TW201708401A - Thermosetting resin composition, resin film with carrier, printed wiring board and semiconductor device - Google Patents

Abstract

An object of the present invention is to provide a thermosetting resin composition and a resin film with a carrier each capable of suppressing a warpage of a semiconductor device and improving connection reliability thereof, and to provide a semiconductor device having a reduced warpage and excellent connection reliability. A thermosetting resin composition of the present invention is used for forming a dielectric layer included in a printed wiring board. The thermosetting resin composition contains a thermosetting resin, an inorganic filler and a (meth) acrylic block copolymer. Further, when the thermosetting resin composition is subjected to a heat treatment at 230 DEG C for 2 hours to obtain a cured product thereof, a glass-transition temperature of the cured product is 180 DEG C or more.

Description

Thermosetting resin composition, resin film with carrier, printed wiring board, and semiconductor device

The present invention relates to a thermosetting resin composition, a resin film with a carrier, a printed wiring board, and a semiconductor device.

In recent years, with the high performance of electronic devices and the demand for light and thin, the high-density aggregation of electronic components and the high-density mounting are progressing. The semiconductor devices used in these electronic devices are rapidly evolving toward miniaturization. Therefore, the printed wiring board on which the electronic component including the semiconductor element is mounted tends to be thinner, and the inner core substrate of the printed wiring board has a thickness of about 0.8 mm. In addition, a package stack (hereinafter referred to as "POP") in which semiconductor packages using a core substrate of 0.4 mm or less are laminated with each other is mounted on a mobile device (for example, a mobile phone, a smart phone, a tablet personal computer, etc.).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2011-144361

According to this, as the semiconductor device is miniaturized, the thickness of the semiconductor element and the sealing material which are responsible for most of the rigidity of the semiconductor device is extremely thin, and the semiconductor device is likely to be warped. Moreover, since the proportion of the printed wiring board as a constituent member becomes large, the physical properties and behavior of the printed wiring board greatly affect the warpage of the semiconductor device.

On the other hand, from the viewpoint of global environmental protection, the maximum temperature at which the solder ball is mounted on the printed wiring board or the solder reflow step is extremely high when the printed wiring board is mounted on the solder ball. Since the melting point of the lead-free solder is generally about 210 degrees, the maximum temperature in the reflow step exceeds 260 degrees.

Therefore, in the semiconductor package in which the POP is heated up and down, the thermal expansion difference between the semiconductor element and the printed wiring board mounted on the semiconductor element is extremely large, and large warpage may occur.

A related art of a printed wiring board that solves such a problem can be described, for example, in Patent Document 1 below.

Patent Document 1 (JP-A-2011-144361) discloses that an insulating layer composed of a resin composition can be reduced by using a resin composition containing a cyanate resin and a naphthyl ether type epoxy resin. The rate of thermal expansion.

However, even if the resin composition of Patent Document 1 is used, it is still insufficient. The effect of suppressing warpage of the semiconductor device is satisfied.

In view of the above-mentioned circumstances, the present invention provides a thermosetting resin composition for a semiconductor device which is excellent in warpage and connection reliability, and a resin film with a carrier, and which is excellent in warpage and connection reliability. Semiconductor device.

As a result of intensive studies, the inventors of the present invention have found that by containing a (meth)acrylic block copolymer, a thermosetting resin composition having a specific glass transition temperature can effectively reduce the obtained cured product at a high temperature. The coefficient of linear expansion below. By using such a cured product on the insulating layer of the printed wiring board, stress caused by the difference between the linear expansion coefficient of the semiconductor element and the linear expansion coefficient of the printed wiring board can be reduced, and the semiconductor element can be suppressed from being printed. When the positional displacement of the wiring board occurs, it is found that the warpage of the semiconductor device can be suppressed, and the connection reliability between the semiconductor element and the printed wiring board can be improved.

The thermosetting resin composition according to the present invention is a thermosetting resin composition for forming an insulating layer of a printed wiring board; and contains a thermosetting resin, an inorganic filler, and a (meth)acrylic block. The copolymerization temperature of the thermosetting resin composition obtained by heat-treating at 230 ° C for 2 hours to obtain a cured product is 180 ° C or higher.

Here, the glass transition temperature is obtained in a region obtained by dynamic viscoelasticity measurement at a temperature rise rate of 5 ° C/min and a frequency of 1 Hz, and is stored in a region above 150 ° C. The temperature at which the tangent tan δ tip peak is lost.

Further, the resin film with a carrier provided by the present invention includes a carrier substrate and a resin film which is provided on the carrier substrate and is composed of the thermosetting resin composition.

Furthermore, the printed wiring board according to the present invention is provided with a stacked layer containing a cured product of the above-mentioned thermosetting resin composition.

Furthermore, the printed wiring board according to the present invention includes a solder resist layer containing a cured product of the thermosetting resin composition.

Further, according to the semiconductor device of the present invention, the semiconductor element is mounted on the circuit layer of the printed wiring board.

According to the present invention, it is possible to realize a thermosetting resin composition of a semiconductor device which is excellent in warpage and connection reliability, a resin film with a carrier, and a semiconductor device which is excellent in warpage and connection reliability.

1‧‧‧Resin film with carrier

10‧‧‧ resin film

12‧‧‧ Carrier substrate

100‧‧‧Resin film with carrier

105‧‧‧metal foil

300‧‧‧Printed wiring substrate

301‧‧‧Insulation

303‧‧‧metal layer

305‧‧‧Insulation

307‧‧‧ access hole

308‧‧‧Electroless metallized film

309‧‧‧Electroplating metal layer

311‧‧‧ core layer

317‧‧‧Stacking

400‧‧‧Semiconductor device

401‧‧‧ solder mask

407‧‧‧Semiconductor components

410‧‧‧ solder bumps

413‧‧‧ Sealing material

Fig. 1 is a cross-sectional view showing an example of a configuration of a resin film with a carrier in the embodiment.

Fig. 2 is a cross-sectional view showing an example of a configuration of a printed wiring board of the embodiment.

Fig. 3 is a cross-sectional view showing an example of a configuration of a printed wiring board of the embodiment.

Fig. 4 is a cross-sectional view showing an example of a configuration of a semiconductor device of the embodiment.

Fig. 5 is a cross-sectional view showing an example of a configuration of a semiconductor device of the embodiment.

Hereinafter, an embodiment of the present invention will be described using a schematic diagram. In the drawings, the same components are denoted by the same reference numerals, and the description is omitted as appropriate. Moreover, the schematic diagram of the figure does not match the actual size ratio. In addition, the "~" between the numbers in the text indicates "above" to "below" unless otherwise stated.

First, the thermosetting resin composition (P) (hereinafter also referred to as "resin composition (P)") of the present embodiment will be described.

The resin composition (P) of the present embodiment is used for forming an insulating layer of a printed wiring board. The insulating layer of the printed wiring substrate may be, for example, an insulating layer of a stacked layer or a solder resist layer.

In the present embodiment, for example, a thermosetting resin film formed using the resin composition (P) is laminated on a circuit layer, and an insulating layer of a stacked layer or a solder resist layer is formed by heat-hardening.

The resin composition (P) can be, for example, a solvent-containing varnish.

On the other hand, the resin composition (P) may be in the form of a film. The film-like resin composition (P) is obtained, for example, by subjecting a resin film obtained by applying the varnish-like resin composition (P) to a solvent removal treatment. Further, by laminating the film-like resin composition (P) on the carrier substrate, a resin film with a carrier can be formed.

The resin composition (P) contains a thermosetting resin (A), an inorganic filler (B), and a (meth)acrylic block copolymer (C). Hereinafter, each component of the resin composition (P) will be described in detail.

(thermosetting resin (A))

The thermosetting resin (A) is not particularly limited, and preferably has a low linear expansion ratio and a high elastic modulus, and is excellent in thermal shock resistance. Further, the glass transition temperature of the thermosetting resin (A) is preferably 160 ° C or more and 350 ° C or less, more preferably 180 ° C or more and 300 ° C or less. By using the thermosetting resin (A) having such a glass transition temperature, the effect of further improving the heat resistance of the lead-free solder reflow of the obtained printed wiring board (insulating layer) can be obtained.

The thermosetting resin (A) can be, for example, an epoxy resin, a maleimide compound, or a benzoic acid. One type or two or more types of the compound, the cyanate resin, and the like are selected.

Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol E epoxy resin, bisphenol S epoxy resin, and bisphenol M epoxy resin (4, 4'-(1,3-phenylene diisopropylidene) bisphenol epoxy resin), bisphenol P epoxy resin (4,4'-(1,4-phenylene diisopropyl) Bisphenol type epoxy resin such as bisphenol type epoxy resin, bisphenol Z type epoxy resin (4,4'-cyclohexadiene bisphenol type epoxy resin); phenol novolac type epoxy resin, A Phenolic epoxy resin, tetraphenol ethane type phenolic epoxy resin, phenolic epoxy resin such as phenolic epoxy resin having condensed cyclic aromatic hydrocarbon structure; biphenyl type epoxy resin; Aralkyl type epoxy resin such as base type epoxy resin or biphenyl aralkyl type epoxy resin; naphthene ether type epoxy resin, naphthol type epoxy resin, naphthalene glycol type epoxy resin, difunctional group a naphthalene type epoxy resin such as a tetrafunctional naphthalene type epoxy resin, a dinaphthyl type epoxy resin or a naphthalene aralkyl type epoxy resin; a fluorene type epoxy resin; a phenoxy type epoxy resin; Ethylenic epoxy resin Ethylene type epoxy resin; adamantane type epoxy resin;

One type of these may be used alone or two or more types may be used in combination, and one type or two or more types of prepolymers may be used in combination.

Among the epoxy resins, from the viewpoint of further improving the heat resistance and insulation reliability of the obtained printed wiring board, it is preferable to use a bisphenol type epoxy resin, a novolac type epoxy resin, a biphenyl type epoxy resin, One or more selected from the group consisting of an aralkyl type epoxy resin, a naphthalene type epoxy resin, a fluorene type epoxy resin, and a dicyclopentadiene type epoxy resin, and more preferably an aralkyl type ring One or more selected from the group consisting of an oxygen resin, a phenolic epoxy resin having a condensed cyclic aromatic hydrocarbon structure, and a naphthalene epoxy resin.

As the bisphenol A type epoxy resin, "EPIKOTE 828EL" and "YL980" manufactured by Mitsubishi Chemical Corporation can be used. As the bisphenol F-type epoxy resin, "jER806H" and "YL983U" manufactured by Mitsubishi Chemical Corporation and "EPICLON 830S" manufactured by DIC Corporation can be used. As the bifunctional naphthalene type epoxy resin, "HP4032", "HP4032D", and "HP4032SS" manufactured by DIC Corporation can be used. As the tetrafunctional naphthalene type epoxy resin, "HP4700" and "HP4710" manufactured by DIC Corporation can be used. As the naphthol type epoxy resin, "ESN-475V" manufactured by Nippon Steel Chemical Co., Ltd., "NC7000L" manufactured by Nippon Kayaku Co., Ltd., or the like can be used. For the aralkyl type epoxy resin, "NC3000" manufactured by Nippon Kayaku Co., Ltd. can be used. "NC3000H", "NC3000L", "NC3000S", "NC3000S-H", "NC3100", "ESN-170" and "ESN-480" manufactured by Nippon Steel Chemical Co., Ltd. For the biphenyl type epoxy resin, "YX4000", "YX4000H", "YX4000HK" and "YL6121" manufactured by Mitsubishi Chemical Corporation can be used. As the 环氧树脂-type epoxy resin, "YX8800" manufactured by Mitsubishi Chemical Corporation can be used. As the naphthalene ether type epoxy resin system, "HP6000", "EXA-7310", "EXA-7311", "EXA-7311L", and "EXA7311-G3" manufactured by DIC Corporation can be used.

