JP2019194281A - Resin composition, resin film, metal-clad laminate, printed wiring board and semiconductor package - Google Patents

Abstract

To provide a resin composition which is excellent in high-frequency characteristics (low dielectric constant and low dielectric loss tangent) and can obtain uniform plate thickness even when being pressure-bonded to a circuit board by heat press molding; and a resin film, a metal-clad laminate, a printed wiring board and a semiconductor package using the resin composition.SOLUTION: There are provided a resin composition which contains (A) a compound having a maleimide group, a divalent group having at least two imide bonds and two saturated or unsaturated divalent hydrocarbon groups, (B) an organic peroxide, and (C) one or more curing accelerators selected form the group consisting of an organic peroxide different from the component (B), an organic metal catalyst and an amine compound; and a resin film, a metal-clad laminate, a printed wiring board and a semiconductor package using the resin composition.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a resin composition, a resin film, a metal-clad laminate, a printed wiring board, and a semiconductor package.

  In mobile communication devices represented by mobile phones and their base station devices, network infrastructure devices such as servers and routers, or large computers, the speed of signals used and the increase in capacity have been increasing year by year. As a result, printed circuit boards mounted on these electronic devices are required to support higher frequencies, and dielectric properties (low dielectric constant and low dielectric loss tangent) in the high frequency band that can reduce transmission loss (hereinafter referred to as “low dielectric constant”) Substrate materials excellent in high frequency characteristics) are demanded. In recent years, as an application that handles such high-frequency signals, in addition to the electronic devices described above, a new system that handles high-frequency wireless signals in the ITS (Intelligent Transport Systems) field (related to automobiles and traffic systems) and indoor short-range communication fields. In the future, it is expected that a substrate material with low transmission loss will be required for printed wiring boards mounted on these devices.

  Conventionally, a fluororesin having a low relative dielectric constant and dielectric loss tangent has been used as a substrate material that requires low transmission loss. However, since the fluororesin has a high melting temperature and melt viscosity and low fluidity, it is necessary to perform press molding under high temperature conditions. In addition, polyphenylene ether (PPO, PPE) resins are known as thermoplastic polymers exhibiting excellent high-frequency characteristics. However, since polyphenylene ether is a high molecular weight polymer having a high melt viscosity, it has the same moldability problem as fluororesin. Have

  On the other hand, a prepreg obtained by using a thermosetting resin composition (see Patent Document 1) is excellent in low-temperature meltability and can be press-molded at a relatively low temperature. However, since the glass cloth used as a reinforcing material for the prepreg has a structure in which warp and weft are woven, there is a weave and there is a gap without a glass cloth called a basket hole. Therefore, a portion having a high glass cloth presence ratio and a portion having a high resin presence ratio are mixed in the plane, and the dielectric characteristics are non-uniform in the plane. Further, E glass cloth, which is a general glass cloth, has insufficient high frequency characteristics. From the above, when considering the high-frequency characteristics necessary for the millimeter wave band, a resin film that does not contain a substrate such as glass cloth is suitable.

  In recent years, a printed wiring board having a build-up laminate system having an inner via hole (IVH) structure in which only a necessary layer is connected with a non-through hole has been developed and is rapidly spreading. For the insulating layer of the build-up layer, a resin film not containing glass cloth is often used for thinning. In addition, in millimeter wave band antenna applications where high-spec high-frequency characteristics are required, the requirements for precision in insulating layer thickness and relative dielectric constant variation are severe, so resin films that do not contain glass cloth are more advantageous. .

  From the background as described above, studies have been made on resin films that do not contain glass cloth. Resin films are required to have a low coefficient of thermal expansion because of the demand for reducing the amount of warpage, and in order to obtain excellent reliability, high adhesion to a conductor is also required. In addition, from the viewpoint of productivity, good handleability that does not cause stickiness, powder falling, or the like is also required.

Patent Document 2 discloses an interlayer insulating resin film with an adhesion auxiliary layer that is pressed against a circuit board while being pressurized and heated in a laminate.
Patent Document 3 discloses a resin film based on a polyimide resin that can improve dielectric properties and heat resistance.

Japanese Patent Laid-Open No. 2006-135859 JP 2014-101398 A JP 2016-131244 A

The resin films disclosed in Patent Documents 2 and 3 can efficiently produce a multilayer wiring board by a method in which the resin film is pressure-bonded to a circuit board by a laminate that is thermocompression bonded at a relatively low pressure. However, since the laminating method uses a vacuum laminator for the purpose of improving circuit embeddability and the like, the manufacturing apparatus is restricted and the substrate manufacturing process is limited.
On the other hand, when a resin film is pressure-bonded to a circuit board by hot press molding that is cured while thermocompression bonding, there arises a problem that in-plane variation of the thickness of the multilayer wiring board to be formed occurs. When the in-plane variation of the plate thickness occurs, the characteristic impedance fluctuates particularly when a multilayer wiring board is used, which is one factor that causes distortion in the high-frequency signal.
Therefore, in order to expand the selectable range of the manufacturing process of the wiring board, a resin composition capable of obtaining a uniform plate thickness is required even when the circuit board is pressure-bonded by hot press molding.

  In view of such a current situation, the present invention provides a resin composition excellent in high-frequency characteristics (low dielectric constant, low dielectric loss tangent), and capable of obtaining a uniform plate thickness even when crimped to a circuit board by hot press molding, and the resin An object is to provide a resin film, a metal-clad laminate, a printed wiring board, and a semiconductor package using the composition.

As a result of intensive studies to solve the above problems, the present inventors have found that the problems can be solved by a resin composition in which a specific resin and a specific curing accelerator are combined. That is, the present invention relates to the following [1] to [14].
[1] (A) a compound having a maleimide group, a divalent group having at least two imide bonds, and a saturated or unsaturated divalent hydrocarbon group;
(B) an organic peroxide;
(C) A resin composition containing at least one curing accelerator selected from the group consisting of an organic peroxide, an organometallic catalyst, and an amine compound different from the component (B).
[2] The resin composition according to the above [1], wherein the (B) organic peroxide has a one-minute half-life temperature of more than 160 ° C and not more than 230 ° C.
[3] The resin according to the above [2], wherein the component (C) is an organic peroxide different from the component (B), and the one-minute half-life temperature of the organic peroxide is 100 to 160 ° C. Composition.
[4] The resin composition according to [1] or [2], wherein the component (C) is an organometallic catalyst, and the organometallic catalyst is a carboxylic acid metal salt.
[5] The resin composition according to the above [1] or [2], wherein the component (C) is an amine compound, and the amine compound is an aminosilane coupling agent.
[6] (D) The resin composition according to any one of [1] to [5], further including a thermosetting resin different from the component (A).
[7] The resin composition according to any one of [1] to [6], further including (E) an inorganic filler.
[8] The resin composition according to any one of [1] to [7], wherein the component (A) is a compound represented by the following general formula (A-6).

