KR20130037686A - B stage sheet, metal foil with applied resin, metal substrate and led substrate - Google Patents

Abstract

The B stage sheet is comprised from the epoxy resin which has a biphenyl structure, the hardening | curing agent which has a partial structure represented by following General formula (IIa) etc., an inorganic filler, and the semi-hardened | cured material of the epoxy resin composition containing an elastomer. In the following formula, m and n represent a positive number, and Ar represents the group represented by the following general formula (IIIa) or (IIIb). R ¹¹ and R ¹⁴ represent a hydrogen atom or a hydroxyl group. R ¹² and R ¹³ represent a hydrogen atom or an alkyl group.
[Formula 1]

Description

B stage sheet, metal foil with resin, metal substrate, and LED substrate {B STAGE SHEET, METAL FOIL WITH APPLIED RESIN, METAL SUBSTRATE AND LED SUBSTRATE}

The present invention relates to a B stage sheet, a metal foil with a resin, a metal substrate, and an LED substrate.

With the progress of densification and compactness of electronic devices, heat dissipation of electronic parts such as semiconductors has become a big problem. Therefore, the resin composition which has high thermal conductivity and high electrical insulation is calculated | required, and has been put into practical use as a heat conductive sealing material and a heat conductive adhesive agent.

For the high heat dissipation of the epoxy resin composition, a method of adding a substance having a higher thermal conductivity than the fused silica commonly used in sealing epoxy resin compositions such as crystalline silica, alumina and aluminum nitride as an inorganic filler has been conventionally reported. When a large amount of crystalline silica, alumina, aluminum nitride, or the like is added in order to obtain sufficient heat dissipation, moldability such as fluidity and curability of the epoxy resin composition is often decreased, or insulation reliability is often caused.

Regarding the approach from the inorganic filler, reports such as attempting high heat dissipation of the sealing epoxy resin composition have also been observed in recent years. For example, Japanese Patent No. 2874089 discloses a combination of a so-called mesogen-type resin having a biphenyl skeleton and the like and a novolakized resin such as catechol and resorcinol to increase the orientation of the resin skeleton to reduce internal thermal resistance. It is disclosed that it is possible to increase the heat dissipation of the epoxy resin composition.

Moreover, Japanese Unexamined Patent Publication No. 2008-13759 discloses an epoxy resin composition containing an epoxy resin showing a liquid crystal and an alumina powder, and is said to have high thermal conductivity and excellent processability.

In addition, Japanese Patent Application Laid-Open No. 2007-262398 discloses an epoxy resin composition containing an epoxy resin having a biphenyl skeleton, a curing agent having an xanthene skeleton, and an inorganic filler, whereby a cured resin excellent in heat dissipation can be formed. .

However, with respect to novolaked resins, such as catechol and resorcinol, which are described in Japanese Patent No. 2874089, gelation tends to occur at the time of resin synthesis, a softening point is high, and difficulty in producing an epoxy resin composition for sealing is used. There was a problem.

Moreover, in the epoxy resin composition of Unexamined-Japanese-Patent No. 2008-13759, sufficient electrical insulation may not be obtained in some cases.

SUMMARY OF THE INVENTION The present invention has been made in view of the above, and a B-stage sheet capable of forming a cured resin having excellent thermal conductivity and excellent electrical insulation, and having excellent flexibility, and a metal foil with a resin, a metal substrate, and an LED substrate using the same It is a subject to offer.

The present invention includes the following aspects.

Epoxy resin containing the epoxy resin which has a partial structure represented by <1> following general formula (I), the hardening agent which has a partial structure represented by at least one of following general formula (IIa)-(IId), an inorganic filler, and an elastomer B stage sheet which is a semi-carbide of the composition.

[Formula 1]

(In General Formula (I), R <^1> -R <^8> represents a hydrogen atom or a methyl group each independently.)

[Formula 2]

(3)

[Formula 4]

[Chemical Formula 5]

(M and n respectively independently represent a positive number, and Ar represents group represented by either of the following general formula (IIIa) and (IIIb) in general formula (IIa)-(IId).)

[Formula 6]

(In General Formula (IIIa) and (IIIb), R ¹¹ and R ¹⁴ each independently represent a hydrogen atom or a hydroxyl group. R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.)

<2> The said inorganic filler is the 1st alumina group whose particle diameter D50 is 7 micrometers or more and 35 micrometers or less corresponding to 50% of accumulation from the small particle size side of a weight cumulative particle size distribution, and the said particle diameter D50 is 1 micrometer or more and less than 7 micrometers. The first alumina group in the total mass of the first alumina group, the second alumina group, and the third alumina group, including the second alumina group and the third alumina group having the particle diameter D50 of less than 1 μm. The content rate of the said alumina group is 60 mass% or more and 70 mass% or less, The content rate of the said 2nd alumina group is 15 mass% or more and 30 mass% or less, Moreover, the content rate of the said 3rd alumina group is 1 mass% or more and 25 mass% or less, The B stage sheet as described in said <1> whose content ratio (2nd alumina group / 3rd alumina group) of the said 2nd alumina group with respect to a 3rd alumina group is 0.9 or more and 1.7 or less on a mass basis.

<3> The B stage sheet according to the above <2>, wherein a content ratio (first alumina group / second alumina group) of the first alumina group to the second alumina group is 2.0 or more and 5.0 or less on a mass basis.

The <4> above-mentioned elastomer is a B stage sheet in any one of said <1>-<3> containing the acrylic elastomer of a weight average molecular weight 100,000 or more and 800,000 or less.

The B stage sheet in any one of said <1>-<4> whose content rate (hardening agent / epoxy resin) of the said hardening | curing agent with respect to the total content of <5> said epoxy resin is 0.95 or more and 1.25 or less on an equivalent basis.

Metal foil with resin provided with <6> metal foil and the B stage sheet in any one of said <1>-<5> arrange | positioned on the said metal foil.

<7> metal support body, the cured resin layer which is the hardened | cured material of the B-stage sheet in any one of said <1>-<5> arrange | positioned on the said metal support body, and metal foil arrange | positioned on the said cured resin layer Metal substrate.

It consists of a <8> metal support body, the cured resin layer which is the hardened | cured material of the B stage sheet in any one of said <1>-<5> arrange | positioned on the said metal support body, and the metal foil arrange | positioned on the said cured resin layer. An LED substrate comprising a circuit layer and an LED element disposed on the circuit layer.

The hardening | curing agent and inorganic filler which are arrange | positioned on the <9> metal foil and the said metal foil, and have a partial structure represented by at least one of the following general formula (IIa)-(IId) which have a partial structure represented by following General formula (I). Metal foil with resin provided with the semi-hardened resin layer which is a semi-hardened material of the epoxy resin composition containing an elastomer.

[Formula 7]

(In General Formula (I), R <^1> -R <^8> represents a hydrogen atom or a methyl group each independently.)

[Formula 8]

[Chemical Formula 9]

[Formula 10]

[Formula 11]

(M and n represent a positive number, and Ar represents the group represented by either of the following general formula (IIIa) or (IIIb) in general formula (IIa)-(IId).)

[Chemical Formula 12]

(In General Formula (IIIa) and (IIIb), R ¹¹ and R ¹⁴ each independently represent a hydrogen atom or a hydroxyl group. R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.)

A curing agent which is disposed on a <10> metal support and the said metal support, and has a partial structure represented by at least one of the following general formula (IIa)-(IId) which has a partial structure represented by following General formula (I), The metal substrate provided with the cured resin layer which is the hardened | cured material of the resin composition containing an inorganic filler and an elastomer, and the metal foil arrange | positioned on the said cured resin layer.

[Chemical Formula 13]

(In General Formula (I), R <^1> -R <^8> represents a hydrogen atom or a methyl group each independently.)

[Formula 14]

[Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

(M and n represent a positive number, and Ar represents the group represented by either of the following general formula (IIIa) or (IIIb) in general formula (IIa)-(IId).)

[Chemical Formula 18]

(In General Formula (IIIa) and (IIIb), R ¹¹ and R ¹⁴ each independently represent a hydrogen atom or a hydroxyl group. R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.)

The resin composition containing the epoxy resin which has a partial structure represented by <11> following General formula (I), the hardening agent, inorganic filler, and elastomer which have a partial structure represented by at least one of following General formula (IIa)-(IId) is metal foil The manufacturing method of metal foil with resin containing the process of apply | coating on a layer, and forming a resin layer, and the B stage forming process which heat-processes the said resin layer and makes it a semi-hardened resin layer.

[Formula 19]

(In General Formula (I), R <^1> -R <^8> represents a hydrogen atom or a methyl group each independently.)

[Chemical Formula 20]

[Chemical Formula 21]

[Formula 22]

(23)

(M and n represent a positive number, and Ar represents the group represented by either of the following general formula (IIIa) or (IIIb) in general formula (IIa)-(IId).)

&Lt; EMI ID =

(In General Formula (IIIa) and (IIIb), R ¹¹ and R ¹⁴ each independently represent a hydrogen atom or a hydroxyl group. R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.)

ADVANTAGE OF THE INVENTION According to this invention, the resin hardened | cured material which has the outstanding thermal conductivity and the outstanding electrical insulation can be formed, and the B-stage sheet excellent in flexibility, the metal foil with resin using this, a metal substrate, and LED board | substrate can be provided.

1 is a graph showing an example of a weight average molecular weight change of a phenol resin at the time of synthesis of the curing agent (1) according to the present embodiment.
FIG. 2 is a graph showing an example of the nucleus number change of molecules of a phenol resin at the time of synthesis of the curing agent (1) according to the present embodiment.
It is a figure which shows an example of the GPC chart of the phenol resin which is the hardening | curing agent (1) which concerns on this embodiment.
4 is a graph showing an example of a weight average molecular weight change of the phenol resin at the time of synthesis of the curing agent (3) according to the present embodiment.
FIG. 5 is a graph showing an example of the change in the nucleus number of molecules of a phenol resin at the time of synthesis of the curing agent (3) according to the present embodiment.
It is a figure which shows an example of the GPC chart of the phenol resin which is the hardening | curing agent (3) which concerns on this embodiment.
FIG. 7: is a figure which shows an example of the FD-MS chart of the phenol resin which is the hardening | curing agent (3) which concerns on this embodiment.
8 is a schematic cross-sectional view showing an example of the LED substrate according to the present embodiment.
9 is a perspective view illustrating an example of the LED substrate according to the present embodiment.

In the present specification, the term "step" is included in the term as long as the desired action of the step is achieved, even if it is not only distinguished from the independent step but also from other steps.

In addition, the numerical range shown using "-" in this specification shows the range which includes the numerical value described before and after "-" as minimum value and the maximum value, respectively.

