JP6816566B2 - Resin compositions, adhesive films, prepregs, multilayer printed wiring boards and semiconductor devices - Google Patents

Description

The present invention relates to resin compositions, adhesive films, prepregs, multilayer printed wiring boards and semiconductor devices.

In recent years, the miniaturization and high performance of electronic devices have progressed, and in multi-layer printed wiring boards, the build-up layer is multi-layered, and there is a demand for finer wiring and higher density.
The insulating layer used for such a build-up layer is required to have an adhesive force so that the conductor layer constituting the circuit pattern does not peel off from the insulating layer.
In order to increase the adhesive force between the conductor layer and the insulating layer, for example, it is effective to increase the roughened shape of the interface between the conductor layer and the insulating layer. However, from the viewpoint of wiring formability and electrical characteristics, it is preferable that the roughened shape of the interface is small, and improvement of the adhesive force by another method is required.

Various efforts have been made to meet such demands. For example, Patent Document 1 discloses an epoxy resin and a resin composition containing an active ester curing agent containing a phosphorus atom. It is described that the insulating layer formed by this resin composition has a small arithmetic mean roughness (Ra) on the surface of the insulating layer, and a plated conductor layer having sufficient peel strength can be formed on the insulating layer.

Japanese Unexamined Patent Publication No. 2012-251133

Here, in the resin composition disclosed in Patent Document 1, the insulating layer formed by the resin composition is roughened, and the insulating layer after the roughening is plated. To form a plated conductor layer, and when an insulating layer is formed on a conductor layer having a small surface arithmetic mean roughness (Ra), the adhesiveness with the conductor layer (hereinafter, also referred to as "peel strength"). It was not considered from the viewpoint of improving.
The problem to be solved by the present invention is to use a resin composition capable of forming an insulating layer having excellent peel strength on a conductor layer having a small surface arithmetic mean roughness (Ra), the resin composition. It is to provide an adhesive film, a prepreg, a multilayer printed wiring board, and a semiconductor device.

As a result of diligent studies to solve the above problems, the present inventors have found that the above problems can be solved by a resin composition containing an epoxy resin and a curing agent having a specific functional group, and have found that the present invention can be solved. It came to be completed.
That is, the present invention provides the following [1] to [15].
[1] A resin composition containing (A) an epoxy resin and (B) a curing agent having an amino group and a carboxy group.
[2] The component (B) contains a divalent aromatic group, one of which is bonded to an amino group or a group containing an amino group, and the other bonding group is carboxy. The resin composition according to the above [1], wherein a group containing a group or a carboxy group is bonded.
[3] The resin composition according to the above [1] or [2], wherein the component (B) contains a sulfur atom.
[4] The resin composition according to any one of the above [1] to [3], wherein the component (B) is represented by the following general formula (1).

(In the formula, R ¹ and R ² each independently represent a single bond or a divalent organic group.)

[5] A divalent hydrocarbon group in which R ¹ and R ² in the general formula (1) are independently selected from the group consisting of an alkylene group, an alkenylene group and an alkynylene group, and the divalent hydrocarbon. The resin composition according to the above [4], which is a divalent group in which a group is combined with an ether bond or a sulfide group, or a single bond.
[6] The resin composition according to the above [4], wherein R ² in the general formula (1) is a divalent organic group containing a sulfide group.
[7] The contents of the component (B) are 1 to 30 parts by mass with respect to 100 parts by mass of the non-volatile content (excluding the inorganic filler) in the resin composition. The resin composition according to any one of [6].
[8] The resin composition according to any one of the above [1] to [7], which further contains (C) a curing accelerator.
[9] The resin composition according to any one of the above [1] to [8], which further contains (D) a phenoxy resin.
[10] Ratio of the total number of active hydrogen to the epoxy group of the curing agent having (B) amino group and carboxy group to the total number of epoxy groups of (A) epoxy resin in the resin composition [active hydrogen / epoxy group] ] Is 0.2 to 2, the resin composition according to any one of the above [1] to [9].
[11] The resin composition according to any one of the above [1] to [10], wherein the peel strength of the cured product is 0.32 kN / m or more with respect to a copper foil having an arithmetic mean roughness (Ra) of 200 nm. Stuff.
[12] An adhesive film formed by forming a layer of the resin composition according to any one of the above [1] to [11] on a support.
[13] A prepreg obtained by impregnating a sheet-shaped reinforcing base material with the resin composition according to any one of the above [1] to [11].
[14] A multilayer printed wiring board containing a cured product of the resin composition according to any one of the above [1] to [11].
[15] A semiconductor device using the multilayer printed wiring board according to the above [14].

According to the present invention, a resin composition capable of forming an insulating layer having excellent peel strength on a conductor layer having a small surface arithmetic mean roughness (Ra), an adhesive film using the resin composition, and the like. Prepregs, multilayer printed wiring boards and semiconductor devices can be provided.

[Resin composition]
The resin composition of the present invention contains (A) an epoxy resin and (B) a curing agent having an amino group and a carboxy group.
Hereinafter, each component constituting the resin composition of the present invention will be described.

<(A) Epoxy resin>
The epoxy resin (A) (hereinafter, also referred to as “component (A)”) is not particularly limited, but an epoxy resin having two or more epoxy groups in one molecule is preferable, and three or more epoxys in one molecule. An aromatic epoxy resin having a group and solid at a temperature of 20 ° C. is more preferable. The aromatic epoxy resin in the present invention means an epoxy resin having an aromatic ring structure in its molecule.
As the epoxy resin (A), one type may be used alone, or two or more types may be used in combination.

Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin and other bisphenol type epoxy resins; phenol novolac type epoxy resin, cresol novolac type epoxy. Novolak type epoxy resin such as resin, biphenyl aralkyl novolac type epoxy resin; epoxy resin containing naphthalene skeleton such as naphthol type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin; glycidylamine type epoxy resin, tert-butyl -Catecor type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, Examples thereof include a trimethylol type epoxy resin, a halogenated epoxy resin, and a glycidyl ester type epoxy resin.
Among these, from the viewpoint of improving heat resistance, insulation reliability and peel strength, bisphenol A type epoxy resin, biphenyl aralkylnovolac type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, naphthylene ether type Epoxy resins, epoxy resins having a butadiene structure, and glycidyl ester type epoxy resins are preferable, and biphenyl aralkylnovolac type epoxy resins are more preferable.
Examples of the biphenyl aralkyl novolac type epoxy resin include compounds having a structural unit represented by the following general formula (2), and compounds represented by the following general formula (3) are preferable.