(In the formula, R represents the divalent group having at least two imide bonds, Q represents the saturated or unsaturated divalent hydrocarbon group, and n represents an integer of 1 to 10.)
[9] Any of the above [1] to [8], wherein the saturated or unsaturated divalent hydrocarbon group of the component (A) is a divalent aliphatic hydrocarbon group having 8 to 100 carbon atoms. A resin composition according to claim 1.
[10] The resin composition according to any one of [1] to [9], wherein the cured product has a relative dielectric constant at 10 GHz of 3.0 or less.
[11] A resin film containing the resin composition according to any one of [1] to [10].
[12] A metal-clad laminate obtained by stacking one or more resin films according to [11] above, placing metal foils on both surfaces thereof, and performing hot press molding.
[13] A printed wiring board formed using the resin film according to [11] or the metal-clad laminate according to [12].
[14] A semiconductor package in which a semiconductor element is mounted on the printed wiring board according to [13].

  According to the present invention, a resin composition, a resin film, and a metal-clad laminate that are excellent in high-frequency characteristics (low dielectric constant, low dielectric loss tangent) and that can be obtained with a uniform thickness even when pressed on a circuit board by hot press molding. A printed wiring board and a semiconductor package can be provided.

It is the schematic of the test piece used for the measurement of plate | board thickness in-plane variation.

  Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments. Further, in this specification, the high frequency region refers to a region of 300 MHz to 300 GHz, and the frequency region of an antenna used for a high multilayer, millimeter wave radar particularly refers to 3 GHz to 300 GHz.

[Resin composition]
The resin composition of the present embodiment is
(A) a compound having a maleimide group, a divalent group having at least two imide bonds, and a saturated or unsaturated divalent hydrocarbon group (hereinafter also referred to as “component (A)”);
(B) an organic peroxide (hereinafter also referred to as “component (B)”),
(C) One or more curing accelerators (hereinafter also referred to as “component (C)”) selected from the group consisting of organic peroxides, organometallic catalysts, and amine compounds different from the component (B). It contains.

The resin composition of the present embodiment has excellent high-frequency characteristics that both the relative dielectric constant and the dielectric loss tangent in the high-frequency region are low by having the above specific composition. Moreover, since the resin composition of this embodiment is comparable to a fluororesin system and has a high frequency characteristic exceeding that of a polyphenylene ether resin system, it can be applied to applications in a higher frequency region (70 GHz or more) including millimeter wave signals. is there.
In addition, since the resin composition of the present embodiment has the specific composition described above, a uniform plate thickness can be obtained even when the resin composition is pressure-bonded to a circuit board by hot press molding, and thus there is a restriction on a manufacturing apparatus such as a vacuum laminator. This does not occur, and the selection range of the substrate manufacturing process can be expanded.
Further, conventionally, when a glass cloth or the like is not arranged in the resin composition in the resin film, the handleability of the resin film is deteriorated and the strength tends not to be sufficiently maintained. Since the resin film containing the product contains the component (A) having a flexible aliphatic skeleton, it is thin and easy to handle without having a glass cloth or the like (tackiness, cracking, powder falling, etc.) It is also excellent in appearance.
Furthermore, since the resin composition of this embodiment is excellent in adhesiveness with a conductor, a low profile foil having a small surface roughness can be used without any problem.

<(A) component>
The component (A) includes a maleimide group, a divalent group having at least two imide bonds (hereinafter also referred to as “bonding group (a1)”), and a saturated or unsaturated divalent hydrocarbon group (hereinafter referred to as “ A bonding group (also referred to as “a2)”).
In addition, a maleimide group shall not be included in the imide bond contained in a coupling group (a1).
(A) A component may be used individually by 1 type and may use 2 or more types together.

  The component (A) may be an N-aromatic substituted maleimide group-containing compound in which the maleimide group is bonded to an aromatic ring, and the N-aliphatic substituted maleimide in which the maleimide group is bonded to an aliphatic chain Although it may be a group-containing compound, it is preferably an N-aliphatic substituted maleimide group-containing compound.

(Binding group (a1))
The bonding group (a1) is a divalent group having at least two imide bonds, and a group represented by the following general formula (A-1) is preferable.

(In the formula, R ^A1 represents a tetravalent organic group.)

The number of carbon atoms of the tetravalent organic group represented by R ^A1, from the viewpoint of handling property as a resin film, preferably 1 to 20, more preferably 4 to 15, 6 to 10 is more preferred.
The tetravalent organic group represented by R ^A1 includes a tetravalent aliphatic hydrocarbon group, a tetravalent alicyclic hydrocarbon group, a tetravalent aromatic hydrocarbon group, and a hydrocarbon group having a tetravalent siloxane skeleton. Etc. In addition, these groups may contain hetero atoms, such as oxygen, nitrogen, and a sulfur atom, C1-C10 alkyl group, C2-C10 alkenyl group, C6-C12 aryl group And the like. When it has a substituent, the carbon number of R ^A1 means the carbon number including the carbon number of these substituents.
Among these, a tetravalent aromatic hydrocarbon group is preferable from the viewpoint of mechanical strength. Examples of the tetravalent aromatic hydrocarbon group include a benzenetetrayl group, a naphthalenetetrayl group, a biphenyltetrayl group, a diphenylethertetrayl group, and a 2,2-bis (4-phenoxyphenyl) propanetetrayl group. . Among these, a benzenetetrayl group is preferable.
R ^A1 is a tetravalent residue of an acid anhydride having two or more anhydride rings in one molecule, that is, an acid anhydride group (—C (═O) OC (= A tetravalent group excluding two O)-) is preferred. As an acid anhydride, the acid anhydride used for manufacture of the (A) component mentioned later is mentioned.

  The bonding group (a1) is preferably a group represented by the following formula (A-2) from the viewpoint of mechanical strength, and from the viewpoint of dielectric properties, the following formula (A-3) or the following formula (A-4). The group represented by these is preferable.

Component (A) may have only one linking group (a1) or may have two or more, but from the viewpoint of fluidity and circuit embedding properties, it has two or more. Is preferred. The plurality of bonding groups (a1) may be the same or different.
(A) As for the number of the coupling groups (a1) which a component contains, 1-40 are preferable in 1 molecule, 2-20 are more preferable, and 3-10 are more preferable. When the number of the linking groups (a1) is equal to or higher than the lower limit value, moderate viscosity is obtained and excellent in low thermal expansion, and when the number is less than the upper limit value, excellent dielectric properties are obtained.

(Binding group (a2))
The linking group (a2) is a saturated or unsaturated divalent hydrocarbon group. The hydrocarbon group may be linear, branched or cyclic.
8-100 are preferable, as for carbon number of a coupling group (a2), 10-70 are more preferable, and 15-50 are more preferable.
Examples of the linking group (a2) include a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, and a divalent group obtained by combining these. Among these, a high-frequency characteristic and a resin film are used. From the viewpoint of easy handling, a divalent aliphatic hydrocarbon group is preferred.