In addition, when referring to the quantity of each component in a composition in this specification, when there exist two or more substances corresponding to each component in a composition, unless otherwise indicated, the total amount of the said two or more substance which exists in a composition is meant.

<B stage sheet>

The B stage sheet of this invention is (A) at least 1 sort (s) of epoxy resin (henceforth a "specific epoxy resin") which has a partial structure represented by following General formula (I), and (B) following General formula (IIa) It contains at least 1 type of hardening | curing agent (henceforth a "specific hardening | curing agent") which has a partial structure represented by at least one of (IId), at least 1 sort (s) of (C) inorganic filler, and (D) elastomer It is a semi-hardened | cured material of the epoxy resin composition.

(25)

In General Formula (I), R <^1> -R <^8> represents a hydrogen atom or a methyl group each independently.

(26)

(27)

(28)

[Formula 29]

In General Formulas (IIa) to (IId), m and n each independently represent a positive number, and Ar represents a group represented by any one of the following General Formulas (IIIa) and (IIIb).

(30)

In General Formulas (IIIa) and (IIIb), R ¹¹ and R ¹⁴ each independently represent a hydrogen atom or a hydroxyl group. R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

The B stage sheet of the present invention is a reaction product of (A) at least one epoxy resin having a partial structure represented by the following general formula (I), a dihydroxyarylene group and an aldehyde group and having a hydroxyl group equivalent of 60 or more and 130 or less (C) at least one kind of inorganic filler, and (D) at least one kind of an elastomer. The epoxy resin composition of the present invention is preferably a semi-cured product of an epoxy resin composition containing at least one kind of a curing agent containing a phenol resin, (C)

By making an epoxy resin composition (henceforth a "resin composition" hereafter) into the said structure, excellent thermal conductivity and excellent electrical insulation can be made compatible, and the B stage sheet which has the outstanding flexibility can be comprised. Moreover, the metal foil with resin excellent in flexibility can be obtained by arrange | positioning the said B stage sheet on metal foil.

Each component which comprises an epoxy resin composition is demonstrated below.

(A) epoxy resin

The epoxy resin constituting the epoxy resin composition is not particularly limited as long as it has a divalent partial structure represented by the following general formula (I) and at least one epoxy group. Especially, it is preferable that it is a compound which has a partial structure represented by the following general formula (I) and at least 2 epoxy groups, and has a partial structure represented by the following general formula (I) and at least 2 epoxy groups, and the said partial structure is a principal chain It is preferable that it is a compound which comprises a part.

When an epoxy resin has the partial structure represented by General formula (I), when it is set as the resin hardened | cured material, it becomes possible to form the higher order structure which has a high order. As a result, excellent thermal conductivity and high heat dissipation can be realized.

(31)

R ¹ to R ⁸ each independently represent a hydrogen atom or a methyl group.

Resin which has a biphenyl structure represented by general formula (I) has the characteristic that molecular orientation is easy. This feature advantageously acts to lower the resistance of the heat resistance in the cured product of the epoxy resin composition, and consequently increases the heat dissipation of the cured product and gives high heat dissipation.

As an epoxy resin which has a partial structure represented by General formula (I), a biphenyl type epoxy resin and a biphenylene type epoxy resin are mentioned. Specifically, the compound represented by the following general formula (IV), the compound represented by (V), etc. are mentioned.

(32)

General formula (IV) of, R ¹ ~ R ⁸ each independently represents a substituted or unsubstituted hydrocarbon having a carbon number of hydrogen atoms or 1 ~ 10, n represents an integer of 0 to 3.

From the viewpoint of fluidity, n is preferably 0 to 2, more preferably n is 0 or 1, and particularly preferably n is 0.

Examples of the substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, butyl group, isopropyl group and isobutyl group.

Among them, R ¹ to R ⁸ are preferably hydrogen atoms or methyl groups from the viewpoint of thermal conductivity.

As a biphenyl type epoxy resin represented by the said General formula (IV), 4,4'-bis (2, 3- epoxy propoxy) biphenyl or 4, 4'-bis (2, 3- epoxy propoxy)- Epoxy resins based on 3,3 ', 5,5'-tetramethylbiphenyl, epichlorhydrin and 4,4'-biphenol or 4,4'-(3,3 ', 5,5'- And epoxy resins obtained by reacting tetramethyl) biphenol. Among them, 4,4'-bis (2,3-epoxypropoxy) -3,3 ', 5,5'-tetramethylbiphenyl as a main component from the viewpoint of preventing a decrease in the glass transition temperature of the cured product. Epoxy resins are preferred.

An epoxy resin represented by formula (IV) ^{is, R 1, R 3, R} 6 and and R ⁸ is a methyl ^{group, R 2, R 4, R} 5 and R ⁷ is composed mainly of the compound are hydrogen atoms, n = 0 Epicoat YX4000H (manufactured by Mitsubishi Chemical Co., Ltd.), R ¹ , R ³ , R ⁶ and R ⁸ are methyl groups, R ² , R ⁴ , R ⁵ and R ⁷ are hydrogen atoms, n = A phosphorus compound and R ¹ to R ⁸ "Epicoat YL6121H" (Mitsubishi Chemical Co., Ltd. make, brand name) etc. which are this hydrogen atom and which are a mixture of compounds of n = 0 are available from a market.

Moreover, the epoxy resin etc. which are represented by following General formula (IV) are mentioned as said biphenylene type epoxy resin.

(33)

In the general formula ^{(V), R 1 ~ R} 9 are each independently a hydrogen atom, an aralkyl group of 1 to 10 carbon atoms in the alkyl group, having 1 to 10 carbon atoms, an alkoxy group, having 6 to 10 aryl group, or a 6 to 10 carbon atoms in the N represents the integer of 0-10.

Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, butyl group, isopropyl group and isobutyl group. Examples of the alkoxy group having 1 to 10 carbon atoms include methoxy group, ethoxy group, propoxy group and butoxy group. As a C6-C10 aryl group, a phenyl group, a tolyl group, a xylyl group, etc. are mentioned. Examples of the aralkyl group having 7 to 10 carbon atoms include benzyl group and phenethyl group.

Especially, R <^1> -R <^9> has a hydrogen atom or a methyl group from a flexible viewpoint of a B stage sheet.

As biphenyl type epoxy resin represented by the said General formula (V), NC-3000 (Nippon Kayaku Co., Ltd. brand name) can be obtained as a commercial item, for example.

As said epoxy resin, it is preferable to contain at least 1 sort (s) of the compound represented by said general formula (IV) or general formula (V) from a viewpoint of thermal conductivity, electrical insulation, and the flexibility of a B-stage sheet, From a thermal conductivity viewpoint, It is more preferable to contain at least 1 sort (s) of the compound represented by general formula (IV).

In addition to the epoxy resin which has a partial structure represented by the said General formula (I), the said epoxy resin composition has other epoxy resins other than the epoxy resin which has a partial structure represented by the said General formula (I), the effect of this invention. You may contain in the range which does not inhibit.

As other epoxy resin, it can select suitably from the epoxy resin generally used.

As another epoxy resin, For example, phenols, such as a phenol novolak-type epoxy resin and an ortho cresol novolak-type epoxy resin, phenol, cresol, a xylenol, a resorcinol, catechol, bisphenol A, bisphenol F, and / Or a naphthol such as α-naphthol, β-naphthol or dihydroxynaphthalene and a compound having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylicaldehyde under condensation or cocondensation under an acidic catalyst Epoxidized volac resins, diglycidyl ethers such as bisphenol A, bisphenol F, bisphenol S, bisphenol A / D, phenols and / or naphthols, and dimethoxyparaxylene or bis (methoxymethyl) biphenyl Polybasic acids such as epoxides of phenol and aralkyl resins, stilbene type epoxy resins, hydroquinone type epoxy resins, phthalic acid and dimer acid, Glycidyl-ester type epoxy resin obtained by reaction of piclohydrin, glycidylamine type | mold epoxy resin obtained by reaction of polyamine and epichlorohydrin, such as diaminodiphenylmethane and isocyanuric acid, and cyclopenta Epoxides, such as a dicyclopentadiene type epoxy resin, a dimer of hydroxy naphthalene and / or dihydroxy naphthalene, which are epoxides of the co-condensation resin of diene and phenols, a triphenol methane type epoxy resin, and a trimethylol propane type epoxy resin , Terpene-modified epoxy resins, linear aliphatic epoxy resins obtained by oxidizing olefin bonds with peracids such as peracetic acid, cycloaliphatic epoxy resins, sulfur atom-containing epoxy resins, and these epoxy resins are silicone, acrylonitrile, butadiene, isoprene rubber , Epoxy resin modified with polyamide resin, etc. may be mentioned. have.

These may be used alone or in combination of two or more.

Although there is no restriction | limiting in particular as content rate of the epoxy resin in the total solid of the said epoxy resin composition, It is preferable that they are 3 mass% or more and 10 mass% or less from a viewpoint of thermal conductivity, electrical insulation, and the flexibility of a B stage sheet, and the hardened | cured material mentioned later It is more preferable that they are 4 mass% or more and 7 mass% or less from a physical viewpoint.

In addition, solid content in an epoxy resin composition means the residue which removed the volatile component from the component which comprises an epoxy resin composition.

Moreover, the content rate of the epoxy resin which has the partial structure represented by the said General formula (I) in the epoxy resin contained in the said epoxy resin composition is not specifically limited. It is preferable to set it as 60 mass% or more of the whole epoxy resin from a viewpoint of thermal conductivity, It is more preferable to set it as 70 mass% or more, It is especially preferable to set it as 80 mass% or more from a viewpoint of further improving thermal conductivity.

It is preferable that the said epoxy resin composition further contains at least 1 sort (s) chosen from the epoxy resin which has a naphthalene ring from a flexible viewpoint at the time of constructing a B stage sheet.

The epoxy resin having the naphthalene ring is not particularly limited as long as it is a compound having at least one naphthalene ring and at least one epoxy group. For example, HP4032D (made by DIC Corporation) is mentioned.

When the said epoxy resin composition contains another epoxy resin (preferably epoxy resin which has a naphthalene ring), there is no restriction | limiting in particular in the content rate. For example, it can be 0.01 mass% or more and 15 mass% or less with respect to the said specific epoxy resin, and it is preferable that they are 0.01 mass% or more and 12 mass% or less. By such a content rate, thermal conductivity, electrical insulation, and the flexibility of a B stage sheet improve more effectively.

(B) curing agent

The said epoxy resin composition contains at least 1 sort (s) of the hardening | curing agent (specific hardening | curing agent) which has at least 1 sort (s) of partial structure represented by at least one of the following general formula (IIa)-(IId). By combining a specific curing agent and a specific epoxy resin, excellent thermal conductivity can be achieved. Moreover, the said epoxy resin composition may further contain other hardening agents other than a specific hardening agent as needed.

