KR102669725B1 - Prepreg - Google Patents

Abstract

[Problem] Provision of prepreg that improves handling properties, embedding properties, and copper plating peel strength and does not cause warping, printed wiring boards using the prepreg, and semiconductor devices.
[Solution] Contains a sheet-like fiber base material and a resin composition impregnated into the sheet-like fiber base material, wherein the resin composition includes (a) an elastic polymer, (b) a thermosetting resin having an aromatic structure, and (c) an inorganic filler. A prepreg containing, and the average maximum length of the domains contained in a cured product obtained by heat curing a resin composition is 15 μm or less.

Description

prepreg {PREPREG}

The present invention relates to prepregs. It also relates to printed wiring boards and semiconductor devices using prepreg.

As a manufacturing method for wiring boards (printed wiring boards), the build-up method of alternately stacking circuit-formed conductor layers and insulating layers is widely used, and the insulating layers are formed by curing prepreg and curing resin compositions. It is known that this happens (for example, see Patent Document 1).

Japanese Patent Publication No. 2015-82535

In recent years, in the manufacture of printed wiring boards, there has been an increasing demand for improvements in the handling properties, embedding properties, and peel strength of prepregs. In addition, demands for suppressing warping that occurs when forming an insulating layer using prepreg are also increasing.

The object of the present invention was made to solve the above problems, and provides a prepreg with improved handling properties, embedding properties, and copper plating peel strength, and which does not cause warping, a printed wiring board using the same, and a semiconductor device. It's in doing.

That is, the present invention includes the following contents.

[1] Contains a sheet-like fiber base material and a resin composition impregnated into the sheet-like fiber base material, and the resin composition contains (a) an elastomer, (b) a thermosetting resin having an aromatic structure, and (c) an inorganic filler. do,

A prepreg containing a cured product obtained by heat curing a resin composition and having an average maximum domain length of 15 μm or less.

[2] The prepreg according to [1], wherein the resin composition contains (d) organic particles.

[3] [1] or [2] wherein the component (a) is one or more resins selected from the group consisting of a glass transition temperature of 25°C or lower or a liquid state at 25°C and a functional group capable of reacting with the component (b). The prepreg described in ].

[4] (a) The components are butadiene structural unit, polysiloxane structural unit, (meth)acrylate structural unit, alkylene structural unit, alkyleneoxy structural unit, isoprene structural unit, isobutylene structural unit, chloroprene structural unit, The prepreg according to any one of [1] to [3], which has one or more structural units selected from urethane structural units and polycarbonate structural units.

[5] The prepreg according to any one of [1] to [4], which contains, as the component (b), an epoxy resin that is in a solid state at a temperature of 20°C.

[6] As the component (b), it contains an epoxy resin that is liquid at a temperature of 20°C and an epoxy resin that is solid at a temperature of 20°C, and the mass ratio of the liquid epoxy resin to the solid epoxy resin is 1:0.3 to 1:10, [ The prepreg according to any one of [1] to [5].

[7] The prepreg according to [5] or [6], which is an epoxy resin that is solid at a temperature of 20°C and does not contain a resin with a molecular weight of 400 or more having a naphthalene skeleton.

[8] When the mass of component (a) in the resin composition is A and the mass of component (b) is B, (A/(A+B) x 100 is 20 to 70, [1] to [7] The prepreg described in any one of the above.

[9] The prepreg according to any one of [1] to [8], wherein the content of the component (c) is 25 to 70% by mass, based on 100% by mass of the non-volatile component in the resin composition.

[10] When the mass of component (a) in the resin composition is A, the mass of component (b) is B, and the mass of component (d) is D, (D/(A+B+D)) x 100 The prepreg according to any one of [2] to [9], which is 10 or less.

[11] The prepreg according to any one of [1] to [10], for forming an insulating layer of a printed wiring board.

[12] The prepreg according to any one of [1] to [11], for forming a build-up layer of a printed wiring board.

[13] A printed wiring board comprising an insulating layer formed by the prepreg according to any one of [1] to [12].

[14] A semiconductor device comprising the printed wiring board according to [13].

According to the present invention, it is possible to provide a prepreg that improves handling properties, embedding properties, and copper plating peel strength and does not cause warping, a printed wiring board using the prepreg, and a semiconductor device.

Figure 1 is a cross-sectional photograph of the cured prepreg of Example 1.
Figure 2 is a cross-sectional photograph of the cured prepreg of Example 2.
Figure 3 is a cross-sectional photograph of the cured prepreg of Comparative Example 1.

Hereinafter, the prepreg, printed wiring board, and semiconductor device of the present invention will be described in detail.

[Prepreg]

The prepreg of the present invention contains a sheet-like fiber base material and a resin composition impregnated into the sheet-like fiber base material, and the resin composition includes (a) an elastic polymer, (b) a thermosetting resin having an aromatic structure, and (c) It is characterized in that it contains an inorganic filler and that the average maximum length of the domains contained in the cured product obtained by thermosetting the resin composition is 15 μm or less.

From the viewpoint of improving the handling properties, embedding properties, and copper plating peel strength of the prepreg, the average maximum length of the domains contained in the cured product obtained by thermosetting the resin composition is preferably 15 μm or less and 10 μm or less, 5㎛ or less is more preferable, and it is even more preferable that it cannot be identified (domain does not exist). By setting the average maximum length of the domain to 15 μm or less, the embedding property of the prepreg can be improved.

The average maximum length of the domain can be measured as follows. Cross-sectional observation was performed on the prepreg that was heat-cured at 100°C for 30 minutes and then at 170°C for 30 minutes using a FIB-SEM combination device (“SMI3050SE” manufactured by SII Nanotechnology Co., Ltd.). In detail, a cross-section in the direction perpendicular to the surface of the prepreg was cut with a FIB (focused ion beam), and a cross-sectional SEM image (observation width of 60 μm, observation magnification of 2,000 times) was acquired. Cross-sectional SEM images of five randomly selected locations were observed, the largest domain present in the cross-sectional SEM image was selected, the maximum length of each selected domain was measured, and the average value was taken as the average maximum length. The maximum length refers to the length of the longest straight line that can be drawn in the domain area. In a cured product obtained by thermosetting a resin composition, the components of the resin composition are not uniformly mixed and may be unevenly distributed. When observing the cross-sectional SEM image of the cured product in which such uneven distribution of constituents occurred, a sea island structure due to the uneven distribution of constituents appears. In the present invention, a domain refers to an island portion of such a sea island structure.

Details will be described later, but when manufacturing a wiring board, the wiring layer is embedded in the prepreg of the present invention, thereby forming an embedded wiring layer. The prepreg of the present invention has improved handling properties, embedding properties, and copper plating peel strength, and from the viewpoint of suppressing the occurrence of warpage, the resin composition is (a) an elastomer, (b) a thermosetting material with an aromatic structure. Contains resin and (c) inorganic filler. If necessary, the resin composition may further contain additives such as (d) organic particles, (e) curing agent, (f) curing accelerator, (g) thermoplastic resin, and (h) flame retardant. Hereinafter, each component contained in the resin composition will be described in detail.

(Resin composition)

<(a) Elastomer>

The resin composition contains component (a). By containing a flexible resin such as component (a), the handling properties, embedding properties, and copper plating peel strength of the prepreg are improved, and the occurrence of warping, etc. can be suppressed.

The component (a) is not particularly limited as long as it is a flexible resin, but it is preferable to have a functional group capable of reacting with the component (b) described later. Among these, it is preferable that the resin has a glass transition temperature of 25°C or lower or is liquid at 25°C and is at least one type selected from resins having a functional group capable of reacting with component (b).

The glass transition temperature of the resin having a glass transition temperature (Tg) of 25°C or lower is preferably 20°C or lower, and more preferably 15°C or lower. The lower limit of the glass transition temperature is not particularly limited, but can usually be -15°C or higher. Additionally, the resin that is liquid at 25°C is preferably a resin that is liquid at 20°C or lower, and more preferably is a resin that is liquid at 15°C or lower.

In one suitable embodiment, the functional group capable of reacting with component (b) is at least one functional group selected from the group consisting of a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, and a urethane group. Among these, the functional group is preferably a hydroxyl group, an acid anhydride group, an epoxy group, or a phenolic hydroxyl group, and a hydroxyl group, an acid anhydride group, or an epoxy group is more preferable. However, when it contains an epoxy group as a functional group, the thermosetting resin with an aromatic structure is not contained as component (a) to distinguish it from component (b).

From the viewpoint of improving the handling properties of the prepreg of the present invention, the components (a) include butadiene structural units such as polybutadiene and hydrogenated polybutadiene, polysiloxane structural units such as silicone rubber, (meth)acrylate structural units, and carbon. alkylene structural units having 2 to 15 carbon atoms (preferably 3 to 10 carbon atoms, more preferably 5 to 6 carbon atoms), alkyleneoxy structural units having 2 to 15 carbon atoms (preferably carbon atoms) having one or more structural units selected from the group consisting of 3 to 10 atoms, more preferably 5 to 6 carbon atoms, isoprene structural units, isobutylene structural units, chloroprene structural units, urethane structural units, and polycarbonate structural units. It is preferable that it has one or more structural units selected from butadiene structural units, urethane structural units, and (meth)acrylate structural units. In addition, “(meth)acrylate” refers to methacrylate and acrylate.

