WO2014178348A1 - Phenolic resin, epoxy resin composition and cured product using same, copper-clad laminate, and semiconductor sealing material - Google Patents

Abstract

The present invention addresses the problem of providing a novel phenolic resin that, when used as an epoxy resin curing agent, gives a cured product that exhibits excellent characteristics such as thermal resistance, moisture resistance, permittivity, and dielectric dissipation. The present invention additionally address the problem of providing: an epoxy resin composition containing the novel phenolic resin and an epoxy resin; a cured product of the epoxy resin composition; a copper-clad laminate in which the epoxy resin composition is used as a matrix resin; and a semiconductor sealing material that uses the epoxy resin composition. Provided are a phenolic resin that is represented by formula (1), an epoxy resin composition, and a cured product, a copper-clad laminate, and a semiconductor sealing material that use the epoxy resin composition.

Description

Phenolic resin, epoxy resin composition and cured product using the same, copper-clad laminate, semiconductor encapsulant

The present invention relates to a novel phenol resin. In addition, an epoxy resin composition comprising the phenol resin, a cured product thereof, a copper-clad laminate using the epoxy resin composition as a matrix resin, and a semiconductor sealing material using the epoxy resin composition About.

Phenol resin is suitably used as a curing agent for epoxy resin. Epoxy resin composition with phenol resin as curing agent is excellent in various properties such as heat resistance and moisture resistance, printed wiring board materials, interlayer insulation materials for built-up boards, semiconductor sealing materials, conductive adhesive materials, etc. Widely used in the field of semiconductors and electronic components.
In recent years, downsizing, high performance, and high functionality of information equipment are rapidly progressing. In particular, the clock frequency of personal computers, peripheral devices, digital communication devices, and the like has been steadily increasing at the same time as the advancement of mounting technology and high integration of semiconductors, and has already exceeded 3 GHz. Also in mobile communication such as mobile phones, the frequency used shifts to the high frequency band. For this reason, high-speed signal transmission, high frequency response, and the like have been demanded more than before. For this reason, materials used in the field of semiconductors and electronic components are required to have higher characteristics than before. Among them, low dielectric constant and low characteristics, particularly high-speed signal transmission characteristics and characteristics corresponding to high frequencies, are required. Dielectric loss tangent is required.

In recent years, semiconductor packages tend to be thinner in order to cope with higher mounting density. As the semiconductor mounting method is changed to the surface mounting method, the cracking occurs due to the expansion of water in the sealing material due to the solder crack resistance, that is, the heat of the solder, with respect to the substrate material or the semiconductor sealing material. Therefore, it is required to have excellent moisture resistance (water resistance) and high heat resistance.

In response to these requirements, it has been proposed to use thermoplastic low dielectric constant resins such as fluororesin, polyphenylene ether resin, polystyrene, polyether ether ketone, polypropylene, etc., but these are heat resistant, solvent resistant, It was not satisfactory in terms of reliability, workability, or cost.

Patent Document 1 proposes a copper-clad laminate having a low dielectric constant and a low dielectric loss tangent using a phenol novolac type phenol resin, a cresol novolac type phenol resin, or a bisphenol A novolac type phenol resin as an epoxy resin curing agent. The dielectric constant, dielectric loss tangent and moisture resistance were not satisfactory.

JP-A-6-192391

An object of the present invention is to provide a novel phenol resin having excellent properties such as heat resistance, moisture resistance, dielectric constant and dielectric loss tangent when the cured product is used as an epoxy resin curing agent. Further, an epoxy resin composition containing the novel phenol resin and epoxy resin, a cured product thereof, a copper-clad laminate using the epoxy resin composition as a matrix resin, and a semiconductor sealing material using the epoxy resin composition Is to provide.

As a result of intensive studies to solve the above problems, the present inventors have introduced a naphthalene structure into the skeleton of the phenol resin and introduced an aliphatic hydrocarbon group having 1 to 20 carbon atoms into the side chain. The present inventors have found that the cured product can obtain a novel phenol resin having excellent characteristics such as high heat resistance, high moisture resistance, low dielectric constant and low dielectric loss tangent, and have completed the present invention.

The present invention relates to the following matters.
1. A phenol resin represented by the following general formula (1).

（ここで、Ａはそれぞれ独立に下記一般式（２－１）又は一般式（２－２）で表される１価又は２価の基からなり、但しＡの少なくとも一つは下記一般式（２－２）で表される１価又は２価の基からなり、Ｂは下記一般式（３）で表される２価の基からなり、ｎは０～１００の整数を表す。）

(Here, each A independently comprises a monovalent or divalent group represented by the following general formula (2-1) or general formula (2-2), provided that at least one of A is represented by the following general formula ( 2-2) is composed of a monovalent or divalent group, B is composed of a divalent group represented by the following general formula (3), and n is an integer of 0 to 100.)

（ここで、Ｒ^１は炭素数１～１０の脂肪族炭化水素基、アルコキシ基、アリール基、又はアラルキル基からなり、ｐは１又は２の整数を表し、ｒは０～３の整数を表し、但しｐ＋ｒは２価の基においては１～４の整数を表す。）

(Wherein R ¹ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group, an aryl group, or an aralkyl group, p is an integer of 1 or 2, and r is an integer of 0 to 3) (However, p + r represents an integer of 1 to 4 in the case of a divalent group.)

（ここで、Ｒ^２は炭素数１～１０の脂肪族炭化水素基、アルコキシ基、アリール基、又はアラルキル基からなり、ｑは１又は２の整数を表し、ｍは０～３の整数を表す。）

(Wherein R ² is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group, an aryl group, or an aralkyl group, q represents an integer of 1 or 2, and m represents an integer of 0 to 3) .)

