KR101308326B1 - Resin composition, b stage sheet, metal foil with resin, metal substrate, and led substrate - Google Patents

Abstract

The resin composition has a bifunctional epoxy resin having a biphenyl skeleton, a phenol resin, and a first alumina group having a particle size D50 corresponding to cumulative 50% at the small particle size side of the weight cumulative particle size distribution of 7 µm or more and 25 µm or less, the particle size. 2nd alumina group whose D50 is 1 micrometer or more and less than 7 micrometers, and the 3rd alumina group whose said particle diameter D50 is less than 1 micrometer, The content ratio of the said phenol resin with respect to the total content of an epoxy resin (phenol resin / epoxy resin) is It is comprised so that it may become 1.00 or more and 1.25 or less on an equivalent basis.

Description

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

The present invention relates to a resin composition, 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 it is put to practical use as a heat conductive sealing material and a heat conductive adhesive agent.

In connection with the above, Unexamined-Japanese-Patent No. 2008-13759 discloses the epoxy resin composition containing the epoxy resin which shows liquid crystal, and an alumina powder, and is said to have high thermal conductivity and excellent workability.

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

The present invention provides a resin composition capable of forming a cured resin product having a high thermal conductivity and high electrical insulation, and a B stage sheet, a metal foil with a resin, a metal substrate, and an LED substrate formed using the same. do.

The present invention includes the following aspects.

The first alumina group having a bifunctional epoxy resin having a <1> biphenyl skeleton, a phenol resin, and a particle size D50 corresponding to the cumulative 50% at the small particle size side of the weight cumulative particle size distribution of 7 µm or more and 25 µm or less, the particle diameter D50 The 2nd alumina group which is 1 micrometer or more and less than 7 micrometers, and the 3rd alumina group whose said particle diameter D50 is less than 1 micrometer, The content ratio of the said phenol resin with respect to the total content of an epoxy resin (phenol resin / epoxy resin) is It is a resin composition which is 1.00 or more and 1.25 or less on an equivalent basis.

<2> The said phenol resin is a resin composition as described in said <1> which has a structural unit represented with the following general formula (I).

[Formula 1]

(In General Formula (I), R ¹ Represents an alkyl group, an aryl group, or an aralkyl group, R ² and R ³ each independently represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, m is an integer of 0 to 2, n is 1 to 7 Represents an integer)

The bifunctional epoxy resin which has <3> said biphenyl skeleton is a resin composition as described in said <1> or <2> containing the compound represented by following General formula (III).

[Formula 2]

(In General Formula (III), R <^1> -R <^8> represents a hydrogen atom or a C1-C10 hydrocarbon group each independently, and n represents the integer of 0-3.)

The first alumina group having a bifunctional epoxy resin having a <4> biphenyl skeleton, a phenol resin, and a particle size D50 corresponding to the cumulative 50% at the small particle size side of the weight cumulative particle size distribution of 7 µm or more and 25 µm or less, the particle diameter D50 The said 2nd alumina group which is 1 micrometer or more and less than 7 micrometers, and the said 3rd alumina group whose said particle diameter D50 is less than 1 micrometer, The said alumina group in the total mass of a said 1st alumina group, a 2nd alumina group, and a 3rd alumina group. 60 mass% or more and 70 mass% or less of the content of 1 alumina group, 15 mass% or more and 30 mass% or less of the said 2nd alumina group, and 1 mass% or more and 25 mass% or less of the said 3rd alumina group And the content rate (2nd alumina group / 3rd alumina group) of the said 2nd alumina group with respect to the said 3rd alumina group is 1.2 or more and 1.7 or less on a mass basis.

The content ratio (1st alumina group / 2nd alumina group) of the said 1st alumina group with respect to <5> said 2nd alumina group is a resin composition as described in said <4> which is 2.0 or more and 5.0 or less on a mass basis.

It is a B stage sheet which consists of a semi-hardened resin composition derived from the resin composition in any one of <6> said <1>-<5>.

It is metal foil with resin provided with <7> metal foil and the semi-hardened resin layer derived from the resin composition in any one of said <1>-<5> arrange | positioned on the said metal foil.

With a <8> metal support body, the cured resin layer derived from the resin composition 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.

The circuit which consists of a <9> metal support body, the cured resin layer derived from the resin composition 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. It is a LED substrate provided with a layer and LED element arrange | positioned on the said circuit layer.

ADVANTAGE OF THE INVENTION According to this invention, the resin composition which can form the hardened | cured material of resin which has high thermal conductivity and high electrical insulation, and the B stage sheet | seat formed using this, the metal foil with resin, a metal substrate, and LED board | substrate formed using this can be provided. have.

1 is a schematic cross-sectional view showing an example of an LED substrate according to the present invention.
2 is a perspective view showing an example of the LED substrate according to the present invention.

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 an independent step but also clearly distinguishable 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 there is particular notice, the total amount of the said several substance which exists in a composition is meant. do.

<Resin composition>

The resin composition of this invention is a bifunctional epoxy resin which has a biphenyl frame | skeleton, a phenol resin, and the 1st alumina group whose particle diameter D50 corresponding to 50% of accumulation on the small particle size side of a weight accumulation particle size distribution is 7 micrometers or more and 25 micrometers or less. , The second alumina group having a particle size D50 of 1 µm or more and less than 7 µm, and the third alumina group having a particle size D50 of less than 1 µm, wherein the content ratio of the phenol resin to the total content of the epoxy resin (phenol resin / epoxy Resin) is 1.00 or more and 1.25 or less on an equivalent basis.

Moreover, the resin composition of this invention contains other epoxy resins other than the bifunctional epoxy resin which has a biphenyl skeleton, and other components as needed in addition to the said essential component.

By containing at least three kinds of alumina different in particle size D50 from each other, and the content ratio of the phenol resin to the total content of the epoxy resin is in a specific range, high thermal conductivity and high electrical insulation are achieved. In addition, the said resin composition shows the sheet | seat flexibility excellent when a B stage sheet is comprised, for example.

In this invention, although the content rate of a phenol resin with respect to the total content of an epoxy resin is 1.00 or more and 1.25 or less on an equivalent basis, it is preferable that they are 1.00 or more and 1.22 or less from a viewpoint of thermal conductivity and electrical insulation.

In addition, the equivalent standard in this invention defines the content ratio of an epoxy resin and a phenol resin based on the number of the epoxy groups contained in an epoxy resin, and the hydroxyl group number of the phenol resin reacting with the epoxy group 1: 1. Means that.

In addition, the total content of an epoxy resin means the total content of the bifunctional epoxy resin which has the said biphenyl skeleton, and other epoxy resins other than the bifunctional epoxy resin which has the said biphenyl skeleton.

In addition, the content rate of the said equivalent standard is specifically calculated from the following formula.

Formula content ratio (phenol resin / epoxy resin) = Σ (phenol resin amount / phenol resin equivalent) / Σ (epoxy resin amount / epoxy equivalent epoxy resin)

Moreover, the resin composition of this invention is 1st alumina whose bifunctional epoxy resin which has a biphenyl frame | skeleton, a phenol resin, and particle size D50 corresponding to 50% of accumulation on the small particle size side of a weight accumulation particle size distribution are 7 micrometers or more and 25 micrometers or less. Group, a second alumina group having a particle size D50 of 1 μm or more and less than 7 μm, and a third alumina group having a particle size D50 of less than 1 μm, wherein the total mass of the first alumina, the second alumina group, and the third alumina group is included. The content rate of the said 1st alumina group in the inside is 60 mass% 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, and also the content rate of the said 3rd alumina group is 1 mass It is% or more and 25 mass% or less, and the content rate (2nd alumina group / 3rd alumina group) of the said 2nd alumina group with respect to the said 3rd alumina group is 1.2 or more and 1.7 or less by mass reference | standard.

Moreover, the resin composition of this invention contains another component as needed in addition to the said essential component.

When the alumina contained in the resin composition has a specific particle size distribution, alumina particles having different particle diameters fill the pores with each other, and the alumina is filled with high density. In addition to this, high thermal conductivity and high electrical insulation are achieved by containing a bifunctional epoxy resin and a phenol resin having a biphenyl skeleton. In addition, the said resin composition shows the sheet | seat flexibility excellent when a B stage sheet is comprised, for example.

Moreover, the said resin composition is a bifunctional epoxy resin which has a biphenyl frame | skeleton, a phenol resin, and the 1st alumina group whose particle size D50 corresponding to 50% of cumulative accumulation on the small particle diameter side of a weight cumulative particle size distribution is 7 micrometers or more and 25 micrometers or less, In the total mass of the said 1st alumina group, the 2nd alumina group, and the 3rd alumina group containing the 2nd alumina group whose said particle diameter D50 is 1 micrometer or more and less than 7 micrometers, and the said particle size D50 is less than 1 micrometer. The content rate of the said 1st alumina group is 60 mass% or more and 70 mass% or less, Moreover, the content rate of the said 2nd alumina group is 15 mass% or more and 30 mass% or less, and also the content rate of the said 3rd alumina group is 1 mass% or more It is 25 mass% or less, and the content rate (2nd alumina group / 3rd alumina group) of the said 2nd alumina group with respect to the said 3rd alumina group is 1.2 or more and 1.7 or less by mass reference | standard, and Epoxy Content of the phenol resin to the total content of the resin (a phenolic resin / epoxy resin), preferably less than 1.00 to 1.25 equivalent basis.

When the alumina contained in the resin composition has a specific particle size distribution, and the content ratio of the phenol resin to the total content of the epoxy resin is in a specific range, better thermal conductivity and higher electrical insulation are achieved. In addition, the said resin composition shows the outstanding sheet | seat external appearance, and shows the outstanding sheet | seat flexibility, when a B stage sheet is comprised, for example.