Among these epoxy resins, an aralkyl type epoxy resin is particularly preferable. Thereby, the heat resistance and flame retardancy of the moisture absorbing solder of the insulating layer can be further improved.

The aralkyl type epoxy resin is, for example, represented by the following formula (1):

Among them, A and B represent an aromatic ring such as a benzene ring or a biphenyl structure. Further, hydrogen of the aromatic ring of A and B may be substituted. The substituent system may be, for example, a methyl group, an ethyl group, a propyl group, a phenyl group or the like. The n system represents a repeating unit, for example, an integer of 1 to 10.

Specific examples of the aralkyl type epoxy resin represented by the above formula (1) include, for example, the following (1a) and (1b): [Chemical 2] (In the formula, n is an integer from 1 to 5.)

(In the formula, n is an integer from 1 to 5.)

The epoxy resin other than the above is preferably a novolac type epoxy resin having a condensed cyclic aromatic hydrocarbon structure. Thereby, the heat resistance and low thermal expansion property of the obtained printed wiring board can be further improved.

The phenolic epoxy resin having a condensed cyclic aromatic hydrocarbon structure is, for example, naphthalene, anthracene, phenanthrene, fused tetraphenyl, , hydrazine, extended triphenyl, tetraphene, or other phenolic epoxy resin having a condensed cyclic aromatic structure. The phenolic epoxy resin having a condensed cyclic aromatic hydrocarbon structure is excellent in low thermal expansion property because the plural aromatic rings can be arranged in a regular manner. Moreover, since the glass transition temperature is also high, heat resistance is excellent. Further, since the molecular weight of the repeating structure is large, the flame retardancy is superior to that of the conventional novolac type epoxy resin.

The phenolic epoxy resin having a condensed cyclic aromatic hydrocarbon structure is obtained by subjecting a phenolic phenol resin synthesized from a phenol compound, an aldehyde compound, and a condensed cyclic aromatic hydrocarbon compound to epoxidation.

The phenolic compound is not particularly limited, and examples thereof include phenol; cresols such as o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2,4-xylenol, and 2,5. - xylenols such as xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol; cresols such as 2,3,5-tricresol; o-ethylphenol And ethyl phenols such as ethyl phenol and p-phenol; alkyl phenols such as propofol, butanol and third butanol; phenylphenols such as o-phenylphenol, m-phenylphenol and p-phenylphenol; Naphthalenediols such as 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene; polyphenols such as resorcinol, catechol, hydroquinone, gallic phenol, benzenetriol Alkyl polyphenols such as alkyl resorcinol, alkyl catechol, alkyl hydroquinone. Among these, phenol is preferred from the cost side and the effect of imparting a decomposition reaction.

The aldehyde compound is not particularly limited, and examples thereof include formaldehyde, paraformaldehyde, and trisole. Alkane, acetaldehyde, propionaldehyde, polyoxymethylene, trichloroacetaldehyde, hexamethylenetetramine, furfural, glyoxal, n-butyraldehyde, hexanal, allylaldehyde, benzaldehyde, crotonaldehyde, acrolein, tetra Formaldehyde, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde, dihydroxybenzaldehyde, trihydroxybenzaldehyde, 4-hydroxy-3-methoxyaldehyde paraformaldehyde, and the like.

The condensed ring aromatic hydrocarbon compound is not particularly limited, and examples thereof include a naphthalene derivative such as methoxynaphthalene or butoxynaphthalene; an anthracene derivative such as methoxyfluorene; and a phenanthrene derivative such as methoxyphenanthrene; Tetraphenyl derivative; Derivatives; anthracene derivatives; extended triphenyl derivatives; benzene well derivatives.

The novolac type epoxy resin having a condensed ring aromatic hydrocarbon structure is not particularly limited, and examples thereof include a methoxynaphthalene-modified ortho-cresol novolac epoxy resin and a butoxynaphthalene-modified (p-) cresol novolac. Epoxy resin, methoxy naphthalene modified phenolic epoxy resin, and the like. Among these, a novolac type epoxy resin having a condensed cyclic aromatic hydrocarbon structure represented by the following formula (V) is preferred.

(In the formula (V), the Ar-condensed cyclic aromatic hydrocarbon group is specifically a structure represented by (Ar1) to (Ar4) in the following formula (VI). Further, the R system may be mutually different or different. a hydrogen atom; a hydrocarbon group having a carbon number of 1 or more and 10 or less; an aryl group such as a halogen element, a phenyl group or a benzyl group; and a group selected from an organic group containing a glycidyl ether. Further, n, p, and q are groups. An integer of 1 or more. In addition, the values of p and q may be the same or different for each repeating unit.)

(R in the formula (VI) may be the same or different, from a hydrogen atom; a hydrocarbon group having 1 or more and 10 or less carbon atoms; a halogen element; an aryl group such as a phenyl group or a benzyl group; The selected group among the organic groups of the ether.)

Further, the epoxy resin other than the above is preferably a naphthol type epoxy resin, a naphthalene glycol type epoxy resin, a naphthalene type such as a bifunctional to tetrafunctional naphthalene type epoxy resin or a naphthene ether type epoxy resin. Epoxy resin. Thereby, the heat resistance and low thermal expansion property of the obtained printed wiring board can be further improved. Here, the "naphthalene type epoxy resin" means a group having a naphthalene ring skeleton and having two or more epoxy propyl groups.

Further, since the π-π stacking effect of the naphthalene ring is higher than that under the benzene ring, the naphthalene type epoxy resin is particularly excellent in low thermal expansion property and low heat shrinkability. Moreover, since it has a multi-ring structure, the straightening effect is high and the glass transition temperature is extremely high, so the change in heat shrinkage before and after reflow is small. The naphthol type epoxy resin can be represented, for example, by the following general formula (VII-1), and the naphthalene glycol type epoxy resin can be represented by the following formula (VII-2), and a bifunctional to tetrafunctional naphthalene type. The epoxy resin can be represented by the following formulas (VII-3), (VII-4), and (VII-5), and the anthranilyl ether type epoxy resin can be expressed, for example, by the following general formula (VII-6):

(n is a numerical value of an average of 1 or more and 6 or less, and R is a glycidyl group or a hydrocarbon group having 1 or more and 10 or less carbon atoms.)

[Chemistry 7]

(wherein R ¹ represents a hydrogen atom or a methyl group; and R ² represents an alkyl group independently substituted by a hydrogen atom, a carbon number of 1 to 4, an aralkyl group, a naphthyl group or a glycidyl propyl ether group. Naphthyl; o and m are each an integer from 0 to 2, and any of o or m is 1 or more.)

The lower limit of the weight average molecular weight (Mw) of the epoxy resin is not particularly limited, but is preferably Mw300 or more, more preferably Mw800 or more. When the Mw is at least the above lower limit value, the adhesion of the insulating layer can be suppressed. The upper limit of Mw is not particularly limited, and is preferably Mw 20,000 or less, more preferably Mw 15,000 or less. When the Mw is at most the above upper limit value, the handleability of the resin composition (P) can be improved, and the insulating layer can be easily formed. The Mw of the epoxy resin can be measured, for example, by GPC.

The content of the epoxy resin contained in the resin composition (P) is preferably 3.0% by mass or more when the total solid content of the resin composition (P) (that is, the component other than the solvent) is 100% by mass. 20.0% by mass or less, more preferably 5.0% by mass or more and 15.0% by mass or less. When the content of the epoxy resin is at least the above lower limit value, the operability can be improved, and the insulating layer can be easily formed. When the content of the epoxy resin is at most the above upper limit value, the strength and flame retardancy of the printed wiring board are improved, or the linear expansion coefficient of the printed wiring board is lowered, and the warpage effect is improved.

In the resin composition (P) of the present embodiment, the thermosetting resin (A) preferably contains a maleimide compound and a benzoic acid. One or two or more kinds of thermosetting resins (A2) are selected among the compound and the cyanate resin. Thereby, the linear expansion coefficient of the obtained printed wiring board can be further reduced. In addition, in the resin composition (P) of the present embodiment, the thermosetting resin (A) may further contain an epoxy resin in addition to the thermosetting resin (A2).

The content of the thermosetting resin (A2) contained in the resin composition (P) is not particularly limited, and when the total solid content (that is, the component other than the solvent) of the resin composition (P) is 100% by mass, It is preferably 1.0% by mass or more and 25.0% by mass or less, more preferably 3.0% by mass or more and 20.0% by mass or less. When the content of the thermosetting resin (A2) is within the above range, the cured product of the prepreg obtained and the low heat shrinkability and chemical resistance of the resin substrate can be further improved.

The maleimide group of the maleimide compound has a planar structure of a five-membered ring, and the double bond of the maleimide group easily interacts between molecules, resulting in a polarity It is high, and thus exhibits strong intermolecular interactions with maleimide groups, benzene rings, other planar structures, and the like, and inhibits molecular motion. Therefore, by containing the maleimide compound in the resin composition (P), the linear expansion coefficient of the obtained insulating layer can be lowered, the glass transition temperature can be increased, and the heat resistance can be improved.

The maleimide compound is preferably a maleimide compound having at least two maleimide groups in the molecule.

The maleimide compound having at least two maleimide groups in the molecule may, for example, be 4,4'-diphenylmethanebis-s-butyleneimine or an exophenyl group. Bis-m-butylene diimide, p-phenylene bis-butenylene diimide, 2,2-bis[4-(4-methyleneimide phenoxy)phenyl]propane, double -(3-ethyl-5-methyl-4-maleimidophenylene)methane, 4-methyl-1,3-phenylenebissuccinimide, N,N '-Ethyl dim-butylene diimide, N,N'-hexamethylene dimethyleneimine, bis(4-methyleneimine phenyl) ether, double 4-m-butylenediamine phenyl) fluorene, 3,3-dimethyl -5,5-Diethyl-4,4-diphenylmethane bis-n-butylene imide, bisphenol A diphenyl ether bis-s-butylene diimide, etc. An imine group compound; a compound having three or more maleimide groups in a molecule such as polyphenylmethane maleimide or the like.

These may be used alone or in combination of two or more. Among these maleimide compounds, from the viewpoint of low water absorption, etc., 4,4'-diphenylmethanebissuccinimide, 2,2-bis[4- (4-m-butyleneimine phenoxy)phenyl]propane, bis-(3-ethyl-5-methyl-4-maleimidoiminophenyl)methane, polyphenylmethane Maleimide, bisphenol A diphenyl ether, di-n-butylene diimide.

Further, the maleimide compound preferably contains a maleimide compound represented by the following formula (1): (In the formula (1), n ₁ is an integer of 0 or more and 10 or less; and X ₁ is independently an alkylene group having 1 or more and 10 or less carbon atoms, a group represented by the following formula (1a), and a formula "-SO". _a group represented by ₂ -", a group represented by "-CO-", an oxygen atom or a single bond; and each of R ₁ is independently a hydrocarbon group having 1 or more and 6 or less carbon atoms; and a is an integer of 0 or more and 4 or less, respectively. ;b is an integer of 0 or more and 3 or less, respectively.)

(In the above formula (1a), Y is a hydrocarbon group having an aromatic ring having 6 or more and 30 or less carbon atoms; and n ₂ is an integer of 0 or more.)

