KR20220024430A - Laminates, cured products and electronic components - Google Patents

Abstract

Provided are a laminate and the like having an ultra-thin copper foil and a resin layer, which is excellent in laser drilling processability and reflow resistance, and in which the cured product of the resin layer has a low dielectric loss tangent. A laminate having at least a carrier foil, an ultra-thin copper foil having a thickness of 0.1 to 6 µm, and a resin layer in order, wherein the resin layer comprises (A) an epoxy resin, (B) a compound having an active ester group, and (C) an inorganic filler. It is a laminate, etc. characterized in that it comprises a.

Description

Laminates, cured products and electronic components

The present invention relates to a laminate, a cured product, and an electronic component.

As a material which forms electronic components, such as a printed wiring board, copper foil with resin (RCC:Resin Coated Cupper) which is a laminated body of copper foil and curable resin layer is used (for example, patent document 1). As a copper foil with resin used conventionally, what has a curable resin layer which apply|coated and produced the epoxy resin composition to copper foil is widely known.

In addition, in order to further refine a circuit pattern in recent years, the MSAP method (Modified Semi-Additive Process) is applied in many cases instead of the conventional subtractive method. For example, with respect to a circuit board on which a circuit pattern is formed, a copper foil with resin is laminated with a heat lamination so that the resin layer side is in contact with the circuit board and heat-cured, and then laser processing, desmear processing, plating processing, etc. are performed to build up a wiring board. There is a way to manufacture it.

Japanese Patent Laid-Open No. 2006-89595

When a circuit was formed using copper foil with resin by the above manufacturing methods, there existed a problem that defects, such as expansion|swelling, were easy to generate|occur|produce at the time of solder reflow. Moreover, the defect at the time of such solder reflow was so remarkable that the copper foil of copper foil with resin was thin.

When copper foil is thickened in order to suppress the defect at the time of solder reflow, laser processing becomes difficult. Then, first, after thickening the copper foil of copper foil with resin and thermocompression-bonding copper foil with resin, after thinning copper foil with etching liquid, performing a laser process was also examined. However, it is difficult to form a thin film with a uniform thickness, and for that reason, there existed a problem that an aperture diameter became non-uniform|heterogenous when drilling was carried out with a laser.

Moreover, since transmission loss tends to increase with the adoption of high-speed communication, ie, high frequency, in recent years, the material of an electronic component is also calculated|required by the low dielectric loss tangent which can suppress a transmission loss.

Here, an object of the present invention is a laminate having an ultra-thin copper foil and a resin layer, the cured product of the resin layer having a low dielectric loss tangent, excellent in laser drilling processability and reflow resistance, and a cured resin layer of the laminate , and to provide an electronic component having the cured product.

The present inventors have intensively studied for the realization of the above object, and as a result of intensive examination, the above problems can be solved by forming a resin layer containing an epoxy resin, a compound having an active ester group, and an inorganic filler on an ultra-thin copper foil with a carrier foil. , and led to the completion of the invention.

That is, the laminate of the present invention is a laminate having at least a carrier foil, an ultra-thin copper foil having a thickness of 0.1 to 6 µm, and a resin layer in order, wherein the resin layer comprises (A) an epoxy resin and (B) an active ester. It is characterized by including a compound having a group and (C) an inorganic filler.

It is preferable that the ratio of the total amount of the epoxy groups of the said (A) epoxy resin in the said resin layer / the total amount of the active ester groups of the compound which has the said (B) active ester group in the laminated body of this invention is 0.20-0.60.

When the compounding quantity of the said (C) inorganic filler of the laminated body of this invention makes the nonvolatile component in the said resin layer 100 mass %, it is preferable that it is 50 mass % or more.

In the laminate of the present invention, the compound having an active ester group (B) has the following general formula (1)

(wherein, each of X ₁ is independently a group having a benzene ring or a naphthalene ring, k represents 0 or 1, and n is 0.25 to 1.5 on average of repeating units).

In the laminate of the present invention, the compound having an active ester group (B) has the following general formula (2):

(In formula (2), X ₂ is each independently the following formula (3):

A group represented by or the following formula (4):

is a group represented by

m is an integer from 1 to 6, n is each independently an integer from 1 to 5, q is each independently an integer from 1 to 6,

In formula (3), each k is independently an integer of 1 to 5,

In the formula (4), Y is a group represented by the formula (3) (k is each independently an integer of 1 to 5), and t is each independently an integer of 0 to 5)

It is preferable that it is a compound which has a structure part represented by and has a structure in which the both terminals are monovalent|monohydric aryloxy groups.

It is preferable that the ratio of the total amount of the epoxy groups of the said (A) epoxy resin / the total amount of the active ester groups of the compound which has the said (B) active ester group in the said resin layer in the laminated body of this invention is 0.20-0.50.

It is preferable that the dielectric loss tangent of the laminated body of this invention of the hardened|cured material of the said resin layer is 0.01 or less.

The electronic component of this invention has the hardened|cured material obtained by hardening|curing the said resin layer of the said laminated body, It is characterized by the above-mentioned.

ADVANTAGE OF THE INVENTION According to this invention, the laminated body which has an ultra-thin copper foil and a resin layer, the hardened|cured material of the resin layer is excellent in laser drilling processability and reflow property, and the low dielectric loss tangent, the resin layer hardened|cured material of the said laminated body, and this An electronic component having a cured product can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing which showed one Embodiment of the laminated body of this invention.

The laminate of the present invention is a laminate having at least a carrier foil, an ultra-thin copper foil having a thickness of 0.1 to 6 µm, and a resin layer in order, wherein the resin layer has (A) an epoxy resin and (B) an active ester group. It is characterized by including a compound and (C) an inorganic filler. Since the ultra-thin copper foil is supported by carrier foil, it is excellent in handleability, and manufacture of a laminated body and lamination of a laminated body become easy. Moreover, since thinning of the copper foil by the etching after thermocompression bonding which becomes a cause of the nonuniformity of a film thickness is not requested|required, it is excellent also in laser drilling processability. Moreover, by combining the ultra-thin copper foil with a thickness of 0.1-6 micrometers and the resin layer containing said (A)-(C) component, it is excellent in reflow property, and can obtain the hardened|cured material of low dielectric loss tangent. In this specification, when the surface of ultra-thin copper foil is roughened, the uneven part shall not be included in thickness. In other words, the thickness of ultra-thin copper foil in the case of roughening process of ultra-thin copper foil is also called the thickness of the part except the unevenness|corrugation of the roughening process surface, ie, the bulk (base) part except the profile of a roughening process surface.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing which showed one Embodiment of the laminated body of this invention. The laminate 1 is laminated in order of a carrier foil 2 , an ultra-thin copper foil 3 , and a resin layer 4 .

In the laminate of the present invention, it is preferable that the ratio of the total amount of epoxy groups of (A) epoxy resin/(B) the total amount of active ester groups of the compound having active ester groups in the resin layer is 0.20 to 0.60, high heat resistance and low dielectric loss tangent A cured product having both and a low coefficient of linear thermal expansion is obtained. In general, when a compound having an active ester group is blended in a large amount, the crosslinking density of the cured product is lowered, the glass transition temperature (Tg) of the cured product is lowered, and heat resistance is deteriorated. Although there is no case where a compound having an active ester group in excess of equivalent is blended, even when blended in the specific amount, a cured product having a surprisingly high glass transition temperature (Tg), a low dielectric loss tangent and a low coefficient of linear thermal expansion can be obtained. As a result, it is excellent in reflow property, and the hardened|cured material of a low dielectric loss tangent can be obtained.

Although the detailed mechanism is not clear, if the ratio of a compound having an active ester group, preferably a compound having an active ester group having a structure of the following general formula (1) or (2), is increased, the structure of the active ester, that is, a rigid and molecular When the volume ratio of the aromatic ester structure with high orientation becomes large, since the motion of the chain|strand-shaped part between crosslinking points is controlled, it is thought that the glass transition temperature improved. The total amount of the epoxy group of the said (A) epoxy resin can be calculated|required by dividing the compounding quantity of the (A) epoxy resin contained in a composition by the epoxy equivalent of (A) epoxy resin. The total amount of active ester groups of the compound having an active ester group (B) can be obtained by dividing the compounding amount of the compound having an active ester group (B) contained in the composition by the equivalent weight of the active ester of the compound having an active ester group (B) there is. The upper limit of the ratio of the total amount is preferably 0.50 or less, more preferably 0.40 or less, particularly preferably 0.30 or less, from the viewpoint of obtaining a cured product having a lower dielectric loss tangent.

Below, the resin layer which the laminated body of this invention has, ultra-thin copper foil, and carrier foil are demonstrated. In addition, in this specification, when expressing a numerical range with "to", it shall mean the range (that is, ... more than ... less) including those numerical values.