（ここで、Ｒ^３及びＲ^４はそれぞれ独立に水素原子又は炭素数１～２０の脂肪族炭化水素基からなり、但しＲ^３及びＲ^４のいずれかは炭素数１～２０の脂肪族炭化水素基からなる。）

(Wherein R ³ and R ⁴ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, provided that either R ³ or R ⁴ is an aliphatic hydrocarbon having 1 to 20 carbon atoms. It consists of a group.)

2. Item 2. The phenol resin according to Item 1, wherein the monovalent or divalent group represented by the general formula (2-2) is 30 to 100 mol% of A100 mol%.

3. Item 3. The phenol resin according to Item 1 or 2, wherein one of R ^{3 and} R ^{4 in} the general formula (3) is a hydrogen atom, and the other of R ³ or R ⁴ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms. .

4). A compound represented by the following general formula (2-2 ′) or a mixture of a compound represented by the following general formula (2-2 ′) and a compound represented by the following general formula (2-1 ′); A compound represented by the following general formula (3 ′) is subjected to condensation polymerization (a naphthalene structure is introduced into the resin skeleton, and an aliphatic hydrocarbon group having 1 to 20 carbon atoms is introduced as a side chain of the resin). ) The resulting phenolic resin.

（ここで、Ｒ^１は炭素数１～１０の脂肪族炭化水素基、アルコキシ基、アリール基、又はアラルキル基からなり、ｐは１又は２の整数を表し、ｒは０～３の整数を表す。）

(Wherein R ¹ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group, an aryl group, or an aralkyl group, p is an integer of 1 or 2, and r is an integer of 0 to 3) .)

（ここで、Ｒ^２は炭素数１～１０の脂肪族炭化水素基、アルコキシ基、アリール基、又はアラルキル基からなり、ｑは１又は２の整数を表し、ｍは０～３の整数を表す。）

(Wherein R ² is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group, an aryl group, or an aralkyl group, q represents an integer of 1 or 2, and m represents an integer of 0 to 3) .)

（ここで、Ｒ^３及びＲ^４はそれぞれ独立に水素原子又は炭素数１～２０の脂肪族炭化水素基からなり、但しＲ^３及びＲ^４のいずれかは炭素数１～２０の脂肪族炭化水素基からなる。）

(Wherein R ³ and R ⁴ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, provided that either R ³ or R ⁴ is an aliphatic hydrocarbon having 1 to 20 carbon atoms. It consists of a group.)

5. An epoxy resin obtained by epoxidizing the phenol resin according to any one of Items 1 to 4.

6). An epoxy resin composition comprising the phenol resin according to any one of Items 1 to 4 and an epoxy resin.

7). [5] An epoxy resin composition comprising the epoxy resin according to [5] above and a phenol resin.

8). A cured product obtained by curing the epoxy resin composition according to Item 6 or 7.

9. A copper-clad laminate using the epoxy resin composition according to item 6 or 7 as a matrix resin.

10. A semiconductor encapsulant using the epoxy resin composition according to item 6 or 7.

According to the present invention, when used as an epoxy resin curing agent, it is possible to provide a novel phenol resin in which the cured product has excellent properties such as heat resistance, moisture resistance, dielectric constant, and dielectric loss tangent. Further, an epoxy resin composition containing the novel phenol resin and epoxy resin, a cured product thereof, a copper-clad laminate using the epoxy resin composition as a matrix resin, and a semiconductor sealing material using the epoxy resin composition Can be provided.

1 is a GPC chart of a phenol resin obtained in Example 1. 2 is a GPC chart of a phenol resin obtained in Example 2. 4 is a GPC chart of a phenol resin obtained in Example 3. 6 is a GPC chart of a phenol resin obtained in Example 4. 6 is a GPC chart of a phenol resin obtained in Example 5. 6 is a GPC chart of a phenol resin obtained in Example 6. 3 is a GPC chart of a phenol resin obtained in Comparative Example 1. 5 is a GPC chart of a phenol resin obtained in Comparative Example 2. 6 is a GPC chart of a phenol resin obtained in Comparative Example 3.

Hereinafter, embodiments of the present invention will be described in detail.
The phenol resin of the present invention is represented by the general formula (1).
In general formula (1), each A independently comprises a monovalent or divalent group represented by general formula (2-1) or general formula (2-2), provided that at least one of A is represented by the general formula It consists of a monovalent or divalent group represented by (2-2). In other words, A is composed of both a group represented by the general formula (2-1) and a group represented by the general formula (2-2), or a group represented by the general formula (2-2) Consists of represented groups only.

In the present invention, from the viewpoint of heat resistance, the monovalent or divalent group represented by the general formula (2-2) is 0.1 to 100 mol% with respect to A100 mol%, preferably It is 10 to 100 mol%, more preferably 30 to 100 mol%, still more preferably 50 to 100 mol%, particularly preferably 100 mol%.

In the general formula (2-1) and the general formula (2-2), R ¹ and R ² represent substituents such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and an octyl group. An aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be linear or branched; preferably a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group, an octyloxy group, etc. May be an alkoxy group of 1 to 10; an aryl group such as a phenyl group or a naphthyl group; or an aralkyl group such as a phenylmethyl group or a phenylethyl group, but has no substituent from an economical viewpoint ( A structure in which r or m is 0 is desirable.

In General formula (1), B consists of a bivalent group represented by General formula (3). R ³ and R ^{4 in} the general formula (3) consist of a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and at least one of R ³ and R ⁴ is an aliphatic group having 1 to 20 carbon atoms. Consists of a hydrocarbon group. In other words, in B, R ³ and R ⁴ are both aliphatic hydrocarbon groups having 1 to 20 carbon atoms, or one of R ³ and R ⁴ is a hydrogen atom and the other is 1 carbon atom. ~ 20 aliphatic hydrocarbon groups.
In the present invention, the aliphatic hydrocarbon group having 1 to 20 carbon atoms constituting at least one of R ³ and R ⁴ is an important chemical structure for achieving a low dielectric constant and a low dielectric loss tangent. It has 3 or more carbon atoms, more preferably 4 or more carbon atoms, more preferably 5 or more carbon atoms, and considering heat resistance, it is preferably 15 or less carbon atoms, more preferably 12 or less carbon atoms, still more preferably 10 carbon atoms. It is as follows.