The number of carbon atoms of the divalent aliphatic hydrocarbon group is preferably 8 to 100 from the viewpoint of easily making the molecular structure three-dimensional and increasing the free volume of the polymer to lower the density, that is, lower the dielectric constant. 70 is more preferable, and 15-50 is still more preferable.
Examples of the divalent aliphatic hydrocarbon group include an alkylene group, a cycloalkylene group, an alkenylene group, a cycloalkenylene group, and a divalent group obtained by combining these. Among these, an alkylene group, a cycloalkylene group, and a divalent group obtained by combining these are preferable.
As the alkylene group, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, tetradecylene group, hexadecylene group, octadecylene group And nonadecylene group. The alkylene group herein includes an alkylidene group, and includes a straight chain and a branched chain that is a structural isomer thereof.
Examples of the cycloalkylene group include a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, and a cyclodecylene group.
In addition, these groups may contain hetero atoms, such as oxygen, nitrogen, and a sulfur atom, C1-C10 alkyl group, C2-C10 alkenyl group, C6-C12 aryl group And the like. In the case of having a substituent, the carbon number of the divalent aliphatic hydrocarbon group means the carbon number including the carbon number of these substituents.
Examples of the divalent aromatic hydrocarbon group include a benzylene group, a phenylene group, and a naphthylene group.

  As the bonding group (a2), a group represented by the following general formula (A-5) is preferable from the viewpoint of high-frequency characteristics and handleability when a resin film is used.

(Wherein, R ^A2 and R ^A3 each independently represents an alkylene group having ^{4 to} 50 carbon atoms, R ^A4 represents an alkyl group having 4 to 50 carbon atoms, and R ^A5 represents an alkyl group having 2 to 50 carbon atoms. Group.)

5-25 are preferable, as for carbon number of the alkylene group which R ^{< A2>} , R ^<A3> shows, 6-15 are more preferable, and 7-10 are more preferable.
^{Examples of} the alkylene group represented by R ^A2 and R ^A3 include a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, and a decamethylene group.

Number of carbon atoms of the alkyl group R ^A4 represents preferably 5 to 25, more preferably 6 to 15, more preferably 7-10.
^Examples of the alkyl group represented by R ^A4 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, and n-heptyl group. , N-octyl group, n-decyl group and the like. Among these, n-hexyl group is preferable.

The number of carbon atoms of the alkyl group represented by R ^A5 is preferably 5 to 25, more preferably 6 to 15, more preferably 7-10.
Examples of the alkyl group represented by R ^A5 include the same groups as those described above for R ^A4 . Among these, n-octyl group is preferable.

Component (A) may have only one linking group (a2) or two or more, but from the viewpoint of fluidity and circuit embedding properties, Is preferred. The plurality of bonding groups (a2) may be the same or different.
(A) As for the number of the coupling | bonding groups (a2) which a component contains, 1-40 are preferable in 1 molecule, 2-20 are more preferable, and 3-10 are more preferable. When the number of the linking groups (a2) is not less than the above lower limit value, excellent dielectric properties can be obtained, and when it is not more than the above upper limit value, it has excellent low thermal expansion.

The weight average molecular weight (Mw) of the component (A) is preferably from 500 to 10,000, and preferably from 1,000 to 9,000, from the viewpoints of high-frequency characteristics, handleability when used as a resin film, fluidity, and circuit embedding properties. Is more preferable, 1,500 to 7,000 is more preferable, and 1,700 to 5,000 is particularly preferable.
The weight average molecular weight of the component (A) can be measured by a gel permeation chromatography (GPC) method. The measurement conditions of GPC are as follows.
Pump: L-6200 [manufactured by Hitachi High-Technologies Corporation]
Detector: L-3300 RI [manufactured by Hitachi High-Technologies Corporation]
Column oven: L-655A-52 [manufactured by Hitachi High-Technologies Corporation]
Column: TSK Guardcolumn HHR-L, TSKgel G4000HHR, TSKgel G2000HHR [all trade names, manufactured by Tosoh Corporation]
Column size: 6.0 × 40 mm (guard column), 7.8 × 300 mm (column)
Eluent: Tetrahydrofuran Sample concentration: 30 mg / 5 mL
Injection volume: 20 μL
Flow rate: 1.00 mL / min Measurement temperature: 40 ° C

  The method for producing the component (A) is not particularly limited. For example, an acid anhydride and a diamine are reacted to synthesize an amine-terminated compound having two or more imide bonds, and then the amine-terminated compound is excessive. A method of introducing a maleimide group at the terminal by reacting with maleic anhydride of the above may be mentioned.

  Examples of acid anhydrides include pyromellitic anhydride, maleic anhydride, succinic anhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic acid. And acid dianhydrides, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, and the like. Among these, pyromellitic anhydride is preferable from the viewpoint of dielectric properties.

  Diamine amine, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) as the diamine Biphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, 1,3-bis [2- (4-aminophenyl) -2-propyl] benzene, 1,4-bis [2- (4-amino) Phenyl) -2-propyl] benzene, polyoxyalkylenediamine, [3,4-bis (1-aminoheptyl) -6-hexyl-5- (1-octenyl)] cyclohexene, [1,2-bis (1- Aminooctyl) -3-octyl-4-hexyl] cyclohexane and the like.

  As the component (A), a compound represented by the following general formula (A-6) is preferable.

(In the formula, R represents a linking group (a2), Q represents a linking group (a1), and n represents an integer of 1 to 10).

  (A) A commercial item may be used for a component. Examples of commercially available products of component (A) include an imide-extended bismaleimide compound manufactured by Designa Molecules Incorporated, specifically BMI-1500 represented by the following general formula (A-7), Examples thereof include BMI-1700 represented by the following general formula (A-8), BMI-3000, BMI-5000, BMI-9000 represented by the following general formula (A-9).

(In the formula, n ₁ represents an integer of 1 to 10.)

(In the formula, n ₂ represents an integer of 1 to 10.)

(In the formula, n ₃ represents an integer of 1 to 10.)

  The content of the component (A) in the resin composition of the present embodiment is the resin component contained in the resin composition from the viewpoint of uniformity of the obtained plate thickness, high frequency characteristics, low thermal expansion, and adhesion to the conductor. The total amount is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, and still more preferably 70 parts by mass or more. Moreover, 100 mass parts or less may be sufficient with respect to 100 mass parts of total amounts of the resin component contained in a resin composition, and content of (A) component may be 90 mass parts or less.

<(B) Organic peroxide>
(B) The organic peroxide acts as a polymerization initiator for the component (A), and decomposes into one having unpaired electrons when exposed to energy such as light and heat.
(B) An organic peroxide may be used individually by 1 type, and may use 2 or more types together.

