stacked by a conventional method, copper foil is laminated | stacked suitably, and it is under pressure of 1-10 MPa. A copper-clad laminate can be obtained by thermocompression bonding at 170 to 250 ° C. for 10 minutes to 3 hours.

  In order to produce an epoxy resin composition prepared for a semiconductor encapsulant, an epoxy resin, a curing agent, a compounding agent such as a filler, and the like, if necessary, an extruder, a kneader, a roll, etc. It is sufficient to obtain a melt-mixed type epoxy resin composition by mixing well until it is uniform. At that time, silica is usually used as the filler, and the filling ratio is preferably in the range of 30 to 95% by mass per 100 parts by mass of the epoxy resin composition. In order to improve moisture resistance and solder crack resistance, and to reduce the linear expansion coefficient, it is particularly preferably 70 parts by mass or more, and in order to significantly increase these effects, 80 parts by mass or more further enhances the effect. be able to. For semiconductor package molding, the composition is molded by casting, using a transfer molding machine, an injection molding machine or the like, and further heated at 50 to 200 ° C. for 2 to 10 hours to form a semiconductor device which is a molded product. There is a way to get it.

  When using the epoxy resin composition of the present invention as a resist ink, for example, using a cationic polymerization catalyst as a curing agent of the epoxy resin composition, and further adding a pigment, talc, and filler, Then, after apply | coating on a printed circuit board by a screen printing system, the method of setting it as a resist ink hardened | cured material is mentioned.

  When the epoxy resin composition of the present invention is used as a conductive paste, for example, a method of dispersing fine conductive particles in the epoxy resin composition to form a composition for an anisotropic conductive film, which is liquid at room temperature Examples of the method include a paste resin composition for circuit connection and an anisotropic conductive adhesive. As a method for obtaining an interlayer insulating material for a build-up substrate from the curable resin composition of the present invention, for example, the curable resin composition appropriately blended with rubber, filler, etc., spray coating method on a wiring board on which a circuit is formed, After applying using a curtain coating method or the like, it is cured. Then, after drilling a predetermined through-hole part etc. as needed, it treats with a roughening agent, forms the unevenness | corrugation by washing the surface with hot water, and metal-treats, such as copper. As the plating method, electroless plating or electrolytic plating treatment is preferable, and examples of the roughening agent include an oxidizing agent, an alkali, and an organic solvent. Such operations are sequentially repeated as desired, and a build-up base can be obtained by alternately building up and forming the resin insulating layer and the conductor layer having a predetermined circuit pattern. However, the through-hole portion is formed after the outermost resin insulating layer is formed. In addition, a resin-coated copper foil obtained by semi-curing the resin composition on the copper foil is thermocompression-bonded at 170 to 250 ° C. on a circuit board on which a circuit is formed, thereby forming a roughened surface and plating treatment. It is also possible to produce a build-up substrate by omitting the process.

  The method for producing an adhesive film for buildup from the curable resin composition of the present invention is, for example, a multilayer printed wiring board in which the curable resin composition of the present invention is applied on a support film to form a resin composition layer. And an adhesive film for use.

  When the curable resin composition of the present invention is used for a build-up adhesive film, the adhesive film is softened under the temperature condition of the laminate in the vacuum laminating method (usually 70 ° C. to 140 ° C.), and simultaneously with the lamination of the circuit board, It is important to show fluidity (resin flow) that allows resin filling in via holes or through holes present in a circuit board, and it is preferable to blend the above-described components so as to exhibit such characteristics.

  Here, the diameter of the through hole of the multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm. It is usually preferable to allow resin filling in this range. When laminating both surfaces of the circuit board, it is desirable to fill about 1/2 of the through hole.

  Specifically, the method for producing the adhesive film described above is, after preparing the varnish-like curable resin composition of the present invention, coating the varnish-like composition on the surface of the support film, further heating, Or it can manufacture by drying an organic solvent by hot air spraying etc. and forming the layer ((alpha)) of a curable resin composition.

  The thickness of the formed layer (α) is usually not less than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm.

  In addition, the said layer ((alpha)) may be protected with the protective film mentioned later. By protecting with a protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches.

