WO2018181286A1 - プリプレグの製造方法、プリプレグ、積層板、プリント配線板及び半導体パッケージ - Google Patents

プリプレグの製造方法、プリプレグ、積層板、プリント配線板及び半導体パッケージ Download PDF

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WO2018181286A1
WO2018181286A1 PCT/JP2018/012387 JP2018012387W WO2018181286A1 WO 2018181286 A1 WO2018181286 A1 WO 2018181286A1 JP 2018012387 W JP2018012387 W JP 2018012387W WO 2018181286 A1 WO2018181286 A1 WO 2018181286A1
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prepreg
group
epoxy resin
resin composition
thermosetting resin
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PCT/JP2018/012387
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English (en)
French (fr)
Japanese (ja)
Inventor
芳克 白男川
垣谷　稔
清水　浩
圭祐 串田
辰徳 金子
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日立化成株式会社
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Priority to CN201880034594.4A priority Critical patent/CN110678505B/zh
Priority to JP2019509871A priority patent/JP7120219B2/ja
Priority to KR1020197031500A priority patent/KR102478431B1/ko
Publication of WO2018181286A1 publication Critical patent/WO2018181286A1/ja
Priority to JP2022123936A priority patent/JP7459900B2/ja
Priority to JP2024038196A priority patent/JP2024071417A/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/06—Copolymers with vinyl aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/24—Thermosetting resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2435/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
    • C08J2435/06—Copolymers with vinyl aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins

Definitions

  • the present invention relates to a prepreg manufacturing method, a prepreg, a laminated board, a printed wiring board, and a semiconductor package.
  • the wiring board In multilayer printed wiring boards, it is important to have high electrical connection reliability and excellent high-frequency characteristics between multiple layers of wiring patterns formed with fine wiring pitch, and high connection reliability with semiconductor chips. Sex is required.
  • the wiring board In particular, in recent years, in a mother board such as a multi-function mobile phone terminal, the wiring board has a wiring width (L) and a spacing (S) (hereinafter referred to as wiring) along with high-speed communication, high wiring density, and extremely thin wiring board. In some cases, the width and the interval are combined to be expressed as [L / S]). With such narrowing of L / S, it is becoming difficult to stably produce a wiring board with a high yield.
  • a layer without a wiring pattern called a “skip layer” is provided in a part of the layers in consideration of a communication failure or the like.
  • the amount of wiring design increases and the number of layers of the wiring board increases.
  • the provision of the skip layer causes a problem that the thickness of the motherboard further increases.
  • L / S impedance can be easily controlled by lowering the dielectric constant of the insulating material, so L / S can be stably produced in a shape close to the current design, and the number of layers can be reduced by reducing skip layers.
  • the insulating material used for the wiring board is required to have a material characteristic with a small relative dielectric constant.
  • a mother board used for a multifunctional mobile phone terminal or the like is required to be connected by a small-diameter laser via when connecting between layers as the wiring density increases and the pattern width narrows.
  • filled plating is often used, and the connectivity at the interface between inner layer copper and plated copper is very important, so there is a tendency to improve the laser workability of the base material. .
  • a step of removing resin residual components is performed.
  • the desmear treatment is performed on the bottom surface and the wall surface of the laser via, when the resin component of the base material is dissolved in a large amount by the desmear treatment, the shape of the laser via may be remarkably deformed due to the dissolution of the resin. Various problems such as non-uniformity around the plating may occur. For this reason, it is required that the amount of the resin component of the base material dissolved by the desmear treatment, that is, the so-called desmear dissolution amount is an appropriate value.
  • a resin composition containing an epoxy resin see Patent Document 1
  • a resin composition containing polyphenylene ether and bismaleimide see Patent Document 2
  • a resin composition containing polyphenylene ether and a cyanate resin (patent Reference 3)
  • a resin composition containing at least one of styrene-based thermoplastic elastomers and / or triallyl cyanurate see Patent Document 4
  • a resin composition containing polybutadiene see Patent Document 5
  • polyphenylene A resin composition obtained by pre-reacting an ether resin, a polyfunctional maleimide and / or polyfunctional cyanate resin, and liquid polybutadiene see Patent Document 6
  • a compound having an unsaturated double bond group are provided.
  • insulating materials used for wiring boards tend to require various characteristics such as reducing the relative dielectric constant.
  • the dimensional variation of the prepreg varies with respect to interlayer connection by small diameter laser vias. Is also one of the most important characteristics.
  • a multi-step lamination method is required as a method for laminating the prepreg, and the prepreg is subjected to a plurality of heat amounts and stress during lamination. For this reason, when the variation in the dimensional change of the prepreg is large (meaning the variation in the amount of heat shrinkage), a misalignment of vias connecting the layers may occur each time the layers are stacked.
  • the prepreg containing the conventional resin composition does not sufficiently suppress the variation in the dimensional change, and there is room for further improvement in this respect. .
  • an object of the present invention is to provide a method for manufacturing a prepreg with a small variation in dimensional change, and to provide a prepreg, a laminate, a printed wiring board, and a semiconductor package with a small variation in dimensional change.
  • Another object of the present invention is to provide a prepreg, a laminated board, a printed wiring board, and a semiconductor package that are less likely to cause misalignment of vias.
  • the present inventors impregnated a thermosetting resin composition into a substrate, and then B-staged the thermosetting resin composition to obtain a prepreg precursor. After obtaining the prepreg, the surface of the prepreg precursor is heat-treated at a predetermined heat source temperature to obtain a prepreg. It came to do.
  • the present invention has been completed based on such knowledge.
  • the present invention relates to the following [1] to [20].
  • the surface heat treatment step is a step of heat-treating the surface of the prepreg precursor at a heat source temperature of 200 to 700 ° C.
  • the surface heat treatment step is a step of heat-treating the surface of the prepreg precursor so that the surface temperature of the prepreg precursor is 40 to 130 ° C.
  • a method for producing a prepreg. [3] The prepreg according to [1] or [2], further including a step of cooling the prepreg precursor to 5 to 60 ° C. after the step of obtaining the prepreg precursor and before the surface heat treatment step. Manufacturing method.
  • thermosetting resin composition contains (A) a maleimide compound.
  • the component (A) includes (a1) a maleimide compound having at least two N-substituted maleimide groups, (a2) a monoamine compound represented by the following general formula (a2-1), and (a3) The method for producing a prepreg according to the above [5], which is a maleimide compound having an N-substituted maleimide group obtained by reacting with a diamine compound represented by the general formula (a3-1).
  • R A4 represents an acidic substituent selected from a hydroxyl group, a carboxy group, and a sulfonic acid group
  • R A5 represents an alkyl group having 1 to 5 carbon atoms or a halogen atom.
  • t is an integer of 1 to 5
  • u is an integer of 0 to 4
  • 1 ⁇ t + u ⁇ 5 provided that when t is an integer of 2 to 5, a plurality of R A4 may be the same
  • a plurality of R A5 may be the same or different.
  • X A2 represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms or —O—.
  • R A6 and R A7 each independently represents an alkyl having 1 to 5 carbon atoms.
  • thermosetting resin composition further comprises (B) an epoxy resin, The above [5] or (C) containing a copolymer resin having a structural unit derived from a substituted vinyl compound and a structural unit derived from maleic anhydride, and (D) silica treated with an aminosilane coupling agent.
  • the component (B) is a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a naphthalene type epoxy resin, an anthracene type epoxy resin, a biphenyl type epoxy resin, a biphenyl aralkyl novolak type epoxy resin, and The method for producing a prepreg according to the above [7], which is at least one selected from the group consisting of dicyclopentadiene type epoxy resins.
  • R C1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • R C2 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkyl group having 6 to 20 carbon atoms
  • a prepreg comprising a base material and a thermosetting resin composition and having a standard deviation ⁇ of 0.012% or less determined according to the following method.
  • Standard deviation ⁇ calculation method A copper foil having a thickness of 18 ⁇ m is stacked on both surfaces of one prepreg, and heat-press molding is performed at 190 ° C. and 2.45 MPa for 90 minutes, thereby producing a double-sided copper-clad laminate having a thickness of 0.1 mm. With respect to the double-sided copper clad laminate thus obtained, a hole having a diameter of 1.0 mm is formed in the plane at the locations 1 to 8 shown in FIG. Use an image measuring machine to determine the distance between each of the three points in the warp direction (1-7, 2-6, 3-5) and weft direction (1-3, 8-4, 7-5) shown in FIG. And measure each distance as the initial value.
  • thermosetting resin composition contains (A) a maleimide compound.
  • thermosetting resin composition further comprises (B) an epoxy resin, The above [10] or (C) containing a copolymer resin having a structural unit derived from a substituted vinyl compound and a structural unit derived from maleic anhydride, and (D) silica treated with an aminosilane coupling agent.
  • the thermosetting resin composition contains (G) an epoxy resin and (H) an epoxy resin curing agent.
  • thermosetting resin composition contains (K) a silicone-modified maleimide compound and (L) an imidazole compound.
  • thermosetting resin composition contains (G) an epoxy resin and (H) an epoxy resin curing agent.
  • thermosetting resin composition contains (K) a silicone-modified maleimide compound and (L) an imidazole compound.
  • the present invention it is possible to provide a method for producing a prepreg with a small variation in dimensional change, and to provide a prepreg, a laminate, a printed wiring board, and a semiconductor package with a small variation in dimensional change.
  • the present invention can also provide a prepreg, a laminated board, a printed wiring board, and a semiconductor package that are less likely to cause misalignment of vias.
  • the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
  • the lower limit value and the upper limit value of the numerical range can be arbitrarily combined with the lower limit value and the upper limit value of other numerical ranges, respectively.
  • each component and material illustrated in this specification may be used individually by 1 type, and may use 2 or more types together.
  • the content of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. Means. Embodiments in which the items described in this specification are arbitrarily combined are also included in the present invention.
  • the present invention includes a step (step 1) of obtaining a prepreg precursor by impregnating a base material with a thermosetting resin composition and then B-staging the thermosetting resin composition to obtain the prepreg precursor.