The alkylene group of 1 or more and 10 or less of X ₁ is not particularly limited, and is preferably a linear or branched alkyl group.

The linear alkyl group may specifically be, for example, a methylene group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an exopeptide group, a hydrazine group, and a hydrazine group. Base, trimethylene, tetramethylene, pentamethylene, hexamethylene and the like.

Further, the branched chain alkyl group may specifically be, for example, -C(CH ₃ ) ₂ -(extended isopropyl), -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C (CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ ) ₂ - alkyl methylene; -CH ( CH ₃ )CH ₂ -, -CH(CH ₃ )CH(CH ₃ )-, -C(CH ₃ ) ₂ CH ₂ -, -CH(CH ₂ CH ₃ )CH ₂ -, -C(CH ₂ CH ₃ An alkyl group such as ₂ -CH ₂ - is ethyl or the like.

Further, the carbon number of the alkylene group of X ₁ may be 1 or more and 10 or less, preferably 1 or more and 7 or less, more preferably 1 or more and 3 or less. Specifically, examples of the alkylene group having such a carbon number include a methylene group, an exoethyl group, a propyl group, and an isopropyl group.

Further, R ₁ is each independently a hydrocarbon group having 1 or more and 6 or less carbon atoms, preferably a hydrocarbon group having 1 or 2 carbon atoms (specifically, a methyl group or an ethyl group).

Further, a is independently an integer of 0 or more and 4 or less, preferably an integer of 0 or more and 2 or less, more preferably 0. Further, b is independently an integer of 0 or more and 3 or less, preferably 0 or 1, more preferably 0.

Further, n ₁ is an integer of 0 or more and 10 or less, preferably an integer of 0 or more and 6 or less, more preferably an integer of 0 or more and 4 or less, and an integer of 0 or more and 3 or less. And maleic acyl imine-based compound containing at least more preferably 1 or more compounds of the above formula (1), n ₁ is. Thereby, the insulating layer obtained from the resin composition (P) can exhibit more excellent heat resistance.

Further, in the above formula (1a), Y is a hydrocarbon group having an aromatic ring and having a carbon number of 6 or more and 30 or less, and n ₂ is an integer of 0 or more.

The hydrocarbon group having an aromatic ring and having a carbon number of 6 or more and 30 or less may be composed only of an aromatic ring, and may have a hydrocarbon group other than the aromatic ring. Y may have one or two or more aromatic ring systems. When two or more, the aromatic ring systems may be the same or different. Further, the aromatic ring system may be either a monocyclic structure or a polycyclic structure.

Specifically, the hydrocarbon group having an aromatic ring and having a carbon number of 6 or more and 30 or less may, for example, be benzene, biphenyl, naphthalene, anthracene, anthracene, phenanthrene, anthracene, and indene. A terpene group of two hydrogen atoms is removed from a core having an aromatic compound by a terpene, a phenalene or the like.

Further, the aromatic hydrocarbon groups may have a substituent. Here, the "aromatic hydrocarbon group has a substituent" means that some or all of the hydrogen atoms constituting the aromatic hydrocarbon group are substituted with a substituent. The substituent system can be, for example, an alkyl group.

The alkyl group used as the substituent is preferably a linear alkyl group. Further, the carbon number is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and particularly preferably 1 or more and 4 or less. Specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a second butyl group and the like.

Such a group Y preferably has a group in which two hydrogen atoms are removed from benzene or naphthalene, and the group represented by the above formula (1a) is preferably any one of the following formulas (1a-1) and (1a-2). The base shown. Thereby, the insulating layer obtained from the resin composition (P) can exhibit more excellent heat resistance.

In the above formulae (1a-1) and (1a-2), R ₄ is each independently a hydrocarbon group having 1 or more and 6 or less carbon atoms. The e-systems are each independently an integer of 0 or more and 4 or less, and preferably 0.

Further, in the group represented by the above formula (1a), the n ₂ group may be an integer of 0 or more, preferably an integer of 0 or more and 5 or less, more preferably an integer of 1 or more and 3 or less, or a particularly excellent system. 1 or 2.

View of the above issues, according to (1) shown in two maleic imide compound of the formula XI, X ₁ is preferably a carbon-based number of 1 or more and 3 or less linear or branched chain alkylene, R & lt ₁ The hydrocarbon group of 1 or 2, a is an integer of 0 or more and 2 or less, b is 0 or 1, and n ₁ is an integer of 0 or more and 4 or less. Alternatively, X ₁ is preferably a group represented by any one of the above formulas (1a-1) and (1a-2), and e is 0. Thereby, the insulating layer obtained from the resin composition (P) exhibits more excellent low heat shrinkability and chemical resistance.

A preferred embodiment of the maleimide compound represented by the above formula (1) is more preferably a maleimide compound represented by the following formula (1-1).

Further, the maleimide compound may contain another type of maleimide compound different from the maleimide compound represented by the above formula (1).

Such a maleimide compound may, for example, be 1,6'-bis-s-butyleneimine-(2,2,4-trimethyl)hexane or hexamethylenediamine. Maleimide, N,N'-1,2-extended ethylbis-synylenediimide, N,N'-1,3-propenylbis-synylenediimide, An aliphatic maleimide compound such as N,N'-1,4-tetramethylenebis-sandimide, or a bis-iminyl diimide imine or the like. Among these, 1,6'-bis-synyleneimide-(2,2,4-trimethyl)hexane and quinone imine extended di-n-butylene diimine are preferable. The maleimide compound may be used singly or in combination of two or more.

The bis-iminyl extended-type dim-butylene iminoimide is, for example, a maleimide compound represented by the following formula (a1), a maleimide compound represented by the following formula (a2), The maleimide compound represented by the following formula (a3) and the like. Specific examples of the maleimide compound represented by the formula (a1) include, for example, BMI-1500 (manufactured by Designer Molecules, molecular weight: 1,500). Specific examples of the maleimide compound represented by the formula (a2) include, for example, BMI-1700 (manufactured by Designer Molecules, molecular weight: 1700), BMI-1400 (manufactured by Designer Molecules, molecular weight: 1400), and the like. . Specific examples of the maleimide compound represented by the formula (a3) include, for example, BMI-3000 (manufactured by Designer Molecules, molecular weight: 3000).

In the above formula (a1), n represents an integer of 1 or more and 10 or less.

In the above formula (a2), n represents an integer of 1 or more and 10 or less.

In the above formula (a3), n represents an integer of 1 or more and 10 or less.

The lower limit of the weight average molecular weight (Mw) of the maleimide compound is not particularly limited, but is preferably Mw of 400 or more, more preferably Mw of 800 or more. When the Mw is at least the above lower limit value, the adhesion of the insulating layer can be suppressed. The upper limit of Mw is not particularly limited, but is preferably Mw 4000 or less, more preferably Mw 2500 or less. When Mw is at most the above upper limit value, when the insulating layer is produced, the handleability of the resin composition (P) can be improved, and the insulating layer can be easily formed. The Mw system of the maleimide compound is, for example, GPC (condensed) It can be measured by gel penetration chromatography analyzer and standard material: polystyrene conversion.

Further, the maleimide compound may also be a reactant of a maleimide compound and an amine compound. As the amine compound, at least one selected from the group consisting of an aromatic diamine compound and a monoamine compound can be used.

The aromatic diamine compound may, for example, be o-dimethoxyaniline, o-tolidine, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 4,4'-bis (4- Aminophenoxy)biphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, meta-phenylenediamine, p-phenylenediamine, o-xylenediamine, 4,4 '-Diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl hydrazine, 3,3'- Diaminodiphenyl hydrazine, 1,5-diaminonaphthalene, 4,4'-(p-phenylenediphenylene)diphenylamine, 2,2-[4-(4-aminophenoxy) Phenyl]propane, 4,4'-diamino-3,3'-dimethyl-diphenylmethane, bis(4-(4-aminophenoxy)phenyl)anthracene, and the like.

Examples of the monoamine compound include o-aminophenol, m-aminophenol, p-aminophenol, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, o-aminobenzenesulfonic acid, and m-aminoamine. Alkylbenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline, o-aniline, m-aniline, p-aniline, o-methylaniline, m-methylaniline, p-methyl Aniline, o-ethylaniline, m-ethylaniline, p-ethylaniline, o-vinylaniline, m-vinylaniline, p-vinylaniline, o-allylaniline, m-allylaniline, p-allylaniline, and the like.

The reaction of the maleimide compound with the amine compound allows the reaction to proceed in an organic solvent. The reaction temperature is, for example, 70 to 200 ° C, and the reaction time is, for example, 0.1 to 10 hours.

The content of the maleimide compound contained in the resin composition (P) is not particularly limited, and when the total solid content (that is, the component other than the solvent) of the resin composition (P) is 100% by mass It is preferably 1.0% by mass or more and 25.0% by mass or less, more preferably 3.0% by mass or more and 20.0% by mass or less. When the content of the maleimide compound is within the above range, the low heat shrinkage property and the chemical resistance of the obtained insulating layer can be further improved.

The cyanate resin is not particularly limited. For example, a cyanide compound can be reacted with a phenol or a naphthol, and if necessary, prepolymerization can be carried out by heating or the like. Further, a commercially available product prepared in accordance with this can also be used.

The resin composition (P) is a cyanate resin used as the thermosetting resin (A), whereby the linear expansion coefficient of the obtained insulating layer can be reduced. Further, by using a cyanate resin, electrical characteristics (low dielectric constant, low dielectric loss), mechanical strength, and the like of the obtained insulating layer can be improved.

Examples of the cyanate resin include a phenol type cyanate resin, a bisphenol type cyanate resin, a bisphenol E type cyanate resin, and a tetramethyl bisphenol F type cyanate resin. An acid ester resin; a naphthol aralkyl type cyanate resin obtained by reacting a naphthol aralkyl type phenol resin with a cyanogen halide; a dicyclopentadiene type cyanate resin; a biphenyl alkyl type cyanide An acid ester resin or the like. Among these, a novolac type cyanate resin or a naphthol aralkyl type cyanate resin is preferable, and a novolac type cyanate resin is more preferable. By using a novolac type cyanate resin, the crosslinking density of the obtained insulating layer can be increased, and heat resistance can be improved.

This reason can be formed, for example, by a phenolic cyanate resin after hardening reaction to form three ring. Further, it is considered that the phenolic cyanate resin has a high proportion of benzene rings in the structure and is easily carbonized. Further, the insulating layer containing a phenolic type cyanate resin has excellent rigidity. Therefore, the heat resistance of the obtained insulating layer can be further improved.

As the novolac type cyanate resin, for example, the following general formula (I) can be used:

The average repeating unit n of the phenolic type cyanate resin represented by the general formula (I) is an arbitrary integer. The average repeating unit n is not particularly limited, but is preferably 1 or more, more preferably 2 or more. When the average repeating unit n is at least the above lower limit value, the heat resistance of the novolac type cyanate resin can be improved, and the occurrence of detachment or volatilization of the low-volume body can be suppressed during heating. Further, the average repeating unit n is not particularly limited, but is preferably 10 or less, more preferably 7 or less. When n is at most the above upper limit value, the melt viscosity can be suppressed from being improved, and the formability of the insulating layer can be improved.