[Epoxy resin]

The resin composition of this invention contains at least 1 sort (s) of bifunctional epoxy resin which has a biphenyl skeleton. The epoxy resin contains at least one biphenyl skeleton and is not particularly limited as long as it is a compound having two epoxy groups.

Specifically, a biphenyl type epoxy resin and a biphenylene type epoxy resin are mentioned, for example.

As said biphenyl type epoxy resin, the epoxy resin etc. which are represented by following General formula (III) are mentioned.

(3)

Formula (Ⅲ) of, R ¹ ~ R ⁸ are, each independently, represents a hydrogen atom, or a substituted or unsubstituted hydrocarbon having a carbon number of 1 ~ 10, n represents an integer of 0 to 3.

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

Especially, R <^1> -R <^8> has a hydrogen atom or a methyl group from a thermal conductivity viewpoint.

As a biphenyl type epoxy resin represented by the said General formula (III), 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. Especially, from a viewpoint which can suppress the fall of the glass transition temperature of hardened | cured material, 4,4'-bis (2, 3- epoxy propoxy) -3, 3 ', 5, 5'- tetramethyl biphenyl are a main component. An epoxy resin to say is preferable. As such a compound, YX-4000 (made by Japan Epoxy Resin Co., Ltd.), YL-6121H (made by Japan Epoxy Resin Co., Ltd.), YSLV-80XY (made by Touto Chemical Co., Ltd.), etc. can be obtained as a commercial item.

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

[Formula 4]

R <^1> -R <^9> is respectively independently a hydrogen atom, a C1-C10 alkyl group, a C1-C10 alkoxy group, a C6-C10 aryl group, or a C6-C10 in general formula (IV). An alkyl group is represented and n represents the integer of 0-10.

Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, and an isobutyl group. Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a tolyl group and a xylyl group. Examples of the aralkyl group having 7 to 10 carbon atoms include a benzyl group and a 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 (IV), NC-3000 (Nippon Kayaku Co., Ltd. brand name) can be obtained as a commercial item, for example.

As a bifunctional epoxy resin which has a biphenyl frame | skeleton in this invention, at least 1 of the compound represented by said general formula (III) or general formula (IV) from a viewpoint of thermal conductivity, electrical insulation, and the flexibility of a B stage sheet | seat. It is preferable to contain a species, and it is more preferable to contain at least 1 type of the compound represented by general formula (III) from a thermal conductivity viewpoint.

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

In addition, solid content in a resin composition means the residual component which removed the volatile component from the component which comprises a resin composition.

The resin composition of this invention may contain another epoxy resin in addition to the bifunctional epoxy resin which has the said biphenyl skeleton. As another epoxy resin, if it does not have a biphenyl skeleton, a conventionally well-known epoxy resin can be used without a restriction | limiting in particular.

Specifically, such as phenol novolak type epoxy resin, orthocresol novolak type epoxy resin, epoxy resin having triphenylmethane skeleton, phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, etc. Condensation or co-condensation of phenols and / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene and compounds having aldehyde groups such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylicaldehyde under acidic catalysts Glyci obtained by the reaction of polybasic acids such as bisphenol A, bisphenol F, bisphenol S, stilbene type epoxy resin, hydroquinone type epoxy resin, phthalic acid, dimer acid, and epichlorohydrin Poly, such as a diester type epoxy resin, diamino diphenylmethane, and isocyanuric acid Glycidylamine type epoxy resin obtained by reaction of Min and epichlorohydrin, the epoxide of the co-condensation resin of dicyclopentadiene and phenol, the epoxy resin which has a naphthalene ring, a phenol aralkyl resin, and a biphenylene skeleton Epoxides of aralkyl type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins, trimethylolpropane type epoxy resins, terpene modified epoxy resins, and olefin bonds obtained by oxidizing peroxides such as peracetic acid. A shape aliphatic epoxy resin, an alicyclic epoxy resin, a sulfur atom containing epoxy resin, etc. are mentioned, These may be used independently and may be used in combination of 2 or more type.

It is preferable that the resin composition of this invention 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 (manufactured by DIC Corporation) can be mentioned.

When the resin composition of this invention 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 bifunctional epoxy resin which has the said biphenyl skeleton, It is preferable that they are 0.01 mass% or more and 12 mass% or less. Such a content ratio improves the thermal conductivity, the electrical insulation, and the flexibility of the B stage sheet more effectively.

In addition, in this invention, when another epoxy resin is added to the bifunctional epoxy resin which has the said biphenyl skeleton, the content rate of the said phenol resin with respect to epoxy resin total amount is 1.00 or more and 1.25 or less on an equivalent basis.

When the resin composition of this invention contains another epoxy resin (preferably epoxy resin which has a naphthalene ring), content ratio of bifunctional epoxy resin which has a biphenyl skeleton, and another epoxy resin (biphenyl skeleton The bifunctional epoxy resin / other epoxy resins having) are not particularly limited. For example, from a flexible viewpoint, it can be 80/20 or more, it is preferable that it is 90/10 or more, and it is more preferable that it is 95/5 or more.

[Phenolic resin]

The resin composition of this invention contains at least 1 sort (s) of phenol resin. Although it does not restrict | limit especially as said phenol resin, What contains phenol resin (Hereinafter, it may be called "novolak resin") containing at least 1 sort (s) of the compound which has a structural unit represented by following General formula (I). desirable. The said phenol resin acts as a hardening | curing agent of an epoxy resin, for example.

By containing the phenol resin which has a specific structure, thermal conductivity can be improved effectively and the usable time in the state before hardening can be made long enough.

[Chemical Formula 5]

In said general formula (I), R <^1> represents an alkyl group, an aryl group, or an aralkyl group. The alkyl group, the aryl group, and the aralkyl group represented by R ¹ may further have a substituent if possible, and examples of the substituent include an alkyl group, an aryl group, a halogen atom, and a hydroxyl group.

m represents 0-2 and when m is 2, two R <^1> may be the same and may differ. In the present invention, from the viewpoint of thermal conductivity, m is preferably 0 or 1, and more preferably 0.

And n represents 1 to 7.

It is preferable that the phenol resin in this invention is a compound which has a structural unit represented by the said General formula (I), but may have 2 or more types of structural units represented by the said General formula (I). When the phenol resin in this invention has 2 or more types of structural units represented by the said General formula (I), any one of R <^1> -R <^3> , m, and n should just mutually differ.

Although it is preferable that the phenol resin in this invention contains at least 1 sort (s) of the compound which has a structural unit represented by the said General formula (I), It is 2 or more types of compounds which have a structural unit represented by the said General formula (I). It may contain. When the phenol resin in this invention contains 2 or more types of compounds which have a structural unit represented by the said General formula (I), the 2 or more types of compounds differ in the structural unit represented by General formula (I), Any of structural units other than the structural unit represented by general formula (I), and a thing with a different molecular weight may be sufficient.

The phenol resin in the present invention preferably contains a partial structure derived from resorcinol as a phenolic compound from the viewpoint of thermal conductivity, but at least one kind of a partial structure derived from a phenolic compound other than resorcinol. It may further contain. As phenolic compounds other than resorcinol, phenol, cresol, catechol, hydroquinone, etc. are mentioned, for example. The said phenol resin may contain the partial structure derived from these individually by 1 type, or in combination of 2 or more types.

The partial structure derived from a phenolic compound here means the monovalent or divalent group comprised by removing one or two hydrogen atoms from the benzene ring part of a phenolic compound. The position at which the hydrogen atom is removed is not particularly limited.

In the present invention, as the partial structure derived from phenolic compounds other than resorcinol, phenol, cresol, catechol, hydroquinone, 1,2,3-trihydroxy from the viewpoint of thermal conductivity, adhesion, and storage stability It is preferably a partial structure derived from at least one selected from benzene, 1,2,4-trihydroxybenzene, and 1,3,5-trihydroxybenzene, and at least 1 selected from catechol and hydroquinone. It is more preferable that it is a partial structure derived from a species.

Although there is no restriction | limiting in particular about the content rate of the partial structure derived from the resorcinol in the said phenol resin, From a viewpoint of thermal conductivity and storage stability, containing of the partial structure derived from the resorcinol with respect to the total mass of a phenol resin is contained. It is preferable that a ratio is 55 mass% or more, It is more preferable that it is 80 mass% or more, It is further more preferable that it is 90 mass% or more.

In general formula (I), R <^2> and R <^3> represents a hydrogen atom, an alkyl group, an aryl group, a phenyl group, or an aralkyl group each independently. The alkyl group, phenyl group, aryl group, and aralkyl group represented by R <^2> and R <^3> may have a substituent further if possible, and an alkyl group, an aryl group, a halogen atom, a hydroxyl group, etc. are mentioned as this substituent.

R ² in the present invention And R ³ is preferably a hydrogen atom, an alkyl group, or an aryl group from the viewpoint of storage stability and thermal conductivity, more preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and even more preferably a hydrogen atom. .

Moreover, it is also preferable that at least one of R <^2> and R <^3> is an aryl group from a heat resistant viewpoint.

As a phenol resin in this invention, it is preferable that it is a phenol resin containing the compound which has a partial structure specifically represented by any of General formula (Ia)-General formula (If) shown below.

[Formula 6]

In general formula (Ia)-general formula (If), i and j show the content rate (mass%) of the structural unit derived from each phenolic compound, i is 5-30 mass%, j is 70- It is 95 mass%, and the sum total of i and j is 100 mass%.