  • the step 3 is a surface heat treatment step of obtaining a prepreg by heat-treating the surface of the prepreg precursor so that the surface temperature of the prepreg precursor becomes 40 to 130 ° C. after the step of obtaining the prepreg precursor.
  • step 2 the step of cooling the prepreg precursor to 5 to 35 ° C.
  • step 2 the step of cooling the prepreg precursor to 5 to 35 ° C.
  • Step 1 is a step of impregnating a base material with a thermosetting resin composition, and then B-staging the thermosetting resin composition to obtain a prepreg precursor.
  • a method of impregnating a base material with a thermosetting resin composition A hot-melt method, a solvent method, etc. are mentioned.
  • the hot melt method is a method of directly impregnating a base material with a thermosetting resin composition whose viscosity has been reduced by heating.
  • the thermosetting resin composition is once applied to coated paper having excellent peelability.
  • the solvent method is a method of impregnating a base material in a state where a thermosetting resin composition contains an organic solvent to form a resin varnish. Can be mentioned.
  • thermosetting resin composition in which the thermosetting resin composition is B-staged can be obtained by impregnating the base material with the thermosetting resin composition and then performing a heat treatment.
  • the B-staging may be performed simultaneously with the heating in laminating the resin film on the substrate. That is, the resin film may be laminated to the substrate while being heated, and the heating may be continued as it is to obtain a prepreg precursor by B-staging the thermosetting resin composition.
  • the heating temperature at the time of lamination and the heating temperature at the B-stage may be the same or different.
  • the heating temperature when laminating the resin film on the substrate is not particularly limited, but is preferably 15 to 150 ° C, 20 to 130 ° C, or 20 to 100 ° C.
  • the B-staging may be performed simultaneously with the heating for drying the resin varnish. That is, after the base material is immersed in the resin varnish, the organic solvent is dried by heating, and the heating is continued as it is, so that the thermosetting resin composition is B-staged to obtain a prepreg precursor.
  • the heating temperature at the time of lamination and the heating temperature at the B-stage may be the same or different.
  • the heating temperature for drying the resin varnish is not particularly limited, but is preferably 10 to 190 ° C., 15 to 180 ° C., or 15 to 170 ° C.
  • the conditions for B-staging in this step 1 are not particularly limited as long as the thermosetting resin composition can be B-staged, and may be appropriately determined according to the type of the thermosetting resin.
  • the heating temperature is, for example, preferably 70 to 190 ° C., 80 to 180 ° C., 120 to 180 ° C., or 140 to 180 ° C.
  • the heating method is not particularly limited, and examples thereof include a heating method using a panel heater, a heating method using hot air, a heating method using high frequency, a heating method using magnetic lines, a heating method using a laser, and a heating method combining these. Among these, a heating method using a panel heater and a heating method using hot air are simple and preferable.
  • the heating time is, for example, 1 to 30 minutes, 2 to 20 minutes, 2 to 10 minutes, or 2 to 6 minutes.
  • Step 2 is a step of cooling the prepreg precursor obtained in Step 1. That is, in step 2, the prepreg precursor obtained by subjecting the thermosetting resin composition to B-stage by performing heat treatment in step 1 is cooled to at least a temperature lower than the temperature at which the heat treatment was performed. It is a process. By performing step 2, the thermosetting resin composition is subjected to a thermal history that is generally imparted when producing a prepreg, such as B-staging and cooling, and the obtained prepreg precursor is There is a tendency to inherently cause strains and the like that cause dimensional changes in the prepreg.
  • the strain caused by the thermal history of heating (step 1) and cooling (step 2) before the step 3 to be described later are eliminated by the step 3 and the dimensional change.
  • This is preferable because it is easy to effectively achieve uniform amount.
  • the strain caused by the thermal history of heating (step 1) and cooling (step 2) once eliminated by step 3 does not occur even if the same thermal history is applied after step 3, Or even if it occurs, it becomes very small, and the prepreg obtained by the present invention tends to have very little variation in dimensional change.
  • the prepreg precursor may be cooled by natural cooling or may be performed using a cooling device such as a blower or a cooling roll. In addition, it is preferable to perform cooling with a blower from the viewpoint of productivity.
  • the surface temperature of the prepreg precursor after cooling in this step is usually 5 to 60 ° C., preferably 10 to 45 ° C., more preferably 10 to 30 ° C., and even more preferably room temperature.
  • room temperature refers to an ambient temperature without temperature control such as heating and cooling, and is generally about 15 to 25 ° C., but may vary depending on the weather, season, etc. It is not limited.
  • Step 3 is a surface heat treatment step for obtaining a prepreg by heat-treating the surface of the prepreg precursor at a heat source temperature of 200 to 700 ° C. with respect to the prepreg precursor obtained in the step 1 or the step 2. It can also be referred to as a surface heat treatment step in which the surface of the prepreg precursor is heat-treated so that the surface temperature of the body becomes 40 to 130 ° C. to obtain a prepreg.
  • a prepreg having a small variation in the dimensional change amount is obtained.
  • this step 3 eliminates the distortion of the base material in the prepreg precursor obtained in step 1 or 2, and reduces the dimensional change during curing due to the distortion. Therefore, it is considered that the variation in the dimensional change amount is reduced. By reducing the variation in the dimensional change amount, the occurrence of via misalignment is reduced.
  • the heating method of the surface heat treatment in step 3 is not particularly limited, and is a heating method using a panel heater, a heating method using hot air, a heating method using high frequency, a heating method using magnetic lines, a heating method using a laser, a heating method combining these, and the like. Is mentioned. Among these, from the viewpoint of easy control of the surface temperature, a heating method using a panel heater and a heating method using hot air are preferable.
  • the surface heat treatment is carried out at a heat source temperature of 200 to 700 ° C., but from the viewpoint of keeping the prepreg productivity better, and keeping the prepreg in the B-stage state, the moldability is kept good.
  • the heat source temperature in the surface heat treatment is preferably 250 to 700 ° C., more preferably 300 to 600 ° C., and further preferably 350 to 550 ° C.
  • the surface heat treatment is performed at a surface temperature of the prepreg precursor of, for example, preferably 40 to 40 from the viewpoint of reducing variation in dimensional change while maintaining good prepreg moldability.
  • the temperature is 130 ° C., more preferably 40 to 110 ° C., still more preferably 60 to 90 ° C. It is preferable that the surface temperature of the prepreg precursor is within the above range at the heat source temperature.
  • the heating time of the surface heat treatment is not particularly limited, but the viewpoint of keeping the prepreg productivity good, and maintaining the prepreg in the B-stage state, the dimensional change varies while keeping the moldability good. From the viewpoint of reduction, 1.0 to 10.0 seconds are preferred, 1.5 to 6.0 seconds are more preferred, and 2.0 to 4.0 seconds are even more preferred.
  • Increase in surface temperature of prepreg precursor due to surface heat treatment (that is, absolute value of difference between surface temperature before surface heat treatment and maximum surface temperature reached during surface heat treatment) has good moldability of prepreg From the viewpoint of reducing the variation in the amount of dimensional change while maintaining the temperature, it is preferably 5 to 110 ° C, more preferably 20 to 90 ° C, and further preferably 40 to 70 ° C.
  • the detailed heating conditions of the surface heat treatment may be obtained as long as the surface temperature of the prepreg precursor is higher than the surface temperature before the surface heat treatment is performed by setting the heat source temperature in the above-described range. It is not particularly limited as long as it does not significantly affect various properties (for example, fluidity) of the prepreg, and may be appropriately determined according to the type of the thermosetting resin.
  • the prepreg obtained in step 3 is preferably subjected to a cooling step for cooling the prepreg from the viewpoints of prepreg handling and tackiness.
  • the prepreg may be cooled by natural cooling or using a cooling device such as a blower or a cooling roll.
  • the temperature of the prepreg after cooling is usually 5 to 80 ° C., preferably 8 to 50 ° C., more preferably 10 to 30 ° C., and further preferably room temperature.
  • the content in terms of solid content of the thermosetting resin composition in the prepreg of the present invention obtained as described above is preferably 20 to 90% by mass, more preferably 30 to 85% by mass, and 50 to 80% by mass. Is more preferable.
  • the thickness of the prepreg of the present invention is, for example, 0.01 to 0.5 mm, and is preferably 0.02 to 0.3 mm from the viewpoint of enabling moldability and high-density wiring, and 0.05 to 0.00 mm. 2 mm is more preferable.
  • base material As a base material which comprises the prepreg of this invention, a sheet-like reinforcement base material is used, The well-known thing used for the laminated board for various electrical insulation materials can be used.
  • the material of the base material include natural fibers such as paper and cotton linter; inorganic fibers such as glass fiber and asbestos; organic fibers such as aramid, polyimide, polyvinyl alcohol, polyester, tetrafluoroethylene, and acrylic; and mixtures thereof. Can be mentioned. Among these, glass fiber is preferable from the viewpoint of flame retardancy.
  • Glass fiber base materials include woven fabrics using E glass, C glass, D glass, S glass, etc., or glass woven fabrics in which short fibers are bonded with an organic binder; Can be mentioned. More preferably, it is a glass woven fabric using E glass. These base materials have shapes, such as a woven fabric, a nonwoven fabric, a robink, a chopped strand mat, or a surfacing mat, for example. In addition, a material and a shape are selected by the use and performance of the target molding, and 1 type may be used independently and 2 or more types of materials and shapes can also be combined as needed.
  • the thickness of the substrate is, for example, 0.01 to 0.5 mm, and is preferably 0.015 to 0.2 mm, and preferably 0.02 to 0.15 mm from the viewpoint of enabling moldability and high-density wiring. More preferred. From the viewpoint of heat resistance, moisture resistance, workability, and the like, these substrates are preferably those that have been surface-treated with a silane coupling agent or the like, or those that have been mechanically subjected to fiber opening treatment.