(In the formula, R ³ represents a hydrogen atom or a methyl group.)

(Wherein, R ³ is as defined above, m. A plurality of R ³ each other an integer of 1 to 20 may being the same or different.)

As the epoxy resin (A), a commercially available product may be used. Examples of the commercially available (A) epoxy resin include "jER (registered trademark) 828EL", "YL980" and "828US" manufactured by Mitsubishi Chemical Corporation, which are bisphenol A type epoxy resins; bisphenol F type epoxy resins. "JER (registered trademark) 806H" and "YL983U" manufactured by Mitsubishi Chemical Co., Ltd .; "HP4032", "HP4032D", "HP4032SS" and "EXA4032SS" manufactured by DIC Co., Ltd., which are naphthalene type bifunctional epoxy resins; "HP4700" and "HP4710" manufactured by DIC Co., Ltd., which are tetrafunctional epoxy resins; "ESN-475V" manufactured by Toto Kasei Co., Ltd., which is a naphthol type epoxy resin; Daicel Chemical Industry Co., Ltd., which is an epoxy resin having a butadiene structure. "PB-3600"; "NC-3000-H", "NC-3000-L" and "NC-3100" manufactured by Nippon Kayaku Co., Ltd., which are epoxy resins having a biphenyl structure, and Mitsubishi Chemical Co., Ltd. "YX4000", "YX4000H", "YX4000HK" and "YL6121"; "YX8800" manufactured by Mitsubishi Chemical Co., Ltd., which is an anthracene type epoxy resin; "EXA-" manufactured by DIC Co., Ltd., which is a naphthylene ether type epoxy resin. 7310 ”,“ EXA-7311 ”,“ EXA-7311L ”and“ EXA7311-G3 ”;“ EX711 ”and“ EX721 ”manufactured by Nagase ChemteX Corporation, which are glycidyl ester type epoxy resins, and“ EX721 ”manufactured by Printec Co., Ltd. Examples thereof include "R540".

The epoxy equivalent of the epoxy resin (A) is preferably 50 to 500 g / mol, more preferably 150 to 400 g / mol, and even more preferably 200 to 350 g / mol, from the viewpoint of enhancing heat resistance, low thermal expansion and peel strength.

The content of the epoxy resin (A) in the resin composition of the present invention is a non-volatile component in the resin composition from the viewpoint of enhancing heat resistance, low thermal expansion and peel strength, and improving the elongation rate of the cured product. (However, the inorganic filler is excluded.) With respect to 100 parts by mass, 10 to 80 parts by mass is preferable, 20 to 70 parts by mass is preferable, and 30 to 50 parts by mass is further preferable.
In the present specification, the non-volatile component in the resin composition is a non-volatile component excluding a volatile substance such as a solvent, and is a component that remains without volatilizing when the resin composition is dried. Including liquid, starch syrup-like and wax-like substances at room temperature. Here, the room temperature is 25 ° C. in the present specification.

<(B) Hardener having amino group and carboxy group>
The curing agent (B) having an amino group and a carboxy group (hereinafter, also referred to as “component (B)”) is not particularly limited as long as it has an amino group and a carboxy group.
As the component (B), one type may be used alone, or two or more types may be used in combination.

The number of amino groups contained in one molecule of the component (B) is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1. The amino group contained in the component (B) is preferably a primary amino group or a secondary amino group, and more preferably a primary amino group.
The number of carboxy groups contained in the component (B) is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1.

The component (B) contains a divalent aromatic group, one of which is bonded to an amino group or a group containing an amino group, and the other bonding group is a carboxy group or a carboxy group. It is preferable that the group containing the above is bonded (hereinafter, the compound is also referred to as “component (B) containing an aromatic group”).
Further, it is preferable that the two linking groups of the divalent aromatic group are present at the para position.
Examples of the divalent aromatic group include a phenylene group, a naphthylene group, a biphenylene group, an anthranylene group and the like. Among these, a phenylene group is preferable, and a 1,4-phenylene group is more preferable.
The divalent aromatic group may have a substituent, and the substituent is preferably electron-donating from the viewpoint of increasing the electron density of the amino group and the carboxy group. Examples of the electron-donating substituent include an alkyl group, an amino group, a hydroxyl group and the like.

The amino group and the carboxy group contained in the component (B) may be bonded to the bonding portion of the divalent aromatic group by a single bond, and may be between the amino group and the divalent aromatic group and / or. A divalent organic group may be interposed between the carboxy group and the divalent aromatic group. As the divalent organic group, for example, a divalent hydrocarbon group selected from the group consisting of an alkylene group, an alkenylene group and an alkynylene group, or a combination of the divalent hydrocarbon group and an ether bond or a sulfide group. Divalent groups and the like can be mentioned. The number of carbon atoms of the divalent hydrocarbon group is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 or 2.
Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group and the like. Examples of the alkenylene group include a vinylene group, a propenylene group, a butenylene group and the like. Examples of the alkynylene group include an ethynylene group and a propynylene group.
The divalent organic group may have a substituent, but from the viewpoint of steric hindrance, it is preferable that the number of substituents is small.

