JP2004149758A - Hardenable resin film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hardenable resin film and an electrically insulative material capable of simultaneously filling through-holes bored on the film and forming interlayer insulation layers and of producing built-up multi-layer printed-circuit boards by using the interlayer insulating layer in no need of grinding step. <P>SOLUTION: As for the hardenable resin film, the coefficient of linear expansion (X) in [ppm] is measured through the thermomechanical analysis after the resin is hardened, the reaction heat (Y) in [J/g] on the hardening reaction is measured through the differential scanning calorimetry (DSC) where X and Y satisfy the formula (1) Y ≤-2.67X+374∼ and the complex viscosity is 10,000-100,000 Pa s. The hardened resin film satisfying these conditions is used for producing build-up multi-layered printed circuit boards. <P>COPYRIGHT: (C)2004,JPO

Description

【０１３１】
【表２】

【０１３２】
【表３】

【０１３３】
表１〜３に示す結果において、実施例の硬化物はいずれも、平滑性指標が全て２．５μｍ以下であるのに対して、比較例１、２は平滑性が大きい値を示し、不十分である。
また、実施例の硬化物はすべて、スルーホールの埋め込み性が良好であるが、比較例３は２５℃での複素粘度が大きく、スルーホールの埋め込み性が不良である。
これらの比較から、本発明の実施例のいずれもが、スルーホールの埋め込み性と十分小さな平滑性と表面粗度とを同時に達成できており、比較例より優れることは明らかである。
【０１３４】
【発明の効果】
本発明の硬化樹脂フィルムを使用すると、スルーホールの穴埋め及び層間絶縁層を同時に形成することが可能となり、さらにこれを用いてビルドアップ多層プリント配線板を製造することができる。従って、スルーホール用の穴埋め剤及び層間絶縁材料の１種類の硬化性樹脂フィルムで提供することができる。このため、穴埋め工程における位置決め精度及び穴埋め剤の塗布量の制御が不必要となる。また、研磨工程が不必要となる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a curable resin film. More specifically, the present invention relates to a curable resin film suitable as a multilayer printed wiring board interlayer insulating material capable of simultaneously filling a through hole and forming an interlayer insulating layer.
[0002]
[Prior art]
In the manufacture of multi-layer printed wiring board interlayer insulation board by conventional build-up, after filling and heat-curing the through-hole with a hole-filling agent (fill-filling ink or conductive paste) to ensure flatness around the opening of the through-hole The periphery of the through hole is polished (Patent Document 1). By this polishing step, a flat interlayer insulating layer can be formed, and further multilayering can be performed.
[0003]
[Patent Document 1]
JP 2001-127435 A
[0004]
[Problems to be solved by the invention]
In the conventional manufacturing method, two kinds of the filling agent for the through hole and the interlayer insulating material are essential, the control of the positioning accuracy and the application amount of the filling agent in the filling process are complicated, and the polishing process is complicated. There are problems such as the need for a long time. That is, an object of the present invention is to solve these problems and to provide an insulating material capable of simultaneously filling a through hole and forming an interlayer insulating layer.
[0005]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above problems, and as a result, in the production of a multilayer printed wiring board, a curable resin film that satisfies a specific relationship between a coefficient of linear expansion after curing and a reaction heat at the time of a curing reaction. The present inventors have found that the formation of the interlayer insulating layer and the filling of the through holes can be simultaneously performed at the same time, and have reached the present invention.
That is, the curable resin film of the present invention has a linear expansion coefficient (X) [ppm] after curing measured by thermomechanical analysis (TMA) and a curing reaction measured by differential scanning calorimetry (DSC). The reaction heat (Y) [mJ / mg] at the time satisfies the formula (1), and the complex viscosity at 25 ° C. is 10,000 to 100,000 Pa · s.
Y ≦ −2.67X + 374 (1)
[0006]
BEST MODE FOR CARRYING OUT THE INVENTION
The coefficient of expansion (X) after curing in the present invention is determined by using a thermo-mechanical analysis (TMA) after curing the curable resin film, according to The Institute for Interconnecting and Packaging Electronic Circuits. In accordance with the method specified in 2.4.41.3 of test method IPC-TM-650, the linear expansion coefficient was obtained from the following equation (2) using the measured values of the length at 30 ° C. and 170 ° C. (X) is calculated.
(X) = [(B)-(A)] × 10 ⁶ / [(170-30) × (A)] (2)
Here, (A) is the length at 30 ° C., and (B) is the length at 170 ° C.
[0007]
In addition, the reaction heat (Y) at the time of the curing reaction in the present invention uses a value measured by differential scanning calorimetry (DSC) in accordance with JIS K7122-1987 "Method for measuring heat of transition of plastic".
The heat of reaction (Y) is determined from the following equation (3).
(Y) = ΔH / S [J / g] (3)
Here, ΔH is the total calorific value [J] calculated from the peak area of the calorific value-time (temperature) curve of the obtained DSC, and S is the sample amount (g).
[0008]
The linear expansion coefficient (X) [ppm] after curing and the reaction heat (Y) [J / g] during the curing reaction satisfy Expression (1) from the viewpoint of smoothness around the through-hole opening. is necessary.
Y ≦ −2.67X + 374 (1)
More preferably, it satisfies Y ≦ −2.67X + 350, particularly preferably Y ≦ −2.67X + 260, and most preferably Y ≦ −2.67X + 170.
If the smoothness around the opening of the through hole is impaired, the yield tends to decrease when an interlayer insulating layer and a conductor circuit are further formed in a region including the periphery of the opening of the through hole.
[0009]
The linear expansion coefficient (X) [ppm] is preferably 1 to 140, more preferably 2 or more, particularly preferably 3 or more, and further preferably 100 or less, from the viewpoint of flatness around the opening of the through hole. Particularly preferably, it is 60 or less.
If (X) is less than 1, the difference in the coefficient of linear expansion from the constituent materials of the other printed wiring boards becomes large, resulting in poor thermal shock resistance. If (X) exceeds 140, the smoothness around the opening of the through hole is impaired. There's a problem.
[0010]
The heat of reaction (Y) [J / g] during the curing reaction is preferably from 10 to 230, more preferably from 20 to 200, and particularly preferably from 30 to 160, from the viewpoint of flatness around the opening of the through hole. That is, the heat of reaction (Y) [J / g] at the time of the curing reaction is preferably 10 or more, more preferably 20 or more, particularly preferably 30 or more, and preferably 230 or less, more preferably 200 or less, particularly preferably 200 or less. Preferably it is 160 or less.
[0011]
As the thermomechanical analyzer for measuring the linear expansion coefficient (X) after curing specified in the present invention, a commercially available thermomechanical analyzer (TMA) analyzer can be used. For example, TMA manufactured by Seiko Instruments Inc. / SS6100 etc. can be used.
As described above, the measured value is used in accordance with the method specified in 2.4.41.3 (1995 version) of the test method IPC-TM-650 of the American Printed Circuit Industry Association. . This test method has been published on the Internet homepage of the American Printed Circuit Manufacturers Association.
As a measurement sample, a film obtained by heating and curing a film at 170 ° C. for 90 minutes is used. After the curing, a load is applied to the measurement sample, the inside of the measurement cell is kept at 30 ° C. for 30 minutes, and then the temperature of the measurement cell is raised from 30 ° C. to 230 ° C. at a rate of 10 ° C./min.
The length at 30 ° C. is (A) [mm], and the length at 170 ° C. is (B) [mm].
(X) = [(B)-(A)] × 10 ⁶ / [(170-30) × (A)] (2)
[0012]
As a differential scanning calorimeter for measuring the reaction heat (Y), a commercially available differential scanning calorimeter (DSC) measuring apparatus can be used, and for example, DSC6100 manufactured by Seiko Instruments Inc. can be used.
The measurement conforms to JIS K7122-1987 “Method of measuring heat of transition of plastic”. However, the measurement is performed by adopting “when measuring the transition heat adjusted in a standard state” specified as “condition adjustment of the test piece” in the above JIS as the measurement condition.
The measurement sample is weighed in an aluminum measuring pan, and is kept at 30 ° C. for 30 minutes, and then heated up to 30 to 270 ° C. at 5 ° C./min. The weighed sample weight is defined as S [g], the peak area is determined from a calorific value-time (temperature) curve obtained by the measurement, the total calorific value calculated from this is defined as ΔH [J], and the reaction heat (Y) is expressed by the following formula. (3) required.
Heat of reaction (Y) = ΔH / S [J / g] (3)
[0013]
The complex viscosity (Pa · s) at 25 ° C. (hereinafter, 25 ° C. complex viscosity) of the curable resin film of the present invention is 10,000 to 100,000 from the viewpoint of film handling properties (such as cracking of the film). It is necessary to be. It is more preferably at least 20,000, particularly preferably at least 30,000, further preferably at most 80,000, particularly preferably at most 60,000. When the complex viscosity at 25 ° C. is less than 10,000, the resin is too weak to cause cracks in the resin film, and when the complex viscosity is more than 100,000, the resin is too hard to crack easily in the resin film. .