  • thermosetting resin composition in addition to sufficiently suppressing the variation in dimensional change by using the following components of the thermosetting resin composition while utilizing the method for producing the prepreg of the present invention, High heat resistance, high metal foil adhesiveness, high glass transition temperature, low thermal expansion, moldability, and plating wraparound (laser processability) can be satisfied. From this viewpoint, it is preferable to use the following thermosetting resin composition.
  • thermosetting resin composition The thermosetting resin composition that can be used in the present invention is not particularly limited, but in addition to sufficiently suppressing variation in dimensional change, it has high heat resistance, high metal foil adhesion, and high glass. From the viewpoint of satisfying the transition temperature, low thermal expansibility, moldability, and plating rotability (laser processability), (A) a thermosetting resin composition containing a maleimide compound (hereinafter, thermosetting resin composition [I ] Is preferred. From the same viewpoint, the thermosetting resin composition [I] further comprises (B) an epoxy resin, (C) a copolymer resin having a structural unit derived from a substituted vinyl compound and a structural unit derived from maleic anhydride.
  • thermosetting resin composition [I] further comprises (B) an epoxy resin, (C) a copolymer resin having a structural unit derived from a substituted vinyl compound and a structural unit derived from maleic anhydride.
  • thermosetting resin composition [I] preferably contains (E) a curing agent, and from the viewpoint of flame retardancy, (F) preferably contains a flame retardant.
  • thermosetting resin composition [G) an epoxy resin and (H) an epoxy resin curing agent, and, if necessary, (I) a curing accelerator and (J) an inorganic filler Or (K) a silicone-modified maleimide compound and (L) an imidazole compound, and (M) a thermosetting resin composition containing an inorganic filler, if necessary. III].
  • Component (A) is a maleimide compound (hereinafter sometimes referred to as maleimide compound (A)), preferably a maleimide compound having an N-substituted maleimide group, and more preferably (a1) at least two N A maleimide compound having a substituted maleimide group [hereinafter abbreviated as maleimide compound (a1)], (a2) the following general formula (a2-1) (In General Formula (a2-1), R A4 represents an acidic substituent selected from a hydroxyl group, a carboxy group, and a sulfonic acid group, and R A5 represents an alkyl group having 1 to 5 carbon atoms or a halogen atom.
  • maleimide compound (A)) preferably a maleimide compound having an N-substituted maleimide group, and more preferably (a1) at least two N A maleimide compound having a substituted maleimide group [hereinafter abbreviated as maleimide compound (a1)], (a2) the following general
  • t is an integer of 1 to 5
  • u is an integer of 0 to 4
  • 1 ⁇ t + u ⁇ 5 provided that when t is an integer of 2 to 5, a plurality of R A4 may be the same
  • a plurality of R A5 may be the same or different.
  • X A2 represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms or —O—.
  • R A6 and R A7 each independently represents an alkyl having 1 to 5 carbon atoms.
  • diamine compound (a3) a diamine compound represented by the following [hereinafter abbreviated as diamine compound (a3)].
  • diamine compound (a3) a diamine compound represented by the following [hereinafter abbreviated as diamine compound (a3)].
  • the description regarding the maleimide compound (A) can also be read as the description of the maleimide compound having an N-substituted maleimide group.
  • the weight average molecular weight (Mw) of the maleimide compound (A) is preferably 400 to 3,500, more preferably 400 to 2,300, and still more preferably 800 from the viewpoints of solubility in organic solvents and mechanical strength. ⁇ 2,000.
  • the weight average molecular weight in this specification is a value measured by gel permeation chromatography (GPC) method (standard polystyrene conversion) using tetrahydrofuran as an eluent, and more specifically described in Examples. It is a value measured by the method.
  • the maleimide compound (a1) is a maleimide compound having at least two N-substituted maleimide groups.
  • a maleimide compound having an aliphatic hydrocarbon group (but no aromatic hydrocarbon group is present) between any two maleimide groups among a plurality of maleimide groups hereinafter referred to as fat
  • a maleimide compound containing an aromatic hydrocarbon group between any two maleimide groups of the plurality of maleimide groups hereinafter referred to as aromatic hydrocarbon group Referred to as a containing maleimide.
  • an aromatic hydrocarbon group-containing maleimide is preferable from the viewpoints of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability, and plating revolving property.
  • the aromatic hydrocarbon group-containing maleimide only needs to contain an aromatic hydrocarbon group between any combination of two maleimide groups selected arbitrarily, and is also an aliphatic hydrocarbon together with the aromatic hydrocarbon group. It may have a group.
  • maleimide compound (a1) from the viewpoint of high heat resistance, low relative dielectric constant, high metal foil adhesiveness, high glass transition temperature, low thermal expansion, moldability, and plating rotation, two or more per molecule Maleimide compounds having 5 N-substituted maleimide groups are preferred, and maleimide compounds having 2 N-substituted maleimide groups in one molecule are more preferred.
  • a maleimide compound (a1) following general formula (a1) from a viewpoint of high heat resistance, a low dielectric constant, high metal foil adhesiveness, high glass transition temperature, low thermal expansion property, moldability, and plating revolving property.
  • aromatic hydrocarbon group-containing maleimide represented by any of the following general formulas (a1-1), (a1-2) or (a1-4) is more preferred, and the aromatic hydrocarbon group-containing maleimide represented by the following general formula (a1-2) is particularly preferred.
  • R A1 to R A3 each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
  • X A1 represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, —O—, —C ( ⁇ O) —, —S—, —SS— or a sulfonyl group.
  • p, q, and r are each independently an integer of 0-4.
  • s is an integer of 0 to 10.
  • Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R A1 to R A3 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and n-pentyl group.
  • the aliphatic hydrocarbon group is preferably 1 to 1 carbon atoms from the viewpoints of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability, and plating swirlability.
  • 3 is an aliphatic hydrocarbon group, more preferably a methyl group or an ethyl group.
  • Examples of the alkylene group having 1 to 5 carbon atoms represented by X A1 include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, and a 1,5-pentamethylene group. Is mentioned.
  • the alkylene group is preferably an alkylene group having 1 to 3 carbon atoms from the viewpoints of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability, and plating rotation. Group, more preferably a methylene group.
  • Examples of the alkylidene group having 2 to 5 carbon atoms represented by X A1 include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, and an isopentylidene group.
  • an isopropylidene group is preferable from the viewpoints of high heat resistance, low relative dielectric constant, high metal foil adhesiveness, high glass transition temperature, low thermal expansion, moldability, and plating rotation.
  • X A1 is preferably an alkylene group having 1 to 5 carbon atoms or an alkylidene group having 2 to 5 carbon atoms among the above options.
  • p, q, and r are each independently an integer of 0 to 4, and have high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and roundness with plating.
  • each is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.
  • s is an integer of 0 to 10, and is preferably 0 to 5, more preferably 0 to 3, from the viewpoint of availability.
  • the aromatic hydrocarbon group-containing maleimide compound represented by the general formula (a1-3) is preferably a mixture in which s is 0 to 3.
  • maleimide compound (a1) examples include N, N′-ethylene bismaleimide, N, N′-hexamethylene bismaleimide, bis (4-maleimidocyclohexyl) methane, and 1,4-bis (maleimide).
  • Methyl) cyclohexane or other aliphatic hydrocarbon group-containing maleimide N, N ′-(1,3-phenylene) bismaleimide, N, N ′-[1,3- (2-methylphenylene)] bismaleimide, N, N ′-[1,3- (4-methylphenylene)] bismaleimide, N, N ′-(1,4-phenylene) bismaleimide, bis (4-maleimidophenyl) methane, bis (3-methyl-4- Maleimidophenyl) methane, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, bis (4-maleimide) Phenyl) ether, bis (4-maleimidophenyl) sulfone, bis (4-maleimidophenyl) sulfide, bis (4-maleimidophenyl) ketone, 1,4-bis (4-maleimidophenyl)
  • bis (4-maleimidophenyl) methane bis (4-maleimidophenyl) sulfone, bis (4-maleimidophenyl) sulfide, bis (4 -Maleimidophenyl) disulfide, N, N ′-(1,3-phenylene) bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane are preferred, and bis (4-Maleimidophenyl) methane and N, N ′-(1,3-phenylene) bismaleimide are preferred, and bis (4-maleimidophenyl) methane is particularly preferred from the viewpoint of solubility in a solvent.
  • the maleimide compound (a1) one type may be used alone, or two or more types may be used in combination.
  • the monoamine compound (a2) is a monoamine compound represented by the following general formula (a2-1).
  • R A4 represents an acidic substituent selected from a hydroxyl group, a carboxy group, and a sulfonic acid group.
  • R A5 represents an alkyl group having 1 to 5 carbon atoms or a halogen atom.
  • t is an integer of 1 to 5
  • u is an integer of 0 to 4
  • 1 ⁇ t + u ⁇ 5 is satisfied.
  • t is an integer of 2 to 5
  • a plurality of R A4 may be the same or different.
  • u is an integer of 2 to 4
  • a plurality of R A5 may be the same or different.
  • the acidic substituent represented by R A4 is preferably a hydroxyl group or a carboxy group from the viewpoint of solubility and reactivity, and more preferably a hydroxyl group in consideration of heat resistance.
  • t is an integer of 1 to 5, and preferably 1 to 3 from the viewpoints of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and plating-around properties.
  • Examples of the alkyl group having 1 to 5 carbon atoms represented by R A5 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl group. Can be mentioned.
  • the alkyl group is preferably an alkyl group having 1 to 3 carbon atoms.
  • Examples of the halogen atom represented by R A5 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • u is an integer of 0 to 4, and preferably 0 to 3 from the viewpoints of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and plating rotation.
  • the monoamine compound (a2) from the viewpoint of high heat resistance, low relative dielectric constant, high metal foil adhesiveness, high glass transition temperature, low thermal expansion, moldability, and plating revolving property, the following general formula ( a monoamine compound represented by a2-2) or (a2-3), more preferably a monoamine compound represented by the following general formula (a2-2).
  • R A4 , R A5 and u in the general formulas (a2-2) and (a2-3) are the same as those in the general formula (a2-1), and preferred ones are also the same.