The phenol resin in this invention contains the structural unit represented by either general formula (Ia) and general formula (Ie) from a viewpoint of thermal conductivity and storage stability, i is 5-20 mass%, j is 80 It is preferable that it is-95 mass%, including the structural unit represented by general formula (Ia), i is 2-10 mass%, and it is more preferable that j is 90-98 mass%.

It is preferable that the phenol resin in this invention contains the compound which has a structural unit represented by the said General formula (I), and it is more preferable to contain at least 1 sort (s) of the compound represented by the following General formula (II).

[Formula 7]

In General Formula (II), R ¹¹ represents a monovalent group derived from a hydrogen atom or a phenolic compound represented by the following General Formula (IIp), and R ¹² represents a monovalent group derived from a phenolic compound. Further, ^{R 1, R 2, R 3} , m and n have the same meanings ^{R 1, R 2, R 3} , m and n, respectively in formula (Ⅰ).

The monovalent group derived from the phenolic compound represented by R <^12> is a monovalent group comprised by removing one hydrogen atom from the benzene ring part of a phenolic compound, and the position where a hydrogen atom is removed is not specifically limited.

[Formula 8]

P shows the integer of 1-3 in general formula (IIp). Further, R ^1, R ² and R ³ are each the same meaning as that of R ^1, R ² and R ³ in the formula (Ⅰ), m represents an integer of 0-2.

The phenolic compound in R ¹¹ and R ¹² is not particularly limited as long as it is a compound having a phenolic hydroxyl group. Specifically, phenol, cresol, catechol, resorcinol, hydroquinone, etc. are mentioned, for example. Especially, it is preferable that it is at least 1 sort (s) chosen from cresol, catechol, and resorcinol from a viewpoint of thermal conductivity and storage stability.

As a number average molecular weight of the said phenol resin, it is preferable that it is 800 or less from a viewpoint of thermal conductivity, It is more preferable that it is 300 or more and 700 or less, It is more preferable that it is 350 or more and 550 or less.

In the resin composition of this invention, the phenol resin containing the compound which has a structural unit represented by the said General formula (I) may contain the monomer which is a phenolic compound which comprises a phenol resin. Although there is no restriction | limiting in particular as content ratio (the following may be called "monomer content ratio") of the monomer which is a phenolic compound which comprises a phenol resin, 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, by being 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 phenol resin, 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 phenol resin in the resin composition of this invention, if the content rate of the said phenol resin with respect to the total amount of an epoxy resin is 1.00 or more and 1.25 or less on an equivalent basis, there will be no restriction | limiting in particular. It is preferable that it is 1.00 or more and 1.22 or less from a viewpoint of thermal conductivity, electrical insulation, the flexibility of a B-stage sheet, and usable time, It is more preferable that it is 1.00 or more and 1.20 or less from a viewpoint of insulation at the time of moisture absorption, It is especially 1.00 or more and 1.10 or less desirable.

The resin composition of this invention is a compound which has the epoxy resin containing the compound represented by the said General formula (III) or (IV), and the structural unit represented by the said General formula (I) from a thermal conductivity and an electrical insulation viewpoint. It is preferable that the content rate of the said phenol resin with respect to the total content of an epoxy resin is 1.00 or more and 1.22 or less on an equivalent basis, and the epoxy resin containing the compound represented by the said General formula (III) containing the phenol resin to contain, and the said It is more preferable that the phenol resin containing the compound which has a structural unit represented by General formula (I) is contained, and the content rate of the said phenol resin with respect to the total content of an epoxy resin is 1.00 or more and 1.22 or less on an equivalent basis.

In addition to the said phenol resin, the resin composition of this invention may contain other hardening | curing agents other than a phenol resin as needed. As other curing agents, conventionally known curing agents can be used without particular limitation. Specifically, polyaddition type hardeners, such as an amine hardener and a mercaptan type hardener, latent hardeners, such as imidazole, etc. can be used.

[Alumina]

The resin composition of this invention is the 1st alumina group whose particle size D50 is 7 micrometers or more and 25 micrometers or less corresponding to the cumulative 50% in the small particle size side of a weight cumulative particle size distribution, the 2nd alumina group whose said particle diameter D50 is 1 micrometer or more and less than 7 micrometers, and The particle diameter D50 contains at least three kinds of alumina groups of the third alumina having a size of less than 1 µm. Therefore, the particle size distribution of the alumina contained in the said resin composition has at least 3 peaks corresponding to the 1st-3rd alumina group, respectively. Moreover, the peak area of each peak is based on the content rate of each alumina group.

In the present invention, the particle size D50 of the alumina is measured using a laser diffraction method and corresponds to the particle size at which the weight accumulation becomes 50% when the weight accumulation particle size distribution curve is drawn from the small particle size side.

Particle size distribution measurement using the laser diffraction method can be performed using the laser diffraction scattering particle size distribution measuring apparatus (For example, the Beckman Coulter company make, LS230).

In the said 1st alumina group, particle size D50 corresponding to 50% of accumulation on the small particle size side of a weight accumulation particle size distribution is 7 micrometers or more and 25 micrometers or less. 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 resin composition is 60 mass% or more and 70 mass% or less, and it is 62 mass% or more and 70 mass% from a viewpoint of thermal conductivity and electrical insulation. It is more preferable that it is the following.

Moreover, the said 2nd alumina group is 1 micrometer or more and less than 7 micrometers in particle size D50 corresponding to 50% of accumulation on the small particle size side of a weight cumulative 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 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. More preferably, it is more preferable that they are 18.5 mass% or more and 25 mass% or less.

In the said 3rd alumina group, the particle size D50 corresponding to 50% of accumulation on the small particle size side of a weight accumulation particle size distribution is 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 resin composition is 1 mass% or more and 25 mass% or less, and it is 5 mass% or more and 20 mass% from a viewpoint of thermal conductivity and electrical insulation. It is more preferable that it is the following, and it is still more preferable that they are 10 mass% or more and 18 mass% or less.

In addition, in this invention, there is no restriction | limiting in particular in the content rate (2nd alumina group / 3rd alumina group) of the said 2nd alumina group with respect to the said 3rd alumina group. It is preferable that they are 1.2 or more and 1.7 or less from a viewpoint of thermal conductivity and electrical insulation, It is more preferable that they are 1.25 or more and 1.65 or less, It is still more preferable that they are 1.3 or more and 1.6 or less from a viewpoint of reducing the space | gap in a sheet | seat.

On the other hand, the content ratio (first alumina group / second alumina group) of the first alumina group to the second alumina group is not particularly limited, but is preferably 2.0 or more and 5.0 or less from the viewpoint of thermal conductivity and electrical insulation, It is more preferable that they are 2.5 or more and 4.0 or less from a viewpoint of reducing the space | gap in a sheet | seat.

The alumina in the resin composition of this invention contains 60 mass% or more and 68 mass% or less of the 1st alumina group whose particle diameter D50 is 10 micrometers or more and 22 micrometers or less from a viewpoint of thermal conductivity, electrical insulation, and sheet | seat flexibility, and also a particle size 18 mass% or more and 27 mass% or less of the 2nd alumina group whose D50 is 2 micrometers or more and 6 micrometers or less, 5 mass% or more and 20 mass% or less of the 3rd alumina group whose particle diameter D50 is 0.1 micrometer or more and 0.8 micrometer or less, It is preferable that the content rate of the said 2nd alumina group with respect to a said 3rd alumina group is 1.25 or more and 1.65 or less,

62 mass% or more and 65 mass% or less of the 1st alumina group whose particle diameter D50 is 15 micrometers or more and 20 micrometer or less, and 20 mass% or more and 25 mass% or less of the 2nd alumina group whose particle diameter D50 is 3 micrometers or more and 5 micrometers or less, Furthermore, it is more preferable that 10 mass% or more and 15 mass% or less contain the 3rd alumina group whose particle diameter D50 is 0.2 micrometer or more and 0.6 micrometer or less, and it is more preferable that the content rate of the said 2nd alumina group with respect to a said 3rd alumina group is 1.3 or more and 1.6 or less. Do.

The alumina in the present invention is not particularly limited as long as it has the particle size distribution described above, 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 sort (s) 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.

Moreover, it is further more preferable that the said 1st alumina group and the 2nd alumina group are alumina which consists of single crystal particle of (alpha)-alumina from a thermal conductivity viewpoint.

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, single crystal particles of α-alumina It is more preferable that it is an alumina which consists of.

As said 1st to 3rd alumina group, it can select from a commercially available thing suitably. Further, the alumina powder which becomes the transition alumina by the transition alumina or the heat treatment is calcined in an atmosphere gas containing hydrogen chloride (for example, JP-A-6-191833, JP-A 6-191836, etc.). May be prepared.

Although there is no restriction | limiting in particular in the content rate of the alumina contained in the resin composition of this invention, It can be 85 mass% or more and 95 mass% or less in solid content which comprises a resin composition, From a thermal conductivity, an electrical insulation, and a sheet flexibility, It is more preferable that they are 88 mass% or more and 92 mass% or less.

In addition, solid content in a resin composition means the residual component which removed the volatile component from the component which comprises a resin composition.

The resin composition of this invention may add the alumina as a main component in addition to the said 1st-3rd alumina group, and may contain the inorganic fiber whose number average fiber diameter is 1 micrometer-50 micrometers. In this invention, "the inorganic fiber which has alumina as a main component" means the inorganic fiber which contains 50 mass% or more of alumina. Especially, it is preferable that it is an inorganic fiber containing 70 mass% or more of alumina, and it is more preferable that it is an inorganic fiber containing 90 mass% or more of alumina. Although the number average fiber diameter of such an inorganic fiber is 1 micrometer-50 micrometers, Preferably they are 1 micrometer-30 micrometers, More preferably, they are 1 micrometer-20 micrometers. Moreover, the fiber length of such an inorganic fiber is 0.1 mm-100 mm normally.