The phenol resin of the present invention can be suitably obtained by subjecting a phenol component and an aldehyde component to a condensation polymerization reaction in the presence of an acidic catalyst. The resin skeleton has a naphthalene structure and side chains having 1 to 20 carbon atoms. And a divalent hydrocarbon group having an aliphatic hydrocarbon group.
In the present invention, the phenol component is a compound represented by the general formula (2-2 ′) or a compound represented by the general formula (2-2 ′) and the general formula (2-1 ′). A mixture with the compound to be prepared.
In the present invention, from the viewpoint of heat resistance, the compound represented by the general formula (2-2 ′) is 0.1 to 100 mol%, preferably 10 to 100 mol%, out of 100 mol% of the phenol component. More preferably, it is 30 to 100 mol%, further preferably 50 to 100 mol%, particularly preferably 100 mol%.

As a compound (mono- or dihydroxynaphthalene) having a naphthalene skeleton having one or two hydroxyl groups represented by the general formula (2-2 ′), one hydroxyl group such as α-naphthol and β-naphthol is used. Compounds having a naphthalene skeleton and derivatives thereof, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7- Examples thereof include compounds having a naphthalene skeleton having two hydroxyl groups, such as dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene and 2,6-dihydroxynaphthalene, and derivatives thereof.

Here, the derivative refers to 1 to 3 substituents such as an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group, an aryl group, and an aralkyl group in the naphthalene skeleton together with one or two hydroxyl groups. It is a compound which has this. Examples of the hydrocarbon group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and an octyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group, and an octyloxy group. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the aralkyl group include a phenylmethyl group and a phenylethyl group. Among these, specifically, α-naphthol, β-naphthol, 1-hydroxy-2-methyl-naphthalene and the like are preferable, and α-naphthol and β-naphthol are more preferable.

In the present invention, the other component of the phenol component is an aliphatic group having one or two hydroxyl groups in the benzene ring represented by the general formula (2-1 ′) and optionally having 1 to 10 carbon atoms. It is a compound having 1 to 3 substituents such as a hydrocarbon group, an alkoxy group, an aryl group, and an aralkyl group. Examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and an octyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group, and an octyloxy group. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the aralkyl group include a phenylmethyl group and a phenylethyl group. Among these, specifically, phenol, cresol, xylenol, ethylphenol, phenylphenol, allylphenol, resorcin, and the like can be preferably exemplified, and among them, phenol is particularly preferable.

In the present invention, the aldehyde component is a compound represented by the general formula (3 ′). That is, it consists of monoaldehydes having an aliphatic hydrocarbon group having 1 to 20 carbon atoms and / or monoketones having an aliphatic hydrocarbon group having 1 to 20 carbon atoms. The aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferably 3 or more carbon atoms, more preferably 4 or more carbon atoms, still more preferably 5 or more carbon atoms, and preferably 15 or less carbon atoms in consideration of heat resistance. More preferably, it has 12 or less carbon atoms, more preferably 10 or less carbon atoms.
Examples of aldehydes having an aliphatic hydrocarbon group having 1 to 20 carbon atoms include butyraldehyde, valeraldehyde, hexyl aldehyde, heptyl aldehyde, octyl aldehyde, nonyl aldehyde, decyl aldehyde, undecyl aldehyde, laurin aldehyde, tridecyl aldehyde, etc. In terms of heat resistance, dielectric constant, and dielectric loss tangent, hexyl aldehyde, heptyl aldehyde, and octyl aldehyde are preferable.
Examples of ketones having an aliphatic hydrocarbon group having 1 to 20 carbon atoms include methyl isobutyl ketone, dibutyl ketone, methyl amyl ketone, dihexyl ketone, diheptyl ketone, dioctyl ketone, dinonyl ketone, didecyl ketone, diundecyl ketone, and dilaurin ketone. However, dihexyl ketone, diheptyl ketone, and dioctyl ketone are preferable from the viewpoints of heat resistance, dielectric constant, and dielectric loss tangent.
These aldehyde components may be used alone or in combination of two or more.

In the phenol resin of the present invention, the reaction temperature and reaction time during production are not particularly limited. Usually, the reaction is carried out in the absence of a solvent or in the presence of water or an organic solvent such as methanol or methyl ethyl ketone, the reaction temperature is 0 to 150 ° C., preferably 60 to 120 ° C., and the reaction time is the reaction temperature or used. Although it varies depending on the type and amount of the catalyst, it is 0.5 to 24 hours, preferably 1 to 8 hours. The reaction pressure is usually carried out at normal pressure, but there is no problem even if it is carried out under a slight pressure or reduced pressure.

In the reaction step, a catalyst may or may not be used, but an acid catalyst is preferably used. The acid catalyst is not particularly limited, and known acids such as hydrochloric acid, oxalic acid, sulfuric acid, phosphoric acid, paratoluenesulfonic acid may be used alone or in combination of two or more, but sulfuric acid, oxalic acid or paratoluene Sulfonic acid is particularly preferred. Although there is no restriction | limiting in particular in the usage-amount of a phenol component and an aldehyde component, Preferably 1.0 time mole or more phenol component is used with respect to 1 mol of aldehyde components. More preferably, it is 1.5 to 20 times mol.

After completion of the reaction, the phenol resin according to the present invention can be obtained by removing unreacted phenol component and acid catalyst if necessary. A general method for removing the unreacted phenol component is to apply heat while blowing steam under reduced pressure or under reduced pressure, and distill the phenol component out of the system. The removal of the acid catalyst includes a method such as washing with water.