  • Examples of the monoamine compound (a2) include o-aminophenol, m-aminophenol, p-aminophenol, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, o-aminobenzenesulfonic acid, Examples thereof include monoamine compounds having an acidic substituent, such as m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, and 3,5-dicarboxyaniline.
  • a monoamine compound (a2) may be used individually by 1 type, and may use 2 or more types together.
  • the diamine compound (a3) is a diamine compound represented by the following general formula (a3-1).
  • X A2 represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms or —O—.
  • R A6 and R A7 each independently represents an alkyl group having 1 to 5 carbon atoms, a halogen atom, or a hydroxyl group. Represents a carboxy group or a sulfonic acid group, and v and w are each independently an integer of 0 to 4.
  • X A2 is preferably a methylene group.
  • Examples of the alkyl group having 1 to 5 carbon atoms represented by R A6 and R A7 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl group. Groups and the like.
  • the alkyl group is preferably an alkyl group having 1 to 3 carbon atoms.
  • v and w are preferably integers of 0 to 2, more preferably 0 or 1, and still more preferably 0.
  • the diamine compound (a3) is preferably a diamine compound represented by the following general formula (a3-1 ′).
  • a3-1 ′ a diamine compound represented by the following general formula (a3-1 ′).
  • X A2 , R A6 , R A7 , v and w are the same as those in the general formula (a3-1), and preferred embodiments are also the same.
  • diamine compound (a3) examples include 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenylpropane, 2,2′-bis (4, 4'-diaminodiphenyl) propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'- Diaminodiphenylethane, 3,3'-diethyl-4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylthioether, 3,3'-dihydroxy-4,4'-diamino Diphenylmethane, 2,2 ', 6,6'-tetramethyl-4,4
  • 4,4′-diaminodiphenylmethane and 3,3′-diethyl-4,4′-diaminodiphenylmethane are preferable from the viewpoint of inexpensiveness, and 4,4′- from the viewpoint of solubility in a solvent.
  • Diaminodiphenylmethane is more preferred.
  • the reaction of the maleimide compound (a1), monoamine compound (a2) and diamine compound (a3) is preferably carried out by reacting at a reaction temperature of 70 to 200 ° C. for 0.1 to 10 hours in the presence of an organic solvent.
  • the reaction temperature is more preferably 70 to 160 ° C., further preferably 70 to 130 ° C., and particularly preferably 80 to 120 ° C.
  • the reaction time is more preferably 1 to 6 hours, still more preferably 1 to 4 hours.
  • the reaction of the maleimide compound (a1), the monoamine compound (a2), and the diamine compound (a3) is preferably performed in an organic solvent.
  • the organic solvent is not particularly limited as long as it does not adversely affect the reaction.
  • alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether
  • ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone
  • ether solvents such as tetrahydrofuran; toluene, xylene, mesitylene
  • Aromatic solvents such as dimethylformamide, dimethylacetamide, nitrogen atom-containing solvents including amide solvents such as N-methylpyrrolidone; sulfur atom-containing solvents including sulfoxide solvents such as dimethylsulfoxide; ethyl acetate, ⁇ - Examples thereof include ester solvents such as butyrolactone.
  • alcohol solvents are preferable from the viewpoint of solubility
  • ketone solvents, and ester solvents are preferable from the viewpoint of solubility
  • cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, and ⁇ -butyrolactone are more preferable from the viewpoint of low toxicity.
  • cyclohexanone, propylene glycol monomethyl ether, and dimethylacetamide are more preferable, and dimethylacetamide is particularly preferable.
  • An organic solvent may be used individually by 1 type, and may use 2 or more types together.
  • an organic solvent Preferably it is 25 with respect to a total of 100 mass parts of a maleimide compound (a1), a monoamine compound (a2), and a diamine compound (a3) from a viewpoint of solubility and reaction efficiency.
  • the amount may be ⁇ 1,000 parts by mass, more preferably 40 to 700 parts by mass, and still more preferably 60 to 250 parts by mass.
  • reaction catalyst You may implement reaction of a maleimide compound (a1), a monoamine compound (a2), and a diamine compound (a3) in presence of a reaction catalyst as needed.
  • the reaction catalyst include amine-based catalysts such as triethylamine, pyridine, and tributylamine; imidazole-based catalysts such as methylimidazole and phenylimidazole; and phosphorus-based catalysts such as triphenylphosphine.
  • a reaction catalyst may be used individually by 1 type, and may use 2 or more types together.
  • the amount of the reaction catalyst used is not particularly limited, but is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total mass of the maleimide compound (a1) and the monoamine compound (a2).
  • the component (B) is an epoxy resin (hereinafter sometimes referred to as an epoxy resin (B)), preferably an epoxy resin having at least two epoxy groups in one molecule.
  • the epoxy resin having at least two epoxy groups in one molecule include glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, and glycidyl ester type epoxy resins. Among these, a glycidyl ether type epoxy resin is preferable.
  • the epoxy resin (B) is classified into various epoxy resins depending on the main skeleton, and in each of the above-mentioned types of epoxy resins, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, etc.
  • Bisphenol type epoxy resin bisphenylaralkyl novolak type epoxy resin, phenol novolak type epoxy resin, alkylphenol novolak type epoxy resin, cresol novolak type epoxy resin, naphthol alkylphenol copolymer novolak type epoxy resin, naphthol aralkyl cresol copolymer novolak type epoxy resin, Bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin and other novolac epoxy resins; stilbene epoxy Resin; Triazine skeleton-containing epoxy resin; Fluorene skeleton-containing epoxy resin; Naphthalene-type epoxy resin; Anthracene-type epoxy resin; Triphenylmethane-type epoxy resin; Biphenyl-type epoxy resin; Xylylene-type epoxy resin; Dicyclopentadiene-type epoxy resin It is classified into alicyclic epoxy resin.
  • bisphenol F type epoxy resin phenol novolac type epoxy resin
  • phenol novolac type epoxy resin at least one selected from the group consisting of cresol novolac type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, biphenylaralkyl novolak type epoxy resin and dicyclopentadiene type epoxy resin, and low thermal expansion Cresol novolac type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl novolak type epoxy resin and phenol novolac type More preferably at least one selected from the group consisting of epoxy resin, more preferably a cresol novolak type epoxy resin.
  • An epoxy resin (B) may be used individually by 1 type, and may use 2 or more types together.
  • the epoxy equivalent of the epoxy resin (B) is preferably 100 to 500 g / eq, more preferably 120 to 400 g / eq, still more preferably 140 to 300 g / eq, and particularly preferably 170 to 240 g / eq.
  • the epoxy equivalent is the mass of the resin per epoxy group (g / eq), and can be measured according to the method defined in JIS K 7236 (2001).
  • epoxy resin (B) As a commercially available product of the epoxy resin (B), a cresol novolac type epoxy resin “EPICLON (registered trademark) N-673” (manufactured by DIC Corporation, epoxy equivalent: 205 to 215 g / eq), a naphthalene type epoxy resin “HP-4032” (Mitsubishi Chemical Corporation, epoxy equivalent: 152 g / eq), biphenyl type epoxy resin “YX-4000” (Mitsubishi Chemical Corporation, epoxy equivalent: 186 g / eq), dicyclopentadiene type epoxy resin “HP-7200H” (DIC Corporation, epoxy equivalent; 280 g / eq) and the like.
  • the epoxy equivalent is a value described in the catalog of the product manufacturer.
  • Component (C) is a copolymer resin having a structural unit derived from a substituted vinyl compound and a structural unit derived from maleic anhydride (hereinafter sometimes referred to as copolymer resin (C)).
  • the substituted vinyl compound include aromatic vinyl compounds, aliphatic vinyl compounds, and functional group-substituted vinyl compounds.
  • the aromatic vinyl compound include styrene, 1-methylstyrene, vinyltoluene, dimethylstyrene and the like.
  • Examples of the aliphatic vinyl compound include propylene, butadiene, isobutylene and the like.
  • Examples of the functional group-substituted vinyl compound include acrylonitrile; a compound having a (meth) acryloyl group such as methyl acrylate and methyl methacrylate.
  • a compound having a (meth) acryloyl group such as methyl acrylate and methyl methacrylate.
  • an aromatic vinyl compound is preferable, and styrene is more preferable.
  • a copolymer resin having a structural unit represented by the following general formula (Ci) and a structural unit represented by the following formula (C-ii) is preferable.
  • R C1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • R C2 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkyl group having 6 to 20 carbon atoms
  • Examples of the alkyl group having 1 to 5 carbon atoms represented by R C1 and R C2 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl group. Groups and the like.
  • the alkyl group is preferably an alkyl group having 1 to 3 carbon atoms.
  • Examples of the alkenyl group having 2 to 5 carbon atoms represented by R C2 include an allyl group and a crotyl group.
  • the alkenyl group is preferably an alkenyl group having 3 to 5 carbon atoms, more preferably an alkenyl group having 3 or 4 carbon atoms.
  • Examples of the aryl group having 6 to 20 carbon atoms represented by R C2 include a phenyl group, a naphthyl group, an anthryl group, and a biphenylyl group.
  • the aryl group is preferably an aryl group having 6 to 12 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms.
  • x is preferably 0 or 1, more preferably 0.
  • R C1 is a hydrogen atom and x is 0, derived from the structural unit represented by the following general formula (Ci-1), that is, styrene The structural unit is preferred.
  • the ratio is preferably from 1 to 9, more preferably from 2 to 9, even more preferably from 3 to 8, particularly preferably from 3 to 7.
  • the content ratio of the structural unit represented by the general formula (Ci) to the structural unit represented by the formula (C-ii) [(Ci) / (Cii)] (molar ratio) Similarly, it is preferably 1 to 9, more preferably 2 to 9, further preferably 3 to 8, and particularly preferably 3 to 7.
  • the total content of the structural unit derived from the substituted vinyl compound and the structural unit derived from maleic anhydride in the copolymer resin (C), and the structural unit represented by the general formula (Ci) and the formula ( The total content of the structural unit represented by C-ii) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and particularly preferably substantially 100% by mass. %.