[Formula 34]

(35)

(36)

[Formula 37]

In General Formulas (IIa) to (IId), m and n each independently represent a positive number and represent the number of repetitions of each repeating unit. Ar represents a group represented by any one of the following general formulas (IIIa) and (IIIb).

(38)

In General Formulas (IIIa) and (IIIb), R ¹¹ and R ¹⁴ each independently represent a hydrogen atom or a hydroxyl group. R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

The hardening | curing agent which has a partial structure represented by at least one of general formula (IIa)-(IId) can be produced | generated simultaneously by the manufacturing method mentioned later, and has a partial structure of at least 2 sort (s) chosen from general formula (IIa)-(IId). It can be produced as a mixture of compounds.

That is, the said specific hardening | curing agent may contain the compound which has only the partial structure represented by either of general formula (IIa)-(IId), and has at least 2 type of partial structure selected from general formula (IIa)-(IId). It may contain a compound.

In general formula (IIa)-(IId), if the substitution position of a hydroxyl group is on an aromatic ring, it will not specifically limit.

Regarding each of General Formulas (IIa) to (IId), a plurality of Ar's may all have the same atomic group, or may contain two or more atomic groups. Moreover, the partial structure represented by General Formula (IIa)-(IId) may be contained as a principal chain skeleton of a hardening | curing agent, and may be contained as a part of side chain. Moreover, each repeating unit which comprises the partial structure represented by either of general formula (IIa)-(IId) may be contained at random, may be contained regularly, and may be contained in block form.

In the partial structure represented by any of General Formulas (IIa) to (IId), Ar represents a group represented by any one of General Formulas (IIIa) and (IIIb).

R ¹¹ and R ¹⁴ in the general formulas (IIIa) and (IIIb) are each independently a hydrogen atom or a hydroxyl group, but are preferably hydroxyl groups from the viewpoint of thermal conductivity. The substitution position of R ¹¹ and R ¹⁴ is not particularly limited.

In addition, R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms in R ¹² and R ¹³ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tertiary butyl group, pentyl group, hexyl group, Heptyl group and octyl group are mentioned. Moreover, the substitution position of R <^12> and R <^13> in general formula (IIIa) and (IIIb) is not specifically limited.

Ar in General Formulas (IIa) to (IId) is a group derived from dihydroxybenzene from the viewpoint of achieving the effect of the present invention, particularly excellent thermal conductivity (in formula (IIIa), R ¹¹ is a hydroxyl group) It is preferable that it is at least 1 sort (s) chosen from group which R <^12> and R <^13> is a hydrogen atom, and group derived from dihydroxy naphthalene (group which R <^14> is hydroxyl group in general formula (IIIb)).

Here, "group derived from dihydroxy benzene" means the bivalent group comprised by removing two hydrogen atoms from the aromatic ring part of dihydroxy benzene, and the position where a hydrogen atom is removed is not specifically limited. The same meaning also applies to the group derived from dihydroxynaphthalene.

Moreover, from the viewpoint of the productivity and fluidity of the epoxy resin composition, Ar is more preferably a group derived from dihydroxybenzene, and a group derived from 1,2-dihydroxybenzene (catechol) and 1,3-. It is more preferable that it is at least 1 sort (s) chosen from the group which consists of groups derived from dihydroxybenzene (resorcinol).

Further, from the viewpoint of increasing the thermal conductivity in particular, it is preferable to contain a group derived from at least 1,3-dihydroxybenzene (resorcinol) as Ar, and as Ar, 1,3-dihydroxybenzene (resorcith). It is especially preferable that the content rate of the structural unit containing group derived from knol) is 60 mass% or more in the gross mass of the partial structure represented by General Formula (IIa)-(IId).

About m and n in general formula (IIa)-(IId), it is preferable that it is m / n = 20/1-1/5 from a fluid viewpoint, and it is more preferable that it is 20/1-5/1, More preferably from 20/1 to 10/1. Moreover, it is preferable that (m + n) is 20 or less from a fluid viewpoint, It is more preferable that it is 15 or less, It is further more preferable that it is 10 or less.

The lower limit of (m + n) is not particularly limited.

Specific curing agents having a partial structure represented by at least one of General Formulas (IIa) to (IId) include, in particular, when Ar is at least one of substituted or unsubstituted dihydroxybenzenes and substituted or unsubstituted dihydroxynaphthalenes. Compared with the novolakized resin etc., the synthesis | combination is easy and there exists a tendency for the hardening | curing agent with a low softening point to be obtained. Therefore, there exists an advantage that manufacture and handling of the resin composition containing such a resin also become easy.

In addition, the hardening | curing agent which has a partial structure represented by any of general formula (IIa)-(IId) facilitates the said partial structure as the fragment component by Field Desorption Ionization Mass-Spectrometry: Field Desorption Ionization Mass Spectrometry (FD-MS). Can be specified.

The molecular weight of the specific curing agent is not particularly limited. From the viewpoint of fluidity, the number average molecular weight is preferably 2000 or less, more preferably 1500 or less, and even more preferably 350 or more and 1500 or less.

Moreover, as a weight average molecular weight, it is preferable that it is 2000 or less, It is more preferable that it is 1500 or less, It is further more preferable that it is 400 or more and 1500 or less.

The number average molecular weight and weight average molecular weight of the said specific hardening | curing agent are measured by the conventional method using GPC.

The hydroxyl equivalent of the said specific hardening | curing agent is not specifically limited. From the viewpoint of the crosslinking density involved in the heat resistance, the hydroxyl equivalent of the specific curing agent is preferably 60 or more and 130 or less, more preferably 65 or more and 120 or less, further preferably 70 or more and 110 or less in average value.

Moreover, the said epoxy resin composition may contain the monomer component mentioned later as a low molecular diluent in addition to a specific hardening | curing agent. It is preferable that the content rate of a monomer component is 40 mass% or less in the gross mass of a hardening | curing agent. The hydroxyl equivalent of a hardening | curing agent in this case becomes like this. Preferably it is 60-80 in average value.

The manufacturing method of the hardening | curing agent (specific hardening | curing agent) which has a partial structure represented by at least one of general formula (IIa)-(IId) is not specifically limited. For example, the method of using the intramolecular ring closure reaction by the self-oxidation of the following dihydroxyarenes can be used. That is, for example, catechol (1,2-dihydroxybenzene, R ¹¹ in general formula (IIIa) Is a hydroxyl group, R ¹² and R ¹³ The phenols and aldehydes containing 20 mol%-90 mol% of this compound, such as hydrogen, can be manufactured by making them react with acid catalysts, such as oxalic acid, like normal novolak resin.

Reaction conditions can be suitably selected according to the structure etc. of a specific hardening | curing agent. For example, when formaldehyde is used as aldehydes, the reaction is carried out under reflux conditions at around 100 ° C. This reflux reaction is carried out for 1 to 8 hours, and the temperature in the reaction system is then raised to 120 ° C to 180 ° C while removing water in a conventional manner. At this time, the atmosphere is preferably an oxidizing atmosphere (for example, in an air stream). By continuing this state for 2 to 24 hours after that, the compound which has a partial structure represented by general formula (IIa) and (IIb) in a system is produced, and a desired hardening | curing agent can be obtained.

Moreover, in the intramolecular ring-closure reaction by the self-oxidation of the said dihydroxyarene, the part represented by at least one of general formula (IIa)-(IId) by making it react similarly using resorcinol, catechol, and aldehydes. A mixture of compounds having a structure is produced. In addition, by reacting resorcinol and aldehydes in the same manner, a mixture of compounds having a partial structure represented by at least one of the general formulas (IIa), (IIc) and (IId) is produced. Further, by reacting hydroquinone, catechol and aldehydes in the same manner, a mixture of compounds having a partial structure represented by at least one of the general formulas (IIa) and (IIb) is produced.

The specific curing agent is a phenol resin composition obtained by reacting dihydroxyarenes and aldehydes under an acidic catalyst, wherein the hydroxyl group equivalent is the theoretical hydroxyl group equivalent (about 60) of the novolak resin of dihydroxyarene. It is a big phenol resin composition in comparison. By using such a phenol resin composition as a hardening | curing agent, it is thought that the effect of assisting the orientation of an epoxy resin and raising the heat dissipation property of an epoxy resin composition as a result is acquired. The reason why the hydroxyl equivalent is larger than the theoretical value is considered to be that the dihydroxyarenes are subjected to intramolecular ring-closure reaction during the reaction and contain a phenol resin having a partial structure as in the general formulas (IIa) to (IId). .

As dihydroxyarene used for manufacture of a specific hardening | curing agent, monocyclic dihydroxyarene, such as catechol, resorcinol, and hydroquinone, and 1, 5- dihydroxy naphthalene, 1, 6-di Polycyclic type dihydroxy arene, such as dihydroxy naphthalene, such as hydroxy naphthalene and 1, 4- dihydroxy naphthalene, is mentioned. These may be used alone or in combination of two or more.

Moreover, as aldehyde, aldehydes normally used for phenol resin synthesis, such as formaldehyde, acetaldehyde, benzaldehyde, salicylicaldehyde, are mentioned. These may be used alone or in combination of two or more.

It is preferable to react these dihydroxyarenes and aldehydes using 0.3 mol-0.9 mol of aldehydes with respect to 1 mol of dihydroxyarenes in presence of an acid catalyst. More preferably, 0.4 mol-0.8 mol of aldehydes are used.

By using 0.3 mol or more of aldehydes, there is a tendency that the content rate of the dibenzoxanthene derivative can be increased, and the amount of unreacted dihydroxyarene can be suppressed to increase the amount of resin produced. Moreover, when aldehydes are 0.9 mol or less, it exists in the tendency for gelatinization in a reaction system to be suppressed and reaction control becomes easy.

Examples of the acid used as the acid catalyst include organic acids such as oxalic acid, acetic acid, p-toluenesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, and methanesulfonic acid, and inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid. have. These acids may be used alone or in combination of two or more.

It is preferable that the usage-amount of an acid catalyst shall be 0.0001 mol-0.1 mol with respect to 1 mol of dihydroxy arenes used, for example. More preferably, 0.001 to 0.05 mol is used. When the usage-amount of an acid catalyst is 0.0001 mol or more, the process of intramolecular dehydration ring closure at 120-180 degreeC will become short time. Moreover, when it is 0.1 mol or less, the process of catalyst removal tends to become easier, and it becomes easy to apply to the system which is ionic impurity in semiconductor use etc.