(B) The one minute half-life temperature of the organic peroxide provides good curability under hot press molding temperature conditions (generally 230 ° C. or lower) while keeping the fluidity of the resin composition in an appropriate range. From a viewpoint, 160 degreeC and 230 degrees C or less are preferable, 165-200 degreeC is more preferable, and 170-180 degreeC is further more preferable.
In addition, (B) 1 minute half-life temperature of an organic peroxide means the temperature which (B) organic peroxide decomposes | disassembles and the residual amount becomes 1/2 in 1 minute. The 1 minute half-life temperature can be measured by the following method.
[Measurement method of half-life temperature for 1 minute]
Using benzene, a 0.1 mol / L organic peroxide solution is prepared and enclosed in a glass ampoule that has been purged with nitrogen. This is immersed in an oil bath set at a predetermined temperature (three-point measurement in the vicinity of the 10-hour half-life temperature) to thermally decompose the organic peroxide in the solution. In general, the decomposition of organic peroxide in a dilute solution can be treated approximately as a primary reaction, so the amount of decomposed organic peroxide (x), decomposition rate constant (k), time (t), organic peroxide If it is assumed that the initial concentration (a) is, the following equations (1) and (2) are established.
dx / dt = k (ax) (1)
ln a / (ax) = kt (2)
Moreover, since the half-life is the time until the organic peroxide concentration is reduced to half of the initial value due to decomposition, the half-life is represented by (t1 / 2), and (a / 2) is expressed in (x) of (2). By substituting, it can be expressed by the following equation (3).
kt _1/2 = ln (2) (3)
Therefore, the organic peroxide is thermally decomposed at a certain temperature, the relationship between time (t) and ln [(a) / (ax)] is plotted, and the decomposition rate constant (k ), The half-life (t1 / 2) at that temperature can be obtained from the equation (3).
Then, the thermal decomposition is performed at several temperatures, the half-life (t1 / 2) at each temperature is measured, and the relationship between ln (t1 / 2) and (1 / T) is plotted, The temperature at which the half-life is 1 minute can be determined from the obtained straight line.

  (B) As the organic peroxide, 1,1-di (t-butylperoxy) cyclohexane, 2,2-di (t-butylperoxy) butane, 2,2-di (4,4-di-) peroxyketals such as t-butylperoxycyclohexyl) propane and 1,1-di (t-amylperoxy) cyclohexane; hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide; t-butyl Alkyl peroxides such as peroxyacetate and t-amylperoxyisononanoate; t-butylcumyl peroxide, di-t-butyl peroxide, dicumyl peroxide, di-t-hexyl peroxide, 1,3 -Dialkyl peroxides such as bis (2-t-butylperoxyisopropyl) benzene; Peroxyesters such as butyl peroxyacetate, t-butylperoxybenzoate and t-butylperoxyisopropyl monocarbonate; peroxy such as t-butylperoxyisopropyl carbonate and polyethertetrakis (t-butylperoxycarbonate) Carbonates; and diacyl peroxides such as dibenzoyl peroxide. Among these, 1,3-bis (2-t-butylperoxyisopropyl) benzene is preferable from the viewpoint of the uniformity of the obtained plate thickness.

  The content of the organic peroxide (B) in the resin composition of the present embodiment is 0.1 to 5 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of uniformity of the obtained plate thickness. Is preferable, 0.4-3 mass parts is more preferable, and 0.7-2 mass parts is further more preferable.

<(C) component>
Component (C) is an organic peroxide different from component (B) (hereinafter also referred to as “(c1) organic peroxide” or “(c1) component”), an organometallic catalyst (hereinafter referred to as “(c2)”. One or more types of curing acceleration selected from the group consisting of “organic metal catalyst” or “(c2) component”) and an amine compound (hereinafter also referred to as “(c3) amine compound” or “(c3) component”) It is an agent.
The resin composition of this embodiment adjusts the fluidity and curability of the resin composition at the time of hot press molding to an appropriate range by using the above-described component (B) and component (C) in combination. Thus, even when the resin composition of the present embodiment is pressure-bonded to a circuit board, a uniform plate thickness can be obtained. Hereinafter, the components (c1) to (c3) will be described.

((C1) organic peroxide)
(C1) The organic peroxide should just be an organic peroxide different from (B) component, and the same thing as what was illustrated as (B) component is mentioned.
(C1) The 1 minute half-life temperature of the organic peroxide keeps the flowability of the resin composition within an appropriate range, and prevents curing from proceeding excessively when the resin composition is applied and dried. From a viewpoint, 100-160 degreeC is preferable, 130-160 degreeC is more preferable, 150-160 degreeC is further more preferable.
The 1 minute half-life temperature of the component (c1) is preferably lower than the 1-minute half life temperature of the component (B) from the viewpoint of the uniformity of the obtained plate thickness. Since the radical is generated at a relatively low temperature by lowering the 1-minute half-life temperature of the component (c1) below the 1-minute half-life temperature of the component (B), the reaction rate in the B-stage film during coating is high Thus, the curing reaction can be started before the resin flow becomes excessive at the time of hot pressing. The difference in half-life temperature for 1 minute between component (B) and component (c1) [1-minute half-life temperature for component (B) −one-minute half-life temperature for component (c1)] is preferably 5 to 30 ° C. 10 -25 ° C is more preferable, and 12-20 ° C is more preferable.
Among these, as the component (c1), t-butyl peroxyisopropyl monocarbonate is preferable.
As the component (c1), one type may be used alone, or two or more types may be used in combination.

  When the resin composition of this embodiment contains (c1) component, the content is 0.1-5 mass with respect to 100 mass parts of (A) component from a viewpoint of the uniformity of the plate | board thickness obtained. Part is preferable, 0.4-3 parts by mass is more preferable, and 0.7-2 parts by mass is more preferable.

((C2) Organometallic catalyst)
(C2) The organometallic catalyst has the effect of lowering the reaction start temperature of (B) the organic peroxide by an oxidation-reduction reaction and initiating the curing reaction before the resin flow becomes excessive.
(C2) Examples of the organometallic catalyst include organometallic salts and organometallic complexes.
Examples of the metal constituting the organometallic salt or organometallic complex include iron, copper, zinc, cobalt, nickel, manganese, tin, and the like.
The organic metal salt is preferably a carboxylic acid metal salt, such as iron naphthenate, copper naphthenate, zinc naphthenate, cobalt naphthenate, nickel naphthenate, manganese naphthenate, tin naphthenate, etc .; zinc octylate And octylic acid metal salts such as tin octylate and manganese octylate; and 2-ethylhexanoic acid metal salts such as zinc 2-ethylhexanoate.
Examples of the organometallic complex include dibutyltin maleate and lead acetylacetonate.
(C2) The organometallic catalyst may be used alone or in combination of two or more.

  When the resin composition of the present embodiment contains (c2) an organometallic catalyst, the content is 0.1 to 100 parts by mass of component (A) from the viewpoint of uniformity of the obtained plate thickness. 5 mass parts is preferable, 0.4-3 mass parts is more preferable, and 0.7-2 mass parts is further more preferable.