The number average molecular weight of the phenol resin represented by the general formula (1) of the present invention is not particularly limited, but is preferably 250 to 20000, more preferably 400 to 10,000 from the viewpoint of workability and heat resistance. More preferably, it is 500 to 2000.

The softening point of the phenol resin represented by the general formula (1) of the present invention is not particularly limited, but is preferably 45 to 180 ° C, more preferably 50 to 150 ° C from the viewpoint of workability and heat resistance. Yes, more preferably 50 to 120 ° C.

The melt viscosity (ICI viscosity) of the phenol resin represented by the general formula (1) of the present invention is not particularly limited, but from the viewpoint of fluidity and heat resistance, the melt viscosity at 150 ° C. (ICI viscosity) is preferably The pressure is 10 to 1500 mPa · s, more preferably 30 to 1200 mPa · s, and still more preferably 50 to 900 mPa · s.

The hydroxyl group equivalent of the phenol resin represented by the general formula (1) of the present invention is not particularly limited, but is preferably 100 to 550 g / eq, more preferably from the viewpoint of heat resistance, dielectric constant and dielectric loss tangent. 120 to 500 g / eq, more preferably 150 to 300 g / eq.

The phenolic resin of the present invention can be used in various fields in the same manner as ordinary phenolic resins. For example, the phenol resin of the present invention can be suitably used as a curing agent for epoxy resins. When used as a curing agent for an epoxy resin, it is mixed with an epoxy resin according to a known method and used as an epoxy resin composition.

Further, the phenol resin of the present invention can be epoxidized to form a novolac type epoxy resin. That is, the epoxy resin of the present invention is an epoxy resin obtained by epoxidizing the phenol resin of the present invention.
The epoxidation reaction is not limited, but the phenol resin is converted into a glycidyl ether at 10 to 120 ° C. in the presence of an epihalohydrin and an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. It can implement suitably by making it.

A known method can be suitably employed for the glycidyl etherification reaction.
As the epihalohydrins, substituted or unsubstituted epihalohydrins such as epichlorohydrin, α-methylepichlorohydrin, γ-methylepichlorohydrin, epibromohydrin, etc. can be used, but they are easily available industrially and react with hydroxyl groups. It is preferable to use epichlorohydrin from the viewpoint of good properties.
The usage-amount of epihalohydrins is not specifically limited, Although it can select suitably according to the target molecular weight, Usually an excess amount is used with respect to the hydroxyl group of a phenol resin.
The alkali metal hydroxide used for the reaction may be a solid or an aqueous solution thereof. When using an aqueous solution, water and epihalohydrin are continuously flowed out of the reaction system under reduced pressure or normal pressure while adding an aqueous solution of alkali metal hydroxide to the reaction system to remove moisture. Then, a method of continuously returning the epihalohydrins into the reaction system can be employed. The amount of the alkali metal hydroxide used can be 0.8 to 2.0 mol, preferably 0.9 to 1.3 mol, per mol of the hydroxyl group of the phenol resin.
In the reaction, it is preferable in the progress of the reaction that alcohols such as methanol, ethanol and isopropyl alcohol, aprotic polar solvents such as dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran and dioxane are present.

The epoxy resin of the present invention can also be used in various fields in the same manner as ordinary epoxy resins. The epoxy resin of the present invention can be suitably used as an epoxy resin composition by mixing, for example, amines, amides, acid anhydrides, phenol resins and the like as a curing agent.

One embodiment of the epoxy resin composition of the present invention is characterized by containing an epoxy resin and the phenol resin of the present invention. In this case, the epoxy resin is not particularly limited, and glycidyl ether type epoxy resin such as bisphenol F type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, triphenylmethane type epoxy resin, biphenyl type epoxy resin, glycidyl An ester type epoxy resin, a glycidylamine type epoxy resin, or the like can be suitably used. Although the phenol resin of this invention has a role of the hardening | curing agent of an epoxy resin, it can also be used, for example, mixing with amines, amides, an acid anhydride, and another phenol resin. When a mixture of the phenol resin of the present invention and another phenol resin is used as the curing agent, examples of the other phenol resin include phenol resins such as a phenol novolac resin, a phenol aralkyl resin, and a phenol biphenylene resin. . However, in order to obtain a cured product excellent in low dielectric constant and low dielectric loss tangent, the ratio of the phenol resin of the present invention to the total phenol resin of the curing agent is 10 to 100% by mass, preferably 50 to 100% by mass. More preferably, it is 70 to 100% by mass, and further preferably 100% by mass.

Another embodiment of the epoxy resin composition of the present invention is characterized by containing the epoxy resin of the present invention. In this case, the epoxy resin is an epoxy resin other than the epoxy resin of the present invention, for example, glycidyl such as bisphenol F type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, triphenylmethane type epoxy resin, biphenyl type epoxy resin, etc. You may mix and use an ether type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, etc. As the curing agent, known epoxy resin curing agents can be used, and examples thereof include amines, amides, acid anhydrides, phenol resins, and the like, but the phenol resin of the present invention may also be used.

In the epoxy resin composition of the present invention, in each embodiment, the blending ratio of the curing agent can be appropriately selected. For example, when a fail resin is used as a curing agent, an amount such that the number of moles of the phenolic hydroxyl group of the phenol resin is 0.2 to 1.2 with respect to 1 mole of the epoxy group of the epoxy resin is preferable. The amount is 0.3 to 1.0 mol.

The epoxy resin composition of the present invention is a known component such as a curing accelerator, a filler, a flame retardant, a coupling agent, a colorant, and the like, which are used in ordinary epoxy resin compositions other than epoxy resins and curing agents. The additive may be included.
Examples of the curing accelerator include organic phosphine compounds and their boron salts, tertiary amines, quaternary ammonium salts, imidazoles and their tetraphenylboron salts.
As the filler, either an organic filler or an inorganic filler can be suitably used. However, inorganic fillers such as amorphous silica, crystalline silica, alumina, and glass are preferable.
Examples of the flame retardant include triphenyl phosphate (TPP), tricresyl phosphate (TCP), and cresyl diphenyl phosphate (CDP).