One suitable embodiment of component (a) is a saturated and/or unsaturated butadiene resin containing a functional group that is liquid at 25°C. Examples of the saturated and/or unsaturated butadiene resin containing a functional group that is liquid at 25°C include a saturated and/or unsaturated butadiene resin containing an acid anhydride group that is liquid at 25°C, a saturated and/or unsaturated butadiene resin containing a phenolic hydroxyl group that is liquid at 25°C, A group consisting of saturated and/or unsaturated butadiene resins containing epoxy groups that are liquid at 25°C, saturated and/or unsaturated butadiene resins containing isocyanate groups that are liquid at 25°C, and saturated and/or unsaturated butadiene resins containing urethane groups that are liquid at 25°C. At least one type of resin selected from Here, “saturated and/or unsaturated butadiene resin” refers to a resin containing a saturated butadiene skeleton and/or an unsaturated butadiene skeleton. In these resins, even if the saturated butadiene skeleton and/or unsaturated butadiene skeleton are contained in the main chain, they are located in the side chain. It may be contained.

The number average molecular weight (Mn) of the saturated and/or unsaturated butadiene resin containing a functional group that is liquid at 25°C is preferably 500 to 50,000, more preferably 1,000 to 10,000. Here, the number average molecular weight (Mn) of the resin is the number average molecular weight in terms of polystyrene measured using GPC (gel permeation chromatography).

The functional group equivalent weight of the saturated and/or unsaturated butadiene resin containing a functional group that is liquid at 25°C is preferably 100 to 10,000, more preferably 200 to 5,000. In addition, the functional group equivalent is the mass of the resin containing 1 equivalent of the functional group. For example, the epoxy equivalent weight of the resin can be measured according to JIS K7236.

As the saturated and/or unsaturated butadiene resin containing an epoxy group that is liquid at 25°C, an epoxy resin containing a saturated and/or unsaturated butadiene skeleton that is liquid at 25°C is preferred, and an epoxy resin containing a polybutadiene skeleton that is liquid at 25°C is preferred. An epoxy resin containing a liquid hydrogenated polybutadiene skeleton is more preferable, an epoxy resin containing a polybutadiene skeleton that is liquid at 25°C, and an epoxy resin containing a hydrogenated polybutadiene skeleton that is liquid at 25°C are more preferred. Here, the “epoxy resin containing a hydrogenated polybutadiene skeleton” refers to an epoxy resin in which at least part of the polybutadiene skeleton is hydrogenated, and does not necessarily need to be an epoxy resin in which the polybutadiene skeleton is completely hydrogenated. Specific examples of the polybutadiene skeleton-containing resin that is liquid at 25°C and the hydrogenated polybutadiene skeleton-containing resin that is liquid at 25°C include “PB3600” and “PB4700” (polybutadiene skeleton epoxy resin) manufactured by Daicel Co., Ltd. and Nagase Chem. and “FCA-061L” (hydrogenated polybutadiene skeleton epoxy resin) manufactured by Tex Co., Ltd.

As the saturated and/or unsaturated butadiene resin containing an acid anhydride group that is liquid at 25°C, an acid anhydride resin containing a saturated and/or unsaturated butadiene skeleton that is liquid at 25°C is preferred. As the saturated and/or unsaturated butadiene resin containing a phenolic hydroxyl group that is liquid at 25°C, a phenolic resin containing a saturated and/or unsaturated butadiene skeleton that is liquid at 25°C is preferred. As the saturated and/or unsaturated butadiene resin containing an isocyanate group that is liquid at 25°C, an isocyanate resin containing a saturated and/or unsaturated butadiene skeleton that is liquid at 25°C is preferable. As the saturated and/or unsaturated butadiene resin containing a urethane group that is liquid at 25°C, a urethane resin containing a saturated and/or unsaturated butadiene skeleton that is liquid at 25°C is preferred.

Another suitable embodiment of the component (a) is an acrylic resin containing a functional group whose Tg is 25°C or lower. Examples of the acrylic resin containing a functional group with a Tg of 25°C or lower include an acrylic resin containing an acid anhydride group with a Tg of 25°C or lower, an acrylic resin containing a phenolic hydroxyl group with a Tg of 25°C or lower, an acrylic resin containing an isocyanate group with a Tg of 25°C or lower, and acrylic resin containing an isocyanate group with a Tg of 25°C or lower. At least one type of resin selected from the group consisting of acrylic resins containing urethane groups below and acrylic resins containing epoxy groups with Tg below 25°C is preferred.

The number average molecular weight (Mn) of the functional group-containing acrylic resin with a Tg of 25°C or lower is preferably 10,000 to 1,000,000, more preferably 30,000 to 900,000. Here, the number average molecular weight (Mn) of the resin is the number average molecular weight in terms of polystyrene measured using GPC (gel permeation chromatography).

The functional group equivalent of the functional group-containing acrylic resin with a Tg of 25°C or lower is preferably 1,000 to 50,000, more preferably 2,500 to 30,000.

As the epoxy group-containing acrylic resin with a Tg of 25°C or lower, an epoxy group-containing acrylic acid ester copolymer resin with a Tg of 25°C or lower is preferable, and a specific example thereof is “SG-80H” (epoxy group-containing acrylic acid ester copolymer) manufactured by Nagase Chemtex Co., Ltd. Composite resin (number average molecular weight (Mn): 350000 g/mol, epoxy value 0.07 eq/kg, Tg 11°C), “SG-P3” manufactured by Nagase Chemtex Co., Ltd. (epoxy group-containing acrylic acid ester copolymer resin (water Average molecular weight (Mn): 850000 g/mol, epoxy 0.21 eq/kg, Tg 12°C).

As the acrylic resin containing an acid anhydride group with a Tg of 25°C or lower, an acrylic acid ester copolymer resin containing an acid hydride group with a Tg of 25°C or lower is preferable.

As the phenolic hydroxyl group-containing acrylic resin with a Tg of 25°C or lower, a phenolic hydroxyl group-containing acrylic acid ester copolymer resin with a Tg of 25°C or lower is preferable, and a specific example thereof is “SG-790” (epoxy group) manufactured by Nagase Chemtex Co., Ltd. and acrylic acid ester copolymer resin (number average molecular weight (Mn): 500,000 g/mol, hydroxyl value: 40 mgKOH/kg, Tg -32°C).

In addition, a suitable embodiment of component (a) is a polyimide resin having a butadiene structural unit, a urethane structural unit, and an imide structural unit in the molecule, and the polyimide resin preferably has a phenol structure at the molecule terminal. .

The number average molecular weight (Mn) of the polyimide resin is preferably 1000 to 100000, more preferably 10000 to 15000. Here, the number average molecular weight (Mn) of the resin is the number average molecular weight in terms of polystyrene measured using GPC (gel permeation chromatography).

The acid value of the polyimide resin is preferably 1 KOH/g to 30 KOH/g, more preferably 10 KOH/g to 20 KOH/g.

The content of the butadiene structure in the polyimide resin is preferably 60 to 95% by mass, more preferably 75 to 85% by mass.

For details of the polyimide resin, the description in International Publication No. 2008/153208 can be taken into consideration, and this content is incorporated into this specification.

The content of component (a) in the resin composition is not particularly limited, but is preferably 80 mass% or less, more preferably 50 mass% or less, and still more preferably 45 mass% or less. Moreover, the lower limit is preferably 5 mass% or more, more preferably 10 mass% or more, and even more preferably 25 mass% or more.

In addition, in the present invention, unless otherwise specified, the content of each component in the resin composition is a value assuming that the non-volatile component in the resin composition is 100% by mass.

<(b) Thermosetting resin with aromatic structure>

(b) As the thermosetting resin having an aromatic structure, conventionally known thermosetting resins used when forming the insulating layer of a wiring board can be used, and among these, an epoxy resin having an aromatic structure is more preferable.

The epoxy resin having an aromatic structure (hereinafter also simply referred to as “epoxy resin”) is not particularly limited as long as it has an aromatic structure. An aromatic structure is a chemical structure generally defined as aromatic, and also includes polycyclic aromatics and aromatic heterocycles. As epoxy resins, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolac type. Epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin with aromatic structure, epoxy resin with aromatic structure. Glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin with an aromatic structure, epoxy resin with a butadiene structure with an aromatic structure, alicyclic epoxy resin with an aromatic structure, Heterocyclic epoxy resin, spiro ring-containing epoxy resin having an aromatic structure, cyclohexanedimethanol type epoxy resin having an aromatic structure, naphthylene ether type epoxy resin, trimethylol type epoxy resin having an aromatic structure, tetraphenylethane type epoxy resin, Bixylenol type epoxy resin, etc. can be mentioned. Epoxy resins may be used individually, or two or more types may be used in combination. The component (b) is preferably at least one selected from bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and biphenyl-type epoxy resin.

It is preferable that the epoxy resin contains an epoxy resin having two or more epoxy groups in one molecule. When the non-volatile component of the epoxy resin is 100% by mass, it is preferable that at least 50% by mass or more is an epoxy resin having two or more epoxy groups in one molecule. Among these, it is preferable to contain a solid epoxy resin (hereinafter referred to as “solid epoxy resin”) at a temperature of 20°C, and it may also contain a liquid epoxy resin (hereinafter referred to as “liquid epoxy resin”) at a temperature of 20°C. good night.