As such inorganic fibers, commercially available ones are usually used, and specifically, include artex (manufactured by Sumitomo Chemical Co., Ltd.), denka arsen (manufactured by Denki Chemical Industry Co., Ltd.), mufftec bulk fiber (manufactured by Mitsubishi Chemical Sanza Co., Ltd.), and the like. Can be mentioned.

When using such an inorganic fiber, the usage-amount is 5 mass%-70 mass% normally with respect to the mass of the said 1st-3rd alumina group, Preferably it is 5 mass%-50 mass%, Alumina and an inorganic fiber The amount by which the total mass of turns into 30 mass%-95 mass% is normally used in solid content of a resin composition.

In addition to the said alumina, the resin composition of this invention may further contain inorganic fillers other than alumina as needed. Examples of the inorganic filler include non-conductive materials such as magnesium oxide, aluminum nitride, boron nitride, silicon nitride, silicon oxide, aluminum hydroxide, barium sulfate, and the like. Examples of conductive materials include gold, silver, nickel, and copper. These inorganic fillers can be used individually by 1 type or in mixture of 2 or more types.

In addition to the said essential component, the resin composition of this invention may contain the other component as needed. As another component, a solvent, a silane coupling agent, a dispersing agent, an antisettling agent, etc. are mentioned, for example.

As said solvent, if the hardening reaction of a resin composition is not inhibited, the organic solvent normally used can be selected suitably and can be used suitably.

It is preferable that the resin composition of this invention contains a silane coupling agent. By containing a silane coupling agent, it forms a covalent bond (corresponding to the binder agent) between the surface of the alumina material and the organic resin surrounding the periphery thereof, thereby effectively transferring heat or preventing the ingress of moisture. This contributes to the improvement of insulation reliability.

As a silane coupling agent, a commercially available thing can be used normally, In consideration of reducing compatibility with an epoxy resin or a phenol resin, and reducing the heat conduction loss in the interface of a resin layer and an alumina, an epoxy group, an amino group, and a mercapto group are added to the terminal. It is preferable to use the silane coupling agent which has a ureido group or a hydroxyl group.

Specifically, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltri Methoxysilane, 3-aminopropyltrimethoxysilane, 3-phenylaminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptotriethoxysilane, 3-ureidopropyltriethoxy Silane etc. are mentioned, Furthermore, the silane coupling agent oligomer represented by SC-6000KS2 (made by Hitachi Chemical Co., Ltd.) is mentioned.

These silane coupling agents may be used singly or in combination of two or more.

A dispersing agent can be added to the resin composition of this invention. As the dispersant, a dispersant which is effective in dispersing alumina can be used without particular limitation. As a dispersing agent, the Ajisper series manufactured by Ajinomoto Finetec Co., Ltd., the HIPLAAD series 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.

<B stage sheet>

The B stage sheet of this invention consists of a semi-hardened resin composition derived from the said 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 resin composition on a release film, and forming a resin film, for example, and the process of heat-processing the said resin film to the B stage state. have.

By heat-processing and forming the said resin composition, it is excellent in thermal conductivity and electrical insulation, and excellent in flexibility as a B stage sheet | seat and usable time.

In the a viscosity of the B stage of the invention the sheet is a resin sheet, at room temperature (25 ° ^{C) 10 4 Pa · s ~ 10} 5 Pa · than having s a, 10 ² Pa at ^{100 ℃ · s ~ 10 3 Pa} · The viscosity falls with s. Moreover, the cured resin layer after hardening mentioned later does not melt | dissolve 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, for example, a resin film can be obtained by apply | coating varnish-shaped resin composition which added the solvent, such as methyl ethyl ketone and cyclohexanone, on release films, such as PET film, and drying.

Application can be carried out according to a known method. Specifically as a coating method, methods, such as a comma coater, a die coater, a lip coater, and a gravure coater, are mentioned. As a coating method for forming a resin layer with a predetermined thickness, the comma coater method which passes a to-be-coated object between gaps, the die coater 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 coater method.

Since the hardening reaction hardly advances, the resin layer after application | coating has flexibility, but it lacks the 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. Therefore, this invention B-strates a resin composition by the heat processing mentioned later.

In this invention, if conditions which heat-process the obtained resin film can be semi-hardened to a B stage state, it will not specifically limit, It can select suitably according to the structure of a resin composition. In the present invention, a heat treatment method selected from a thermal vacuum press, a heat roll laminate, or the like is preferable for the purpose of removing voids (voids) in the resin layer generated during coating. Thereby, a flat B stage sheet can be manufactured efficiently.

Specifically, the 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 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, 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. Do. Alternatively, two or more resin films may be laminated and hot-pressed.

<Metal foil with resin>

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

The semi-cured resin layer is obtained by heat-treating the resin composition so as to be in 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.

Although it will not restrict | limit especially if it is 1 micrometer-200 micrometers as thickness of the said metal foil, Flexibility improves more by using metal foil which is 10 micrometers or more and 150 micrometers or less.

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

The metal foil to which the resin is adhered can be produced by applying the resin composition onto a metal foil and drying to form a resin layer (resin film), and heat-treating the resin layer so as to be in a B-stage state (semi-cured state).

Although the manufacturing conditions of 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. Drying temperature is about 80 to 180 degreeC, and drying time can be determined by the balance with the gelation time of a varnish, and there is no restriction | limiting in particular. 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 a 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 mentioned.

<Metal substrate>

The metal substrate of this invention is equipped with a metal support body, the resin layer derived from the said resin composition arrange | positioned on the said metal support body, and the metal foil arrange | positioned on the said resin layer. When the resin layer derived from the said resin composition arrange | positioned between a metal support body and metal foil is formed by heat-processing 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 depending on the purpose. Specifically, for example, it is preferable to use a metal such as aluminum or iron to make the thickness from 0.5 mm to 5 mm from the viewpoint of workability.

Moreover, the metal foil arrange | positioned on a 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. It manufactures on a metal support body, such as aluminum, forming a resin layer by apply | coating and drying the said resin composition in the same manner to the above, and arrange | positioning a metal foil on a resin layer again, heating and pressurizing it, and hardening a resin layer, and manufacturing it. can do. Moreover, after attaching 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-pressurizing and hardening a resin layer.

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

<LED substrate>

As shown in FIG. 1 and FIG. 2, the LED board | substrate 100 of this invention is a metal support body 14, the cured resin layer 12 derived from the said resin composition arrange | positioned on the said metal support body, 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 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 substrate of the present invention is manufactured, for example, by a manufacturing method including a step of forming a circuit layer on a metal foil on the metal substrate obtained as described above to form a circuit layer, and a step of disposing the LED element on the formed circuit layer can do.

In the step of circuit processing the metal foil on the metal substrate, a commonly used method such as fort-liso 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. Unless otherwise stated, "parts" and "%" are on a mass basis.

<Resin synthesis example 1>

To a 3 L separable flask equipped with a stirrer, a cooler, and a thermometer, 594 g of resorcinol, 66 g of catechol, 316.2 g of 37% formalin, 15 g of oxalic acid, and 100 g of water were put at 100 ° C while being heated in an oil bath. It heated up. The reaction was continued for 4 hours at reflux temperature.

Then, the temperature in a flask was heated up at 170 degreeC, distilling water off. The reaction was continued for 8 hours while maintaining the temperature at 170 ° C. Thereafter, the mixture was concentrated under reduced pressure for 20 minutes to remove water in the system, and the phenol resin having a structural unit represented by General Formula (I) was taken out. The number average molecular weight of the obtained phenol resin was 530, and the weight average molecular weight was 930. Moreover, the phenol equivalent of phenol resin is 65 g / eq. Respectively.

&Lt; Example 1 &gt;

In a container with a 1-liter lid made of polypropylene, 56.80 g (63.0% (to gross alumina total mass)) of alumina (Sumitomo Chemical Co., Ltd., Sumikorandom AA18) having a particle size D50 of 18 µm and a particle size D50 of 3 20.29 g (22.5% (to gross alumina total mass)) of alumina (Sumitomo Chemical Co., Ltd., Sumiko Random AA3) having a diameter of 13.3 g of alumina (Sumitomo Chemical Co., Ltd. 14.5% (to the total mass of alumina)) was weighed, and 12.18 g of 2-butanone (manufactured by Wako Pure Chemical Industries, Ltd.) as a solvent and 0.099 g of a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403), and a dispersant (cus) 2.80g (solid content) of 0.180g and the phenol resin obtained by resin synthesis example 1 were added and stirred for Moto Chemical Co., Ltd. make, ED-113). 5.914 g of a bifunctional epoxy resin having a biphenyl skeleton (manufactured by Mitsubishi Chemical Co., Ltd., YL6121H, epoxy equivalent 172 g / eq.) And a naphthalene epoxy resin (manufactured by DIC Corporation, HP4032D, epoxy equivalent 140 g / eq.) Were used. 0.657 g and 0.012 g of imidazole compound (manufactured by Shikoku Chemical Co., Ltd., 2PHZ) were 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-shaped resin composition 1.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in the resin composition 1 was 1.18.

The resin composition 1 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 Industries, Ltd.), and it was 20 at 100 degreeC. Drying was performed for a minute. The film thickness after drying was 100 占 퐉. The PET film (made by Teijin Dupont Film Co., Ltd., A53) was reinstalled on the resin layer after drying, and a vacuum press was performed for 15 second at 130 degreeC and a degree of vacuum of 1 Mpa using a vacuum laminator (manufactured by MEIKI Corporation), and A sheet molding (B stage sheet) was obtained.