Further, as the cyanate resin, a naphthol aralkyl type cyanate resin represented by the following general formula (II) is preferably used. The naphthol aralkyl type cyanate resin represented by the following general formula (II) is, for example, a naphthol such as α-naphthol or β-naphthol, and a para-diol, α,α'-dimethyl Naphthol aralkyl obtained by reacting oxy-p-xylene, 1,4-bis(2-hydroxy-2-propyl)benzene or the like A phenolic resin obtained by condensation with a cyanogen halide. The repeating unit n of the general formula (II) is preferably an integer of 10 or less. If the repeating unit n is below 10, a more uniform insulating layer can be obtained. Further, there is a tendency that it is less likely to cause intramolecular polymerization during synthesis, improve liquid separation when washing, and prevent a decrease in yield.

(In the formula, R represents each independently a hydrogen atom or a methyl group; and n represents an integer of 1 or more and 10 or less.)

In addition, the cyanate resin may be used singly or in combination of two or more kinds, and one or two or more kinds of the prepolymers may be used in combination.

The content of the cyanate resin contained in the resin composition (P) is not particularly limited, and when the total solid content (that is, the component other than the solvent) of the resin composition (P) is 100% by mass, it is preferably 1.0% by mass or more and 25.0% by mass or less, more preferably 3.0% by mass or more and 20.0% by mass or less. If the content of the cyanate resin is within the above range, the storage elastic modulus E' of the obtained insulating layer can be further improved.

Benzo Compounds with benzo a compound of the ring. Benzo The compound may be one or more selected from the group consisting of a compound represented by the following formula (2) and a compound represented by the following formula (3), for example.

(In the above formula (2), X ₂ is independently an alkylene group having 1 or more and 10 or less carbon atoms, a group represented by the above formula (1a), a group represented by the formula "-SO ₂ -", and "-CO-". The group represented by a group, an oxygen atom or a single bond; and each of R ₂ is independently a hydrocarbon group having 1 or more and 6 or less carbon atoms; and c is independently an integer of 0 or more and 4 or less.)

(In the above formula (3), X ₃ is independently an alkylene group having 1 or more and 10 or less carbon atoms, a group represented by the above formula (1a), a group represented by the formula "-SO ₂ -", and "-CO-". The group represented by a group, an oxygen atom or a single bond; and each of R ₃ is independently a hydrocarbon group having 1 or more and 6 or less carbon atoms; and d is independently an integer of 0 or more and 4 or less.)

The X ₂ and X ₃ in the above formula (2) and the above formula (3) can be, for example, the same as the description of X _{1 in} the above formula (1). Further, R ₂ and R ₃ in the above formula (2) and the above formula (3) can be, for example, the same as the description of R _{1 in} the above formula (1), and in the above formula (2) and the above formula (3). The c and d systems can be set to be the same as the description of a in the above formula (1).

Benzo The compound represented by the above formula (2) and the compound represented by the above formula (3) are preferably a compound represented by the above formula (2). Thereby, the insulating layer obtained from the resin composition (P) can exhibit more excellent low heat shrinkability and chemical resistance.

Further, the above-described formula (2) preferred is the above compound X ₂ is 1 or more carbon atoms and 3 or less linear or branched chain alkylene, R ₂ is a hydrocarbon group of 1 or 2, c is 0 The above and an integer of 2 or less. Alternatively, it is preferable that X ₂ is a group represented by any one of the above formulas (1a-1) and (1a-2), and c is 0. Thereby, the insulating layer obtained from the resin composition (P) can exhibit more excellent low heat shrinkability and chemical resistance.

Benzo A preferred example of the compound is, for example, a compound represented by the following formula (2-1), a compound represented by the following formula (2-2), a compound represented by the following formula (2-3), and the following formula: One or two or more selected from the group consisting of the compound represented by the formula (3-1), the compound represented by the following formula (3-2), and the compound represented by the following formula (3-3).

[Chem. 21] (In the above formula (2-3), R is independently a hydrocarbon group having 1 to 4 carbon atoms.)

Benzene contained in the resin composition (P) The content of the compound is not particularly limited, and when the total solid content of the resin composition (P) (that is, the component other than the solvent) is 100% by mass, it is preferably 1.0% by mass or more and 25.0% by mass or less, more preferably It is 3.0% by mass or more and 20.0% by mass or less. Benzo When the content of the compound is within the above range, the low heat shrinkability and chemical resistance of the obtained insulating layer can be further improved.

The resin composition (P) of the present embodiment is an inorganic filler (B) containing a necessary component. Thereby, the storage elastic modulus E' of the obtained insulating layer can be improved. Also, the coefficient of linear expansion of the obtained insulating layer can be lowered.

Examples of the inorganic filler (B) include talc, calcined clay, uncalcined clay, mica, glass, etc.; oxides such as titanium oxide, aluminum oxide, soft alumina, cerium oxide, and molten cerium oxide; Carbonate such as calcium carbonate, magnesium carbonate or hydrotalcite; hydroxide such as aluminum hydroxide, magnesium hydroxide or calcium hydroxide; barium sulfate, calcium sulfate and calcium sulfite Sulfate or sulfite; zinc borate, barium metaborate, aluminum borate, calcium borate, sodium borate, etc.; nitrides such as aluminum nitride, boron nitride, tantalum nitride, carbon nitride; barium titanate, Titanate such as barium titanate and the like.

Among these, talc, alumina, glass, cerium oxide, mica, aluminum hydroxide, magnesium hydroxide, and more preferably cerium oxide are preferred. The inorganic filler (B) may be used alone or in combination of two or more.

The average particle diameter of the inorganic filler (B) is not particularly limited, but is preferably 0.01 μm or more, and more preferably 0.05 μm or more. When the average particle diameter of the inorganic filler (B) is at least the above lower limit value, the viscosity of the varnish can be suppressed from being improved, and the workability at the time of producing the insulating layer can be improved. Further, the average particle diameter of the inorganic filler (B) is not particularly limited, but is preferably 5.0 μm or less, more preferably 2.0 μm or less, and particularly preferably 1.0 μm or less. When the average particle diameter of the inorganic filler (B) is at most the above upper limit value, it is possible to suppress the occurrence of precipitation of the inorganic filler (B) in the varnish, and to obtain a more uniform resin layer. Moreover, when the circuit size L/S of the printed wiring board is less than 20 μm/20 μm, it is possible to suppress the influence on the insulation between the wirings.

The average particle diameter of the inorganic filler (B) is determined by, for example, a laser diffraction type particle size distribution measuring apparatus (manufactured by HORIBA, LA-500), and the particle size distribution of the particles is measured on a volume basis, and the median diameter (D ₅₀₎ can be measured. ) Set to the average particle size.

In addition, the inorganic filler (B) is not particularly limited, and an inorganic filler having an average particle diameter of monodisperse or an inorganic filler having an average particle diameter of polydisperse can be used. In addition, the inorganic fillers having an average particle diameter of monodisperse and/or polydisperse may be used singly or in combination of two or more.

When the inorganic filler (B) is a cerium oxide particle, it is preferably cerium oxide particles having an average particle diameter of 5.0 μm or less, more preferably cerium oxide particles having an average particle diameter of 0.1 μm or more and 4.0 μm or less. The cerium oxide particles are 0.2 μm or more and 2.0 μm or less. Thereby, the filling property of the inorganic filler (B) can be further improved.

The content of the inorganic filler (B) is not particularly limited, and when the total solid content (that is, the component other than the solvent) of the resin composition (P) is 100% by mass, it is preferably 50.0% by mass or more and 90.0% by mass. % or less, more preferably 55.0% by mass or more and 80.0% by mass or less. When the content of the inorganic filler (B) is within the above range, the obtained insulating layer can be particularly low in thermal expansion and low in water absorption.

The resin composition (P) contains a (meth)acrylic block copolymer (C). Thereby, the stress of the obtained insulating layer can be alleviated, or the adhesion to other members such as the circuit layer can be further improved. Moreover, the coefficient of linear expansion of the obtained insulating layer at a high temperature can be lowered.

The (meth)acrylic block copolymer (C) is a block copolymer containing a (meth)acrylic monomer as an essential monomer component. Examples of the above (meth)acrylic monosystem include methyl acrylate, ethyl acrylate, n-butyl acrylate, tributyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, and methyl group. Ethyl acrylate, n-butyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, isostearyl methacrylate, etc. (meth) acrylate having an alicyclic structure such as cyclohexyl acrylate or cyclohexyl methacrylate; (meth) acrylate having an aromatic ring such as benzyl methacrylate; methacrylic acid-2- (fluorinated) alkyl (meth) acrylate such as trifluoroethyl ester; acrylic acid, methacrylic acid, cis-butyl a carboxyl group-containing acrylic monomer having a carboxyl group in a molecule such as adipic acid or maleic anhydride; 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, methacrylic acid-2 a hydroxyl group-containing acrylic monomer having a hydroxyl group in a molecule such as hydroxyethyl ester, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate or mono(meth)acrylate of glycerin; a methacrylic acid ring Acrylic acid monomer having epoxy group in the molecule of oxypropyl acrylate, methyl methacrylate, propyl methacrylate, methacrylic acid-3,4-epoxycyclohexyl methyl ester; allyl acrylate, methacrylic acid acryl An allyl-containing acrylic monomer having an allyl group in an ester or the like; a molecule such as γ-methacryloxypropyltrimethoxydecane or γ-methylpropenyloxypropyltriethoxydecane a hydrazino group-containing acrylic monomer having a hydrolyzable decyl group; a benzotriazole system such as 2-(2'-hydroxy-5'-methacrylomethoxyethylphenyl)-2H-benzotriazole Ultraviolet absorbing group of ultraviolet absorbing acrylic monomers and the like.

Further, the (meth)acrylic block copolymer (C) may be used as a monomer component as a monomer other than the above (meth)acrylic monomer. Examples of the single system other than the above (meth)acrylic monomer include aromatic vinyl compounds such as styrene and α-methylstyrene; conjugated dienes such as butadiene and isoprene; and ethylene; Olefins such as propylene and isobutylene, and the like.

The (meth)acrylic block copolymer (C) is not particularly limited, and may, for example, be a diblock copolymer composed of two polymer blocks or a triblock composed of three polymer blocks. A copolymer, a multi-block copolymer composed of four or more polymer blocks, and the like.

Among these, the (meth)acrylic block copolymer (C) is heat resistant, The viewpoint of improvement in light resistance and crack resistance is preferably, for example, a polymer block (S) (soft block) having a lower glass transition temperature (Tg), and having a Tg higher than a polymer block. (S) polymer block (H) (hard block) array of HS structure diblock copolymer; polymer block (S) and polymer block (H) staggered copolymer; A triblock copolymer having a polymer block (S) and an HSH structure having a polymer block (H) at both ends.

Further, the polymer Tg of the polymer block (S) constituting the (meth)acrylic block copolymer (C) is not particularly limited, but is preferably less than 30 °C. Further, the polymer Tg constituting the polymer block (H) is not particularly limited, but is preferably 30 ° C or higher. When the (meth)acrylic block copolymer (C) has a plurality of polymer blocks (H), each of the polymer blocks (H) may have the same composition or may be different. Similarly, the (meth)acrylic block copolymer (C) has a plurality of polymer blocks (S), and each polymer block (S) has the same composition or may be different.

The monomer component constituting the polymer block (H) is not particularly limited, and for example, a monomer having a homopolymer Tg of 30 ° C or higher can be used. Such a single system may, for example, be methyl methacrylate, styrene, acrylamide or acrylonitrile.

The monomer component constituting the polymer block (S) is not particularly limited, and for example, a monomer having a homopolymer Tg of less than 30 ° C can be used. Examples of such a single system include C _2-10 alkyl acrylate such as butyl acrylate or 2-ethylhexyl acrylate; butadiene (1,4-butadiene).