  • the weight average molecular weight (Mw) of the copolymer resin (C) is preferably 4,500 to 18,000, more preferably 5,000 to 18,000, more preferably 6,000 to 17,000, still more preferably. It is 8,000 to 16,000, particularly preferably 8,000 to 15,000, most preferably 9,000 to 13,000.
  • the technique for lowering the dielectric constant of an epoxy resin by using a copolymer resin of styrene and maleic anhydride when applied to a printed wiring board material, results in insufficient impregnation into the substrate and copper foil peel strength. Therefore, it generally tends to be avoided. For this reason, the use of the copolymer resin (C) generally tends to be avoided, but the present invention uses the copolymer resin (C) while the components (A) and (B). And a thermosetting resin composition having high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature and low thermal expansion, and excellent moldability and plating-around properties. It was discovered and accomplished.
  • the copolymer resin (C) can be produced by copolymerizing a substituted vinyl compound and maleic anhydride.
  • the substituted vinyl compound is as described above.
  • a substituted vinyl compound may be used individually by 1 type, and may use 2 or more types together.
  • various polymerizable components may be copolymerized.
  • substituents such as allyl groups, methacryloyl groups, acryloyl groups, and hydroxy groups are introduced into the substituted vinyl compounds, particularly aromatic vinyl compounds, through Friedel-Crafts reactions or reactions using metal catalysts such as lithium. May be.
  • copolymer resin Commercial products can also be used as the copolymer resin (C).
  • silica treated with an aminosilane coupling agent hereinafter, sometimes referred to as silica (D) treated with an aminosilane coupling agent
  • low thermal expansibility is obtained.
  • the drop-off of silica is suppressed by improving the adhesion with the components (A) to (C)
  • the effect of suppressing deformation of the laser via shape due to excessive desmear can be obtained. Therefore, it is preferable.
  • the aminosilane coupling agent is preferably a silane coupling agent having a silicon-containing group represented by the following general formula (D-1) and an amino group.
  • D-1 is an alkyl group having 1 to 3 carbon atoms or an acyl group having 2 to 4 carbon atoms.
  • Y is an integer of 0 to 3
  • Examples of the alkyl group having 1 to 3 carbon atoms represented by R D1 include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Among these, a methyl group is preferable.
  • Examples of the acyl group having 2 to 4 carbon atoms represented by RD1 include an acetyl group, a propionyl group, and an acrylic group. Among these, an acetyl group is preferable.
  • the aminosilane coupling agent may have one amino group, two amino groups, or three or more, but usually one amino group or Have two.
  • aminosilane coupling agents having one amino group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl- Examples thereof include N- (1,3-dimethyl-butylidene) propylamine and 2-propynyl [3- (trimethoxysilyl) propyl] carbamate, but are not particularly limited thereto.
  • aminosilane coupling agents having two amino groups include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, Examples include 1- [3- (trimethoxysilyl) propyl] urea and 1- [3- (triethoxysilyl) propyl] urea, but are not particularly limited thereto.
  • silica (D) treated with an aminosilane coupling agent as an inorganic filler other than the component (D), for example, an epoxysilane coupling agent, a phenylsilane coupling agent, an alkylsilane coupling agent Alkenyl silane coupling agents, alkynyl silane coupling agents, haloalkyl silane coupling agents, siloxane coupling agents, hydrosilane coupling agents, silazane coupling agents, alkoxy silane coupling agents, chlorosilane cups Ring agent, (meth) acryl silane coupling agent, amino silane coupling agent, isocyanurate silane coupling agent, ureido silane coupling agent, mercapto silane coupling agent, sulfide silane coupling agent or Silica treated with a socyanate silane coupling agent or the like; Silica that has not been surface-treated can be used, but from the viewpoint of the above effect, silica (D) treated with an aminosi
  • the silica (D) processed with the aminosilane type coupling agent may be used together, and the silica processed with the above-mentioned other coupling agent.
  • the content of silica treated with another coupling agent is preferably 50 with respect to 100 parts by mass of silica (D) treated with an aminosilane coupling agent. It is at most 30 parts by mass, more preferably at most 15 parts by mass, particularly preferably at most 10 parts by mass, most preferably at most 5 parts by mass.
  • silica examples include precipitated silica produced by a wet method and having a high water content, and dry method silica produced by a dry method and containing almost no bound water or the like.
  • dry process silica examples include crushed silica, fumed silica, and fused silica (fused spherical silica) depending on the production method.
  • Silica is preferably fused silica from the viewpoint of low thermal expansibility and high fluidity when filled in a resin.
  • the average particle diameter of the silica is not particularly limited, but is preferably 0.1 to 10 ⁇ m, more preferably 0.1 to 6 ⁇ m, still more preferably 0.1 to 3 ⁇ m, and particularly preferably 1 to 3 ⁇ m.
  • the average particle diameter of silica 0.1 ⁇ m or more By making the average particle diameter of silica 0.1 ⁇ m or more, the fluidity at the time of high filling can be kept good, and by making it 10 ⁇ m or less, the mixing probability of coarse particles is reduced to make coarse particles. It is possible to suppress the occurrence of defects due to it.
  • the average particle diameter is a particle diameter at a point corresponding to a volume of 50% when the cumulative frequency distribution curve by the particle diameter is obtained with the total volume of the particles being 100%, and a laser diffraction scattering method is used. It can be measured with a particle size distribution measuring device.
  • the specific surface area of the silica is preferably 4 cm 2 / g or more, more preferably 4 to 9 cm 2 / g, still more preferably 5 to 7 cm 2 / g.
  • the thermosetting resin composition [I] may further contain a curing agent (hereinafter sometimes referred to as a curing agent (E)) as the component (E).
  • a curing agent hereinafter sometimes referred to as a curing agent (E)
  • the curing agent (E) include dicyandiamide; chain aliphatic amines other than dicyandiamide, such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, diethylaminopropylamine, tetramethylguanidine, and triethanolamine; Isophoronediamine, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, bis (4-amino-3-methyldicyclohexyl) methane, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) -2,4,8 , 10-t
  • dicyandiamide is preferable from the viewpoints of metal foil adhesion and low thermal expansion.
  • the dicyandiamide is represented by H 2 N—C ( ⁇ NH) —NH—CN, and the melting point is usually 205 to 215 ° C., and higher purity is 207 to 212 ° C.
  • Dicyandiamide is a crystalline substance and may be orthorhombic or plate-like. Dicyandiamide preferably has a purity of 98% or more, more preferably has a purity of 99% or more, and still more preferably has a purity of 99.4% or more.
  • commercially available products can be used. For example, commercially available products such as those manufactured by Nippon Carbide Industries Co., Ltd., Tokyo Chemical Industry Co., Ltd., Kishida Chemical Co., Ltd., and Nacalai Tesque Co., Ltd. can be used. .
  • thermosetting resin composition [I] may further contain a flame retardant (hereinafter sometimes referred to as a flame retardant (F)) as the component (F).
  • a flame retardant hereinafter sometimes referred to as a flame retardant (F)
  • dicyandiamide and the like also have an effect as a flame retardant, but in the present invention, those that can function as a curing agent are classified as curing agents and are not included in the component (F). .
  • the flame retardant examples include halogen-containing flame retardants containing bromine and chlorine; phosphorus flame retardants; nitrogen flame retardants such as guanidine sulfamate, melamine sulfate, melamine polyphosphate and melamine cyanurate; cyclophosphazene and polyphosphazene And phosphazene flame retardants such as inorganic flame retardants such as antimony trioxide.
  • a phosphorus flame retardant is preferable.
  • the phosphorus flame retardant include an inorganic phosphorus flame retardant and an organic phosphorus flame retardant.
  • inorganic phosphorus flame retardants include red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate and ammonium polyphosphate; inorganic nitrogen-containing phosphorus compounds such as phosphate amides Phosphoric acid; phosphine oxide and the like.
  • organic phosphorus flame retardants include aromatic phosphate esters, monosubstituted phosphonic acid diesters, disubstituted phosphinic acid esters, disubstituted phosphinic acid metal salts, organic nitrogen-containing phosphorus compounds, cyclic organophosphorus compounds, Examples thereof include phosphorus-containing phenol resins.
  • aromatic phosphate esters and metal salts of disubstituted phosphinic acids are preferred.
  • the metal salt is preferably any one of a lithium salt, a sodium salt, a potassium salt, a calcium salt, a magnesium salt, an aluminum salt, a titanium salt, and a zinc salt, and preferably an aluminum salt.
  • aromatic phosphates are more preferable.
  • aromatic phosphate ester examples include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylenyl phosphate, resorcinol bis (diphenyl phosphate), 1,3 -Phenylenebis (di-2,6-xylenyl phosphate), bisphenol A-bis (diphenyl phosphate), 1,3-phenylenebis (diphenyl phosphate) and the like.
  • Examples of monosubstituted phosphonic acid diesters include divinyl phenylphosphonate, diallyl phenylphosphonate, and bis (1-butenyl) phenylphosphonate.
  • Examples of the disubstituted phosphinic acid ester include phenyl diphenylphosphinate and methyl diphenylphosphinate.
  • Examples of the metal salt of disubstituted phosphinic acid include a metal salt of dialkylphosphinic acid, a metal salt of diallylphosphinic acid, a metal salt of divinylphosphinic acid, a metal salt of diarylphosphinic acid, and the like.
  • these metal salts are preferably any of lithium salt, sodium salt, potassium salt, calcium salt, magnesium salt, aluminum salt, titanium salt, and zinc salt.
  • organic nitrogen-containing phosphorus compound include phosphazene compounds such as bis (2-allylphenoxy) phosphazene and dicresyl phosphazene; melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, and the like.
  • cyclic organophosphorus compound examples include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa- And 10-phosphaphenanthrene-10-oxide.
  • at least one selected from an aromatic phosphate ester, a metal salt of a disubstituted phosphinic acid and a cyclic organic phosphorus compound is preferable, and an aromatic phosphate ester is more preferable.