The said epoxy resin composition may further contain other hardening agents other than a specific hardening agent in the range which does not impair the effect of this invention. As another hardening | curing agent, it can select suitably from the hardening | curing agent generally used for sealing, the adhesive epoxy resin composition, etc. Specific examples of the other curing agent include phenols such as phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, and aminophenol; naphthols such as α-naphthol, β-naphthol, and dihydroxynaphthalene; A novolak-type phenol resin obtained by condensing or co-condensing at least one selected from the group consisting of the phenols and naphthols and a compound having an aldehyde group such as formaldehyde, benzaldehyde, and salicylic acid under an acidic catalyst; Dicyclopentadiene types, such as a dicyclopentadiene type phenol novolak resin synthesize | combined by copolymerization with at least 1 sort (s) chosen from the group which consists of phenols and naphthol, and cyclopentadiene, and a dicyclopentadiene type naphthol novolak resin Phenolic resin; Terpene modified phenol resins; Triphenol methane type phenol resin etc. are mentioned.

The content rate of the other hardening | curing agent contained in the said epoxy resin composition is not specifically limited, unless the effect of this invention is impaired, It is suitably selected.

The said epoxy resin composition may contain the monomer which is a phenolic compound which comprises a specific hardening | curing agent. Although there is no restriction | limiting in particular as content ratio of the monomer which is a phenolic compound which comprises a specific hardening | curing agent (Hereinafter, it may be called "monomer content ratio."), It is preferable that it is 5-80 mass%, and it is 15-60 mass% More preferably, it is more preferable that it is 20-50 mass%.

By the monomer content ratio being 20 mass% or more, the viscosity rise of a phenol resin is suppressed and the adhesiveness of an inorganic filler improves more. Moreover, when it is 50 mass% or less, a higher density structure is formed by the crosslinking reaction at the time of hardening, and the outstanding thermal conductivity and heat resistance can be achieved.

Moreover, as a monomer of the phenolic compound which comprises a specific hardening | curing agent, resorcinol, catechol, and hydroquinone are mentioned, It is preferable to contain at least resorcinol as a monomer.

Moreover, as a content rate of the said hardening | curing agent in the said epoxy resin composition, the content rate of the said hardening | curing agent with respect to the total amount of an epoxy resin from a viewpoint of thermal conductivity, electrical insulation, the flexibility of the B stage sheet, and pot life. It is preferable that it is 0.95 or more and 1.25 or less on this basis, It is more preferable that it is 1.00 or more and 1.25 or less, It is more preferable that it is 1.00 or more and 1.22 or less, It is further more preferable that it is 1.00 or more and 1.20 or less from a viewpoint of the insulation at the time of moisture absorption, 1.00 or more 1.10 It is especially preferable that it is the following.

An equivalent standard is what prescribes | regulates the content rate of an epoxy resin and a hardening | curing agent based on the number of epoxy groups contained in an epoxy resin, and the functional group number (preferably hydroxyl number) of the hardening | curing agent reacting with this epoxy group and 1: 1. it means.

In addition, the total content of an epoxy resin means the total content of the said specific epoxy resin and other epoxy resins other than the said specific epoxy resin.

Therefore, when the said hardening | curing agent is a phenol resin, the content rate of the said equivalent standard is specifically calculated from the following formula.

Formula content ratio (phenolic resin / epoxy resin) = Σ (phenolic resin amount / hydroxyl equivalent of phenolic resin) / Σ (epoxy resin amount / epoxy equivalent of epoxy resin)

(C) inorganic filler

The said epoxy resin composition contains at least 1 sort (s) of an inorganic filler. Inorganic fillers may be appropriately selected from inorganic fillers commonly used in the art. Specific examples of the non-conductive material include alumina, aluminum nitride, boron nitride, silicon nitride, silicon oxide, magnesium oxide, aluminum hydroxide, barium sulfate, and the like. Moreover, gold, silver, nickel, copper, etc. are mentioned as an electroconductive thing. These can be used individually by 1 type or in mixture of 2 or more types.

Among them, alumina is more preferable from the viewpoint of thermal conductivity, electrical insulation, and flexibility of the B stage sheet.

The inorganic filler may be an inorganic filler having a particle size distribution having a single peak, or a combination of plural kinds of inorganic fillers having different particle size distributions. Especially, it is preferable to combine three or more types of inorganic fillers which show a different particle size distribution from a thermal conductivity viewpoint, and it is more preferable that they combine three or more types of alumina groups which show a different particle size distribution.

When the inorganic filler is, for example, a combination of three kinds of inorganic fillers each having a different particle size distribution, the particle size distribution of the inorganic filler contained in the epoxy resin composition is at least corresponding to each of the three kinds of inorganic fillers. Has three peaks. The peak area of each peak depends on the content of each inorganic filler.

When the said inorganic filler combines several types of alumina particle groups, the mixing ratio can be suitably selected according to the number of the alumina particle groups to combine, the average particle diameter of each alumina particle group, etc.

Among them, the first alumina group having a particle diameter D50 of 7 μm or more and 35 μm or less corresponding to the cumulative 50% from the small particle size side of the weight cumulative particle size distribution, the second alumina group having a particle size D50 of 1 μm or more and less than 7 μm; And a content rate of the first alumina group in the total mass of the first alumina group, the second alumina group, and the third alumina group, including a third alumina group having the particle diameter D50 of less than 1 μm. % Or more and 70 mass% or less, Furthermore, the content rate of the said 2nd alumina group is 15 mass% or more and 30 mass% or less, Moreover, the content rate of the said 3rd alumina group is 1 mass% or more and 25 mass% or less, It is preferable that the content rate (2nd alumina group / 3rd alumina group) of the said 2nd alumina group with respect to is 0.9 or more and 1.7 or less on a mass basis.

More preferably, the content ratio (second alumina group / third alumina group) of the second alumina group to the third alumina group is 0.9 or more and 1.1 or less on a mass basis. As described above, the third alumina group is contained in approximately the same amount as the second alumina group, so that the flexibility of the B stage sheet can be enhanced without hindering the thermal conductivity, and the fluidity can be brought to a more optimal level.

Moreover, it is more preferable that the content rate (1st alumina group / 2nd alumina group) of the said 1st alumina group with respect to the said 2nd alumina group is 2.0 or more and 5.0 or less by mass reference | standard, 2.5 from a viewpoint of reducing the space | gap in a sheet | seat. It is more preferable that it is more than 4.0. By containing a 1st alumina group in the said range with respect to a 2nd alumina group, high thermal conductivity and dispersibility can be satisfy | filled.

The particle diameter D50 of the inorganic filler (preferably alumina) is measured using a laser diffraction method and corresponds to the particle diameter where the weight accumulation becomes 50% when the weight accumulation particle size distribution curve is drawn from the small particle size side. The particle size distribution measurement using the laser diffraction method can be performed using the laser diffraction scattering particle size distribution measuring apparatus (for example, Beckman Coulter company make, LS230).

It is preferable that the said 1st alumina group has 7 micrometers-35 micrometers of particle diameters D50 corresponding to 50% of accumulation from the small particle size side of a weight cumulative particle size distribution. It is preferable that they are 10 micrometers or more and 25 micrometers or less from a viewpoint of thermal conductivity and electrical insulation, and it is more preferable that they are 15 micrometers or more and 25 micrometers or less from a viewpoint of maintaining the flatness of a sheet | seat.

Moreover, it is preferable that the content rate of the 1st alumina group in the gross mass of the alumina contained in the said epoxy resin composition is 60 mass% or more and 70 mass% or less, and it is 62 mass% or more and 70 mass% or less from a viewpoint of thermal conductivity and electrical insulation. More preferred.

The second alumina group preferably has a particle diameter D50 of 1 µm or more and less than 7 µm, corresponding to the cumulative 50% from the small particle diameter side of the weight accumulation particle size distribution. It is preferable that they are 2 micrometers or more and 6 micrometers or less from a viewpoint of thermal conductivity and electrical insulation, and it is more preferable that they are 3 micrometers or more and 5 micrometers or less from a viewpoint of reducing the space | gap in a sheet | seat.

It is preferable that the content rate of the 2nd alumina group in the gross mass of the alumina contained in the said epoxy resin composition is 15 mass% or more and 30 mass% or less, and it is 18 mass% or more and 27 mass% or less from a viewpoint of thermal conductivity and electrical insulation. It is preferable that it is 18.5 mass% or more and 25 mass% or less.

It is preferable that the said 3rd alumina group has a particle diameter D50 corresponding to 50% of accumulation from the small particle diameter side of a weight accumulation particle size distribution of less than 1 micrometer. It is preferable that they are 0.1 micrometer or more and 0.8 micrometer or less from a viewpoint of thermal conductivity and electrical insulation, and it is more preferable that they are 0.2 micrometer or more and 0.6 micrometer or less from a viewpoint of reducing the space | gap in a sheet | seat.

Moreover, it is preferable that the content rate of the 3rd alumina group in the gross mass of the alumina contained in the said epoxy resin composition is 1 mass% or more and 25 mass% or less, and it is 5 mass% or more and 20 mass% or less from a viewpoint of thermal conductivity and electrical insulation. More preferably, it is more preferable that they are 10 mass% or more and 18 mass% or less.

The alumina in the present invention is not particularly limited as long as it has the particle size distribution already described, and any of α-alumina, β-alumina, γ-alumina, δ-alumina, θ-alumina and the like may be used. It is preferable that at least 1 type of the said 1st-3rd alumina group is alpha-alumina, and it is more preferable to consist only of alpha-alumina from a thermal conductivity viewpoint.

Further, the first alumina group and the second alumina group are more preferably alumina composed of single crystal particles of α-alumina from the viewpoint of thermal conductivity.

On the other hand, the third alumina group is preferably α-alumina, γ-alumina, δ-alumina, or θ-alumina, more preferably α-alumina, and from the viewpoint of thermal conductivity, alumina consisting of single crystal particles of α-alumina. More preferably.

As said 1st-3rd alumina group, it can select from a commercially available thing suitably. In addition, by calcining the alumina powder which becomes a transition alumina by transition alumina or heat processing in the atmosphere gas containing hydrogen chloride (for example, refer Unexamined-Japanese-Patent No. 6-191833, Unexamined-Japanese-Patent No. 6-191836, etc.). ) May be manufactured.

There is no restriction | limiting in particular in the content rate of the inorganic filler (preferably alumina) contained in the said epoxy resin composition. It can be 85 mass% or more and 95 mass% or less in solid content which comprises an epoxy resin composition, and it is more preferable that they are 88 mass% or more and 92 mass% or less from a viewpoint of thermal conductivity, electrical insulation, and sheet flexibility.

In addition, solid content in an epoxy resin composition means the residue which removed the volatile component from the component which comprises an epoxy resin composition.

(D) elastomer

The said epoxy resin composition contains at least 1 sort (s) of elastomer. By containing an elastomer, the flexibility of the B stage sheet can be improved, and the excess fluidity of the resin at the time of pressing can be suppressed.