  The above-mentioned support film and protective film are made of polyolefin such as polyethylene, polypropylene and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester such as polyethylene naphthalate, polycarbonate, polyimide, and further. Examples thereof include metal foil such as pattern paper, copper foil, and aluminum foil. In addition, the support film and the protective film may be subjected to a release treatment in addition to the mud treatment and the corona treatment.

  Although the thickness of a support film is not specifically limited, Usually, it is 10-150 micrometers, Preferably it is used in 25-50 micrometers. Moreover, it is preferable that the thickness of a protective film shall be 1-40 micrometers.

  The above support film is peeled off after being laminated on a circuit board or after forming an insulating layer by heat curing. If the support film is peeled after the adhesive film is heat-cured, adhesion of dust and the like in the curing process can be prevented. In the case of peeling after curing, the support film is usually subjected to a release treatment in advance.

  Next, the method for producing a multilayer printed wiring board using the adhesive film obtained as described above is, for example, when the layer (α) is protected with a protective film, Lamination is performed on one or both sides of the circuit board by, for example, vacuum laminating so that α) is in direct contact with the circuit board. The laminating method may be a batch method or a continuous method using a roll. Further, the adhesive film and the circuit board may be heated (preheated) as necessary before lamination.

Lamination conditions are preferably a pressure bonding temperature (laminating temperature) of 70 to 140 ° C., a pressure bonding pressure of preferably 1 to 11 kgf / cm 2 (9.8 × 10 ^{4 to} 107.9 × 10 ⁴ N / m 2), and air pressure. Lamination is preferably performed under a reduced pressure of 20 mmHg (26.7 hPa) or less.

  The method for obtaining the cured product of the present invention may be based on a general curing method for a curable resin composition, but for example, the heating temperature condition may be appropriately selected depending on the kind of curing agent to be combined and the use. However, what is necessary is just to heat the composition obtained by the said method in the temperature range of about room temperature-250 degreeC.

  Therefore, the use of the phenolic resin dramatically improves the solvent solubility of the phenolic resin, and when it is cured, it can exhibit heat resistance and a low coefficient of thermal expansion and can be applied to the latest printed wiring board materials. . In addition, the phenol resin can be easily and efficiently produced by the production method of the present invention, and a molecular design corresponding to the target level of performance described above becomes possible.

The method for obtaining the cured product of the present invention may be based on a general method for curing an epoxy resin composition. For example, the heating temperature condition may be appropriately selected depending on the type and use of the curing agent to be combined. What is necessary is just to heat the composition obtained by the said method in the temperature range of about room temperature-250 degreeC. As the molding method and the like, a general method of the epoxy resin composition is used, and a condition specific to the epoxy resin composition of the present invention is not particularly required.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the following, “parts” and “%” are based on weight unless otherwise specified. The melt viscosity (ICI viscosity) at 150 ° C. was carried out according to ASTM D4287. GPC was measured under the following conditions.
[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “H _XL -L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (Differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.
(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).

Synthesis Example 1 [Synthesis of Epoxy Resin (a-1)]
To a flask equipped with a thermometer, a condenser tube, a fractionating tube, a nitrogen gas inlet tube, and a stirrer, 432.4 g (4.00 mol) of o-cresol and 158.2 g (1.00 mol) of 2-methoxynaphthalene 179.3 g (2.45 mol) of a 41 mass% formaldehyde aqueous solution was added, 9.0 g of oxalic acid was added, the temperature was raised to 100 ° C., and the reaction was carried out at 100 ° C. for 3 hours. Subsequently, 73.2 g (1.00 mol) of a 41% aqueous formaldehyde solution was added dropwise over 1 hour while collecting water with a fractionating tube. After completion of the dropwise addition, the temperature was raised to 150 ° C. over 1 hour, and further reacted at 150 ° C. for 2 hours. After completion of the reaction, 1500 g of methyl isobutyl ketone was further added, transferred to a separatory funnel and washed with water. Subsequently, after washing with water until the washing water showed neutrality, unreacted o-cresol, 2-methoxynaphthalene, and methyl isobutyl ketone were removed from the organic layer under heating and reduced pressure to obtain a phenol resin. The obtained phenol resin has a hydroxyl group equivalent of 164 g / eq. Met.
Further, while purging a flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer with nitrogen gas purge, 164 g (1 equivalent of hydroxyl group) of the obtained phenol resin (A-1) and 463 g of epichlorohydrin (5.0 mol) ), 139 g of n-butanol and 2 g of tetraethylbenzylammonium chloride were charged and dissolved. After raising the temperature to 65 ° C., the pressure was reduced to an azeotropic pressure, and 90 g (1.1 mol) of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Thereafter, stirring was continued for 0.5 hours under the same conditions. During this time, the distillate distilled by azeotropic distillation was separated with a Dean-Stark trap, the water layer was removed, and the reaction was carried out while returning the oil layer to the reaction system. Thereafter, unreacted epichlorohydrin was distilled off under reduced pressure. 590 g of methyl isobutyl ketone and 177 g of n-butanol were added to the crude epoxy resin thus obtained and dissolved. Further, 10 g of a 10% aqueous sodium hydroxide solution was added to this solution and reacted at 80 ° C. for 2 hours, and then washing with water 150 g was repeated three times until the pH of the washing solution became neutral. Next, the system was dehydrated by azeotropic distillation, and after microfiltration, the solvent was distilled off under reduced pressure to obtain an epoxy resin (a-1). The epoxy equivalent of the obtained epoxy resin is 250 g / eq. Met.