A preferred example of the (meth)acrylic block copolymer (C) is that the polymer block (S) is a polymer composed of butyl acrylate (BA) as a main monomer, and the polymer is Block (H) is a polymerization composed of methyl methacrylate (MMA) as the main monomer Polymethyl methacrylate-block-polybutyl acrylate-block-polymethyl methacrylate terpolymer (PMMA-b-PBA-b-PMMA), PMMA-b-PBA, and the like.

From the viewpoint of improvement in heat resistance, light resistance, and crack resistance, the above-mentioned PMMA-b-PBA-b-PMMA and PMMA-b-PBA are preferred. Further, the above-mentioned PMMA-b-PBA-b-PMMA and PMMA-b-PBA may have a hydrophilic group (for example, a hydroxyl group, a carboxyl group, or an amine) as needed in order to improve the compatibility with the thermosetting resin (A) or the like. A monomer such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate or (meth) acrylate, etc., is copolymerized in the PMMA block and/or the PBA block.

The number average molecular weight (Mn) of the (meth)acrylic block copolymer (C) is not particularly limited, but is preferably 3,000 or more and 500,000 or less, more preferably 5,000 or more and 100,000 or less. When the number average molecular weight (Mn) is at least the above lower limit value, the toughness of the obtained cured product can be further improved, and as a result, the crack resistance can be further improved. On the other hand, when the number average molecular weight (Mn) is at most the above upper limit value, the compatibility with the thermosetting resin (A) can be improved.

The (meth)acrylic block copolymer (C) can be produced by a known or customary method for producing a block copolymer.

Further, the (meth)acrylic block copolymer (C) may be, for example, a trade name of "Nanostrength M52N", "Nanostrength M22N", "Nanostrength M51", "Nanostrength M52", "Nanostrength M53", "Nanostrength" M22" (made by ARKEMA, PMMA-b-PBA-b-PMMA); trade name "Nanostrength D51N" (made by ARKEMA, PMMA-b-PBA), trade name "Nanostrength E21", "Nanostrength E41" (ARKEMA) system, Commercial products such as PSt (polystyrene)-b-PBA-b-PMMA).

The content of the (meth)acrylic block copolymer (C) contained in the resin composition (P) is not particularly limited, and the total solid content of the resin composition (P) (that is, the component other than the solvent) is set. When it is 100% by mass, it is preferably 0.1% by mass or more and less than 10.0% by mass, more preferably 1.0% by mass or more and 8.0% by mass or less. When the content of the (meth)acrylic block copolymer (C) is within the above range, the stress of the obtained insulating layer can be further alleviated, or the adhesion to other members such as the circuit layer can be further improved.

Further, a hardening accelerator and a coupling agent may be appropriately blended in the resin composition (P) as needed.

The resin composition (P) may contain, for example, a curing accelerator. Thereby, the hardenability of the resin composition (P) can be improved. As the hardening accelerator, those which promote the hardening reaction of the thermosetting resin (A) can be used, and the type is not particularly limited. In the present embodiment, the curing accelerator may contain, for example, zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, zinc octoate, acetoacetate cobalt (II), acetylacetate (III), and the like. Organometallic salt; tertiary amine such as triethylamine, tributylamine, diazabicyclo[2,2,2]octane; 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2- Ethyl-4-ethylimidazole, 2-phenyl-4-ethylimidazole, 2-phenyl-4-methyl-5-hydroxyimidazole, 2-phenyl-4-methyl-5-hydroxymethyl Imidazoles such as imidazole and 2-phenyl-4,5-dihydroxyimidazole; phenolic compounds such as phenol, bisphenol A and nonylphenol; organic acids such as acetic acid, benzoic acid, salicylic acid and p-toluenesulfonic acid; One or more of the salt compounds are selected. Among these, from the viewpoint of further improving the curability of the resin composition (P), it is more preferable to contain an onium salt compound.

The onium salt compound which can be used as the hardening accelerator is not particularly limited, and for example, a compound represented by the following general formula (2) can be used: (In the formula (2), P represents a phosphorus atom; and R ₃ , R ₄ , R ₅ and R ₆ each represent an organic group having a substituted or unsubstituted aromatic ring or a heterocyclic ring, or a substituted or unsubstituted aliphatic group, It may be different from each other. A ^- line means that there are at least one n(n≧1) valence proton-donating anion in the molecule which will be released from the proton outside the molecule, or its wrong anion.)

For example, when the total solid content (that is, the component other than the solvent) of the resin composition (P) is 100% by mass, the content of the curing accelerator is preferably 0.01% by mass or more, and more preferably 0.1% by mass or more. When the content of the curing accelerator is at least the above lower limit value, the curability of the resin composition (P) can be more effectively improved. On the other hand, when the content of the curing accelerator is, for example, 100% by mass of the total solid content of the resin composition (P) (that is, a component other than the solvent), it is preferably 5% by mass or less, more preferably 1 mass. %the following. By setting the content of the curing accelerator to be equal to or lower than the above upper limit, the storage stability of the thermosetting resin composition (P) can be improved.

Further, the resin composition (P) may also contain a coupling agent. The coupling agent may be directly added during the preparation of the resin composition (P), or may be added to the inorganic filler (B) in advance. By using the coupling agent, the wettability of the interface between the inorganic filler (B) and each resin can be improved. Therefore, it is preferred to use a coupling agent to improve the heat resistance of the obtained insulating layer.

The coupling agent may, for example, be a decane coupling agent such as an epoxy decane coupling agent, a cationic decane coupling agent or an amino decane coupling agent; a titanate coupling agent and a polyasoxy oil type coupling agent. The coupling agent may be used alone or in combination of two or more.

Thereby, the wettability of the interface between the inorganic filler (B) and each resin can be improved, and the heat resistance of the obtained insulating layer can be further improved.

As the decane coupling agent, various materials can be used, and examples thereof include epoxy decane, amino decane, alkyl decane, urea decane, decyl decane, vinyl decane, and the like.

Specific examples of the compound include γ-aminopropyltriethoxydecane, γ-aminopropyltrimethoxydecane, and N-β(aminoethyl)γ-aminopropyltrimethoxydecane. , N-β (aminoethyl) γ-aminopropyl methyl dimethoxy decane, N-phenyl γ-aminopropyl triethoxy decane, N-phenyl γ-aminopropyl Trimethoxydecane, N-β(aminoethyl)γ-aminopropyltriethoxydecane, N-6-(aminohexyl)3-aminopropyltrimethoxydecane, N-(3 -(trimethoxydecylpropyl)-1,3-benzenedimethane, γ-glycidoxypropyltriethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ- Glycidoxypropylmethyldimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ-mercaptopropyltrimethoxydecane, methyltrimethoxydecane , γ-ureidopropyl triethoxy decane, vinyl triethoxy decane, etc., one or a combination of these may be used alone Use two or more. Among these, epoxy decane, decyl decane, and amino decane are preferred, and amino decane is more preferably a primary amino decane or an aniline decane.

The amount of the coupling agent to be added depends on the specific surface area of the inorganic filler (B), and is not particularly limited. When the total solid content of the resin composition (P) (that is, the component other than the solvent) is 100% by mass. It is preferably 0.01% by mass or more and 2% by mass or less, more preferably 0.05% by mass or more and 1% by mass or less.

When the content of the coupling agent is at least the above lower limit value, the inorganic filler (B) can be sufficiently coated, and the heat resistance of the obtained insulating layer can be improved. In addition, when the content of the coupling agent is at most the above upper limit value, it is possible to suppress the influence on the reaction, and it is possible to suppress a decrease in bending strength or the like of the obtained insulating layer.

Further, in the resin composition (P), for example, a pigment, a dye, an antifoaming agent, a leveling agent, an ultraviolet absorber, a foaming agent, an antioxidant, or the like may be added without damaging the object of the present invention. Additives other than the above components such as a flame retardant or an ion trapping agent.

Examples of the pigments include kaolin, synthetic iron oxide red, cadmium yellow, nickel titanium yellow, strontium yellow, chromium hydroxide, chromium oxide, cobalt aluminate, synthetic ultramarine blue, and the like; polycyclic pigments such as phthalocyanine; Nitrogen pigments, etc.

Examples of the dyes include isoindolinone, isoporphyrin, quinoline yellow, dibenzopyran, pyrrolopyrroledione, anthracene, peperone, anthracene, anthracene, , quinacridone, benzimidazolone, purpurin, phthalocyanine, methylimine and the like.

The resin composition (P) is, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethyl acetate, cyclohexane, heptane, cyclohexane, cyclohexanone, tetrahydrofuran, dimethylformamide, Ultrasonic dispersion method, high-pressure collision type in organic solvents such as dimethylacetamide, dimethyl hydrazine, ethylene glycol, celecoxib, carbitol, anisole, and N-methylpyrrolidone A resin varnish (I) can be formed by dissolving, mixing, and stirring various types of mixers such as a dispersion method, a high-speed rotary dispersion method, a bead milling method, a high-speed shear dispersion method, and a rotation-revolving dispersion method.

The solid content of the resin varnish (I) is not particularly limited, but is preferably 40% by mass or more and 80% by mass or less, more preferably 50% by mass or more and 70% by mass or less. Thereby, the workability and film formability of the resin varnish (I) can be further improved.

In addition, the resin composition (P) of the present embodiment may be a fiber base material or a paper base material which does not contain, for example, a glass fiber base material. Thereby, a resin composition (P) which is particularly suitable for forming a stacked layer and a solder resist layer can be realized.

In the above resin composition (P), the ratio of each component is as follows.

When the total solid content (that is, the component other than the solvent) of the resin composition (P) is 100% by mass, the ratio of the thermosetting resin (A) is preferably 8.0% by mass or more and 40.0% by mass or less, and the inorganic filler is contained. The ratio of (B) is preferably 50.0% by mass or more and 90.0% by mass or less, and the ratio of the (meth)acrylic block copolymer (C) is preferably 0.1% by mass or more and less than 10.0% by mass.

The ratio of the thermosetting resin (A) is more preferably 10.0% by mass or more and 30.0% by mass or less, and the ratio of the inorganic filler (B) is more preferably 55.0% by mass or more and 80.0% by mass or less, and (meth)acrylic acid is embedded. The proportion of the segment copolymer (C) is more preferably 1.0% by mass. It is 8.0 mass% or less.

In addition, from the viewpoint of improving the rigidity and heat resistance of the printed wiring board obtained by using the resin composition (P), the resin composition (P) is subjected to heat treatment at a temperature of 230 ° C for 2 hours to obtain a cured glass transition temperature system. 180 ° C or more, preferably 200 ° C or more, more preferably 230 ° C or more. The relevant upper limit is preferably, for example, 400 ° C or lower. The glass transition temperature can be measured using a dynamic viscoelasticity analyzer (DMA). Further, the glass transition temperature is a corresponding temperature at which a tangent tan δ peak value is lost in a region of 150 ° C or higher in a curve obtained by dynamic viscoelasticity measurement at a temperature increase rate of 5 ° C/min and a frequency of 1 Hz.

In the cured product, when the glass transition temperature obtained by the dynamic viscoelasticity measurement satisfies the above range, the rigidity of the obtained printed wiring board can be improved, and the warpage of the printed wiring board during mounting can be reduced. As a result, in the semiconductor device obtained, the positional deviation of the semiconductor element on the printed wiring board can be suppressed, and the connection reliability between the semiconductor element and the printed wiring board can be improved.