The resulting sheet product was excellent in flexibility.

[evaluation]

The sheet molding obtained above was inserted into the stainless steel plate of thickness 2mm, and it processed in 140 degreeC for 2 hours and again at 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 sheet hardened | cured material was measured in accordance with the thermal wave thermal analysis method using the thermal-diffusion rate and thermal conductivity measuring apparatus (Iphase mobile, eye phase company make). The measurement results are shown in Table 1.

(Electric insulation)

The obtained sheet hardened | cured material is sandwiched between electrodes of diameter 25mm, and the minimum insulation breakdown voltage is measured on the conditions of alternating current (500V / sec) using the HAT-300-100RHO type breakdown voltage measuring apparatus (made by Yamazaki Industrial Co., Ltd.). It was. The measurement results are shown in Table 1.

(Sheet polished)

The gloss of the obtained sheet hardened | cured material was observed visually, and it evaluated in accordance with the following evaluation criteria.

Evaluation criteria

A: There was gloss uniformly on the whole sheet surface.

B: Glossy but fine irregularities existed on the whole sheet surface.

C: The gloss was observed on the whole sheet | seat whole surface.

D: There was no gloss on the whole sheet surface.

(Alumina particle size)

About the varnish-shaped resin composition 1, 0.5 g is disperse | distributed to 50 g of methanol, a suitable quantity is put into the laser diffraction scattering particle size distribution measuring apparatus (made by Beckman Coulter, LS230), and the particle size distribution of the alumina in a resin composition The measurement was performed. The measurement results are shown in Table 1.

&Lt; Example 2 &gt;

In Example 1, 62.66 g (69.5% (to alumina total mass) of alumina) whose particle diameter D50 was 20 micrometers as an alumina, and alumina whose particle diameter D50 was 3 micrometers 10.73 g (11.9% (alumina) of 16.77 g (18.6% (relative to alumina total mass)) and alumina (Sumitomo Chemical Co., Ltd., Sumiko Random AA04) manufactured by Sumitomo Chemical Co., Ltd. A varnish-shaped resin composition 2 was prepared in the same manner as in Example 1, except that)) to the total mass was used. The sheet molding was obtained using the obtained varnish-shaped resin composition 2, and it evaluated similarly. The evaluation results are shown in Table 1.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in the resin composition 2 was 1.18.

The resulting sheet product was excellent in flexibility.

&Lt; Example 3 &gt;

In Example 1, it was the same as Example 1 except having changed the addition amount of the phenol resin into 2.805g, the addition amount of the bifunctional epoxy resin which has a biphenyl skeleton to 6.072g, and the addition amount of the naphthalene type epoxy resin to 0.675g, respectively. The varnish-shaped resin composition 3 was prepared. The sheet molding was obtained using the obtained varnish-shaped resin composition 3, and it evaluated similarly. The evaluation results are shown in Table 1.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in the resin composition 3 was 1.08.

Further, the resulting sheet molded product was excellent in flexibility.

<Example 4>

In Example 1, it was the same as Example 1 except having changed the addition amount of the phenol resin into 2.713 g, the addition amount of the bifunctional epoxy resin which has a biphenyl skeleton to 6.154 g, and the addition amount of the naphthalene type epoxy resin to 0.683 g, respectively. The varnish-shaped resin composition 4 was prepared. The sheet molding was obtained using the obtained varnish-shaped resin composition 4, and it evaluated similarly.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in the resin composition 4 was 1.03.

Further, the resulting sheet molded product was excellent in flexibility.

&Lt; Example 5 &gt;

In Example 1, it was the same as Example 1 except having changed the addition amount of the phenol resin into 2.893g, the addition amount of the bifunctional epoxy resin which has a biphenyl skeleton to 5.991g, and the addition amount of the naphthalene type epoxy resin to 0.666g, respectively. The varnish-shaped resin composition 5 was prepared. The sheet molding was obtained using the obtained varnish-shaped resin composition 5, and it evaluated similarly.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in the resin composition 5 was 1.16.

Further, the resulting sheet molded product was excellent in flexibility.

&Lt; Example 6 &gt;

In Example 1, it was the same as Example 1 except having changed the addition amount of the phenol resin into 2.979 g, the addition amount of the bifunctional epoxy resin which has a biphenyl skeleton to 5.914 g, and the addition amount of the naphthalene type epoxy resin to 0.657 g, respectively. The varnish-shaped resin composition 6 was prepared. The sheet molding was obtained using the obtained varnish-shaped resin composition 6, and it evaluated similarly.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in the resin composition 6 was 1.20.

Further, the resulting sheet molded product was excellent in flexibility.

&Lt; Example 7 &gt;

In Example 1, it was the same as Example 1 except having changed the addition amount of the phenol resin into 2.713g, the addition amount of the bifunctional epoxy resin which has a biphenyl skeleton to 6.495g, and the addition amount of the naphthalene type epoxy resin to 0.342g, respectively. The varnish-shaped resin composition 7 was prepared. The sheet molding was obtained using the obtained varnish-shaped resin composition 7, and it evaluated similarly.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in the resin composition 7 was 1.05.

Further, the resulting sheet molded product was excellent in flexibility.

&Lt; Example 8 &gt;

Example 1 WHEREIN: Except having changed the addition amount of the phenol resin into 2.893g, the addition amount of the bifunctional epoxy resin which has a biphenyl skeleton to 6.324g, and the addition amount of the naphthalene type epoxy resin to 0.333g, respectively, and is the same as Example 1. The varnish-shaped resin composition 8 was prepared. The sheet molding was obtained using the obtained varnish-shaped resin composition 8, and it evaluated similarly.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in the resin composition 8 was 1.15.

Further, the resulting sheet molded product was excellent in flexibility.

&Lt; Example 9 &gt;

In Example 1, it was the same as Example 1 except having changed the addition amount of the phenol resin into 2.979 g, and the addition amount of the bifunctional epoxy resin which has a biphenyl skeleton to 6.242 g, and the addition amount of the naphthalene type epoxy resin, respectively to 0.329 g. The varnish-shaped resin composition 9 was prepared. The sheet molding was obtained using the obtained varnish-shaped resin composition 9, and it evaluated similarly.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in the resin composition 9 was 1.22.

Further, the resulting sheet molded product was excellent in flexibility.

&Lt; Example 10 &gt;

In Example 1, it was the same as Example 1 except having changed the addition amount of the phenol resin into 2.713 g, the addition amount of the bifunctional epoxy resin which has a biphenyl skeleton to 6.837g, and the addition amount of the naphthalene type epoxy resin, respectively to 0g. The varnish-shaped resin composition 10 was prepared. The sheet molding was obtained using the obtained varnish-shaped resin composition 10, and it evaluated similarly.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in the resin composition 10 was 1.04.

Further, the resulting sheet molded product was excellent in flexibility.

&Lt; Example 11 &gt;

Example 1 WHEREIN: Except having changed the addition amount of the phenol resin to 2.893g, the addition amount of the bifunctional epoxy resin which has a biphenyl skeleton to 6.657g, and the addition amount of the naphthalene type epoxy resin, respectively, to 0g. The varnish-shaped resin composition 11 was prepared. The sheet molding was obtained using the obtained varnish-shaped resin composition 11, and it evaluated similarly.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in the resin composition 11 was 1.15.

Further, the resulting sheet molded product was excellent in flexibility.

&Lt; Example 12 &gt;

Example 1 WHEREIN: Except having changed the addition amount of the phenol resin to 2.979 g, the addition amount of the bifunctional epoxy resin which has a biphenyl skeleton to 6.571g, and the addition amount of the naphthalene type epoxy resin, respectively, to 0 g, respectively. The varnish-shaped resin composition 12 was prepared. The sheet molding was obtained using the obtained varnish-shaped resin composition 12, and it evaluated similarly.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in the resin composition 12 was 1.22.

Further, the resulting sheet molded product was excellent in flexibility.

&Lt; Example 13 &gt;

In Example 1, the alumina was 62.66 g (69.5% (relative to the total alumina total mass)) of alumina having a particle diameter D50 of 20 µm (manufactured by Showa Denko Co., Ltd.), and alumina having a particle diameter D50 of 3 µm ( 10.73 g (11.9% (alumina) of 16.77 g (18.6% (relative to alumina total mass)) and alumina (Sumitomo Chemical Co., Ltd., Sumiko Random AA04) manufactured by Sumitomo Chemical Co., Ltd. The amount of the phenol resin was changed to 2.713 g, the amount of the bifunctional epoxy resin having a biphenyl skeleton was changed to 6.154 g and the amount of the naphthalene epoxy resin was changed to 0.683 g, respectively. In the same manner as in Example 1, a varnish-shaped resin composition 13 was prepared. The sheet molding was obtained using the obtained varnish-shaped resin composition 13, and it evaluated similarly.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in the resin composition 13 was 1.06.

Further, the resulting sheet molded product was excellent in flexibility.

&Lt; Example 14 &gt;

In Example 1, the alumina was 62.66 g (69.5% (relative to the total alumina total mass)) of alumina having a particle diameter D50 of 20 µm (manufactured by Showa Denko Co., Ltd.), and alumina having a particle diameter D50 of 3 µm ( 10.73 g (11.9% (alumina) of 16.77 g (18.6% (relative to alumina total mass)) and alumina (Sumitomo Chemical Co., Ltd., Sumiko Random AA04) manufactured by Sumitomo Chemical Co., Ltd. The amount of the phenol resin was changed to 2.89 g, and the amount of the bifunctional epoxy resin having a biphenyl skeleton was changed to 5.991 g and the amount of the naphthalene epoxy resin was changed to 0.666 g, respectively. In the same manner as in Example 1, a varnish-shaped resin composition 14 was prepared. The sheet molding was obtained using the obtained varnish-shaped resin composition 14, and it evaluated similarly.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in the resin composition 14 was 1.15.