Synthesis Example 2 [Synthesis of Epoxy Resin (a-2)]
To a flask equipped with a thermometer, a condenser tube, a fractionating tube, a nitrogen gas inlet tube, and a stirrer, 432.4 g (4.00 mol) of o-cresol and 158.2 g (1.00 mol) of 2-methoxynaphthalene 292.7 g (4.00 mol) of a 41% formaldehyde aqueous solution was added, 9.0 g of oxalic acid was added, the temperature was raised to 100 ° C., and the mixture was reacted at 100 ° C. for 3 hours. Subsequently, 73.2 g (1.00 mol) of a 41 mass% formaldehyde aqueous solution was dropped over 1 hour while collecting water with a fractionating tube. After completion of the dropwise addition, the temperature was raised to 150 ° C. over 1 hour, and further reacted at 150 ° C. for 2 hours. After completion of the reaction, 1500 g of methyl isobutyl ketone was further added, transferred to a separatory funnel and washed with water. Subsequently, after washing with water until the washing water showed neutrality, unreacted o-cresol, 2-methoxynaphthalene, and methyl isobutyl ketone were removed from the organic layer under heating and reduced pressure to obtain a phenol resin. The obtained phenol resin has a hydroxyl group equivalent of 170 g / eq. Met.
Further, an epoxy resin was prepared in the same manner as in Synthesis Example 1 except that 170 g (1 equivalent of hydroxyl group) of the obtained phenol resin was used while purging nitrogen gas to a flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer. (A-2) was obtained. The epoxy equivalent of the obtained epoxy resin is 274 g / eq. Met.

Synthesis Example 3 [Synthesis of Epoxy Resin (a-3)]
In a flask equipped with a thermometer, condenser, fractionator, and stirrer, 141.2 g of phenol (1.5 and 79.1 g (0.50 mol) of 2-methoxynaphthalene and 32.6 g of 92% by mass paraformaldehyde ( Formaldehyde unit (1.00 mol) was added, 5.0 g of oxalic acid was added, and the temperature was raised to 100 ° C. over 1 hour, followed by reaction for 2 hours at 100 ° C. After the reaction, 700 g of methyl isobutyl ketone was further added. After washing with water until the washing water shows neutrality, unreacted phenol, 2-methoxynaphthalene, and methyl isobutyl ketone are removed from the organic layer under heating and reduced pressure. The hydroxyl equivalent was 200 g / eq.
In addition, an epoxy resin (synthetic example 1) was used except that a flask equipped with a thermometer, a dropping funnel, a condenser tube, and a stirrer was replaced with 200 g of the obtained phenol resin (1 equivalent of hydroxyl group) while purging with nitrogen gas. a-3) was obtained. The epoxy equivalent of the obtained epoxy resin is 290 g / eq. Met.