There is no restriction | limiting in particular as a kind of elastomer, A conventionally well-known elastomer can be used according to heat resistance or availability. Especially, it is preferable that they are 100,000 or more and 800,000 or less elastomer from a viewpoint of a viscosity characteristic, It is more preferable that they are 300,000 or more and 700,000 or less elastomer, It is still more preferable that they are 400,000 or more and 650,000 or less elastomer. Do.

Moreover, it is preferable that an elastomer is an acrylic elastomer from a viewpoint of compatibility with an epoxy resin, and it is more preferable that it is an acrylic elastomer which is a methyl methacrylate / butyl acrylate / ethyl acrylate / glycidyl copolymer.

Moreover, it is also preferable that it is an acrylic elastomer which does not contain a nitrile rubber component in a copolymerization component. By not containing a nitrile rubber component in a copolymerization component, an electrical reliability can be improved more.

The elastomer preferably contains an acrylic elastomer having a weight average molecular weight of 100,000 to 800,000 from the viewpoint of the flexibility and fluidity of the B stage sheet, and preferably contains an acrylic elastomer having a weight average molecular weight of 300,000 to 700,000. More preferred.

Moreover, it is preferable that it is 70 mass% or more in the total mass of the elastomer contained in the said epoxy resin composition, and, as for the content rate of the acrylic elastomer whose weight average molecular weights contained in the said elastomer are 100,000 or more and 800,000 or less, it is more preferable that it is 90 mass% or more.

In addition, the weight average molecular weight of an elastomer is measured by the conventional method using GPC.

When the said epoxy resin composition contains the elastomer which has a predetermined weight average molecular weight, even if it contains a specific epoxy resin and a specific hardening agent, it can suppress that melt viscosity of the B stage sheet of semi-hardened state becomes too low. As a result, excessive flowability can be suppressed even when high stress (press or the like) is applied before gelation.

There is no restriction | limiting in particular in the content rate of the elastomer contained in the said epoxy resin composition. The content rate of the elastomer can be 0.5 mass% or more and 5.0 mass% or less in solid content which comprises an epoxy resin composition, and it is more preferable that they are 0.5 mass% or more and 2.0 mass% or less from a viewpoint of thermal conductivity and sheet flexibility.

It is preferable that the said epoxy resin composition contains at least 1 sort (s) of a hardening accelerator in addition to the said essential component. By containing a hardening accelerator, gel time can be adjusted easily to a desired range.

As a hardening accelerator, the hardening accelerator normally used can be used without a restriction | limiting in particular. Examples of curing accelerators include, for example, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] nonene, 5,6-dibutylamino Cycloamidine compounds, such as -1,8- diazabicyclo [5.4.0] undeca-7-ene, and maleic anhydride, 1, 4- benzoquinone, 2, 5- toluquinone, 1 to these compounds , 4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1, Compounds having an intramolecular polarization formed by adding compounds having π bonds such as quinone compounds such as 4-benzoquinone and phenyl-1,4-benzoquinone, diazophenylmethane and phenol resins; Tertiary amine compounds such as benzyldimethylamine, triethanolamine, dimethylaminoethanol and tris (dimethylaminomethyl) phenol and derivatives thereof; Imidazole compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole and derivatives thereof; Maleic anhydride in organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine, phenylphosphine and organic phosphine thereof, and Organic phosphorus compounds such as a compound having an intramolecular polarization formed by adding a compound having a π bond such as a quinone compound, diazophenylmethane and a phenol resin; Tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate, triphenylphosphinetetraphenylborate, 2-ethyl-4-methylimidazoletetraphenylborate, N-methylmorpholine tetraphenylborate and derivatives thereof; Can be mentioned. These may be used individually by 1 type, or may be used in combination of 2 or more type. An organophosphorus compound is preferable from a viewpoint of reliability and moldability.

Although the content rate of the hardening accelerator in the said epoxy resin composition will not be restrict | limited especially if it is an amount which hardening acceleration effect is achieved, 0.1-10 mass% is preferable with respect to an epoxy resin. It exists in the tendency which the sclerosis | hardenability in a short time is excellent in the content rate of a hardening accelerator being 0.1 mass% or more. Moreover, when content rate of a hardening accelerator is 10 mass% or less, it becomes suppressed that a hardening rate becomes too fast and there exists a tendency for favorable hardened | cured material to be obtained.

It is preferable that the said epoxy resin composition contains at least 1 sort (s) of a coupling agent. Thereby, adhesiveness of the resin component and inorganic filler which consist of an epoxy resin and a hardening | curing agent can be improved.

Examples of the coupling agent include silane coupling agents such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, and vinyl silane, titanium compounds, aluminum chelates, aluminum / zirconium compounds, and the like. These may be used individually by 1 type or in combination of 2 or more types.

As a silane coupling agent, a commercially available thing can be used normally, but considering the compatibility with an epoxy resin or a hardening | curing agent, and reducing the heat conduction loss in the interface of a resin layer and an inorganic filler, an epoxy group, an amino group, a mercapto group, It is preferable to use a silane coupling agent having a ureido group or a hydroxyl group.

Specifically, 3-glycidoxy propyl trimethoxy silane, 3-glycidoxy propyl triethoxy silane, 3-glycidoxy propyl methyl diethoxy silane, 3-glycidoxy propyl methyl dimethoxy silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy silane, 3-aminopropyltriethoxy silane, 3- (2-aminoethyl) aminopropyltrimethoxy silane, 3- (2-aminoethyl) aminopropyltri Methoxy silane, 3-aminopropyltrimethoxy silane, 3-phenylaminopropyltrimethoxy silane, 3-mercaptopropyltrimethoxy silane, 3-mercaptotriethoxy silane, 3-ureidopropyltriethoxy Silane etc. are mentioned, The silane coupling agent oligomer represented by SC-6000KS2 (made by Hitachi Chemical Co., Ltd.), etc. are mentioned.

These silane coupling agents can also use together single 1 type or 2 types or more.

It is preferable that it is 0.05 mass%-5 mass% with respect to an inorganic filler, and, as for the content rate of the coupling agent in the said epoxy resin composition, 0.1 mass%-2.5 mass% are more preferable. It exists in the tendency for moisture resistance to improve more that the content rate of a coupling agent is 0.05 mass% or more. Moreover, there exists a tendency for a thermal conductivity to improve more that the content rate of a coupling agent is 5 mass% or less.

The epoxy resin composition may contain a dispersant. As the dispersant, any dispersant which is effective in dispersing the inorganic filler can be used without particular limitation. As a dispersing agent, the Ajisper series manufactured by Ajinomoto Fine-Tech Co., Ltd., the HIPLAAD series manufactured by Kusumoto Chemical Co., Ltd., the homogenol series by Kao Corporation, etc. are mentioned, for example. These dispersants may be used alone or in combination of two or more.

The B stage sheet of this invention consists of a semi-hardened material of the said epoxy resin composition, and has a sheet-like shape.

A B stage sheet can be manufactured by the manufacturing method including the process of apply | coating and drying the said epoxy resin composition on a release film, and forming a resin film, and the process of heat-processing the said resin film to the B stage state, for example. Can be.

By heat-processing and forming the said epoxy resin composition, it is excellent in thermal conductivity and electrical insulation, and excellent in flexibility and pot life as a B stage sheet.

The B stage sheet of the present invention is a viscosity of a resin sheet, which is 10 ⁴ Pa · s to 10 ⁵ Pa · s at normal temperature (25 degrees), while 10 ² Pa · s to 10 ³ Pa · s at 100 ° C. The viscosity falls. In addition, the cured resin layer after hardening mentioned later is not melted even by heating. In addition, the said viscosity is measured by dynamic viscoelasticity measurement (frequency 1 hertz, load 40g, temperature rising rate 3 degree-C / min).

Specifically, a resin film can be obtained by apply | coating the varnish-like epoxy resin composition which added the solvent, such as methyl ethyl ketone and cyclohexanone, on release films, such as PET film, for example.

Application can be performed by a well-known method. Specifically as a coating method, methods, such as a comma coat, a die coat, a lip coat, and a gravure coat, are mentioned. As a coating method for forming a resin layer with a predetermined thickness, the comma coating method which passes a to-be-coated object between gaps, the diecoat method which apply | coats the resin varnish which adjusted the flow volume from a nozzle, etc. are applicable. For example, when the thickness of the resin layer before drying is 50 micrometers-500 micrometers, it is preferable to use the comma coat method.

Since the resin layer after application | coating hardly progresses hardening reaction, it has flexibility, but lacks flexibility as a sheet | seat, and lacks sheet independence in the state which removed the said PET film as a support body, and handling is difficult. Then, this invention B-stages a resin composition by the heat processing mentioned later.

In the present invention, the conditions for subjecting the obtained resin film to heat treatment are not particularly limited as long as the epoxy resin composition can be semi-cured to the B-stage state and can be appropriately selected in accordance with the constitution of the epoxy resin composition. In the present invention, a heat treatment method selected from a heat vacuum press, a heat roll laminate, and the like is preferable. Thereby, the space | gap (void) in the resin layer produced at the time of coating can be reduced, and a flat B stage sheet can be manufactured efficiently.

Specifically, the epoxy resin composition can be semi-cured in a B-stage state by, for example, a heat press treatment under vacuum (for example, 1 MPa) at a heating temperature of 80 ° C to 130 ° C for 1 second to 30 seconds. .

The thickness of the said B stage sheet can be suitably selected according to the objective, For example, it can be 50 micrometers or more and 200 micrometers or less, and it is preferable that they are 60 micrometers or more and 150 micrometers or less from a viewpoint of thermal conductivity, electrical insulation, and sheet flexibility. Moreover, it can also manufacture by heat-pressing, laminating | stacking two or more layers of resin films.

<Metal foil with resin>

The metal foil with resin of this invention is equipped with metal foil and the semi-hardened resin layer which is a semi-hardened body of the said epoxy resin composition arrange | positioned on the said metal foil. By having the semi-hardened resin layer derived from the said epoxy resin composition, it is excellent in thermal conductivity, electrical insulation, and flexibility.

The said semi-hardened resin layer is obtained by heat-processing the said resin composition so that it may become a B stage state.

Although it does not restrict | limit especially as gold foil, copper foil, aluminum foil as said metal foil, Copper foil is generally used.

As thickness of the said metal foil, it can be 1 micrometer or more and 210 micrometers or less, for example. Especially, it is preferable that they are 10 micrometers or more and 150 micrometers or less, and it is more preferable that they are 18 micrometers or more and 105 micrometers or less. By using such metal foil, flexibility improves more.