In order to achieve such a glass transition temperature, the types and blending amounts of the thermosetting resin (A), the inorganic filler (B), the (meth)acrylic block copolymer (C), and the curing accelerator are appropriately controlled. Wait, it is important.

In addition, the cured product obtained by heat-treating the resin composition (P) at 230 ° C for 2 hours is subjected to dynamic viscoelasticity measurement at a temperature increase rate of 5 ° C / min and a frequency of 1 Hz, and is 30 ° C or higher. And the peak value of the loss tangent tan δ in the region less than 180 ° C is set to X ₁ , and the peak value of the loss tangent tan δ in the region above 180 ° C is set to X ₂ , X ₁ /X ₂ is compared Preferably, it is 0.40 or less, more preferably 0.35 or less.

In the cured product, if X ₁ /X _{2 is} at most the above upper limit value, the stress of the obtained insulating layer can be further alleviated, or the adhesion to other members such as the circuit layer can be further improved. The relevant lower limit is preferably, for example, 0.15 or more.

The resin composition (P) is subjected to heat treatment at, for example, a temperature of 230 ° C for 2 hours from the viewpoint of insulation reliability of the printed wiring board under high temperature and high humidity and further improvement of connection reliability between the semiconductor element and the printed wiring board. The obtained cured product has an average linear expansion coefficient calculated as α ₁ from the range of from 50 ° C to 150 ° C in the in-plane direction, and an average linear expansion coefficient calculated from the range of 150 ° C to 250 ° C is set to α. _{At 2} o'clock, the difference (α _{2 -} α ₁ ) between α ₂ and α ₁ is preferably 20.0 ppm / ° C or less, more preferably 15.0 ppm / ° C or less, and particularly preferably 10.0 ppm / ° C or less.

In the present embodiment, the average linear expansion coefficients α ₁ and α ₂ are TMA (thermo-mechanical analysis) devices (manufactured by TA Instruments, Q400), and the temperature ranges from 30 ° C to 260 ° C, the temperature increase rate is 10 ° C/min, and the load is 10 g. The average value of the coefficient of linear expansion (CTE) in the plane direction (XY direction) measured under the condition of the compression mode.

In the hardened material, if (α ₂ -α ₁ ) is at most the above upper limit value, the obtained printed wiring board can be reduced in the difference in linear expansion coefficient between the circuit layer and the insulating layer even if the ambient temperature largely changes. The change in the derived stress. Therefore, the obtained printed wiring board and the semiconductor device can maintain the adhesion between the circuit layer and the insulating layer even when the temperature changes drastically for a long period of time. From the above, it is considered that by using such a resin composition (P), the insulation reliability of the obtained printed wiring board under high temperature and high humidity can be improved.

Further, when (α _{2 -} α ₁ ) is at most the above upper limit value in the cured product, the obtained semiconductor device can reduce linear expansion between the printed wiring board and the semiconductor element even if the ambient temperature largely changes. The difference in coefficient causes a change in the derived stress. As a result, the warpage of the semiconductor device can be further suppressed, and the positional shift of the semiconductor element to the printed wiring board can be further suppressed, and the connection reliability and temperature cycle reliability between the semiconductor element and the printed wiring board at a high temperature can be further improved.

In addition, from the viewpoint of further improving the insulation reliability of the printed wiring board under high temperature and high humidity and the connection reliability between the semiconductor element and the printed wiring board, the resin composition (P) is applied at, for example, a temperature of 230 ° C. The cured product obtained by the hourly heat treatment has an average linear expansion coefficient α ₂ calculated from the range of from 150 ° C to 250 ° C in the in-plane direction, preferably 45.0 ppm/° C. or less, more preferably 35.0 ppm/° C. or less. The best system is 27.0ppm/°C or less. The relevant lower limit value is not particularly limited, and may be, for example, 0.1 ppm/° C. or more.

In the hardened material, if the average linear expansion coefficient α ₂ satisfies the above range, it is possible to reduce the difference in linear expansion coefficient between the circuit layer and the insulating layer when the obtained printed wiring board is exposed to a relatively high temperature such as solder reflow. stress. Therefore, the obtained printed wiring board and the semiconductor device can maintain the adhesion between the circuit layer and the insulating layer even when the temperature changes drastically for a long period of time. Thereby, the insulation reliability of the obtained printed wiring board under high temperature and high humidity can be further improved.

Further, in the cured product, if the average linear expansion coefficient α ₂ satisfies the above range, the linear expansion coefficient between the printed wiring board and the semiconductor element can be alleviated when the obtained semiconductor device is exposed to a relatively high temperature such as solder reflow. The difference caused by the change in the derived stress. As a result, the warpage of the semiconductor device can be further suppressed, and the positional shift of the semiconductor element to the printed wiring board can be further suppressed, and the connection reliability and temperature cycle reliability between the semiconductor element and the printed wiring board at a high temperature can be further improved.

In order to achieve such average linear expansion coefficients α ₁ , α ₂ , and α ₂ -α ₁ , the thermosetting resin (A), the inorganic filler (B), and the (meth)acrylic block copolymer (C) are appropriately controlled. ), the type of hardening accelerator, etc., the amount of blending, etc., are important.

In addition, from the viewpoint of further improving the balance of rigidity, heat resistance, and stress relaxation ability of the printed wiring board obtained by using the resin composition (P), the resin composition (P) is subjected to, for example, a temperature of 230 ° C for 2 hours. The cured product obtained by the heat treatment has a storage elastic modulus E' ₂₅₀ at 250 ° C of preferably 12 GPa or less, _more preferably 10 GPa or less, and particularly preferably 5 GPa or less. The relevant lower limit value is not particularly limited, and may be, for example, 1 GPa or more.

In the cured product, if the storage elastic modulus E' _{250 at} 250 ° C satisfies the above range, the performance of the obtained printed wiring board can be improved in rigidity, heat resistance, and stress relaxation ability, and the printed wiring can be further reduced during mounting. The substrate is warped. As a result, the semiconductor device obtained in the related art can further suppress the positional shift of the semiconductor element to the printed wiring board, and can further improve the connection reliability between the semiconductor element and the printed wiring board.

In order to achieve such a storage elastic modulus E' ₂₅₀ , the types of the thermosetting resin (A), the inorganic filler (B), the (meth)acrylic block copolymer (C), and the curing accelerator are appropriately controlled. , the amount of blending, etc., is important.

Next, the resin film 100 with a carrier will be described.

Fig. 1 is a cross-sectional view showing an example of a configuration of a resin film 100 with a carrier in the embodiment. The resin film 100 with a carrier is used for forming an insulating layer of a stacked layer or a solder resist layer of a printed wiring substrate. As shown in FIG. 1, the carrier-attached resin film 100 is provided with, for example, a carrier substrate 12 and a resin film 10 provided on the carrier substrate 12. The resin film 10 is composed of the resin composition (P) of the present embodiment. Therefore, as described above, the reliability of the semiconductor device provided with the insulating layer formed by using the resin film 100 with the carrier can be improved.

The resin film 100 with a carrier is formed by applying a varnish-like resin composition (P) to the carrier substrate 12 to form a coating film, and then forming a resin film 10 by performing solvent removal treatment on the coating film. Can be manufactured. The carrier substrate 12 is not particularly limited, and is made of, for example, PET (Poly ethylene terephthalate) or copper foil. Further, the film thickness of the resin film 10 is not particularly limited, and may be, for example, 5 μm or more and 300 μm or less. Thereby, the resin film 10 suitable for forming the insulating layer in the stacked layer or the solder resist layer can be realized.

In the present embodiment, for example, the insulating layer in the stacked layer or the solder resist layer can be formed by using the resin film 100 with a carrier as described below. First, on the side of the circuit board on which the conductor circuit pattern is provided, the resin film 100 to which the carrier is attached is attached to the circuit board so as to face the circuit board. The attachment of the resin film 100 with a carrier can be carried out, for example, by laminating a resin film 100 with a carrier on a circuit board, followed by vacuum heating and press molding. Next, the carrier substrate 12 is peeled off from the resin film 10. Next, the resin film 10 remaining on the circuit board is thermally cured. Thereby, the resin film 10 is hardened and hardened by covering the conductor circuit pattern on the circuit board. An insulating layer made of a film.

Next, the printed wiring board 300 of the present embodiment will be described. 2 and 3 are cross-sectional views showing an example of the configuration of the printed wiring board 300 of the present embodiment.

The printed wiring board 300 includes, for example, a core layer 311 and a solder resist layer 401 as shown in FIG. 2 . Further, the printed wiring board 300 may include, for example, a core layer 311, a stacked layer 317, and a solder resist layer 401 as shown in FIG.

In the present embodiment, the "via hole 307" is a hole for electrically coupling the layers, and may be any through hole or non-through hole.

The printed wiring board 300 of the present embodiment may be a single-sided printed wiring board, or may be a double-sided printed wiring board or a multilayer printed wiring board. The "double-sided printed wiring board" refers to a printed wiring board in which a metal layer 303 is laminated on both surfaces of the insulating layer 301. In addition, the "multilayer printed wiring board" is a printed wiring board in which one or more stacked layers 317 are laminated on the core layer 311 by a plating via method or a stacking method.

Here, in the printed wiring board 300 of the present embodiment, at least one layer selected from the insulating layer 305 and the solder resist layer 401 of the stacked layer 317 is preferably formed of a cured product of the resin composition (P) of the present embodiment. All of the layers selected from the insulating layer 305 and the solder resist layer 401 of the stacked layer 317 are formed of a cured product of the resin composition (P) of the present embodiment.

The metal layer 303 is, for example, a circuit layer, and includes a metal foil 105 and/or an electroless metal plating film 308 and an electrolytic metal plating layer 309.

When the printed wiring substrate 300 is a multilayer printed wiring substrate as shown in FIG. 3, the metal layer 303 is a circuit layer in the core layer 311 or the stacked layer 317.

The metal layer 303 is formed on the surface of the metal foil 105 or the insulating layer 301 by chemical treatment or plasma treatment, for example, by an SAP (Semi-Addition Process) method. After the electroless metal plating film 308 is applied to the metal foil 105 or the insulating layer 301, the non-circuit forming portion is protected by the plating resist, and the electrolytic metal plating layer 309 is applied by electrolytic plating, by removing the plating layer and removing it by rapid etching. The electroless metal plating film 308 forms a metal layer 303 on the metal foil 105 or the insulating layer 301.

When the circuit size of the metal layer 303 is expressed by a line and a space (L/S), it can be set to 25 μm / 25 μm or less, preferably 15 μm / 15 μm or less. If the circuit size is reduced to form fine wiring, the insulation reliability between the wirings is lowered. However, the printed wiring board 300 of the present embodiment can perform fine wiring having a line and a space (L/S) of 15 μm/15 μm or less, and can achieve a reduction in line and space (L/S) as low as about 10 μm/10 μm.

The thickness of the metal layer 303 is not particularly limited, and is usually 5 μm or more and 25 μm or less.

The thickness of the insulating layer 301 in the core layer 311 (also covering the insulating layer 301 in the printed wiring substrate 300 not including the stacked layer 317) is preferably 0.025 mm or more and 0.3 mm or less. If the thickness of the insulating layer 301 is within the above range, mechanical strength and production can be obtained. The balance of properties is particularly excellent, and it can be applied to the insulating layer 301 of a thin printed wiring board.

The thickness of the insulating layer 305 in the stacked layer 317 is preferably 0.015 mm or more and 0.05 mm or less. When the thickness of the insulating layer 305 is within the above range, it is possible to obtain particularly excellent balance between mechanical strength and productivity, and it can be applied to the insulating layer 305 of a thin printed wiring board.