The component (B) preferably contains a sulfur atom from the viewpoint of enhancing the chemical bond force with the metal atom, and has a thiol group or a sulfide group from the viewpoint of having a lone electron pair for the sulfur atom to coordinate with the metal. Is more preferable, and it is more preferable to contain a sulfide group.
The thiol group or sulfide group is preferably contained in the divalent organic group. That is, the component (B) is the component (B) containing the aromatic group, and is between the amino group and the divalent aromatic group and / or between the carboxy group and the divalent aromatic group. A divalent organic group is interposed therein, and the divalent organic group is preferably a divalent group in which the divalent hydrocarbon group and the sulfide group are combined, and an alkylenethio group (alkylene thio group). -S-R-; R represents an alkylene group) is more preferable. The carbon number of the alkylene group of the alkylenethio group is as described as the preferable carbon number of the divalent hydrocarbon group.
The alkylenethio group may be present either between the amino group and the divalent aromatic group or between the carboxy group and the divalent aromatic group, but the carboxy group and the divalent aromatic group. It is preferable that the thio group in the alkylene thio group is bonded to the divalent aromatic group, and the alkylene group is bonded to the carboxy group. ..

As the component (B), a compound represented by the following general formula (1) is preferable from the viewpoint of improving the peel strength due to the chemical adhesive force with copper.

(In the formula, R ¹ and R ² each independently represent a single bond or a divalent organic group.)

The divalent organic group represented by R ¹ and R ² in the general formula (1) is between the amino group and the divalent aromatic group and / or between the carboxy group and the divalent aromatic group. It is explained in the same manner as the divalent organic group present in.
That is, as R ¹ and R ² , a divalent hydrocarbon group selected from the group consisting of an alkylene group, an alkenylene group and an alkynylene group, the divalent hydrocarbon group and an ether bond or a sulfide group were combined. It is preferably a divalent group or a single bond. Specific examples of the divalent hydrocarbon group and the preferable number of carbon atoms are as described above.
The divalent organic group is preferably a divalent group containing a thiol group or a sulfide group from the viewpoint of further enhancing the chemical bonding force with the metal atom, and the divalent hydrocarbon group and the sulfide group Is preferably a divalent group in which is combined, and more preferably an alkylenethio group (-S-R-; R indicates an alkylene group). The carbon number of the alkylene group of the alkylenethio group is as described as the preferable carbon number of the divalent hydrocarbon group.
Among these, R ¹ is preferably a single bond.
Further, R ² is preferably a divalent organic group, and preferably contains a sulfide group from the viewpoint of further enhancing the chemical bonding force with the metal atom. From the same viewpoint, R ² is more preferably a divalent group in which the divalent hydrocarbon group is combined with an ether bond or a sulfide group, and the divalent hydrocarbon group and the sulfide group are used. Is more preferably a divalent group in which is combined, and particularly preferably the alkylenethio group.

As the component (B), a known amino acid compound can be used, for example, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-amino-3-methylbenzoic acid, 2-amino. Compounds having an aromatic amino group and an aromatic carboxy group such as -5-methylbenzoic acid, 2-amino-6-methylbenzoic acid, 3,4-diaminobenzoic acid; 3-aminophenylacetic acid, 4-aminophenyl Compounds having aromatic amino groups and aliphatic carboxy groups such as acetic acid, 4-aminohydrosilicic acid (3- (4-aminophenyl) propionic acid), 2- (4-aminophenylthio) acetic acid; 4-( Aminomethyl) Compounds having an aliphatic amino group such as benzoic acid and an aromatic carboxy group; 3-aminopropionic acid, 4-aminobutanoic acid, 5-aminopentanoic acid, 2,5 diaminopentanoic acid, 3-amino-3 -Examples include compounds having an aliphatic amino group such as phenylpropionic acid and an aliphatic carboxy group. Among these, 4-aminohydrosilicic acid and 2- (4-aminophenylthio) acetic acid are more preferable, and 2- (4-aminophenylthio) acetic acid is further preferable, from the viewpoint of increasing the peel strength.

The content of the component (B) in the resin composition of the present invention is 1 to 1 to 100 parts by mass of the non-volatile component (excluding the inorganic filler) in the resin composition from the viewpoint of increasing the peel strength. 30 parts by mass is preferable, 3 to 20 parts by mass is more preferable, and 5 to 15 parts by mass is further preferable.

The ratio [active hydrogen / epoxy group] of the total number of active hydrogens to the epoxy groups of the component (B) to the total number of epoxy groups of the (A) epoxy resin in the resin composition of the present invention is the resin composition. From the viewpoint of improving the mechanical strength and water resistance of the cured product, 0.2 to 2 is preferable, 0.5 to 1.5 is more preferable, and 0.9 to 1.2 is further preferable.
The total number of epoxy groups in the (A) epoxy resin in the resin composition is the value obtained by dividing the solid content mass (g) of each (A) epoxy resin by the epoxy equivalent (g / mol). It is the total value for the epoxy resin, and the total number of active hydrogens of the component (B) is the value obtained by dividing the solid content mass (g) of each component (B) by the active hydrogen equivalent, and all the components (B). It is the total value of. Examples of the active hydrogen contained in the component (B) include active hydrogen derived from an amino group and active hydrogen derived from a carboxy group.

<(C) Curing accelerator>
The resin composition of the present invention preferably further contains (C) a curing accelerator. When the resin composition contains (C) a curing accelerator, the component (A) and the component (B) can be efficiently cured.
The (C) curing accelerator is not particularly limited, and examples thereof include amine-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, phosphonium-based curing accelerators, and metal-based curing accelerators. An imidazole-based curing accelerator is preferable.
(C) As the curing accelerator, one type may be used alone, or two or more types may be used in combination.

The imidazole-based curing accelerator is not particularly limited, but 2-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 1,2-dimethyl imidazole, 2-ethyl-4-methyl imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1- Cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium tri Meritate, 1-cyanoethyl-2-phenylimidazolium trimerite, 2,4-diamino-6- [2'-methylimidazolyl- (1')] -ethyl-s-triazine, 2,4-diamino-6 -[2'-Undecylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s -Triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5 -Dihydroxymethylimidazole, 2-phenyl-4-methyl-5hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium Examples include imidazole compounds such as chloride, 2-methylimidazoline, and 2-phenylimidazolin; an adduct of an imidazole compound and an epoxy resin.

When the resin composition of the present invention contains (C) a curing accelerator, the content thereof is 0.005 with respect to 100 parts by mass of the non-volatile content (excluding the inorganic filler) in the resin composition. ~ 1 part by mass is preferable, 0.01 to 0.5 part by mass is more preferable, and 0.05 to 0.2 part by mass is further preferable. (C) When the content of the curing accelerator is at least the above lower limit value, a sufficient curing rate tends to be obtained, and when it is at least the above upper limit value, the resin composition tends to be excellent in storage stability.