[resin layer]

The said resin layer contains (A) an epoxy resin, (B) the compound which has an active ester group, and (C) an inorganic filler. The said resin layer can be obtained by apply|coating and drying the resin composition containing (A) an epoxy resin, (B) the compound which has an active ester group, and (C) an inorganic filler.

[(A) Epoxy Resin]

(A) Epoxy resin is resin which has an epoxy group, Any conventionally well-known thing can be used. The bifunctional epoxy resin which has two epoxy groups in a molecule|numerator, the polyfunctional epoxy resin which has many epoxy groups in a molecule|numerator, etc. are mentioned. Moreover, the hydrogenated bifunctional epoxy resin may be sufficient. In addition, any of a solid epoxy resin, a semi-solid epoxy resin, and a liquid epoxy resin may be sufficient as (A) epoxy resin. In this specification, the solid epoxy resin refers to an epoxy resin that is solid at 40 ° C., the semi-solid epoxy resin refers to an epoxy resin that is solid at 20 ° C. and is liquid at 40 ° C., and the liquid epoxy resin is an epoxy resin that is liquid at 20 ° C. say resin. Judgment of the liquid phase is carried out in accordance with the attached sheet 2 "Method for confirming liquid phase" of the Ministry of Home Affairs Ordinance (Ordinance No. For example, it carries out by the method of Paragraph 23-25 of Unexamined-Japanese-Patent No. 2016-079384. (A) An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.

In the present invention, as described above, it is preferable that the ratio of the total amount of epoxy groups of (A) epoxy resin in the resin layer/total amount of active ester groups of the compound having (B) active ester groups in the resin layer is 0.20 to 0.60, in that case, (A) It is preferable that the epoxy resin contains at least any one of a trifunctional or more than trifunctional liquid epoxy resin and trifunctional or more than trifunctional semi-solid epoxy resin. When a trifunctional or higher functional liquid epoxy resin or a trifunctional or higher trifunctional semi-solid epoxy resin is included, the glass transition temperature can be improved while maintaining a low dielectric loss tangent. As a commercial item of such a trifunctional or more than trifunctional liquid epoxy resin, TEPIC-VL by Nissan Chemical Corporation, jER630 by Mitsubishi Chemical Corporation, etc. can be used, for example. Moreover, as a commercial item of such a trifunctional or more than trifunctional semi-solid epoxy resin, Mitsubishi Chemical Corporation jER604 etc. can be used, for example.

Moreover, (A) Preferably the epoxy equivalent of an epoxy resin is 100-5000 g/eq., More preferably, it is 150-3000 g/eq. For example, as (A) an epoxy resin, you may contain the liquid or semi-solid epoxy resin whose epoxy equivalent is 350-1000 g/eq.

(A) Epoxy resin is not limited to the above, For example, as a solid epoxy resin, naphthalene-type epoxy resins, such as EPICLON HP-4700 by DIC Corporation, naphthalene skeleton-containing novolac-type epoxy, such as NC-7000 by Nippon Kayaku Corporation Resin, naphthol aralkyl type epoxy resins, such as ESN-475V by the Nitetsu Chemical & Materials company; Epoxy products (trisphenol-type epoxy resins) of condensates of phenols and aromatic aldehydes having phenolic hydroxyl groups, such as EPPN-502H manufactured by Nippon Kayaku Corporation; Dicyclopentadiene type epoxy resins, such as EPICLON HP-7200H by DIC; Biphenyl aralkyl type epoxy resins, such as Nippon Kayaku Corporation NC-3000H and NC-3000L; novolak-type epoxy resins such as EPICLON N680 by DIC and EOCN-104S by Nippon Kayaku; Biphenyl type epoxy resins, such as YX-4000 by Mitsubishi Chemical Corporation; phosphorus-containing epoxy resins such as TX0712 manufactured by Nitetsu Chemical &Materials; Tris(2,3-epoxypropyl) isocyanurate, such as TEPIC by Nissan Chemicals, etc. are mentioned. By including a solid epoxy resin, the glass transition temperature of hardened|cured material becomes high and it is excellent in heat resistance. When the ratio of the total amount of epoxy groups of (A) epoxy resin in the resin layer/total amount of active ester groups of the compound having active ester groups (B) in the resin layer is 0.20 to 0.60, it is a higher Tg among solid epoxy resins and excellent in reflow property Also, from the viewpoint of obtaining a cured product having a low dielectric loss tangent, an aralkyl-type epoxy resin such as ESN-475V or NC3000H, that is, an epoxy resin containing a divalent group bonded to an alkylene group and an arylene group is preferable. Examples of the alkylene group include a methylene group, a methyl methylene group, an ethylene group, a propylene group, and a trimethylene group. Examples of the arylene group include a phenylene group, a biphenylene group, and a naphthylene group.

As semi-solid epoxy resins, EPICLON860, EPICLON900-IM, EPICLON EXA-4816, EPICLON EXA-4822 manufactured by DIC, Epottot YD-134 manufactured by Nittetsu Chemical & Materials, jER834, jER872 manufactured by Mitsubishi Chemical, ELA-Chemical Company manufactured by Sumitomo Chemical Bisphenol-A epoxy resins, such as 134; Naphthalene type epoxy resins, such as EPICLON HP-4032 by DIC; Aromatic aminoepoxy resins, such as phenol novolak-type epoxy resins, such as DIC Corporation EPICLON N-740, and Mitsubishi Chemical Corporation jER604, etc. are mentioned. By including a semi-solid epoxy resin, the glass transition temperature (Tg) of hardened|cured material is high, the coefficient of linear thermal expansion (CTE) becomes low, and it is excellent in crack resistance. By including a semi-solid epoxy resin, it is excellent in the storage stability of a dry film, and a crack and peeling can be prevented.

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, glycidylamine type epoxy resin, aminophenol type epoxy resin Aromatic aminoepoxy resins, such as an epoxy resin, an alicyclic epoxy resin, a heterocyclic epoxy resin, etc. are mentioned. By including a liquid epoxy resin, it is excellent in the softness|flexibility of a laminated body.

(A) It is preferable that an epoxy resin uses together a solid epoxy resin, and at least either one of a liquid epoxy resin and a semi-solid epoxy resin. Moreover, you may use together a solid epoxy resin, a liquid epoxy resin, and a semi-solid epoxy resin.

(A) The compounding quantity of the epoxy resin is preferably 50 mass% or less, more preferably 40 mass% or less, from the viewpoint of obtaining a cured product having a lower dielectric loss tangent when the nonvolatile component in the resin layer is 100 mass%. And it is especially preferable that it is 30 mass % or less. Moreover, from a viewpoint of the intensity|strength of hardened|cured material, it is preferable that a minimum is 1 mass % or more, and it is more preferable that it is 3 mass % or more.

The laminate resin layer of this invention may contain thermosetting resins other than (A) epoxy resin in the range which does not impair the effect of this invention, For example, an isocyanate compound, a block isocyanate compound, an amino resin, benzoxazine A well-known and usual thermosetting resin, such as resin, carbodiimide resin, a cyclocarbonate compound, a polyfunctional oxetane compound, an episulfide resin, and maleimide resin, can be used.

[(B) compound having an active ester group]

(B) It is preferable that the compound which has an active ester group is a compound which has two or more active ester groups in 1 molecule. A compound having an active ester group can generally be obtained by a condensation reaction between a carboxylic acid compound and a hydroxy compound. Especially, the compound which has an active ester group obtained using a phenol compound or a naphthol compound as a hydroxy compound is preferable. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p- Cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzo and phenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadienyldiphenol, and phenol novolac. In addition, (B) as a compound which has an active ester group, the naphthalenediol alkyl/benzoic acid type may be sufficient. (B) The compound which has an active ester group may be used individually by 1 type, and may be used in combination of 2 or more type. (B) The compound having an active ester group preferably has any of benzene, α-naphthol, β-naphthol and dicyclopentadiene skeleton.

(B) When the compounding quantity of the compound having an active ester group is 100 mass % of the nonvolatile component in the resin layer, from the viewpoint of the strength of the cured product, the upper limit is preferably 50 mass % or less, more preferably 45 mass % or less And it is especially preferable that it is 40 mass % or less. Moreover, it is preferable that it is 5 mass % or more, and, as for a minimum, it is more preferable that it is 10 mass % or more at the point from which the hardened|cured material of a lower dielectric loss tangent is obtained.

(B) Among the compounds having an active ester group, compounds having an active ester group of the following (B1) and (B2) can be suitably used. Moreover, the compound which has the active ester group of (B2) is more preferable at the point which can make the dielectric loss tangent of hardened|cured material lower.

