Resin composition, resin-attached metal foil, laminate sheet, printed wiring board and semiconductor package

Abstract

To provide: a resin composition which enables manufacture of a resin-attached metal foil with warpage reduced; a resin-attached metal foil made using the resin composition; a laminate sheet; a printed wiring board; and a semiconductor package.SOLUTION: There are provided: a resin composition containing (A) a thermosetting resin, and (B) a compound having two or more oxyalkylene bonds and a reactive group; a resin-attached metal foil made using the resin composition; a laminate sheet; a printed wiring board; and a semiconductor package.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present embodiment relates to a resin composition, a resin-coated metal foil, a laminate, a printed wiring board, and a semiconductor package. [Background technology]

[0002] 2. Description of the Related Art With the trend toward smaller size and higher performance of electronic devices in recent years, there is a demand for printed wiring boards to have higher wiring density and integration than ever before, as well as thinner substrates. In order to meet these requirements, resin-coated metal foils, which do not use fiber substrates such as glass cloth and have a resin layer formed on a metal foil, are used in the manufacture of printed wiring boards. Since resin-coated metal foils do not contain fiber substrates such as glass cloth, they can be made thin, and since they have excellent smoothness and fine wiring properties of the insulating layer, they are also suitable for high wiring density and high integration. Furthermore, since resin-coated metal foils do not contain fiber substrates such as glass cloth, they have excellent dielectric properties and are applied to printed wiring boards that require high frequency compatibility.

[0003] The resin-attached metal foil is usually produced by applying a thermosetting resin composition containing a solvent onto a metal foil, followed by heating and drying. At this time, the volume of the thermosetting resin composition shrinks due to the evaporation of the solvent and the thermosetting resin composition going into the B-stage, so the resin-attached metal foil may warp toward the resin layer. The occurrence of such warping is a factor that reduces the productivity when manufacturing a printed wiring board using the resin-attached metal foil, and is therefore desirably suppressed.

[0004] Patent Document 1 discloses a method for producing resin-coated metal foil in which a thermosetting resin composition is applied to the surface of the metal foil and then the foil is passed through a drying oven to heat and dry it to the B-stage, as a method for suppressing warping of the ends of the resin-coated metal foil, and is characterized in that the heating temperature at a position that is 80% of the total length from the entrance to the exit of the drying oven is 100°C or more higher than the heating temperature near the entrance of the drying oven, and the heating temperature from this position to the exit is 30°C or more lower. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2004-025624 A Summary of the Invention [Problem to be solved by the invention]

[0006] It is said that the technology of Patent Document 1 can produce a resin-coated metal foil with reduced warping at the edges. However, the manufacturing method of Patent Document 1 has a restriction that only materials suitable for the drying conditions can be used.

[0007] In addition, the inventors have found that the amount of warping can be reduced by applying a specific mechanical treatment to a warped resin-coated metal foil. However, if the thickness of the resin layer of the resin-coated metal foil is increased, cracks may occur in the resin layer when mechanical treatment is applied. Therefore, there is a demand for a technology that provides a resin-coated metal foil with small warping even without mechanical treatment.

[0008] In view of the current situation, an objective of this embodiment is to provide a resin composition capable of producing a resin-coated metal foil with little warping, and a resin-coated metal foil, a laminate, a printed wiring board, and a semiconductor package using the resin composition. [Means for solving the problem]

[0009] That is, this embodiment provides the following [1] to

[14] . [1] (A) a thermosetting resin; (B) a compound having two or more oxyalkylene bonds and a reactive group; A resin composition comprising: [2] The resin composition according to the above [1], wherein the component (A) is at least one selected from the group consisting of maleimide resins and epoxy resins. [3] The resin composition according to the above [1] or [2], wherein the oxyalkylene bond contained in the component (B) is a bond represented by the following formula (B-1-1) or the following formula (B-1-2): [ka] [4] The resin composition according to any one of the above [1] to [3], wherein the component (B) has two or more reactive groups. [5] The resin composition according to any one of the above [1] to [4], wherein the reactive group possessed by the component (B) is an epoxy group. [6] The resin composition according to any one of the above [1] to [5], wherein the content of the (B) component is 1 to 40 mass% relative to the total amount (100 mass%) of resin components in the resin composition. [7] The resin composition according to any one of the above [1] to [6], further comprising (C) a curing accelerator. [8] The resin composition according to any one of the above [1] to [7], further comprising (D) an inorganic filler. [9] A laminate comprising a cured product of the resin composition according to any one of the above [1] to [8] and a metal foil.

[10] A printed wiring board having a cured product of the resin composition according to any one of [1] to [8] above.

[11] A semiconductor package comprising the printed wiring board according to

[10] above and a semiconductor element.

[12] A metal foil and a resin layer laminated on one surface of the metal foil, A resin-coated metal foil, wherein the resin layer contains the resin composition according to any one of the above [1] to [8] or a semi-cured product of the resin composition.

[13] A printed wiring board formed using the resin-coated metal foil described in

[12] above, comprising a cured product of the resin layer.