The conditions for curing the epoxy resin composition of the present invention can be appropriately selected. For example, a cured product can be obtained by heat treatment at 50 to 300 ° C., preferably 130 to 250 ° C., for 0.01 to 20 hours, preferably 0.1 to 10 hours.

The cured product of the epoxy resin composition of the present invention has excellent properties such as moisture resistance, low dielectric and low dielectric loss tangent, and heat resistance. For this reason, it can be suitably used in the field of semiconductors and electronic components as printed wiring board materials, interlayer insulating materials for built-up boards, semiconductor sealing materials, conductive adhesive materials, and the like.

The copper-clad laminate of the present invention is characterized by using the epoxy resin composition of the present invention as a matrix resin. Specifically, the copper-clad laminate of the present invention obtains a prepreg by impregnating a base material with the epoxy resin composition of the present invention, laminates the prepreg and copper foil, and cures and forms integrally. Can be obtained.

As the base material used for the prepreg, for example, a known base material such as paper, glass cloth, glass mat, aramid fiber, carbon fiber or the like can be used.

The conditions for drying the substrate impregnated with the epoxy resin composition of the present invention can be appropriately selected. For example, the substrate can be heated in a temperature range of 80 to 200 ° C. in a drying furnace.
A predetermined number of prepregs thus obtained and a copper foil are laminated and laminated, and the copper foil and a plurality of prepregs are cured and integrated by heating and pressing, for example, with a press heated to about 50 to 250 ° C. Can be obtained.

When the epoxy resin composition is impregnated into a substrate such as glass cloth, the epoxy resin composition can be uniformly dissolved in a solvent and used as a varnish for appropriate impregnation. Examples of the solvent at that time include methyl ethyl ketone, N, N-dimethylformamide, acetone, and methyl isobutyl ketone.

The epoxy resin composition of the present invention can be suitably used as a semiconductor sealing material. In that case, the epoxy resin composition is a method in which a compounding agent such as an epoxy resin, a curing agent for epoxy resin, and an inorganic filler is sufficiently melt-mixed until uniform using an extruder, kneader, roll or the like as necessary. Prepared by Silica is usually used as the inorganic filler at that time, and the filling rate is preferably in the range of 30 to 95 parts by weight per 100 parts by weight of the epoxy resin composition, and particularly, flame retardant. 70 parts by mass or more is particularly preferable in order to improve the moisture resistance and solder crack resistance and decrease the linear expansion coefficient, and 80 parts by mass or more is more effective in order to significantly increase these effects. Can be increased. The semiconductor encapsulating material of the present invention uses the epoxy resin composition of the present invention, and is molded by casting or using a transfer molding machine, an injection molding machine, etc., and further at 50 to 200 ° C. for 2 to 10 The semiconductor chip can be suitably sealed by a method of curing by heating for a period of time.

Next, the present invention will be specifically described with reference to examples and comparative examples. In the following, “part” and “%” are based on mass unless otherwise specified. The present invention is not limited to these examples.

A method for measuring the characteristics used in the following examples is shown below.
1) Measuring method of hydroxyl equivalent of phenol resin The hydroxyl equivalent of phenol resin was measured by a method in which phenol resin was acetylated with acetyl chloride, excess acetyl chloride was decomposed with water and titrated with alkali. The specific procedure is as follows.
To a solution obtained by dissolving 1 g of a sample in 10 mL of 1,4-dioxane, 10 mL of an anhydrous toluene solution of 1.5 mol / L acetyl chloride is added and cooled to 0 ° C. To this, 2 mL of pyridine is added and reacted in a water bath at 60 ± 1 ° C. for 1 hour. After the reaction, the reaction mixture is cooled, 25 mL of pure water is added and mixed to sufficiently decompose acetyl chloride. Next, 25 mL of acetone and phenolphthalein are added to this solution, and titration is performed using a 1 mol / L aqueous potassium hydroxide solution until the sample solution turns reddish purple. A blank (no sample) is also measured by the above operation.
The hydroxyl equivalent was calculated by the following formula.
Hydroxyl equivalent [g / eq] = (1000 × W) / (f × (ba))
Here, W, f, b, and a are as follows.
W: Sample weight [g]
f: Factor of 1 mol / L potassium hydroxide aqueous solution b: Amount of 1 mol / L potassium hydroxide aqueous solution required for blank measurement [mL]
a: Amount of 1 mol / L potassium hydroxide aqueous solution required for sample measurement [mL]

2) Measuring method of softening point The softening point measuring apparatus FP83HT by METTLER TOLEDO Co., Ltd. was used, and it measured on the temperature increase rate of 2 degree-C / min conditions.

3) Method for measuring number average molecular weight (Mn) GPC measurement was performed under the following conditions using a gel permeation chromatograph analyzer HLC-8220GPC manufactured by Tosoh Corporation, and Mn was calculated from a calibration curve of standard polystyrene.
Column: TSK-GEL H type G2000H × L 4 G3000H × L 1 G4000H × L 1 Measurement conditions Temperature: 40 ° C.
Solvent: THF
Supply pressure: 14.2 MPa
Flow rate: 1 mL / min Detector: UV

4) Measuring method of 150 ° C. melt viscosity (ICI viscosity) Using an ICI cone plate viscometer MODEL CV-1S manufactured by TOA Kogyo Co., Ltd., setting the plate temperature to 150 ° C., and weighing a predetermined amount of the sample. A weighed sample was placed on the plate portion, pressed from above with a cone, allowed to stand for 90 seconds, the cone was rotated, and the torque value was read as ICI viscosity.