Examples of the solid epoxy resin include naphthalene-type tetrafunctional epoxy resin, cresol novolac-type epoxy resin, dicyclopentadiene-type epoxy resin with an aromatic structure, trisphenol-type epoxy resin, naphthol-type epoxy resin, biphenyl-type epoxy resin, and naphthylene. Ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin are preferred, naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, and biphenyl type epoxy resin. , naphthylene ether type epoxy resin is more preferable, and naphthalene type tetrafunctional epoxy resin and naphthylene ether type epoxy resin are more preferable. Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin), "HP-4700", "HP-4710" (naphthalene-type tetrafunctional epoxy resin), and "N-690" (cresol) manufactured by DIC Co., Ltd. novolac type epoxy resin),「N-695」(cresol novolac type epoxy resin),「HP-7200」,「HP-7200L」,「HP-7200HH」,「HP-7200H」,「HP-7200HHH」 (Dicyclopentadiene type epoxy resin),「EXA7311」,「EXA7311-G3」,「EXA7311-G4」,「EXA7311-G4S」,「HP6000」(naphthylene ether type epoxy resin), Nippon Kayaku Co., Ltd. Manufactured as “EPPN-502H” (trisphenol type epoxy resin), “NC7000L” (naphthol novolac type epoxy resin), “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl type epoxy resin), “ESN475V” (naphthol type epoxy resin), “ESN485” (naphthol novolac type epoxy resin) manufactured by Nippon Chemical Co., Ltd., “YX4000H”, “YL6121” (biphenyl type) manufactured by Mitsubishi Chemical Corporation epoxy resin), “YX4000HK” (bixylenol type epoxy resin), “YL7760” (bisphenol AF type epoxy resin), “YX8800” (anthracene type epoxy resin), “PG-100” manufactured by Osaka Gas Chemical Co., Ltd., “CG-500”, “YL7800” (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “jER1010” (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “jER1031S” (tetra phenylethane type epoxy resin), “157S70” (bisphenol novolak type epoxy resin), “YX4000HK” (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “YX8800” (anthracene type epoxy resin), Osaka Gas “PG-100” and “CG-500” manufactured by Chemical Co., Ltd., “YL7800” (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd., and “jER1031S” (Tetra) manufactured by Mitsubishi Chemical Co., Ltd. phenylethane type epoxy resin), etc. can be mentioned. These may be used individually, or two or more types may be used in combination.

From the viewpoint of keeping the average maximum length of the domain to 15 μm or less, it is preferable that the solid epoxy resin does not contain a resin having a naphthalene skeleton and a molecular weight of 400 or more (it is more preferable that it does not contain a resin having a naphthalene skeleton and a molecular weight of 350 or more) and it is more preferable that it does not contain a resin having a naphthalene skeleton. Additionally, it is preferable that the solid epoxy resin does not contain a resin having a triphenyl skeleton. Moreover, as a solid epoxy resin, it is preferable that it does not contain bisphenol novolac resin. Moreover, as a solid epoxy resin, it is preferable that it does not contain an epoxy resin with a molecular weight of 1000 or more that has a biphenyl skeleton (it is more preferable that it does not contain a resin that has a biphenyl skeleton).

Additionally, the solid epoxy resin may be selected from epoxy resins having an alicyclic structure (e.g., dicyclopentadiene-type epoxy resins), resins containing a xylene skeleton, cresol novolak-type epoxy resins, and tetraphenylethane-type epoxy resins. It is preferable to contain one or more of the following, and among these, it is more preferable to contain an epoxy resin having an alicyclic structure.

Liquid epoxy resins include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol AF-type epoxy resin, naphthalene-type epoxy resin, glycidyl ester-type epoxy resin with an aromatic structure, and glycidylamine-type epoxy resin with an aromatic structure. Resins, phenol novolak-type epoxy resins, alicyclic epoxy resins having an ester skeleton with an aromatic structure, cyclohexanedimethanol-type epoxy resins with an aromatic structure, and epoxy resins with a butadiene structure with an aromatic structure are preferred, and bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, and naphthalene type epoxy resin are more preferable, and bisphenol A type epoxy resin and bisphenol F type epoxy resin are more preferable. Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Corporation, and "828US" and "jER828EL" (bisphenol A type) manufactured by Mitsubishi Chemical Corporation. epoxy resin), “jER807” (bisphenol F-type epoxy resin), “jER152” (phenol novolac-type epoxy resin), “630”, “630LSD” (glycidylamine-type epoxy resin), Nippon Tetsu Sumiking Chemicals ( “ZX1059” (mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin) manufactured by Nagase Chemtex Co., Ltd., “EX-721” (glycidyl ester type epoxy resin) manufactured by Nagase Chemtex Co., Ltd. Examples include “Ceroxide 2021P” manufactured by Daicel (alicyclic epoxy resin with an ester skeleton) and “ZX1658” and “ZX1658GS” (liquid 1,4-glycidylcyclohexane) manufactured by Nippon Chemical Co., Ltd. You can. These may be used individually, or two or more types may be used in combination.

The liquid epoxy resin is preferably an epoxy resin with an aromatic ring structure that has two or more epoxy groups per molecule and is liquid at a temperature of 20°C, and the solid epoxy resin is preferably an epoxy resin that has three or more epoxy groups per molecule and is in a solid state at a temperature of 20°C. An epoxy resin having a phosphorus aromatic ring structure is preferred.

By using a liquid epoxy resin, the handling properties and resin flow of the prepreg can be improved, and by using a solid epoxy resin, heat resistance and electrical properties can be improved while suppressing tack of the prepreg. In order to provide the effects of both liquid epoxy resin and solid epoxy resin, when liquid epoxy resin and solid epoxy resin are used together as epoxy resin, their quantity ratio (liquid epoxy resin: solid epoxy resin) is mass ratio, A range of 1:0.1 to 1:20 is preferred. From the viewpoint of obtaining the above effect, the ratio of liquid epoxy resin to solid epoxy resin (liquid epoxy resin:solid epoxy resin) is more preferably in the range of 1:0.3 to 1:10, and 1:0.6 to 1:1 in mass ratio. A range of 9 is more preferable.

The content of the epoxy resin in the resin composition is preferably 4% by mass or more, more preferably 5% by mass or more, and even more preferably 6% by mass or more from the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability. . The upper limit of the content of the epoxy resin is not particularly limited as long as the effect of the present invention is achieved, but is preferably 50% by mass or less, more preferably 30% by mass or less.

From the viewpoint of suppressing warping of the prepreg, when the mass of component (a) is A and the mass of component (b) is B, A/(A+B)×100 is preferably 20 to 70, and 30 to 70. 68 is more preferable, and 35 to 65 is more preferable. By setting A/(A+B)×100 to 20 to 70, warping can be effectively suppressed.

The epoxy equivalent weight of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, further preferably 80 to 2000, and even more preferably 110 to 1000. By falling within this range, the crosslinking density of the cured product becomes sufficient and an insulating layer with small surface roughness can be produced. In addition, the epoxy equivalent can be measured according to JIS K7236 and is the mass of the resin containing 1 equivalent of an epoxy group.

The weight average molecular weight of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and still more preferably 400 to 1500. Here, the weight average molecular weight of the epoxy resin is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC). Additionally, molecular weights of 1000 or less can be measured by GC/MS (gas chromatography mass spectrometry).

<(c) Inorganic filler>

The material of the inorganic filler is not particularly limited, but examples include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, Aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate. , barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly suitable. Additionally, spherical silica is preferred as the silica. One type of inorganic filler may be used alone, or two or more types may be used in combination.

The average particle diameter of the inorganic filler is preferably 2 μm or less, more preferably 1.5 μm or less, further preferably 1.2 μm or less, and still more preferably 1 μm or less from the viewpoint of good embedding properties. The lower limit of the average particle diameter is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, and still more preferably 0.1 μm or more. Commercially available inorganic fillers having such an average particle diameter include, for example, "YC100C", "YA050C", "YA050C-MJE", and "YA010C" manufactured by Adomatex Co., Ltd., and "YA010C" manufactured by Denki Chemical Co., Ltd. UFP-30”, “Seal Peel NSS-3N”, “Seal Peel NSS-4N”, “Seal Peel NSS-5N” manufactured by Tokuyama Co., Ltd., “SOC4”, “SOC2”, “SOC1” manufactured by Adomatex Co., Ltd. , “BMB-05” manufactured by Kawai Sekidan Kogyo Co., Ltd., etc.

The average particle diameter of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis using a laser diffraction scattering type particle size distribution measuring device, and the median diameter can be measured as the average particle diameter. The measurement sample can preferably be one in which an inorganic filler is dispersed in water by ultrasonic waves. As a laser diffraction scattering type particle size distribution measuring device, "LA-500" manufactured by Horiba Chemicals Co., Ltd., etc. can be used.

From the viewpoint of improving moisture resistance and dispersibility, inorganic fillers include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilane compounds, organosilazane compounds, and titanate coupling agents. It is preferable that it is treated with one or more types of surface treatment agents such as a coupling agent. Commercially available surface treatment agents include, for example, “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. and “KBM803” (3-mercapto) manufactured by Shin-Etsu Chemical Co., Ltd. Propyltrimethoxysilane), “KBE903” (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM573” (N-phenyl-3-aminopropyl triethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. Methoxysilane), Shin-Etsu Chemical Co., Ltd. “SZ-31” (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. “KBM103” (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. ( “KBM-4803” (long-chain epoxy type silane coupling agent) manufactured by Note), etc. may be mentioned.

The degree of surface treatment by a surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m 2 or more, more preferably 0.1 mg/m 2 or more, and even more preferably 0.2 mg/m 2 or more. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin varnish or the melt viscosity in sheet form, 1 mg/m2 or less is preferable, 0.8 mg/m2 or less is more preferable, and 0.5 mg/m2 or less is still more preferable. .

The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, “EMIA-320V” manufactured by Horiba Seksho Co., Ltd. can be used.