Further, the resulting sheet molded product was excellent in flexibility.

&Lt; Example 15 &gt;

In Example 1, the alumina was 62.66 g (69.5% (relative to the total alumina total mass)) of alumina having a particle diameter D50 of 20 µm (manufactured by Showa Denko Co., Ltd.), and alumina having a particle diameter D50 of 3 µm ( 10.73 g (11.9% (alumina) of 16.77 g (18.6% (relative to alumina total mass)) and alumina (Sumitomo Chemical Co., Ltd., Sumiko Random AA04) manufactured by Sumitomo Chemical Co., Ltd. To the total mass), the amount of the phenol resin added is 2.805 g, the amount of the bifunctional epoxy resin having a biphenyl skeleton is changed to 6.072 g and the amount of the naphthalene epoxy resin is changed to 0.675 g, respectively. Was added in the same manner as in Example 1 except that the amount of the bifunctional epoxy resin having a biphenyl skeleton was changed to 5.914 g and the amount of the naphthalene epoxy resin added to 0.657 g, respectively. , Thereby preparing a resin composition 15 of the varnish-like. The sheet molding was obtained using the obtained varnish-shaped resin composition 15, and it evaluated similarly.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in the resin composition 15 was 1.21.

Further, the resulting sheet molded product was excellent in flexibility.

&Lt; Example 16 &gt;

In Example 1, the alumina was 62.66 g (69.5% (relative to the total alumina total mass)) of alumina having a particle diameter D50 of 20 µm (manufactured by Showa Denko Co., Ltd.), and alumina having a particle diameter D50 of 3 µm ( 10.73 g (11.9% (alumina) of 16.77 g (18.6% (to the total mass of alumina)) and alumina (Sumitomo Chemical Co., Ltd., Sumicorandom AA04) manufactured by Sumitomo Chemical Co., Ltd. The amount of phenol resin was changed to 2.713 g, the amount of the bifunctional epoxy resin having a biphenyl skeleton was changed to 6.495 g and the amount of the naphthalene epoxy resin was changed to 0.342 g, respectively. In the same manner as in Example 1, a varnish-shaped resin composition 16 was prepared. The sheet molding was obtained using the obtained varnish-shaped resin composition 16, and it evaluated similarly.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in the resin composition 16 was 1.06.

Further, the resulting sheet molded product was excellent in flexibility.

&Lt; Example 17 &gt;

In Example 1, the alumina was 62.66 g (69.5% (relative to the total alumina total mass)) of alumina having a particle diameter D50 of 20 µm (manufactured by Showa Denko Co., Ltd.), and alumina having a particle diameter D50 of 3 µm ( 10.73 g (11.9% (alumina) of 16.77 g (18.6% (relative to alumina total mass)) and alumina (Sumitomo Chemical Co., Ltd., Sumiko Random AA04) manufactured by Sumitomo Chemical Co., Ltd. The amount of the phenol resin was changed to 2.89 g, and the amount of the bifunctional epoxy resin having a biphenyl skeleton was changed to 6.324 g and the amount of the naphthalene epoxy resin added to 0.333 g, respectively. In the same manner as in Example 1, a varnish-shaped resin composition 17 was prepared. The sheet molding was obtained using the obtained varnish-shaped resin composition 17, and it evaluated similarly.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in the resin composition 17 was 1.16.

Further, the resulting sheet molded product was excellent in flexibility.

&Lt; Example 18 &gt;

In Example 1, the alumina was 62.66 g (69.5% (relative to the total alumina total mass)) of alumina having a particle diameter D50 of 20 µm (manufactured by Showa Denko Co., Ltd.), and alumina having a particle diameter D50 of 3 µm ( 10.73 g (11.9% (alumina) of 16.77 g (18.6% (relative to alumina total mass)) and alumina (Sumitomo Chemical Co., Ltd., Sumiko Random AA04) manufactured by Sumitomo Chemical Co., Ltd. The amount of the phenol resin was changed to 2.979 g, the amount of the bifunctional epoxy resin having a biphenyl skeleton was changed to 6.242 g, and the amount of the naphthalene epoxy resin was changed to 0.329 g. In the same manner as in Example 1, a varnish-shaped resin composition 18 was prepared. The sheet molding was obtained using the obtained varnish-shaped resin composition 18, and it evaluated similarly.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in the resin composition 18 was 1.18.

Further, the resulting sheet molded product was excellent in flexibility.

&Lt; Example 19 &gt;

In Example 1, the alumina was 62.66 g (69.5% (relative to the total alumina total mass)) of alumina having a particle diameter D50 of 20 µm (manufactured by Showa Denko Co., Ltd.), and alumina having a particle diameter D50 of 3 µm ( 10.73 g (11.9% (alumina) of 16.77 g (18.6% (relative to alumina total mass)) and alumina (Sumitomo Chemical Co., Ltd., Sumiko Random AA04) manufactured by Sumitomo Chemical Co., Ltd. The amount of the phenol resin was changed to 2.713 g, the amount of the bifunctional epoxy resin having a biphenyl skeleton was changed to 6.837 g, and the amount of the naphthalene epoxy resin was changed to 0 g. In the same manner as in Example 1, a varnish-shaped resin composition 19 was prepared. The sheet molding was obtained using the obtained varnish-shaped resin composition 19, and it evaluated similarly.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in the resin composition 19 was 1.05.

Further, the resulting sheet molded product was excellent in flexibility.

&Lt; Example 20 &gt;

In Example 1, the alumina was 62.66 g (69.5% (relative to the total alumina total mass)) of alumina having a particle diameter D50 of 20 µm (manufactured by Showa Denko Co., Ltd.), and alumina having a particle diameter D50 of 3 µm ( 10.73 g (11.9% (alumina) of 16.77 g (18.6% (relative to alumina total mass)) and alumina (Sumitomo Chemical Co., Ltd., Sumiko Random AA04) manufactured by Sumitomo Chemical Co., Ltd. The amount of phenol resin was changed to 2.893 g, the amount of bifunctional epoxy resin having a biphenyl skeleton was changed to 6.657 g and the amount of naphthalene epoxy resin was changed to 0 g, respectively. In the same manner as in Example 1, a varnish-shaped resin composition 20 was prepared. The sheet molding was obtained using the obtained varnish-shaped resin composition 20, and it evaluated similarly.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in the resin composition 20 was 1.14.

Further, the resulting sheet molded product was excellent in flexibility.

&Lt; Example 21 &gt;

In Example 1, the alumina was 62.66 g (69.5% (relative to the total alumina total mass)) of alumina having a particle diameter D50 of 20 µm (manufactured by Showa Denko Co., Ltd.), and alumina having a particle diameter D50 of 3 µm ( 10.73 g (11.9% (alumina) of 16.77 g (18.6% (relative to alumina total mass)) and alumina (Sumitomo Chemical Co., Ltd., Sumiko Random AA04) manufactured by Sumitomo Chemical Co., Ltd. The amount of the phenol resin was changed to 2.979 g, the amount of the bifunctional epoxy resin having a biphenyl skeleton was changed to 6.571 g, and the amount of the naphthalene epoxy resin was changed to 0 g. In the same manner as in Example 1, a varnish-shaped resin composition 21 was prepared. The sheet molding was obtained using the obtained varnish-shaped resin composition 21, and it evaluated similarly.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in the resin composition 21 was 1.03.

Further, the resulting sheet molded product was excellent in flexibility.

&Lt; Example 22 &gt;

In Example 1, 56.80 g (63.0% (to alumina total mass) of alumina) having a particle size D50 of 24 µm (AX-116, manufactured by Shinnitetsu Materials Co., Ltd.) and a particle size D50 of 4.5 µm were used as the alumina. 18.93 g (21.0% (to gross alumina total mass)) of phosphorus alumina (manufactured by Shinnitetsu Materials Micron, Inc., AX3-32) and 14.42 g of alumina (LS235, manufactured by Nippon Light Metal Co., Ltd.) having a particle size D50 of 0.5 µm (16.0% (to the total mass of alumina)) and the addition amount of the phenol resin to 2.713 g, the addition amount of the bifunctional epoxy resin having a biphenyl skeleton to 6.154 g, and the addition amount of the naphthalene epoxy resin to 0.683 g, respectively. A varnish-shaped resin composition 22 was prepared in the same manner as in Example 1 except for the above. The sheet molding was obtained using the obtained varnish-shaped resin composition 22, and it evaluated similarly.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in the resin composition 22 was 1.05.

Further, the resulting sheet molded product was excellent in flexibility.

<Example 23>

In Example 1, 56.80 g (63.0% (to alumina total mass) of alumina) having a particle size D50 of 24 µm (AX-116, manufactured by Shinnitetsu Materials Co., Ltd.) and a particle size D50 of 4.5 µm were used as the alumina. 18.93 g (21.0% (to gross alumina total mass)) of phosphorus alumina (manufactured by Shinnitetsu Materials Micron, Inc., AX3-32) and 14.42 g of alumina (LS235, manufactured by Nippon Light Metal Co., Ltd.) having a particle size D50 of 0.5 µm (16.0% (to the total mass of alumina)) and the addition amount of the phenol resin to 2.893 g, the addition amount of the bifunctional epoxy resin having a biphenyl skeleton to 5.991 g, and the addition amount of the naphthalene epoxy resin to 0.666 g, respectively. A varnish-shaped resin composition 23 was prepared in the same manner as in Example 1 except for the above. The sheet molding was obtained using the obtained varnish-shaped resin composition 23, and it evaluated similarly.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in the resin composition 23 was 1.16.