[14] A semiconductor package comprising the printed wiring board according to

[13] above and a semiconductor element. Effect of the Invention

[0010] According to the present embodiment, it is possible to provide a resin composition capable of producing a resin-coated metal foil with little warping, and a resin-coated metal foil, a laminate, a printed wiring board, and a semiconductor package using the resin composition. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] In this specification, a numerical range indicated using "~" indicates a range that includes the numerical values ​​before and after "~" as the minimum and maximum values, respectively. For example, the expression "numerical range "X to Y" (X and Y are real numbers) means a numerical range that is equal to or greater than X and equal to or less than Y. In this specification, the expression "equal to or greater than X" means X and a numerical value that exceeds X. In this specification, the expression "equal to or less than Y" means Y and a numerical value that is less than Y. Each lower limit and upper limit of a numerical range described herein may be arbitrarily combined with the lower limit or upper limit of any other numerical range. In the numerical ranges described in this specification, the lower or upper limit of the numerical range may be replaced with values ​​shown in the examples.

[0012] Unless otherwise specified, each of the components and materials exemplified in this specification may be used alone or in combination of two or more. In this specification, the content of each component in a resin composition means, when a plurality of substances corresponding to each component are present in the resin composition, the total amount of the plurality of substances present in the resin composition, unless otherwise specified.

[0013] In this specification, the term "solid content" refers to components other than the solvent, and includes those that are liquid at room temperature. Here, in this specification, room temperature means 25°C.

[0014] The weight average molecular weight (Mw) in this specification means a value measured in terms of polystyrene by gel permeation chromatography (GPC). Specifically, the weight average molecular weight (Mw) in this specification can be measured by the method described in the examples.

[0015] In this specification, the term "semi-cured product" is synonymous with a resin composition in the B-stage state according to JIS K 6800 (2006), and the term "cured product" is synonymous with a resin composition in the C-stage state according to JIS K 6800 (2006).

[0016] The mechanism of action described in this specification is speculation and does not limit the mechanism by which the effects of the present embodiment are achieved.

[0017] Any combination of the descriptions in this specification is also included in this embodiment.

[0018] [Resin composition] The resin composition of the present embodiment is (A) a thermosetting resin; (B) a compound having two or more oxyalkylene bonds and a reactive group; The resin composition comprises: In this specification, each component may be abbreviated as component (A), component (B), etc., and other components may be abbreviated in the same manner.

[0019] The reason why the resin composition of the present embodiment enables production of a resin-coated metal foil with little warping is not clear, but is presumed to be as follows. The component (B) contained in the resin composition of the present embodiment has a highly flexible oxyalkylene bond, which is believed to facilitate relaxation of stress caused by volumetric shrinkage that occurs when the resin composition of the present embodiment is B-staged to form a resin layer, thereby enabling the production of a resin-coated metal foil with minimal warpage. In addition, since component (B) has a reactive group, it is less likely to volatilize when the resin composition of this embodiment is B-staged to form a resin layer, and volumetric shrinkage due to volatilization of component (B) itself is less likely to occur. This is also presumably one of the reasons why it is possible to produce a resin-coated metal foil with little warping. Hereinafter, each component that may be contained in the resin composition of the present embodiment will be described in order.

[0020] <(A) Thermosetting resin> Examples of the (A) thermosetting resin include epoxy resin, phenol resin, maleimide resin, cyanate resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, unsaturated polyester resin, allyl resin, dicyclopentadiene resin, silicone resin, triazine resin, melamine resin, etc. Among these, the (A) thermosetting resin is preferably at least one selected from the group consisting of epoxy resin, cyanate resin, and maleimide resin, and more preferably at least one selected from the group consisting of maleimide resin and epoxy resin, from the viewpoint of heat resistance and conductor adhesion. Thermosetting resins having two or more oxyalkylene bonds are classified as component (B). The (A) thermosetting resin may be used alone or in combination of two or more kinds.

[0021] [Maleimide resin] The maleimide resin is more preferably one or more types selected from the group consisting of maleimide resins having one or more N-substituted maleimide groups and derivatives of the maleimide resins (hereinafter also referred to as "maleimide-based resins"). In the following description, a maleimide resin having one or more N-substituted maleimide groups may be referred to as a "maleimide resin (AX)" or an "(AX) component." Furthermore, a maleimide resin derivative having one or more N-substituted maleimide groups may be referred to as a "maleimide resin derivative (AY)" or an "(AY) component".

[0022] (Maleimide resin (AX)) The maleimide resin (AX) is not particularly limited as long as it is a maleimide resin having one or more N-substituted maleimide groups. From the viewpoints of conductor adhesion and heat resistance, the maleimide resin (AX) is preferably an aromatic maleimide resin having two or more N-substituted maleimide groups, and more preferably an aromatic bismaleimide resin having two N-substituted maleimide groups.

[0023] In this specification, "aromatic maleimide resin" refers to a compound having an N-substituted maleimide group directly bonded to an aromatic ring. In addition, in this specification, "aromatic bismaleimide resin" refers to a compound having two N-substituted maleimide groups directly bonded to an aromatic ring. In addition, in this specification, "aromatic polymaleimide resin" refers to a compound having three or more N-substituted maleimide groups directly bonded to an aromatic ring. In addition, in this specification, "aliphatic maleimide resin" refers to a compound having an N-substituted maleimide group directly bonded to an aliphatic hydrocarbon.

[0024] The maleimide resin (AX) is preferably a maleimide resin represented by the following general formula (A-1).

[0025] [ka] (In the formula, X A1 is a divalent organic group.