((C3) amine compound)
(C3) The amine compound has an effect of suppressing the resin flow from being excessive by increasing the viscosity of the resin composition by hydrogen bonding with the acid contained in the material.
(C3) Amine compounds include aminosilane coupling agents, dicyandiamide, benzoguanamine, triethylamine, tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, 1,8 -Diazabicyclo (5,4,0) -undecene and the like. Of these, aminosilane coupling agents are preferred.
Examples of aminosilane coupling agents include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and the like. Among these, 3-aminopropyltriethoxysilane is preferable.
(C3) An amine compound may be used individually by 1 type, and may use 2 or more types together.

  When the resin composition of this embodiment contains (c3) an amine compound, the content is 0.1-5 with respect to 100 mass parts of (A) component from a viewpoint of the uniformity of the plate | board thickness obtained. Mass parts are preferred, 0.4-3 parts by mass are more preferred, and 0.7-2 parts by mass are even more preferred.

The resin composition of the present embodiment may contain all of the components (c1) to (c3), or may contain any two of the components (c1) to (c3), Any one of the components (c1) to (c3) may be contained.
The content of the component (C) in the resin composition of the present embodiment is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of uniformity of the obtained plate thickness. 0.4-3 mass parts is more preferable, and 0.7-2 mass parts is further more preferable.

<(D) component: thermosetting resin different from said (A) component>
It is preferable that the resin composition of this embodiment contains the thermosetting resin different from (A) component as (D) component.
Examples of the component (D) include maleimide compounds other than the component (A) (hereinafter also referred to as “(d1) maleimide compound”), (d2) cyanate ester resins, and the like.
(D) A component may be used individually by 1 type and may use 2 or more types together.

  When the resin composition of this embodiment contains (D) component, 5-50 mass parts is preferable with respect to 100 mass parts of total amounts of the resin component contained in the resin composition, and 10-30 Mass parts are more preferred, and 15 to 25 parts by mass are even more preferred.

((D1) maleimide compound)
The resin composition of this embodiment contains (d1) a maleimide compound in addition to the component (A), thereby maintaining high dielectric properties, high adhesion to the conductor, heat resistance, and low thermal expansion. Flame retardancy, workability (drilling, cutting), etc. can be improved.
(D1) A maleimide compound may be used individually by 1 type, and may use 2 or more types together.

  (D1) The maleimide compound is preferably a polymaleimide compound containing two or more maleimide groups, and more preferably a bismaleimide compound containing two maleimide groups. (D1) The maleimide compound is preferably a compound represented by the following general formula (d-1).

In the general formula (d-1), A ^d1 represents a divalent group represented by the following general formula (d-2), (d-3), (d-4), or (d-5).

In general formula (d-2), R ^<d1> shows a hydrogen atom, a C1-C5 aliphatic hydrocarbon group, or a halogen atom each independently.

In the general formula (d-3), R ^d2 and R ^d3 each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, and A ^d2 represents an alkylene having 1 to 5 carbon atoms. A group represented by a group or an alkylidene group, an ether group, a sulfide group, a sulfonyl group, a ketone group, a single bond, or the following general formula (d-3 ′);

In general formula (d-3 ′), R ^d4 and R ^d5 each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom, and A ^d3 represents one having 1 to 5 carbon atoms. An alkylene group or an alkylidene group, an ether group, a sulfide group, a sulfonyl group, a ketone group or a single bond is shown.

  In general formula (d-4), i is an integer of 1-10.

In General Formula (d-5), R ^d6 and R ^d7 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and j is an integer of 1 to 8.

R ^d1 in general formula (d-2), R ^d2 and R ^d3 in general formula (d-3), R ^d4 and R ^d5 in general formula (d-3 ′), general formula (d-5) Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ^d6 and R ^d7 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, An n-pentyl group and the like can be mentioned. The aliphatic hydrocarbon group may be an aliphatic hydrocarbon group having 1 to 3 carbon atoms or a methyl group.
Examples of the alkylene group having 1 to 5 carbon atoms represented by A ^{d2 in the} general formula (d-3) and A ^d3 in the general formula (d-3 ′) include a methylene group, an ethylene group, a propylene group, a butylene group, and pentylene. Groups and the like.
As the alkylidene group having 1 to 5 carbon atoms represented by A ^{d2 in the} general formula (d-3) and A ^d3 in the general formula (d-3 ′), an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, Examples thereof include an isobutylidene group and a pentylidene group.

  (D1) As maleimide compounds, 1,2-dimaleimidoethane, 1,3-dimaleimidopropane, bis (4-maleimidophenyl) methane, bis (3-ethyl-4-maleimidophenyl) methane, bis (3- Ethyl-5-methyl-4-maleimidophenyl) methane, 2,7-dimaleimidofluorene, N, N ′-(1,3-phenylene) bismaleimide, N, N ′-[1,3- (4-methyl) Phenylene)] bismaleimide, bis (4-maleimidophenyl) sulfone, bis (4-maleimidophenyl) sulfide, bis (4-maleimidophenyl) ether, 1,3-bis (3-maleimidophenoxy) benzene, 1, 3-bis [3- (3-maleimidophenoxy) phenoxy] benzene, bis (4-maleimidophenyl) ketone, 2, -Bis [4- (4-maleimidophenoxy) phenyl] propane, bis [4- (4-maleimidophenoxy) phenyl] sulfone, bis [4- (4-maleimidophenoxy) phenyl] sulfoxide, 4,4′-bis ( 3-maleimidophenoxy) biphenyl, 1,3-bis [2- (3-maleimidophenyl) propyl] benzene, 1,3-bis [1- [4- (3-maleimidophenoxy) phenyl] -1-propyl] benzene Bis (maleimidocyclohexyl) methane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, bis (maleimidophenyl) thiophene, etc. It is done. Among these, bis (4-maleimidophenyl) methane is preferable from the viewpoint of the thermal expansion coefficient and the adhesion to the conductor.

When the resin composition of the present embodiment contains (d1) a maleimide compound, the content thereof is a resin composition from the viewpoint of high adhesion to a conductor, heat resistance, low thermal expansion, flame retardancy, and workability. 5 to 50 parts by mass is preferable, 10 to 30 parts by mass is more preferable, and 15 to 25 parts by mass is even more preferable with respect to 100 parts by mass of the total amount of the resin components contained in.
Moreover, content ratio ((A) component: (d1) component) of (A) component and (d1) component in the resin composition of this embodiment is mass ratio, and is 60: 40-40: 60. Is preferable, 70:30 to 30:70 is more preferable, and 75:25 to 85:15 is more preferable.

((D2) cyanate ester resin)
(D2) Examples of cyanate ester resins include 2,2-bis (4-cyanatophenyl) propane, bis (4-cyanatophenyl) ethane, bis (3,5-dimethyl-4-cyanatophenyl) methane, , 2-bis (4-cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane, α, α′-bis (4-cyanatophenyl) -m-diisopropylbenzene, phenol addition di Examples include a cyanate ester compound of a cyclopentadiene polymer, a phenol novolac-type cyanate ester compound, and a cresol novolac-type cyanate ester compound. Among these, 2,2-bis (4-cyanatophenyl) propane is preferable in consideration of the low cost, the high-frequency characteristics, and the overall balance of other characteristics.
(D2) Cyanate ester resin may be used individually by 1 type, and may use 2 or more types together.