The content of the inorganic filler in the resin composition is preferably 10 mass% or more, more preferably 15 mass% or more, and even more preferably 25 mass% or more from the viewpoint of obtaining an insulating layer with a low coefficient of thermal expansion. The upper limit of the content of the inorganic filler in the resin composition is preferably 80 mass% or less, more preferably 70 mass% or less, and even more preferably 65 mass% or less from the viewpoint of the mechanical strength of the insulating layer, especially elongation.

<(d) Organic particles>

As the resin composition, any organic particles (also referred to as organic fillers) that can be used when forming the insulating layer of a printed wiring board may be used, and examples include rubber particles, polyamide fine particles, and silicon particles. Moreover, as component (d), it is preferable that it does not have the functional group in component (a). The component (d) preferably has a solubility in methyl ethyl ketone of less than 5 (g/100g) at 25°C.

The average particle diameter of the organic particles can be preferably 2 μm or less, more preferably 1 μm or less, and even more preferably 0.5 μm or less. There is no particular limitation regarding the lower limit, but it is 0.01 μm or more. The average particle diameter is the average value of 50 measurements of each organic particle using a laser diffraction/scattering particle diameter distribution measuring device or the like.

As the rubber particles, commercially available products may be used, for example, “EXL-2655” manufactured by Dow Chemical Nippon Co., Ltd., “AC3816N” manufactured by Gantz Chemical Co., Ltd., etc.

When the resin composition contains organic particles, the content of organic particles is preferably 0.1% by mass to 20% by mass, more preferably 0.2% by mass to 10% by mass, and even more preferably 0.3% by mass to 5% by mass. , or 0.5% by mass to 4% by mass.

When the mass of component (a) in the resin composition is A, the mass of component (b) is B, and the mass of component (d) is D, (D/(A+B+D)) x 100 is 10 or less. is preferable, 8 or less is more preferable, and 5 or less is even more preferable. By setting (D/(A+B+D))×100 to 10 or less, phase separation of each component is suppressed, and the average maximum length of the domain can be made to 15 μm or less. (d) When mixing components (that is, when D is not 0), the lower limit of (D/(A+B+D))×100 is preferably 1 or more.

<(e) Hardener>

The curing agent is not particularly limited as long as it has the function of curing thermosetting resins such as epoxy resins, and examples include phenol-based curing agents, naphthol-based curing agents, active ester-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, and Carbodiimide-based curing agents, etc. can be mentioned. One type of hardening agent may be used individually, or two or more types may be used together. The component (e) is preferably at least one selected from phenol-based curing agents, naphthol-based curing agents, active ester-based curing agents, and cyanate ester-based curing agents.

As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolac structure or a naphthol-based curing agent having a novolac structure is preferable from the viewpoint of heat resistance and water resistance. Furthermore, from the viewpoint of adhesion to the wiring layer, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable. Among these, a phenol novolak curing agent containing a triazine skeleton is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion to the wiring layer.

Specific examples of phenol-based curing agents and naphthol-based curing agents include, for example, “MEH-7700”, “MEH-7810”, and “MEH-7851” manufactured by Meiwa Kasei Co., Ltd., and “MEH-7851” manufactured by Nippon Kayaku Co., Ltd. "NHN", "CBN", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495V", "SN375", "manufactured by Shin-Niptetsu Sumikkin Co., Ltd. SN395", "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500", "HPC-" manufactured by DIC Co., Ltd. 9500”, etc.

From the viewpoint of obtaining an insulating layer with excellent adhesion to the wiring layer, an active ester-based curing agent is also preferable. There is no particular limitation on the active ester-based curing agent, but in general, ester groups with high reaction activity, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are used at 2 per molecule. Compounds having more than one compound are preferably used. The active ester-based curing agent is preferably obtained by condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound. Particularly from the viewpoint of improving heat resistance, active ester-based curing agents obtained from carboxylic acid compounds and hydroxy compounds are preferable, and active ester-based curing agents obtained from carboxylic acid compounds, phenol compounds, and/or naphthol compounds are more preferable. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. As phenol compounds or naphthol compounds, for example, hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, Trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac, etc. are mentioned. Here, “dicyclopentadiene-type diphenol compound” refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

Specifically, an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylate of phenol novolak, and an active ester compound containing a benzoylate of phenol novolac. Active ester compounds are preferable, and among these, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene type diphenol structure are more preferable. “Dicyclopentadiene-type diphenol structure” refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

Commercially available active ester curing agents include active ester compounds containing a dicyclopentadiene type diphenol structure, such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC-8000H-65TM" ”, “EXB-8000L-65TM” (manufactured by DIC Corporation), an active ester compound containing a naphthalene structure, “EXB9416-70BK” (manufactured by DIC Corporation), an active ester containing the acetylated product of phenol novolac "DC808" (manufactured by Mitsubishi Chemical Corporation) as a compound, "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoylate of phenol novolak, an active ester that is an acetylate of phenol novolac As a system hardener, “DC808” (manufactured by Mitsubishi Chemical Co., Ltd.), and as an active ester curing agent, which is a benzoylate of phenol novolak, “YLH1026” (manufactured by Mitsubishi Chemical Co., Ltd.), “YLH1030” (manufactured by Mitsubishi Chemical Co., Ltd.) manufactured by Mitsubishi Chemical Corporation), “YLH1048” (manufactured by Mitsubishi Chemical Corporation), etc.

Specific examples of the benzoxazine-based curing agent include “HFB2006M” manufactured by Showa Chemical Co., Ltd., and “P-d” and “F-a” manufactured by Shikoku Chemical Industry Co., Ltd.

Examples of cyanate ester-based curing agents include bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylenecyanate), and 4,4'-methylenebis(2,6- dimethylphenylcyanate), 4,4'-ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4- Cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanate) Bifunctional cyanate resins such as natephenyl)thioether and bis(4-cyanatephenyl)ether, polyfunctional cyanate resins derived from phenol novolak and cresol novolac, etc., some of these cyanate resins are triazinated. Prepolymers, etc. can be mentioned. Specific examples of cyanate ester-based curing agents include "PT30" and "PT60" (both phenol novolak-type polyfunctional cyanate ester resins), "BA230", and "BA230S75" (bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. and prepolymers in which part or all of the polymer is triazylated to form a trimer.

Specific examples of carbodiimide-based curing agents include “V-03” and “V-07” manufactured by Niseibo Chemical Co., Ltd.

The content of the curing agent in the resin composition is not particularly limited, but is preferably 30 mass% or less, more preferably 25 mass% or less, and still more preferably 20 mass% or less. Additionally, the lower limit is not particularly limited, but is preferably 2% by mass or more.

<(f) Curing accelerator>

Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. Accelerators and metal-based curing accelerators are preferable, and amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are more preferable. The curing accelerator may be used individually, or two or more types may be used in combination.

Examples of phosphorus-based curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenyl borate, n-butylphosphonium tetraphenyl borate, tetrabutylphosphonium decanoate, and (4-methylphenyl)triphenyl. Examples include phosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and triphenylphosphine and tetrabutylphosphonium decanoate are preferred.

Examples of amine-based curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8. -Diazabicyclo(5,4,0)-undecene, etc. are mentioned, and 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene are preferable.

Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl. Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Midazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl -4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimeritate, 1-cyanoethyl-2-phenylimidazolium Trimeritate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s- Triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a ]Imidazole compounds such as benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and the relationship between imidazole compounds and epoxy resins Examples include duct bodies, and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferred.

As an imidazole-based curing accelerator, a commercial product may be used, for example, “P200-H50” manufactured by Mitsubishi Chemical Corporation.

Examples of guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, and diphenylguanidine. , trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1, 1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, etc., dicyandiamide, 1,5,7-triazabicyclo[4.4.0]deca-5-ene is preferred.

Examples of the metal-based curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Examples include organic zinc complexes, organic iron complexes such as iron(III) acetylacetonate, organic nickel complexes such as nickel(II) acetylacetonate, and organic manganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

The content of the curing accelerator in the resin composition is not particularly limited, but is preferably 0.01% by mass to 3% by mass when the total amount of nonvolatile components of the thermosetting resin and the curing agent is 100% by mass.

<(g) Thermoplastic resin>

Thermoplastic resins include, for example, phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamidoimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, and polyphenylene. Examples include ether resin, polycarbonate resin, polyetheretherketone resin, and polyester resin. Among these, thermoplastic resins having an aromatic structure are preferable, for example, phenoxy resins having an aromatic structure, and thermoplastic resins having an aromatic structure. Polyvinyl acetal resin, polyimide resin with an aromatic structure, polyamideimide resin with an aromatic structure, polyetherimide resin with an aromatic structure, polysulfone resin with an aromatic structure, polyethersulfone resin with an aromatic structure, aromatic structure A polyphenylene ether resin having a polyether ether ketone resin having an aromatic structure, or a polyester resin having an aromatic structure is preferable, and a phenoxy resin having an aromatic structure is more preferable. Thermoplastic resins may be used individually, or two or more types may be used in combination.

The weight average molecular weight of the thermoplastic resin in terms of polystyrene is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and even more preferably in the range of 20,000 to 60,000. The weight average molecular weight of the thermoplastic resin in terms of polystyrene is measured by gel permeation chromatography (GPC). Specifically, the weight average molecular weight of the thermoplastic resin in terms of polystyrene was measured using LC-9A/RID-6A manufactured by Shimadzu Sesakusho Co., Ltd. as a measuring device and Shodex K-800P/Showa Denko Co., Ltd. manufactured by Showa Denko Co., Ltd. as a column. K-804L/K-804L can be calculated by using chloroform or the like as a mobile phase, measuring the column temperature at 40°C, and using a standard polystyrene calibration curve.