Example 1 (Production Method of Epoxy Resin (A-1))
179.5 g of epoxy resin (a-1) obtained in Synthesis Example 1, 76.9 g of epoxy resin (a-2) obtained in Synthesis Example 2, 9,10-dihydro-9-oxa-10-phospha 30.2 g of phenanthrene-10-oxide was charged. After the preparation, the temperature was raised to 90 ° C., 0.020 part of triphenylphosphine was added, and the mixture was reacted at 150 ° C. for 7 hours. A target resin having a melt viscosity (ICI viscosity, 150 ° C.) of 5.4 dPa · s was obtained. Hereinafter, this is abbreviated as an epoxy resin (A-1). A GPC chart of the obtained epoxy resin is shown in FIG.

Example 2 (Method for producing epoxy resin (A-2))
In Example 1, 250 g of the epoxy resin (a-1) obtained in Synthesis Example 1 and 65 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide were charged as the epoxy resin used. In the same manner, a target resin having a phosphorus atom content of 3.0% by weight and an epoxy equivalent of 452 g / eq was obtained. Hereinafter, this is abbreviated as an epoxy resin (A-2).

Example 3 (Method for producing epoxy resin (A-3))
In Example 1, 250 g of the epoxy resin (a-1) obtained in Synthesis Example 1 and 14 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide were charged as the epoxy resin used. In the same manner, a target resin having a phosphorus atom content of 0.7% by weight and an epoxy equivalent of 282 g / eq was obtained. Hereinafter, this is abbreviated as an epoxy resin (A-3).

Example 4 (Method for producing epoxy resin (A-4))
In Example 1, 290 g of the epoxy resin (a-3) obtained in Synthesis Example 3 and 40 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide were used as the epoxy resin to be used. Similarly, a target resin having a phosphorus atom content of 1.7% by weight and an epoxy equivalent of 405 g / eq was obtained. Hereinafter, this is abbreviated as an epoxy resin (A-4).

Comparative Synthesis Example 1
A four-necked glass separable flask equipped with a stirrer, thermometer, condenser, and nitrogen gas introducing device was charged with 843 g of orthocresol novolac epoxy resin having an epoxy equivalent of 204 g / eq and 16.0 g of bisphenol A, and nitrogen. The mixture was stirred while introducing gas, and heated to dissolve. After adding 0.02 g of triphenylphosphine as a catalyst and reacting at 150 ° C. for 3 hours, 141.0 g of the above-mentioned HCA was added for further reaction. A target resin having a phosphorus content of 2.0% by weight and an epoxy equivalent of 299 g / eq was obtained. Hereinafter, this is abbreviated as an epoxy resin (A-5).

Examples 5 to 10 and Comparative Example 1
With the formulation shown in Table 1, an epoxy resin composition (varnish) was prepared and cured under the following conditions to produce a double-sided copper-clad laminate, and various tests were performed. In the table, “TD-2090” is a phenol novolac resin (“PHENOLITE 2090-60M” hydroxyl equivalent 104 g / eq. Manufactured by DIC Corporation), and “LA-7054” is an aminotriazine novolak resin (“PHENOLITE manufactured by DIC Corporation”). 7054 ", a hydroxyl equivalent weight of 125 g / eq.), And the values described in each table represent the mass of the solid content.
As aluminum hydroxide in the table, Sumitomo Chemical product name: CL-303 was used.

[Adjustment of varnish]
The varnish is prepared by dissolving an epoxy resin in methyl ethyl ketone, and then a curing agent (dissolved in N, N′-dimethylformamide in the case of dicyandiamide) and a curing accelerator (2-ethyl-4-methyl). Imidazole) was added and dissolved (or dispersed) to finally prepare a mixed solution in which the nonvolatile content of the composition was 58% by mass. The amount of curing accelerator was such that the gel time of the prepreg was 120 seconds at 170 ° C.
[Laminate production conditions]
Base material: 100 μm; glass cloth “# 2116” manufactured by Nitto Boseki Co., Ltd.
Number of plies: 6
Pre-pregation conditions: 160 ° C / 2 weight copper foil: 18 µm; Nikko Metal Co., Ltd. JTC foil curing conditions: 200 ° C, 40 kg / cm ² after 1.5 hours molding Plate thickness: 0.8 mm