[0026] X in the above general formula (A-1) A1 is a divalent organic group. X in the above general formula (A-1) A1 Examples of the divalent organic group represented by the formula (A-2) include a divalent organic group represented by the formula (A-3) below, a divalent organic group represented by the formula (A-4) below, a divalent organic group represented by the formula (A-5) below, and a divalent organic group represented by the formula (A-6) below.

[0027] [ka] (In the formula, R A1 is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A1 is an integer from 0 to 4. * represents a binding site.

[0028] R in the above general formula (A-2) A1 Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by include an alkyl group having 1 to 5 carbon atoms, such as 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, etc.; an alkenyl group having 2 to 5 carbon atoms; an alkynyl group having 2 to 5 carbon atoms. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In the above general formula (A-2), n A1 is an integer of 0 to 4, and from the viewpoint of availability, is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0. A1 If is an integer equal to or greater than 2, multiple R A1 They may be the same or different.

[0029] [ka] (In the formula, R A2 and R A3 Each of X is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A2 is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, a single bond, or a divalent organic group represented by the following general formula (A-3-1): A2 and n A3 are each independently an integer of 0 to 4. * represents a binding site.

[0030] R in the above general formula (A-3) A2 and RA3 The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R A1 The same can be mentioned.

[0031] X in the above general formula (A-3) A2 Examples of the alkylene group having 1 to 5 carbon atoms represented by include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, a 1,5-pentamethylene group, etc. The alkylene group having 1 to 5 carbon atoms is preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms, and further preferably a methylene group. X in the above general formula (A-3) A2 Examples of the alkylidene group having 2 to 5 carbon atoms represented by include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, and an isopentylidene group.

[0032] In the above general formula (A-3), n A2 and n A3 each independently represents an integer of 0 to 4. n A2 or n A3 If is an integer equal to or greater than 2, multiple R A2 R A3 They may be the same or different from each other.

[0033] X in the above general formula (A-3) A2 The divalent organic group represented by the general formula (A-3-1) is as follows:

[0034] [ka] (In the formula, R A4 and R A5 Each of X is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A3is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond. A4 and n A5 are each independently an integer of 0 to 4. * represents a binding site.

[0035] R in the above general formula (A-3-1) A4 and R A5 The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R A1 The same can be mentioned. X in the above general formula (A-3-1) A3 The alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by the above X A2 The same can be mentioned. In the above general formula (A-3-1), n A4 and n A5 are each independently an integer of 0 to 4, and from the viewpoint of availability, each is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0. n A4 or n A5 If is an integer equal to or greater than 2, multiple R A4 R A5 They may be the same or different from each other.

[0036] [ka] (In the formula, n A6 is an integer between 0 and 10. * represents a binding site.)

[0037] [ka] (In the formula, n A7 is a number from 0 to 5. * represents a binding site.)

[0038] [ka] (In the formula, R A6 and R A7 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. A8 is an integer from 1 to 8. * represents a binding site.

[0039] R in the above general formula (A-6) A6 and R A7 The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R A1 The same can be mentioned. In the above general formula (A-6), n A8 If is an integer equal to or greater than 2, multiple R A6 R A7 They may be the same or different from each other.

[0040] (Maleimide resin derivatives (AY)) The maleimide resin derivative (AY) is preferably a resin containing a structure derived from a maleimide resin having one or more N-substituted maleimide groups (i.e., the maleimide resin (AX)) and a structure derived from a diamine compound [hereinafter, sometimes referred to as an "aminomaleimide resin."].

[0041] An example of a structure derived from the maleimide resin (AX) contained in the aminomaleimide resin is a structure formed by a Michael addition reaction between at least one N-substituted maleimide group among the N-substituted maleimide groups contained in the maleimide resin (AX) and an amino group contained in a diamine compound. The content of the structure derived from the maleimide resin (AX) in the aminomaleimide resin is preferably from 5 to 95% by mass, more preferably from 30 to 93% by mass, and further preferably from 60 to 90% by mass. The structure derived from the maleimide resin (AX) contained in the aminomaleimide resin may be of one type alone or of two or more types.

[0042] An example of a structure derived from a diamine compound contained in an aminomaleimide resin is a structure formed by a Michael addition reaction between one or both of two amino groups contained in a diamine compound and an N-substituted maleimide group contained in the maleimide resin (AX). The content of the structure derived from the diamine compound in the aminomaleimide resin is not particularly limited, but is preferably 5 to 95 mass %, more preferably 7 to 70 mass %, and further preferably 10 to 40 mass %. The structure derived from the diamine compound contained in the aminomaleimide resin may be of one type alone or of two or more types.

[0043] The amino group contained in the diamine compound is preferably a primary amino group. As the diamine compound, an aromatic diamine compound having two amino groups directly bonded to an aromatic ring, or a silicone compound having two primary amino groups is preferred. Examples of aromatic diamine compounds include 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisaniline, 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline, and 3,3'-diethyl-4,4'-diaminodiphenylmethane.

[0044] [Epoxy resin] The epoxy resin is preferably an epoxy resin having two or more epoxy groups.

[0045] Epoxy resins are classified into, for example, glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, glycidyl ester type epoxy resins, etc. Among these, glycidyl ether type epoxy resins are preferred.