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, and naphthalene. and a phenoxy resin having at least one skeleton selected from the group consisting of an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. One type of phenoxy resin may be used alone, or two or more types may be used in combination. Specific examples of phenoxy resins include "1256" and "4250" (both phenoxy resins containing a bisphenol A skeleton), "YX8100" (phenoxy resins containing a bisphenol S skeleton), and "YX6954" manufactured by Mitsubishi Chemical Corporation. (phenoxy resin containing bisphenol acetophenone skeleton), and in addition, "FX280" and "FX293" manufactured by Nippon Chemical Co., Ltd., and "YX6954BH30" and "YX7553" manufactured by Mitsubishi Chemical Corporation. ", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", and "YL7482".

Examples of the polyvinyl acetal resin include polyvinyl formal resin and polyvinyl butyral resin, with polyvinyl butyral resin being preferred. Specific examples of polyvinyl acetal resins include, for example, Denka Butyral 4000-2, Denka Butyral 5000-A, Denka Butyral 6000-C, and Denka Butyral manufactured by Denki Chemical Co., Ltd. Butyral 6000-EP", S-Lec BH series, BX series (e.g. BX-5Z), KS series (e.g. KS-1), BL series, BM series, etc. manufactured by Sekisui Chemicals Co., Ltd. can be mentioned.

Specific examples of polyimide resins include “Rica Coat SN20” and “Rica Coat PN20” manufactured by Shin Nippon Rika Co., Ltd.

Specific examples of polyamide-imide resin include “Viromax HR11NN” and “Viromax HR16NN” manufactured by Toyobo Seki Co., Ltd.

Specific examples of the polyether sulfone resin include “PES5003P” manufactured by Sumitomo Chemical Co., Ltd.

Specific examples of the polyphenylene ether resin include the oligophenylene ether-styrene resin "OPE-2St 1200" manufactured by Mitsubishi Chemical Corporation.

Specific examples of polysulfone resins include polysulfone “P1700” and “P3500” manufactured by Solvay Advanced Polymers Co., Ltd.

Among these, phenoxy resin and polyvinyl acetal resin are preferable as thermoplastic resin. Therefore, in one suitable embodiment, the thermoplastic resin contains at least one selected from the group consisting of phenoxy resin and polyvinylacetal resin.

When the resin composition contains a thermoplastic resin, the content of the thermoplastic resin is preferably 0.5% by mass to 60% by mass, more preferably 3% by mass to 50% by mass, and even more preferably 5% by mass to 40% by mass. am.

<(h) Flame retardant>

Examples of flame retardants include organophosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, and metal hydroxides. Flame retardants may be used individually, or two or more types may be used in combination.

As a flame retardant, a commercially available product may be used, for example, "HCA-HQ" manufactured by Sanko Co., Ltd., "PX-200" manufactured by Ohachi Chemical Co., Ltd., etc.

When the resin composition contains a flame retardant, the content of the flame retardant is not particularly limited, but is preferably 0.5% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, and even more preferably 0.5% by mass to 10% by mass. Mass percentage is more preferable.

<Other ingredients>

The resin composition may further contain other additives as needed. Examples of such other additives include organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds, and thickeners, antifoaming agents, and leveling agents. Resin additives such as adhesives, adhesion imparting agents, and colorants can be mentioned.

(Sheet-like fiber substrate)

The sheet-like fiber substrate used in the prepreg of the present invention is not particularly limited, and commonly used prepreg substrates such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used.

A specific example of a glass cloth that can be used as a sheet-like fiber substrate is “Style 1027MS” manufactured by Asahi Shuebel Co., Ltd. (warp density 75 pieces/25 mm, weft density 75 pieces/25 mm, fabric weight 20 g/m2, Thickness 19㎛), “Style 1037MS” manufactured by Asahi Shuebel Co., Ltd. (warp density 70/25mm, weft density 73/25mm, fabric weight 24g/㎡, thickness 28㎛), Arisa Co., Ltd. “1078” manufactured by Wasesakusho (warp density 54/25mm, weft density 54/25mm, fabric weight 48g/㎡, thickness 43㎛), “1037NS” manufactured by Arisawa Sesakusho Co., Ltd. (Warp density 72/25mm, Weft density 69/25mm, Fabric weight 23g/㎡, Thickness 21㎛), “1027NS” manufactured by Arisawa Sesakusho Co., Ltd. (Warp density 75/25mm, Weft density 75/25mm, fabric weight 19.5g/㎡, thickness 16㎛), “1015NS” manufactured by Arisawa Sesakusho Co., Ltd. (warp density 95/25mm, weft density 95/25mm, Fabric weight 17.5g/㎡, thickness 15㎛), “1000NS” manufactured by Arisawa Sesakusho Co., Ltd. (warp density 85/25mm, weft density 85/25mm, fabric weight 11g/㎡, thickness 10 ㎛), etc. can be mentioned. In addition, specific examples of liquid crystal polymer nonwoven fabrics include "Vecrus" (basis weight 6 g/m2 to 15 g/m2) and "Vektran" manufactured by Kuraray Co., Ltd. using an aromatic polyester nonwoven fabric melt flow method. .

From the viewpoint of reducing the thickness of the printed wiring board, the thickness of the prepreg is preferably 50 μm or less, more preferably 40 μm or less, further preferably 30 μm or less, and even more preferably 20 μm or less.

The prepreg of this invention may be laminated with a protective film or metal foil as needed.

As a protective film, for example, polyester such as polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyethylene naphthalate (hereinafter sometimes abbreviated as “PEN”), and polycarbonate (hereinafter “PC”). 」), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Additionally, as a protective film, a support body with a mold release layer may be used. Examples of the release agent used in the release layer of the support with a release layer include one or more types of release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. The support with the release layer may be a commercially available product, for example, “SK-1”, “AL-5”, and “SK-1” manufactured by Lintech Co., Ltd., which are PET films with a release layer containing an alkyd resin-based release agent as a main component. AL-7”, “Lumira T6AM” manufactured by Toray Co., Ltd., etc.

The metal foil contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The metal foil may be a single metal layer or an alloy layer, and examples of the alloy layer include, for example, an alloy of two or more metals selected from the above group (e.g., nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy) A layer formed of can be mentioned. Among these, from the viewpoint of versatility of forming metal foil, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or a nickel-chromium alloy, copper-nickel alloy, or copper titanium An alloy layer of an alloy is preferable, and a monometallic layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy is more preferable, and a monometallic layer of copper is more preferable. Additionally, the metal foil may be one in which a plurality of metal foils are laminated.

[Method for manufacturing prepreg]

The prepreg of the present invention can be manufactured by known methods such as hot melt method and solvent method. In the hot melt method, the resin composition is coated once on a release paper with good peelability from the resin composition without dissolving it in an organic solvent, and then laminated on a sheet-like fiber base material or applied directly to the sheet-like fiber base material using a die coater. W, we are manufacturing prepreg. In addition, in the solvent method, the sheet-like fiber base material is impregnated with the resin composition by immersing the sheet-like fiber base material in varnish in which the resin composition is dissolved in an organic solvent, and then dried to produce a prepreg. Additionally, the prepreg can also be manufactured by sandwiching a sheet-like fiber base material between two resin sheets made of a resin composition on both sides of the sheet-like fiber base material and continuously heat-laminating the sheet-like fiber base material under heating and pressurizing conditions.

In addition, the prepreg manufacturing method may be performed by a roll-to-roll method or a batch method using a long sheet-like fiber substrate.

The prepreg of the present invention exhibits the characteristic of suppressing the occurrence of warpage. The size of the warp is preferably less than 1.5 cm, more preferably 1.3 cm or less or -1 cm or less, and more preferably 0 cm. Warpage can be measured according to the method described in <Evaluation of Warpage> described later.

The prepreg of the present invention exhibits good handling properties. In one embodiment, even if the prepreg is peeled off after the prepreg is once stacked on the substrate, there is no adhesion of resin or the like on the substrate. Handling properties can be measured according to the method described in <Evaluation of Handling Properties> described later.

The prepreg of the present invention exhibits good embedding properties. In one embodiment, when laminating on a substrate with a wiring layer, prepreg can be laminated on the wiring layer in a void-free state. Embedding properties can be measured according to the method described in <Evaluation of pattern embedding properties> in the Examples described later.

The prepreg of the present invention exhibits good copper peel strength (copper plating peel strength). In one embodiment, it is preferably 1.5 kgf/cm or less, more preferably 1.3 kgf/cm or less, and even more preferably 1.0 kgf/cm or less. There is no particular limitation regarding the lower limit, but it is 0.4 kgf/cm or more. Copper peel strength can be measured according to the method described in <Measurement of copper peel strength (copper plating peel strength)> in the Examples described later.

[Printed wiring board and its manufacturing method]

The printed wiring board of the present invention can be manufactured by a method including the following steps (I) and (II) using the above prepreg.

(I) A process of laminating a prepreg on an inner layer substrate so that it is bonded to the inner layer substrate.

(II) Process of forming an insulating layer by heat curing the prepreg

The “inner layer substrate” used in step (I) mainly refers to substrates such as glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates, or one side of the substrate. Alternatively, it refers to a circuit board with conductor layers (circuits) patterned on both sides. In addition, when manufacturing a printed wiring board, an inner layer circuit board of an intermediate product on which an insulating layer and/or a conductor layer must be additionally formed is also included in the "inner layer substrate" referred to in the present invention. If the printed wiring board is a circuit board with embedded components, it is good to use an inner layer board with embedded components.