(Example 1)
In a 500 mL three-necked round bottom flask equipped with a thermometer, charging / distilling outlet and stirrer, phenol 42.83 g, α-naphthol 32.31 g, n-octylaldehyde 51.20 g, methanol 36.00 g and paratoluenesulfonic acid 0 .105 g was charged and stirred in a nitrogen stream at 100 ° C. for 5 hours. Thereafter, the catalyst, α-naphthol and phenol in the resin were distilled off by washing with water at 95 ° C. and dehydration under reduced pressure to obtain a phenol resin. A GPC chart of the obtained phenol resin is shown in FIG. The softening point of this resin was 59.4 ° C, the hydroxyl equivalent was 223 g / eq, Mn was 1122, and the ICI viscosity was 100 mPa · s at 150 ° C.

(Example 2)
In a 500 mL three-necked round bottom flask equipped with a thermometer, charging / distilling outlet and stirrer, phenol 21.73 g, α-naphthol 64.63 g, n-octylaldehyde 51.20 g, methanol 47.00 g and paratoluenesulfonic acid 0 121 g was charged and stirred at 100 ° C. for 5 hours in a nitrogen stream. Thereafter, the catalyst, α-naphthol and phenol in the resin were distilled off by washing with water at 95 ° C. and dehydration under reduced pressure to obtain a phenol resin. The GPC chart of the obtained phenol resin is shown in FIG. The softening point of this resin was 84.9 ° C., the hydroxyl group equivalent was 244 g / eq, Mn was 1131, and the ICI viscosity was 360 mPa · s at 150 ° C.

(Example 3)
A 500 mL three-necked round bottom flask equipped with a thermometer, condenser, charging / distilling outlet and stirrer was charged with 73.44 g of α-naphthol, 22.98 g of pure water, and 0.367 g of paratoluenesulfonic acid. The temperature was raised while stirring. 21.60 g of butyraldehyde was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was further stirred at 100 ° C. for 3 hours. After the reaction was completed, the catalyst in the resin was removed by washing with water at 95 ° C. The temperature was raised to 140 ° C., and free α-naphthol was removed by blowing water vapor under reduced pressure to obtain a phenol resin. The GPC chart of the obtained phenol resin is shown in FIG. The softening point of this resin was 101.4 ° C., the hydroxyl group equivalent was 186 g / eq, Mn was 614, and the ICI viscosity was 840 mPa · s at 150 ° C.

Example 4
A 500 mL three-necked round bottom flask equipped with a thermometer, a charging / distilling outlet and a stirrer was charged with 73.44 g of α-naphthol, 38.40 g of n-octylaldehyde, 0.103 g of paratoluenesulfonic acid, and 34.00 g of methanol. Stir at 100 ° C. for 4 hours. Thereafter, the catalyst in the resin was removed by washing with water at 95 ° C. The temperature was raised to 150 ° C., and free α-naphthol was removed by blowing water vapor under reduced pressure to obtain a phenol resin. The GPC chart of the obtained phenol resin is shown in FIG. The softening point of this resin was 98.7 ° C., the hydroxyl group equivalent was 239 g / eq, Mn was 1022, and the ICI viscosity was 560 mPa · s at 150 ° C.

(Example 5)
A 500 mL three-necked round bottom flask equipped with a thermometer, charging / distilling outlet and stirrer was charged with 41.62 g of α-naphthol, 31.28 g of lauric aldehyde, and 0.058 g of paratoluenesulfonic acid, and stirred at 100 ° C. for 6 hours. . Thereafter, the catalyst and α-naphthol in the resin were distilled away by washing with methanol / water = 50/200 (mass / mass) at 80 ° C., and dehydrating under reduced pressure to obtain a phenol resin. A GPC chart of the obtained phenol resin is shown in FIG. The softening point of this resin was 46.2 ° C., the hydroxyl equivalent was 288 g / eq, Mn was 1083, and the ICI viscosity was 50 mPa · s at 150 ° C.

(Example 6)
A 500 mL three-necked round bottom flask equipped with a thermometer, charging / distilling outlet and stirrer was charged with 48.00 g of 1,6-dihydroxynaphthalene, 25.60 g of n-octylaldehyde, and 31.54 g of methyl ethyl ketone, and in a nitrogen stream 80 A phenol resin was obtained by stirring at 11 ° C. for 11 hours. A GPC chart of the obtained phenol resin is shown in FIG. The hydroxyl equivalent of this resin was 147 g / eq, and Mn was 1413.

(Comparative Example 1)
A 500 mL three-necked round bottom flask equipped with a thermometer, charging / distilling outlet and stirrer was charged with 94.0 g of phenol, 75.29 g of n-octylaldehyde and 0.132 g of paratoluenesulfonic acid, and heated to 100 ° C. in a nitrogen stream. And stirred for 24 hours. Thereafter, in order to remove the catalyst in the resin, washing was performed at 95 ° C. Furthermore, the temperature was raised to 150 ° C., and free phenol was removed by blowing water vapor under heating and decompression to obtain a phenol resin. A GPC chart of the obtained phenol resin is shown in FIG. The softening point of this resin was 40.8 ° C., the hydroxyl equivalent was 217 g / eq, Mn was 1036, and the ICI viscosity was 10 mPa · s at 150 ° C.

(Comparative Example 2)
A 500 mL three-necked round bottom flask equipped with a thermometer, condenser, charging / distilling outlet and stirrer was charged with 97.92 g of α-naphthol, 30.64 g of pure water and 0.970 g of oxalic acid, and stirred from room temperature to 100 ° C. While raising the temperature. 28.57 g of 42% formalin aqueous solution was added dropwise over 1 hour. After completion of dropping, the mixture was further stirred at 100 ° C. for 1 hour, and then heated to 180 ° C. in 3 hours. After the reaction was completed, the temperature was raised to 200 ° C., and free α-naphthol was removed by blowing water vapor under reduced pressure to obtain a phenol resin. A GPC chart of the obtained phenol resin is shown in FIG. The softening point of this resin was 130.1 ° C., the hydroxyl group equivalent was 156 g / eq, Mn was 628, and the ICI viscosity was 4000 mPa · s or more at 150 ° C.