[0046] Epoxy resins are classified into various types according to the difference in the main skeleton. Specifically, the epoxy resins are classified into bisphenol type epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, and bisphenol S type epoxy resins; novolac type epoxy resins such as bisphenol A novolac type epoxy resins, bisphenol F novolac type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, biphenyl novolac type epoxy resins, and naphthol novolac type epoxy resins; aralkyl type epoxy resins such as phenol aralkyl type epoxy resins, biphenyl aralkyl type epoxy resins, and naphthol aralkyl type epoxy resins; stilbene type epoxy resins; naphthylene ether type epoxy resins; biphenyl type epoxy resins; dihydroanthracene type epoxy resins; naphthalene type epoxy resins; epoxy resins containing a saturated dicyclopentadiene skeleton; cyclohexane dimethanol type epoxy resins; spiro ring-containing epoxy resins; heterocyclic epoxy resins; alicyclic epoxy resins; aliphatic chain epoxy resins; rubber-modified epoxy resins; and the like. Among these, naphthalene type epoxy resins are preferred.

[0047] ((A) Thermosetting resin content) The content of the thermosetting resin (A) in the resin composition of this embodiment is preferably 20 to 99 mass%, more preferably 50 to 98 mass%, and even more preferably 65 to 95 mass%, relative to the total amount (100 mass%) of the resin components in the resin composition of this embodiment. When the content of the (A) thermosetting resin is equal to or greater than the lower limit, the heat resistance, moldability, processability, and conductor adhesion tend to be improved. When the content of the (A) thermosetting resin is equal to or less than the upper limit, the dielectric properties tend to be improved.

[0048] In this specification, the term "resin component" refers to a resin and a compound that forms a resin through a curing reaction. In the resin composition of the present embodiment, for example, the component (A) and the component (B) correspond to the resin component. When the resin composition of the present embodiment contains, as optional components, a resin or a compound that forms a resin through a curing reaction in addition to the above components, these optional components are also included in the resin component. On the other hand, components (C) and (D) described below are not included in the resin component.

[0049] The content of the resin component in the resin composition of this embodiment is preferably 10 to 90 mass%, more preferably 30 to 80 mass%, and even more preferably 50 to 70 mass%, relative to the total solid content (100 mass%) of the resin composition of this embodiment. When the content of the resin component is equal to or more than the lower limit, the heat resistance, moldability, processability, and conductor adhesion tend to be improved. When the content of the resin component is equal to or less than the upper limit, the low thermal expansion property tends to be improved.

[0050] <(B) Compound Having Two or More Oxyalkylene Bonds and Reactive Groups> There are no particular limitations on the component (B) so long as it is a compound having two or more oxyalkylene bonds and a reactive group. The component (B) may be used alone or in combination of two or more types.

[0051] The number of carbon atoms in the alkylene group constituting the oxyalkylene bond in component (B) is preferably 1 to 5, more preferably 2 to 4, and even more preferably 2 or 3, from the viewpoint of easier suppression of warping of the resin-coated metal foil. The alkylene group may or may not have a substituent. When the alkylene group has a substituent, the number of carbon atoms of the substituent is included in the number of carbon atoms of the alkylene group.

[0052] The oxyalkylene bond is represented, for example, by the following general formula (B-1).

[0053] [ka] (R B1is an alkylene group having 2 to 5 carbon atoms.

[0054] R B1 Examples of the alkylene group having 2 to 5 carbon atoms represented by include an ethylene group, a propylene group, a butylene group, and a pentylene group. In this specification, the alkylene group also includes an alkylidene group. Among these, an ethylene group and a propylene group are preferred from the viewpoint of more easily suppressing warping of the resin-coated metal foil. From a similar viewpoint, the oxyalkylene bond is preferably a bond represented by the following formula (B-1-1) or the following formula (B-1-2).

[0055] [ka]

[0056] The bond represented by the above general formula (B-1-1) can be formed by a ring-opening addition reaction of ethylene oxide, and the bond represented by the above general formula (B-1-2) can be formed by a ring-opening addition reaction of propylene oxide.

[0057] The number of oxyalkylene bonds in the (B) component is 2 or more, preferably 2 to 20, more preferably 2 to 12, and even more preferably 2 to 6, from the viewpoint of easier suppression of warping of the resin-coated metal foil.

[0058] Examples of the reactive group contained in the (B) component include an epoxy group, an N-substituted maleimide group, an amino group, a carboxy group, a hydroxy group, an isocyanate group, and a (meth)acryloyl group. Among these, an epoxy group is preferred. The epoxy group may be contained in a glycidyl group.

[0059] From the viewpoint of easier suppression of warping of the resin-coated metal foil, the number of reactive groups possessed by component (B) is preferably 2 or more, more preferably 2 to 5, even more preferably 2 or 3, and even more preferably 2.

[0060] The component (B) is preferably a compound having a reactive group and a structure formed by addition reaction of an alkylene oxide with a phenolic hydroxyl group of a phenol compound. The phenol compound to be subjected to the addition reaction of the alkylene oxide is preferably, for example, a bisphenol compound such as bisphenol A, bisphenol F, or bisphenol S. That is, the component (B) is preferably a compound having a structure and reactive group obtained by addition reaction of an alkylene oxide to a bisphenol compound, and more preferably a compound having a structure and reactive group obtained by addition reaction of ethylene oxide or propylene oxide to a bisphenol compound.