When the resin composition of the present embodiment contains (d2) cyanate ester resin, the content thereof is from the viewpoints of dielectric properties, conductor adhesion, heat resistance, low thermal expansion, flame retardancy, and processability. 5-50 mass parts is preferable with respect to 100 mass parts of total amounts of the resin component contained in the resin composition, 10-30 mass parts is more preferable, and 15-25 mass parts is more preferable.
Moreover, content ratio ((A) component: (d2) component) of (A) component and (d2) component in the resin composition of this embodiment is a mass ratio, and is 60: 40-40: 60. Is preferable, 70:30 to 30:70 is more preferable, and 75:25 to 85:15 is more preferable.

<(E) Inorganic filler>
The resin composition of the present embodiment may further contain (E) an inorganic filler.
(E) As inorganic filler, silica, alumina, titanium oxide, mica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate , Calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay such as calcined clay, talc, aluminum borate, silicon carbide and the like.
(E) An inorganic filler may be used individually by 1 type, and may use 2 or more types together.

(E) The average particle diameter of the inorganic filler is preferably 0.01 to 20 μm, more preferably 0.1 to 10 μm, and still more preferably 0.2 to 1 μm. In this specification, the average particle diameter is a particle diameter at a point corresponding to a volume of 50% when a cumulative frequency distribution curve based on the particle diameter is obtained with the total volume of the particles being 100%, and the laser diffraction scattering method is used. It can be measured with the used particle size distribution measuring device or the like.
(E) The shape of the inorganic filler is not particularly limited, and may be, for example, spherical, crushed, needle-shaped or plate-shaped, but is preferably spherical.

When the resin composition of this embodiment contains (E) an inorganic filler, the content is included in the resin composition from the viewpoint of low thermal expansion, uniformity of the obtained plate thickness, and handleability of the resin film. 50 to 400 parts by mass is preferable, 100 to 350 parts by mass is more preferable, and 200 to 300 parts by mass is more preferable with respect to 100 parts by mass of the total amount of resin components to be obtained.
Moreover, (E) content of an inorganic filler is a volume ratio, and 3-65 volume% is preferable in a resin composition, and 5-60 volume% is more preferable.
(E) When the content of the inorganic filler is in the above range, good low thermal expansion, moldability, and chemical resistance can be obtained.

When (E) an inorganic filler is used, a coupling agent may be used for the purpose of improving the dispersibility of the (E) inorganic filler and the adhesion to the organic component in the resin composition. Examples of coupling agents include silane coupling agents and titanate coupling agents. These may be used alone or in combination of two or more.
Although the usage-amount of a coupling agent is not specifically limited, 0.1-5 mass parts is preferable with respect to 100 mass parts of (E) inorganic fillers, and 0.5-3 mass parts is more preferable. If it is this range, there will be little fall of various characteristics and the feature by use of (E) inorganic filler can be exhibited effectively.
In the case of using a coupling agent, a so-called integral blend treatment method in which (E) an inorganic filler is added to the resin composition and then a coupling agent is added may be used. A method of using (E) an inorganic filler obtained by subjecting the filler to a surface treatment with a dry or wet coupling agent is preferable. By using this method, the feature of (E) inorganic filler can be expressed more effectively.
The (E) inorganic filler may be blended as a slurry in which the (E) inorganic filler is previously dispersed in an organic solvent for the purpose of improving dispersibility.

<Other ingredients>
The resin composition of the present embodiment is, in addition to the above-described components, other resins such as a thermosetting resin and a thermoplastic resin other than the above-described components, as necessary, within a range that does not impair the effects of the present invention. Components; antioxidants, flow regulators, additives such as curing accelerators other than the components (B) and (C); flame retardants; organic solvents and the like may be included.
As for the other components, one kind may be used alone, or two or more kinds may be used in combination.
Examples of the other resin components include saturated thermoplastic elastomers such as styrene-ethylene-butylene copolymers. Moreover, as a flame retardant, flame retardants, such as a bromine type, a phosphorus type, and a metal hydroxide, etc. are mentioned.

(Organic solvent)
In order to facilitate the production of the resin film described later, the resin composition of the present embodiment is also in a varnish state in which each component is dissolved and / or dispersed in an organic solvent (hereinafter also referred to as “resin varnish”). Good.
Examples of the organic solvent include alcohols such as methanol, ethanol and butanol; ethers such as ethyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, carbitol and butyl carbitol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene, mesitylene; esters such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, ethyl acetate; N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl- Nitrogen-containing compounds such as 2-pyrrolidone. Among these, aromatic hydrocarbons such as toluene, xylene, and mesitylene, which are good solvents for the component (A), and these aromatic hydrocarbons and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. The mixed solvent is preferable because the appearance when it is used as a film is improved.
An organic solvent may be used individually by 1 type, and may use 2 or more types together.
When using a resin composition as a varnish, it is preferable to adjust the usage-amount of a solvent so that the solid content (nonvolatile content) density | concentration in a varnish may be 5-80 mass%. In addition, in the process of manufacturing the resin film described later, the amount of the solvent can be adjusted by evaporating the solvent after applying the resin composition. In this case, the resin varnish can be prepared to have a solid content (nonvolatile content) concentration and a varnish viscosity so that a good appearance and a desired film thickness can be obtained.

The relative dielectric constant at 10 GHz of the cured product of the resin composition of the present embodiment is preferably 3.5 or less, more preferably 3.3 or less, and even more preferably 3.1 or less from the viewpoint of being suitably used in a high frequency band. 3.0 or less is particularly preferable. The lower limit value of the relative dielectric constant is not particularly limited, but may be, for example, 1.0 or more.
Further, from the viewpoint of suitable use in the high frequency band, the dielectric loss tangent of the cured product of the resin composition of the present embodiment is preferably 0.004 or less, and more preferably 0.003 or less. The lower limit value of the dielectric loss tangent is not particularly limited, but may be 0.0001 or more, for example.
The relative dielectric constant and dielectric loss tangent are measured by the methods described in the examples.

  The resin flow amount (%) of the resin composition of the present embodiment is preferably 5 to 25%, more preferably 6 to 20%, and still more preferably 8 to 18% from the viewpoint of uniformity of the obtained plate thickness. The amount of resin flow is measured by the method described in the examples.

  The resin composition of the present embodiment is suitable as a resin composition used for forming an interlayer insulating layer, and the interlayer insulating layer formed from the resin composition of the present embodiment has a high frequency characteristic and a uniform plate thickness. Therefore, it is suitable as an interlayer insulating layer for printed wiring boards, particularly as an interlayer insulating layer for build-up layers.