Next, an example of a method of manufacturing the printed wiring board 300 will be described. However, the method of manufacturing the printed wiring board 300 of the present embodiment is not limited to the following examples.

First, an insulating layer 301 and a metal-clad laminate formed of a metal foil 105 laminated thereon are prepared.

Next, part or all of the metal foil 105 is removed by an etching process.

Next, a via hole 307 is formed in the insulating layer 301. The via hole 307 can be formed, for example, by using a drill press or laser irradiation. The laser system used in laser irradiation may be, for example, an excimer laser, a UV laser, a carbon dioxide gas laser, or the like. The resin residue or the like after the via hole 307 is formed may be removed by using an oxidizing agent such as permanganate or dichromate.

Further, the via hole 307 may be formed in the insulating layer 301 before the metal foil 105 is removed by an etching process.

Next, the surface of the metal foil 105 or the insulating layer 301 is subjected to a chemical liquid treatment or a plasma treatment.

The chemical liquid treatment is not particularly limited, and for example, a method of oxidizing agent solution having a mechanical decomposition action or the like can be used. In addition, the plasma processing system can directly illuminate a substance to be a target substance with a strong oxidation active species (plasma, radical, etc.), and remove the organic residue.

Next, a metal layer 303 is formed. The metal layer 303 can be formed, for example, by a semi-additive process (SAP) or a modified semi-addictive process (MSAP). Hereinafter, specific description will be given.

First, an electroless metal plating film 308 is formed on the surface of the metal foil 105 or the insulating layer 301 and the via hole 307 by electroless plating, and the printed wiring board 300 is electrically connected to both sides. Further, the via hole 307 can be appropriately filled with a conductor paste or a resin paste. The electroless plating method will be described. For example, first, a catalyst core is provided on the surface of the metal foil 105 or the insulating layer 301 in the via hole 307. The catalyst core is not particularly limited, and for example, a noble metal ion or a palladium colloid can be used. Next, an electroless metal plating film 308 is formed by electroless plating treatment using the catalyst core as a core. For the electroless plating treatment, for example, copper sulfate, formaldehyde, a binder, sodium hydroxide or the like can be used. In addition, after electroless plating, it is preferable to carry out heat treatment at 100 to 250 ° C to stabilize the plating film. It is particularly preferable from the viewpoint of heat treatment at 120 to 180 ° C to form a film capable of suppressing oxidation. Further, the average thickness of the electroless plated metal film 308 is, for example, about 0.1 to 2 μm.

Next, a plating resist having a predetermined opening pattern is formed on the metal foil 105 and/or the electroless metal plating film 308. This opening pattern corresponds to, for example, a circuit pattern. Anti-plating layer Particularly, a known material can be used, and a liquid form and a dry film can be used. When the fine wiring is formed, it is preferable to use a photosensitive dry film or the like for the plating resist. An example of using a photosensitive dry film will be described. For example, a photosensitive dry film is laminated on the electroless metal plating film 308, and the non-circuit forming region is exposed to light to be cured, and the unexposed portion is dissolved and removed by the developing solution. The plating resist is formed by the residual photosensitive film which is hardened.

Next, an electrolytic metal plating layer 309 is formed by electrical plating treatment at least inside the opening pattern of the plating resist layer and on the metal foil 105 and/or the electroless metal plating film 308. The electric plating treatment is not particularly limited, and a known method such as a conventional printed wiring board can be used. For example, a method of flowing a current into the plating solution while being immersed in a plating solution such as copper sulfate is used. The electrolytic metal plating layer 309 may be a single layer or a multilayer structure. The material of the electrolytic metal plating layer 309 is not particularly limited, and for example, any one of copper, copper alloy, 42 alloy, nickel, iron, chromium, tungsten, gold, and solder can be used.

Next, the plating resist is removed using an alkaline stripper, sulfuric acid, or a commercially available photoresist stripper.

Next, the metal foil 105 and/or the electroless metal plating film 308 other than the region where the electrolytic metal plating layer 309 is formed are removed. The metal foil 105 and/or the electroless metal plating film 308 can be removed, for example, by using soft etching (rapid etching) or the like. Here, the soft etching treatment can be performed, for example, using an etching solution containing sulfuric acid and hydrogen peroxide. Thereby, the metal layer 303 can be formed. The metal layer 303 is composed of a metal foil 105 and/or an electroless metal plating film 308 and an electrolytic metal plating layer 309.

Furthermore, the stacked layer 317 is repeatedly applied on the metal layer 303 as needed, and then A plurality of layers can be formed by performing a step of interlayer connection and circuit formation by a semi-additive process. Then, the solder resist layer 401 is laminated on the metal layer 303.

According to the above, the printed wiring board 300 of the present embodiment can be obtained.

Next, a description will be given of the semiconductor device 400 of the present embodiment. 4 and 5 are cross-sectional views showing an example of the configuration of the semiconductor device 400 of the present embodiment. The printed wiring substrate 300 can be used for the semiconductor device 400 shown in FIGS. 4 and 5. The method of manufacturing the semiconductor device 400 is not particularly limited, and for example, the following method can be employed.

First, by performing a reflow process, the semiconductor element 407 is fixed to the connection terminal belonging to a part of the circuit layer via the solder bump 410. Then, the semiconductor device 407, the solder bump 410, and the like are sealed by the sealing material 413, whereby the semiconductor device 400 shown in FIGS. 4 and 5 can be obtained.

The embodiments of the present invention have been described above, but the present invention is not limited to the examples of the present invention, and various configurations other than the above may be employed.

Further, in the above embodiment, the semiconductor element 407 and the circuit layer of the printed wiring board 300 are connected by the solder bumps 410, but are not limited thereto. For example, the semiconductor element 407 and the circuit layer of the printed wiring board 300 may be connected by a bonding wire.

[Examples]

Hereinafter, the present invention will be described using an embodiment and a comparative example, but the present invention is Not limited to these. In addition, in the examples, "parts" means "parts by mass" unless otherwise stated. Further, each thickness is expressed by an average film thickness.

In the examples and comparative examples, the following materials were used:

Epoxy resin 1: aralkyl type epoxy resin (NC3000, manufactured by Nippon Kayaku Co., Ltd.)

Epoxy Resin 2: Naphthyl ether epoxy resin (HP6000, DIC)

Epoxy resin 3: tetrafunctional naphthalene type epoxy resin (Epicron HP-4710, manufactured by DIC Corporation)

Epoxy resin 4: naphthol type epoxy resin (NC7000L, manufactured by Nippon Kayaku Co., Ltd.)

Epoxy resin 5: bisphenol F type epoxy resin (EPICLON 830S, manufactured by DIC Corporation)

Cyanate resin 1: p-xylene modified naphthol aralkyl type cyanate resin represented by general formula (II) [naphthol aralkyl type phenol resin ("SN-485 derivative" manufactured by Tohto Kasei Co., Ltd.) Reactant with cyanogen chloride]

Amine compound 1: 2,2-[4-(4-aminophenoxy)phenyl]propane (manufactured by Wakayama Seiki Co., Ltd., BAPP amine equivalent 103)

Amine compound 2: a terminal amino group modified dimethyl polyfluorene (manufactured by Shin-Etsu Chemical Co., Ltd., X22-161A (number average molecular weight: 1,600)

Maleimide compound 1: In the formula (1), n ₁ is 0 or more and 3 or less, X ₁ is a group represented by "-CH ₂ -", a is 0, and b is 0 (BMI- 2300, Daiwa Chemical Industrial Co., Ltd., Mw=750)

Maleimide compound 2: a bis-n-butylene imino compound represented by formula (a1) (BMI-1500, manufactured by Designer Molecules, molecular weight 1500)

Maleimide compound 3: a compound of the formula (1) wherein n ₁ is 0, X ₁ is a group represented by the formula (1a-1), and e is 0 (BMI-4000, manufactured by Daiwa Kasei Kogyo Co., Ltd., Mw=570)

Maleimide compound 4: a bis-n-butylene imino compound represented by formula (a2) (BMI-1400, manufactured by Designer Molecules, molecular weight 1400)

Maleimide compound 5: a compound of the formula (1) wherein n ₁ is 0, X ₁ is a group represented by "-CH ₂ -", a is 2, and R ₁ is a methyl group and an ethyl group (BMI) -5100, Daiwa Chemical Industrial Co., Ltd., Mw=443)

Benzo Compound 1: Benzene represented by formula (2-1) Compound (Pd type benzophenone) , Shikoku Chemical Industry Co., Ltd.)

Low stress material 1: Acrylic block copolymer (block copolymer of acrylic monomer (PMMA-b-PBA-b-PMMA; b=block), number average molecular weight: about 10,000, manufactured by ARKEMA, Nanostrength M51 )

Low stress material 2: Acrylic block copolymer (block copolymer of acrylic monomer (PMMA-b-PBA-b-PMMA; b=block), number average molecular weight: about 16,000, manufactured by ARKEMA, Nanostrength M52 )

Low stress material 3: Acrylic block copolymer (block copolymer of acrylic monomer (PMMA-b-PBA-b-PMMA; b=block), number average molecular weight: about 19,000, manufactured by ARKEMA, Nanostrength M22 )

Low stress material 4: Acrylic block copolymer (block copolymer of acrylic monomer (PMMA-b-PBA; b = block), number average molecular weight: about 8,000, manufactured by ARKEMA, Nanostrength D51N)

Low stress material 5: two-terminal epoxy functional alkoxysilane oligomer (TSL9906, manufactured by Momentive New Materials Co., Ltd.)

Low stress material 6: Acrylic random copolymer (containing carboxylic acid, hydroxyl group and acrylonitrile group, number average molecular weight: about 500,000, SG-708-6, manufactured by Nagase ChemteX)

Low stress material 7: acrylic block copolymer [block copolymer of acrylic acid monomer (PMMA-b-PBA-b-PMMA; b = block, mercapto group having a functional group) number average molecular weight: about 16,000 , ARKEMA company, Nanostrength M52N]

Low stress material 8: acrylic block copolymer [block copolymer of acrylic acid monomer (PMMA-b-PBA-b-PMMA; b = block, mercapto group having a functional group) number average molecular weight: about 24,000 , ARKEMA company, Nanostrength M22N]

Low stress material 9: Acrylic block copolymer (block copolymer of acrylic monomer (PMMA-b-PBA-b-PMMA; b=block), number average molecular weight: about 32,000, manufactured by ARKEMA, Nanostrength M53 )

Inorganic filler 1: cerium oxide particles (SC2050, manufactured by Admatech Co., Ltd., average particle size 0.5 μm)

Inorganic filler 2: cerium oxide particles (SC4050, manufactured by Admatech Co., Ltd., average particle diameter: 1.1 μm)

Hardening accelerator 1: Phosphorus-based catalyst belonging to the phosphonium salt compound of the above formula (2) (made by SUMITOMO BAKELITE, C05-MB)

Hardening accelerator 2: 2-phenylimidazole (manufactured by Shikoku Kasei Co., Ltd., 2PZ-PW)

Next, the manufacture of the resin film with a carrier will be described. The composition of the resin varnish used is as shown in Table 1 and Table 3 (parts by mass), and the evaluation results of the resin film with a carrier obtained are shown in Table 2 and Table 4. In addition, C1 to C21 in Tables 2 and 4 refer to "resin film 1 with carrier" to "resin film 21 with carrier".