Lamination of the inner layer substrate and the prepreg can be performed, for example, by heat-pressing the prepreg to the inner layer substrate. Examples of members for heat-pressing the prepreg to the inner layer substrate (hereinafter also referred to as “heat-pressing members”) include heated metal plates (SUS head plates, etc.) or metal rolls (SUS rolls). In addition, it is preferable not to press the heat-compression member directly on the prepreg, but to press it through an elastic material such as heat-resistant rubber so that the prepreg sufficiently follows the surface irregularities of the inner layer substrate.

Lamination of the inner layer substrate and the prepreg may be performed by a vacuum lamination method. In the vacuum lamination method, the heat-pressing temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, and the heat-compression pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably is in the range of 0.29 MPa to 1.47 MPa, and the heat compression time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions of 26.7 hPa or less.

Lamination can be performed by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressurized laminator manufactured by Meiki Sesakusho Co., Ltd. and a vacuum applicator manufactured by Nichigo Morton Co., Ltd.

After lamination, the laminated prepreg may be smoothed by pressing a heat-pressing member under normal pressure (atmospheric pressure) from the support side, for example. The press conditions for the smoothing treatment can be the same as the heat-pressing conditions for the above-described lamination. Smoothing treatment can be performed using a commercially available laminator. Additionally, the lamination and smoothing treatment may be performed continuously using the commercially available vacuum laminator described above.

In step (II), the prepreg is heat-cured to form an insulating layer.

The heat curing conditions of the prepreg are not particularly limited, and conditions normally employed when forming the insulating layer of a printed wiring board may be used.

For example, the heat curing conditions of prepreg vary depending on the type of resin composition, etc., but the curing temperature is in the range of 120°C to 240°C (preferably in the range of 150°C to 220°C, more preferably 170°C). to 240°C), and the curing time can be in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

Before heat curing the prepreg, the prepreg may be preheated at a temperature lower than the curing temperature. For example, prior to heat curing the prepreg, the prepreg is cured for 5 minutes at a temperature of 50°C to 120°C (preferably 60°C to 110°C, more preferably 70°C to 100°C). You may preheat it for more than 5 minutes (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

When manufacturing a printed wiring board, the steps of (III) making a hole in the insulating layer, (IV) roughening the insulating layer, and (V) forming a conductor layer may be additionally performed. These steps (III) to (V) may be performed according to various methods known to those skilled in the art that are used in the production of printed wiring boards.

Process (III) is a process of drilling holes in the insulating layer, thereby forming holes such as via holes and through holes in the insulating layer. Step (III) may be performed using, for example, a drill, laser, or plasma, depending on the composition of the resin composition used to form the insulating layer. The size and shape of the hole may be determined appropriately according to the design of the printed wiring board.

Process (IV) is a process of roughening the insulating layer. The procedures and conditions of the roughening process are not particularly limited, and known procedures and conditions normally used when forming the insulating layer of a printed wiring board can be adopted. For example, the insulating layer can be roughened by performing swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid in this order. The swelling liquid is not particularly limited, and includes an alkaline solution, a surfactant solution, etc., and is preferably an alkaline solution. As the alkaline solution, a sodium hydroxide solution or a potassium hydroxide solution is more preferable. Examples of commercially available swelling liquids include “Swelling Deep Securiganth P” and “Swelling Deep Securiganth SBU” manufactured by Atotech Japan Co., Ltd. The swelling treatment using the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in a swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the cured body in a swelling liquid at 40°C to 80°C for 5 to 15 minutes. The oxidizing agent is not particularly limited, but examples include an alkaline permanganate solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 80°C for 10 to 30 minutes. Additionally, the concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as “Concentrate Compact CP” and “Dosing Solution Securiganth P” manufactured by Atotech Japan Co., Ltd. Additionally, as the neutralizing liquid, an acidic aqueous solution is preferable, and as a commercial product, for example, “Reduction Solution Securigant P” manufactured by Atotech Japan Co., Ltd. Treatment with a neutralizing liquid can be performed by immersing the treated surface, which has undergone roughening treatment with an oxidizing agent, in a neutralizing liquid at 30°C to 80°C for 5 to 30 minutes. In terms of workability, etc., a method of immersing the object that has been roughened with an oxidizing agent in a neutralizing liquid at 40°C to 70°C for 5 to 20 minutes is preferable.

In one embodiment, the arithmetic mean roughness (Ra) of the surface of the insulating layer after roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, further preferably 300 nm or less, 250 nm or less, and 200 nm. Hereinafter, it is 150 nm or less, or 100 nm or less. The arithmetic mean roughness (Ra) of the surface of the insulating layer can be measured using a non-contact surface roughness meter. A specific example of a non-contact surface roughness machine is “WYKO NT3300” manufactured by BCO Instruments.

Process (V) is a process of forming a conductor layer.

The conductor material used in the conductor layer is not particularly limited. In a suitable embodiment, the conductor layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. do. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (e.g., nickel-chromium alloy, copper-nickel alloy, and copper-titanium A layer formed of an alloy) may be mentioned. Among these, from the viewpoint of versatility of forming the conductor layer, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy or copper-nickel alloy , an alloy layer of a copper-titanium alloy is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of a nickel-chromium alloy is more preferable, and a single metal layer of copper This is more preferable.

The conductor layer may have a single-layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductor layer has a multi-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc, or titanium, or an alloy layer of nickel-chromium alloy.

The thickness of the conductor layer depends on the desired design of the printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer using a conventionally known technique such as a semiadditive method or a fulladditive method. Below, an example of forming a conductor layer by the semiadditive method will be shown.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, on the formed plating seed layer, a mask pattern is formed to expose a portion of the plating seed layer corresponding to the desired wiring pattern. After forming a metal layer by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. Thereafter, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer with a desired wiring pattern.

The printed wiring board of the present invention may be provided with an insulating layer that is a cured product of the prepreg of the present invention and an embedded wiring layer embedded in the insulating layer.

As a manufacturing method of such a printed wiring board,

(1) A process of preparing a substrate with a wiring layer having an inner layer substrate and a wiring layer provided on at least one side of the substrate,

(2) A step of laminating the prepreg of the present invention on a substrate with a wiring layer so that the wiring layer is embedded in the prepreg, and heat curing to form an insulating layer,

(3) a process of interconnecting wiring layers, and

(4) Includes a process for removing the substrate.

It is preferable to have a metal layer made of copper foil or the like on both sides of the inner layer substrate used in this manufacturing method, and it is more preferable that the metal layer has a structure in which two or more metal layers are laminated. The details of step (1) are that a dry film (photosensitive resist film) is laminated on an inner layer substrate, exposed and developed under desired conditions using a photomask to form a patterned dry film. A wiring layer is formed by electroplating using the developed pattern dry film as a plating mask, and then the pattern dry film is peeled.

The conditions for lamination of the inner layer substrate and the dry film are the same as those of the above-described process (II), and the preferable range is also the same.

After the dry film is laminated on the inner layer substrate, exposure and development are performed using a photomask under predetermined conditions to form a desired pattern on the dry film.

The line (circuit width)/space (width between circuits) ratio of the wiring layer is not particularly limited, but is preferably 20/20 μm or less (i.e., pitch 40 μm or less), more preferably 18/18 μm or less (pitch 36 μm or less). ㎛ or less), more preferably 15/15 ㎛ or less (pitch 30 ㎛ or less). The lower limit of the line/space ratio of the wiring layer is not particularly limited, but is preferably 0.5/0.5 μm or more, and more preferably 1/1 μm or more. The pitch need not be the same throughout the wiring layer.

After forming a pattern on the dry film, a wiring layer is formed, and the dry film is peeled off. Here, the formation of the wiring layer can be performed by a plating method using a dry film on which a desired pattern is formed as a plating mask.

The conductor material used in the wiring layer is not particularly limited. In a suitable embodiment, the wiring layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. . The wiring layer may be a single metal layer or an alloy layer, and examples of the alloy layer include, for example, an alloy of two or more metals selected from the above group (e.g., nickel/chromium alloy, copper/nickel alloy, and copper/titanium alloy) ) can be mentioned.

The thickness of the wiring layer depends on the desired design of the printed wiring board, but is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, further preferably 10 μm to 20 μm, or 15 μm.

After forming the wiring layer, the dry film is peeled off. Peeling of the dry film can be performed by a known method. If necessary, unnecessary wiring patterns may be removed by etching or the like to form a desired wiring pattern.

Step (2) is a step of laminating the prepreg of the present invention on a substrate with a wiring layer so that the wiring layer is embedded in the prepreg, and heat curing it to form an insulating layer. The conditions for lamination of the substrate with the wiring layer and the prepreg are the same as those of the above-mentioned step (II), and the preferable range is also the same.

The step (3) is not particularly limited as long as the wiring layers can be connected between layers, but is at least one of the steps of forming a via hole in the insulating layer and forming a conductor layer, and the step of polishing or grinding the insulating layer to expose the wiring layer. It is desirable to have a process of . The process of forming a via hole in the insulating layer and forming a conductor layer is as described above.

The polishing or grinding method of the insulating layer is not particularly limited as long as the printed wiring layer can be exposed and the polishing or grinding surface is horizontal. Conventionally known polishing or grinding methods can be applied, for example, chemical machinery. Examples include a chemical mechanical polishing method using a polishing device, a mechanical polishing method such as buffing, and a surface grinding method using a grindstone rotation.