<(D) Phenoxy resin>
The resin composition of the present invention preferably further contains (D) a phenoxy resin. When the resin composition of the present invention contains the (D) phenoxy resin, the mechanical strength of the cured product can be improved, and further, the film molding ability when used in the form of an adhesive film can be improved. ..
Here, "phenoxy resin" is a general term for polymers whose main chain is a polyaddition structure of an aromatic diol and an aromatic diglycidyl ether, and in the present specification, the weight average molecular weight is 10,000. Refers to the above. When the polymer having a heavy addition structure of an aromatic diol and an aromatic diglycidyl ether in the main chain has an epoxy group, those having a weight average molecular weight of 10,000 or more are classified as (D) phenoxy resin and by weight. Those having an average molecular weight of less than 10,000 are classified as (A) epoxy resins.
As the phenoxy resin (D), one type may be used alone, or two or more types may be used in combination.

(D) Phenoxy resin is classified into bisphenol A type phenoxy resin, bisphenol F type phenoxy resin, bisphenol A / bisphenol F mixed type epoxy resin, etc. according to the structure of the main chain skeleton. Among these, bisphenol A type phenoxy resin Is preferable.

The epoxy equivalent of the phenoxy resin (D) is preferably 1,000 to 15,000 g / mol, more preferably 3,000 to 12,000 g / mol, and even more preferably 5,000 to 9,000 g / mol.

The weight average molecular weight of the phenoxy resin (D) is preferably 10,000 to 80,000, more preferably 25,000 to 60,000, and even more preferably 35,000 to 50,000. (D) When the weight average molecular weight of the phenoxy resin is at least the above lower limit value, the effect of improving the film molding ability and the mechanical strength tends to be sufficiently exhibited, and when it is at least the above upper limit value, it is mixed with other resin components. The compatibility tends to be good, and it tends to be suitable for forming high-density fine wiring.
The weight average molecular weight in the present invention is measured by a gel permeation chromatography (GPC) method (in terms of polystyrene). Specifically, the weight average molecular weight by the GPC method is determined by using LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex K-800P / K-804L / K manufactured by Showa Denko KK as a column. -804 L can be measured using chloroform or the like as a mobile phase at a column temperature of 40 ° C. and calculated using a standard polystyrene calibration curve.

When the resin composition of the present invention contains (D) phenoxy resin, the content thereof is 10 to 80% by mass with respect to 100 parts by mass of the non-volatile content (excluding the inorganic filler) in the resin composition. Parts are preferable, 20 to 70 parts by mass is more preferable, and 40 to 60 parts by mass is further preferable. When the content of the phenoxy resin (D) is at least the above lower limit value, the film forming ability and the mechanical strength tend to be improved, and when it is at least the above upper limit value, the increase in the melt viscosity tends to be suppressed.

<(E) Thermoplastic resin>
The resin composition of the present invention may further contain (E) a thermoplastic resin.
As the thermoplastic resin (E), one type may be used alone, or two or more types may be used in combination.
Examples of the thermoplastic resin (E) include polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetherether ketone resin, polyester resin and the like. ..

<(F) Inorganic filler>
The resin composition of the present invention may further contain (F) an inorganic filler. When the resin composition of the present invention contains the (F) inorganic filler, the coefficient of thermal expansion of the obtained insulating layer can be further reduced.
(F) As the inorganic filler, one type may be used alone, or two or more types may be used in combination.
The inorganic filler (F) is not particularly limited, and is, for example, silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride. , Aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate and the like. Among these, silica is preferable from the viewpoint of excellent handleability of varnish and low coefficient of thermal expansion. Examples of silica include amorphous silica, pulverized silica, fused silica, crystalline silica, synthetic silica, hollow silica, and the like, and among these, fused silica is preferable. Further, the silica is preferably spherical. Examples of commercially available spherical molten silica include "SO-C2" and "SO-C1" manufactured by Admatex Co., Ltd.

The average particle size of the inorganic filler (F) is not particularly limited, but is preferably 5 μm or less, more preferably 1 μm or less, and 0.3 μm or less from the viewpoint of forming fine wiring on the insulating layer. More preferred. On the other hand, the lower limit of the average particle size of the (F) inorganic filler is 0 from the viewpoint of preventing the viscosity of the varnish from increasing and the handleability from decreasing when the resin composition is made into a varnish. It is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more.
(F) The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating the particle size distribution of (F) the inorganic filler on a volume basis with a laser diffraction / scattering type particle size distribution measuring device and using the median diameter as the average particle size. As the measurement sample, (F) an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction type particle size distribution measuring device, LA-500, 750, 950 or the like manufactured by HORIBA, Ltd. can be used.

(F) The inorganic filler is a surface treatment agent such as an epoxysilane-based coupling agent, an aminosilane-based coupling agent, a mercaptosilane-based coupling agent, a silane-based coupling agent, an organosilazane compound, and a titanate-based coupling agent. Those that have been treated to improve their moisture resistance are preferable.

When the resin composition of the present invention contains (F) an inorganic filler, the content thereof varies depending on the properties required for the resin composition, but the non-volatile content in the resin composition (however, the inorganic filler is used. Excludes.) With respect to 100 parts by mass, 20 to 85 parts by mass is preferable, 30 to 80 parts by mass is more preferable, and 35 to 75 parts by mass is further preferable. (F) When the content of the inorganic filler is at least the above lower limit value, the coefficient of thermal expansion of the cured product tends to be lowered, and when it is at least the above upper limit value, the hardened product tends to be suppressed from becoming brittle. Peel strength tends to improve.