As the metal foil, nickel, nickel-phosphorus, nickel-tin alloys, nickel-iron alloys, lead, lead-tin alloys, etc. are used as intermediate layers, and on both sides, a copper layer of 0.5 µm to 15 µm and a copper layer of 10 µm to 300 µm. You may use the composite foil of the 3-layered structure which provided this, or the 2-layered composite foil which combined aluminum and copper foil.

Metal foil with resin can be manufactured by forming a resin layer (resin film) by apply | coating and drying the said resin composition on metal foil, and heat-processing so that the said resin layer may become a B stage state (semi-cured state).

Although the manufacturing conditions of the metal foil with resin are not specifically limited, In the resin layer after drying, it is preferable that the organic solvent used for resin varnish volatilizes 80 mass% or more from a viewpoint of the electrical insulation at the time of metal substrate preparation, or an external appearance. Do. The drying temperature is about 80 ° C to 180 ° C, and the drying time can be determined in consideration of the balance with the gelation time of the varnish, and there is no particular limitation. It is preferable to apply | coat so that the thickness of the resin layer after drying may be 50 micrometers-200 micrometers, and, as for the application amount of resin varnish, it is more preferable that it becomes 60 micrometers-150 micrometers.

In addition, the formation method and heat processing conditions of a resin layer are as having already described.

<Metal substrate>

The metal substrate of this invention is equipped with a metal support body, the cured resin layer which is the hardened | cured material of the said epoxy resin composition arrange | positioned on the said metal support body, and the metal foil arrange | positioned on the said cured resin layer. Since the cured resin layer arrange | positioned between a metal support body and metal foil is formed by heat-processing the said epoxy resin composition so that it may become a hardened state, it is excellent in adhesiveness, thermal conductivity, and electrical insulation.

The material and thickness of the metal support are appropriately selected according to the purpose. Specifically, the thickness is preferably 0.5 mm or more and 5 mm or less from the viewpoint of workability using a metal such as aluminum or iron.

Moreover, the metal foil arrange | positioned on cured resin layer is the same meaning as the metal foil in the metal foil with said resin, and its preferable aspect is also the same.

The metal substrate of this invention can be manufactured as follows, for example. The resin layer is formed by applying and drying the epoxy resin composition on a metal support such as aluminum in the same manner as above, further disposing a metal foil on the resin layer, and heating and pressurizing it to cure the resin layer. It can manufacture. Moreover, after adhering the metal foil with the said resin on a metal support body so that a resin layer may oppose a metal support body, it can also manufacture by heat-pressing and hardening a resin layer.

The conditions of the heating and pressure treatment which harden the said resin layer are suitably selected according to the structure of an epoxy resin composition. For example, it is preferable that heating temperature is 80 degreeC-250 degreeC, pressure is 0.5 MPa-8.0 MPa, and it is more preferable that heating temperature is 130 degreeC-230 degreeC, and pressure is 1.5 MPa-5.0 MPa.

<LED board | substrate>

The LED board | substrate 100 of this invention is a metal support body 14, the cured resin layer 12 which is the hardened | cured material of the said epoxy resin composition arrange | positioned on the said metal support body, as shown in FIG. 8 and FIG. 9, and the said The circuit layer 10 which consists of metal foil arrange | positioned on the cured resin layer 12, and the LED element 20 arrange | positioned on the said circuit layer are provided.

By forming the said cured resin layer excellent in adhesiveness, thermal conductivity, and electrical insulation on a metal support body, it becomes possible to efficiently dissipate the heat radiate | emitted from an LED element.

The LED board | substrate of this invention is manufactured by the manufacturing method including the process of forming a circuit layer by carrying out the circuit processing to the metal foil on the metal substrate obtained as mentioned above, and the process of arrange | positioning an LED element on the formed circuit layer, for example. can do.

In the step of circuit processing the metal foil on the metal substrate, a commonly used method such as photolithography can be applied. Moreover, also about the process of arrange | positioning an LED element on a circuit layer, the method normally used can be used without a restriction | limiting in particular.

Example

Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. In addition, "part" and "%" are mass references | standards unless there is particular notice.

(Synthesis of Curing Agent (1))

220 g of catechol, 81.1 g of 37% formaldehyde, 2.5 g of oxalic acid, and 100 g of water were put into a 2 L separable flask equipped with a stirrer, a cooler, and a thermometer, and the temperature was raised to 100 ° C while being heated in an oil bath. The mixture was refluxed at around 104 ° C., and the reaction was continued for 3 hours at reflux temperature. Then, the temperature in a flask was heated up at 150 degreeC, distilling water off. Reaction was continued for 12 hours, maintaining 150 degreeC. After the reaction, the mixture was concentrated for 20 minutes under reduced pressure, and water and the like in the system were removed to obtain a phenol resin which is the target curing agent (1).

When the structure was confirmed by FD-MS about the obtained hardening | curing agent (1), presence of the partial structure represented by general formula (IIa) and the partial structure represented by general formula (IIb) was confirmed.

The change of the weight average molecular weight at the time of the synthesis | combination of a hardening | curing agent (1) was shown in FIG. . Moreover, the GPC chart of the obtained phenol resin was shown in FIG.

In addition, the change of the content rate of FIG. 2 was calculated | required from the chart similar to FIG. 3 obtained by taking out a product every fixed time, and performing GPC, and a monomer, a dimer, a trimer, and a tetramer or more are the GPC charts of FIG. The content of the content is determined from the peak area by making the last peak a monomer, the second peak from the last dimer, the third peak from the last trimer, and the previous tetramer or more. Therefore, even if it is a dimer and a trimer, it is not all the same component, and each is considered to be a phenol resin mixture.

As the reaction proceeds, as shown in FIG. 1, the weight average molecular weight is lowered, as shown in FIG. 2, the stable dimer and the trimer are generated, and the hydroxyl equivalent is large relative to the theoretical value (about 60). From the point, the point using catechol, etc., it is thought that the mixture of the phenol resin which has a partial structure represented by said general formula (IIa), and the phenol resin which has a partial structure represented by general formula (IIb) is obtained.

In addition, it is thought that the compound which has the partial structure represented by the said General formula (IIb) is obtained by making the compound which has the partial structure represented by the said General formula (IIa) first at the said reaction conditions, and this dehydrating again.

(Synthesis of Curing Agent (2))

Into a 3 L separable flask equipped with a stirrer, a cooler, and a thermometer, 462 g of resorcinol, 198 g of catechol, 316.2 g of 37% formaldehyde, 15 g of oxalic acid, and 300 g of water were added, and heated to an oil bath at 100 ° C. The temperature was raised to. The mixture was refluxed at around 104 ° C. and the reaction was continued at reflux for 4 hours. Then, the temperature in a flask was heated up at 170 degreeC, distilling water off. The reaction was continued for 8 hours while maintaining 170 ° C. After the reaction, the mixture was concentrated for 20 minutes under reduced pressure, and water and the like in the system were removed to obtain a phenol resin which is the target curing agent (2).

When the structure was confirmed by FD-MS about the obtained hardening | curing agent (2), presence of the partial structure represented by general formula (IIa) and the partial structure represented by general formula (IIb) was confirmed.

(Synthesis of Hardener (3))

627 g of resorcinol, 33 g of catechol, 316.2 g of 37% formalin, 15 g of oxalic acid, and 300 g of water were added to a 3 L separable flask equipped with a stirrer, a cooler, and a thermometer, and heated to an oil bath at 100 ° C. It heated up. The mixture was refluxed at around 104 ° C. and the reaction was continued at reflux for 4 hours. Then, the temperature in a flask was heated up at 170 degreeC, distilling water off. The reaction was continued for 8 hours while maintaining 170 ° C. After the reaction, the mixture was concentrated for 20 minutes under reduced pressure, water and the like in the system were removed to obtain a phenol resin which is the desired curing agent (3).

Moreover, when the structure was confirmed by FD-MS about the obtained hardening | curing agent (3), the presence of all the partial structures represented by general formula (IIa)-(IId) was confirmed.

The change of the weight average molecular weight at the time of the synthesis | combination of a hardening | curing agent (3) was shown in FIG. 4, and the change of the content rate of a monomer, a dimer, a trimer, and a tetramer or more is shown in FIG. Moreover, the GPC chart of the obtained phenol resin was shown in FIG.

Since catechol and resorcinol are used, it is thought that the mixture of the phenol resin which has the partial structure represented by general formula (IIa)-(IId) is obtained.

In addition, under the above reaction conditions, a compound having a partial structure represented by General Formula (IIa) is first produced, and the compound having a partial structure represented by at least one of General Formulas (IIb) to (IId) is produced by dehydration again. I think.

In addition, about the hardening | curing agent obtained above, measurement of the physical property value was performed as follows.

The measurement of the number average molecular weight (Mn) and the weight average molecular weight (Mw) was performed using Hitachi, Ltd. high speed liquid chromatography L6000, and Shimadzu Corporation data analysis device C-R4A. The GPC column for analysis used G2000HXL and G3000HXL by Toso Corporation. The sample concentration was measured at a flow rate of 1.0 ml / min using 0.2 mass% and tetrahydrofuran for the mobile phase. A calibration curve was prepared using a polystyrene standard sample, and the number average molecular weight and the like were calculated using the polystyrene conversion value.

The hydroxyl equivalent was measured by acetyl chloride-potassium hydroxide titration. In addition, since the color of the solution was dark, determination of the titration end point was performed by potentiometric titration instead of the coloration method by the indicator. Specifically, the hydroxyl group of the measurement resin is acetylated in a pyridine solution, the excess reagent is decomposed into water, and the resulting acetic acid is titrated with a potassium hydroxide / methanol solution.

The physical properties of each curing agent are shown below.

A curing agent (1): the general formula (IIa) and (IIb) with a mixture of compounds having at least one partial structure shown in, Ar is and R ¹¹ = hydroxyl group in the general formula ^{(IIIa), R 12 = R} 13 = It was a phenol resin composition containing the hardening | curing agent (hydroxyl equivalent 112, number average molecular weight 400, weight average molecular weight 550) which is group derived from 1, 2- dihydroxy benzene (catechol) which is a hydrogen atom.

A curing agent (2): the formula (IIa) ~ (IId) with a mixture of compounds having at least one partial structure shown in, and R ¹¹ = hydroxyl group in Ar is the formula ^{(IIIa), R 12 = R} 13 = Group derived from 1,2-dihydroxybenzene (catechol) which is a hydrogen atom or group originating from 1,3-dihydroxybenzene (resorcinol) (hydroxyl equivalent 108, number average molecular weight 540, weight average It was a phenol resin composition containing molecular weight 1,000).

A curing agent (3): the general formula (IIa) ~ (IId) with a mixture of compounds having at least one partial structure shown in, and R ¹¹ = hydroxyl group in Ar is the formula ^{(IIIa), R 12 = R} 13 = A group derived from 1,2-dihydroxybenzene (catechol) which is a hydrogen atom and a group derived from 1,3-dihydroxybenzene (resorcinol), and a monomer component (resorcinol) is used as a low molecular diluent. It was a phenol resin containing 35% of hardening | curing agents (hydroxyl equivalent 62, number average molecular weight 422, weight average molecular weight 564).