[0014]
The complex viscosity (Pa · s) at 80 ° C (hereinafter referred to as 80 ° C complex viscosity) of the curable resin film of the present invention is 100 to 5,000 from the viewpoint of fillability of through-holes (ease of filling). Preferably, it is more preferably 300 or more, particularly preferably 500 or more, and further preferably 4,000 or less, particularly preferably 3,000 or less. If the complex viscosity is less than 100 at 80 ° C., there is a problem that the resin easily oozes from the peripheral portion when the film is pressed and bonded to the substrate, and if it is more than 5,000, the resin is difficult to fill in the through holes. is there.
[0015]
The complex viscosity [Pa · s] at 25 ° C. and 80 ° C. in the present invention is a value measured by a viscoelasticity measuring device (for example, ARES manufactured by Rheometric Scientific Co., Ltd.). The measurement method of the viscoelasticity measuring device mentioned here is a method of measuring the viscoelasticity when rotational shear stress is applied to the measurement sample.
In the viscoelasticity measurement, a measurement sample is sandwiched between two disk-shaped sample fixing jigs held in parallel to a specific gap (a distance between a disk and a disk), and one of the disk-fixing jigs is placed in a circle. Is rotated about the center of the disk, and a rotational shear stress is applied in the circumferential direction of the disk to measure. The applied rotational shear stress is 2 × 10 ^-3 A sinusoidal vibration is applied with an amplitude of [rad].
[0016]
The measurement conditions are shown below.
Sample fixing jig: 25 mm diameter aluminum disk (for example, ARES-DP25A manufactured by Rheometric Scientific Hook)
Sample: disk shape with a diameter of 25 mm and a thickness of 0.500 mm
Gap distance: 0.500 mm
Rotational shear stress amplitude: 2 × 10 ^-3 [Rad]
Sinusoidal shear stress frequency: 1.5915 Hz
Temperature rising rate: After holding at 0 ° C. for 20 minutes, the temperature is raised from 0 ° C. to 150 ° C. at 10 ° C./min.
[0017]
The complex viscosity at 25 ° C. and 80 ° C. is read from the time (temperature) -complex viscosity curve obtained by the measurement, and this is defined as the complex viscosity.
[0018]
The curable resin film of the present invention comprises a curable resin composition comprising a curable resin (A), a filler (B), and, if necessary, an additive (C).
As the filler (B), known inorganic fillers and organic fillers can be used.
[0019]
Examples of the inorganic filler include silicon oxide, titanium oxide, calcium carbonate, aluminum oxide, barium sulfate, barium titanate, titanium oxide, calcium carbonate, and aluminum oxide, with silicon oxide being preferred.
The melting point (° C.) of the inorganic filler is preferably from 300 to 2000, more preferably from 400 to 1900, particularly preferably from 500 to 1800. That is, the melting point (° C.) of the inorganic filler is preferably 300 or more, more preferably 400 or more, particularly preferably 500 or more, and preferably 2000 or less, more preferably 1900 or less, and particularly preferably 1800 or less. If the melting point (° C.) of the inorganic filler is less than 300, there is a problem that the coefficient of linear expansion of the cured product of the curable resin becomes large, and if it is more than 2,000, it becomes difficult to obtain the filler.
[0020]
Examples of the organic filler include fluororesin powder, polyether sulfone powder, and nylon powder.
The glass transition temperature (° C.) of the organic filler is preferably 170 to 300, more preferably 190 to 280, and particularly preferably 210 to 260. That is, the glass transition temperature (° C.) of the organic filler is preferably 170 or more, more preferably 190 or more, particularly preferably 210 or more, and preferably 300 or less, more preferably 280 or less, and particularly preferably 260 or less. is there. When the melting point (° C.) of the organic filler is less than 170, there is a problem that the linear expansion coefficient of the cured product of the curable resin becomes large, and when it is more than 300, it becomes difficult to obtain the filler.
[0021]
The volume average particle size (μm) of these fillers is preferably 0.01 to 50, more preferably 0.02 or more, particularly preferably 0.03 or more, and further preferably 30 or less, particularly preferably 10 or less. It is as follows. If the volume average particle size (μm) of the filler is smaller than 0.01, there is a problem that the complex viscosity of the curable resin becomes large, and if it is larger than 50, there is a problem that the linear expansion coefficient becomes large.
[0022]
Among these fillers, silicon oxide, fluorine powder, and polyether sulfone powder are preferable, and silicon oxide is more preferable, from the viewpoints of cost, electric characteristics (such as insulating property and dielectric constant), heat resistance, and chemical resistance. .
The content (% by weight) of the filler is preferably from 34 to 85, more preferably 38 or more, and particularly preferably 43, based on the weight of the curable resin composition, from the viewpoint of smoothness around the through-hole opening and the like. And more preferably 70 or less, particularly preferably 60 or less. When the content (% by weight) of the filler is less than 34, there is a problem that the linear expansion coefficient of the cured product becomes large, and when it is more than 85, the film becomes brittle and the elongation of the cured product is reduced.
[0023]
The curable resin (A) includes a thermosetting resin, a photocurable resin, and the like.
Examples of the thermosetting resin include an epoxy resin (A1), a polyimide resin, and a resin having another reactive group. Examples of the thermosetting resin include an epoxy resin described in JP-A-2001-279116 and JP-A-2002-88242. A polyimide resin described in the gazette and a resin having another reactive group described in JP-A-2001-279110 can be used.
Examples of the photocurable resin include an epoxy resin and a resin having another reactive group. For example, the epoxy resin described in JP-A-2002-105117 and the other resins described in JP-A-11-214815 are disclosed. Resins having a reactive group can be used.
Among these curable resins, a thermosetting resin is preferable from the viewpoint of simplicity of the curing reaction and the like, and an epoxy resin (A1) is more preferable from the viewpoint of cost and dielectric properties.
[0024]
The epoxy resin (A1) as a thermosetting resin is composed of an epoxide and a curing agent.
As the epoxide, the above-mentioned known compounds can be used, and for example, glycidyl ether epoxide, glycidyl ester epoxide, glycidylamine epoxide, alicyclic epoxide and the like can be used.
[0025]
Examples of the glycidyl ether type epoxide include glycidyl ether of dihydric phenol, glycidyl ether of polyhydric phenol, glycidyl ether of dihydric alcohol, and glycidyl ether of polyhydric alcohol.
Examples of the glycidyl ether of a dihydric phenol include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, and bisphenol S diglycidyl ether.
Examples of the glycidyl ether of a polyhydric phenol include dihydroxynaphthyl cresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, and dinaphthyltriol triglycidyl ether.
Examples of the glycidyl ether of a dihydric alcohol include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and polyethylene glycol (weight average molecular weight (hereinafter, Mw): 150-4,000) diglycidyl ether and polypropylene glycol (Mw: 180-5,000) diglycidyl ether.
Examples of the glycidyl ether of the polyhydric alcohol include trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol hexaglycidyl ether and poly (polymerization degree 2 to 5) glycerin polyglycidyl ether.
[0026]
As the glycidyl ester type epoxide, glycidyl ester of carboxylic acid, glycidyl ester type polyepoxide and the like are used.
Examples of the glycidyl ester of a carboxylic acid include glycidyl methacrylate, diglycidyl phthalate, diglycidyl isophthalate, diglycidyl terephthalate, and triglycidyl trimellitate.
[0027]
As the glycidylamine type epoxide, glycidyl aromatic amine, glycidyl alicyclic amine, glycidyl heterocyclic amine and the like are used.
Examples of the glycidyl aromatic amine include N, N-diglycidylaniline, N, N-diglycidyltoluidine, N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane, N, N, N ′, N′-tetraglycidyl Diaminodiphenyl sulfone and N, N, N ', N'-tetraglycidyldiethyldiphenylmethane.
Examples of the glycidyl alicyclic amine include bis (N, N-diglycidylaminocyclohexyl) methane (a hydrogenated compound of N, N, N ', N'-tetraglycidyldiaminodiphenylmethane) and N, N, N', N ' -Tetraglycidyl dimethylcyclohexylenediamine (hydrogenated compound of N, N, N ', N'-tetraglycidylxylylenediamine) and the like.
Examples of the glycidyl heterocyclic amine include trisglycidylmelamine and N-glycidyl-4-glycidyloxypyrrolidone.
[0028]
Examples of the alicyclic epoxide include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxydicyclopentyl ether and 3,4-epoxy-6-methyl. Cyclohexylmethyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate and the like.
[0029]
Among these epoxides, glycidyl ether epoxides, glycidyl ester epoxides and glycidylamine epoxides are preferred from the viewpoints of cost and heat resistance, and more preferred are glycidyl ether epoxides and glycidyl ester epoxides. As these epoxides, these may be used alone, or two or more selected from them may be used as a mixture.
[0030]
The number of epoxy groups in the epoxide is preferably at least 2 in number average, more preferably 2 to 500, and further preferably 3 or more, more preferably 4 or more, and still more preferably 5 or more. The number is most preferably 6 or more. The upper limit is more preferably 300 or less, particularly preferably 100 or less, still more preferably 50 or less, and most preferably 40 or less. When the number of epoxy groups is in this range, the curable resin film of the present invention tends to have better thermal shock resistance and dielectric properties.
[0031]
The weight average molecular weight (hereinafter, abbreviated as Mw) of the epoxide is preferably 300 to 10,000, more preferably 400 or more, particularly preferably 500 or more, and still more preferably 9, from the viewpoint of thermal shock resistance and the like. 000 or less, particularly preferably 5,000 or less.