<Other ingredients>
The resin composition of the present invention may contain other components, if necessary, as long as the effects of the present invention are not impaired. Other components include thermosetting resins other than (A) epoxy resins such as vinylbenzyl compounds, acrylic compounds, maleimide compounds, and blocked isocyanate compounds; organic phosphorus-based flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, and silicones. Flame-retardant agents such as flame-retardants and metal hydroxides; Organic fillers such as silicon powder, nylon powder, and fluorine powder; rubbers such as core-shell type rubber particles, cross-linked acrylonitrile butadiene rubber particles, cross-linked styrene-butadiene rubber particles, and acrylic rubber particles. Particles; Thickeners such as Orben and Benton; Silicone-based, Fluorine-based and Polymer-based defoaming agents or leveling agents; Examples thereof include colorants such as blue, phthalocyanine green, iodin green, disazo yellow, and carbon black.
These other components may be used alone or in combination of two or more.

The method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method in which each of the above components is added with a solvent or the like, if necessary, and mixed using a rotary mixer or the like.

The resin composition of the present invention may be in the state of a varnish containing an organic solvent (hereinafter, also referred to as “resin varnish”) from the viewpoint of increasing the productivity of the adhesive film or the like described later.
Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone and cyclohexanone; acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; carbitol such as cellosolve and butyl carbitol. Kind: Aromatic hydrocarbons such as toluene and xylene; amide-based solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. As the organic solvent, one type may be used alone, or two or more types may be used in combination.
The solid content concentration of the resin varnish is not particularly limited, but is preferably 50 to 90% by mass, more preferably 60 to 80% by mass.

The peel strength of the cured product of the resin composition of the present invention with respect to a copper foil having an arithmetic mean roughness (Ra) of 200 nm is preferably 0.32 kN / m or more, and preferably 0.34 kN / m or more. Is more preferable, and 0.36 kN / m or more is further preferable. The higher the peel strength is, the more preferable it is, but from the viewpoint of ease of manufacture and the like, it may be 1.0 kN / m or less. The peel strength can be measured by the method described in Examples.

<Use of resin composition>
The use of the resin composition of the present invention is not particularly limited, and for example, an insulating resin sheet such as an adhesive film or a prepreg; a circuit board, a solder resist, an underfill material, a die bonding material, a semiconductor encapsulant, a hole filling resin, etc. It can be used in a wide range of applications where a resin composition such as a component-embedded resin is required.
Among these, in the production of a multilayer printed wiring board, it can be suitably used as a resin composition for forming an insulating layer (resin composition for an insulating layer of a multilayer printed wiring board), and a conductor layer is formed by plating. A resin composition for forming a build-up layer (multilayer printing), which can be more preferably used as a resin composition for forming a conductor layer by plating (a resin composition for an insulating layer of a multilayer printed wiring board). It can be more preferably used as a resin composition for a build-up layer of a wiring board).
The resin composition of the present invention can be applied to a circuit board in the state of a varnish to form an insulating layer, but industrially, it is generally used in the form of a sheet-like laminated material such as an adhesive film or a prepreg. preferable. The softening point of the resin composition is preferably 40 to 150 ° C. from the viewpoint of the laminateability of the sheet-like laminated material.

[Adhesive film]
The adhesive film of the present invention is formed by forming a layer of the resin composition of the present invention on a support.
The adhesive film of the present invention is prepared by applying a method known to those skilled in the art, for example, the resin varnish to a support using a die coater or the like, and drying the organic solvent by heating, hot air blowing, or the like to dry the support. It can be produced by forming a resin composition layer on the resin composition layer.

The drying conditions after coating on the support are not particularly limited, but the drying is such that the content of the organic solvent in the resin composition layer after drying is preferably 10% by mass or less, more preferably 5% by mass or less. Let me. Specific conditions vary depending on the amount of organic solvent in the resin varnish, the boiling point of the organic solvent, etc., but for example, a resin varnish containing 30 to 60% by mass of an organic solvent is used at 50 to 150 ° C. for about 3 to 10 minutes. By drying, the resin composition layer can be suitably formed.

The thickness of the resin composition layer in the adhesive film is preferably equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer included in the circuit board is usually 5 to 70 μm, the resin composition layer is preferably 10 to 100 μm, more preferably 20 to 80 μm.

Examples of the support include a polyolefin film such as polyethylene, polypropylene and polyvinyl chloride, a polyester film such as polyethylene terephthalate (hereinafter, also referred to as “PET”) and polyethylene naphthalate, and various plastic films such as a polycarbonate film and a polyimide film; Release paper: Examples include metal foil such as copper foil and aluminum foil. The support and the protective film described later may be subjected to surface treatment such as matte treatment and corona treatment, and release of silicone resin-based mold release agent, alkyd resin-based mold release agent, fluororesin-based mold release agent and the like. A mold release treatment may be applied with a mold agent.
The thickness of the support is not particularly limited, but is preferably 10 to 150 μm, more preferably 25 to 50 μm.

When a copper foil is used as the support, the copper foil as the support can also be used as the conductor layer. Examples of the copper foil include rolled copper and electrolytic copper foil.
The thickness of the copper foil may be determined according to the intended use, but is preferably 2 to 36 μm, more preferably 10 to 25 μm, for example.
Since the resin composition of the present invention has excellent peel strength, it can exhibit sufficient peel strength even for copper foil having a small arithmetic mean roughness (Ra). Therefore, the arithmetic mean roughness (Ra) of the copper foil is preferably 300 nm or less, more preferably 250 nm or less, further preferably 220 nm or less, and further preferably 50 nm or more, from the viewpoint of achieving both excellent peel strength and wiring formability. Is preferable, 60 nm or more is more preferable, and 70 nm or more is further preferable.
The arithmetic mean roughness (Ra) of the copper foil can be measured by the method described in Examples.

A protective film similar to the support can be further laminated on the surface of the resin composition layer where the support is not in close contact. The thickness of the protective film is not particularly limited, but is, for example, 1 to 40 μm. By laminating the protective film, it is possible to prevent dust and the like from adhering to the surface of the resin composition layer and scratches. The adhesive film can also be rolled up and stored.