Comparative hardening | curing agent (1): Phenol novolak resin of the hydroxyl equivalent 105 (Meiwha Chemical Co., Ltd. make, brand name "H-100").

Comparative hardening | curing agent (2): Naphthol novolak resin of the hydroxyl equivalent equivalent 180 (Toto Chemical Co., Ltd. make, brand name "SN-170L").

&Lt; Example 1 &gt;

In a container with a 1 L lid made of polypropylene, 56.8 g (63% (to the total mass of alumina)) of alumina (Sumitomo Chemical Co., Ltd., Sumikorandom AA18) having a particle diameter D50 of 18 µm as an inorganic filler, 20.3 g (22.5% (to the total mass of alumina) of alumina) of alumina (Sumitomo Chemical Co., Ltd., Sumikoland AA3) having a particle diameter D50 of 3 µm, and alumina (Sumitomo Chemical Co., Ltd. product, Sumiko) having a particle diameter D50 of 0.4 µm 13.1 g (14.5% (relative to alumina total mass)) of random AA04) was weighed, and 0.10 g of a silane coupling agent (Shin-Etsu Chemical Co., Ltd., KBM403) was used as a solvent and methyl ethyl ketone (manufactured by Wako Junyaku Co., Ltd.). To 13.4 g of dispersant (0.18 g of Dispersing Agent (manufactured by Kusumoto Chemical Co., Ltd., ED-113)), 2.9 g (solid content) of curing agent (1), and elastomer, to a weight average molecular weight of 610,000 methyl methacrylate / butyl acrylate / acrylic acid 0.08 g of a methyl / methacrylate glycidyl copolymer-type acrylic elastomer (Nagase Chemtex Co., Ltd., HTR860-P3- # 25) was added and stirred. Further, 5.9 g of a bifunctional epoxy resin having a biphenyl skeleton (manufactured by Mitsubishi Chemical Corporation, YL6121H, and an epoxy equivalent of 172 g / eq.), And an imidazole compound (curing accelerator, manufactured by Shikoku Chemical Industry Co., Ltd., 2PZ-CN) were 0.012. g was added. Furthermore, 500 g of zirconia balls of 5 mm in diameter were charged, and after stirring for 48 hours at 100 rpm on a ball mill mount, the zirconia balls were separated by filtration to obtain a varnish-like epoxy resin composition.

The varnish-like epoxy resin composition obtained above was apply | coated on PET film (Teijin DuPont film company make, A53) using the applicator which has a 250 micrometers gap, and a table coater (made by Tester Industry Co., Ltd.), and 100 degreeC Drying was carried out for 20 minutes at. The film thickness after drying was 100 micrometers. PET film (Teijin DuPont Film Company make, A53) was mounted on the resin layer after drying.

Subsequently, using a vacuum laminator (manufactured by Mikey Co., Ltd.), vacuum pressing was performed at 130 ° C. under a vacuum degree of 1 MPa for 15 seconds to obtain a sheet molded product (B stage sheet).

The obtained sheet molding was excellent in flexibility.

[evaluation]

The sheet molding obtained above was sandwiched between two stainless steel plates of thickness 2mm, and it processed in 140 degreeC for 2 hours, and also 190 degreeC for 2 hours in the box type drier, and obtained the sheet hardened | cured material. The following evaluation was performed about the obtained sheet hardened | cured material. The evaluation results are shown in Table 1.

(Thermal conductivity)

The thermal conductivity of the obtained hardened | cured sheet was measured by the thermal wave thermal analysis method using the thermal-diffusion rate and the thermal conductivity measuring apparatus (Iphase mobile, the eye phase company make).

(Electric insulation)

The obtained sheet hardened | cured material is sandwiched between electrodes of diameter 25mm, and minimum insulation breakdown voltage is made on the conditions of alternating current (500V / sec) using the HAT-300-100RHO type breakdown voltage measuring apparatus (made by Yamazaki Industrial Co., Ltd.). Measured.

(Alumina Particle Diameter)

0.5 g of the varnish-like resin composition was dispersed in 50 g of methanol, and an appropriate amount was added to a laser diffraction scattering particle size distribution analyzer (manufactured by Beckman Coulter, LS230) to measure the particle size distribution of the alumina in the resin composition. Was carried out.

(Flexibility of B stage sheet)

The flexibility of the B stage sheet was evaluated as follows.

The produced B stage sheet was cut out to length 100mm and width 10mm, and what removed the surface PET film was made into the sample for evaluation. Made of aluminum, a sample is placed on a jig overlaid with a multi-stage disc of 20 mm with a diameter of 20 mm to 140 mm, and the minimum diameter that is bent without breaking at 25 ° C. is measured, and the B stage sheet is flexible according to the following evaluation criteria. Sex was evaluated.

Evaluation criteria

A: The minimum radius was 20 mm.

B: The minimum radius was 40 mm or 60 mm, and there was a practical limit.

C: The minimum radius was 80 mm or more.

<Example 2>

In Example 1, 62.0 g (69% (to the total alumina total mass)) of alumina (Showa Denko Co., AS-20) having a particle diameter D50 of 20 µm as an inorganic filler, and a particle diameter D50 of 3 µm 16.8 g of phosphorus alumina (manufactured by Sumitomo Chemical, Sumikorandom AA3) (19% (to the total mass of alumina)), and 10.7 g of alumina (Sumitomo Chemical, Sumikolandum AA04) having a particle diameter D50 of 0.4 µm ( A varnish-like epoxy resin composition was prepared in the same manner as in Example 1 except that 12% (relative to alumina total mass) was used.

The sheet molding was obtained using the obtained varnish-like epoxy resin composition, and it evaluated similarly to the above. The evaluation results are shown in Table 1.

Moreover, the obtained sheet molding was excellent in flexibility.

<Example 3>

In Example 1, 49.3 g (63% (to the total alumina total mass) of alumina) having an alumina having a particle diameter D50 of 30 µm (Shin-Nitetsu Materials Micron, AL35-63) as the inorganic filler, and a particle diameter 14.1 g (18% (to the total mass of alumina) of alumina) of alumina (Shin-Nitetsu Materials Micron, Inc., AX3-32) having a D50 of 4.2 μm, and alumina having a particle diameter D50 of 0.45 μm (manufactured by Nippon Light Metal Co., Ltd.) , LS235), 13.3 g (17% (to the total mass of alumina)), and 1.57 g (2% (to the total mass of alumina)) of alumina having a particle diameter D50 of 0.7 m A varnish-like epoxy resin composition was prepared in the same manner as in Example 1 except that was used.

The sheet molding was obtained using the obtained varnish-like epoxy resin composition, and it evaluated similarly to the above. The evaluation results are shown in Table 1.

Moreover, the obtained sheet molding was excellent in flexibility.

<Example 4>

In Example 1, the varnish-like epoxy resin composition was prepared like Example 1 except having used the hardening | curing agent (2) instead of the hardening | curing agent (1).

The sheet molding was obtained using the obtained varnish-like epoxy resin composition, and it evaluated similarly to the above. The evaluation results are shown in Table 1.

Moreover, the obtained sheet molding was excellent in flexibility.

<Example 5>

In Example 2, the varnish-like epoxy resin composition was prepared like Example 2 except having used the hardening | curing agent (2) instead of the hardening | curing agent (1).

The sheet molding was obtained using the obtained varnish-like epoxy resin composition, and it evaluated similarly to the above. The evaluation results are shown in Table 1.

Moreover, the obtained sheet molding was excellent in flexibility.

<Example 6>

In Example 3, the varnish-like epoxy resin composition was prepared like Example 3 except having used the hardening | curing agent (2) instead of the hardening | curing agent (1).

The sheet molding was obtained using the obtained varnish-like epoxy resin composition, and it evaluated similarly to the above. The evaluation results are shown in Table 1.

Moreover, the obtained sheet molding was excellent in flexibility.

<Example 7>

In Example 1, except having used the hardening | curing agent (3) instead of the hardening | curing agent (1), it carried out similarly to Example 1, and prepared the varnish-like epoxy resin composition.

The sheet molding was obtained using the obtained varnish-like epoxy resin composition, and it evaluated similarly to the above. The evaluation results are shown in Table 1.

Moreover, the obtained sheet molding was excellent in flexibility.

&Lt; Example 8 &gt;

In Example 2, the varnish-like epoxy resin composition was prepared like Example 2 except having used the hardening | curing agent (3) instead of the hardening | curing agent (1).

The sheet molding was obtained using the obtained varnish-like epoxy resin composition, and it evaluated similarly to the above. The evaluation results are shown in Table 1.

Moreover, the obtained sheet molding was excellent in flexibility.

&Lt; Example 9 &gt;

An epoxy resin composition in the form of a varnish was prepared in the same manner as in Example 3 except that the curing agent (3) was used instead of the curing agent (1).

The sheet molding was obtained using the obtained varnish-like epoxy resin composition, and it evaluated similarly to the above. The evaluation results are shown in Table 1.

Moreover, the obtained sheet molding was excellent in flexibility.

&Lt; Comparative Example 1 &

Example 1 WHEREIN: Except having used the comparative hardening | curing agent 1 (softening point 85 degreeC, the phenol novolak resin of hydroxyl equivalent 105, Meiwa Kasei Co., Ltd. make, brand name "H-100") instead of the hardening | curing agent (1), In the same manner as in 1, a varnish-like epoxy resin composition was prepared.

The sheet molding was obtained using the obtained varnish-like epoxy resin composition, and it evaluated similarly to the above. The evaluation results are shown in Table 1.

Moreover, the obtained sheet molding was not able to satisfy | fill flexibility.

<Comparative Example 2>

In Example 2, except having used the comparative hardening | curing agent 1 (softening point 85 degreeC, the phenol novolak resin of hydroxyl equivalent 105, Meiwa Kasei Corporation make, brand name "H-100") instead of the hardening | curing agent 1, Example In the same manner as in 2, a varnish-like epoxy resin composition was prepared.

The sheet molding was obtained using the obtained varnish-like epoxy resin composition, and it evaluated similarly to the above. The evaluation results are shown in Table 1.

Moreover, the obtained sheet molding was not able to satisfy | fill flexibility.

&Lt; Comparative Example 3 &

Example 3 WHEREIN: Except having used the comparative hardening | curing agent 1 (softening point 85 degreeC, the phenol novolak resin of hydroxyl equivalent 105, Meiwa Kasei Co., Ltd. make, brand name "H-100") instead of the hardening | curing agent (1), In the same manner as in 3, a varnish-like epoxy resin composition was prepared.