Further, the resulting sheet molded product was excellent in flexibility.

&Lt; Example 24 &gt;

In Example 1, 56.80 g (63.0% (to alumina total mass) of alumina) having a particle size D50 of 24 µm (AX-116, manufactured by Shinnitetsu Materials Co., Ltd.) and a particle size D50 of 4.5 µm were used as the alumina. 18.93 g (21.0% (to gross alumina total mass)) of phosphorus alumina (manufactured by Shinnitetsu Materials Micron, Inc., AX3-32) and 14.42 g of alumina (LS235, manufactured by Nippon Light Metal Co., Ltd.) having a particle size D50 of 0.5 µm (16.0% (to the total mass of alumina)) and the addition amount of the phenol resin to 2.979 g, the addition amount of the bifunctional epoxy resin having a biphenyl skeleton to 5.914 g, and the addition amount of the naphthalene epoxy resin to 0.657 g, respectively. A varnish-shaped resin composition 24 was prepared in the same manner as in Example 1 except for the above. The sheet molding was obtained using the obtained varnish-shaped resin composition 24, and it evaluated similarly.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in the resin composition 24 was 1.20.

Further, the resulting sheet molded product was excellent in flexibility.

&Lt; Example 25 &gt;

In Example 1, 56.80 g (63.0% (to alumina total mass) of alumina) having a particle size D50 of 24 µm (AX-116, manufactured by Shinnitetsu Materials Co., Ltd.) and a particle size D50 of 4.5 µm were used as the alumina. 18.93 g (21.0% (to gross alumina total mass)) of phosphorus alumina (manufactured by Shinnitetsu Materials Micron, Inc., AX3-32) and 14.42 g of alumina (LS235, manufactured by Nippon Light Metal Co., Ltd.) having a particle size D50 of 0.5 µm (16.0% (to the total mass of alumina)) and the addition amount of the phenol resin to 2.713 g, the addition amount of the bifunctional epoxy resin having a biphenyl skeleton to 6.495 g, and the addition amount of the naphthalene epoxy resin to 0.342 g, respectively. A varnish-shaped resin composition 25 was prepared in the same manner as in Example 1 except for the above. The sheet molding was obtained using the obtained varnish-shaped resin composition 25, and it evaluated similarly.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in the resin composition 25 was 1.06.

Further, the resulting sheet molded product was excellent in flexibility.

&Lt; Example 26 &gt;

In Example 1, 56.80 g (63.0% (to alumina total mass) of alumina) having a particle size D50 of 24 µm (AX-116, manufactured by Shinnitetsu Materials Co., Ltd.) and a particle size D50 of 4.5 µm were used as the alumina. 18.93 g (21.0% (to gross alumina total mass)) of phosphorus alumina (manufactured by Shinnitetsu Materials Micron, Inc., AX3-32) and 14.42 g of alumina (LS235, manufactured by Nippon Light Metal Co., Ltd.) having a particle size D50 of 0.5 µm (16.0% (to the total mass of alumina)) and the amount of addition of the phenol resin to 2.893 g, the amount of addition of the bifunctional epoxy resin having a biphenyl skeleton to 6.324 g and the amount of addition of the naphthalene epoxy resin to 0.333 g, respectively. A varnish-shaped resin composition 26 was prepared in the same manner as in Example 1 except for the above. The sheet molding was obtained using the obtained varnish-shaped resin composition 26, and it evaluated similarly.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in the resin composition 26 was 1.13.

Further, the resulting sheet molded product was excellent in flexibility.

&Lt; Example 27 &gt;

In Example 1, 56.80 g (63.0% (to alumina total mass) of alumina) having a particle size D50 of 24 µm (AX-116, manufactured by Shinnitetsu Materials Co., Ltd.) and a particle size D50 of 4.5 µm were used as the alumina. 18.93 g (21.0% (to gross alumina total mass)) of phosphorus alumina (manufactured by Shinnitetsu Materials Micron, Inc., AX3-32) and 14.42 g of alumina (LS235, manufactured by Nippon Light Metal Co., Ltd.) having a particle size D50 of 0.5 µm (16.0% (to the total mass of alumina)) and the addition amount of the phenol resin to 2.979 g, the addition amount of the bifunctional epoxy resin having a biphenyl skeleton to 6.242 g, and the addition amount of the naphthalene epoxy resin to 0.329 g, respectively. A varnish-shaped resin composition 27 was prepared in the same manner as in Example 1 except for the above. The sheet molding was obtained using the obtained varnish-shaped resin composition 27, and it evaluated similarly.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in the resin composition 27 was 1.22.

Further, the resulting sheet molded product was excellent in flexibility.

&Lt; Example 28 &gt;

In Example 1, 56.80 g (63.0% (to alumina total mass) of alumina) having a particle size D50 of 24 µm (AX-116, manufactured by Shinnitetsu Materials Co., Ltd.) and a particle size D50 of 4.5 µm were used as the alumina. 18.93 g (21.0% (to gross alumina total mass)) of phosphorus alumina (manufactured by Shinnitetsu Materials Micron, Inc., AX3-32) and 14.42 g of alumina (LS235, manufactured by Nippon Light Metal Co., Ltd.) having a particle size D50 of 0.5 µm (16.0% (to the total mass of alumina)) and the addition amount of the phenol resin to 2.713 g, the addition amount of the bifunctional epoxy resin having a biphenyl skeleton to 6.837 g, and the addition amount of the naphthalene epoxy resin to 0 g, respectively. A varnish-shaped resin composition 28 was prepared in the same manner as in Example 1 except for the above. The sheet molding was obtained using the obtained varnish-shaped resin composition 28, and it evaluated similarly.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in the resin composition 28 was 1.05.

Further, the resulting sheet molded product was excellent in flexibility.

<Example 29>

In Example 1, 56.80 g (63.0% (to alumina total mass) of alumina) having a particle size D50 of 24 µm (AX-116, manufactured by Shinnitetsu Materials Co., Ltd.) and a particle size D50 of 4.5 µm were used as the alumina. 18.93 g (21.0% (to gross alumina total mass)) of phosphorus alumina (manufactured by Shinnitetsu Materials Micron, Inc., AX3-32) and 14.42 g of alumina (LS235, manufactured by Nippon Light Metal Co., Ltd.) having a particle size D50 of 0.5 µm (16.0% (to the total mass of alumina)) and the addition amount of the phenol resin to 2.893 g, the addition amount of the bifunctional epoxy resin having a biphenyl skeleton to 6.657 g, and the addition amount of the naphthalene epoxy resin to 0 g, respectively. A varnish-shaped resin composition 29 was prepared in the same manner as in Example 1 except for the above. The sheet molding was obtained using the obtained varnish-shaped resin composition 29, and it evaluated similarly.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in the resin composition 29 was 1.15.

Moreover, the obtained sheet molding was excellent in flexibility.

<Example 30>

In Example 1, 56.80 g (63.0% (to alumina total mass) of alumina) having a particle size D50 of 24 µm (AX-116, manufactured by Shinnitetsu Materials Co., Ltd.) and a particle size D50 of 4.5 µm were used as the alumina. 18.93 g (21.0% (to gross alumina total mass)) of phosphorus alumina (manufactured by Shinnitetsu Materials Micron, Inc., AX3-32) and 14.42 g of alumina (LS235, manufactured by Nippon Light Metal Co., Ltd.) having a particle size D50 of 0.5 µm (16.0% (to the total mass of alumina)) and the addition amount of the phenol resin to 2.979 g, the addition amount of the bifunctional epoxy resin having a biphenyl skeleton to 6.571 g, and the addition amount of the naphthalene epoxy resin to 0 g, respectively. A varnish-shaped resin composition 30 was prepared in the same manner as in Example 1 except for the above. The sheet molding was obtained using the obtained varnish-shaped resin composition 30, and it evaluated similarly.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in the resin composition 30 was 1.21.

Further, the resulting sheet molded product was excellent in flexibility.

&Lt; Example 31 &gt;

In Example 1, it was the same as Example 1 except having changed the addition amount of the phenol resin into 2.619 g, the addition amount of the bifunctional epoxy resin which has a biphenyl skeleton to 6.238 g, and the addition amount of the naphthalene type epoxy resin to 0.693 g, respectively. The varnish-shaped resin composition 31 was prepared. The sheet molding was obtained using the obtained varnish-shaped resin composition 31, and it evaluated similarly.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in the resin composition 31 was 1.00.

Further, the resulting sheet molded product was excellent in flexibility.

<Example 32>

In Example 1, it was the same as Example 1 except having changed the addition amount of the phenol resin into 2.619 g, the addition amount of the bifunctional epoxy resin which has a biphenyl skeleton to 6.931g, and the addition amount of the naphthalene type epoxy resin, respectively to 0g. The varnish-shaped resin composition 32 was prepared. The sheet molding was obtained using the obtained varnish-shaped resin composition 32, and it evaluated similarly.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in the resin composition 32 was 1.00.

Further, the resulting sheet molded product was excellent in flexibility.