(B1)

The compound having an active ester group of (B1) includes (b1) a phenol resin having a molecular structure in which phenols are nodated via an alicyclic hydrocarbon group, (b2) an aromatic dicarboxylic acid or a halide thereof, and (b3) an aromatic monohydroxy It has a structure obtained by reacting a compound. 0.05 to 0.75 moles of phenolic hydroxyl groups in the (b1) phenol resin, and (b3) aromatic monohydroxy compounds, based on 1 mole of the carboxyl group or acid halide group in the (b2) aromatic dicarboxylic acid or its halide It is preferable to have a structure obtained by making it react in the ratio used as 0.25 to 0.95 mol.

Here, (b1) in the phenol resin, the molecular structure in which phenols are nodated through an aliphatic cyclic hydrocarbon group includes a structure obtained by polyaddition reaction of an unsaturated aliphatic cyclic hydrocarbon compound containing two double bonds in one molecule with phenols. there is. Examples of the phenols include phenol and substituted phenols in which one or more alkyl groups, alkenyl groups, allyl groups, aryl groups, aralkyl groups or halogen groups are substituted. Specifically, cresol, xylenol, ethyl phenol, isopropyl phenol, butyl phenol, octyl phenol, nonyl phenol, vinyl phenol, isopropenyl phenol, allyl phenol, phenyl phenol, benzyl phenol, chlorophenol, bromine phenol, naphthol, Although dihydroxynaphthalene etc. are illustrated, it is not limited to these. Moreover, you may use these mixtures. Among these, phenol is especially preferable at the point which is excellent in fluidity|liquidity and sclerosis|hardenability.

In addition, specific examples of the unsaturated alicyclic cyclic hydrocarbon compound include dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, 5-vinylnorborna-2-ene, α-pinene, β-pinene, limonene, and the like. can be heard Among these, dicyclopentadiene is preferable from the point of characteristic balance, especially heat resistance and hygroscopicity. In addition, since dicyclopentadiene is contained in petroleum fraction, industrial dicyclopentadiene may contain other aliphatic or aromatic dienes as impurities. It is preferable that it is a product with a purity of 90 mass % or more of pentadiene.

Next, the (b2) aromatic dicarboxylic acid or halide thereof is an aromatic dicarboxylic acid such as isophthalic acid, terephthalic acid, 1,4-, 2,3- or 2,6-naphthalenedicarboxylic acid, and these and acid halides such as acid fluoride, acid chloride, acid bromide, and acid iodide. Among these, the acid chloride of an aromatic dicarboxylic acid from a point with especially favorable reactivity, especially, the dichloride of isophthalic acid and the dichloride of a terephthalic acid are preferable, and the dichloride of isophthalic acid is especially preferable.

Next, as an aromatic monohydroxy compound, For example, phenol; alkylphenols such as o-cresol, m-cresol, p-cresol and 3,5-xylenol; aralkyl phenols such as o-phenylphenol, p-phenylphenol, 2-benzylphenol, 4-benzylphenol, and 4-(α-cumyl)phenol; and naphthols such as α-naphthol and β-naphthol. Among these, ?-naphthol and ?-naphthol are particularly preferable because the dielectric loss tangent of the cured product is lowered.

(B1) The active ester compound has a structure obtained by reacting (b1) a phenol resin, (b2) an aromatic dicarboxylic acid or halide thereof, and (b3) an aromatic monohydroxy compound, in particular the following general formula (1) )

(Wherein, X ₁ is a group having a benzene ring or a naphthalene ring, k represents 0 or 1, and n is an average value of the repeating units of 0.05 to 2.5.)

The structure represented by is particularly preferable in that the dielectric loss tangent of the cured product is low and the solution viscosity when dissolved in an organic solvent is low. The group having a benzene ring or a naphthalene ring is not particularly limited, and may be a phenyl group, a naphthyl group, or the like, and a benzene ring or a naphthalene ring may be bonded to the molecular terminal via other atoms, or may have a substituent. Further, (B1) the active ester compound is preferably one having a naphthalene ring at the molecular terminal thereof.

In particular, in the general formula (1), it is preferable that the value of n, ie, the average value of the repeating units, is in the range of 0.25 to 1.5 because the solution viscosity is low and the production of the laminate is easy. Moreover, in the said General formula (1), it is preferable that the value of k is 0 from a viewpoint of high heat resistance and low dielectric loss tangent.

Here, n in the said General formula (1) can be calculated|required as follows.

[Method of finding n in general formula (1)]

Styrene-equivalent molecular weights (α1, α2, α3, α4) corresponding to n=1, n=2, n=3, and n=4, respectively, and n=1, n=2, n by GPC measurement performed under the following conditions The ratios (β1/α1, β2/α2, β3/α3, β4/α4) of each theoretical molecular weight (β1, β2, β3, β4) of =3 and n=4 are obtained, and these (β1/α1 to β4/ Find the average value of α4). Let the numerical value which multiplied this average value by the number average molecular weight (Mn) calculated|required by GPC be an average molecular weight. Next, the value of n is computed for the molecular weight of the said general formula (1) as the said average molecular weight.

(GPC measurement conditions)

Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation,

Column: Guard column "H _XL -L" manufactured by Tosoh Corporation

+ "TSK-GEL G2000HXL" made by Tosoh Corporation

+ "TSK-GEL G2000HXL" made by Tosoh Corporation

+ "TSK-GEL G3000HXL" made by Tosoh Corporation

+ "TSK-GEL G4000HXL" made by Tosoh Corporation

Detector: RI (Differential Refraction Diameter)

Data processing: "GPC-8020 Model II Version 4.10" manufactured by Tosoh Corporation

Measurement conditions: Column temperature 40°C

Developing solvent tetrahydrofuran

Flow rate 1.0ml/min

Standard: According to the measurement manual of "GPC-8020 Model II Version 4.10", the following monodisperse polystyrene with known molecular weight was used.

(Use polystyrene)

"A-500" made by Tosoh Corporation

"A-1000" made by Tosoh Corporation

"A-2500" made by Tosoh Corporation

"A-5000" made by Tosoh Corporation

"F-1" made by Tosoh Corporation

"F-2" made by Tosoh Corporation

"F-4" made by Tosoh Corporation

"F-10" made by Tosoh Corporation

"F-20" made by Tosoh Corporation

"F-40" made by Tosoh Corporation

Tosoh Corporation "F-80"

Toso Corporation "F-128"

Sample: What filtered the 1.0 mass % tetrahydrofuran solution in conversion of resin solid content with the micro filter (50 microliters).

Specifically, in the method of reacting (b1) phenol resin, (b2) aromatic dicarboxylic acid or halide thereof, and (b3) aromatic monohydroxy compound, each of these components can be reacted in the presence of an alkali catalyst.

As an alkali catalyst which can be used here, sodium hydroxide, potassium hydroxide, triethylamine, pyridine, etc. are mentioned. Among these, sodium hydroxide and potassium hydroxide can be used in the state of aqueous solution especially, and it is preferable at the point which productivity becomes favorable.

Specifically, in the reaction, (b1) a phenol resin, (b2) an aromatic dicarboxylic acid or a halide thereof, and (b3) an aromatic monohydroxy compound are mixed in the presence of an organic solvent, and the alkali catalyst or an aqueous solution thereof is mixed The method of making it react, dripping continuously or intermittently is mentioned. In that case, it is preferable that the range of the density|concentration of the aqueous solution of an alkali catalyst is 3.0 to 30%. Moreover, as an organic solvent which can be used here, toluene, dichloromethane, etc. are mentioned.

After completion of the reaction, in the case of using an aqueous alkali catalyst solution, the reaction solution is separated still, the aqueous layer is removed, and the remaining organic layer is repeatedly washed until the aqueous layer is almost neutral to obtain the desired resin. can

Since the compound having an active ester group of (B1) obtained in this way is usually obtained as an organic solvent solution, it is mixed with other ingredients as it is, and the amount of the organic solvent is adjusted in a timely manner to prepare the desired curable resin composition. can In addition, the active ester compound of (B1) is characterized by a low melt viscosity when dissolved in an organic solvent to form a resin solution, and specifically, in the case of using an active ester resin in a toluene solution with a nonvolatile content of 65%. The solution viscosity is 300 to 10,000 mPa·s (25°C).

(B2)

The compound having an active ester group of (B2) has the following general formula (2):

It has a resin structure having a structural moiety represented by and both ends of which are monovalent aryloxy groups.

(In formula (2), X ₂ is each independently the following formula (3):

A group represented by or the following formula (4):

is a group represented by , m is an integer of 1 to 6, n is each independently an integer of 1 to 5, q is each independently an integer of 0 to 6, in formula (3), k is each independently an integer of 1 to 5, in formula (4), Y is a group represented by the formula (3) (k is each independently an integer of 1 to 5), and t is each independently an integer of 0 to 5)

The compound having an active ester group of (B2) is in the general formula (2)

The partial structure represented by is preferably a structure derived from a modified naphthalene compound having a hydroxyl equivalent of 170 to 200 g/eq.