[0061] From the viewpoint of making it easier to suppress warping of the resin-coated metal foil, the component (B) is preferably a compound represented by the following general formula (B-2).

[0062] [ka] (In the formula, R B1 R in the above general formula (B-1) B1 is the same as R B2 and R B3 Each of X is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. B1 is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a divalent organic group represented by a single bond. B1 and n B2 Each of m independently represents an integer of 0 to 4. B1 and m B2 Each independently is a number from 1 to 10. B1 and Y B2 each independently represents a group containing a reactive group.

[0063] R in the above general formula (B-2) 1 A preferred embodiment of the formula (B-1) is 1 This is the same as the preferred embodiment of In the above general formula (B-2), mB1 and m B2 are each independently a number from 1 to 10, preferably a number from 1 to 6, and more preferably a number from 1 to 3.

[0064] R in the above general formula (B-2) B2 and R B3 Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by include an alkyl group having 1 to 5 carbon atoms, such as 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, etc.; an alkenyl group having 2 to 5 carbon atoms; an alkynyl group having 2 to 5 carbon atoms. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In the above general formula (B-2), n B1 and n B2 each independently represents an integer of 0 to 4. n B1 or n B2 If is an integer equal to or greater than 2, multiple R B1 R B2 They may be the same or different from each other.

[0065] Y in the above general formula (B-2) B1 and Y B2 Examples of the group containing a reactive group represented by the formula (I) include the groups containing the reactive group exemplified above. Among these, a group containing an epoxy group is preferable, and a glycidyl group is more preferable.

[0066] In the resin composition of this embodiment, the content of component (B) is preferably 1 to 40 mass%, more preferably 3 to 35 mass%, even more preferably 5 to 30 mass%, still more preferably 7 to 25 mass%, and particularly preferably 11 to 20 mass%, relative to the total amount (100 mass%) of the resin components in the resin composition of this embodiment. When the content of the (B) component is equal to or more than the lower limit, the occurrence of warping of the resin-coated metal foil and the occurrence of cracks on the surface of the resin layer tend to be more easily suppressed. Also, when the content of the (B) component is equal to or less than the upper limit, the heat resistance of the cured product of the resin layer tends to be more improved.

[0067] <(C) Curing accelerator> From the viewpoint of accelerating the curing reaction of the resin composition, the resin composition of the present embodiment preferably further contains (C) a curing accelerator. The curing accelerator (C) may be used alone or in combination of two or more kinds.

[0068] Examples of the (C) curing accelerator include amine-based curing accelerators, imidazole-based curing accelerators, phosphorus-based curing accelerators, organometallic salts, acid catalysts, organic peroxides, etc. In the present embodiment, imidazole-based curing accelerators are not classified as amine-based curing accelerators. Examples of the amine-based curing accelerator include amine compounds having primary to tertiary amines, such as triethylamine, pyridine, tributylamine, and dicyandiamide; and quaternary ammonium compounds. Examples of the imidazole-based curing accelerator include imidazole compounds such as methylimidazole, phenylimidazole, and 2-undecylimidazole; and isocyanate-masked imidazoles such as an addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole. Examples of the phosphorus-based curing accelerator include tertiary phosphines such as triphenylphosphine; and quaternary phosphonium compounds such as an addition product of p-benzoquinone and tri-n-butylphosphine. Examples of the organic metal salt include carboxylates of manganese, cobalt, zinc, and the like. An example of the acid catalyst is p-toluenesulfonic acid. Examples of organic peroxides include dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3,2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, t-butylperoxyisopropyl monocarbonate, and α,α'-di(t-butylperoxy)diisopropylbenzene. Among these, from the viewpoints of dielectric properties, heat resistance, adhesion to a conductor, and elastic modulus, amine-based curing accelerators, imidazole-based curing accelerators, and phosphorus-based curing accelerators are preferred, phosphorus-based curing accelerators are more preferred, and quaternary phosphonium compounds are even more preferred.

[0069] When the resin composition of the present embodiment contains the curing accelerator (C), the content thereof is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and even more preferably 0.1 to 1 part by mass, relative to 100 parts by mass of the total of the components (A) and (B). When the content of the (C) curing accelerator is equal to or greater than the lower limit, a sufficient curing acceleration effect tends to be obtained, and when the content of the (C) curing accelerator is equal to or less than the upper limit, storage stability tends to be improved.

[0070] <(D) Inorganic filler> The resin composition of the present embodiment preferably further contains (D) an inorganic filler. The resin composition of the present embodiment tends to easily achieve superior low thermal expansion properties and heat resistance by containing the inorganic filler (D). The (D) inorganic filler may be used alone or in combination of two or more kinds.

[0071] (D) Examples of inorganic fillers include 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, talc, aluminum borate, and silicon carbide. Among these, silica, alumina, mica, and talc are preferred from the viewpoint of low thermal expansion, heat resistance, and flame retardancy, silica and alumina are more preferred, and silica is even more preferred. As silica, amorphous silica is preferred from the viewpoint of dispersibility and moldability.