[Prepreg]
The prepreg of the present invention is obtained by impregnating the resin composition of the present invention into a sheet-shaped reinforcing base material.
The prepreg of the present invention can be produced, for example, by impregnating a sheet-shaped reinforcing base material made of fibers with a hot melt method or a solvent method by the hot melt method or the solvent method, and heating and semi-curing the resin composition of the present invention.
In the hot melt method, a coated paper having excellent peelability from the resin composition is once coated without dissolving the resin composition in an organic solvent, and the resin composition is laminated on a sheet-like reinforcing base material to produce a prepreg. A method or a method of producing a prepreg by directly coating a sheet-like reinforcing base material with a die coater without dissolving the resin composition in an organic solvent.
In the solvent method, a resin composition is dissolved in an organic solvent in the same manner as an adhesive film to prepare a resin varnish, a sheet-shaped reinforcing base material is immersed in the resin varnish, and the sheet-shaped reinforcing base material is impregnated with the resin varnish. After that, it is a method of drying.

As the sheet-shaped reinforcing base material, well-known materials used for various laminated plates for electrical insulating materials can be used. As the material of the sheet-like reinforcing base material, natural fibers such as paper and cotton linter; inorganic fibers such as glass fiber and asbestos; organic fibers such as aramid, polyimide, polyvinyl alcohol, polyester, tetrafluoroethylene and acrylic; and a mixture thereof. And so on. Among these, glass fiber is preferable from the viewpoint of flame retardancy. As the glass fiber base material, a woven cloth using E glass, C glass, D glass, S glass, etc. or a glass woven cloth in which short fibers are bonded with an organic binder; a mixture of glass fibers and cellulose fibers, etc. Can be mentioned. More preferably, it is a glass woven cloth using E glass.
These sheet-shaped reinforcing base materials have shapes such as woven fabrics, non-woven fabrics, robinks, chopped strand mats, and surfaced mats. The material and shape are selected according to the intended use and performance of the molded product, and one type may be used alone, or two or more types of materials and shapes may be combined as needed.
The thickness of the sheet-shaped reinforcing base material is not particularly limited, and can be, for example, about 0.01 to 0.5 mm, and is surface-treated with a silane coupling agent or the like or mechanically opened. Is preferable from the viewpoint of heat resistance, moisture resistance and processability.
One prepreg may be used, or preferably 2 to 20 prepregs may be stacked if necessary.

[Multilayer printed wiring board]
The multilayer printed wiring board of the present invention contains a cured product of the resin composition of the present invention.
The multilayer printed wiring board of the present invention is not particularly limited, but can be suitably manufactured by using, for example, the adhesive film or prepreg of the present invention. Hereinafter, a method for manufacturing the multilayer printed wiring board of the present invention using the adhesive film of the present invention or the prepreg of the present invention will be described.

<Manufacturing method of multilayer printed wiring board using the adhesive film of the present invention>
An example of a method for manufacturing a multilayer printed wiring board using the adhesive film of the present invention will be described.
The multilayer printed wiring board of the present invention can be manufactured, for example, by laminating the adhesive film of the present invention on a circuit board. Specifically, the following steps (1) to (6) [However, step (3) is optional. ] Can be produced, and the support may be peeled off or removed after the steps (1), (2) or (3).
(1) A step of laminating the adhesive film of the present invention on one side or both sides of a circuit board [hereinafter, referred to as a laminating step (1)].
(2) A step of thermosetting the laminated adhesive film to form an insulating layer [hereinafter, referred to as an insulating layer forming step (2)].
(3) A step of drilling a hole in a circuit board on which an insulating layer is formed [hereinafter, referred to as a drilling step (3)].
(4) A step of roughening the surface of the insulating layer with an oxidizing agent [hereinafter, referred to as a roughening treatment step (4)].
(5) A step of forming a conductor layer by plating on the surface of the roughened insulating layer [hereinafter, referred to as a conductor layer forming step (5)].
(6) A step of forming a circuit on the conductor layer [hereinafter, referred to as a circuit forming step (6)].

The laminating step (1) is a step of laminating the adhesive film of the present invention on one side or both sides of the circuit board.
Examples of the substrate used for the circuit board include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a heat-curable polyphenylene ether substrate, and the like. Here, the circuit board means a circuit board having a patterned conductor layer (circuit) formed on one side or both sides of the board as described above. Further, in a multi-layer printed wiring board in which conductor layers and insulating layers are alternately laminated, one or both sides of the outermost layer of the multi-layer printed wiring board is a conductor layer (circuit) in which a pattern is processed. It is included in the circuit board mentioned above. The surface of the conductor layer may be roughened in advance by blackening treatment, copper etching or the like.

In the above-mentioned lamination, when the adhesive film has a protective film, after removing the protective film, the adhesive film and the circuit board are preheated as necessary, and the adhesive film is pressed and heated on the circuit board. Crimping. In the adhesive film of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is preferably used. The laminating conditions are not particularly limited, but for example, the crimping temperature (lamination temperature) is preferably 70 to 140 ° C., and the crimping pressure is preferably 1 to 11 kgf / cm ² (9.8 × 10 ^{4 to} 107). It is preferably .9 × 10 ⁴ N / m ² ) and laminated under a reduced pressure of 20 mmHg (26.7 hPa) or less. Further, the laminating method may be a batch method or a continuous method using a roll. Vacuum laminating can be done using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum applicator manufactured by Nichigo Morton Co., Ltd., a vacuum pressurized laminator manufactured by Meiki Co., Ltd., a roll-type dry coater manufactured by Hitachi Industries, Ltd., and Hitachi AC Co., Ltd. Examples include a vacuum laminator manufactured by Hitachi.

Further, the laminating step of heating and pressurizing under reduced pressure can also be performed using a general vacuum hot press machine. For example, it can be performed by pressing a heated metal plate such as a SUS plate from the support layer side. The pressing conditions are such that the degree of decompression is usually 1 × 10 ⁻² MPa or less, preferably 1 × 10 ^-3 MPa or less. Although heating and pressurization can be performed in one step, it is preferable to carry out the heating and pressurization in two or more steps from the viewpoint of controlling the exudation of the resin. For example, the first stage of the press, the temperature is 70 to 150 ° C., the range of pressure 1~15kgf / cm ^2, the second stage of the press, the temperature is 150 to 200 ° C., a pressure of 1~40kgf / cm ² It is preferable to carry out within the range. The time of each step is preferably 30 to 120 minutes. Examples of commercially available vacuum hot press machines include MNPC-V-750-5-200 manufactured by Meiki Co., Ltd. and VH1-1603 manufactured by Kitagawa Seiki Co., Ltd.