In formula (2), in order to clarify the relationship between m and n, some patterns are exemplified below, but the active ester resin of (B2) is not limited thereto.

For example, when m=1, the formula (2) shows the structure of the following formula (2-I).

In formula (2-I), n is an integer of 1-5, and q is an integer of 0-6 each independently. In addition, similarly to the relationship between m and n, also about q, when n is 2 or more, it shows that each q is an integer of 0-6 independently.

In addition, for example, when m=2, Formula (2) shows the structure of following Formula (2-II).

In formula (2-II), n is each independently an integer of 1-5, and q is each independently an integer of 0-6. In addition, similarly to the relationship between m and n, also about q, when n is 2 or more, it shows that each q is an integer of 0-6 independently.

Since the compound having an active ester group of (B2) has a naphthylene ether structural moiety in the molecular main skeleton, superior heat resistance and flame retardancy can be imparted to the cured product, and the structural moiety has the following structural moiety

Since it has a structure bonded to the cured product, it is possible to combine superior dielectric properties with the cured product. Moreover, in the resin structure of the compound which has an active ester group of (B2), by setting it as having an aryloxy group as a structure at both ends, also in a multilayer printed circuit board use, the improvement of the thermal decomposition resistance of hardened|cured material with a sufficiently high degree is acquired.

The compound having an active ester group as (B2) preferably has a softening point in the range of 100 to 200°C, particularly in the range of 100 to 190°C, from the viewpoint of particularly excellent heat resistance of the cured product.

The compound which has an active ester group of (B2) WHEREIN: The thing in which m in Formula (2) is an integer of 1-6 is mentioned. Especially, it is preferable that m is an integer of 1-5. Moreover, it is mentioned that n in Formula (2) is an integer of 1-5 each independently. Especially, it is preferable that n is an integer of 1-3.

In formula (2), the relationship between m and n is described just in case, for example, when m is an integer of 2 or more, n of 2 or more occurs, but n is an independent value in that case. The same value or different values may be sufficient as long as it exists in the numerical range of said n.

In the compound having an active ester group of (B2), in formula (2), when q is 1 or more, X ₂ is substituted at any position in the naphthalene ring structure.

Examples of the aryloxy groups at both terminals of the resin structure include those derived from monohydric phenol compounds such as phenol, cresol, p-t-butylphenol (para-tert-butylphenol), 1-naphthol, and 2-naphthol. Especially, from a viewpoint of the thermal decomposition resistance of hardened|cured material, a phenoxy group, a tolyloxy group, or 1-naphthyloxy group is preferable, and 1-naphthyloxy group is more preferable.

Hereinafter, the manufacturing method of the compound which has an active ester group of (B2) is demonstrated in detail.

The method for producing a compound having an active ester group of (B2) is a step of reacting a dihydroxynaphthalene compound with benzyl alcohol in the presence of an acid catalyst to obtain a benzyl-modified naphthalene compound (hereinafter, this step is abbreviated as “Step 1”) ), followed by a step of reacting the obtained benzyl-modified naphthalene compound, an aromatic dicarboxylate, and a monohydric phenol-based compound (hereinafter, this step may be abbreviated as “Step 2”).

That is, by first reacting the dihydroxynaphthalene compound with benzyl alcohol in the presence of an acid catalyst in step 1, the naphthylene structure as a main skeleton has phenolic hydroxyl groups at both ends thereof, and the naphthylene structure A benzyl-modified naphthalene compound having a structure in which a benzyl group is bonded to an aromatic nucleus in a pendant shape can be obtained. Here, it should be particularly noted that, in general, when a dihydroxynaphthalene compound is naphthylene etherized under an acid catalyst, it is very difficult to control the molecular weight and becomes a high molecular weight compound, whereas in the above production method, benzyl alcohol is used in combination. By doing so, such a high molecular weight increase can be suppressed, and resin suitable for an electronic material use can be obtained.

In addition, by adjusting the amount of benzyl alcohol used, it is possible not only to control the content of benzyl groups in the target benzyl-modified naphthalene compound, but also to control the melt viscosity itself of the benzyl-modified naphthalene compound. That is, in general, the reaction ratio of the dihydroxynaphthalene compound to benzyl alcohol is 1/0.1 to 1/0.1 to the reaction ratio of the dihydroxynaphthalene compound to benzyl alcohol (dihydroxynaphthalene compound)/(benzyl alcohol) on a molar basis. Although it can be selected from the range of 1/10, the reaction ratio of the dihydroxynaphthalene compound and benzyl alcohol (dihydroxynaphthalene compound)/(benzyl) on a molar basis from the balance of heat resistance, flame retardancy, dielectric properties, and thermal decomposition resistance. Alcohol) is preferably in the range of 1/0.5 to 1/4.0.

The dihydroxynaphthalene compound usable herein is, for example, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-di Hydroxynaphthalene etc. are mentioned. Among these, the cured product of the obtained benzyl-modified naphthalene compound has much better flame retardancy, and the dielectric loss tangent of the cured product is also lowered and the dielectric properties are improved, so 1,6-dihydroxynaphthalene or 2,7-dihydroxy Naphthalene is preferable, and 2,7-dihydroxynaphthalene is more preferable.

The acid catalyst that can be used in the reaction of the dihydroxynaphthalene compound and benzyl alcohol in step 1 is, for example, inorganic acids such as phosphoric acid, sulfuric acid, hydrochloric acid, oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, fluoro Friedel Crafts catalysts, such as organic acids, such as methanesulfonic acid, aluminum chloride, zinc chloride, stannic chloride, ferric chloride, and diethyl sulfuric acid, are mentioned.

In addition, the amount of the acid catalyst used can be appropriately selected depending on the target modification rate, etc., for example, in the case of an inorganic acid or an organic acid, 0.001 to 5.0 parts by mass, preferably based on 100 parts by mass of the dihydroxynaphthalene compound is in the range of 0.01 to 3.0 parts by mass, and in the case of Friedel Crafts catalyst, 0.2 to 3.0 moles, preferably 0.5 to 2.0 moles, per 1 mole of the dihydroxynaphthalene compound.

The reaction of the dihydroxynaphthalene compound and benzyl alcohol in the step 1 may be performed in the absence of a solvent or in a solvent from the viewpoint of improving the uniformity in the reaction system. Examples of the solvent include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, ethylene glycol monomethyl ether, Mono or diethylene glycol such as ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, and diethylene glycol monobutyl ether diether; non-polar aromatic solvents such as benzene, toluene, and xylene; aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide; Chlorobenzene etc. are mentioned.

A specific method for carrying out the reaction in step 1 is dissolving the dihydroxynaphthalene compound, benzyl alcohol and the acid catalyst in the absence of a solvent or in the presence of the solvent, and at a temperature of about 60 to 180°C, preferably about 80 to 160°C. It can be done under conditions. In addition, although reaction time is not specifically limited, It is preferable that it is 1 to 10 hours. Therefore, the reaction can be specifically carried out by maintaining the above temperature for 1 to 10 hours. In addition, it is preferable to distill off the water generated during the reaction out of the system using a fractionation tube or the like, from the viewpoint that the reaction proceeds quickly and the productivity is improved.

Moreover, in order to suppress the coloring of the benzyl-modified naphthalene compound obtained when it is large, you may add antioxidant and a reducing agent to a reaction system. Examples of the antioxidant include hindered phenol-based compounds such as 2,6-dialkylphenol derivatives, divalent sulfur-based compounds, and phosphite-based compounds containing trivalent phosphorus atoms. Examples of the reducing agent include hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hydrosulfite or salts thereof.

After completion of the reaction, the acid catalyst is removed by neutralization treatment, water washing treatment, or decomposition, and the target resin having a phenolic hydroxyl group can be isolated by general operations such as extraction and distillation. Neutralization treatment and water washing treatment may be performed according to a conventional method, for example, a basic substance such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, triethylenetetramine or aniline can be used as the neutralizing agent.

Here, as said aromatic dicarboxylate, specifically, phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid acid chloride and the like. Among them, isophthalic acid chloride and terephthalic acid chloride are preferable from the viewpoint of balance between solvent solubility and heat resistance.

Specific examples of the monohydric phenol-based compound include phenol, cresol, p-t-butylphenol, 1-naphthol, and 2-naphthol. Among them, phenol, cresol, and 1-naphthol are preferable from the viewpoint of good reactivity with carboxylic acid chloride, and 1-naphthol is more preferable from the viewpoint of good thermal decomposition resistance.

Here, in the method of reacting the benzyl-modified naphthalene compound, the aromatic dicarboxylate, and the monohydric phenol-based compound, specifically, each of these components can be reacted in the presence of an alkali catalyst.