[Physical property test conditions]
Each of the obtained laminates was tested for physical properties such as moisture and solder resistance, solder float, oven heat resistance, peel strength, dielectric constant, dielectric loss tangent, and flame retardancy.
Moisture and solder resistance:
After processing at 121 ° C / 100% humidity with PCT (pressure cooker test),
It was immersed in a solder bath at 260 ° C. for 30 seconds and the state was observed.
Criteria: ○ No change, ΔMeasling, x blister generation solder float The laminate was left in a solder bath heated to 288 ° C., and the time until swelling occurred on the surface was examined. (Evaluation up to 60 minutes)
Oven heat resistance:
The plate was left in a dryer at 288 ° C. for 2 hours, and the presence or absence of swelling on the surface of the laminate was confirmed.
Peel strength:
Conforms to JIS-K6481.
Dielectric constant, dielectric loss tangent:
The frequency of the cured product after being stored in a room at 23 ° C. and 50% humidity for 24 hours after being completely dried by an impedance material analyzer “HP4291B” manufactured by Agilent Technologies, using a method according to JIS-C-6481. The dielectric constant and dielectric loss tangent at 100 MHz were measured.
Combustion test: Conforms to UL-94 vertical test.
Glass transition temperature: measured by DMA method after removing copper foil by etching (temperature rising speed 3 ° C / min)

Claims (12)

An epoxy resin composition comprising an epoxy resin (A) and a curing agent (B) as essential components,
The epoxy resin (A) is
Glycidyloxy group-containing aromatic hydrocarbon group (E),
An alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (X), and
Each structural site of a divalent hydrocarbon group (Y) selected from a methylene group, an alkylidene group, and an aromatic hydrocarbon structure-containing methylene group, and
The glycidyloxy group-containing aromatic hydrocarbon group (E) and the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (X) are selected from the methylene group, the alkylidene group, and the aromatic hydrocarbon structure-containing methylene group. An epoxy resin (a1) having a structure bonded through a divalent hydrocarbon group (Y) in the molecular structure;
An epoxy resin composition comprising an epoxy resin having a molecular structure obtained by reacting an active hydrogen atom-containing aromatic phosphine compound (a2). The active hydrogen atom-containing aromatic phosphine compound (a2) is represented by the following structural formula a2-1.

(Wherein R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) or the following structural formula a2-2

(In formula, R < ³ >, R < ⁴ > represents a hydrogen atom or a C1-C6 alkyl group each independently.)
The epoxy resin composition according to claim 1, which is a compound represented by the formula: The epoxy resin composition according to claim 1, wherein the phosphorus atom content in the epoxy resin (A) is 0.1 to 5.0% by weight. The epoxy resin composition according to claim 1, wherein an epoxy equivalent of the epoxy resin (A) is 250 to 700 g / eq. The epoxy resin composition according to claim 1, further comprising an inorganic filler (C) in addition to the epoxy resin (A) and the curing agent (B). The epoxy resin composition according to claim 1, wherein the curing agent (B) is selected from the group consisting of dicyandiamide, a novolac resin, and a nitrogen atom-containing phenol compound. Hardened | cured material formed by hardening | curing the epoxy resin composition as described in any one of Claims 1-6. A circuit board using the epoxy resin composition according to any one of claims 1 to 6. An epoxy resin composition is used in any one of claims 1 to 6, and a build-up material A semiconductor sealing material using the epoxy resin composition according to any one of claims 1 to 6. Glycidyloxy group-containing aromatic hydrocarbon group (E),
An alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (X), and
Each structural site of a divalent hydrocarbon group (Y) selected from a methylene group, an alkylidene group, and an aromatic hydrocarbon structure-containing methylene group, and
The glycidyloxy group-containing aromatic hydrocarbon group (E) and the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (X) are selected from the methylene group, the alkylidene group, and the aromatic hydrocarbon structure-containing methylene group. Structure obtained by reacting an epoxy resin (a1) having a structure bonded through a divalent hydrocarbon group (Y) in the molecular structure with an active hydrogen atom-containing aromatic phosphine compound (a2) The epoxy resin characterized by having. From the above, the active hydrogen atom-containing aromatic phosphine compound (a2) is represented by the following structural formula a2-1.

(Wherein R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) or the following structural formula a2-2

(In formula, R < ³ >, R < ⁴ > represents a hydrogen atom or a C1-C6 alkyl group each independently.)
The epoxy resin of Claim 11 which is a compound represented by these.

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