  • the aromatic phosphate is preferably an aromatic phosphate represented by the following general formula (F-1) or (F-2), and the metal salt of the disubstituted phosphinic acid is:
  • a metal salt of a disubstituted phosphinic acid represented by the general formula (F-3) is preferable.
  • R F1 to R F5 are each independently an alkyl group having 1 to 5 carbon atoms or a halogen atom.
  • E and f are each independently an integer of 0 to 5, and g, h and i are each It is an integer of 0 to 4 independently.
  • R F6 and R F7 are each independently an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 14 carbon atoms.
  • M is a lithium atom, a sodium atom, a potassium atom, a calcium atom, a magnesium atom, an aluminum atom, a titanium atom, or a zinc atom.
  • j is an integer of 1 to 4.
  • Examples of the alkyl group having 1 to 5 carbon atoms represented by R F1 to R F5 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl group. Groups and the like.
  • the alkyl group is preferably an alkyl group having 1 to 3 carbon atoms.
  • Examples of the halogen atom represented by R F1 to R F5 include a fluorine atom.
  • e and f are preferably integers of 0 to 2, and more preferably 2.
  • g, h and i are preferably integers of 0 to 2, more preferably 0 or 1, and still more preferably 0.
  • Examples of the alkyl group having 1 to 5 carbon atoms represented by R F6 and R F7 include the same groups as in R F1 to R F5 .
  • Examples of the aryl group having 6 to 14 carbon atoms represented by R F6 and R F7 include a phenyl group, a naphthyl group, a biphenylyl group, and an anthryl group.
  • the aromatic hydrocarbon group is preferably an aryl group having 6 to 10 carbon atoms.
  • j is equal to the valence of the metal ion, that is, varies within the range of 1 to 4 corresponding to the type of M.
  • M is preferably an aluminum atom.
  • j is 3 when M is an aluminum atom.
  • the content of the components (A) to (D) is not particularly limited, but with respect to 100 parts by mass of the sum of the components (A) to (C),
  • the component (A) is preferably 15 to 65 parts by mass
  • the component (B) is 15 to 50 parts by mass
  • the component (C) is 10 to 45 parts by mass
  • the component (D) is preferably 30 to 70 parts by mass.
  • thermosetting resin composition [I] when it is 65 parts by mass or less, the fluidity and moldability of the thermosetting resin composition [I] tend to be good.
  • component (B) when it is 15 parts by mass or more with respect to 100 parts by mass of the total of the components (A) to (C), high heat resistance, high glass transition temperature and low thermal expansion tend to be obtained.
  • it when it is 50 parts by mass or less, it tends to be high heat resistance, low relative dielectric constant, high glass transition temperature, and low thermal expansion.
  • component (C) is 10 parts by mass or more with respect to 100 parts by mass of the sum of the components (A) to (C), high heat resistance and a low relative dielectric constant tend to be obtained.
  • thermosetting resin composition [I] tend to be good.
  • the content thereof is 0.5 to 6 parts by mass with respect to 100 parts by mass of the total of the components (A) to (C). It is preferable that When the component (E) is 0.5 parts by mass or more with respect to 100 parts by mass of the total of the components (A) to (C), high metal foil adhesion and excellent low thermal expansion tend to be obtained. On the other hand, when it is 6 parts by mass or less, high heat resistance tends to be obtained.
  • the content is from the viewpoint of flame retardancy, with respect to 100 parts by mass of the sum of the components (A) to (C).
  • the amount is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass.
  • the phosphorus atom content is 0.1 to 3 masses per 100 mass parts of the total of the components (A) to (C). Is preferably 0.2 to 3 parts by mass, more preferably 0.5 to 3 parts by mass.
  • thermosetting resin composition [I] can contain other components such as an additive and an organic solvent as needed within a range not impairing the effects of the present invention. These may contain 1 type independently, and may contain 2 or more types.
  • additives include inorganic fillers other than the component (D), curing accelerators, colorants, antioxidants, reducing agents, ultraviolet absorbers, fluorescent brighteners, adhesion improvers, organic fillers, and the like. Is mentioned. These may be used individually by 1 type and may use 2 or more types together.
  • thermosetting resin composition [I] may contain an organic solvent from the viewpoint of facilitating handling by dilution and easy manufacture of a prepreg described later.
  • the thermosetting resin composition containing an organic solvent may be referred to as a resin varnish.
  • the organic solvent is not particularly limited.
  • alcohol solvents, ketone solvents, and nitrogen atom-containing solvents are preferable, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl cellosolve, and propylene glycol monomethyl ether are more preferable, and methyl ethyl ketone and methyl isobutyl ketone are preferable. More preferred is methyl ethyl ketone.
  • An organic solvent may be used individually by 1 type, and may use 2 or more types together.
  • the content of the organic solvent in the thermosetting resin composition [I] may be appropriately adjusted to such an extent that the thermosetting resin composition [I] can be easily handled.
  • the solid content concentration (concentration of components other than the organic solvent) derived from the thermosetting resin composition [I] is preferably 30 to 90% by mass, and more preferably, as long as the workability is in the range. Is 40 to 80% by mass, more preferably 50 to 80% by mass.
  • the epoxy resin composition [II] contains the (A) maleimide compound contained in the thermosetting resin composition [I].
  • the present invention is not particularly limited to this embodiment, and may contain the (A) maleimide compound.
  • (G) epoxy resin which epoxy resin composition [II] contains the same thing as (B) epoxy resin in the said thermosetting resin composition [I] is mentioned, It demonstrates similarly.
  • bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl novolak type epoxy resin and dicyclopentadiene type epoxy resin At least one selected from the group consisting of: cresol novolak type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl novolak type from the viewpoint of low thermal expansion and high glass transition temperature More preferably, at least one selected from the group consisting of epoxy resins and phenol novolac type epoxy resins, biphenylaralkyl novolac type epoxy Fat is more preferable.
  • Epoxy resin curing agent examples include various phenol resin compounds, acid anhydride compounds, amine compounds, hydragit compounds, and the like.
  • the phenol resin compound examples include novolak type phenol resins and resol type phenol resins.
  • the acid anhydride compound examples include phthalic anhydride, benzophenone tetracarboxylic dianhydride, methyl hymic acid, and the like. It is done.
  • the amine compound include dicyandiamide, diaminodiphenylmethane, and guanylurea.
  • these epoxy resin curing agents from the viewpoint of improving reliability, a novolac type phenol resin is preferable, and a cresol novolac resin is more preferable.
  • novolac type phenol resin a commercially available product may be used, for example, a phenol novolac resin such as “TD2090” (trade name, manufactured by DIC Corporation), or a cresol such as “KA-1165” (trade name, manufactured by DIC Corporation). Examples thereof include novolac resin. Further, for example, commercially available products of triazine ring-containing novolac type phenol resins such as “Phenolite LA-1356” (trade name, manufactured by DIC Corporation), “Phenolite LA7050 series” (trade name, manufactured by DIC Corporation), and the like. Examples thereof include triazine-containing cresol novolak resins such as “Phenolite LA-3018” (trade name, manufactured by DIC Corporation).
  • the epoxy resin composition [II] may contain (I) a curing accelerator and (J) an inorganic filler, if necessary.
  • the epoxy resin composition [II] preferably contains (I) a curing accelerator from the viewpoint of promoting the reaction between the (G) epoxy resin and the (H) epoxy resin curing agent.
  • Curing accelerators include, for example, imidazole compounds such as 2-phenylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate; organophosphorus compounds such as triphenylphosphine Onium salts such as phosphonium borate; amines such as 1,8-diazabicycloundecene; 3- (3,4-dichlorophenyl) -1,1-dimethylurea and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, imidazole compounds are preferable, and 2-ethyl-4-methylimidazole is more preferable.
  • the epoxy resin composition [II] preferably contains an inorganic filler (J) from the viewpoint of low thermal expansion.
  • an inorganic filler for example, silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, titanium Examples thereof include barium acid, strontium titanate, calcium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. These may be used individually by 1 type and may use 2 or more types together. Among these, silica is preferable from the viewpoint of a low thermal expansion coefficient.
  • the average particle size of the inorganic filler is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, and further preferably 0.3 ⁇ m or more.
  • the inorganic filler may be subjected to a surface treatment.
  • a silane coupling agent treatment may be performed as the surface treatment.
  • the silane coupling agent include amino silane coupling agents, vinyl silane coupling agents, and epoxy silane coupling agents. Among these, silica subjected to surface treatment with an aminosilane coupling agent is preferable.
  • the content of the components (G) to (J) is not particularly limited, but with respect to 100 parts by mass of the sum of the components (G) to (J), (G 5) to 50 parts by weight of component (H), 5 to 50 parts by weight of component (H), 0.001 to 1 part by weight of component (I), and 20 to 80 parts by weight of component (J). More preferably, (G) component is 5 to 35 parts by mass, (H) component is 5 to 40 parts by mass, and (I) component is 0.1 parts by mass with respect to 100 parts by mass of the sum of components (G) to (J). 001 to 1 part by mass, component (J) is 35 to 80 parts by mass.
  • the epoxy resin composition [II] can contain other components such as an additive and an organic solvent as necessary within a range not impairing the effects of the present invention. These may contain 1 type independently, and may contain 2 or more types.
  • additive examples include a colorant, an antioxidant, a reducing agent, an ultraviolet absorber, a fluorescent brightener, an adhesion improver, and an organic filler. These may be used individually by 1 type and may use 2 or more types together.
  • the silicone-modified maleimide compound is not particularly limited as long as it is a maleimide compound having a siloxane skeleton.
  • a maleimide compound (k-1) having at least two N-substituted maleimide groups in one molecule [hereinafter also referred to as “maleimide compound (k-1)”] and at least two second maleimide groups in one molecule.
  • Preferred examples include addition reaction products with a siloxane compound (k-2) having a primary amino group [hereinafter also referred to as “siloxane compound (k-2)”], and maleimide compound (k-1) and siloxane compound ( More preferred is an addition reaction product of k-2) and a monoamine compound [hereinafter also referred to as “monoamine compound (k-3)”].