Examples of the alkali catalyst usable here include sodium hydroxide, potassium hydroxide, triethylamine, and pyridine. Among these, sodium hydroxide and potassium hydroxide can be used in the state of aqueous solution especially, and it is preferable at the point which productivity becomes favorable.

Specifically, in the above reaction, each of the above components is mixed in the presence of an organic solvent, and the alkali catalyst or an aqueous solution thereof may be continuously or intermittently added dropwise to the reaction. In that case, it is preferable that the range of the density|concentration of the aqueous solution of an alkali catalyst is 3.0-30 mass %. Moreover, as an organic solvent which can be used here, toluene, dichloromethane, chloroform, etc. are mentioned.

After completion of the reaction, in the case of using an aqueous alkali catalyst solution, the reaction solution is left still, the aqueous layer is removed, and the remaining organic layer is washed repeatedly until the aqueous layer is almost neutral to obtain the desired resin. can

The compound having an active ester group of (B2) obtained in this way is preferable if the softening point is 100 to 200°C, since the solubility in the organic solvent increases.

The said resin layer may contain hardening|curing agents other than the compound which has (B) active ester group within the range which does not impair the effect of this invention, For example, the compound which has a phenolic hydroxyl group, polycarboxylic acid, and its acid anhydride , a compound having a cyanate ester group, a compound having a maleimide group, an alicyclic olefin polymer, and the like.

((C) inorganic filler)

The laminate resin layer of this invention contains (C) inorganic filler. In addition, (C) by mixing the inorganic filler, cure shrinkage of the obtained cured product is suppressed, the CTE is low, and adhesion, hardness, crack resistance by matching the thermal strength with a conductor layer such as copper around the insulating layer, etc. can improve the thermal properties of As the inorganic filler, a conventionally known inorganic filler can be used, and although it is not limited to a specific one, for example, silica such as barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, and spherical silica, talc, clay, and NOI Extender pigments such as Burg's silica particles, boehmite, magnesium carbonate, calcium carbonate, titanium oxide, aluminum oxide, aluminum hydroxide, silicon nitride, aluminum nitride, calcium zirconate, copper, tin, zinc, nickel, silver, palladium, aluminum, Metal powders, such as iron, cobalt, gold|metal|money, and platinum, are mentioned. It is preferable that an inorganic filler is a spherical particle. Among them, silica is preferable, suppresses cure shrinkage of the cured product of the curable composition, lowers CTE, and improves properties such as adhesion and hardness. It is preferable that the average particle diameter (median diameter, D50) of an inorganic filler is 0.01-10 micrometers. As an inorganic filler, it is preferable from a viewpoint of slitting property that it is a silica whose average particle diameter is 0.01-3 micrometers. In addition, in this specification, the average particle diameter of an inorganic filler is the average particle diameter including the particle diameter of not only the particle diameter of a primary particle but the secondary particle (aggregate). An average particle diameter can be calculated|required by the measuring apparatus by a laser diffraction type particle size distribution measuring apparatus and a dynamic light scattering method. As a measuring apparatus by a laser diffraction method, Microtrac MT3300EXII manufactured by Microtrac Bell Corporation, as a measuring apparatus by a dynamic light scattering method, Microtrac Bell Nanotrac Wave II UT151 is mentioned.

(C) It is preferable that an inorganic filler is the inorganic filler by which the surface treatment was carried out. As the surface treatment, a surface treatment with a coupling agent or a surface treatment without introducing an organic group such as an alumina treatment may be performed. The method for surface treatment of the inorganic filler is not particularly limited, a known and usual method may be used, and the surface of the inorganic filler may be treated with a surface treatment agent having a curable reactive group, for example, a coupling agent having a curable reactive group as an organic group.

It is preferable that the surface treatment of an inorganic filler is surface treatment by a coupling agent. As a coupling agent, coupling agents, such as a silane type, a titanate type, an aluminate type, and a zircoaluminate type, can be used. Among them, a silane-based coupling agent is preferable. Examples of such a silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, N-(2-aminomethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-amino Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-anilinopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-( 3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and the like. and these may be used alone or in combination. It is preferable that these silane coupling agents are previously immobilized on the surface of an inorganic filler by adsorption|suction or reaction. Here, the processing amount of the coupling agent with respect to 100 mass parts of inorganic fillers is 0.5-10 mass parts, for example.

As the curing reactor, a thermosetting reactor is preferable. Examples of the thermosetting reactive group include a hydroxyl group, a carboxyl group, an isocyanate group, an amino group, an imino group, an epoxy group, an oxetanyl group, a mercapto group, a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an ethoxyethyl group, and an oxazoline group. Among them, at least one of an amino group and an epoxy group is preferable. In addition, the surface-treated inorganic filler may have a photocurable reactor in addition to a thermosetting reactor.

In addition, the inorganic filler subjected to the surface treatment may be contained in the resin layer in a surface-treated state, and the inorganic filler and the surface treatment agent are separately blended in the resin composition for forming the resin layer, and the inorganic filler is surface-treated in the composition. However, it is preferable to mix|blend the inorganic filler which surface-treated previously. By mix|blending the inorganic filler surface-treated in advance, the fall of the crack resistance etc. by the surface treating agent which may remain|survive in the surface treatment which may remain|survive when mix|blending separately can be prevented. In the case of surface treatment in advance, it is preferable to mix a pre-dispersion in which an inorganic filler is pre-dispersed in a solvent or a curable resin, the surface-treated inorganic filler is pre-dispersed in a solvent, and the pre-dispersion is blended into the composition, or the surface is untreated. It is more preferable to mix|blend the said preliminary dispersion liquid into a composition after surface-treating sufficiently when pre-dispersing the inorganic filler of in a solvent.

(C) The inorganic filler may be blended with an epoxy resin or the like in a powder or solid state, or may be blended with an epoxy resin or the like after mixing with a solvent or a dispersing agent to form a slurry.

(C) An inorganic filler may be used individually by 1 type, and may be used as a 2 or more type mixture. (C) When the compounding quantity of an inorganic filler makes the non-volatile component in a resin layer 100 mass %, from a viewpoint of CTE reduction, 30 mass % or more is preferable, 50 mass % or more is more preferable, 60 mass % or more This is more preferable, and 65 mass % or more is especially preferable. Moreover, from a viewpoint of the toughness of a cured film, 90 mass % or less is preferable, and 85 mass % or less is more preferable.

(curing accelerator)

The resin layer may contain a curing accelerator. The curing accelerator accelerates the thermosetting reaction and is used to further improve properties such as adhesion, chemical resistance, and heat resistance. Specific examples of such a curing accelerator include imidazole and derivatives thereof; guanamines such as acetoguanamine and benzoguanamine; polyamines such as diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine, and polybasic hydrazide; their organic acid salts and/or epoxy adducts; amine complexes of boron trifluoride; triazine derivatives such as ethyldiamino-S-triazine, 2,4-diamino-S-triazine, and 2,4-diamino-6-xylyl-S-triazine; Trimethylamine, triethanolamine, N,N-dimethyloctylamine, N-benzyldimethylamine, pyridine, dimethylaminopyridine, N-methylmorpholine, hexa(N-methyl)melamine, 2,4,6-tris(dimethylamino amines such as phenol), tetramethylguanidine, and m-aminophenol; polyphenols such as polyvinylphenol, polyvinylphenol bromide, phenol novolac, and alkylphenol novolak; organic phosphines such as tributylphosphine, triphenylphosphine, and tris-2-cyanoethylphosphine; phosphonium salts such as tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide and hexadecyl tributyl phosphonium chloride; quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride; the polybasic acid anhydride; photocationic polymerization catalysts such as diphenyliodonium tetrafluoroboroate, triphenylsulfonium hexafluoroantimonate, and 2,4,6-triphenylthiopyrylium hexafluorophosphate; styrene-maleic anhydride resin; A conventionally known curing accelerator such as an equimolar reaction product of phenyl isocyanate and dimethylamine, an equimolar reaction product of an organic polyisocyanate such as tolylene diisocyanate and isophorone diisocyanate and dimethylamine, and a metal catalyst. Among the curing accelerators, imidazole and its derivatives and dimethylaminopyridine are preferable, and imidazole and its derivatives are more preferable from the viewpoint of obtaining a cured product having a higher Tg and a low dielectric loss tangent.

A hardening accelerator can be used individually by 1 type or in mixture of 2 or more types. The compounding quantity of a hardening accelerator is 5 mass % or less from a viewpoint of resin layer storage stability before thermosetting reaction when the sum total of the compound which has (A) epoxy resin and (B) active ester group in a resin layer is 100 mass %. It is preferable, 3 mass % or less is more preferable, 0.01 mass % or more is preferable from a sclerosing|hardenable viewpoint, and 0.1 mass % or more is more preferable.