[0032]
Known curing agents can be used, for example, carboxylic acids, acid anhydrides, amine compounds, phenols, and the like.
As the carboxylic acid, an aromatic carboxylic acid and an alicyclic carboxylic acid are used.
Known aromatic carboxylic acids can be used, and examples thereof include phthalic acid, isophthalic acid, terephthalic acid, and trimellitic acid.
As the alicyclic carboxylic acid, known ones can be used, and cyclohexane-1,2-dicarboxylic acid (aromatic hydrogenation compound of phthalic acid) and cyclohexane-1,3-dicarboxylic acid (aromatic hydrogenation of isophthalic acid) can be used. Compounds) and the like.
Known acid anhydrides can be used, and examples thereof include phthalic anhydride, maleic anhydride, and 4-methylcyclohexane-1,2-dicarboxylic anhydride.
[0033]
As the amine compound, an aromatic amine compound, an aliphatic amine compound, an alicyclic amine compound, or the like is used.
As the aromatic amine compound, known compounds can be used, and examples thereof include 1,3-phenylenediamine, 1,4-phenylenediamine, and 4,4′-diphenylmethanediamine.
As the aliphatic amine compound, known compounds can be used, and examples thereof include ethylenediamine, propylenediamine, trimethylenediamine, diethylenetriamine, and iminobispropylamine.
As the alicyclic amine compound, known compounds can be used, and cyclohexylene-1,3-diamine (hydrogenated aromatic nucleus compound of 1,3-phenylenediamine), cyclohexylene-1,4-diamine (1,4 -Hydrogenated aromatic nucleus compound of phenylenediamine), bis (aminocyclohexyl) methane (hydrogenated compound of aromatic nucleus of 4,4'-diphenylmethanediamine) and the like.
Known phenols can be used, and cresol / novolak resin (Mw: 320 to 32,000), phenol novolak resin (Mw: 360 to 36,000), naphthyl cresol, tris (hydroxyphenyl) methane, and dinaphthyl Triol, tetrakis (4-hydroxyphenyl) ethane, 4,4′-oxybis (1,4-phenylethyl) tetracresol and the like can be mentioned.
[0034]
Of these curing agents, phenol is preferred from the viewpoint of reliability.
These curing agents may be used alone or as a mixture.
[0035]
The equivalent ratio of the epoxide to the curing agent (epoxide / curing agent) is preferably from 0.7 to 1.3, more preferably 0.8 or more, particularly preferably 0.9 or more, and further preferably 1. 2 or less, particularly preferably 1.1 or less. If the equivalent ratio of the epoxide to the curing agent (epoxide / curing agent) is smaller than 0.7, there are problems such as a low Tg of the cured product and a decrease in strength. Also, if it is larger than 1.3, there are problems such as a low Tg of the cured product and a decrease in strength.
[0036]
A thermosetting catalyst can be added to the epoxy resin as the thermosetting resin. When the curable resin is an epoxy resin, a known catalyst such as an imidazole catalyst and a tertiary amine can be used as the thermosetting catalyst.
When this thermosetting catalyst is used, the addition amount (% by weight) of the thermosetting catalyst is preferably 0.1 to 10, more preferably 0.3 or more, based on the total weight of the curable resin composition. It is particularly preferably at least 0.5, more preferably at most 7, particularly preferably at most 5.
[0037]
A polyimide resin as a thermosetting resin comprises a diamine and a tetracarboxylic dianhydride.
As the diamine, the above-mentioned known ones can be used. For example, paraphenylenediamine, 2,2′-bis (4-aminophenoxyphenyl) propane, bis (2- (4-aminophenoxy) ethoxy) ethane and the like can be used. Can be used.
As the tetracarboxylic dianhydride, the above-mentioned known compounds and the like can be used. For example, pyromellitic dianhydride and benzophenonetetracarboxylic dianhydride can be used.
[0038]
The resin having another reactive group as the thermosetting resin includes a compound having a polymerizable double bond and the like, and the above-mentioned known compounds and the like can be used.For example, cyclooctadiene, dicyclopentadiene, methyl Tetrahydroindene, norbornadiene, 2-propenyl-2,5-norbornadiene, norbornene, propenoxyethyl vinyl ether, propenoxypropyl (meth) acrylate, propenoxypropyl vinyl ether, ethylene glycol diallyl ether and the like can be used.
[0039]
As the thermal radical generator, known compounds (such as those described in JP-A-08-134178) can be used, and for example, peroxides, azo compounds, disulfide compounds, and the like can be used.
The content (% by weight) of these thermal radical generators is preferably 0.1 to 10, more preferably 0.3 or more, and particularly preferably 0.5 or more, based on the total weight of the curable resin composition. And more preferably 7 or less, particularly preferably 5 or less.
[0040]
The epoxy resin as the photocurable resin is composed of the above epoxide and a photocuring catalyst.
As the epoxide, the same epoxide or the like as described above can be used.
As the photo-curing catalyst, known cationic polymerization catalysts and the like (such as those described in JP-A-08-134178) can be used. For example, aromatic pyridinium salts, aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts, benzyl Examples thereof include a sulfonium salt, a cinnamyl sulfonium salt and an aromatic selenium salt, and as counter ions thereof, anions such as PF6-, AsF6- and BF4- are used.
The content (% by weight) of these photocuring catalysts is preferably 0.1 to 10, more preferably 0.3 or more, particularly preferably 0.5 or more, based on the total weight of the curable resin composition. And more preferably 7 or less, particularly preferably 5 or less.
[0041]
Other resins having a reactive group as a photocurable resin include a compound having a polymerizable double bond and a photoradical generator.
As the compound having a polymerizable double bond, a compound having a polymerizable double bond similar to the above can be used.
As the photoradical generator, known compounds (such as those described in JP-A-08-134178) can be used, and for example, peroxides, azo compounds, disulfide compounds, and the like can be used.
The content (% by weight) of these photoradical generators is preferably 0.1 to 10, more preferably 0.3 or more, and particularly preferably 0.5 or more, based on the total weight of the curable resin composition. And more preferably 7 or less, particularly preferably 5 or less.
[0042]
These curable resins (A) may be used alone or in combination of two or more. As a combination of two or more, for example, a combination of an epoxy resin and a resin having another reactive group (for example, a combination described in JP-A-2002-80525) and a combination of an epoxy resin and a polyimide resin (for example, 2001-356519) and the like. Of these two or more combinations, it is preferable to combine the epoxy resin with another resin from the viewpoint of cost, dielectric properties, and the like.
[0043]
It is desirable to add the following polymer epoxy resin (A1-1) to these curable resins from the viewpoints of thermal shock resistance and the strength of the cured film. Epoxy compounds having at least two and having a glass transition temperature before curing of 50 to 150 ° C. and a Mw of 10,000 to 1,000,000 are preferred.
The content (% by weight) of the high-molecular epoxy resin (A1-1) is preferably 2 to 70, more preferably 5 or more, particularly preferably 10 or more, based on the total weight of the curable resin. It is preferably at most 50, particularly preferably at most 30. If the content (% by weight) of the polymer epoxy resin (A1-1) is less than 2, there is a problem that the strength of the film is reduced, and if it is more than 70, there is a problem that the complex viscosity of the curable resin composition is increased.
[0044]
As the polymer epoxy resin, known resins such as those described in JP-A-2001-279116 can be used, and a styrene / glycidyl (meth) acrylate copolymer (Mw: 2,000 to 500,000, styrene: 5 to 95% by weight) %), Styrene / glycidyl (meth) acrylate / alkyl (meth) acrylate (Mw: 2,000 to 500,000, styrene: 5 to 95% by weight, alkyl (meth) acrylate: 1 to 40% by weight) copolymer And glycidyl ester type polyepoxides such as polyglycidyl (meth) acrylate.
Among these high-molecular epoxy resins, glycidyl ester type polyepoxide is preferable from the viewpoint of cost and reliability, and styrene / glycidyl methacrylate copolymer and styrene / glycidyl methacrylate / alkyl (meth) acrylate are more preferable from the viewpoint of dielectric properties. It is a copolymer.
As the curing agent, the thermosetting catalyst and the photocuring catalyst for the polymer epoxy resin, the same ones as described above are used, and the respective amounts used are the same as above.
[0045]
It is desirable to add the following thermoplastic resin (Q) to these curable resins (A) from the viewpoint of thermal shock resistance and peel strength with copper plating. That is, as the thermoplastic resin (Q), the absolute value of the difference between the solubility parameters of the polymer epoxy resins (A1-1) and (Q) is 0.5 to 3.0, and the weight average molecular weight is 5 A thermoplastic resin having a molecular weight of from 1,000 to 1,000,000 is preferred.
[0046]
The absolute value of the difference between the solubility parameter (hereinafter abbreviated as SP value) between the polymer epoxy resin (A1-1) and the thermoplastic resin (Q) is 0.5 to 3.0, preferably 0. 0.6-2.5, more preferably 0.7-2.0, particularly preferably 0.8-1.8, even more preferably 0.9-1.5, most preferably 1.0-1. 2. When the solubility parameter is in this range, an insulator excellent in thermal shock resistance is easily obtained, and the peel strength with copper plating is improved.