(Comparative Example 3)
A bisphenol A type phenol resin comprising bisphenol A and formaldehyde represented by the following formula (4), having a hydroxyl group equivalent of 118 g / eq, a softening point of 126 ° C., and Mn of 1023. A GPC chart of this resin is shown in FIG.

Hereinafter, the epoxy resin composition containing the phenol resin of the present invention will be described.

First, the material used in the example relating to the epoxy resin composition will be described.
1) Epoxy resin Bisphenol A type epoxy resin 828EL: manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 186 g / eq
2) Epoxy resin curing agent Phenol resins of Examples 1 to 6 and Comparative Examples 1 to 3 3) Curing accelerator 2-ethyl-4-methylimidazole 2E4MZ: manufactured by Shikoku Kasei Kogyo Co., Ltd.

The composition of the epoxy resin composition was determined as follows.
An epoxy resin composition was obtained by blending the epoxy resin and an epoxy resin curing agent in such an amount that the equivalent ratio of the hydroxyl group equivalent to the epoxy equivalent was blended. The blending amount of the curing accelerator was adjusted so that the gel time at the measurement temperature of 170 ° C. of the epoxy resin composition was 280 seconds to 320 seconds.
Table 1 shows the composition of the epoxy resin composition (the amount of the epoxy resin curing agent and the curing accelerator based on 100 parts by mass of the epoxy resin).

The gel time of the epoxy resin composition was measured by the following method.
Equipment used: Cyber Co., Ltd. Automatic curing time measuring device Measurement conditions: 170 ° C 600 rpm
Measurement method: First, an epoxy resin composition mixed at a ratio shown in Table 1 was prepared into a 60 mass% methyl ethyl ketone (MEK) solution. Next, about 0.6 mL of the MEK solution of the epoxy resin composition was weighed on the hot plate of the apparatus and measured. The time when the torque became 20% of the measurement upper limit torque value of the apparatus was measured as the gel time.

Next, the evaluation method of the hardened | cured material obtained from an epoxy resin composition is shown below.
1) Heat resistance (glass transition temperature)
The cured epoxy product was cut into a size of 35 mm × 4 mm × 2 mm and used as a measurement sample. The glass transition temperature was evaluated using a dynamic viscoelasticity measuring device (DMA: “RSA G2” manufactured by TA Instruments, Inc .; frequency 1.0 Hz, temperature rising rate 3 ° C./min).
2) Water absorption rate The epoxy cured product was cut into a size of 30 mm × 15 mm × 4 mm to obtain a measurement sample. The sample was immersed in pure water at 95 ° C., and the mass increase rate calculated from the mass before immersion and the mass after immersion for 24 hours was defined as the water absorption rate. The water absorption is an index representing moisture resistance, and a smaller value indicates that the moisture resistance is good.
3) Dielectric constant and dielectric loss tangent The epoxy resin cured product is cut out into 1.5 mm x 1.5 mm x 80 mm dimensions as a measurement sample, and a cavity resonance method using "ADMSO-10 (1 GHz)" manufactured by AET Co., Ltd. Then, the dielectric constant and dielectric loss tangent at 1 GHz of the test piece after storing for 48 hours in a room of 23 ° C. and 50% humidity after absolute drying were measured.

(Example 7)
After the phenol resin, the epoxy resin, and the curing accelerator obtained in Example 1 were melt-mixed at the ratios shown in Table 1, the melt mixture was poured into a mold and heat-treated at 200 ° C. for 5 hours. Cured epoxy resin was obtained by curing.
The cured product was evaluated after being cut into a predetermined size. The evaluation results are shown in Table 1.

(Example 8)
Except having used the phenol resin obtained in Example 2 instead of the phenol resin obtained in Example 1, the same operation as Example 7 was performed and the epoxy resin hardened material was obtained. Table 1 shows the composition and evaluation results of the cured product.

Example 9
Except having used the phenol resin obtained in Example 3 instead of the phenol resin obtained in Example 1, the same operation as Example 7 was performed and the epoxy resin hardened material was obtained. Table 1 shows the composition and evaluation results of the cured product.

(Example 10)
Except having used the phenol resin obtained in Example 4 instead of the phenol resin obtained in Example 1, the same operation as Example 7 was performed and the epoxy resin hardened material was obtained. Table 1 shows the composition and evaluation results of the cured product.

(Example 11)
Except having used the phenol resin obtained in Example 5 instead of the phenol resin obtained in Example 1, the same operation as Example 7 was performed and the cured epoxy resin was obtained. Table 1 shows the composition and evaluation results of the cured product.

Example 12
Except having used the phenol resin obtained in Example 6 instead of the phenol resin obtained in Example 1, the same operation as Example 7 was performed and the epoxy resin hardened | cured material was obtained. Table 1 shows the composition and evaluation results of the cured product.

(Comparative Example 4)
Except using the phenol resin obtained in Comparative Example 1 instead of the phenol resin obtained in Example 1, the same operation as in Example 7 was performed to obtain a cured epoxy resin. Table 1 shows the composition and evaluation results of the cured product.

(Comparative Example 5)
Except using the phenol resin obtained in Comparative Example 2 instead of the phenol resin obtained in Example 1, the same operation as in Example 7 was performed to obtain a cured epoxy resin. Table 1 shows the composition and evaluation results of the cured product.

(Comparative Example 6)
Except having used the bisphenol A type phenol resin of the comparative example 3 instead of the phenol resin obtained in Example 1, the same operation as Example 7 was performed and the epoxy resin hardened | cured material was obtained. Table 1 shows the composition and evaluation results of the cured product.