(thermoplastic resin (polymer resin))

The said resin layer can contain a thermoplastic resin further in order to improve the mechanical strength of the cured film obtained. It is preferable that a thermoplastic resin is soluble in a solvent. When it is soluble in a solvent, the flexibility of a resin layer improves, and generation|occurrence|production of a crack and powder fall can be suppressed. As the thermoplastic resin, a thermoplastic polyhydroxypolyether resin, a phenoxy resin which is a condensate of epichlorohydrin and various difunctional phenol compounds, or various acid anhydrides or acid chlorides for the hydroxyl group of the hydroxy ether moiety present in its skeleton are used. The esterified phenoxy resin, polyvinyl acetal resin, polyamide resin, polyamideimide resin, a block copolymer, etc. are mentioned. A thermoplastic resin can be used individually by 1 type or in combination of 2 or more type. Among these thermoplastic resins, since the glass transition temperature can be improved while maintaining the dielectric loss tangent low, a phenoxy resin is preferable. From a viewpoint of making small the roughness of the hardened|cured material surface after desmear, polyvinyl acetal resin is preferable.

As polyvinyl acetal resin, it is obtained by acetalizing polyvinyl alcohol resin with an aldehyde, for example. The aldehyde is not particularly limited, and for example, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, amyl aldehyde, hexylaldehyde, heptylaldehyde, 2-ethylhexylaldehyde, cyclohexylaldehyde, furfural, benzaldehyde, 2- methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, phenylacetaldehyde, β-phenylpropionaldehyde, etc. are mentioned, and butyraldehyde is preferable.

Specific examples of the phenoxy resin include FX280 and FX293 manufactured by Nittetsu Chemicals & Materials, YX8100, YX6954, YL6954, YL6974, and YX7200 manufactured by Mitsubishi Chemical. Moreover, as a specific example of polyvinyl acetal resin, Sekisui Chemical Co., Ltd. S-Rec KS series, As a polyamide resin, Hitachi Chemical Corporation KS5000 series, Nippon Kayaku Co., Ltd. BP series, Furthermore, as a polyamideimide resin, KS9000 series manufactured by Hitachi Kasei Corporation, etc. are mentioned. The compounding quantity of the said thermoplastic resin is 0.1 mass % or more from a viewpoint of the mechanical strength of the cured film obtained when the sum total of the compound which has (A) epoxy resin and (B) active ester group in a resin layer is 100 mass %, , 0.3 mass % or more is more preferable. Moreover, from a viewpoint of the dielectric characteristic of a cured film, 30 mass % or less is preferable, and 20 mass % or less is more preferable.

(rubber-like particles)

The resin layer may contain rubber-like particles as needed. Examples of such rubber particles include polybutadiene rubber, polyisopropylene rubber, urethane-modified polybutadiene rubber, epoxy-modified polybutadiene rubber, acrylonitrile-modified polybutadiene rubber, carboxyl group-modified polybutadiene rubber, acrylonitrile modified with a carboxyl group or a hydroxyl group. butadiene rubber, crosslinked rubber particles thereof, core-shell rubber particles, etc. are mentioned, and can be used individually by 1 type or in combination of 2 or more types. These rubber-like particles are added in order to improve the flexibility of the cured film obtained, to improve crack resistance, to enable surface roughening treatment with an oxidizing agent, and to improve adhesion strength with copper foil or the like.

The range of 0.005-15 micrometers is preferable and, as for the average particle diameter of rubber-like particle|grains, the range of 0.2-10 micrometers is more preferable. The average particle diameter of the rubber-like particle in this invention can be measured by the method similar to the average particle diameter of the said inorganic filler.

(flame retardant)

The resin layer may contain a flame retardant. Examples of the flame retardant include hydrated metals such as aluminum hydroxide and magnesium hydroxide, red phosphorus, ammonium phosphate, ammonium carbonate, zinc borate, zinc stannate, molybdenum compound, bromine compound, chlorine compound, phosphate ester, phosphorus-containing polyol, phosphorus-containing amine, Melamine cyanurate, a melamine compound, a triazine compound, a guanidine compound, a silicone polymer, etc. can be used. A flame retardant can be used individually by 1 type or in combination of 2 or more types.

(organic solvent)

The organic solvent is not particularly limited, and examples thereof include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum solvents. More specifically, Ketones, such as methyl ethyl ketone, cyclohexanone, methyl butyl ketone, and methyl isobutyl ketone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol ethers such as glycol monomethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol butyl ether acetate; alcohols such as ethanol, propanol, 2-methoxypropanol, n-butanol, isobutyl alcohol, isopentyl alcohol, ethylene glycol and propylene glycol; aliphatic hydrocarbons such as octane and decane; In addition to petroleum solvents, such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha, N,N- dimethylformamide (DMF), tetrachloroethylene, turpentine, etc. are mentioned. In addition, Maruzen Sekiyu Chemical Swasol 1000, Swasol 1500, Standard Sekiyu Osaka Hatsubaisho Co., Ltd. Sorvesso 100, Sorvesso 150, Sankyo Chemical Co., Ltd. solvent #100, solvent #150, Shell Chemicals Japan company make You may use organic solvents, such as Shellsol A100, Shellsol A150, Idemitsu Kosan Co., Ltd. Ipsol No. 100, and Ifsol No. 150. An organic solvent can be used individually by 1 type or in combination of 2 or more type.

It is preferable that the amount of residual solvent in a resin layer is 0.5-10.0 mass %. When a residual solvent is 10.0 mass % or less, the bump at the time of thermosetting is suppressed and the flatness of the surface becomes more favorable. Moreover, it can suppress that melt viscosity becomes low too much and resin flows out, and flatness becomes favorable. If the residual solvent is 0.5 mass % or more, the fluidity|liquidity at the time of lamination is favorable, and flatness and embedding property become more favorable.

(Other Ingredients)

The resin layer may also contain, if necessary, organic fillers such as silicone powder, fluorine powder, nylon powder, phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, etc. of conventionally known colorants, conventionally known thickeners such as asbesto, orben, bentone, and non-dissolved silica; Conventionally known additives such as adhesion-imparting agents, titanates, and aluminum can be used.

[Ultra-thin copper foil]

In this invention, the thickness of ultra-thin copper foil is 0.1-6 micrometers. The formation method of the ultra-thin copper foil is not particularly limited, and it can be formed by a known method by a wet film forming method such as an electroless copper plating method or an electrolytic copper plating method, a dry film forming method such as sputtering or chemical vapor deposition, or a combination thereof. . The electrolytic plating method is preferable from a viewpoint that thickness control of ultra-thin copper foil is easy. For example, after an auxiliary metal layer such as a nickel layer is formed on the carrier foil, it is immersed in a copper solution having a copper concentration of 20 to 100 g/L and a sulfuric acid concentration of 100 to 300 g/L, and a current density of 5 to 30 A/dm ² At It electrolyzes and can form ultra-thin copper foil.

It is preferable that the roughening process is carried out on the surface of ultra-thin copper foil. A roughening process is not specifically limited, What is necessary is just to form by a well-known and usual method. For example, a roughening process can be performed by performing the covering-plating process for preventing the burning-plating process of depositing a fine copper particle on ultra-thin copper foil, and the fall-off|omission of the fine copper particle made to deposit. For example, in a burning plating process, using an acidic copper sulfate solution containing a copper concentration of 10 g/L and a sulfuric acid concentration of 120 g/L, a roughening process is performed at a liquid temperature of 25 degreeC, and a current density of 15 A/dm ² , The coating plating after that In the process, using an acidic copper sulfate solution containing a copper concentration of 70 g/L and a sulfuric acid concentration of 120 g/L, electrodeposition may be performed under smooth plating conditions of a liquid temperature of 40° C. and a current density of 15 A/dm ² .

It is preferable that 10-point average roughness Rz of the surface by the side of the resin layer of ultra-thin copper foil is 4.0 micrometers or less from a viewpoint of the formability of a fine circuit. More preferably, it is 3.0 micrometers or less, More preferably, it is 2.5 micrometers or less. Moreover, from an adhesive viewpoint with a resin layer, it is preferable that it is 0.5 micrometer or more, and it is more preferable that it is 1.0 micrometer or more. Here, the 10-point average roughness Rz is a parameter that can be determined based on JIS B0601:2001, and in the roughness curve of the reference length, the average of the heights of the 5th from the highest peak to the highest, and the valley of the highest depth It is the average sum of the depths of the 5th valley from the bottom to the deepest. The 10-point average roughness Rz uses a commercially available three-dimensional surface structure analysis microscope (eg, zygo New View 5032 (manufactured by Zygo)) and commercially available analysis software (eg, Metro Pro Ver.8.0.2), , can be measured by setting the low-frequency filter to a condition of 11 μm. At this time, the non-measuring surface of the foil is fixed in close contact with the sample stand, and six fields of view of 108 µm × 144 µm are selected and measured within the range of a square with one side of the sample piece being 1 cm, and the measurement obtained from the six measurement points The average value of the values is employed as a representative value.