[0047]
The SP value is represented by the following equation.
SP value (δ) = (ΔH / V) 1/2
Here, in the formula, ΔH represents a molar heat of evaporation (cal), and V represents a molar volume (cm 3). ΔH and V are the total (合計 ei) of the molar evaporation heats (△ ei) of the atomic groups described in “POLYMER ENGINEERING ANDFEBRAUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS.” (Pages 151 to 153). ΔH) and the total volume (V) of the molar volume (△ vi) can be used.
[0048]
(Q) has a weight average molecular weight of 5,000 to 1,000,000, preferably 5,000 to 800,000, more preferably 10,000 to 600,000, and particularly preferably 50,000 to 400. 000, most preferably 60,000 to 100,000. When the weight average molecular weight of (Q) is smaller than 5,000, the resin is dissolved in the curable resin, and the Tg of the cured product of the curable resin is lowered, and the elastic modulus of the cured product is increased. If it is larger than 000, there is a problem that the complex viscosity of the curable resin composition increases.
[0049]
Next, the chemical structure of the thermoplastic resin (Q) will be described.
As (Q), a thermoplastic resin (Q1) having a carbon-carbon double bond and a thermoplastic resin (Q2) having a carbon-nitrogen bond can be used.
Examples of the thermoplastic resin (Q1) having a carbon-carbon double bond include ring-opening polymerization of polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, acrylonitrile-butadiene copolymer, and norbornene. And the like, and can be easily obtained as the following commercial products.
[0050]
Commercially available products (trade names) include, for example, JSR BR series (manufactured by JSR Corporation) as polybutadiene, JSR IR series (manufactured by JSR Corporation) as polyisoprene, and JSR TR series (JSR Corporation) as a styrene-butadiene copolymer. And styrene-isoprene copolymers such as JSRSIS series (manufactured by JSR Corporation) and norbornene ring-opening polymers such as Nosorex series (manufactured by JSR Corporation).
[0051]
Examples of the thermoplastic resin (Q2) having a carbon-nitrogen bond include polyamide, polyurethane, polyurea, polyimide, polyamino acid, and a reaction product (q) between a bifunctional epoxy (p) and a monofunctional primary amine (r). Is used.
[0052]
As the polyamide, a polyamide obtained by reacting a diamine having 2 to 18 carbon atoms with a dicarboxylic acid having 6 to 20 carbon atoms or more is used.
Examples of the diamine include diamine (l) having a primary amino group and diamine (m) having a secondary amino group.
[0053]
As the diamine (l) having a primary amino group, an aliphatic diamine (2 to 18 carbon atoms) (11), an alicyclic polyamine (4 to 15 carbon atoms) (12) and the like can be used.
[0054]
As the aliphatic diamine (11), an alkylenediamine having 2 to 6 carbon atoms, an aromatic diamine containing an aromatic ring (8 to 15 carbon atoms) or the like is used.
Examples of the alkylenediamine include ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, and hexamethylenediamine.
Examples of the aromatic ring-containing aliphatic diamine include xylylenediamine and tetrachloro-p-xylylenediamine.
[0055]
Examples of the alicyclic diamine (12) include 1,3-diaminocyclohexane, isophoronediamine, mensendiamine, and 4,4′-methylenedicyclohexanediamine (hydrogenated methylenedianiline).
[0056]
Examples of the diamine (m) having a secondary amino group include those obtained by replacing the primary amino group (-NH2 group) in (1) with -NH-R (R is an alkyl group having 1 to 4 carbon atoms). Examples thereof include di (methylamino) ethylene, di (ethylamino) hexane, and 1,3-di (methylamino) cyclohexane.
[0057]
Examples of the dicarboxylic acid (n) used in the production of polyamide include divalent aromatic polycarboxylic acids (C6 to C20 or more) (n1) and divalent aliphatic or alicyclic dicarboxylic acids ( (C6-20 or more) (n2) etc. can be used.
Examples of the aromatic dicarboxylic acid (n1) include phthalic acid, isophthalic acid, and terephthalic acid.
Examples of the aliphatic or alicyclic dicarboxylic acid (n2) include hydrogenated aromatic nuclei of aromatic dicarboxylic acid (n1), dimer acid, oxalic acid, maleic acid, succinic acid, adipic acid, dodecenyl succinic acid, and the like. Can be
[0058]
In the reaction for obtaining the polyamide, an amine compound other than diamine, a carboxyl group-containing compound other than dicarboxylic acid, and the like can be used in addition to diamine and dicarboxylic acid for the purpose of adjusting the molecular weight and the like.
[0059]
Examples of the polyurethane as the thermoplastic resin (Q2) having a carbon-nitrogen bond include those obtained from the reaction of a dihydric phenol or dihydric alcohol having 2 to 100 or more carbon atoms with a diisocyanate having 6 to 20 carbon atoms. Used.
[0060]
Examples of the dihydric phenol include bisphenol F, bisphenol A, bisphenol B, bisphenol AD, bisphenol S, halogenated bisphenol A (eg, tetrachlorobisphenol A, etc.), catechin, resorcinol, hydroquinone, 1,5-dihydroxynaphthalene, Dihydroxybiphenyl, octachloro-4,4′-dihydroxybiphenyl, tetramethylbiphenyl, 9,9′-bis (4-hydroxyphenyl) fluorene and the like.
Examples of the dihydric alcohol include ethylene glycol, propylene glycol, tetramethylene glycol, 1,6-hexanediol, polyethylene glycol (Mw 150 to 4,000), polypropylene glycol (Mw 180 to 5,000), and polytetramethylene glycol ( Mw 200 to 5,000), neopentyl glycol, and EO and / or PO (1 to 20 mol) adduct of bisphenol A.
[0061]
As the diisocyanate, an aromatic diisocyanate (o1) having 6 to 20 carbon atoms (excluding the carbon in the NCO group; the same applies hereinafter), an aliphatic diisocyanate (o2) having 2 to 18 carbon atoms, and a 4 to 15 carbon atoms Alicyclic diisocyanate (o3) and araliphatic diisocyanate (o4) having 8 to 15 carbon atoms can be used.
[0062]
Examples of the aromatic diisocyanate (o1) include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), 2,4′- or 4,4′- Diphenylmethane diisocyanate (MDI), 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatodiphenylmethane, Examples thereof include 1,5-naphthylene diisocyanate.
[0063]
Examples of the aliphatic diisocyanate (o2) include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and bis (2-isocyanatoethyl). ) Fumarate, bis (2-isocyanatoethyl) carbonate and 2-isocyanatoethyl-2,6-diisocyanatohexanoate;
[0064]
Examples of the alicyclic diisocyanate (o3) include, for example, isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2 -Isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate.
[0065]
Examples of the araliphatic polyisocyanate (o4) include m- or p-xylylene diisocyanate (XDI).
[0066]
In the reaction for obtaining the polyurethane, an isocyanate compound other than diisocyanate can be used for the purpose of adjusting the molecular weight and the like.
[0067]
As the polyurea as the thermoplastic resin (Q2) having a carbon-nitrogen bond, those obtained from the reaction of a diamine having 2 to 18 carbon atoms and a diisocyanate having 6 to 20 carbon atoms are used.
Examples of the diamine include the diamines described above.
Examples of the diisocyanate include the aforementioned diisocyanates.
[0068]
In the reaction for obtaining polyurea, an amine compound other than diamine or an isocyanate group-containing compound other than diisocyanate can be used for the purpose of adjusting the molecular weight and the like.
[0069]
As the polyimide as the thermoplastic resin (Q2) having a carbon-nitrogen bond, a polyimide obtained by reacting a diamine having 2 to 18 carbon atoms with a dicarboxylic acid having 6 to 20 or more carbon atoms is used.
Examples of the diamine include the diamines described above.
Examples of the dicarboxylic acid include the dicarboxylic acids described above.
In the reaction for obtaining the polyimide, an amine compound other than diamine, a carboxyl group-containing compound other than dicarboxylic acid, or the like can be used for the purpose of adjusting the molecular weight or the like.
[0070]
Examples of the polyamino acid as the thermoplastic resin (Q2) having a carbon-nitrogen bond include a condensate of an aminocarboxylic acid having 2 to 12 carbon atoms and a ring-opening polymer of a lactam having 6 to 12 carbon atoms.
Examples of the aminocarboxylic acid include amino acids (glycine, alanine, valine, leucine, isoleucine, phenylalanine, etc.), ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocaprin Acids, 11-aminoundecanoic acid and 12-aminododecanoic acid.
Examples of the lactam include caprolactam, enantholactam, laurolactam, and undecanolactam.
In the reaction for obtaining a polyamino acid, the above-mentioned diamine compound, another amino compound, the above-mentioned dicarboxylic acid, another carboxyl group-containing compound, or the like can be used for the purpose of adjusting the molecular weight or the like.
[0071]
Examples of the thermoplastic resin (Q2) having a carbon-nitrogen bond include a reaction product (q) of a bifunctional epoxy (p) and a monofunctional primary amine (r).
Examples of the bifunctional epoxy (p) include diglycidyl ether (p1) of dihydric phenol (C6 to C30); dihydric alcohol [alkylene glycol having 2 or more carbon atoms or dihydric phenol having 6 or more carbon atoms] Diglycidyl ether (p2); divalent glycidyl ester (p3); divalent glycidylamine (p4); divalent alicyclic epoxide ( p5) and the like.