  • a siloxane compound (k-2) having a primary amino group
  • maleimide compound (k-1) and siloxane compound More preferred is an addition reaction product of k-2) and a monoamine compound [hereinafter also referred to as “monoamine compound (k-3)”
  • the maleimide compound (k-1) the same compounds as the maleimide compound (a1) in the description of the (A) maleimide compound in the thermosetting resin composition [I] can be used.
  • the siloxane compound (k-2) preferably contains a structural unit represented by the following general formula (k-2-1).
  • R k1 and R k2 each independently represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a phenyl group having a substituent.
  • Examples of the alkyl group having 1 to 5 carbon atoms represented by R k1 and R k2 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl group. Groups and the like.
  • As the alkyl group an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable.
  • Examples of the substituent of the phenyl group in the “phenyl group having a substituent” include an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, and an alkynyl group having 2 to 5 carbon atoms. .
  • Examples of the alkyl group having 1 to 5 carbon atoms are the same as those described above.
  • Examples of the alkenyl group having 2 to 5 carbon atoms include a vinyl group and an allyl group.
  • Examples of the alkynyl group having 2 to 5 carbon atoms include ethynyl group and propargyl group.
  • R k1 and R k2 are each preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group.
  • siloxane compound (k-2) a siloxane diamine represented by the following general formula (k-2-2) is more preferable.
  • R k1 and R k2 are the same as those in general formula (k-2-1).
  • R k3 and R k4 each independently represent 1 to 5 represents an alkyl group, a phenyl group, or a phenyl group having a substituent, wherein R k5 and R k6 each independently represents a divalent organic group, and m is an integer of 2 to 100.
  • the alkyl group having 1 to 5 carbon atoms, the phenyl group, and the phenyl group having a substituent represented by R k3 and R k4 are described in the same manner as described for R k1 and R k2 .
  • R k3 and R k4 a methyl group is preferable.
  • the divalent organic group represented by R k5 and R k6 include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, —O—, or a divalent linking group in which these are combined.
  • the alkylene group include alkylene groups having 1 to 10 carbon atoms such as a methylene group, an ethylene group, and a propylene group.
  • Examples of the alkenylene group include alkenylene groups having 2 to 10 carbon atoms.
  • Examples of the alkynylene group include alkynylene groups having 2 to 10 carbon atoms.
  • Examples of the arylene group include arylene groups having 6 to 20 carbon atoms such as a phenylene group and a naphthylene group.
  • R k5 and R k6 an alkylene group and an arylene group are preferable.
  • m is preferably an integer of 2 to 50, more preferably an integer of 3 to 40, still more preferably an integer of 5 to 30, and further preferably an integer of 7 to 30.
  • the functional group equivalent of the siloxane compound (k-2) is not particularly limited, but is preferably 300 to 3,000 g / mol, more preferably 300 to 2,000 g / mol, and still more preferably 300 to 1,500 g / mol. is there.
  • a commercially available product can be used as the siloxane compound (k-2).
  • Examples of commercially available products include “KF-8010” (functional group equivalent of amino group: 430 g / mol), “X-22-161A” (functional group equivalent of amino group: 800 g / mol), “X-22- 161B "(functional group equivalent of amino group: 1,500 g / mol),” KF-8012 "(functional group equivalent of amino group: 2,200 g / mol),” KF-8008 "(functional group equivalent of amino group: 5,700 g / mol), “X-22-9409” (functional group equivalent of amino group: 700 g / mol), “X-22-1660B-3” (functional group equivalent of amino group: 2,200 g / mol) (Above, manufactured by Shin-Etsu Chemical Co., Ltd.), “BY-16-853U” (functional group equivalent of amino group: 460 g / mol), “BY-16-853” (functional group equivalent of amino
  • the same compounds as the monoamine compound (a2) in the thermosetting resin composition [I] can be used, and preferable ones are also the same.
  • one embodiment of the (K) silicone-modified maleimide compound is a reaction between the maleimide compound (k-1), the siloxane compound (k-2), and, if necessary, the monoamine compound (k-3). Can be manufactured.
  • the respective use ratios of the maleimide compound (k-1), the siloxane compound (k-2) and the monoamine compound (k-3) used as necessary are from the viewpoint of prevention of gelation and heat resistance.
  • the maleimide group equivalent of the maleimide compound (k-1) preferably exceeds the sum of the equivalents of primary amino groups of the siloxane compound (k-2) and the monoamine compound (k-3), and the maleimide compound (k-
  • the ratio of the equivalent of the maleimide group of 1) to the sum of the equivalents of primary amino groups of the siloxane compound (k-2) and the monoamine compound (k-3) [(k-1) / [(k-2) + (K ⁇ 3)] is preferably from 1 to 15, more preferably from 2 to 10, and even more preferably from 3 to 10.
  • the reaction temperature is preferably 70 to 150 ° C., more preferably 90 to 130 ° C. from the viewpoint of productivity and uniform reaction.
  • the reaction time is not particularly limited, but is preferably 0.1 to 10 hours, and more preferably 1 to 6 hours.
  • Examples of the (L) imidazole compound include 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-1- Methylimidazole, 1,2-diethylimidazole, 1-ethyl-2-methylimidazole, 2-ethyl-4-methylimidazole, 4-ethyl-2-methylimidazole, 1-isobutyl-2-methylimidazole, 2-phenyl- 4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4 -
  • the content of the components (K) to (M) is not particularly limited, but with respect to 100 parts by mass of the sum of the components (K) to (M),
  • the component (K) is preferably 15 to 80 parts by mass, the component (L) is 0.01 to 5 parts by mass, and the component (M) is preferably 15 to 80 parts by mass. More preferably, for 100 parts by mass of the sum of the components (K) to (M), the component (K) is 30 to 65 parts by mass, the component (L) is 0.01 to 3 parts by mass, and the component (M) is 30 to 65 parts by mass.
  • thermosetting resin composition [III] can contain other components such as an additive and an organic solvent as necessary within the range not impairing the effects of the present invention. These may contain 1 type independently, and may contain 2 or more types.
  • additive examples include a colorant, an antioxidant, a reducing agent, an ultraviolet absorber, a fluorescent brightener, an adhesion improver, and an organic filler. These may be used individually by 1 type and may use 2 or more types together.
  • the prepreg obtained by the production method of the present invention has little variation in the amount of dimensional change. Further, if the thermosetting resin composition is used, the prepreg has high heat resistance, high metal foil adhesion, and high glass transition temperature. Also, it has excellent low thermal expansibility, formability, and wraparound (laser processability).
  • the following prepregs can be provided.
  • the prepreg obtained by the production method of the present invention also corresponds to the following prepreg.
  • the following prepreg can be produced by the production method of the present invention.
  • a prepreg comprising a base material and a thermosetting resin composition and having a standard deviation ⁇ of 0.012% or less determined according to the following method.
  • Standard deviation ⁇ calculation method A copper foil having a thickness of 18 ⁇ m is stacked on both surfaces of one prepreg, and heat-press molding is performed at 190 ° C. and 2.45 MPa for 90 minutes, thereby producing a double-sided copper-clad laminate having a thickness of 0.1 mm.
  • a hole having a diameter of 1.0 mm is formed in the plane at the locations 1 to 8 shown in FIG.
  • the outer layer copper foil is removed and heated at 185 ° C. for 60 minutes in a dryer. After cooling, in the same manner as the initial value measurement method, three points each in the warp direction (1-7, 2-6, 3-5) and the weft direction (1-3, 8-4, 7-5) Measure distance.
  • An average value of the change rates is obtained from the change rate [(measured value after heat treatment ⁇ initial value) ⁇ 100 / initial value] with respect to the initial value of each measurement distance, and the standard deviation ⁇ with respect to the average value is calculated.
  • the image measuring machine is not particularly limited, but for example, “QV-A808P1L-D” (manufactured by Mitutoyo) can be used.
  • the standard deviation ⁇ is preferably 0.011% or less, more preferably 0.010% or less, and further preferably 0.009% or less.
  • the lower limit value of the standard deviation ⁇ is not particularly limited, but is usually 0.003% or more, 0.005% or more, 0.006% or more, 0.007 % Or more.
  • the laminated board of this invention contains the said prepreg and metal foil.
  • it can be manufactured by using one sheet of the prepreg or stacking 2 to 20 sheets as necessary, and arranging metal foil on one side or both sides thereof, preferably by heating and laminate molding.
  • positioned metal foil may be called a metal-clad laminated board.
  • the metal of the metal foil is not particularly limited as long as it is used for electrical insulating materials, but from the viewpoint of conductivity, preferably copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, Iron, titanium, chromium, or an alloy containing at least one of these metal elements is preferable, copper and amylnium are more preferable, and copper is more preferable.
  • a known molding method of a laminated plate for an electrical insulating material and a multilayer plate can be applied, for example, using a multistage press, a multistage vacuum press, continuous molding, an autoclave molding machine, etc.
  • Molding can be performed at 100 to 250 ° C., a pressure of 0.2 to 10 MPa, and a heating time of 0.1 to 5 hours.
  • the prepreg of the present invention and the printed wiring board for inner layer can be combined and laminated to produce a multilayer board.
  • the thickness of the metal foil is preferably 0.5 to 150 ⁇ m, more preferably 1 to 100 ⁇ m, still more preferably 5 to 50 ⁇ m, and particularly preferably 5 to 30 ⁇ m.
  • a plating layer by plating metal foil.
  • the metal of the plating layer is not particularly limited as long as it can be used for plating.
  • the metal of the plating layer is preferably made of copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, and an alloy containing at least one of these metal elements. Preferably it is selected.
  • a plating method For example, a well-known method, for example, the electroplating method and the electroless-plating method, can be utilized.
  • the present invention also provides a printed wiring board comprising the prepreg or the laminated board.