[0072] (D) Average particle size of inorganic filler (D 50 From the viewpoint of dispersibility of the (D) inorganic filler and fine wiring properties, the thickness is preferably 0.01 to 20 μm, more preferably 0.1 to 10 μm, further preferably 0.2 to 1 μm, and particularly preferably 0.3 to 0.8 μm. In this specification, the average particle diameter (D 50 ) is the particle size at the point corresponding to 50% volume when the cumulative frequency distribution curve of particle sizes is calculated assuming the total volume of the particles to be 100%. The average particle size of the (D) inorganic filler can be measured, for example, by a particle size distribution measuring device using a laser diffraction scattering method. The shape of the (D) inorganic filler may be, for example, spherical or crushed, with the spherical shape being preferred.

[0073] In the resin composition of the present embodiment, a coupling agent may be used for the purpose of improving the dispersibility of the inorganic filler (D) and the adhesion between the inorganic filler (D) and the organic component. Examples of the coupling agent include a silane coupling agent and a titanate coupling agent.

[0074] When the resin composition of the present embodiment contains an inorganic filler (D), the content of the inorganic filler (D) is preferably 10 to 70 mass%, more preferably 20 to 60 mass%, and even more preferably 30 to 50 mass%, relative to the total solid content (100 mass%) of the resin composition. When the content of the (D) inorganic filler is equal to or greater than the lower limit, the low thermal expansion and heat resistance tend to be improved. When the content of the (D) inorganic filler is equal to or less than the upper limit, the moldability and conductor adhesion tend to be improved.

[0075] <Other ingredients> The resin composition of the present embodiment may further contain one or more selected from the group consisting of resin materials other than the above components, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, lubricants, flame retardants, organic solvents, and other additives, as necessary. Each of these may be used alone or in combination of two or more. The amount of these used is not particularly limited, and may be used as necessary within a range that does not impair the effects of the present embodiment.

[0076] (Organic solvent) The resin composition of the present embodiment may contain an organic solvent from the viewpoint of facilitating handling and facilitating production of a prepreg, which will be described later. The organic solvent may be used alone or in combination of two or more kinds.

[0077] Examples of organic solvents include alcohol-based solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether-based solvents such as tetrahydrofuran; aromatic hydrocarbon-based solvents such as toluene, xylene, and mesitylene; nitrogen-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; sulfur-containing solvents such as dimethyl sulfoxide; and ester-based solvents such as γ-butyrolactone.

[0078] <Method of producing resin composition> The resin composition of the present embodiment can be produced by mixing the above-mentioned components. When mixing the components, the components may be dissolved or dispersed while being stirred. The order in which the raw materials are mixed, the mixing temperature, the mixing time, and other conditions are not particularly limited and may be set arbitrarily depending on the types of raw materials, etc.

[0079] [Metal foil with resin] The resin-coated metal foil of this embodiment is A metal foil and a resin layer laminated on one surface of the metal foil, The resin layer is a resin-attached metal foil containing the resin composition of the present embodiment or a semi-cured product of the resin composition.

[0080] <Resin layer> The thickness of the resin layer is preferably 5 to 1,000 μm, more preferably 10 to 500 μm, even more preferably 20 to 200 μm, still more preferably 30 to 100 μm, and particularly preferably 40 to 70 μm. When the thickness of the resin layer is equal to or greater than the lower limit, the circuit embedding property tends to be improved, whereas when the thickness of the resin layer is equal to or less than the upper limit, the wiring density tends to be increased.

[0081] Metal foil Examples of the metal foil include copper foil, tin foil, tin-lead alloy foil, nickel foil, etc. Among these, copper foil is preferable. The copper foil preferably has a copper content of 95% by mass or more. From the viewpoint of use in semiconductor packages, the metal foil is preferably one that complies with the JIS standard (electrolytic copper foil for printed wiring boards: JIS C6512, rolled copper foil for printed wiring boards: JIS C6513) or the IPC standard (IPC 4562 standard Grades 1, 2, 3).

[0082] The surface of the metal foil on which the resin layer is to be formed may be subjected to a roughening treatment from the viewpoint of adhesion. In addition to the above-mentioned roughening treatment, the metal foil may have secondary particles, tertiary particles, an anti-rust layer, a heat-resistant layer, or the like formed of, for example, a single element selected from nickel, cobalt, copper, and zinc, or an alloy containing one or more of these elements. In addition to the above layers, the surface may be subjected to a surface treatment such as a chromate treatment or a silane coupling treatment.

[0083] The thickness of the metal foil may be appropriately adjusted depending on the application of the resin-coated metal foil, and is preferably 0.1 to 40 μm, more preferably 1 to 30 μm, and further preferably 1.5 to 20 μm. When the thickness of the metal foil is equal to or greater than the lower limit, the handleability of the resin-coated metal foil tends to be further improved, whereas when the thickness of the metal foil is equal to or less than the upper limit, the wiring density tends to be more favorable.

[0084] The resin-coated metal foil of this embodiment is suitable as a resin-coated metal foil for forming an insulating layer of a printed wiring board such as a multilayer printed wiring board, or as a resin-coated metal foil for sealing a semiconductor in a semiconductor package.

[0085] <Method of manufacturing resin-coated metal foil> The resin-attached metal foil of the present embodiment can be produced, for example, by applying a resin composition containing an organic solvent (hereinafter, the resin composition containing an organic solvent may be referred to as a "resin varnish") to a metal foil and then drying by heating.