In the following description, alkylene oxides having 2 to 4 carbon atoms are abbreviated as AO; ethylene oxide as EO; and propylene oxide as PO.
[0072]
Examples of the diglycidyl ether (p1) of dihydric phenol (C6 to C30) include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, and bisphenol S diglycidyl. Ether, halogenated bisphenol A diglycidyl ether, tetrachlorobisphenol A diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, 1,5-dihydroxynaphthalenediglycidyl ether, dihydroxybiphenyldiglycidyl ether, octachloro -4,4'-dihydroxybiphenyldiglycidyl ether, tetramethylbiphenyldiglycidyl And glycidyl ether obtained from the reaction of 2 mol of bisphenol A with 3 mol of epichlorohydrin.
[0073]
Examples of the diglycidyl ether (p2) of a dihydric alcohol [alkylene glycol having 2 or more carbon atoms or an AO of 1 to 90 mol adduct of dihydric phenol having 6 or more carbon atoms] include ethylene glycol diglycidyl ether and propylene glycol diglycidyl. Ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol (Mw 150 to 4,000) diglycidyl ether, polypropylene glycol (Mw 180 to 5,000) diglycidyl ether, polytetramethylene glycol ( Mw 200-5,000) Diglycidyl ether, neopentyl glycol diglycidyl ether, and a jig of EO and / or PO (total 1-20 mol) adduct of bisphenol A Glycidyl ether and the like.
[0074]
As the divalent glycidyl ester (p3), for example, the following (p31) to (p32) can be used.
(P31) Diglycidyl esters of divalent aromatic polycarboxylic acids (C6 to C20 or more) phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, and the like.
(P32) Diglycidyl esters of divalent aliphatic or alicyclic carboxylic acids (C6 to C20 or more).
(P31) Aromatic nucleus water additive, diglycidyl dimer acid ester, diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate, diglycidyl pimerate and the like.
[0075]
As the divalent glycidylamine (p4), for example, the following (p41) to (p43) can be used.
(P41) Examples of the diglycidyl aromatic amine having two glycidyl groups (aromatic amine having 6 to 20 or more carbon atoms) include N, N-diglycidylaniline and N, N-diglycidyltoluidine.
[0076]
(P42) Examples of the polyglycidyl alicyclic amine having two glycidyl groups (alicyclic amine having 6 to 20 or more carbon atoms) include N, N, N ′, N′-tetraglycidylxylylenediamine. Hydrogenated compounds and the like.
(P43) Examples of the diglycidyl heterocyclic amine having two glycidyl groups (heterocyclic amine having 6 to 20 carbon atoms or more) include N-glycidyl-4-glycidyloxypyrrolidone.
[0077]
As the divalent alicyclic epoxide (p5), for example, an alicyclic epoxide having 6 to 50 or more carbon atoms, Mw of 98 to 5,000, and 2 epoxy groups can be used, and for example, vinylcyclohexene Dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxy dicyclopentyl ether, and the like.
Of these (p), (p2) is preferable from the viewpoint of reducing the elastic modulus of the reactant (q), and (p1) and (p2) from the viewpoint of adjusting the glass transition temperature of the reactant (q). Particularly preferred is the combination of
[0078]
As a reactant (q) as a thermoplastic resin (Q2) having a carbon-nitrogen bond, as a monofunctional primary amine (r) as a reaction partner of a bifunctional epoxy (p), for example, one having 1 to 18 carbon atoms Examples thereof include an aliphatic amine (r1) and an aromatic amine (r2) having 6 to 18 carbon atoms.
Examples of the aliphatic amine (r1) include methylamine, dimethylamine, methylbutylamine, undecylamine, decalylamine, and octadecylamine.
Examples of the aromatic amine (r2) include aniline, p-methylaniline, p-undecylaniline, m-methoxyaniline, and naphthylamine.
(R) is preferably (r1) from the viewpoint of lowering the elastic modulus of the reactant (q).
[0079]
As a reaction product (q) of the bifunctional epoxy and the monofunctional primary amine, one or more of (p1) and (p2) is used as the bifunctional epoxy (p), and (r1) is used as the monofunctional primary amine. Are preferred.
In the reaction between the bifunctional epoxy and the monofunctional primary amine, an epoxy group-containing compound other than those described above, an amine compound, and the like can be used for the purpose of adjusting the molecular weight and the like.
[0080]
Among these thermoplastic resins (Q), from the viewpoint of the dielectric constant, a thermoplastic resin (Q1) having a carbon-nitrogen bond and a reaction product (q) of a bifunctional epoxy and a monofunctional primary amine are preferable. More preferred are polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, norbornene ring-opening polymer, and reaction product of bifunctional epoxy and monofunctional primary amine.
[0081]
The content of the carbon-carbon double bond or carbon-nitrogen bond in (Q) is from 5 × 10 −5 to 3.5 × 10 −2 mol / g per 1 g of (Q) from the viewpoint of adhesion and the like. g is preferable, in the case of a carbon-carbon double bond, more preferably 1.0 × 10 −4 to 3.5 × 10 −2 mol / g, and in the case of a carbon-nitrogen bond, 1 × 10 −4 to 3.5 × 10-2 mol / g is more preferred. In particular, from the viewpoint of the dielectric constant, the ratio is preferably 1.0 × 10 −3 to 2.5 × 10 −2 mol / g in the case of a carbon-carbon double bond, and 5 × 10 −4 to 2.0 in the case of a carbon-nitrogen bond. 5 × 10−2 mol / g is preferred.
[0082]
When the content of the carbon-carbon double bond or the carbon-nitrogen bond is less than this range, the thermoplastic resin on the surface of the insulating layer is hardly eluted by the oxidizing agent, so that it is difficult to form fine irregularities, and the adhesion to the electroless plating. Properties tend not to be good. On the other hand, if it exceeds this range, the heat resistance of the cured product tends to deteriorate.
The carbon-carbon double bond or carbon-nitrogen bond may be present in either the main chain skeleton or the side chain skeleton of the resin as long as it is present in (Q), but is present in the main chain skeleton of the resin. Is preferred.
[0083]
The weight ratio of (A1-1) to (Q) is preferably from 40/60 to 98/2 as a weight ratio in terms of pure content excluding the solvent, and more preferably from 50/50 to from the viewpoint of resin strength. 96/4, from the viewpoint of heat resistance, particularly preferably 55/45 to 90/10, most preferably 60/40 to 85/15.
[0084]
When the curable resin contains (Q), it is preferable that (Q) is uniformly dispersed in (A1-1).
[0085]
When (Q) is dispersed in (A1-1), the dispersion average particle size of (Q) is not particularly limited, but is preferably 0.001 to 50 μm, and further from the viewpoint of resin strength, It is preferably from 0.005 to 20 μm, particularly preferably from 0.01 to 10 μm, and particularly preferably from 0.05 to 5 μm, most preferably from 0.1 to 2 μm from the viewpoint of adhesion. If the dispersion average particle size of (Q) is smaller than 0.001, there is a problem that the adhesion between the cured product of the curable resin and the copper plating is reduced, and if it is larger than 50, the elastic modulus of the curable resin and the cured product is reduced. There are problems such as an increase in the size and a decrease in adhesion of the cured product to copper plating.
The dispersion average particle diameter is obtained by subjecting the curable resin composition to a curing treatment at 180 ° C. for 3 hours, observing the cross section with a scanning electron microscope, and calculating the arithmetic average of the particle diameters of at least 10 (Q) particles. Desired.
[0086]
The content (% by weight) of the curable resin is preferably from 25 to 66, more preferably from 30 to 66, based on the weight of the curable resin composition, from the viewpoint of smoothness and mechanical strength around the through-hole opening. 62, particularly preferably 40 to 57. That is, the content (% by weight) of the curable resin is preferably 25 or more, more preferably 30 or more, particularly preferably 40 or more, and preferably 66 or less, based on the weight of the curable resin composition. It is more preferably 62 or less, particularly preferably 57 or less.
[0087]
Additives added as needed include, for example, flame retardants, thickeners, defoamers, leveling agents, and adhesion promoters. As the flame retardant, known flame retardants such as phosphorus-based flame retardants and halogen-based flame retardants (the above-mentioned patent publications) can be used. When a flame retardant is used, the addition amount (% by weight) of the flame retardant is preferably from 0.5 to 30 based on the total weight of the curable resin composition, and more preferably from the viewpoint of exhibiting flame retardancy. 1 to 15, particularly preferably 2 to 10. That is, in this case, the addition amount (% by weight) of the flame retardant is preferably 0.5 or more, more preferably 1 or more, particularly preferably 2 or more, based on the total weight of the curable resin composition. It is preferably 30 or less, more preferably 15 or less, and particularly preferably 10 or less.
[0088]
As the thickener, known thickeners such as asbestos and benton (the above patent publications and the like) can be used. When a thickener is used, the amount (% by weight) of the thickener is preferably 0.01 to 5, more preferably 0.1 to 4, and particularly preferably 0.1 to 4, based on the total weight of the curable resin composition. Preferably it is 0.5-3. That is, in this case, the addition amount (% by weight) of the thickener is preferably 0.01 or more, more preferably 0.1 or more, and particularly preferably 0.5 or more, based on the total weight of the curable resin composition. The number is preferably 5 or less, more preferably 4 or less, and particularly preferably 3 or less.