[Resin film]
The resin film of this embodiment is a resin film containing the resin composition of this embodiment.
The resin film of the present embodiment is preferably provided with a resin layer composed of a semi-cured product or a cured product of the resin composition of the present embodiment described above, and may be a combination of the resin layer and another layer. Good.
As an aspect which combined the said resin layer and another layer, the structure provided with a support base material and the said resin layer formed on this support base material is mentioned, for example. This support base material may be a base material used as a base during the production of the resin film, or may be one attached after the production.
Examples of the supporting substrate include metal foil and polyethylene terephthalate (PET) film.

Although the manufacturing method in particular of the resin film of this embodiment is not restrict | limited, For example, the following method is mentioned.
First, each component included in the resin composition of the present embodiment is mixed to obtain a resin composition. At this time, an organic solvent is preferably added to these components and stirred by a known method to obtain a resin varnish.

Next, after applying the resin varnish obtained above on a support substrate using a kiss coater, roll coater, comma coater, die coater, etc., in a heating and drying furnace, for example, 70 to 250 ° C. When it is used, the solvent is dried at a temperature higher than the volatility of the solvent), preferably at a temperature of 100 to 200 ° C., for 1 to 30 minutes, preferably 3 to 15 minutes. Thereby, a resin film provided with a resin layer in a state where the resin composition is semi-cured (B-staged) can be obtained.
In addition, the resin film provided with the semi-cured resin layer is further cured by heating in a heating furnace at a temperature of 170 to 250 ° C., preferably 185 to 230 ° C. for 60 to 150 minutes. A resin film having a resin layer is obtained. In addition, even if it is from the resin composition which is not made into the form of a varnish, after forming a resin composition into a film form, a resin film can be produced with the same heating method.

  The thickness of the resin film (resin layer in the case of having a support base material) of the present embodiment may be appropriately determined according to the required performance, but is preferably 1 to 200 μm from the viewpoint of embedding the conductor layer of the circuit board. 10 to 100 μm is more preferable, 15 to 80 μm is more preferable, and 20 to 60 μm is particularly preferable.

[Manufacture of metal-clad laminate]
The metal-clad laminate of the present embodiment is obtained by stacking one or more resin films of the present embodiment, placing metal foil on both surfaces, and hot press molding.
The manufacturing method of the metal-clad laminate of this embodiment includes, for example, one or more of the resin films of this embodiment, and a metal foil is disposed on one or both sides, and the heating temperature is, for example, 170 to 250. C., preferably 185-230.degree. C., pressure bonding is 0.5-5.0 MPa, for example, and heating time is, for example, 60-150 minutes. A metal-clad laminate with foil is obtained. The heating and pressurization are preferably performed under reduced pressure. For example, the degree of vacuum is 10 kPa or less, preferably 5 kPa or less. Moreover, it is preferable to implement a heating and pressurization from 30 minutes to a shaping | molding completion time from the start.

[Manufacture of printed wiring boards]
The printed wiring board of this embodiment is formed using the resin film of this embodiment or the metal-clad laminate of this embodiment.
Although the manufacturing method in particular of the printed wiring board of this embodiment is not restrict | limited, For example, the following method is mentioned.
First, the resin film of the present embodiment is disposed on one or both surfaces of the core substrate subjected to circuit formation processing, or the resin film of the present embodiment is disposed between a plurality of core substrates, and heat press molding is performed. Glue each layer. Subsequently, the printed wiring board of this embodiment can be manufactured by performing circuit formation processing by laser drilling, drilling, metal plating, metal etching, or the like by a known method. When placing the resin film on or between the core substrates, if the resin film has a supporting base material, the supporting base material is peeled off in advance or the resin layer is attached to the core substrate. It can be peeled after.
As one form of the printed wiring board of this embodiment, a multilayer printed wiring board may be formed by laminating a plurality of laminated boards on which wiring patterns are formed as described above.

[Semiconductor package]
The semiconductor package of this embodiment is obtained by mounting a semiconductor element on the printed wiring board of this embodiment. The semiconductor package of this embodiment can be manufactured by mounting a semiconductor element such as a semiconductor chip or a memory at a predetermined position of the printed wiring board and sealing the semiconductor element with a sealing resin or the like.

Hereinafter, the present invention will be described in more detail based on examples and comparative examples. However, the present invention is not limited to the following examples.
The obtained resin composition was evaluated by the following method.

[Appearance of resin film]
The surface of the resin film obtained in each example was visually observed and evaluated based on the following criteria.
○: The surface has no unevenness, streaks, etc., and the surface is uniform.
X: The surface has unevenness, streaks, etc. and lacks surface smoothness.

[Handling of resin film]
The handleability of the resin film obtained in each example was evaluated based on the following criteria by touching the surface of the resin film at 25 ° C. and cutting the resin film with a cutter knife.
○: There is no stickiness on the surface, and there is no resin cracking or powder falling during cutting.
X: The surface has a stickiness, or has a resin crack or powder fall at the time of cutting.

[Measurement of resin flow]
After measuring the weight (initial weight Wo) of four resin films with a support cut to a length of 102 mm and a width of 102 mm, these four resin films were stacked, sandwiched between two release films, It is sandwiched between steel plates at room temperature. The steel sheet sandwiched between the samples was set on a heating plate heated to 120 ° C., and the pressure was reduced to 1.12 ± 0.05 Pa within 5 seconds, and the state was maintained for 10 minutes. Thereafter, the sample (cured product of the resin film) was taken out from the hot platen, a circle having a diameter of 81.1 mm was punched from the center of the sample using a punching press, and the weight (W) of the disc sample was measured. The resin flow was calculated by the following formula.

[Measurement of variation in plate thickness]
The measurement of variation in the plate pressure surface is made by stacking two resin films from which the PET film has been peeled off on “MCL-HS100” (trade name, manufactured by Hitachi Chemical Co., Ltd.), and on both sides of the low profile copper foil (F3) having a thickness of 18 μm. -WS, M surface Rz: 3 μm, manufactured by Furukawa Electric Co., Ltd.) is disposed so that the roughened (M) surface is in contact with the resin layer, and a mirror plate is placed thereon, heating temperature is 200 ° C., and pressure is applied. A laminated plate for thickness evaluation was produced by heating and pressing under press conditions of 0 MPa and a pressure bonding time of 70 minutes. The thickness of the laminate (500 mm square) obtained by etching the outer layer copper foil is divided into 100 parts, the thickness at the center position of each test piece (50 mm square) is measured, and the center part (B) shown in FIG. The difference between the average thickness of the test piece and the average thickness of the outer peripheral portion (A) was evaluated. FIG. 1 shows a schematic diagram of a test piece used for measurement of variation in the plate thickness in-plane.

[Measurement of dielectric properties (dielectric constant, dielectric loss tangent)]
Dielectric characteristics were measured by etching the outer layer copper foil of the double-sided copper-clad laminate obtained in each example using a cavity resonator perturbation method. The conditions were a frequency: 10 GHz and a measurement temperature: 25 ° C.