[0086] As a coating device for coating the resin varnish, for example, a coating device known to those skilled in the art, such as a comma coater, a bar coater, a kiss coater, a roll coater, a gravure coater, a die coater, etc. These coating devices may be appropriately selected depending on the film thickness to be formed. The drying conditions after the resin varnish is applied may be appropriately determined depending on the content, boiling point, etc. of the organic solvent, and are not particularly limited. For example, in the case of a resin varnish containing 40 to 60 mass % of an aromatic hydrocarbon solvent, the drying temperature is not particularly limited, but from the viewpoints of productivity and appropriately B-staging the resin composition, it is preferably 50 to 200°C, more preferably 80 to 150°C, and even more preferably 100 to 130°C. In addition, in the case of the above-mentioned resin varnish, the drying time is not particularly limited, but from the viewpoints of productivity and appropriately B-staging the resin composition, it is preferably 1 to 30 minutes, more preferably 2 to 15 minutes, and even more preferably 3 to 10 minutes.

[0087] [Laminate] The laminate of the present embodiment is a laminate having a cured product of the resin composition of the present embodiment and a metal foil. Incidentally, a laminate having a metal foil is sometimes called a metal-clad laminate.

[0088] The metal of the metal foil may be the same as that used in the resin-coated metal foil of this embodiment.

[0089] The laminate of this embodiment can be produced, for example, by laminating the resin-coated metal foil of this embodiment and molding it under heat and pressure. For the hot pressure molding, for example, a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, or the like can be used. The conditions for the hot and press molding are not particularly limited, but may be, for example, a temperature of 100 to 300° C., a time of 10 to 300 minutes, and a pressure of 1.5 to 5 MPa.

[0090] [Printed wiring board] The printed wiring board of the first aspect of this embodiment is a printed wiring board having a cured product of the resin composition of this embodiment. The printed wiring board of the second aspect of this embodiment is a printed wiring board formed using the resin-coated metal foil of this embodiment, and includes a cured product of the resin layer. Hereinafter, the printed wiring boards of the first and second aspects are referred to as "printed wiring boards of this embodiment." The printed wiring board of the present embodiment can be manufactured, for example, by forming a conductor circuit on an insulating layer made of a cured product of the resin composition of the present embodiment or a cured product of the resin layer of the resin-coated metal foil of the present embodiment, by a known method. Furthermore, a multi-layered printed wiring board can be manufactured by further performing a multi-layering adhesive process as necessary. The conductor circuit can be formed, for example, by appropriately performing a hole drilling process, a metal plating process, an etching process of a metal foil, or the like.

[0091] [Semiconductor package] The semiconductor package of this embodiment is a semiconductor package that includes the printed wiring board of this embodiment and a semiconductor element. The semiconductor package of this embodiment can be manufactured, for example, by mounting a semiconductor chip, a memory, and the like on the printed wiring board of this embodiment by a known method. EXAMPLES

[0092] The present embodiment will be specifically described below with reference to examples, although the present embodiment is not limited to the following examples.

[0093] [Method of measuring weight average molecular weight (Mw)] The values ​​were calculated from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). The calibration curve was approximated by a third-order equation using standard polystyrene: TSKstandard POLYSTYRENE (Type; A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [manufactured by Tosoh Corporation, product name]. The measurement conditions for GPC are shown below. Device: Pump: L-6200 type [manufactured by Hitachi High-Technologies Corporation] Detector: L-3300 type RI [Hitachi High-Technologies Corporation] Column oven: L-655A-52 [Hitachi High-Technologies Corporation] Column: Guard column: TSK Guardcolumn HHR-L + column: TSKgel G4000HHR + TSKgel G2000HHR (all manufactured by Tosoh Corporation, product names) Column size: 6.0 x 40 mm (guard column), 7.8 x 300 mm (column) Eluent: Tetrahydrofuran Sample concentration: 30mg / 5mL Injection volume: 20μL Flow rate: 1.00mL / min Measurement temperature: 40℃

[0094] Manufacturing Example 1 (Production of aminomaleimide resin) In a 5-liter reaction vessel equipped with a thermometer, a stirrer, and a moisture content meter with a reflux condenser, capable of heating and cooling, 100 parts by mass of 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 13.5 parts by mass of 3,3'-diethyl-4,4'-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., product name: KAYAHARD (registered trademark) AA), and 171 parts by mass of propylene glycol monomethyl ether were added and reacted for 2 hours under reflux. This was concentrated at the reflux temperature for 3 hours to produce an aminomaleimide resin-containing liquid with a solid content concentration of 65% by mass. The weight-average molecular weight (Mw) of the obtained aminomaleimide resin was about 2,700.

[0095] Examples 1 to 5, Comparative Examples 1 to 6 (Production of resin composition) Each component shown in Table 1 was mixed with methyl isobutyl ketone in the amounts shown in Table 1, and then the mixture was stirred and mixed at 25° C. or while heating to 50 to 80° C. to prepare a resin composition having a solid content concentration of about 50% by mass. Note that in Table 1, the unit of the amount of each component is parts by mass, and in the case of a solution, it means parts by mass converted into solid content.

[0096] (Manufacturing of resin-coated metal foil) The resin composition obtained in each example was applied onto one side of a low-profile copper foil having a thickness of 18 μm (manufactured by Mitsui Mining & Smelting Co., Ltd., product name "3EC-VLP-18") so that the thickness of the resin layer after drying would be the thickness shown in Table 1. The resin composition was applied onto the roughened surface of the low-profile copper foil. Thereafter, the resin composition was heated and dried at 105° C. for 5 minutes to bring the resin composition into a B-stage state, and a metal foil with resin was produced.