[0089]
As the antifoaming agent, known antifoaming agents such as silicone-based antifoaming agents, polyether-based antifoaming agents, alcohol-based antifoaming agents, and oil-based antifoaming agents can be used. When an antifoaming agent is used, the amount (% by weight) of the antifoaming agent is preferably from 0.01 to 5, more preferably from 0.1 to 4, based on the total weight of the curable resin composition. Preferably it is 0.5-3. That is, in this case, the addition amount (% by weight) of the defoaming agent is preferably 0.01 or more, more preferably 0.1 or more, and particularly preferably 0.5 or more, based on the total weight of the curable resin composition. The number is preferably 5 or less, more preferably 4 or less, and particularly preferably 3 or less.
[0090]
As the leveling agent, known leveling agents such as a silicone leveling agent, a polyether-based leveling agent, and an alcohol-based leveling agent (the above-mentioned patent publications) can be used. When a leveling agent is used, the amount (% by weight) of the leveling agent is preferably from 0.01 to 10, more preferably from 0.1 to 7, and particularly preferably based on the total weight of the curable resin composition. 0.5 to 5. That is, in this case, the amount (% by weight) of the leveling agent is preferably 0.01 or more, more preferably 0.1 or more, and particularly preferably 0.5 or more, based on the total weight of the curable resin composition. And preferably 10 or less, more preferably 7 or less, particularly preferably 5 or less.
[0091]
As the adhesion-imparting agent between the curable resin and the cured product and the substrate or the copper plating, a known adhesion-imparting agent such as a silane coupling agent (the above-mentioned patent publication) can be used. When the adhesion-imparting agent is used, the amount (% by weight) of the adhesion-imparting agent is preferably from 0.01 to 10, more preferably from 0.1 to 7, based on the total weight of the curable resin composition. Particularly preferably, it is 0.5 to 5. That is, in this case, the addition amount (% by weight) of the adhesion promoter is preferably 0.01 or more, more preferably 0.1 or more, and particularly preferably 0.5 or more, based on the total weight of the curable resin composition. The number is preferably 10 or less, more preferably 7 or less, and particularly preferably 5 or less.
[0092]
The curable resin composition can be obtained by uniformly mixing a filler, a curable resin, and additives to be added as necessary with a known mixing device or the like.
The temperature (° C.) for uniform mixing is usually 0 to 150, preferably 10 to 130, more preferably 20 to 110, and particularly preferably 30 to 100. That is, the temperature (° C.) is usually 0 or higher, preferably 10 or higher, more preferably 20 or higher, particularly preferably 30 or higher, and usually 150 or lower, preferably 130 or lower, and further preferably It is 110 or less, particularly preferably 100 or less. As the mixing device, any device can be used as long as it can mix the filler with the liquid material. For example, a planetary mixer, a bead mill, a three-roller, a two-roller and the like can be used. The stirring and mixing time is, for example, a time until most of the aggregates contained in the filler are eliminated (for example, determined while measuring the particle size distribution) and the like, and is appropriately determined. If necessary, the curable resin composition may remove coarse particles and the like by filtration.
[0093]
The curable resin film of the present invention is obtained by dissolving and / or dispersing a curable resin composition in a solvent to form a resin solution (resin dispersion solution), and using the resin solution with a known film manufacturing apparatus such as a roll coater. It can be manufactured by coating on top.
The solvent is not particularly limited as long as it can dissolve and / or disperse the curable resin composition and can adjust the resin solution to have physical properties (viscosity and the like) applicable to a film production apparatus. Known solvents such as pyrrolidone, N, N-dimethylformamide, dimethylsulfoxide, toluene, ethanol, cyclohexanone, methanol, methyl ethyl ketone, ethyl acetate, acetone and xylene can be used. Among these solvents, those having a boiling point of 200 ° C. or less (toluene, ethanol, cyclohexane, methanol, methyl ethyl ketone, ethyl acetate, acetone, and xylene) are preferable from the viewpoint of the drying temperature of the film.
[0094]
The support film used in processing the curable resin film is a support used for the purpose of facilitating the handling of the curable resin film, and may have a certain strength, and a known support film or the like can be used. For example, a polyethylene terephthalate (PET) film, a polypropylene film, a polyethylene film, and the like can be used.
[0095]
The thickness (μm) of the curable resin film of the present invention is preferably 1 to 100, more preferably 5 to 80, and particularly preferably 10 to 60. That is, the thickness (μm) of the curable resin film of the present invention is preferably 1 or more, more preferably 5 or more, particularly preferably 10 or more, and preferably 100 or less, more preferably 80 or less, and particularly preferably. Is 60 or less.
[0096]
The amount (% by weight) of the residual solvent after drying of the curable resin film of the present invention is determined from the viewpoint of the penetration of the curable resin film into the through-holes and the handling (cracking of the film). Based on the weight before curing), it is preferably 0.1 to 5.0, more preferably 0.2 to 4.0, and particularly preferably 0.3 to 3.0. That is, the amount (% by weight) of the residual solvent after curing (drying) of the curable resin film of the present invention is preferably 0.1 or more, more preferably 0, based on the weight of the curable resin film (before curing). 0.2 or more, particularly preferably 0.3 or more, and preferably 5.0 or less, more preferably 4.0 or less, particularly preferably 3.0 or less. If the amount of the residual solvent is too large, voids or the like are likely to be generated in the through holes when the curable resin film is cured, and if the amount of the residual solvent is too small, the handling (cracking of the film) of the curable resin film is performed. Tends to worsen.
[0097]
In addition, this residual solvent amount is measured by the following method.
The curable resin film applied and manufactured on the support film is cut out to 10 cm × 10 cm together with the support film without peeling the support film, and used as a measurement sample, and its weight (W1) is measured. The weight (W2) of a separately prepared support film of 10 cm × 10 cm is measured. The measurement sample and the 10 cm × 10 cm support film are each dried by a circulating drier at 150 ° C. for 10 minutes. The weight (W3) of the measurement sample after drying and the weight (W4) of the support film are measured, and a value calculated from the following equation is obtained. The average value of the five measurements is taken as the residual solvent amount.
Residual solvent amount = (1- (W3-W4) / (W1-W2)) × 100 [%]
[0098]
The cured product of the present invention can be easily produced by thermally curing the above curable film.
The conditions for the heat curing are as follows: 80 to 250 ° C (preferably 120 to 200 ° C, more preferably 150 to 200 ° C) for 0.1 to 15 hours (preferably 0.2 to 5 hours, more preferably 0.1 to 5 hours). 5 to 3 hours).
[0099]
The boiling water absorption of the cured product of the present invention is 3.00 to 0.001%, preferably 2.50 to 0.005%, more preferably 2.00 to 0.01%, and particularly preferably 1. 0 to 0.05%.
The boiling water absorption is measured in accordance with JIS K7209 (2000) 6.3B method.
The cured product of the present invention has a volume resistance of 10 ¹⁰ -10 ¹⁹ Ω / cm, preferably 10 ¹² ~ 5 × 10 ¹⁸ Ω / cm, more preferably 10 ¹⁴ -10 ¹⁸ Ω / cm, particularly preferably 10 ¹⁶ ~ 5 × 10 ¹⁷ Ω / cm, which is excellent in electrical insulation as compared with conventionally used insulating materials such as epoxy resin and polyimide resin.
The volume resistance is measured according to JIS K6011 (1995).
[0100]
The heat resistance of the cured product of the present invention is the same as that of a conventional insulator, and even if it is brought into contact with a solder at 300 ° C. for 1 minute, no abnormality such as sagging of the pattern, breakage and blistering is observed, and it is resistant to various solvents. The chemical resistance is also very good.
The cured product of the present invention is also excellent in 10% sulfuric acid resistance, 10% hydrochloric acid resistance, 10% nitric acid resistance and 10% sodium hydroxide resistance as measured by the method specified in JIS K6911 (1995) 5.32. .
[0101]
As a method of using the curable film of the present invention as an insulator, for example, when used as an interlayer insulating material, after laminating the curable film of the present invention to a substrate, hot pressing, after heat curing, necessary In accordance with a method of performing roughening, forming a conductive circuit, and the like, further laminating a base material, repeating this operation, and, if necessary, heating and curing to form a multilayer.
When the curable film is used as a part of the substrate material of the multi-layer substrate, after laminating the curable film to the base material, hot pressing, performing processing such as drilling as necessary, and repeating this operation. Finally, a method of forming a multilayer by heating and curing is exemplified.
In addition, it can also be used as a printed wiring board as it is, without using a base material.
[0102]
When used as an interlayer insulating material such as a multilayer circuit board of an electronic circuit, one interlayer insulating layer may be composed of a single layer or multiple layers, and its thickness (after curing) is preferably 1 to 100 μm, more preferably 15 to 100 μm. 50 μm.
[0103]
The conditions of the hot press include a temperature of 25 to 180 ° C. (preferably 50 to 150 ° C.), a pressure of 0.01 MPa to 10 MPa (preferably 0.1 to 1 MPa), and a time of 1 to 1200 seconds (preferably 10 to 300 seconds). Are preferred.