Hereinafter, a prepreg using the epoxy resin composition of the present invention and a copper-clad laminate using the prepreg will be described.

First, materials used in the following examples will be described.
1) Epoxy resin Bisphenol A type epoxy resin 828EL: manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 186 g / eq
2) Epoxy resin curing agent Phenol resin of Example 4 3) Curing accelerator 2-Ethyl-4-methylimidazole 2E4MZ: Shikoku Kasei Kogyo Co., Ltd. 4) Solvent Methyl ethyl ketone (hereinafter MEK): Wako Pure Chemical Industries, Ltd. 5 ) Glass cloth Non-alkali treated glass cloth M7628-105: Arisawa Manufacturing Co., Ltd. 6) Copper foil Electrolytic copper foil CF-T9B-THE: Fukuda Metal Foil Powder Co., Ltd., thickness 35 μm

Next, the evaluation method of a laminated board is shown below.
1) Peel strength A laminate obtained by forming a strip-like copper foil having a width of 10 mm by etching was used as a test piece. Using an autograph (“AG-5000D” manufactured by Shimadzu Corporation), the 90 ° copper foil peel strength was measured at a test speed of 50 mm / min.
2) Heat resistance (glass transition temperature)
The laminated plate after the etching treatment was cut out to 12 mm × 40 mm to obtain a test piece. The glass transition temperature was evaluated using a dynamic viscoelasticity measuring device (DMA: “RSA G2” manufactured by TA Instruments, Inc .; frequency 1.0 Hz, temperature rising rate 3 ° C./min).

(Example 13)
The phenol resin obtained in Example 4, the epoxy resin, the curing accelerator, and methyl ethyl ketone as the solvent were blended in the proportions shown in Table 2 to prepare a varnish composed of the epoxy resin composition. This varnish was impregnated with glass cloth and dried at 130 ° C. for 15 minutes to obtain a prepreg. This prepreg is cut out to 150 mm × 95 mm, and after stacking 8 sheets, it is sandwiched between copper foils, pressed with a hot press heated to 170 ° C., and then heat-treated at 200 ° C. for 90 minutes to obtain a copper-clad laminate. It was.
Evaluation was performed on the laminate after removing unnecessary portions of the copper foil on the surface of the copper-clad laminate with an etching solution and washing. The evaluation results are shown in Table 2.

As can be seen from the above examples and comparative examples, the cured product obtained by curing the epoxy resin composition composed of the phenol resin of the present invention is compared with a cured product made of a general epoxy-phenol resin, Excellent heat resistance, moisture resistance, dielectric constant and dielectric loss tangent. Moreover, the copper clad laminated board was able to be suitably produced suitably using the epoxy resin composition comprised from the phenol resin of this invention. The phenolic resin of the present invention is used as a copper-clad laminate, a semiconductor encapsulant, etc., for a semiconductor or electronic component such as a copper-clad laminate material, an interlayer insulating material for a built-up substrate, a semiconductor encapsulant, or a conductive adhesive material. Very useful for applications.

According to the present invention, when used as an epoxy resin curing agent, it is possible to provide a novel phenol resin in which the cured product has excellent properties such as heat resistance, moisture resistance, dielectric constant, and dielectric loss tangent. Further, an epoxy resin composition containing the novel phenol resin and epoxy resin, a cured product thereof, a copper-clad laminate using the epoxy resin composition as a matrix resin, and a semiconductor sealing material comprising the epoxy resin composition Can be provided.

Claims (10)

A phenol resin represented by the following general formula (1).

(Here, each A independently comprises a monovalent or divalent group represented by the following general formula (2-1) or general formula (2-2), provided that at least one of A is represented by the following general formula ( 2-2) is composed of a monovalent or divalent group, B is composed of a divalent group represented by the following general formula (3), and n is an integer of 0 to 100.)

(Wherein R ¹ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group, an aryl group, or an aralkyl group, p is an integer of 1 or 2, and r is an integer of 0 to 3) (However, p + r represents an integer of 1 to 4 in the case of a divalent group.)

(Wherein R ² is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group, an aryl group, or an aralkyl group, q represents an integer of 1 or 2, and m represents an integer of 0 to 3) .)

(Wherein R ³ and R ⁴ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, provided that either R ³ or R ⁴ is an aliphatic hydrocarbon having 1 to 20 carbon atoms. It consists of a group.) The phenol resin according to claim 1, wherein the monovalent or divalent group represented by the general formula (2-2) is 30 to 100 mol% of A100 mol%. 3. The phenol resin according to claim 1, wherein one of R ^{3 and} R ^{4 in} the general formula (3) is a hydrogen atom, and the other of R ^{3 and} R ⁴ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms. . A compound represented by the following general formula (2-2 ′) or a mixture of a compound represented by the following general formula (2-2 ′) and a compound represented by the following general formula (2-1 ′); A phenol resin obtained by condensation polymerization with a compound represented by the following general formula (3 ′).

(Wherein R ¹ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group, an aryl group, or an aralkyl group, p is an integer of 1 or 2, and r is an integer of 0 to 3) .)

(Wherein R ² is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group, an aryl group, or an aralkyl group, q represents an integer of 1 or 2, and m represents an integer of 0 to 3) .)

(Wherein R ³ and R ⁴ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, provided that either R ³ or R ⁴ is an aliphatic hydrocarbon having 1 to 20 carbon atoms. It consists of a group.) An epoxy resin obtained by epoxidizing the phenol resin according to any one of claims 1 to 4. An epoxy resin composition comprising the phenol resin according to any one of claims 1 to 4 and an epoxy resin. An epoxy resin composition comprising the epoxy resin according to claim 5 and a phenol resin. Hardened | cured material formed by hardening | curing the epoxy resin composition of Claim 6 or 7. A copper-clad laminate using the epoxy resin composition according to claim 6 or 7 as a matrix resin. The semiconductor sealing material using the epoxy resin composition of Claim 6 or 7.

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