[0097] (Manufacturing resin boards with copper foil on both sides) The resin-coated metal foil obtained above was cut to a size of 250 mm in length x 250 mm in width, and two pieces were stacked together with the resin layer sides facing each other. The pieces were then heated and pressurized at a temperature of 230°C, a pressure of 2.0 MPa, and a time of 60 minutes to harden the resin layer, thereby producing a resin board with copper foil on both sides.

[0098] [Evaluation method] The evaluations were carried out according to the following methods, and the results are shown in Table 1.

[0099] (Check for cracks on the resin layer surface) The surface of the resin layer of the resin-coated metal foil obtained in each example was visually observed to check for the presence or absence of cracks and the number of cracks, and was evaluated according to the following criteria. A: No cracks B: Number of cracks: 1 / 50mm 2 Above, 20 pieces / 50mm 2 below C: Number of cracks: 21 / 50mm 2 Above, 99 pieces / 50mm 2 below D: Number of cracks: 100 / 50mm 2 End

[0100] (Method of measuring glass transition temperature) The resin plate with copper foil on both sides obtained in each example was immersed in a 10 mass% solution of ammonium persulfate (manufactured by Mitsubishi Gas Chemical Co., Ltd.) which is a copper etching solution, to remove the copper foil. The obtained resin plate was cut into a width of 5.0 mm and a length of 20 mm, and then dried at 105°C for 1 hour to obtain a test piece. The test piece was clamped at both ends in the long side direction of the test piece with upper and lower grippers with a gap of 10 mm between the grippers. Next, the dimensional change was measured using a thermomechanical analyzer (TMA) (manufactured by Seiko Instruments Inc., product name "SS6100") in a tensile mode, in a temperature range of 30 to 300°C, at a heating rate of 5°C / min, and with a load of 4g. The inflection point of the dimensional change with respect to temperature was determined as the glass transition temperature.

[0101] (Measurement of warpage of resin-coated metal foil) The resin-coated metal foil obtained in each example was cut into a size of 500 mm x 400 mm, placed on a flat desk, and the height of the warped corners was measured with a ruler. The maximum value of these was evaluated as the amount of warping (mm).

[0102] [Table 1]

[0103] Details of each component listed in Table 1 are as follows. [Component (A)] Maleimide resin: Aminomaleimide resin produced in Production Example 1 (Solid Epoxy) Naphthalene-type epoxy resin: DIC Corporation, product name "HP-9540" (liquid epoxy) Naphthalene-type epoxy resin: DIC Corporation, product name "HP-4032" Dicyclopentadiene epoxy resin: DIC Corporation, product name "HP-7200L" Phenol novolac epoxy resin: DOW, product name "DEN-438"

[0104] [(B) Component] Propylene oxide modified bisphenol A diglycidyl ether: a compound represented by the following formula (B-3) [ka] (In the formula, m 1 and m 2 is a number between 1 and 2.)

[0105] [Comparative ingredients] Acrylic polymer: Nagase ChemteX Corporation, product name "SG-P3"

[0106] [(C) component] Curing accelerator: Addition product of p-benzoquinone and tri-n-butylphosphine

[0107] [(D) component] Inorganic filler: amorphous silica (spherical, average particle size: 0.5 μm)

[0108] From the results shown in Table 1, it is evident that the resin-coated metal foils of Examples 1 to 5 of this embodiment have a small amount of warping even when the resin layer is made thick.

Claims

1. (A) a thermosetting resin; (B) a compound having two or more oxyalkylene bonds and a reactive group; A resin composition comprising:

2. The resin composition according to claim 1, wherein the component (A) is at least one selected from the group consisting of maleimide resins and epoxy resins.

3. The resin composition according to claim 1, wherein the oxyalkylene bond contained in the component (B) is a bond represented by the following formula (B-1-1) or the following formula (B-1-2): 【Chemistry 1】

4. The resin composition according to claim 1 , wherein the component (B) has two or more reactive groups.

5. The resin composition according to claim 1 , wherein the reactive group contained in the component (B) is an epoxy group.

6. The resin composition according to claim 1, wherein the content of the (B) component is 1 to 40 mass% relative to the total amount (100 mass%) of the resin components in the resin composition.

7. The resin composition according to claim 1 , further comprising (C) a curing accelerator.

8. The resin composition according to claim 1 , further comprising (D) an inorganic filler.

9. A laminate comprising a cured product of the resin composition according to any one of claims 1 to 8 and a metal foil.

10. A printed wiring board having a cured product of the resin composition according to any one of claims 1 to 8.

11. A semiconductor package comprising the printed wiring board according to claim 10 and a semiconductor element.

12. A metal foil and a resin layer laminated on one surface of the metal foil, A resin-coated metal foil, wherein the resin layer comprises the resin composition according to any one of claims 1 to 8 or a semi-cured product of the resin composition.

13. A printed wiring board formed using the resin-coated metal foil according to claim 12, A printed wiring board comprising the cured resin layer.

14. A semiconductor package comprising the printed wiring board according to claim 13 and a semiconductor element.

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