Holes (via holes, through holes, etc.) for conducting between the layers of the multilayer substrate can be formed by a usual method, and for example, a method using a laser (carbon dioxide, YAG, excimer, etc.), a drill or the like can be used.
Roughening can be performed by a usual method, for example, a method described in JP-B-6-49852 can be used.
The conductive circuit can be formed by an ordinary method, for example, a sputtering method, an electroless method, or the like can be used.
[0104]
The insulator made of the cured product of the curable film of the present invention can be widely used as an insulator, for example, suitable as an overcoat material, an interlayer insulating material, a printed circuit board, and the like, and particularly as an overcoat material and an interlayer insulating material. It is suitable.
It is most suitable as an overcoat material or an interlayer insulating material for electronic devices (semiconductor devices, light emitting diodes, various memories, etc.), hybrid ICs, MCMs, electric wiring circuit boards or display components.
[0105]
Furthermore, the curable resin film of the present invention is suitable as a through-hole filling agent and interlayer insulating material in a build-up substrate manufacturing process. When applied to this application, since the smoothness around the through-hole opening is extremely high, even if the through-hole is filled and the interlayer insulating layer is formed at the same time, the decrease in the yield of the conductor circuit formation in the next step is extremely small. In addition, a substrate in which the curable resin film of the present invention is used to fill a through hole and form an interlayer insulating layer at the same time is suitable for use as a printed wiring board by a build-up method. And the printed wiring board by such a build-up method is used for electric products such as a personal computer, a camera-integrated VTR, a digital video camera, a mobile phone, a car navigation system, and a digital camera.
[0106]
【Example】
Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Unless otherwise specified, parts mean parts by weight and% means% by weight.
[0107]
<Synthesis Example 1> Production of Styrene / Glycidyl Methacrylate Copolymer Solution (X1) 5 parts of methyl ethyl ketone (hereinafter referred to as MEK) was charged into a reaction vessel replaced with nitrogen, and the temperature was raised to 80 ° C. 20 parts of glycidyl methacrylate (hereinafter referred to as GMA) uniformly dissolved in the replaced container, 20 parts of styrene (hereinafter referred to as St), 5 parts of 2-ethylhexyl acrylate (hereinafter referred to as 2EHA), 20 parts of MEK and azo A mixture consisting of 1.5 parts of bisisobutyronitrile was dropped into the reaction vessel over 4 hours.
After completion of the dropwise addition, the mixture was aged at 100 ° C. for 5 hours to obtain a GMA / St / 2EHA copolymer.
The Mw (molecular weight in terms of polystyrene measured by GPC) of this copolymer was 30,000, and the glass transition temperature was 58 ° C. The calculated SP value of the GMA / St / 2EHA copolymer having this ratio is 10.7. The epoxy equivalent (measured according to JIS K7236) of this copolymer was 320.
This copolymer was diluted with MEK so that the solid content became 50%, to obtain a polymer epoxy resin solution (X-1) of the present invention.
[0108]
<Synthesis Example 2> Production of styrene / glycidyl methacrylate copolymer solution (X2) in which SBS resin is dispersed
Except that 30 parts of a styrene-butadiene copolymer (JSR-TR2250 manufactured by JSR Corporation; hereinafter abbreviated as SBS resin) is further added to the mixture to be dropped, in the same manner as in Synthesis Example 1, except that the SBS resin-dispersed GMA / An St / 2EHA copolymer was obtained.
The epoxy equivalent of the GMA / St / 2EHA copolymer in which the obtained SBS resin was dispersed was 527 (measured according to JIS K7236). The Mw of the SBS resin, which is a thermoplastic resin used here, is 115,000 (molecular weight in terms of polystyrene measured by GPC), and the calculated SP value is 9.3. The calculated SP value of the GMA / St / 2HEA copolymer having this ratio is 10.7.
The resulting styrene / glycidyl methacrylate copolymer in which the SBS resin is dispersed is diluted using MEK so that the solid content becomes 50%, and a polymer epoxy resin solution in which the thermoplastic resin of the present invention is dispersed. (X-2) was obtained.
[0109]
<Example 1>
6.6 parts of the resin solution (X-1) obtained in Synthesis Example 1, 15 parts of a glycidyl ether type epoxy resin (Epicoat 152, manufactured by Japan Epoxy Resin Co., Ltd.), and silicon oxide powder (Admafine SO-E2 manufactured by Admatech, Inc.) 45 parts of a phenolic curing agent (phenol novolak resin, PSM-4326 manufactured by Gunei Chemical Co., Ltd.), and an epoxy ring-opening catalyst (manufactured by San Apro, SA) -102) 1 part was added to 19 parts of MEK to obtain a resin solution.
Next, this resin solution was applied to a 50 μm-thick PET film (600 mm × 600 mm) by a roll coater so that the resin thickness after drying became 50 μm, and then dried at 90 ° C. for 7 minutes to obtain a curable resin. Film (C-1) was obtained.
[0110]
Then, for the curable resin film (C-1), the tensile strength after curing, the tensile elongation after curing, the linear expansion coefficient after curing, the reaction heat at the time of the curing reaction, and the complex viscosity are measured, and these values are determined. The results are shown in Table 1.
[0111]
Further, a curable resin film (C-1) was pressure-bonded to both sides of a copper-clad BT resin substrate having a thickness of 300 μm and a thickness of 800 μm, in which 100 through holes were opened, using a vacuum pressure-bonding machine.
The copper-clad BT resin substrate used here was manufactured by Mitsubishi Gas Chemical Industry Co., Ltd. under the trade name of CCL-HL830. × 10 holes), and the front and back surfaces of the copper surface were roughened by 2 μm (treated with MEC etch bond CZ-8100 manufactured by MEC Corporation). The vacuum compression bonding was performed using a pressure type vacuum laminator V130 manufactured by Nichigo Morton Co., Ltd. at a pressure of 80 ° C., 0.8 kgf / cm 2, and a degree of vacuum of 2 mmHg or less. After allowing the substrate on which the film was pressed to cool to 30 ° C., the PET film was peeled off. This substrate was cured at 170 ° C. for 90 minutes to obtain a substrate (D-1) in which the through-hole filling and the interlayer insulating layer were simultaneously formed.
With respect to this substrate (D-1), the filling property of the through hole and the smoothness around the opening of the through hole were evaluated, and the results are shown in Table 1.
[0112]
<Example 2>
Example 1 Example 1 was repeated except that the number of parts used was changed to 7.8 parts of the resin solution (X-1), 19 parts of a glycidyl ether type epoxy compound, 36 parts of silicon oxide, and 12 parts of a phenolic curing agent. In the same manner as in the above, a curable resin film (C-2) and a substrate (D-2) were obtained.
[0113]
<Example 3>
In Example 1, 12 parts of a glycidyl ether-type epoxy compound (Epicoat 154, manufactured by Japan Epoxy Resin) is used instead of the glycidyl ether-type epoxy resin (Epicoat 152, manufactured by Japan Epoxy Resin), and the other components are used. In the same manner as in Example 1 except that the number of parts was changed to 46 parts of silicon oxide and 8 parts of a phenolic curing agent, and 3 parts of a flame retardant (brominated epoxy resin, YDB-500 manufactured by Toto Kasei Co., Ltd.) were added. Thus, a curable resin film (C-3) and a substrate (D-3) were obtained.
[0114]
<Example 4>
In Example 1, the number of parts used was changed to 4.8 parts of the resin solution (X-1), 8 parts of a glycidyl ether type epoxy compound, 80 parts of silicon oxide, 5 parts of a phenolic curing agent, and 38 parts of MEK, respectively. A curable resin film (C-4) and a substrate (D-4) were obtained in the same manner as in Example 1 except that 2 parts of a flame retardant (brominated epoxy resin, YDB-500 manufactured by Toto Kasei) was added. .
[0115]
<Example 5>
In Example 1, 23 parts of a glycidyl ether-type epoxy compound (Epicoat 154, manufactured by Japan Epoxy Resin) was used in place of the glycidyl ether-type epoxy resin (Epicoat 152, manufactured by Japan Epoxy Resin). 13.2 parts of resin solution (X-1), 43 parts of silicon oxide (Admafine, SO-E2 manufactured by Admatech), 15 parts of phenolic hardener, and 32 parts of MEK were changed to a flame retardant (brominated epoxy). A curable resin film (C-5) and a substrate (D-5) were obtained in the same manner as in Example 1, except that 6 parts of resin, YDB-500 (Toto Kasei) was added.
[0116]
<Example 6>
In the same manner as in Example 1 except that 11 parts of the resin solution (X-2) was used instead of the resin solution (X-1), the curable resin film (C-6) and the substrate (D) were used. -6) was obtained.
[0117]
<Example 7>
In the same manner as in Example 2, except that 13 parts of the resin solution (X-2) was used instead of the resin solution (X-1), the curable resin film (C-7) and the substrate (D) were used. -7) was obtained.
[0118]
Example 8
In the same manner as in Example 3 except that 11 parts of the resin solution (X-2) was used instead of the resin solution (X-1), the curable resin film (C-8) and the substrate (D -8) was obtained.
[0119]
<Example 9>
In the same manner as in Example 4 except that 8 parts of the resin solution (X-2) was used instead of the resin solution (X-1), the curable resin film (C-9) and the substrate (D -9) was obtained.