[1] Manufacture of resin film 1 with carrier

Each component was dissolved or dispersed according to the solid content ratio shown in Table 1, and 70% by mass of a nonvolatile component was adjusted with methyl ethyl ketone, and the resin varnish 1 was prepared by stirring using a high-speed stirring apparatus.

After the obtained resin varnish 1 was applied onto a PET film belonging to a carrier substrate, the solvent was removed at 140 ° C for 2 minutes to form a thermosetting resin film having a thickness of 30 μm. Thereby, the resin film 1 with a carrier is obtained.

[2] Manufacture of resin film 2~21 with carrier

The resin film 2 to 21 with a carrier was produced in the same manner as the resin film 1 with a carrier except that the type of the resin varnish was changed as shown in Table 2 and Table 4.

(Example 1)

1. Manufacturing of printed wiring substrate

Extremely thin surface of double-sided copper-clad laminate (made by SUMITOMO BAKELITE, LAZ-4785TH-G, thickness of 0.2mm) made of ultra-thin copper foil (manufactured by Mitsui Mining & Mining Co., Ltd., Myclocin Ex, 2.0 μm) On the copper foil layer, after performing a roughening treatment of about 1 μm, a layered connection is formed by using a carbon dioxide gas laser. 80 μm through hole. Subsequently, the mixture was immersed in a 60 ° C swelling solution (Stowing Japan, Swelling Dip Securiganth P) for 5 minutes, and further immersed in a potassium permanganate aqueous solution (Concentrate Compact CP, manufactured by Atotech Japan Co., Ltd.) at 80 ° C for 2 minutes. And then, the desmear treatment in the through hole is performed. Next, electroless copper plating having a thickness of 0.5 μm was applied to form a photoresist layer for electrolytic copper plating having a thickness of 18 μm, and copper plating was performed by pattern plating, followed by heating at 150 ° C for 30 minutes to perform post-hardening. Next, the plating resist was peeled off and the rapid etching was performed in full, and a circuit pattern was formed on both sides of L/S = 15/15 μm.

With respect to the circuit board on which the circuit pattern has been formed, a two-stage vacuum pressure type layer is used after the resin film 1 with the carrier obtained as described above is laminated on both sides in a manner that the thermosetting resin film is opposed to the circuit pattern. Pressing device (MVLP-500, manufactured by Nihon Seisakusho Co., Ltd.), decompressing for 30 seconds, below 10hPa, according to the first condition: temperature 120 ° C, pressure 0.8 MPa, 30 seconds, second condition: SUS mirror plate, The temperature was 120 ° C, the pressure was 1.0 MPa, and 60 seconds, and vacuum heating and press forming was performed. Next, the carrier substrate was peeled off from the resin film 1 with a carrier, and then the thermosetting resin film on the circuit pattern was cured at 230 ° C for 2 hours. Then, the circuit processing is performed by the semi-additive method, and the solder resist layer is formed by laminating the resin film 1 with the carrier obtained as described above on both sides, and a laser opening is applied to obtain a printed wiring board.

2. Manufacturing of semiconductor devices

On the obtained printed wiring board, a semiconductor element having a solder bump of 10 mm × 10 mm × 100 μm was mounted, sealed with a primer (manufactured by SUMITOMO BAKELITE Co., Ltd., CRP-4160G), and cured at 150 ° C for 2 hours. Finally, the implementation of crystal A semiconductor device was obtained by cutting the sheet into 15 mm × 15 mm.

(Examples 2 to 18 and Comparative Examples 1 to 3)

A semiconductor device was produced in the same manner as in Example 1 except that the types of the resin film with the carrier were changed to those shown in Tables 2 and 4.

Further, the following evaluations were carried out for each of the resin film and the semiconductor device with the carrier. The evaluation results are shown in Table 2 and Table 4.

(1) Glass transition temperature

The measurement of the glass transition temperature was carried out by dynamic viscoelasticity measurement (DMA apparatus, manufactured by TA Instruments, Q800).

A PET film belonging to the carrier substrate was peeled off from the resin film with the carrier obtained, and three sheets were laminated to obtain a resin sheet having a thickness of 90 μm. Next, the resin sheet was subjected to heat treatment at 230 ° C for 2 hours to obtain a cured product.

A test piece of 8 mm × 40 mm was cut out from the obtained cured product, and dynamic viscoelasticity measurement was performed on the test piece at a temperature increase rate of 5 ° C / min and a frequency of 1 Hz.

Here, the glass transition temperature is a temperature indicating that the loss tangent tan δ has a maximum value in a region of 150 ° C or higher.

Furthermore, X ₁ /X _{2 is} calculated. Here, in the region where X ₁ is 30° C. or higher and less than 180° C., the loss tangent tan δ has a maximum temperature; and in the region where X ₂ is 180° C. or more, the loss tangent tan δ has a maximum temperature.

(2) Storage elastic modulus E'

The measurement of the storage elastic modulus E' was carried out by dynamic viscoelasticity measurement (DMA apparatus, manufactured by TA Instruments, Q800).

A PET film belonging to the carrier substrate was peeled off from the resin film with the carrier obtained, and three sheets were laminated to obtain a resin sheet having a thickness of 90 μm. Next, the resin sheet was subjected to heat treatment at 230 ° C for 2 hours to obtain a cured product.

A test piece of 8 mm × 40 mm was cut out from the obtained cured product, and the storage elastic modulus at 250 ° C was measured for the test piece according to the heating rate of 5 ° C / min and the frequency of 1 Hz, and the storage elastic modulus E at 250 ° C was calculated. ₂₅₀ .

(3) Linear expansion coefficient

A PET film belonging to the carrier substrate was peeled off from the resin film with the carrier obtained, and three sheets were laminated to obtain a resin sheet having a thickness of 90 μm. Next, the resin sheet was subjected to heat treatment at 230 ° C for 2 hours to obtain a cured product.

A test piece of 8 mm × 40 mm was cut out from the obtained cured product, and a thermomechanical analysis device TMA (manufactured by TA Instruments, Q400) was used for the test piece, and the temperature range was 30 to 260 ° C, the temperature increase rate was 10 ° C / min, the load was 10 g, and compression was performed. The conditions of the model were subjected to a two-cycle measurement thermomechanical analysis (TMA). The average value α _{1 of the} linear expansion coefficients in the plane direction (XY direction) in the range of 50 ° C to 150 ° C and the average value α _{2 of the} linear expansion coefficients in the plane direction (XY direction) in the range of 150 ° C to 250 ° C were calculated.

In addition, the coefficient of linear expansion is the value of the second cycle.

(4) Warpage evaluation of semiconductor devices

The warpage of the obtained semiconductor device at 260 ° C was carried out using a temperature-variable laser three-dimensional measuring machine (manufactured by Hitachi Technologies and Services Co., Ltd. LS220-MT100MT50) Evaluation. In the sample chamber of the measuring machine, the semiconductor element is placed face down, the displacement in the height direction is set, and the maximum displacement difference is set as the amount of warpage. The evaluation criteria are as follows:

◎: The amount of warpage is less than 30μm

○: The amount of warpage is 30 μm or more and less than 50 μm.

×: warpage amount is 50 μm or more

(5) Evaluation of insulation reliability between wires

The insulation reliability evaluation of the fine circuit pattern of the printed wiring board L/S=15/15 μm obtained was performed. The insulation resistance in continuous wetness was evaluated under conditions of a temperature of 130 ° C, a humidity of 85%, and an applied voltage of 3.3 V. In addition, a resistance value of 10 ⁶ Ω or less is regarded as a failure. The evaluation criteria are as follows:

◎: No problem for more than 500 hours

○: 200~Unexpected 500 hours of failure (substantially does not constitute a problem)

×: Failure occurred after less than 200 hours

Claims (17)

A thermosetting resin composition comprising a thermosetting resin composition for forming an insulating layer of a printed wiring board, comprising a thermosetting resin, an inorganic filler, and a (meth)acrylic block copolymer; The thermosetting resin composition is heat-treated at 230 ° C for 2 hours to obtain a cured glass having a glass transition temperature of 180 ° C or higher; wherein the glass transition temperature is at a temperature increase rate of 5 ° C / min and a frequency of 1 Hz, using dynamic viscosity In the curve obtained by the elastic measurement, there is a temperature corresponding to the loss of the tangent tan δ peak in the region above 150 °C. The thermosetting resin composition of claim 1, wherein the cured product obtained by subjecting the thermosetting resin composition to heat treatment at 230 ° C for 2 hours is subjected to a temperature increase rate of 5 ° C / min and a frequency of 1 Hz. In the dynamic viscoelasticity measurement, the peak value of the loss tangent tan δ in the region of 30 ° C or more and less than 180 ° C is set as X ₁ , and the peak value of the loss tangent tan δ in the region above 180 ° C is set. When it is X ₂ , X ₁ /X ₂ is 0.40 or less. The thermosetting resin composition of claim 1, wherein the (meth)acrylic block copolymerization system contains: from the polymer block (S), and more than the polymer block (S) A high block glass transition temperature (Tg) polymer block (H) is a diblock copolymer having an aligned structure, a copolymer in which the polymer block (S) and the polymer block (H) are staggered, and a middle One or two or more kinds of the triblock copolymers having the above polymer block (S) and having the above polymer block (H) at both ends are selected. The thermosetting resin composition of claim 3, wherein the above polymer block (S) A polymer composed of butyl acrylate; and the polymer block (H) is a polymer composed of methyl methacrylate. The thermosetting resin composition of claim 1, wherein the (meth)acrylic block copolymer has a number average molecular weight (Mn) of 3,000 or more and 500,000 or less. The thermosetting resin composition of claim 1, wherein the insulating layer is used for forming a stacked layer or a solder resist layer of the above printed wiring substrate. The thermosetting resin composition of claim 1, wherein the inorganic filler contains cerium oxide particles. The thermosetting resin composition of claim 1, wherein the in-plane direction obtained by heat-treating the thermosetting resin composition at 230 ° C for 2 hours to obtain a cured product is calculated from 50 ° C to 150 ° C. When the average linear expansion coefficient is set to α ₁ and the average linear expansion coefficient is calculated from 150 ° C to 250 ° C to be α ₂ , the difference between α ₂ and α ₁ (α _{2 -} α ₁ ) is 20.0 ppm / Below °C. The thermosetting resin composition of claim 8, wherein the average linear expansion coefficient α ₂ is 45.0 ppm/° C. or less. The thermosetting resin composition of claim 1, wherein the thermosetting resin composition is heat-treated at 230 ° C for 2 hours to obtain a cured product, and the storage elastic modulus E ₂₅₀ of 12 GPa or less at 250 ° C . The thermosetting resin composition of claim 1, wherein the content of the (meth)acrylic block copolymer is less than the total solid content of the thermosetting resin composition is 100% by mass. 10.0% by mass. The thermosetting resin composition of claim 1, wherein the thermosetting resin contains a maleimide compound, benzo One or two or more of the compound and the cyanate resin are selected. The thermosetting resin composition of claim 12, wherein the thermosetting resin further contains an epoxy resin. A resin film with a carrier, comprising: a carrier substrate; and a resin film which is provided on the carrier substrate and which is composed of the thermosetting resin composition according to any one of claims 1 to 13. A printed wiring board comprising a stacked layer, wherein the stacked layer contains a cured product of the thermosetting resin composition according to any one of claims 1 to 13. A printed wiring board comprising a solder resist layer containing the cured product of the thermosetting resin composition according to any one of claims 1 to 13. A semiconductor device in which a semiconductor element is mounted on a circuit layer of a printed wiring board according to claim 15 or 16.