Step (4) is a step of removing the inner layer substrate and forming the printed wiring board of the present invention. The method of removing the inner layer substrate is not particularly limited. In one preferred embodiment, the inner layer substrate is peeled from the printed wiring board at the interface of the metal layer on the inner layer substrate, and the metal layer is removed by etching with, for example, an aqueous copper chloride solution.

[Semiconductor device]

The semiconductor device of the present invention is characterized by including the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

Semiconductor devices include various semiconductor devices used in electrical appliances (e.g., computers, mobile phones, digital cameras, televisions, etc.) and vehicles (e.g., motorcycles, automobiles, trains, ships, aircraft, etc.). there is.

The semiconductor device of the present invention can be manufactured by mounting components (semiconductor chips) in conduction points of a printed wiring board. A “continuity location” is a “location on a printed wiring board that transmits an electric signal,” and the location may be on the surface or buried. Additionally, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The semiconductor chip mounting method when manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically includes a wire bonding mounting method, a flip chip mounting method, and a bumpless build-up layer. A mounting method using (BBUL), a mounting method using an anisotropic conductive film (ACF), a mounting method using a non-conductive film (NCF), etc. Here, the “mounting method using a bumpless build-up layer (BBUL)” refers to a “mounting method in which a semiconductor chip is directly embedded in a recessed portion of a printed wiring board and the semiconductor chip is connected to the wiring on the printed wiring board.”

[Example]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. In addition, in the following description, “part” and “%” mean “part by mass” and “% by mass”, respectively, unless otherwise specified.

First, the measurement method and evaluation method in evaluating physical properties will be explained.

[Preparation of substrate for measurement and evaluation]

(1) Production of inner layer circuit board

IPC MULTI-PURPOSE TEST BOARD NO. was applied to a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness of 35 μm, substrate thickness of 0.8 mm, “R5715ES” manufactured by Matsushita Denko Co., Ltd.). A pattern of IPC C-25 (comb pattern with line/space ratio = 600/660 ㎛ (floating rate 48%)) was formed. Next, both sides of the substrate were roughened with a microetchant (“CZ8100” manufactured by MEC Co., Ltd.) to produce an inner layer circuit board.

(2) Lamination of prepreg

The prepregs prepared in the following examples and comparative examples and copper foil with a carrier (“MT-Ex” manufactured by Mitsui Kinjogu Kogyo Co., Ltd., copper foil thickness 3 μm) were placed on the top and bottom of the inner layer circuit board so that the copper foil was on the outside. It was placed and pressed at a temperature of 190°C for 90 minutes at a pressure of 20kgf/cm2 to obtain a laminate.

[evaluation]

<Evaluation of pattern embedding>

After peeling the carrier copper from the laminate obtained in (2) above, the copper was peeled off by immersing the remaining copper in an iron chloride solution, and 3 cm 2 of the surface of the insulating layer was scanned under a microscope (“Microscope VK-8510” manufactured by KEYENCE Co., Ltd.). ), the case where there were no wrinkles or voids was designated as “○”, and the case where there were wrinkles or voids was designated as “×”.

<Measurement of copper peel strength (copper plating peel strength)>

After peeling the carrier copper from the laminate obtained in (2) above, electrolytic copper plating was performed to form a conductor layer (copper layer) with a total thickness of 30 μm. For the obtained board with a conductor layer, a notch surrounding a partial area of 10 mm in width and 100 mm in length was inserted, and one end thereof was peeled off and used with clamps (T.S.E Co., Ltd., Autocom type tester AC-50C-SL). ), and the load (kgf/cm (N/cm)) when 35 mm was pulled off in the vertical direction at a speed of 50 mm/min at room temperature (25°C) was measured. The case where the peeling strength was 0.4 kgf/cm or more was designated as “○”, and the case where it was less than 0.4 kgf/cm was designated as “×”.

<Evaluation of bending>

The prepregs produced in the following Examples and Comparative Examples were placed on one side of copper foil (“JTC Foil” manufactured by JX Nikko Nissei Kinzoku Co., Ltd., copper foil thickness: 70 μm), and the temperature was adjusted at a pressure of 20 kgf/cm. An evaluation sample was obtained by pressing at 190°C for 90 minutes. Among the four sides of the obtained copper foil with prepreg, two sides were fixed to a SUS plate with polyimide tape, and the value of warpage was determined by determining the height of the highest point from the SUS plate. And, if the size of the warp is 0 cm or more but less than 1.5 cm, it is marked as 「○」, if it is -1 cm or more but less than 0 cm or 1.5 cm or more but less than 3 cm, it is marked as 「△」, and if it is less than -1 cm or 3.5 cm or more, it is marked as 「×. 」. In addition, regarding the size of the warp, when the prepreg was placed facing upward, the case where it bent toward the prepreg side was set as "+", and the case where it bent toward the copper foil side was set as "-".

<Evaluation of prepreg handling>

The prepreg produced in the following examples was stacked on the substrate obtained in (1) above at atmospheric pressure and then peeled off, and 3 cm 2 of the surface was observed using a microscope (“Microscope VK-8510” manufactured by KEYENCE Co., Ltd.). The case where there was no resin adhesion on the substrate was designated as “○”, and the case where there was resin adhesion on the substrate was designated as “×”.

<Measurement of average maximum length of domain>

The average maximum length of the domain was measured using a FIB-SEM combination device (“SMI3050SE” manufactured by SII Nanotechnology Co., Ltd.). A cross-section in the direction perpendicular to the surface of the prepreg, which was heat-cured at 100°C for 30 minutes and then at 170°C for 30 minutes, was cut using FIB (focused ion beam), and a cross-sectional SEM image (observation width of 60 μm) was obtained. , observation magnification of 2,000 times) was acquired. Cross-sectional SEM images of five randomly selected locations were observed, the largest domain present in the cross-sectional SEM image was selected, the maximum length of each selected domain was measured, and the average value was taken as the average maximum length.

[Example 1]

28 parts of butadiene-based elastomer prepared as follows, 5 parts of dicyclopentadiene-type epoxy resin (“HP-7200L” manufactured by DIC Co., Ltd., epoxy equivalent 245), and 5 parts of bisphenol-type epoxy resin (Shinnittetsu Chemical Co., Ltd.) Note) Manufactured as “ZX1059”, a 1:1 mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin, epoxy equivalent weight approximately 169) 3 parts were heated and dissolved in 15 parts of methyl ethyl ketone (MEK) while stirring. In addition, 1 part of a curing accelerator (1B2PZ, 1-benzyl-2-phenylimidazole, manufactured by Shikoku Chemicals Co., Ltd., and a MEK solution containing 5% by mass of non-volatile components) and organic particles (manufactured by Aika Kogyo Co., Ltd., 1 part of Staphylloid AC3816N) and spherical silica (“SOC4” manufactured by Adomatex Co., Ltd.) surface-treated with a phenylaminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) as an inorganic filler. 11 parts (average particle diameter: 1.0 μm) were mixed and uniformly dispersed with a high-speed rotating mixer to produce resin varnish 1.

<Preparation of prepreg>

Resin varnish 1 was impregnated into style WEA2013 manufactured by Nitto Boseki Co., Ltd. (warp density 46/25 mm, weft density 44/25 mm, fabric mass 81 g/m2, thickness 71 ㎛), and dried in a vertical drying furnace for 135 µm. A prepreg was prepared by drying at ℃ for 5 minutes. The resin composition content in the prepreg was 48% by mass, and the thickness of the prepreg was 90 μm. Additionally, the length of the prepreg in the vertical direction was 30 cm, and the length in the horizontal direction was 20 cm.

<Synthesis of butadiene-based elastomer>

In a reaction vessel, 50 g of G-3000 (bifunctional hydroxyl-terminated polybutadiene, number average molecular weight = 5047 (GPC method), hydroxyl equivalent = 1798 g/eq., solid content 100% by mass: manufactured by Nippon Soda Co., Ltd.) and 23.5 g of IFZOL 150 (aromatic hydrocarbon-based mixed solvent: manufactured by Idemitsu Seki Chemical Co., Ltd.) and 0.005 g of dibutyltin laurate were mixed and dissolved uniformly. When it became uniform, the temperature was raised to 50°C, and while stirring again, 4.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent = 87.08 g/eq.) was added, and the reaction was performed for about 3 hours. Next, the reaction product was cooled to room temperature, and then 8.96 g of benzophenone tetracarboxylic dianhydride (acid anhydride equivalent = 161.1 g/eq.), 0.07 g of triethylenediamine, and ethyldiglycol acetate (Daicel Chemical Co., Ltd.) 40.4 g (manufactured by Co., Ltd.) was added, the temperature was raised to 130°C while stirring, and the reaction was performed for about 4 hours. The disappearance of the NCO peak at 2250 cm ^-1 was confirmed by FT-IR. Confirmation of the disappearance of the NCO peak was considered the end point of the reaction, and the reactant was cooled to room temperature and filtered through a 100-mesh filter to obtain a butadiene-based elastomer.

Properties of butadiene-based elastomer:

Viscosity: 7.5Pa·s (25℃, E-type viscometer)

Acid value: 16.9㎎KOH/g

Solid content: 50% by mass

Number average molecular weight: 13723

Content of polybutadiene structural moiety: 50 × 100/(50 + 4.8 + 8.96) = 78.4 mass%

[Example 2]

Instead of spherical silica (“SOC4” manufactured by Adomatex Co., Ltd., average particle diameter 1.0 μm) 11 parts, diamond-shaped boehmite (“BMB-05” manufactured by Kawai Sekidan Kogyo Co., Ltd., average particle diameter 0.5 μm) 15 Resin varnish 2 and prepreg 2 were produced in the same manner as in Example 1, except that the parts were used.