[Carrier foil]

The formation method of carrier foil is not specifically limited, Copper foil, aluminum foil, stainless steel (SUS) foil, the resin film which coated the surface with metal, etc. are mentioned, It is preferable that it is copper foil. The copper foil may be an electrolytic copper foil or a rolled copper foil may be sufficient as it. The thickness of carrier foil is 250 micrometers or less normally, Preferably it is 9-200 micrometers.

A commercial item may be used for ultra-thin copper foil and carrier foil, for example, MT18Ex, MT18FL, MT18SD-H by Mitsui Kinzoku Kogyo which are ultra-thin copper foil with carrier foil, etc. may be used for it.

[Laminate]

The laminate of this invention should just have carrier foil, 0.1-6 micrometers thick ultra-thin copper foil, and a resin layer in this order, and may have another layer further as needed. For example, you may have a peeling layer and an auxiliary metal layer between carrier foil and ultra-thin copper foil, and you may have a protective film on a resin layer.

As a peeling layer, either an organic peeling layer and an inorganic peeling layer may be sufficient. As an organic component of an organic peeling layer, nitrogen-containing organic compounds, such as a triazole compound, sulfur-containing organic compound, carboxylic acid, etc. are mentioned. As an example of the inorganic component of an inorganic peeling layer, Ni, Mo, Co, Cr, Fe, Ti, W, P, Zn, a chromate-treated film|membrane, etc. are mentioned.

As an auxiliary metal layer, the layer containing nickel and/or cobalt is preferable, and stability of the peeling strength of carrier foil becomes favorable with this auxiliary metal layer.

A protective film is provided on the resin layer in order to improve handleability while preventing that a particle|grain etc. adhere to the surface of a resin layer. As the protective film, for example, a polyester film such as polyethylene terephthalate or polyethylene naphthalate, a polyimide film, a polyamideimide film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a polystyrene film, etc. Although the containing film, the surface-treated paper, etc. can be used, Among these, a polyester film, a polyethylene film, and a polypropylene film are preferable. Although the thickness in particular of a protective film is not restrict|limited, It is suitably selected according to a use in the range of about 5-150 micrometers. The mold release process may be given to the surface which provides the resin layer of a protective film.

The method for producing a laminate of the present invention is not particularly limited, for example, (A) an epoxy resin, (B) a compound having an active ester group, and (C) an inorganic filler on a commercially available ultra-thin copper foil with carrier foil. It can manufacture by apply|coating the resin composition to do, making it dry, and forming the resin layer as a dry coating film.

It is preferable that the laminated body of this invention is copper foil with resin (RCC) used for manufacture of a multilayer wiring board. What is necessary is just to use a conventionally well-known method as a manufacturing method of the electronic component using the laminated body of this invention. In addition, the method of hardening the laminated body resin layer of this invention is not specifically limited, What is necessary is just to harden by a conventionally well-known method, For example, what is necessary is just to heat and harden|cure at 150-230 degreeC. As a manufacturing method of the printed wiring board using the laminated body of this invention, the following method is mentioned, for example. With respect to the circuit board in which the circuit pattern was formed, the laminated body of this invention is laminated|stacked by heat lamination and thermosetted so that the resin layer side may contact|connect. The thermosetting may be cured in an oven or cured by a hot plate press. Next, a circuit may be formed by a modified semi-additive process (MSAP) method as all or part of an ultra-thin copper foil as a wiring layer, and a build-up wiring board may be manufactured. Moreover, you may manufacture the buildup wiring board in which the ultra-thin copper foil was removed and the circuit was formed by the semi-additive process (SAP) method. Moreover, you may manufacture a printed wiring board by direct build-up on wafer which repeats lamination|stacking and circuit formation of copper foil with resin on a semiconductor integrated circuit alternately. Moreover, you may use the coreless buildup method in which the resin layer and the conductor layer were laminated|stacked alternately, without using a core board|substrate. What is necessary is just to peel carrier foil in any after lamination, after thermosetting, after laser processing, or after desmear processing.

The laminate of the present invention can be preferably used for forming a permanent protective film of electronic components, particularly multilayer printed wiring boards, and among them, can be preferably used for forming an interlayer insulating layer. Since the hardened|cured material of the resin layer of the laminated body of this invention is excellent in a dielectric characteristic, it can use suitably for the high frequency use in which transmission loss becomes a subject. Specific examples of high-frequency applications include, for example, a substrate for millimeter-wave radar or millimeter-wave sensor for automatic operation, a motherboard for high-speed communication-compatible mobile, or SLP (substrate type) for forming a circuit by a modified semi-additive process (MSAP) method. (Substrate-Like) PCB), application processor (AP) for mobile and personal computers, HDI (High Density Interconnect) or PKG (package) boards for smartphones, tablets or personal computers, high-level boards for servers or routers for base stations, A board|substrate for antennas, etc. are mentioned. You may form a wiring board by bonding wiring using the laminated body of this invention. As an electronic component, use other than a printed wiring board, for example, passive components, such as an inductor, may be sufficient. Further, according to the laminate of the present invention, when the total amount of active ester groups is large, that is, in the resin layer, (A) the total amount of epoxy groups of the epoxy resin/(B) the ratio of the total amount of active ester groups of the compound having active ester groups is 0.20 Even in the case of 0.60 to 0.60, since a fine pattern can be formed with good adhesion on the insulating layer, it is suitable for, for example, circuit formation applications of line/space = 35 µm or less/35 µm or less.

Although the dielectric loss tangent of the hardened|cured material of this invention is not specifically limited, According to this invention, it is possible to obtain the hardened|cured material of a low dielectric loss tangent, For example, it is 0.005 or less, further 0.003 or less, Furthermore, it is also possible to set it as 0.002 or less.

Example

Hereinafter, the present invention will be specifically described by showing examples and comparative examples of the present invention, but it goes without saying that the present invention is not limited to the following examples. In addition, in the following, "part" and "%" are both based on mass unless otherwise indicated.

<Synthesis of compound having an active ester group>

(Synthesis Example 1: Synthesis of a compound having an active ester group of (B-1))

203.0 g of isophthalic acid chloride (number of moles of acid chloride groups: 2.0 mol) and 1338 g of toluene were dissolved in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a flow dividing tube, and a stirrer by replacing the inside of the input system with reduced pressure nitrogen. Next, 96.0 g (0.67 mol) of α-naphthol and 220 g of dicyclopentadienephenol resin (number of moles of phenolic hydroxyl groups: 1.33 mol) were charged, and the inside of the system was purged with nitrogen under reduced pressure to dissolve. Then, while 1.12 g of tetrabutylammonium bromide was dissolved and nitrogen gas purging was performed, the system inside was controlled to 60 degreeC or less, and 400 g of 20% sodium hydroxide aqueous solution was dripped over 3 hours.

Then, stirring was continued for 1.0 hour under these conditions. After completion of the reaction, the liquid was separated and the aqueous layer was removed. In addition, water was added to the toluene in which the reactant was dissolved, stirred and mixed for about 15 minutes, and the mixture was left to separate and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer reached 7. Thereafter, water was removed by decanter dehydration to obtain an active ester resin (B-1) in a state of a toluene solution having a nonvolatile content of 65%. The ester group equivalent in terms of solid content of the obtained active ester resin (B-1) was 223 g/eq.

(Synthesis Example 2: Synthesis of a compound having an active ester group of (B-2))

2,7-dihydroxynaphthalene 320 g (2.0 mol), benzyl alcohol 184 g (1.7 mol), and para-toluenesulfonic acid monohydrate 5.0 g were put into a flask equipped with a thermometer, dropping funnel, cooling tube, flow dividing tube, and stirrer. and stirred while blowing nitrogen at room temperature. Then, it heated up to 150 degreeC, and stirred for 4 hours, distilling the produced|generated water out of the system. After completion of the reaction, 900 g of methyl isobutyl ketone and 5.4 g of a 20% aqueous sodium hydroxide solution were added for neutralization, the aqueous layer was removed by liquid separation, washed with water 3 times with 280 g of water, and the methyl isobutyl ketone was removed under reduced pressure. 460 g of a benzyl-modified naphthalene compound (B-2 intermediate) was obtained. The obtained benzyl-modified naphthalene compound (B-2 intermediate) was a black solid, and the hydroxyl equivalent was 180 g/eq.