The insulating layer forming step (2) is a step of thermosetting the adhesive film laminated on the circuit board to form an insulating layer.
In the insulating layer forming step (2), first, the adhesive film laminated on the circuit board is cooled to around room temperature, and then the support is peeled off when peeling off. After that, an insulating layer can be formed on the circuit board by thermosetting the adhesive film. The conditions for thermosetting may be appropriately selected according to the type and content of the resin component in the resin composition, but are preferably 150 to 220 ° C. for 20 to 180 minutes, and more preferably 160 to 210 ° C. for 30. Selected in the range of ~ 120 minutes.

After forming the insulating layer by the above method, via holes, through holes and the like may be formed through the drilling step (3), if necessary.
If the support is not peeled off after forming the insulating layer and before curing, it may be peeled off here. Drilling can be performed by, for example, a known method such as a drill, a laser, or plasma, and if necessary, these methods can be combined, but drilling with a laser such as a carbon dioxide gas laser or a YAG laser is the most common method. is there.

In the roughening treatment step (4), the surface of the insulating layer is roughened with an oxidizing agent.
In the case of wet plating, the surface of the insulating layer is subjected to a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order to form an uneven anchor.
The swelling treatment with the swelling liquid is performed, for example, by immersing the insulating layer in the swelling liquid at 50 to 80 ° C. for 5 to 20 minutes. Examples of the swelling solution include an alkaline solution and a surfactant solution, and an alkaline solution is preferable. Examples of the alkaline solution include a sodium hydroxide solution and a potassium hydroxide solution. Examples of commercially available swelling solutions include Swelling Dip Securiganth P (registered trademark) P (registered trademark) and Swelling Dip Securiganth (registered trademark) SBU (Swelling) manufactured by Atotech Japan Co., Ltd. Dip Securiganth SBU) and the like.
The roughening treatment with an oxidizing agent is performed, for example, by immersing the insulating layer in an oxidizing agent solution at 60 to 80 ° C. for 10 to 30 minutes. Examples of the oxidizing agent include an alkaline permanganate solution in which potassium permanganate, sodium permanganate and the like are dissolved in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid and the like. .. The concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as Concentrate Compact CP manufactured by Atotech Japan Co., Ltd. and Dozing Solution Security (registered trademark) P.
The neutralization treatment with a neutralizing solution is carried out by immersing in the neutralizing solution at 30 to 50 ° C. for 3 to 10 minutes. The neutralizing solution is preferably an acidic aqueous solution, and examples of commercially available products include reduction solution solution Securigant (registered trademark) P manufactured by Atotech Japan Co., Ltd.

In the conductor layer forming step (5), a conductor layer is formed by plating on the surface of the roughened insulating layer.
As the plating method, there are dry plating and wet plating, and as the dry plating, known methods such as thin film deposition, sputtering, and ion plating can be used.
As the wet plating, a method in which electroless plating and electrolytic plating are combined is preferable, but a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating.
The metal for plating is not particularly limited as long as it is a metal that can be used for plating. Examples of the metal for plating include copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, alloys containing at least one of these metal elements, and the like. Among them, copper and nickel are preferable, and copper is more preferable.

In the subsequent circuit forming step (6), as a method of patterning the conductor layer and forming a circuit, for example, a subtractive method, a full additive method, a semi-additive method (SAP: SemiAdditive Process), and a modified semi-additive method (m). -A known method such as (SAP: modified Semi Adaptive Process) can be used.

In the steps (1) to (6), the mode in which the insulating layer formed from the adhesive film is plated to form a circuit has been described, but the adhesive film of the present invention has a copper foil as a support. In that case, the copper foil as the support can also be used as the conductor layer.
In that case, for example, steps (1) to (3) are carried out without peeling off the copper foil which is the support, and the circuit forming step which is the step (6) is performed on the copper foil which is the support. It is also possible to form a circuit.

<Multilayer printed wiring board using the prepreg of the present invention>
Next, an example of a method for manufacturing a multilayer printed wiring board using the prepreg of the present invention will be described. First, one or several prepregs of the present invention are laminated on the circuit board, sandwiched between metal plates via a release film, and vacuum press-laminated under pressure and heating conditions. The pressurizing and heating conditions are preferably a pressure of 5 to 40 kgf / cm ² (49 × 10 ^{4 to} 392 × 10 ⁴ N / m ² ) and a temperature of 120 to 200 ° C. for 20 to 100 minutes. Further, as with the adhesive film, it is also possible to laminate the prepreg on the circuit board by the vacuum laminating method and then heat-cure it. Then, in the same manner as described above, after roughening the cured prepreg surface, a conductor layer can be formed by plating to manufacture a multilayer printed wiring board.

[Semiconductor device]
The semiconductor device of the present invention uses the multilayer printed wiring board of the present invention.
The semiconductor device of the present invention can be manufactured, for example, by mounting a semiconductor chip on a conductive portion of the multilayer printed wiring board of the present invention. The "conduction point" is a "place for transmitting an electric signal in the multilayer printed wiring board", and the place may be a surface or an embedded place. Further, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The method for mounting the semiconductor chip in manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and no bumps. Examples thereof include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF).

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.

[Measurement and evaluation method]
The resin compositions obtained in each example were measured and evaluated by the following methods.

<Measurement of peel strength>
(1) Curing of Resin Composition The adhesive film obtained in each example was heated at 170 ° C. for 30 minutes to cure the resin composition layer of the adhesive film to form an insulating layer.
(2) Installation of copper-clad laminate A copper-clad laminate for supporting the adhesive film during the peel test is attached to the entire surface of the insulating layer side formed above with double-sided tape, and the copper foil (support) / A laminate in the order of insulating layer / double-sided tape / copper-clad laminate was obtained.
(3) Measurement of peel strength A copper foil with a width of 5 mm is attached to the copper foil surface (that is, the copper foil that is the support of the adhesive film), and the copper wiring is immersed in a 10% ammonium persulfate aqueous solution at 50 ° C. Was formed. This one end was peeled off and grasped with a gripper, and the load (kN / m) when the length of 10 mm was peeled off at a pulling speed of 5 mm / min in the vertical direction was measured at room temperature.