[Measurement of thermal expansion coefficient]
The thermal expansion coefficient (plate thickness direction, temperature range: 30 to 150 ° C.) was obtained by etching a copper foil on both sides of the double-sided copper-clad laminate obtained in each example, and using a test piece cut into 5 mm squares. The measurement was performed according to the IPC method using TMA (TA Instruments, Q400).

[Measurement of peeling strength of copper foil]
The copper foil peeling strength was measured according to the copper-clad laminate test standard JIS C 6481 for the double-sided copper-clad laminate obtained in each example.

Examples 1-10, Comparative Examples 1-5
(Preparation of resin varnish)
In a 300 ml four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, the compounding composition shown in Table 1 (the compounding amount in the table is part by mass, solution (excluding organic solvent) or dispersion liquid) In the case of, each component was added so that the solid content equivalent amount), and stirred at 25 ° C. for 1 hour. Subsequently, it filtered through # 200 nylon mesh (opening 75 micrometers), and prepared the resin varnish.

(Production of resin film)
The resin varnish obtained above was coated on a PET film having a thickness of 38 μm (made by Teijin Ltd., trade name: G2-38) as a supporting substrate using a comma coater, and then dried at 130 ° C. A resin film with a PET film having a resin layer thickness of 65 μm was prepared.

(Production of double-sided copper-clad laminate)
The PET film is peeled off from the obtained resin film with a PET film, and two of these films are stacked, and a low profile copper foil having a thickness of 18 μm (F3-WS, M surface Rz: 3 μm, manufactured by Furukawa Electric Co., Ltd.) ) Is placed so that the roughened (M) surface is in contact with the resin layer, and a mirror plate is placed thereon, and heated and pressed under the pressing conditions of a heating temperature of 210 ° C., a pressing pressure of 3.0 MPa, and a pressing time of 80 minutes. It molded and produced the double-sided copper clad laminated board (thickness: 0.1 mm).

In addition, the symbol of each material in Table 1 is as follows.
[(A) component]
BMI-3000: Imide-extended bismaleimide (compound represented by general formula (A-9)), weight average molecular weight: about 3,000 (manufactured by Designer Molecules Incorporated)
[Component (B)]
Perbutyl P: 1,3-bis (2-t-butylperoxyisopropyl) benzene (manufactured by NOF Corporation, 1 minute half-life temperature: Example: 174.5 ° C.)
[Component (C)]
Perbutyl I: t-butyl peroxyisopropyl monocarbonate (manufactured by NOF Corporation, 1 minute half-life temperature: 158.8 ° C.)
・ Copper naphthenate (Kanto Chemical Co., Ltd.)
KBM-903: 3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
[(D) component]
BMI-1000: bis (4-maleimidophenyl) methane (manufactured by Daiwa Kasei Kogyo Co., Ltd.)
BADDY: 2,2-bis (4-cyanatophenyl) propane (Lonza)
[(E) component]
Silica: spherical fused silica, average particle size: 0.5 μm, surface treatment: phenylaminosilane coupling agent (1% by mass / solid content), dispersion medium: methyl isobutyl ketone (MIBK), solid content concentration 70% by mass, density 2.2 g / cm ³ , trade name: SC-2050KNK, manufactured by Admatechs Corporation)
[Organic solvent]
・ Toluene (Kanto Chemical Co., Ltd.)

* 1: Silica and methyl isobutyl ketone are blended as silica slurry.

  From the results in Table 1, it can be seen that the resin films using the resin compositions of Examples 1 to 10 have good appearance, handleability and resin flow, and have small variations in the plate thickness. In addition, the cured products obtained from the resin compositions of Examples 1 to 10 were both low in dielectric constant and dielectric loss tangent, and excellent in thermal expansion characteristics and copper foil peeling strength. On the other hand, the resin compositions of Comparative Examples 1 to 5 were inferior in resin flow amount and plate thickness in-plane variation. For these reasons, the resin composition of the present embodiment can provide a uniform thickness even when it is pressure-bonded to a circuit board by hot press molding, and has high frequency characteristics, low thermal expansion, and high adhesion to a conductor. It was confirmed that the resin composition had at the standard.

  The resin composition of this invention can provide the resin film which can respond | correspond to pressurization and heat press molding because the resin flow was controlled. In addition, since the relative permittivity and the dielectric loss tangent are low, the transmission loss characteristic is exhibited even in a high frequency band exceeding the millimeter wave band, and the thermal expansion characteristic and the copper foil peeling strength are combined. Therefore, for mobile communication devices that handle high-frequency signals of 1 GHz or higher and their base station devices, servers, routers and other network-related electronic devices and large-sized computers and other electronic devices, etc. It is useful as an insulating layer material for antennas used in millimeter wave radars that are required to be used.

Claims (14)

(A) a compound having a maleimide group, a divalent group having at least two imide bonds, and a saturated or unsaturated divalent hydrocarbon group;
(B) an organic peroxide;
(C) A resin composition containing at least one curing accelerator selected from the group consisting of an organic peroxide, an organometallic catalyst, and an amine compound different from the component (B).   (B) The resin composition of Claim 1 whose 1 minute half-life temperature of an organic peroxide is 160 degreeC or more and 230 degrees C or less.   The resin composition according to claim 2, wherein the component (C) is an organic peroxide different from the component (B), and the one-minute half-life temperature of the organic peroxide is 100 to 160 ° C.   The resin composition according to claim 1 or 2, wherein the component (C) is an organometallic catalyst, and the organometallic catalyst is a carboxylic acid metal salt.   The resin composition according to claim 1 or 2, wherein the component (C) is an amine compound, and the amine compound is an aminosilane coupling agent.   (D) The resin composition according to any one of claims 1 to 5, further comprising a thermosetting resin different from the component (A).   (E) The resin composition of any one of Claims 1-6 which further contains an inorganic filler. The resin composition according to any one of claims 1 to 7, wherein the component (A) is a compound represented by the following general formula (A-6).

(In the formula, R represents the divalent group having at least two imide bonds, Q represents the saturated or unsaturated divalent hydrocarbon group, and n represents an integer of 1 to 10.)   The saturated or unsaturated divalent hydrocarbon group which said (A) component has is C8-C100 bivalent aliphatic hydrocarbon group of any one of Claims 1-8. Resin composition.   The resin composition of any one of Claims 1-9 whose relative dielectric constant in 10 GHz of hardened | cured material is 3.0 or less.   The resin film containing the resin composition of any one of Claims 1-10.   A metal-clad laminate obtained by stacking one or more of the resin films according to claim 11, disposing metal foils on both sides thereof, and performing hot press molding.   A printed wiring board formed using the resin film according to claim 11 or the metal-clad laminate according to claim 12.   A semiconductor package comprising a semiconductor element mounted on the printed wiring board according to claim 13.