<Example 33>

In a container with a 1-liter lid made of polypropylene, 56.80 g (63.0% (to gross alumina total mass)) of alumina (Sumitomo Chemical Co., Ltd., Sumikorandom AA18) having a particle size D50 of 18 µm and a particle size D50 of 3 20.29 g (22.5% (to gross alumina total mass)) of alumina (Sumitomo Chemical Co., Ltd., Sumiko Random AA3) having a diameter of 13.3 g of alumina (Sumitomo Chemical Co., Ltd. 14.5% (to the total mass of alumina)) was weighed, and 12.18 g of 2-butanone (manufactured by Wako Pure Chemical Industries, Ltd.) as a solvent and 0.099 g of a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403), and a dispersant (cus) 0.180 g of Moto Kasei Co., Ltd. make, ED-113), 2.98 g of a phenol resin (Hitachi Kasei Kogyo Co., Ltd., notanac resin having a structural unit represented by formula (I), phenol equivalent 65 g / eq.) g (high Minute) was added thereto and stirred. 5.914 g of a bifunctional epoxy resin having a biphenyl skeleton (manufactured by Mitsubishi Chemical Co., Ltd., YL6121H, epoxy equivalent 172 g / eq.) And a naphthalene epoxy resin (manufactured by DIC Corporation, HP4032D, epoxy equivalent 140 g / eq.) Were used. 0.657 g and 0.012 g of imidazole compound (manufactured by Shikoku Chemical Co., Ltd., 2PHZ) were 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-shaped resin composition 33. The sheet molding was obtained using the obtained varnish-shaped resin composition 33, and it evaluated similarly. The evaluation results are shown in Table 1.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in the resin composition 33 was 1.18.

The resulting sheet product was excellent in flexibility.

<Example 34>

In Example 33, 62.66 g (69.5% (to alumina total mass) of alumina) whose particle diameter D50 was 20 micrometers as alumina, and alumina whose particle diameter D50 was 3 micrometers (62.66g) 10.73 g (11.9% (alumina) of 16.77 g (18.6% (relative to alumina total mass)) and alumina (Sumitomo Chemical Co., Ltd., Sumiko Random AA04) manufactured by Sumitomo Chemical Co., Ltd. A varnish-shaped resin composition 34 was prepared in the same manner as in Example 1 except that)) with respect to the total mass was used. The sheet molding was obtained using the obtained varnish-shaped resin composition 34, and it evaluated similarly. The evaluation results are shown in Table 1.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in the resin composition 34 was 1.18.

The resulting sheet product was excellent in flexibility.

&Lt; Comparative Example 1 &

In Example 1, 62.66 g (69.5% (to gross alumina total mass)) of alumina having a particle diameter D50 of 20 µm (69.5% (to the total mass of alumina)) as an alumina, and alumina of a particle diameter D50 of 4.5 µm (thinnet) 18.39 g (20.4% (to alumina total mass)) of Tetsu Materials Co., Ltd. (Micron, Inc.) and 9.10 g (10.1%) of alumina (LS235, manufactured by Nippon Light Metal Co., Ltd.) having a particle size of D50 of 0.5 µm Except for changing the addition amount of a) and the addition amount of the phenol resin to 2.322 g, the addition amount of the bifunctional epoxy resin having a biphenyl skeleton to 6.506 g, and the addition amount of the naphthalene epoxy resin to 0.723 g, respectively. In the same manner as in 1, a varnish-shaped resin composition C1 was prepared. The sheet molding was obtained using the obtained varnish-shaped resin composition C1, and it evaluated similarly.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in resin composition C1 was 0.85.

Further, the resulting sheet molded product was excellent in flexibility.

&Lt; Comparative Example 2 &

In Comparative Example 1, the amount of the phenol resin added was 3.226 g, and the amount of the bifunctional epoxy resin having a biphenyl skeleton was changed to 5.692 g, and the amount of the naphthalene epoxy resin was changed to 0.632 g, respectively. The varnish-like resin composition C2 was prepared. The sheet molding was obtained using the obtained varnish-shaped resin composition C2, and it evaluated similarly.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in resin composition C2 was 1.36.

Further, the resulting sheet molded product was excellent in flexibility.

&Lt; Comparative Example 3 &

In Comparative Example 1, the amount of the phenol resin added was 2.523 g, the amount of the bifunctional epoxy resin having a biphenyl skeleton was changed to 7.027 g, and the amount of the naphthalene epoxy resin was changed to 0 g. The varnish-shaped resin composition C3 was prepared. The sheet molding was obtained using the obtained varnish-shaped resin composition C3, and it evaluated similarly.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in resin composition C3 was 0.95.

Further, the resulting sheet molded product was excellent in flexibility.

&Lt; Comparative Example 4 &

In Comparative Example 1, 63.11 g (70.0% (to alumina total mass) of alumina) having a particle size of D50 of 39 μm as an alumina, and alumina having a particle size of D50 of 3 μm (63.11 g) 13.52 g (15.0% (to the total mass of alumina)) of Sumitomo Chemical Co., Ltd., Sumicorandom AA3) and 13.52 g (15.0%) of alumina (Sumitomo Chemical Co., Ltd., Sumikoran AA04) having a particle size D50 of 0.4 µm Comparative Example 1 except that)) and the amount of the phenol resin added were 2.523 g, the amount of the bifunctional epoxy resin having a biphenyl skeleton was changed to 6.325 g, and the amount of the naphthalene epoxy resin was changed to 0.702 g, respectively. In the same manner as in the above, a varnish-shaped resin composition C4 was prepared. The sheet molding was obtained using the obtained varnish-shaped resin composition C4, and it evaluated similarly.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in resin composition C4 was 0.94.

The resulting sheet product was excellent in flexibility.

<Comparative Example 5>

In Comparative Example 4, the same amount as that of Comparative Example 4 was changed except that the amount of the phenol resin was changed to 3.146 g, the amount of the bifunctional epoxy resin having a biphenyl skeleton was changed to 5.764 g, and the amount of the naphthalene epoxy resin was changed to 0.640 g, respectively. The varnish-shaped resin composition C5 was prepared. The sheet molding was obtained using the obtained varnish-shaped resin composition C5, and it evaluated similarly.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in resin composition C5 was 1.29.

The resulting sheet product was excellent in flexibility.

&Lt; Comparative Example 6 &gt;

In Comparative Example 4, the amount of the phenol resin added was 2.424 g, and the amount of the bifunctional epoxy resin having a biphenyl skeleton was changed to 7.126 g and the amount of the naphthalene epoxy resin respectively changed to 0 g. The varnish-shaped resin composition C6 was prepared. The sheet molding was obtained using the obtained varnish-shaped resin composition C6, and it evaluated similarly.

In addition, the content rate of the phenol resin with respect to the total content of the epoxy resin in resin composition C6 was 0.88.

The resulting sheet product was excellent in flexibility.

In the sheet hardened | cured material obtained by hardening | curing the resin composition of this invention in Table 1, it turns out that it is compatible at the level excellent in thermal conductivity and electrical insulation.

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

All documents, patent applications, and technical specifications described herein are incorporated by reference herein to the same extent as if the individual documents, patent applications, and technical specifications were specifically incorporated by reference and are also recorded separately. It is incorporated.

Claims (10)

Bifunctional epoxy resin which has a biphenyl skeleton,
Phenolic resin,
A first alumina group having a particle size D50 of 7 μm or more and 25 μm or less, a second alumina group having a particle size D50 of 1 μm or more and less than 7 μm, and a particle size D50 of 1 μm corresponding to a cumulative 50% at the small particle size side of the weight accumulation particle size distribution; It contains less than the 3rd alumina group,
The content ratio (phenol resin / epoxy resin) of the said phenol resin with respect to the total content of an epoxy resin is 1.00 or more and 1.25 or less on an equivalent basis,
The resin composition whose content ratio (2nd alumina group / 3rd alumina group) of the said 2nd alumina group with respect to the said 3rd alumina group is 1.2 or more and 1.7 or less by mass basis. The method of claim 1,
The said phenol resin contains the phenol resin which has a structural unit represented with the following general formula (I).
[Formula 1]

(In general formula (I), R <^1> represents an alkyl group, an aryl group, or an aralkyl group, R <^2> and R <^3> represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group each independently, m is 0-2 N represents 1 to 7) The method of claim 1,
The bifunctional epoxy resin which has the said biphenyl skeleton contains the compound represented by the following general formula (III).
(2)

(In General Formula (III), R <^1> -R <^8> represents a hydrogen atom or a C1-C10 hydrocarbon group each independently, and n represents the integer of 0-3.) 3. The method of claim 2,
The bifunctional epoxy resin which has the said biphenyl skeleton contains the compound represented by the following general formula (III).
(2)

(In General Formula (III), R <^1> -R <^8> represents a hydrogen atom or a C1-C10 hydrocarbon group each independently, and n represents the integer of 0-3.) Bifunctional epoxy resin which has a biphenyl skeleton,
Phenolic resin,
A first alumina group having a particle size D50 of 7 μm or more and 25 μm or less, a second alumina group having a particle size D50 of 1 μm or more and less than 7 μm, and a particle size D50 of 1 μm corresponding to a cumulative 50% at the small particle size side of the weight accumulation particle size distribution; It contains less than the 3rd alumina group,
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,
The resin composition whose content ratio (2nd alumina group / 3rd alumina group) of the said 2nd alumina group with respect to the said 3rd alumina group is 1.2 or more and 1.7 or less by mass basis. The method of claim 5, wherein
The resin composition 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 B stage sheet which consists of a semi-hardened resin composition derived from the resin composition of any one of Claims 1-6. Metal foil with resin provided with metal foil and the semi-hardened resin layer derived from the resin composition of any one of Claims 1-6 arrange | positioned on the said metal foil. A metal substrate provided with a metal support body, the cured resin layer derived from the resin composition of any one of Claims 1-6 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 derived from the resin composition of any one of Claims 1-6 arrange | positioned on the said metal support body, the metal foil arrange | positioned on the said cured resin layer, An LED substrate comprising an LED element disposed on a circuit layer.

Images