[0120]
<Example 10>
A curable resin film (C-10) and a substrate (D) were prepared in the same manner as in Example 5 except that 8 parts of the resin solution (X-2) was used instead of the resin solution (X-1). -10) was obtained.
[0121]
<Comparative Example 1>
16 parts of a glycidyl ether type epoxy compound (manufactured by Yuka Shell Epoxy, Epicoat 828), 20 parts of a glycidyl ether type epoxy compound (manufactured by Dainippon Ink and Chemicals, Inc., Epicron 7051), and a flame retardant (brominated epoxy resin, manufactured by Toto Kasei Co., Ltd.) YDB-500) 40 parts, silicon oxide (Admafine manufactured by Admatech Co., Ltd., SO-E2) 20 parts and an epoxy ring-opening catalyst (2,4-diamino-6- (2-methyl-1-imidazolylethyl) -1,3). , 5-triazine isocyanuric acid adduct) (4 parts) was added to MEK (100 parts) to obtain a resin solution.
Thereafter, in the same manner as in Example 1, a curable resin film (C-11) and a substrate (D-11) were obtained.
[0122]
<Comparative Example 2>
In Example 1, 14.4 parts of the resin solution (X-1), 35 parts of a glycidyl ether type epoxy compound (Epicoat 152, manufactured by Japan Epoxy Resin Co., Ltd.), and 30 parts of silicon oxide (Admafine, SO-E2 manufactured by Admatech, Inc.) And a phenolic curing agent (phenol novolak resin, PSM-4326 manufactured by Gunei Chemical Industry Co., Ltd.) in the same manner as in Example 1 except that the number of parts used was changed to 22 parts and MEK 27 parts. 12) and a substrate (D-12) were obtained.
[0123]
<Comparative Example 3>
In Example 1, 10 parts of a glycidyl ether-type epoxy compound (Epicoat 154, manufactured by Japan Epoxy Resin) was used instead of the glycidyl ether-type epoxy resin (Epicoat 152, manufactured by Japan Epoxy Resin Co.). In the same manner as in Example 1 except that each of the parts was changed to 75 parts of silicon oxide, 7 parts of a phenolic curing agent, and 38 parts of MEK, and 2 parts of a flame retardant (brominated epoxy resin, YDB-500 manufactured by Toto Kasei Co., Ltd.) were added. Thus, a curable resin film (C-13) and a substrate (D-13) were obtained.
In addition, only in this comparative example, the evaluation of the amount of dent on the through hole was not performed because the embedding property in the through hole was “×”.
[0124]
In addition, each performance evaluation was performed by the following method.
<Tensile strength and tensile elongation after curing>
The measurement sample used was obtained by curing a curable resin film by heating at 170 ° C. for 90 minutes. Using the cured film, tensile strength and tensile elongation after curing were measured according to JIS K7113 (1995).
[0125]
<Coefficient of linear expansion after curing>
As described in detail above, the measurement was performed in accordance with the method specified in 2.4.41.3 of the test method IPC-TM-650 of the American Printed Circuit Industry Association.
The measurement sample used was obtained by curing a curable resin film by heating at 170 ° C. for 90 minutes. The size of the sample is (length) 15 mm x (width) 2 mm x (thickness) 0.040 mm at 25 ° C, and the length and width of the cured film are measured with a caliper. The thickness was measured with a film thickness meter, and each was measured to the order of 0.001 mm. Using TMA / SS6100 manufactured by Seiko Instruments Inc., a 30 mN load was applied to the measurement sample, and the inside of the measurement cell was held at 30 ° C. for 30 minutes. Then, the measurement cell temperature was increased from 30 ° C. to 230 ° C. at 10 ° C./min. The temperature rose.
The length at 30 ° C. was (A) [mm] and the length at 170 ° C. was (B) [mm], and the coefficient of linear expansion (X) was determined by the following equation.
(X) = [(B)-(A)] × 10 ⁶ / [(170-30) × (A)] (2)
[0126]
<Reaction heat during curing reaction>
Using a DSC 6100 manufactured by Seiko Instruments Inc., 5 mg of a curable resin film sample was weighed into an aluminum measuring pan (P / N 52-023C, P / N 52-023P) and held at 30 ° C. for 30 minutes. The temperature was raised to 30 to 270 ° C at 5 ° C / min. The weighed sample weight is defined as S [g], the peak area at 80 to 230 ° C. is obtained from the obtained calorific value-time (temperature) curve, and the total calorific value calculated from this is defined as ΔH [J]. I asked more.
Heat of reaction (Y) = ΔH / S [J / g] (3)
[0127]
<Complex viscosity>
The measurement was performed under the following conditions using ARES manufactured by Rheometric Scientific Hook.
Sample fixing jig: 25 mm diameter aluminum disk (for example, ARES-DP25A manufactured by Rheometric Scientific Hook)
Sample: disk shape with a diameter of 25 mm and a thickness of 0.500 mm
Gap distance: 0.500 mm
Rotational shear stress amplitude: 2 × 10 ^-3 [Rad]
Sinusoidal shear stress frequency: 1.5915 Hz
Temperature rising rate: After holding at 0 ° C. for 20 minutes, the temperature is raised from 0 ° C. to 150 ° C. at 10 ° C./min.
The complex viscosity at 25 ° C. and 80 ° C. was read from the time (temperature) -complex viscosity curve obtained in the measurement, and this was defined as the complex viscosity.
[0128]
<Embeddability of through hole>
The resin shape of the cross section passing through the center of the through hole was visually observed and evaluated according to the following criteria.
○: The inside of the through hole is filled with resin
×: Part of the through hole is not filled with resin
[0129]
<Smoothness around through hole opening>
Using a shape measuring microscope (manufactured by KEYENCE CORPORATION, ultra-depth shape measuring microscope VK-8550), the center position of the resin surface of the through-hole opening and 150 μm outside from the outer diameter of the through-hole opening. The height difference of the resin surface was measured for ten through holes, and the average value of these height differences (amount of dents) was used as an index of smoothness.
[0130]
[Table 1]

[0131]
[Table 2]

[0132]
[Table 3]

[0133]
In the results shown in Tables 1 to 3, all of the cured products of Examples have smoothness indices of 2.5 μm or less, whereas Comparative Examples 1 and 2 show values with large smoothness and are insufficient. It is.
In addition, all of the cured products of Examples have good through hole embedding properties, but Comparative Example 3 has a large complex viscosity at 25 ° C. and poor through hole embedding properties.
From these comparisons, it is clear that all of the examples of the present invention can simultaneously achieve the through hole filling property, sufficiently small smoothness and surface roughness, and are superior to the comparative examples.
[0134]
【The invention's effect】
By using the cured resin film of the present invention, it is possible to fill the through holes and to form the interlayer insulating layer at the same time, and it is possible to manufacture a build-up multilayer printed wiring board using this. Therefore, it can be provided by one kind of curable resin film of a filling material for through holes and an interlayer insulating material. Therefore, it is not necessary to control the positioning accuracy and the amount of the filling agent applied in the filling process. Further, a polishing step is not required.

Claims (13)

The linear expansion coefficient (X) [ppm] after curing measured by thermomechanical analysis and the reaction heat (Y) [J / g] at the time of curing reaction measured by differential scanning calorimetry are represented by the formula ( A curable resin film which satisfies 1) and has a complex viscosity at 25 ° C of 10,000 to 100,000 Pa · s.
Y ≦ −2.67X + 374 (1) The curable resin film according to claim 1, wherein the complex viscosity at 80 ° C. is 100 to 5,000 Pa · s. The curable resin film according to claim 1, wherein the curable resin film is used as a hole filling / interlayer insulating material for simultaneously filling a through hole and forming an interlayer insulating layer. The curable resin film according to any one of claims 1 to 3, comprising a curable resin composition comprising a curable resin (A), a filler (B), and an additive (C) added as needed. The curable film according to claim 4, wherein the curable resin (A) is an epoxy resin (A1). The curable resin film according to claim 4, wherein the content of the filler (B) is 34 to 85% by weight based on the weight of the curable resin film. As a curable resin, a polymer epoxy resin having at least two epoxy groups in a molecule, a glass transition temperature before curing of 50 to 150 ° C., and a weight average molecular weight of 10,000 to 1,000,000 ( The curable resin film according to any one of claims 4 to 6, comprising A1-1). The curable resin film according to claim 7, wherein the polymer epoxy resin (A1-1) is contained in an amount of 2 to 70% by weight based on the total weight of the curable resin (A). It further contains a thermoplastic resin (Q), and the absolute value of the difference between the solubility parameters of the high-molecular epoxy resin (A1-1) and (Q) is 0.5 to 3.0. The curable resin film according to claim 7, wherein the weight average molecular weight is 5,000 to 1,000,000. The resin film according to claim 9, wherein the thermoplastic resin (Q) is dispersed in the curable resin composition, and has an average dispersed particle size of 0.01 to 10 m. The curable resin film according to any one of claims 4 to 10, wherein the filler (B) is a silicon oxide having a volume average particle diameter of 0.01 to 50 µm. A cured product obtained by curing the curable resin film according to claim 1. An insulator comprising the cured product according to claim 12.