The sheet molding was obtained using the obtained varnish-like epoxy resin composition, and it evaluated similarly to the above. The evaluation results are shown in Table 1.

Moreover, the obtained sheet molding was not able to satisfy | fill flexibility.

&Lt; Comparative Example 4 &

Example 1 WHEREIN: Except having used the comparative hardening | curing agent (2) (softening point 85 degreeC, naphthol novolak resin (Toto Chemical Co., Ltd. make, brand name "SN-170L") instead of the hardening | curing agent 1), Example 1 In the same manner as in the above, a varnish-like epoxy resin composition was prepared.

The sheet molding was obtained using the obtained varnish-like epoxy resin composition, and it evaluated similarly to the above. The evaluation results are shown in Table 1.

Moreover, the obtained sheet molding was not able to satisfy | fill flexibility.

<Comparative Example 5>

Example 2 WHEREIN: Except having used the comparative hardening | curing agent (2) (softening point 85 degreeC, naphthol novolak resin (The Toto Chemical Co., Ltd. make, brand name "SN-170L") instead of the hardening | curing agent 1), Example 2 In the same manner as in the above, a varnish-like epoxy resin composition was prepared.

The sheet molding was obtained using the obtained varnish-like epoxy resin composition, and it evaluated similarly to the above. The evaluation results are shown in Table 1.

Moreover, the obtained sheet molding was not able to satisfy | fill flexibility.

&Lt; Comparative Example 6 &gt;

Example 3 WHEREIN: Except having used the comparative hardening | curing agent (2) (softening point 85 degreeC, naphthol novolak resin (The Toto Chemical Co., Ltd. make, brand name "SN-170L") instead of the hardening | curing agent 1), Example 3 In the same manner as in the above, a varnish-like epoxy resin composition was prepared.

The sheet molding was obtained using the obtained varnish-like epoxy resin composition, and it evaluated similarly to the above. The evaluation results are shown in Table 1.

Moreover, the obtained sheet molding was not able to satisfy | fill flexibility.

&Lt; Comparative Example 7 &

In Example 7, it carried out similarly to Example 7 except having changed into the bifunctional epoxy resin (DOW Chemical Co., DER332, epoxy equivalent 175g / eq.) Which does not have a biphenyl skeleton as an epoxy resin, and a varnish phase An epoxy resin composition was prepared.

The sheet molding was obtained using the obtained varnish-like epoxy resin composition, and it evaluated similarly to the above. The evaluation results are shown in Table 1.

Moreover, the obtained sheet molding was flexibility B evaluation.

&Lt; Comparative Example 8 &gt;

In Example 8, it carried out similarly to Example 8 except having changed into bifunctional epoxy resin (DOW Chemical Co., DER332, epoxy equivalent 175g / eq.) Which does not have a biphenyl skeleton as an epoxy resin, and a varnish phase An epoxy resin composition was prepared.

The sheet molding was obtained using the obtained varnish-like epoxy resin composition, and it evaluated similarly to the above. The evaluation results are shown in Table 1.

Moreover, the obtained sheet molding was B evaluation which satisfy | filled flexibility.

&Lt; Comparative Example 9 &

In Example 9, it carried out similarly to Example 9 except having changed into bifunctional epoxy resin (DOW Chemical Co., DER332, epoxy equivalent 175g / eq.) Which does not have a biphenyl skeleton as an epoxy resin, An epoxy resin composition was prepared.

The sheet molding was obtained using the obtained varnish-like epoxy resin composition, and it evaluated similarly to the above. The evaluation results are shown in Table 1.

Moreover, the obtained sheet molding was B evaluation which satisfy | filled flexibility.

&Lt; Comparative Example 10 &

In Example 7, the varnish-like epoxy resin composition was prepared like Example 7 except not having added the elastomer.

The sheet molding was obtained using the obtained varnish-like epoxy resin composition, and it evaluated similarly to the above. The evaluation results are shown in Table 1.

Moreover, the obtained sheet molding was not able to satisfy | fill flexibility.

<Comparative Example 11>

In Example 8, the varnish-like epoxy resin composition was prepared like Example 8 except not having added the elastomer.

The sheet molding was obtained using the obtained varnish-like epoxy resin composition, and it evaluated similarly to the above. The evaluation results are shown in Table 1.

Moreover, the obtained sheet molding was not able to satisfy | fill flexibility.

<Comparative Example 12>

In Example 9, the varnish-like epoxy resin composition was prepared like Example 9 except not having added the elastomer.

The sheet molding was obtained using the obtained varnish-like epoxy resin composition, and it evaluated similarly to the above. The evaluation results are shown in Table 1.

Moreover, the obtained sheet molding was not able to satisfy | fill flexibility.

In Table 1, "-" shows the thing which does not contain.

From Table 1, it turns out that the hardened | cured material of the B stage sheet of this invention shows the outstanding thermal conductivity and the outstanding electrical insulation. Moreover, it turns out that the flexibility of B stage sheet is excellent.

As for the indication of Japanese application 2010-152346 and Japanese application 2010-152347, the whole is taken in into this specification by reference.

All documents, patent applications, and technical specifications described in this specification are hereby incorporated by reference to the same extent as if each document, patent application, and technical specification was specifically incorporated by reference. Is brought in.

Claims (11)

An epoxy resin having a partial structure represented by the following General Formula (I),
A curing agent having a partial structure represented by at least one of the following General Formulas (IIa) to (IId);
Inorganic fillers,
B-stage sheet which is a semi-carbide of an epoxy resin composition containing an elastomer.
[Formula 1]

(In General Formula (I), R <^1> -R <^8> represents a hydrogen atom or a methyl group each independently.)
(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

(M and n respectively independently represent a positive number, and Ar represents group represented by either of the following general formula (IIIa) and (IIIb) in general formula (IIa)-(IId).)
[Chemical Formula 6]

(In General Formula (IIIa) and (IIIb), R ¹¹ and R ¹⁴ each independently represent a hydrogen atom or a hydroxyl group. R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) The method of claim 1,
The said inorganic filler is the 1st alumina group whose particle diameter D50 is 7 micrometers or more and 35 micrometers or less corresponding to 50% of accumulation from the small particle size side of a weight cumulative particle size distribution, and the 2nd alumina whose said particle diameter D50 is 1 micrometer or more and less than 7 micrometers. A group and a third alumina group having a particle diameter D50 of less than 1 μm,
60 mass% or more and 70 mass% or less of the content rate of the said 1st alumina group in the gross mass of a said 1st alumina group, a 2nd alumina group, and a 3rd alumina group, and the content rate of the said 2nd alumina group is 15 It is mass% or more and 30 mass% or less, Furthermore, the content rate of the said 3rd alumina group is 1 mass% or more and 25 mass% or less,
B-stage sheet whose content ratio (2nd alumina group / 3rd alumina group) of the said 2nd alumina group with respect to the said 3rd alumina group is 0.9 or more and 1.7 or less by mass basis. The method of claim 2,
The B-stage sheet whose content ratio (1st alumina group / 2nd alumina group) of the said 1st alumina group with respect to the said 2nd alumina group is 2.0 or more and 5.0 or less on a mass basis. The method according to any one of claims 1 to 3,
The elastomer is a B stage sheet containing an acrylic elastomer having a weight average molecular weight of 100,000 to 800,000. The method according to any one of claims 1 to 4,
B-stage sheet whose content rate (hardening agent / epoxy resin) of the said hardening | curing agent with respect to the total content of the said epoxy resin is 0.95 or more and 1.25 or less on an equivalent basis. Metal foil with resin provided with metal foil and the B stage sheet in any one of Claims 1-5 arrange | positioned on the said metal foil. A metal substrate provided with a metal support body, the cured resin layer which is the hardened | cured material of the B stage sheet | seat of any one of Claims 1-5 arrange | positioned on the said metal support body, and the metal foil arrange | positioned on the said cured resin layer. The circuit layer which consists of a metal support body, the cured resin layer which is the hardened | cured material of the B stage sheet of any one of Claims 1-5 arrange | positioned on the said metal support body, and the metal foil arrange | positioned on the said cured resin layer, An LED substrate comprising an LED element disposed on the circuit layer. Metal Foil,
It is arrange | positioned on the said metal foil, and contains the epoxy resin which has a partial structure represented by the following general formula (I), the hardening | curing agent which has a partial structure represented by at least one of the following general formula (IIa)-(IId), an inorganic filler, and an elastomer Metal foil with resin provided with the semi-hardened resin layer which is a semi-hardened material of an epoxy resin composition.
(7)

(In General Formula (I), R <^1> -R <^8> represents a hydrogen atom or a methyl group each independently.)
[Chemical Formula 8]

[Chemical Formula 9]

[Formula 10]

(11)

(M and n respectively independently represent a positive number, and Ar represents group represented by either of the following general formula (IIIa) or (IIIb) in general formula (IIa)-(IId).)
[Chemical Formula 12]

(In General Formula (IIIa) and (IIIb), R ¹¹ and R ¹⁴ each independently represent a hydrogen atom or a hydroxyl group. R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) A metal support,
It is disposed on the metal support and contains an epoxy resin having a partial structure represented by the following general formula (I), a curing agent, an inorganic filler, and an elastomer having a partial structure represented by at least one of the following general formulas (IIa) to (IId). Cured resin layer which is hardened | cured material of resin composition to say,
The metal substrate provided with the metal foil arrange | positioned on the said cured resin layer.
[Chemical Formula 13]

(In General Formula (I), R <^1> -R <^8> represents a hydrogen atom or a methyl group each independently.)
[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

(M and n respectively independently represent a positive number, and Ar represents group represented by either of the following general formula (IIIa) or (IIIb) in general formula (IIa)-(IId).)
[Chemical Formula 18]

(In General Formula (IIIa) and (IIIb), R ¹¹ and R ¹⁴ each independently represent a hydrogen atom or a hydroxyl group. R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) Applying the resin composition containing the epoxy resin which has a partial structure represented by the following general formula (I), the hardening agent which has a partial structure represented by at least one of the following general formula (IIa)-(IId), an inorganic filler, and an elastomer on metal foil. Forming a resin layer,
The manufacturing method of metal foil with resin containing the B staged process which heat-processes the said resin layer and makes it a semi-hardened resin layer.
[Chemical Formula 19]

(In General Formula (I), R <^1> -R <^8> represents a hydrogen atom or a methyl group each independently.)
[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

(23)

(M and n respectively independently represent a positive number, and Ar represents group represented by either of the following general formula (IIIa) or (IIIb) in general formula (IIa)-(IId).)
[Formula 24]

(In General Formula (IIIa) and (IIIb), R ¹¹ and R ¹⁴ each independently represent a hydrogen atom or a hydroxyl group. R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.)

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