  • the printed wiring board of the present invention can be produced by subjecting a metal foil of a metal-clad laminate to circuit processing. For example, after forming a resist pattern on the surface of the metal foil, the unnecessary portion of the metal foil is removed by etching, the resist pattern is peeled off, a necessary through hole is formed by a drill, and a resist pattern is formed again. It can be performed by plating for conducting through holes and finally peeling off the resist pattern.
  • the above-described metal-clad laminate is further laminated on the surface of the printed wiring board thus obtained under the same conditions as described above, and further, the circuit is processed in the same manner as described above to obtain a multilayer printed wiring board. Can do. In this case, it is not always necessary to form a through hole, a via hole may be formed, and both can be formed. Such multi-layering is performed as many times as necessary.
  • the semiconductor package of the present invention is obtained by mounting a semiconductor on the printed wiring board of the present invention.
  • the semiconductor package of the present invention can be manufactured by mounting a semiconductor chip, a memory or the like at a predetermined position of the printed wiring board of the present invention.
  • thermosetting resin composition Using the thermosetting resin composition according to the present invention, a resin varnish, a prepreg precursor produced using a resin varnish, a prepreg obtained by subjecting the prepreg precursor to surface heat treatment, and a copper-clad laminate are produced, The produced copper clad laminate was evaluated.
  • the evaluation method is shown below.
  • Relative permittivity (Dk)> Using a network analyzer “8722C” (manufactured by Hewlett-Packard Company), the relative dielectric constant of the double-sided copper-clad laminate at 1 GHz was measured by a triplate structure linear line resonator method.
  • the test piece size is 200 mm x 50 mm x thickness 0.8 mm.
  • a straight line (line length 200 mm) with a width of 1.0 mm is formed by etching at the center of one side of one double-sided copper-clad laminate, and the back side is A ground layer was formed by leaving copper on the entire surface.
  • For the other double-sided copper-clad laminate one side was etched entirely and the back side was a ground layer.
  • These two double-sided copper-clad laminates were stacked with the ground layer on the outside to form a strip line. The measurement was performed at 25 ° C. The smaller the relative dielectric constant, the better.
  • Metal foil adhesion (copper foil peel strength)> Metal foil adhesion was evaluated by copper foil peel strength.
  • the double-sided copper-clad laminate produced in each example was immersed in a copper etching solution “ammonium persulfate (APS)” (manufactured by ADEKA) to form a copper foil having a width of 3 mm to produce an evaluation board.
  • the peel strength of the copper foil was measured using “AG-100C” (manufactured by Shimadzu Corporation). It shows that it is excellent in metal foil adhesiveness, so that a value is large.
  • Glass transition temperature (Tg)> The double-sided copper-clad laminate produced in each example was immersed in a copper etching solution “Ammonium Persulfate (APS)” (manufactured by ADEKA Corporation) to produce a 5 mm square evaluation substrate from which the copper foil was removed.
  • APS Ammonium Persulfate
  • Q400EM (manufactured by TA Instruments) was used to observe the thermal expansion characteristics at 30 to 260 ° C. in the plane direction (Z direction) of the evaluation substrate, and the inflection point of the expansion amount was defined as the glass transition temperature.
  • Tg thermal expansion coefficient below Tg (denoted as “ ⁇ Tg”) and the thermal expansion coefficient above Tg (denoted as “> Tg”) are shown separately.
  • the copper-clad laminate is desired to be further reduced in thickness, and in conjunction with this, the prepreg constituting the copper-clad laminate is also being considered to be thinner. Since the thinned prepreg is likely to warp, it is desired that the prepreg warp during heat treatment be small. In order to reduce the warpage, it is effective that the coefficient of thermal expansion in the surface direction of the substrate is small.
  • the difference between the plating thickness at the top of the laser hole and the plating thickness at the bottom of the laser hole is preferably within 10% of the plating thickness at the top of the laser hole. The existence ratio (%) of holes included in this range in the hole was determined.
  • (A) component The solution of the maleimide compound (A) manufactured by the following manufacture example 1 was used.
  • [Production Example 1] In a reaction vessel having a volume of 1 L equipped with a thermometer, a stirrer and a moisture meter with a reflux condenser, 19.2 g of 4,4′-diaminodiphenylmethane, 174.0 g of bis (4-maleimidophenyl) methane, p-aminophenol 6.6 g and dimethylacetamide 330.0 g were added and reacted at 100 ° C.
  • the weight average molecular weight (Mw) was converted from a calibration curve using standard polystyrene by gel permeation chromatography (GPC).
  • the calibration curve is standard polystyrene: TSK standard POLYSTYRENE (Type; A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [manufactured by Tosoh Corporation] Was approximated by a cubic equation.
  • the GPC conditions are shown below.
  • Component (D) fused silica treated with an aminosilane coupling agent (average particle size: 1.9 ⁇ m, specific surface area 5.8 m 2 / g)
  • Other inorganic filler “F05-30” (untreated crushed silica, average particle size: 4.2 ⁇ m, specific surface area 5.8 m 2 / g, manufactured by Fukushima Ceramics Co., Ltd.)
  • (E) component Dicyandiamide (Nippon Carbide Industries Co., Ltd.)
  • Examples 1 to 13, Comparative Examples 1 to 4 Each component shown above was blended as shown in Tables 1 to 4 below (however, in the case of a solution, the solid content is shown), and methyl ethyl ketone was added so that the nonvolatile content of the solution was 65 to 75% by mass.
  • resin varnishes were prepared for the thermosetting resin compositions of each Example and each Comparative Example. Each resin varnish obtained was impregnated with IPC standard # 3313 glass cloth (0.1 mm), dried with a panel heater set at a temperature of 160 ° C. for 4 minutes to be B-staged (step 1), and then at room temperature (step 1). The mixture was allowed to cool to about 20 ° C. (step 2) to obtain a prepreg precursor.
  • the prepreg was used as it was.
  • the obtained prepreg precursor was subjected to surface heat treatment (product surface temperature 70 ° C.) for 3 seconds with a panel heater whose surface heat treatment was set to a temperature of 500 ° C.
  • a prepreg was produced by cooling to 20 ° C. (step 3).
  • Copper foil “3EC-VLP-18” manufactured by Mitsui Kinzoku Co., Ltd.
  • the temperature is 190 ° C. and the pressure is 25 kgf / cm 2 (2.45 MPa).
  • a 18 ⁇ m thick copper foil “3EC-VLP-18” (manufactured by Mitsui Kinzoku Co., Ltd.) is stacked on both sides of one prepreg, and heated for 90 minutes at a temperature of 190 ° C. and a pressure of 25 kgf / cm 2 (2.45 MPa).
  • a double-sided copper-clad laminate having a thickness of 0.1 mm (for one prepreg) was prepared, and the dimensional variation was measured and evaluated using the double-sided copper-clad laminate according to the above-described method.
  • Example 14 instead of preparing the resin varnish in Example 1, a resin varnish was prepared using the following components. 19 parts by mass of biphenylaralkyl novolac type epoxy resin (Nippon Kayaku Co., Ltd., trade name: NC-3000, epoxy equivalent: 280 to 300 g / eq), cresol novolac resin (manufactured by DIC Corporation, trade name: KA-1165), Hydroxyl equivalent: 119 g / eq) 16 parts by mass, 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd.) 0.02 parts by mass, fused silica (manufactured by Admatechs Co., Ltd., treated with an aminosilane coupling agent) A resin varnish (solid content concentration: 70% by mass) was prepared by mixing 65 parts by mass of silica (average particle size: 2 ⁇ m) and diluting with a solvent (methyl ethyl ketone).
  • a resin varnish solid content
  • Example 2 Other steps were performed in the same manner as in Example 1 to obtain a prepreg.
  • a double-sided copper-clad laminate was prepared by the same method as in Example 1, and when the dimensional variation was measured and evaluated using the double-sided copper-clad laminate, the standard deviation ⁇ The value was 0.010%.
  • Example 15 instead of preparing the resin varnish in Example 1, a resin varnish was prepared using the following components.
  • a reaction vessel with a volume of 2 L that can be heated and cooled, equipped with a stirrer and a moisture quantifier with a reflux condenser, 75.7 g of KF-8010 (both end amine-modified silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.) and bis ( 4-maleimidophenyl) methane (trade name: BMI-1000, manufactured by Daiwa Kasei Kogyo Co., Ltd.) 168.0 g, p-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) 6.4 g, and solvent (methyl ethyl ketone) 250.0 g And reacted at 100 ° C.
  • KF-8010 both end amine-modified silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.
  • bis ( 4-maleimidophenyl) methane trade name
  • a silicone-modified maleimide compound 49.5 parts by mass of the silicone-modified maleimide compound, 50 parts by mass of fused silica (manufactured by Admatex Co., Ltd., fused silica treated with an aminosilane coupling agent) and 0.5 parts by mass of an isocyanate mask imidazole (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) , Trade name: G-809L) was mixed and diluted with a solvent (methyl ethyl ketone) to prepare a resin varnish (solid content concentration: 70% by mass). Other steps were performed in the same manner as in Example 1 to obtain a prepreg. Using the obtained prepreg, a double-sided copper-clad laminate was prepared by the same method as in Example 1, and when the dimensional variation was measured and evaluated using the double-sided copper-clad laminate, the standard deviation ⁇ The value was 0.009%.
  • the following was found.
  • the standard deviation ⁇ was smaller than that of the comparative example in which the surface heat treatment was not performed, and the variation in the dimensional change was sufficiently suppressed.
  • the heat resistance of the reflow solder is 10 cycles or more, which is higher than the required heat resistance level, low dielectric constant, high metal foil adhesion and high glass transition temperature are obtained, and low thermal expansion is achieved. Indicated. Moreover, since it jumped out of the glass cloth from the wall surface and had an appropriate roughened shape, it was confirmed that it has good plating revolving property.
  • the embedding property of the resin was good, and abnormalities such as blurring and voids were not confirmed.
  • the specific permittivity and the metal foil adhesion were better than those in Examples 11 to 13, and other characteristics were stably expressed.
  • the prepreg obtained by the present invention and a laminate comprising the prepreg are useful as printed wiring boards for electronic devices because of little variation in dimensional change.

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