To a flask equipped with a thermometer, a dropping funnel, a cooling tube, a flow dividing tube, and a stirrer, 203.0 g of isophthalic acid chloride (number of moles of acid chloride groups: 2.0 moles) and 1400 g of toluene were charged, and the inside of the system was purged under reduced pressure and nitrogen was dissolved. Next, 96.0 g (0.67 mol) of α-naphthol and 240 g (the number of moles of phenolic hydroxyl groups: 1.33 mol) of a benzyl-modified naphthalene compound (B-2 intermediate) were added, and the system was dissolved under reduced pressure by nitrogen substitution. Then, dissolving 0.70 g of tetrabutylammonium bromide and nitrogen gas purging, the inside of a system was controlled to 60 degrees C or less, and 400 g of 20% sodium hydroxide aqueous solution was dripped over 3 hours. Then, stirring was continued for 1.0 hour under these conditions. After completion of the reaction, the liquid was separated and the aqueous layer was removed. In addition, water was added to the toluene layer in which the reactant was dissolved, stirred and mixed for 15 minutes, and the mixture was left to separate and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer reached 7. Then, the water|moisture content was removed by decanter dehydration, and the active ester resin (B-2) in the state of the toluene solution of 65 mass % of nonvolatile matters was obtained. The ester group equivalent in terms of solid content of the obtained active ester resin (B-2) was 230 g/eq.

<Preparation of curable resin composition>

It kneaded and mixed at the ratio (mass part) shown in Tables 1 and 2 with various components shown in the "resin layer" of the Examples and Comparative Examples of Tables 1 and 2 below to prepare a curable resin composition. In addition, the numerical value in a table|surface shows a mass part (non-volatile matter conversion).

<Measurement of dielectric loss tangent (DF)>

Using a film applicator, the curable resin composition was applied on the glossy side of copper foil (F2-WS manufactured by Furukawa Denki Kogyo Co., Ltd., 18 μm thick) for each Example and Comparative Example, and dried at 90° C. for 10 minutes in a hot air circulation drying furnace. Then, after hardening at 200 degreeC for 60 minutes then, copper foil was peeled and the about 40-micrometer-thick post-hardening film (cured film) was produced. The obtained cured film was cut to a measurement size (size of 50 mm x 60 mm), and the dielectric loss tangent of 10 GHz at 23 ° C was measured using an SPDR dielectric resonator and a network analyzer (both manufactured by Agilent), and the following criteria were used. evaluated.

◎: less than 0.003

○: 0.003 or more and less than 0.010

×: 0.010 or more

<Production of RCC with carrier foil (copper foil with resin)>

Using a film applicator, each of Examples 1 to 14 and the curable resin composition of Comparative Example 1 were laminated with a carrier-equipped ultra-thin copper foil (MT18Ex manufactured by Mitsui Kinzoku Kogyo Co., Ltd., 3 µm thick) (roughness Rz of copper foil = 2 µm) ) and dried at 90° C. for 10 minutes in a hot air circulation drying furnace to prepare RCC (copper foil with resin) with a carrier foil having a thickness of about 40 μm of the resin layer.

<Production of RCC (Copper Foil with Resin)>

Using a film applicator, the curable resin compositions of Comparative Examples 2 and 3 were respectively applied to the laminated side of the electrolytic copper foil (3EC-M2S-VLP manufactured by Mitsui Kinzoku Kogyo Co., Ltd., 18 µm thick) (the roughness of copper foil Rz = 2 µm). It was coated and dried at 90° C. for 10 minutes in a hot air circulation drying furnace to prepare RCC (copper foil with resin) having a resin layer thickness of about 40 μm.

<Evaluation of laser drilling workability>

(i) In the case of the RCC with carrier foil of Examples 1 to 14 and Comparative Example 1 prepared above

After laminating the surface of RCC by the side of the resin layer on the surface of a board|substrate, and making it thermocompression-bonded at 4.0 MPa and 200 degreeC for 90 minutes, the carrier foil was peeled and the copper clad laminated board for evaluation was produced.

(ii) In the case of RCCs of Comparative Examples 2 and 3 prepared above

The surface of the RCC on the resin layer side was laminated on the surface of the substrate, and after thermocompression bonding at 4.0 MPa and 200° C. for 90 minutes, the copper foil of the laminate was used with a cupric chloride etchant, the thickness of the copper foil The whole surface was etched so that it might become about 3 micrometers, and the copper clad laminated board for evaluation was produced.

Thereafter, the copper clad laminate produced in (i) (ii) was subjected to laser drilling under the conditions of a pulse width of 12 µsec., a pulse energy of 8 mJ, and a laser beam diameter of 97 µm using a carbon dioxide gas laser. About ten holes formed by laser drilling, the diameters of the x-direction and the y-direction were measured, their average value was computed, and it was set as the hole diameter after processing. The difference between the maximum value and the minimum value of the hole diameters (out of 10 points) after processing was judged as (double-circle) that became less than 3 micrometers, and 3 micrometers or more were made into x determination.

<Evaluation of reflow resistance>

First, the copper-clad laminate was cut out to 10 cm x 10 cm in length and width, and the process was repeated 10 times in a reflow furnace (up to 285°C). After the treatment, it was visually confirmed, and when there was no appearance defect such as swelling, it was judged as ◎, and when there was an appearance defect such as swelling, it was judged as x.

*1: EXA-835LV manufactured by DIC (mixed product of bisphenol A epoxy resin and bisphenol F type epoxy resin, liquid, epoxy equivalent: 165 g/eq.)

*2: Nippon Kayaku Co., Ltd. NC-3000H (biphenyl aralkyl type epoxy resin, solid, epoxy equivalent: 290 g/eq.)

*3: Active ester resin B-1 synthesized in Synthesis Example 1 (active ester equivalent: 223 g/eq.)

*4: Active ester resin B-2 synthesized in Synthesis Example 2 (active ester equivalent: 230 g/eq.)

*5: TD-2090 manufactured by DIC (phenol novolac, hydroxyl equivalent: 105 g/eq.)

*6: SO-C2 manufactured by Admatex Co., Ltd. treated with phenylaminosilane (spherical silica, average particle size: 0.5 µm)

*7: Mitsubishi Chemical Corporation jER YX7200B35 (phenoxy resin)

*8: Shikoku Chemical Co., Ltd. 2E4MZ (2-ethyl-4-methylimidazole)

*9: The thickness of the copper foil before etching. About 3 μm after etching.

From the result shown in the said table|surface, it turns out that the laminated body of this invention is excellent in laser drilling property and reflow property, and the hardened|cured material of a resin layer is a low dielectric loss tangent.

1: Laminate
2: carrier foil
3: Ultra-thin copper foil
4: resin layer

Claims (8)

A laminate comprising at least a carrier foil, an ultra-thin copper foil having a thickness of 0.1 to 6 µm, and a resin layer in order,
The said resin layer contains (A) an epoxy resin, (B) a compound which has an active ester group, and (C) an inorganic filler, The laminated body characterized by the above-mentioned. The laminate according to claim 1, wherein the ratio of the total amount of the epoxy groups of the (A) epoxy resin/the total amount of the active ester groups of the compound having the (B) active ester group in the resin layer is 0.20 to 0.60. The compounding quantity of the said (C) inorganic filler is 50 mass % or more when the non-volatile component in the said resin layer is 100 mass %, The laminated body of Claim 1 or 2 characterized by the above-mentioned. The compound according to any one of claims 1 to 3, wherein (B) the compound having an active ester group has the following general formula (1)

(Wherein, X ₁ is each independently a group having a benzene ring or a naphthalene ring, k represents 0 or 1, and n is an average of 0.25 to 1.5 repeating units.) laminate. The compound according to any one of claims 1 to 3, wherein (B) the compound having an active ester group has the following general formula (2):

(In formula (2), X ₂ is each independently the following formula (3):

A group represented by or the following formula (4):

is a group represented by
m is an integer from 1 to 6, n is each independently an integer from 1 to 5, q is each independently an integer from 1 to 6,
In formula (3), each k is independently an integer of 1 to 5,
In the formula (4), Y is a group represented by the formula (3) (k is each independently an integer of 1 to 5), and t is each independently an integer of 0 to 5)
A laminate, characterized in that it is a compound having a structure having a structural moiety represented by and both ends of which are monovalent aryloxy groups. The ratio of the total amount of the epoxy groups of the (A) epoxy resin to the total amount of the active ester groups of the compound having the (B) active ester groups in the resin layer according to any one of claims 1 to 5, is 0.20 to 0.50. A laminate, characterized in that. The laminate according to any one of claims 1 to 6, wherein the dielectric loss tangent of the cured product of the resin layer is 0.01 or less. It has a hardened|cured material obtained by hardening|curing the said resin layer of the laminated body in any one of Claims 1-7, The electronic component characterized by the above-mentioned.

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