[Example 3]

55 parts of an epoxy group-containing acrylic acid ester copolymer (“SG-P3” manufactured by Nagase Chemtex Co., Ltd., number average molecular weight (Mn): 850,000 g/mol, epoxy value of 0.21 eq/kg), and a bisphenol-type epoxy resin (Shinnittetsu Co., Ltd.) “ZX1059” manufactured by Gaku Co., Ltd., a 1:1 mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin, epoxy equivalent weight approximately 169) 1 part, and 1 part of bisphenol novolak-type epoxy resin (manufactured by Mitsubishi Chemical Corporation) 3.5 parts of “157S70” (epoxy equivalent 210) were dissolved by heating while stirring. In addition, 4 parts of a cresol novolak-based curing agent containing a triazine skeleton (“LA3018-50P” manufactured by DIC Co., Ltd., hydroxyl equivalent weight 151, 1-methoxy-2-propanol solution containing 50% non-volatile components), and a curing accelerator. (1B2PZ manufactured by Shikoku Chemicals Co., Ltd., 1-benzyl-2-phenylimidazole, MEK solution containing 5% by mass of non-volatile components) 0.1 part, and 0.8 parts of organic particles (Staphylloid AC3816N manufactured by Aika Kogyo Co., Ltd.) As an inorganic filler, 10 parts of diamond-shaped boehmite (“BMB-05” manufactured by Kawai Sekidan Kogyo Co., Ltd., average particle diameter 0.5 μm) was mixed and uniformly dispersed with a high-speed rotating mixer to produce resin varnish 3. . Prepreg 3 was produced in the same manner as in Example 1, except that Resin Varnish 3 was used instead of Resin Varnish 1.

[Example 4]

Resin varnish 4 and prepreg 4 were produced in the same manner as in Example 1, except that the addition amount of spherical silica (“SOC4” manufactured by Adomatex Co., Ltd., average particle diameter 1.0 μm) was changed to 40 parts.

[Example 5]

The amount of butadiene-based elastomer added was 10 parts, the amount of spherical silica (“SOC4” manufactured by Adomatex Co., Ltd., average particle diameter 1.0 μm) added was 7 parts, and the organic particles (made by Aika Kogyo Co., Ltd., Staphylloid). Resin varnish 5 and prepreg 5 were produced in the same manner as in Example 1, except that the addition amount of AC3816N) was changed to 0.6 part.

[Example 6]

5 parts of the butadiene-based elastomer prepared as above, 9 parts of dicyclopentadiene-type epoxy resin (“HP-7200L” manufactured by DIC Co., Ltd., epoxy equivalent 245), and 9 parts of bisphenol-type epoxy resin (Shinnittetsu Chemical Co., Ltd. Note) 4 parts of the product “ZX1059”, a 1:1 mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin, epoxy equivalent weight approximately 169) were heated and dissolved in 15 parts of methyl ethyl ketone (MEK) while stirring. In addition, 1 part of curing accelerator (1B2PZ manufactured by Shikoku Chemicals Co., Ltd., MEK solution with 5% by mass of non-volatile components), 1 part of organic particles (Staphylloid AC3816N manufactured by Aika Kogyo Co., Ltd.), and an inorganic filler. Mix 10 parts of spherical silica (“SOC4” manufactured by Adomatex Co., Ltd., average particle diameter 1.0 μm) surface-treated with a phenylaminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), Resin varnish 6 was produced by uniformly dispersing it with a high-speed rotating mixer. Prepreg 6 was produced in the same manner as in Example 1, except that Resin Varnish 6 was used instead of Resin Varnish 1.

[Example 7]

Resin varnish 7 and prepreg 7 were produced in the same manner as in Example 1, except that the addition amount of butadiene-based elastic polymer was changed to 40 parts.

[Example 8]

Resin varnish 8 and prepreg 8 were produced in the same manner as in Example 1, except that the addition amount of spherical silica (“SOC4” manufactured by Adomatex Co., Ltd., average particle diameter 1.0 μm) was changed to 5 parts.

[Example 9]

Resin varnish 9 and prepreg 9 were produced in the same manner as in Example 1, except that the addition amount of spherical silica (“SOC4” manufactured by Adomatex Co., Ltd., average particle diameter 1.0 μm) was changed to 60 parts.

[Comparative Example 1]

28 parts of the butadiene-based elastomer prepared as above, and a bisphenol-type epoxy resin (“ZX1059” manufactured by Nippon Chemical Co., Ltd., a 1:1 mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin, epoxy equivalent) About 169) 2.5 parts and 5 parts of bisphenol novolak-type epoxy resin (“157S70” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 210) were dissolved in 15 parts of methyl ethyl ketone (MEK) by heating while stirring. In addition, 1 part of a curing accelerator (1B2PZ, 1-benzyl-2-phenylimidazole, manufactured by Shikoku Chemicals Co., Ltd., and a MEK solution containing 5% by mass of non-volatile components) and organic particles (manufactured by Aika Kogyo Co., Ltd., 1 part of Staphylloid AC3816N) and spherical silica (“SOC4” manufactured by Adomatex Co., Ltd.) surface-treated with a phenylaminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) as an inorganic filler. 11 parts (average particle diameter: 1.0 μm) were mixed and uniformly dispersed with a high-speed rotating mixer to produce resin varnish 10. Prepreg 10 was produced in the same manner as in Example 1, except that Resin Varnish 10 was used instead of Resin Varnish 1.

[Comparative Example 2]

Resin varnish 11 and prepreg 11 were produced in the same manner as in Example 1, except that the addition amount of organic particles (Staphylloid AC3816N, manufactured by Aika Kogyo Co., Ltd.) was changed to 4 parts.

[Comparative Example 3]

Resin varnish 12 and prepreg 12 were produced in the same manner as in Example 1, except that the butadiene-based elastic polymer was not added.

From the table, it can be seen that the prepregs of Examples 1 to 9 have improved handling properties, embedding properties, and copper plating peel strength, and do not cause warping. In addition, the prepregs of Comparative Examples 1, 2, and Comparative Example 3 containing no component (a), in which the average maximum length of the domain exceeds 15 μm, have any of the handling properties, embedding properties, copper plating peel strength, and warpage. It can be seen that one is inferior to the prepregs of Examples 1 to 9. In the measurement of the copper plating peel strength of Comparative Example 1, a part of the copper foil swelled just by heating the prepreg, and the copper foil peeled off thereafter, so the copper plating peel strength could not be measured.

Additionally, as shown in Figure 1, Example 1 had an average maximum domain length of 7.2 μm. As shown in Figure 2, in Example 2, the average maximum length of the domain is so small that it cannot be confirmed, and it can be seen that each component such as inorganic filler is dispersed. On the other hand, as shown in FIG. 3, Comparative Example 1 is considered to be inferior in embedding property and copper plating peel strength to Examples 1 to 9 because the average maximum length of the domain is 18.0 μm.

In Examples 6 and 7, since (A/(A+B))×100 is outside the range of 20 to 70, other examples where (A/(A+B))×100 are within the range of 20 to 70 Although the bending was lower than in the example, there was no actual damage during use.

In Examples 8 and 9, since the content of the inorganic filler is outside the range of 25 to 70% by mass, the warpage is lower than that of other examples where the content of the inorganic filler is within the range of 25 to 70% by mass. However, in actual use, There was no damage.

Claims (14)

It contains a sheet-like fiber base material and a resin composition impregnated into the sheet-like fiber base material,
The resin composition contains (a) an elastomer, (b) a thermosetting resin having an aromatic structure, and (c) an inorganic filler,
The component (a) is at least one resin selected from resins that have a glass transition temperature of 25°C or lower or a liquid state at 25°C and have a functional group capable of reacting with the component (b),
(c) The content of the component is 25 to 70% by mass, based on 100% by mass of the non-volatile component in the resin composition,
A prepreg containing a cured product obtained by thermosetting a resin composition and having an average maximum domain length of 15 μm or less. The prepreg according to claim 1, wherein the resin composition contains (d) organic particles. The method of claim 1, wherein component (a) is a butadiene structural unit, a polysiloxane structural unit, a (meth)acrylate structural unit, an alkylene structural unit, an alkyleneoxy structural unit, an isoprene structural unit, an isobutylene structural unit, and chloroprene. A prepreg having one or more structural units selected from structural units, urethane structural units, and polycarbonate structural units. The prepreg according to claim 1, which contains, as component (b), an epoxy resin that is in a solid state at a temperature of 20°C. The method of claim 1, wherein the component (b) contains an epoxy resin that is liquid at a temperature of 20°C and an epoxy resin that is solid at a temperature of 20°C, and the mass ratio of the liquid epoxy resin to the solid epoxy resin is 1:0.3 to 1:10. Phosphorus, prepreg. The prepreg according to claim 5, which is an epoxy resin that is solid at a temperature of 20°C and does not contain a resin having a naphthalene skeleton and a molecular weight of 400 or more. The prepreg according to claim 1, wherein when the mass of component (a) in the resin composition is A and the mass of component (b) is B, (A/(A+B)) x 100 is 20 to 70. The method according to claim 2, wherein the mass of component (a) in the resin composition is A, the mass of component (b) is B, and the mass of component (d) is D, (D/(A+B+D)) A prepreg where ×100 is 10 or less. The prepreg according to claim 1, which is used for forming an insulating layer of a printed wiring board. The prepreg according to claim 1, which is used for forming a build-up layer of a printed wiring board. A printed wiring board comprising an insulating layer formed by the prepreg according to any one of claims 1 to 10. A semiconductor device comprising the printed wiring board according to claim 11.
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