<Measurement of Arithmetic Mean Roughness (Ra) of Copper Foil Glossy Surface>
Copper foil used as a support for the adhesive film in each example (copper foil thickness 18 μm, manufactured by Furukawa Denki Kogyo Co., Ltd., trade name: F2-WS) The surface roughness of the glossy surface is measured by a non-contact type surface roughness meter. (Manufactured by Becoin Sturments, trade name: WYKO NT3300) was measured using a 10x lens, and the average value of the 20 points was taken as the arithmetic mean roughness (Ra) of the copper foil glossy surface.

<Example 1>
(B) As a curing agent having an amino group and a carboxy group, 9 parts by mass of 2- (4-aminophenylthio) acetic acid (manufactured by Wako Pure Chemical Industries, Ltd., functional group equivalent: about 61 g / mol) was added to dimethylacetamide 47. It was dissolved in parts by mass. There, as (A) epoxy resin, 40 parts by mass of biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: NC-3000-H, epoxy equivalent: about 290 g / mol), (C) as a curing accelerator. , 2-Phenylimidazole (hereinafter, also referred to as "2PZ") 0.12 parts by mass, (D) As phenoxy resin, phenoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: 1256B40, epoxy equivalent: about 6,700 ~ 8,000 g / mol) 51 parts by mass was mixed to prepare a varnish-like resin composition (resin varnish).
Next, the resin varnish was applied to a glossy surface of a copper foil (manufactured by Furukawa Denki Kogyo Co., Ltd., trade name: F2-WS, copper foil thickness: 18 μm), and the thickness of the resin composition layer after drying was 50 μm. The film was uniformly applied with a die coater and dried at 85 to 95 ° C. (90 ° C. on average) for 10 minutes to obtain an adhesive film.

<Example 2, Comparative Examples 1 to 4>
A resin varnish and an adhesive film were produced in the same manner as in Example 1 except that the type and content of each component were changed as shown in Table 1.

Details of the curing agent used in each example are as follows.
(1) Hardener having an amino group and a carboxy group [Component (B)]
B-1: 2- (4-aminophenylthio) acetic acid (manufactured by Wako Pure Chemical Industries, Ltd., functional group equivalent: approx. 61 g / mol)
B-2: 4-Aminohydrocinnamic acid (manufactured by Tokyo Chemical Industry Co., Ltd., functional group equivalent: approx. 55 g / mol)
(2) Hardener having an amino group [(B') component (comparative component)]
B'-3: m-trizine (manufactured by Wako Pure Chemical Industries, Ltd., functional group equivalent: approx. 53 g / mol)
B'-4: 1,4-bis (3-aminopropyl) piperazine (manufactured by Wako Pure Chemical Industries, Ltd., functional group equivalent: approx. 50 g / mol)
(3) Hardener having a carboxy group [(B') component (comparative component)]
B'-5: 3,3'-thiodipropionic acid (manufactured by Wako Pure Chemical Industries, Ltd., functional group equivalent: approx. 89 g / mol)
B'-6: Pimelic acid (manufactured by Wako Pure Chemical Industries, Ltd., functional group equivalent: approx. 80 g / mol)

From the results in Table 1, it can be seen that the resin compositions of Examples 1 and 2 have high peel strength with respect to the copper foil having a small arithmetic mean roughness (Ra). On the other hand, the resin compositions of Comparative Examples 1 and 2 using a curing agent having only an amino group and Comparative Examples 3 and 4 using a curing agent having only a carboxy group had lower peel strength than those of Examples.

According to the present invention, a resin composition capable of forming an insulating resin layer having sufficient peel strength on a conductor layer having a small arithmetic mean roughness (Ra), an adhesive film, a prepreg, and a multilayer printed wiring board using the resin composition. And semiconductor devices can be provided. These are useful for electrical products such as computers, mobile phones, digital cameras, televisions; vehicles such as motorcycles, automobiles, trains, ships, and aircraft.

Claims (11)

A resin composition containing (A) an epoxy resin and (B) a curing agent having an amino group and a carboxy group , wherein the component (B) is represented by the following general formula (1). Composition.

(In the formula, R ¹ represents a single bond or a divalent organic group, and R ² represents a divalent organic group containing a sulfide group.) R ¹ in the general formula (1) is a divalent hydrocarbon group selected from the group consisting of an alkylene group, an alkenylene group and an alkynylene group, and the divalent hydrocarbon group is combined with an ether bond or a sulfide group. The resin composition according to claim 1 , which is a divalent group or a single bond. The first or second claim, wherein the content of the component (B) is 1 to 30 parts by mass with respect to 100 parts by mass of the non-volatile content (excluding the inorganic filler) in the resin composition. Resin composition. The resin composition according to any one of claims 1 to 3 , further comprising (C) a curing accelerator. The resin composition according to any one of claims 1 to 4 , further comprising (D) a phenoxy resin. The ratio of the total number of active hydrogens to the epoxy groups of the curing agent having an amino group and a carboxy group to the total number of epoxy groups of the (A) epoxy resin in the resin composition [active hydrogen / epoxy group] is The resin composition according to any one of claims 1 to 5 , which is 0.2 to 2. The resin composition according to any one of claims 1 to 6 , wherein the peel strength of the cured product is 0.32 kN / m or more with respect to a copper foil having an arithmetic mean roughness (Ra) of 200 nm. An adhesive film formed by forming a layer of the resin composition according to any one of claims 1 to 7 on a support. A prepreg obtained by impregnating a sheet-like reinforcing base material with the resin composition according to any one of claims 1 to 7 . A multilayer printed wiring board containing a cured product of the resin composition according to any one of claims 1 to 7 . A semiconductor device using the multilayer printed wiring board according to claim 10 .